WO2004022714A2 - Organic species that facilitate charge transfer to or from nanostructures - Google Patents

Organic species that facilitate charge transfer to or from nanostructures Download PDF

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Publication number
WO2004022714A2
WO2004022714A2 PCT/US2003/027847 US0327847W WO2004022714A2 WO 2004022714 A2 WO2004022714 A2 WO 2004022714A2 US 0327847 W US0327847 W US 0327847W WO 2004022714 A2 WO2004022714 A2 WO 2004022714A2
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Prior art keywords
composition
nanostructure
moiety
substituent
matrix
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PCT/US2003/027847
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French (fr)
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WO2004022714A3 (en
Inventor
Jeffery A. Whiteford
Mihai A. Buretea
Erik Scher
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Nanosys, Inc.
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Priority to AU2003272275A priority Critical patent/AU2003272275A1/en
Priority to CA002497451A priority patent/CA2497451A1/en
Priority to EP03754451A priority patent/EP1537187B1/en
Priority to JP2004534640A priority patent/JP2006511634A/en
Publication of WO2004022714A2 publication Critical patent/WO2004022714A2/en
Publication of WO2004022714A3 publication Critical patent/WO2004022714A3/en

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/58Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances
    • G01N33/588Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances with semiconductor nanocrystal label, e.g. quantum dots
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82BNANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N13/00Treatment of microorganisms or enzymes with electrical or wave energy, e.g. magnetism, sonic waves
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124Intrinsically conductive polymers
    • H01B1/128Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/655Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20Light-sensitive devices
    • H01G9/2027Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20Light-sensitive devices
    • H01G9/2059Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50Photovoltaic [PV] devices
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention is in the field of nanotechnology. More particularly, the present invention is directed to conductive ligands and matrices for use with nanostructures, as well as related methods for producing and using the conductive compositions, and related devices incorporating the conductive compositions.
  • Polymer-based light-emitting and photovoltaic devices including those incorporating nanocrystal-containing polymers are known in the art.
  • the performance of polymer-based photovoltaic devices has been improved, e.g., by embedding semiconductor nanocrystals into the polymer matrix.
  • nanocomposite-based photovoltaic devices are described in USSN 60/408,722, filed September 5, 2002; USSN 60/421,353, filed October 25, 2002 and USSN 60/452038, filed March 4, 2003.
  • the performance of these and other devices that employ nanocrystals can be further improved.
  • Semiconducting nanocrystals can be designed with specific optical properties and/or electronic structures, in part by controlling the size and shape of the nanocrystals used as part of the light harvesting element in the photovoltaic devices.
  • the polymeric matrix encompassing the nanocrystal can be selected to also absorb light.
  • charge transport within the photovoltaic device is generally limited by matrix constraints, rather than by the absorption properties of the nanocrystals. As a result, charge transport through the matrix and/or among the nanocrystals is an important element of optimal photovoltaic operation.
  • Nanocrystal syntheses typically produce particles having surfaces coated with a surfactant layer, e.g., a layer of molecules having long aliphatic chains, such as alkyl phosphonic acids, alkyl amines, alkyl carboxylic acids, alkyl phosphines or alkyl phosphine oxides. These ligands form a substantially non-conductive layer on the nanocrystal surface. In applications in which it is desirable to efficiently remove or add charges to nanocrystalline structures, the residual aliphatic ligand layer limits the charge transfer to the surface. Synthesis of water soluble semiconductor nanocrystals capable of light emission are described, for example, in USPN 6,251,303 to Bawendi et al. entitled “Water-soluble fluorescent nanocrystals" (June 6, 2001) and USPN 6,319,426 to Bawendi et al. titled “Water-soluble fluorescent semiconductor " (November 20, 2001).
  • a surfactant layer e.g., a layer of molecules having long
  • compositions small molecules, oligomers and polymers that can be used to modify charge transport across a surface or a nanostructure (e.g., nanocrystal) surface, or within a nanostructure (e.g., nanocrystal- containing matrix, as well as methods for making and using the novel compositions.
  • compositions contain a conjugated organic species and at least one binding group capable of interacting with a nanostructure (e.g., nanocrystal) surface; during use, the compositions are coupled via the binding group to the nanostructure (e.g., nanocrystal) surface, such that the compositions are substantially conductive to electrons and/or holes being transported by/through the nanostructure (e.g., nanocrystal) (e.g., during the process of extracting or injecting the electrons or holes).
  • a conjugated organic species e.g., nanocrystal
  • the compositions are coupled via the binding group to the nanostructure (e.g., nanocrystal) surface, such that the compositions are substantially conductive to electrons and/or holes being transported by/through the nanostructure (e.g., nanocrystal) (e.g., during the process of extracting or injecting the electrons or holes).
  • compositions of the present invention can optionally be derivatized with additional chemical groups, e.g., to enhance the electronic conjugation of the core organic species, to couple adjacent nanostructures (e.g., nanocrystals), or to facilitate dispersion, mixing and/or blending of nanostructures (e.g., nanocrystals) in various matrices.
  • additional chemical groups e.g., to enhance the electronic conjugation of the core organic species, to couple adjacent nanostructures (e.g., nanocrystals), or to facilitate dispersion, mixing and/or blending of nanostructures (e.g., nanocrystals) in various matrices.
  • the present invention provides conductive compositions for modification of charge transport across a nanostructure (e.g., nanocrystal)-containing matrix.
  • the conductive composition typically include a) a conjugated organic moiety as the "body structure," or core of the conductive molecule; b) a nanostructure (e.g., nanocrystal)- binding "head group” coupled to the body structure at a first position on the conjugated organic moiety; and c) a "tail group” coupled to the body structure at a second position on the conjugated organic moiety.
  • the conductive composition facilitates the injection and/or extraction of charge (electron and/or hole) with respect to the attached nanostructure, thereby modifying charge transport across a nanostructure-containing matrix.
  • the body structure typically comprises a conjugated alkyl moiety or a conjugated aryl moiety (e.g., a phenylene, thiophene, ethene, ethyne, aniline, fluorene, pyridine, perylene, phenanthralene, anthracene, an alkynyl, or a polynuclear aromatic moiety).
  • a conjugated alkyl moiety or a conjugated aryl moiety e.g., a phenylene, thiophene, ethene, ethyne, aniline, fluorene, pyridine, perylene, phenanthralene, anthracene, an alkynyl, or a polynuclear aromatic moiety.
  • Chemical structures for use as the functionahzed head group include, but are not limited to, one or more phosphonic acid, carboxylic acid, amine, phosphine, sulfonate, sulfmate, or thiol moieties.
  • Tail group structures can be either conducting or nonconducting chemical moieties; preferred tail group substituents include, but are not limited to, 1-propyne, 1-butyne, 1-pentyne, 1-hexyne, 1- heptyne, 1-octyne, 1-nonyne, 1-decyne, or an alkyne comprising between 3 and 22 carbons.
  • either or both the head group and the tail group further include one or more thiophene moieties positioned between the body structure and the head or tail substituent.
  • the tail group also includes a nanostructure (e.g., nanocrystal)-binding moiety (e.g., a phosphonic acid, carboxylic acid, amine, phosphine, or thiol moiety).
  • a nanostructure-binding head group and/or nanostructure- binding tail group can provide either a single chemical moiety for attachment to the nanostructure (i.e., monodentate) or multiple binding moieties (i.e., multidentate).
  • these moieties are chosen or selected for their ability to bind to selected types of nanostructures (for example, the head group(s) selectively bind p-type nanocrystals while the tail group(s) selectively bind n-type nanocrystals).
  • the body structure optionally includes one or more additional substituents, or "sidechains,” coupled to the conjugated organic species.
  • the sidechains are O-linked or N-linked sidechains coupled to the conjugated organic moiety. Addition of the sidechain (or other substituent) to the body structure preferably does not destroy the conjugation of the core organic species; rather, in some embodiments, the sidechain moiety or moieties extend the conjugation.
  • substituents for use as sidechain elements can include, but are nor limited to, an electron donating group, an electron withdrawing group, a conducting chemical structure, a nonconducting chemical structure, or various reactive functional groups or polymerizable elements (such as an acrylate moiety, a methacrylate moiety, or a vinyl moiety).
  • the sidechain is matched functionally and/or electronically to the nanostructure (e.g., nanocrystal)-containing matrix; in other embodiment, the sidechain element simply alters the solubility of the composition.
  • the conjugated compositions of the present invention have two sidechain substituents coupled to the body structure; however, the chemical compositions of the side chains need not be identical.
  • the sidechains can be employed to link and or align adjacent nanostructures.
  • Exemplary sidechain substituents for use in the compositions of the present invention include, but are not limited to, an O-linked hexane moiety, an O-linked 2- ethylhexyl moiety, an O-linked octyl moiety, an O-linked decyl moiety, an N-linked hexane moiety, an N-linked 2-ethylhexyl moiety, an N-linked octyl moiety, and an N-linked decyl moiety.
  • any N-linked or O-linked alkyl moiety having between 1 and 22 (or more) carbons are contemplated for use in the present invention.
  • the body structure employed in the conductive composition is an oligomeric or polymeric structure, rather than a monomeric chemical structure.
  • exemplary multimeric body structure components include, but are not limited to, poly(phenylene), poly(thiophene), poly(ethene), poly(ethyne), poly(aniline), poly(fiuorene), poly(pyridine), poly(polynuclear) moieties, and combinations thereof.
  • the multimeric body structure is composed of two or more monomeric body structure elements linked by a linker region, such as a dithiophene moiety.
  • the linker element allows or enhances electronic conjugation between the body structure elements.
  • the multimeric body structure can optionally include one or more sidechains coupled to one or more elements of the oligomeric or polymeric structure.
  • the present invention also provides polymeric conductive compositions for use with nanostructure (e.g., nanocrystal) structures (e.g., in the case of nanocrystals, either as a nanocrystal coating or as a polymer matrix).
  • nanostructure e.g., nanocrystal
  • structures e.g., in the case of nanocrystals, either as a nanocrystal coating or as a polymer matrix.
  • the polymeric conductive compositions have the structure [H x -B y -T z ] n , wherein H comprises at least one functionahzed head group capable of binding to a nanostructure surface or at least one head group bound to a nanostructure surface; wherein B comprises a body structure comprising one or more conjugated organic moieties, wherein a first conjugated organic moiety is coupled to a proximal functionahzed head group or bound head group; wherein T comprises at least one tail group coupled to the body structure; and wherein x, y, z and n independently comprise integers equal to or greater than 1.
  • the sum of the integers x, y, z and n is equal to or greater than 5, such that at least one element (head, body or tail) is present in more than one "copy" in the polymeric conductive composition.
  • the polymeric conductive composition is synthesized by polymerization of monomeric precursors through coupling of various polymerizable elements on one or more of the substituents.
  • the head group optionally is one or more phosphonic acid, carboxylic acid, amine, phosphine, phosphine oxide or thiol moieties;
  • the body structure is optionally a phenylene, thiophene, ethene, ethyne, aniline, fluorene, pyridine, perylene, phenanthralene, anthracene, an alkenyl moiety, a polynuclear aromatic moiety, or polymer thereof; and the tail group is optionally a 1-propyne, 1-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, 1-nonyne, 1-decyne, or an alkyne comprising between 3 and 22 carbons.
  • the body structure further comprises one or more O-linked or N-linked substituents (e.g., electron donating or electron withdrawing groups, conducting chemical structures, or nonconducting chemical structures) coupled to one or more polymer subunits (e.g., member conjugated organic moieties).
  • O-linked of N-linked substituents can be used, e.g., to alter the electronic signature of the composition, or alter the solubility of the polymeric conductive composition.
  • the present invention provides nanostructure (e.g., nanocrystal) -containing matrix compositions.
  • the nanostructure-matrix composition includes a nanostructure coupled to a conductive composition (e.g., ligand) of the present invention, and a matrix positioned proximal to the ligand-conjugated exterior surface of the nanostructure.
  • the matrix is also covalently coupled to the nanostructure-bound conductive composition.
  • the conductive composition is functionally or electronically matched to one or more substituents of the matrix.
  • the nanostructure (e.g., nanocrystal)-containing matrix composition includes a nanostructure and a matrix composed of the polymeric conductive composition of the present invention.
  • a portion of the nanostructure exterior surface is coupled to the polymeric matrix.
  • the nanostructure is derivatized or functionahzed with a conductive composition of the present invention prior to being embedded in the polymeric conductive composition.
  • the polymeric conductive composition and the nanostructure-bound conductive composition are matched functionally and/or electronically.
  • the matrix composition and the conductive composition can optionally be covalently coupled.
  • the nanostructure-matrix composition includes a conductive composition of the present invention coupled at a first position to a first nanostructure (e.g., nanocrystal) and coupled at a second position to a second nanostructure, and a matrix positioned proximal to the exterior surfaces of the nanostructure.
  • a first nanostructure e.g., nanocrystal
  • the second nanostructure is a n-type nanocrystal.
  • the present invention also provides methods of synthesizing an organic composition that facilitates charge transfer for use in a nanostructure-containing device.
  • the organic compositions made using these methods are particularly suitable for use in a photovoltaic device.
  • the methods include the steps of: a) providing a conjugated organic precursor, wherein the conjugated organic precursor comprises at least three positions available for attachment of substituent modules (e.g., head, tail and sidechain); b) providing a first substituent module, wherein the first substituent module comprises a phosphonic acid derivative, a carboxylic acid derivative, an amine derivative, a phosphine derivative, a thiol derivative, a thiophene derivative, or a combination thereof; c) providing a second substituent module, wherein the second substituent module comprises an alkyne derivative comprising between three and 22 carbons; d) optionally providing a third substituent module, wherein the optional third substituent module comprises an alkyl derivative comprising between one and 22 carbons; and e) coupling
  • At least one substituent of the first, second or third substituent modules is capable of binding to a nanostructure surface (or, optionally, the component is already bound to a nanostructure surface). Coupling of the various modules to the body structure does not destroy the electronic conjugation of the body structure. Rather, in a preferred embodiment, coupling of one or more of the substituent modules to the body structure extends the conjugation of the body structure.
  • the first substituent module is a thiophene derivative.
  • the thiophene-containing head group substituent module can be prepared, for example, by a) providing an arylhalide core structure; b) lithiating the arylhalide core structure at a first halide position and reacting with chlorotrimethylsilane (TMSCl) to yield a TMS-aryl intermediate core structure; c) lithiating the intermediate core structure at a second halide position and reacting the product with trimethyltinchloride (Me 3 SnCl) to yield a stannylated second intermediate; and d) combining the second intermediate with a halogenated thiophene to form a first substituent module comprising a TMS-aryl-thiophene derivative.
  • TMSCl chlorotrimethylsilane
  • Coupling the phosphite moiety to the TMS-aryl-thiophene derivative can be achieved, for example, by performing a palladium-catalyzed phosphite- aryl coupling.
  • the first substituent module can be functionahzed with the nanostructure- binding moiety (e.g., the phosphite group) either prior to coupling of the module to the body structure, or after the module has been attached.
  • Coupling of an alkyne moiety employed as the second substituent module can be performed, e.g., via a Sonogashira coupling.
  • the body structure has been functionahzed with thiophene moieties at the first (e.g., head) and/or second (e.g., tail) positions prior to addition of the head and tail moieties.
  • thiophene moieties at the first (e.g., head) and/or second (e.g., tail) positions prior to addition of the head and tail moieties.
  • Various reactions can be employed to couple the optional third substituent to the body structure.
  • alkylation reactions e.g., a Williamson ether synthesis, a Friedel-Crafts alkylation reaction, or other aromatic electrophilic substitution reaction
  • alkylation reactions can be used to couple the third substituent to the conjugated organic precursor at a third position having a hydroxyl or amine moiety, to form a sidechain-substituted intermediate composition.
  • the optional third substituent module (e.g., one or more sidechains) is coupled to the conjugated organic precursor prior to attachment of the first and/or second substituent modules.
  • providing and coupling the third substituent module can include: a) providing about 1.1 molar equivalents of a halogenated derivative of a sidechain substituent; b) combining the halogenated derivative with the conjugated organic precursor in the presence of potassium carbonate (K 2 CO ) and dimethyl formamide (DMF) to form a reaction mixture; and c) heating the reaction mixture to about 70°C, thereby coupling the third substituent to the conjugated organic moiety.
  • K 2 CO potassium carbonate
  • DMF dimethyl formamide
  • additional sidechain substituents can be added to the conjugated organic precursor during the third substituent coupling step.
  • coupling the third substituent module optionally further includes coupling a fourth substituent to the body structure at a fourth position.
  • the third and fourth substituents can be the same or different chemical species.
  • the methods of making the conductive composition also include the step of coupling or cojoining the head group (and any other nanostructure-binding moieties incorporated into the composition) to an external surface of a nanostructure, thereby providing a nanostructure-bound composition.
  • this step an be performed during the synthesis of the conductive composition (e.g., solid phase synthesis).
  • the methods of making the conductive composition can optionally further include the step of polymerizing the organic composition after coupling the composition to the nanostructure surface, thereby forming a polymerized conjugated organic composition.
  • the present invention also provides methods of modifying an interaction between a nanostructure (such as a nanocrystal) and an external matrix.
  • the methods include the steps of a) treating a nanostructure with a conductive composition the present invention; and b) forming a nanostructure -containing matrix comprising the treated nanostructure and a matrix composition, thereby modifying the interaction between the nanostructure and the external matrix.
  • the conductive composition applied to the nanostructure can be polymerized in situ, to form a polymerized conductive composition.
  • the matrix composition into which the coated nanostructure is placed constitutes the polymeric conductive composition of the present invention.
  • the present invention also provides devices, such as optoelectric devices, photovoltaic devices and light-emitting devices (LEDs) incorporating the conductive compositions of the present invention.
  • the conductive compositions of the present invention can be coupled to either nanoscale and non-nanoscale (e.g., bulk crystalline) assemblies.
  • the devices of the present invention typically include a first electrode surface and a second electrode surface, and having a semiconductor or nanostructure-containing matrix composition comprising the conductive compositions disposed between the two electrodes and electrically coupled to the first electrode surface and the second electrode surface.
  • the conductive compositions of the present invention are incorporated into photovoltaic devices, such as those described in U.S.
  • compositions of the present invention can be used for charge injection into a fluorescent core/shell nanostructure containing device, e.g., to make an LED for use as a display or white light source.
  • Figure 1 provides exemplary conductive compositions of the present invention.
  • Figure 2 provides additional exemplary conductive compositions of the present invention.
  • Figure 3 depicts a chemical synthesis scheme for one embodiment of the compositions of the present invention.
  • Figure 4 depicts a chemical synthesis scheme for another embodiment of the compositions of the present invention.
  • Figure 5 depicts a chemical synthesis scheme for a further embodiment of the compositions of the present invention.
  • Figure 6 depicts a chemical synthesis scheme for an additional embodiment of the compositions of the present invention.
  • Figure 7 depicts a chemical synthesis scheme for a further embodiment of the compositions of the present invention.
  • Figure 8 provides a pictorial representation of a further embodiment of the present invention depicting both monomeric and polymeric conductive compositions.
  • Figures 9 through 19 provide mass spectral and/or NMR data for exemplary intermediates and compositions of the present invention.
  • Figures 20 through 28 depict additional chemical synthesis schemes for additional embodiments of the present invention.
  • the present invention provides conductive small molecules, oligomers and polymers that can be used to modify charge transport across a nanostructure surface or within a nanostructure-containing matrix (e.g., a nanocomposite, e.g., comprising one or more nanocrystals, e.g., one or more inorganic nanocrystals).
  • a nanostructure-containing matrix e.g., a nanocomposite, e.g., comprising one or more nanocrystals, e.g., one or more inorganic nanocrystals.
  • Photovoltaic devices convert light (solar energy) into storable energy.
  • a nanocomposite e.g., a nanocrystal- containing composition
  • the absorption results in the formation of an electron-hole pair (also termed an "exciton").
  • the electron and hole can either recombine or remain separated, depending in part upon the configuration of the nanocomposite. Recombination of electrons and holes is desirable in some applications (e.g., light emission in LEDs) and undesirable in other applications.
  • the electron and hole preferably do not recombine, but rather travel to opposite electrodes.
  • nanostructures typically comprise one or more surface ligands (such as surfactant molecules introduced during synthesis) that are nonconductive in nature.
  • surface ligands such as surfactant molecules introduced during synthesis
  • compositions of the present invention are designed to moderate, enhance, or otherwise control the transport (e.g., separation) of the electron and hole generated in the nanocomposite.
  • the compositions are coupled to the nanocrystal surface, such that a conjugated organic species in the composition interacts electronically with the electrons and/or holes being transmitted through the nanocrystal. As noted above, this is in contrast with the currently-available organic nanocrystalline coatings, which are nonconductive in nature.
  • conductive composition refers to a monomeric
  • oligomeric or polymeric composition having the capacity for electron conduction, hole conduction, or the ability to otherwise undergo charge transfer.
  • conjugated organic moiety refers to an organic (i.e., carbon- containing) molecule having two or more double bonds alternating with single bonds, and as such includes both linear and cyclic structures.
  • alkyl refers to a chemical substituent consisting of or containing the monovalent group C n H 2n , where n is an integer greater than zero.
  • aryl refers to a chemical substituent consisting of or containing an aromatic group.
  • the terms “monodentate” and “multidentate” refers to a number of attachment sites (monodentate having one site and multidentate having more than one site).
  • polymerizable element refers to a chemical substituent or moiety capable of undergoing a self-polymerization and or co-polymerization reaction, and as such, includes, but is not limited to, vinyl derivatives, butadienes, trienes, tetraenes, diolefins, acetylenes, diacetylenes, styrene derivatives, as well as other reactive functional groups known to one of skill in the art.
  • oligomeric and polymeric are used interchangeably herein to refer to multimeric structures having more than one component monomer or subunit.
  • matrix refers to a material, often a polymeric material, into which a second material (e.g., a nanocrystalline composition) is embedded or surrounded.
  • the matrix can be a conductive composition, a semiconductive composition, or a non-conductive composition.
  • a “nanostructure” is a structure having at least one region or characteristic dimension with a dimension of less than about 500 nm, e.g., less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm. Typically, the region or characteristic dimension will be along the smallest axis of the structure. Examples of such structures include nanowires, nanorods, nanotubes, branched nanocrystals, nanotetrapods, tripods, bipods, nanocrystals, nanodots, quantum dots, nanoparticles, branched tetrapods (e.g., inorganic dendrimers), and the like.
  • Nanostructures can be substantially homogeneous in material properties, or in certain embodiments can be heterogeneous (e.g. heterostructures). Nanostructures can be, e.g., substantially crystalline, substantially monocrystalline, polycrystalline, amorphous, or a combination thereof. In one aspect, each of the three dimensions of the nanostructure has a dimension of less than about 500 nm, e.g., less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm. Nanostructures can comprise one or more surface ligands (e.g., surfactants).
  • surface ligands e.g., surfactants
  • crystalline or “substantially crystalline”, when used with respect to nanostructures, refer to the fact that the nanostructures typically exhibit long-range ordering across one or more dimensions of the structure. It will be understood by one of skill in the art that the term “long range ordering” will depend on the absolute size of the specific nanostructures, as ordering for a single crystal cannot extend beyond the boundaries of the crystal. In this case, “long-range ordering” will mean substantial order across at least the majority of the dimension of the nanostructure.
  • a nanostructure can bear an oxide or other coating, or can be comprised of a core and at least one shell. In such instances it will be appreciated that the oxide, shell(s), or other coating need not exhibit such ordering (e.g.
  • crystalline refers to the central core of the nanostructure (excluding the coating layers or shells).
  • crystalline or “substantially crystalline” as used herein are intended to also encompass structures comprising various defects, stacking faults, atomic substitutions, and the like, as long as the structure exhibits substantial long range ordering (e.g., order over at least about 80% of the length of at least one axis of the nanostructure or its core).
  • the interface between a core and the outside of a nanostructure or between a core and an adjacent shell or between a shell and a second adjacent shell may contain non-crystalline regions and may even be amorphous. This does not prevent the nanostructure from being crystalline or substantially crystalline as defined herein.
  • the term "monocrystalline" when used with respect to a nanostructure indicates that the nanostructure is substantially crystalline and comprises substantially a single crystal.
  • “monocrystalline” indicates that the core is substantially crystalline and comprises substantially a single crystal.
  • a “nanocrystal” is a nanostructure that is substantially monocrystalline.
  • a nanocrystal thus has at least one region or characteristic dimension with a dimension of less than about 500 nm, e.g., less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm.
  • the region or characteristic dimension will be along the smallest axis of the structure. Examples of such structures include nanowires, nanorods, nanotubes, branched nanowires, nanotetrapods, nanotripods, nanobipods, nanocrystals, nanodots, quantum dots, nanoparticles, nanoribbons, and the like.
  • Nanostructures can be substantially homogeneous in material properties, or in certain embodiments can be heterogeneous (e.g. heterostructures).
  • a nanocrystal can comprise one or more surface ligands (e.g., surfactants).
  • the nanocrystal is optionally substantially single crystal in structure (a "single crystal nanostructure” or a "monocrystalline nanostructure”).
  • nanostructures for use in the present invention can be fabricated from essentially any convenient material or material, preferably the nanostructure is prepared from an inorganic material, e.g., an inorganic conductive or semiconductive material.
  • a conductive or semi-conductive nanostructure often displays 1- dimensional quantum confinement, e.g., an electron can often travel along only one dimension of the structure.
  • Nanocrystals can be substantially homogeneous in material properties, or in certain embodiments can be heterogeneous (e.g. heterostructures).
  • the term "nanocrystal” is intended to encompass substantially monocrystalline nanostructures comprising various defects, stacking faults, atomic substitutions, and the like, as well as substantially monocrystalline nanostructures without such defects, faults, or substitutions.
  • the core of the nanocrystal is typically substantially monocrystalline, but the shell(s) need not be.
  • the nanocrystals can be fabricated from essentially any convenient material or materials.
  • a "nanowire” is a nanostructure that has one principle axis that is longer than the other two principle axes. Consequently, the nanowire has an aspect ratio greater than one; nanowires of this invention have an aspect ratio greater than about 1.5 or greater than about 2. Short nanowires, sometimes referred to as nanorods, typically have an aspect ratio between about 1.5 and about 10. Longer nanowires have an aspect ratio greater than about 10, greater than about 20, greater than about 50, or greater than about 100, or even greater than about 10,000.
  • the diameter of a nanowire is typically less than about 500 nm, preferably less than about 200 nm, more preferably less than about 150 nm, and most preferably less than about 100 nm, about 50 nm, or about 25 nm, or even less than about 10 nm or about 5 nm.
  • the nanowires employed in the present invention can be substantially homogeneous in material properties, or in certain embodiments can be heterogeneous (e.g. nanowire heterostructures).
  • the nanowires can be fabricated from essentially any convenient material or materials.
  • the nanowires can comprise "pure" materials, substantially pure materials, doped materials and the like, and can include insulators, conductors, and semiconductors. Nanowires are typically substantially crystalline and/or substantially monocrystalline.
  • Nanowires can have a variable diameter or can have a substantially uniform diameter, that is, a diameter that shows a variance less than about 20% (e.g., less than about 10%, less than about 5%, or less than about 1%) over the region of greatest variability and over a linear dimension of at least 5 nm (e.g., at least 10 nm, at least 20 nm, or at least 50 nm). Typically the diameter is evaluated away from the ends of the nanowire (e.g. over the central 20%, 40%, 50%, or 80% of the nanowire).
  • a nanowire can be straight or can be e.g. curved or bent, over the entire length of its long axis or a portion thereof.
  • a nanowire or a portion thereof can exhibit two- or three- dimensional quantum confinement.
  • Nanowires according to this invention can expressly exclude carbon nanotubes, and, in certain embodiments, exclude “whiskers” or “nanowhiskers”, particularly whiskers having a diameter greater than 100 nm, or greater than about 200 nm.
  • Nanorods, nanowires and other nanostructures are described in detail in Attorney Docket No. 40-000820US co-filed herewith, the contents of which are incorporated herein in their entirety.
  • An "aspect ratio” is the length of a first axis of a nanostructure divided by the average of the lengths of the second and third axes of the nanostructure, where the second and third axes are the two axes whose lengths are most nearly equal each other.
  • the aspect ratio for a perfect rod would be the length of its long axis divided by the diameter of a cross-section perpendicular to (normal to) the long axis.
  • the "band gap difference" between HOMO and LUMO states refers the energy necessary make the transition across the "band gap” region separating the valence and conduction bands.
  • the present invention provides conductive compositions for modification of charge transport, e.g., across a nanostructure-containing matrix.
  • the compositions are used in conjunction with a nanostructure composition, such as a nanocrystal-containing photovoltaic matrix.
  • the conductive compositions of the present invention can be employed with non-nanoscale semiconductive components.
  • the conductive compositions of the present invention typically include three basic components: a core element or "body structure," a "head group” coupled to the body structure at a first position and capable of associating with a nanostructure surface, and a "tail” group coupled to the body structure at a second position.
  • the conductive composition can optionally include one or more "sidechain” elements coupled to the body structure at additional locations (i.e. third position, fourth position, etc).
  • the elements comprising the conductive compositions of the present invention work together to provide a conductive coating on the bound surface (e.g., a nanocrystal surface), or a polymeric matrix encompassing the semiconductor surface, thereby permitting and/or enhancing electron and/or hole transfer.
  • a conductive coating on the bound surface e.g., a nanocrystal surface
  • a polymeric matrix encompassing the semiconductor surface
  • the conductive compositions (e.g., ligand-type coatings and/or polymeric matrices) of the present invention assist in the generation of the electric potential.
  • the assistance can be, for example, via donation (injection) of an electron to the nanocrystal or other semiconductive material, or via conduction (extraction) of the hole away from the nanocrystal or semiconductor.
  • the charge mobility (movement of the electrons) enhanced by the conductive compositions of the present invention is sufficiently fast so as to avoid recombination of the electron and hole.
  • a conjugated organic moiety is selected for the core of the conductive composition.
  • This conjugated moiety typically is either a conjugated alkyl moiety or a conjugated aryl moiety.
  • Exemplary body structures for use in the compositions of the present invention include, but are not limited to, phenylene, thiophene, ethene, ethyne, aniline, pyridine, phenanthralene, various alkenyl structures, and the like.
  • a polynuclear aromatic moiety e.g., a polynuclear aromatic hydrocarbon, or
  • PAH is employed as the conjugated organic moiety.
  • exemplary PAH compounds include, but are not limited to, anthracene, benzo[a]anthracene, chrysene, fluorene, perylene, naphthalene, acenaphthene, acenaphthalene, phenanthrene, pyrene, benzo[a]pyrene, and the like.
  • the function of the conjugated organic moiety is to provide hole transport from the crystal to the polymer matrix (and optionally, to an electrode or electrode surface of, e.g., a photovoltaic device). Movement of the hole along this conjugated "backbone" of the conductive composition (e.g., charge transport) is enhanced by selecting or matching the electronic characteristics of the body structure, such that hole transport from the nanocrystal to the polymer matrix is favored over electron transport (i.e., the body structure element of the conductive composition has a higher HOMO energy level than the nanocrystal and a lower HOMO level than the surrounding polymer).
  • the conductive composition of the present invention can be modularly designed for enhanced electron transport.
  • the body structure is an oligomeric or polymeric structure, such as poly(phenylene), poly(thiophene), poly(ethene), poly(ethyne), poly(aniline), poly(fluorene), poly(pyridine), poly (PAH), and the like.
  • the extent of polymerization can range from just a few repeating elements (e.g., 2, 3, 4, 5, 6, etc) or longer polymers (e.g., having tens of repeating units).
  • additional or alternative oligomeric or polymeric conjugated structures known to one of skill in the art can also be employed as the body structure of the present composition.
  • the conductive compositions of the present invention further include a "head group" coupled to the body structure at a first position on the conjugated organic moiety.
  • the head group is a functionahzed element capable of binding to a nanostructure surface.
  • the head group is a bound head group (e.g., for embodiments in which the composition is associated with the nanostructure). Both the bound and functionahzed chemical structures are considered “head groups" in the present invention.
  • Exemplary chemical moieties for use as functionahzed head groups in the present invention include, but are not limited to, phosphonic acid, phosphinic acid, carboxylic acid, amine, amine oxide, phosphine, phosphine oxide, phosphonate, phosphonite, hydroxyl, and thiol moieties.
  • nitrogen-containing aromatic compounds or heterocycles e.g., imidazoles, benzoimidazoles, pyridines, pyrimidines, purines, or quinolines
  • nitrogen-containing aromatic compounds or heterocycles e.g., imidazoles, benzoimidazoles, pyridines, pyrimidines, purines, or quinolines
  • exemplary compounds include, but are not limited to, derivatives of 2- methylpyridine, 3-ethylpyridine, 4-chloropyridine, collidine, dimethylquinoline, and other compounds commonly used as nanostructure growth terminators.
  • the functionahzed (or bound) head group is a monodentate structure (e.g., a single moiety capable of binding the nanostructure).
  • the head group is a multidentate structure capable of a plurality of interactions with the nanostructure surface.
  • the head group element includes one or more polymerizable elements.
  • the polymerizable element can be employed, in some embodiments, to prepare conductive compositions having a plurality of head group modules attached (e.g., linearly) to a single body structure.
  • One such composition would have the formula (H x )-B-T, in which x copies of the head moiety (H) are attached to a body structure (B) and tail group (T), e.g., during synthesis of the conjugated composition.
  • the polymerizable elements on the head group are used to polymerize proximal elements of the conductive composition.
  • the polymerization can occur between two head groups, or between a head group and another element of the conductive composition (e.g., a tail group or optional sidechain).
  • An exemplary composition of this nature is described by the formula (H-B-T) n , where n represents the number (or average number) of member compositions in the polymer.
  • proximal elements are preferably polymerized after attachment to the nanostructure surface, in some polymeric embodiments, the elements are polymerized prior to exposure to the nanostructure.
  • the conductive compositions of the present invention also include a tail group coupled to the body structure at a second position (tail position) on the conjugated organic moiety.
  • a tail group coupled to the body structure at a second position (tail position) on the conjugated organic moiety.
  • Either conducting or a non-conducting chemical structures can be employed as tail groups in the present invention.
  • the tail group is an alkyne structure composed of n carbons (where n is equal to 3-22); however, even larger alkyne structures (having greater than 22 carbons) are also contemplated for use in the compositions of the present invention.
  • Exemplary alkynes for use in the present invention include, but are not limited to, 1-propyne, 1-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1- octyne, 1-nonyne, and 1-decyne.
  • any alkyne comprising between 3 and 22 carbons (or longer) can be employed as a tail group in the present invention.
  • other moieties having "rigid" elements such methylene, aryl, acetylene and alkene groups, can be used as tail groups in the present invention.
  • the more rigid constituents can be used to produce more conductive compositions (and, in the embodiment in which the conductive compositions include polymerizable elements, a more thermodynamically predictable product).
  • the alkyne structure can be linear or branched, depending in part upon the particular system in which the composition will be employed.
  • the increased steric hindrances incurred by branched alkynyl chain employed as tail groups can affect the conjugation of the conductive composition (e.g., by altering the positioning of an aryl component of the body structure). Changes in the molecule-molecule and polymer-molecule order, stacking and packing can also have an effect on the electronic properties and charge transport capabilities.
  • linear (e.g., non- branched) alkyl chains are prefe ⁇ ed for use as tail group moieties.
  • the tail group further includes a thiophene moiety; when present, the thiophene is preferably positioned between the alkyne moiety and the body structure (e.g., the thiophene couples the tail group to the conjugated organic species at the second position of the body structure).
  • the tail group further includes a chemical functionality capable of binding to the nanostructure surface. As described for the head group element, the tail group can be either a monodentate or a multidentate structure.
  • the nanostructure-binding functionality incorporated into the tail group is optionally used, for example, for coupling to a second nanostructure surface (e.g., forming a bridging composition between proximal nanocrystals).
  • the conductive composition of the present invention can include a di-alkyne or di-alkene tail group substituent having the formula CC-(CH2) n -CC, in which CC represents either double or triple bonded carbon atoms (flanking an alkyl chain, in this embodiment).
  • a nanostructure binding moiety e.g., phosphanate
  • the presence of multiple alkyne or alkene moieties within the tail group module can be used to alter the geometry of the tail and can affect the binding of the head group.
  • the nanostructure binding moiety incorporated into the tail group can be the same or different moiety as present in the head group.
  • the nanostructure binding moiety incorporated into the tail group can be used to bind to the same nanostructure as the head group, or it can be coupled to an adjacent crystal (i.e., linking the crystals).
  • different nanostructure binding moieties favoring attachment to different nanostructure structures are employed in the multi-dentate conductive compositions of the present invention (forming, e.g., an asymmetric bidentate conductive composition). Such compositions can be employed, e.g., to align nanostructures within a two crystal system.
  • the tail group includes one or more polymerizable elements.
  • the polymerizable element can be employed, in some embodiments, to prepare conductive compositions having a plurality of tail group modules attached (e.g., linearly) to a single body structure.
  • One such composition would have the formula H-B-(T Z ), in which z copies of the tail moiety are attached to the body structure.
  • the polymerizable elements on the tail group are used to polymerize proximal elements of the conductive composition, similar to that described for the optional polymerizable elements on the head group (e.g., between two tail groups, or between a tail group and another element of the conductive composition). While the proximal elements are preferably polymerized after attachment to the nanostructure surface, the polymerizable elements can be coupled prior to exposure of the composition to the nanostructure.
  • the body structure optionally includes one or more sidechains coupled to the conjugated organic species.
  • the conductive composition includes two, three, or four side chains (although additional sidechains are conceivable given an appropriately- configured body structure).
  • Changes in sidechain composition can be used, e.g., to alter the solubility of the conductive composition, for electronic adjustment of the composition, and/or for polymerization purposes.
  • the sidechain can optionally include a carbonyl ester moiety; as a result of the electron- withdrawing property of the carbonyl, the conductive composition containing this sidechain will enhance (favor) electron transfer.
  • incorporation of a simple alkyl chain as the sidechain substituent will favor hole transfer by virtue of the electron donating nature of the substituent.
  • Either conducting or a non-conducting chemical structures can be employed as sidechains in the present invention.
  • Conducting chemical structures have the added advantage of extending the conjugation of the organic core structure.
  • the sidechains are O-linked or N-linked chemical structures (e.g., are coupled to an existing hydroxyl or amine group on the body structure).
  • Exemplary sidechain moieties for use in the present invention include, but are not limited to, an O-linked or N-linked hexane moiety, an O-linked or N-linked 2-ethylhexyl moiety, an O-linked or N-linked octyl moiety, an O-linked or N-linked decyl moiety.
  • any O-linked or N-linked alkyl moiety comprising between 5 and 22 (or more) carbons can be used as a sidechain component (including alkane, alkene, alkyne, vinyl, and aryl structures).
  • the chemical substituents employed as sidechain elements can optionally be either electron donating groups or electron withdrawing groups, depending upon the intended use.
  • electron withdrawing groups are preferred; in contrast, for transport of the "holes", electron donating groups function better.
  • a first sidechain is coupled to the body structure at a first sidechain position (i.e., a third position on the conjugated organic species), and a second sidechain is coupled to the body structure at a second sidechain position (i.e., a fourth position on the conjugated organic species).
  • the sidechains can be identical chemical moieties, or they can differ in their chemical structure.
  • the side chain(s) can have the same chemical composition as the head group or the tail group.
  • the sidechain substituent is matched functionally and or electronically to a matrix composition of the nanostructure- containing matrix.
  • the sidechain optionally can include functionalities which interact with matrix functionalities (e.g., affinity binding, ionic interactions, covalent interactions and/or bond formation, and the like).
  • the sidechain elements can be used to affect the electronic signature of the surrounding matrix.
  • the distance between the conductive composition (e.g., ligand) and the polymer matrix, the aryl group matrix -matrix stacking distance and packing order, and/or the matrix-ligand stacking distance and packing can be altered or controlled by varying the sidechain element of the conductive composition, thereby affecting the interaction of the side chain with the smrounding matrix and modifying the electronic signature of the matrix-ligand- nanostructure system.
  • the length of the alkyl portion of the sidechain can be used to influence solubility; as such and can be any length or branching scheme. Both solubility and electronic properties can be adjusted simultaneously (or independently) via various combinations of the sidechain elements.
  • the side group includes one or more polymerizable elements.
  • the polymerizable elements on the sidechains interact with each other , thereby crosslinking individual members of the conductive composition to form a polymeric conductive composition.
  • the polymerization can occur between sidechains on adjacent conductive compositions, or between a sidechain and another element of the conductive composition (e.g., a head group or tail group). While the proximal elements are preferably polymerized after attachment to the nanostructure surface, in some embodiments, the elements are polymerized prior to exposure to the nanostructure.
  • the polymerizable element can be employed to prepare extended sidechain components (e.g., as a means for coupling additional moieties to the conductive composition).
  • Exemplary chemical moieties which can be incorporated as sidechain elements include, but are not limited to, alkyl (e.g., alkane, alkene, or alkyne) chains ranging in length from one carbon to 22 carbons (or longer), carbonyls, acrylates, methacrylates, cinnamic esters, and the like.
  • the sidechain element includes a carbonyl ester having a diene moiety, such as butadiene (e.g., O-C(O)-(CH ) n - butadiene).
  • the diene moiety which can be positioned anywhere along the esterified alkyl chain (e.g., near the carbonyl, towards the middle of the alkyl chain, at the terminus distal to the O-linkage, etc.). can then optionally be polymerized, for example, with light via a 2+2 or 4+4 polymerization reaction. See, for example, Paleos (ed.) Polymerization in Organized Media (Gordon and Breach Science Publishers, Philadelphia, 1992.
  • the modular approach to the chemical synthesis of the conductive compositions of the present invention lends itself to a number of combinations of various head moieties, tail groups, and optional side chain elements.
  • one or more of the constituents of the conductive compositions can optionally include polymerizable elements.
  • the present invention also provides oligomeric and polymer conductive compositions for use with nanostructures.
  • the oligomeric and/or polymeric compositions can be used as either coatings on nanostructures, or as the matrix into which the nanostructure in embedded.
  • the nanostructure is coated with a first conductive composition of the present invention, and the embedded in an additional (e.g., second) polymeric conductive composition.
  • different types of nanostructures e.g., p-type and n-type nanocrystals
  • One way to accomplish efficient charge transport is by designing an electronic "stairway" for both holes and electrons via bandgap adjustment, where the matrix polymer may have a highest occupied molecular orbital (HOMO) level slightly higher than the HOMO of a nanostructure-bound conductive composition ligand (which itself has a HOMO level higher than that of the nanostructure). Since the energetically favored pathway for hole transport is from lower to higher HOMO levels, this design will promote hole transport from the nanostructure to the ligand to the polymer to the electrode. Conversely, the matrix polymer can have a LUMO (lowest unoccupied molecular orbital) level slightly lower than the ligand LUMO, and the ligand LUMO may be lower than the crystal LUMO level.
  • HOMO highest occupied molecular orbital
  • any of the elements of the of the conductive compositions of present invention can include one or more of the polymerizable elements.
  • Exemplary chemical substituents which can be incorporated into the composition but are not limited to, vinyl derivatives, butadienes, trienes, tetraenes, diolefms, acetylenes, diacetylenes, styrene derivatives and the like.
  • the polymerizable element can be situated at the end of the selected element, or it an be internal (e.g., amidst an alkyl chain substituent).
  • Various polymerization schemes are contemplated in the present invention, including, but not limited to, polyaddition reactions (thermal, photo-induced or radiation-induced); polycondensations; oxidative couplings, and the like.
  • a prefe ⁇ ed polymerization scheme is vinyl polymerization of sidechain substituents in adjacent conductive compositions..
  • the polymeric conductive compositions of the present invention typically have the structure [H x -B y -T z ] n , where H represents the head group, B represents the body structure, and T represents the tail group.
  • the subscripts x, y and z represent the number of repeating elements (of head group, body structure, or tail group, respectively) present in a "monomeric" subunit of the polymer, while the value for n provides for the number of monomeric units present in the polymer; these values are integers.
  • An embodiment in which x, y, z and n all equal 1 is equivalent to the monomeric conductive composition as previously described.
  • the sum of these integers (x+y+z+n) is an integer greater than 4 (i.e., 5 or greater).
  • Figure 8 depicts exemplary polymeric conductive compositions of the present invention in which multiple body structure components are depicted with similar or dissimilar sidechain elements attached.
  • N is an integer, ranging in value from 1 (i.e., the monomeric form of the composition) to 10 or more, (e.g., to 15, 2, 25, 50, 100, etc.)
  • Sidechains can also be present, coupled to one or more of the body structures in the polymeric conductive composition; these optional sidechains are not depicted in the formula independent of body structure B, but are optionally present.
  • the sidechain moiety is present on a majority of the body structures present (i.e., on at least 50% of the body structures); in further embodiments, the sidechain is present on at least 75%, 90%, 95%, 99% or essentially all of the member body structures.
  • these sidechain moieties can be the same chemical functionality; alternatively, the composition of the sidechain varies from body structure to body structure.
  • the body structures of the polymer alternate between attachment of two different sidechain moieties.
  • the plurality of sidechains present in the composition is a random mixture of two, three, four, or more chemical substituents.
  • At least one head group moiety of the polymeric conductive composition is bound to the nanostructure surface.
  • a majority of the head groups e.g., at least 50%, about 75%, about 90%, about 95%>, about 99%, or essentially all of the head groups
  • polymerization can be performed either prior to or after binding of the conductive composition to the nanostructure structure; furthermore, the polymer can be partially crosslinked in an initial step, and further crosslinked upon interaction with the nanostructure structure.
  • compositions including the conductive composition or polymer in combination with the nanostructure structure are also contemplated in the present invention.
  • the conductive compositions would also be useful in charge injection/extraction from other, non nanoscale surfaces, e.g., bulk crystalline materials, etc.
  • nanostructures and other nanoscale compositions are prefe ⁇ ed embodiment, the conductive compositions described herein can be used for charge injection/extraction from other, non nanoscale surfaces, e.g., bulk crystalline materials, etc., and as such are not limited to either nanoscale and non-nanoscale (e.g., bulk crystalline) assemblies.
  • the nanostructure-containing matrices comprise a nanostructure having an exterior surface, wherein a portion of the nanostructure exterior surface is cojoined to a conductive composition of the present invention; and a matrix component positioned proximal to the conjugated exterior surface of the nanostructure.
  • the conductive composition employed in the nanostructure-containing matrices can be either a monomeric composition or a polymeric version, e.g., coating the nanostructure.
  • the matrix component can be either a conductive matrix or a nonconductive matrix, depending on the use envisioned for the product.
  • Exemplary matrices for use in the present invention include, but are not limited to, poly-3-hexylthiophene (P3HT), poly(p-phenylene vinylene (PPV), and poly(2-methoxy, 5 ethyl (2' hexyloxy) p-phenylene vinylene (MEH-PPV).
  • P3HT poly-3-hexylthiophene
  • PV poly(p-phenylene vinylene
  • MEH-PPV poly(2-methoxy, 5 ethyl (2' hexyloxy) p-phenylene vinylene
  • the nanostructure-containing matrices of the present invention include, but are not limited to, a nanostructure and a matrix composition positioned proximal to an exterior surface of the nanostructure, wherein the matrix composition comprises a polymerized embodiment of the conductive compositions of the present invention.
  • the conductive polymer having the structure [T x -B y -H 2 ] n is contemplated, wherein H comprises at least one functionalized head group capable of binding to a nanostructure surface; wherein B comprises a body structure comprising one or more conjugated organic moieties, wherein a first conjugated organic moiety is coupled to the at least one functionalized head group; wherein T comprises at least one tail group coupled to the body structure; and wherein x, y, z and n independently comprise integers equal to or greater than 1.
  • the polymerization is achieved via crosslinking of polymerizable units on the elements (for example, the sidechain) of the composition.
  • the conductive polymeric composition of the matrix is covalently coupled to a further conductive composition applied to the nanostructure.
  • this additional conductive composition is functionally and/or electronically matched to one or more components of the conductive polymeric matrix.
  • Exemplary polymers for use in the present invention include, but are not limited to, thermoplastic polymers (e.g., polyolefms, polyesters, polysilicones, polyacrylonitrile resins, polystyrene resins, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, or fluoroplastics); thermosetting polymers (e.g., phenolic resins, urea resins, melamine resins, epoxy resins, polyurethane resins); engineering plastics (e.g., polyamides, polyacrylate resins, polyketones, polyimides, polysulfones, polycarbonates, polyacetals); and liquid crystal polymers, including main chain liquid crystal polymers (e.g., poly(hydroxynapthoic acid)) and side chain liquid crystal polymers (e.g., poly [n-((4'(4"- cyanphenyl)phenoxy)alkyl)vinyl ether]).
  • Certain embodiments include conductive organic polymers; see e.g. T. A. Skatherin (ed.) 1986 Handbook of Conducting Polymers I. (Marcel Dekker, New York).
  • conductive polymers for use as matrices of the present invention include, but are not limited to, poly(3-hexylthiophene) (P3HT), poly[2-methoxy, 5-(2'-ethyl-hexyloxy)-p-phenylene-vinylene] (MEH-PPV), poly(p-phenylene vinylene) (PPV), and polyaniline.
  • Nanostructures include, but are not limited to nanoscale and non-nanoscale (e.g., bulk crystalline) assemblies.
  • Nanostructures such as nanocrystals, nanowires, nanorods, nanoparticles and the like, can be fabricated by a number of mechanisms known to one of skill in the art. Furthermore, their size can be controlled by any of a number of convenient methods that can be adapted to different materials. For example, synthesis of nanocrystals of various composition is described in, e.g., Peng et al. (2000) "Shape control of CdSe nanocrystals" Nature 404:59-
  • the collection or population of nanostructures is substantially monodisperse in size and/or shape. See e.g., US patent application 20020071952 by Bawendi et al entitled “Preparation of nanocrystallites.”
  • the diameter of the inorganic nanowires can be varied, for example, to control the wavelength emitted by fluorescent nanowires.
  • the diameter of the nanowires is preferably between about 2 nm and about 100 nm, more preferably between about 2 nm and about 5 nm or between about 10 nm and about 50 nm.
  • the length of the nanowires can also be varied.
  • the inorganic nanowires have an aspect ratio between about 10 and about 10,000 (e.g., between about 20 and about 10,000, between about 50 and about 10,000, or between about 100 and about 10,000).
  • the nanowires can be fabricated of essentially any convenient material (e.g., a semiconducting material, a fe ⁇ oelectric material, a metal, etc.) and can comprise essentially a single material or can be heterostructures.
  • the nanostructures employed in the nanostructure-containing matrices of the present invention can be fabricated from essentially any convenient materials.
  • the nanocrystals can comprise an inorganic materials, e.g., a semiconducting material, for example a material comprising a first element selected from group2 or from group 12 of the periodic table and a second element selected from group 16 (e.g., ZnS, ZnO, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe, and like materials); a material comprising a first element selected from group 13 and a second element selected from group 15 (e.g., GaN, GaP, GaAs, GaSb, InN, InP, InA
  • group 15 e
  • nanocrystalline structures for use in the present invention can be found, for example, USSN 60/421,353 filed October 25, 20002 and co- filed provisional application USSN 60/452,038 filed March 4, 2003, by Scher et al. and titled "Nanocomposite Based Photovoltaic Devices.”
  • the devices of the present invention employ nanocrystals comprising CdSe, CdTe and or InP as the nanocrystal materials.
  • METHODS OF SYNTHESIZING CONDUCTIVE COMPOSITIONS [0113]
  • the present invention also provides methods of synthesizing an organic species that facilitates charge transfer, e.g., for use in a nanostructure-containing photovoltaic device. The methods provide a modular approach to the synthesis procedure, such that various head groups, tail groups, and side chains can be independently coupled to the selected body structure.
  • the methods of the present invention include the steps of a) providing a conjugated organic precursor, wherein the conjugated organic precursor comprises at least three positions available for attachment of substituent modules; b) providing a first substituent module (e.g., a head group or other nanostructure binding moiety), wherein the first substituent module comprises a nanostructure binding moiety, such as a phosphonic acid derivative, a carboxylic acid derivative, an amine derivative, a phosphine derivative, a thiol derivative, a thiophene derivative, or a combination thereof; and c) providing a second substituent module (e.g., a tail group), wherein the second substituent module comprises an alkyne derivative comprising between three and 22 carbons.
  • a first substituent module e.g., a head group or other nanostructure binding moiety
  • the first substituent module comprises a nanostructure binding moiety, such as a phosphonic acid derivative, a carboxylic acid derivative, an amine derivative, a phos
  • the method further includes providing a third substituent module (e.g., the sidechains), wherein the optional third substituent module comprises an alkyl derivative comprising between one and 22 carbons.
  • the substituent modules are then coupled to the conjugated organic precursor (e.g.., the body structure): the first substituent module at a first position, coupling the second substituent module at a second position, and the optional third substituent module at a third position, thereby synthesizing the organic composition.
  • the first, second and third positions delineate available attachment sites on the conjugated organic moiety, and are not representative either order of attachment during synthesis or IUPAC numbering conventions with respect to the conjugated organic species).
  • the optional third substituents are coupled to the body structure prior to attachment of the first (head) and second (tail) substituents.
  • coupling of the modules to the body structure does not destroy the electronic conjugation of the body structure; furthermore, at least one substituent of the first, second or third substituent modules is capable of binding to a nanostructure surface (or is already bound to a nanostructure surface).
  • the body structure provides the core of the conjugated organic species of the present invention.
  • the body structure is a conjugated organic species that either can be functionalized (e.g., by halogenation) or can be reacted with other functionalized moieties (head group, tail group, sidechains) to prepare the conductive compositions of the present invention.
  • the conjugated organic precursor is selected from any of a number of conjugated alkyl moieties or conjugated aryl moieties known to one of skill in the art.
  • exemplary conjugated organic precursors such as phenylene, thiophene, ethene, ethyne, aniline, fluorene, and pyridine derivatives, alkenyl moieties, or perylene, phenanthralene, anthracene, alkenyl or other polynuclear aromatic moieties (or polymeric derivatives thereof), have been discussed in previous sections.
  • coupling of one or more of the substituent modules to the body structure extends the conjugation of the body structure. Exemplary body structures are provided in Table 2.
  • One advantage to the convergent component synthesis ("modular") approach to the design and manufacture of the conductive compositions of the present invention is the ability to adjust or "tune" the reactivity of each component for the synthetic scheme.
  • the rate of aryl-aryl coupling can be increased or decreased by selecting an appropriate electron donating group or an electron withdrawing group on each respective component. Electron withdrawing groups tend to accelerate the oxidative addition step in palladium-catalyzed coupling reactions (see, e.g., Kuehl et. al. (1997) Organometallics 16: 1897).
  • the rate of coupling increases.
  • the enhancement in coupling may be accomplished by the electron withdrawing group weakening the aryl halide or aryl-stannane bond, thus affording a more facile insertion of the palladium catalyst between these moieties.
  • attaching the alkynyl tail group moiety to a thiophene precursor, followed by trimethylstannane attachment, and subsequently coupling this component to the body results in a faster coupling rate and higher overall yields than stepwise assembly.
  • a slower coupling rate is observed if the alkynyl moiety was added after the thiophene and body component were coupled in a divergent stepwise fashion.
  • the conductive compositions of the present invention often include one or two sidechains, or "arms,” (i.e., third and fourth substituent modules) coupled to the body structure.
  • the optional third and fourth substituent modules are coupled to the conjugated organic precursor prior to coupling the first (head) and/or second (tail) substituent modules.
  • the conjugated organic precursor can be alkylated at the third position having a hydroxyl or amine moiety, to form an O-linked or N-linked sidechain-substituted intermediate composition.
  • sidechain moieties functionalized with a halide can be used to alkylate the selected conjugated organic species and provide a sidechain- substituted body structure using procedures known in the art.
  • providing the third substituent module comprises providing about 1.1 molar equivalents of a halogenated derivative of the selected sidechain substituent; and coupling the third substituent module with the conjugated organic precursor comprises the steps of a) combining the halogenated sidechain derivative with the conjugated organic precursor in the presence of, e.g., potassium carbonate (K CO 3 ) and dimethyl formamide (DMF), to form a reaction mixture; and b) heating the reaction mixture to about 70°C, thereby coupling the third substituent to the conjugated organic moiety.
  • K CO 3 potassium carbonate
  • DMF dimethyl formamide
  • a similar reaction can be designed for coupling functionalized sidechain moieties to amine-containing body structure precursors.
  • the sidechain-coupled body structure for use as a substrate in generating the compositions of the present invention can be purchased from various suppliers (e.g., SIGMA-Aldrich) when available.
  • the coupling reactions for the third and fourth substituents are typically performed simultaneously (e.g., in a single reaction mixture).
  • hydroquinone (1,4-dihydroxybenzene).
  • Table 3 provides exemplary substrates for use in the synthesis procedures described herein, based upon a hydroquinone body structure having two sidechain substitutions coupled at the hydroxyl positions of the core hydroquinone structure.
  • the first substituent module comprises the functionalized nanostructure- binding head group.
  • the first substituent module comprises diethylphosphite
  • coupling the first substituent module to the body structure can be performed via a palladium-catalyzed phosphite-aryl coupling reaction.
  • a larger head module (precursor) is prepared having a nanostructure binding moiety (e.g., a phosphite) and a conjugated species (e.g., a benzene ring or a thiophene) for linking the nanostructure binding moiety to the body structure.
  • a nanostructure binding moiety e.g., a phosphite
  • a conjugated species e.g., a benzene ring or a thiophene
  • the arylhalide core structure is lithiated at a first halide position and reacted with chlorotrimethylsilane (TMSCl) to yield a TMS-aryl intermediate core structure; the TMS-intermediate core structure is then lithiated at a second halide position and reacted with trimethyltinchloride (Me SnCl) to yield a stannylated second intermediate.
  • TMSCl chlorotrimethylsilane
  • Me SnCl trimethyltinchloride
  • the lithiating reactions can be performed in the reverse order.
  • the product of these reactions is then combined with, e.g., a halogenated thiophene as the conjugated species, to form the first substituent module, which in this embodiment comprises a TMS-aryl-thiophene derivative.
  • the nanostructure-binding moiety e.g., a phosphite group
  • a palladium-catalyzed mechanism either before or after attachment of the head module to the body structure.
  • nanostructure binding moieties that can be used in the present invention include, but are not limited to, those depicted in Table 4.
  • the conductive composition also includes a tail group, typically positioned distal to the nanostructure-binding head group.
  • the tail group can also include one or more nanostructure binding moieties; in these embodiment, the conductive compositions can be used as a linker between adjacent nanostructures or nanostructures.
  • the conductive compositions of the present invention can also be employed as alignment ligands, e.g., for orienting and/or a ⁇ anging the associated nanostructures (see, for example, US application Attorney Docket No. 40-003300US and PCT application Attorney Docket No. 40-003300PC co-filed herewith).
  • Coupling of the second substituent module(e.g., the alkyne-containing tail moiety) can be accomplished by performing an aryl coupling reaction using palladium catalysts.
  • Exemplary reaction protocols include, but are not limited to, Sonogashira couplings (Sonogashira et al. 1975 Tetrahedron Lett. 50: 4467-4470), Suzuki couplings (Miyaura 1979 Tetrahedron Lett. 3437), Hartwig-Buchwald couplings (for N-linked substituents), Heck reactions (Patel et al. 1977 J. Org. Chem. 42:3903), and the like.
  • copper-mediated reactions such as the Ullmann coupling and Stephens-Castro coupling can be used to couple the second substituent module to the body structure.
  • the catalyst for this or for other reactions described herein
  • the catalyst can be provided on a solid support or coupled to a soluble polymer, to improve recovery of the material (see, for example, Bergbreiter "Soluble polymer-bound catalysts” Bergbreiter and Martin (Eds.), (1989) Functional Polymers (Plenum Press, New York, pp. 143-158); Tafesh and Beller (1995) "First Selective Reduction of Aromatic Nitro Compounds Using Water Soluble Catalysts" Tetrahedron Lett. 36:9305.
  • Exemplary chemical constituents for use as tail group moieties in the present invention include, but are not limited to, the structures shown in Table 5.
  • the synthetic methods further include the step of coupling the head group to an external surface of a structur , such as nanocrystal (or other nanostructure), thereby providing a nanocrystal-bound composition.
  • a structur such as nanocrystal (or other nanostructure)
  • the head group can be coupled to a non-nanoscale surface and the conductive composition employed in conjunction with a non-nanoscale semiconductor composition.
  • Semiconductor and nanoscale semiconductor compositions are known in the art. Nanostructures having external surfaces that can be employed in the coupling step can be prepared from any of the exemplary semiconducting materials described previously.
  • the nanocrystals are group II/VI or group III/V structures, for which coupling the head group to the external surface of a nanocrystal comprises, e.g., association of free electrons available in the head group with proximal metal moieties of the nanocrystal.
  • the head group module employed can be chosen based upon the composition of the structure or nanoscale structure to be contacted, such that a conductive composition can be prepared, e.g., for any nanostructure/nanocrystal composition, without undue experimentation.
  • the methods of the present invention can also optionally include the step of polymerizing the organic composition after coupling the composition to the nanostructure surface, thereby forming a polymerized organic composition.
  • Nanostructure-containing device of the present invention are particularly suited for use in a photovoltaic device. See, for example, Huynh et al. (2002) Science 295:2425-2427; Huynh et al. (1999) Adv. Mater. 11:923-927; Greenham et al. (1996) Phys. Rev. B-Condens Matter 54:17628-17637; and Greenham et al.
  • the present invention also provides methods of modifying an interaction between a nanostructure and an external matrix.
  • the methods include the steps of a) treating a nanostructure with the conductive composition of the present invention; and b) forming a nanostructure-containing matrix comprising the treated nanostructure and a matrix composition.
  • treating the nanostructure can also include polymerizing the conductive composition to form a polymerized conductive composition.
  • the polymeric conductive composition described herein are employed as matrices in the methods.
  • K ts will optionally additionally comprise instructions for performing the methods, packaging materials, one or more containers which contain the conductive compositions or materials used to prepare the compositions, and/or the like.
  • kits embodying the methods and devices herein optionally comprise one or more of the following: (1) various components (body structures, head groups, tail groups, sidechains) for the modular synthesis of the conductive compositions of the present invention; (2) one or more preparations of nanocrystals or other nanostructures; (3) components and/or instructions for the preparation of nanocrystakmatrix compositions; (4) instructions for practicing the methods described herein; and/or (5) packaging materials.
  • the present invention provides for the use of any component or kit herein, for the practice of any method herein, and/or for the use of any apparatus or kit to practice any method herein.
  • EXAMPLE 1 SYNTHESIS OF MODEL CONDUCTIVE COMPOSITION 4-DECYNYL- BENZENE-1 -PHOSPHONIC ACID
  • a synthesis protocol was designed to test the modular approach to synthesis of the conductive compositions of the present invention (Figure 3).
  • the model conductive composition 5b was prepared using l-iodo-4-bromobenzene as a precursor to the body structure, 1-decyne as the tail group moiety, and diethylphosphite as the head group moiety.
  • degassed diethyl phosphite 4 (26.26 mmol, 3.63 g) was added via syringe under argon.
  • the reaction vessel was sealed, the mixture sti ⁇ ed and heated to 100° C for 2h.
  • the solvent was removed by roto-evaporation, and the residue dissolved in ethyl acetate (200 mL) and washed with saturated aqueous ammonium chloride (3 x 75 mL), dried over sodium sulfate, filtered and the solvent removed by roto-evaporation.
  • EXAMPLE 2 SYNTHESIS OF CONDUCTIVE COMPOSITION 16 [0147]
  • One advantage to the methods of the present invention is the modular approach to synthesis of the various conductive compositions of interest. Using this approach allows for the preparation and use of common synthetic intermediates and core structures.
  • An exemplary synthesis scheme for the preparation of a conductive composition of the present invention is depicted in Figure 4 and described in further detail herein.
  • the various components of the composition (body structure, head group, tail group) are synthesized as individual structures, which are then coupled together to form the conductive composition.
  • the sidearm moieties are coupled to the body element prior to incorporation of the head and tail elements.
  • One prefe ⁇ ed sidearm component for use in the conductive composition is an O-linked hexyl moiety.
  • another intermediate useful for the synthesis of 2,5-dihexoxy-containing conductive compositions isl,4 diiodo-2,5-dihexoxybenzene (compound 13; see also Figure
  • This core structure consisting of an aromatic body structure (benzene) and the two O- linked sidearm chains can be prepared from hydroquinone (compound 10) by standard procedures such as provided in Figure 4. While the following syntheses focus on hydroquinone-based body structures (e.g., various sidechains O-linked to a benzene core), other aryl and/or aromatic core structures are also contemplated and can be used to generate conductive compositions of the present invention. Exemplary conductive compositions employing alternative core structures are shown, for example, in Figure 2.
  • the body structure includes one or more thiophene moieties coupled to an aromatic ring core structure. This can be achieved synthetically by either providing thiophene-containing core structures or by providing thiophene-containing head or tail group moieties.
  • J ⁇ exemplary thiophene-containing body structure (including the coupled sidearms) is l,4-dithiophene-2,5 -dihexoxybenzene
  • This compound which is a precursor to the iodinated intermediate compound 15b, is prepared as follows. To a 100 mL schlenk tube with stirbar and Teflon valve, palladium dichloride (1.0 mmol, 0.177g), triphenylarsene (2.0 mmol, 0.610 g), and
  • N-iodosuccinimide (2.49 mmol, 0.560 g) was added in one portion, the reaction vessel sealed with a Teflon sleeved stopper and the reaction mixture sti ⁇ ed at ambient temperature for 4.5 h then heated to 40 °C and sti ⁇ ed for an additional 22 h.
  • the two sidearm moieties of the conductive composition need not be identical or symmetrical in structure.
  • two differing sidearm moieties are employed in the modular synthesis of the conductive composition 21.
  • 4-methoxyphenol compound 17 was alkylated at the unprotected hydroxyl group using 1.1 equivalents of 1-iodohexane
  • Another common intermediate employed in the synthesis of some embodiments of the present invention is the thiophene-containing tail group moiety, 1- stannyl-5-decynyl-thiophene (compound 22), in which a thiophene moiety and tail group are joined prior to coupling to the body structure (in contrast to the synthetic schemes depicted in Figure 4 and Figure 5, in which the thiophene moiety is joined to the body structure prior to coupling of the tail group moiety).
  • This thiophene-tail group intermediate can be prepared as follows ( Figure 6).
  • the reaction vessel was fitted with an addition funnel and trimethyltin chloride (57.4 mL, 1.0 M solution in tetrahydrofuran) was cannula transfe ⁇ ed to the funnel under positive argon pressure through a septum.
  • the trimethyltin chloride solution was added dropwise to the stirring lithium salt solution over a period of 15 min. at -78°C.
  • the reaction mixture was allowed to warm to ambient temperature with stirring overnight.
  • the solvent was removed in vacuo on the schlenk line and trapped in a IL schlenk flask.
  • EXAMPLE 5 SYNTHESIS OF CONJUGATED COMPOSITION 25
  • Another example of a conjugated composition of the present invention is compound 25 shown in Table 1 and Figure 6. This composition was prepared using the thiophene-derivatized tail group moiety 22b and body structure 15b as follows.
  • reaction mixture was diluted with ethyl acetate (250 mL) and washed with de-ionized water (100 mL), the organic layer separated and solvent removed in vacuo. Purification by silica flash chromatography (4% ethyl acetate: 96% hexane) afforded a precursor to compound 23 (precursor structure not shown) as a yellow oily solid (0.360 g, 23% yield).
  • a thiophene-coupled head group moiety 24 was prepared for attachment to the body structure, via coupling to the non- iodinated thiophene of compound 15b. Addition of the precursor head group moiety 24 to the crude reaction product 23 to form conductive composition 25 was performed as provided in Figure 6.
  • EXAMPLE 6 SYNTHESIS OF CONJUGATED COMPOSITION 28
  • a further example of a conjugated composition of the present invention is compound 28 as shown in Table 1 and Figure 7. This composition was prepared using the thiophene-containing body structure 15b and a benzyl-containing tail moiety in a similar manner as described in Figure 7. Alternatively, compound 28 could have been synthesized using the intermediate depicted in Figure 10 (i.e., by using a body structure having the benzyl ring instead of a head group having the benzyl ring).
  • the conductive composition depicted in Figure 11 could be synthesized in a similar modular manner, using body structure 15b, a benzylated head group (such as shown in Figure 9, and a thiophene-containing tail group (e.g., compound 22).
  • EXAMPLE 7 AN ALTERNATE METHOD FOR MODULAR SYNTHESIS OF COMPOUND 25
  • conductive composition 25 An alternate modular approach to preparation of conductive composition 25 is also contemplated, as depicted in Figure 20.
  • dithiophene elements are attached as a unit to the body structure, rather than using thiophene-containing head and tail group components.
  • iodinated body structure 13 is prepared from hydroquinone 10 as described above. The iodine moieties are then replaced with two dithiophene structures to form compound 30. Intermediate 30 is then joined to tail group
  • EXAMPLE 8 SYNTHESIS OF CONJUGATED COMPOSITION 31 [0163] Di-iodinated intermediate 13 can also be used in the synthesis of an additional embodiment of the conductive compositions of the present invention, compound 31, as described in Figure 21.
  • Embodiments of the present invention are contemplated in which one or more components of the conductive composition (e.g., body structure, head, tail) are present in multiple units.
  • some embodiments include body structures prepared by coupling or polymerizing two or more body structures. The coupling can be performed either prior to or after attachment of the head and tail moieties to the respective body structure members.
  • compositions having the structure [H x -B y -T z ] n , wherein H comprises at least one functionalized head group capable of binding to a nanocrystal surface (or, for nanostructure- bound embodiments, at least one head group bound to a nanocrystal surface); wherein B comprises a body structure comprising one or more conjugated organic moieties, wherein a first conjugated organic moiety is coupled to a proximal functionalized head group or bound head group; wherein T comprises at least one tail group coupled to the body structure; and wherein x, y, z and n independently comprise integers equal to or greater than 1.
  • Figure 22 provides a synthetic scheme for preparation of a conductive composition (compound 36) incorporating two core body structure components, a p-xylene unit (derived from compound 32) and an O-alkylated hydroxyquinone unit (compound 12).
  • a conductive composition compound 36
  • a p-xylene unit derived from compound 32
  • an O-alkylated hydroxyquinone unit compound 12
  • the final product in this example, can also be considered to have one large body component having two aromatic rings coupled by a dithiophene moiety, and having a tail moiety attached to a first end of the overall body structure and a head moiety attached to a second end of the overall body structure.
  • the distinction between body structure, head group and tail group elements is partially based upon the synthetic approach chosen (note the two modular approaches to compound 25 as described above), and as such should not be considered limiting.
  • Compound 36 can be synthesized as provided in Figure 23.
  • compound 41 can also by synthesized as shown in Figure 24.
  • the first portion of the body structure (compound 38) is prepared and then coupled to the tail group 22 (to form intermediate 39); a second body structure portion (compound 20) is stannylated and coupled to a head group (to form intermediate 40), and then these synthetic intermediates are joined to form compound 41.
  • Compounds 36 and 41 are of particular interest, since these compositions also embody an additional optional feature of the present invention, one of the polymerization aspects of the conductive composition.
  • the sidearm elements of the p-xylene derived portion of the body structure can be reacted with a ketone functional group as shown in Figure 23, for example, in the presence of a stereoselective base, such as lithium diisopropyl amide (LDA).
  • a stereoselective base such as lithium diisopropyl amide (LDA).
  • LDA lithium diisopropyl amide
  • This embodiment is particularly of interest in nanostructure-matrix compositions having both n-type and p-type nanocrystals incorporated into the matrix. Coupling of an n-type nanocrystal to an adjacent p-type nanocrystal will allow for an even more efficient transmission of electrons and holes within the matrix.
  • EXAMPLE 10 SYNTHESIS OF CONDUCTIVE COMPOSITION 43 [0169]
  • Di-iodinated intermediate 13 can also be used in the synthesis of an additional embodiment of the conductive compositions of the present invention, compound 43 (see Figure 25).
  • intermediate 30 is prepared as described above.
  • the head group and tail group moieties are then coupled to the body structure using the protocols described in Figure 25, to generate compound 43.
  • EXAMPLE 11 SYNTHESIS OF CONDUCTIVE COMPOSITION 46 [0170] Di-iodinated intermediate 13 can also be used in the synthesis of an additional embodiment of the conductive compositions of the present invention, compound 46 (see Figure 26).
  • reaction mixture was recooled to -78°C and trimethyltin chloride (0.997 mL, 1.0 M solution in tetrahydrofuran) was added dropwise via syringe to the stirring lithium salt solution at - 78°C.
  • the reaction mixture was allowed to warm to ambient temperature with stirring overnight.
  • the solvent was removed in vacuo on the schlenk line and trapped in a IL schlenk flask.
  • the resulting residue was extracted with hexanes (3 X 50 mL) and cannula filtered followed by in vacuo solvent removal to afford intermediate compound 44 as a yellow oil.
  • EXAMPLE 12 SYNTHESIS OF CONDUCTIVE COMPOSITION 50 [0174] Compound 50 is prepared using iodinated body structure 48, as shown in
  • FIG. 27 To a 250 mL schlenk tube with stirbar and Teflon valve, palladium dichloride (2.05 mmol, 0.363g), triphenylarsene (4.1 mmol, 1.255 g), and LiCl (41 mmol, 1.759 g) were added in a glove box. On a schlenk line, l,4-diiodo-2-(2-ethylhexoxy)-5- methoxybenzene (compound 47b, 20.5 mmol, 10.0 g), was added and the vessel placed under vacuum and backfilled with argon (3 x).
  • degassed dimethylformamide (DMF, 100 mL) was cannula transfe ⁇ ed under positive argon pressure.
  • the vessel was sealed and heated to 100°C for 1 day.
  • the reaction mixture was cooled and diluted with ethyl acetate (500 mL) and washed with saturated aqueous sodium thiosulfate (3 x 150 mL) and brine (3 x 150 mL).
  • the organic layer was separated, dried over sodium sulfate, filtered and the solvent removed by roto-evaporation.
  • reaction mixture was cooled to -78°C and w-butyl lithium (10.53 mL, 1.6 M solution in hexanes,) was added dropwise via syringe and the reaction mixture was sti ⁇ ed for lh.
  • a THF solution 70 mL of 1,2-diiodoethane (21.91 mmol, 6.174 g) was cannula transfe ⁇ ed to the stirring lithium salt solution at -78°C.
  • the reaction mixture was allowed to warm to ambient temperature with stirring overnight.
  • the iodinated body structure 48 is then coupled to the tail moiety to form intermediate compound 49 (as described in Figure 27).
  • intermediate compound 49 (as described in Figure 27).
  • palladium dichloride (0.32 mmol, 0.057g)
  • triphenylarsene (0.64 mmol, 0.197 g)
  • LiCl (6.43 mmol, 0.277 g)
  • l-stannyl-5-decynyl-thiophene 22b were added in a glove box.
  • compound 48 was dissolved in degassed dimethylformamide and cannula transfe ⁇ ed to the schlenk tube under positive argon pressure.
  • reaction mixture was placed under vacuum, backfilled with argon, the vessel sealed and heated to 100°C for up to 1 day.
  • the reaction mixture was diluted with ethyl acetate (250 mL) and washed with de-ionized water (100 mL), the organic layer separated and solvent removed in vacuo. Purification by silica flash chromatography (5-15% ethyl acetate: 95-85% hexane) afforded the precursor compound as a yellow oil (2.83 g, 71% yield).
  • reaction mixture was recooled to -78°C and diethylphosphonate chloride (0.4.56 mmol, 0.658 mL) was added dropwise via syringe to the stirring lithium salt solution at -78°C.
  • the reaction mixture was allowed to warm to ambient temperature with stirring overnight.
  • the solvent was removed by roto-evaporation and the resulting residue was dissolved in ethyl acetate (150 mL), dried over sodium sulfate, filtered. Purification by silica flash chromatography (5-15% ethyl acetate: 95-85% hexane) afforded the precursor compound as an orange oil.
  • Figure 28 provides an alternate approach to the synthesis of conductive composition 25.
  • EXAMPLE 14 PREPARATION OF NANOSTRUCTURES
  • organic surfactants such as trioctyl phosphine (TOP), trioctyl phosphine oxide (TOPO), hexadecyl phosphonic acid (HDP A), octadecyl phosphonic acid (ODPA), and tri-n-butyl phosphine (TBP) are commonly present in nanostructure preparations as prepared by standard techniques cited herein.
  • any excess organic surfactant is removed from the nanostructure preparation prior to association with the conductive compositions of the present invention.
  • a solvent mixture prepared from a first solvent in which a nanostructure is soluble e.g., toluene or chloroform
  • a second solvent in which the nanostructure is not soluble e.g., isopropanol or longer chain alcohol, or an acetate such as ethyl acetate. While the ratio of first solvent to second solvent as prepared in the solvent mixture typically ranges between 1 : 1 and 10
  • An additional quantity of the second solvent is then added in a quantity sufficient to precipitate the nanostructures (but not the excess surfactants) from the solvent mixture.
  • the precipitated nanostructures are then separated from the solvent mixture (e.g., by centrifuging), thereby removing excess organic surfactant from the nanostructures.
  • the precipitated nanostructures can be washed with the solvent mixture one or more additional times, e.g., if analysis determines that the nanostructure preparation still contains an undesirable quantity of excess surfactant.
  • any excess organic salts can be removed from the nanocrystal reaction mixture by performing a pyridine exchange on the nanocrystals in the nanocrystal reaction mixture, and precipitating the organic salts while leaving the nanocrystals in solution.
  • the pyridine exchange is performed, for example, by heating the nanocrystal reaction mixture to 150°C for about 1 hour.

Abstract

The present invention provides compositions (small molecules, oligomers and polymers) that can be used to modify charge transport across a nanocrystal surface or within a nanocrystal-containing matrix, as well as methods for making and using the novel compositions.

Description

ORGANIC SPECIES THAT FACILITATE CHARGE TRANSFER TO OR
FROM NANOSTRUCTURES
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is related to US provisional applications USSN 60/408,722, filed September 5, 2002; and USSN 60/452,232, filed March 4, 2003. The present application claims priority to and benefit of each of these prior applications, which are hereby incorporated herein by reference in their entirety for all purposes.
FIELD OF THE INVENTION
[0002] The present invention is in the field of nanotechnology. More particularly, the present invention is directed to conductive ligands and matrices for use with nanostructures, as well as related methods for producing and using the conductive compositions, and related devices incorporating the conductive compositions.
BACKGROUND OF THE INVENTION
[0003] Polymer-based light-emitting and photovoltaic devices, including those incorporating nanocrystal-containing polymers are known in the art. The performance of polymer-based photovoltaic devices has been improved, e.g., by embedding semiconductor nanocrystals into the polymer matrix. For example, nanocomposite-based photovoltaic devices are described in USSN 60/408,722, filed September 5, 2002; USSN 60/421,353, filed October 25, 2002 and USSN 60/452038, filed March 4, 2003. However, the performance of these and other devices that employ nanocrystals can be further improved.
[0004] Semiconducting nanocrystals can be designed with specific optical properties and/or electronic structures, in part by controlling the size and shape of the nanocrystals used as part of the light harvesting element in the photovoltaic devices. In addition, the polymeric matrix encompassing the nanocrystal can be selected to also absorb light. However, charge transport within the photovoltaic device is generally limited by matrix constraints, rather than by the absorption properties of the nanocrystals. As a result, charge transport through the matrix and/or among the nanocrystals is an important element of optimal photovoltaic operation.
[0005] Nanocrystal syntheses typically produce particles having surfaces coated with a surfactant layer, e.g., a layer of molecules having long aliphatic chains, such as alkyl phosphonic acids, alkyl amines, alkyl carboxylic acids, alkyl phosphines or alkyl phosphine oxides. These ligands form a substantially non-conductive layer on the nanocrystal surface. In applications in which it is desirable to efficiently remove or add charges to nanocrystalline structures, the residual aliphatic ligand layer limits the charge transfer to the surface. Synthesis of water soluble semiconductor nanocrystals capable of light emission are described, for example, in USPN 6,251,303 to Bawendi et al. entitled "Water-soluble fluorescent nanocrystals" (June 6, 2001) and USPN 6,319,426 to Bawendi et al. titled "Water-soluble fluorescent semiconductor " (November 20, 2001).
[0006] While conductive polymers are known in the art (see, for example, H. S.
Nalwa (ed.), Handbook of Organic Conductive Molecules and Polymers. John Wiley & Sons 1997; USPN 6,399,224 to Li, "Conjugated Polymers with Tunable Charge Injection Ability"; and USPN 5,504,323 to Heeger et al., "Dual function conducting polymer diodes"), these polymers do not have any functional group(s) that can bind strongly to a nanocrystal surface. As such, these polymers do not make optimal contact with the nanocrystal.
[0007] The performance of nanocrystal-based light-emitting and photovoltaic devices would be improved if the removal or addition of charges via the nanocrystals was more energetically efficient. Accordingly, there exists a need in the art for improved ligands for use with nanocrystal structures. The present invention meets these and other needs by providing novel compositions for use with nanocrystals, as well as methods for making and using the novel compositions. A complete understanding of the invention will be obtained upon review of the following.
SUMMARY OF THE INVENTION
[0008] The present invention provides compositions (small molecules, oligomers and polymers) that can be used to modify charge transport across a surface or a nanostructure (e.g., nanocrystal) surface, or within a nanostructure (e.g., nanocrystal- containing matrix, as well as methods for making and using the novel compositions. The compositions contain a conjugated organic species and at least one binding group capable of interacting with a nanostructure (e.g., nanocrystal) surface; during use, the compositions are coupled via the binding group to the nanostructure (e.g., nanocrystal) surface, such that the compositions are substantially conductive to electrons and/or holes being transported by/through the nanostructure (e.g., nanocrystal) (e.g., during the process of extracting or injecting the electrons or holes). The compositions of the present invention can optionally be derivatized with additional chemical groups, e.g., to enhance the electronic conjugation of the core organic species, to couple adjacent nanostructures (e.g., nanocrystals), or to facilitate dispersion, mixing and/or blending of nanostructures (e.g., nanocrystals) in various matrices.
[0009] In one aspect, the present invention provides conductive compositions for modification of charge transport across a nanostructure (e.g., nanocrystal)-containing matrix. The conductive composition typically include a) a conjugated organic moiety as the "body structure," or core of the conductive molecule; b) a nanostructure (e.g., nanocrystal)- binding "head group" coupled to the body structure at a first position on the conjugated organic moiety; and c) a "tail group" coupled to the body structure at a second position on the conjugated organic moiety. After formation of an exciton in the nanostructure (e.g., nanocrystal)-containing matrix, the conductive composition facilitates the injection and/or extraction of charge (electron and/or hole) with respect to the attached nanostructure, thereby modifying charge transport across a nanostructure-containing matrix.
[0010] The modular nature of the composition (and the corresponding methods for synthesizing the composition) lends itself toward modification or adjustment of the various elements of the composition (head, body, tail) based upon the desired use. As such, various constituents can be used for the different composition elements. For example, the body structure typically comprises a conjugated alkyl moiety or a conjugated aryl moiety (e.g., a phenylene, thiophene, ethene, ethyne, aniline, fluorene, pyridine, perylene, phenanthralene, anthracene, an alkynyl, or a polynuclear aromatic moiety). Chemical structures for use as the functionahzed head group include, but are not limited to, one or more phosphonic acid, carboxylic acid, amine, phosphine, sulfonate, sulfmate, or thiol moieties. Tail group structures can be either conducting or nonconducting chemical moieties; preferred tail group substituents include, but are not limited to, 1-propyne, 1-butyne, 1-pentyne, 1-hexyne, 1- heptyne, 1-octyne, 1-nonyne, 1-decyne, or an alkyne comprising between 3 and 22 carbons. Optionally, either or both the head group and the tail group further include one or more thiophene moieties positioned between the body structure and the head or tail substituent.
[0011] In some embodiments, the tail group also includes a nanostructure (e.g., nanocrystal)-binding moiety (e.g., a phosphonic acid, carboxylic acid, amine, phosphine, or thiol moiety). Furthermore, the nanostructure-binding head group and/or nanostructure- binding tail group can provide either a single chemical moiety for attachment to the nanostructure (i.e., monodentate) or multiple binding moieties (i.e., multidentate). Optionally, these moieties are chosen or selected for their ability to bind to selected types of nanostructures (for example, the head group(s) selectively bind p-type nanocrystals while the tail group(s) selectively bind n-type nanocrystals).
[0012] The body structure optionally includes one or more additional substituents, or "sidechains," coupled to the conjugated organic species. In some embodiments, the sidechains are O-linked or N-linked sidechains coupled to the conjugated organic moiety. Addition of the sidechain (or other substituent) to the body structure preferably does not destroy the conjugation of the core organic species; rather, in some embodiments, the sidechain moiety or moieties extend the conjugation. As such, substituents for use as sidechain elements can include, but are nor limited to, an electron donating group, an electron withdrawing group, a conducting chemical structure, a nonconducting chemical structure, or various reactive functional groups or polymerizable elements (such as an acrylate moiety, a methacrylate moiety, or a vinyl moiety). In some embodiments, the sidechain is matched functionally and/or electronically to the nanostructure (e.g., nanocrystal)-containing matrix; in other embodiment, the sidechain element simply alters the solubility of the composition. Preferably, the conjugated compositions of the present invention have two sidechain substituents coupled to the body structure; however, the chemical compositions of the side chains need not be identical. Optionally, the sidechains can be employed to link and or align adjacent nanostructures.
[0013] Exemplary sidechain substituents for use in the compositions of the present invention include, but are not limited to, an O-linked hexane moiety, an O-linked 2- ethylhexyl moiety, an O-linked octyl moiety, an O-linked decyl moiety, an N-linked hexane moiety, an N-linked 2-ethylhexyl moiety, an N-linked octyl moiety, and an N-linked decyl moiety. However, any N-linked or O-linked alkyl moiety having between 1 and 22 (or more) carbons are contemplated for use in the present invention.
[0014] In some embodiments of the present invention, the body structure employed in the conductive composition is an oligomeric or polymeric structure, rather than a monomeric chemical structure. Exemplary multimeric body structure components include, but are not limited to, poly(phenylene), poly(thiophene), poly(ethene), poly(ethyne), poly(aniline), poly(fiuorene), poly(pyridine), poly(polynuclear) moieties, and combinations thereof. Optionally, the multimeric body structure is composed of two or more monomeric body structure elements linked by a linker region, such as a dithiophene moiety. Preferably the linker element allows or enhances electronic conjugation between the body structure elements. As with the monomeric embodiments, the multimeric body structure can optionally include one or more sidechains coupled to one or more elements of the oligomeric or polymeric structure.
[0015] The present invention also provides polymeric conductive compositions for use with nanostructure (e.g., nanocrystal) structures (e.g., in the case of nanocrystals, either as a nanocrystal coating or as a polymer matrix). The polymeric conductive compositions have the structure [Hx-By-Tz]n, wherein H comprises at least one functionahzed head group capable of binding to a nanostructure surface or at least one head group bound to a nanostructure surface; wherein B comprises a body structure comprising one or more conjugated organic moieties, wherein a first conjugated organic moiety is coupled to a proximal functionahzed head group or bound head group; wherein T comprises at least one tail group coupled to the body structure; and wherein x, y, z and n independently comprise integers equal to or greater than 1. The sum of the integers x, y, z and n is equal to or greater than 5, such that at least one element (head, body or tail) is present in more than one "copy" in the polymeric conductive composition. The polymeric conductive composition is synthesized by polymerization of monomeric precursors through coupling of various polymerizable elements on one or more of the substituents.
[0016] In these polymeric conductive compositions, the head group optionally is one or more phosphonic acid, carboxylic acid, amine, phosphine, phosphine oxide or thiol moieties; the body structure is optionally a phenylene, thiophene, ethene, ethyne, aniline, fluorene, pyridine, perylene, phenanthralene, anthracene, an alkenyl moiety, a polynuclear aromatic moiety, or polymer thereof; and the tail group is optionally a 1-propyne, 1-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, 1-nonyne, 1-decyne, or an alkyne comprising between 3 and 22 carbons. In further embodiments, the body structure further comprises one or more O-linked or N-linked substituents (e.g., electron donating or electron withdrawing groups, conducting chemical structures, or nonconducting chemical structures) coupled to one or more polymer subunits (e.g., member conjugated organic moieties). These O-linked of N-linked substituents can be used, e.g., to alter the electronic signature of the composition, or alter the solubility of the polymeric conductive composition. [0017] As an additional aspect, the present invention provides nanostructure (e.g., nanocrystal) -containing matrix compositions. In one embodiment, the nanostructure-matrix composition includes a nanostructure coupled to a conductive composition (e.g., ligand) of the present invention, and a matrix positioned proximal to the ligand-conjugated exterior surface of the nanostructure. Optionally, the matrix is also covalently coupled to the nanostructure-bound conductive composition. In a preferred embodiment, the conductive composition is functionally or electronically matched to one or more substituents of the matrix.
[0018] In another embodiment, the nanostructure (e.g., nanocrystal)-containing matrix composition includes a nanostructure and a matrix composed of the polymeric conductive composition of the present invention. In one embodiment, a portion of the nanostructure exterior surface is coupled to the polymeric matrix. In another embodiment, the nanostructure is derivatized or functionahzed with a conductive composition of the present invention prior to being embedded in the polymeric conductive composition. Optionally, the polymeric conductive composition and the nanostructure-bound conductive composition are matched functionally and/or electronically. In addition, the matrix composition and the conductive composition can optionally be covalently coupled.
[0019] In a further embodiment of the present invention, the nanostructure-matrix composition includes a conductive composition of the present invention coupled at a first position to a first nanostructure (e.g., nanocrystal) and coupled at a second position to a second nanostructure, and a matrix positioned proximal to the exterior surfaces of the nanostructure. In one optional example, the first nanostructure is a p-type nanocrystal, and the second nanostructure is a n-type nanocrystal.
[0020] The present invention also provides methods of synthesizing an organic composition that facilitates charge transfer for use in a nanostructure-containing device. The organic compositions made using these methods are particularly suitable for use in a photovoltaic device. The methods include the steps of: a) providing a conjugated organic precursor, wherein the conjugated organic precursor comprises at least three positions available for attachment of substituent modules (e.g., head, tail and sidechain); b) providing a first substituent module, wherein the first substituent module comprises a phosphonic acid derivative, a carboxylic acid derivative, an amine derivative, a phosphine derivative, a thiol derivative, a thiophene derivative, or a combination thereof; c) providing a second substituent module, wherein the second substituent module comprises an alkyne derivative comprising between three and 22 carbons; d) optionally providing a third substituent module, wherein the optional third substituent module comprises an alkyl derivative comprising between one and 22 carbons; and e) coupling the first substituent module at a first position, coupling the second substituent module at a second position, and optionally coupling the third substituent module at a third position, thereby synthesizing the organic composition.
[0021] At least one substituent of the first, second or third substituent modules is capable of binding to a nanostructure surface (or, optionally, the component is already bound to a nanostructure surface). Coupling of the various modules to the body structure does not destroy the electronic conjugation of the body structure. Rather, in a preferred embodiment, coupling of one or more of the substituent modules to the body structure extends the conjugation of the body structure.
[0022] In some embodiments of the present invention, the first substituent module is a thiophene derivative. The thiophene-containing head group substituent module can be prepared, for example, by a) providing an arylhalide core structure; b) lithiating the arylhalide core structure at a first halide position and reacting with chlorotrimethylsilane (TMSCl) to yield a TMS-aryl intermediate core structure; c) lithiating the intermediate core structure at a second halide position and reacting the product with trimethyltinchloride (Me3SnCl) to yield a stannylated second intermediate; and d) combining the second intermediate with a halogenated thiophene to form a first substituent module comprising a TMS-aryl-thiophene derivative. Coupling the phosphite moiety to the TMS-aryl-thiophene derivative can be achieved, for example, by performing a palladium-catalyzed phosphite- aryl coupling. The first substituent module can be functionahzed with the nanostructure- binding moiety (e.g., the phosphite group) either prior to coupling of the module to the body structure, or after the module has been attached.
[0023] Coupling of an alkyne moiety employed as the second substituent module can be performed, e.g., via a Sonogashira coupling. Optionally, the body structure has been functionahzed with thiophene moieties at the first (e.g., head) and/or second (e.g., tail) positions prior to addition of the head and tail moieties. [0024] Various reactions can be employed to couple the optional third substituent to the body structure. For example, alkylation reactions (e.g., a Williamson ether synthesis, a Friedel-Crafts alkylation reaction, or other aromatic electrophilic substitution reaction) can be used to couple the third substituent to the conjugated organic precursor at a third position having a hydroxyl or amine moiety, to form a sidechain-substituted intermediate composition.
[0025] In a preferred embodiment, the optional third substituent module (e.g., one or more sidechains) is coupled to the conjugated organic precursor prior to attachment of the first and/or second substituent modules. For example, providing and coupling the third substituent module can include: a) providing about 1.1 molar equivalents of a halogenated derivative of a sidechain substituent; b) combining the halogenated derivative with the conjugated organic precursor in the presence of potassium carbonate (K2CO ) and dimethyl formamide (DMF) to form a reaction mixture; and c) heating the reaction mixture to about 70°C, thereby coupling the third substituent to the conjugated organic moiety.
[0026] Optionally, additional sidechain substituents can be added to the conjugated organic precursor during the third substituent coupling step. For example, coupling the third substituent module optionally further includes coupling a fourth substituent to the body structure at a fourth position. The third and fourth substituents can be the same or different chemical species.
[0027] In some embodiments of the present invention, the methods of making the conductive composition also include the step of coupling or cojoining the head group (and any other nanostructure-binding moieties incorporated into the composition) to an external surface of a nanostructure, thereby providing a nanostructure-bound composition. Optionally, this step an be performed during the synthesis of the conductive composition (e.g., solid phase synthesis).
[0028] For embodiments utilizing substituent modules having polymerizable components incorporated therein, the methods of making the conductive composition can optionally further include the step of polymerizing the organic composition after coupling the composition to the nanostructure surface, thereby forming a polymerized conjugated organic composition. [0029] As a further aspect, the present invention also provides methods of modifying an interaction between a nanostructure (such as a nanocrystal) and an external matrix. The methods include the steps of a) treating a nanostructure with a conductive composition the present invention; and b) forming a nanostructure -containing matrix comprising the treated nanostructure and a matrix composition, thereby modifying the interaction between the nanostructure and the external matrix. Optionally, the conductive composition applied to the nanostructure can be polymerized in situ, to form a polymerized conductive composition. In another embodiment, the matrix composition into which the coated nanostructure is placed constitutes the polymeric conductive composition of the present invention.
[0030] The present invention also provides devices, such as optoelectric devices, photovoltaic devices and light-emitting devices (LEDs) incorporating the conductive compositions of the present invention. The conductive compositions of the present invention can be coupled to either nanoscale and non-nanoscale (e.g., bulk crystalline) assemblies. The devices of the present invention typically include a first electrode surface and a second electrode surface, and having a semiconductor or nanostructure-containing matrix composition comprising the conductive compositions disposed between the two electrodes and electrically coupled to the first electrode surface and the second electrode surface. In one embodiment, the conductive compositions of the present invention are incorporated into photovoltaic devices, such as those described in U.S. patent applications USSN 60/421,353, filed October 25, 2002; USSN 60/452,038 filed March 4, 2003; US application Attorney Docket No. 40-001320US filed September 4, 2003; and international application Attorney Docket No. 40-001320PC. Alternatively, the compositions of the present invention can be used for charge injection into a fluorescent core/shell nanostructure containing device, e.g., to make an LED for use as a display or white light source.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Figure 1 provides exemplary conductive compositions of the present invention.
[0032] Figure 2 provides additional exemplary conductive compositions of the present invention. [0033] Figure 3 depicts a chemical synthesis scheme for one embodiment of the compositions of the present invention.
[0034] Figure 4 depicts a chemical synthesis scheme for another embodiment of the compositions of the present invention.
[0035] Figure 5 depicts a chemical synthesis scheme for a further embodiment of the compositions of the present invention.
[0036] Figure 6 depicts a chemical synthesis scheme for an additional embodiment of the compositions of the present invention.
[0037] Figure 7 depicts a chemical synthesis scheme for a further embodiment of the compositions of the present invention.
[0038] Figure 8 provides a pictorial representation of a further embodiment of the present invention depicting both monomeric and polymeric conductive compositions.
[0039] Figures 9 through 19 provide mass spectral and/or NMR data for exemplary intermediates and compositions of the present invention.
[0040] Figures 20 through 28 depict additional chemical synthesis schemes for additional embodiments of the present invention.
DETAILED DESCRIPTION
[0041] The present invention provides conductive small molecules, oligomers and polymers that can be used to modify charge transport across a nanostructure surface or within a nanostructure-containing matrix (e.g., a nanocomposite, e.g., comprising one or more nanocrystals, e.g., one or more inorganic nanocrystals).
[0042] Photovoltaic devices convert light (solar energy) into storable energy. When light is absorbed by nanocrystalline structures in a nanocomposite (e.g., a nanocrystal- containing composition), the absorption results in the formation of an electron-hole pair (also termed an "exciton"). The electron and hole can either recombine or remain separated, depending in part upon the configuration of the nanocomposite. Recombination of electrons and holes is desirable in some applications (e.g., light emission in LEDs) and undesirable in other applications. [0043] In nanocomposites employed in photovoltaic devices, for example, the electron and hole preferably do not recombine, but rather travel to opposite electrodes. However, nanostructures (e.g., nanowires, branched nanowires, nanocrystals, amorphous nanostructures, nanoparticles, nanotetrapods, etc.) typically comprise one or more surface ligands (such as surfactant molecules introduced during synthesis) that are nonconductive in nature. See e.g., US patent application 60/389,029 (filed June 13, 2002) by Empedocles entitled "Nanotechnology enabled optoelectronics" and Milliron et al. (2003) "Electroactive surfactant designed to mediate electron transfer between CdSe nanocrystals and organic semiconductors" Adv. Mater. 15:58-61. The presence of these nonconductive nanostructure coatings reduces the efficiency of charge separation in the photovoltaic device. The compositions of the present invention are designed to moderate, enhance, or otherwise control the transport (e.g., separation) of the electron and hole generated in the nanocomposite. During use, the compositions are coupled to the nanocrystal surface, such that a conjugated organic species in the composition interacts electronically with the electrons and/or holes being transmitted through the nanocrystal. As noted above, this is in contrast with the currently-available organic nanocrystalline coatings, which are nonconductive in nature.
DEFINITIONS
[0044] Before describing the present invention in detail, it is to be understood that this invention is not limited to particular devices or biological systems, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. As used in this specification and the appended claims, the singular forms "a", "an" and "the" include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to "a nanocrystal surface" or a "nanostructure surface" includes a combination of two or more surfaces; reference to "a substituent" includes mixtures of substituents, and the like.
[0045] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although any methods and materials similar or equivalent to those described herein can be used in the practice for testing of the present invention, the preferred materials and methods are described herein. In describing and claiming the present invention, the following terminology will be used in accordance with the definitions set out below.
[0046] The term "conductive composition" as used herein refers to a monomeric
(e.g. ligand), oligomeric or polymeric composition having the capacity for electron conduction, hole conduction, or the ability to otherwise undergo charge transfer.
[0047] The term "conjugated organic moiety" refers to an organic (i.e., carbon- containing) molecule having two or more double bonds alternating with single bonds, and as such includes both linear and cyclic structures.
[0048] The term "functionahzed" as used herein refers to the presence of a reactive chemical moiety or functionality.
[0049] The term "alkyl" as used herein refers to a chemical substituent consisting of or containing the monovalent group CnH2n, where n is an integer greater than zero.
[0050] The term "aryl" as used herein refers to a chemical substituent consisting of or containing an aromatic group.
[0051] The terms "monodentate" and "multidentate" refers to a number of attachment sites (monodentate having one site and multidentate having more than one site).
[0052] The term "polymerizable element," as used herein, refers to a chemical substituent or moiety capable of undergoing a self-polymerization and or co-polymerization reaction, and as such, includes, but is not limited to, vinyl derivatives, butadienes, trienes, tetraenes, diolefins, acetylenes, diacetylenes, styrene derivatives, as well as other reactive functional groups known to one of skill in the art.
[0053] The terms "oligomeric" and "polymeric" are used interchangeably herein to refer to multimeric structures having more than one component monomer or subunit.
[0054] The term "matrix" as used herein refers to a material, often a polymeric material, into which a second material (e.g., a nanocrystalline composition) is embedded or surrounded. The matrix can be a conductive composition, a semiconductive composition, or a non-conductive composition.
[0055] " A "nanostructure" is a structure having at least one region or characteristic dimension with a dimension of less than about 500 nm, e.g., less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm. Typically, the region or characteristic dimension will be along the smallest axis of the structure. Examples of such structures include nanowires, nanorods, nanotubes, branched nanocrystals, nanotetrapods, tripods, bipods, nanocrystals, nanodots, quantum dots, nanoparticles, branched tetrapods (e.g., inorganic dendrimers), and the like. Nanostructures can be substantially homogeneous in material properties, or in certain embodiments can be heterogeneous (e.g. heterostructures). Nanostructures can be, e.g., substantially crystalline, substantially monocrystalline, polycrystalline, amorphous, or a combination thereof. In one aspect, each of the three dimensions of the nanostructure has a dimension of less than about 500 nm, e.g., less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm. Nanostructures can comprise one or more surface ligands (e.g., surfactants).
[0056] The terms "crystalline" or "substantially crystalline", when used with respect to nanostructures, refer to the fact that the nanostructures typically exhibit long-range ordering across one or more dimensions of the structure. It will be understood by one of skill in the art that the term "long range ordering" will depend on the absolute size of the specific nanostructures, as ordering for a single crystal cannot extend beyond the boundaries of the crystal. In this case, "long-range ordering" will mean substantial order across at least the majority of the dimension of the nanostructure. In some instances, a nanostructure can bear an oxide or other coating, or can be comprised of a core and at least one shell. In such instances it will be appreciated that the oxide, shell(s), or other coating need not exhibit such ordering (e.g. it can be amorphous, polycrystalline, or otherwise). In such instances, the phrase "crystalline," "substantially crystalline," "substantially monocrystalline," or "monocrystalline" refers to the central core of the nanostructure (excluding the coating layers or shells). The terms "crystalline" or "substantially crystalline" as used herein are intended to also encompass structures comprising various defects, stacking faults, atomic substitutions, and the like, as long as the structure exhibits substantial long range ordering (e.g., order over at least about 80% of the length of at least one axis of the nanostructure or its core). In addition, it will be appreciated that the interface between a core and the outside of a nanostructure or between a core and an adjacent shell or between a shell and a second adjacent shell may contain non-crystalline regions and may even be amorphous. This does not prevent the nanostructure from being crystalline or substantially crystalline as defined herein. [0057] The term "monocrystalline" when used with respect to a nanostructure indicates that the nanostructure is substantially crystalline and comprises substantially a single crystal. When used with respect to a nanostructure heterostructure comprising a core and one or more shells, "monocrystalline" indicates that the core is substantially crystalline and comprises substantially a single crystal.
[0058] A "nanocrystal" is a nanostructure that is substantially monocrystalline. A nanocrystal thus has at least one region or characteristic dimension with a dimension of less than about 500 nm, e.g., less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm. Typically, the region or characteristic dimension will be along the smallest axis of the structure. Examples of such structures include nanowires, nanorods, nanotubes, branched nanowires, nanotetrapods, nanotripods, nanobipods, nanocrystals, nanodots, quantum dots, nanoparticles, nanoribbons, and the like. Nanostructures can be substantially homogeneous in material properties, or in certain embodiments can be heterogeneous (e.g. heterostructures). Optionally, a nanocrystal can comprise one or more surface ligands (e.g., surfactants). The nanocrystal is optionally substantially single crystal in structure (a "single crystal nanostructure" or a "monocrystalline nanostructure"). While nanostructures for use in the present invention can be fabricated from essentially any convenient material or material, preferably the nanostructure is prepared from an inorganic material, e.g., an inorganic conductive or semiconductive material. A conductive or semi-conductive nanostructure often displays 1- dimensional quantum confinement, e.g., an electron can often travel along only one dimension of the structure. Nanocrystals can be substantially homogeneous in material properties, or in certain embodiments can be heterogeneous (e.g. heterostructures). The term "nanocrystal" is intended to encompass substantially monocrystalline nanostructures comprising various defects, stacking faults, atomic substitutions, and the like, as well as substantially monocrystalline nanostructures without such defects, faults, or substitutions. In the case of nanocrystal heterostructures comprising a core and one or more shells, the core of the nanocrystal is typically substantially monocrystalline, but the shell(s) need not be. The nanocrystals can be fabricated from essentially any convenient material or materials.
[0059] A "nanowire" is a nanostructure that has one principle axis that is longer than the other two principle axes. Consequently, the nanowire has an aspect ratio greater than one; nanowires of this invention have an aspect ratio greater than about 1.5 or greater than about 2. Short nanowires, sometimes referred to as nanorods, typically have an aspect ratio between about 1.5 and about 10. Longer nanowires have an aspect ratio greater than about 10, greater than about 20, greater than about 50, or greater than about 100, or even greater than about 10,000. The diameter of a nanowire is typically less than about 500 nm, preferably less than about 200 nm, more preferably less than about 150 nm, and most preferably less than about 100 nm, about 50 nm, or about 25 nm, or even less than about 10 nm or about 5 nm. The nanowires employed in the present invention can be substantially homogeneous in material properties, or in certain embodiments can be heterogeneous (e.g. nanowire heterostructures). The nanowires can be fabricated from essentially any convenient material or materials. The nanowires can comprise "pure" materials, substantially pure materials, doped materials and the like, and can include insulators, conductors, and semiconductors. Nanowires are typically substantially crystalline and/or substantially monocrystalline. Nanowires can have a variable diameter or can have a substantially uniform diameter, that is, a diameter that shows a variance less than about 20% (e.g., less than about 10%, less than about 5%, or less than about 1%) over the region of greatest variability and over a linear dimension of at least 5 nm (e.g., at least 10 nm, at least 20 nm, or at least 50 nm). Typically the diameter is evaluated away from the ends of the nanowire (e.g. over the central 20%, 40%, 50%, or 80% of the nanowire). A nanowire can be straight or can be e.g. curved or bent, over the entire length of its long axis or a portion thereof. In certain embodiments, a nanowire or a portion thereof can exhibit two- or three- dimensional quantum confinement. Nanowires according to this invention can expressly exclude carbon nanotubes, and, in certain embodiments, exclude "whiskers" or "nanowhiskers", particularly whiskers having a diameter greater than 100 nm, or greater than about 200 nm. Nanorods, nanowires and other nanostructures are described in detail in Attorney Docket No. 40-000820US co-filed herewith, the contents of which are incorporated herein in their entirety.
[0060] An "aspect ratio" is the length of a first axis of a nanostructure divided by the average of the lengths of the second and third axes of the nanostructure, where the second and third axes are the two axes whose lengths are most nearly equal each other. For example, the aspect ratio for a perfect rod would be the length of its long axis divided by the diameter of a cross-section perpendicular to (normal to) the long axis. [0061] The "band gap difference" between HOMO and LUMO states refers the energy necessary make the transition across the "band gap" region separating the valence and conduction bands.
CONDUCTIVE COMPOSITION
[0062] In one aspect, the present invention provides conductive compositions for modification of charge transport, e.g., across a nanostructure-containing matrix. The compositions are used in conjunction with a nanostructure composition, such as a nanocrystal-containing photovoltaic matrix. Alternatively, the conductive compositions of the present invention can be employed with non-nanoscale semiconductive components. The conductive compositions of the present invention typically include three basic components: a core element or "body structure," a "head group" coupled to the body structure at a first position and capable of associating with a nanostructure surface, and a "tail" group coupled to the body structure at a second position. In addition, the conductive composition can optionally include one or more "sidechain" elements coupled to the body structure at additional locations (i.e. third position, fourth position, etc).
[0063] Each of these components is described in greater detail below. The elements comprising the conductive compositions of the present invention work together to provide a conductive coating on the bound surface (e.g., a nanocrystal surface), or a polymeric matrix encompassing the semiconductor surface, thereby permitting and/or enhancing electron and/or hole transfer. For example, when light impinges upon a nanocrystal component of an optoelectric device (such as a photovoltaic device), the photon is absorbed by the nanocrystal creating an exciton within the nanocrystal. By conducting the electron away from the hole, one creates an electric potential that can be exploited. The conductive compositions (e.g., ligand-type coatings and/or polymeric matrices) of the present invention assist in the generation of the electric potential. The assistance can be, for example, via donation (injection) of an electron to the nanocrystal or other semiconductive material, or via conduction (extraction) of the hole away from the nanocrystal or semiconductor. In a preferred embodiment, the charge mobility (movement of the electrons) enhanced by the conductive compositions of the present invention is sufficiently fast so as to avoid recombination of the electron and hole. A further discussion of charge separation and conduction as it relates to the conductive compositions and related devices of the present invention (e.g., photovoltaic devices and LEDs) can be found in provisional application USSN 60/452,038 to Scher et al., filed March 4, 2003 and titled "Nanocomposite-Based Photovoltaic Devices."
Body structure [0064] A conjugated organic moiety is selected for the core of the conductive composition. This conjugated moiety typically is either a conjugated alkyl moiety or a conjugated aryl moiety. Exemplary body structures for use in the compositions of the present invention include, but are not limited to, phenylene, thiophene, ethene, ethyne, aniline, pyridine, phenanthralene, various alkenyl structures, and the like. In some embodiments, a polynuclear aromatic moiety (e.g., a polynuclear aromatic hydrocarbon, or
PAH) is employed as the conjugated organic moiety. Exemplary PAH compounds include, but are not limited to, anthracene, benzo[a]anthracene, chrysene, fluorene, perylene, naphthalene, acenaphthene, acenaphthalene, phenanthrene, pyrene, benzo[a]pyrene, and the like.
[0065] In one embodiment, the function of the conjugated organic moiety is to provide hole transport from the crystal to the polymer matrix (and optionally, to an electrode or electrode surface of, e.g., a photovoltaic device). Movement of the hole along this conjugated "backbone" of the conductive composition (e.g., charge transport) is enhanced by selecting or matching the electronic characteristics of the body structure, such that hole transport from the nanocrystal to the polymer matrix is favored over electron transport (i.e., the body structure element of the conductive composition has a higher HOMO energy level than the nanocrystal and a lower HOMO level than the surrounding polymer). Alternatively, the conductive composition of the present invention can be modularly designed for enhanced electron transport.
[0066] In some embodiments of the present invention, the body structure is an oligomeric or polymeric structure, such as poly(phenylene), poly(thiophene), poly(ethene), poly(ethyne), poly(aniline), poly(fluorene), poly(pyridine), poly (PAH), and the like. The extent of polymerization can range from just a few repeating elements (e.g., 2, 3, 4, 5, 6, etc) or longer polymers (e.g., having tens of repeating units). Furthermore, additional or alternative oligomeric or polymeric conjugated structures known to one of skill in the art can also be employed as the body structure of the present composition. Head group [0067] The conductive compositions of the present invention further include a "head group" coupled to the body structure at a first position on the conjugated organic moiety. In the unbound configuration, the head group is a functionahzed element capable of binding to a nanostructure surface. Optionally, the head group is a bound head group (e.g., for embodiments in which the composition is associated with the nanostructure). Both the bound and functionahzed chemical structures are considered "head groups" in the present invention.
[0068] Exemplary chemical moieties for use as functionahzed head groups in the present invention include, but are not limited to, phosphonic acid, phosphinic acid, carboxylic acid, amine, amine oxide, phosphine, phosphine oxide, phosphonate, phosphonite, hydroxyl, and thiol moieties.
[0069] Alternatively, nitrogen-containing aromatic compounds or heterocycles (e.g., imidazoles, benzoimidazoles, pyridines, pyrimidines, purines, or quinolines) can also be used as nanostructure-binding head group moieties in the compositions of the present invention. Exemplary compounds include, but are not limited to, derivatives of 2- methylpyridine, 3-ethylpyridine, 4-chloropyridine, collidine, dimethylquinoline, and other compounds commonly used as nanostructure growth terminators.
[0070] In some embodiments, the functionahzed (or bound) head group is a monodentate structure (e.g., a single moiety capable of binding the nanostructure). In an alternate embodiment, the head group is a multidentate structure capable of a plurality of interactions with the nanostructure surface.
[0071] Optionally, the head group element includes one or more polymerizable elements. The polymerizable element can be employed, in some embodiments, to prepare conductive compositions having a plurality of head group modules attached (e.g., linearly) to a single body structure. One such composition would have the formula (Hx)-B-T, in which x copies of the head moiety (H) are attached to a body structure (B) and tail group (T), e.g., during synthesis of the conjugated composition. Alternatively, the polymerizable elements on the head group are used to polymerize proximal elements of the conductive composition. The polymerization can occur between two head groups, or between a head group and another element of the conductive composition (e.g., a tail group or optional sidechain). An exemplary composition of this nature is described by the formula (H-B-T)n, where n represents the number (or average number) of member compositions in the polymer. While the proximal elements are preferably polymerized after attachment to the nanostructure surface, in some polymeric embodiments, the elements are polymerized prior to exposure to the nanostructure.
Tail group [0072] The conductive compositions of the present invention also include a tail group coupled to the body structure at a second position (tail position) on the conjugated organic moiety. Either conducting or a non-conducting chemical structures can be employed as tail groups in the present invention. Typically, the tail group is an alkyne structure composed of n carbons (where n is equal to 3-22); however, even larger alkyne structures (having greater than 22 carbons) are also contemplated for use in the compositions of the present invention. Exemplary alkynes for use in the present invention include, but are not limited to, 1-propyne, 1-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1- octyne, 1-nonyne, and 1-decyne. Optionally, any alkyne comprising between 3 and 22 carbons (or longer) can be employed as a tail group in the present invention. Alternatively, other moieties having "rigid" elements, such methylene, aryl, acetylene and alkene groups, can be used as tail groups in the present invention. The more rigid constituents can be used to produce more conductive compositions (and, in the embodiment in which the conductive compositions include polymerizable elements, a more thermodynamically predictable product).
[0073] The alkyne structure can be linear or branched, depending in part upon the particular system in which the composition will be employed. For example, in some embodiments, the increased steric hindrances incurred by branched alkynyl chain employed as tail groups can affect the conjugation of the conductive composition (e.g., by altering the positioning of an aryl component of the body structure). Changes in the molecule-molecule and polymer-molecule order, stacking and packing can also have an effect on the electronic properties and charge transport capabilities. In a preferred embodiment, linear (e.g., non- branched) alkyl chains are prefeπed for use as tail group moieties.
[0074] In some embodiments, the tail group further includes a thiophene moiety; when present, the thiophene is preferably positioned between the alkyne moiety and the body structure (e.g., the thiophene couples the tail group to the conjugated organic species at the second position of the body structure). [0075] Optionally, the tail group further includes a chemical functionality capable of binding to the nanostructure surface. As described for the head group element, the tail group can be either a monodentate or a multidentate structure. When present, the nanostructure-binding functionality incorporated into the tail group is optionally used, for example, for coupling to a second nanostructure surface (e.g., forming a bridging composition between proximal nanocrystals).
[0076] For example, in a further embodiment, the conductive composition of the present invention can include a di-alkyne or di-alkene tail group substituent having the formula CC-(CH2)n-CC, in which CC represents either double or triple bonded carbon atoms (flanking an alkyl chain, in this embodiment). Optionally, a nanostructure binding moiety (e.g., phosphanate) is incorporated within the tail element, e.g., at a site distal to the site for attachment to the body structure (as represented by the formula (OH)2P(O)-CC- (CH2)n-CC-). The presence of multiple alkyne or alkene moieties within the tail group module can be used to alter the geometry of the tail and can affect the binding of the head group. The nanostructure binding moiety incorporated into the tail group can be the same or different moiety as present in the head group. Optionally, the nanostructure binding moiety incorporated into the tail group can be used to bind to the same nanostructure as the head group, or it can be coupled to an adjacent crystal (i.e., linking the crystals). In a further embodiment, different nanostructure binding moieties favoring attachment to different nanostructure structures are employed in the multi-dentate conductive compositions of the present invention (forming, e.g., an asymmetric bidentate conductive composition). Such compositions can be employed, e.g., to align nanostructures within a two crystal system.
[0077] In another embodiment of the present invention, the tail group includes one or more polymerizable elements. As described previously, the polymerizable element can be employed, in some embodiments, to prepare conductive compositions having a plurality of tail group modules attached (e.g., linearly) to a single body structure. One such composition would have the formula H-B-(TZ), in which z copies of the tail moiety are attached to the body structure. Alternatively, the polymerizable elements on the tail group are used to polymerize proximal elements of the conductive composition, similar to that described for the optional polymerizable elements on the head group (e.g., between two tail groups, or between a tail group and another element of the conductive composition). While the proximal elements are preferably polymerized after attachment to the nanostructure surface, the polymerizable elements can be coupled prior to exposure of the composition to the nanostructure.
Optional sidechains [0078] The body structure optionally includes one or more sidechains coupled to the conjugated organic species. Optionally, the conductive composition includes two, three, or four side chains (although additional sidechains are conceivable given an appropriately- configured body structure).
[0079] Changes in sidechain composition can be used, e.g., to alter the solubility of the conductive composition, for electronic adjustment of the composition, and/or for polymerization purposes. For example, the sidechain can optionally include a carbonyl ester moiety; as a result of the electron- withdrawing property of the carbonyl, the conductive composition containing this sidechain will enhance (favor) electron transfer. Alternatively, incorporation of a simple alkyl chain as the sidechain substituent will favor hole transfer by virtue of the electron donating nature of the substituent.
[0080] Either conducting or a non-conducting chemical structures can be employed as sidechains in the present invention. Conducting chemical structures have the added advantage of extending the conjugation of the organic core structure.
[0081] In a prefeπed embodiment, the sidechains are O-linked or N-linked chemical structures (e.g., are coupled to an existing hydroxyl or amine group on the body structure). Exemplary sidechain moieties for use in the present invention include, but are not limited to, an O-linked or N-linked hexane moiety, an O-linked or N-linked 2-ethylhexyl moiety, an O-linked or N-linked octyl moiety, an O-linked or N-linked decyl moiety. Optionally, any O-linked or N-linked alkyl moiety comprising between 5 and 22 (or more) carbons can be used as a sidechain component (including alkane, alkene, alkyne, vinyl, and aryl structures).
[0082] As noted above, the chemical substituents employed as sidechain elements can optionally be either electron donating groups or electron withdrawing groups, depending upon the intended use. For example, in embodiments in which the modification of charge transport involves electron transport, electron withdrawing groups are preferred; in contrast, for transport of the "holes", electron donating groups function better. [0083] In a prefeπed embodiment, a first sidechain is coupled to the body structure at a first sidechain position (i.e., a third position on the conjugated organic species), and a second sidechain is coupled to the body structure at a second sidechain position (i.e., a fourth position on the conjugated organic species). The sidechains can be identical chemical moieties, or they can differ in their chemical structure. Optionally, the side chain(s) can have the same chemical composition as the head group or the tail group.
[0084] In some embodiments of the present invention, the sidechain substituent is matched functionally and or electronically to a matrix composition of the nanostructure- containing matrix. For example, the sidechain optionally can include functionalities which interact with matrix functionalities (e.g., affinity binding, ionic interactions, covalent interactions and/or bond formation, and the like). Alternatively, the sidechain elements can be used to affect the electronic signature of the surrounding matrix. For example, the distance between the conductive composition (e.g., ligand) and the polymer matrix, the aryl group matrix -matrix stacking distance and packing order, and/or the matrix-ligand stacking distance and packing can be altered or controlled by varying the sidechain element of the conductive composition, thereby affecting the interaction of the side chain with the smrounding matrix and modifying the electronic signature of the matrix-ligand- nanostructure system.
[0085] The length of the alkyl portion of the sidechain can be used to influence solubility; as such and can be any length or branching scheme. Both solubility and electronic properties can be adjusted simultaneously (or independently) via various combinations of the sidechain elements.
[0086] In another embodiment of the present invention, the side group includes one or more polymerizable elements. In some embodiments of the compositions of the present invention, the polymerizable elements on the sidechains interact with each other , thereby crosslinking individual members of the conductive composition to form a polymeric conductive composition. The polymerization can occur between sidechains on adjacent conductive compositions, or between a sidechain and another element of the conductive composition (e.g., a head group or tail group). While the proximal elements are preferably polymerized after attachment to the nanostructure surface, in some embodiments, the elements are polymerized prior to exposure to the nanostructure. [0087] Alternatively, the polymerizable element can be employed to prepare extended sidechain components (e.g., as a means for coupling additional moieties to the conductive composition).
[0088] Exemplary chemical moieties which can be incorporated as sidechain elements include, but are not limited to, alkyl (e.g., alkane, alkene, or alkyne) chains ranging in length from one carbon to 22 carbons (or longer), carbonyls, acrylates, methacrylates, cinnamic esters, and the like. In some embodiments, the sidechain element includes a carbonyl ester having a diene moiety, such as butadiene (e.g., O-C(O)-(CH )n- butadiene). The diene moiety, which can be positioned anywhere along the esterified alkyl chain (e.g., near the carbonyl, towards the middle of the alkyl chain, at the terminus distal to the O-linkage, etc.). can then optionally be polymerized, for example, with light via a 2+2 or 4+4 polymerization reaction. See, for example, Paleos (ed.) Polymerization in Organized Media (Gordon and Breach Science Publishers, Philadelphia, 1992.
[0089] Furthermore, the modular approach to the chemical synthesis of the conductive compositions of the present invention (e.g., convergent periphery modification) lends itself to a number of combinations of various head moieties, tail groups, and optional side chain elements.
[0090] Exemplary conductive compositions of the present invention are provided in
Table 1 below, and in the figures and examples.
able 1 : Exemplary conductive compositions
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
POLYMER EMBODIMENT
[0091] As noted above, one or more of the constituents of the conductive compositions can optionally include polymerizable elements. The present invention also provides oligomeric and polymer conductive compositions for use with nanostructures. The oligomeric and/or polymeric compositions can be used as either coatings on nanostructures, or as the matrix into which the nanostructure in embedded. Optionally, the nanostructure is coated with a first conductive composition of the present invention, and the embedded in an additional (e.g., second) polymeric conductive composition. In an additional embodiment, different types of nanostructures (e.g., p-type and n-type nanocrystals) are coupled or crosslinked within a matrix via the conductive compositions of the present invention.
[0092] One way to accomplish efficient charge transport is by designing an electronic "stairway" for both holes and electrons via bandgap adjustment, where the matrix polymer may have a highest occupied molecular orbital (HOMO) level slightly higher than the HOMO of a nanostructure-bound conductive composition ligand (which itself has a HOMO level higher than that of the nanostructure). Since the energetically favored pathway for hole transport is from lower to higher HOMO levels, this design will promote hole transport from the nanostructure to the ligand to the polymer to the electrode. Conversely, the matrix polymer can have a LUMO (lowest unoccupied molecular orbital) level slightly lower than the ligand LUMO, and the ligand LUMO may be lower than the crystal LUMO level. This will favor electron transport from the polymer via the ligand and nanostructure to the electrode. We have performed model calculations of the bandgap, HOMO and LUMO levels of the ligands and polymer, showing that this can be achieved by tuning both the ligand and the polymer to meet these requirements. One way to accomplish this is to use similar components for the polymer and the oligomer so the electronic signatures of each are similar but can be tuned slightly to afford the appropriate electronic stairway for hole and electron transport, respectively.
Polymerizable elements [0093] Any of the elements of the of the conductive compositions of present invention (head group, body structure, tail group, and/or sidechains) can include one or more of the polymerizable elements. Exemplary chemical substituents which can be incorporated into the composition, but are not limited to, vinyl derivatives, butadienes, trienes, tetraenes, diolefms, acetylenes, diacetylenes, styrene derivatives and the like.
Exemplary sidechain substituents and/or derivatives (and mechanisms for coupling or crosslinking) are provided, for example, in Paleos, supra, and Kraft et al. (1998)
"Electroluminescent Conjugated Polymers - Seeing Polymers in a New Light" Angew
Chem. Int. Ed. 37:402-428.
[0094] For the crosslinking reaction, the polymerizable element can be situated at the end of the selected element, or it an be internal (e.g., amidst an alkyl chain substituent). Various polymerization schemes are contemplated in the present invention, including, but not limited to, polyaddition reactions (thermal, photo-induced or radiation-induced); polycondensations; oxidative couplings, and the like. A prefeπed polymerization scheme is vinyl polymerization of sidechain substituents in adjacent conductive compositions..
Polymeric compositions [0095] In a prefeπed embodiment, the polymeric conductive compositions of the present invention typically have the structure [Hx-By-Tz]n, where H represents the head group, B represents the body structure, and T represents the tail group. The subscripts x, y and z represent the number of repeating elements (of head group, body structure, or tail group, respectively) present in a "monomeric" subunit of the polymer, while the value for n provides for the number of monomeric units present in the polymer; these values are integers. An embodiment in which x, y, z and n all equal 1 is equivalent to the monomeric conductive composition as previously described. Thus, for the polymeric composition of the invention, the sum of these integers (x+y+z+n) is an integer greater than 4 (i.e., 5 or greater). Figure 8 depicts exemplary polymeric conductive compositions of the present invention in which multiple body structure components are depicted with similar or dissimilar sidechain elements attached. N is an integer, ranging in value from 1 (i.e., the monomeric form of the composition) to 10 or more, (e.g., to 15, 2, 25, 50, 100, etc.)
[0096] Sidechains can also be present, coupled to one or more of the body structures in the polymeric conductive composition; these optional sidechains are not depicted in the formula independent of body structure B, but are optionally present. In some polymeric embodiments of the present invention, the sidechain moiety is present on a majority of the body structures present (i.e., on at least 50% of the body structures); in further embodiments, the sidechain is present on at least 75%, 90%, 95%, 99% or essentially all of the member body structures. Optionally, these sidechain moieties can be the same chemical functionality; alternatively, the composition of the sidechain varies from body structure to body structure. For example, in one embodiment, the body structures of the polymer alternate between attachment of two different sidechain moieties. In another embodiment, the plurality of sidechains present in the composition is a random mixture of two, three, four, or more chemical substituents.
[0097] When in use (e.g., in the presence of nanostructures), at least one head group moiety of the polymeric conductive composition is bound to the nanostructure surface. Optionally, a majority of the head groups (e.g., at least 50%, about 75%, about 90%, about 95%>, about 99%, or essentially all of the head groups) are in the bound form. As noted in a previous section, polymerization can be performed either prior to or after binding of the conductive composition to the nanostructure structure; furthermore, the polymer can be partially crosslinked in an initial step, and further crosslinked upon interaction with the nanostructure structure. Thus, compositions including the conductive composition or polymer in combination with the nanostructure structure (e.g., nanostructure-containing matrices) are also contemplated in the present invention.
NANOSTRUCTURE-MATRIX
[0098] The conductive compositions would also be useful in charge injection/extraction from other, non nanoscale surfaces, e.g., bulk crystalline materials, etc. Thus, while nanostructures and other nanoscale compositions are prefeπed embodiment, the conductive compositions described herein can be used for charge injection/extraction from other, non nanoscale surfaces, e.g., bulk crystalline materials, etc., and as such are not limited to either nanoscale and non-nanoscale (e.g., bulk crystalline) assemblies. In one embodiment, the nanostructure-containing matrices comprise a nanostructure having an exterior surface, wherein a portion of the nanostructure exterior surface is cojoined to a conductive composition of the present invention; and a matrix component positioned proximal to the conjugated exterior surface of the nanostructure. The conductive composition employed in the nanostructure-containing matrices can be either a monomeric composition or a polymeric version, e.g., coating the nanostructure. The matrix component can be either a conductive matrix or a nonconductive matrix, depending on the use envisioned for the product. Exemplary matrices for use in the present invention include, but are not limited to, poly-3-hexylthiophene (P3HT), poly(p-phenylene vinylene (PPV), and poly(2-methoxy, 5 ethyl (2' hexyloxy) p-phenylene vinylene (MEH-PPV).
[0099] In another embodiment, the nanostructure-containing matrices of the present invention include, but are not limited to, a nanostructure and a matrix composition positioned proximal to an exterior surface of the nanostructure, wherein the matrix composition comprises a polymerized embodiment of the conductive compositions of the present invention. For example, the conductive polymer having the structure [Tx-By-H2]n is contemplated, wherein H comprises at least one functionalized head group capable of binding to a nanostructure surface; wherein B comprises a body structure comprising one or more conjugated organic moieties, wherein a first conjugated organic moiety is coupled to the at least one functionalized head group; wherein T comprises at least one tail group coupled to the body structure; and wherein x, y, z and n independently comprise integers equal to or greater than 1. The polymerization is achieved via crosslinking of polymerizable units on the elements (for example, the sidechain) of the composition.
[0100] In a further embodiment of the present invention, the conductive polymeric composition of the matrix is covalently coupled to a further conductive composition applied to the nanostructure. In a prefeπed embodiment, this additional conductive composition is functionally and/or electronically matched to one or more components of the conductive polymeric matrix.
Matrices [0101] A wide variety of nanostructure-compatible polymers are known to those of skill in the art (see e.g., Demus et al. (ed.) 1998 Handbook of Liquid Crystals Volumes 1-4, John Wiley and Sons, Inc., Hoboken, NJ); Brandrup (ed.) 1999 Polymer Handbook. (John Wiley and Sons, Inc.) ; Harper 2002 Handbook of Plastics. Elastomers, and Composites. 4th edition (McGraw-Hill, Columbus, OH); and Kraft et al. (1998) Angew. Chem. Int. Ed. 37:402-428. While either conductive or nonconductive polymers can be used in conjunction with the conductive compositions of the present invention, prefeπed embodiments of the present invention employ conductive polymers.
[0102] Exemplary polymers for use in the present invention include, but are not limited to, thermoplastic polymers (e.g., polyolefms, polyesters, polysilicones, polyacrylonitrile resins, polystyrene resins, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, or fluoroplastics); thermosetting polymers (e.g., phenolic resins, urea resins, melamine resins, epoxy resins, polyurethane resins); engineering plastics (e.g., polyamides, polyacrylate resins, polyketones, polyimides, polysulfones, polycarbonates, polyacetals); and liquid crystal polymers, including main chain liquid crystal polymers (e.g., poly(hydroxynapthoic acid)) and side chain liquid crystal polymers (e.g., poly [n-((4'(4"- cyanphenyl)phenoxy)alkyl)vinyl ether]). Certain embodiments include conductive organic polymers; see e.g. T. A. Skatherin (ed.) 1986 Handbook of Conducting Polymers I. (Marcel Dekker, New York). Examples of conductive polymers for use as matrices of the present invention include, but are not limited to, poly(3-hexylthiophene) (P3HT), poly[2-methoxy, 5-(2'-ethyl-hexyloxy)-p-phenylene-vinylene] (MEH-PPV), poly(p-phenylene vinylene) (PPV), and polyaniline.
Nanostructures [0103] As noted previously, structures for use in the present invention include, but are not limited to nanoscale and non-nanoscale (e.g., bulk crystalline) assemblies.
Nanostructures, such as nanocrystals, nanowires, nanorods, nanoparticles and the like, can be fabricated by a number of mechanisms known to one of skill in the art. Furthermore, their size can be controlled by any of a number of convenient methods that can be adapted to different materials. For example, synthesis of nanocrystals of various composition is described in, e.g., Peng et al. (2000) "Shape control of CdSe nanocrystals" Nature 404:59-
61; Puntes et al. (2001) "Colloidal nanocrystal shape and size control: The case of cobalt"
Science 291 :2115-2117; USPN 6,306,736 to Alivisatos et al. (October 23, 2001) entitled
"Process for forming shaped group III-V semiconductor nanocrystals, and product formed using process"; USPN 6,225,198 to Alivisatos et al. (May 1, 2001) entitled "Process for forming shaped group II- VI semiconductor nanocrystals, and product formed using process"; USPN 5,505,928 to Alivisatos et al. (April 9, 1996) entitled "Preparation of III-V semiconductor nanocrystals"; USPN 5,751,018 to Alivisatos et al. (May 12, 1998) entitled "Semiconductor nanocrystals covalently bound to solid inorganic surfaces using self- assembled monolayers"; USPN 6,048,616 to Gallagher et al. (April 11, 2000) entitled "Encapsulated quantum sized doped semiconductor particles and method of manufacturing same"; and USPN 5,990,479 to Weiss et al. (November 23, 1999) entitled "Organo luminescent semiconductor nanocrystal probes for biological applications and process for making and using such probes."
[0104] Growth of nanowires having various aspect ratios, including nanowires with controlled diameters, is described in, e.g., Gudiksen et al (2000) "Diameter-selective synthesis of semiconductor nanowires" J. Am. Chem. Soc. 122:8801-8802; Cui et al. (2001) "Diameter-controlled synthesis of single-crystal silicon nanowires" Appl. Phys. Lett. 78: 2214-2216; Gudiksen et al. (2001) "Synthetic control of the diameter and length of single crystal semiconductor nanowires" J. Phys. Chem. B 105:4062-4064; Morales et al. (1998) "A laser ablation method for the synthesis of crystalline semiconductor nanowires" Science 279:208-211; Duan et al. (2000) "General synthesis of compound semiconductor nanowires" Adv. Mater. 12:298-302; Cui et al. (2000) "Doping and electrical transport in silicon nanowires" J. Phys. Chem. B 104:5213-5216; Peng et al. (2000), supra; Puntes et al. (2001), supra; USPN 6,225,198 to Alivisatos et al. , supra; USPN 6,036,774 to Lieber et al. (March 14, 2000) entitled "Method of producing metal oxide nanorods"; USPN 5,897,945 to Lieber et al. (April 27, 1999) entitled "Metal oxide nanorods"; USPN 5,997,832 to Lieber et al. (December 7, 1999) "Preparation of carbide nanorods"; Urbau et al. (2002) "Synthesis of single-crystalline perovskite nanowires composed of barium titanate and strontium titanate" J. Am. Chem. Soc, 124, 1186; Yun et al. (2002) "Feπoelectric Properties of Individual Barium Titanate Nanowires Investigated by Scanned Probe Microscopy" Nano Letters 2, 447; and published PCT application nos. WO 02/17362, and WO 02/080280.
[0105] Growth of branched nanowires (e.g., nanotetrapods, tripods, bipods, and branched tetrapods) is described in, e.g., Jun et al. (2001) "Controlled synthesis of multi- armed CdS nanorod architectures using monoεurfactant system" J. Am. Chem. Soc. 123:5150-5151; and Manna et al. (2000) "Synthesis of Soluble and Processable Rod- ,Aπow-, Teardrop-, and Tetrapod-Shaped CdSe Nanocrystals" J. Am. Chem. Soc. 122:12700-12706. Synthesis of nanoparticles is described in, e.g., USPN 5,690,807 to Clark Jr. et al. (November 25, 1997) entitled "Method for producing semiconductor particles"; USPN 6,136,156 to El-Shall, et al. (October 24, 2000) entitled "Nanoparticles of silicon oxide alloys"; USPN 6,413,489 to Ying et al. (July 2, 2002) entitled "Synthesis of nanometer-sized particles by reverse micelle mediated techniques"; and Liu et al. (2001) "Sol-Gel Synthesis of Free-Standing Feπoelectric Lead Zirconate Titanate Nanoparticles" J. Am. Chem. Soc. 123:4344. Synthesis of nanoparticles is also described in the above citations for growth of nanocrystals, nanowires, and branched nanowires, where the resulting nanostructures have an aspect ratio less than about 1.5.
[0106] Synthesis of core-shell nanostructure heterostructures are described in, e.g.,
Peng et al. (1997) "Epitaxial growth of highly luminescent CdSe/CdS core/shell nanocrystals with photostability and electronic accessibility" J. Am. Chem. Soc. 119:7019- 7029; Dabbousi et al. (1997) "(CdSe)ZnS core-shell quantum dots: Synthesis and characterization of a size series of highly luminescent nanocrystallites" J. Phys. Chem. B 101:9463-9475; Manna et al. (2002) "Epitaxial growth and photochemical annealing of graded CdS/ZnS shells on colloidal CdSe nanorods" J. Am. Chem. Soc. 124:7136-7145; and Cao et al. (2000) "Growth and properties of semiconductor core/shell nanocrystals with InAs cores" J. Am. Chem. Soc. 122:9692-9702. Similar approaches can be applied to growth of other core-shell nanostructures. See, for example, USPN 6,207,229 (March 27, 2001) and USPN 6,322,901 (November 27, 2001) to Bawendi et al. entitled "Highly luminescent color-selective materials".
[0107] Growth of homogeneous populations of nanowires, including nanowire heterostructures in which the different materials are distributed at different locations along the long axis of the nanowire is described in, e.g., published PCT application nos. WO 02/17362, and WO 02/080280; Gudiksen et al. (2002) "Growth of nanowire superlattice structures for nanoscale photonics and electronics" Nature 415:617-620; Bjork et al. (2002) "One-dimensional steeplechase for electrons realized" Nano Letters 2:86-90; Wu et al. (2002) "Block-by-block growth of single-crystalline Si/SiGe superlattice nanowires" Nano Letters 2, 83-86; and US patent application 60/370,095 (April 2, 2002) to Empedocles entitled " Nanowire heterostructures for encoding information." Similar approaches can be applied to growth of other heterostructures. [0108] In certain embodiments, the collection or population of nanostructures is substantially monodisperse in size and/or shape. See e.g., US patent application 20020071952 by Bawendi et al entitled "Preparation of nanocrystallites."
[0109] The diameter of the inorganic nanowires can be varied, for example, to control the wavelength emitted by fluorescent nanowires. The diameter of the nanowires is preferably between about 2 nm and about 100 nm, more preferably between about 2 nm and about 5 nm or between about 10 nm and about 50 nm. The length of the nanowires can also be varied. In certain embodiments, the inorganic nanowires have an aspect ratio between about 10 and about 10,000 (e.g., between about 20 and about 10,000, between about 50 and about 10,000, or between about 100 and about 10,000).
[0110] The nanowires can be fabricated of essentially any convenient material (e.g., a semiconducting material, a feπoelectric material, a metal, etc.) and can comprise essentially a single material or can be heterostructures.
[0111] The nanostructures employed in the nanostructure-containing matrices of the present invention can be fabricated from essentially any convenient materials. E.g., the nanocrystals can comprise an inorganic materials, e.g., a semiconducting material, for example a material comprising a first element selected from group2 or from group 12 of the periodic table and a second element selected from group 16 (e.g., ZnS, ZnO, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe, and like materials); a material comprising a first element selected from group 13 and a second element selected from group 15 (e.g., GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, and like materials); a material comprising a group 14 element (Ge, Si, and like materials); a material such as PbS, PbSe, PbTe, A1S, A1P, and AlSb; or an alloy or a mixture thereof. Further details regarding nanocrystalline structures for use in the present invention can be found, for example, USSN 60/421,353 filed October 25, 20002 and co- filed provisional application USSN 60/452,038 filed March 4, 2003, by Scher et al. and titled "Nanocomposite Based Photovoltaic Devices."
[0112] In a prefeπed embodiment, the devices of the present invention employ nanocrystals comprising CdSe, CdTe and or InP as the nanocrystal materials. METHODS OF SYNTHESIZING CONDUCTIVE COMPOSITIONS [0113] The present invention also provides methods of synthesizing an organic species that facilitates charge transfer, e.g., for use in a nanostructure-containing photovoltaic device. The methods provide a modular approach to the synthesis procedure, such that various head groups, tail groups, and side chains can be independently coupled to the selected body structure.
[0114] The methods of the present invention include the steps of a) providing a conjugated organic precursor, wherein the conjugated organic precursor comprises at least three positions available for attachment of substituent modules; b) providing a first substituent module (e.g., a head group or other nanostructure binding moiety), wherein the first substituent module comprises a nanostructure binding moiety, such as a phosphonic acid derivative, a carboxylic acid derivative, an amine derivative, a phosphine derivative, a thiol derivative, a thiophene derivative, or a combination thereof; and c) providing a second substituent module (e.g., a tail group), wherein the second substituent module comprises an alkyne derivative comprising between three and 22 carbons. Optionally, the method further includes providing a third substituent module (e.g., the sidechains), wherein the optional third substituent module comprises an alkyl derivative comprising between one and 22 carbons. The substituent modules are then coupled to the conjugated organic precursor (e.g.., the body structure): the first substituent module at a first position, coupling the second substituent module at a second position, and the optional third substituent module at a third position, thereby synthesizing the organic composition. (The first, second and third positions delineate available attachment sites on the conjugated organic moiety, and are not representative either order of attachment during synthesis or IUPAC numbering conventions with respect to the conjugated organic species). Typically, the optional third substituents are coupled to the body structure prior to attachment of the first (head) and second (tail) substituents. Preferably, coupling of the modules to the body structure does not destroy the electronic conjugation of the body structure; furthermore, at least one substituent of the first, second or third substituent modules is capable of binding to a nanostructure surface (or is already bound to a nanostructure surface).
Synthesis of Core Body Structures with Attached Sidechain Moieties [0115] The body structure provides the core of the conjugated organic species of the present invention. Typically, the body structure is a conjugated organic species that either can be functionalized (e.g., by halogenation) or can be reacted with other functionalized moieties (head group, tail group, sidechains) to prepare the conductive compositions of the present invention.
[0116] Preferably, the conjugated organic precursor is selected from any of a number of conjugated alkyl moieties or conjugated aryl moieties known to one of skill in the art. Exemplary conjugated organic precursors, such as phenylene, thiophene, ethene, ethyne, aniline, fluorene, and pyridine derivatives, alkenyl moieties, or perylene, phenanthralene, anthracene, alkenyl or other polynuclear aromatic moieties (or polymeric derivatives thereof), have been discussed in previous sections. Optionally, coupling of one or more of the substituent modules to the body structure extends the conjugation of the body structure. Exemplary body structures are provided in Table 2.
TABLE 2: Exemplary conjugated organic moieties for use as Body Structures
Figure imgf000038_0001
[0117] One advantage to the convergent component synthesis ("modular") approach to the design and manufacture of the conductive compositions of the present invention is the ability to adjust or "tune" the reactivity of each component for the synthetic scheme. For example, the rate of aryl-aryl coupling can be increased or decreased by selecting an appropriate electron donating group or an electron withdrawing group on each respective component. Electron withdrawing groups tend to accelerate the oxidative addition step in palladium-catalyzed coupling reactions (see, e.g., Kuehl et. al. (1997) Organometallics 16: 1897). Thus, by including an electron withdrawing substituent on one of the components, the rate of coupling increases. While not limiting the present invention to a specific mechanism, the enhancement in coupling may be accomplished by the electron withdrawing group weakening the aryl halide or aryl-stannane bond, thus affording a more facile insertion of the palladium catalyst between these moieties. For example, attaching the alkynyl tail group moiety to a thiophene precursor, followed by trimethylstannane attachment, and subsequently coupling this component to the body results in a faster coupling rate and higher overall yields than stepwise assembly. A slower coupling rate is observed if the alkynyl moiety was added after the thiophene and body component were coupled in a divergent stepwise fashion.
[0118] The conductive compositions of the present invention often include one or two sidechains, or "arms," (i.e., third and fourth substituent modules) coupled to the body structure. In a prefeπed embodiment of the methods, the optional third and fourth substituent modules are coupled to the conjugated organic precursor prior to coupling the first (head) and/or second (tail) substituent modules. For example, the conjugated organic precursor can be alkylated at the third position having a hydroxyl or amine moiety, to form an O-linked or N-linked sidechain-substituted intermediate composition.
[0119] For example, sidechain moieties functionalized with a halide (e.g., I or Br) can be used to alkylate the selected conjugated organic species and provide a sidechain- substituted body structure using procedures known in the art. As an example, for the hydroxyl-containing conjugated organic precursors described herein, providing the third substituent module comprises providing about 1.1 molar equivalents of a halogenated derivative of the selected sidechain substituent; and coupling the third substituent module with the conjugated organic precursor comprises the steps of a) combining the halogenated sidechain derivative with the conjugated organic precursor in the presence of, e.g., potassium carbonate (K CO3) and dimethyl formamide (DMF), to form a reaction mixture; and b) heating the reaction mixture to about 70°C, thereby coupling the third substituent to the conjugated organic moiety. A similar reaction can be designed for coupling functionalized sidechain moieties to amine-containing body structure precursors. Alternatively, the sidechain-coupled body structure for use as a substrate in generating the compositions of the present invention can be purchased from various suppliers (e.g., SIGMA-Aldrich) when available.
[0120] In the case of body structures having two (or more) identical sidechain moieties, the coupling reactions for the third and fourth substituents are typically performed simultaneously (e.g., in a single reaction mixture).
[0121] One prefeπed body structure used in the methods and compositions of the present invention is hydroquinone (1,4-dihydroxybenzene). Table 3 provides exemplary substrates for use in the synthesis procedures described herein, based upon a hydroquinone body structure having two sidechain substitutions coupled at the hydroxyl positions of the core hydroquinone structure.
TABLE 3: Exemplary Body Structures with Attached Sidechains
Figure imgf000041_0001
[0122] As indicated in the tabular data above, the two sidechain elements at positions 1 and 4 of the hydroquinone body structure can, but need not, be the same chemical entity. Synthesis of Head Group Moieties [0123] The first substituent module comprises the functionalized nanostructure- binding head group. For example, for embodiments in which the first substituent module comprises diethylphosphite, coupling the first substituent module to the body structure can be performed via a palladium-catalyzed phosphite-aryl coupling reaction.
[0124] In alternate embodiment, a larger head module (precursor) is prepared having a nanostructure binding moiety (e.g., a phosphite) and a conjugated species (e.g., a benzene ring or a thiophene) for linking the nanostructure binding moiety to the body structure. Synthesis of the head module can be achieved, for example, by providing an arylhalide core structure and performing two lithium-halogen exchange reactions. The arylhalide core structure is lithiated at a first halide position and reacted with chlorotrimethylsilane (TMSCl) to yield a TMS-aryl intermediate core structure; the TMS-intermediate core structure is then lithiated at a second halide position and reacted with trimethyltinchloride (Me SnCl) to yield a stannylated second intermediate. Optionally, the lithiating reactions can be performed in the reverse order. The product of these reactions is then combined with, e.g., a halogenated thiophene as the conjugated species, to form the first substituent module, which in this embodiment comprises a TMS-aryl-thiophene derivative. The nanostructure-binding moiety (e.g., a phosphite group) can then be coupled to the aryl portion of the bound head group module, via a palladium-catalyzed mechanism (either before or after attachment of the head module to the body structure).
[0125] Exemplary nanostructure binding moieties that can be used in the present invention include, but are not limited to, those depicted in Table 4.
TABLE 4: Exemplary Synthetic Substrates having nanostructure Binding Moieties for use as Head Groups
Figure imgf000043_0001
Synthesis of Tail Moieties
[0126] The conductive composition also includes a tail group, typically positioned distal to the nanostructure-binding head group. Optionally, the tail group can also include one or more nanostructure binding moieties; in these embodiment, the conductive compositions can be used as a linker between adjacent nanostructures or nanostructures. Optionally, for embodiments having self-organizing properties incorporated therein, the conductive compositions of the present invention can also be employed as alignment ligands, e.g., for orienting and/or aπanging the associated nanostructures (see, for example, US application Attorney Docket No. 40-003300US and PCT application Attorney Docket No. 40-003300PC co-filed herewith).
[0127] Coupling of the second substituent module(e.g., the alkyne-containing tail moiety) can be accomplished by performing an aryl coupling reaction using palladium catalysts. Exemplary reaction protocols include, but are not limited to, Sonogashira couplings (Sonogashira et al. 1975 Tetrahedron Lett. 50: 4467-4470), Suzuki couplings (Miyaura 1979 Tetrahedron Lett. 3437), Hartwig-Buchwald couplings (for N-linked substituents), Heck reactions (Patel et al. 1977 J. Org. Chem. 42:3903), and the like. Alternatively, copper-mediated reactions such as the Ullmann coupling and Stephens-Castro coupling can be used to couple the second substituent module to the body structure. Optionally, the catalyst (for this or for other reactions described herein) can be provided on a solid support or coupled to a soluble polymer, to improve recovery of the material (see, for example, Bergbreiter "Soluble polymer-bound catalysts" Bergbreiter and Martin (Eds.), (1989) Functional Polymers (Plenum Press, New York, pp. 143-158); Tafesh and Beller (1995) "First Selective Reduction of Aromatic Nitro Compounds Using Water Soluble Catalysts" Tetrahedron Lett. 36:9305.
[0128] Exemplary chemical constituents for use as tail group moieties in the present invention include, but are not limited to, the structures shown in Table 5.
TABLE 5: Exemplary Alkyne precursors for use as Tail Groups
T1
T2
Figure imgf000045_0001
T3
Figure imgf000045_0002
Modular Synthesis of Conductive Compositions [0129] By preparing the body structure (with or without the optional accompanying sidechains), head group and tail group moieties separately, various different conductive compositions can easily and rapidly be prepared. This modular approach to the chemical synthesis of the conductive compositions of the present invention lends itself to a number of combinations of various head moieties, tail groups, and optional side chain elements, some of which are provided in Figure 1 and Figure 2.
[0130] Optionally, the synthetic methods further include the step of coupling the head group to an external surface of a structur , such as nanocrystal (or other nanostructure), thereby providing a nanocrystal-bound composition. Alternatively, the head group can be coupled to a non-nanoscale surface and the conductive composition employed in conjunction with a non-nanoscale semiconductor composition. Semiconductor and nanoscale semiconductor compositions are known in the art. Nanostructures having external surfaces that can be employed in the coupling step can be prepared from any of the exemplary semiconducting materials described previously. In a prefeπed embodiment, the nanocrystals are group II/VI or group III/V structures, for which coupling the head group to the external surface of a nanocrystal comprises, e.g., association of free electrons available in the head group with proximal metal moieties of the nanocrystal. The head group module employed can be chosen based upon the composition of the structure or nanoscale structure to be contacted, such that a conductive composition can be prepared, e.g., for any nanostructure/nanocrystal composition, without undue experimentation.
[0131] Furthermore, the methods of the present invention can also optionally include the step of polymerizing the organic composition after coupling the composition to the nanostructure surface, thereby forming a polymerized organic composition.
[0132] Nanostructure-containing device of the present invention are particularly suited for use in a photovoltaic device. See, for example, Huynh et al. (2002) Science 295:2425-2427; Huynh et al. (1999) Adv. Mater. 11:923-927; Greenham et al. (1996) Phys. Rev. B-Condens Matter 54:17628-17637; and Greenham et al. (1997) Synthetic Metals 84:545-546; as well as the exemplary nanocrystal-containing photovoltaic devices described in provisional applications USSN 60/408,722 filed September 5, 2002; USSN 60/421,353, filed October 25, 2002 and USSN 60/452,038fιled on March 4, 2003. The conductive compositions of the present invention can also be employed in the polymer/ nanocomposite photovoltaic devices described in USPN 6,239,355; USPN 6,512,172, as well as dye- sensitized crystal photovoltaic devices, e.g., as described in USPN 5,728,487; and USPN 6,245,988.
[0133] Synthesis of water soluble semiconductor nanocrystals capable of light emission are described, for example, in USPN 6,251,303 to Bawendi et al. entitled "Water- soluble fluorescent nanocrystals" (June 6, 2001) and USPN 6,319,426 to Bawendi et al. titled "Water-soluble fluorescent semiconductor " (November 20, 2001).
METHOD OF MODIFYING INTERACTION BETWEEN NANOSTRUCTURE AND MATRIX
[0134] As an additional aspect, the present invention also provides methods of modifying an interaction between a nanostructure and an external matrix. The methods include the steps of a) treating a nanostructure with the conductive composition of the present invention; and b) forming a nanostructure-containing matrix comprising the treated nanostructure and a matrix composition. Optionally, treating the nanostructure can also include polymerizing the conductive composition to form a polymerized conductive composition. In some embodiments of the methods, the polymeric conductive composition described herein are employed as matrices in the methods. USES OF THE METHODS. DEVICES AND COMPOSITIONS OF THE PRESENT INVENTION
[0135] Modifications can be made to the methods and materials as described above without departing from the spirit or scope of the invention as claimed, and the invention can be put to a number of different uses, including:
[0136] The use of any method herein, to prepare a conductive composition for use in modifying an interaction involving a nanostructure, e.g., an interaction between a nanocrystal and a matrix.
[0137] The use of any method herein, to associate a conductive composition of the present invention with one or more nanostructures.
[0138] The use of a method or a conductive composition of the present invention in the manufacture of a nanostructure-containing device.
[0139] A kit or system using of any one of the conductive compositions, nanostructurexonductive composition; nanostructure:matrix compositions, or methods hereinbefore described. K ts will optionally additionally comprise instructions for performing the methods, packaging materials, one or more containers which contain the conductive compositions or materials used to prepare the compositions, and/or the like.
[0140] In an additional aspect, the present invention provides kits embodying the methods and devices herein. Kits of the invention optionally comprise one or more of the following: (1) various components (body structures, head groups, tail groups, sidechains) for the modular synthesis of the conductive compositions of the present invention; (2) one or more preparations of nanocrystals or other nanostructures; (3) components and/or instructions for the preparation of nanocrystakmatrix compositions; (4) instructions for practicing the methods described herein; and/or (5) packaging materials.
[0141] In a further aspect, the present invention provides for the use of any component or kit herein, for the practice of any method herein, and/or for the use of any apparatus or kit to practice any method herein.
EXAMPLES
[0142] The following examples are offered to illustrate, but not to limit the claimed invention. It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims.
[0143] Methods for the synthesis of the conductive compositions of the present invention are provided herein and in the accompanying figures. Additional information regarding synthesis techniques can be found in, for example, Fessendon and Fessendon, (1982) Organic Chemistry, 2nd Edition, Willard Grant Press, Boston Mass; Carey & Sundberg, (1990) Advanced Organic Chemistry, 3rd Edition, Parts A and B, Plenum Press, New York; and March (1985) Advanced Organic Chemistry, 3rd Edition, John Wiley and Sons, New York. Optionally, the standard chemical reactions described therein are modified to enhance reaction efficiency, yield, and/or convenience.
EXAMPLE 1: SYNTHESIS OF MODEL CONDUCTIVE COMPOSITION 4-DECYNYL- BENZENE-1 -PHOSPHONIC ACID
[0144] A synthesis protocol was designed to test the modular approach to synthesis of the conductive compositions of the present invention (Figure 3). The model conductive composition 5b was prepared using l-iodo-4-bromobenzene as a precursor to the body structure, 1-decyne as the tail group moiety, and diethylphosphite as the head group moiety.
To a 500 mL schlenk flask with egg-shaped stirbar under argon, palladium dichloride (1.0 mmol, 0.177g), copper(I) iodide (2.36 mmol, 0.450 g), and triphenylphosphine (2.0 mmol,
0.525g) were added in a glovebox under argon. On a schlenk line, l-iodo-4-bromo-benzene
(50 mmol, 14.15 g, compound 1) was added, the vessel was stoppered, and the flask was placed under vacuum and backfilled with argon (3X). The flask was fitted with a septum under positive argon pressure and degassed diisopropyl amine (lOOmL) was added via cannula under positive argon pressure with stirring. Next, degassed 1-decyne (50 mmol,
6.91 g, compound 2) was added via syringe under argon. Finally, dry, degassed tetrahydrofuran was added via cannula transfer under argon, the vessel sealed with a glass stopper and allowed to stir at ambient for 16 h followed by heating to 55°C for one hour.
After cooling to ambient temperature, the solvent was removed by roto-evaporation, the residue dissolved in diethyl ether (200 mL) and washed with ammonium chloride (sat. aqueous, 3 x 100 mL). The organic layer was separated and dried over magnesium sulfate, filtered and the solvent removed by roto-evaporation. The resulting oil was dissolved in hexanes and plugged through silica gel. Removal of the solvent resulted in a yellow oil of
4-decynyl-bromo-benzene 3 (14.34g, 98% yield). [0145] This material was used without further purification for the attachment of phosphonate ester moiety. To a 100 mL schlenk tube with a Teflon valve and stirbar containing the above compound 3 (23.87 mmol, 7.0g), palladium(0)tetrakis [triphenylphosphine] (1.19 mmol, 1.38g) was added. On a schlenk line, degassed triethyl amine (11 mL) and degassed toluene were then sequentially added via syringe under argon. Next, degassed diethyl phosphite 4 (26.26 mmol, 3.63 g) was added via syringe under argon. The reaction vessel was sealed, the mixture stiπed and heated to 100° C for 2h. The solvent was removed by roto-evaporation, and the residue dissolved in ethyl acetate (200 mL) and washed with saturated aqueous ammonium chloride (3 x 75 mL), dried over sodium sulfate, filtered and the solvent removed by roto-evaporation. Isolation by silica gel chromatography (1:1 Ethyl Acetate:Hexanes) afforded 4-decynyl-benzene-l- diethylphosphonate 5a as a colorless oil (7.19 g, 90% yield) 1H NMR (CDC13) δ 7.70 (m, 2 H), 7.45 (m, 2 H), 4.10 (m, 4 H), 2.42 (t, 2 H), 1.61 (m, 2 H), 1.45 (m, 2H), 1.32 (t, 8H), 1.27 (m, 6 H), 0.89 (t, 3 H). MS signal derived from the phosphonated benzyl ring without the coupled tail group (a side product of the reaction) is shown in Figure 9.
[0146] Hydrolysis of the ester to the phosphonic acid was accomplished by the following. To a 250 mL schlenk flask containing compound 5a (10 mmol, 3.5 g) and dry dichloromethane (65 mL), Trimethylsilylbromide (40 mmol, 6.1g) was added via syringe under argon with stirring. After stirring for 4.5 h at ambient temperature, the solvent was removed in vacuo on the schlenk line. Next acetone (32 mL) and water (0.775 mL) were added and the mixture stiπed at ambient temperature for 45 min. Removal of the acetone/water by roto-evaporation followed by addition of dichloromethane and roto- evaporation of all solvent afforded the phosphonic acid derivative 5b (2.9 g, 100% yield). 1H NMR (CDC13, Figure 18) δ 7.75 (m, 2 H), 7.45 (m, 2 H), 2.44 (t, 2 H), 1.63 (m, 2 H), 1.45 (m, 2H), 1.32 (t, 8H), 0.93 (t, 3 H). {1H}31P NMR (CDC13, Figure 19) δ 24.0
EXAMPLE 2: SYNTHESIS OF CONDUCTIVE COMPOSITION 16 [0147] One advantage to the methods of the present invention is the modular approach to synthesis of the various conductive compositions of interest. Using this approach allows for the preparation and use of common synthetic intermediates and core structures. An exemplary synthesis scheme for the preparation of a conductive composition of the present invention is depicted in Figure 4 and described in further detail herein. In this modular approach, the various components of the composition (body structure, head group, tail group) are synthesized as individual structures, which are then coupled together to form the conductive composition.
Preparation of the head group precursor [0148] One common intermediate in the synthesis of some embodiments of the present invention is the activated head group precursor compound 9, which can be prepared based upon known synthetic protocols such as those provided in Figure 4.
Coupling of sidearm moieties to the body structure [0149] In many of the embodiments of the present invention, the sidearm moieties are coupled to the body element prior to incorporation of the head and tail elements. One prefeπed sidearm component for use in the conductive composition is an O-linked hexyl moiety. As such, another intermediate useful for the synthesis of 2,5-dihexoxy-containing conductive compositions isl,4 diiodo-2,5-dihexoxybenzene (compound 13; see also Figure
14). This core structure consisting of an aromatic body structure (benzene) and the two O- linked sidearm chains can be prepared from hydroquinone (compound 10) by standard procedures such as provided in Figure 4. While the following syntheses focus on hydroquinone-based body structures (e.g., various sidechains O-linked to a benzene core), other aryl and/or aromatic core structures are also contemplated and can be used to generate conductive compositions of the present invention. Exemplary conductive compositions employing alternative core structures are shown, for example, in Figure 2.
Addition of thiophene elements to body structure [0150] In a prefeπed embodiment, the body structure includes one or more thiophene moieties coupled to an aromatic ring core structure. This can be achieved synthetically by either providing thiophene-containing core structures or by providing thiophene-containing head or tail group moieties. JΛΛ exemplary thiophene-containing body structure (including the coupled sidearms) is l,4-dithiophene-2,5 -dihexoxybenzene
(compound 15a). This compound, which is a precursor to the iodinated intermediate compound 15b, is prepared as follows. To a 100 mL schlenk tube with stirbar and Teflon valve, palladium dichloride (1.0 mmol, 0.177g), triphenylarsene (2.0 mmol, 0.610 g), and
LiCl (20 mmol, 0.859 g) were added in a glove box. On a schlenk line, l,4-diiodo-2,5- dihexoxybenzene 13 (10 mmol, 5.30 g), was added and the vessel placed under vacuum and backfilled with argon (3 x). Next, degassed dimethylformamide (DMF) was cannula transfeπed under positive argon pressure. The vessel was sealed and heated to 100°C for up to 6 days. The reaction mixture was cooled and diluted with ethyl acetate (200 mL) and washed with saturated aqueous sodium bicarbonate (125 mL), deionized water (50 mL) and brine (150 mL). The organic layer was placed under vacuum and the solvent removed and trapped in a 250 mL schlenk flask. Purification by flash chromatography (Ethyl acetate: hexanes, 0, 1, 2, and 5% gradient) and solvent removal by roto-evaporation afforded yellow crystals of l,4-dithiophene-2,5-dihexoxybenzene (2.2 g, 49% yield, compound 15a). 1H NMR (CDC13, Figure 16) δ 7.53 (d, 2 H), 7.34 (d, 2 H), 7.25 (s, 2H), 7.09 (dd, 2 H), 4.09 (t, 4H), 1.91 (m, 4 H), 1.55 (m, 4H), 1.36 (m, 8H), 0.93 (t, 6 H); 13C{1H} (CDCI3) δ 149.2, 139.3, 126.8, 125.8, 125.2, 123.0, 112.9, 69.9, 31.9, 29.7, 26.2, 22.9, 14.4.
[0151] Intermediate 15a was then converted to compound 15b by iodination of one of the thiophene elements as follows. To a 100 mL schlenk flask with Teflon valve and stirbar, l,4-dithiophene-2,5-dihexoxybenzene 15a (2.49 mmol, 1.10 g) was added and the flask closed with a stopper and placed under vacuum and backfilled with argon (3x). Next, dry chloroform (30 mL) was cannula transfeπed under positive argon pressure and the mixture stiπed. To the stiπed solution under argon, N-iodosuccinimide (2.49 mmol, 0.560 g) was added in one portion, the reaction vessel sealed with a Teflon sleeved stopper and the reaction mixture stiπed at ambient temperature for 4.5 h then heated to 40 °C and stiπed for an additional 22 h. After cooling the crude reaction mixture was plugged through silica gel (5% ethylacetate: 95% hexane), then washed with 10% aqueous sodium thiosulfate (3 x 50 mL), brine (50 mL) and the organic layer dried over sodium sulfate filtered and the solvent removed by roto-evaporation to afford the crude material compound 15b as a yellow oily solid (1.40 g, 99% yield). 1H ΝMR (CDCI3, Figure 13) δ 7.53 (m, 1 H), 7.43 (d, 1H), 7.35 (m, 1 H), 7.26-7.20 (m, 3H), 7.13 (d, 1H) 7.09 (dd, 1 H), 7.02 (s, 1H), 4.09 (t, 4H), 2.45 (t, 2H), 1.93 (m, 4 H), 1.70-1.25 (m, 24H), 0.94 (m, 9 H); MALDI-TOF MS (M+H) 569 m/z.
Coupling of the tail and head groups [0152] Addition of the tail group and head group moieties to the iodinated intermediate 15b leads to conductive composition 16. The tail moiety is coupled to the iodinated thiophene element of the body structure as shown in Figure 4, in a manner similar to that previously described for compound 5a. Coupling of the head group is the final step in the synthesis of the desired conductive composition 16. EXAMPLE 3: SYNTHESIS OF COMPOSITIONS HAVING ASYMMETRIC SIDEARM ELEMENTS
[0153] The two sidearm moieties of the conductive composition need not be identical or symmetrical in structure. In another embodiment of the compositions of the present invention, two differing sidearm moieties are employed in the modular synthesis of the conductive composition 21. As shown in Figure 5, 4-methoxyphenol (compound 17) was alkylated at the unprotected hydroxyl group using 1.1 equivalents of 1-iodohexane
(compound 11) in the presence of potassium carbonate and DMF at 70°C, to form intermediate compound 18 (see Figure 15), which was iodinated (compound 19, Figure 17), derivatized with thiophene moieties, and coupled to a 1-decyne tail moiety (Tl) and a thiophene-phosphonate head group (H3) in a manner similar to Example 2.
EXAMPLE 4: SYNTHESIS OF TAIL GROUP MOIETY l-STANNYL-5-DECYNYL- THIOPHENE
[0154] Another common intermediate employed in the synthesis of some embodiments of the present invention is the thiophene-containing tail group moiety, 1- stannyl-5-decynyl-thiophene (compound 22), in which a thiophene moiety and tail group are joined prior to coupling to the body structure (in contrast to the synthetic schemes depicted in Figure 4 and Figure 5, in which the thiophene moiety is joined to the body structure prior to coupling of the tail group moiety). This thiophene-tail group intermediate can be prepared as follows (Figure 6). To a 100 mL schlenk tube with resealable Teflon valve and egg-shaped stirbar, palladium dichloride (0.413 mmol, 0.073 g), triphenylphosphine (0.826 mmol, 0.217g), and copper(I) iodide (0.413 mmol, 0.079 g) were added in the glove box. On the schlenk line, degassed 2-bromothiophene 8 (20.66 mmol,
3.37 g), diisopropyl amine (30 mL), 1-decyne 2 (20.66 mmol, 2.86 g) and toluene (50 mL) were added sequentially via syringe under argon. The reaction vessel was sealed with the valve, the reaction mixture heated to 100 ° C and stiπed overnight. The reaction mixture was cooled to ambient temperature, and the solvent removed by roto-evaporation. The residue was dissolved in diethyl ether (250 mL) washed with saturated aqueous ammonium chloride (3 x 125 mL), dried over sodium sulfate, filtered, and the solvent was removed by roto-evaporation, affording a yellow oil. Purification by plugging through silica gel with hexanes afforded 2-decynyl thiophene (compound 22a) as a light yellow oil (4.32 g, 95% yield). 1H NMR (CDC13) δ 7.18 (d, 1 H), 7.12 (d, 2 H), 6.94 (dd, 1H), 2.44 (t, 2 H), 1.70- 1.30 (m, 12 H), 0.92 (t, 3 H); GC/MS (M+ 220 m/z). This compound was used without further purification.
[0155] To a 1 L schlenk flask with egg-shaped stirbar in a glove box, the 2- decynylthiophene 22a (57.44 mmol, 12.658 g) was added by pipette. On a schlenk line, tetrahydrofuran (300 mL) was cannula transfeπed to the reaction vessel through a septum. The reaction mixture was cooled to -78°C and n-butyl lithium (35.9 mL, 1.6 M solution in hexanes,) was added dropwise via syringe and the reaction mixture stiπed for 45 min. The reaction vessel was fitted with an addition funnel and trimethyltin chloride (57.4 mL, 1.0 M solution in tetrahydrofuran) was cannula transfeπed to the funnel under positive argon pressure through a septum. The trimethyltin chloride solution was added dropwise to the stirring lithium salt solution over a period of 15 min. at -78°C. The reaction mixture was allowed to warm to ambient temperature with stirring overnight. The solvent was removed in vacuo on the schlenk line and trapped in a IL schlenk flask. The resulting residue was dissolved in diethyl ether (500 mL) washed with brine (3 x 200 mL), dried over magnesium sulfate, filtered and the solvent removed by roto-evaporation to afford l-stannyl-5-decynyl- thiophene 22b as a light brown oil (20.6 g, 94% yield). 1H NMR (CDC13) δ 7.20 (d, 1 H), 7.00 (d, 2 H), 2.43 (t, 2 H), 1.60 (m, 2 H), 1.44(m, 2H), 1.30 (m, 8H), 0.899 (t, 3 H), 0.37 (s, 9H); GC/MS (M+) 384 m/z, (M+-CH3) 369 m/z.
EXAMPLE 5: SYNTHESIS OF CONJUGATED COMPOSITION 25 [0156] Another example of a conjugated composition of the present invention is compound 25 shown in Table 1 and Figure 6. This composition was prepared using the thiophene-derivatized tail group moiety 22b and body structure 15b as follows.
[0157] To a 50 mL schlenk tube with a stirbar, palladium dichloride (0.12 mmol,
0.021g), triphenylarsene (0.24 mmol, 0.073 g), LiCl (2.4 mmol, 0.103 g) and l-stannyl-5- decynyl-thiophene 22b, were added in a glove box. On a schlenk line, compound 15b was dissolved in degassed dimethylformamide and cannula transfeπed to the schlenk tube under positive argon pressure. The reaction mixture was placed under vacuum, backfilled with argon, the vessel sealed and heated to 100°C for up to 4 days. The reaction mixture was diluted with ethyl acetate (250 mL) and washed with de-ionized water (100 mL), the organic layer separated and solvent removed in vacuo. Purification by silica flash chromatography (4% ethyl acetate: 96% hexane) afforded a precursor to compound 23 (precursor structure not shown) as a yellow oily solid (0.360 g, 23% yield). 1H NMR (CDC13) δ 7.54 (m, 1 H), 7.35 (d, 1 H), 7.25-7.16 (m, 4H), 7.09 (dd, 1 H), 4.09 (m, 4H), 1.93 (m, 4 H), 1.56 (m, 4H), 1.39 (m, 8H), 0.94 (m, 9H); MALDI TOF MS (M+H) 661 m/z.
[0158] To a 50 mL schlenk flask with Teflon valve, stirbar and the precursor to compound 23 (0.515 mmol 0.340 g) and chloroform (6.2 mL), N-iodosuccinimide (0.515 mmol, 0.116 g) was added in one portion under argon. The reaction vessel was sealed and the mixture heated to 40°C for 22 h. The reaction mixture was diluted with ethyl acetate (100 mL) washed with 10% aqueous sodium thiosulfate (3 x 25 mL), brine (2 x 25 mL), dried over magnesium sulfate, filtered and plugged through silica gel with ethyl acetate. Solvent removal by roto-evaporation afforded the crude product 23 as a sticky yellow solid which was used without further purification (0.402 g, 99%). Η ΝMR (CDC13) δ 7.72 (d, 1 H), 7.56 (m, 1 H),7.50 (d, lH),7.40-7.32 (m, 2H), 7.30-7.20 (m, 2H), 7.11 (dd, 1 H), 5.18 (t, 2H), 4.13 (m, 4H), 2.15 (m, 2H), 1.95 (m, 4H), 1.58 (m, 8H), 1.50-1.20 (m, 14H), 1.28 0.93 (m, 9 H).
[0159] In this particular embodiment of the invention, a thiophene-coupled head group moiety 24 was prepared for attachment to the body structure, via coupling to the non- iodinated thiophene of compound 15b. Addition of the precursor head group moiety 24 to the crude reaction product 23 to form conductive composition 25 was performed as provided in Figure 6.
EXAMPLE 6: SYNTHESIS OF CONJUGATED COMPOSITION 28 [0160] A further example of a conjugated composition of the present invention is compound 28 as shown in Table 1 and Figure 7. This composition was prepared using the thiophene-containing body structure 15b and a benzyl-containing tail moiety in a similar manner as described in Figure 7. Alternatively, compound 28 could have been synthesized using the intermediate depicted in Figure 10 (i.e., by using a body structure having the benzyl ring instead of a head group having the benzyl ring).
[0161] The conductive composition depicted in Figure 11 could be synthesized in a similar modular manner, using body structure 15b, a benzylated head group (such as shown in Figure 9, and a thiophene-containing tail group (e.g., compound 22). EXAMPLE 7: AN ALTERNATE METHOD FOR MODULAR SYNTHESIS OF COMPOUND 25
[0162] An alternate modular approach to preparation of conductive composition 25 is also contemplated, as depicted in Figure 20. In this approach, dithiophene elements are attached as a unit to the body structure, rather than using thiophene-containing head and tail group components. In this synthetic approach, iodinated body structure 13 is prepared from hydroquinone 10 as described above. The iodine moieties are then replaced with two dithiophene structures to form compound 30. Intermediate 30 is then joined to tail group
2and a phosphonic acid head group, as shown in Figure 20, to form conductive composition
25.
EXAMPLE 8: SYNTHESIS OF CONJUGATED COMPOSITION 31 [0163] Di-iodinated intermediate 13 can also be used in the synthesis of an additional embodiment of the conductive compositions of the present invention, compound 31, as described in Figure 21.
EXAMPLE 9: SYNTHESIS OF POLYMERIZABLE CONDUCTIVE POLYMERS [0164] Embodiments of the present invention are contemplated in which one or more components of the conductive composition (e.g., body structure, head, tail) are present in multiple units. For example, some embodiments include body structures prepared by coupling or polymerizing two or more body structures. The coupling can be performed either prior to or after attachment of the head and tail moieties to the respective body structure members. These embodiments are genetically described as conductive compositions having the structure [Hx-By-Tz]n, wherein H comprises at least one functionalized head group capable of binding to a nanocrystal surface (or, for nanostructure- bound embodiments, at least one head group bound to a nanocrystal surface); wherein B comprises a body structure comprising one or more conjugated organic moieties, wherein a first conjugated organic moiety is coupled to a proximal functionalized head group or bound head group; wherein T comprises at least one tail group coupled to the body structure; and wherein x, y, z and n independently comprise integers equal to or greater than 1.
[0165] Figure 22 provides a synthetic scheme for preparation of a conductive composition (compound 36) incorporating two core body structure components, a p-xylene unit (derived from compound 32) and an O-alkylated hydroxyquinone unit (compound 12). It should be noted, however, that although two body structure components are employed from a synthesis perspective, the final product (in this example, compound 36) can also be considered to have one large body component having two aromatic rings coupled by a dithiophene moiety, and having a tail moiety attached to a first end of the overall body structure and a head moiety attached to a second end of the overall body structure. As with many embodiments of the chemical compositions of the present invention, the distinction between body structure, head group and tail group elements is partially based upon the synthetic approach chosen (note the two modular approaches to compound 25 as described above), and as such should not be considered limiting.
[0166] Compound 36 can be synthesized as provided in Figure 23. In a similar manner, compound 41 can also by synthesized as shown in Figure 24. In this modular approach, the first portion of the body structure (compound 38) is prepared and then coupled to the tail group 22 (to form intermediate 39); a second body structure portion (compound 20) is stannylated and coupled to a head group (to form intermediate 40), and then these synthetic intermediates are joined to form compound 41.
[0167] Compounds 36 and 41 are of particular interest, since these compositions also embody an additional optional feature of the present invention, one of the polymerization aspects of the conductive composition. As shown in Figure 23, the sidearm elements of the p-xylene derived portion of the body structure can be reacted with a ketone functional group as shown in Figure 23, for example, in the presence of a stereoselective base, such as lithium diisopropyl amide (LDA). The cross-reactivity between the ketone- containing conductive compositions (preferably on different nanostructures) leads to crosslinking of the adjacent conductive compositions.
[0168] This embodiment is particularly of interest in nanostructure-matrix compositions having both n-type and p-type nanocrystals incorporated into the matrix. Coupling of an n-type nanocrystal to an adjacent p-type nanocrystal will allow for an even more efficient transmission of electrons and holes within the matrix.
EXAMPLE 10: SYNTHESIS OF CONDUCTIVE COMPOSITION 43 [0169] Di-iodinated intermediate 13 can also be used in the synthesis of an additional embodiment of the conductive compositions of the present invention, compound 43 (see Figure 25). For the synthesis of this compound, intermediate 30 is prepared as described above. The head group and tail group moieties are then coupled to the body structure using the protocols described in Figure 25, to generate compound 43.
EXAMPLE 11 : SYNTHESIS OF CONDUCTIVE COMPOSITION 46 [0170] Di-iodinated intermediate 13 can also be used in the synthesis of an additional embodiment of the conductive compositions of the present invention, compound 46 (see Figure 26).
[0171] To a 50 mL schlenk flask with egg-shaped stirbar in a glove box, precursor
22b (0.997 mmol, 0.659 g) was added. The vessel was stoppered, placed under vacuo and backfilled with argon (3x). On a schlenk line, tetrahydrofuran (5 mL) was cannula transfeπed to the reaction vessel through a septum. The reaction mixture was cooled to - 78°C and w-butyl lithium (0.623 mL, 1.6 M solution in hexanes,) was added dropwise via syringe and the reaction mixture warmed to -50°C and stiπed for lh. The reaction mixture was recooled to -78°C and trimethyltin chloride (0.997 mL, 1.0 M solution in tetrahydrofuran) was added dropwise via syringe to the stirring lithium salt solution at - 78°C. The reaction mixture was allowed to warm to ambient temperature with stirring overnight. The solvent was removed in vacuo on the schlenk line and trapped in a IL schlenk flask. The resulting residue was extracted with hexanes (3 X 50 mL) and cannula filtered followed by in vacuo solvent removal to afford intermediate compound 44 as a yellow oil. 1H NMR (CDC13) δ 7.67 (d, 1 H), 7.45 (d, 1 H), 7.28-7.22 (m, 2 H) 7.20 (d, IH) 7.15 (d, IH), 7.03 (s, 2H), 4.12 (m, 4H), 2.46 (t, 2 H), 1.93 (m, 4H), 1.62 (m, 2 H), 1.44 (m, 2H), 1.39 (m, 8H), 0.95 (m, 9 H), 0.37 (s, 9H).
[0172] To prepare functionalized head moiety 45, compound 13 (50.0 mmol,
14.15g) and palladium(0)tetrakis [triphenylphosphine] (2.50 mmol, 2.89 g) were added to a 200 mL schlenk tube with a Teflon valve and stirbar. On a schlenk line, degassed triethyl amine (20.9 mL) and degassed toluene (50 mL) were then sequentially added via syringe under argon. Next, degassed diethyl phosphite (50.0 mmol, 6.91 g) was added via syringe under argon. The reaction vessel was sealed, the mixture stiπed at ambient temperature for 12 h followed by heating to 50 °C for lh. The solvent was removed by roto-evaporation, and the residue dissolved in ethyl acetate (500 mL) and washed with saturated aqueous ammonium chloride (3 x 200 mL), dried over magnesium sulfate, filtered and the solvent removed by roto-evaporation. Isolation by silica gel chromatography (1:1 Ethyl Acetate: Hexanes) afforded compound 45 as a colorless oil (9.17 g, 62% yield) 1H NMR (CDC13) δ 7.90-7.50 (m, 4 H), 4.30-4.10 (m, 4 H) 1.50-1.30 (m, 6H); {1H}31P NMR (CDCl3) δ l8.8 (s).
[0173] To a 50 mL schlenk tube with a stirbar, palladium dichloride (0.06 mmol,
0.01 Og), triphenylarsene (0.10 mmol, 0.031 g), LiCl (1.0 mmol, 0.043 g) and compound 45 (1.05 mmol, 0.370g), were added in a glove box. On a schlenk line, compound 44 was dissolved in degassed dimethylformamide (6 mL) and cannula transfeπed to the schlenk tube under positive argon pressure. The reaction mixture was placed under vacuum, backfilled with argon, the vessel sealed and heated to 100°C for 12 h. The reaction mixture was diluted with ethyl acetate (250 mL) and washed with de-ionized water (100 mL), the organic layer separated and solvent removed in vacuo. Purification by silica flash chromatography (ethyl acetate: hexane 1:1) afforded compound 46 as a yellow oily solid (0.124 g, 14 % yield). . 1H NMR (CDCI3) δ 7.85-7.80 (m, 2 H) 7.76-7.72 (m, 2H) 7.65 (d, 1 H), 7.46 (d, 1 H), 7.42 (d, 2 H) 7.25 (m, 2H) 7.15 (d, IH), 7.04 (s, IH), 7.03 (s, IH) 4.15 (m, 4H), 2.46 (t, 2 H), 1.97 (m, 4H), 1.62 (m, 2 H), 1.42 (m, 2H), 1.37 (m, 8H), 0.95 (m, 9 H); {1H}31P NMR (CDC13) δ 19.6 (s).
EXAMPLE 12: SYNTHESIS OF CONDUCTIVE COMPOSITION 50 [0174] Compound 50 is prepared using iodinated body structure 48, as shown in
Figure 27. To a 250 mL schlenk tube with stirbar and Teflon valve, palladium dichloride (2.05 mmol, 0.363g), triphenylarsene (4.1 mmol, 1.255 g), and LiCl (41 mmol, 1.759 g) were added in a glove box. On a schlenk line, l,4-diiodo-2-(2-ethylhexoxy)-5- methoxybenzene (compound 47b, 20.5 mmol, 10.0 g), was added and the vessel placed under vacuum and backfilled with argon (3 x). Next, degassed dimethylformamide (DMF, 100 mL) was cannula transfeπed under positive argon pressure. The vessel was sealed and heated to 100°C for 1 day. The reaction mixture was cooled and diluted with ethyl acetate (500 mL) and washed with saturated aqueous sodium thiosulfate (3 x 150 mL) and brine (3 x 150 mL). The organic layer was separated, dried over sodium sulfate, filtered and the solvent removed by roto-evaporation. Purification by flash chromatography (Ethyl acetate: hexanes, 0, 1, 2, 5 and 10 % gradient) and solvent removal by roto-evaporation afforded of l,4-dithiophene-2-(2-ethylhexoxy)-5-methoxybenzene (7.55 g, 92% yield) as a colorless oil. Η NMR (CDCI3) δ 7.56 (m, 2 H), 7.37 (d, 2 H), 7.29 (s, IH), 7.26 (s, IH), 7.13 (m, 2 H), 4.01 (d, 2H), 3.97 (s, 3H), 1.87 (m, 1 H), 1.61 (m, 4H), 1.38 (m, 8H), 1.00 (t, 3 H), 0.98 (t, 3H).
[0175] To a 500 mL schlenk flask with egg-shaped stirbar in a glove box, the reaction product (16.85 mmol, 6.75 g) was added. The vessel was stoppered, placed under vacuo and backfilled with argon (3X). On a schlenk line, tetrahydrofuran (241 mL) was cannula transfeπed to the reaction vessel through a septum. Next N,N-Tetramethyl ethylenediamine (16.85 mmol, 1.96 g) was transfeπed to the reaction mixture via syringe. The reaction mixture was cooled to -78°C and w-butyl lithium (10.53 mL, 1.6 M solution in hexanes,) was added dropwise via syringe and the reaction mixture was stiπed for lh. A THF solution (70 mL) of 1,2-diiodoethane (21.91 mmol, 6.174 g) was cannula transfeπed to the stirring lithium salt solution at -78°C. The reaction mixture was allowed to warm to ambient temperature with stirring overnight. The solvent was removed by roto-evaporation and the residue dissolved in ethyl acetate (225 mL) and washed with 10% sodium thiosulfate (1 x 150 mL) and brine (200 mL). The organic layer was separated, dried over magnesium sulfate, filtered and the solvent removed by roto-evaporation. Purification by flash chromatography (Ethyl acetate: hexanes, 0, 1, 2, 5 and 10 % gradient) and solvent removal by roto-evaporation afforded 4-iodo-(l,4-dithiophene-2-(2-ethylhexoxy)-5- methoxybenzene (compound 48, 6.21 g, 70% yield) as a yellow oil. Η NMR (CDC13) δ 7.55 (m, 1 H), 7.38 (d, 1 H), 7.29 (s, IH), 7.25 (d, IH), 7.21 (d, IH), 7.20 (s, IH), 7.13 (dd, 1 H), 4.01 (d, 2H), 3.99 (s, 3H), 1.88 (m, 1 H), 1.61 (m, 4H), 1.36 (m, 8H), 1.01 (t, 3 H), 0.98 (t, 3H).
[0176] The iodinated body structure 48 is then coupled to the tail moiety to form intermediate compound 49 (as described in Figure 27). To a 100 mL schlenk tube with a stirbar, palladium dichloride (0.32 mmol, 0.057g), triphenylarsene (0.64 mmol, 0.197 g), LiCl (6.43 mmol, 0.277 g) and l-stannyl-5-decynyl-thiophene 22b, were added in a glove box. On a schlenk line, compound 48 was dissolved in degassed dimethylformamide and cannula transfeπed to the schlenk tube under positive argon pressure. The reaction mixture was placed under vacuum, backfilled with argon, the vessel sealed and heated to 100°C for up to 1 day. The reaction mixture was diluted with ethyl acetate (250 mL) and washed with de-ionized water (100 mL), the organic layer separated and solvent removed in vacuo. Purification by silica flash chromatography (5-15% ethyl acetate: 95-85% hexane) afforded the precursor compound as a yellow oil (2.83 g, 71% yield). 1H NMR (CDC13) δ 7.57 (d, 1 H), 7.47 (m, 1 H), 7.38 (m, IH), 7.32-7.25 (m, 2 H), 7.17 (d, IH), 7.13 (dd, IH) 7.09-7.00 (m, 2H), 4.00 (m, 2H), 3.99 (s, 3H), 2.47 (t, 2H) 1.87 (m, IH), 1.63 (m, 4H), 1.45 (m, 2H), 1.36 (m, 8H), 1.30-0.94 (m, 9H) ); MALDI TOF MS (M+H) 618 m/z.
[0177] To a 100 mL schlenk flask with egg-shaped stirbar in a glove box, precursor
49 (4.56 mmol, 2.82 g) was added. The vessel was stoppered, placed under vacuo and backfilled with argon (3x). In a drybox, tetrahydrofuran (23.3 mL) was pipetted to the reaction vessel and the substrate dissolved at ambient temperature. The reaction mixture was cooled to -78°C and n-butyl lithium (2.85 mL, 1.6 M solution in hexanes,) was added dropwise via syringe and the reaction mixture warmed to -50°C and stiπed for lh. The reaction mixture was recooled to -78°C and diethylphosphonate chloride (0.4.56 mmol, 0.658 mL) was added dropwise via syringe to the stirring lithium salt solution at -78°C. The reaction mixture was allowed to warm to ambient temperature with stirring overnight. The solvent was removed by roto-evaporation and the resulting residue was dissolved in ethyl acetate (150 mL), dried over sodium sulfate, filtered. Purification by silica flash chromatography (5-15% ethyl acetate: 95-85% hexane) afforded the precursor compound as an orange oil.
EXAMPLE 13: SYNTHESIS OF CONDUCTIVE COMPOSITION 25
[0178] Figure 28 provides an alternate approach to the synthesis of conductive composition 25.
EXAMPLE 14: PREPARATION OF NANOSTRUCTURES [0179] Excess organic surfactants such as trioctyl phosphine (TOP), trioctyl phosphine oxide (TOPO), hexadecyl phosphonic acid (HDP A), octadecyl phosphonic acid (ODPA), and tri-n-butyl phosphine (TBP) are commonly present in nanostructure preparations as prepared by standard techniques cited herein. Optionally, any excess organic surfactant is removed from the nanostructure preparation prior to association with the conductive compositions of the present invention. This can be achieved, for example, by adding a solvent mixture prepared from a first solvent in which a nanostructure is soluble (e.g., toluene or chloroform) and a second solvent in which the nanostructure is not soluble (e.g., isopropanol or longer chain alcohol, or an acetate such as ethyl acetate). While the ratio of first solvent to second solvent as prepared in the solvent mixture typically ranges between 1 : 1 and 10:1, one prefeπed solvent mixture is 4 parts toluene to one part isopropanol.
[0180] An additional quantity of the second solvent is then added in a quantity sufficient to precipitate the nanostructures (but not the excess surfactants) from the solvent mixture. The precipitated nanostructures are then separated from the solvent mixture (e.g., by centrifuging), thereby removing excess organic surfactant from the nanostructures. Optionally, the precipitated nanostructures can be washed with the solvent mixture one or more additional times, e.g., if analysis determines that the nanostructure preparation still contains an undesirable quantity of excess surfactant.
[0181] Additionally, any excess organic salts can be removed from the nanocrystal reaction mixture by performing a pyridine exchange on the nanocrystals in the nanocrystal reaction mixture, and precipitating the organic salts while leaving the nanocrystals in solution. The pyridine exchange is performed, for example, by heating the nanocrystal reaction mixture to 150°C for about 1 hour.
[0182] While the foregoing invention has been described in some detail for purposes of clarity and understanding, it will be clear to one skilled in the art from a reading of this disclosure that various changes in form and detail can be made without departing from the true scope of the invention. For example, all the techniques and apparatus described above can be used in various combinations. All publications, patents, patent applications, and/or other documents cited in this application are incorporated by reference in their entirety for all purposes to the same extent as if each individual publication, patent, patent application, and/or other document were individually indicated to be incorporated by reference for all purposes.

Claims

CLAIMSWHAT IS CLAIMED IS:
1. A conductive composition for modification of charge transport across a nanostructure-containing matrix, the composition comprising: a body structure comprising a conjugated organic moiety; a head group coupled to the body structure at a first position on the conjugated organic moiety, wherein the head group comprises a functionalized head group capable of binding to a nanostructure surface or a head group bound to a nanostructure surface; and a tail group coupled to the body structure at a second position on the conjugated organic moiety; wherein one or more elements of the conductive composition are capable of removing or adding charges to a nanostructure upon attachment to a surface of the nanostructure, thereby modifying charge transport across a nanostructure-containing matrix.
2. The composition of claim 1, wherein the nanostructure is a nanocrystal.
3. The composition of claim 1, wherein the nanostructure is an inorganic nanocrystal.
4. The composition of claim 1 , wherein the functionalized head group comprises one or more phosphonic acid, carboxylic acid, amine, phosphine, or thiol moieties.
5. The composition of claim 1 , wherein the functionalized head group or bound head group comprises a monodentate structure.
6. The composition of claim 1, wherein the functionalized head group or bound head group comprises a multidentate structure.
7. The composition of claim 1, wherein the body structure comprises a conjugated alkyl moiety or a conjugated aryl moiety.
8. The composition of claim 7, wherein the body structure comprises a phenylene, thiophene, ethene, ethyne, aniline, fluorene, pyridine, perylene, phenanthralene, anthracene, alkenyl or polynuclear aromatic moiety.
9. The composition of claim 1, wherein the body structure further comprises one or more O-linked or N-linked sidechain coupled to the conjugated organic moiety.
10. The composition of claim 9, wherein the sidechain comprises an electron donating group.
11. The composition of claim 9, wherein the sidechain comprises an electron withdrawing group.
12. The composition of claim 9, wherein the sidechain comprises a conducting chemical structure, whereby the one or more sidechain extends the conjugation of the body structure.
13. The composition of claim 9, wherein the sidechain comprises a polymerizable element.
14. The composition of claim 13, wherein the polymerizable element comprises an acrylate moiety, a methacrylate moiety, or a vinyl moiety.
15. The composition of claim 9, wherein a first sidechain is coupled to the body structure at a first sidechain position, and wherein a second sidechain is coupled to the body structure at a second sidechain position.
16. The composition of claim 15, wherein the first and second sidechains are different chemical moieties.
17. The composition of claim 15, wherein the first and second sidechains are identical chemical moieties.
18. The composition of claim 9, wherein the sidechain alters a solubility of the composition.
19. The composition of claim 9, wherein the sidechain is matched functionally and/or electronically to a matrix composition of the nanostructure-containing matrix.
20. The composition of claim 9, wherein the sidechain comprises an O-linked hexane moiety, an O-linked 2-ethylhexyl moiety, an O-linked octyl moiety, an O-linked decyl moiety, or an O-linked alkyl moiety comprising between 5 and 22 carbons.
21. The composition of claim 9, wherein the sidechain comprises an N-linked hexane moiety, an N-linked 2-ethylhexyl moiety, an N-linked octyl moiety, an N-linked decyl moiety, or an N-linked alkyl moiety comprising between 5 and 22 carbons.
22. The composition of claim 9, wherein the sidechain comprises a chemical substituent having greater than 22 carbons.
23. The composition of claim 9, wherein the one or more sidechain and the tail group comprise identical chemical compositions.
24. The composition of claim 1 , wherein the body structure comprises an oligomeric or polymeric structure.
25. The composition of claim 24, wherein the body structure comprises a poly(phenylene), poly(thiophene), poly(ethene), poly(ethyne), poly(aniline), poly(fluorene), poly(pyridine), or a poly(polynuclear aromatic) moiety.
26. The composition of claim 24, wherein the body structure further comprises one or more sidechain coupled to one or more elements of the oligomeric or polymeric structure.
27. The composition of claim 1, wherein the tail group comprises a conducting chemical structure.
28. The composition of claim 1, wherein the tail group comprises a nonconducting chemical structure.
29. The composition of claim 1, wherein the tail group comprises an alkene or an alkyne moiety.
30. The composition of claim 1, wherein the tail group comprises 1-propyne, 1-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, 1-nonyne, 1-decyne, or an alkyne comprising between 3 and 22 carbons.
31. The composition of claim 1 , wherein the tail group comprises an alkyne comprising more than 22 carbons.
32. The composition of claim 30, wherein the tail group further comprises a thiophene moiety positioned between the body structure and an alkyne moiety.
33. The composition of claim 1, wherein the tail group comprises a chemical functionality capable of binding to the nanostructure surface or an additional nanostructure surface.
34. The composition of claim 1, wherein the tail group comprises a monodentate structure.
35. The composition of claim 1, wherein the tail group comprises a multidentate structure.
36. The composition of claim 1, wherein the tail group comprises a polymerizable element.
37. A conductive composition for modification of charge transport across a nanostructure-containing matrix, the composition having the formula:
Figure imgf000065_0001
38. The conductive composition of claim 37, wherein the nanostructure is a nanocrystal.
39. A conductive composition for modification of charge transport across a nanostructure-containing matrix, the composition having the formula:
Figure imgf000065_0002
40. The conductive composition of claim 39, wherein the nanostructure is a nanocrystal.
41. A conductive composition for modification of charge transport across a nanostructure-containing matrix, the composition having the formula:
Figure imgf000065_0003
42. The conductive composition of claim 41, wherein the nanostructure is a nanocrystal.
43. A conductive composition for modification of charge transport across a nanostructure-containing matrix, the composition having the formula:
Figure imgf000066_0001
44. The conductive composition of claim 43, wherein the nanostructure is a nanocrystal.
45. A conductive composition for modification of charge transport across a nanocrystal- containing matrix, the composition having the formula:
Figure imgf000066_0002
46. The conductive composition of claim 45, wherein the nanostructure is a nanocrystal.
47. A conductive composition for modification of charge transport across a nanostructure-containing matrix, the composition having the formula:
Figure imgf000066_0003
48. The conductive composition of claim 43, wherein the nanostructure is a nanocrystal.
49. A conductive composition for modification of charge transport across a nanostructure-containing matrix, the composition having the formula:
Figure imgf000067_0001
50. The conductive composition of claim 43, wherein the nanostructure is a nanocrystal.
51. A conductive composition for modification of charge transport across a nanostructure-containing matrix, the composition having the formula:
Figure imgf000067_0002
52. The conductive composition of claim 43, wherein the nanostructure is a nanocrystal.
53. A conductive composition for modification of charge transport across a nanostructure-containing matrix, the composition having the formula:
Figure imgf000068_0001
54. The conductive composition of claim 43, wherein the nanostructure is a nanocrystal.
55. A conductive composition for modification of charge transport across a nanostructure-containing matrix, the composition having the formula:
Figure imgf000068_0002
56. The conductive composition of claim 43, wherein the nanostructure is a nanocrystal.
57. A conductive composition for modification of charge transport across a nanostructure-containing matrix, the composition having the formula:
Figure imgf000068_0003
58. The conductive composition of claim 43, wherein the nanostructure is a nanocrystal.
59. A polymeric conductive composition comprising the structure [Hx-By-Tz]n, wherein H comprises at least one functionalized head group capable of binding to a nanostructure surface or at least one head group bound to a nanostructure surface; wherein B comprises a body structure comprising one or more conjugated organic moieties, wherein a first conjugated organic moiety is coupled to a proximal functionalized head group or bound head group; wherein T comprises at least one tail group coupled to the body structure; and wherein x, y, z and n independently comprise integers equal to or greater than 1 and wherein x+y+z+n is equal to or greater than 5.
60. The polymeric conductive composition of claim 59, wherein the head group comprises one or more phosphonic acid, carboxylic acid, amine, phosphine, or thiol moieties.
61. The polymeric conductive composition of claim 59, wherein the body structure comprises a phenylene, thiophene, ethene, ethyne, aniline, fluorene, pyridine, perylene, phenanthralene, anthracene, alkenyl or polynuclear aromatic moiety.
62. The polymeric conductive composition of claim 59, wherein the body structure comprises poly(phenylene), poly(thiophene), poly(ethene), poly(ethyne), poly(aniline), poly(fluorene), poly(pyridine) moiety, or poly(polynuclear aromatic) moiety.
63. The polymeric conductive composition of claim 59, wherein the tail group comprises 1-propyne, 1-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, 1-nonyne, 1- decyne, or an alkyne comprising between 3 and 22 carbons.
64. The polymeric conductive composition of claim 59, wherein the body structure further comprises one or more O-linked or N-linked substituents coupled to one or more member conjugated organic moieties, wherein the substituents alter an electronic signature or a solubility of the polymeric conductive composition.
65. The polymeric conductive composition of claim 64, wherein the polymeric conductive composition is polymerized through polymerizable elements on the one or more substituents.
66. The polymeric conductive composition of claim 64, wherein the one or more substituents independently comprise an electron donating group, an electron withdrawing group, a conducting chemical structure, or a nonconducting chemical structure.
67. A nanostructure matrix composition comprising: a nanostructure comprising an exterior surface, wherein a portion of the nanostructure exterior surface is bound to the conductive composition of claim 1; and, a matrix positioned proximal to the conjugated exterior surface of the nanostructure.
68. The nanostructure matrix composition of claim 67, wherein the matrix comprises poly-3-hexylthiophene (P3HY).
69. The nanostructure matrix composition of claim 67, wherein the matrix is covalently coupled to the conductive composition of claim 1.
70. The nanostructure matrix composition of claim 67, wherein the conductive composition is functionally or electronically matched to one or more substituents of the matrix.
71. The nanostructure matrix composition of claim 67, wherein the nanostructure is a nanocrystal.
72. A nanostructure-containing matrix composition comprising: a nanostructure comprising an exterior surface; and a matrix composition positioned proximal to the exterior surface of the nanostructure, wherein the matrix composition comprises a conductive polymer having the structure [Tx-By-Hz]n, wherein H comprises at least one functionalized head group capable of binding to a nanostructure surface; wherein B comprises a body structure comprising one or more conjugated organic moieties, wherein a first conjugated organic moiety is coupled to the at least one functionalized head group; wherein T comprises at least one tail group coupled to the body structure; and wherein x, y, z and n independently comprise integers equal to or greater than 1.
73. The nanostructure-containing matrix composition of claim 72, wherein a portion of the nanocrystal exterior surface is conjugated with the conductive composition of claim 1.
74. The nanostructure matrix composition of claim 73, wherein the matrix composition and the conductive composition are matched functionally and/or electronically.
75. The nanostructure matrix composition of claim 73, wherein the matrix composition and the conductive composition are covalently coupled.
76. The nanostructure matrix composition of claim 73, wherein the nanostructure is a nanocrystal.
77. A method of synthesizing an organic composition that facilitates charge transfer for use in a nanostructure-containing device, the method comprising: a) providing a conjugated organic precursor, wherein the conjugated organic precursor comprises at least three positions available for attachment of substituent modules; b) providing a first substituent module, wherein the first substituent module comprises a phosphonic acid derivative, a carboxylic acid derivative, an amine derivative, a phosphine derivative, a thiol derivative, a thiophene derivative, or a combination thereof; c) providing a second substituent module, wherein the second substituent module comprises an alkyne derivative comprising between three and 22 carbons; and d) optionally providing a third substituent module, wherein the optional third substituent module comprises an alkyl derivative comprising between one and 22 carbons; e) coupling the first substituent module at a first position, coupling the second substituent module at a second position, and optionally coupling the third substituent module at a third position, thereby synthesizing the organic composition; wherein coupling of the modules to the body structure does not destroy an electronic conjugation of the body structure, and, wherein at least one substituent of the first, second or third substituent modules is capable of binding to a nanostructure surface or is already bound to a nanostructure surface.
78. The method of claim 77, wherein the conjugated organic precursor comprises a conjugated alkyl moiety or a conjugated aryl moiety.
79. The method of claim 78, wherein the conjugated organic precursor comprises a phenylene, thiophene, ethene, ethyne, aniline, fluorene, pyridine, perylene, phenanthralene, anthracene, alkenyl or polynuclear aromatic derivative.
80. The method of claim 78, wherein the conjugated organic precursor comprises a poly(phenylene), poly(thiophene), poly(ethene), poly(ethyne), poly(aniline), poly(fluorene), or poly(pyridine) derivative.
81. The method of claim 77, wherein coupling of one or more of the substituent modules to the body structure extends the conjugation of the body structure.
82. The method of claim 77, wherein the optional third substituent module is coupled to the conjugated organic precursor prior to coupling the first and or second substituent modules.
83. The method of claim 77, wherein providing the first substituent module comprises providing a thiophene derivative.
84. The method of claim 83, wherein providing the first substituent module comprises: a) providing an arylhalide core structure; b) lithiating the arylhalide core structure at a first halide position and reacting with chlorotrimethylsilane (TMSCl) to yield a TMS-aryl intermediate core structure; c) lithiating of the TMS-intermediate core structure at a second halide position and reacting with trimefhyltinchloride (Me3SnCl) to yield a stannylated second intermediate; and, d) combining the second intermediate with a halogenated thiophene to form a first substituent module comprising a TMS-aryl-thiophene derivative.
85. The method of claim 83, wherein the first substituent module comprises an aryl- thiophene moiety and wherein coupling the first substituent module comprises: a) performing a Stille coupling to form an iodinated intermediate; b) exchanging an iodine substituent of the iodinated intermediate for a TMS substituent; and, c) coupling a phosphite group to the aryl portion of the bound first substituent module via a palladium-catalyzed mechanism.
86. The method of claim 83, wherein the first substituent module comprises diethylphosphite, and wherein coupling the first substituent module comprises performing a palladium-catalyzed phosphite-aryl coupling.
87. The method of claim 77, wherein coupling the second substituent module comprises performing a Sonogashira coupling.
88. The method of claim 77, wherein the steps of providing the first substituent and/or providing the second substituent comprise generating thiophene derivatives of the first and/or second substituents.
89. The method of claim 77, wherein coupling the optional third substituent module comprises alkylating the conjugated organic precursor at third position comprising a hydroxyl or amine moiety, to form a sidechain-substituted intermediate composition.
90. The method of claim 77, wherein providing the third substituent module comprises providing about 1.1 molar equivalents of a halogenated derivative of a sidechain substituent; and wherein coupling the third substituent module with the conjugated organic precursor comprises: i) combining the halogenated derivative with the conjugated organic precursor in the presence of potassium carbonate (K2CO3) and dimethyl formamide (DMF) to form a reaction mixture; and, ii) heating the reaction mixture to about 70°C, thereby coupling the third substituent to the conjugated organic moiety.
91. The method of claim 77, wherein coupling the third substituent further comprises coupling a fourth substituent to the body structure at a fourth position.
92. The method of claim 91, wherein the third substituent and the fourth substituent comprises different chemical species.
93. The method of claim 91, wherein the third substituent and the fourth substituent comprises identical chemical species, and wherein the steps of coupling the first substituent and coupling the fourth substituent are performed in a single reaction mixture.
94. The method of claim 77, further comprising: f) coupling the head group to an external surface of a nanocrystal, thereby providing a nanocrystal-bound composition.
95. The method of claim 94, wherein the nanostructure comprises CdTe or InP.
96. The method of claim 94, wherein coupling the head group to the external surface of the nanostructure comprises interacting one or more free electrons in the head group with proximal metal moieties of the nanostructure.
97. The method of claim 94, further comprising: g) polymerizing the organic composition after coupling the composition to the nanocrystal surface, thereby forming a polymerized organic composition.
98. The method of claim 77, wherein the nanostructure-containing device comprises a photovoltaic device.
99. A method of modifying an interaction between a nanostructure and an external matrix, the method comprising: treating a nanostructure with the conductive composition of claim 1; and, forming a nanostructure-containing matrix comprising the treated nanostructure and a matrix composition.
100. The method of claim 99, wherein treating the nanostructure further comprises polymerizing the conductive composition of claim 1 to form a polymerized conductive composition.
101. The method of claim 99, wherein the matrix composition comprises the polymeric conductive composition of claim 59.
102. The method of claim 99, wherein the nanostructure is a nanocrystal.
103. A device comprising: a) a first electrode surface; b) the nanostructure matrix composition of claim 67 electrically coupled to the first electrode surface; and, c) a second electrode surface electrically coupled to the nanostructure -containing matrix composition.
104. The device of claim 103, wherein the nanostructure matrix composition comprises one or more nanocrystals.
105. A device comprising: d) a first electrode surface; e) the nanostructure-containing matrix composition of claim 72 electrically coupled to the first electrode surface; and, f) a second electrode surface electrically coupled to the nanostructure -containing matrix composition.
106. The device of claim 105, wherein the nanostructure-containing matrix composition comprises one or more nanocrystals.
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Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7195733B2 (en) 2004-04-27 2007-03-27 The Board Of Trustees Of The University Of Illinois Composite patterning devices for soft lithography
JP2008507570A (en) * 2004-07-29 2008-03-13 エコール ポリテクニーク フェデラル ドゥ ローザンヌ(エーペーエフエル) 2,2-bipyridine ligand, sensitizing dye and dye-sensitized solar cell
WO2008096239A1 (en) 2007-02-07 2008-08-14 Universita' Degli Studi Di Bari Organic thin film transistors comprising thienyl oligomers and their use as gaseous phase sensors
WO2008104301A2 (en) 2007-02-27 2008-09-04 Bayer Technology Services Gmbh Hybrid organic solar cells with photoactive semiconductor nanoparticles enclosed in surface modifiers
US7521292B2 (en) 2004-06-04 2009-04-21 The Board Of Trustees Of The University Of Illinois Stretchable form of single crystal silicon for high performance electronics on rubber substrates
US7557367B2 (en) 2004-06-04 2009-07-07 The Board Of Trustees Of The University Of Illinois Stretchable semiconductor elements and stretchable electrical circuits
DE102008035559A1 (en) 2008-07-30 2010-02-11 Rupert Goihl Light or voltage source has one or more luminophores in combination with electro-conductive particles, where light is generated from light source by electrically stimulated luminescence of luminophores
US7662313B2 (en) 2002-09-05 2010-02-16 Nanosys, Inc. Oriented nanostructures and methods of preparing
US7799699B2 (en) 2004-06-04 2010-09-21 The Board Of Trustees Of The University Of Illinois Printable semiconductor structures and related methods of making and assembling
US7943491B2 (en) 2004-06-04 2011-05-17 The Board Of Trustees Of The University Of Illinois Pattern transfer printing by kinetic control of adhesion to an elastomeric stamp
GB2484743A (en) * 2010-10-23 2012-04-25 Univ Montfort Organic photoconductive material
WO2013151142A1 (en) * 2012-04-05 2013-10-10 コニカミノルタ株式会社 Organic photoelectric conversion element and solar cell using same
US9647171B2 (en) 2009-05-12 2017-05-09 The Board Of Trustees Of The University Of Illinois Printed assemblies of ultrathin, microscale inorganic light emitting diodes for deformable and semitransparent displays
US9691873B2 (en) 2011-12-01 2017-06-27 The Board Of Trustees Of The University Of Illinois Transient devices designed to undergo programmable transformations
US9723122B2 (en) 2009-10-01 2017-08-01 Mc10, Inc. Protective cases with integrated electronics
US9765934B2 (en) 2011-05-16 2017-09-19 The Board Of Trustees Of The University Of Illinois Thermally managed LED arrays assembled by printing
US9936574B2 (en) 2009-12-16 2018-04-03 The Board Of Trustees Of The University Of Illinois Waterproof stretchable optoelectronics
US9986924B2 (en) 2010-03-17 2018-06-05 The Board Of Trustees Of The University Of Illinois Implantable biomedical devices on bioresorbable substrates
US10052066B2 (en) 2012-03-30 2018-08-21 The Board Of Trustees Of The University Of Illinois Appendage mountable electronic devices conformable to surfaces
US10064269B2 (en) 2008-03-05 2018-08-28 The Board Of Trustees Of The University Of Illinois Stretchable and foldable electronic devices
US10355113B2 (en) 2004-06-04 2019-07-16 The Board Of Trustees Of The University Of Illinois Controlled buckling structures in semiconductor interconnects and nanomembranes for stretchable electronics
US10349860B2 (en) 2011-06-03 2019-07-16 The Board Of Trustees Of The University Of Illinois Conformable actively multiplexed high-density surface electrode array for brain interfacing
US10361180B2 (en) 2007-01-17 2019-07-23 The Board Of Trustees Of The University Of Illinois Optical systems fabricated by printing-based assembly
US10441185B2 (en) 2009-12-16 2019-10-15 The Board Of Trustees Of The University Of Illinois Flexible and stretchable electronic systems for epidermal electronics
US10918298B2 (en) 2009-12-16 2021-02-16 The Board Of Trustees Of The University Of Illinois High-speed, high-resolution electrophysiology in-vivo using conformal electronics
US10925543B2 (en) 2015-11-11 2021-02-23 The Board Of Trustees Of The University Of Illinois Bioresorbable silicon electronics for transient implants
US11029198B2 (en) 2015-06-01 2021-06-08 The Board Of Trustees Of The University Of Illinois Alternative approach for UV sensing
US11118965B2 (en) 2015-06-01 2021-09-14 The Board Of Trustees Of The University Of Illinois Miniaturized electronic systems with wireless power and near-field communication capabilities
WO2023157814A1 (en) * 2022-02-17 2023-08-24 日産化学株式会社 Method for producing phenyl phosphonic acid ester and phenyl phosphonic acid compound

Families Citing this family (208)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6919119B2 (en) * 2000-05-30 2005-07-19 The Penn State Research Foundation Electronic and opto-electronic devices fabricated from nanostructured high surface to volume ratio thin films
US7205048B2 (en) * 2001-09-17 2007-04-17 Invitrogen Corporation Functionalized fluorescent nanocrystal compositions and methods of making
US8294025B2 (en) * 2002-06-08 2012-10-23 Solarity, Llc Lateral collection photovoltaics
US7291782B2 (en) * 2002-06-22 2007-11-06 Nanosolar, Inc. Optoelectronic device and fabrication method
US7253017B1 (en) 2002-06-22 2007-08-07 Nanosolar, Inc. Molding technique for fabrication of optoelectronic devices
US7594982B1 (en) 2002-06-22 2009-09-29 Nanosolar, Inc. Nanostructured transparent conducting electrode
US6946597B2 (en) * 2002-06-22 2005-09-20 Nanosular, Inc. Photovoltaic devices fabricated by growth from porous template
AU2003279708A1 (en) * 2002-09-05 2004-03-29 Nanosys, Inc. Nanostructure and nanocomposite based compositions and photovoltaic devices
US7572393B2 (en) * 2002-09-05 2009-08-11 Nanosys Inc. Organic species that facilitate charge transfer to or from nanostructures
US7083586B2 (en) * 2003-02-03 2006-08-01 Dj Orthopedics, Llc Patellofemoral brace
US6936761B2 (en) * 2003-03-29 2005-08-30 Nanosolar, Inc. Transparent electrode, optoelectronic apparatus and devices
US7511217B1 (en) 2003-04-19 2009-03-31 Nanosolar, Inc. Inter facial architecture for nanostructured optoelectronic devices
US7645934B1 (en) * 2003-04-29 2010-01-12 Nanosolar, Inc. Nanostructured layer and fabrication methods
US7462774B2 (en) * 2003-05-21 2008-12-09 Nanosolar, Inc. Photovoltaic devices fabricated from insulating nanostructured template
US7605327B2 (en) * 2003-05-21 2009-10-20 Nanosolar, Inc. Photovoltaic devices fabricated from nanostructured template
US7422790B1 (en) 2003-09-04 2008-09-09 Nanosys, Inc. Methods of processing nanocrystals, and compositions, devices and systems including same
FR2862955B1 (en) * 2003-12-02 2006-03-10 Commissariat Energie Atomique INORGANIC NANOCRYSTALS WITH ORGANIC COATING LAYER, PROCESS FOR THEIR PREPARATION, AND MATERIALS THEREOF
US7645397B2 (en) * 2004-01-15 2010-01-12 Nanosys, Inc. Nanocrystal doped matrixes
WO2005067524A2 (en) * 2004-01-15 2005-07-28 Nanosys, Inc. Nanocrystal doped matrixes
US7057881B2 (en) * 2004-03-18 2006-06-06 Nanosys, Inc Nanofiber surface based capacitors
US20050214190A1 (en) * 2004-03-25 2005-09-29 Seoul National University Method of synthesizing nanorods by reaction of metal-surfactant complexes injected using a syringe pump
US7773404B2 (en) 2005-01-07 2010-08-10 Invisage Technologies, Inc. Quantum dot optical devices with enhanced gain and sensitivity and methods of making same
US20080055581A1 (en) * 2004-04-27 2008-03-06 Rogers John A Devices and methods for pattern generation by ink lithography
GB0409877D0 (en) * 2004-04-30 2004-06-09 Univ Manchester Preparation of nanoparticle materials
US8828792B2 (en) * 2004-05-25 2014-09-09 The Trustees Of The University Of Pennsylvania Nanostructure assemblies, methods and devices thereof
US7968273B2 (en) 2004-06-08 2011-06-28 Nanosys, Inc. Methods and devices for forming nanostructure monolayers and devices including such monolayers
US8563133B2 (en) 2004-06-08 2013-10-22 Sandisk Corporation Compositions and methods for modulation of nanostructure energy levels
US8088483B1 (en) 2004-06-08 2012-01-03 Nanosys, Inc. Process for group 10 metal nanostructure synthesis and compositions made using same
TWI406890B (en) * 2004-06-08 2013-09-01 Sandisk Corp Post-deposition encapsulation of nanostructures : compositions, devices and systems incorporating same
CN102064102B (en) * 2004-06-08 2013-10-30 桑迪士克公司 Methods and devices for forming nanostructure monolayers and devices including such monolayers
WO2005122293A2 (en) * 2004-06-08 2005-12-22 Princeton University Formation of ordered thin films of organics on metal oxide surfaces
US7776758B2 (en) 2004-06-08 2010-08-17 Nanosys, Inc. Methods and devices for forming nanostructure monolayers and devices including such monolayers
WO2005123637A1 (en) * 2004-06-17 2005-12-29 Riken Single crystal, material for nanowiring, electronic device, and process for producing material for nanowiring
US7247670B2 (en) * 2004-08-24 2007-07-24 General Electric Company Nanotubes and methods of dispersing and separating nanotubes
US7794600B1 (en) * 2004-08-27 2010-09-14 Nanosys, Inc. Purification of nanocrystal solutions by chromatography
US7365395B2 (en) * 2004-09-16 2008-04-29 Nanosys, Inc. Artificial dielectrics using nanostructures
US8089152B2 (en) * 2004-09-16 2012-01-03 Nanosys, Inc. Continuously variable graded artificial dielectrics using nanostructures
US8558311B2 (en) 2004-09-16 2013-10-15 Nanosys, Inc. Dielectrics using substantially longitudinally oriented insulated conductive wires
WO2006118595A2 (en) * 2004-09-17 2006-11-09 Nanosys, Inc. Nanostructured thin films and their uses
US7842432B2 (en) * 2004-12-09 2010-11-30 Nanosys, Inc. Nanowire structures comprising carbon
US8278011B2 (en) 2004-12-09 2012-10-02 Nanosys, Inc. Nanostructured catalyst supports
US7939218B2 (en) * 2004-12-09 2011-05-10 Nanosys, Inc. Nanowire structures comprising carbon
CN101107737B (en) 2004-12-09 2012-03-21 奈米系统股份有限公司 Nanowire-based membrane electrode assemblies for fuel cells
US7811479B2 (en) * 2005-02-07 2010-10-12 The Trustees Of The University Of Pennsylvania Polymer-nanocrystal quantum dot composites and optoelectronic devices
WO2006124625A2 (en) * 2005-05-12 2006-11-23 Nanosys, Inc. Use of nanoparticles in film formation and as solder
US9297092B2 (en) * 2005-06-05 2016-03-29 Qd Vision, Inc. Compositions, optical component, system including an optical component, devices, and other products
US8845927B2 (en) * 2006-06-02 2014-09-30 Qd Vision, Inc. Functionalized nanoparticles and method
CN101292365B (en) * 2005-06-17 2012-04-04 依路米尼克斯公司 Photovoltaic wire of nano structure and manufacturing method thereof
US20090050204A1 (en) * 2007-08-03 2009-02-26 Illuminex Corporation. Photovoltaic device using nanostructured material
US20100193768A1 (en) * 2005-06-20 2010-08-05 Illuminex Corporation Semiconducting nanowire arrays for photovoltaic applications
US20070001581A1 (en) * 2005-06-29 2007-01-04 Stasiak James W Nanostructure based light emitting devices and associated methods
GB2472541B (en) * 2005-08-12 2011-03-23 Nanoco Technologies Ltd Nanoparticles
JP4982675B2 (en) * 2005-08-31 2012-07-25 国立大学法人九州工業大学 Electrolyte composition and dye-sensitized solar cell
GB0522027D0 (en) * 2005-10-28 2005-12-07 Nanoco Technologies Ltd Controlled preparation of nanoparticle materials
KR101390619B1 (en) 2005-11-21 2014-04-30 나노시스, 인크. Nanowire structures comprising carbon
WO2007070645A2 (en) * 2005-12-14 2007-06-21 Massachusetts Institute Of Technology Bio-sensitized solar cells (bssc)
KR20080097462A (en) * 2006-02-16 2008-11-05 솔렉슨트 코포레이션 Nanoparticle sensitized nanostructured solar cells
AU2007216983A1 (en) * 2006-02-17 2007-08-30 Solexant Corp. Nanostructured electroluminescent device and display
WO2007126412A2 (en) 2006-03-03 2007-11-08 The Board Of Trustees Of The University Of Illinois Methods of making spatially aligned nanotubes and nanotube arrays
WO2008070028A2 (en) * 2006-12-01 2008-06-12 Qd Vision, Inc. Improved composites and devices including nanoparticles
US8849087B2 (en) 2006-03-07 2014-09-30 Qd Vision, Inc. Compositions, optical component, system including an optical component, devices, and other products
US7524746B2 (en) * 2006-03-13 2009-04-28 Evident Technologies, Inc. High-refractive index materials comprising semiconductor nanocrystal compositions, methods of making same, and applications therefor
CN101411000A (en) * 2006-03-23 2009-04-15 索莱赞特公司 Photovoltaic device containing nanoparticle sensitized carbon nanotubes
WO2007112088A2 (en) * 2006-03-24 2007-10-04 Qd Vision, Inc. Hyperspectral imaging device
US9212056B2 (en) * 2006-06-02 2015-12-15 Qd Vision, Inc. Nanoparticle including multi-functional ligand and method
EP2025015A2 (en) * 2006-06-02 2009-02-18 Innovalight, Inc. Photoactive materials containing group iv nanostructures and optoelectronic devices made therefrom
US7442575B2 (en) * 2006-09-29 2008-10-28 Texas Christian University Method of manufacturing semiconductor nanowires
US7816669B1 (en) * 2006-10-13 2010-10-19 Hewlett-Packard Development Company, L.P. Light emitting system and methods for controlling nanocrystal distribution therein
US20080142075A1 (en) * 2006-12-06 2008-06-19 Solexant Corporation Nanophotovoltaic Device with Improved Quantum Efficiency
US20080246076A1 (en) * 2007-01-03 2008-10-09 Nanosys, Inc. Methods for nanopatterning and production of nanostructures
US20090136785A1 (en) * 2007-01-03 2009-05-28 Nanosys, Inc. Methods for nanopatterning and production of magnetic nanostructures
KR101430261B1 (en) * 2007-02-23 2014-08-14 삼성전자주식회사 Organosilicon Nanocluster, Method for preparing the same and Method for preparing Thin Film using the same
KR101686669B1 (en) * 2007-03-19 2016-12-14 나노시스, 인크. Methods for encapsulating nanocrystals
US20100155749A1 (en) * 2007-03-19 2010-06-24 Nanosys, Inc. Light-emitting diode (led) devices comprising nanocrystals
US20100110728A1 (en) 2007-03-19 2010-05-06 Nanosys, Inc. Light-emitting diode (led) devices comprising nanocrystals
EP2432015A1 (en) * 2007-04-18 2012-03-21 Invisage Technologies, Inc. Materials, systems and methods for optoelectronic devices
US8563348B2 (en) * 2007-04-18 2013-10-22 Nanoco Technologies Ltd. Fabrication of electrically active films based on multiple layers
US20100044676A1 (en) 2008-04-18 2010-02-25 Invisage Technologies, Inc. Photodetectors and Photovoltaics Based on Semiconductor Nanocrystals
US8525287B2 (en) 2007-04-18 2013-09-03 Invisage Technologies, Inc. Materials, systems and methods for optoelectronic devices
US20080264479A1 (en) 2007-04-25 2008-10-30 Nanoco Technologies Limited Hybrid Photovoltaic Cells and Related Methods
EP2171763A2 (en) * 2007-06-26 2010-04-07 Solarity, Inc. Lateral collection photovoltaics
US8784701B2 (en) 2007-11-30 2014-07-22 Nanoco Technologies Ltd. Preparation of nanoparticle material
AU2009219983A1 (en) * 2008-02-25 2009-09-03 Nanoco Technologies Limited Semiconductor nanoparticle capping agents
EP2259377B1 (en) * 2008-03-19 2020-06-03 Sharp Kabushiki Kaisha Solar cell
US8470701B2 (en) 2008-04-03 2013-06-25 Advanced Diamond Technologies, Inc. Printable, flexible and stretchable diamond for thermal management
WO2009129540A1 (en) * 2008-04-18 2009-10-22 Invisage Technologies, Inc. Photodetectors and photovoltaics based on semiconductor nanocrystals
US8203195B2 (en) 2008-04-18 2012-06-19 Invisage Technologies, Inc. Materials, fabrication equipment, and methods for stable, sensitive photodetectors and image sensors made therefrom
WO2010005707A1 (en) * 2008-06-16 2010-01-14 The Board Of Trustees Of The University Of Illinois Medium scale carbon nanotube thin film integrated circuits on flexible plastic substrates
GB0813273D0 (en) * 2008-07-19 2008-08-27 Nanoco Technologies Ltd Method for producing aqueous compatible nanoparticles
GB0814458D0 (en) * 2008-08-07 2008-09-10 Nanoco Technologies Ltd Surface functionalised nanoparticles
US8372726B2 (en) 2008-10-07 2013-02-12 Mc10, Inc. Methods and applications of non-planar imaging arrays
JP5646492B2 (en) 2008-10-07 2014-12-24 エムシー10 インコーポレイテッドMc10,Inc. Stretchable integrated circuit and device with sensor array
US8097926B2 (en) 2008-10-07 2012-01-17 Mc10, Inc. Systems, methods, and devices having stretchable integrated circuitry for sensing and delivering therapy
US8886334B2 (en) 2008-10-07 2014-11-11 Mc10, Inc. Systems, methods, and devices using stretchable or flexible electronics for medical applications
US8389862B2 (en) 2008-10-07 2013-03-05 Mc10, Inc. Extremely stretchable electronics
WO2010048407A1 (en) 2008-10-24 2010-04-29 Nanosys, Inc. Electrochemical catalysts for fuel cells
GB0820101D0 (en) * 2008-11-04 2008-12-10 Nanoco Technologies Ltd Surface functionalised nanoparticles
US8540889B1 (en) 2008-11-19 2013-09-24 Nanosys, Inc. Methods of generating liquidphobic surfaces
GB0821122D0 (en) * 2008-11-19 2008-12-24 Nanoco Technologies Ltd Semiconductor nanoparticle - based light emitting devices and associated materials and methods
US8343575B2 (en) 2008-12-30 2013-01-01 Nanosys, Inc. Methods for encapsulating nanocrystals and resulting compositions
US11198270B2 (en) 2008-12-30 2021-12-14 Nanosys, Inc. Quantum dot films, lighting devices, and lighting methods
US10214686B2 (en) 2008-12-30 2019-02-26 Nanosys, Inc. Methods for encapsulating nanocrystals and resulting compositions
WO2010087842A1 (en) * 2009-01-30 2010-08-05 Hewlett-Packard Development Company Polymer and polymer-nanoparticle compositions
GB0901857D0 (en) * 2009-02-05 2009-03-11 Nanoco Technologies Ltd Encapsulated nanoparticles
JP2009182333A (en) * 2009-02-05 2009-08-13 Sony Corp Electronic device and method of manufacturing the same
JP6236202B2 (en) 2009-05-01 2017-11-22 ナノシス・インク. Matrix with functional groups for dispersion of nanostructures
JP5686988B2 (en) * 2009-05-04 2015-03-18 シャープ株式会社 Catalyst layer used for membrane electrode assembly for fuel cell, membrane electrode assembly for fuel cell using the same, fuel cell, and production method thereof
HUE059099T2 (en) 2009-05-19 2022-10-28 Oned Mat Inc Nanostructured materials for battery applications
GB0916699D0 (en) 2009-09-23 2009-11-04 Nanoco Technologies Ltd Semiconductor nanoparticle-based materials
GB0916700D0 (en) * 2009-09-23 2009-11-04 Nanoco Technologies Ltd Semiconductor nanoparticle-based materials
US20110232717A1 (en) * 2010-02-18 2011-09-29 OneSun, LLC Semiconductors compositions for dye-sensitized solar cells
KR101257152B1 (en) * 2010-03-16 2013-04-23 엘에스전선 주식회사 Semiconductive Composition And The Power Cable Using The Same
GB201005601D0 (en) 2010-04-01 2010-05-19 Nanoco Technologies Ltd Ecapsulated nanoparticles
WO2011156507A1 (en) 2010-06-08 2011-12-15 Edward Hartley Sargent Stable, sensitive photodetectors and image sensors including circuits, processes, and materials for enhanced imaging performance
US8519444B2 (en) 2010-09-10 2013-08-27 Taiwan Semiconductor Manufacturing Company, Ltd. Modified design rules to improve device performance
KR102496406B1 (en) 2010-11-10 2023-02-06 나노시스, 인크. Quantum dot films, lighting devices, and lighting methods
US9442285B2 (en) 2011-01-14 2016-09-13 The Board Of Trustees Of The University Of Illinois Optical component array having adjustable curvature
WO2012158832A2 (en) 2011-05-16 2012-11-22 Qd Vision, Inc. Method for preparing semiconductor nanocrystals
EP2712491B1 (en) 2011-05-27 2019-12-04 Mc10, Inc. Flexible electronic structure
WO2013028253A1 (en) 2011-08-19 2013-02-28 Qd Vision, Inc. Semiconductor nanocrystals and methods
JP5888976B2 (en) * 2011-09-28 2016-03-22 富士フイルム株式会社 Conductive composition, conductive member and method for producing the same, touch panel and solar cell
WO2013078242A1 (en) 2011-11-22 2013-05-30 Qd Vision, Inc. Methods for coating semiconductor nanocrystals
WO2013078249A1 (en) * 2011-11-22 2013-05-30 Qd Vision Inc. Method of making quantum dots
WO2013078245A1 (en) 2011-11-22 2013-05-30 Qd Vision, Inc. Method of making quantum dots
US10008631B2 (en) 2011-11-22 2018-06-26 Samsung Electronics Co., Ltd. Coated semiconductor nanocrystals and products including same
WO2013078247A1 (en) 2011-11-22 2013-05-30 Qd Vision, Inc. Methods of coating semiconductor nanocrystals, semiconductor nanocrystals, and products including same
WO2013115898A2 (en) 2012-02-05 2013-08-08 Qd Vision, Inc. Semiconductor nanocrystals, methods for making same, compositions, and products
US9139770B2 (en) 2012-06-22 2015-09-22 Nanosys, Inc. Silicone ligands for stabilizing quantum dot films
TWI596188B (en) 2012-07-02 2017-08-21 奈米系統股份有限公司 Highly luminescent nanostructures and methods of producing same
US9171794B2 (en) 2012-10-09 2015-10-27 Mc10, Inc. Embedding thin chips in polymer
US9695354B2 (en) * 2012-11-20 2017-07-04 Merck Patent Gmbh Formulation in high-purity solvent for producing electronic devices
CA2905883C (en) 2013-03-14 2021-09-14 William P. Freeman Alkyl-acid ligands for nanocrystals
WO2014159927A2 (en) 2013-03-14 2014-10-02 Nanosys, Inc. Method for solventless quantum dot exchange
CA2905913C (en) 2013-03-14 2021-07-13 Nanosys, Inc. Polyhedral oligomeric silsesquioxane nanocrystal stabilization ligands
US9617472B2 (en) 2013-03-15 2017-04-11 Samsung Electronics Co., Ltd. Semiconductor nanocrystals, a method for coating semiconductor nanocrystals, and products including same
WO2015057930A1 (en) 2013-10-17 2015-04-23 Nanosys, Inc. Light emitting diode (led) devices
EP3066523B1 (en) 2013-11-05 2020-02-26 Nanosys, Inc. Backlight unit for display devices adapted to reduce light leakage
US10421899B2 (en) 2014-03-10 2019-09-24 3M Innovative Properties Company Composite nanoparticles including a thiol-substituted silicone
KR101821086B1 (en) 2014-04-02 2018-01-22 쓰리엠 이노베이티브 프로퍼티즈 캄파니 Composite nanoparticles including a thioether ligand
KR20230048161A (en) 2014-07-16 2023-04-10 나노시스, 인크. Silicone ligands for quantum dots
US10703870B2 (en) 2015-03-12 2020-07-07 Lg Chem, Ltd. Composition for optical film, and optical film comprising same
US10984735B2 (en) 2015-04-17 2021-04-20 Nanosys, Inc. White point uniformity in display devices
CN107922832B (en) 2015-08-19 2021-05-25 3M创新有限公司 Perfluoroether stabilized quantum dots
KR20180052679A (en) 2015-09-09 2018-05-18 나노시스, 인크. Highly luminous cadmium nanocrystals with blue emission
CN108026443B (en) 2015-09-15 2020-07-10 3M创新有限公司 Additive stabilized composite nanoparticles
CN108026444B (en) 2015-09-15 2020-08-04 3M创新有限公司 Additive stabilized composite nanoparticles
EP3377591A1 (en) 2015-11-18 2018-09-26 3M Innovative Properties Company Copolymeric stabilizing carrier fluid for nanoparticles
US9658489B1 (en) 2015-12-31 2017-05-23 Nanosys, Inc. Backlight units for display devices
JP2019504811A (en) 2016-01-19 2019-02-21 ナノシス・インク. InP quantum dots having GaP and AlP shells and method for producing the same
WO2017142782A1 (en) 2016-02-17 2017-08-24 3M Innovative Properties Company Quantum dots with stabilizing fluorochemical copolymers
WO2017142781A1 (en) 2016-02-17 2017-08-24 3M Innovative Properties Company Matrix for quantum dot film article
JP6955502B2 (en) 2016-02-26 2021-10-27 ナノシス・インク. Nanostructure composition with low cadmium content and its use
WO2017172462A1 (en) 2016-04-01 2017-10-05 3M Innovative Properties Company Quantum dots with stabilizing fluorochemical agents
CA3021763A1 (en) 2016-04-26 2017-11-02 Nanosys, Inc. Stable inp quantum dots with thick shell coating and method of producing the same
EP3242333B1 (en) * 2016-05-03 2020-09-09 Nokia Technologies Oy An apparatus and method of forming an apparatus comprising a graphene field effect transistor
KR102481314B1 (en) 2016-05-19 2022-12-23 나노시스, 인크. Method for improving the morphology of core/shell quantum dots for highly luminescent nanostructures
CN109790452A (en) 2016-05-20 2019-05-21 3M创新有限公司 Quantum dot with mixed amine and mercaptan ligand
CA3026102A1 (en) 2016-06-06 2017-12-14 Nanosys, Inc. Method for synthesizing core shell nanocrystals at high temperatures
KR20190031505A (en) 2016-07-20 2019-03-26 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Stabilized styrene polymers for quantum dots
US11345849B2 (en) 2016-07-20 2022-05-31 3M Innovative Properties Company Stabilizing styrenic polymer for quantum dots
CN109790454A (en) 2016-09-19 2019-05-21 3M创新有限公司 With the fluorescent nano particles that function amido organosilicon is stable
US11320577B2 (en) 2016-10-31 2022-05-03 Nanosys, Inc. Radiation absorbing element for increasing color gamut of quantum dot based display devices
US10782014B2 (en) 2016-11-11 2020-09-22 Habib Technologies LLC Plasmonic energy conversion device for vapor generation
WO2018144548A1 (en) 2017-01-31 2018-08-09 Nanosys, Inc. Rapid thickening of aminosilicones to promote emulsion stability and adhesion of uv-curable quantum dot enhancement film emulsions
US20200115630A1 (en) 2017-03-14 2020-04-16 3M Innovative Properties Company Additive stabilized composite nanoparticles
US11407937B2 (en) 2017-05-10 2022-08-09 Nanosys, Inc. In-situ cross-linking of emulsified quantum dot-containing domains within a carrier resin
EP3622038A1 (en) 2017-05-10 2020-03-18 Nanosys, Inc. Silicone copolymers as emulsification additives for quantum dot resin premix
JP7175286B2 (en) 2017-06-05 2022-11-18 ナノシス・インク. Quantum Dot-Acid Stabilization of Resin Concentrates and Premixes
WO2018226925A1 (en) 2017-06-07 2018-12-13 Nanosys, Inc. Thiolated hydrophilic ligands for improved quantum dot reliability in resin films
CN111051468A (en) 2017-06-23 2020-04-21 纳米系统公司 Homogeneous anaerobically stable quantum dot concentrates
CN110799623B (en) * 2017-06-29 2023-06-27 默克专利股份有限公司 Composition comprising semiconductor luminescent nanoparticles
US20190015650A1 (en) 2017-07-16 2019-01-17 Massachusetts Institute Of Technology Microneedle tattoo patches and use thereof
JP7194168B2 (en) 2017-08-16 2022-12-21 ナノシス・インク. PEG-based ligands with enhanced dispersibility and improved performance
US10935842B2 (en) 2017-08-25 2021-03-02 Nanosys, Inc. Nanostructure based display devices
US11092850B2 (en) 2017-08-25 2021-08-17 Nanosys, Inc. Using multiple excitation wavelengths in nanostructure based display devices
US11029559B2 (en) 2017-08-25 2021-06-08 Nanosys, Inc. Nanostructure based display devices
EP3695163A1 (en) 2017-10-10 2020-08-19 Katholieke Universiteit Leuven Lightguide plate
TW201923027A (en) 2017-10-25 2019-06-16 美商納諾西斯有限公司 Stable InP quantum dots with thick shell coating and method of producing the same
CN111465660B (en) 2017-10-27 2022-11-04 纳米系统公司 Use of multifunctional ligands for improving performance and stability of quantum dot inks
US20190273178A1 (en) 2018-03-05 2019-09-05 Nanosys, Inc. Decreased Photon Reabsorption in Emissive Quantum Dots
WO2019231828A1 (en) 2018-05-30 2019-12-05 Christian Ippen METHOD FOR SYNTHESIS OF BLUE-EMITTING ZnSe1-xTex ALLOY NANOCRYSTALS
KR20200002692A (en) 2018-06-29 2020-01-08 나노시스, 인크. Wavelength Tuning of ZnSe Quantum Dots Using In3+ Salts as Dopants
EP3824218A1 (en) 2018-07-24 2021-05-26 Nanosys, Inc. Methods of improving efficiency of displays using quantum dots with integrated optical elements
WO2020040982A1 (en) 2018-08-21 2020-02-27 Nanosys, Inc. Quantum dots with charge-transporting ligands
US11428988B2 (en) 2018-08-31 2022-08-30 Nanosys, Inc. Increasing color gamut performance and efficiency in quantum dot color conversion layers
KR20210116633A (en) 2019-01-24 2021-09-27 나노시스, 인크. Small Molecule Passivation of Quantum Dots for Increased Quantum Yield
TW202033736A (en) 2019-01-24 2020-09-16 美商納諾西斯有限公司 Thin shell quantum dots for enhanced blue light absorption
JP2022523330A (en) 2019-02-05 2022-04-22 ナノシス・インク. Method for synthesizing inorganic nanostructures using molten salt chemistry
CN113710773A (en) 2019-04-15 2021-11-26 纳米系统公司 Method for improving quantum yield of indium phosphide quantum dots
EP3928361A1 (en) 2019-04-19 2021-12-29 Nanosys, Inc. Flexible electroluminescent devices
US20220206341A1 (en) 2019-05-08 2022-06-30 Nanosys, Inc. Nanostructure based display devices with improved light extraction efficiency
CN115678542A (en) 2019-06-20 2023-02-03 纳米系统公司 Quaternary nanostructure based on bright silver
JP2022539982A (en) 2019-07-11 2022-09-14 ナノシス・インク. Blue-emitting nanocrystals with cubic and fluorinated passivation
CN114867818A (en) 2019-08-12 2022-08-05 纳米系统公司 Blue light emitting ZnSe with Low full Width half maximum 1-x Te x Synthesis of alloy nanocrystals
WO2021050641A1 (en) 2019-09-11 2021-03-18 Nanosys, Inc. Nanostructure ink compositions for inkjet printing
WO2021141945A1 (en) 2020-01-06 2021-07-15 Nanosys, Inc. Rohs compliant mixed quantum dot films
EP4073203A2 (en) 2020-01-08 2022-10-19 Nanosys, Inc. Quantum dots with donor-acceptor ligands
KR20210149950A (en) * 2020-06-02 2021-12-10 삼성디스플레이 주식회사 Quantum dot composition, light emitting diode and manufacturing method of the same
US20220077354A1 (en) 2020-07-08 2022-03-10 Nanosys, Inc. Method of improving performance of devices with qds comprising thin metal oxide coatings
TW202231627A (en) 2020-09-28 2022-08-16 美商納諾西斯有限公司 Thermally stable polythiol ligands with pendant solubilizing moieties
WO2022087245A1 (en) 2020-10-22 2022-04-28 Nanosys, Inc. Electroluminescent devices with hybrid transport layers
TW202230848A (en) 2020-10-22 2022-08-01 美商納諾西斯有限公司 Electroluminescent devices with organic transport layers
TW202229159A (en) 2020-12-22 2022-08-01 美商納諾西斯有限公司 Films comprising bright silver based quaternary nanostructures
EP4314193A1 (en) 2021-04-01 2024-02-07 Shoei Chemical Inc. Stable aigs films
WO2023287886A1 (en) 2021-07-13 2023-01-19 Nanosys, Inc. Tunable illumination device
US20230229087A1 (en) 2022-01-19 2023-07-20 Nanosys, Inc. Uv-curable quantum dot formulations
WO2023183619A1 (en) 2022-03-25 2023-09-28 Nanosys, Inc. Silica composite microparticles comprising nanostructures
WO2023220050A1 (en) 2022-05-09 2023-11-16 Nanosys, Inc. Microled-based display device and method of manufacturing same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002035580A2 (en) 2000-10-24 2002-05-02 Molecular Electronics Corporation Three-terminal field-controlled molecular devices

Family Cites Families (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2004A (en) * 1841-03-12 Improvement in the manner of constructing and propelling steam-vessels
US2002A (en) * 1841-03-12 Tor and planter for plowing
JP2584288B2 (en) * 1988-08-31 1997-02-26 富士写真フイルム株式会社 Electrophotographic photoreceptor
US5225495A (en) * 1991-07-10 1993-07-06 Richard C. Stewart, II Conductive polymer film formation using initiator pretreatment
WO1993010564A1 (en) 1991-11-22 1993-05-27 The Regents Of The University Of California Semiconductor nanocrystals covalently bound to solid inorganic surfaces using self-assembled monolayers
US5505928A (en) 1991-11-22 1996-04-09 The Regents Of University Of California Preparation of III-V semiconductor nanocrystals
US6320200B1 (en) * 1992-06-01 2001-11-20 Yale University Sub-nanoscale electronic devices and processes
US5434288A (en) * 1992-12-01 1995-07-18 Monsanto Company PLA2 inhibitors
US6048616A (en) 1993-04-21 2000-04-11 Philips Electronics N.A. Corp. Encapsulated quantum sized doped semiconductor particles and method of manufacturing same
US5504323A (en) 1993-12-07 1996-04-02 The Regents Of The University Of California Dual function conducting polymer diodes
WO1995018456A1 (en) 1993-12-29 1995-07-06 Ecole Polytechnique Federale De Lausanne Photoelectrochemical cell and electrolyte therefor
US5690807A (en) 1995-08-03 1997-11-25 Massachusetts Institute Of Technology Method for producing semiconductor particles
US6649129B1 (en) 1995-11-13 2003-11-18 Teledyne Tekmar Company Method and apparatus for concentrating a VOC sample
US5897945A (en) 1996-02-26 1999-04-27 President And Fellows Of Harvard College Metal oxide nanorods
US6036774A (en) 1996-02-26 2000-03-14 President And Fellows Of Harvard College Method of producing metal oxide nanorods
EP0792688A1 (en) 1996-03-01 1997-09-03 Dow Corning Corporation Nanoparticles of silicon oxide alloys
US6721083B2 (en) * 1996-07-19 2004-04-13 E Ink Corporation Electrophoretic displays using nanoparticles
JP3504079B2 (en) 1996-08-31 2004-03-08 株式会社東芝 Method for manufacturing semiconductor light emitting diode device
JP4049839B2 (en) * 1996-11-08 2008-02-20 昭和電工株式会社 Method for producing antistatic treatment material
US5997832A (en) 1997-03-07 1999-12-07 President And Fellows Of Harvard College Preparation of carbide nanorods
US6413489B1 (en) 1997-04-15 2002-07-02 Massachusetts Institute Of Technology Synthesis of nanometer-sized particles by reverse micelle mediated techniques
AU743120B2 (en) 1997-05-07 2002-01-17 Ecole Polytechnique Federale De Lausanne Metal complex photosensitizer and photovoltaic cell
EP0917208A1 (en) 1997-11-11 1999-05-19 Universiteit van Utrecht Polymer-nanocrystal photo device and method for making the same
US6322901B1 (en) 1997-11-13 2001-11-27 Massachusetts Institute Of Technology Highly luminescent color-selective nano-crystalline materials
US5990479A (en) 1997-11-25 1999-11-23 Regents Of The University Of California Organo Luminescent semiconductor nanocrystal probes for biological applications and process for making and using such probes
GB9815271D0 (en) * 1998-07-14 1998-09-09 Cambridge Display Tech Ltd Particles and devices comprising particles
US6251303B1 (en) 1998-09-18 2001-06-26 Massachusetts Institute Of Technology Water-soluble fluorescent nanocrystals
EP1129496A2 (en) 1998-10-09 2001-09-05 The Trustees of Columbia University in the City of New York Solid-state photoelectric device
US6244988B1 (en) * 1999-06-28 2001-06-12 David H. Delman Interactive exercise system and attachment module for same
JP2001085713A (en) * 1999-09-14 2001-03-30 Fuji Photo Film Co Ltd Photoelectric transducer and solar battery
US6225198B1 (en) 2000-02-04 2001-05-01 The Regents Of The University Of California Process for forming shaped group II-VI semiconductor nanocrystals, and product formed using process
US6306736B1 (en) 2000-02-04 2001-10-23 The Regents Of The University Of California Process for forming shaped group III-V semiconductor nanocrystals, and product formed using process
US6399224B1 (en) 2000-02-29 2002-06-04 Canon Kabushiki Kaisha Conjugated polymers with tunable charge injection ability
KR100360308B1 (en) * 2000-07-03 2002-11-18 한국화학연구원 Organic compounds comprising acetylene group, Vacuum deposition polymerization method using the compounds, Thin film prepared by the method, and Electroluminous element employing the film
US20020010645A1 (en) * 2000-07-12 2002-01-24 David Hagen Backend commerce engine
JP2002050779A (en) * 2000-08-03 2002-02-15 Fuji Photo Film Co Ltd Photoelectric transfer element, photocell using the same and its manufacturing method
JP5013650B2 (en) 2000-08-22 2012-08-29 プレジデント・アンド・フェローズ・オブ・ハーバード・カレッジ Doped elongated semiconductors, growth of such semiconductors, devices containing such semiconductors, and the manufacture of such devices
US6649138B2 (en) * 2000-10-13 2003-11-18 Quantum Dot Corporation Surface-modified semiconductive and metallic nanoparticles having enhanced dispersibility in aqueous media
US6899829B2 (en) * 2000-11-30 2005-05-31 Shipley Company, L.L.C. Conductive polymer colloidal compositions with selectivity for non-conductive surfaces
DE60037199T2 (en) * 2000-12-08 2008-10-02 Sony Deutschland Gmbh Coordinated multifunctional linker molecules for electronic charge transport through organic-inorganic composite structures and application thereof
JP2004532133A (en) 2001-03-30 2004-10-21 ザ・リージェンツ・オブ・ザ・ユニバーシティ・オブ・カリフォルニア Method for assembling nanostructures and nanowires and device assembled therefrom
TWI245795B (en) * 2001-08-17 2005-12-21 Merck Patent Gmbh Mono-, oligo- and polyalkylidenefluorenes and their use as charge transport materials
US7777303B2 (en) * 2002-03-19 2010-08-17 The Regents Of The University Of California Semiconductor-nanocrystal/conjugated polymer thin films
US20040026684A1 (en) 2002-04-02 2004-02-12 Nanosys, Inc. Nanowire heterostructures for encoding information
JP4736324B2 (en) * 2002-04-22 2011-07-27 コニカミノルタホールディングス株式会社 Semiconductor device and manufacturing method thereof
EP1537445B1 (en) 2002-09-05 2012-08-01 Nanosys, Inc. Nanocomposites
AU2003279708A1 (en) 2002-09-05 2004-03-29 Nanosys, Inc. Nanostructure and nanocomposite based compositions and photovoltaic devices

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002035580A2 (en) 2000-10-24 2002-05-02 Molecular Electronics Corporation Three-terminal field-controlled molecular devices

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
FRANCKE ET AL.: "Synthesis of a-m-Difunctionalized Oligo- and Poly(p-phenyleneethynylene)s", MACROMOLECULES, vol. 31, 1998, pages 2457 - 2453
PEARSON ET AL.: "Molecular scale electronics Syntheses and Testing", SYNTHETIC METALS, vol. 84, 1997, pages 303 - 306
See also references of EP1537187A4

Cited By (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7662313B2 (en) 2002-09-05 2010-02-16 Nanosys, Inc. Oriented nanostructures and methods of preparing
US7195733B2 (en) 2004-04-27 2007-03-27 The Board Of Trustees Of The University Of Illinois Composite patterning devices for soft lithography
US10204864B2 (en) 2004-06-04 2019-02-12 The Board Of Trustees Of The University Of Illinois Stretchable form of single crystal silicon for high performance electronics on rubber substrates
US11088268B2 (en) 2004-06-04 2021-08-10 The Board Of Trustees Of The University Of Illinois Methods and devices for fabricating and assembling printable semiconductor elements
US10374072B2 (en) 2004-06-04 2019-08-06 The Board Of Trustees Of The University Of Illinois Methods and devices for fabricating and assembling printable semiconductor elements
US7521292B2 (en) 2004-06-04 2009-04-21 The Board Of Trustees Of The University Of Illinois Stretchable form of single crystal silicon for high performance electronics on rubber substrates
US7557367B2 (en) 2004-06-04 2009-07-07 The Board Of Trustees Of The University Of Illinois Stretchable semiconductor elements and stretchable electrical circuits
US7622367B1 (en) 2004-06-04 2009-11-24 The Board Of Trustees Of The University Of Illinois Methods and devices for fabricating and assembling printable semiconductor elements
US10355113B2 (en) 2004-06-04 2019-07-16 The Board Of Trustees Of The University Of Illinois Controlled buckling structures in semiconductor interconnects and nanomembranes for stretchable electronics
US7799699B2 (en) 2004-06-04 2010-09-21 The Board Of Trustees Of The University Of Illinois Printable semiconductor structures and related methods of making and assembling
US7943491B2 (en) 2004-06-04 2011-05-17 The Board Of Trustees Of The University Of Illinois Pattern transfer printing by kinetic control of adhesion to an elastomeric stamp
US11456258B2 (en) 2004-06-04 2022-09-27 The Board Of Trustees Of The University Of Illinois Stretchable form of single crystal silicon for high performance electronics on rubber substrates
US9768086B2 (en) 2004-06-04 2017-09-19 The Board Of Trustees Of The University Of Illinois Methods and devices for fabricating and assembling printable semiconductor elements
US9761444B2 (en) 2004-06-04 2017-09-12 The Board Of Trustees Of The University Of Illinois Methods and devices for fabricating and assembling printable semiconductor elements
JP2008507570A (en) * 2004-07-29 2008-03-13 エコール ポリテクニーク フェデラル ドゥ ローザンヌ(エーペーエフエル) 2,2-bipyridine ligand, sensitizing dye and dye-sensitized solar cell
US11309305B2 (en) 2007-01-17 2022-04-19 The Board Of Trustees Of The University Of Illinois Optical systems fabricated by printing-based assembly
US10424572B2 (en) 2007-01-17 2019-09-24 The Board Of Trustees Of The University Of Illinois Optical systems fabricated by printing-based assembly
US10361180B2 (en) 2007-01-17 2019-07-23 The Board Of Trustees Of The University Of Illinois Optical systems fabricated by printing-based assembly
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WO2008096239A1 (en) 2007-02-07 2008-08-14 Universita' Degli Studi Di Bari Organic thin film transistors comprising thienyl oligomers and their use as gaseous phase sensors
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WO2023157814A1 (en) * 2022-02-17 2023-08-24 日産化学株式会社 Method for producing phenyl phosphonic acid ester and phenyl phosphonic acid compound

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