WO2010059646A2 - Compositions d’aminobenzène et dispositifs et procédés associés - Google Patents

Compositions d’aminobenzène et dispositifs et procédés associés Download PDF

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WO2010059646A2
WO2010059646A2 PCT/US2009/064857 US2009064857W WO2010059646A2 WO 2010059646 A2 WO2010059646 A2 WO 2010059646A2 US 2009064857 W US2009064857 W US 2009064857W WO 2010059646 A2 WO2010059646 A2 WO 2010059646A2
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composition
polymer
fluorinated
arylamine
represented
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PCT/US2009/064857
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WO2010059646A3 (fr
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Christopher T. Brown
Venkataramanan Seshadri
Jing Wang
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Plextronics, Inc.
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Priority to EP09764124.5A priority Critical patent/EP2356168B1/fr
Priority to KR1020117010677A priority patent/KR101669559B1/ko
Priority to JP2011536609A priority patent/JP5774996B2/ja
Publication of WO2010059646A2 publication Critical patent/WO2010059646A2/fr
Publication of WO2010059646A3 publication Critical patent/WO2010059646A3/fr

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    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/103—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a diaryl- or triarylmethane dye
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/92—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the nitrogen atom of at least one of the amino groups being further bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0246—Polyamines containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/02—Alignment layer characterised by chemical composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/04—Charge transferring layer characterised by chemical composition, i.e. conductive
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • OLEDs organic light emitting diodes
  • OOVs organic photo voltaics
  • One way this need is met is through development of new materials for these devices that enhance device output and prolong device lifetime.
  • a particularly promising approach lies in the development of new materials for device layers such as the hole injection, hole transport, and hole extraction layers.
  • HILs hole injection layers
  • HTLs hole transport layers
  • HILs hole injection layers
  • HTLs hole transport layers
  • Hole injection layers and hole transport layers can present difficult problems, however, because of the solubilities of the component materials (or lack thereof) in processing solvents, and because of the dopants and/or acids needed for HIL performance. Dopants and acids should be chosen judicially to minimize their contributions to device operation (e.g., efficiency and degradation).
  • hole injection and/or hole transport layer components are processable from selected solvents such as, for example, non-aqueous and/or aprotic high-purity solvent in order to minimize deleterious effects on device operation.
  • solvents such as, for example, non-aqueous and/or aprotic high-purity solvent
  • a need also exists to develop layers that are compatible with the deposition of subsequent layers by vapor or solution processes.
  • compositions for use in, for example, hole transporting layers (HTLs) or hole injection layers (HILs) are provided, as well as methods of making the compositions and devices fabricated from the compositions.
  • HTLs hole transporting layers
  • HILs hole injection layers
  • compositions can comprise at least one semiconductive organic material, and an optional dopant, and can be substantially free, or totally free, of an insulating matrix component.
  • the compositions can, for example, produce improved HILs and HTLs that, when incorporated into electronic devices such as OLEDs or OPVs, can lead to increases in the performance of the devices.
  • compositions comprising a polymeric or oligomeric backbone comprising at least one repeat moiety comprising at least one arylamine, and at least one repeat moiety comprising at least one fluorinated alkyleneoxy.
  • the repeat moiety comprising arylamine and the repeat moiety comprising fluorinated alkyleneoxy are alternating moieties.
  • the arylamine comprises triarylamine.
  • the arylamine moiety comprises at least two nitrogen atoms.
  • the fluorinated alkyleneoxy comprises a C 1 -C 1 O alkylene ether.
  • the fluorinated alkyleneoxy comprises a fluorinated C 1 -C 1O vinyl ether.
  • the fluorinated alkyleneoxy comprises a trifluoroalkyleneoxy moiety.
  • the composition comprises a soluble, linear polymer comprising the arylamine and the fluorinated alkyleneoxy. In one embodiment, the composition is crosslinked.
  • Ar 1 comprises arylamine
  • Ar 2 comprises an aryl
  • R 1 and R 2 are independently selected from C 1 -C 1 O fluorinated alkylenes.
  • the repeat units (I) and (II) are alternating.
  • Ar 1 is represented by
  • J , J and J are independently selected from hydrogen, C 1 -C 1O alkyl, perfluoroalkyl, thioalkyl, alkoxy, alkylaryl, arylalkyl, aryloxy, heteroaryl, cyano, halo and alkylthio groups, k is an integer from 1 to 4, m is an integer from 1 to 5, and n is an integer from 1 to 5.
  • Ar 1 is represented by
  • Ar is represented by
  • J , J and J are independently selected from hydrogen, C 1 -C 1O alkyl, perfluoroalkyl, thioalkyl, alkoxy, alkylaryl, arylalkyl, aryloxy, heteroaryl, cyano, halo and alkylthio groups, k is an integer from 1 to 4, m is an integer from 1 to 5, and n is an integer from 1 to 5.
  • Ar 2 is represented by
  • R 3 is an optionally fluorinated C 1 -C 1O alkyl, and Z is an integer from 1 to 5.
  • Ar 2 is represented by
  • R and R are independently selected from fluoroalkyl. In one embodiment, R 1 and R 2 are trifluoroethyl, and wherein the oligomer or polymer is insoluble and crosslinked or soluble.
  • Another embodiment provides a method of making an oligomer orpolymer comprising: co-polymerizing a first monomer represented by
  • Ar 4 and Ar 5 are independently chosen from an aryl moiety or an arylamine moiety, such that at least one of Ar 4 and Ar 5 being an arylamine, and R 5 and R 6 independently represent a fluorinated C 1 -C 1 O alkylene.
  • Ar 4 is represented by
  • J , J and J are independently selected from hydrogen, C 1 -C 1O alkyl, perfluoroalkyl, thioalkyl, alkoxy, alkylaryl, arylalkyl, aryloxy, heteroaryl, cyano, halo and alkylthio groups, k is an integer from 1 to 4, m is an integer from 1 to 5, and n is an integer from 1 to 5.
  • Ar 4 is represented by
  • Ar is represented by where z is 1-5. In one embodiment, Ar 5 is represented by
  • J 1 , J 2 and J 3 are independently selected from hydrogen, C 1 -C 1O alkyl, perfluoroalkyl, thioalkyl, alkoxy, alkylaryl, arylalkyl, aryloxy, heteroaryl, cyano, halo and alkylthio groups, k is an integer from 1 to 4, m is an integer from 1 to 5, and n is an integer from 1 to 5.
  • Ar 5 is represented by
  • Ar 5 is represented by
  • R 3 is an optionally fluorinated C 1 -C 1O alkyl, and Z is an integer from 1 to 5.
  • R 5 and R 6 are independently selected from fluorinated C 1 -C 1O alkylene. In one embodiment, R 5 and R 6 are trifluoroalkylene.
  • Ar 4 and Ar 5 are independently chosen from an aryl moiety or an arylamine moiety, such that at least one of Ar 4 and Ar 5 being an arylamine, and R 5 and R 6 independently represent a fluorinated C 1 -C 1O alkylene.
  • Ar 4 is represented by
  • Ar is represented by
  • J 1 , J 2 and J 3 are independently selected from hydrogen, C 1 -C 1O alkyl, perfluoroalkyl, thioalkyl, alkoxy, alkylaryl, arylalkyl, aryloxy, heteroaryl, cyano, halo and alkylthio groups, k is an integer from 1 to 4, m is an integer from 1 to 5, and n is an integer from 1 to 5.
  • Ar 4 is represented by
  • Ar 5 is represented by
  • J 1 , J 2 and J 3 are independently selected from hydrogen, C 1 -C 1 O alkyl, perfluoroalkyl, thioalkyl, alkoxy, alkylaryl, arylalkyl, aryloxy, heteroaryl, cyano, halo and alkylthio groups, k is an integer from 1 to 4, m is an integer from 1 to 5, and n is an integer from 1 to 5.
  • Ar 5 is represented by
  • Ar 5 is represented by
  • R 3 is an optionally fluorinated C 1 -C 1O alkyl, and Z is an integer from 1 to 5.
  • R 5 and R 6 are independently selected from fluorinated C 1 -C 1O alkylenes. In one embodiment, R 5 and R 6 are trifluoroalkylenes.
  • composition comprising: an oligomer or polymer comprising repeat units represented by
  • Ar is an arylamine, Ar comprises an aryl, and R and R are independently selected from C 1 -C 1O fluorinated alkyls; and at least one solvent.
  • the composition further comprises at least one n-type material, or at least one p- type polymer.
  • the composition further comprises at least one conjugated polymer.
  • the composition further comprises at least one dopant.
  • the composition further comprises at least one quantum dot.
  • the composition further comprises from about 50%wt to about 99%wt of said at least one solvent.
  • the composition further comprises from about 0.01%wt to about 5%wt of said oligomer or polymer.
  • Ar 1 is represented by
  • J 1 , J 2 and J 3 are independently selected from hydrogen, C 1 -C 1 O alkyl, perfluoroalkyl,thioalkyl, alkoxy, alkylaryl, arylalkyl, aryloxy, heteroaryl, cyano, halo and alkylthio groups, k is an integer from 1 to 4, m is an integer from 1 to 5, and n is an integer from 1 to 5; and Ar 2 is represented by
  • R is an optionally fluorinated C 1 -C 1 O alkyl, and Z is an integer from 1 to 5.
  • Ar 1 is represented by
  • Ar 1 is an arylamine
  • Ar 2 comprises an aryl
  • R 1 and R 2 are independently selected from C 1 -C 1 O fluorinated alkyl.
  • said device is an OLED, PLED, PHOLED or OPV device.
  • said layer is a hole injection layer.
  • said layer is a hole transport layer.
  • said layer is a photoactive layer.
  • said layer is an electron blocking layer.
  • said layer further c
  • said layer further comprises a p-type polymer.
  • said layer further comprises a conjugated polymer.
  • said layer further comprises quantum dots.
  • said oligomer or polymer is doped.
  • compositions comprising: (i) at least one arylamine, and (2) at least one fluorovinylether unit covalently linked to the arylamine.
  • the composition is a monomer, oligomer, or polymer.
  • the composition is a monomer; in one embodiment, the composition is an oligomer; in one embodiment, the composition is a polymer.
  • a composition consists essentially of: (i) at least one arylamine, and (2) at least one fluorovinylether unit covalently linked to the arylamine.
  • composition comprising a polymeric or oligomeric backbone comprising at least one repeat moiety adapted to provide hole transport and at least one fluorinated alkyl eneoxy repeat moiety.
  • composition comprising a polymeric or oligomeric backbone comprising at least one repeat moiety adapted to provide hole transport and at least one fluorinated repeat moiety, wherein the fluorinated repeat moiety is adapted from a monomer represented by
  • R is represented by one of
  • Another embodiment provides a method comprising: reacting at least one arylamine comprising at least two secondary amine moieties with at least one arylbromide, wherein the arylbromide comprises alkylenoxy units, to form a arylamine monomer comprising alkyleneoxy units, wherein the reaction is carried out with use of an organometallic complex.
  • the reaction is carried out with use of phase transfer catalysis.
  • One advantage of some embodiments is in providing a polymer with better operational stability. Another advantage of some embodiments is in providing a polymer which facilitates charge injection into device layers. Another advantage of some embodiments is in providing polymers compatible with orthogonal solvents for preparing solution processed device layers. Yet another advantage of some embodiments is in providing a relatively simple method of making a polymer for hole injection or hole extraction layer. Still another advantage of some embodiments is in providing materials which assist in reducing the leakage current for OPV devices.
  • Fig. 1 shows absorbance and fluorescence spectra of thin films of poly(TPD-TFVBPA) on a glass substrate.
  • Fig. 2 is UV-vis-NIR spectra of thin films of poly(TPD-TFVBPA) doped with 4-isopropyl-
  • Fig. 3a and 3b are IVL measurements for a comparative hole injection layer and a hole injection layer according to an embodiment, respectively.
  • Fig. 4 shows 1 H-NMR spectra of an embodiment for the copolymer.
  • Fig. 5 shows gel permeation chromatographic analysis of an embodiment for the copolymer.
  • Fig. 7 Shows Fluorine NMR of TPD-TFV monomer
  • Fig. 8 Shows GPC for poly(nap-(TPD-TFV)
  • Fig. 9 Shows NMR for poly(nap-(TPD-TFV)
  • Fig. 10 a,b show IVL measurement for devices 4,5,6 and comparative example.
  • Fig. 1 Ia, b show IVL measurement for devices 7, 8, 9 and comparative example.
  • Fig. 12 shows UV and photo luminescent spectra of HTL 3 film.
  • Fig. 13 shows transparency measurement of HTL 3 film.
  • TPD 4,4'-bis(m-tolyphenylamino) biphenyl.
  • poly(TPD-TFVBPA) refers to the polymer prepared as prepared below in working example 1.
  • TPD-TFV refers to the compound as prepared below in working example 2.
  • poly(nap-TPD-TFV) refers to the polymer as prepared below in working example 3.
  • compositions provided herein can comprise at least one semiconductive component, and an optional dopant, and can be substantially free of an insulating matrix component.
  • the compositions can be used to form improved HTLs or HILs that, when incorporated into electronic devices such as OLEDs or OPVs, can result in increased device performance.
  • the compositions can include ink formulations that can be used to form HILs in OLEDs.
  • OLEDs constructed with the compositions can exhibit increases in efficiency and brightness.
  • the present compositions thus can provide an improved hole injection technology that can be used in applications involving organic electroluminescence, in particular, in OLEDs and other lighting displays and/or applications.
  • the semiconductive component when present as either an HIL or HTL layer in a device, can permit charge injection to take place throughout the bulk of the layer rather than at the surface of the layer.
  • compositions can also contain a dopant that can function as a doping agent for compositions of one or more semiconducting polymers. Doping of the semiconducting materials and polymer can enable rapid charge transport through the bulk of the present compositions when incorporated into an organic electronic device, increasing the performance of the device.
  • the semiconductive doped polymers of the compositions can produce HILs or HTLs having higher conductivities, which lower the series resistance of organic electronic devices. This is in contrast to other hole injection technologies which can produce HILs or HTLs having much lower conductivities (and, as a consequence, devices with higher series resistance).
  • the compositions can produce HILs or HTLs that are substantially transparent to visible light, even if the thickness of the layer is higher than usual, for example, on the order of about 60 nm to about 200 nm.
  • the HIL or HTL can transmit about 85% to about 90% or greater (i.e., %T > 85-90%) of light having a wavelength of about 400-800 nm.
  • an additional advantage for at least some embodiments can be the formation of substantially transparent HILs or HTLs having moderately high thicknesses. Thick HILs or HTLs can also be used to eliminate shorts in semiconductor devices without adversely impacting operating voltage.
  • the present embodiments include, for example, aminobenzene monomers, oligomers, and polymers (including co-polymers), methods of making the same and compositions and devices formed using the monomers, oligomers, and polymers.
  • the polymers can comprise at least one arylamine moiety and at least one halogenated alkyleneoxy moiety such as fluorinated alkyleneoxy moiety.
  • a method of making the oligomers or polymers can comprise, for example, co-polymerizing a monomer comprising hydroxyl groups with a monomer comprising halogenated or fluorinated alkyleneoxy groups.
  • the oligomers or polymers can be used in ink compositions and further used to form functional layers in various devices.
  • Polymers and copolymers are generally known in the art. See, for example, Billmeyer, Textbook of Polymer Science, 3 rd Ed., 1984; Allcock, Lampe, Contemporary Polymer Chemistry, 1981. Polymers and copolymers can comprise polymeric and copolymeric backbones which further comprise atoms and side groups bonded to the backbone.
  • the polymers and copolymers can be soluble, linear molecules.
  • The can comprise repeat moieties.
  • a co-polymer comprises a backbone comprising at least one arylamine repeat moiety and at least one fluorinated alkyleneoxy repeat moiety.
  • the moieties can be alternating.
  • Oligomers can be made.
  • Crosslinked materials can be made including lightly crosslinked and heavily crosslinked materials. Network materials can be made.
  • Oligomers are known in the art and can be lower molecular weight forms of polymers. Oligomers can be linear or crosslinked. Network oligomers can be prepared. Oligomer molecular weight can be, for example, 1,000 g/mol or less, or 750 g/mol or less (Mn).
  • Hole transport materials are known in the art including, for example, arylamine materials and compounds.
  • Arylamine repeat moieties are known in the art. See, for example, Lim et al, Organic Letters, 2006, 8, 21, 4703-4706; Fukase et al, Polymers for Advanced Technologies, 13, 601-604 (2002). Shirota, Y. et al., Chem. Rev. 107, 2007, 953-1010; Z. Li and H. Meng, Eds., Organic Light-Emitting Materials and Devices, CRC Press (Taylor and Francis Group, LLC), Boca Raton (2007) and references therein.
  • the arylamine moieties can each comprise at least one nitrogen atom and at least one benzene ring.
  • they can comprise one benzene ring bonded to a nitrogen atom; two benzene rings bonded to a nitrogen atom; or three benzene rings bonded to a nitrogen atom.
  • the repeat moiety can be adapted to provide hole injection and/or hole transport properties.
  • hole transport compositions and repeat moieties may additionally be selected to include but are not limited to thiophenes, pyrroles, aryloxy and organometallic complex moieties. See, for example, Shirota, Y. et al, Chem. Rev. 107, 2007, 953-1010; Z. Li and H. Meng, Eds., Organic Light-Emitting Materials and Devices, CRC Press (Taylor and Francis Group, LLC), Boca Raton (2007) and references therein.
  • the arylamine moiety can comprise at least one triarylamine.
  • the arylamine moiety can comprise a bistriarylamine, such as, but not limited to, N,N-diphenylbenzeneamine.
  • the benzene ring(s) may be bonded to at least one other benzene ring through a direct covalent bond, a covalent bond through at least one carbon atom or a covalent bond through an oxygen atom.
  • the benzene ring(s) may be fused with another benzene ring through one or two carbon atoms shared between the rings. Two or more rings can be fused together.
  • the benzene rings can be substituted or unsubstituted. As a non-limiting example, they can be substituted with one or more C 1 -C 1 O alkyl, perfluoroalkyl, thioalkyl, alkoxy, alkylaryl, arylalkyl, aryloxy, heteroaryl, cyano, halo and alkylthio groups, or a combination thereof.
  • Arylamines are also described in, for example, U.S. patent 7,166,010; WO 2003037844; and WO 2008032631 , which are hereby incorporate by reference in their entirety.
  • a moiety can help space the hole transport functionality. This moiety can be different from the arylamine moiety described above.
  • Spacers such as halogenated and fluorinated alkyleneoxy repeat moieties are known in the art. See, for example, Iacono et al., Chem. Commun., 2006, 4844-4846; Babb et al., Macromolecules, 1996, 29, 852-860; Smith et al., Pofym. Int., 2007, 56, 1142-1146; Smith et al., J. Am. Chem. Soc, 2004, 126, 12772-12773; Kim et al., Org. Lett., 2006, 8, 4703-4706.
  • Fluorinated alkyleneoxy repeat moieties can comprise at least one fluorine atom, at least one oxygen atom, and at least one alkylene moiety which can be a C 1 -C 1O alkylene. More preferably, the alkylene moiety can be a C 1 -Cs alkylene, such as, but not limited to an ethylene.
  • the C 1 -C 1O alkylene can be linear, branched or cyclic.
  • the C 1 -C 1 O alkylene can be fluorinated with at least one fluoro, chloro, bromo or iodo group, or combination thereof.
  • the alkylene moiety is fluorinated with at least one fluoro group such as, for example, forming a trifluoroethylene moiety.
  • the alkylene moiety is perflourinated.
  • the fluorinated alkoxy moieties which can be converted to fluorinated alkyleneoxy, can further comprise at least one aryl, arylalkyl, haloarylalkyl, diarylamine, or a triarylamine.
  • the aryl moiety is N,N-diphenylbenzeneamine.
  • the benzene ring(s) of the aryl moiety can be covalently bonded to the alkyl portion or to the oxygen atom.
  • the benzene ring of the aryl moiety is bonded to the oxygen atom of the fluorinated alkoxy moiety.
  • the repeat moieties, arylamine and fluorinated alkyleneoxy are the only repeat units.
  • the copolymer can consist of or can consist essentially of these two types of repeat moieties.
  • the arylamine can be replaced by another hole transport moiety.
  • Vinyl ether, fluorinated vinyl ether, and perfluorinated vinyl ether moieties can be used including both in polymerized or unpolymerized forms, and combinations thereof.
  • oligomers, polymers, and co-polymers can be further described with structures as follows.
  • they comprise repeat units represented by
  • Ar comprises an arylamine
  • Ar comprises an aryl
  • R and R are independently selected from C 1 -C 1O fluorinated alkylenes.
  • the repeat units (I) and (II) can be alternating.
  • Ar 1 can comprise or be a triarylamine where the benzene rings are optionally substituted.
  • Ar 1 can be represented by
  • J , J and J are independently selected from hydrogen, C 1 -C 1O alkyl, perfluoroalkyl, thioalkyl, alkoxy, alkylaryl, arylalkyl, aryloxy, heteroaryl, cyano, halo and alkylthio groups; k is an integer from 1 to 4; m is an integer from 1 to 5; and n is an integer from 1 to 5.
  • Ar 1 can be represented by
  • Ar can comprise or be, for example, an aryl, arylalkyl, haloarylalkyl, diarylamine or a triarylamine.
  • Ar 2 can be an aryl comprising a benzene ring or at least two benzene rings covalently bonded to each other.
  • Ar 2 can be an arylene.
  • Ar 2 is represented by wherein z is an integer from 1 to 5.
  • Ar 2 can be an aryl comprising a polycyclic aromatic ring or an aryl comprising a substituent having 2-10 carbon atoms.
  • the polycyclic aromatic ring can have, for example, two or more rings fused together.
  • Ar can be represented by
  • n is an integer from 1 to 5. Isomeric forms of the linkages can be used.
  • Ar 2 can be a triarylamine.
  • the structures for Ar 2 also can be the structures for Ar 1 .
  • Ar 2 can be an arylalkyl or a haloarylalkyl.
  • Ar 2 can be represented by:
  • R 3 is an optionally fluorinated C 1 -C 1 Q alkyl, such as an optionally fluorinated C 1 -C alkyl, and z is an integer from 1 to 5.
  • R 3 may be a linear, branched or cyclic alkyl.
  • Ar 2 can be represented by:
  • R 1 and R 2 can be, for example, independently selected from C 1 -C 1O alkyl, such as C 1 -C 1O fluoroalkyl.
  • R and R are trifluoroethylene.
  • a co-polymer can comprise a repeat unit represented by — [— O Ar 3 O R 4 — V-
  • Ar 3 can be an arylamine
  • R 4 can be a C 1 -C 1 O fluorinated alkylene.
  • Ar 3 can be a diaryl or a triaryl amine.
  • the structures for Ar 2 also can be the structures described above for Ar 1 and/or Ar 2 .
  • One first monomer can be adapted to provide a hole transporting function.
  • One second monomer can be used to provide a spacer function to separate and connect hole transport moieties.
  • Monomers can be selected to include a broad range of basic moieties with appropriate hydroxyl or fluorinated alkyleneoxy substituents to be useful in this invention. See, for example, Polycyclic Aromatic Hydrocarbons, Harvey, R. G., Wiley- VCH, 1996; Polycyclic Hydrocarbons Vol. I and II, Clar, E, Academic Press, 1964.
  • Monomers can be prepared or obtained which provide the arylamine repeat moiety in the resulting polymer.
  • one set of monomers can comprise a hole transport moiety and two hydroxyl end groups, such as, but not limited to, hydroxylaryl groups or aminohydroxylaryl groups.
  • the hole transport moiety can comprise at least one aryl group.
  • the hole transport functionality can comprise 1-10 aryl groups.
  • Ar is independently selected from, for example, aryl groups such as benzene, naphthalene, biphenyl, and may be optionally substituted, and R is alkyl or ethyleneoxy and may be optionally substituted.
  • substitutions may be selected to provide, for example, desired energetic (HOMO- LUMO, triplet, singlet), mobility and thermodynamic properties for optimal handling, efficiency, and/or operational lifetime.
  • monomers can be prepared or obtained which provide the fluorinated alkylenoxy repeat moiety in the resulting polymer.
  • another set of monomers can include arylamines which include fluorinated alkyleneoxy group(s).
  • these monomers can comprise a spacer moiety and two, three, or more trifluorovinyloxy end groups.
  • the spacer moiety can comprise at least one aryl group.
  • the spacer moiety can comprise 1-10 aryl groups.
  • Monomers can be bifunctional so that linear, soluble oligomers or polymers can be prepared.
  • an A monomer can be adapted to react with a B monomer to form an A-B copolymer.
  • a and B can be combined before polymerization to form A-B, and then A-B can be polymerized.
  • monomers can be tri-, terra-, or higher functional so that networks can form.
  • the monomers can be adapted to comprise phenolic or hydroxyl groups and/or trifluorovinylether groups, which can add together in a polymerization reaction.
  • a monomer comprises reactive fluorinated alkenes.
  • Fluorinated alkenes can react with each other to provide coupling for oligomerization or polymerization including, for example, cycloaddition reactions.
  • trifluorovinyl ether-containing compounds can be useful reactive monomers that undergo thermal cyclopolymerization to afford perfluorocyclobutane (PFCB) polymers.
  • One embodiment provides a method comprising: reacting at least one arylamine comprising at least two secondary amine moieties with at least one arylbromide, wherein the arylbromide comprises alkylenoxy units, to form a arylamine monomer comprising alkyleneoxy units, wherein the reaction is carried out with use of an organometallic complex such as, for example, zero valent palladium complex such as Pd 2 (dba) 3 . See, for example, working example 2; see in contrast comparative example 2A.
  • the reaction can be carried out under phase transfer conditions with use of combinations of water, organic solvent (e.g., toluene), and phase transfer catalyst. Strong base can be used such as, for example, KOH.
  • the arylamine comprising at least two secondary amine moieties can be, for example, N 5 N'- diphenylbenzidine.
  • POLYMER SYNTHESIS Polymer synthesis methods are known in the art. See, for example, Billmeyer, Textbook of Polymer Science, 3 rd Ed., 1984; Allcock, Lampe, Contemporary Polymer Chemistry, 1981. Examples include, but are not limited to, step growth, condensation polymerization, addition polymerization, free-radical polymerization, cationic polymerization, anionic polymerization and coordination polymerization.
  • the polymerization reaction includes the reaction of a compound comprising a hydroxyl group, such as a hydroxyaryl group, with a compound comprising fluorinated alkyleneoxy groups. These methods can be also used to produce oligomers as known in the art.
  • a first monomer comprising at least two hydroxyl groups is co- polymerized with a second monomer comprising at least two fluorinated alkyleneoxy groups.
  • the second monomer comprises at least two trifluoroethyleneoxy groups.
  • Ar 4 can be represented by
  • z is an integer from 1 to 5.
  • Ar 4 can be represented by
  • J , J and J are independently selected from hydrogen, C 1 -C 1O alkyl, perfluoroalkyl, thioalkyl, alkoxy, alkylaryl, arylalkyl, aryloxy, heteroaryl, cyano, halo and alkylthio groups; k is an integer from 1 to 4; m is an integer from 1 to 5; and n is an integer from 1 to 5.
  • Ar 4 can be represented by
  • Ar 5 can be represented by
  • z is an integer from 1 to 5.
  • Ar 5 can be represented by
  • J , J and J are independently selected from hydrogen, C 1 -C 1O alkyl, perfluoroalkyl, thioalkyl, alkoxy, alkylaryl, arylalkyl, aryloxy, heteroaryl, cyano, halo and alkylthio groups; k is an integer from 1 to 4; m is an integer from 1 to 5; and n is an integer from 1 to 5.
  • Ar 5 can be represented by
  • Ar 5 can be represented by
  • R 3 can be an optionally fluorinated C 1 -C 1 O alkyl, such as an optionally fluorinated C 1 -C 1 O alkyl, and z is an integer from 1 to 5.
  • R 3 may be a linear, branched or cyclic alkyl.
  • R 5 and R 6 can be independently selected from fluorinated alkylenes such as, but not limited to, fluorinated C 1 -C 1O alkylenes.
  • R 5 and R 6 are independently selected from fluorinated C 1 -C 1 O alkylene, such as trifluoro ethylene.
  • one monomer is used to form a polymer.
  • the monomer can comprise at least one hydroxyarylamine moiety and at least one fluorinated C 1 -C 1O alkyleneoxy moiety.
  • a polymer is formed by polymerizing a monomer represented by:
  • Polymerization can be carried out in various solvents. Examples include Dimethyl sulfoxide, tetramethylenesulfoxide, dimethylformamide, dimethylacetamide, N- methylpyrrollidinone, tetrahydrofuran, dioxane and acetonitrile, and combinations thereof.
  • Polymerization can be carried out in the presence of various catalysts.
  • catalysts include sodium tert-butoxide, sodium methoxide, potassium tert-butoxide and potassium methoxide.
  • polymers resulting from such polymerization include, for example:
  • Molecular weight is not particularly limited, but the resulting polymers can have, for example, a number average molecular weight from, for example, about 1,000 g/mol to about 100,000 g/mol, or from about 5,000 g/mol to about 50,000 g/mol, or from about 10,000 g/mol to about 20,000 g/mol.
  • Polydispersity is not particularly limited, but the resulting polymers can have, for example, a PDI of 1-5 or from 1-2.
  • Polymers can be prepared such that crosslinking agents can be combined with the monomer or polymer to impart resultant films with properties necessary to support solution processing on top of the material.
  • crosslinking agents for example, pendant alkylenoxy, alkene, or benzocyclobutane groups could be utilized during annealing to impart a crosslinked structure with sufficient insolubility for subsequent processing.
  • a material or component could be added to the polymer in the ink to provide for a crosslinked or entangled film structure that would also impart film with sufficient insolubility for subsequent processing on top of the film. See, for example, Thompson et al, Chem.Mat., 2007, 19, 4827-4832; Meerholtz et al., App. Phys. Lett., 2007, 91, 103507; Marks et al., App. Phys. Lett., 2003, 82, 331-333; and Towns et al., WO 2006/043087.
  • Monomers, oligomers, and polymers can also be prepared as follows:
  • Z 1 and Z 2 are independently selected from a hole transport linkages and spacer linkages, provided at least one Of Z 1 and Z 2 is a hole transport linkage, and the spacer linkage being selected from aromatics such as, for example, phenyl, naphthyl, and the like, alkylene, polyether, perfluoropolyether and perfluoroalkoxy.
  • the spacer linkage does not need to provide hole transport or extended conjugation.
  • polymers wherein the polymers are endcapped so as to eliminate chain termini with a fluorine or hydroxyl group as these may lead to operational instability.
  • Polymers may be treated following synthesis to remove remaining fluorine substituents with phenol or an alkoxide. Terminal hydroxyl groups may also be blocked by alkylation with activated arenes or alkyl alkylating agents such as methyliodide.
  • polymers can be end-capped in situ during polymerization using a monofunctional material as known in polymer chemistry.
  • the polymer could also be end-capped with cross-linkable functionalities such as a trifluorovinyloxy, vinylenic, acetylenic, oxetane, trichlorosilyl, trialkoxysilyl, epoxy to enhance intractability of layers.
  • cross-linkable functionalities such as a trifluorovinyloxy, vinylenic, acetylenic, oxetane, trichlorosilyl, trialkoxysilyl, epoxy to enhance intractability of layers.
  • Incorporation of above groups can be accomplished either in situ during polymerization using monofunctional monomers with appropriate functional groups as described above or by a post-polymerization procedure. Representative and non-limiting examples of end-capping agents are shown below,
  • the polymers and copolymers can be soluble. They can be soluble in organic solvents.
  • Polymers of the present embodiments can advantageously serve as materials for hole injection layers, hole transport layers, a photoactive layers and electron blocking layers.
  • these polymers are stable and relatively resistant to hole transport degradation which can be brought on when excited states are generated in the polymer.
  • Such polymers may offer added operational stability to various devices.
  • These polymers can also increase the dielectric constant at an interface where the polymer is applied as a layer, thereby facilitating charge injection. Typically, this is understood within the context of band bending types of arguments.
  • a properly oriented dipole at an interface can provide a sufficient internal field to allow for Fermi-level pinning between layers and thus, charge injection, despite a vacuum level misalignment.
  • these polymers exhibit orthogonal solvent compatibility for solution processed layers, which is highly useful for device layer formation. Without wishing to be limited to any particular theory, it is believed that the fluorinated chains contribute to orthogonal solvent compatibility of the polymers.
  • a polymer is selected to provide suitable HOMO- LUMO energetic properties such as to minimize deleterious impact on device operation.
  • Polymers and co-polymers described herein can be combined with solvents, other polymers (as blends), additives, dopants or a combination thereof to form compositions such as inks that can be cast as a layer in various devices.
  • a composition comprises a co-polymer comprising repeat units represented by:
  • Ar 1 is an arylamine
  • Ar 2 is an aryl
  • R 1 and R 2 are independently selected from C 1 -C 1 O fluorinated alkyls; and at least one solvent.
  • the composition can comprise one of more of the following solvents: chlorobenzene, chloroform, 1,2- dichloroethane, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, trichlorobenzene, 1,3,5-trichlorobenzene, dichloromethane, ethylbenzoate, methylbenzoate, propylacetate, ethylacetate, butylacetate, phenylacetate, cyclohexanone, methyl iso-butyl ketone, pentanone, cyclohexane, methylethylketone, N,N-dimethylformamide, N 5 N- dimethylacetamide, N-methylpyrrolidinone, pyridine, piperidine, N-methylpyrrole, acetonitrile, benzonitrile, tetrahydrofuran, dio
  • the ink is substantially free from or totally free from protic solvents.
  • the amount of protic solvent can be less than 1 wt.%, or less than 0.1 wt.%.
  • Solvents are to be selected to provide an ink that yields a film of desired physical properties and performance with easily controllable thickness, composition and quality to provide an ink with a utility in a device that meets application needs.
  • the solvents may be selected from the lists found in the following references: Cheremisinoff, N. P. In Industrial Solvents Handbook Second Edition; Marcel Dekker: New York, NY, 2003; Ash, M.; Ash, In Handbook of Solvents; Synapse Information Resources Inc; 2 nd Edition, 2003; Wypych, G. In Handbook of Solvents (Chemical); Noyes Publications, 1 st Edition, 2000; Hansen, C. M.; Durkee, J.; Kontogeorgis, G. In Hanson Solubility Parameters: A User 's Handbook; Taylor and Francis, Inc, 2007 and hereby incorporated by reference in their entirety.
  • the amount of solvent in an ink formulation can be between about 10%wt and about 99%wt, such as between about 90%wt and about 99% wt.
  • the weight percent of the co-polymers in an ink composition can be between about 0.01%wt and about 10%wt, such as between about 0.1 %wt and about 1.0%wt.
  • the ink composition can further comprise at least one n-type polymer.
  • the ink composition can further comprise at least one p-type polymer.
  • the ink composition can further comprise at least one conjugated polymer.
  • the polymers of the present embodiments are combined with n-type polymers.
  • the n- and p-type materials can be mixed in a ratio of for example from about 0.1 to 4.0 (p-type) to about 1 (n-type) based on a weight, or from about 1.1 to about 3.0 (p-type) to about 1 (n-type) or from about 1.1 to about 1.5 (p- type) to about 1 (n-type).
  • the amount of each type of material or the ratio between the two types of components can be varied for the particular application.
  • compositions optionally comprise one or more dopants.
  • Dopants are typically used to obtain a desired conductive state for a polymer component of an HIL or HTL and often result in improved device performance. For example, upon oxidation of a semi-conductive polymer by a redox dopant, electrons are removed from the valence band of the polymer. This change in oxidation state results in the formation of new energy states for the polymer. The energy levels are accessible to some of the remaining electrons in the valence band, allowing the polymer to function as a conductor/semi-conductor.
  • the conductive conjugated polymer can be doped with a redox dopant.
  • suitable redox dopants include, but are not limited to, quinones, boranes, carbocations, bora-tetraazapentalenes, aminium or ammonilium salts, sulfonium salts, oxonium salts, selenonoium salts, nitrosonium salts, arsonium salts, phosphonium salts, iodonium salts, select metal (e.g. silver) salts, or combinations thereof.
  • Suitable redox dopants include, but not limited to, those disclosed in U.S. Patent Numbers 5,853,906 and 5,968,674, which are hereby incorporated by reference in their entireties.
  • the redox dopant can also be selected to provide a suitable charge balancing counter- anion.
  • the type of dopant anion can affect the doping level of the conductive polymer and the device performance for devices prepared from these solutions.
  • the size and nature of the dopant anion can be an important parameter for modulating the efficiency of a device.
  • the anion/counterion can be a sulfonate anion, a chloride anion, a bromide anion, an iodide anion, an optionally substituted arylsulfonate anion, an optionally substituted alkylsulfonate anion, a perfluoroalkylsulfonate anion,.
  • X and Y can be independently selected from a halide (F, Cl, Br and I), cyanide, nitro, another optionally substituted aryl; p ⁇ 4; n ⁇ IO; or a material represented by formulat (ii) below:
  • M P or Sb
  • Ar is chosen independently from phenyl, naphthyl, anthracenyl, phenanthryl, thienyl, pyrrolyl, furyl, pyridyl, imidazolyl, benzimidazolyl; and X and Y can be independently selected from a halide (F, Cl, Br and I), cyanide, nitro, another optionally substituted aryl; p ⁇ 4; n ⁇ IO.
  • the composition can be distinctly different from the combination of original components (i.e., semi-conductive polymer and/or redox dopant may or may not be present in the final composition in the same form before mixing).
  • the semi-conductive conjugated polymer and the dopant, or redox dopant can refer to components that will react to form a doped conjugated polymer.
  • some embodiments allow for removal of reaction byproducts from the doping process.
  • the iodonium redox dopant can result in organic byproducts that can be washed away from the doped polymer.
  • the redox dopant is a photoacid.
  • suitable photoacids include, but are not limited to, onium salts such as sulfonium and iodonium salts, for example, as described in Journal of Polymer Science Part A, Polymer Chem. 37, 4241- 4254, 1999, hereby incorporated by reference in its entirety.
  • Iodonium salts are known in the art. Doping of a conductive polymer, such as a neutral polyarylamine, can be achieved using photoacids such as iodonium salts or diaryl iodonium salts, and in particular, diphenyl iodonium salts.
  • the aryl groups such as a phenyl group in the iodonium salt can be optionally substituted as known in the art.
  • the redox dopant may be a lipophilic iodonium salt.
  • the iodonium salt is represented by: X-
  • R 1 R 2 wherein independently R 1 is an optionally substituted aryl group, independently R 2 is an optionally substituted aryl group, and X " is an anion.
  • Doping of a neutral polyarylamine can also be achieved using a photoacid such as a sulfonium salt.
  • a photoacid such as a sulfonium salt.
  • Sulfonium salts are known in the art.
  • the aryl groups in the sulfonium salt can be optionally substituted as known in the art.
  • the sulfonium salt is represented by:
  • R 2 wherein independently R 1 is an optionally substituted arene, independently R 2 is a optionally substituted arene, R 3 is a optionally substituted arene, and X " is an anion.
  • the dopant can comprise an optionally substituted diphenyl iodonium salt with a molecular weight of, for example, about 100 g/mol to about 500 g/mol, or approximately 300 g/mol.
  • the dopant is the photoacid 4-isopropyl-4'- methyldiphenyliodonium tetrakis(pentafluorophenylborate) (IMDPIB(PhFs) 4 ), represented by:
  • iodonium salts examples include, but are not limited to, diphenyliodonium hexafluorophosphate (DPIPFe), diphenyliodonium para-toluene sulfonate (DPITos), bis-(4-tert-butylphenyl) iodonium trifluoromethane sulfonate ( 1 BDPITFSO 3 ), and diphenyliodonium perfluoro-1 -butane sulfonate (DPIPFBSO 3 ).
  • the iodonium salt can be a low molecular weight compound or it can be coupled to a high molecular compound such as a polymer.
  • the redox dopant may be a sulphonium salt.
  • suitable sulphonium salts include, but are not limited to, triphenylsulphonium hexafluorophosphate, triphenylsulphonium para-toluene sulfonate, bis-(4-tert-butylphenyl) sulphonium trifluoromethane sulfonate, and diphenylsulphonium perfluoro-1 -butane sulfonate.
  • Other onium salts may be used provided such that effective doping can be achieved for select counterions.
  • quinones Another class of dopants that can be used includes quinones.
  • suitable quinones include, but are not limited to, tetrafluorotetracyano-/?-quinodimethane (F 4 TCNQ), trifluorotetracyano-p-quinodimethane (F 3 TCNQ), difluorotetracyano-p-quinodimethane (F 2 TCNQ), fluorotetracyano-/?- quinodimethane (FTCNQ), dichloro dicyanoquinine (DDQ), o-chloranil and cyanil.
  • F 4 TCNQ tetrafluorotetracyano-/?-quinodimethane
  • F 3 TCNQ trifluorotetracyano-p-quinodimethane
  • F 2 TCNQ difluorotetracyano-p-quinodimethane
  • FTCNQ fluorotetracyano-/?- quinodimethane
  • DDQ dichloro dicyanoquinine
  • Suitable dopants include quinonediimine derivatives, including, e.g., those disclosed in U.S. Pat. No. 6,908,783 by Kuehl et al, which is incorporated by reference herein in its entirety.
  • ammonium salts Another class of dopants that can be used includes ammonium salts.
  • Ammonium radical cations can be used as a redox additive to the formulation to undergo electron transfer.
  • the byproducts formed need not necessarily be removed from the composition, as they are also hole transporting moieties and are less likely to adversely affect transport.
  • suitable ammonium salts include, but are not limited to, tris-(4-bromophenyl)amine antimony hexachloride.
  • bora-tetraazapentalenes examples include bora-tetraazapentalenes. Examples of a bora- tetraazapentalene are represented by:
  • R 1 , R 2 , R 3 are independently hydrogen, an optionally substituted or unsubstituted alkyl, a heteroalkyl, an aryl, a heteroaryl, a fused carbocycle or a fused heterocycle group, and wherein independently R 4 and R 5 are fluorine, hydrogen, an optionally substituted or unsubstituted alkyl, a heteroalkyl, an aryl, a heteroaryl, a fused carbocycle or fused heterocycle, or, together with the boron atom, a boron-containing heterocycle.
  • R 4 and R 5 are fluorine, hydrogen, an optionally substituted or unsubstituted alkyl, a heteroalkyl, an aryl, a heteroaryl, a fused carbocycle or fused heterocycle, or, together with the boron atom, a boron-containing heterocycle.
  • Another class of useful dopants is a silver salt, such as silver tetrafluoroborate, silver tetraphenylborate, silver hexafluorophosphate. Silver ions may undergo electron transfer to or from silver metal and the conductive polymer salt; US Patents 5,853,906 and 5,968,674.
  • the dopant is typically formulated first with the semiconductive polymer, to ensure that doping of the polymer occurs.
  • the composition is an ink formulation that is prepared by combining the conjugated polymer with the dopant to form a semiconductive polymer-dopant mixture.
  • a stock solution of the semiconductive conjugated polymer e.g., one made by dissolving or dispersing the semiconductive polymer in an organic solvent
  • the dopant is covalently attached to the conductive conjugated polymer.
  • the compositions are prepared by combining the conductive polymer-dopant with the semiconducting matrix component to form the composition.
  • compositions can comprise between about 1% and 99% by weight ("wt%,” or "% (w/w)") of the semiconductive conjugated polymer, and, if a dopant is present, between about 0 % and 75 % by weight dopant. Weight percentages for each component are calculated on the basis of the weight of all solids in the composition.
  • the compositions comprise about 10% to about 90%, about 15% to about 80%, about 25% to about 75%, about 30% to about 70%, or about 35% to about 65% by weight of the semiconductive conjugated polymer with respect to the total amount of semiconductive polymer, and dopant, if present.
  • the dopant can be present in an amount that corresponds to the molar amount of repeat units of the semiconductive conjugated polymer.
  • the dopant is typically present in the composition in an amount of about 0.01 moles dopant/moles semiconductive polymer repeat unit ("m/ru") to about 1 m/ru, wherein m is the molar amount of dopant and ru is the molar amount of semiconductive polymer repeat units.
  • the dopant is present in an amount of about 0.01 m/ru to about 0.5 m/ru, about 0.1 m/ru to about 0.4 m/ru, or about 0.2 m/ru to about 0.3 m/ru.
  • the dopant is present in an amount of about 0.2-0.3 m/ru.
  • a dopant is not present in the composition.
  • a device comprises a layer comprising a co-polymer comprising repeat units represented by
  • Ar is an arylamine
  • Ar comprises an aryl
  • R and R are independently selected from C 1 -C 1 O fiuorinated alkyleneoxy.
  • the device can be, but is not limited to, OLED, PLED, PHOLED or OPV devices.
  • the polymers can be used, for example, to form a hole injection layer.
  • the polymers can be used to form a hole transport layer.
  • the polymers can be used to form a photoactive layer.
  • the polymers can be used to form an electron blocking layer.
  • Devices can be made according known methods in the art using the polymers of the present embodiments.
  • the compositions, including inks, can be deposited as hole injection layers, hole transporting layers, electron blocking layers, and active layers in various devices.
  • the polymer compositions can be, for example, deposited by spin casting, ink jetting, doctor blading, spray casting, dip coating, vapor depositing, or any other known deposition method, on top of the HIL film.
  • the deposited film can be then, for example, optionally annealed at about 40 to about 250 0 C, or from about 150 to 180 0 C, for about one minutes to two hours, such as 10 min to an hour, in, for example, an inert atmosphere.
  • the thickness of the layers cast with the polymer compositions can be, for example, from about 10 nm to about 300 nm thick, or from 30 nm to 60 nm , 60 nm to 100 nm , or 100 nm to 200 nm.
  • the film then can be optionally dried/annealed at 110 to 200 0 C for 1 min to an hour, optionally in an inert atmosphere. Methods for annealing are known in the art. Solvent annealing can be also carried out.
  • organic electronic devices that can be fabricated from the present compositions include, but are not limited to, OLEDs, PLEDs, PHOLEDs, SMOLEDs, ESDs, photovoltaic cells, as well as supercapacitors, hybrid capacitors, cation transducers, drug release devices, electrochromics, sensors, FETs, actuators, and membranes.
  • OLEDs organic electronic devices
  • PLEDs PHOLEDs
  • SMOLEDs electros
  • ESDs electrochromics
  • sensors sensors
  • FETs field effect transistor
  • membranes cation transducers
  • Another application is as an electrode modifier including an electrode modifier for an organic field effect transistor (OFETS).
  • OFETS organic field effect transistor
  • Other applications include those in the field of printed electronics, printed electronics devices, and roll-to-roll production processes.
  • the compositions discussed herein may be a coating on an electrode.
  • compositions can be used to form HTLs for organic photovoltaic devices (OPVs).
  • Organic photovoltaics are generally described in, for example, Organic Photovoltaic s, S-S, Sun, N. Sariciftci, 2005.
  • OPVs are known in the art. See, for example, US Patent Publ. No. 2006/0076050, published April 13, 2006; see also WO 2008/018931, published February 14, 2008, including descriptions of OPV active layers. See also U.S. provisional Appl. No. 61/043,654, filed April 9, 2008, by Williams et al, entitled "Hole Collection Layer Compositions and Photovoltaic Devices," which is herein incorporated by reference in its entirety.
  • the devices can comprise, for example, multi-layer structures that include, for example, an anode, including a transparent conductor such as indium tin oxide (ITO) on glass or PET; a hole injection layer and/or a hole transport layer; a P/N bulk heterojunction layer; a conditioning layer such as LiF; and a cathode such as for example Ca, Al, or Ba.
  • a variety of photoactive layers can be used in OPV devices.
  • Photovoltaic devices can be prepared with photoactive layers comprising fullerene derivatives mixed with, for example, conducting polymers as described in for example US Patent Nos. 5,454,880 (Univ. CaL); 6,812,399; and 6,933,436.
  • photoactive layers may comprise blends of conducting polymers, blends of conducting polymers and semiconducting nanoparticles, and bilayers of small molecules such as pthalocyanines, fullerenes, and porphyrins.
  • LEDs and OLEDs are generally described in, for example, Organic Light-Emitting Materials and Devices (Ed., Z. Li, H. Meng), 2007. See also, for example, EP 1950818 (Samsung SDI)
  • the present compositions can be used to form HILs for OLED devices.
  • OLED devices are known in the art. See, for example, US Patent Appl. Publ. No. US 2006/00787661 Al, published April 13, 2006. See also Hammond et al., US Patent Appl. Publ. No.
  • the devices can comprise, for example, multi-layer structures that include, for example, an anode, including a transparent conductor such as ITO on glass or PET or PEN; a hole injection layer; an electroluminescent layer such as a polymer layer; a conditioning layer such as LiF, and a cathode such as for example Ca, Al, or Ba. See also US Patent Nos. 4,356,429 and 4,539,507 (Kodak). Materials for and methods of preparing each of these layers or components are well known in the art.
  • conjugated polymers which emit light for use in electroluminescent layers in OLEDS, are described, for example, in US Patent Nos. 5,247,190 and 5,401,827 (Cambridge Display Technologies). See also Kraft et al, "Electroluminescent Conjugated Polymers - Seeing Polymers in a New Light," Angew. Chem. Int. Ed., 1998, 37, 402-428, including device architecture, physical principles, solution processing, multilayering, blends, and materials synthesis and formulation, which is hereby incorporated by reference in its entirety.
  • Light emitters known in the art and commercially available can be used, including various conducting polymers as well as organic molecules, such as materials available from Sumation, Lumtec, Merck Yellow, Merck Blue, American Dye Sources (ADS), Kodak (e.g, A1Q3 and the like), and even Aldrich such as BEHP-PPV.
  • Such polymer and small-molecule materials are well known in the art and are described in, for example, U.S. Pat. No. 5,047,687 issued to VanSlyke; and Bredas, J. -L., Silbey, R., eds., Conjugated Polymers, Kluwer Academic Press, Dordrecht (1991). See also "Organic Light- Emitting Materials and Devices," Z. Li and H.
  • the fabricated devices can be tested for device performance using methods known in the art. For example, for OLEDs, methods known in the art can be used to measure such device performance parameters as brightness, efficiency, and lifetime.
  • OLED performance measurements are typically carried out at 10 mA/cm .
  • the protocol outlined below can be used to measure OLED device performance parameters of current density (niA/ cm ), operating voltage (V), brightness (cd/m ), and efficiency (cd/A).
  • Typical OLED device voltages can be, for example, from about 2 to about 15, or about 2 to about 8, or about 2 to 5, or from about 3 to about 14, or from about 3 to about 7.
  • Typical device brightness can be, for example, at least 100 cd/m 2 , or at least 500 cd/m 2 , or at least 750 cd/m 2 , or at least 1,000 cd/m 2 .
  • Typical device efficiencies can be, for example, at least 0.25 cd/A, or at least 0.45 cd/A, or at least 0.60 cd/A, or at least 0.70 cd/A, or at least 1.00 cd/A, or at least 2.5 cd/A, at least 4.00 cd/A, or at least 5.00 cd/A.
  • Typical device lifetimes can be measured at 50 mA/cm 2 or up to 75 mA/cm 2 in hours and can be, for example, at least 50 hours, or at least 100 hours, or at least about 900 hours, or at least 1,000 hours, or at least 1100 hours, or at least 2,000 hours, or at least 5,000 hours, or at least 10,000 h, or at least 20,000 h, or at least 50,000 h.
  • the present compositions when used as HILs or HTLs in organic devices, typically lead to increases in device parameters such as power efficiency.
  • the present compositions, when used as HILs in OLEDs can lead to increases in efficiency of at least 5 %, or at least about 10% or greater, up to about 50%, depending on the operating voltage and quantum efficiency of the OLED in the absence of a good hole injection layer, compared to OLEDs fabricated using traditional HILs that contain an insulating matrix component.
  • TPD- (OH) 2 TPD- (OH) 2 which can be prepared in a manner similar to that found in J. Mater. Chem. (2008), 18(12), 1296-1301.
  • 5 mL anhydrous N,N-dimethylformamide (DMF) was injected into the septa sealed flask and upon dissolution of the solids, 98 mg potassium tert-butoxide was added. The solution turned light yellow from orange-red.
  • the reaction was continued at room temperature for another 8 hrs and precipitated by pouring into 250 mL ethanol at room temperature.
  • the precipitated polymer was centrifuged and dried in a vacuum oven after decanting supernatant. About 1.4 gms of dry solids were obtained, which was dissolved again in 15 mL anhydrous tetrahydrofuran and precipitated into 200 mL ethanol.
  • the polymer was then centrifuged and the supernatant decanted.
  • the white polymer was then placed on a 0.45 ⁇ m PVDF hydrophobic membrane filter and washed with ethanol ( ⁇ 50 mL).
  • the polymer was finally dried in a vacuum oven at room temperature for 24 hours to obtain 0.88 gms of white powder.
  • reaction mixture was purified via column chromatography using methylene chloride-hexane mixtures to obtain 4.3 g of white solids.
  • 1 H NMR indicated presence of tert-butyl groups on the compound and 19 F NMR indicated possible undesired conversion of the trifluorovinyloxy functionality to some other fluorinated alkyl species. This suggested possible undesired nucleophilic substitution of tert-butoxide on the trifluorovinyloxy functionality.
  • the reaction mixture was then heated to 50 0 C for 7 hrs and, subsequently, 0.2 rnL perfluoro(5-methyl-3,6-dioxanon-l-ene) was injected and the reaction continued overnight at room temperature.
  • the polymer was then precipitated into 100 mL methanol (semi-conductor grade, Aldrich) and centrifuged at 2000 rpm for 15 min. After discarding the supernatant, the centrifugate was shaken with 100 mL methanol (semi-conductor grade, Aldrich) and centrifuged again at 2000 rpm for 15min.
  • the white polymer was dried in a vacuum oven at room temperature after carefully pouring out the supernatant.
  • T g glass transition temperatures
  • T m melting points
  • Td eC omp,onset decomposition onset temperatures
  • HIL ink compositions were prepared using PoIy(TPD-TFVBPA) and IMDPIB(PhFs) 4 , as dopant.
  • the compositions are shown in Table 1 below.
  • the ink composition were obtained using the following general procedure: separate stock solutions of PoIy(TPD-TFVBPA) and IMDPIB(PhF 5 ) 4 , in chlorobenzene or PMA were first prepared, each containing 1% (w/w) solids. Various amounts of each stock solution were then combined as indicated in Table 1.
  • the resulting combined solution was refluxed for 2 h under a nitrogen blanket and stored in the glove -box.
  • HIL Hole injection layer
  • Ink compositions 1-9 from Tables 1 and 2 were spun on top of the ITO surfaces to prepare an HIL layer.
  • a different HIL layer serving as a comparative benchmark (“Comparative HIL 1 ”) was formed from an ink composition shown in Table 3 below:
  • P3MEET-S is sulfonated poly(3-methoxyethoxyethoxythiophene) as described in US Patent Publication No. 2008/0248313 filed July 13, 2007, assigned to Plextronics, Inc.
  • Fig. 1 shows absorbance and fluorescence spectra of thin films of poly(TPD-TFVBPA) on a glass substrate.
  • Fig. 2 shows UV-vis-NIR spectra of thin films of poly(TPD-TF VBPA) doped with 4-isopropyl- 4'methyldiphenyliodonium tetrakis(pentafluorophenyl)borate cast on a glass substrate from a solution in chlorobenzene and annealed at three temperatures. A doping profile for oxidation of polymer was observed.
  • OLED devices were fabricated following procedures known in the art.
  • the devices were fabricated on indium tin oxide (ITO) surfaces deposited on glass substrates.
  • ITO surface was pre-patterned to define the pixel area of 0.05 cm 2 .
  • the device substrates were cleaned by ultrasonication in a dilute soap solution for 20 minutes followed by distilled water washes. This was followed by ultrasonication in isopropanol for 20 minutes.
  • the substrates were dried under nitrogen flow, followed by treatment in a UV-Ozone chamber operating at 300 W for 20 minutes.
  • the cleaned substrates were then coated with an HIL ink formulation and dried at 90- 170 0 C for 5-15 minutes to form an HIL film layer. Dry film thicknesses ranged from approximately 20 nm to 60 nm.
  • the coating process was done on a spin coater, but can be similarly achieved with spray coating, ink-jetting, contact printing, or any other deposition method capable of resulting in an HIL film of the desired thickness.
  • the substrates were then transferred to a vacuum chamber where the remaining layers of the device stack were deposited by physical vapor deposition.
  • the devices thus obtained were encapsulated with a glass cover slip to prevent exposure to ambient conditions by means of a UV-light curing epoxy resin cured at 80 W/cm UV exposure for 4 minutes.
  • Performance tests were conducted on the OLED devices of Example 6 and 7.
  • performance is quantified by a combination of different parameters such as operating voltage (should be low), brightness in nits (should be bright, luminous), efficiency in units of cd/A (reflecting how much electric charge is needed to obtain light from the device), and the lifetime under operation (time required to reach half of the initial luminance value at the start of the test).
  • the overall performance is very important in a comparative evaluation of HIL performance. Performance of the devices was tested using the using the following procedures.
  • the OLED devices comprise pixels on a glass substrate whose electrodes extend outside the encapsulated area of the device which contain the light emitting portion of the pixels.
  • the typical area of each pixel in such devices is 0.05 cm .
  • the electrodes were contacted with a current source meter such as a Keithley 2400 source meter with a bias applied to the indium tin oxide electrode while the aluminum electrode is earthed. This procedure results in positively charged carriers (holes) and negatively charged carriers being injected into the device which form excitons and generate light.
  • the HIL layer of the device assists the injection of charge carriers into the light emitting layer, resulting in a low operating voltage of the device (defined as the voltage required to run a given current density through the pixel).
  • Another Keithley 2400 source meter was used to address a large area silicon photodiode.
  • This photodiode was maintained at zero volts bias by the 2400 source meter and placed in direct contact with area of the glass substrate directly below the lighted area of the OLED pixel.
  • the photodiode was used to collect the light generated by the OLED device, converting it into photocurrent which is in turn read by the source meter.
  • the photodiode current generated is quantified into optical units (candelas/sq. meter) by calibrating it with the help of a Minolta CS-200 Chromameter.
  • Voltage-current- light or IVL data for the OLED pixels of the devices were generated as follows: During the testing of the device, the Keithley 2400 source meter addressing the OLED pixel applied a voltage sweep to it. The resultant current passing through the pixel was measured. At the same time, the current passing through the OLED pixel resulted in light being generated, which then resulted in a photocurrent reading by the other Keithley 2400 source meter connected to the photodiode. This in turn enabled the measurement of other device characteristics, such as the lumens per Watt of electrical input power to the pixel (power efficiency) and candelas per ampere of pixel current.
  • HILs Current density (rnA/ cm 2 ), operating voltage (V), brightness (cd/m 2 ), and efficiency (cd/A) were measured for the OLED devices in Examples 6 and 7.
  • These devices contained HILs formed from ink compositions 1-9 shown in Tables 1 and 2, and a comparative HIL per Table 3. The results are presented in Tables 4, 5, 6 and 7.
  • HILs 1-9 correspond to ink compositions 1-9 of Tables 1 and 2.
  • the Comparative HIL was made as described above in Table 3. Nearly all devices containing a HIL formed from ink compositions 1-9 produced greater brightness and higher efficiency than those containing the comparative HIL.
  • Example 6 OLED Device Fabrication and testing with polv(TPD-TFVBPA)
  • An ink composition comprising poly(TPD-TFVBPA) was cast as the hole injection layer of a device.
  • the device layers deposited on top of the HIL included a hole transporting layer (HTL), an emissive layer (EML), a hole blocking layer (HBL), an electron transporting layer (ETL), and a metal cathode.
  • HTL hole transporting layer
  • EML emissive layer
  • HBL hole blocking layer
  • ETL electron transporting layer
  • metal cathode metal cathode.
  • the materials used were N,7V'(dinaphthalen-l-yl)-N,7V'- diphenyl-benzidine (NPB) as the HTL, bis(2-methyl-8-quinolinolato-Nl,O8)-(l,l '-biphenyl- 4-olato)aluminum (BAIq) doped with tris-(l-phenylisoquinoline)iridium III (Ir(piq)3) for the EML, BAIq as the HBL, and tris(8-hydroxyquinoline)aluminium (A
  • the cathode layer was prepared by the sequential deposition of two metal layers, the first being a 3 nm to 5 nm layer of Ca (0.1 nm/sec) followed by a 200 nm layer of Al (0.5 nm/sec) with the base pressure at 5 x 10 "7 Torr.
  • Fig. 3 shows IVL measurements for devices 1, 2, 3 along with a Comparative HIL example.
  • HILs 1-3 and Comparative HIL exhibit IVL performance that is comparable, if not better, than comparative aqueous HIL.
  • Example 7 OLED Device Fabrication and testing with TPD-TFV (Example 2)
  • An ink composition comprising TPD-TFV was cast as the hole injection layer of a device.
  • the layers deposited on top of the HIL included a hole transporting layer (HTL), an emissive layer (EML), a hole blocking layer (HBL), an electron transporting layer (ETL), and a metal cathode.
  • HTL hole transporting layer
  • EML emissive layer
  • HBL hole blocking layer
  • ETL electron transporting layer
  • metal cathode a metal cathode
  • the materials used were ⁇ /,N'(dinaphthalen-l-yl)- ⁇ /,N'-diphenyl-benzidine (NPB) as the HTL, bis(2-methyl-8-quinolinolato-Nl,O8)-(l,r-biphenyl-4-olato)aluminum (BAIq) doped with tris-(l-phenylisoquinoline)iridium III (Ir(piq)3) for the EML, Bis(2- methylquinolin-8-olato- ⁇ 2 ⁇ /,O)(6-phenyl-2-naphtholato- ⁇ O)aluminium(III) (BAIq') and an electron transport layer ETL and an electron injection layer EIL. All of these materials are commercially available.
  • the cathode layer was prepared by the sequential deposition of a 200 nm layer of Al (0.5 nm/sec) with the base pressure at 5 x 10 "7 Torr.
  • Fig. 10 a,b show IVL measurement for devices 4,5,6 and comparative example.
  • Figure 1 Ia, b show IVL measurement for devices 7, 8, 9 and comparative example.
  • OLED devices can also be tested for their lifetime performance. Lifetime performance can be measured using lifetime testers where a constant current is sourced through the tested devices. The current to the device is adjusted so that it gives a certain initial luminance value. For lifetime performance tests, this value is typically set at 1,000 candela/meter 2 . The luminance decay and voltage rise over time are then noted.
  • OLED devices fabricated in a manner similar to those of Examples 5-7 above were tested for lifetime performance.
  • the OLED devices contained the Comparative HIL and Inventive HIL used for the device efficiency measurements shown in Table 6, and had the general structure ITO/HIL/NPB/BAlq:Ir(piq)3 (15 wt%)/ETL/EIL/Al.
  • the results of the lifetime performance tests are shown in Table 6.
  • devices containing the inventive HIL produced greater brightness and longer lifetimes than those containing the comparative HIL.
  • Example 8 Film Thickness of TPD-TFV monomer with and without l,l,l-Tris(4- triflourovinyloxyphenyPethane (TFVOE)
  • TPD-TFV samples of TPD-TFV were synthesized according to the reaction scheme described above in Example 2.
  • a sample comprising 5 wt% TPD-TFV dissolved in 95 wt % DOWANOLTM PMA propylene glycol methyl ether acetate (available from The Dow Chemical Company, Midland, MI 48674) was prepared as a reference solution.
  • Several experimental solutions were prepared comprising 4.25- 4.75 wt % TPD-TFV, 0.25 - 0.75 wt% TFVOE (Cat# 019500 available from Oakwood Chemical, West Columbia, SC 29172), and 95 wt% DOWANOLTM PMA.
  • a first reaction produces compound (1) according to the scheme below:
  • N3,N6-diphenyl-N3,N6,9-tris(4-(l,2,2-trifluorovinyloxy)phenyl)-9H- carbazole-3,6-diamine Cz-TFV; Compound 4: To a dried flask under N 2 , were added N3,N6-diphenyl-9H-carbazole-3,6-diamine (3) (5 g), l-bromo-4- (trifluorovinyloxy)benzene (14.5g), hexadecyltrimethylammonium bromide (313 mg), aqueous potassium hydroxide (17.8g, 45% in water), 1,4-dioxane (500 mL).
  • the film was from the spinning conditions of 1,000 rpm/60 s in glove box and annealing conditions were 250°C/60 min in glove box on glass.
  • Good film means smooth, clear, and uniform films by visional observation.
  • Cross-linking reaction in films was monitored by FTIR. 1833 cm - " 1 peak is weak, and 965 cm “ 1 peak was used to monitor the cross-linking reaction in films.
  • Annealing temperature 150, 200, and 250C, and annealing time 2, 15, 60 min at these temperatures are studied for HTL 1. There is no peak increase at 250C/60min. However, the film does not remain after toluene wash. Therefore, 5% TFVOE was added to the formulation HTL2.
  • HTL2 HTL2, HTL3 and HTL4 are able to form good films on ITO, and have 90 - 100% film retain after toluene/chlorobenzene wash.
  • Cz-TFV has three cross-linking groups, and performs better for film retain than TPD-TFV.
  • HTL 3 is able to form good films on both aq-HIL and non-aq HILs with consistent thickness.

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Abstract

La présente invention concerne des oligomères et/ou des polymères comportant un squelette qui comprend une arylamine et des fractions alkylèneoxy fluorées qui peuvent être réticulées. Des formulations d'encre et des dispositifs peuvent être élaborés à partir des oligomères ou des polymères, ou de monomères correspondants, ainsi que des compositions dopées. Des couches d'injection et de transport de charges peuvent également être formées. L’invention permet d’obtenir une stabilité améliorée dans des dispositifs électroniques organiques tels que les OLED et les OPV.
PCT/US2009/064857 2008-11-18 2009-11-17 Compositions d’aminobenzène et dispositifs et procédés associés WO2010059646A2 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012003485A2 (fr) 2010-07-02 2012-01-05 Plextronics, Inc. Compositions de transport de trous et dispositifs et procédés associés (i)
WO2012133208A1 (fr) * 2011-03-30 2012-10-04 住友化学株式会社 Composition liquide et procédé de production de film multicouche faisant intervenir cette composition
US8828274B2 (en) 2008-10-27 2014-09-09 Solvay Usa, Inc. Polyarylamine ketones
JP2014526144A (ja) * 2011-07-05 2014-10-02 プレックストロニクス インコーポレーティッド 垂直に相分離している有機半導体材料層
US9112157B2 (en) 2012-05-15 2015-08-18 Solvay Usa, Inc. Hole transport materials including OLED applications

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5110944B2 (ja) * 2007-04-10 2012-12-26 富士フイルム株式会社 新規な架橋性のエーテル系含フッ素化合物およびその製造方法
EP2165707A1 (fr) * 2008-09-23 2010-03-24 Genkyo Tex Sa Dérivés de pyrazolo pyridine en tant qu'inhibiteurs de la NADPH oxydase
EP2166010A1 (fr) * 2008-09-23 2010-03-24 Genkyo Tex Sa Dérivés de pyridine pyrazolo en tant qu'inhibiteurs d'oxydase NADPH
JP5774484B2 (ja) 2008-10-27 2015-09-09 ソルベイ ユーエスエイ インコーポレイテッド 電荷注入層および輸送層
WO2010059240A1 (fr) * 2008-11-21 2010-05-27 Plextronics, Inc. Couches de modification interfaciale dopées pour l’amélioration de la stabilité de cellules solaires organiques à hétérojonction
CN107236258A (zh) 2010-05-11 2017-10-10 索尔维美国有限公司 掺杂的共轭聚合物和装置
EP2764518A1 (fr) 2011-10-04 2014-08-13 Plextronics, Inc. Procédés de dopage améliorés pour injection de trous et couches de transport
US9083006B2 (en) 2012-09-06 2015-07-14 Solvay Usa, Inc. Electroluminescent devices comprising insulator-free metal grids
KR102069555B1 (ko) * 2013-09-26 2020-01-23 엘지디스플레이 주식회사 정공수송물질 및 이를 포함하는 유기전계발광소자
WO2016026123A1 (fr) 2014-08-21 2016-02-25 Dow Global Technologies Llc Compositions comprenant des benzocyclobutènes substitués par de l'oxygène et des diénophiles et dispositifs électroniques contenant celles-ci
DE112015004774T5 (de) 2014-10-21 2017-07-06 Sumitomo Chemical Company, Limited Organische photoelektrische Umwandlungsvorrichtung und Verfahren zu ihrer Herstellung
KR102408799B1 (ko) 2014-12-15 2022-06-13 닛산 가가쿠 가부시키가이샤 정공 캐리어 물질 및 플루오로중합체를 함유하는 조성물 및 그의 용도
JP6648762B2 (ja) 2015-03-03 2020-02-14 日産化学株式会社 正孔輸送化合物とポリマー酸とを含有する組成物及びその使用
EP3286271A4 (fr) 2015-04-22 2018-10-24 Nissan Chemical Corporation Compositions non aqueuses se prêtant à une utilisation en électronique organique
CN107683536A (zh) * 2015-06-30 2018-02-09 富士胶片株式会社 光电转换元件及利用该光电转换元件的太阳能电池
CN107849376B (zh) 2015-07-17 2021-11-30 日产化学工业株式会社 适用于有机电子的包含金属纳米颗粒的非水性油墨组合物
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US10818860B2 (en) * 2016-06-28 2020-10-27 Rohm And Haas Electronic Materials Llc Quantum dot light emitting devices
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997033193A2 (fr) * 1996-02-23 1997-09-12 The Dow Chemical Company Polyarylpolyamines reticulables ou susceptibles de subir un allongement de chaine et films a base de ces composes
US20050187411A1 (en) * 2004-02-19 2005-08-25 Norman Herron Compositions comprising novel compounds and electronic devices made with such compositions
WO2007133633A2 (fr) * 2006-05-09 2007-11-22 University Of Washington Matériaux réticulables transporteurs de trous pour dispositif photoémetteurs organiques

Family Cites Families (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4356429A (en) 1980-07-17 1982-10-26 Eastman Kodak Company Organic electroluminescent cell
US4539507A (en) 1983-03-25 1985-09-03 Eastman Kodak Company Organic electroluminescent devices having improved power conversion efficiencies
GB8909011D0 (en) 1989-04-20 1989-06-07 Friend Richard H Electroluminescent devices
US5047687A (en) 1990-07-26 1991-09-10 Eastman Kodak Company Organic electroluminescent device with stabilized cathode
GB9018698D0 (en) 1990-08-24 1990-10-10 Lynxvale Ltd Semiconductive copolymers for use in electroluminescent devices
US5331183A (en) 1992-08-17 1994-07-19 The Regents Of The University Of California Conjugated polymer - acceptor heterojunctions; diodes, photodiodes, and photovoltaic cells
US5968674A (en) 1997-10-14 1999-10-19 Xerox Corporation Conductive polymer coatings and processes thereof
US5853906A (en) 1997-10-14 1998-12-29 Xerox Corporation Conductive polymer compositions and processes thereof
AT410729B (de) 2000-04-27 2003-07-25 Qsel Quantum Solar Energy Linz Photovoltaische zelle mit einer photoaktiven schicht aus zwei molekularen organischen komponenten
AT411306B (de) 2000-04-27 2003-11-25 Qsel Quantum Solar Energy Linz Photovoltaische zelle mit einer photoaktiven schicht aus zwei molekularen organischen komponenten
DE10153450A1 (de) 2001-10-30 2003-05-22 Covion Organic Semiconductors Verfahren zur Herstellung von Arylaminen
US20040004433A1 (en) 2002-06-26 2004-01-08 3M Innovative Properties Company Buffer layers for organic electroluminescent devices and methods of manufacture and use
US20080223428A1 (en) 2004-04-19 2008-09-18 Zeira Eitan C All printed solar cell array
US20050247340A1 (en) 2004-04-19 2005-11-10 Zeira Eitan C All printed solar cell array
WO2006036755A1 (fr) 2004-09-24 2006-04-06 Plextronics, Inc. Polythiophenes substitues en position 3 regioreguliers heteroatomiques dans des dispositifs electroluminescents
US7790979B2 (en) 2004-09-24 2010-09-07 Plextronics, Inc. Heteroatomic regioregular poly(3-substitutedthiophenes) for photovoltaic cells
GB0423528D0 (en) 2004-10-22 2004-11-24 Cambridge Display Tech Ltd Monomer for making a crosslinked polymer
US7569159B2 (en) 2005-02-10 2009-08-04 Plextronics, Inc. Hole injection/transport layer compositions and devices
WO2006096550A2 (fr) 2005-03-07 2006-09-14 Arkema Inc. Copolymeres blocs conducteurs
KR20070112799A (ko) 2005-03-16 2007-11-27 플렉스트로닉스, 인크 개선된 전자 성능을 갖는 가용성 폴리(티오펜)의 공중합체
KR20080043772A (ko) 2005-08-01 2008-05-19 플렉스트로닉스, 인크 전도성 중합체의 잠재성 도핑
EP1942098A4 (fr) * 2005-08-31 2012-12-19 Hodogaya Chemical Co Ltd Composé arylamine et dispositif organique à électroluminescence
US7652136B2 (en) * 2005-11-15 2010-01-26 The Hong Kong University Of Science And Technology Diarylaminofluorene-based organometallic phosphors and organic light-emitting devices made with such compounds
US7960040B2 (en) * 2006-02-28 2011-06-14 Fujifilm Corporation Organic electroluminescence device
US7884209B2 (en) 2006-03-30 2011-02-08 Novaled Ag Use of bora-tetraazapentalenes
CA2655135C (fr) 2006-06-13 2016-06-07 Plextronics, Inc. Dispositifs photovoltaiques organiques contenant des fullerenes et leurs derives
MY148477A (en) 2006-07-21 2013-04-30 Plextronics Inc Sulfonation of conducting polymers and oled, photovoltaic, and esd devices
JP5262014B2 (ja) * 2006-08-07 2013-08-14 三菱化学株式会社 架橋基を有する有機化合物、有機電界発光素子用組成物および有機電界発光素子
EP2057701A2 (fr) * 2006-08-24 2009-05-13 E.I. Du Pont De Nemours And Company Dispositifs électroniques organiques
JP2010502791A (ja) 2006-09-01 2010-01-28 カーネギー メロン ユニバーシティ ユニバーサルグリニャールメタセシス重合
JP2008069120A (ja) 2006-09-15 2008-03-27 Idemitsu Kosan Co Ltd 芳香族アミン誘導体及びそれらを用いた有機エレクトロルミネッセンス素子
WO2008042873A2 (fr) 2006-10-02 2008-04-10 Plextronics, Inc. Fermes solaires comprenant des modules opv à très bas coût
US20080085210A1 (en) 2006-10-05 2008-04-10 Henry Griesbach Decontamination of filtration media for respiration
EP2109900A1 (fr) 2007-01-08 2009-10-21 Plextronics, Inc. Dispositif photovoltaique a points quantiques
JP5125480B2 (ja) * 2007-01-15 2013-01-23 三菱化学株式会社 正孔輸送材料、該正孔輸送材料を重合させてなる高分子化合物、有機電界発光素子用組成物および有機電界発光素子
KR100846597B1 (ko) 2007-01-24 2008-07-16 삼성에스디아이 주식회사 함불소 화합물 및 탄소계 화합물을 포함하는 유기 발광소자
JP5470706B2 (ja) * 2007-01-25 2014-04-16 三菱化学株式会社 正孔輸送材料、該正孔輸送材料を重合させてなる高分子化合物、有機電界発光素子用組成物および有機電界発光素子

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997033193A2 (fr) * 1996-02-23 1997-09-12 The Dow Chemical Company Polyarylpolyamines reticulables ou susceptibles de subir un allongement de chaine et films a base de ces composes
US20050187411A1 (en) * 2004-02-19 2005-08-25 Norman Herron Compositions comprising novel compounds and electronic devices made with such compositions
WO2007133633A2 (fr) * 2006-05-09 2007-11-22 University Of Washington Matériaux réticulables transporteurs de trous pour dispositif photoémetteurs organiques

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MICHELLE S. LIU, YU-HUA NIU, JAE-WON KA, HIN-LAP YIP, FEI HUANG, JINGDONG LUO, TAE-DONG KIM AND ALEX K.-Y. JEN: "Thermally Cross-Linkable Hole-Transporting Materials for Improving Hole Injection in Multilayer Blue-Emitting Phosphorescent Polymer Light-Emitting Diodes" MACROMOLECULES, vol. 41, 26 November 2008 (2008-11-26), pages 9570-9580, XP002578429 DOI: 10.1021/ma801374w *
YEN-JU CHENG, MICHELLE S. LIU, YONG ZHANG, YUHUA NIU, FEI HUANG, JAE-WON KA, HIN-LAP YIP, YANQING TIAN AND ALEX K.-Y. JEN: "Thermally Cross-Linkable Hole-Transporting Materials on Conducting Polymer: Synthesis, Characterization, and Applications for Polymer Light-Emitting Devices" CHEM.MATER., vol. 20, 29 December 2007 (2007-12-29), pages 413-422, XP002578428 DOI: 10.1021/cm071828o *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8828274B2 (en) 2008-10-27 2014-09-09 Solvay Usa, Inc. Polyarylamine ketones
WO2012003485A2 (fr) 2010-07-02 2012-01-05 Plextronics, Inc. Compositions de transport de trous et dispositifs et procédés associés (i)
WO2012003482A2 (fr) 2010-07-02 2012-01-05 Plextronics, Inc. Compositions de transport de trous et dispositifs et procédés associés (ii)
US8535974B2 (en) 2010-07-02 2013-09-17 Plextronics, Inc. Hole transport compositions and related devices and methods (II)
US8815639B2 (en) 2010-07-02 2014-08-26 Solvay Usa, Inc. Hole transport compositions and related devices and methods (II)
US9577194B2 (en) 2010-07-02 2017-02-21 Nissan Chemical Industries, Ltd. Hole transport compositions and related devices and methods (I)
US10217938B2 (en) 2010-07-02 2019-02-26 Nissan Chemical Industries, Ltd. Hole transport compositions and related devices and methods (I)
WO2012133208A1 (fr) * 2011-03-30 2012-10-04 住友化学株式会社 Composition liquide et procédé de production de film multicouche faisant intervenir cette composition
JP2014526144A (ja) * 2011-07-05 2014-10-02 プレックストロニクス インコーポレーティッド 垂直に相分離している有機半導体材料層
US9112157B2 (en) 2012-05-15 2015-08-18 Solvay Usa, Inc. Hole transport materials including OLED applications

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US8283002B2 (en) 2012-10-09
EP2356168A2 (fr) 2011-08-17
US20130075670A1 (en) 2013-03-28
KR20110087283A (ko) 2011-08-02
WO2010059646A3 (fr) 2010-07-29
KR101669559B1 (ko) 2016-10-28
JP2012509278A (ja) 2012-04-19
EP2356168B1 (fr) 2015-05-27
US20100292399A1 (en) 2010-11-18

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