WO2003010778A1 - n-TYPE THIOPHENE SEMICONDUCTORS - Google Patents

n-TYPE THIOPHENE SEMICONDUCTORS Download PDF

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WO2003010778A1
WO2003010778A1 PCT/US2002/023401 US0223401W WO03010778A1 WO 2003010778 A1 WO2003010778 A1 WO 2003010778A1 US 0223401 W US0223401 W US 0223401W WO 03010778 A1 WO03010778 A1 WO 03010778A1
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fluoroalkyl
type
group
mmol
thiophene
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French (fr)
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Tobin J. Marks
Antonio Facchetti
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Northwestern University
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
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    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/464—Lateral top-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
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    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition

Definitions

  • ⁇ -conjugated thiophene oligomers (nTs) and polymers (polythiophenes-PTs) have attracted great interest as semiconducting elements in organic thin- film transistors (TFTs) J 1 ' 2 - 1 To be useful in such devices and related structures, the
  • nT, 0 ⁇ x ⁇ 5 PT organic material must support a channel of holes or electrons (p- or n-type semiconductor, respectively) created by the gate electrode bias, which switches the device "on". Furthermore, the charge mobility of the material must be sufficiently large to increase the source-drain on-conduction by many orders of magnitude over the "off state. The density of the charge carrier in the channel is modulated by voltage applied at the gate electrode.
  • Electron transporting (n-type) organic materials are relatively rare. However, developing/understanding new n-type materials would enable applications' ⁇ such as bipolar transistors, p-n junction diodes, and complementary circuits as well as afford better fundamental understanding of charge transport in molecular solids. The major barrier to progress however, is that most n-type organics are either environmentally sensitive, have relatively low field mobilities, lack volatility for efficient film growth, and/or are difficult to synthesize. 1 - 56,6 ' 71
  • one or more of the foregoing objects can be achieved by use of one or more of the thiophene compounds, compositions and/or materials of the type described herein, and/or with a suitable substrate material as part of a composite or a device incorporating such a composite.
  • one or more of the preceding objects can be achieved with a method described herein, including the use of a thiophene material as an n-type semiconductor to transport electrons.
  • an organic thin film transistor device which includes a source electrode, a drain electrode and a semiconductor material between the electrodes, the material preferably comprising an n-type fluoroalkyl-substituted polythiophene composition.
  • a method is provided by way of using introduction of substituents to a semiconducting composition to alter charge conduction there through, such that a material which would otherwise be considered a p-type conductor becomes an n-type conductor through a synthetic transformation of the type described herein.
  • Various other properties such as band gap (expansion), electron mobility (increased), electron affinity (increased) and ionization potential (higher) are similarly altered.
  • the present invention includes the first n-type thiophene semiconductor compositions and/or materials, for use with a variety of applications or devices including, but not limited to, organic TFTs.
  • a preferred thiophene composition/material comprises , ⁇ -di ⁇ erfluorohexylsexithiophene
  • DFH-6T sexithiophene-6T
  • DH-6T dihexylsexithiophene
  • the present invention contemplates, in part, a range of fluoroalkylated compositions and/or materials including the corresponding fluoroalkylated oligo- and polythiophene compositions.
  • Fluoroalkylation includes various aikyl chain lengths and fluoro-substitutions thereof, such as would result in an alteration to n-type semiconductivity, as compared to p-type conductivity of the unaltered composition. Similar effects can be achieved by introduction/insertion of electron deficient moieties, such as fluoro- and perfluoroaryl groups and various heterocycles.
  • thiophene cores each with the appropriate insertions and/or fluoroalkyl substituents.
  • a preferred core has about 4-7 conjugated thiophene units.
  • C 5 -C 7 fluoroalkyl substitution is preferred and can be accomplished using commercially-available reagents, but various other substitutions can be achieved through synthesis of the corresponding fluoroalkyl compounds.
  • Thiophene core substitution and heterocycle insertion is, therefore, limited only by the desired degree of n-type semiconductivity.
  • a TFT device with, for instance, a DFH-6T active layer operates in the n-type accumulation mode, indicating DFH-6T and other such thiophene compounds are n- type conductors.
  • the new fluorinated thiophenes of this invention are significantly more chemically and thermally inert, and can be transported quantitatively into the vapor phase without decomposition.
  • the inventive thiophene units have strong ⁇ - ⁇ intermolecular interactions.
  • film growth morphologies can depend on growth temperature and substrate pretreatment and/or functionalization.
  • This invention demonstrates that fluoroalkyl functionalization of a thiophene core substantially enhances thermal stability, volatility, and electron affinity vs. the non- fluoro analogs and affords the first n-type thiophene for use, as an example, in a TFT.
  • DFH-6T film morphology is sensitive to substrate temperature and surface pretreatment, with crystallite size increasing with increasing growth temperature.
  • UV-vis/PL and XRD studies indicate that while DFH-6T has close intermolecular ⁇ -stacking, it is not isostrucrural with the DH-6T analog. Since thiophene oligomers of the prior art are typically p-type, the present invention using n-type semiconductors can provide a pathway by which an all- thiophene complementary circuit can be realized.
  • the present invention further includes thiophene systems such as those represented by general structural formulas 1 -3, as can be prepared in high yield via palladium ⁇ 0)-catalyzed coupling of haloaromatics with stannyl (Stille coupling) and Grignard reagents.
  • thiophene systems such as those represented by general structural formulas 1 -3, as can be prepared in high yield via palladium ⁇ 0)-catalyzed coupling of haloaromatics with stannyl (Stille coupling) and Grignard reagents.
  • One embodiment of this invention includes various prefluoroalkyl and/or fluoroalkyl substituted thiophene oligomers or polymers, as can be represented by the structural formula
  • Ri, R 2 and R 3 are selected from the substituent group consisting of fluoroalkyl moieties, C n H 2n+ ⁇ and where n is about 1-12, H, F and (CH 2 ) a X and where a is about 1-12 and X is selected from the group consisting of amino, hydroxy and carboxylic acid functionalities; and x, y and z are integers from the group of integers consisting of 0 and integers greater than 0.
  • the fluoroalkyl moieties of such compositions can include but are not limited to the corresponding linear, branched and/or cyclic substituents, optionally in the presence of one or more aikyl and/or fluorine substituents.
  • an aikyl substituent can further include a functional group including but not limited to those described in Examples 14 and 15, below, such that the resulting polythiophene composition can be further transformed and or modified.
  • Various other functional groups will be well known to those skilled in the art and made aware of this invention, as will be the corresponding synthetic techniques/procedures by which to effect such a transformation or polythiophene modification.
  • compositions can include those with a fluoroalk3'l moiety having the compositional formula C n F 2n+1 , where n is about 1-8.
  • the compositions of such embodiments can be further modified by choice of integers x, y and z. Regardless of substitution, such preferred embodiments can also include those in which x is about 0-4, y is about 0-8 and z is about 0-12.
  • x is about 0-4, y is about 0-8 and z is about 0-12.
  • the composition of such polythiophenes and the number of conjugated thiophene units is limited only by synthetic technique.
  • Representative structures include but are not limited to the following:
  • compositions la-h were prepared according to Schemes 1 and 2. (See, also, Examples 17 and 17a-g.)
  • Another embodiment of this invention includes various ⁇ -conjugated perfluorophenyl-thiophene oligomers, as can be represented by the structural formula
  • R 1 ⁇ R 2 and R 3 are selected from the substituent group consisting of fluoroalkyl moieties, C n H 2n+ ⁇ and where n is about 1-12, H, F, and (CH 2 ) a X and where a is about 1-12 and X is selected from the group consisting of amino, hydroxy and carboxylic acid functionalities; and x, y and z are integers selected from the group of integers consisting of 0 and integers greater than 0.
  • compositions of this embodiment and the chemical/physical properties corresponding thereto can be modified as described above by choice and extent of thiophene substitution.
  • the compositions of this invention can be further modified by insertion of perfluoroaryl components between conjugated thiophene units. Use thereof in combination with any of the aforementioned substitution parameters can provide a route to choice and design of compositions with specific electronic properties.
  • Representative structures include but are not limited to the following:
  • compositions 2a-b were prepared according to Scheme 3. (See, also, Examples 18a-e.)
  • Another embodiment of the present invention includes various ⁇ -conjugated electron-poor heterocycle (including azine)-thiophene oligomers, as can be represented by the following structural formula
  • R 1 ⁇ R 2 and R 3 are selected from the substituent group consisting of fluoroalkyl moieties, C n H 2n+ ⁇ and where n is about 1-12, H, F, and (CH 2 ) a X and where a is about 1-12 and X is selected from the group consisting of amino, hydroxy and carboxylic acid functionalities; x, y and z are integers selected from the group of integers consisting of 0 and integers greater than 0; and A, B, W and Z are selected from the group of moieties consisting of N and CH.
  • Modification of a polythiophene composition can also be achieved through insertion of a suitable heterocyclic component, the effect of which can be comparable to perfluoroaryl substitutions of the sort described above.
  • a suitable heterocyclic component the effect of which can be comparable to perfluoroaryl substitutions of the sort described above.
  • Several such insertions are illustrated, below, but this embodiment can be extended to include other electron-deficient heterocycles including but not limited to thiadiazine and tetrazine.
  • Polythiophene compositions including such components can be prepared through straight-forward extensions of the general synthetic techniques described herein, such extensions as would be understood by those skilled in the art.
  • the electronic effect afforded such thiophene compositions by heterocycle insertion can be further tailored for a specific end-use application through choice and degree of substitution, as described more fully above.
  • the heterocyclic compositions of this embodiment can vary without limitation corresponding to substituent (R l5 R 2 and R 3 ), optional functional group (amino-, hydroxy- or carboxylic acid groups), heteroatom identity and/or number of thiophene and/or heterocyclic units.
  • the present invention can further include a method of using thiophene structural modification to provide, promote and/or enhance n-type thiophene conductivity.
  • a method includes (1) preparing a polythiophene composition having a plurality of conjugated thiophene components or moieties; (2) providing the composition a structural modification sufficient to promote n-type conductivity, such a modification selected from the group of structural modifications described above and including but not limited to fluoroalkyl substitution, fluorine substitution, fluoroaryl insertion, heterocycle insertion and combinations thereof As described herein and as would be understood to those skilled in the art, such modifications can be made or provided en route to the preparation of such polythiophene compositions.
  • FIGURE 1 shows schematically a synthetic procedure, in accordance with this invention, en route to a representative, but preferred n-type fluoroalkylthiophene material.
  • FIGURE 3 shows reduced pressure (0.01 torr N 2 ) TGA comparison of the volatility characteristics of DHF-6T and DH-6T: weight loss comparison plots (A) for DH-6T and DFH-6T recorded at a ramp rate of 1.5 °C/min; and isothermal data (B) collected at 260 and 290 °C for DFH-6T and DH-6T, respectively.
  • FIGURE 4 shows optical absorption (UV-vis) and emission (PL) spectra of DFH-6T (bold line) and DH-6T (fine line): (A) dilute toluene solution at ca. 80 °C, solution PL excited at 444 nm (DFH-6T) and 436 nm (DH-6T); and (B) as thin films ( ⁇ 1.8 ⁇ m) on glass substrates, film PL spectra excited at 377 nm (DFH-6T) and 363 nm (DH-6T).
  • FIGURE 5 provides plan view SEM images of 100 nm thick DFH-6T films deposited at various substrate temperatures on silicon: (A) 25 °C, (B) 85°C, and (C) 145 °C.
  • FIGURE 6 provides X-ray ⁇ - 2 ⁇ diffractograms of ⁇ 2 ⁇ m thick vacuum- evaporated DFH-6T films grown on Si substrates at various substrate temperatures. Note that the 240 °C spectrum corresponds to a film grown at 200 °C and annealed at 240 °C for 30 min.
  • FIGURE 7 plots graphically (A) source drain current vs. voltage characteristics of DFH-6T TFTs (top contact configuration) at different gate voltages, and (B) source drain current vs. gate of DFH-6T TFTs.
  • FIGURE 8 schematically illustrates several transistor and related integrated circuit devices including therein, in accordance with this invention, a polythiophene thin film of the type described herein.
  • FIGURE 9 provides a reduced pressure (0.01 torr) TGA weight loss comparison of the volatility characteristics of compositions le, lh, 2a, 2b, 3a, 3c, with reference to compositions 6T and DH-6T.
  • FIGURE 10 shows UV-Vis absorption spectra of la-c, le, lh in toluene.
  • FIGURE 11 shows, comparatively, thin film (1.8 ⁇ m) UV-Vis/PL spectra of A) DH-6T, le, and lh B) 2a, b.
  • FIGURE 12 shows, comparatively, toluene solution (saturated) UV- Vis/PL spectra of A) DH-6T and lh B) 2a, b.
  • FIGURE 13 shows cyclic voltammograms illustrating the oxidation and reduction peaks of 2a-b.
  • FIGURE 14 shows cyclic voltammograms illustrating the oxidation and reduction peaks of lh and 3c.
  • FIGURE 15 provides an X-ray diffractogram of approximately 2 ⁇ m- thick vacuum-evaporated film of 2a on silicon substrate grown at 25°C substrate temperature.
  • FIGURES 16 and 17 provide molecular stacking diagrams illustrating material structure and the resulting electrical properties in accordance with those and various other compositions of this invention.
  • DFH-6T was synthesized in high yield via Pd -catalyzed Stille coupling of 5-bromo-5'-perfluorohexyl-dithiophene (6) with 5,5'-di(tributyl-stannyl)dithiophene (Fig. 1). This route affords DFH-6T (1) in high purity and yield ( ⁇ 95%) after multiple gradient sublimation. Note that although monosubstituted perfluoroalkyl thiophene oligomers up to three units have been reported, synthetic yields were typically ⁇ 10%. For example, 3'-perfluorohexylterthiophene was isolated in ⁇ 11% yield.
  • Figure 4 shows optical absorption and emission (PL) spectra of DFH-6T and DH-6T in solution (Fig. 4A) and as thin vapor-deposited films (Fig. 4B).
  • the solution spectra are nearly superimposable, arguing that the energy differences between ground and excited states of the 6T core are only marginally sensitive to ⁇ , ⁇ -substitution and that the HOMO-LUMO gaps of ⁇ 2.4 eV are nearly identical.
  • the spectra of the films exhibit both differences and similarities.
  • both PL spectra have a central peak and two weaker shoulders. The high energy shoulders fall, for both systems, at the same wavelength near the tail of the absorption, yielding estimated film HOMO-LUMO gaps of ⁇ 2.2 eV.
  • DFH-6T exhibits strong green fluorescence ( ⁇ ma ⁇ ⁇ 588 nm) under UV excitation
  • the DH-6T emission intensity is several orders of magnitude weaker and red-shifted by ⁇ 30 nm.
  • the low PL yields of the prior art DH-6T (2) and 6T (3) thin films and blue-shifted absorption maxima vs. solution were previously ascribed to Davydov splitting.
  • the origin of the DFH-6T blue-shifted absorption and enhanced PL efficiency is unknown and warrants further study. While both DH-6T and DFH-6T exhibit strong intermolecular ⁇ - ⁇ interactions, they are not isostructural (vide infra).
  • the first and second anodic peaks of DFH-6T vs. DH-6T exhibit a uniform anodic potential shift ( ⁇ +0.27 V), indicating that introduction of perfluoroalkyl chains on the 6T core substantially increases the ionization potential.
  • substrate temperature The influence of substrate temperature on crystallite size and film morphology for other thiophene semiconductors such as 6T is known to be related to nucleation site density, growth rate, and surface free energy phenomena during growth. Because Si/Si0 2 has a hydrophilic native oxide layer, the surface is not ideal for deposition of a hydrophobic adsorbate. Thus, substrates were also pretreated with CF 3 (CF 2 ) 5 CH 2 CH 2 SiCl 3 to produce a fluorocarbon monolayer. The crystallite dimensions are increased by ⁇ 10% and grain-to-grain, grain-to-substrate interconnections are visibly enhanced.
  • CF 3 (CF 2 ) 5 CH 2 CH 2 SiCl 3 The crystallite dimensions are increased by ⁇ 10% and grain-to-grain, grain-to-substrate interconnections are visibly enhanced.
  • Various other substrate materials known to those skilled in the art can be used in conjunction with this invention, not only to further demonstrate the utility shown in this example, but also in the various composite
  • X-ray diffraction (Cu K ⁇ ) scans of DFH-6T films grown at various temperatures reveal that higher crystalline order is achieved as the substrate temperature is increased to 200 °C. Annealing at 240 °C further enhances microstructural alignment, with the dominant Bragg features assignable to a family of (nOO) reflections corresponding to a real-space periodicity of 36.1 ⁇ 0.2 A, close to the DFH-6T long axis dimension.
  • the crystal structure of DFH-6T has not been determined, the XRD data suggest preferential molecular orientation with long axes along the substrate normal, in which case transport in the plane of the film would benefit from close ⁇ - ⁇ stacking.
  • DFH-6T films grown on CF 3 (CF 2 ) 5 CH 2 CH 2 SiCl 3 -treated Si substrates exhibit sharper XRD reflections, indicating highly ordered films.
  • powder diffraction reveals that DFH-6T and DH-6T are not isostructural, with different unit cell arrangements expected in view of the different packing properties of hydrocarbon vs. perfluorocarbon chains.
  • the device of Fig. 7 was fabricated with Au source-drain contacts. Devices with Al contacts exhibit similar characteristics, which is surprising considering the significantly higher Au work function (5.1 eV) vs. Al (4.3eV), implying, a priori, a higher barrier for electron injection from Au. Values for the field-effect mobility were determined from the transfer characteristics in the saturation regime (Fig. 7b). The highest mobilities of 0.02cm 2 /Vs
  • the reagents 5-bromo-2,2'-dithiophene (4), and 5,5 - bis(tri-n-butylstannyl)-2,2 -dithiophene were prepared according to known synthetic procedures. Other solvents and reagents were purchased from the Aldrich or Lancaster concerns and purified as required.
  • Example 13 ⁇ , ⁇ -Diperfluorohexyl-sexithiophene, DFH-6T (le).
  • Example 14 With reference to structure 7, below, the compounds of this example further illustrate the thiophene compositions, materials and/or films of the type available through this invention.
  • the oligo-and/or polythiophene compounds of this invention including those of and represented by the preceding example are prepared in accordance with the synthetic procedures described herein and straight-forward modifications thereof.
  • Substitution of 5-halo-2,2'-dithiophene with a suitable fluorocarbon provides one intermediate (a).
  • the monohalodithiophene can be halogenated through known techniques for subsequent fluorocarbon substitution at both the 5 and 5' positions, such a dithiophene for use as described herein, as an n-type semiconducting material.
  • Yet another embodiment of this example contemplates substitution at the 5' position, and fluoroalkylation at the 5 position to provide a second intermediate (b).
  • the 5' substituent introduces an aromatic or aikyl moiety including but not limited to amino, hydroxyl and/or carboxylic functional groups for later possible synthetic transformation.
  • Intermediates (a) and/or (b) of this example are coupled with a stannyl (mono - or - bis -) thiophene (mono - or - di -), or further reacted with another intermediate of the type described herein to provide a range of conjugated thiophene units, with the desired degree of fluoroalkylation and/or alternate functionalization.
  • Example 16 Figure 8 illustrates incorporation of a thiophene semiconductor material of the present invention in an n-channel junction field-effect transistor (JFET).
  • the JFET includes a gate region 10 constructed from a p-type semiconductor material and a channel 12 constructed from an n-type thiophene thin film deposited on a suitable substrate.
  • the material of region 10 can be a p-type thiophene semiconductor.
  • a voltage applied to a gate electrode 14 controls current flow through the thin film/substrate composite of channel 12 between the drain electrode 16 and the source electrode 18.
  • thiophene material of the present invention in a number of other transistor applications to provide without limitation p-channel JFETs, bipolar junction transistors of both the npn and pnp type, depletion and enhancement mode MOSFETS of both n and p channel types, and other types of transistors and integrated circuits.
  • the reagents 5-bromo-2,2':5',2"-terthiophene, 5-bromo-2,2 -dithiophene, and 5,5 -bis(tri-n-butylstannyl)-2,2 -dithiophene were prepared according to known procedures. Solvents and chemicals were purchased from Aldrich or Lancaster and purified as required.
  • Example 17b 5-Perfluorohexyl-2,2 -dithiophene and 5,5'-diperfluorohexyl-2,2 -dithiophene.
  • Perfluorohexyl iodide (11.34 g, 25.43 mmol) was added dropwise in such a way as to keep the temperature below 135°C.
  • Example 17e 5.5"'-Diperfluorohexyl-2,2 ': 5 '2 ": 5 "2 '”: 5 '"2 “”:5 “"2 "'”-quaterthiophene.
  • reaction mixture was then heated at 95 °C for 5 h during which time a precipitate formed. After cooling, the bright yellow solid was collected and washed several times with methanol and Et 2 0 to afford the analytically pure product (1.30 g, 1.35 mmol, 79.4 % yield). M.p. 213 °C. Additional purification can be achieved by gradient sublimation.
  • Example 17f 3 Perfluorohexyl-2.2 -dithiophene.
  • a solution of 3-bromo-2.2'- dithiophene (5.00 g, 20.34 mmol) in the same solvent (14 mL) was added dropwise, and the reaction mixture was stirred at 125 °C for 6 h.
  • Example 17g 3-d -Perfluorohexyl -5'-bromo-2,2 -dithiophene.
  • NBS (1.47 g, 8.26 mmol) was added portionwise to a solution of 3-(l-perfluorohexyl)-2,2 - dithiophene (4.00 g, 8.26 mmol) in DMF (70 mL) at -30°C over the period of 6 h.
  • the reaction mixture was left to slowly reach room temperature and, after stirring overnight, was poured onto water (100 mL).
  • the aqueous phase was extracted with ether (3x100 mL) and the combined ethereal phases were washed with water and dried over MgS0 .
  • Example 17h 3 3 ,3'""-Di ⁇ erfluorohexyl-2.2 ': 52 ": 5 "2 '”: 5 '"2 "" 5 ""2 ""'-sexithiophene.
  • reaction mixture was then heated at 90 °C overnight during which time a precipitate formed. After cooling, the bright orange solid was collected and washed several times with ether to afford the analytically pure product (1.80 g, 1.59 mmol, 89.6 % yield). M.p. 217 °C. Additional purification can be achieved by gradient sublimation.
  • Example 18a 5,5'-Bis[l-(4-bromo-2.3,5,6-tetrafluorophenyl ]-2,2 -dithiophene.
  • Example 18b 5,5 , -Bis ⁇ l-[4-(thien-2-yl -2,3,5,6-tetrafluoro ⁇ henyl li-2,2'-dithio ⁇ hene.
  • Example 18c 2-Perfluorophenylthiophene.
  • reaction mixture was refluxed for 10 hours and, after cooling, the precipitate was collected (2.00 g).
  • the solid residue was washed several times with hexane and than crystallized from pyridine (170 mL) to afford the pure compound as an orange solid (0.88 g, 1.81 mmol, 50.5% yield).
  • Example 19d 5,5'-Bis 6-(5-hexylthien-2-yl pyrimid-4-yl)-2,2 -dithiophene.
  • Example 19e 3-(Thien-2-yl)-6-chloropyridazine.
  • Example 20b Absorption and fluorescence emission spectra were recorded to monitor the effect of substitution on the HOMO-LUMO energy gap. By varying the number of thiophene units, it is possible to modulate optical absorption from 300 to 500 nm ( Figure 10). On the other hand, fluorophenyl-azine insertion into the 6T core allows for a very fine tune in the range of 450-500 nm (Table 1). Film PL intensities change of many orders of magnitude with chemical structure. DFH-6T and iso-DFH-6T were found much more efficient that the corresponding unsubstituted and dialkyl substituted systems. 2a is substantially more efficient than 2b in spite of the similar solution absorption/emission and film absorption patterns. Comparative spectra are also shown in Figures 11-12.
  • Compound 1 Oxidation Potentials Reduction Potentials anodic cathodic standard anodic cathodic standard anodic cathodic cathodic
  • DFH-4T 1.31 -0.95 -1.75 -0.76 -1.40 -0.85 -1.57 isoDFH-6T1.01 1.23 0.88 1.06 0.94 1.14 -1.47 1.97 1.06 -1.74 -1.26 -1.86
  • TPMT2PMT 1.42 1.69 1.16 1.41 1.29 1.55 -1.74 -1.87 -1.60 -1.75 -1.67 -1.72
  • TPDT2PDT1.14 1.44 -1.57 -2.01 -1.35 -1.80 -1.79 -1.90
  • n-type thiophene- modified systems of this invention are more chemically and thermally stable than the corresponding p-type ⁇ -isoelectronic oligo- and polythiophenes and can be transported quantitatively into the gas phase without decomposition.
  • fluoro-azine substitution-insertion allows for an effective modulation of optical absorption-emission maximum, optical gap, and photoluminescent efficiencies (quantum yields) both in solution and as thin- deposited films.
  • absolute orbital energies can be estimated.
  • HOMO(LUMO) energies can be determined from the first oxidation(reduction) potentials.
  • deposition method evaporation, spin-coating, casing
  • substrate temperature and pretreatment either highly ordered or amorphous solids can be produced.
  • compositions/materials such as n-type conductivity, electron affinity and electron mobility
  • n-type conductivity, electron affinity and electron mobility can be modified, as described herein, by choice of thiophene structure, fluoroalkyl substitution and/or heterocycle insertion, such modifications as may be desired for a particular end use application.
  • substitution and/or insertion methods disclosed herein can also be applied to various non-thiophene systems, to alter electronic properties and/or provide n-type conductivity.

Abstract

The new fluorocarbon-functionalized and/or heterocycle-modified polythiophenes, in particular, α,φ-diperfluohexylsexithiophene DFH-6T can be straightforwardly prepared in high yield and purity. Introduction of such modifications to a thiophene core affords enhanced thermal stability and volatility, and increased electron affinity versus the unmodified compositions of the prior art. Evaporated films behave as n-type semiconductors, and can be used to fabricate thin film transistors with FET mobilities ∼0.01 cm2/Vs--some of the highest reported to date for n-type organic semiconductors.

Description

n-TYPE THIOPHENE SEMICONDUCTORS
This application claims the benefit of prior United States application serial no. 09/915,206, filed July 24, 2001, the entirety of which is incorporated herein by reference.
The United States Government has rights in this invention pursuant to Grant No. N00421-98-1187 from DARPA and the NSF-MRSEC program (DMR-9632472) to Northwestern University.
Background of the Invention.
Thiophene chemistry and the chemical stability of the thiophene ring hold potential for use of thiophene materials in molecular-based electronics and photonics. In particular, αα -conjugated thiophene oligomers (nTs) and polymers (polythiophenes-PTs) have attracted great interest as semiconducting elements in organic thin- film transistors (TFTs) J1'2-1 To be useful in such devices and related structures, the
Figure imgf000002_0001
nT, 0 < x < 5 PT organic material must support a channel of holes or electrons (p- or n-type semiconductor, respectively) created by the gate electrode bias, which switches the device "on". Furthermore, the charge mobility of the material must be sufficiently large to increase the source-drain on-conduction by many orders of magnitude over the "off state. The density of the charge carrier in the channel is modulated by voltage applied at the gate electrode.
To date, the most noteworthy examples of this family of compounds are unsubstituted, α,ω- and β,β'-dialkylsubstituted nT (n = 4,6), and β-alkylsubstituted PT, where optimized carrier mobilities (0.1-0.6 cm2 V"1 s"1) and on/off ratios (>106) approach those of amorphous silicon.[le'2a'c'e,3] However, without exception, these systems facilitate hole injection and behave as p-type semiconductors, presumably because the thiophene electron-richness renders negative carriers susceptible to trapping by residual impurities such as oxygen[4]. Even so, increasing the number of thiophene units decreases dramatically environmental (air, light) stability and causes processing and purification difficulties.
Electron transporting (n-type) organic materials are relatively rare. However, developing/understanding new n-type materials would enable applications'^ such as bipolar transistors, p-n junction diodes, and complementary circuits as well as afford better fundamental understanding of charge transport in molecular solids. The major barrier to progress however, is that most n-type organics are either environmentally sensitive, have relatively low field mobilities, lack volatility for efficient film growth, and/or are difficult to synthesize.1-56,6'71
As indicated by the foregoing notations, these and other aspects of and teachings of the prior art can be found in the following:
[1] (a) G. Horowitz, F. Kouki, A. El Kassmi, P. Valat, V. Wintgens, F. Gamier, Adv. Mater. 1999, 11, 234. (b) F. Gamier, R. Hajaoui, A. El Kassmi, G. Horowitz, L. Laigre, W. Porzio, M. Armanini, F. Provasoli, Chem. Mater. 1998, 10, 3334. (c) X. C. Li, H. Sirringhaus, F. Gamier, A. B. Holmes, S. C. Moratti, N. Feeder, W. Clegg, S. J. Teat, R. H. Friend, J. Am. Chem. Soc. 1998, 120, 2206. (d) G. Horowitz, F. Kouki, F. Gamier, Adv. Mater. 1998, 10, 382. (e) L. Antolini, G. Horowitz, F. Kouki, F. Gamier, A dv. Mater. 1998. 10, 381. (f) G. Horowitz, Adv. Mater. 1998, 10, 365.
[2] (a) W. Li, H. E. Katz, A. J. Lovinger, J. G. Laquindanum, Chem. Mater. 1999, 11, 458. (b) H. E. Katz, J. G. Laquindanum, A. J. Lovinger, Chem. Mater. 1998, 10, 633. (c) J. G. Laquindanum, H. E. Katz, A. J. Lovinger, J. Am. Chem. Soc. 1998, 120, 664. (d) T. Siegrist, C. Kloc, R. A. Laudise, H. E. Katz, R. C. Haddon, Adv. Mater. 1998, 10, 379. (e) H. E. Katz, J. Mater. Chem. 1997, 7, 369. (f) A. Dodalabapur, L. Torsi, H. E. Katz, Science 1995, 268, 270.
[3] (a) H. Sirringhaus, P. J. Brown, R. H. Friend, K. Bechgaard, B. M. W. Lengeveld-Voss, A. J. H. Spieling, R. A. J. Janssen, E. W. Meijer, P. Herving, D. M. de Leeuw, Nature 1999, 401, 685. (b) G. Barbarella, M. Zambianchi, L. Antolini, P. Ostoja, P. Maccagnani, A. Bongini, E. A. Marseglia, E. Tedesco, G. Gigli, R. Cingolani, J. Am. Chem. Soc. 1999, 121, 8920. (c) J. H. Shδn, C. Kloc, R. A. Laudise, B. Batlogg, Appl. Phys. Lett. 1998, 73, 3574.
[4] Handbook of Heterocyclic Chemistry; A. R. Katritzky Ed.; Pergamon Press: Oxford, 1983.
[5] (a) Y. Y. Lin, A. Dodabalapur, R. Sarpeshkar, Z. Bao, W. Li, K. Baldwin, V. R. Raju, H. E. Katz, Appl. Phys. Lett. 1999, 74, 2714. (b) G. Horowitz, Adv. Mαter. 1998, 10, 365. (c) A. Dodalabapur, J. G. Laquindanum, H. E. Katz, Z. Bao, Appl. Phys. Lett 1996, 69, 4227. (d) N. C. Greenham, S. C. Moratti, D. D. C. Bradley, R. H. Friend, Nature 1993, 365, 628. (e) S. Sze, Semiconductor Devices Physics and Technology; Wiley: New York, 1985; p. 481.
[6] (a) C. P. Jarret, K. Pichler, R. Newbould, R. H. Friend, Synth. Met. 1996, 77, 35. (b) R. C. Haddon, J. Am. Chem. Soc. 1996, 118, 3041. (c) G. Horowitz, F. Kouki, P. Spearman, D. Fichou, C. Nogues, X. Pan, F. Gamier, Adv. Mater. 1996, 8, 242. (d) J. G. Laquindanum, H. E. Katz, A. Dodalabapur, A. J. Lovinger, J. Am. Chem. Soc. 1996, 118, 11331.
[7] The transport properties of metal/α,ω-dicyano-6HT/metal structures are highly metal/interface-dependent; TFT carrier signs and mobilities have not been reported: F. Demanze, A. Yassar, D. Fichou, Synthetic Metals 1999, 101 620.
Summary of the Invention
As shown from the above discussion, there are a considerable number of problems and deficiencies associated with the prior art relating to useful organic n- type semiconductor compounds, compositions and/or materials, including those discussed above. There is a demonstrated need for such materials, compositions, layers and/or composites for thin film deposition and related applications useful in conjunction with the fabrication of thin film transistors and related devices as can be incorporated into an integrated circuit.
Accordingly, it is an object of the present invention to provide new and useful n-type organic materials, together with one or more methods of preparation, overcoming those various shortcomings and deficiencies of the prior art.
It will be understood by those skilled in the art that one or more aspects of this invention can meet certain objectives, while one or more other aspects can meet certain other objectives. Each objective may not apply equally, in all instances, to every aspect of the present invention. As such, the following objects can be viewed in the alternative with respect to any one aspect of the present invention.
It is another object of the present invention to provide a facile, efficient synthetic method for the preparation of an n-type thiophene conductive material, such preparation resulting in high yield and purity of the desired thiophene material.
It is yet another object of the present invention to provide n-type semiconducting thiophene compounds and related materials and/or thin films which can be used in the fabrication of and in conjunction with a variety of circuitry related devices, including, but not limited to, diode, bipolar junction transistor and field-effect transistor (either junction or metal-oxide semiconductor) devices.
It is yet another object of the present invention to provide for the synthetic modification of organic semiconductive molecular solids to alter electronic behavior, in particular the use of such modified thiophenes to provide and facilitate electron transport.
Other objects, features, benefits and advantages of the present invention will be apparent from the foregoing, in light of the summary and the examples and descriptions which follow, and will be readily apparent to those skilled in the art having knowledge of various semiconducting materials, their preparation and subsequent use. Such objects, features, benefits and advantages will be apparent from the above as taken in conjunction with the accompanying examples, tables, graphs, data and all reasonable inferences to be drawn therefrom.
In accordance with one aspect of the present invention, one or more of the foregoing objects can be achieved by use of one or more of the thiophene compounds, compositions and/or materials of the type described herein, and/or with a suitable substrate material as part of a composite or a device incorporating such a composite.
In accordance with another aspect of the present invention, one or more of the preceding objects can be achieved with a method described herein, including the use of a thiophene material as an n-type semiconductor to transport electrons.
In accordance with another aspect of the present invention, one or more of the foregoing objects can be achieved with an organic thin film transistor device which includes a source electrode, a drain electrode and a semiconductor material between the electrodes, the material preferably comprising an n-type fluoroalkyl-substituted polythiophene composition.
In accordance with yet a further aspect of the present invention, a method is provided by way of using introduction of substituents to a semiconducting composition to alter charge conduction there through, such that a material which would otherwise be considered a p-type conductor becomes an n-type conductor through a synthetic transformation of the type described herein. Various other properties such as band gap (expansion), electron mobility (increased), electron affinity (increased) and ionization potential (higher) are similarly altered.
The present invention includes the first n-type thiophene semiconductor compositions and/or materials, for use with a variety of applications or devices including, but not limited to, organic TFTs. A preferred thiophene composition/material comprises ,ω-diρerfluorohexylsexithiophene
Figure imgf000006_0001
DFH-6T
Figure imgf000006_0002
DH-6T, R = "C6Hi3 6T, R = H
designated as DFH-6T, shown above and as structurally compared to the sexithiophene (6T) and dihexylsexithiophene (DH-6T) compositions of the prior art. Fluoroalkyl functionalization of a thiophene core significantly alters the electronic, film growth, and semiconducting properties of the resulting films.
The present invention contemplates, in part, a range of fluoroalkylated compositions and/or materials including the corresponding fluoroalkylated oligo- and polythiophene compositions. Fluoroalkylation includes various aikyl chain lengths and fluoro-substitutions thereof, such as would result in an alteration to n-type semiconductivity, as compared to p-type conductivity of the unaltered composition. Similar effects can be achieved by introduction/insertion of electron deficient moieties, such as fluoro- and perfluoroaryl groups and various heterocycles. Known synthetic procedures can be used or modified as would be known to those skilled in the art made aware of this invention to provide a variety of thiophene cores, each with the appropriate insertions and/or fluoroalkyl substituents. However, for purposes such as processing and subsequent device fabrication, a preferred core has about 4-7 conjugated thiophene units. Likewise, C5-C7 fluoroalkyl substitution is preferred and can be accomplished using commercially-available reagents, but various other substitutions can be achieved through synthesis of the corresponding fluoroalkyl compounds. Thiophene core substitution and heterocycle insertion is, therefore, limited only by the desired degree of n-type semiconductivity.
A TFT device with, for instance, a DFH-6T active layer operates in the n-type accumulation mode, indicating DFH-6T and other such thiophene compounds are n- type conductors. Compared to prior art materials such as DH-6T and 6T, the new fluorinated thiophenes of this invention are significantly more chemically and thermally inert, and can be transported quantitatively into the vapor phase without decomposition. In the solid state, the inventive thiophene units have strong π-π intermolecular interactions. As described below, film growth morphologies can depend on growth temperature and substrate pretreatment and/or functionalization.
This invention demonstrates that fluoroalkyl functionalization of a thiophene core substantially enhances thermal stability, volatility, and electron affinity vs. the non- fluoro analogs and affords the first n-type thiophene for use, as an example, in a TFT. As a representative material of this invention, DFH-6T film morphology is sensitive to substrate temperature and surface pretreatment, with crystallite size increasing with increasing growth temperature. UV-vis/PL and XRD studies indicate that while DFH-6T has close intermolecular π-stacking, it is not isostrucrural with the DH-6T analog. Since thiophene oligomers of the prior art are typically p-type, the present invention using n-type semiconductors can provide a pathway by which an all- thiophene complementary circuit can be realized.
In accordance with the preceding, the present invention further includes thiophene systems such as those represented by general structural formulas 1 -3, as can be prepared in high yield via palladium^ 0)-catalyzed coupling of haloaromatics with stannyl (Stille coupling) and Grignard reagents.
One embodiment of this invention includes various prefluoroalkyl and/or fluoroalkyl substituted thiophene oligomers or polymers, as can be represented by the structural formula
Figure imgf000008_0001
wherein Ri, R2 and R3 are selected from the substituent group consisting of fluoroalkyl moieties, CnH2n+ι and where n is about 1-12, H, F and (CH2)aX and where a is about 1-12 and X is selected from the group consisting of amino, hydroxy and carboxylic acid functionalities; and x, y and z are integers from the group of integers consisting of 0 and integers greater than 0.
The fluoroalkyl moieties of such compositions can include but are not limited to the corresponding linear, branched and/or cyclic substituents, optionally in the presence of one or more aikyl and/or fluorine substituents. Alternatively, an aikyl substituent can further include a functional group including but not limited to those described in Examples 14 and 15, below, such that the resulting polythiophene composition can be further transformed and or modified. Various other functional groups will be well known to those skilled in the art and made aware of this invention, as will be the corresponding synthetic techniques/procedures by which to effect such a transformation or polythiophene modification.
With respect to the aforementioned fluoroalkyl moieties, various properties of such compositions can be modified by aikyl length and extent of aikyl fluorination. Preferred compositions can include those with a fluoroalk3'l moiety having the compositional formula CnF2n+1, where n is about 1-8. The compositions of such embodiments can be further modified by choice of integers x, y and z. Regardless of substitution, such preferred embodiments can also include those in which x is about 0-4, y is about 0-8 and z is about 0-12. However, it should be understood, in the broader context of this invention, that the composition of such polythiophenes and the number of conjugated thiophene units is limited only by synthetic technique.
Representative structures include but are not limited to the following:
Figure imgf000009_0001
Compositions la-h were prepared according to Schemes 1 and 2. (See, also, Examples 17 and 17a-g.)
Figure imgf000010_0001
Bu3Sn- .S..SnB_3 XT 1d
Pd(PPh3)4
F2 F2 F2
Br' J 'C-CC -'C-CF3 F2 F2 .S^SnBιi3
Bu3Sn' % ϊ 1e
Pd(PPh3)4
Scheme 1
Figure imgf000011_0001
Pd(PPh3)4
Scheme 2
Another embodiment of this invention includes various π-conjugated perfluorophenyl-thiophene oligomers, as can be represented by the structural formula
Figure imgf000011_0002
wherein R1} R2 and R3 are selected from the substituent group consisting of fluoroalkyl moieties, CnH2n+ι and where n is about 1-12, H, F, and (CH2)aX and where a is about 1-12 and X is selected from the group consisting of amino, hydroxy and carboxylic acid functionalities; and x, y and z are integers selected from the group of integers consisting of 0 and integers greater than 0.
The compositions of this embodiment and the chemical/physical properties corresponding thereto, can be modified as described above by choice and extent of thiophene substitution. In addition, as the present embodiment illustrates, the compositions of this invention can be further modified by insertion of perfluoroaryl components between conjugated thiophene units. Use thereof in combination with any of the aforementioned substitution parameters can provide a route to choice and design of compositions with specific electronic properties.
Representative structures include but are not limited to the following:
Figure imgf000012_0001
(x = 0, y = 1 , z = 2, R = F)
Figure imgf000012_0002
2b (TB FT2BFT)
(x = 1 , y = 1 , z = 1 , R = F)
Compositions 2a-b were prepared according to Scheme 3. (See, also, Examples 18a-e.)
Figure imgf000013_0001
Figure imgf000013_0002
Scheme 3
Another embodiment of the present invention includes various π-conjugated electron-poor heterocycle (including azine)-thiophene oligomers, as can be represented by the following structural formula
Figure imgf000013_0003
wherein R1} R2 and R3 are selected from the substituent group consisting of fluoroalkyl moieties, CnH2n+ι and where n is about 1-12, H, F, and (CH2)aX and where a is about 1-12 and X is selected from the group consisting of amino, hydroxy and carboxylic acid functionalities; x, y and z are integers selected from the group of integers consisting of 0 and integers greater than 0; and A, B, W and Z are selected from the group of moieties consisting of N and CH.
Modification of a polythiophene composition can also be achieved through insertion of a suitable heterocyclic component, the effect of which can be comparable to perfluoroaryl substitutions of the sort described above. Several such insertions are illustrated, below, but this embodiment can be extended to include other electron-deficient heterocycles including but not limited to thiadiazine and tetrazine. Polythiophene compositions including such components can be prepared through straight-forward extensions of the general synthetic techniques described herein, such extensions as would be understood by those skilled in the art. The electronic effect afforded such thiophene compositions by heterocycle insertion can be further tailored for a specific end-use application through choice and degree of substitution, as described more fully above. Accordingly, as with the preceding fluoroalkyl and perfluoroaryl compositions, the heterocyclic compositions of this embodiment can vary without limitation corresponding to substituent (Rl5 R2 and R3), optional functional group (amino-, hydroxy- or carboxylic acid groups), heteroatom identity and/or number of thiophene and/or heterocyclic units.
Accordingly, as also described elsewhere herein, the present invention can further include a method of using thiophene structural modification to provide, promote and/or enhance n-type thiophene conductivity. Such a method includes (1) preparing a polythiophene composition having a plurality of conjugated thiophene components or moieties; (2) providing the composition a structural modification sufficient to promote n-type conductivity, such a modification selected from the group of structural modifications described above and including but not limited to fluoroalkyl substitution, fluorine substitution, fluoroaryl insertion, heterocycle insertion and combinations thereof As described herein and as would be understood to those skilled in the art, such modifications can be made or provided en route to the preparation of such polythiophene compositions. Alternatively, various synthetic techniques, depending upon the desired modification, can be made subsequent thereto. Such modifications can provide a wide variety of polythiophene compositions, commensurate with the broad scope of this invention, such compositions including but not limited to those embodiments discussed above. Representative structures include but are not limited to the following:
Figure imgf000015_0001
3a (TPDT2PDT) 3c (TPMT2PMT)
(x = 1,y=1,Z=1,R = H,A = B = N, C = Z = CH) (x = 1, y = 1, z= 1, R= H, A = W = N, B = Z= CH)
Figure imgf000015_0002
3b (TPyT2PyT) 3d (DH-TPDT2PDT)
(x = 1,y=1,z=1,R = H, B = N,A = W = Z = CH) (x = 1,y = 1,z = 1,R = CβH13, A = W = N, B = Z = CH)
Compounds 3a-d were prepared according to Scheme 4. (See, also, Examples 19a-
f).
Figure imgf000015_0003
Scheme 4
Brief Description of the Drawings
FIGURE 1 shows schematically a synthetic procedure, in accordance with this invention, en route to a representative, but preferred n-type fluoroalkylthiophene material.
FIGURE 2 shows DSC thermograms of DFH-6T (bold line) and DH-6T (fine line) under N2. Temperature ramp = 1.5 °C/min.
FIGURE 3 shows reduced pressure (0.01 torr N2) TGA comparison of the volatility characteristics of DHF-6T and DH-6T: weight loss comparison plots (A) for DH-6T and DFH-6T recorded at a ramp rate of 1.5 °C/min; and isothermal data (B) collected at 260 and 290 °C for DFH-6T and DH-6T, respectively.
FIGURE 4 shows optical absorption (UV-vis) and emission (PL) spectra of DFH-6T (bold line) and DH-6T (fine line): (A) dilute toluene solution at ca. 80 °C, solution PL excited at 444 nm (DFH-6T) and 436 nm (DH-6T); and (B) as thin films (~ 1.8 μm) on glass substrates, film PL spectra excited at 377 nm (DFH-6T) and 363 nm (DH-6T).
FIGURE 5 provides plan view SEM images of 100 nm thick DFH-6T films deposited at various substrate temperatures on silicon: (A) 25 °C, (B) 85°C, and (C) 145 °C.
FIGURE 6 provides X-ray θ- 2θ diffractograms of ~ 2 μm thick vacuum- evaporated DFH-6T films grown on Si substrates at various substrate temperatures. Note that the 240 °C spectrum corresponds to a film grown at 200 °C and annealed at 240 °C for 30 min.
FIGURE 7 plots graphically (A) source drain current vs. voltage characteristics of DFH-6T TFTs (top contact configuration) at different gate voltages, and (B) source drain current vs. gate of DFH-6T TFTs.
FIGURE 8 schematically illustrates several transistor and related integrated circuit devices including therein, in accordance with this invention, a polythiophene thin film of the type described herein.
FIGURE 9 provides a reduced pressure (0.01 torr) TGA weight loss comparison of the volatility characteristics of compositions le, lh, 2a, 2b, 3a, 3c, with reference to compositions 6T and DH-6T. FIGURE 10 shows UV-Vis absorption spectra of la-c, le, lh in toluene.
FIGURE 11 shows, comparatively, thin film (1.8 μm) UV-Vis/PL spectra of A) DH-6T, le, and lh B) 2a, b.
FIGURE 12 shows, comparatively, toluene solution (saturated) UV- Vis/PL spectra of A) DH-6T and lh B) 2a, b.
FIGURE 13 shows cyclic voltammograms illustrating the oxidation and reduction peaks of 2a-b.
FIGURE 14 shows cyclic voltammograms illustrating the oxidation and reduction peaks of lh and 3c.
FIGURE 15 provides an X-ray diffractogram of approximately 2 μm- thick vacuum-evaporated film of 2a on silicon substrate grown at 25°C substrate temperature.
FIGURES 16 and 17 provide molecular stacking diagrams illustrating material structure and the resulting electrical properties in accordance with those and various other compositions of this invention.
Examples of the Invention
The following non-limiting examples and data illustrate various aspects and features relating to the thiophene compounds, composites, materials and related methods and devices of this invention, and demonstrate their surprising and unexpected utility in the transport of electrons (n-type). Comparably utilities and advantages can be realized using various other embodiments consistent with this invention.
Example 1
DFH-6T was synthesized in high yield via Pd -catalyzed Stille coupling of 5-bromo-5'-perfluorohexyl-dithiophene (6) with 5,5'-di(tributyl-stannyl)dithiophene (Fig. 1). This route affords DFH-6T (1) in high purity and yield (~ 95%) after multiple gradient sublimation. Note that although monosubstituted perfluoroalkyl thiophene oligomers up to three units have been reported, synthetic yields were typically ~ 10%. For example, 3'-perfluorohexylterthiophene was isolated in ~ 11% yield.
Example 2
The comparative thermal properties of DFH-6T and DH-6T were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). In the DSC, both compounds exhibit at least one transition (Fig. 2). Compound DH-6T exhibits a distinct crystal-to-liquid crystal (LC) transition at 292 °C and a LC-to- isotropic transition at 309 °C, while the literature shows crystal-to-LC transition of 2 (300 °C) falls just below the melting point, 308-313 °C. These mesophase formation events are not surprising in view of the molecular architectures. However, the most interesting feature is that the two systems exhibit such similar thermal behavior and almost identical melting points, suggesting that strong DH-6T π-π interactions are preserved upon fluorine substitution.
Example 3
In contrast, the α,ω-fluorocarbon chains have a dramatic effect on the volatility of DFH-6T as shown by TGA (Fig. 3 A). The monotonic % weight loss vs. T demonstrates smooth, clean, quantitative sublimation well below the melting point with negligible residue. In contrast, DH-6T exhibits significant volatility only above the melting point, with the TGA data revealing inflections at ~ 298 and ~ 306 °C, suggesting decomposition processes. In addition, a significant decomposition-related residue (~ 6%) is observed at 320 °C. The enhanced volatility of DFH-6T (vs. DH-6T) is further demonstrated by isothermal TGA (Fig. 3B) where DH-6T sublimation at the lowest possible temperature leaves ~ 8 % decomposition residue.
Example 4
Figure 4 shows optical absorption and emission (PL) spectra of DFH-6T and DH-6T in solution (Fig. 4A) and as thin vapor-deposited films (Fig. 4B). Remarkably, the solution spectra are nearly superimposable, arguing that the energy differences between ground and excited states of the 6T core are only marginally sensitive to α,ω-substitution and that the HOMO-LUMO gaps of ~ 2.4 eV are nearly identical. The spectra of the films exhibit both differences and similarities. First, both PL spectra have a central peak and two weaker shoulders. The high energy shoulders fall, for both systems, at the same wavelength near the tail of the absorption, yielding estimated film HOMO-LUMO gaps of ~ 2.2 eV. However, while DFH-6T exhibits strong green fluorescence (λmaχ ~ 588 nm) under UV excitation, the DH-6T emission intensity is several orders of magnitude weaker and red-shifted by ~ 30 nm. The low PL yields of the prior art DH-6T (2) and 6T (3) thin films and blue-shifted absorption maxima vs. solution were previously ascribed to Davydov splitting. The origin of the DFH-6T blue-shifted absorption and enhanced PL efficiency is unknown and warrants further study. While both DH-6T and DFH-6T exhibit strong intermolecular π-π interactions, they are not isostructural (vide infra).
Example 5
The electronic consequences of DH-6T fluoroalkyl substitution were also investigated by cyclic voltammetry (one-compartment cell with a Pt working electrode, Ag/O.IM AgN03 (CH3CN) reference, Ag counter electrodes). The Ag/AgN03 reference electrode was calibrated against ferrocene/ferrocinium (E1 2 = 0.042 V). Voltammograms of DFH-6T and DH-6T in CHC13/0.10M TBABF4 exhibit two chemically irreversible oxidative waves at +0.68/+0.88 V and +0.41/+0.61 V, respectively, and negligible reductive features, indicating chemically irreversible oxidative processes likely related to polaron and bipolaron formation. The first and second anodic peaks of DFH-6T vs. DH-6T exhibit a uniform anodic potential shift (~ +0.27 V), indicating that introduction of perfluoroalkyl chains on the 6T core substantially increases the ionization potential.
Example 6
SEM reveals DFH-6T film growth depends significantly on substrate temperature and surface pretreatment. Films deposited at 25 °C consist of small crystalline grains (~ 80 x 50 nm ) resulting from rapid condensation on the cold substrate (Fig. 5A), while growth at 85 °C (Fig. 5B) affords elongated grains with larger dimensions (~ 500 x 60 nm ) and random orientation. Growth at 145 °C yields larger crystallites (Fig. 5C: ~ 1000 x 350 nm2), however film morphology is less smooth, probably because DFH-6T volatility prevents uniform adsorption on the hot surface. The influence of substrate temperature on crystallite size and film morphology for other thiophene semiconductors such as 6T is known to be related to nucleation site density, growth rate, and surface free energy phenomena during growth. Because Si/Si02 has a hydrophilic native oxide layer, the surface is not ideal for deposition of a hydrophobic adsorbate. Thus, substrates were also pretreated with CF3(CF2)5CH2CH2SiCl3 to produce a fluorocarbon monolayer. The crystallite dimensions are increased by ~ 10% and grain-to-grain, grain-to-substrate interconnections are visibly enhanced. Various other substrate materials known to those skilled in the art can be used in conjunction with this invention, not only to further demonstrate the utility shown in this example, but also in the various composites and electronic devices described elsewhere herein.
Example 7
X-ray diffraction (Cu K^) scans of DFH-6T films grown at various temperatures (Fig. 6) reveal that higher crystalline order is achieved as the substrate temperature is increased to 200 °C. Annealing at 240 °C further enhances microstructural alignment, with the dominant Bragg features assignable to a family of (nOO) reflections corresponding to a real-space periodicity of 36.1 ± 0.2 A, close to the DFH-6T long axis dimension. Although the crystal structure of DFH-6T has not been determined, the XRD data suggest preferential molecular orientation with long axes along the substrate normal, in which case transport in the plane of the film would benefit from close π-π stacking. Note that DFH-6T films grown on CF3(CF2)5CH2CH2SiCl3-treated Si substrates exhibit sharper XRD reflections, indicating highly ordered films. Finally, powder diffraction reveals that DFH-6T and DH-6T are not isostructural, with different unit cell arrangements expected in view of the different packing properties of hydrocarbon vs. perfluorocarbon chains.
Example 8
Demonstrating use of the present invention in conjunction with a thin film as part of a field effect transistor (FET), field-effect measurements were carried out on top contact TFTs with 30-100 nm DFH-6T films deposited at < 10'6 mbar and at ~ 0.5-1.0 A/s onto n+-Si FET substrates with a 230 nm dry thermal Si02 insulating layer. The substrate temperature was varied between 50°C - 120°C. Prior to DFH-6T deposition, the Si02 surface was silylated with hexamethyldisilazane or CF3(CF2)5CH2CH2SiCl3; both yielded similar TFT results. The devices were completed by evaporating Au or Al source-drain contacts on the DFH-6T. Device characteristics were measured under N2 with an HP parameter analyzer. Fig. 7(a) shows characteristics of a typical DFH-6T FET with Au S-D contacts (channel length L = 75 μm, channel width W = 1.5 mm). Transistor action is observed only for positive gate voltages (Vg> 0) indicating an accumulation layer of mobile electrons is formed at the DFH-6T-Si02 gate dielectric interface. No transistor action is induced by applying a negative gate voltage. Previously, only p-type accumulation (Vg< 0) has been observed in TFTs of alkyl-substituted and unsubstituted oligo- and polythiophene derivatives. The positive signs of both gate voltage (Vg) and source drain current (I<j) show that DFH-6T is a new n-type semiconductor. The present n- type conduction doubtless reflects the greater electron affinity of the fluoro alkyl- substituted sexithiophene.
It is remarkable, surprising and unexpected that this relatively minor substiruent-related change is sufficient to dramatically alter thin- film semiconducting properties from p- to n-type. The only other example of such a majority carrier sign inversion is the unrelated phthalocyanine-^perfluorophthalocyanine system. However, DFH-6T and M(F16Pc) differ markedly in the nature of substituent effects, and the inversion observed here would not be expected. In the M(F16Pc) system, extensive C-H — » C-F substitution leads to a large electronic perturbations of the core structure. Furthermore, the nature of the substituents differs. Whereas perfluoroalkyl chains exhibit only strong σ-inductive electron- withdrawing effects (-1), F atoms attached directly to π-systems exhibit both donating-resonance (+R) and attracting- inductive (-1) characteristics.
Example 9
The device of Fig. 7 was fabricated with Au source-drain contacts. Devices with Al contacts exhibit similar characteristics, which is surprising considering the significantly higher Au work function (5.1 eV) vs. Al (4.3eV), implying, a priori, a higher barrier for electron injection from Au. Values for the field-effect mobility were determined from the transfer characteristics in the saturation regime (Fig. 7b). The highest mobilities of 0.02cm2 /Vs
Figure imgf000022_0001
were obtained for film growth at 80-100°C. For growth temperatures ~ 50°, significantly lower mobilities (<10"4cm2/Vs) are observed, and for temperatures ~ 120°C, a reduced mobility is obtained. This optimum substrate temperature doubtless reflects, among other factors, the grain size distribution temperature dependence in the polycrystalline film. The on/off ratio in these DFH-6T devices is as high as 105. The devices exhibit relatively high turn-on voltages V0 of 25 -35 V, indicating a certain fraction of the induced electron carriers occupies localized trap states. The turn-on voltage increases further during operation. This results in a decrease of the TFT ON-current as a function of time which manifests itself in a non- ideal negative slope of the output characteristics in the saturation regime (Fig. 7(a)). The turn-on- voltage can be somewhat reduced and stabilized by post-growth annealing (Fig. 7(b)).
Example 10
With reference to Fig. 1, the reagents 5-bromo-2,2'-dithiophene (4), and 5,5 - bis(tri-n-butylstannyl)-2,2 -dithiophene were prepared according to known synthetic procedures. Other solvents and reagents were purchased from the Aldrich or Lancaster concerns and purified as required.
Example 11
5-Perfluorohexyl-2,2'-dithiophene (5). A suspension of Cu bronze (3.38 g, 53.16 mmol) in dry DMSO (30 mL) was heated at 125°C for 15 min under nitrogen. Perfluorohexyl iodide (11.34 g, 25.43 mmol) was added dropwise in such a way as to keep the temperature below 135°C. After 45 min, a solution of 5-bromodithiophene (2.50 g, 10.17 mmol) in the same solvent (7.0 mL) was added dropwise, and the reaction mixture was stirred at 125°C for 16h. The reaction was next quenched with cold water (100 mL) and diethyl ether was added (200 mL). After shaking, the mixture was filtered through Celite and the organic phase collected. The aqueous layer was extracted once more with ether (100 mL) and the two organic phases were combined, washed with water, and dried over MgS04. After filtration, the solvent was evaporated to yield a solid (5.18 g) which was chromatographed on silica gel (hexane) to afford pure product as a yellow solid (2.90 g, 5.99 mmol, 58.9 % yield). M.p. 51-53 °C (MeOH); 1H NMR (CDC13): δ 7.31-7.37 (2H, m), 7.28 (IH, d, 2J = 3.6), 7.18 (IH, d, 2J = 3.7), 7.06 (IH, dd); 19F NMR (CDC13): δ -81.07 (3F), -101.64 (2F), -121.83 (4F, broad), -123.11 (2F), -126.43 (F). Anal. Calcd for Cι4H5F13S2: C, 34.72; H, 1.04; F, 51.00. Found: C, 34.96; H, 0.99; F, 49.95; HRMS (El, 70 eV): found m/z 483.9626, calcd for C14H5F13S2 (M+) 483.9625.
Example 12
5-Perfluorohexyl-5'-bromo-2,2 -dithiophene (6). With exclusion of light, NBS (1.02 g, 5.73 mmol) was added to a solution of 5-perfluorohexyldihiophene (2.32 g, 4.79 mmol) in DMF (32 mL). After stirring overnight at 25°C, the reaction mixture was poured into brine (120 mL), and the solution then extracted with ether (3x100 mL). The organic phase was next washed with water, dried over MgS04, filtered, and the solvent evaporated to afford 2.60 g of crude product. Flash chromatography on silica gel (hexane) afforded the title compound as a light yellow solid (2.10 g, 3.73 mmol, 77.8 % yield). Sublimation (50°C/10" Torr) afforded a purer sample. M.p. 63- 65 °C; 1H NMR (CDC13) δ 7.34 (IH, d,), 7.12 (IH, d, 2J = 3.1 ), 7.03 (IH, d, 2J = 3.3), 7.01 (IH, d); 19F NMR (CDC13) δ -81.07 (3F), -101.64 (2F), -121.83 (4F, broad), - 123.11 (2F), -126.43 (2F). (fluorine NMR to be recorded). Anal. Calcd for C14H4BrFι3S2: C, 29.86; H, 0.72; F, 43.86. Found: C,; H,; F,; HRMS (El, 70 eV): found m/z 563.8721, calcd for C14H4BrF13S2 (M+) 563.8709.
Example 13 α,ω-Diperfluorohexyl-sexithiophene, DFH-6T (le). A mixture of 5,5 -bis(tri- «-butylstannyi)-2,2 -dithiophene (1.40 g, 1.88 mmol), 5-perfluorohexyl-5'-bromo-2,2 - dithiophene (2.00 g, 3.55 mmol) and Pd(PPh3)4 (0.050 g, 0.040 mmol) in dry DMF (40 mL) was deareated twice with nitrogen. The reaction mixture was then heated at 80°C for 7 h during which time a precipitate formed. After cooling, the bright orange solid was collected and washed several times with hexane, methanol, and acetone to afford the analytically pure product (1.91 g, 1.69 mmol, 95.2 % yield). M.p. 309°C. Additional purification can be achieved by gradient sublimation. Anal. Calcd for C36H12F26S6: C, 38.24; H, 1.07; F, 43.69. Found: C, 38.16; H, 1.15; F, 43.42; MS (El, 70 eV) 1127.4 (M+, 70%).
Example 14 With reference to structure 7, below, the compounds of this example further illustrate the thiophene compositions, materials and/or films of the type available through this invention. (X is a functional group of the sort described in Example 15, and a=0-12.)
Figure imgf000024_0001
7
Figure imgf000024_0002
7a 1 C6F13 C6F13
7b 1.5 CF3 C2H4X
7c 3 C H9 CF3
7d 4 C3F7 (CH2)aX
7e 5-6 C2F5 CδFι-7
Example 15
In general, the oligo-and/or polythiophene compounds of this invention including those of and represented by the preceding example are prepared in accordance with the synthetic procedures described herein and straight-forward modifications thereof. Substitution of 5-halo-2,2'-dithiophene with a suitable fluorocarbon provides one intermediate (a). Alternatively, the monohalodithiophene can be halogenated through known techniques for subsequent fluorocarbon substitution at both the 5 and 5' positions, such a dithiophene for use as described herein, as an n-type semiconducting material.
Yet another embodiment of this example contemplates substitution at the 5' position, and fluoroalkylation at the 5 position to provide a second intermediate (b). The 5' substituent introduces an aromatic or aikyl moiety including but not limited to amino, hydroxyl and/or carboxylic functional groups for later possible synthetic transformation. Intermediates (a) and/or (b) of this example are coupled with a stannyl (mono - or - bis -) thiophene (mono - or - di -), or further reacted with another intermediate of the type described herein to provide a range of conjugated thiophene units, with the desired degree of fluoroalkylation and/or alternate functionalization.
Example 16 Figure 8 illustrates incorporation of a thiophene semiconductor material of the present invention in an n-channel junction field-effect transistor (JFET). The JFET includes a gate region 10 constructed from a p-type semiconductor material and a channel 12 constructed from an n-type thiophene thin film deposited on a suitable substrate. (As mentioned above, the material of region 10 can be a p-type thiophene semiconductor.) In this device, a voltage applied to a gate electrode 14 controls current flow through the thin film/substrate composite of channel 12 between the drain electrode 16 and the source electrode 18. One of ordinary skill in the art can similarly apply a thiophene material of the present invention in a number of other transistor applications to provide without limitation p-channel JFETs, bipolar junction transistors of both the npn and pnp type, depletion and enhancement mode MOSFETS of both n and p channel types, and other types of transistors and integrated circuits.
Example 17
The reagents 5-bromo-2,2':5',2"-terthiophene, 5-bromo-2,2 -dithiophene, and 5,5 -bis(tri-n-butylstannyl)-2,2 -dithiophene were prepared according to known procedures. Solvents and chemicals were purchased from Aldrich or Lancaster and purified as required.
Example 17a
5-Perfluorohexyl-2,2 :5 '2' '-terthiophene and 5.5'-diρerfluorohexyl-2,2,:5 '2' '- terthiophene. A suspension of copper bronze (1.01 g, 15.9 mmol) in dry DMSO (10 mL) was heated at 125°C for 15 min under nitrogen. Perfluorohexyl iodide (3.40 g, 7.62 mmol) was then added dropwise in such a way as to keep the temperature below 135°C. After 45 min, a warm solution of 5-bromoterthiophene (1.00 g, 3.05 mmol) in the same solvent (10 mL) was added in a single portion, and the reaction mixture was stirred at 125°C for 14h. Distilled cold water (60 mL) was next added to the reaction flask and the resulting precipitate was collected on a Buchner funnel, washed several times with water, and finally dried overnight under vacuum. The crude product (1.40 g) was obtained from this solid by extraction with chloroform (3x50 mL). Column chromatography on silica gel (hexane) afforded the pure fluorinated product (0.76g, 1.34 mmol, 43.9% yield) as a light yellow solid. M.p. 158 °C (zPrOH); 1H NMR (CDC13) δ 7.36 (IH, d, 2J= 3.8), 7.28 (IH, d, 2J= 3.6), 7.22 (IH, d, 2J= 3.7), 7.15- 7.19 (2H, m), 7.12 (IH, d, 2J= 3.8), 7.06 (IH, dd); 19F NMR (CDC13) δ -81.10 (3F), - 101.63 (2F), -121.89 (4F, broad), -123.10 (2F), -126.44 (2F). Anal. Calcd for Cι8H7F13S3: C, 38.17; H, 1.25; F, 43.61. Found: C, 37.95; H, 1.18; F, 44.01; HRMS (El, 70 eV): found m/z 565.9501, calcd for Cι8H7F13S3 (M+) 565.9502. 5,5'- diperfluorohexyl-2,2': 5 ',2 "-terthiophene was obtained as byproduct (0.18 g, 0.201 mmol, 6.7 % yield). M.p. 132 °C (toluene); 1H NMR (CDC13) δ 7.38 (3H, d, 2J= 3.4), 7.22 (2H, d), 7.21 (2H, s); 19F NMR (CDC13) δ -81.08 (6F), -101.61 (4F), -121.90 (8F, broad), -123.07 (4F), -126.43 (4F). Anal. Calcd for C24H6F26S3: C, 32.59; H, 0.685; F, 55.85. Found: C, 32.50; H, 0.69; F, 55.63; HRMS (El, 70 eV): found m/z 883.9226, calcd for C24H6F26S3 (M+) 883.9217.
Example 17b 5-Perfluorohexyl-2,2 -dithiophene and 5,5'-diperfluorohexyl-2,2 -dithiophene. A suspension of copper bronze (3.38 g, 53.16 mmol) in dry DMSO (30 mL) was heated at 125°C for 15 min under nitrogen. Perfluorohexyl iodide (11.34 g, 25.43 mmol) was added dropwise in such a way as to keep the temperature below 135°C. After 45 min, a solution of 5-bromodithiophene (2.50 g, 10.17 mmol) in the same solvent (7 mL) was added dropwise, and the reaction mixture was stirred at 125°C for 16h. The reaction was next quenched with cold water (100 mL) and diethyl ether was added (200 mL). After shaking, the mixture was filtered through Celite and the organic phase collected. The aqueous layer was extracted once more with ether (100 mL) and the two organic phases were combined, washed with water, and dried over MgS04. After filtration, the solvent was evaporated to give a solid (5.18 g) which was chromatographed on silica gel (hexane) to afford two products. 5,5'-diperfluorohexyl- 2,2 '-dithiophene (0.70 g, 0.87 mmol, 8.6 % yield) as a white solid, mp = 97 °C (toluene); 1H NMR (CDC13) δ 7.41 (2H, d, 2J= 3.5), 7.27 (IH, d); 19F NMR (CDC13) δ -81.05 (6F), -101.90 (4F), -121.72 (4F), -121.89 (4F), -123.09 (4F), -126.41 (4F). Anal. Calcd for C2oH4F26S2: C, 29.94; H, 0.50; F, 61.57. Found: C, 29.90; H, 0.57; F, 61.73; HRMS (El, 70 eV): found m/z 801.9336, calcd for C20H4F26S2 (M+) 801.9334. The monosubstituted system was isolated as a yellow solid (2.90 g, 5.99 mmol, 58.9 % yield). M.p. 51-53 °C (MeOH); 1H NMR (CDC13) δ 7.31-7.37 (2H, m), 7.28 (IH, d, = 3.6), 7.18 (IH, d, 2J= 3.7), 7.06 (IH, dd); 19F NMR (CDC13) δ -81.07 (3F), - 101.64 (2F), -121.83 (4F, broad), -123.11 (2F), -126.43 (F). Anal. Calcd for C14H5F13S2: C, 34.72; H, 1.04; F, 51.00. Found: C, 34.96; H, 0.99; F, 49.95; HRMS (El, 70 eV): found m/z 483.9626, calcd for C14H5F13S2 (M+) 483.9625.
Example 17c
5-Perfluorohexyl-5'-bromo-2,2 -dithiophene. With the exclusion of light, NBS (1.02 g, 5.73 mmol) was added to a solution of 5-perfluorohexyldihiophene (2.32 g, 4.79 mmol) in DMF (32 mL). After stirring overnight at room temperature, the reaction mixture was poured onto brine (120 mL) and the solution then extracted with ether (3x100 mL). The organic phase was next washed with water, dried over MgS0 , filtrated, and the solvent evaporated to afford 2.60 g of crude product. Flash chromatography on silica gel (hexane) afforded the title compound as a light yellow solid (2.10 g, 3.73 mmol, 77.8 % yield). Sublimation (50°C/10"3 Torr) afforded a purer sample. M.p. 63-65 °C; 1H NMR (CDC13) δ 7.34 (IH, d,), 7.12 (IH, d, 2J= 3.1 ), 7.03 (IH, d, 2J= 3.3), 7.01 (IH, d); 19F NMR (CDC13) δ -81.07 (3F), -101.64 (2F), -121.83 (4F, broad), -123.11 (2F), -126.43 (2F). (fluorine NMR to be recorded). Anal. Calcd for Cι4H4BrF13S2: C, 29.86; H, 0.72; F, 43.86. Found: C,; H,; F,; HRMS (El, 70 eV): found m/z 563.8721, calcd for C14H4BrF13S2 (M+) 563.8709.
Example 17d
5-(tri-»-Butylstannyl -5 '-( 1 -perfluorohexyl -2,2 -dithiophene. n-BuLi (1.6 M, 1.11 mL) was added dropwise to a solution of 5-bromo-5'-(l-perfluorohexyl)-2,2 - dithiophene (1.00 g, 1.77 mmol) in THF (15 mL) at -78°C. The reaction mixture was stirred at this temperature for 30 min, and then for 1 h at room temperature followed by the addition of tri-n-butyltin chloride (0.59 g, 1.80 mmol). After stirring for 3 h at room temperature, hexane (50 mL) was added to the mixture and the organic phase was washed with a solution of NH4C1 (5%, 20 mL) and water (20 mL). The clear solution was dried over MgS04 and concentrated in vacuo to afford the product as a brown oil (1.32 g, 1.71 mmol, 96.6 % yield). 1H NMR (CDC13) δ 7.36 (IH, d,2J= 3.3), 7.32 (IH, d, J= 3.7), 7.15 (IH, d), 7.09 (IH, d), 1.54-1.60 (6H, m), 1.32-1.38 (6H, m), 1.13 (6H, t, 2J= 8.1), 0.90 (9H, t, 2J= 7.3); 19F NMR (CDC13) δ -81.28 (3F), -101.70 (2F), -121.79 (2F), -122.00 (2F), -123.13 (2F), -126.43 (2F). HRMS (El, 70 eV): found m/z 774.0680, calcd for C26H44S2Sn (M+) 774.0682.
Example 17e 5.5"'-Diperfluorohexyl-2,2 ': 5 '2 ": 5 "2 '": 5 '"2 "":5 ""2 "'"-quaterthiophene. A mixture of 5-(tri-n-butylstannyl)-5'-(l-perfluorohexyl)-2,2 -dithiophene (1.31 g, 1.70 mmol), 5-perfluorohexyl-5'-bromo-2,2 -dithiophene (0.96 g, 1.70 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.05 g, 0.04 mmol) in dry DMF (10 mL) was deareated twice with nitrogen. The reaction mixture was then heated at 95 °C for 5 h during which time a precipitate formed. After cooling, the bright yellow solid was collected and washed several times with methanol and Et20 to afford the analytically pure product (1.30 g, 1.35 mmol, 79.4 % yield). M.p. 213 °C. Additional purification can be achieved by gradient sublimation. 1H NMR (C2C14D2, -60 °C) δ 8.28 (2H, d, 2J = 3.8), 8.09-8.14 (4H, m), 7.08 (IH, d, , J= 4.0); I9F NMR (C2C14D2, -60 °C) δ - 79.64 (3F), -99.88 (2F), -120.10 (4F), -121.41 (2F), -124.64 (2F). Anal. Calcd for C28H8F26S4: C, 34.81; H, 0.84; F, 51.14. Found: C, 34.66; H, 0.94; F, 51.06; MS (El, 70 eV) 965.9 (M+, 100%).
Example 17f 3 -Perfluorohexyl-2.2 -dithiophene. A suspension of copper bronze (6.76 g, 106.32 mmol) in dry DMSO (60 mL) was heated at 125 °C for 15 min under nitrogen. Perfluorohexyl iodide (22.68 g, 50.86 mmol) was added dropwise in such a way as to keep the temperature below 135 °C. After 40 min, a solution of 3-bromo-2.2'- dithiophene (5.00 g, 20.34 mmol) in the same solvent (14 mL) was added dropwise, and the reaction mixture was stirred at 125 °C for 6 h. The reaction was next quenched with cold water (200 mL) and diethyl ether was added (300 mL). After shaking, the mixture was filtered through Celite and the organic phase was collected. The aqueous layer was extracted once more with ether (300 mL) and the two organic phases were combined, washed with water, and dried over MgS04. After filtration, the solvent was evaporated to give a brown oil (~ 9 g) which was chromatographed on silica gel (hexane) to afford the product as a yellow oil (5.20 g, 10.74 mmol, 52.8 % yield). 1H NMR (CDCI3) δ 7.44 (IH, dd, 2J= 5.2 3J= 1.3), 7.41 (IH, d, 2J= 5.5), 7.20-7.24 (2H, m), 7.09 (IH, dd); 19F NMR (CDC13) δ -81.20 (3F), -102.95 (2F), -121.18 (2F), - 122.01 (2F), -123.09 (2F), -126.43 (2F). Anal. Calcd for C14H5F13S2: C, 34.72; H, 1.04; F, 51.00. Found: C, 35.01; H, 1.04; F, 49.98; HRMS (El, 70 eV): found m/z, calcd for C14H5F13S2 (M+).
Example 17g 3-d -Perfluorohexyl -5'-bromo-2,2 -dithiophene. In the absence of light NBS (1.47 g, 8.26 mmol) was added portionwise to a solution of 3-(l-perfluorohexyl)-2,2 - dithiophene (4.00 g, 8.26 mmol) in DMF (70 mL) at -30°C over the period of 6 h. The reaction mixture was left to slowly reach room temperature and, after stirring overnight, was poured onto water (100 mL). The aqueous phase was extracted with ether (3x100 mL) and the combined ethereal phases were washed with water and dried over MgS0 . The solvent was evaporated leaving a brown oil (4.35 g), which was chromatographed on silica gel (hexane) to afford the title compound as a light yellow oil (3.67 g, 6.51 mmol, 78.8 % yield). 1H NMR (CDC13) δ 7.42 (IH, d, 2J= 5.5), 7.21 (IH, d), 6.40 (IH, d, 2J= 3.9), 6.96 (IH, d). 19F NMR (CDC13) δ -81.18 (3F), -103.35 (2F), -121.26 (2F), -122.10 (2F), -123.19 (2F), -126.51 (2F). HRMS (El, 70 eV): found m/z, calcd for C1 H4BrF13S2 (M+).
Example 17h 3 ,3'""-Diρerfluorohexyl-2.2 ': 52 ": 5 "2 '": 5 '"2 "" 5 ""2 ""'-sexithiophene. A mixture of 5,5 -bis(tri-n-butylstannyl)-2,2 -dithiophene (2.00 g, 3.55 mmol), 5- perfluorohexyl-5'-bromo-2,2 -dithiophene (1.40 g, 1.88 mmol) and tetrakis(tiiphenylphosphine)palladium(0) (0.05 g, 0.04 mmol) in dry DMF (40 mL) was deareated twice with nitrogen. The reaction mixture was then heated at 90 °C overnight during which time a precipitate formed. After cooling, the bright orange solid was collected and washed several times with ether to afford the analytically pure product (1.80 g, 1.59 mmol, 89.6 % yield). M.p. 217 °C. Additional purification can be achieved by gradient sublimation. 1H NMR (C2C14D2, 110 °C) δ 7.43 (2H, d, 2J= 5.6), 7.24 (IH, d), 8.14-8.19 (8H, m); 19F NMR (C2C14D2, 110 °C) δ -81.30 (6F), - 102.22 (4F), -120.71 (2F), -121.51 (4F), -122.68 (4F), -125.94 (4F). Anal. Calcd for C36H12F26S6: C, 38.24; H, 1.07; F, 43.69. Found: C, 38.41; H, 1.07; F, 43.60.
Example 18a 5,5'-Bis[l-(4-bromo-2.3,5,6-tetrafluorophenyl ]-2,2 -dithiophene. A mixture of 5,5 '-bis(tri-n-butylstannyl)-2,2 '-dithiophene (4.62 g, 4.87 mmol), 1,4- dibromoperfluorobenzene (6.00 g, 19.48 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.12 g, 0.10 mmol) in dry DMF (20 mL) was deareated twice with nitrogen. The reaction mixture was then heated at 85 °C for 20 h during which time a precipitate formed. After cooling, the orange solid was collected and washed several times with hexane and ether to afford the crude product which was purified by gradient sublimation (2.14 g, 3.42 mmol, 70.2 % yield). M.p. 231 °C. 1H NMR (CDC13) δ 7.60 (2H, d, 2J= 4.1), 7.34 (2H, d); 19F NMR (CDC13) δ - 133.58 (4F), -138.56 (4F). Anal. Calcd for C20H4Br2F8S2: C, 38.72; H, 0.65; F, 24.51. Found: C, 38.75; H, 0.78; F, 24.29.
Example 18b 5,5,-Bis{l-[4-(thien-2-yl -2,3,5,6-tetrafluoroρhenyl li-2,2'-dithioρhene. A mixture of 2-(tri-n-butylstannyl)thiophene (1.35 g, 3.63 mmol), 5,5'-bis[l-(4-bromo- 2,3, 5,6-tetrafluorophenyl)]-2,2 -dithiophene (0.75 g, 1.20 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.02 g, 0.02 mmol) in dry toluene (20 mL) was deareated twice with nitrogen. The reaction mixture was refluxed for 20 h during which time a precipitate formed. After cooling, the orange-gold solid was collected and washed several times with hexane and ether to afford the pure product after gradient sublimation (0.55 g, 0.88, 73.3 % yield). M.p. 319 °C. 1H NMR (C2C14D2, 125 °C) δ 7.71 (IH, d, 2J= 3.8), 7.66 (IH, d, 2J= 3.9), 7.62 (IH, d,2J= 4.6), 7.40 (IH, d), 7.26 (IH, dd); 19F NMR (C2C14D2, 125 °C) δ -140.91 (8F). Anal. Calcd for C28H10F8S4: C, 53.67; H, 1.61; F, 24.26. Found: C, 53.80; H, 1.71; F, 24.35.
Example 18c 2-Perfluorophenylthiophene. A mixture of 2-(tri-n-butylstannyl)thiophene (15.0 g, 40.50 mmol), bromoperfluorobenzene (10.00 g, 40.50 mmol), tetrakis(triphenylphosphine)palladium(0) (0.92 g, 0.80 mmol) and few crystals of 2,6- di-tert-butyl-4-methylphenolo in dry toluene (80 mL) was deaerated twice with nitrogen. The reaction mixture was refluxed 24 h and, after cooling, poured onto a solution of NH4F (5 g, 200 mL of water). After stirring for 30 min, hexane (300 mL) and acetone (150 mL) were added and the mixture was filtered over celite. The organic phase was separated, dried over MgS04, and the solvent was evaporated to afford a brown oil (18.36 g), which was chromatographed on silica gel (hexane) to give the pure product as a white solid (8.25 g, 32.97 mmol, 81.41 % yield). M.p. = 44 °C. 1H NMR (CDC13) δ (IH, dd, 2J= 5.2, 3J= 0.9), (IH, dd, 2J= 3.5), (2H, m). 19F NMR (CDCI3) δ - (4F), - (4F). HRMS (El, 70 eV): found m/z, calcd for C10H3F5S (M+).
Example 18d
2-Perfluorophenyl-5-bromothiophene. In the absence of light NBS (2.45 g, 13.79 mmol) was added to a solution of 2-perfluorophenylthiophene (300 g, 11.99 mmol) in DMF (50 mL). After stirring overnight at room temperature, iced water (200 mL) was added and the precipitate was collected, washed with water, and dried under vacuum to afford the pure product as a white solid (3.70 g, 11.24 mmol, 93.7% yield). Mp = 79 °C. 1H NMR (CDC13) δ 7.30 (IH, d, 2J= 4.0), 7.16 (IH, d). 19F NMR (CDCI3) δ -140.04 (IF), -155.07 (2F), -161.65 (2F). HRMS (El, 70 eV): found m/z, calcd for C10H2BrF5S (M+).
Example 18e
5,5"'-Diperfluorophenyl-2,2 ': 5 '2 ": 5 "2 '": 5 '"2 "": 5 ""2 '""-quaterthiophene. A mixture of 5,5 '-bis(tri-n-butylstannyl)-2,2 -dithiophene (2.26 g, 3.04 mmol), 2- perfluorophenyl-5-bromothiophene (2.00 g, 6.08 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.07 g, 0.06 mmol) in dry DMF (40 mL) was deareated twice with nitrogen. The reaction mixture was refluxed overnight during which time a precipitate formed. After cooling, the orange solid was collected and washed several times with hexane, MeOH, and ether to afford the pure product as an orange solid (1.58 g, 2.38 mmol, 78.3 % yield). Additional purification can be achieved by gradient sublimation. M.p. 246 °C. 1H NMR (C2C14D2, 125 °C) δ 7.50 (2H, d, 2J= 3.5), 7.29 (2H, d), 7.23 (2H, d, 2J= 3.8), 7.19 (IH, d); 19F NMR (C2C14D2, 125 °C) δ -140.03 (2F), -156.40 (4F), -162.66 (4F). Anal. Calcd for C28H8Fι0S4: C, 50.75; H, 1.22; F, 28.67. Found: C, 50.85; H, 1.28; F, 28.95. Example 19a
4,6-Di(thien-2-yl ρyrimidine. A mixture of tri-n-butylstannylthiophene (10.52 g, 28.19 mmol), 4,6-dichloropyrimidine (2.00 g, 13.42 mmol), tetrakis(triphenylphosphine)palladium(0) (0.345 g, 0.30 mmol) and few crystals of 2,6-di-tert-butyl-4-methylphenolo in dry toluene (20 mL) was deareated twice with nitrogen. The reaction mixture was refluxed for 6 hours and, after cooling, a white precipitate was formed in the reaction flask. The solid was collected and the organic phase v/as diluted with ether (100 mL), poured onto a solution of NH4F (3g, 100 ml) and separated. After drying over MgS04, the solvent was evaporated affording a solid material. The two solid phase were combined and crystallized from toluene to give the pure product as a white crystals (2.36 g, 9.66 mmol, 72.0% yield), mp 146 °C; 1H NMR (CDCI3) δ 9.07 (IH, ά, 2J= 1.4), 7.86 (IH, d, 2J= 3.7), 7.83 (IH, d), 7.57 (IH, d, 2J= 5.1), 7.20 (lH, dd).
Example 19b
5,5'-Bis-(6-chloropyrimid-4-yl -2,2 -dithiophene. A mixture of 5,5 -bis(tri-n- butylstannyl)-2,2 -dithiophene (7.58 g, 10.18 mmol), 4,6-dichloropyrimidine (6.00 g, 40.27 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.26 g, 0.22 mmol) in dry toluene (70 mL) was deareated twice with nitrogen. The reaction mixture was refluxed for 6 hours and, after cooling, the precipitate was collected. The solid residue was washed several times with hexane and than with methanol to afford the practically pure compound as a yellow powder (2.80 g, 7.16 mmol, 70.3 % yield), mp 261 °C (sublimation); 1H NMR (CDC13) δ 8.91 (2H, d, J= 1.3), 7.73 (2H, d, J= 4.0), 7.60 (2H, d), 7.37 (2H, d,). ms 390.9(100%) 392.9 (75%). Anal. Calcd for C16H8C12N4S2: C, 49.11; H, 2.06; N, 14.32. Found: C, 49.21; H, 2.19; N, 14.16.
Example 19c
5,5'-Bis 6-(thien-2-yl)pyrimid-4-yl)-2,2 -dithiophene. A mixture of 5,5'-bis(6- chloropyrimid-4-yl)-2,2 -dithiophene (1.40 g, 3.58 mmol), tri-n-butylstannylthiophene (3.00 g, 8.04 mmol), tetrakis(triphenylphosphine)palladium(0) (0.20 g, 0.17 mmol) and few crystals of 2,6-di-tert-butyl-4-methylphenolo in dry toluene (120 mL) was deareated twice with nitrogen. The reaction mixture was refluxed for 10 hours and, after cooling, the precipitate was collected (2.00 g). The solid residue was washed several times with hexane and than crystallized from pyridine (170 mL) to afford the pure compound as an orange solid (0.88 g, 1.81 mmol, 50.5% yield). Extremely pure samples can be obtained after gradient sublimation, mp = 306 °C; 1H NMR (CDC13) δ 9.09 (2H, d, 2J= 1.2), 7.94 (2H, d, 2J= 3.7), 7.85 (2H, d, 2J= 4.0), 7.83 (2H, d), 7.61 (2H, d, 2J= 4.9), 7.41 (2H, d), 7.24 (2H, dd). ms 487.0 (100%). Anal. Calcd for C24H14N4S4: C, 59.23; H, 2.91; N, 11.52. Found: C, 59.17; H, 2.97; N, 11.37.
Example 19d 5,5'-Bis 6-(5-hexylthien-2-yl pyrimid-4-yl)-2,2 -dithiophene. A mixture of 5,5'-bis(6-chloropyrimid-4-yl)-2,2 -dithiophene (1.05 g, 2.68 mmol) ), 2-(tri-«- butylstannyl)-5-hexylthiophene (2.60 g, 5.68 mmol), tetrakis(triphenylphosphine)palladium(0) (0.15 g, 0.13 mmol) and few crystals of 2,6- di-tert-butyl-4-methylphenolo in dry toluene (90 mL) was deareated twice with nitrogen. The reaction mixture was refluxed for 12 hours and, after cooling, the precipitate was collected by centrifugation (1.66 g). The solid residue was washed once with hexane and than dissolved in hot chloroform (150 mL). The warm solution was filtered and the solvent evaporated to give the pure product as a brown solid (1.21 g, 1.85 mmol, 71.1 % yield). An analytical sample was crystallized from toluene and sent to the elemental analysis, mp = 230 °C; 1H NMR (CDC13) δ ???? (2H, d, 2J= 1.2), ???? (2H, d, 2J= 3.7), (2H, d, 2J= 4.0), (2H, d), (2H, d, 2J= 4.9), (2H, d), (2H, dd). Anal. Calcd for C36H38N4S4: C, 66.01; H, 5.86; N, 8.56. Found: C, 65.88; H, 5.57; N, 8.57.
Example 19e 3-(Thien-2-yl)-6-chloropyridazine. A mixture of tri-n-butylstannylthiophene (6.26 g, 16.78 mmol), 3,6-dichloropyridazine (5.00 g, 33.56 mmol), tetrakis(triphenylphosphine)palladium(0) (0.20 g, 0.17 mmol) and few crystals of 1,2- ditert-butyl of 2,6-di-tert-butyl-4-methylphenolo in dry DMF (50 mL) was deareated twice with nitrogen. The reaction mixture was heated at 80°C for 6 hours and, after cooling, poured onto water (100 mL). A white precipitate was collected, washed several times with water and dried under vacuum. This solid was taken up with ether (25 mL) and filtered to afford 3.01 g of almost pure product. Finally, this solid was crystallized from MeOH-H20 to give the pure target compound as white crystals (1.56 g, 7.90 mmol, 47.3% yield). Mp 155 °C; 1H NMR (CDC13) δ 7.75 (IH, d, 2J= 11.0), 7.68 (IH, d, 2J= 3.6), 7.54 (IH, d, 2J= 5.0), 7.51 (IH, d), 7.18 (IH, dd).
Example 19f
5,5'-Bis["6-(thien-2-yl pyridazin-3-yl l-2,2 -dithiophene. A mixture of 3-(thien- 2-yl)-6-chloropyridazine (1.50 g, 7.63 mmol), 5,5'-bis(tri-«-butylstannyl)-2,2 - dithiophene (2.84 g, 3.81 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.09 g, 0.08 mmol) in dry DMF (30 mL) was deareated twice with nitrogen. The reaction mixture was heated at 70 °C overnight. After cooling, the precipitate was collected, washed several times with hexane, MeOH, and ether. After drying the pure product was obtained as a light orange solid (1.60 g, 3.29, 86.3 % yield), mp > 350 °C. Anal. Calcd for C24H14N4S4: C, 59.23; H, 2.91; N, 11.52. Found: C, 58.85; H, 3.11; N, 11.57.C.
Example 20
The data of the following examples illustrate the impact of both perfluoroalkyl and perfluorophenyl/azine substitution on the chemical, thermal, optical and electronic properties of the π-conjugated core by thermal (DSC, TGA), molecular spectroscopy (UV-Vis, PL), and electrochemical (CV, DPP), techniques. Reference systems are the unsubstituted (6T) and α,ω-dihexyl substituted (DH-6T) sexithiophenes of the prior art. Morphological and crystal structure data are also provided.
Figure imgf000034_0001
DH-6T, R= "C6H13 6T, R = H
Example 20a
With reference to Figure 2 (and Example 2), the α,ω-fluorocarbon chains have a dramatic effect on the volatility of most of systems 1 - 3 (Fig. 9). The monotonic % weight retention vs. T demonstrates smooth, clean, quantitative sublimation well below the melting point with negligible residue. In contrast, DH-6T (Fig. 2) exhibits significant volatility only above the melting point, with the TGA data revealing inflections at « 298 and * 306 °C, suggesting decomposition processes. In addition, a significant decomposition-related residue (« 6 %) is observed at 320 °C.
Example 20b Absorption and fluorescence emission spectra were recorded to monitor the effect of substitution on the HOMO-LUMO energy gap. By varying the number of thiophene units, it is possible to modulate optical absorption from 300 to 500 nm (Figure 10). On the other hand, fluorophenyl-azine insertion into the 6T core allows for a very fine tune in the range of 450-500 nm (Table 1). Film PL intensities change of many orders of magnitude with chemical structure. DFH-6T and iso-DFH-6T were found much more efficient that the corresponding unsubstituted and dialkyl substituted systems. 2a is substantially more efficient than 2b in spite of the similar solution absorption/emission and film absorption patterns. Comparative spectra are also shown in Figures 11-12.
Table 1. Absorption (λmax, nm) Data in Toluene Solution and as Thin Film (ca. 1.8 μm).
Compound 'Vmax
Solution Film
DFH-2T 348
DFH-3T 411
DFH-4T 456 429 isoDFH-6T 482 461
DFH-6T 492 526
DH-6T 497 535
BFT4BF 475 456
TBFT2BFT 452 419
BrBFT2BFBr 428
TPMT2PMT 451
TPDT2PDT 462
Table 2. HOMO-LUMO Energy Gap (Eg, eV) from Optical Data.
Compound Eg
Solution Film
DFH-2T 3,57
DFH-3T 3,02
DFH-4T 2,72 2,89 isoDFH-6T 2,58 2,69
DFH-6T 2,52 2,36
DH-6T 2,50 2,32
BFT4BF 2,61 2,72
TBFT2BFT 2,75 2,96
BrBFT2BFBr 2,9
TPMT2PMT 2,75
TPDT2PDT 2,69 Example 20c The effects of fluoroalkyl, fluorophenyl, and azine substitution- insertion were also investigated by cyclic voltammetry (one-compartment cell with Pt electrode, bare Ag reference, Pt counter electrodes). Results are collected on Table 3. Voltammograms of most of the investigated systems in THF/0.10M TBABF exhibit two chemically oxidative and reductive peeks (Figures 13 and 14). Note that the first and second anodic peaks of DFH-6T vs. DH-6T exhibit a uniform anodic shift (« +0.27 V), indicating that introduction of perfluoroalkyl chains on the 6T core substantially increases the ionization potential. The similar HOMO-LUMO gaps of DFH-6T and DH-6T argue that the LUMO of DFH-6T is also ca. 0.27 V below that of DH- 6T, which is confirmed by electrochemical studies on thin films.
Table 3. Anodic (E_), Cathodic(Ec), and Standard (E°) Potentials of Compounds la-c, lh, 2a- b, 3a, and, 3c in THF.
Compound 1 Oxidation Potentials Reduction Potentials anodic cathodic standard anodic cathodic standard anodic cathodic
Et\ E,2 E„\ Ec2 £°ι £°. E_ E_ ED\ E_ £°ι £°2
DFH-2T 1. 9 -1.45
DFH-3T 1.39 -1.48
DFH-4T 1.31 -0.95 -1.75 -0.76 -1.40 -0.85 -1.57 isoDFH-6T1.01 1.23 0.88 1.06 0.94 1.14 -1.47 1.97 1.06 -1.74 -1.26 -1.86
BFT4BF 1.07 1.56 0.89 1.44 0.98 1.50 -1.56 -2.14 -1.38 -1.96 -1.47 -2.05
TBFT2BFT1.43 -1.80 -1.94 -1.70 -1.83 -1.75 -1.88
TPMT2PMT 1.42 1.69 1.16 1.41 1.29 1.55 -1.74 -1.87 -1.60 -1.75 -1.67 -1.72
TPDT2PDT1.14 1.44 -1.57 -2.01 -1.35 -1.80 -1.79 -1.90
Figure imgf000037_0001
A morphological study on evaporated DFH-6T thin films was provided above, Example 6 and Fig. 6. In comparison thereto, general amorphous lc, lh, 2a, 2b, 3a, 3c films can be prepared by rapid evaporation on cold substrates (glass, quartz, silicon). Lower evaporation rates and/or higher substrate temperatures produce much higher ordered microstructures and larger crystalline domains (from SEM data). In addition, thanks to the great volatility of these systems annealing of amorphous films for short period of times dramatically improves microstructure order.
Example 20e
Molecular packing diagrams of DFH-3T and 2a are shown in Figure 16 and 17, respectively. The crystal structure clearly shows the close π-π stacking intermolecular arrangement in these systems, and as can be observed and/or utilized in various other embodiments of this invention.
The preceding examples and data confirm that the n-type thiophene- modified systems of this invention are more chemically and thermally stable than the corresponding p-type π-isoelectronic oligo- and polythiophenes and can be transported quantitatively into the gas phase without decomposition. In particular, fluoro-azine substitution-insertion allows for an effective modulation of optical absorption-emission maximum, optical gap, and photoluminescent efficiencies (quantum yields) both in solution and as thin- deposited films. By combining the electrochemical and optical data, absolute orbital energies can be estimated. HOMO(LUMO) energies can be determined from the first oxidation(reduction) potentials. Modification of an all-thiophene framework by introduction of powerful electron- withdrawing groups or electron-poor heterocycles decreases MO energy levels, allowing for an easier electron injection. Depending on chemical nature of the system, deposition method (evaporation, spin-coating, casing), substrate temperature and pretreatment, either highly ordered or amorphous solids can be produced.
While the principles of this invention have been described in connection with specific embodiments, it should be understood clearly that the summary and descriptions herein, along with the chosen tables, graphs and data provided, are made only by way of example and are not intended to limit the scope of this invention in any manner. For example, a variety of the thiophene materials, of the type described herein, can be utilized as thin films incorporated into a wide range of electronic devices. Such devices and any related circuitry can be fabricated using complementary (n-type and p-type) thiophene materials. The chemical and corresponding physical properties of such compositions/materials such as n-type conductivity, electron affinity and electron mobility can be modified, as described herein, by choice of thiophene structure, fluoroalkyl substitution and/or heterocycle insertion, such modifications as may be desired for a particular end use application. Likewise, the substitution and/or insertion methods disclosed herein can also be applied to various non-thiophene systems, to alter electronic properties and/or provide n-type conductivity. Other advantages and features of this invention will become apparent from the foregoing and any claims made thereto, with the scope thereof determined by the reasonable equivalents, as would be understood by those skilled in the art.

Claims

What is Claimed:
1. An n-type polythiophene composition having the structural
formula
Figure imgf000040_0001
wherein R1? R2 and R3 are selected from the substituent group consisting of fluoroalkyl moieties, CnH2n+1 and where n is about 1-12, H, F and (CH2)aX and where a is about 1-12 and X is selected from the group consisting of amino, hydroxy and carboxylic acid functionalities; and x, y and z are integers selected from the group of integers consisting of 0 and integers greater than 0.
2. The n-type polythiophene composition of claim 1 wherein said fluoroalkyl moiety is selected from the group consisting of linear fluoroalkyl substituents, branched fluoroalkyl substituents and cyclic fluoroalkyl substituents.
3. The n-type polythiophene composition of claim 2 wherein said fluoroalkyl moiety has a compositional formula CnF2n+1> where n is about 1-8.
4. The n-type polythiophene composition of claim 1 wherein x is about 0-4; y is about 0-8, and z is about 0-12.
5. The n-type polythiophene composition of claim 4 wherein said fluoroalkyl moiety has the compositional formula CnF2n+1, where n is about 1- 8.
6. An n-type polythiophene composition having the structural
formula
Figure imgf000040_0002
wherein Rb R2 and R3 are selected from the substituent group consisting of fluoroalkyl moieties, CnH2n+1 and where n is about 1-12, H, F, and (CH2)aX and where a is about 1-12 and X is selected from the group consisting of amino, hydroxy and carboxylic acid functionalities; and x, y and z are integers selected from the group of integers consisting of 0 and integers greater than 0.
7. The n-type polythiophene composition of claim 6 wherein said fluoroalkyl moiety is selected from the group consisting of linear fluoroalkyl substituents, branched fluoroalkyl substituents and cyclic fluoroalkyl substituents.
8. The n-type polythiophene composition of claim 7 wherein said fluoroalkyl moiety has the structural formula CnF2n+1, where n is about 1-8.
9. The n-type polythiophene composition of claim wherein x is about 0-4; y is about 0-8; and z is about 0-12.
10. The n-type polythiophene composition of claim 9 wherein said fluoroalkyl moiety has the structural formula CnF2n+1, where n is about 1-8.
11. An n-type polythiophene composition having the structural formula
Figure imgf000041_0001
wherein Rls R2 and R3 are selected from the substituent group consisting of fluoroalkyl moieties, CnH2n+ι and where n is about 1-12, H, F, and (CH2)aX and where a is about 1-12 and X is selected from the group consisting of amino, hydroxy and carboxylic acid functionalities; and x, y and z are integers selected from the group of integers consisting of 0 and integers greater than 0; and A, B, W and Z are selected from the group of moieties consisting of N and CH.
12. The n-type polythiophene composition of claim 11 wherein said fluoroalkyl moiety is selected from the group consisting of linear fluoroalkyl substituents, branched fluoroalkyl substituents and cyclic fluoroalkyl substituents.
13. The n-type polythiophene composition of claim 12 wherein said fluoroalkyl moiety has the structural formula CnF2n+1, where n is about 1-8.
14. The n-type polythiophene composition of claim 11 wherein x is about 0-4; y is about 0-8; and z is about 1-12.
15. The n-type polythiophene composition of claim 14 wherein said fluoroalkyl moiety has the structural formula CnF2n+1, where n is about 1-8.
16. A method of using thiophene structural modification to promote n-type thiophene conductivity; said method comprising: preparing a polythiophene composition, said composition comprising a plurality of conjugated thiophene moieties; and providing said composition a structural modification sufficient to promote n-type conductivity, said modification selected from the group of structural modifications consisting of fluoroalkyl substitution, fluorine substitution, fluoroaryl insertion, nitrogen heterocycle insertion and combinations thereof.
17. The method of claim 16 wherein said structural modification provides a fluoroalkyl polythiophene composition.
18. The method of claim 17 wherein said structural modification provides an α,ω- diperfluoroalkyl substituted polythiophene.
19. The method of claim 16 wherein said structural modification provides fluoroaryl insertion between said conjugated thiophene moieties.
20. The method of claim 16 wherein said structural modification provides nitrogen heterocycle insertion between said conjugated thiophene moieties.
21. The method of claim 20 wherein said heterocycle was selected from the group consisting of pyridine, pyrimidine, pyridazine, and tetrazine.
22. The method of claim 20 wherein said structural modification provides thiadiazine insertion between said conjugated thiophene moieties.
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