Ink composition

Abstract

To provide a composition that allows high transparency or low absorbance in the visible spectrum (transmittance>90%T) to be retained in an OLED device.SOLUTION: A water-based ink composition comprises (a) a polythiophene compound, (b) one or more metal oxide nanoparticles, (c) one or more dopants, and (d) a liquid carrier comprising one or more organic solvents.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This application claims priority to Japanese Patent Application No. 2017-007066, filed January 18, 2017, and Japanese Patent Application No. 2017-126780, filed June 28, 2017, the entire contents of which are expressly incorporated herein by this reference. The present disclosure relates to ink compositions comprising a polythiophene compound, a dopant, and metal oxide nanoparticles. The present disclosure also relates to the use of such ink compositions in organic electronic devices. [Background technology]

[0002] While there have been useful advances in energy-efficient devices, such as organic-based organic light-emitting diodes (OLEDs), polymer light-emitting diodes (PLEDs), phosphorescent organic light-emitting diodes (PHOLEDs), and organic photovoltaic devices (OPVs), further improvements are still needed to provide better material processing and / or device performance for commercialization. For example, one promising type of material used in organic electronics is conductive polymers, including polythiophenes. However, problems can arise due to the purity, processability, and instability of polymers in their neutral and / or conductive states. Furthermore, it is important to have excellent control over the solubility of polymers used in alternating layers of various device architectures (e.g., orthogonal or alternating solubility properties between adjacent layers in a particular device architecture). For example, these layers, also known as hole-injection layers (HILs) and hole-transport layers (HTLs), can pose challenging challenges given the competing demands and the need for very thin, yet high-quality, films.

[0003] In a typical OLED device stack, the refractive index of most p-doped polymer HILs, such as HILs containing PEDOT:PSS, is around 1.5, while the emissive material generally has a much higher refractive index (1.7 or greater). As a result, additive total internal reflection occurs at the EML / HIL (or HTL / HIL) and HIL / ITO interfaces, resulting in reduced light extraction efficiency.

[0004] There is an unmet need for good platform systems to control the properties of hole injection and hole transport layers, such as solubility, thermal / chemical stability, and electronic energy levels (e.g., HOMO and LUMO), so that these compounds can be tailored for different applications and to function with different compounds, such as light-emitting layers, photoactive layers, and electrodes. Good solubility, solvent intractability, and thermal stability are important properties. Also important is the ability to tune the resistance of the HIL and the thickness of the HIL layer while maintaining high transparency, low absorption, low internal reflection, low operating voltage in OLED systems, and longer lifetime, among other properties. It is also important to be able to tailor a system for a specific application and provide the required balance of these properties.

[0005] Patent Document 1 discloses a non-aqueous ink composition containing a sulfonated conjugated polymer and an amine compound. The presence of an amine compound in the non-aqueous ink composition not only provides the ink composition with good shelf life and stability, but also the thin film formed from the non-aqueous ink composition exhibits excellent uniformity, and the OLED device including the HIL formed from the non-aqueous ink composition exhibits good performance. However, there is a desire for OLED device performance that maintains higher transparency or lower absorbance in the visible spectrum. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2016 / 171935 Summary of the Invention [Problem to be solved by the invention]

[0007] It is an object of the present invention to enable devices comprising the compositions described herein to retain high transparency or low absorbance in the visible spectrum (transmittance >90%T) and to enable tunable film thickness. It is also an object of the present invention to provide improved electrical properties, thermal stability, and operational stability unable to increased lifetime of HILs in devices comprising the compositions described herein. [Means for solving the problem]

[0008] As a result of intensive research, the present inventors have found that an OLED device fabricated using an ink composition containing a polythiophene compound, a dopant, and metal oxide nanoparticles has high transparency, and have completed the present invention.

[0009] That is, the present invention provides the following inventions.

[0010] 1. An ink composition comprising: (a) Polythiophene compound (b) one or more metal oxide nanoparticles; (c) one or more dopants; and (d) a liquid carrier comprising one or more organic solvents A composition comprising:

[0011] 2. The composition according to item 1 above, wherein the polythiophene compound (a) contains a repeating unit represented by the following formula (I): [ka] wherein R1 and R2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, -SO3M, or -O-[ZO] p -R e or R1 and R2 together form -OZO- (wherein M is H, an alkali metal, ammonium, monoalkylammonium, dialkylammonium, or trialkylammonium; Z is a hydrocarbylene group optionally substituted with halogen or Y (wherein Y is a linear or branched alkyl or alkoxyalkyl group having 1 to 10 carbon atoms, and the alkyl or alkoxyalkyl group may be substituted with a sulfonic acid group at any position); p is an integer of 1 or greater; and R e is H, alkyl, fluoroalkyl, or aryl)]

[0012] 3. The ink composition according to item 1 or 2 above, wherein the dopant substance comprises at least one selected from the group consisting of arylsulfonic acid compounds, heteropolyacid compounds, and ionic compounds containing an element belonging to Group 13 or 15 of the long form periodic table.

[0013] 4. The ink composition according to any one of items 1 to 3 above, wherein the dopant substance is an arylsulfonic acid compound represented by formula (2). [ka] [In the formula, X represents O, S, or NH; A represents a naphthalene ring or an anthracene ring which may have substituents other than X and n (SOH) groups; B represents an unsubstituted or substituted hydrocarbon group, a 1,3,5-triazine group, or an unsubstituted or substituted group represented by the following formula (3) or (4): [ka] (wherein W 1represents a single bond, O, S, S(O) group, S(O2) group, or unsubstituted or substituted N, Si, P, or P(O) group; W 2 represents O, S, S(O) group, S(O2) group, or unsubstituted or substituted N, Si, P, P(O) group, and R 46 ~R 59 each independently represents a hydrogen atom or a halogen atom), n represents the number of sulfonic acid groups bonded to A and is an integer satisfying 1≦n≦4, and q represents the number of bonds between B and X and is an integer satisfying 1≦q.

[0014] 5. The ink composition according to any one of items 1 to 3 above, wherein the dopant substance is an arylsulfonic acid compound represented by formula (6). [ka] (wherein X represents O, S or NH; Ar 5 represents an aryl group, and n represents the number of sulfone groups and is an integer of 1 to 4.

[0015] 6. The ink composition according to any one of items 1 to 3 above, wherein the dopant substance is a heteropolyacid compound.

[0016] 7. R1 and R2 are each independently H, fluoroalkyl, —O[C(R a R b )-C(R c R d )-O] p -R e , -OR f where each R a , R b , R c , and R d are each independently H, halogen, alkyl, fluoroalkyl, or aryl; R e is H, alkyl, fluoroalkyl, or aryl; p is 1, 2, or 3; and R f7. The ink composition according to any one of items 2 to 6 above, wherein is alkyl, fluoroalkyl, or aryl.

[0017] 8. The ink composition according to any one of items 2 to 7 above, wherein R1 is H and R2 is other than H.

[0018] 9. The ink composition according to any one of items 2 to 7 above, wherein R1 and R2 are both other than H.

[0019] 10. R1 and R2 are each independently -O[C(R a R b )-C(R c R d )-O] p -R e , or -OR f or R1 and R2 together represent -O-(CH2) q 10. The ink composition according to item 9 above, wherein the ink composition forms —O—.

[0020] 11. R1 and R2 are both -O[C(R a R b )-C(R c R d )-O] p -R e 10. The ink composition according to item 9 above, wherein

[0021] 12. Each R a , R b , R c , and R d are each independently H, (C-C) alkyl, (C-C) fluoroalkyl, or phenyl; and R e 12. The ink composition according to any one of items 7 to 11 above, wherein is (C1-C8) alkyl, (C1-C8) fluoroalkyl, or phenyl.

[0022] 13. A polythiophene having the formula: [ka] 13. The ink composition according to any one of items 2 to 12 above, comprising a repeating unit selected from the group consisting of groups represented by the formula: and combinations thereof.

[0023] 14. The ink composition according to any one of items 2 to 13 above, wherein the polythiophene is sulfonated poly(3-MEET).

[0024] 15. The ink composition according to any one of paragraphs 2 to 14, wherein the polythiophene comprises repeat units according to formula (I) in an amount greater than 50 wt %, typically greater than 80 wt %, more typically greater than 90 wt %, and even more typically greater than 95 wt %, based on the total weight of repeat units.

[0025] 16. The ink composition according to any one of paragraphs 1 to 15, wherein the metal oxide nanoparticles comprise B2O3, B2O, SiO2, SiO, GeO2, GeO, As2O4, As2O3, As2O5, Sb2O3, TeO2, SnO2, SnO, or a mixture thereof.

[0026] 17. The ink composition according to item 16, wherein the metal oxide nanoparticles comprise SiO2.

[0027] 18. The ink composition according to any one of items 1 to 17 above, further comprising one or more amine compounds.

[0028] 19. The ink composition according to item 18, wherein the amine compound is an amine compound containing a tertiary alkylamine compound and an amine compound other than a tertiary alkylamine compound.

[0029] 20. The amine compound other than the tertiary alkylamine compound is a primary alkylamine compound. 20. The ink composition according to item 19 above, wherein

[0030] 21. The ink composition according to item 20 above, wherein the primary alkylamine compound is at least one selected from the group consisting of ethylamine, n-butylamine, t-butylamine, 2-ethylhexylamine, n-hexylamine, n-decylamine, and ethylenediamine.

[0031] 22. The ink composition according to item 21 above, wherein the primary alkylamine compound is 2-ethylhexylamine or n-butylamine.

[0032] 23. The ink composition according to any one of items 1 to 22 above, wherein the liquid carrier is a liquid carrier containing one or more glycol-based solvents (A) and one or more organic solvents (B) other than glycol-based solvents.

[0033] 24. The ink composition according to item 23 above, wherein the glycol solvent (A) is a glycol ether, a glycol monoether, or a glycol.

[0034] 25. The ink composition according to item 23 or 24 above, wherein the organic solvent (B) is a nitrile, an alcohol, an aromatic ether, or an aromatic hydrocarbon.

[0035] 26. The ink composition according to any one of items 23 to 25, wherein the content (weight) of the glycol solvent (A): wtA (weight) and the content (weight) of the organic solvent (B): wtB (weight) satisfy formula (1-1). 0.05≦wtB / (wtA+wtB)≦0.50 (1-1)

[0036] 27. An ink composition comprising: (a) a polythiophene having the formula (I): [ka] wherein R1 and R2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, -SO3M, or -O-[ZO] p -Re or R1 and R2 together form -OZO- (wherein M is H, an alkali metal, ammonium, monoalkylammonium, dialkylammonium, or trialkylammonium; Z is a hydrocarbylene group optionally substituted with halogen or Y (wherein Y is a linear or branched alkyl or alkoxyalkyl group having 1 to 10 carbon atoms, and the alkyl or alkoxyalkyl group may be substituted with a sulfonic acid group at any position); p is an integer of 1 or greater; and R e is H, alkyl, fluoroalkyl, or aryl); (b) one or more metal oxide nanoparticles; (c) one or more dopants (d) a liquid carrier comprising one or more organic solvents; and (e) one or more amine compounds A composition comprising:

[0037] The present invention further provides the following inventions.

[0038] 101. A non-aqueous ink composition comprising: (a) Formula (I): [ka] wherein R1 and R2 are each independently H, alkyl, fluoroalkyl, alkoxy, aryloxy, or -O-[ZO] p -R e (In the formula, Z is an optionally halogenated hydrocarbylene group; p is greater than or equal to 1, and R e is H, alkyl, fluoroalkyl, or aryl). a polythiophene comprising repeat units according to (b) one or more metal oxide nanoparticles; (c) one or more dopants; and (d) a liquid carrier comprising one or more organic solvents A composition comprising:

[0039] 102. The non-aqueous ink composition according to item 101, wherein the dopant substance comprises at least one selected from the group consisting of arylsulfonic acid compounds, heteropolyacid compounds, and ionic compounds containing an element belonging to Group 13 or Group 15 of the long-form periodic table.

[0040] 103. The water-based ink composition according to item 101 or 102 above, wherein the dopant substance is an arylsulfonic acid compound represented by formula (2). [ka] [In the formula, X represents O, S, or NH; A represents a naphthalene ring or an anthracene ring which may have substituents other than X and n (SOH) groups; B represents an unsubstituted or substituted hydrocarbon group, a 1,3,5-triazine group, or an unsubstituted or substituted group represented by the following formula (3) or (4): [ka] (wherein W 1 represents a single bond, O, S, S(O) group, S(O2) group, or unsubstituted or substituted N, Si, P, or P(O) group; W 2 represents O, S, S(O) group, S(O2) group, or unsubstituted or substituted N, Si, P, P(O) group, and R 46 ~R 59 each independently represents a hydrogen atom or a halogen atom), n represents the number of sulfonic acid groups bonded to A and is an integer satisfying 1≦n≦4, and q represents the number of bonds between B and X and is an integer satisfying 1≦q.

[0041] 104. The water-based ink composition according to item 101 or 102 above, wherein the dopant substance is an arylsulfonic acid compound represented by formula (6). [ka] (wherein X represents O, S or NH; Ar 5 represents an aryl group, and n represents the number of sulfone groups and is an integer of 1 to 4.

[0042] 105. The water-based ink composition according to item 101 or 102 above, wherein the dopant substance is a heteropolyacid compound.

[0043] 106. R1 and R2 are each independently H, fluoroalkyl, -O[C(R a R b )-C(R c R d )-O] p -R e , -OR f where each R a , R b , R c , and R d are each independently H, halogen, alkyl, fluoroalkyl, or aryl; R e is H, alkyl, fluoroalkyl, or aryl; p is 1, 2, or 3; and R f 106. The non-aqueous ink composition according to any one of items 101 to 105, wherein is alkyl, fluoroalkyl, or aryl.

[0044] 107. The non-aqueous ink composition according to any one of paragraphs 101 to 106, wherein R1 is H and R2 is other than H.

[0045] 108. The non-aqueous ink composition according to any one of paragraphs 101 to 106, wherein R1 and R2 are both other than H.

[0046] 109. R1 and R2 are each independently -O[C(R a R b )-C(R c R d )-O] p -R e , or -ORf 109. The non-aqueous ink composition according to item 108, wherein

[0047] 110. R1 and R2 are both -O[C(R a R b )-C(R c R d )-O] p -R e 109. The non-aqueous ink composition according to item 108, wherein

[0048] 111. Each R a , R b , Rc, and R d are each independently H, (C-C) alkyl, (C-C) fluoroalkyl, or phenyl; and R e 111. The non-aqueous ink composition according to any one of items 105 to 110 above, wherein is (C1-C8) alkyl, (C1-C8) fluoroalkyl, or phenyl.

[0049] 112. A polythiophene having the formula: [ka] 112. The non-aqueous ink composition according to any one of items 101 to 111, comprising a repeating unit selected from the group consisting of groups represented by the formula: and combinations thereof.

[0050] 113. The non-aqueous ink composition according to any one of items 101 to 112, wherein the polythiophene is sulfonated.

[0051] 114. The non-aqueous ink composition according to item 113 above, wherein the polythiophene is sulfonated poly(3-MEET).

[0052] 115. The non-aqueous ink composition according to any one of paragraphs 101 to 114, wherein the polythiophene comprises repeat units according to formula (I) in an amount greater than 50 wt %, typically greater than 80 wt %, more typically greater than 90 wt %, and even more typically greater than 95 wt %, based on the total weight of the repeat units.

[0053] 116. The non-aqueous ink composition according to any one of paragraphs 101 to 115, wherein the metal oxide nanoparticles comprise B2O3, B2O, SiO2, SiO, GeO2, GeO, As2O4, As2O3, As2O5, Sb2O3, TeO2, SnO2, SnO, or a mixture thereof.

[0054] 117. The non-aqueous ink composition according to paragraph 116, wherein the metal oxide nanoparticles comprise SiO2.

[0055] 118. The non-aqueous ink composition according to any one of items 101 to 117, further comprising one or more amine compounds.

[0056] 119. The non-aqueous ink composition according to item 118, wherein the amine compound is an amine compound containing a tertiary alkylamine compound and an amine compound other than a tertiary alkylamine compound.

[0057] 120. The non-aqueous ink composition according to the above item 119, wherein the amine compound other than a tertiary alkylamine compound is a primary alkylamine compound.

[0058] 121. The non-aqueous ink composition according to item 120 above, wherein the primary alkylamine compound is at least one selected from the group consisting of ethylamine, n-butylamine, t-butylamine, 2-ethylhexylamine, n-hexylamine, n-decylamine, and ethylenediamine.

[0059] 122. The non-aqueous ink composition according to the above item 121, wherein the primary alkylamine compound is 2-ethylhexylamine.

[0060] 123. The non-aqueous ink composition according to any one of items 101 to 122, wherein the liquid carrier is a liquid carrier containing one or more glycol-based solvents (A) and one or more organic solvents (B) other than glycol-based solvents.

[0061] 124. The non-aqueous ink composition according to item 123 above, wherein the glycol solvent (A) is a glycol ether, a glycol monoether, or a glycol.

[0062] 125. The non-aqueous ink composition according to item 123 or 124 above, wherein the organic solvent (B) is a nitrile, an alcohol, an aromatic ether, or an aromatic hydrocarbon.

[0063] 126. The non-aqueous ink composition according to any one of items 123 to 125, wherein the content (wtA) of the glycol solvent (A) and the content (wtB) of the organic solvent (B) satisfy formula (1-1). 0.05≦wtB / (wtA+wtB)≦0.50 (1-1)

[0064] 127. A non-aqueous ink composition comprising: (a) a polythiophene having the formula (I): [ka] wherein R1 and R2 are each independently H, alkyl, fluoroalkyl, alkoxy, aryloxy, or -O-[ZO] p -R e (In the formula, Z is an optionally halogenated hydrocarbylene group; p is greater than or equal to 1, and Re is H, alkyl, fluoroalkyl, or aryl). a polythiophene comprising repeat units according to (b) one or more metal oxide nanoparticles; (c) one or more dopants (d) a liquid carrier comprising one or more organic solvents; and (e) one or more amine compounds A composition comprising: [Effects of the Invention]

[0065] Devices comprising the compositions described herein can have high transparency or low absorbance in the visible spectrum (transmittance >90% T) and can have tunable film thicknesses. Additionally, the electrical properties, thermal stability, and operational stability of HILs in devices comprising the compositions described herein can be improved to an extent that would not have been possible to increase lifetime. DETAILED DESCRIPTION OF THE INVENTION

[0066] As used herein, the terms "a," "an," or "the" mean "one or more" or "at least one," unless otherwise specified.

[0067] As used herein, the term "comprises" encompasses "consisting essentially of" and "consisting of." The term "comprising" encompasses "consisting essentially of" and "consisting of."

[0068] The phrase "free of" means the absence of exogenous addition of the material modified by the phrase, and the absence of detectable amounts of this material observable by analytical techniques known to those skilled in the art (e.g., gas or liquid chromatography, spectrophotometry, light microscopy, etc.).

[0069] Throughout this disclosure, various publications are incorporated by reference. If the meaning of any language in a publication incorporated herein by reference conflicts with the meaning of the language in this disclosure, the meaning of the language in this disclosure shall control unless otherwise specified.

[0070] As used herein, the term "(Cx-Cy)" (where x and y are each integers) in reference to an organic group means that the group may contain from x to y carbon atoms in a group.

[0071] As used herein, the term "alkyl" refers to a monovalent linear or branched saturated hydrocarbon radical, more typically a monovalent linear or branched saturated (C1-C40) hydrocarbon radical, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, octyl, hexadecyl, octadecyl, eicosyl, behenyl, triacontyl, and tetracontyl.

[0072] As used herein, the term "fluoroalkyl" refers to an alkyl group as defined herein, substituted with one or more fluorine atoms, more typically (C-C 40 ) alkyl groups. Examples of fluoroalkyl groups include, for example, difluoromethyl, trifluoromethyl, perfluoroalkyl, 1H,1H,2H,2H-perfluorooctyl, perfluoroethyl, and —CH2CF3.

[0073] As used herein, the term "hydrocarbylene" refers to a hydrocarbon, typically (C-C 40 ) refers to a divalent group formed by removing two hydrogen atoms from a hydrocarbon. Hydrocarbylene groups can be linear, branched, or cyclic, and can be saturated or unsaturated. Examples of hydrocarbylene groups include, but are not limited to, methylene, ethylene, 1-methylethylene, 1-phenylethylene, propylene, butylene, 1,2-benzene, 1,3-benzene, 1,4-benzene, and 2,6-naphthalene.

[0074] As used herein, the term "alkoxy" refers to a monovalent group designated as -O-alkyl, where alkyl is defined as herein. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy.

[0075] As used herein, the term "aryl" refers to a monovalent unsaturated hydrocarbon group containing one or more six-membered carbon rings, where the unsaturation can be represented by three conjugated double bonds. Aryl groups include monocyclic aryls and polycyclic aryls. Polycyclic aryls refer to a monovalent unsaturated hydrocarbon group containing two or more six-membered carbon rings, where the unsaturation can be represented by three conjugated double bonds, where adjacent rings are bonded to each other or fused together by one or more bonds or divalent bridging groups. Examples of aryl groups include, but are not limited to, phenyl, anthracenyl, naphthyl, phenanthrenyl, fluorenyl, and pyrenyl.

[0076] As used herein, the term "aryloxy" refers to a monovalent group designated as -O-aryl, where aryl is defined herein. Examples of aryloxy groups include, but are not limited to, phenoxy, anthracenoxy, naphthoxy, phenanthrenoxy, and fluorenoxy.

[0077] Any substituent or group described herein may be optionally substituted at one or more carbon atoms with one or more of the same or different substituents described herein. For example, a hydrocarbylene group may be further substituted with an aryl or alkyl group. Any substituent or group described herein may also be optionally substituted at one or more carbon atoms with one or more substituents selected from the group consisting of, for example, halogens such as F, Cl, Br, and I; nitro (NO), cyano (CN), and hydroxy (OH).

[0078] As used herein, "hole carrier compound" refers to any compound that can facilitate the movement of holes (i.e., positive charge carriers) and / or block the movement of electrons, for example, in an electronic device. Hole carrier compounds include compounds useful in layers (HTL), hole injection layers (HIL), and electron blocking layers (EBL) of electronic devices, typically organic electronic devices (e.g., organic light emitting devices, etc.).

[0079] As used herein, the term "doped" with respect to a hole carrier compound, e.g., a polythiophene polymer, means that the hole carrier compound has undergone a chemical transformation, typically an oxidation or reduction reaction, more typically an oxidation reaction, facilitated by a dopant. As used herein, the term "dopant" refers to a substance that oxidizes or reduces, typically oxidizes, the hole carrier compound, e.g., a polythiophene polymer. Herein, the process by which the hole carrier compound undergoes a chemical transformation, typically an oxidation or reduction reaction, more typically an oxidation reaction, facilitated by a dopant is referred to as a "doping reaction" or simply "doping." Doping alters the properties of the polythiophene polymer, which may include, but are not limited to, electrical properties (such as resistivity and work function), mechanical properties, and optical properties. During the doping reaction, the hole carrier compound becomes charged, and the dopant becomes an oppositely charged counterion to the doped hole carrier compound as a result of the doping reaction. As used herein, a substance must chemically react with, oxidize, or reduce, typically oxidize, a hole carrier compound to be called a dopant. Substances that do not react with a hole carrier compound but may act as a counterion are not considered dopants in this disclosure. Thus, the term "undoped" with respect to a hole carrier compound, e.g., a polythiophene polymer, means that the hole carrier compound has not undergone a doping reaction as described herein.

[0080] The ink composition of the present disclosure may be non-aqueous or may contain water, but is preferably non-aqueous from the viewpoints of process compatibility in inkjet coating and storage stability of the ink. As used herein, "non-aqueous" means that the total amount of water in the ink composition of the present disclosure is 0 to 2 wt % based on the total amount of the ink composition. Typically, the total amount of water in the ink composition is 0 to 1 wt %, more typically 0 to 0.5 wt %, based on the total amount of the ink composition. In some embodiments, the non-aqueous ink composition of the present disclosure is substantially free of water.

[0081] The polythiophene contained in the ink composition of the present invention is a compound having an average molecular weight of 1,000 to 1,000,000 and composed of multiple structural units (which may be the same or different) derived from a thiophene derivative. In the polythiophene, two adjacent structural units are bonded to each other. Furthermore, when the polythiophene contains two or more different types of structural units, the structural units may be arranged in any order.

[0082] Preferably, the polythiophene contains a repeating unit represented by formula (I): The polythiophenes may be used alone or in combination of two or more kinds. [ka] wherein R1 and R2 are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, -SO3M, or -O-[ZO] p -R eor R1 and R2 together form -OZO-, where M is H, an alkali metal, ammonium, monoalkylammonium, dialkylammonium, or trialkylammonium, Z is a hydrocarbylene group optionally substituted with halogen or Y (wherein Y is a linear or branched alkyl or alkoxyalkyl group having 1 to 10 carbon atoms, and the alkyl or alkoxyalkyl group may be substituted at any position with a sulfonic acid group), p is an integer of 1 or greater, and R e is H, alkyl, fluoroalkyl, or aryl]

[0083] In certain embodiments, R and R are each independently H, fluoroalkyl, —O[C(R a R b )-C(R c R d )-O] p -R e , -OR f or R1 and R2 together represent -O-(CH2) q -O- (where (CH2) q optionally substituted with Y); a , R b , R c , and R d are each independently H, halogen, alkyl, fluoroalkyl, or aryl; R e is H, alkyl, fluoroalkyl, or aryl; p is 1, 2, or 3; R f is alkyl, fluoroalkyl, or aryl; q is 1, 2, or 3; and Y is a linear or branched alkoxyalkyl group having 1 to 10 carbon atoms, which alkoxyalkyl group may be substituted with a sulfonic acid group at any position.

[0084] In certain embodiments, R and R are each independently H, alkyl, fluoroalkyl, alkoxy, aryloxy, or -O-[ZO] p -R e (In the formula, Z is an optionally halogenated hydrocarbylene group; p is greater than or equal to 1, and R e is H, alkyl, fluoroalkyl, or aryl).

[0085] In certain embodiments, R1 is H and R2 is other than H. In such embodiments, the repeat unit is derived from a 3-substituted thiophene.

[0086] Polythiophenes can be regiorandom or regioregular compounds. Due to their asymmetric structure, polymerization of 3-substituted thiophenes produces a mixture of polythiophene structures containing three possible positional chemical bonds between the repeating units. The three available orientations when two thiophene rings are joined are 2,2', 2,5', and 5,5' couplings. 2,2' (i.e., head-to-head) coupling and 5,5' (i.e., tail-to-tail) coupling are referred to as regiorandom couplings. In contrast, 2,5' (i.e., head-to-tail) coupling is referred to as regioregular coupling. The degree of regioregularity can be, for example, about 0-100%, about 25-99.9%, or about 50-98%. Regioregularity can be determined by standard methods known to those skilled in the art, such as, for example, using NMR spectroscopy.

[0087] In certain embodiments, the polythiophene is regioregular. In some embodiments, the regioregularity of the polythiophene may be at least about 85%, typically at least about 95%, and more typically at least about 98%. In some embodiments, the degree of regioregularity may be at least about 70%, typically at least about 80%. In still other embodiments, the regioregular polythiophene has a degree of regioregularity of at least about 90%, typically at least about 98%.

[0088] 3-Substituted thiophene monomers, including polymers derived therefrom, are commercially available or can be prepared by methods known to those skilled in the art. Methods of synthesis, doping, and polymer characterization, including regioregular polythiophenes with pendant groups, are provided, for example, in U.S. Patent No. 6,602,974 to McCullough et al. and U.S. Patent No. 6,166,172 to McCullough et al.

[0089] In another embodiment, R1 and R2 are both other than H. In such an embodiment, the repeat unit is derived from a 3,4-disubstituted thiophene.

[0090] In certain embodiments, R and R are each independently —O[C(R a R b )-C(R c R d )-O] p -R e , or -OR f or R1 and R2 together represent -O-(CH2) q In some embodiments, R1 and R2 both form -O[C(R a R b )-C(R c R d )-O] p -R e R1 and R2 may be the same or different.

[0091] In certain embodiments, each R a , R b , R c , and R d are each independently H, (C-C) alkyl, (C-C) fluoroalkyl, or phenyl; and R e is (C1-C8) alkyl, (C1-C8) fluoroalkyl, or phenyl.

[0092] In some embodiments, R1 and R2 are each -O[CH2-CH2-O] p -Re In some embodiments, R1 and R2 are each -O[CH(CH3)-CH2-O] p -R e is.

[0093] In some embodiments, R e is methyl, propyl, or butyl.

[0094] In certain embodiments, q is 2.

[0095] In some embodiments, —O—(CH) q -O- is substituted at one or more positions with Y. In some embodiments, -O-(CH) q -O- is substituted with Y at one position.

[0096] In some embodiments, q is 2 and Y is a 3-sulfobutoxymethyl group, in which case the -O-(CH)-O- group is preferably substituted at one position with a 3-sulfobutoxymethyl group.

[0097] In some embodiments, the polythiophene has the formula:

[0098] [ka] wherein M is H, an alkali metal, ammonium, monoalkylammonium, dialkylammonium, or trialkylammonium, and combinations thereof.

[0099] As will be apparent to those skilled in the art, the following formula:

[0100] [ka] The repeating unit represented by the following formula:

[0101] [ka] 3-(2-(2-methoxyethoxy)ethoxy)thiophene (referred to herein as 3-MEET) and is derived from a monomer represented by the structure: [ka] The repeating unit represented by the following formula: [ka] wherein M is H, an alkali metal, ammonium, monoalkylammonium, dialkylammonium, or trialkylammonium. Sulfonated 3-(2-(2-methoxyethoxy)ethoxy)thiophene (referred to herein as sulfonated 3-MEET) and is derived from a monomer represented by the structure:

[0102] [ka] The repeating unit represented by the following formula:

[0103] [ka] 3,4-bis(2-(2-butoxyethoxy)ethoxy)thiophene (referred to herein as 3,4-diBEET) and is derived from a monomer represented by the structure:

[0104] [ka] The repeating unit represented by the following formula:

[0105] [ka] 3,4-bis((1-propoxypropan-2-yl)oxy)thiophene (referred to herein as 3,4-diPPT) and is derived from a monomer represented by the structure: [ka] The repeating unit represented by the following formula: [ka] 3,4-ethylenedioxythiophene and is derived from a monomer represented by the structure shown in the formula: [ka] The repeating unit represented by the following formula: [ka] It is derived from a monomer represented by the structure shown below.

[0106] 3,4-Disubstituted thiophene monomers, including polymers derived therefrom, are commercially available or can be prepared by methods known to those skilled in the art. For example, 3,4-disubstituted thiophene monomers can be prepared by reacting 3,4-dibromothiophene with a compound of the formula: HO-[ZO] p -R e or HOR f [where Z, R e , R f and p is as defined herein] with a metal salt, typically the sodium salt.

[0107] Polymerization of 3,4-disubstituted thiophene monomers is carried out by first brominating the 2- and 5-positions of the 3,4-disubstituted thiophene monomer to form the corresponding 2,5-dibromo derivative of the 3,4-disubstituted thiophene monomer. The polymer can then be obtained by GRIM (Grignard metathesis) polymerization of the 2,5-dibromo derivative of the 3,4-disubstituted thiophene in the presence of a nickel catalyst. Such a method is described, for example, in U.S. Pat. No. 8,865,025, which is incorporated herein by reference in its entirety. Another known method for polymerizing thiophene monomers is by oxidative polymerization using metal-free organic oxidants such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) or transition metal halides such as iron(III) chloride, molybdenum(V) chloride, and ruthenium(III) chloride.

[0108] which can be converted to a metal salt, typically the sodium salt, and used to generate 3,4-disubstituted thiophene monomers, of the formula: HO-[ZO] p -R e or HOR fExamples of compounds having the formula (I) are trifluoroethanol, ethylene glycol monohexyl ether (hexyl cellosolve), propylene glycol monobutyl ether (Dowanol PnB), diethylene glycol monoethyl ether (ethyl carbitol), dipropylene glycol n-butyl ether (Dowanol DPnB), diethylene glycol monophenyl ether (phenyl carbitol), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), dipropylene glycol monomethyl ether (Dowanol DPM), diisobutyl carbinol, 2-ethylhexyl alcohol, methyl isobutyl carbinol, ethylene glycol monophenyl ether (Dowanol Eph), propylene glycol monopropyl ether (Dowanol PnP), propylene glycol monophenyl ether (Dowanol PPh), diethylene glycol monopropyl ether (propyl carbitol), diethylene glycol monohexyl ether (hexyl carbitol), 2-ethylhexyl carbitol, dipropylene glycol monopropyl ether (Dowanol DPnP), tripropylene glycol monomethyl ether (Dowanol TPM), diethylene glycol monomethyl ether (methyl carbitol), and tripropylene glycol monobutyl ether (Dowanol TPnB).

[0109] Polythiophenes having repeat units according to formula (I) of the present disclosure can be further modified following their formation by polymerization. For example, polythiophenes having one or more repeat units derived from 3-substituted thiophene monomers may have one or more sites where hydrogen can be replaced with a substituent such as a sulfonic acid group (—SO3H) by sulfonation.

[0110] As used herein, the term "sulfonated" in reference to a polythiophene polymer means that the polythiophene contains one or more sulfonic acid groups (-SO3H). (Such polythiophenes are also referred to as "sulfonated polythiophenes.") Typically, the sulfur atom of the —SO3H group is directly attached to the polythiophene polymer backbone, not to a side group. For purposes of this disclosure, a side group is a monovalent group whose theoretical or actual elimination from the polymer does not shorten the length of the polymer chain. Sulfonated polythiophene polymers and / or copolymers can be prepared using any method known to those skilled in the art. For example, polythiophenes can be sulfonated by reacting the polythiophene with a sulfonating reagent, such as oleum, acetyl sulfate, pyridine SO3, or the like. In another example, a monomer can be sulfonated with a sulfonating reagent and then polymerized by known methods and / or the methods described herein. As will be apparent to those skilled in the art, sulfonic acid groups can result in the formation of corresponding salts or adducts in the presence of basic compounds, such as alkali metal hydroxides, ammonia, and alkylamines (e.g., mono-, di-, and trialkylamines, e.g., triethylamine). Thus, the term "sulfonated" in reference to a polythiophene polymer means that the polythiophene has one or more -SO3M groups, where M is an alkali metal ion (e.g., Na + , Li + , K. + , Rb + , Cs + etc.), ammonium (NH4 + ), mono-, di-, and trialkylammonium (such as triethylammonium).

[0111] Sulfonation of conjugated polymers and sulfonated conjugated polymers (including sulfonated polythiophenes) are described in US Pat. No. 8,017,241 to Seshadri et al., which is incorporated herein by reference in its entirety. Sulfonated polythiophenes are also described in WO 2008 / 073149 and WO 2016 / 171935, which are incorporated herein by reference in their entireties.

[0112] In some embodiments, the polythiophene is sulfonated. In some embodiments, the sulfonated polythiophene has Formula (I): [ka] wherein R1 and R2 are each independently H, alkyl, fluoroalkyl, alkoxy, aryloxy, or -O-[ZO] p -R e (In the formula, Z is an optionally halogenated hydrocarbylene group; p is greater than or equal to 1, and R e is H, alkyl, fluoroalkyl, or aryl). However, either R1 or R2 is -SO3M (M is H, an alkali metal ion, ammonium, monoalkylammonium, dialkylammonium, or trialkylammonium). is a b-polythiophene comprising repeat units according to In certain embodiments, each of R and R is independently H, fluoroalkyl, —O[C(R a R b )-C(R c R d )-O] p -R e , -OR f where each R a , R b , R c , and R d are each independently H, alkyl, fluoroalkyl, or aryl; R e is H, alkyl, fluoroalkyl, or aryl; p is 1, 2, or 3; and R fis alkyl, fluoroalkyl, or aryl. In certain embodiments, R1 is -SO3M and R2 is other than -SO3M. In certain embodiments, R1 is -SO3M and R2 is -O[C(R a R b )-C(R c R d )-O] p -R e , or -OR f is. In certain embodiments, R1 is -SO3M and R2 is -O[C(R a R b )-C(R c R d )-O] p -R e is. In certain embodiments, R1 is -SO3M and R2 is -O-CH2CH2-O-CH2CH2-O-CH3.

[0113] In some embodiments, the sulfonated polythiophene has Formula (I):

[0114] [ka] wherein R1 and R2 are each independently H, alkyl, fluoroalkyl, alkoxy, aryloxy, or -O-[ZO] p -R e (In the formula, Z is an optionally halogenated hydrocarbylene group; p is greater than or equal to 1, and R e is H, alkyl, fluoroalkyl, or aryl). The polythiophene is obtained by sulfonation of a polythiophene containing repeating units according to the formula:

[0115] In certain embodiments, R and R are each independently H, fluoroalkyl, —O[C(R aR b )-C(R c R d )-O] p -R e , -OR f where each R a , R b , R c , and R d are each independently H, alkyl, fluoroalkyl, or aryl; R e is H, alkyl, fluoroalkyl, or aryl; p is 1, 2, or 3; and R f is alkyl, fluoroalkyl, or aryl.

[0116] In certain embodiments, R1 is H and R2 is other than H. In such embodiments, the repeat unit is derived from a 3-substituted thiophene.

[0117] Sulfonated polythiophenes are derived from polythiophenes, which can be regiorandom or regioregular compounds. Due to their asymmetric structure, polymerization of 3-substituted thiophenes produces a mixture of polythiophene structures containing three possible positional chemical bonds between the repeating units. The three available orientations when two thiophene rings are joined are 2,2', 2,5', and 5,5' couplings. 2,2' (i.e., head-to-head) coupling and 5,5' (i.e., tail-to-tail) coupling are referred to as regiorandom couplings. In contrast, 2,5' (i.e., head-to-tail) coupling is referred to as regioregular coupling. The degree of regioregularity can be, for example, about 0-100%, about 25-99.9%, or about 50-98%. Regioregularity can be determined by standard methods known to those skilled in the art, such as using NMR spectroscopy.

[0118] 3-Substituted thiophene monomers, including polymers derived therefrom, are commercially available or can be prepared by methods known to those skilled in the art. Synthetic methods, doping methods, and polymer characterization, including regioregular polythiophenes with pendant groups, are provided, for example, in U.S. Patent No. 6,602,974 to McCullough et al. and U.S. Patent No. 6,166,172 to McCullough et al. Sulfonation of conjugated polymers and sulfonated conjugated polymers, including sulfonated polythiophenes, is described in U.S. Patent No. 8,017,241 to Seshadri et al.

[0119] In some embodiments, R1 is H and R2 is —O[C(R a R b )-C(R c R d )-O] p -R e , or -OR f In some embodiments, R1 is H and R2 is —O[C(R a R b )-C(R c R d )-O] p -R e is.

[0120] In certain embodiments, each R a , R b , R c , and R d are each independently H, (C-C) alkyl, (C-C) fluoroalkyl, or phenyl; R e and R f are each independently H, (C1-C8) alkyl, (C1-C8) fluoroalkyl, or phenyl.

[0121] In certain embodiments, R2 is -O[CH2-CH2-O] p -R e In some embodiments, R2 is -OR f is.

[0122] It can be converted to a metal salt, typically the sodium salt, and attached to a thiophene monomer to form a 3-substituted thiophene, which can then be used to generate the polythiophene to be sulfonated, of the formula: —O[C(R a R b )-C(R c R d )-O] p -R e or HOR f Examples of compounds having the formula (I) are trifluoroethanol, ethylene glycol monohexyl ether (hexyl cellosolve), propylene glycol monobutyl ether (Dowanol PnB), diethylene glycol monoethyl ether (ethyl carbitol), dipropylene glycol n-butyl ether (Dowanol DPnB), diethylene glycol monophenyl ether (phenyl carbitol), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), dipropylene glycol monomethyl ether (Dowanol DPM), diisobutyl carbinol, 2-ethylhexyl alcohol, methyl isobutyl carbinol, ethylene glycol monophenyl ether (Dowanol Eph), propylene glycol monopropyl ether (Dowanol PnP), propylene glycol monophenyl ether (Dowanol PPh), diethylene glycol monopropyl ether (propyl carbitol), diethylene glycol monohexyl ether (hexyl carbitol), 2-ethylhexyl carbitol, dipropylene glycol monopropyl ether (Dowanol DPnP), tripropylene glycol monomethyl ether (Dowanol TPM), diethylene glycol monomethyl ether (methyl carbitol), and tripropylene glycol monobutyl ether (Dowanol TPnB).

[0123] In some embodiments, R e is H, methyl, propyl, or butyl. In certain embodiments, R f is CH2CF3.

[0124] In some embodiments, the sulfonated polythiophene has the formula:

[0125] [ka] It is obtained from a polythiophene containing a repeating unit represented by the formula:

[0126] As will be apparent to those skilled in the art, the following formula:

[0127] [ka] The repeating unit represented by the following formula:

[0128] [ka] 3-(2-(2-methoxyethoxy)ethoxy)thiophene (referred to herein as 3-MEET) It is derived from a monomer represented by the structure shown below.

[0129] Therefore, the following formula:

[0130] [ka] Sulfonation of polythiophenes containing the repeating unit: gives sulfonated poly(3-MEET).

[0131] In some embodiments, the polythiophene is sulfonated poly(3-MEET).

[0132] The polythiophene polymers used in the present disclosure may be homopolymers or copolymers (including statistical, random, gradient, and block copolymers). Polymers containing monomer A and monomer B include block copolymers, such as AB diblock copolymers, ABA triblock copolymers, and -(AB)n- multiblock copolymers. Polythiophenes may also contain repeat units derived from other types of monomers, such as thienothiophene, selenophene, pyrrole, furan, tellurophene, aniline, arylamine, and arylene (e.g., phenylene, phenylenevinylene, and fluorene).

[0133] In some embodiments, the polythiophene comprises repeat units according to Formula (I) in an amount greater than 50 wt%, typically greater than 80 wt%, more typically greater than 90 wt%, and even more typically greater than 95 wt%, based on the total weight of the repeat units.

[0134] As will be apparent to those skilled in the art, depending on the purity of the starting monomer compounds used in the polymerization, the polymer formed may contain repeat units derived from impurities. As used herein, the term "homopolymer" is intended to mean a polymer containing repeat units derived from one type of monomer, but which does not contain repeat units derived from impurities. In some embodiments, the polythiophene is a homopolymer in which essentially all of the repeat units are according to formula (I).

[0135] Polythiophene polymers typically have a number average molecular weight of about 1,000 to 1,000,000 g / mol. More typically, the conjugated polymers have a number average molecular weight of about 5,000 to 100,000 g / mol, and even more typically, about 10,000 to about 50,000 g / mol. Number average molecular weights can be determined by methods known to those skilled in the art, such as, for example, gel permeation chromatography.

[0136] In the present invention, the polythiophene may be used after being treated with a reducing agent. In polythiophenes, some of the repeating units that constitute them may have an oxidized chemical structure called a "quinoid structure." The term "quinoid structure" is used in contrast to the term "benzenoid structure." The latter is a structure containing an aromatic ring, while the former refers to a structure in which a double bond within the aromatic ring moves out of the ring (resulting in the disappearance of the aromatic ring), resulting in the formation of two exocyclic double bonds that are conjugated with other double bonds remaining in the ring. Those skilled in the art can easily understand the relationship between these two structures from the relationship between the structures of benzoquinone and hydroquinone. Quinoid structures for the repeating units of various conjugated polymers are well known to those skilled in the art. As an example, a quinoid structure corresponding to the repeating unit of polythiophene represented by the above formula (I) is shown in the following formula (I'). [ka] wherein R1 and R2 are as defined in formula (I).

[0137] This quinoid structure is formed by the doping reaction and forms part of structures known as "polaron structures" and "bipolaron structures," which impart charge transport properties to polythiophenes. These structures are publicly known. The introduction of a "polaron structure" and / or a "bipolaron structure" is essential in the fabrication of organic EL devices. In fact, this is achieved by intentionally inducing the doping reaction when a charge-transporting thin film formed from a charge-transporting varnish is baked during the fabrication of organic EL devices. The quinoid structure is contained in polythiophenes prior to the doping reaction, presumably because the polythiophenes undergo an unintended oxidation reaction equivalent to the doping reaction during their production (particularly the sulfonation step in the case of sulfonated polythiophenes).

[0138] There is a correlation between the amount of quinoid structures contained in polythiophene and the dispersibility of polythiophene in organic solvents; as the amount of quinoid structures increases, the dispersibility decreases. Therefore, the introduction of quinoid structures after the formation of a charge-transporting thin film from the ink composition does not cause any problems. However, if an excessive amount of quinoid structures is introduced into polythiophene due to the unintended oxidation reaction, it will cause problems during the production of the ink composition. Polythiophenes are known to have variable dispersibility in organic solvents, and one of the reasons for this is thought to be that the amount of quinoid structures introduced into polythiophene due to the unintended oxidation reaction varies depending on the production conditions of each polythiophene. Therefore, when polythiophene is subjected to a reduction treatment using a reducing agent, even if an excessive amount of quinoid structure is introduced into the polythiophene, the quinoid structure is reduced by the reduction, and the dispersibility of the polythiophene in an organic solvent is improved, so that a charge transport thin film with excellent homogeneity can be obtained. This makes it possible to stably produce ink compositions having such properties.

[0139] The reducing agent used in this reduction treatment is not particularly limited as long as it can reduce the quinoid structure and convert it to a non-oxidized structure, i.e., the benzenoid structure (for example, in the case of polythiophene represented by formula (I), the quinoid structure represented by formula (I') is converted to the structure represented by formula (I)), and it is preferable to use, for example, aqueous ammonia, hydrazine, etc. The amount of the reducing agent is usually 0.1 to 10 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of polythiophene to be treated.

[0140] The method and conditions for the reduction treatment are not particularly limited. For example, this treatment can be carried out by simply contacting the polythiophene with a reducing agent in the presence or absence of a suitable solvent. Usually, reduction treatment under relatively mild conditions, such as stirring the polythiophene in 28% aqueous ammonia (e.g., overnight at room temperature), sufficiently improves the dispersibility of the polythiophene in organic solvents. In the case of sulfonated polythiophene, if necessary, the sulfonated polythiophene may be converted into a corresponding ammonium salt, such as a trialkylammonium salt (sulfonated polythiophene amine adduct), and then subjected to the reduction treatment.

[0141] Note that this reduction treatment changes the dispersibility of polythiophene in the solvent, and as a result, polythiophene that was not dissolved in the reaction system at the start of the treatment may dissolve by the end of the treatment. In such cases, the polythiophene can be recovered by adding an organic solvent that is incompatible with polythiophene (e.g., acetone or isopropyl alcohol in the case of sulfonated polythiophene) to the reaction system to precipitate the polythiophene, followed by filtration.

[0142] The ink compositions of the present disclosure may optionally further comprise other hole carrier compounds.

[0143] Optional hole carrier compounds include, for example, low molecular weight compounds or high molecular weight compounds. Optional hole carrier compounds may be non-polymeric or polymeric. Non-polymeric hole carrier compounds include, but are not limited to, crosslinkable and non-crosslinkable small molecules. Examples of non-polymeric hole carrier compounds are N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)benzidine (CAS # 65181-78-4); N,N'-bis(4-methylphenyl)-N,N'-bis(phenyl)benzidine; N,N'-bis(2-naphthalenyl)-N,N'-bis(phenylbenzidine) (CAS # 139255-17-1); 1,3,5-tris(3-methyldiphenylamino)benzene (also known as m-MTDAB); N,N'-bis(1-naphthalenyl)-N,N'-bis(phenyl)benzidine (CAS # 123847-85-8, NPB); 4,4',4"-tris(N,N-phenyl-3-methylphenylamino)triphenylamine (also known as m-MTDATA, CAS # 124729-98-2;4,4'N,N'-Diphenylcarbazole (also known as CBP, CAS # 58328-31-7);1,3,5-Tris(diphenylamino)benzene;1,3,5-Tris(2-(9-ethylcarbazyl-3)ethylene)benzene;1,3,5-Tris[(3-methylphenyl)phenylamino]benzene;1,3-Bis(N-carbazolyl)benzene;1,4-Bis(diphenylamino)benzene;4,4'-Bis(N-carbazolyl)-1,1'-biphenyl;4,4'-Bis(N-carbazolyl)-1,1'-biphenyl;4-(Dibenzylamino)benzaldehyde-N,N-diphenylhydrazone;4-(Diethylamino)benzaldehyde diphenylhydrazone;4-(Dimethylamino)benzaldehyde Diphenylhydrazone;4-(Diphenylamino)benzaldehyde diphenylhydrazone;9-Ethyl-3-carbazolecarboxaldehyde diphenylhydrazone;Copper(II) phthalocyanine;N,N'-Bis(3-methylphenyl)-N,N'-diphenylbenzidine;N,N'-Di[(1-naphthyl)-N,N'-diphenyl]-1,1'-biphenyl)-4,4'-diamine;Examples of suitable amines include, but are not limited to, N,N'-diphenyl-N,N'-di-p-tolylbenzene-1,4-diamine; tetra-N-phenylbenzidine; titanyl phthalocyanine; tri-p-tolylamine; tris(4-carbazol-9-ylphenyl)amine; and tris[4-(diethylamino)phenyl]amine.

[0144] Optional polymeric hole carrier compounds include, but are not limited to, poly[(9,9-dihexylfluorenyl-2,7-diyl)-alt-co-(N,N'-bis{p-butylphenyl}-1,4-diaminophenylene)]; poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(N,N'-bis{p-butylphenyl}-1,1'-biphenylene-4,4'-diamine)]; poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (also known as TFB), and poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine] (commonly referred to as poly-TPD).

[0145] Other optional hole carrier compounds are described, for example, in U.S. Patent Publication Nos. 2010 / 0292399, published November 18, 2010; 2010 / 010900, published May 6, 2010; and 2010 / 0108954, published May 6, 2010. The optional hole carrier compounds described herein are known in the art and commercially available.

[0146] In some embodiments, the polythiophene comprising a repeating unit according to formula (I) is doped with a dopant. Dopants are known in the art. For example, see U.S. Patent No. 7,070,867; U.S. Publication No. 2005 / 0123793; and U.S. Publication No. 2004 / 0113127. The dopant may be an ionic compound. The dopant may include cations and anions. One or more dopants may be used to dope the polythiophene comprising a repeating unit according to formula (I).

[0147] The cation of the ionic compound can be, for example, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ta, W, Re, Os, Ir, Pt, or Au.

[0148] The cations of the ionic compounds can be, for example, gold, molybdenum, rhenium, iron, and silver cations.

[0149] In some embodiments, the dopant may comprise a sulfonate or carboxylate, including alkyl, aryl, and heteroaryl sulfonates or carboxylates. As used herein, "sulfonate" refers to a -SO3M group (where M is H). + or alkali metal ions (e.g., Na + , Li + , K. + , Rb + , Cs + etc.); or ammonium (NH4 + As used herein, "carboxylate" refers to a -COM group, where M is H + or alkali metal ions (e.g., Na + , Li + , K. + , Rb + , Cs + etc.); or ammonium (NH4 + Examples of sulfonate and carboxylate dopants include, but are not limited to, benzoate compounds, heptafluorobutyrate, methanesulfonate, trifluoromethanesulfonate, p-toluenesulfonate, pentafluoropropionate, and polymeric sulfonates, perfluorosulfonate-containing ionomers, and the like.

[0150] In some embodiments, the dopant does not include a sulfonate or a carboxylate.

[0151] In some embodiments, the dopant may include sulfonylimides (e.g., bis(trifluoromethanesulfonyl)imides, etc.); antimonates (e.g., hexafluoroantimonates, etc.); arsenates (e.g., hexafluoroarsenates, etc.); phosphorus compounds (e.g., hexafluorophosphates, etc.); and borates (e.g., tetrafluoroborate, tetraarylborates, and trifluoroborates, etc.). Examples of tetraarylborates include, but are not limited to, halogenated tetraarylborates such as tetrakispentafluorophenylborate (TPFB). Examples of trifluoroborates include, but are not limited to, (2-nitrophenyl)trifluoroborate, benzofurazan-5-trifluoroborate, pyrimidine-5-trifluoroborate, pyridine-3-trifluoroborate, and 2,5-dimethylthiophene-3-trifluoroborate.

[0152] The dopant can be, for example, a material that undergoes one or more electron transfer reactions with the conjugated polymer to form a doped polythiophene. The dopant can be selected to provide an appropriate charge-balancing counteranion. The reaction can occur by mixing the polythiophene with the dopant, as is known in the art. For example, the dopant can undergo spontaneous electron transfer from the polymer to a cation-anion dopant (e.g., a metal salt), leaving the conjugated polymer in its oxidized form with an associated anion and free metal. See, for example, Lebedev et al., Chem. Mater., 1998, 10, 156-163. As disclosed herein, polythiophene and dopant can refer to components that react to form a doped polymer. The doping reaction can be a charge transfer reaction in which charge carriers are generated, and the reaction can be reversible or irreversible. In some embodiments, silver ions can undergo electron transfer to or from silver metal and the doped polymer.

[0153] In the final formulation, the composition may be distinct from the original combination of components (i.e., the polythiophene and / or dopant may or may not be present in the final composition in the same form as before mixing). As the dopant, an inorganic acid, an organic acid, an organic or inorganic oxidizing agent, or the like is used. As the organic acid, a polymer organic acid and / or a low molecular weight organic acid (non-polymer organic acid) is used. In one embodiment, the organic acid is a sulfonic acid and its salt (-SOM, where M is an alkali metal ion (e.g., Na + , Li + , K. + , Rb + , Cs + etc.), ammonium (NH4 + ), mono-, di-, and trialkylammonium (such as triethylammonium). Among the sulfonic acids, arylsulfonic acids are preferred.

[0154] In some embodiments, specific examples of dopants include strong inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid, and phosphoric acid; Lewis acids such as aluminum(III) chloride (AlCl), titanium(IV) tetrachloride (TiCl), boron tribromide (BBr), boron trifluoride etherate (BF·OEt), iron(III) chloride (FeCl), copper(II) chloride (CuCl), antimony(V) pentachloride (SbCl), arsenic(V) pentafluoride (AsF), phosphorus pentafluoride (PF), and tris(4-bromophenyl)aluminum hexachloroantimonate (TBPAH); polymeric organic acids such as polystyrene sulfonic acid; benzenesulfonic acid, tosylic acid, camphorsulfonic acid, and arsenic trichloride (BF·OEt). Examples of oxidizing agents include, but are not limited to, low-molecular-weight organic acids (non-polymer organic acids) such as hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, dodecylbenzenesulfonic acid, 1,4-benzodioxanedisulfonic acid derivatives described in WO 2005 / 000832, arylsulfonic acid derivatives described in WO 2006 / 025342, and dinonylnaphthalenesulfonic acid derivatives described in JP 2005-108828 A; and organic or inorganic oxidizing agents such as 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), iodine, and heteropolyacid compounds.

[0155] In some embodiments, the dopant comprises at least one selected from the group consisting of an arylsulfonic acid compound, a heteropolyacid compound, and an ionic compound containing an element belonging to Group 13 or 15 of the long form periodic table. Particularly preferred dopants include polymeric organic acids such as polystyrene sulfonic acid, 5-sulfosalicylic acid, dodecylbenzenesulfonic acid, 1,4-benzodioxanedisulfonic acid derivatives described in WO 2005 / 000832, and low-molecular-weight organic acids (non-polymeric organic acids) such as dinonylnaphthalenesulfonic acid derivatives described in JP 2005-108828 A. In addition, sulfonic acid derivatives represented by the following formula (2) can also be suitably used.

[0156] [ka] [In the formula, X represents O, S, or NH; A represents a naphthalene ring or an anthracene ring which may have substituents other than X and n (SOH) groups; B represents an unsubstituted or substituted hydrocarbon group, a 1,3,5-triazine group, or an unsubstituted or substituted group represented by the following formula (3) or (4): [ka] (wherein W 1 and W 2 each independently represents O, S, an S(O) group, an S(O2) group, or an unsubstituted or substituted N, Si, P, or P(O) group. 1 R may be a single bond. 46 ~R 59 each independently represents a hydrogen atom or a halogen atom; n represents the number of sulfonic acid groups bonded to A and is an integer satisfying 1≦n≦4; and q represents the number of bonds between B and X and is an integer satisfying 1≦q.

[0157] R in equation (3) or (4) 46 ~R 59 is preferably a fluorine atom, and more preferably all of them are fluorine atoms. 1 is preferably a single bond. Most preferably, W in formula (3) is 1 is a single bond, and R 46 ~R 53 are all fluorine atoms.

[0158] The arylsulfonic acid compound according to the present invention may further be one represented by the following formula (6). [ka] (wherein X represents O, S or NH; Ar 5 represents an aryl group, and n represents the number of sulfone groups and is an integer of 1 to 4.

[0159] In the formula (6), X represents O, S or NH, with O being particularly preferred due to ease of synthesis. n represents the number of sulfone groups bonded to the naphthalene ring and is an integer between 1 and 4, but considering that the compound has high electron accepting ability and high solubility, n is preferably 1 or 2. Among these, a compound represented by the following formula (7) is suitable. [ka] (In the formula, Ar 5 represents an aryl group.

[0160] Examples of the aryl group in formula (6) and formula (7) include aryl groups such as a phenyl group, a xylyl group, a tolyl group, a biphenyl group, and a naphthyl group, and these aryl groups may have a substituent. Examples of the substituent include, but are not limited to, a hydroxyl group, an amino group, a silanol group, a thiol group, a carboxyl group, a phosphoric acid group, a phosphoric acid ester group, an ester group, a thioester group, an amide group, a nitro group, a cyano group, a monovalent hydrocarbon group, an organooxy group, an organoamino group, an organosilyl group, an organothio group, an acyl group, a sulfone group, and a halogen atom. Among these aryl groups, the aryl group represented by the following formula (8) is particularly preferably used. [ka] (In the formula, R 60 ~R 64 are each independently a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms.

[0161] In formula (8), the halogen atom may be any of chlorine, bromine, fluorine and iodine atoms, but in the present invention, a fluorine atom is particularly preferred. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, a 2-ethylhexyl group, an n-decyl group, a cyclopentyl group, and a cyclohexyl group. Examples of halogenated alkyl groups having 1 to 10 carbon atoms include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2,2-pentafluoroethyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 1,1,2,2,3,3,3-heptafluoropropyl group, a 4,4,4-trifluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, and a 1,1,2,2,3,3,4,4,4-nonafluorobutyl group. Examples of the halogenated alkenyl group having 2 to 10 carbon atoms include a perfluorovinyl group, a perfluoropropenyl group (allyl group), and a perfluorobutenyl group. Among these, in consideration of further increasing the solubility in organic solvents, it is particularly preferable to use an aryl group represented by the following formula (9). [ka] (In the formula, R 62 represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a halogenated alkenyl group having 2 to 10 carbon atoms.

[0162] In formula (9), R 62 In particular, a halogenated alkyl group, a halogenated alkynyl group, and a nitro group are preferred, and a trifluoromethyl group, a perfluoropropenyl group, and a nitro group are more preferred.

[0163] Furthermore, the following formula (5a) or Z 1 Ionic compounds comprising an anion represented by the following formula and its counter cation can also be suitably used as dopants. [ka] (wherein E represents an element belonging to Group 13 or 15 of the long period periodic table, and Ar 1 ~Ar 4 each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.

[0164] In formula (5a), E is preferably boron, gallium, phosphorus, or antimony among elements belonging to Group 13 or 15 of the long period periodic table, and more preferably boron.

[0165] In formula (5a), examples of the aromatic hydrocarbon group and aromatic heterocyclic group include monovalent groups derived from a 5- or 6-membered monocycle or 2- to 4-condensed ring. Among these, from the viewpoints of the stability and heat resistance of the compound, monovalent groups derived from a benzene ring, naphthalene ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, and isoquinoline ring are preferred. Furthermore, Ar 1 ~Ar 4 It is more preferable that at least one of the groups has one or more fluorine atoms or chlorine atoms as a substituent. 1 ~Ar 4 It is most preferably a perfluoroaryl group in which all of the hydrogen atoms in the above group are substituted with fluorine atoms. Specific examples of the perfluoroaryl group include a pentafluorophenyl group, a heptafluoro-2-naphthyl group, and a tetrafluoro-4-pyridyl group.

[0166] Z 1Examples of the cation ion include an ion represented by the following formula (5b), hydroxide ion, fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, nitrate ion, nitrite ion, sulfate ion, sulfite ion, perchlorate ion, perbromate ion, periodate ion, chlorate ion, chlorite ion, hypochlorite ion, phosphate ion, phosphite ion, hypophosphite ion, borate ion, isocyanate ion, hydrosulfide ion, tetrafluoroborate ion, hexafluorophosphate ion, and hexachloroantimonate ion; carboxylate ions such as acetate ion, trifluoroacetate ion, and benzoate ion; sulfonate ions such as methanesulfonate and trifluoromethanesulfonate ion; and alkoxy ions such as methoxy ion and t-butoxy ion. [ka] (In the formula, E 2 represents an element belonging to Group 15 of the long-form periodic table, and X represents a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.

[0167] In formula (5b), E 2 is preferably a phosphorus atom, an arsenic atom, or an antimony atom, and is preferably a phosphorus atom in terms of the stability of the compound, ease of synthesis and purification, and toxicity. From the viewpoint of the stability of the compound and ease of synthesis and purification, X is preferably a fluorine atom or a chlorine atom, and most preferably a fluorine atom.

[0168] Among the above, the following formulas (10), (11), (12), and (13): [ka] An ionic compound having a combination of an anion and a cation represented by the following formula (see Japanese Patent No. 5381931 (Patent Document 5)) can be suitably used.

[0169] Heteropolyacid compounds are also particularly preferred as dopants. Heteropolyacid compounds have a structure in which a heteroatom is located at the center of the molecule, typically represented by a Keggin-type chemical structure shown in formula (A) or a Dawson-type chemical structure shown in formula (B), and are polyacids formed by condensing an isopolyacid, which is an oxyacid of vanadium (V), molybdenum (Mo), tungsten (W), or the like, with an oxyacid of a different element. Examples of such oxyacids of different elements include oxyacids of silicon (Si), phosphorus (P), and arsenic (As). [ka]

[0170] Specific examples of heteropolyacid compounds include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, phosphotungstomolybdic acid, and silicotungstic acid. In consideration of the properties of an organic EL device having the resulting thin film, phosphomolybdic acid, phosphotungstic acid, and silicotungstic acid are preferred, with phosphotungstic acid being more preferred. These heteropolyacid compounds may be synthesized by known synthesis methods, but are also commercially available. For example, phosphotungstic acid hydrate (or 12-tungstophosphoric acid n-hydrate, chemical formula: H3(PW 12 O 40 )·nH2O) and phosphomolybdic acid hydrate (also known as 12-Molybdo(VI)phosphoric acid n-hydrate, chemical formula: H3(PMo 12 O 40 )·nH2O (n≒30)) is available from manufacturers such as Kanto Chemical Co., Ltd., Wako Pure Chemical Industries, Ltd., Sigma-Aldrich Japan, Ltd., Nippon Inorganic Chemical Industry Co., Ltd., and Nippon New Metals Co., Ltd.

[0171] In some embodiments, reaction by-products from the doping process may be removed, for example, metals such as silver may be removed by filtration.

[0172] For example, materials can be purified to remove halogens and metals. Halogens include, for example, chlorides, bromides, and iodides. Metals include, for example, dopant cations (including reduced forms of dopant cations) or metals left over from catalyst or initiator residues. Metals include, for example, silver, nickel, and magnesium. The amount can be, for example, less than 100 ppm, or less than 10 ppm, or less than 1 ppm.

[0173] Metal content, including silver content, can be measured by ICP-MS, especially at concentrations above 50 ppm.

[0174] In some embodiments, when the polythiophene is doped with a dopant, the polythiophene and the dopant are mixed to form a doped polymer composition. Mixing can be accomplished using any method known to those skilled in the art. For example, a solution containing the polythiophene can be mixed with another solution containing the dopant. The solvent used to dissolve the polythiophene and the dopant can be one or more of the solvents described herein. The reaction can occur by mixing the polythiophene and the dopant, as known in the art. The resulting doped polythiophene composition comprises, based on the composition, about 40% to 75% by weight of the polymer and about 25% to 55% by weight of the dopant. In another embodiment, the doped polythiophene composition comprises, based on the composition, about 50% to 65% by weight of the polythiophene and about 35% to 50% by weight of the dopant. Typically, the weight of the polythiophene is greater than the weight of the dopant. Typically, the dopant may be a silver salt such as silver tetrakis(pentafluorophenyl)borate in an amount of about 0.25 to 0.5 m / ru (where m is the molar amount of silver salt and ru is the molar amount of polymer repeat units).

[0175] The doped polythiophene is isolated by methods known to those skilled in the art (e.g., by rotary evaporation of the solvent) to obtain a dry or substantially dry material (e.g., a powder). The amount of residual solvent can be, for example, 10% by weight or less, or 5% by weight or less, or 1% by weight or less, based on the dry or substantially dry material. The dry or substantially dry powder can be redispersed or redissolved in one or more fresh solvents.

[0176] The ink compositions of the present disclosure include one or more metal oxide nanoparticles.

[0177] As used herein, the term "metalloid" refers to an element that has intermediate or mixed chemical and / or physical properties between metals and nonmetals. As used herein, the term "metalloid" refers to boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te). In this specification, the term "metal oxide" refers to an oxide of one or a combination of two or more of metals such as tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten), as well as the above-mentioned metalloids.

[0178] As used herein, the term "nanoparticle" refers to nanoscale particles whose primary particle number-average diameter is typically 500 nm or less. The primary particle average diameter can be determined, for example, by transmission electron microscopy (TEM) or by conversion from the specific surface area by the BET method.

[0179] In the method of measuring particle size by TEM, particle size can be measured by processing a projected image of nanoparticles using image processing software and then determining the area-equivalent diameter (defined as the diameter of a circle having the same area as the nanoparticle). Typically, the projected image is processed using image processing software provided with the TEM (e.g., a transmission electron microscope HT7700 (available from Hitachi High-Technologies Corporation)) and created by the TEM manufacturer. The average particle size can be determined as the number average of the circle-equivalent diameters.

[0180] The metal oxide nanoparticles described herein have a number average particle size of 500 nm or less, 250 nm or less, 100 nm or less, or 50 nm or less, or 25 nm or less. Typically, the metal oxide nanoparticles have a number average particle size of about 1 nm to about 100 nm, more typically about 2 nm to about 30 nm.

[0181] Metal oxide nanoparticles suitable for use in the present disclosure include oxides of boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and tungsten (W), or mixed oxides comprising these. Specific, non-limiting examples of suitable metal oxide nanoparticles include, but are not limited to, nanoparticles comprising B2O3, B2O, SiO2, SiO, GeO2, GeO, As2O4, As2O3, As2O5, Sb2O3, Sb2O5, TeO2, SnO2, ZrO2, Al2O3, ZnO, and mixtures thereof.

[0182] In some embodiments, the ink compositions of the present disclosure include one or more metal oxide nanoparticles including B2O3, B2O, SiO2, SiO2, GeO2, GeO, As2O4, As2O3, As2O5, SnO2, SnO, Sb2O3, TeO2, or mixtures thereof.

[0183] In some embodiments, the ink compositions of the present disclosure include one or more metal oxide nanoparticles, including SiO 2 .

[0184] The metal oxide nanoparticles may include one or more organic capping groups. Such organic capping groups may be reactive or non-reactive. Reactive organic capping groups are those that can crosslink, for example, in the presence of UV radiation or a radical initiator.

[0185] In some embodiments, the metal oxide nanoparticles comprise one or more organic capping groups.

[0186] Examples of suitable metal oxide nanoparticles include SiO2 nanoparticles sold by Nissan Chemical under the trademark ORGANOSILICASOL™, which are available as dispersions in a variety of solvents (e.g., methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylacetamide, ethylene glycol, isopropanol, methanol, ethylene glycol monopropyl ether, and propylene glycol monomethyl ether acetate).

[0187] The amount of metal oxide nanoparticles used in the ink compositions described herein can be adjusted and measured as a weight percentage based on the combined weight of the metal oxide nanoparticles and the doped or undoped polythiophene. In some embodiments, the amount of metal oxide nanoparticles is from 1% to 98% by weight, typically from about 2% to about 95% by weight, more typically from about 5% to about 90% by weight, and even more typically from about 10% to about 90% by weight, based on the combined weight of the metal oxide nanoparticles and the doped or undoped polythiophene. In some embodiments, the amount of metal oxide nanoparticles is from about 20% to about 98% by weight, typically from about 25% to about 95% by weight, based on the combined weight of the metal oxide nanoparticles and the doped or undoped polythiophene.

[0188] The ink compositions of the present disclosure may optionally further comprise one or more matrix compounds known to be useful in hole injection layers (HILs) or hole transport layers (HTLs).

[0189] The optional matrix compound may be a low-molecular-weight or high-molecular-weight compound and may be different from the polythiophenes described herein. The matrix compound may be, for example, a synthetic polymer different from polythiophenes. See, for example, U.S. Patent Publication No. 2006 / 0175582, published August 10, 2006. The synthetic polymer may, for example, comprise a carbon backbone. In some embodiments, the synthetic polymer has at least one polymeric side group comprising an oxygen atom or a nitrogen atom. The synthetic polymer may be a Lewis base. Typically, the synthetic polymer comprises a carbon backbone and has a glass transition temperature greater than 25°C. The synthetic polymer may also be a semi-crystalline or crystalline polymer having a glass transition temperature of 25°C or less and / or a melting point greater than 25°C. The synthetic polymer may also comprise one or more acidic groups, such as sulfonic acid groups.

[0190] In some embodiments, the synthetic polymer is a polymeric acid comprising one or more repeating units containing at least one alkyl or alkoxy group substituted with at least one fluorine atom and at least one sulfonic acid (—SOH) residue, optionally interrupted by at least one ether linkage (—O—) group.

[0191] In some embodiments, the polymeric acid comprises a repeat unit according to formula (II) and a repeat unit according to formula (III):

[0192] [ka] [Wherein, each of R5, R6, R7, R8, R9, R 10 , and R 11are independently H, halogen, fluoroalkyl, or perfluoroalkyl; and X is —[OC(R h R i )-C(R j R k )] q -O-[CR l R m ] z -SO3H, where each R h , R i , R j , R k , R l and R m is independently H, halogen, fluoroalkyl, or perfluoroalkyl; q is 0-10; and z is 1-5.

[0193] In some embodiments, each of R5, R6, R7, and R8 is independently Cl or F. In some embodiments, each of R5, R7, and R8 is F and R6 is Cl. In some embodiments, each of R5, R6, R7, and R8 is F.

[0194] In some embodiments, each of R, R 10 , and R 11 is F.

[0195] In certain embodiments, each R h , R i , R j , R k , R l and R m is independently F, (C1-C8)fluoroalkyl, or (C1-C8)perfluoroalkyl.

[0196] In certain embodiments, each R l and R m is F; q is 0; and z is 2.

[0197] In certain embodiments, each of R5, R7, and R8 is F and R6 is Cl; and each R l and Rm is F; q is 0; and z is 2.

[0198] In some embodiments, each of R, R, R, and R is F; and each R l and R m is F; q is 0; and z is 2.

[0199] The ratio of the number of repeating units according to Formula (II) ("n") to the number of repeating units according to Formula (III) ("m") is not particularly limited. The n:m ratio is typically 9:1 to 1:9, more typically 8:2 to 2:8. In some embodiments, the n:m ratio is 9:1. In some embodiments, the n:m ratio is 8:2.

[0200] Polymeric acids suitable for use in the present disclosure can be synthesized using methods known to those skilled in the art or obtained from commercial sources. For example, a polymer comprising a repeating unit according to formula (II) and a repeating unit according to formula (III) can be prepared by converting a monomer represented by formula (IIa) to a monomer represented by formula (IIIa):

[0201] [ka] [Wherein Z1 is —[OC(R h R i )-C(R j R k )] q -O-[CR l R m ] z -SO2F, where R h , R i , R j , R k , R l and R m , q, and z have the same meanings as in the present specification] by a known polymerization method, followed by conversion of the sulfonyl fluoride group to a sulfonic acid group by hydrolysis.

[0202] For example, tetrafluoroethylene (TFE) or chlorotrifluoroethylene (CTFE) may be prepared by reacting one or more fluorinated monomers containing precursor groups of sulfonic acid (e.g., F2C=CF-O-CF2-CF2-SO2F; F2C=CF-[O-CF2-CR 12 FO] q -CF2-CF2-SO2F (where R 12 is F or CF3, and q is 1 to 10); F2C=CF-O-CF2-CF2-CF2-SO2F; and F2C=CF-OCF2-CF2-CF2-CF2-SO2F, etc.

[0203] The equivalent weight of a polymeric acid is defined as the mass (grams) of polymeric acid per mole of acid groups present in the polymeric acid. The equivalent weight of a polymeric acid is from about 400 to about 15,000 g polymer / mol acid, typically from about 500 to about 10,000 g polymer / mol acid, more typically from about 500 to 8,000 g polymer / mol acid, even more typically from about 500 to 2,000 g polymer / mol acid, and even more typically from about 600 to about 1,700 g polymer / mol acid.

[0204] Such polymeric acids are, for example, those sold under the trade name NAFION® by EI DuPont, those sold under the trade name AQUIVION® by Solvay Specialty Polymers, or those sold under the trade name FLEMION® by Asahi Glass Co.

[0205] In some embodiments, the synthetic polymer is a polyethersulfone that includes one or more repeat units that contain at least one sulfonic acid (—SO 3 H) residue.

[0206] In some embodiments, the polyethersulfone has formula (IV):

[0207] [ka] as well as repeating units according to formula (V) and repeating units according to formula (VI):

[0208] [ka] [In the formula, R 12 ~R 20 are each independently H, halogen, alkyl, or SO3H, with the proviso that R 12 ~R 20 at least one of is SO3H; and R 21 ~R 28 are each independently H, halogen, alkyl, or SO3H, with the proviso that R 21 ~R 28 At least one of is SO3H, and R 29 and R 30 are each H or alkyl.

[0209] In some embodiments, R 29 and R 30 and R are each alkyl. 29 and R 30 are methyl, respectively.

[0210] In some embodiments, R 12 ~R 17 , R 19 , and R 20 are H and R, respectively. 18 is SO3H.

[0211] In some embodiments, R 21 ~R 25 , R 27 , and R 28 are H and R, respectively. 26 is SO3H.

[0212] In some embodiments, the polyethersulfone has formula (VII):

[0213] [ka] [wherein a is 0.7 to 0.9, and b is 0.1 to 0.3].

[0214] The polyethersulfone may further comprise other repeating units, which may or may not be sulfonated.

[0215] For example, polyethersulfone may be represented by the formula (VIII):

[0216] [ka] [In the formula, R 31 and R 32 are each independently H or alkyl.

[0217] Any two or more repeat units described herein can be combined to form a repeat unit, and polyethersulfones may include such repeat units. For example, a repeat unit according to formula (IV) can be combined with a repeat unit according to formula (VI) to form a repeat unit according to formula (IX):

[0218] [ka] It is possible to provide a repeating unit according to the following formula:

[0219] Similarly, for example, a repeat unit according to formula (IV) can be combined with a repeat unit according to formula (VIII) to form a repeat unit according to formula (X):

[0220] [ka] It is possible to provide a repeating unit according to the following formula:

[0221] In some embodiments, the polyethersulfone has formula (XI):

[0222] [ka] [wherein a is 0.7 to 0.9, and b is 0.1 to 0.3].

[0223] Polyethersulfones containing one or more repeat units containing at least one sulfonic acid (—SO3H) residue are commercially available; for example, sulfonated polyethersulfone is sold as S-PES by Konishi Chemical Ind. Co., Ltd.

[0224] The optional matrix compound may be a planarizing agent. The matrix compound or planarizing agent may be, for example, a polymer or oligomer such as an organic polymer (e.g., poly(styrene) or a poly(styrene) derivative; poly(vinyl acetate) or a derivative thereof; poly(ethylene glycol) or a derivative thereof; poly(ethylene-co-vinyl acetate); poly(pyrrolidone) or a derivative thereof (e.g., poly(1-vinylpyrrolidone-co-vinyl acetate)); poly(vinylpyridine) or a derivative thereof; poly(methyl methacrylate) or a derivative thereof; poly(butyl acrylate); poly(aryl ether ketone); poly(arylsulfone); poly(ester) or a derivative thereof; or a combination thereof).

[0225] In certain embodiments, the matrix compound is poly(styrene) or a poly(styrene) derivative.

[0226] In one embodiment, the matrix compound is poly(4-hydroxystyrene).

[0227] The optional matrix compound or planarizing agent may, for example, comprise at least one semiconducting matrix component. This semiconducting matrix component is different from the polythiophenes described herein. The semiconducting matrix component may be a semiconducting small molecule or semiconducting polymer, typically consisting of repeating units containing hole-transporting units in the main chain and / or side chains. The semiconducting matrix component may be neutral or doped and is typically soluble and / or dispersible in organic solvents (e.g., toluene, chloroform, acetonitrile, cyclohexanone, anisole, chlorobenzene, o-dichlorobenzene, ethyl benzoate, and mixtures thereof).

[0228] The amount of optional matrix compound can be adjusted and measured as a weight percentage relative to the amount of doped or undoped polythiophene. In some embodiments, the amount of optional matrix compound is 0 to about 99.5 wt %, typically about 10 wt % to about 98 wt %, more typically about 20 wt % to about 95 wt %, and even more typically about 25 wt % to about 45 wt %, relative to the amount of doped or undoped polythiophene. In 0 wt % embodiments, the ink composition is free of matrix compound.

[0229] The ink compositions of the present disclosure optionally include one or more amine compounds. Amine compounds suitable for use in the ink compositions of the present disclosure include, but are not limited to, ethanolamines and alkylamines.

[0230] Examples of suitable ethanolamines include dimethylethanolamine [(CH3)2NCH2CH2OH], triethanolamine [N(CH2CH2OH)3], and N-tert-butyldiethanolamine [t-C4H9N(CH2CH2OH)2].

[0231] Alkylamines include primary, secondary, and tertiary alkylamines. Examples of primary alkylamines include, for example, ethylamine [C2H5NH2], n-butylamine [C4H9NH2], t-butylamine [C4H9NH2], 2-ethylhexylamine, n-hexylamine [C6H 13 NH2], n-decylamine [C 10 H 21 NH], and ethylenediamine [HNCHCHNH]. Secondary alkylamines include, for example, diethylamine [(C2H5)2NH], di(n-propylamine) [(n-C3H9)2NH], di(isopropylamine) [(i-C3H9)2NH], and dimethylethylenediamine [CH3NHCH2CH2NHCH3]. Tertiary alkylamines include, for example, trimethylamine [(CH3)3N], triethylamine [(C2H5)3N], tri(n-butyl)amine [(C4H9)3N], and tetramethylethylenediamine [(CH3)2NCH2CH2N(CH3)2].

[0232] In some embodiments, the amine compound is a tertiary alkylamine. In some embodiments, the amine compound is triethylamine.

[0233] In some embodiments, the amine compound is a mixture of a tertiary alkylamine compound and an amine compound other than the tertiary alkylamine compound.In some embodiments, the amine compound other than the tertiary alkylamine compound is a primary alkylamine compound.Preferably, the primary alkylamine compound is 2-ethylhexylamine or n-butylamine, and more preferably 2-ethylhexylamine.

[0234] The amount of the amine compound can be adjusted and measured as a weight percentage relative to the total amount of the ink composition. In some embodiments, the amount of the amine compound is at least 0.01 wt %, at least 0.10 wt %, at least 1.00 wt %, at least 1.50 wt %, or at least 2.00 wt %, relative to the total amount of the ink composition. In some embodiments, the amount of the amine compound is about 0.01 to about 2.00 wt %, typically about 0.05 wt % to about 1.50 wt %, and more typically about 0.1 wt % to about 1.0 wt %, relative to the total amount of the ink composition. When a sulfonated polythiophene is used, at least a portion of the amine compound may be present in the form of an ammonium salt with the sulfonated conjugated polymer, such as a trialkylammonium salt (sulfonated polythiophene amine adduct).

[0235] Although this amine compound is usually added when preparing the final ink composition, it may also be added in advance at an earlier stage. For example, when a sulfonated polythiophene is used, as described above, an amine compound may be added to the sulfonated polythiophene to convert it into a corresponding ammonium salt, such as a trialkylammonium salt (sulfonated polythiophene amine adduct). If necessary, this ammonium salt may be subjected to a reduction treatment, or an amine compound (e.g., triethylamine) may be added to a solution of the reduced sulfonated polythiophene to precipitate the sulfonated polythiophene as an ammonium salt (e.g., triethylammonium salt) in the form of a powder, which may then be recovered. There are no particular limitations on the method of such treatment, but for example, a method can be employed in which water and triethylamine are added to the reduced sulfonated polythiophene to dissolve it, the solution is stirred under heating (e.g., 60°C), isopropyl alcohol and acetone are added to the resulting solution to cause a precipitate of the triethylammonium salt of the sulfonated conjugated polymer, and the precipitate is collected by filtration.

[0236] The liquid carrier used in the ink composition of the present disclosure comprises one or more organic solvents. In some embodiments, the ink composition consists essentially of or consists of one or more organic solvents. The liquid carrier may be an organic solvent or a solvent mixture containing two or more organic solvents adapted for use and processing with other layers in the device, such as the anode or light-emitting layer.

[0237] Organic solvents suitable for use in the liquid carrier include, but are not limited to, aliphatic and aromatic ketones, organosulfur solvents such as dimethyl sulfoxide (DMSO) and 2,3,4,5-tetrahydrothiophene-1,1-dioxide (tetramethylene sulfone; sulfolane); tetrahydrofuran (THF), tetrahydropyran (THP), tetramethylurea (TMU), N,N'-dimethylpropylene urea, alkylated benzenes (such as xylene and its isomers), halogenated benzenes, N-methylpyrrolidinone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dichloromethane, acetonitrile, dioxanes, ethyl acetate, ethyl benzoate, methyl benzoate, dimethyl carbonate, ethylene carbonate, propylene carbonate, 3-methoxypropionitrile, 3-ethoxypropionitrile, or combinations thereof.

[0238] Aliphatic and aromatic ketones include, but are not limited to, acetone, acetonylacetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl isobutenyl ketone, 2-hexanone, 2-pentanone, acetophenone, ethyl phenyl ketone, cyclohexanone, and cyclopentanone. In some embodiments, ketones with a proton on the carbon alpha to the ketone, such as cyclohexanone, methyl ethyl ketone, and acetone, are avoided.

[0239] Other organic solvents that completely or partially solubilize the polythiophene or swell the polythiophene polymer are also contemplated. Such other solvents may be included in the liquid carrier in varying amounts to adjust ink properties such as wetting, viscosity, and morphology control. The liquid carrier may further include one or more organic solvents that act as non-solvents for the polythiophene polymer.

[0240] Other organic solvents suitable for use in accordance with the present disclosure include ethers such as anisole, ethoxybenzene, dimethoxybenzene, and glycol diethers (glycol diethers), such as ethylene glycol diether (such as 1,2-dimethoxyethane, 1,2-diethoxyethane, and 1,2-dibutoxyethane); diethylene glycol diethers (such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether); propylene glycol diethers (such as propylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol dibutyl ether); dipropylene glycol diethers (such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol dibutyl ether); and higher order analogs of the ethylene glycol and propylene glycol ethers mentioned herein (i.e., tri- and tetra-analogues, e.g., triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, etc.).

[0241] Still other solvents can be considered, such as ethylene glycol monoether acetate and propylene glycol monoether acetate (glycol ester ethers), where the ether can be selected from, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, and cyclohexyl. Also included are higher glycol ether analogs of the above list (di-, tri-, and tetra-, etc.). Examples include, but are not limited to, propylene glycol methyl ether acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate.

[0242] Still other solvents can be considered, such as ethylene glycol diacetate (glycol diesters), and also include higher glycol ether analogs (di-, tri-, and tetra-, etc.). Examples include, but are not limited to, ethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate.

[0243] Alcohols such as, for example, methanol, ethanol, trifluoroethanol, n-propanol, isopropanol, n-butanol, t-butanol, and alkylene glycol monoethers (glycol monoethers) may also be considered for use in the liquid carrier. Examples of suitable glycol monoethers include, but are not limited to, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether (hexyl cellosolve), propylene glycol monobutyl ether (Dowanol PnB), diethylene glycol monoethyl ether (ethyl carbitol), dipropylene glycol n-butyl ether (Dowanol DPnB), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), dipropylene glycol monomethyl ether (Dowanol DPM), diisobutyl carbinol, 2-ethylhexyl alcohol, methyl isobutyl carbinol, propylene glycol monopropyl ether (Dowanol PnP), diethylene glycol monopropyl ether (propyl carbitol), diethylene glycol monohexyl ether (hexyl carbitol), 2-ethylhexyl carbitol, dipropylene glycol monopropyl ether (Dowanol DPnP), tripropylene glycol monomethyl ether (Dowanol TPM), diethylene glycol monomethyl ether (methyl carbitol) and tripropylene glycol monobutyl ether (Dowanol TPnB).

[0244] As disclosed herein, the organic solvents disclosed herein can be used in various proportions in the liquid carrier to improve ink properties such as, for example, substrate wetting, ease of solvent removal, viscosity, surface tension, and jettability.

[0245] In some embodiments, the use of aprotic non-polar solvents can provide the added benefit of extending the lifetime of devices with emitter technology that is sensitive to protons (eg, PHOLEDs, etc.).

[0246] In some embodiments, the liquid carrier comprises dimethyl sulfoxide, ethylene glycol (glycols), tetramethylurea, or a mixture thereof. Examples of suitable glycols include, but are not limited to, ethylene glycol, diethylene glycol, dipropylene glycol, polypropylene glycol, propylene glycol, triethylene glycol, and the like.

[0247] The above glycol diethers, glycol ester ethers, glycol diesters, glycol monoethers, glycols, etc. are collectively referred to as "glycol-based solvents." That is, the "glycol-based solvents" referred to in the present invention are those represented by the formula R 1 -O-(RO)nR 2 (wherein each R is independently a linear C2-C4 unsubstituted alkylene group; R 1 and R 2 are each independently a hydrogen atom, a linear, branched, or cyclic C1-C8 unsubstituted alkyl group, or a linear or branched C1-C8 unsubstituted aliphatic acyl group, and n is an integer of 1 to 6. It is particularly preferred that R is a C2 or C3 unsubstituted alkylene group. It is also particularly preferred that n is an integer of 1 to 4. The alkyl group is preferably a linear, branched, or cyclic C1-C6 unsubstituted alkyl group, more preferably a linear C1-C4 unsubstituted alkyl group, and particularly preferred are a methyl group and an n-butyl group. The acyl group is preferably a linear or branched C2-C6 unsubstituted aliphatic acyl group, more preferably a linear C2-C4 unsubstituted acyl group, and particularly preferred are an acetyl group and a propionyl group. Examples of glycol-based solvents include the following: Glycols such as ethylene glycol, propylene glycol, or their oligomers (dimer to tetramer, for example, diethylene glycol) Glycol monoethers, which are monoalkyl ethers of the glycols Glycol diethers, which are dialkyl ethers of the glycols Glycol monoesters, which are aliphatic carboxylic acid monoesters of the glycols Glycol diesters, which are aliphatic carboxylic acid diesters of the glycols Glycol ester ethers, which are aliphatic carboxylic acid monoesters of the glycol monoethers Considering the coating properties by the inkjet method, it is preferable to use a liquid carrier containing a glycol-based solvent. In the following description, for convenience, the glycol-based solvents may be compared with organic solvents other than these, and the former may be designated as (A) and the latter as (B). In certain embodiments, the liquid carrier is a liquid carrier comprising one or more glycol-based solvents (A). In certain embodiments, the liquid carrier is a liquid carrier comprising one or more glycol-based solvents (A) and one or more organic solvents (B) excluding glycol-based solvents.

[0248] The glycol solvent (A) is preferably a glycol diether, a glycol monoether or a glycol, and these may be mixed. Examples include, but are not limited to, mixing glycol diethers with glycols. Specific examples include the above-mentioned specific examples of glycol diethers and glycols, and preferably, the glycol diethers include triethylene glycol dimethyl ether and triethylene glycol butyl methyl ether, and the glycols include ethylene glycol and diethylene glycol. The organic solvent (B) is preferably a nitrile, an alcohol, an aromatic ether, or an aromatic hydrocarbon. Examples include, but are not limited to, nitriles such as methoxypropionitrile and ethoxypropionitrile; alcohols such as benzyl alcohol and 2-(benzyloxy)ethanol; aromatic ethers such as methylanisole, dimethylanisole, ethylanisole, butylphenyl ether, butylanisole, pentylanisole, hexylanisole, heptylanisole, octylanisole, and phenoxytoluene; and aromatic hydrocarbons such as pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, nonylbenzene, cyclohexylbenzene, or tetralin. Among these, alcohols are more preferred, and among alcohols, 2-(benzyloxy)ethanol is more preferred. By adding an organic solvent (B) to a glycol-based solvent (A), the aggregation of metal oxide nanoparticles can be appropriately controlled while maintaining the solubility of the ink solids during film formation by inkjet coating, allowing for the formation of a flatter film.

[0249] When an organic solvent (B) is added to a glycol-based solvent (A), the content of the glycol-based solvent (A): wtA (weight) and the content (weight) of the organic solvent (B): wtB (weight) It is preferable that the formula (1-1) is satisfied, it is more preferable that the formula (1-2) is satisfied, and it is most preferable that the formula (1-3) is satisfied. 0.05≦wtB / (wtA+wtB)≦0.50 (1-1) 0.10≦wtB / (wtA+wtB)≦0.40 (1-2) 0.15≦wtB / (wtA+wtB)≦0.30 (1-3) (When the composition of the present invention contains two or more glycol-based solvents (A), wtA indicates the total content (weight) of the glycol-based solvents (A), and when the composition of the present invention contains two or more organic solvents (B), wtB indicates the total content (weight) of the organic solvents (B).)

[0250] The amount of liquid carrier in the ink composition of the present disclosure is about 50% to about 99% by weight, typically about 75% to about 98% by weight, and more typically about 90% to about 95% by weight, based on the total weight of the ink composition.

[0251] The total solids content (% TS) in the ink composition of the present disclosure is from about 0.1 wt % to about 50 wt %, typically from about 0.3 wt % to about 40 wt %, more typically from about 0.5 wt % to about 15 wt %, and even more typically from about 1 wt % to about 5 wt %, based on the total weight of the ink composition.

[0252] The ink compositions described herein can be prepared by any suitable method known to those skilled in the art. For example, in one method, an initial aqueous mixture is prepared by mixing an aqueous dispersion of a polythiophene described herein with an aqueous dispersion of a polymeric acid, optionally with another matrix compound, and optionally with additional solvent. The solvent, including water, in the mixture is then removed, typically by evaporation. The resulting dried product is dissolved or dispersed in one or more organic solvents, such as dimethyl sulfoxide, and filtered under pressure to produce a mixture. An amine compound may optionally be added to such a mixture. This mixture is then mixed with a dispersion of metal oxide nanoparticles to produce the final ink composition.

[0253] Alternatively, the ink compositions described herein can be prepared from stock solutions. For example, a stock solution of the polythiophene described herein can be prepared by isolating the polythiophene from an aqueous dispersion in a dry state, typically by evaporation. The dried polythiophene is then combined with one or more organic solvents and, optionally, an amine compound. Optionally, a stock solution of the polymeric acid described herein can be prepared by isolating the polymeric acid from an aqueous dispersion in a dry state, typically by evaporation. The dried polymeric acid is then combined with one or more organic solvents. Stock solutions of other optional matrix materials can be prepared similarly. A stock solution of metal oxide nanoparticles can be prepared, for example, by diluting a commercially available dispersion with one or more organic solvents, which may be the same or different from the solvent(s) contained in the commercially available dispersion. The desired amounts of each stock solution are then combined to form the ink composition of the present disclosure.

[0254] In yet another method, the ink compositions described herein can be prepared by isolating the individual components in a dry state as described herein, but instead of preparing stock solutions, combining the components in a dry state and then dissolving them in one or more organic solvents to provide an NQ ink composition.

[0255] The ink compositions of the present disclosure can be cast and annealed as thin films on a substrate.

[0256] Thus, the present disclosure also provides a method for forming a hole transporting thin film, comprising the steps of: 1) coating a substrate with the ink composition disclosed herein; and 2) Annealing the coating on the substrate to form a hole-transporting thin film. The present invention relates to a method comprising:

[0257] Coating of the ink composition on a substrate can be carried out by methods known in the art, including, for example, spin casting, spin coating, dip casting, dip coating, slot die coating, inkjet printing, gravure coating, doctor blading, and any other method known in the art, for example, for the fabrication of organic electronic devices.

[0258] The substrate may be flexible or rigid, organic or inorganic. Suitable substrate compounds include, for example, glass (including, for example, display glass), ceramic, metal, and plastic thin films.

[0259] As used herein, the term "annealing" refers to any general process for forming a cured layer, typically a thin film, on a substrate coated with the ink composition of the present disclosure. General annealing processes are known to those skilled in the art. Typically, the solvent is removed from the substrate coated with the ink composition. Solvent removal can be achieved, for example, by subjecting the coated substrate to subatmospheric pressure and / or by heating the coating deposited on the substrate to a certain temperature (annealing temperature), maintaining this temperature for a certain period of time (annealing time), and then allowing the resulting layer, typically a thin film, to slowly cool to room temperature.

[0260] The annealing step can be carried out by heating the substrate coated with the ink composition using any method known to those skilled in the art, for example, by heating in an oven or on a hot plate. Annealing can be carried out in an inert environment, for example, in a nitrogen atmosphere or a noble gas atmosphere (e.g., argon gas). Annealing can also be carried out in an air atmosphere.

[0261] In certain embodiments, the annealing temperature is from about 25°C to about 350°C, typically from 150°C to about 325°C, more typically from about 200°C to about 300°C, and even more typically from about 230°C to about 300°C.

[0262] The annealing time is the time during which the annealing temperature is maintained, and is about 3 to about 40 minutes, typically about 15 to about 30 minutes.

[0263] In one embodiment, the annealing temperature is about 25°C to about 350°C, typically 150°C to about 325°C, more typically about 200°C to about 300°C, and even more typically about 250°C to about 300°C, and the annealing time is about 3 to about 40 minutes, typically about 15 to about 30 minutes.

[0264] The present disclosure relates to hole transporting thin films formed by the methods described herein.

[0265] Visible light transmission is important, and good transmission (low absorption) is especially important at thicker films. For example, films produced by the methods of the present disclosure can exhibit a transmittance (typically with the substrate) of at least about 85%, typically at least 90%, of light having a wavelength of about 380-800 nm. In some embodiments, the transmittance is at least about 90%.

[0266] In one embodiment, the thin film produced by the method of the present disclosure has a thickness of about 5 nm to about 500 nm, typically about 5 nm to about 150 nm, and more typically about 50 nm to 120 nm.

[0267] In some embodiments, thin films produced by the methods of the present disclosure exhibit a transmittance of at least about 90% and have a thickness of about 5 nm to about 500 nm, typically about 5 nm to about 150 nm, and more typically about 50 nm to 120 nm. In some embodiments, thin films produced by the methods of the present disclosure exhibit a transmittance (%T) of at least about 90% and have a thickness of about 50 nm to 120 nm.

[0268] Thin films produced by the methods of the present disclosure can be fabricated on substrates that optionally contain electrodes or additional layers used to enhance the electronic properties of the final device. The resulting thin films can be resistant to one or more organic solvents, which can be solvents used as liquid carriers in inks for subsequent coated or deposited layers during device fabrication. For example, thin films can be resistant to toluene, which can be a solvent in inks for subsequent coated or deposited layers during device fabrication.

[0269] The present disclosure also relates to devices comprising thin films prepared by the methods described herein. The devices described herein can be fabricated by methods known in the art, including, for example, solution methods. The ink can be applied and the solvent removed by standard methods. The thin films prepared by the methods described herein can be HIL and / or HTL layers in the device.

[0270] Methods are known in the art and can be used to fabricate organic electronic devices, including, for example, OLED and OPV devices. Methods known in the art can be used to measure luminance, efficiency, and lifetime. Organic light-emitting diodes (OLEDs) are described, for example, in U.S. Pat. Nos. 4,356,429 and 4,539,507 (Kodak). Light-emitting conductive polymers are described, for example, in U.S. Pat. Nos. 5,247,190 and 5,401,827 (Cambridge Display Technologies). Device architectures, physical principles, solution methods, layering, blending, and compound synthesis and formulation are described in Kraft et al., "Electroluminescent Conjugated Polymers—Seeing Polymers in a New Light," Angew. Chem. Int. Ed., 1998, 37, 402-428, which is incorporated herein by reference in its entirety.

[0271] Known in the art and commercially available light emitters can be used, including various conductive polymers and organic molecules, such as compounds available from Sumation, Merck Yellow, Merck Blue, American Dye Sources (ADS), Kodak (e.g., A1Q3), and even Aldrich (e.g., BEHP-PPV). Examples of such organic electroluminescent compounds include: (i) poly(p-phenylene vinylene) and its derivatives substituted at various positions on the phenylene residue; (ii) poly(p-phenylene vinylene) and its derivatives substituted at various positions on the vinylene residue; (iii) poly(p-phenylene vinylene) and its derivatives substituted at various positions on the phenylene residue and also substituted at various positions on the vinylene residue; (iv) poly(arylenevinylenes), where the arylene can be a residue such as naphthalene, anthracene, furylene, thienylene, oxadiazole, and the like; (v) Derivatives of poly(arylene vinylene), in which the arylene may be as in (iv) above and further has substituents at various positions on the arylene; (vi) A derivative of poly(arylene vinylene), wherein the arylene is the same as in (iv) above. and further having substituents at various positions on the vinylene; (vii) Derivatives of poly(arylene vinylene), in which the arylene may be as in (iv) above, and further having substituents at various positions on the arylene and substituents at various positions on the vinylene; (viii) copolymers of arylene vinylene oligomers and non-conjugated oligomers, such as the compounds in (iv), (v), (vi), and (vii); and (ix) poly(p-phenylene) and its derivatives substituted at various positions on the phenylene residue (including ladder polymer derivatives such as poly(9,9-dialkylfluorene)); (x) Poly(arylenes), where the arylene may be a residue such as naphthalene, anthracene, furylene, thienylene, oxadiazole, etc.; and derivatives thereof substituted at various positions on the arylene residue; (xi) Copolymers of oligoarylenes such as the compounds in (x) with non-conjugated oligomers; (xii) Polyquinoline and its derivatives; (xiii) copolymers of polyquinoline and p-phenylene substituted on the phenylene by, for example, alkyl or alkoxy groups to provide solubility; (xiv) Rigid rod polymers and derivatives thereof, such as poly(p-phenylene-2,6-benzobisthiazole), poly(p-phenylene-2,6-benzobisoxazole), poly(p-phenylene-2,6-benzimidazole), and derivatives thereof; (xv) Polyfluorene polymers and copolymers having polyfluorene units.

[0272] Preferred organic light-emitting polymers include SUMATION's Light Emitting Polymers ("LEPs") or families, copolymers, derivatives, or mixtures thereof that emit green, red, blue, or white light; SUMATION's LEPs are available from Sumation KK. Other polymers include polyspirofluorene-like polymers available from Covion Organic Semiconductors GmbH, Frankfurt, Germany (now owned by Merck®).

[0273] Alternatively, instead of polymers, fluorescent or phosphorescent organic small molecules can be used as the organic electroluminescent layer. Examples of small molecule organic electroluminescent compounds include (i) tris(8-hydroxyquinolinato)aluminum (Alq); (ii) 1,3-bis(N,N-dimethylaminophenyl)-1,3,4-oxadiazole (OXD-8); (iii) oxo-bis(2-methyl-8-quinolinato)aluminum; (iv) bis(2-methyl-8-hydroxyquinolinato)aluminum; (v) bis(hydroxybenzoquinolinato)beryllium (BeQ2); (vi) bis(diphenylvinyl)biphenylene (DPVBI); and arylamine-substituted distyrylarylene (DSA amine).

[0274] Such polymers and small molecule compounds are well known in the art and are described, for example, in US Pat. No. 5,047,687.

[0275] Devices can often be fabricated using multilayer structures that can be prepared, for example, by solution or vacuum processes, as well as by printing and patterning techniques. In particular, the use of the embodiments described herein for hole injection layers (HILs), in which the compositions are formulated for use as hole injection layers, can be effectively implemented.

[0276] Examples of HIL in devices include: 1) Hole injection in OLEDs, including PLEDs and SMOLEDs; for example, the HIL in a PLED can be any class of conjugated polymer emitter, where the conjugation involves carbon or silicon atoms. Examples of HILs in SMOLEDs include: SMOLEDs containing fluorescent emitters; SMOLEDs containing phosphorescent emitters; SMOLEDs containing one or more organic layers in addition to the HIL layer; and SMOLEDs in which small molecule layers are processed from solutions or aerosol sprays, or by any other processing method. Further examples include: HILs in OLEDs based on dendrimer or oligomer organic semiconductors; HILs in ambipolar light-emitting FETs, where the HIL is used to regulate charge injection or as an electrode; 2) hole extraction layer in OPV; 3) channel material in transistors; 4) Channel materials in circuits containing combinations of transistors, such as logic gates; 5) electrode materials in transistors; 6) Gate layer in the capacitor; 7) Chemical sensors in which the adjustment of the doping level is achieved by the relationship between the species to be sensed and the conducting polymer; 8) Electrode or electrolyte materials in batteries.

[0277] A variety of photoactive layers can be used in OPV devices. Photovoltaic devices can be prepared with a photoactive layer comprising, for example, a fullerene derivative mixed with a conductive polymer, as described, for example, in U.S. Patent Nos. 5,454,880; 6,812,399; and 6,933,436. Photoactive layers can include blends of conductive polymers, blends of conductive polymers and semiconductor nanoparticles, and bilayers of small molecules such as phthalocyanines, fullerenes, and porphyrins.

[0278] Common electrode compounds and substrates as well as encapsulation compounds can be used.

[0279] In one embodiment, the cathode comprises Au, Ca, Al, Ag, or a combination thereof. In one embodiment, the anode comprises indium tin oxide. In one embodiment, the light-emitting layer comprises at least one organic compound.

[0280] For example, interface modification layers such as interlayers and optical spacer layers can be used.

[0281] An electron transport layer may be used.

[0282] The present disclosure also relates to methods of manufacturing the devices described herein.

[0283] In one embodiment, a method for making a device includes: providing a substrate; depositing a transparent conductor, such as indium tin oxide, on the substrate; providing an ink composition described herein; depositing the ink composition on the transparent conductor to form a hole injection layer or hole transport layer; depositing an active layer on the hole injection layer or hole transport layer (HTL); and depositing a cathode on the active layer.

[0284] As described herein, the substrate may be flexible or rigid, organic or inorganic. Suitable substrate compounds include, for example, glass, ceramic, metal, and plastic thin films.

[0285] In another embodiment, a method of manufacturing a device comprises applying an ink composition described herein as part of a HIL or HTL layer in an OLED, a photovoltaic device, an ESD, a SMOLED, a PLED, a sensor, a supercapacitor, a cation converter, a drug release device, an electrochromic device, a transistor, a field effect transistor, an electrode modifier, an electrode modifier for an organic field effect transistor, an actuator, or a transparent electrode.

[0286] Deposition of the ink composition to form the HIL or HTL layer can be carried out by methods known in the art, including, for example, spin casting, spin coating, dip casting, dip coating, slot die coating, inkjet printing, gravure coating, doctor blading, and any other method known in the art, for example, for the fabrication of organic electronic devices.

[0287] In one embodiment, the HIL layer is thermally annealed. In one embodiment, the HIL layer is thermally annealed at a temperature of about 25° C. to about 350° C., typically 150° C. to about 325° C. In one embodiment, the HIL layer is thermally annealed at a temperature of about 25° C. to about 350° C., typically 150° C. to about 325° C., for about 3 to about 40 minutes, typically about 15 to about 30 minutes.

[0288] According to the present disclosure, HILs or HTLs can be prepared that can exhibit a transmittance (typically with the substrate) of at least about 85%, typically at least about 90%, of light having a wavelength of about 380-800 nm. In some embodiments, the transmittance is at least about 90%.

[0289] In one embodiment, the HIL layer has a thickness of about 5 nm to about 500 nm, typically about 5 nm to about 150 nm, and more typically about 50 nm to 120 nm.

[0290] In some embodiments, the HIL layer exhibits a transmittance of at least about 90% and has a thickness of about 5 nm to about 500 nm, typically about 5 nm to about 150 nm, and more typically about 50 nm to 120 nm. In some embodiments, the HIL layer exhibits a transmittance (%T) of at least about 90% and has a thickness of about 50 nm to 120 nm.

[0291] The inks, methods and processes, thin films, and devices of the present disclosure are further illustrated by the following non-limiting examples. [Example]

[0292] The ingredients used in the following examples are summarized in Table 1 below. [Table 1]

[0293] [1] Preparation of charge-transporting materials [Manufacturing Example 1] Preparation of S-poly(3-MEET) amine adducts An aqueous dispersion of S-poly(3-MEET) (0.598% solids in water) of 500 g was prepared by mixing with 0.858 g of triethylamine. The resulting mixture was rotary evaporated to dryness and then further dried in a vacuum oven at 50°C overnight. The product was isolated as a black powder (3.8 g).

[0294] [Example 1] 2.00 g of the S-poly(3-MEET) amine adduct obtained in Production Example 1 was dissolved in 100 mL of 28% aqueous ammonia (Junsei Chemical Co., Ltd.) and stirred overnight at room temperature. The reaction solution was reprecipitated with 1500 mL of acetone, and the precipitate was collected by filtration. The obtained precipitate was again dissolved in 20 mL of water and 7.59 g of triethylamine (Tokyo Chemical Industry Co., Ltd.) and stirred at 60°C for 1 hour. After cooling, the reaction solution was reprecipitated with a mixed solvent of 1000 mL of isopropyl alcohol and 500 mL of acetone, and the precipitate was collected by filtration. The obtained precipitate was vacuum-dried at 0 mmHg and 50°C for 1 hour to obtain 1.30 g of S-poly(3-MEET)-A treated with aqueous ammonia.

[0295] [2] Preparation of dopants [Example 2-1] Synthesis of Dopant A A sulfonic acid compound (dopant A) represented by the following formula was synthesized according to the method described in WO 2006 / 025342. [ka]

[0296] [Example 2-2] Synthesis of dopant B A sulfonic acid compound (dopant B) represented by the following formula was synthesized according to the method described in WO 2015-111654. [ka]

[0297] [3] Preparation of charge-transporting varnish [Example 3-1] First, 0.030 g of S-poly(3-MEET)-A, the charge transport material obtained in Example 1, was dissolved in 0.46 g of ethylene glycol (Kanto Chemical Co., Ltd.), 1.45 g of diethylene glycol (Kanto Chemical Co., Ltd.), 4.83 g of triethylene glycol dimethyl ether (Tokyo Chemical Industry Co., Ltd.), 1.93 g of 2-(benzyloxy)ethanol (Kanto Chemical Co., Ltd.), and 0.049 g of 2-ethylhexylamine (Tokyo Chemical Industry Co., Ltd.). The solution was prepared by stirring at 350 rpm and 80°C for 1 hour using a hot stirrer. Next, 0.015 g of Dopant A obtained in Example 2-1 was added as a dopant, and the mixture was stirred at 350 rpm and 80°C for 1 hour using a hot stirrer. Finally, 1.24 g of EG-ST was added, and the mixture was stirred using a hot stirrer at 350 rpm and 30°C for 10 minutes. The resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain 3 wt % charge-transporting varnish A.

[0298] [Example 3-2] Charge-transporting varnish B was obtained in the same manner as in Example 3-1, except that dopant B obtained in Example 2-2 was used instead of dopant A.

[0299] [Example 3-3] Charge-transporting varnish C was obtained in the same manner as in Example 3-1, except that phosphotungstic acid (manufactured by Kanto Chemical Co., Inc.) was used as the dopant instead of dopant A.

[0300] [Example 3-4] 0.032 g of the S-poly(3-MEET) amine adduct obtained in Production Example 1 was dissolved in 0.73 g of ethylene glycol (Kanto Chemical Co., Ltd.), 1.93 g of diethylene glycol (Kanto Chemical Co., Ltd.), 0.047 g of BA (Tokyo Chemical Industry Co., Ltd.), 4.83 g of triethylene glycol dimethyl ether (Tokyo Chemical Industry Co., Ltd.), and 0.97 g of 2-(benzyloxy)ethanol (Kanto Chemical Co., Ltd.). The solution was prepared by stirring at 350 rpm and 80°C for 2 hours using a hot stirrer. After returning to room temperature, 0.32 g of a 10% EG solution of dopant A obtained in Example 2-1, which had been prepared in advance, and 1.16 g of EG-ST were added as dopants, and the mixture was stirred at 350 rpm and 30°C for 30 minutes using a hot stirrer. The resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain 3 wt % charge transporting varnish D.

[0301] [Comparative Example 3-1] 0.135 g of S-poly(3-MEET)-A, the charge-transporting material obtained in Example 1, was dissolved in 1.50 g of ethylene glycol (Kanto Chemical Co., Ltd.), 1.50 g of diethylene glycol (Kanto Chemical Co., Ltd.), 5.00 g of triethylene glycol dimethyl ether (Tokyo Chemical Industry Co., Ltd.), 2.00 g of 2-(benzyloxy)ethanol (Kanto Chemical Co., Ltd.), and 0.216 g of 2-ethylhexylamine (Tokyo Chemical Industry Co., Ltd.). The solution was prepared by stirring at 350 rpm and 80°C for 1 hour using a hot stirrer. Next, 0.069 g of Dopant A obtained in Example 2-1 was added as a dopant, and the mixture was stirred at 350 rpm and 80°C for 1 hour using a hot stirrer. The resulting solution was filtered through a PP syringe filter with a pore size of 0.2 μm to obtain a 3 wt % charge-transporting varnish D.

[0302] [4] Preparation and evaluation of thin films Charge-transporting varnishes A and D obtained in Example 3-1 and Comparative Example 3-1 were each spin-coated onto a quartz substrate, dried on a hot plate in the atmosphere at 120°C for 1 minute, and then baked at 230°C for 15 minutes to produce thin films A and D. The average transmittance of the produced thin films in the visible range (wavelength: 400nm to 800nm) at a thickness of 100nm was 99.0% for thin film A and 54.7% for thin film D. This shows that thin film A, which contains metal oxide nanoparticles, is much more transparent than thin film D, which does not contain them.

[0303] [5] Fabrication and characterization of organic EL devices [Example 5-1] Varnish A obtained in Example 3-1 was applied to an ITO substrate using a spin coater, then dried in air at 120°C for 1 minute and baked at 230°C for 15 minutes to form a 50 nm thin film on the ITO substrate. The ITO substrate was a 25 mm x 25 mm x 0.7 mm glass substrate with a 150 nm thick indium tin oxide (ITO) patterned on its surface, and impurities on the surface were removed using an O2 plasma cleaning device (150 W, 30 seconds) before use. Next, the ITO substrate on which the thin film was formed was subjected to a deposition apparatus (vacuum degree 1.0 × 10 -5 A 30-nm film of α-NPD (N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine) was deposited at 0.2 nm / sec using a fluorine-containing fluoride (PA). Next, a 10-nm film of the electron blocking material HTEB-01 (Kanto Chemical Co., Ltd.) was deposited. Next, the emitting layer host material NS60 (Nippon Steel & Sumikin Chemical Co., Ltd.) and the emitting layer dopant material Ir(PPy)3 were co-deposited. The deposition rate was controlled to achieve a 6% Ir(PPy)3 concentration, resulting in a 40-nm layer. Next, thin films of Alq3, lithium fluoride, and aluminum were sequentially deposited to obtain an organic EL device. The deposition rates were 0.2 nm / sec for Alq3 and aluminum, and 0.02 nm / sec for lithium fluoride, resulting in film thicknesses of 20 nm, 0.5 nm, and 80 nm, respectively. To prevent performance degradation due to oxygen and water in the air, the organic EL elements were sealed with sealing substrates before their performance evaluation. Sealing was performed as follows: In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -76°C or less, the organic EL elements were placed between sealing substrates, and the sealing substrates were then bonded together with an adhesive (Moresco Moisture Cut WB90US(P) manufactured by MORESCO Corporation). A moisture scavenger (HD-071010W-40 manufactured by DYNIC Corporation) was placed inside the sealing substrates along with the organic EL elements. The bonded sealing substrates were then irradiated with UV light (wavelength: 365 nm, dose: 6,000 mJ / cm²) and annealed at 80°C for 1 hour to cure the adhesive.

[0304] [ka]

[0305] [Example 5-2] An organic EL device was produced in the same manner as in Example 5-1, except that charge transport varnish B was used instead of charge transport varnish A.

[0306] [Example 5-3] An organic EL device was produced in the same manner as in Example 5-1, except that charge transport varnish C was used instead of charge transport varnish A.

[0307] [Example 5-4] An organic EL device was fabricated in the same manner as in Example 5-1, except that charge transport varnish D was used instead of charge transport varnish A, and the resulting material was dried at 60°C for 5 minutes in air and then baked at 230°C for 15 minutes.

[0308] For the elements of Examples 5-1 to 5-4, the luminance was 1000 cd / m 2 The driving voltage, current density, current efficiency, and external quantum efficiency were measured when the device was driven at 1000 kJ / s. The results are shown in Table 2. [Table 2]

[0309] As shown in Table 2, the EL device including the charge-transporting thin film of the present invention exhibited excellent current efficiency and external quantum efficiency. These results are thought to reflect the high transparency, i.e., low absorbance of visible light, exhibited by the charge-transporting thin film of the present invention due to the inclusion of metal oxide nanoparticles.

Claims

1. (a) a polythiophene compound; (b) one or more metal oxide nanoparticles; (c) one or more dopants; (d) a liquid carrier comprising one or more organic solvents; and (e) one or more amine compounds Including, the amine compound is an amine compound containing a tertiary alkylamine compound and an amine compound other than a tertiary alkylamine compound, The metal oxide nanoparticles are B ２ O ３ , B ２ O, SiO ２ , SiO, GeO ２ , GeO, As ２ O ４ , As ２ O ３ , As ２ O ５ , Sb ２ O ３ , TeO ２ , SnO ２ , SnO, or a mixture thereof.

2. 2. The charge transporting thin film according to claim 1, wherein the polythiophene compound (a) contains a repeating unit represented by the following formula (I): 【Transformation 56】 [In the formula, R １ and R ２ are each independently H, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, aryloxy, —SO ３ M, or —O—[Z—O] ｐ -R ｅ or R １ and R ２ come together to form -O-Z-O- (wherein M is H, an alkali metal, ammonium, monoalkylammonium, dialkylammonium, or trialkylammonium; Z is a hydrocarbylene group optionally substituted with halogen or Y (wherein Y is a linear or branched alkyl or alkoxyalkyl group having 1 to 10 carbon atoms, and the alkyl or alkoxyalkyl group may be substituted with a sulfonic acid group at any position); p is an integer of 1 or greater; and R ｅ is H, alkyl, fluoroalkyl, or aryl).

3. R １ and R ２ are each independently H, —SO ３ M, fluoroalkyl, —O[C(R ａ R ｂ )-C(R ｃ R ｄ )-O] ｐ -R ｅ , or -OR ｆ where each R ａ , R ｂ , R ｃ , and R ｄ are each independently H, halogen, alkyl, fluoroalkyl, or aryl; R ｅ is H, alkyl, fluoroalkyl, or aryl; p is 1, 2, or 3; and R ｆ is alkyl, fluoroalkyl, or aryl, or R １ and R ２ But together they form -O-(CH ２ ) ｑ 3. The charge transporting thin film according to claim 2, wherein q is 1, 2, or 3 and the group forms --O--.

4. R １ is H and R ２ The charge transporting thin film according to claim 3, wherein is other than H.

5. R １ and R ２ The charge transporting thin film according to claim 3, wherein both of are other than H.

6. R １ and R ２ are each independently -SO ３ M, -O[C(R ａ R ｂ )-C(R ｃ R ｄ )-O] ｐ -R ｅ , or -OR ｆ or R １ and R ２ But together they form -O-(CH ２ ) ｑ 6. The charge transporting thin film according to claim 5, which forms --O--.

7. R １ and R ２ However, both are -O[C(R ａ R ｂ )-C(R ｃ R ｄ )-O] ｐ -R ｅ 6. The charge transporting thin film according to claim 5, wherein

8. Each R ａ , R ｂ , R ｃ , and R ｄ are each independently H, (C １ -C ８ ) alkyl, (C １ -C ８ ) fluoroalkyl, or phenyl; and R ｅ However, (C １ -C ８ ) alkyl, (C １ -C ８ 8. The charge transporting thin film according to claim 3, wherein the aryl group is fluoroalkyl, or phenyl.

9. The polythiophene compound (a) is represented by the following formula: 【Chemistry 57】 9. The charge transporting thin film according to claim 2, comprising a repeating unit selected from the group consisting of groups represented by the formula: and combinations thereof.

10. 7. The charge transporting thin film according to claim 2, wherein the polythiophene compound (a) is sulfonated poly(3-MEET).

11. 11. The charge transporting thin film according to claim 2, wherein the polythiophene compound (a) comprises repeat units according to formula (I) in an amount greater than 50 wt%, typically greater than 80 wt%, more typically greater than 90 wt%, and even more typically greater than 95 wt%, based on the total weight of repeat units.

12. 12. The charge-transporting thin film according to claim 1, wherein the dopant comprises at least one selected from the group consisting of an arylsulfonic acid compound, a heteropolyacid compound, and an ionic compound containing an element belonging to Group 13 or Group 15 of the long form periodic table.

13. 13. The charge transporting thin film according to claim 1, wherein the dopant is an arylsulfonic acid compound represented by formula (2). 【Chemistry 58】 [wherein X represents O, S or NH, A represents a group consisting of X and n (SO ３ B represents a naphthalene ring or an anthracene ring which may have a substituent other than a (H) group, and B represents an unsubstituted or substituted hydrocarbon group, a 1,3,5-triazine group, or an unsubstituted or substituted group of the following formula (3) or (4): 【Chemistry 59】 (wherein W １ represents a single bond, O, S, S(O) group, S(O ２ ) group, or an unsubstituted or substituted N, Si, P, or P(O) group; W ２ represents O, S, S(O) groups, S(O ２ ) group, or an unsubstituted or substituted N, Si, P, or P(O) group; R ４６ ~R ５９ each independently represents a hydrogen atom or a halogen atom), n represents the number of sulfonic acid groups bonded to A and is an integer satisfying 1≦n≦4, and q represents the number of bonds between B and X and is an integer satisfying 1≦q.

14. 13. The charge transporting thin film according to claim 1, wherein the dopant is an arylsulfonic acid compound represented by formula (6). 【Transformation 60】 (wherein X represents O, S or NH; Ar ５ represents an aryl group, and n represents the number of sulfone groups and is an integer of 1 to 4.

15. 13. The charge transporting thin film according to claim 1, wherein the dopant is a heteropolyacid compound.

16. Metal oxide nanoparticles are SiO ２ The charge transporting thin film of claim 1 , comprising:

17. 2. The charge transporting thin film according to claim 1, wherein the amine compound other than the tertiary alkylamine compound is a primary alkylamine compound.

18. 18. The charge transporting thin film according to claim 17, wherein the primary alkylamine compound is at least one selected from the group consisting of ethylamine, n-butylamine, t-butylamine, 2-ethylhexylamine, n-hexylamine, n-decylamine, and ethylenediamine.

19. 19. The charge transporting thin film according to claim 18, wherein the primary alkylamine compound is 2-ethylhexylamine or n-butylamine.

20. The charge transporting thin film according to any one of claims 1 to 19, wherein the liquid carrier is a liquid carrier comprising one or more glycol-based solvents (A) and one or more organic solvents (B) other than glycol-based solvents.

21. 21. The charge transporting thin film according to claim 20, wherein the glycol-based solvent (A) is a glycol ether, a glycol monoether, or a glycol.

22. 22. The charge transporting thin film according to claim 20, wherein the organic solvent (B) is a nitrile, an alcohol, an aromatic ether, or an aromatic hydrocarbon.

23. The charge transporting thin film according to any one of claims 20 to 22, wherein the content (weight) of the glycol-based solvent (A): wtA (weight) and the content (weight) of the organic solvent (B): wtB (weight) satisfy formula (1-1). 0.05≦wtB / (wtA+wtB)≦0.50 (1-1) 24. An electronic device comprising the charge transport thin film according to any one of claims 1 to 23.

25. 25. The electronic device of claim 24, wherein the charge transport thin film is a hole injection layer.

26. 26. The electronic device according to claim 24 or 25, which is an organic EL element.

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