CN102239107B - Electron transfer agent is used to prepare nanocrystalline method - Google Patents

Electron transfer agent is used to prepare nanocrystalline method Download PDF

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CN102239107B
CN102239107B CN200980148625.XA CN200980148625A CN102239107B CN 102239107 B CN102239107 B CN 102239107B CN 200980148625 A CN200980148625 A CN 200980148625A CN 102239107 B CN102239107 B CN 102239107B
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nanocrystalline
precursor
transfer agent
electron transfer
mixture
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CN102239107A (en
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E.塔尔斯基
J.巴特尔
J.特里维
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Life Technologies Corp
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    • 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00Selenium; Tellurium; Compounds thereof
    • C01B19/007Tellurides or selenides of metals
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/80Particles consisting of a mixture of two or more inorganic phases

Abstract

There is provided for preparing the nanocrystalline compositions of core and method, the nucleation and growth stage that the precursor of the method use mismatch and two or more electron transfer agent are formed with independently controlled particle.

Description

Electron transfer agent is used to prepare nanocrystalline method
Cross reference to related applications
This application claims the priority of the U.S. Provisional Application sequence number 61/102,589 submitted on October 3rd, 2008, in it Hold and be incorporated to by reference of text.
The statement of the inventor's patent right that produce lower to federal government sponsored research
A part for embodiment disclosed herein be with national standard and Institute for Research and Technology and the conjunction of the US Department of Commerce Make to carry out under the governmental support of agreement No. 70NANB4H3053.Government has certain right in the embodiment of the disclosure.
Technical field
The disclosure provides the method using two kinds of electron transfer agent synthesizing nano-particles.More particularly, the disclosure provides system Make and can be used for multiple field, including biology, analyze and combinatorial chemistry, medical diagnosis, genetic analysis, solar energy conversion and display The method of the nanoparticle of device.
Background technology
Semiconductor nano has a unique optical property between individual molecule and agglomerated mass, and for Kinds of experiments method in biology, chemistry, medical science and hereditism detects, follows the tracks of and observes individual molecule and microbiological More and more important with for biological chemical structure.They provide and are prone to observe and enough bright with the single nanocrystalline realization of enable Conscientiously the fluorescence signal observed.
The multiple method being formed core nanocrystalline by metal-anion binary salt is known in the art.These methods are led to Often can be according to the type of reactant used with based on how the mechanism of the supposition compared the oxidation state of reactant and produce is divided Class.
In the first approach, the metal reacted with each other and nonmetallic ingredient all provide with its neutral atomic form.Such as, Murray et al., J. Am. Chem. Soc., 1993,115:8706 describes dimethyl cadmium (Me2Cd) with trioctylphosphine selenium Changing the reaction of phosphine (TOPSe), both reactants discharge neutral cadmium (Cd the most respectively0) and selenium (Se0) atom, so that not Need electron transfer in order to make their oxidation state is mated.Owing to this reactant is in the form being suitable for reacting to each other, this feelings Condition is considered " coupling " of oxidation state: both need not oxidation or reduction just can react, and also do not resulted in the unbalance of clean electronics. This type of reaction is generally carried out very fast, because cadmium and the selenium atom immediate response when collision forms cadmium selenide (CdSe).
In Equations of The Second Kind, this metal and nonmetallic ingredient all provide with their ionic species.Such as, Peng et al., J Am. Chem. Soc., 2001,123:183 describe at TOPO and phosphonic acid ligand, such as hexyl phosphonic acids (HPA), myristyl Aska-Rid. (CdO) is used to prepare CdSe and cadmium telluride as cadmium ion source in the presence of phosphonic acids (TDPA) or octyl phosphonic acid (OPA) (CdTe).Cadmium salt discharges Cd in the solution2+Ion.The most double (trimethyl silyl) sulfide (TOPSe) are released in the solution Put Se2-.These reactions are carried out the most very fast, owing to this cadmium immediate response as sulphion forms cadmium sulfide (CdSe).Should Response type is considered as " coupling ", because also without oxidation or each species of reducing, and they can be with suitable chemistry Metering reaction is to manufacture neutral products.
At each these kind of apoplexy due to endogenous wind, intermediate high reactivity each other is made it difficult to Control granularity, rates of particles and Size dispersity.Reaction species discharges the most in the solution, will be with the speed of diffusion-controlled or the fastest speed Rate is reacted.In some cases, use part or solvent can slightly slow down this reaction, but these approach are not provided that control The general way that particle generates.
Especially, such as, it is often impossible to preventing this type of reaction from being formed, new nanocrystalline (referred to as nucleation, it makes it difficult to Control to be directed at the reaction of existing nanocrystalline upper interpolation shell).Typically require and on nanocrystalline, form shell for some purposes, because of Chemistry and the light stability of this nanocrystal is significantly improved for this shell.This shell generally by nanocrystalline from the core of lower section different and Complementary semi-conducting material is made;Therefore, if hull shape becomes reaction to cause nucleation, then can be formed and be blended in one with those wanted The different composition having from wanting risen the most nanocrystalline.And once they are formed as a mixture, it is extremely difficult to separate these Nanocrystalline.
In the third approach, the precursor of mismatch can be selected so that a kind of precursor carries the most in the solution For neutral atom, the most another kind of precursor with ion.Such as, (it is Cd to alkyl phosphonic acid cadmium2+The source of ion) and selenizing three pungent (it is Se to base phosphine (TOPSe)0Source) mixture can serve as the precursor of mismatch.This type of precursor can not react formation neutrals Class, unless there is the electron transfer agent oxidation state with one of regulation reactive species, thus provides " the coupling that can react " species.Such as, reducing agent can be used for Cd2+Add electronics to provide two kinds of nonionic species (i.e. Cd0And Se0), or can To Se0Add electronics to provide two kinds of ionic species (i.e. Cd2+And Se2-).Arbitrary approach, once atom species is " coupling ", Their reaction can be carried out, but this reaction can not be carried out in the case of not having this type of electron transfer agent.Or, there is phase Two kinds of ionic species (i.e. two kinds cationes or two kinds of aniones) with electric charge also will be " mismatch ".It is, for example possible to use carry For the precursor of the mismatch of two kinds of cationic species, one of which species is reduced to offer can stand the moon that " coupling " reacts Ionic species.Such as, Se2+Or Se4+Can be reduced to provide selenium anion Se2-, it can occur and metal cation thing Class, such as Cd2+Reaction.In another example, two kinds of cationic species all can be reduced to neutral species.Fig. 1 describes How the incremental process of nucleation and growth participates in explanation reducing agent.
In another example, in the reaction between neutral species and anionic species, oxidant can serve as this electricity Sub-transfer agent.Such as, Cd0And Se-2Can serve as the precursor of mismatch, wherein use oxidant so that by Se-2It is oxidized to Se0, obtain Obtain two kinds of neutral species that " coupling " can be occurred to react.To the needs of this electronic transfer process and reagent by greatly Ground is ignored: due to the small-scale of reaction included and complexity, the effect of electron transfer agent generally by be present in raw material or The impurity the most accidentally generated realizes.
It has been reported that have some reactions of the electron transfer agent of addition: such as, Zehnder and Treadway, the U.S. Patent US 7,147,712 describes use accelerator (it can be oxygen or reducing agent) to promote and control nucleation and promote crystalline substance Bulk-growth.Add single reducing agent to cause nucleation, or nanocrystalline originally forming, and once nucleation occurs, promote nanometer Brilliant growth.The method provides rates of particles and the control to final size.But, owing to identical reducing agent is used for In this nucleation and growth stage, it is only capable of being realized the separation in two stages by indirect means.
Need nonetheless remain for manufacturing nanocrystalline products with high product yield with to the high control level of granularity with particle dispersibility Method, and it also requires control the nanocrystalline nucleation and growth stage respectively.
Summary of the invention
Provided herein is to use two kinds of electron transfer agents to be temporarily separated under conditions of avoiding or reducing nucleation as far as possible The nucleation and growth stage is with the method controlled and promote nanocrystalline growth.These methods provide and show product repeatability and be subject to Control performance and the nanocrystalline preparation method of this type of nanocrystalline new compositions.The method of the present invention can independently control nanometer The nucleation and growth stage of brilliant preparation.
Examples provided herein is by using independently controlled nanocrystalline formation favourable with the electron transfer agent of growth Provide there is the nanocrystalline of reproducible Product characteristics.The method strong adaptability, because they are even to nanocrystalline system The speed adding reagent in standby reaction exists when some changes and can also reproducibly provide nanocrystalline.In certain embodiments, Use two kinds of reducing agents to control the process of nanocrystalline formation.
In one aspect, the method manufacturing nanocrystalline colony, including: providing mixture, this mixture comprises: before first Body;Second precursor, wherein this first precursor and this second precursor have the oxidation state of mismatch;Present in an amount at least sufficient to produce required nucleation amount Strong electron transfer agent;With the weak electron transfer agent being different from this strong electron transfer agent;And be heated to being enough to draw by this mixture The temperature a period of time sent out colony nanocrystalline and formed.
In yet another aspect, manufacture nanocrystalline method, including: provide and comprise the first precursor and the mixing of the second precursor Thing, wherein this first precursor and this second precursor have the oxidation state of mismatch;Mixed to this be enough to the amount producing required nucleation amount Compound adds the strong electron transfer agent less than stoichiometry;Optionally heat mixture together to produce required nucleation amount; Needed for being enough to produce, the amount of nanocrystalline increment adds weak electron transfer agent in this mixture;And optionally this mixture is added Heat be enough to produce a period of time of required nanocrystalline increment.
At another aspect, manufacture nanocrystalline method, including: provide before comprising the first precursor, the second precursor and the 3rd The mixture of body, wherein this first and second precursor has an oxidation state of mismatch, and wherein the 3rd precursor has and is matched with This first precursor or the oxidation state of this second precursor;And this mixture optionally is heated to being adequate to bring about the temperature of nanocrystalline formation A period of time.
With reference to its specific embodiment, and consider the example being included herein further, other of this method and compositions Aspect and advantage are by apparent by description in greater detail below.It being understood that term used herein is only used for Specific embodiment is described rather than in order to limit.
Accompanying drawing explanation
Fig. 1 shows that two kinds of single reducing agents can be used for promotion nucleation and life subsequently in the formation that ZnTe is nanocrystalline Long.
Fig. 2 shows that weak reductant comes from for nanocrystalline growth stage, the most this weak reductant This precursor compound itself.Zinc Undecylenate is the precursor compound also providing for weak reductant as unsaturated carboxylic acid ester group Example.As shown in the higher level of absorbance in right side in fig. 2, for Zinc Undecylenate, rates of particles is higher than stearic acid Zinc.Zinc Undecylenate promotes crystal growth by providing weak reductant group.
Detailed description of the invention
Following detailed description with reference to included by herein and embodiment can be more easily understood embodiment as herein described. It being understood that terminology employed herein is only used for describing specific embodiment, and be not intended to limit.
Unless otherwise defined, all technology used herein and scientific terminology are general with embodiment disclosed herein art What logical technical staff was generally understood that has identical implication.
" one " used herein or " a kind of " refer to " at least one " or " one or more ".
" about " used herein refers to that this numerical value is approximation, and little variation is not significantly affected by the disclosed embodiments Enforcement.When using numerical value to limit, unless context illustrates separately, " about " refers to that this numerical value can change ± 10% and keep In the range of disclosed embodiment.
" nanoparticle " used herein refers at least one key dimension any particle in nano-scale range.Nanometer Particle is generally of at least one key dimension in about 1 to 1000 nanometer range.
The example of nanoparticle includes nanocrystalline, as core shell is nanocrystalline, add any firm association organic coating or can With other material in this nanocrystal surface.Nanoparticle can also include that exposed core shell is nanocrystalline, and has such as The core of the layer of other material that TDPA, OPA, TOP, TOPO maybe can not be removed by Conventional solvents from this surface nanocrystalline or Core shell is nanocrystalline.Nanoparticle can have the ligand layer that can be cross-linked further in its surface;And nanoparticle is permissible There is the other or another table that can change these particle properties (such as improving or reduce the dissolubility in water or other solvent) Finishing coat.This layer from the teeth outwards is included in term " nanoparticle ".
" nanocrystalline " used herein refers to the nanoparticle being made up of the inorganic substances being generally of ordered crystalline structure. It may refer to have the nanocrystalline of the nuclei of crystallization (core is nanocrystalline), or refers to that core shell is nanocrystalline.Nanocrystalline it is generally of full-size For 1-100 nanometer, preferred maximum dimension is about the nuclear diameter of 1 to 50 nanometer.
Core is nanocrystalline is it not to be applied the nanocrystalline of shell;It is typically semiconductor nano, and generally it is by single half Conductor material is made.It can have homogenizing composition, or its composition can change with the degree of depth of this nanocrystalline inside.Many classes The nanocrystalline of type is known, prepares nanocrystal and is known in the art its method applying shell.Disclosed herein Nanocrystalline may often be such that bright fluorescence nano, and the nanoparticle prepared by them be generally also bright, such as have to About 10%, the most at least about 20%, the most at least about 30%, the most at least about 40% and the quantum of the most at least about 50% or bigger less Productivity.They in use or exempt from the surface ligand of deterioration during storing advantageously to have protection for nanocrystalline Layer.
" quantum dot " used herein refers to the nano junction being made up of the material when body being quasiconductor or insulant Crystal grain, it has adjustable photophysical property near ultraviolet (UV) to far infrared (IR).
" water solublity " is used for referring to this material (item) to dissolve in maybe and can be suspended in containing group water solution, such as water or water base herein In solution or buffer solution (including those in biology or molecular detection system well known by persons skilled in the art).Although Water soluble nanometer particles is not genuine " dissolving " for this term is in the sense that the little molecule describing separate solvent, it Solvation being suspended in the solvent compatible with their extexine, thus, it is easy to the nanoparticle quilt being dispersed in water It is considered water miscible or water dispersible.Water soluble nanometer particles may be considered as hydrophilic, because its surface can With compatible with water and there is water solublity.
" hydrophobic nano particle " used herein refers to can be easily dispersed in or be dissolved in immiscible with water molten Agent, such as the nanoparticle in hexane, toluene etc..This nanoparticle is generally not readily dispersible in water.
" hydrophilic " used herein refers to the surface nature of solid, or the bulk property of liquid, wherein this solid or liquid Body shows than miscibility higher in low dielectric media or dissolubility in high dielectric media.For example, in methanol It is considered as hydrophilic than the higher material of dissolubility in varsol such as decane.
Nanoparticle can synthesize, such as spherical, rod, plate-like, triangle, nanometer with the shape of different complexities Ring, nanoshell, quadrangle, nano wire etc..These geometries each have different character: the spatial distribution of surface charge, The orientation dependence of the polarization of incident light wave and the spatial dimension of electric field.In certain embodiments, disclosed herein nanocrystalline It is subsphaeroidal.
In certain embodiments, nanoparticle provided herein can be to have the nanocrystal covered by semiconductor shell Core shell is nanocrystalline.The thickness that can make shell is adapted to provide for required particle properties.The thickness of shell can affect wavelength of fluorescence, amount Sub-productivity, fluorescent stability and other light stability characteristic.
This nanocrystal can be by any metal forming semiconductor nano that suitably becomes known for nonmetal with shell Atom is made.The semi-conducting material being suitable to this core and/or shell includes but not limited to include 2-16 race, 12-16 race, 13- 15 races and the material of the 14th race's element base semiconductor, as ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, MgS、MgSe、MgTe、CaS、CaSe、CaTe、SrS、SrSe、SrTe、BaS、BaSe、BaTe、GaN、GaP、GaAs、GaSb、 InP, InAs, InSb, AlS, AlP, AlSb, PbS, PbSe, Ge and Si and its ternary and quaternary mixture.Generally, this core shell Nanocrystalline core is made up of different semi-conducting materials from shell, it means that the binary semiconductor material of the core of core shell is at least A kind of atomic type is different from the atomic type in the shell that this core shell is nanocrystalline.This nanocrystal and shell can by any properly The metal of known formation semiconductor nano make with non-metallic atom.Techniques known in the art manufacture can be used partly to lead Body is nanocrystalline.See for example United States Patent (USP) Nos. 6,048,616,5,990,479,5,690,807,5,505,928 and 5,262, International Patent Publication No. WO 99/26299 disclosed in 27,357 and 1999 on Mays.These methods are normally manufactured in its surface On there is hydrophobic ligand coating nanocrystalline protecting them from rapid degradation.
Nanocrystalline can by its launch light percentage ratio quantum yield characterize.Such as, disclosed herein nanocrystalline Quantum yield can be greater than about 10%, greater than about 20%, greater than about 30%, greater than about 40%, greater than about 50%, greater than about 60%, Scope between any two of greater than about 70%, greater than about 80%, greater than about 90% and these values.This quantum yield is the biggest In about 30%, preferably greater than 50%, more than 70% and sometimes more than 80%.
In certain embodiments, the metallic atom of the shell in nanocrystal is selected from Cd, Hg, Zn, Be, Al, Ga, Mn, Cu And Mg.The second element in these quasiconductor shells can be selected from S, Se, Te, O, P, As, N and Sb.
This nanoparticle can have any suitably sized;Generally, its size can be provided in the UV-of electromagnetic spectrum can See the fluorescence of part, because this scope is convenient for monitoring biology and biochemical activity in associated media.Size with Relation between wavelength of fluorescence is known, thus makes less may the needs of nanoparticle select to provide suitable ripple under small size Long certain material, core as nanocrystalline as being designed to the least core shell in InP.
In Common examples, nanocrystalline diameter described herein can be about 1 nanometer to about 100 nanometers, the most directly Footpath is about 1 to about 50 nanometer, and diameter is about 1 to about 25 nanometer sometimes.The more specifically scope of nanocrystalline size can include but It is not limited to: about 0.5 nanometer to about 5 nanometers, about 1 nanometer to about 50 nanometers, about 2 nanometers to about 50 nanometers, about 1 nanometer are received to about 20 Rice, about 2 nanometers to about 20 nanometers or about 2 to about 10 nanometers.Nanocrystalline more specifically size example can include but not limit In: about 0.1 nanometer, about 0.5 nanometer, about 1 nanometer, about 2 nanometers, about 3 nanometers, about 4 nanometers, about 5 nanometers, about 6 nanometers, about 7 receive Rice, about 8 nanometers, about 9 nanometers, about 10 nanometers, about 11 nanometers, about 12 nanometers, about 13 nanometers, about 14 nanometers, about 15 nanometers, about 16 Nanometer, about 17 nanometers, about 18 nanometers, about 19 nanometers, about 20 nanometers, about 25 nanometers, about 30 nanometers, about 35 nanometers, about 40 nanometers, About 45 nanometers, about 50 nanometers, and the scope between any two of these values.For basic and aspheric nanocrystalline, example Such as rod, its minimum dimension can be about 1 to about 100 nanometer, or about 1 nanometer is to about 50 nanometers, or about 1 nanometer is to about 25 Nanometer, about 1 nanometer to about 10 nanometers or sometimes about 1 nanometer are to 5 nanometers.
In certain embodiments, provided herein is that diameter is less than about 10 nanometers or diameter is less than about 7 nanometers or straight Footpath is less than about the nanocrystal of 5 nanometers.These nanocrystalline small sizes are favourable in numerous applications, especially because herein Disclosed in nanocrystalline become clear unexpectedly under their size.
The monochromatic goods of typical nanoparticle have the crystal that size and dimension is the most identical.Nanocrystalline generally It is considered as spherical or subglobose, but can essentially be any shape.Or, this nanocrystalline shape can be aspheric Shape.Such as, for redder color, nanocrystalline shape can be changed into oblate spherical.The most about 60%, at least about 70%, this particle of at least about 80%, at least about 90%, at least about 95% and preferably about 100% is of the same size.Can be with Root-mean-square (" rms ") the measurement size deviation of diameter, it is less than about 30%rms, preferably less than about 20%rms, more preferably less than about 10%rms.Dimensional discrepancy can be less than about 10%rms, less than about 9%rms, less than about 8%rms, less than about 7%rms, be less than about 6% Rms, less than about 5%rms or the scope between any two of these values.The colony of this particle is sometimes referred to as being " single dispersing ".Ordinary skill will recognize that, nanocrystalline, if the specific dimensions of semiconductor nano is generally with particle size distribution Form obtains.
It is well known that, the color (transmitting light) of this semiconductor nano can be by changing this nanocrystalline size and composition Come " tuning ".The nanocrystalline wavelength that can absorb wide spectrum, and launch the light of narrow wavelength.This excites and launches wavelength the most not With, and the most overlapping.The nanoparticle of single dispersing colony can be characterized as them and produce the fluorescent emission with opposite, narrow wavestrip. The example of luminous width (FWHM) includes less than about 200 nanometers, less than about 175 nanometers, less than about 150 nanometers, less than about 125 receives Rice, less than about 100 nanometers, less than about 75 nanometers, less than about 60 nanometers, less than about 50 nanometers, less than about 40 nanometers, less than about 30 Nanometer, less than about 20 nanometers and less than about 10 nanometers.Launch width and launch full width at half maximum (FWHM) place of band preferably less than about 50 nanometers, and more preferably less than about 35 nanometers.This transmitting light preferably has the transmitting wavelength of symmetry.This luminescence maxima generally exists At any wavelength of about 200 nanometers to about 2,000 nanometers.The example of luminescence maxima includes but not limited to: about 200 nanometers, about 400 nanometers, about 600 nanometers, about 800 nanometers, about 1,000 nanometers, about 1,200 nanometers, about 1,400 nanometers, about 1,600 nanometers, About 1,800 nanometers, about 2,000 nanometer, and the scope between any two of these values.In certain embodiments, green is Desirable, therefore select the wavelength in green area.
This nanoparticle can have the face coat increasing various functionalities.Such as, this nanocrystalline can scribble lipid, Phospholipid, fatty acid, Polynucleotide, Polyethylene Glycol, first antibody, second antibody, antibody fragment, protein or nucleic acid base aptamers, Biotin, streptavidin, protein, peptide, organic molecule, organic or inorganic dyestuff, precious metal or noble-metal-cluster.
The spectral characteristic of nanoparticle generally can use any suitable photo measure or light gathering unit to be monitored.This The example of kind of device is CCD(charge-coupled image sensor) photographing unit, video equipment, CTT imaging, the number that is contained on fluorescence microscope Camera, photomultiplier tube, exometer and photometer, the microscope of various structure, and even human eye.Luminescence can be carried out continuously prison Survey or be monitored at one or more discontinuous time points.The light stability of nanoparticle and susceptiveness allow long-time note The change of record electromotive force.
In certain embodiments, nanoparticle provided herein can be the nanoparticle single dispersing colony of similar composition A member.This monodisperse particle colony is characterised by its table in terms of the diameter or minimum dimension of this core in certain embodiments Reveal the deviation of less than about 30%rms, preferably less than about 20%rms, more preferably less than about 10%rms.In certain embodiments, should Monodisperse particle colony shows less than about 5% or the deviation of less than about 3%rms in terms of the diameter or minimum dimension of this core.This Field those of ordinary skill is it will be recognized that nanocrystalline, if the specific dimensions of semiconductor nano is actually with particle size distribution form Obtain.
The nanoparticle of single dispersing colony is characterised by that they produce the fluorescence radiation with opposite, narrow wavelength band.One In a little embodiments, this monodisperse particle colony is characterised by when being radiated, and this colony's transmitted bandwidth is less than about 60 nanometers half High overall with (FWHM), or less than about 50 nanometers FWHM and the light sometimes less than about 40 nanometers FWHM.
In certain embodiments, in this article described ligand-modified before, by adding to this semiconductor nano nucleus Outer covering layer or shell, thus by modified for core semiconductor nano to improve efficiency and the stability of its fluorescence radiation.There is shell permissible It is that (its infringement should half preferably as the surface defect of this semiconductor nano nucleus surface can produce the trap in electronics or hole The electrical and optical properties of conductor nanocrystal) or other non-radiative energy loss mechanism (its photon energy absorbed that dissipated Or the most slightly affect the wavelength of fluorescence radiation), thus cause launching widening of band.In this semiconductor nano nucleus surface Insulating barrier can provide the atomic energy hop of chemical potential in interface, and this eliminates the energy state of the trap that may act as electronics and hole. This obtains higher efficiency in luminescence process.
Suitably shell material includes having the semi-conducting material than this higher band-gap energy of semiconductor nano nucleus.Except Having than outside this higher band-gap energy of semiconductor nano nucleus, suitable shell material should have relative to core semiconductor nano Good conduction band and valence band offset.Therefore, this conduction band desirably can be higher than this core semiconductor nano and valence band can be desirable Ground is less than this core semiconductor nano.For launch visible (such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, GaP, GaAs, GaN) or the semiconductor nano nucleus of energy of near-infrared (such as InP, InAs, InSb, PbS, PbSe), it is possible to use band-gap energy Amount shell material in ultraviolet region.Exemplary shell material includes but not limited to: CdS, CdSe, InP, InAs, ZnS, ZnSe, ZnTe, GaP, GaN and chalcogenide magnesium, such as MgS, MgSe and MgTe.For the semiconductor nano nucleus luminous at nearly IR, also Band-gap energy shell material in visibility region light can be used, such as CdS or CdSe.The preparation of the semiconductor nano of coating can See such as Dabbousi et al. (1997) J. Phys. Chem. B 101:9463, Hines et al. (1996) J. Phys. Chem. 100:468-471, Peng et al. (1997) J. Am. Chem. Soc. 119:7019-7029 and Kuno et al. (1997) J. Phys. Chem. 106:9869.In the art it will further be understood that the actual fluorescence ripple of specific nanocrystal Long size and the composition thereof depending on this core, the most above-mentioned classification is approximation, and is described as in visible or near infrared region Luminous nanocrystal actually can be luminous with longer or shorter wavelength according to the size of this core.
When using core shell fluorescence semiconductor nanocrystalline, the most advantageously make this nanoparticle the least;Thus exist In some embodiments, this nanocrystalline diameter can be less than about 20 nanometers, and generally less than about 8 nanometers, and diameter is less than about 6 sometimes Nanometer, and in certain embodiments, this nanocrystalline diameter or be smaller in size than about 5 nanometers, or diameter or be smaller in size than 4 and receive Rice.
Nanocrystalline precursor can be described as the first precursor and the second precursor sometimes.This first precursor can be the salt containing metal, as The halogenide of metal, carboxylate, phosphonate, carbonate, hydroxide or diketone (diketonate) or its salt-mixture are (such as Halogenated carboxylic acid salt, such as (halo) (oleic acid) Cd), wherein this metal can be such as Cd, Zn, Mg, Be, Mn, Cu, Co, Pb Hg, Al, Ga, In or Tl.This second precursor can be such as O, S, Se, Te, N, P, As or Sb.This second precursor mixture can wrap Include amine, such as primary amine (such as C8-C20Alkylamine).This second precursor can include such as phosphine chalcogenide, double (silicyl) sulfur Belong to compound, dioxygen species, ammonium salt or three (silicyl) phosphine etc..
In one embodiment, this first precursor and this second precursor can be by making metal or metalline and reducing agent Contact the precursor to be formed containing metal and combine.This reducing agent can include alkylphosphines, 1,2-glycol or aldehyde, such as C6-C20Alkyl Glycol or C6-C20Aldehyde.
Suitably the example of metalline can include but not limited to acetylacetone,2,4-pentanedione cadmium, cadmium iodide, cadmium bromide, Caddy (Cleary), Cadmium hydrate., cadmium carbonate, cadmium acetate, Aska-Rid., zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc hydroxide, carbonic acid Zinc, zinc acetate, zinc oxide, magnesium acetylacetonate, magnesium iodide, magnesium bromide, magnesium chloride, magnesium hydroxide, magnesium carbonate, magnesium acetate, oxidation Magnesium, acetylacetone,2,4-pentanedione hydrargyrum, mercuric iodixde, mercuric bromide, mercuric chloride, mercuric hydroxide, carbonic acid hydrargyrum, mercuric acetate, aluminium acetylacetonate, silver iodide, Aluminium bromide, aluminum chloride, aluminium hydroxide, aluminium carbonate, aluminium acetate, acetylacetone,2,4-pentanedione gallium, gallium iodide, gallium bromide, gallium chloride, hydroxide Gallium, carbonic acid gallium, acetic acid gallium, Indium Tris acetylacetonate, indium iodide, indium bromide, indium chloride, indium hydroxide, carbonic acid indium, indium acetate, acetyl Acetone thallium, thallium iodide, thallium bromide, thallium chloride, thallium hydroxide, thallium carbonate or thallium acetate.Suitably metalline also includes such as Carboxylate, such as oleate, stearate, myristate and palmitate, mixing halogenation carboxylate, such as M (halogenation) (oleic acid) Salt, and phosphonate.
Alkyl can be side chain or the non-branched saturated hydrocarbons group of 1 to 100 carbon atom, preferably 1 to 30 carbon atom, as Methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, octyl group, decyl, myristyl, cetyl, 20 Alkyl, tetracosyl etc., and cycloalkyl, such as cyclopenta, cyclohexyl etc..Optionally, alkyl can be containing 1 to 6 Selected from-O-,-S-,-M-and the linker of-NR-, wherein R is hydrogen, or C1-C8 alkyl or low-grade alkenyl.
Before being mixed with this second precursor by this metalline, this metalline can contact with ligand solvent to be formed Precursor containing metal.Typical ligand solvent includes alkylphosphines, alkylphosphine oxide, alkyl phosphonic acid, alkyl phosphinic acid or contains carboxylic Acid solvent;But, other ligand solvent, as pyridine, furan and amine are also applied for this nanocrystalline production.Suitably ligand solvent Example include pyridine, tri-n-octyl phosphine (TOP) and TOPO (TOPO).Also include containing acid solvent, as oleic acid, Stearic acid, myristic acid, Palmic acid, TDPA, OPA etc..This ligand solvent can include 1,2-glycol or aldehyde.This 1,2-glycol Or aldehyde can promote the reaction between metalline and the second precursor, obtain during improving growth course and being somebody's turn to do is nanocrystalline Quality.
This second precursor is typically chalcogenide donor or group V element, such as phosphine chalcogenide, double (silicyl) chalcogen Compound, dioxygen, ammonium salt or three (silicyl) phosphine.Suitable second precursor includes dioxygen, elementary sulfur, double (trimethyl silyl Base) selenides ((TMS)2Se), trialkyl selenizing phosphine, such as selenizing (tri-n-octyl phosphine) (TOPSe) or selenizing (tri-n-butyl phosphine) (TBPSe), trialkyl telluride phosphine, as telluride (tri-n-octyl phosphine) (TOPTe) or six propyl group phosphorus Disnalon (Ferrer). tellurides (HPPTTe), Double (trimethyl silyl) tellurides ((TMS)2Te), sulfur, double (trimethyl silyl) sulfide ((TMS)2S), three alkane Base phosphine sulfide, such as sulfuration (tri-n-octyl phosphine) (TOPS), three (dimethylamino) arsine, ammonium salt, such as ammonium halide (such as NH4Cl), Phosphatization three (trimethyl silyl) ((TMS)3P), three (trimethyl silyl) arsenide ((TMS)3As) or three (trimethyls Silicyl) antimonide ((TMS)3Sb).In certain embodiments, this first precursor and this second precursor can be at same point Part in son.
" ligand solvent " used herein refer to can effectively coordinating to the solvent of nanocrystal surface, as TOP, TOPO, TDPA, OPA, carboxylic acid and amine." ligand solvent " also includes being generally used for nanocrystalline somatomedin and in this nanocrystal surface shape Become coating or the phosphine of layer, phosphine oxide, phosphonic acids, phosphinic acid, amine and carboxylic acid.They eliminate do not have provide bonding electronics to Just the heteroatomic varsol being coordinated with this nanocrystal surface, such as hexane, toluene, hexadecane, octadecylene etc..Do not contain coordination To the hetero atom of nanocrystal surface, the varsol such as O, S, N or P is referred to herein as non-coordinating solvent.It should be noted that term " solvent " is in its normal manner in these terms: it refers to load, dissolve or dispersion and the reaction between them Medium, but its be generally not involved in this reaction material reaction or not by the reaction of this reaction material modification.
Precursor
The formation of nanoparticle generally includes two different stages: first stage, nucleation, needs a large amount of precursor to be agglomerated into Core (i.e. nucleation), and second stage, growth, add on existing core including precursor.When precursor atom mates (i.e. in type Being non-ionic (neutral), or one is cation, another is anion), they the most quickly react. This type of fast reaction generally produces a large amount of nucleation, even also such when nucleation is unacceptable time, and can be because growing and becoming Core occurs simultaneously and results in the particle colony of shortage uniform particle size.
Control to be valuable to the independence of the two formation stages, because nucleation stage determines nanoparticle productivity, And growth stage determines the final size of nanoparticle.
It is important that nucleation stage is separated with growth stage in nanocrystalline formation so that all this is nanocrystalline substantially Concurrently forming, the time quantum that growth phase is same the most together is to obtain being uniformly distributed of nano-particles size, it is provided that core is nanocrystalline Single dispersing colony.If forming new small core after other particle has been formed and grown a period of time, it may be difficult to obtain Obtain uniform size.
The method that separate this nucleation and growth stage that to each separate phases control strengthen is provided herein.
This method controls two stages of particle formation by using " mismatch " precursor to realize." mismatch " precursor exists Do not add or can not react in the case of lost electrons so that the precursor in solution is all deposited with complementary ionic state or middle condition ?;Otherwise, they can not be in conjunction with formation neutral products.It is present in together with the precursor of mismatch in this reactant mixture by control The quantity of electron transfer agent and character, it is possible to use there is not electron transfer agent, in the case of reducing agent or oxidant The reactive shortcoming of " mismatch " precursor, temporarily to control the nucleation and growth stage that particle is formed.
If a kind of precursor provides the neutral species for nanocrystalline formation in the solution, and other precursor is used anti- Ionic species is provided under the conditions of Ying in the solution, if or this precursor each provide and there is the ionic species of identical charges (i.e., Two kinds of cationes or two kinds of aniones), precursor provided herein will be considered as " mismatch ".The example bag of the precursor of mismatch Include and provide a kind of nonionic (i.e. neutral) species or another kind of cation precursor pairing a kind of cationic species is provided Precursor, or cloudy with the offer one of the precursor pairing providing a kind of nonionic (i.e. neutral) species or another kind of anionic species The precursor of ionic species.Relevant species is present in this hull shape and becomes the reaction species under reaction condition.
In certain embodiments, it is possible to use binary oxidizer system.In further embodiments, it is possible to use binary is also Former dose of system.In further embodiments, it is possible to use mixed electronic transfer agent system (i.e. a kind of oxidant and a kind of reduction Agent).In some such embodiments, it is possible to use one group of precursor, one of which provides neutral species, another kind of provide sun from Sub-species.In this system, reducing agent can be added this neutrality species to be reduced to anion, or by cationic species also Originally it was neutral alumina state.
In certain embodiments, this first precursor can comprise metallic atom M, and this second precursor can comprise nonmetal former Sub-X, wherein selects this precursor so that their oxidation state is mismatch.
This nanocrystal and shell can be by any suitable known metal forming semiconductor nano and non-metallic atoms Make.The semi-conducting material being suitable to this core and/or shell includes but not limited to include 2-16 race, 12-16 race, 13-15 race With the material of the 14th race's element base semiconductor, as ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, MgS, MgSe、MgTe、CaS、CaSe、CaTe、SrS、SrSe、SrTe、BaS、BaSe、BaTe、GaN、GaP、GaAs、GaSb、InN、 InP, InAs, InSb, AlAs, AlP, AlSb, PbS, PbSe, Ge and Si and its binary, ternary and quaternary mixture.
The selection of the composition of this semi-conductor nano particles affects the characteristic spectrum emission wavelength of this particle.Thus, it is possible to base The specific composition of nanoparticle provided herein is selected in the spectral regions of monitoring.Such as, the energy in visible-range is launched Semiconductor nano include but not limited to CdS, CdSe, CdTe, ZnSe, ZnTe, GaP and GaAs.In transmitting near infrared range The semiconductor nano of energy includes but not limited to InP, InAs, InSb, PbS and PbSe.Finally, blue light is launched near ultraviolet The example of the semiconductor nano of energy includes but not limited to ZnS and GaN.In each case, can be by nanocrystalline at this The shell increased on core realizes this wavelength of fluorescence of additional tuning to a certain degree.
The precursor that can be used as this " first " precursor in method disclosed herein includes containing selected from the periodic table of elements The compound of the element (such as Zn, Cd, Hg, Mg, Ca, Sr, Ba etc.) of the 2nd race and the 12nd race, containing selected from the periodic table of elements The compound of element (Al, Ga, In etc.) of the 13rd race, and element containing the 14th race selected from the periodic table of elements (Si, Ge, Pb etc.) compound.This precursor of many forms can be used for the methods disclosed herein.
The example of the compound that can be used as the first precursor can be organo-metallic compound, such as metal alkyl species, or salt, As metal halide, metal acetate, metal carboxylate, metal phosphinate hydrochlorate, metal phosphinate salt, metal-oxide or other Salt.In certain embodiments, this first precursor provides neutral species in the solution.Such as, metal alkyl species, such as diethyl zinc (Et2Or dimethyl cadmium is typically considered in solution neutral zinc atom (Zn Zn)0) source.In further embodiments, this first Precursor provides ionic species (i.e. metal cation) in the solution.Such as, zinc chloride (ZnCl2) and other zinc halide, zinc acetate (Zn (OAc)2) and zinc polycarboxylate be typically considered Zn in solution2+The source of cation.
It is only used as example, suitably provides the first precursor of neutral metal species to include metal diaikyl source, such as dimethyl Cadmium (Me2Cd), diethyl zinc (Et2Zn) etc..Suitably the first precursor of metal cation is provided to include such as cadmium in the solution Salt, such as cadmium acetate (Cd (OAc)2), cadmium nitrate (Cd (NO3)2), Aska-Rid. (CdO) and other cadmium salt;And zinc salt, such as zinc chloride (ZnCl2), zinc acetate (Zn (OAc)2), zinc oleate (Zn (oleic acid)2), chloro (oleic acid) zinc, Zinc Undecylenate, zinc salicylate and Other zinc salt.In certain embodiments, this first precursor is the salt of Cd or Zn.In certain embodiments, it is the halogen of Cd or Zn Compound, acetate, carboxylate or oxide salt.In further embodiments, this first precursor is M (O2CR) salt of X-form, its Middle M is Cd or Zn;X is halogen or O2CR;And R is optionally for undersaturated C4-C24Alkyl.Can be used as the first precursor the 2nd, 12, other suitable form of 13 and 14 race's elements is known in the art.
The precursor that can be used as " second " precursor in method disclosed herein includes containing selected from the 16th of the periodic table of elements The compound of the element (such as S, Se, Te etc.) of race, element (N, P, As, Sb containing the 15th race selected from the periodic table of elements Etc.) compound, containing selected from the periodic table of elements the 14th race element (Ge, Si etc.) compound and containing selected from unit The compound of the element (halogenide) of the 17th race of element periodic chart.This precursor of many forms can be used for method disclosed herein. It being understood that in certain embodiments, this second precursor will provide neutral species in the solution, and in other embodiments In, this second precursor will provide ionic species in the solution.
It should be understood that in certain embodiments, nanoparticle core and/or shell can contain more than two kinds of precursors.Such as, may be used To use same procedure described herein to use three kinds of precursors to form ternary nano particle, use four kinds of precursors to form four Unit's nanoparticle, etc..
When this first precursor comprises metal cation, this second precursor will provide uncharged the most in the solution (i.e. neutral) non-metallic atom.In Common examples, when this first precursor comprises metal cation, this second precursor is contributed Neutral chalcogen, most commonly S0、Se0Or Te0
Be adapted to provide for the second precursor of neutral chalcogen include such as elementary sulfur (usually at amine, such as decyl amine, oleyl amine Or dioctylamine, or alkene, the solution form as in octadecylene), and the trialkyl phosphine adduct of S, Se and Te.This type of trialkyl phosphine Adduct is sometimes described herein as R3P=X, wherein X is S, Se or Te, and each R independently be H and can be maybe straight chain, prop up Chain, ring-type or a combination thereof and can be undersaturated C1-C24 alkyl.This type of exemplary second precursor includes three (normal-butyls Phosphine) selenides (TBP=Se), three (n-octyl phosphine) selenides (TOP=Se) and corresponding sulfur and tellurium reagent, TBP=S, TOP=S, TBP=Te and TOP=Te.These reagent are often through by required element, such as Se, S or Te and suitable ligand solvent, such as TOP Or TBP mixing is formed.There is provided under the reaction conditions the precursor of anionic species generally with the of neutral metal atom is provided One precursor (such as alkyl metal cpd and other compound above-mentioned or known in the art) is used together.
In certain embodiments, this second precursor provides electronegative nonmetallic ion (such as S in the solution-2、Se-2 Or Te-2).The example suitably providing the second precursor of ionic species includes silyl compound, such as double (trimethyl silyl Base) selenides ((TMS)2Se), double (trimethyl silyl) sulfide ((TMS)2And double (trimethyl silyl) telluride S) Thing ((TMS)2Te).Being also included in interior is the compound of hydrogenation, such as H2Se、H2S、H2Te;And slaine, as NaHSe, NaSH or NaHTe.In which case it is possible to use neutral metal species is oxidized to react in " coupling " by oxidant In the cationic species reacted with anionic pre-cursors, oxidant maybe can be used to improve the oxidation state of this anionic pre-cursors, to carry For the neutral species that " coupling " react can be stood together with neutral metal species.
Other exemplary organic precursor is described in the U.S. Patent number 6,207,299 and 6,322 authorizing Bawendi et al., In 901, use weak acid as the synthetic method of precursor material by Qu et al., (2001), Nano Lett., 1 (6): 333- 337 disclosures, its each disclosure be expressly incorporated herein by reference of text.
This first and this second precursor can mix with suitable solvent with formed be used for method disclosed herein solution. Solvent or solvent mixture for forming the first precursor solution can be with solvent or the solvents for forming the second precursor solution Mixture is identical or different.This precursor can individually dissolve, or they can be mixed together in single solution.
Before or after precursor is admixed together, and this solvent and/or precursor can mixed with this weak reductant Before or after conjunction, carry out the heating of mixture.In certain embodiments, the first precursor, the second precursor and weak reductant are all appointed It is selected in suitable solvent or solvent mixture and mixes to be formed reactant mixture, and subsequently should before adding strong reductant Reactant mixture is heated to suitable temperature.
Order and the speed of adding precursor are generally most important to method disclosed herein.
In certain embodiments, thus with the speed only limited by the practical considerations relevant to keeping desired reaction temperature Rate adds this precursor, and can add this precursor as quickly as possible in the case of temperature controls to allow.Similarly, this precursor can To be all present in this reactant mixture, when it is heated to desired reaction temperature, and can reach operate temperature it One or both these electron transfer agents of rear addition.In certain embodiments, that this is the not strongest before reaching desired reaction temperature Electron transfer agent joins in reactant mixture.
Ligand solvent
Suitably ligand solvent include (illustratively unrestricted) hydro carbons, amine, alkylphosphines, alkylphosphine oxide, carboxylic acid, Ether, furan, phosphonic acids (phospho-acids), pyridine and mixture thereof.This solvent can essentially wrap solvent-laden mixture, Generally it is referred to as " dicyandiamide solution " in the art.In a preferred embodiment, this solvent comprises at least one ligand solvent.One In a little embodiments, this dicyandiamide solution comprises secondary amine and trialkyl phosphine (such as TBP or TOP), phosphonic acids (such as TDPA, OPA) or three Alkylphosphine oxide (such as TOPO).
Ligand solvent can be the mixture of the most noncoordinating solvent (such as alkane) and part defined below.
Suitably hydro carbons includes 10 to about 30 alkanes of carbon atom, alkene and aromatic hydrocarbon;Example includes octadecylene and angle Shark alkane.This hydro carbons can comprise alkane, alkene and aromatic fractions, such as the mixture of alkylbenzene (such as sym-trimethylbenzene .).
Suitably amine includes but not limited to monoalkylamine, dialkylamine and trialkylamine, such as trioctylamine, dioctylamine, pungent Amine, oleyl amine, decyl amine, dodecyl amine, cetylamine etc..It is former that the usual each alkyl of alkyl of these amine contains about 6-24 carbon Son, can include undersaturated carbon-carbon bond, and each amine generally has the carbon of a total of about 10-30 carbon atom in its all alkyl Total atom number.
Exemplary alkyl phosphine includes but not limited to trialkyl phosphine, tri-n-butyl phosphine (TBP), tri-n-octyl phosphine (TOP) etc.. The each alkyl of alkyl of these phosphines contains about 6-24 carbon atom, can contain undersaturated carbon-carbon bond, and each phosphine is in its institute There is in alkyl the total number of carbon atoms with a total of about 10-30 carbon atom.
Suitably alkylphosphine oxide includes but not limited to trialkyl phosphine oxides, TOPO (TOPO) etc. Deng.The each alkyl of alkyl of these phosphine oxides contains about 6-24 carbon atom, can contain undersaturated carbon-carbon bond, and often Individual phosphine oxide has the total number of carbon atoms of a total of about 10-30 carbon atom in its all alkyl.
Exemplary fatty acid includes but not limited to stearic acid, oleic acid, Palmic acid, myristic acid and lauric acid, and formula R- Other carboxylic acid of COOH, wherein R is C6-C24Alkyl and undersaturated carbon-carbon bond can be contained.
Exemplary ether and furan include but not limited to oxolane and methylation pattern, glyme etc..
Suitably phosphonic acids and phosphinic acid include but not limited to hexyl phosphonic acids (HPA), tetradecylphosphonic acid (TDPA) and octyl group Phosphonic acids (OPA), and be usually used in combination with alkylphosphine oxide, such as TOPO.Suitably phosphonic acids and phosphinic acid have formula RPO3H2Or R2PO2H, the most each R independently be C6-C24 alkyl, and can contain undersaturated carbon-carbon bond.
Exemplary pyridines includes but not limited to pyridine, alkylation pyridine, nicotinic acid etc..
Suitably alkene includes such as octadecylene, Squalene and other undersaturated C4-C30 hydro carbons.
Solvent can be used alone or in combination.TOP-TOPO dicyandiamide solution is usually used in this area, other relevant (such as fourth Base) system is the most such.Such as, TOP with TOPO can be used in combination to be formed cadmium solution, and TOP can be individually used for forming selenium molten Liquid (such as TOP+cadmium acetate or TOP+cadmium nitrate).
Technical grade solvent can be used, it is possible to have benefited from useful impurity in this kind solvent (such as TOP and/or TOPO) Exist.In certain embodiments, this solvent comprises at least one ligand solvent.In a kind of preferred embodiment, this solvent is Pure.Generally, it means that this solvent contains the electron transfer agent that can be used as less than 10 volume % and more preferably less than 5 volume % Impurity.Therefore, the solvent such as TOPO that purity is 90% or 97% and TOP that purity is 90% is particularly well-suited to disclosed herein Method, and purity higher than 99% solvent be preferred.
There is a small amount of impurity and the source of the electron transfer agent outside expectation can be provided, if they promote the shell precursor of mismatch Nucleation, this target that can cause realizing embodiment disclosed herein.Additionally, particular agent can be in a kind of system Weak reducing/oxidizing agent, or be strong reducing/oxidizing agent in different systems, or invalid reducing/oxidizing agent: weak and strong certainty Depend on being formed the concrete shell precursor and the solvent of employing reacted and temperature for this nanocrystal.
Such as, in some systems, one of solvent or precursor the unsaturated bond provided can be as described Weak reducing/oxidizing agent;In other systems, it cannot effectively serve as weak reducing/oxidizing agent, and to add weak reduction/ Oxidant is to promote nanocrystalline growth, even if there is unsaturated bond, as at the slaine containing unsaturated group (such as oleic acid Salt) in.
In order to accurately control two stages of nanocrystalline formation, therefore, the most desirably differentiate and measure for these Any strong or weak reducing/oxidizing agent present in the solvent of method and reagent.Therefore, in certain embodiments, to be used for this Its effect in specific system of the Evaluation of the method described in literary composition.For the reagent of this method, solvent, reducing agent or front The suitability of body can by its test to observe this material whether be used as in described system strong reducing/oxidizing agent or Determine containing the impurity as strong reducing/oxidizing agent.When reagent is used as strong reducing/oxidizing agent or containing as strong reduction/oxygen During the impurity of agent, should remove for the methods disclosed herein, substitute or purify this reagent further.
Part
In a kind of preferred embodiment, part includes in the reaction.Part is and precursor and/or nanoparticle complexation Compound.Suitably part includes (illustratively unrestricted) phosphonic acids, as hexyl phosphonic acids and tetradecylphosphonic acid (TDPA), Octyl phosphonic acid (OPA), carboxylic acid, such as the isomer of octadecanoid acid, amine, amide, alcohol and ether.In some cases, this part with should Solvent can be identical.
Electron transfer agent: reducing agent
In embodiment disclosed herein, control particle formed the nucleation and growth stage can by use without The precursor of the mismatch that electron transfer agent adds or can not react in the case of lost electrons realizes.Use two kinds of single electronics Transfer agent, particularly one or more reducing agents, enabling promote nucleation independently or grow to desirable degree, and improving this Being temporarily separated of two formation stages.This method makes it possible to independently control rates of particles and granularity, it is also possible to produces and has The particle of more narrow size distribution.
The reducing agent (going back original reagent) of " by force " used herein or " higher " refers in the reaction using this reducing agent Nucleation can be promoted under actual conditions or promote the reducing agent causing particle to be formed.The reducing agent of " weak " or " more weak " refers in institute With not promoting actual nucleation under actual conditions or promote to cause particle to be formed, but can promote that particle is raw under these conditions Long goes back original reagent.
It will be apparent to one skilled in the art that specific reductant is strong reductant or weak reductant depends on the circumstances, And depend on the special reaction condition using this reducing agent.As required by nucleation, electron transfer particle in growth Surface (i.e. during growth stage) is easier to make for than on dissociated ion in the solution.To given system (nanometer Brilliant formation reacts) for, this tested reducing agent can be determined by and show as strong reductant or weak reduction under these conditions This tested reducing agent is divided into strong or weak by agent.By under suitable reaction condition do not exist any primary nanocrystalline ( In initial action mixture add nanocrystalline) in the case of make described specific precursor contact with this tested reducing agent determine so that If it occur that nucleation can be observed, it may be determined that whether specific tested reducing agent is strong reductant: generally, if nucleation with Notable speed, such as, occur with the speed than the nucleation rate up at least about 50% when there is not this tested reducing agent, and this is tested also Former dose promotes nucleation, and is considered strong reductant in this system.If the existence of this tested reducing agent does not significantly improves into Core speed, then the strong reductant during it is not this system.
Under becoming reaction condition at hull shape, receive in the primary (addition) with the same type formed by this precursor Described specific precursor is made to contact with this tested reducing agent in the presence of meter Jing, it may be determined that whether specific tested reducing agent is weak going back Former dose: generally, if nanocrystalline growth occurs with the speed improved, such as with faster than growth when there is not this tested reducing agent The speed of rate high at least twice, this tested reducing agent may be considered that the reducing agent being adapted for promoting nanocrystalline growth.It is thus Can be suitable weak reductant, as long as it is not used as strong reductant in described system.
If tested reducing agent is suitable to promote nanocrystalline growth by above-mentioned test, but in the most described specific system Strong reductant, this tested reducing agent is considered weak reductant.Owing to the relative intensity of reducing agent depends on these factors, This function classification of reducing agent is the method that can be used for sorting out weak or strong reductant, and it can be applied to appoint by routine test What specific tested reducing agent.
Owing at electron transfer particle surface in growth, (i.e. during growth stage) ratio is dissociating in the solution Can more easily carry out on ion, as required by nucleation, nucleation needs the reducing agent more higher than growth.Reactivity side The difference in face make it possible to by provide a small amount of strong electron transfer agent (it quickly consumes in nucleation process) and more substantial more Weak electron transfer agent (it makes it possible to grow continuously) makes two stages separate.The nanocrystalline size of this core can be raw by monitoring Wavelength of fluorescence in long phase process is readily determined.
In the embodiment provided in this article, the amount of the strong reductant that can use in being reacted by control regulates nucleation Degree.In certain embodiments, can be be enough to promote that aequum nucleation amount adds strong reductant.In other embodiments In, can with relative to precursor to be restored less than stoichiometric amount add strong reductant.In some such embodiments, The addition of strong reductant can be the stoichiometric reaction of nanocrystalline precursor the desired amount of less than about 1/10th, about ten/ One, less than about 2/10ths, less than about 3/10ths or less than about 4/10ths.In certain embodiments, addition is strong The amount of reducing agent can be stoichiometric reaction the desired amount of about 1/10th.
Once strong reductant has exhausted (this can the most quickly occur), the extra shape of basic stopping Become little core.Thus, the amount limiting strong reductant makes it possible to separate nucleation stage with growth stage.This method makes it possible to Enough independent control rates of particles and granularity, and the particle with narrower distribution of sizes can also be manufactured potentially.Due to before this Body keeps mismatch, and the continued propagation of nanocrystal needs to add the second electron transfer agent.Add weak reductant and make particle growth, But further nucleation will not be promoted, the particle of uniform-dimension is thus provided.
Owing to reaction can be controlled by the use of electron transfer agent, it is carefully controlled the speed adding precursor in reaction (as in some nanocrystalline preparation method) is the most unnecessary.This nanocrystalline precursor can mix being not resulted in sub-cooled reaction The most disposable on-demand interpolation in the case of compound;Precursor need not be slowly added to prevent in many embodiments of these methods Unwanted new karyomorphism becomes.It practice, this precursor can be mixed and heated in a suitable solvent with optional weak reductant , without there is nanocrystalline formation (this can cause) by adding strong reductant in required reaction condition.
In a preferred embodiment, this strong reductant can add under being enough to the running temperature that nucleation occurs.Temperature at this Under degree, it is believed that when adding strong reductant, quick explosion type nucleation occurs, the most quickly consume this reducing agent.In these conditions Under, all cores are nanocrystalline to be formed at substantially the same time, and the time quantum that all syntrophism is identical subsequently, to cause being uniformly distributed of granularity, carries For monodispersed particle colony.
It will be understood by those skilled in the art that specific reductant is strong reductant or weak reductant depends on wherein making By the special reaction condition of this reducing agent.
Suitably reducing agent can include (illustratively unrestricted) chemical compound, such as tertiary phosphine, secondary phosphine, primary phosphine (example Such as diphenylphosphine, dicyclohexylphosphontetrafluoroborate and dioctyl phosphine);Amine (such as decyl amine and cetylamine);Hydrazine;Hydroxyphenyl compound is (such as Hydroquinone and phenol);Hydrogen;Hydride (such as sodium borohydride, lithium triethylborohydride, sodium hydride and lithium aluminium hydride reduction etc.); Metal (such as hydrargyrum and potassium);Borine (such as THF:BH3And B2H6);Aldehyde (such as benzaldehyde and butyraldehyde);Alcohol and mercaptan (such as second Alcohol and thioglycolic);Reproducibility halogenide (such as I-And I3 -);Alkene (such as oleic acid);Alkyne;With multifunctional reducing agent, i.e. Containing the single chemical species having more than a reducing agent part, each reducing agent part has identical or different reducing power, Such as three-(hydroxypropyl) phosphine and ethanolamine);Etc..
Generally, hydride (metal hydride of similar aluminum hydride, or metallic boron hydrides) and borine are used as strong reductant. Other reducing agent can serve as strong reductant or weak reductant, depends on concrete reaction condition.Such as, alkylphosphines can be The synthesis of CdSe is used as strong reductant, but will be weak reductant in the synthesis of ZnTe.Other reducing agent, such as alkene, chain Alkynes, amine etc. are usually weak reductant.
In certain embodiments, this weak reductant can be provided by the component of one of precursor.Such as, unsaturated carboxylic acid ester group Group, such as oleate, can be used as the weak reductant of embodiment disclosed herein.Fig. 2 describes a kind of reaction, wherein Zn2+Species With the tellurium precursor of mismatch, TOPTe reacts.In the first width figure on the left side, Zn2+Salt is saturated salt, the most there is not weak reductant. In the second width figure on right side, this salt includes undersaturated hydroxy-acid group, and it provides reducing agent.The rates of particles of two kinds of reactions is all Low, demonstrate the need for strong reductant to promote effective nucleation;But, use this salt unsaturated carboxylic acid bright as the reaction of weak reductant Show and result in faster nanocrystalline formation.
In certain embodiments, it is provided that weak reductant, sometimes can be with M (O to promote nanocrystalline growth2C-R’)nForm Carboxylate metal salt form provides this to contain metal precursor, and wherein M is this metal, and n is the 1-3 determined by this metallic atom oxidation state Integer, and R ' is C4-C100Unsaturated alkyl.In further embodiments, this salt can comprise this type of salt unsaturated carboxylic acid Counter ion counterionsl gegenions and other counter ion counterionsl gegenions one or more, such as halide ion.These provide and are not adding in reactant mixture The approach that facilitates of weak reductant is provided in the case of entering additional materials, and ensure that reactive chemistry metering can provide every precursor former At least one weak reductant molecule of son.But, in some systems, it must be determined that these act as weak reductant rather than serve as Strong reductant.
In further embodiments, solvent, as alkene, alkyne or amine solvent may act as weak reductant.Big when being desirable for For excess weak reductant time, this method is particularly useful.But, in some systems, must determine that this solvent acts as weak going back Former dose rather than serve as strong reductant.
Estimate to exist to use electro-chemical systems (K-A system) as the relevant specific advantages of this reducing agent, i.e. Negative electrode serves as electron source.By utilizing electrode as the source of reduction equivalent, easily calculate coulomb equivalent, and directly control them Transfer rate.The use of electrode can also control the physical positioning of reduction movable, and directly forms grain at electrode surface The electromotive force of subarray.Owing to this negative electrode will be placed in reative cell, material select to be preferably the most not with this precursor, part or be coordinated molten The material of agent reaction.Anode is generally positioned at outside reaction vessel, and therefore material selects unrestricted, it is possible to use any public affairs The anode material known.Exemplary cathode materials includes platinum, silver or carbon.Illustrative methods bag to negative electrode conveying reproducibility equivalent Include use in bipolar electrode (working electrode with to electrode) or three electrodes (working electrode, to electrode and reference electrode) structure constant Electric current or potentiostat.
It is applicable to the selection of reducing agent of specific combination of precursors in those skilled in the art's limit of power.
Electron transfer agent: oxidant
In embodiment disclosed herein, control particle formed the nucleation and growth stage can by use without The precursor of the mismatch that electron transfer agent adds or can not react in the case of lost electrons realizes.Use two kinds of single electronics Transfer agent, particularly one or more oxidants, enabling promote nucleation independently or grow to desirable degree, and improving this Being temporarily separated of two formation stages.This method makes it possible to independently control rates of particles and granularity, it is also possible to produces and has The particle of more narrow size distribution.
" by force " used herein or " higher " oxidant (oxidising agent) refer to the tool in the reaction using this oxidant Nucleation can be promoted under concrete conditions in the establishment of a specific crime or promote the oxidant causing particle to be formed." weak " or " more weak " oxidant refers in use Nucleation can not be promoted under actual conditions or promote to cause particle to be formed, but the oxygen of particle growth can be promoted under these conditions Agent.
It will be apparent to one skilled in the art that specific oxidant is strong oxidizer or weak oxidant depends on the circumstances, And depend on the special reaction condition using this oxidant.As required by nucleation, electron transfer particle in growth Surface (i.e. during growth stage) can more easily be carried out than on dissociated ion in the solution.To given system For (nanocrystalline formed reaction), this tested oxidant can be determined by and show as strong oxidizer or weak under these conditions Oxidant, thus be strong or weak by this tested oxidizer classification.By there is not any primary under suitable reaction condition Described specific precursor is made to connect with this tested oxidant in the case of nanocrystalline (add in initial action mixture is nanocrystalline) Touch and determine so that if it occur that nucleation can be observed, it may be determined that whether specific tested oxidant is strong oxidizer: generally, If nucleation is with notable speed, such as, send out with the speed than nucleation rate when there is not this tested oxidant up at least about 50% Raw, this tested oxidant promotes nucleation, and is considered strong oxidizer in this system.If the existence of this tested oxidant fails Significantly improve this nucleation rate, the then strong oxidizer during it is not this system.
Under becoming reaction condition at hull shape, receive in the primary (addition) with the same type formed by this precursor Described specific precursor and this tested oxidising agent is made, it may be determined that whether specific tested oxidant is weak oxygen in the presence of meter Jing Agent: generally, if nanocrystalline growth occurs with the speed improved, such as with faster than growth when there is not this tested oxidant The speed of rate high at least twice, this tested oxidant can be adapted for promoting the oxidant of nanocrystalline growth.It can be thus Suitably weak oxidant, as long as it is not used as strong oxidizer in described system.
If tested oxidant is suitable to promote nanocrystalline growth by above-mentioned test, but in the most described specific system Strong oxidizer, this tested oxidant can be weak oxidant.Owing to the relative intensity of oxidant depends on these factors, oxidant The classification of this function be the method that can be used for sorting out weak or strong oxidizer, it can be applied to any specific by routine test Tested oxidant.
Owing at the electron transfer generally particle surface in growth, (i.e. during growth stage) ratio exists in the solution Can more easily carry out on dissociated ion, as required by nucleation, nucleation needs the oxidant more higher than growth.Reaction Difference in terms of property makes it possible to by providing a small amount of strong electron transfer agent (it quickly consumes in nucleation process) and greater amount More weak electron transfer agent (it makes it possible to grow continuously) make two stages separate.The nanocrystalline size of this core can be by prison Wavelength of fluorescence during control growth stage is readily determined.
In the method provided in this article, the amount of the strong oxidizer that can use in being reacted by control regulates nucleation Degree.In certain embodiments, can be be enough to promote that the amount of required nucleation amount adds strong oxidizer.In preferred embodiment In, can with relative to precursor to be restored less than stoichiometric amount add strong oxidizer.In some such embodiments In, the amount of the strong oxidizer of addition can be the stoichiometric reaction the desired amount of less than about 1/10th of this nanocrystalline precursor, About 1/10th, less than about 2/10ths, less than about 3/10ths or less than about 4/10ths.In a particular embodiment, add The amount of strong oxidizer can be stoichiometric reaction the desired amount of about 1/10th.
Once strong oxidizer has exhausted (this can the most quickly occur), the extra shape of basic stopping Become little core.Thus, the amount limiting strong oxidizer makes it possible to separate nucleation stage with growth stage.This method makes it possible to Enough independent control rates of particles and granularity, and the particle with narrower distribution of sizes can also be manufactured potentially.Due to before this Body keeps mismatch, and the continued growth of nanocrystal needs to add the second electron transfer agent.Add weak oxidant and make particle growth, But further nucleation will not be promoted, the particle of uniform-dimension is thus provided.
Realize the control to reaction owing to the use of electron transfer agent (usually oxidant) can be passed through, be carefully controlled The speed (as in some nanocrystalline preparation method) unnecessarily of precursor is added in reaction.This nanocrystalline precursor is permissible The most disposable on-demand interpolation in the case of being not resulted in sub-cooled reactant mixture;In many embodiments of these methods Precursor need not be slowly added to prevent unwanted new karyomorphism from becoming.It practice, this precursor can close with optional weak oxidant Being mixed and heated to required reaction condition in suitable solvent, without there is nanocrystalline formation, (this can be by adding Strong oxdiative Agent causes).
In a preferred embodiment, this strong oxidizer can add under being enough to the running temperature that nucleation occurs.Temperature at this Under degree, it is believed that when adding strong oxidizer, quick explosion type nucleation occurs, the most quickly consume this oxidant.In these conditions Under, all cores are nanocrystalline to be formed at substantially the same time, and the time quantum that all syntrophism is identical subsequently, to cause being uniformly distributed of granularity, carries For monodispersed particle colony.
It will be understood by those skilled in the art that specific oxidant is strong oxidizer or weak oxidant depends on wherein making By the special reaction condition of this oxidant.Suitably oxidant can include (illustratively unrestricted) chemical compound, such as: Potassium nitrate;Hypochlorous acid, chlorous acid, chloric acid, the salt halogen compounds similar with other of perchloric acid;T-butyl hypochlorate;Halogen, as Fluorine, chlorine, bromine and iodine;Permanganate and compound;Ammonium ceric nitrate;Hexavalent chromium compound, such as chromic acid and dichromic acid, and three oxidations Chromium, pyridinium chlorochromateAnd chromate/dichromate compound (PCC);Peroxide compound;Tollens reagent;Sulfur aoxidizes Thing;Persulfuric acid;Oxygen;Ozone;Osmic acid.;Nitric acid;Nitrous oxide;Silver (I) compound;Copper (II) compound;Molybdenum (IV) is changed Compound;Ferrum (III) compound;Manganese (IV) compound;N-methylmorpholine-N-oxide and other N-oxide;Trimethylamine N- Oxide;3-chlorine benzylhydroperoxide and other peroxy acid;Or peracetic acid.
In certain embodiments, this weak oxidant can be provided by the component of one of precursor.
Estimate to exist to use electro-chemical systems (K-A system) as the relevant specific advantages of this oxidant, i.e. Negative electrode serves as electron source.By utilizing electrode as the source of oxidation equivalent, easily calculate coulomb equivalent, and directly control them Transfer rate.The use of electrode can also control the physical positioning of oxidation activity, and directly forms grain at electrode surface The electromotive force of subarray.Owing to this negative electrode will be placed in reative cell, material select to be preferably the most not with this precursor, part or be coordinated molten The material of agent reaction.Anode is generally positioned at outside reaction vessel, and therefore material selects unrestricted, it is possible to use any public affairs The anode material known.Exemplary cathode materials includes platinum, silver or carbon.Illustrative methods bag to negative electrode conveying oxidisability equivalent Include use in bipolar electrode (working electrode with to electrode) or three electrodes (working electrode, to electrode and reference electrode) structure constant Electric current or potentiostat.
Use strong and/or that the manufacture of weak electron transfer agent is nanocrystalline method
Provided herein is that the precursor using mismatch in the presence of the electron transfer agent added manufactures nanocrystalline side Method.In certain embodiments, use two kinds of different electron transfer agents individually to control the nucleation and growth stage that particle is formed.
In one aspect, provided herein is to manufacture the nanocrystalline or method of its colony, and the method includes: (a) provides Comprise the first precursor, the second precursor, first (the strongest) electron transfer agent (such as, be enough to be formed the nucleation of desired level Amount), second (the most weak) electron transfer agent (such as, be enough to be formed the amount of the nanocrystalline growth of desired level) and optional solvent The mixture of (such as ligand solvent);(b) this mixture heats sufficiently to cause temperature a period of time of nanocrystalline formation.
In certain embodiments, this nanocrystalline formation reacts generation in continuous flow reactor system.Real at other Executing in example, this nanocrystalline formation reacts generation in batch reactor system.
In certain embodiments, this first and second electron transfer agent is oxidant.In further embodiments, this first It is reducing agent with the second electron transfer agent.In certain embodiments, this first electron transfer agent is oxidant, and this second electronics Transfer agent is reducing agent, or on the contrary.
In certain embodiments, by this is strong and weak electron transfer agent is by this first precursor or the oxidation state of this second precursor Change into middle condition.In further embodiments, strong by this and weak electron transfer agent mate this first precursor with this before second The oxidation state of body.
In certain embodiments, the method farther includes step (c), cools down this mixture and nanocrystalline enters one to stop One-step growth or dilute this mixture to stop nanocrystalline further growth.In certain embodiments, the method farther includes Separate the nanocrystalline step being obtained by this method.In further embodiments, the method further include at separation or regardless of To the step of this nanocrystalline interpolation shell in the case of from.
The component (the i.e. first precursor, the second precursor, the first reducing agent and the second reducing agent) of this reactant mixture can be appointed Be selected in solvent or solvent mixture and add in any order, and can add this mixture one or more components it Before or add this mixture one or more components during heat this reaction.This precursor usually with suitable solvent or Solvent mixture mixing is to form the solution for method disclosed herein.Solvent for this first precursor and the second precursor can With identical or different.
In certain embodiments, formation comprises the first precursor, the second precursor, the first electron transfer agent, the second electron transfer Agent and the mixture of optional solvent, be heated to being adequate to bring about temperature a period of time of nanocrystalline formation subsequently by this mixture.
In common embodiment, as further described herein, under the reaction condition used, this is first years old Electron transfer agent is strong electron transfer agent, and this second electron transfer agent is weak electron transfer agent.
In further embodiments, heating comprises the first precursor, the second precursor, weak electron transfer agent and optional solvent Mixture;Electron transfer agent is be enough to promote that nucleation adds to the amount of desirable degree by force, and to be adequate to bring about nanocrystalline formation Temperature and time heats this reactant mixture.
In a further embodiment, heating comprises the mixed of the first precursor, weak electron transfer agent and the first optional solvent Compound;Optionally the second precursor in the second solvent (it can be identical or different with the first solvent) is joined the mixing of heating In thing;Subsequently be enough to promote that the amount of nucleation adds strong electron transfer agent, and hold being adequate to bring about at a temperature of nanocrystalline formation Continuous heating a period of time.
In further embodiments, be enough to promote nucleation crystal formation at a temperature of heating comprise the first precursor, second Precursor, strong electron transfer agent and the mixture of optional solvent;With this mixture backward adding weak electron transfer agent to promote Particle growth, and it is being adequate to bring about further this reactant mixture a period of time of heating at a temperature of nanocrystalline formation.
In yet other embodiments, the mixture comprising the first precursor, the second precursor and optional solvent is heated to Be enough to occur the temperature of nucleation in the presence of strong electron transfer agent, the mixture with backward heating is simultaneously introduced strong electron transfer Agent and weak electron transfer agent, be then adequate to bring about continuation heating a period of time at a temperature of nanocrystalline formation.
In a preferred embodiment, this first electron transfer agent and the second electron transfer agent are different.Particularly preferably Embodiment in, as further described herein, this first electron transfer agent is strong oxidizer/reducing agent, and this Two-electron shift agent is weak oxidant/reducing agent.This first electron transfer agent and this second electron transfer agent can independently be Chemical oxidizing agent/reducing agent or negative electrode.
In yet another aspect, it is provided that manufacture the nanocrystalline or method of its colony;The method includes: provides and comprises the first precursor With the mixture of the second precursor, wherein this first precursor and this second precursor have the oxidation state of mismatch;Needed for being enough to produce The amount of nucleation amount adds the strong electron transfer agent less than stoichiometry in this mixture;Optionally mixture is heated together with Nucleation amount needed for generation;Be enough to the amount producing required nanocrystalline increment add in this mixture weak electron transfer Agent;And optionally heat this mixture and be enough to produce a period of time of required nanocrystalline increment.
In certain embodiments, this is strong and weak electron transfer agent is oxidant.In further embodiments, this strong and light current Sub-transfer agent is reducing agent.In certain embodiments, this strong electron transfer agent is oxidant and this strong electron transfer agent is reduction Agent, or on the contrary.
In certain embodiments, this strong electron transfer agent is provided being enough to be formed the amount of required nucleation level.Real at some Executing in example, needed for being enough to be formed, the amount of nanocrystalline level of growth provides this weak electron transfer agent.
In certain embodiments, by this is strong and weak electron transfer agent is by this first precursor or the oxidation state of this second precursor Change into middle condition.In further embodiments, strong by this and weak electron transfer agent mates this first precursor and this is before second The oxidation state of body.
In yet another aspect, it is provided that manufacture that core is nanocrystalline or the method for its colony;The method includes:
A () provides the first mixture comprising the first precursor, the second precursor and optional solvent;B () is at strong electron transfer In the presence of agent, this first mixture is heated to sufficiently high to promote the temperature of nucleation;C () adds strong electron transfer agent to provide Second mixture, wherein be enough to promote that the amount of nucleation adds this strong electron transfer agent;(d) this second mixture is heated to It is adequate to bring about temperature a period of time of nanocrystalline formation.
In certain embodiments, the method farther includes step (e), cools down this second mixture to stop this nanocrystalline Further growth, or dilute this reactant mixture to stop further growth.The method optionally farther includes from reaction mixed Compound separates this nanocrystalline step.The method the most optionally include to nanocrystalline upper from the core of this reactant mixture or to point From the step of the nanocrystalline upper interpolation shell of core.
In a preferred embodiment, during adding this strong electron transfer agent, this first mixture is maintained at enough High to promote at a temperature of nucleation.
In a preferred embodiment, the method farther includes to add weak electron transfer agent, wherein turns at addition forceful electric power Move before agent, add this weak electron transfer agent simultaneously or after.
In certain embodiments, this first mixture comprises weak electron transfer agent further.In some such embodiments In, provide this weak electron transfer agent by solvent or by the unsaturated group being present on one of precursor.
In further embodiments, step (c) adds weak before or while further including at the strong electron transfer agent of addition Electron transfer agent.In some such embodiments, add the transfer of this weak electron discretely simultaneously and with this strong electron transfer agent Agent.
In a further embodiment, step (c) adds light current after further including at this strong electron transfer agent of addition Sub-transfer agent.In some such embodiments, after being enough to a period of time making nucleation crystal formation, add this weak electron turn Move agent.In further embodiments, after strong electron transfer agent but before nucleation stage completes, add the transfer of this weak electron Agent.
In certain embodiments, this is strong and weak electron transfer agent is oxidant.In further embodiments, this strong and light current Sub-transfer agent is reducing agent.In certain embodiments, this strong electron transfer agent is oxidant, and this strong electron transfer agent is reduction Agent, or on the contrary.
In certain embodiments, by this is strong and weak electron transfer agent is by this first precursor or the oxidation state of this second precursor Change into middle condition.In further embodiments, strong by this and weak electron transfer agent mates this first precursor and this is before second The oxidation state of body.
In another further aspect, provided herein is to manufacture the nanocrystalline or method of its colony, including: (a) provides mixture, It comprises: (i) the first precursor;(ii) the second precursor, wherein this first precursor and this second precursor have the oxidation state of mismatch; (iii) strong electron transfer agent;(iv) it is different from the weak electron transfer agent of this strong electron transfer agent;The most optional one or many Plant solvent;(b) this mixture is heated to being adequate to bring about temperature a period of time of nanocrystalline formation.
Further, can be suitable to the substantial amounts of mismatch maintaining growth after nucleation has occurred and that to together with make With a small amount of " coupling " precursor.Should " coupling " precursor can immediate response, thus in the situation that there is not strong electron transfer agent Lower initiation nucleation.Once " coupling " precursor exhausts, and in reactant mixture, the existence of weak electron transfer agent can be used for maintaining growth, And not there is extra nucleation.Such as, a small amount of reactive higher zinc precursor, as diethyl zinc can be with R3P=Se together, with More substantial Zn2+Precursor is used in combination.This Zn0Precursor, such as diethyl zinc, can use the desired amount of to cause with substantial amount Nucleation.Once it has exhausted (this can quickly occur at a temperature of appropriate reaction), this Zn2+Precursor is with to required extent of growth Say that enough amounts exist, in order in the presence of weak electron transfer agent, produce required nanocrystalline size.Can be by monitoring fluorescence Wavelength is readily determined this nanocrystalline size during this growth stage.
In one aspect, provided herein is to manufacture the nanocrystalline or method of its colony, and the method includes: (a) provides Comprising the first precursor, the second precursor, the 3rd precursor and the mixture of optional solvent, wherein this first and second precursor has mistake The oxidation state joined, and wherein the 3rd precursor has and is matched with this first precursor or the oxidation state of the second precursor;(b) this is mixed Compound is heated to being adequate to bring about temperature a period of time of nanocrystalline formation.
In certain embodiments, this mixture comprises weak electron transfer agent further.In some such embodiments, Before adding the 3rd precursor, add this weak reductant simultaneously or after.
In certain embodiments, this weak electron transfer agent is oxidant.In further embodiments, this weak electron transfer agent It it is reducing agent.
In certain embodiments, this nanocrystalline formation reacts generation in continuous flow reactor system.Real at other Executing in example, this nanocrystalline formation reacts generation in batch reactor system.
In yet another aspect, provided herein is to manufacture that core is nanocrystalline or the method for its colony, and the method includes: (a) Thering is provided the first mixture comprising the first precursor, the second precursor and optional solvent, wherein this first and second precursor has mistake The oxidation state joined;B this first mixture is heated to sufficiently high to promote the temperature of nucleation in the presence of the 3rd precursor by (), its In the 3rd precursor have and this first precursor or the oxidation state of this second precursor match;C () is be enough to promote that the amount of nucleation adds Enter the 3rd precursor;(d) this second mixture is heated to being adequate to bring about temperature a period of time of nanocrystalline formation.
In some embodiments of methods described herein, this strong electron transfer agent is chemical reducing agent, selected from tertiary phosphine;Secondary Phosphine;Primary phosphine;Amine;Hydrazine;Hydroxyphenyl compound;Hydrogen;Hydride;Metal;Borine;Aldehyde;Alcohol;Mercaptan;Reproducibility halogenide;With many officials Can reducing agent.
In some embodiments of methods described herein, this strong electron transfer agent is chemical oxidizing agent, such as: potassium nitrate;Secondary Chloric acid, chlorous acid, chloric acid, the salt halogen compounds similar with other of perchloric acid;T-butyl hypochlorate;Halogen, such as fluorine, chlorine, bromine And iodine;Permanganate and compound;Ammonium ceric nitrate;Hexavalent chromium compound, such as chromic acid and dichromic acid, and chromic acid, chlorine chromium Acid pyridineAnd chromate/dichromate compound (PCC);Peroxide compound;Tollens reagent;Oxysulfide;Over cure Acid;Oxygen;Ozone;Osmic acid.;Nitric acid;Nitrous oxide;Silver (I) compound;Copper (II) compound;Molybdenum (IV) compound;Ferrum (III) compound;Manganese (IV) compound;N-methylmorpholine-N-oxide and other N-oxide;Trimethylamine-N-oxide; 3-chlorine benzylhydroperoxide and other peroxy acid;Or peracetic acid.
In the other embodiments of methods described herein, this strong oxidizer/reducing agent is negative electrode.In some such enforcement In example, this negative electrode is made up of the material selected from platinum, silver and carbon.
In the Common examples of this method, to add this strong oxidizer/reducing agent less than stoichiometry.At some this In the embodiment of sample, the amount of the strong oxidizer/reducing agent of addition is stoichiometric reaction the desired amount of less than about 1/10th, about 1/10th, less than about 2/10ths, less than about 3/10ths or less than about 4/10ths.In a preferred embodiment, add The amount of strong oxidizer/reducing agent less than stoichiometric reaction the desired amount of about 1/10th.In a preferred embodiment, at foot This strong oxidizer/reducing agent is added under running temperature with generation nucleation.
In some embodiment of this method, this reactant mixture is heated to being enough to promote the temperature of nucleation, and keeps At a constant temperature, this Strong oxdiative/reducing agent it is simultaneously introduced.
In some embodiments of methods described herein, this weak electron transfer agent is chemical reducing agent, and it is selected from: tertiary phosphine; Secondary phosphine;Primary phosphine;Amine;Hydrazine;Hydroxyphenyl compound;Hydrogen;Hydride;Metal;Borine;Aldehyde;Alcohol;Mercaptan;Reproducibility halogenide;Many Sense reducing agent.
In some embodiments of methods described herein, this weak electron transfer agent is chemical oxidizing agent, such as: potassium nitrate;Secondary Chloric acid, chlorous acid, chloric acid, the salt halogen compounds similar with other of perchloric acid;T-butyl hypochlorate;Halogen, such as fluorine, chlorine, bromine And iodine;Permanganate and compound;Ammonium ceric nitrate;Hexavalent chromium compound, such as chromic acid and dichromic acid, and chromic acid, chlorine chromium Acid pyridineAnd chromate/dichromate compound (PCC);Peroxide compound;Tollens reagent;Oxysulfide;Over cure Acid;Oxygen;Ozone;Osmic acid.;Nitric acid;Nitrous oxide;Silver (I) compound;Copper (II) compound;Molybdenum (IV) compound;Ferrum (III) compound;Manganese (IV) compound;N-methylmorpholine-N-oxide and other N-oxide;Trimethylamine-N-oxide; 3-chlorine benzylhydroperoxide and other peroxy acid;Or peracetic acid.
In the other embodiments of methods described herein, this weak oxidant/reducing agent is negative electrode.In some such enforcement In example, this negative electrode is made up of the material selected from platinum, silver and carbon.
In some embodiments of method provided herein, this solvent selected from hydro carbons, amine, alkylphosphines, alkylphosphine oxide, Carboxylic acid, ether, furan, phosphonic acids, pyridine and mixture thereof.In some such embodiments, this solvent comprises solvent mixture.? In common embodiment, this reactant mixture comprises at least one solvent, preferably at least a kind of ligand solvent.
In the particular embodiment, use comprises alkylphosphines and alkylphosphine oxide, such as the solvent mixture of TOP/TOPO. In further embodiments, use and comprise amine, particularly secondary amine and alkylphosphines or the solvent mixture of alkylphosphine oxide.Example As, dioctylamine can be used in combination with TBP, TOP or TOPO.The example of concrete solvent includes such as TOPO, TOP, tributyl Phosphine, decyl amine, dioctylamine, oleyl amine, octadecane, squalane, oleic acid, stearic acid, tetradecylphosphonic acid and mixture thereof.
In certain embodiments, this first precursor comprises metallic atom, and this second precursor does not contains metallic atom.Concrete In embodiment, when in the reactant mixture in heating, this first precursor can become contribution metal cation to karyomorphism.At some In such embodiment, this first precursor can be the salt of Cd or Zn.In the particular embodiment, this first precursor can be The halogenide of Cd, Zn, In or Ga, acetate, carboxylate, phosphonate or oxide salt.
In certain embodiments, when it is in the reactant mixture of heating, this second precursor can be contributed for karyomorphism The uncharged non-metallic atom become.In the particular embodiment, this second precursor can be R3The group of P=X form, wherein X It is S, Se or Te, and each R independently be H or C1-C100Alkyl.In the particular embodiment, this second precursor is three-(positive fourth Base phosphine) selenides (TBP=Se), three-(n-octyl phosphine) selenides (TOP=Se), (butyl phosphine) sulfide (TBP=S), three-(just Octyl group phosphine) sulfide (TOP=S), (butyl phosphine) tellurides (TBP=Te) or three-(n-octyl phosphine) tellurides (TOP=Te).
In common embodiment, in addition to this first precursor and the second precursor, there is not other precursor.
In certain embodiments, in addition to this first precursor and the second precursor, there is the 3rd precursor.In some such realities Executing in example, the 3rd precursor provides to be had and this first precursor or the reactive species of the oxidation state of the second precursor match.One In a little such embodiments, the 3rd precursor provides neutral metal species.Such as, the 3rd precursor can be to provide neutral metal Species, such as Zn0Or Cd0Metal diaikyl precursor (such as Et2Zn or Me2Cd).In further embodiments, before the 3rd Body can become contribute charged non-metallic atom to karyomorphism.Such as, the 3rd precursor can provide S2-Or Se2-
As described herein, this nanocrystal can be by any suitable known metal of semiconductor nano that formed with non- Metallic atom is made.In certain embodiments, this core can comprise CdSe, CdS, CdTe, InP, InAs, ZnS, ZnSe, ZnTe, GaP or its mixture.
Further, provided herein is that the core manufactured by one of method specifically described herein is nanocrystalline.
In the most described method, heating steps generally is being adequate to bring about at a temperature of temporary transient discrete uniform nucleation entering OK, this results in single nanocrystalline single dispersing colony.Generally, this heating steps is in the range of about 150-350 DEG C, more preferably Carry out at a temperature in the range of about 220-350 DEG C.Additionally, mixing and heating steps can be in emptyings and with such as the indifferent gas of nitrogen Body is filled and/or carries out in the container of purging.This filling can be regularly, or when can purge appointment the most continuously Between.In certain embodiments, this blend step can include cooling step, example before being exposed to this first or second reducing agent As, it is cooled to the temperature in the range of about 50 to 150 DEG C.
It being understood that above-mentioned scope is exemplary only, and be not meant to limit by any way, due to actual temperature Scope can change with the relative stability of reducing agent, precursor, part and solvent.Higher or lower temperature is to specific reaction For can be suitable.It is adapted to provide for the time of nanoparticle with the determination of temperature conditions in this area using normal experiment In the limit of power of technical staff.
In the case of getting rid of oxygen and moisture, advantageously carry out nanocrystalline formation reaction specifically described herein.Real at some Execute in example, this reaction in an inert atmosphere, as carried out in glove box.Solvent and reagent also generally strictly purify to remove moisture removal With oxygen and other impurity, and generally it is exposed to the method and apparatus of moisture and/or oxygen and processes and turn with being designed as reducing as far as possible Move.Additionally, this mixing and heating steps can be in emptyings and with as the noble gas of nitrogen is filled and/or enters in the container of purging OK.This filling can be regularly, or can purge the appointment time the most continuously.If solvent and reagent realize required shell Forming reaction and do not introduce strong reductant in reaction, their purity is enough.
Often including amine for these solvents reacted, exemplary such as hexadecylamine, dioctylamine is that another closes Suitable example.Amine solvent is difficult to fully purify the system for the sensitiveest, as reacted for ZnTe nanocrystal (because should Reactive component and product show the highest susceptiveness to moisture and air).When the most under an inert atmosphere with purification When solvent and reagent carry out nanocrystalline preparation, carry out the most special preventive measure with step to purify for preparing ZnTe Nanocrystalline amine solvent.Amine as these solvents reacted is placed on emptying repeatedly and immediately with the filling of anhydrous inert atmosphere In flask.Anhydrous Na OH dried at more than 100 DEG C the most in a vacuum or KOH is added with in this amine solvent backward, outstanding Supernatant liquid stirs at least 8 hours.This amine filters to remove solid under an inert atmosphere, distills the most under an inert atmosphere, and lazy Property atmosphere under store.
Synthesis ZnTe is particularly preferred example for realizing method disclosed herein, because Zn2+With Te0The most extremely difficult molten In liquid, free reduction, causes extremely difficult nucleation in the case of being added without strong reductant.In the situation that there is not strong electron transfer agent Under, at ZnCl2With Bu3The mixture of P=Te is not observed nucleation (being i.e. formed without particle).This be due to tellurium used with Mismatch between the oxidation state of zinc precursor: zinc chloride is+2 oxidation state under the reaction conditions, but tellurium precursor Bu3P=Te is anti-at this Te is provided under the conditions of Ying0.It is believed that uncharged tellurium species can not easily with Zn+2Reaction, reaction to be occurred requires Te0 It is reduced to Te2-, or by Zn+2It is reduced to Zn0.Add strong electron transfer agent (i.e. reducing agent) likely via by Te0It is reduced to Te2- Make it possible to react.The method provided in example 1 uses lithium triethylborohydride (LiEt3BH) nucleation is promoted also as strong Former dose.Oleic acid is used as weak reductant in the method, causes at LiEt3BH exhaust after can continued growth, even when with the lowest LiEt is added in stoichiometric levels3During BH the most such.
In addition to the control to granularity and productivity improved, the further benefit of the inventive method comes from disclosed herein The improvement of the intrinsic scale of embodiment and manufacturability.Most popular chalcogenide zinc particles synthesis example uses diethyl zinc (produce the Zn of a large amount of gas0Source), add changeableness and limit manufacturability.When using zinc salt, their resistance to reduction Property usually require that use produce gas strong reductant.This method can be to use this type of reducing agent less than stoichiometry.Under In the example in face, the addition of strong reductant is stoichiometric reaction the desired amount of 1/10th.Additionally, as it has been described above, the party Method makes nanocrystalline synthesis the most reliable because its less depend on similar nanocrystalline precursor adding rate situation (because of Controlled reaction rate is provided) for this reducing agent.
Use nanocrystalline method provided herein
Nanocrystalline can be used for of core manufactured by methods provided herein utilizes condition well known by persons skilled in the art Formation core shell is nanocrystalline.
Additionally, by these methods manufacture nanocrystalline can be as known in the art by existing in nanocrystal surface The modification of part come further modified.Such as, the part in nanocrystal surface can be exchanged for other part to receive to this Rice is brilliant introduces new character, such as water solublity.Manufacture that to have the nanocrystalline method of water soluble ligand coating known in the art 's.Such as, Adams et al. provides by manufacturing water-soluble to the hydrophobic nano crystalline substance surface amphipathic polymerization material coating of applying The method that property is nanocrystalline, United States Patent (USP) No. 6,649,138.The method is brilliant from hydrophobic nano, as have hydrophobic ligand (as Trialkyl phosphine, trialkyl phosphine oxides, alkylamine or alkyl phosphoric acid) the described herein nanocrystalline beginning of coating.Be added to by The outer layer of multiple amphipathic dispersant molecule compositions comprising at least two water repellent region and at least two hydrophilic region.? In some embodiments, this amphipathic nature polyalcohol comprises acrylic or methacrylic acid polymer, and this polymer has some with dredging Aqueous amido, has a monoalkylamine of at least 4-12 carbon such as each alkyl or dialkylamine is converted into the acrylic of amide Group;And there are some free hydroxy-acid groups to improve water solublity.These and other being applicable to this purposes is the most amphipathic Dispersant is described in the 14-18 hurdle of the patent of Adams, and its content is incorporated herein by this reference.
The most in one aspect, disclosed embodiment provides and has amphipathic dispersant coating as described in Adams et al. As herein described nanocrystalline.This is nanocrystalline thus has water solublity, makes them be applicable to multiple known use such as quantum dot Nanocrystalline method.The method that is nanocrystalline and that manufacture them dissolved is disclosed in herein.
Cover with paint, lacquer, colour wash, etc. other nanocrystalline method and be described in United States Patent (USP) 6,955,855 and United States Patent (USP) No. by Naasani et al. In 7,198,847.These methods include being coated with this nanometer with little water soluble ligand, such as imidazo-containing compounds (such as dipeptides) Brilliant.Suitable imidazo-containing compounds is described on the 7th hurdle of ' 855 Naasani patent.
Term " imidazo-containing compounds " refers to that for present specification and claims having at least one can be used for key Alloy belongs to, such as zinc or other metal cation, or the imidazole group (such as imidazole ring) of the substrate containing this cationoid point Son.In the part paid close attention to, preferably at least one imidazole fragment is at the end section relative to this molecular structure.Generally, imidazoles Ring nitrogen is commonly used as ligand so that bond wire ion effectively, such as zinc or cadmium.In one embodiment, this contains imidazoles Compound comprises aminoacid, or the two or more aminoacid (such as this area is referred to as " peptidyl " or " oligopeptide ") linked together, It can include but not limited to histidine, carnosine, anserine, baleen (baleine), homocarnosine, 1-Methyl histidine, 3-methyl Histidine, imidazoles lysine, the ornithine (such as 5-Methylimidazole. ketone) containing imidazoles, alanine (such as (β)-(2-containing imidazoles Imidazole radicals)-L (α) alanine), β-alanylhistamine (carcinine), histamine etc..Aminoacid containing imidazoles can use ability (see for example Stankova et al., 1999, J. Peptide Sci. 5:392-398, it is open in method synthesis known to territory Content is incorporated herein by this reference).
Term " aminoacid " as known in the art and refers to containing at least for present specification and claims One amino and the compound of at least one carboxyl.As known in the art, amino may be located at the position adjacent with carboxyl Put.As known in the art, amino may be located on the position adjacent with carboxyl, or may reside in along amino molecule Any position.In addition at least one imidazole fragment, this aminoacid can comprise one or more additional reaction further Property functional group (such as amino, mercaptan, carboxyl, carboxylic acid amides etc.).This aminoacid can be D(dextrorotation) configuration or L(left-handed) structure The naturally occurring aminoacid of type, synthesizing amino acid, modified amino acid, amino acid derivativges, amino acid precursor.Such as this area Know that the example of derivant can include but not limited to N-methylated derivative, amide or ester, and wherein has aminoacid like that The composition of function (such as gives water solublity, abundant in the range of the pH of about pH 6 to about pH 10 as coating as herein described Buffering, the sense of coating as raising fluorescence intensity, and there is one or more binding molecule probe effectively of can be used for Reactive functional).The aminoacid of aforementioned amino acid class can use in a preferred embodiment, and preferably aminoacid can be single It is solely used in the compositions of disclosed embodiment, and gets rid of the aminoacid outside preferred amino acid.Histidine is particularly preferred For being coated with the imidazo-containing compounds of this functionalization, fluorescence nano.
Disclosed herein nanocrystalline on part can also cross-link improve the stability of this nanocrystalline compositions and change Its characteristic kind.Disclosed herein nanocrystalline on surface ligand coating can with Naasani describe method, use various crosslinking Agent cross-links.Preferred cross-linking agent in disclosed embodiment includes those that Naasani et al. describes, including three (methylols) Phosphine (THP) and three (methylol) phosphino--propionic ester (THPP).The nanocrystalline of water soluble ligand coating with crosslinking is thus this The disclosed another kind of embodiment of literary composition.
The nanocrystalline method that can be used for tracking molecule known in the art manufactured by these methods.Such as, they can To be connected on plurality of target molecule by known method.Generally, they are connected on affinity molecule or for changing further. This type of changes further and can be used for introducing selected target interested (or goods) molecule in nanocrystal surface, such as antibody Or other concrete affinity molecule.The method that this type of affinity molecule is connected on fluorescence carrier is known in the art, and can To be easily adjusted for this method: see for example United States Patent (USP) No. 6,423,551, it also describes and can be used for nanometer Brilliant surface is connected to target molecule and is connected to some bi-functional reagents of nanocrystal surface.These methods can be additionally used in nanometer Introducing a large amount of or one layer of functionalized molecule on brilliant surface, wherein this functionalized molecule can provide new surface to this nanoparticle Character, such as water dispersible.In certain embodiments, it is provided that can be used for detecting required target compound, cell or organelle Modified to connect the nanocrystalline of affinity molecule.
Affine point of the nanocrystalline method that may be coupled to for following the trail of, identify or position molecule interested of this modification On son, described affinity molecule is bonded on the molecule that this is interested, it was demonstrated that molecule interested exists and it is distributed or location Wherein.This is nanocrystalline can be additionally used in the distribution of the binding tests molecule to show this affinity molecule and admit.Once it is determined that target Compound, selecting in the range of the general ability of those skilled in the art of suitable affinity molecule;Such as, conventional method can be used In manufacturing or identifying the antibody being suitable to be bonded on target molecule interested specifically.This antibody thus may be coupled to herein Disclosed in nanocrystalline on, use this nanocrystalline as fluorescent labeling, its be subsequently used in identification the existence of target compound, position Put or mobile.In certain embodiments, it is provided that by by can the suitable affinity molecule that is bonded on target molecule of selectivity It is connected on nanocrystalline, and makes to be connected to the nanocrystalline of affinity molecule and contact with target molecule to identify or follow the trail of target molecule Method.Follow the trail of or detection can realize by using the conventional method following the trail of fluorescent-labeled portions, as used fluorescence imaging system System, microscope or photographing unit.
In certain embodiments, it is provided that functionalization specifically described herein is nanocrystalline.This is nanocrystalline may be coupled to affine point On son, this affinity molecule is to select to be bonded to specifically on target molecule interested.It is connected on this affinity molecule Nanocrystalline optionally it is bonded on target molecule interested form fluorescently-labeled complex.Target molecule interested includes Protein, enzyme, receptor, nucleic acid, hormone and the cell surface antigen feature of concrete cell type.
Specifically described herein or that quote many technology and method are that those skilled in the art fully understand and typically by routine Method application.In appropriate circumstances, unless otherwise specified, the code specified generally according to manufacturer and/or parameter perform Including the program using commercial reagent box and reagent.
The discussion of conventional method presented herein is for illustration purposes only.Other alternative approach and embodiment are to reading originally It is apparent from for those skilled in the art of invention.
Unless clearly stated separately, the one group of project connected by conjunction "or" should not be construed as requiring phase in this group Repel mutually, but be interpreted as "and/or".Although the item of embodiment disclosed herein can be described or claimed in the singular Mesh, key element or component, be limited to odd number unless specifically stated, and plural number is also contemplated in the range of it.
All patents referred to herein, patent application, patent disclosure, journal of writings and other list of references all draw through this In full it is expressly incorporated herein.
As use in claims and description, word " comprise " (and any type of comprise, as " comprise " and " comprises " and " comprised "), " having " (and any type of have, such as " have " and " has "), " including " (and any type of include, such as " includes " and " include ") or " containing " (and any shape Containing of formula, such as " contains " and " contain ") be to include end points or open end points, and be not excluded for adding, do not arrange The key element lifted or method step.
There is provided the following example to guide as about manufacture and the further of use the methods disclosed herein, and it is not It is interpreted as the restriction of the various embodiments to these methods.
Example 1
Form ZnTe core nanocrystalline
Unless otherwise specified, all reagent used are anhydrous, and all operations is carried out under an inert atmosphere.By chlorine Change 250 milliliters of round-bottomed flasks that zinc (685 milligrams, 5 mMs) is weighed to have two 14/20 joints and ground glass plug In.Add dioctylamine (35 milliliters) and oleic acid (1.6 milliliters, 5 mMs), and magnetic stirring bar is installed on flask.By glass Glass plug fat liquoring is also closed, and a glass connector rubber septum stoppers, installation adapter and stainless steel hot on a joint Galvanic couple, it is connected on the temperature controller of 180 watts of heating mantles of a regulation.This flask is placed in heating mantle, and will live Tether and receive on flowing nitrogen source and open it.Temperature controller is set, in order to flask is heated to 115 DEG C and in this temperature Under keep under mild agitation this temperature until zinc salt dissolve.Subsequently this flask is evacuated and refills nitrogen three times.
This temperature is then increased to 230 DEG C, now adds the 1M in the tributylphosphine of 15 milliliters through partition by syringe Tellurium solution, slightly cools down flask contents.When temperature returns to 220 DEG C, rapidly join the oxolane of 1 milliliter through syringe In 1M lithium triethylborohydride solution.This temperature improves to 240 DEG C and keeps 15 seconds to 30 minutes, until reaching required grain Degree, the most quickly cools down.

Claims (33)

1. the method manufacturing nanocrystalline colony, including:
Thering is provided mixture, described mixture comprises:
First precursor;
Second precursor, wherein said first precursor and described second precursor have the oxidation state of mismatch;
Strong electron transfer agent, presents in an amount at least sufficient to produce required nucleation amount;With
It is different from the weak electron transfer agent of described strong electron transfer agent;And
It is heated to described mixture being adequate to bring about temperature a period of time that nanocrystalline colony is formed.
The method of the nanocrystalline colony of manufacture the most according to claim 1, the most nanocrystalline formation reacts at batch reactor System occurs.
The method of the nanocrystalline colony of manufacture the most according to claim 1, the most nanocrystalline formation reacts anti-in flowing continuously Answer in device system and occur.
The method of the nanocrystalline colony of manufacture the most according to claim 1, wherein by described strong electron transfer agent and described The described oxidation state of described first precursor or described second precursor is changed into middle condition by weak electron transfer agent.
The method of the nanocrystalline colony of manufacture the most according to claim 1, wherein by described strong electron transfer agent and described Weak electron transfer agent mates described first precursor and the described oxidation state of described second precursor.
The method of the nanocrystalline colony of manufacture the most according to claim 1, wherein said strong electron transfer agent and described light current Sub-transfer agent is reducing agent.
The method of the nanocrystalline colony of manufacture the most according to claim 1, wherein said strong electron transfer agent and described light current Sub-transfer agent is oxidant.
The method of the nanocrystalline colony of manufacture the most according to claim 1, heats described in one or more the most before combination Precursor and electron transfer agent.
The method of the nanocrystalline colony of manufacture the most according to claim 6, wherein said reducing agent is selected from: tertiary phosphine, secondary phosphine, primary Phosphine, amine, hydrazine, hydroxyphenyl compound, hydrogen, hydride, metal, borine, aldehyde, alcohol, mercaptan, reproducibility halogenide, multifunctional reduction Agent and mixture thereof.
The method of the nanocrystalline colony of manufacture the most according to claim 7, wherein said oxidant is selected from potassium nitrate;Secondary chlorine Hydrochlorate, chlorite, chlorate, perchlorate;T-butyl hypochlorate;Halogen;Permanganate;Ammonium ceric nitrate;Cr VI chemical combination Thing;Peroxide compound;Tollens reagent;Oxysulfide;Persulfuric acid;Oxygen;Ozone;Osmic acid.;Nitric acid;Nitrous oxide; Silver (I) compound;Copper (II) compound;Molybdenum (IV) compound;Ferrum (III) compound;Manganese (IV) compound;N-methylmorpholine- N-oxide;Trimethylamine-N-oxide;3-chlorine benzylhydroperoxide, peroxy acid;And mixture.
The method of the 11. nanocrystalline colonies of manufacture according to claim 1, wherein said strong electron transfer agent is negative electrode.
The method of the 12. nanocrystalline colonies of manufacture according to claim 1, wherein said weak electron transfer agent is negative electrode.
The method of the 13. nanocrystalline colonies of manufacture according to claim 1, farther includes solvent at described mixture.
The method of the 14. nanocrystalline colonies of manufacture according to claim 13, wherein said solvent is selected from hydro carbons, amine, alkyl Phosphine, alkylphosphine oxide, carboxylic acid, ether, furan, phosphonic acids, pyridine and mixture thereof.
The method of the 15. nanocrystalline colonies of manufacture according to claim 13, wherein said solvent is ligand solvent.
The method of the 16. nanocrystalline colonies of manufacture according to claim 1, farther includes to cool down described mixture.
The method of the 17. nanocrystalline colonies of manufacture according to claim 1, wherein said first precursor select free Cd, Zn, Ga, In, Al, Pb, Ge, Si, Hg, Mg, Ca, Sr, Ba and the salt of mixture composition thereof.
The method of the 18. nanocrystalline colonies of manufacture according to claim 1, wherein said second precursor is R3P=X, wherein X is S, Se or Te, and each R independently be H or C1-C24Alkyl.
The method of the 19. nanocrystalline colonies of manufacture according to claim 1, wherein said second precursor is dissolved in alkyl S, Se or Te in phosphine, alkene or amine.
The method of the 20. nanocrystalline colonies of manufacture according to claim 1, wherein said second precursor is dissolved in tributylphosphine Or in tri octyl phosphine.
The method of the 21. nanocrystalline colonies of manufacture according to claim 1, farther includes:
Optionally separate described nanocrystalline colony;With
Shell is applied to each described nanocrystalline colony.
The method of the 22. nanocrystalline colonies of manufacture according to claim 21, wherein said shell material selected from ZnS, ZnSe, ZnTe、CdS、CdSe、CdTe、HgS、HgSe、HgTe、MgS、MgSe、MgTe、CaS、CaSe、CaTe、SrS、SrSe、SrTe、 BaS, BaSe, BaTe and mixture thereof.
The method of the 23. nanocrystalline colonies of manufacture according to claim 21, wherein said shell material selected from GaN, GaP, GaAs, GaSb, InP, InAs, InSb, AlS, AlP, AlSb, PbS, PbSe, Ge, Si and mixture thereof.
The method of the 24. nanocrystalline colonies of manufacture according to claim 1, wherein said first precursor or described second precursor May act as described weak electron transfer agent.
The method of the 25. nanocrystalline colonies of manufacture according to claim 1, wherein to be enough to be used in required nanocrystalline growth Amount provides described weak electron transfer agent.
The method of the 26. nanocrystalline colonies of manufacture according to claim 10, wherein said peroxy acid is peracetic acid.
27. manufacture nanocrystalline method, including:
Offer comprises the first precursor and the mixture of the second precursor, wherein said first precursor and described second precursor and has mismatch Oxidation state;
The strong electron transfer agent less than stoichiometry is added being enough to the amount producing required nucleation amount in described mixture;
Optionally heat mixture together to produce required nucleation amount;
Needed for being enough to produce, the amount of nanocrystalline increment adds weak electron transfer agent in described mixture;With
The heating of described mixture optionally be enough to produce a period of time of required nanocrystalline increment.
The method that 28. manufactures according to claim 27 are nanocrystalline, wherein said nanocrystalline formation reacts in intermittent reaction Device system occurs.
The method that 29. manufactures according to claim 27 are nanocrystalline, wherein said nanocrystalline formation reacts in flowing continuously Reactor assembly occurs.
The method that 30. manufactures according to claim 27 are nanocrystalline, wherein by described strong electron transfer agent and described weak The described oxidation state of described first precursor or described second precursor is changed into middle condition by electron transfer agent.
The method that 31. manufactures according to claim 27 are nanocrystalline, is wherein mated by described strong and weak electron transfer agent Described first precursor and the described oxidation state of described second precursor.
The method that 32. manufactures according to claim 27 are nanocrystalline, wherein said strong electron transfer agent and described weak electron Transfer agent is reducing agent.
The method that 33. manufactures according to claim 27 are nanocrystalline, wherein said strong electron transfer agent and described weak electron Transfer agent is oxidant.
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