UV-patternable polymer blends for organic thin-film transistors

Abstract

A polymer blend comprises at least one organic semiconductor (OSC) polymer, at least one crosslinking agent, and at least one photoinitiator, wherein the at least one OSC polymer is a diketopyrrolopyrrole-fused thiophene polymer, the fused thiophene being β-substituted, and wherein the crosslinking agent comprises at least one of the following: acrylates, epoxides, oxetanes, alkenes, alkynes, azides, thiols, allyloxysilanes, phenols, anhydrides, amines, cyanates, isocyanates, silyl hydrides, cinnamates, coumarins, fluorosulfates, silyl ethers, or combinations thereof.

Description

background 1. Technical field

[0002] The present disclosure relates to UV-patternable organic semiconductor / cross-linker polymer blends as semiconductor layers in organic thin film transistors (OTFTs). 2. Background technology

[0004] Organic thin-film transistors (OTFTs) have attracted widespread attention as an alternative to conventional silicon-based technologies, which require high-temperature and high-vacuum deposition processes, as well as complex photolithographic patterning methods. The semiconductor (i.e., organic semiconductor, OSC) layer is an important component in OTFTs, which can significantly affect the performance of the device.

[0005] Conventional inorganic TFT device array fabrication techniques often rely on photolithography as a patterning process. However, photolithography often involves harsh oxygen (O2) plasma during pattern transfer or photoresist removal, as well as aggressive developing solvents, which can severely damage the OSC layer and lead to significant degradation of device performance.

[0006] The present disclosure proposes improved UV-patternable organic semiconductor / crosslinker polymer blends and their use in the OSC layer of organic thin film transistors. Summary of the invention

[0007] In some embodiments, a polymer blend comprises: at least one organic semiconductor (OSC) polymer and at least one cross-linker, wherein the at least one OSC polymer is a diketopyrrolopyrrole-fused thiophene polymeric material, wherein the fused thiophene is beta-substituted, and wherein the cross-linker comprises at least one of: an acrylate, an epoxide, an oxetane, an alkene, an alkyne, an azide, a thiol, an allyloxysilane, a phenol, an anhydride, an amine, a cyanate, an isocyanate, a silyl hydride, a cinnamate, a coumarin, a fluorosulfate, a silyl ether, or a combination thereof.

[0008] In one aspect that may be combined with any other aspect or embodiment, the at least one OSC polymer is present in an amount ranging from 1 wt% to 99 wt%; and the at least one cross-linking agent is present in an amount ranging from 1 wt% to 99 wt%.

[0009] In one aspect that may be combined with any other aspect or embodiment, the at least one OSC polymer is present in an amount ranging from 50 wt% to 80 wt%; and the at least one cross-linking agent is present in an amount ranging from 25 wt% to 55 wt%.

[0010] In one aspect that may be combined with any other aspect or embodiment, the at least one cross-linking agent comprises a first cross-linking agent and a second cross-linking agent, the first cross-linking agent being present in an amount ranging from 30 wt % to 50 wt %; and the second cross-linking agent being present in an amount ranging from 0.5 wt % to 25 wt %.

[0011] In one aspect that may be combined with any other aspect or embodiment, the polymer blend further comprises: at least one photoinitiator, wherein the at least one photoinitiator is present in an amount ranging from 0.1 wt% to 10 wt%.

[0012] In one aspect that may be combined with any other aspect or embodiment, the at least one photoinitiator is present in an amount ranging from 0.1 wt% to 5.0 wt%.

[0013] In one aspect that may be combined with any other aspect or embodiment, the polymer blend further comprises: at least one of an antioxidant, a lubricant, a compatibilizer, a leveling agent, or a nucleating agent present in an amount ranging from 0.05 wt % to 5 wt %.

[0014] In one aspect that may be combined with any other aspect or embodiment, the at least one OSC polymer comprises a repeating unit of Formula 1 or Formula 2, or a salt, isomer, or analog thereof:

[0015]

[0016]

[0017] Wherein, in Formula 1 and Formula 2: m is an integer greater than or equal to 1; n is 0, 1 or 2; R1, R2, R3, R4, R5, R6, R7 and R8 can independently be hydrogen, substituted or unsubstituted C4 or higher alkyl, substituted or unsubstituted C4 or higher alkenyl, substituted or unsubstituted C4 or higher alkynyl, or C5 or higher cycloalkyl; a, b, c and d are independently integers greater than or equal to 3; e and f are integers greater than or equal to zero; X ​​and Y are independently covalent bonds, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted fused aryl or fused heteroaryl, alkyne or alkene; and A and B can independently be any one of S or O, provided that: (i) at least R1 or R2 is one; one of R3 or R4; one of R5 or R6; and one of R7 or R8 is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, or a cycloalkyl; (ii) if any one of R1, R2, R3 or R4 is hydrogen, then R5, R6, R7 or R8 is not hydrogen; (iii) if any one of R5, R6, R7 or R8 is hydrogen, then R1, R2, R3 or R4 is not hydrogen; (iv) e and f cannot be 0 at the same time; (v) if any one of e or f is 0, then c and d are independently integers greater than or equal to 5; and (vi) the polymer has a molecular weight, wherein the molecular weight of the polymer is greater than 10,000.

[0018] In one aspect that may be combined with any other aspect or embodiment, the at least one cross-linking agent comprises at least one of: (A) a polymer selected from:

[0019]

[0020]

[0021] wherein n is an integer greater than or equal to 2, or (B) is a small molecule selected from the following:

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028] or, (C) a combination thereof.

[0029] In one aspect that may be combined with any other aspect or embodiment, the at least one photoinitiator comprises at least one free radical photoinitiator.

[0030] In one aspect that may be combined with any other aspect or embodiment, the at least one photoinitiator comprises at least one cationic photoinitiator.

[0031] In one aspect that may be combined with any other aspect or embodiment, the at least one photoinitiator comprises: 1-hydroxy-cyclohexyl-phenyl-ketone (184); 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (369); diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO); 2-isopropylthioxanthone (ITX); 1-[4-(phenylthio)phenyl]-1,2-octanedione 2- (O-benzoyl oxime) (HRCURE-OXE01); 2,2-dimethoxy-1,2-diphenylethan-1-one (BDK); benzoyl peroxide (BPO); hydroxyacetophenone (HAP); 2-hydroxy-2-methylphenylpropionone (1173); 2-methyl-4'-(methylthio)-2-morpholinopropionone (907); 2-benzyl-2-(dimethylamino)-4'-morpholinopropylpropionone (IHT-PI 910); ethyl 4-(dimethylamino)benzoate (EDB); methyl o-benzoylbenzoate (OMBB); bis-(2,6-dimethoxybenzoyl)-phenylphosphine oxide (BAPO); 4-benzoyl-4'-methyldiphenyl sulfide (BMS); benzophenone (BP); 1-chloro-4-propoxythioxanthone (CPTX); chlorothioxanthone (CTX); 2,2-diethoxyacetophenone (DEAP); diethylthioxanthone (DETX); 2-dimethylaminoethyl benzoate Ester (DMB); 2,2-dimethoxy-2-phenylacetophenone (DMPA); 2-ethylanthraquinone (2-EA); ethyl p-N,N-dimethyl-dimethylaminobenzoate (EDAB); 2-ethylhexyl dimethylaminobenzoate (EHA); 4,4-bis-(diethylamino)-benzophenone (EMK); methylbenzophenone (MBF); 4-methylbenzophenone (MBP); Michler's ketone (MK); 2-methyl-1-[4(methylthio)phenyl]-2-morpholinoacetone (1) (MMMP); 4-phenylbenzophenone (PBZ); 2,4,6-trimethylbenzoyl-ethoxyphenylphosphine oxide (TEPO); bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate; bis(4-tert-butylphenyl)iodonium p-toluenesulfonate; bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; tert-butyloxycarbonyl (boc) methoxyphenyl diphenylsulfonium trifluoromethanesulfonate; (4-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate; diphenyliodonium hexafluorophosphate; Diphenyliodonium nitrate; diphenyliodonium p-toluenesulfonate; diphenyliodonium triflate; (4-fluorophenyl)diphenylsulfonium triflate; N-hydroxynaphthaleneimide triflate; N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate; (4-iodophenyl)diphenylsulfonium triflate; (4-methoxyphenyl)diphenylsulfonium triflate; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine;(4-methylthiophenyl)methylphenylsulfonium trifluoromethanesulfonate; 1-naphthyldiphenylsulfonium trifluoromethanesulfonate; (4-phenoxyphenyl)diphenylsulfonium trifluoromethanesulfonate; (4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate; triarylsulfonium hexafluoroantimonate mixed at 50% by weight in propylene carbonate; triarylsulfonium hexafluorophosphate mixed at 50% by weight in propylene carbonate; triphenylsulfonium perfluoro-1-butanesulfonate; triphenylsulfonium trifluoromethanesulfonate; tri(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate; tri(4-tert-butylphenyl)sulfonium trifluoromethanesulfonate; aryldiazonium salt; diaryliodonium salt; triarylsulfonium salt; arylferrocenium salt; or a combination thereof. ;

[0032] In one aspect that may be combined with any other aspect or embodiment, the at least one cross-linking agent comprises a C=C bond, a thiol, an oxetane, a halide, an azide, or a combination thereof.

[0033] In some embodiments, a polymer blend consists of at least one organic semiconductor (OSC) polymer and at least one cross-linker, wherein the at least one OSC polymer is a diketopyrrolopyrrole-fused thiophene polymeric material, wherein the fused thiophene is beta-substituted, and wherein the cross-linker comprises at least one of an acrylate, an epoxide, an oxetane, an alkene, an alkyne, an azide, a thiol, an allyloxysilane, a phenol, an anhydride, an amine, a cyanate, an isocyanate, a silyl hydride, a cinnamate, a coumarin, a fluorosulfate, a silyl ether, or a combination thereof.

[0034] In one aspect that may be combined with any other aspect or embodiment, the at least one OSC polymer comprises a repeating unit of Formula 1 or Formula 2, or a salt, isomer, or analog thereof:

[0035]

[0036]

[0037] Wherein, in Formula 1 and Formula 2: m is an integer greater than or equal to 1; n is 0, 1 or 2; R1, R2, R3, R4, R5, R6, R7 and R8 can independently be hydrogen, substituted or unsubstituted C4 or higher alkyl, substituted or unsubstituted C4 or higher alkenyl, substituted or unsubstituted C4 or higher alkynyl, or C5 or higher cycloalkyl; a, b, c and d are independently integers greater than or equal to 3; e and f are integers greater than or equal to zero; X ​​and Y are independently covalent bonds, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted fused aryl or fused heteroaryl, alkyne or alkene; and A and B can independently be any one of S or O, provided that: (i) at least R1 or R2 is one; one of R3 or R4; one of R5 or R6; and one of R7 or R8 is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, or a cycloalkyl; (ii) if any one of R1, R2, R3 or R4 is hydrogen, then R5, R6, R7 or R8 is not hydrogen; (iii) if any one of R5, R6, R7 or R8 is hydrogen, then R1, R2, R3 or R4 is not hydrogen; (iv) e and f cannot be 0 at the same time; (v) if any one of e or f is 0, then c and d are independently integers greater than or equal to 5; and (vi) the polymer has a molecular weight, wherein the molecular weight of the polymer is greater than 10,000.

[0038] In one aspect that may be combined with any other aspect or embodiment, the at least one cross-linking agent comprises at least one of: (A) a polymer selected from:

[0039]

[0040] wherein n is an integer greater than or equal to 2, or (B) is a small molecule selected from the following:

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048] or, (C) a combination thereof.

[0049] In one aspect that may be combined with any other aspect or embodiment, the polymer blend further comprises: at least one photoinitiator.

[0050] In one aspect that may be combined with any other aspect or embodiment, the at least one photoinitiator comprises: 1-hydroxy-cyclohexyl-phenyl-ketone (184); 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (369); diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO); 2-isopropylthioxanthone (ITX); 1-[4-(phenylthio)phenyl]-1,2-octanedione 2- (O-benzoyl oxime) (HRCURE-OXE01); 2,2-dimethoxy-1,2-diphenylethan-1-one (BDK); benzoyl peroxide (BPO); hydroxyacetophenone (HAP); 2-hydroxy-2-methylphenylpropionone (1173); 2-methyl-4'-(methylthio)-2-morpholinopropionone (907); 2-benzyl-2-(dimethylamino)-4'-morpholinopropylpropionone (IHT-PI 910); ethyl 4-(dimethylamino)benzoate (EDB); methyl o-benzoylbenzoate (OMBB); bis-(2,6-dimethoxybenzoyl)-phenylphosphine oxide (BAPO); 4-benzoyl-4'-methyldiphenyl sulfide (BMS); benzophenone (BP); 1-chloro-4-propoxythioxanthone (CPTX); chlorothioxanthone (CTX); 2,2-diethoxyacetophenone (DEAP); diethylthioxanthone (DETX); 2-dimethylaminobenzoic acid ethyl ester (DMB); 2,2-dimethoxy-2-phenylacetophenone (DMPA); 2-ethylanthraquinone (2-EA); ethyl p-N,N-dimethyl-dimethylaminobenzoate (EDAB); 2-ethylhexyl dimethylaminobenzoate (EHA); 4,4-bis-(diethylamino)-benzophenone (EMK); methylbenzophenone (MBF); 4-methylbenzophenone (MBP); Michler's ketone (MK); 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino Acetone (1) (MMMP); 4-phenylbenzophenone (PBZ); 2,4,6-trimethylbenzoyl-ethoxyphenylphosphine oxide (TEPO); bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate; bis(4-tert-butylphenyl)iodonium p-toluenesulfonate; bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; tert-butyloxycarbonylmethoxyphenyldiphenylsulfonium trifluoromethanesulfonate; (4-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; diphenyliodonium hexafluorophosphate; di Phenyliodonium nitrate; diphenyliodonium p-toluenesulfonate; diphenyliodonium trifluoromethanesulfonate; (4-fluorophenyl)diphenylsulfonium trifluoromethanesulfonate; N-hydroxynaphthalimide trifluoromethanesulfonate; N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate; (4-iodophenyl)diphenylsulfonium trifluoromethanesulfonate; (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate; 2-(4-methoxyphenylphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine;(4-methylthiophenyl)methylphenylsulfonium trifluoromethanesulfonate; 1-naphthyldiphenylsulfonium trifluoromethanesulfonate; (4-phenoxyphenyl)diphenylsulfonium trifluoromethanesulfonate; (4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate; triarylsulfonium hexafluoroantimonate mixed at 50% by weight in propylene carbonate; triarylsulfonium hexafluorophosphate mixed at 50% by weight in propylene carbonate; triphenylsulfonium perfluoro-1-butanesulfonate; triphenylsulfonium trifluoromethanesulfonate; tri(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate; tri(4-tert-butylphenyl)sulfonium trifluoromethanesulfonate; aryldiazonium salt; diaryliodonium salt; triarylsulfonium salt; arylferrocenium salt; or a combination thereof. ; BRIEF DESCRIPTION OF THE DRAWINGS

[0051] The present disclosure can be more fully understood through the following specific embodiments in conjunction with the accompanying drawings, in which:

[0052] Figures 1A to 1E A conventional technique for patterning an organic semiconductor blend using a photoresist is exemplified.

[0053] Figures 2A to 2C A patterning technique of an organic semiconductor blend according to some embodiments is illustrated.

[0054] Figure 3 An exemplary OTFT device according to some embodiments is illustrated.

[0055] Figure 4 An exemplary OTFT device according to some embodiments is illustrated.

[0056] Figures 5 to 10D Illustrated is a test OFET device prepared according to some embodiments. d -V g curve.

[0057] Figures 11A to 11D The OSC polymer blend according to some embodiments is illustrated ( Fig.11A and 11B ) and OSC polymer / crosslinker blends ( Fig. 11C and 11D ) confocal laser scanning microscopy (CLSM) image. DETAILED DESCRIPTION

[0058] The exemplary embodiments shown in the accompanying drawings will now be described in detail. Whenever possible, the same reference numerals are used in the accompanying drawings to represent the same or similar parts. The components in the accompanying drawings are not necessarily drawn to scale, but the focus is on illustrating the principles of the exemplary embodiments. It should be understood that the application is not limited to the details or methodology set forth in the specification or illustrated in the accompanying drawings. It should also be understood that the terms are for descriptive purposes only and should not be considered restrictive.

[0059] In addition, any examples listed in this specification are illustrative rather than restrictive, and only list some of the many possible embodiments of the claimed invention. Other appropriate modifications and adjustments to various conditions and parameters are common in the art and are obvious to those skilled in the art, and are within the spirit and scope of the present disclosure.

[0060] definition

[0061] The term "alkyl" refers to a branched or unbranched saturated hydrocarbon chain monovalent radical having from 1 to 40 carbon atoms. The term is exemplified by radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, tetradecyl, and the like. Alkyl groups may be substituted or unsubstituted.

[0062] The term "substituted alkyl" refers to: (1) an alkyl group as defined above having 1, 2, 3, 4 or 5 substituents, typically 1 to 3 substituents, selected from the group consisting of alkenyl, alkynyl, alkoxy, aralkyl, aldehyde, cycloalkyl, cycloalkenyl, acyl, acylamino, acyl halide, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxyl, carboxyalkyl, arylthiol, ester, heteroarylthio, heterocyclicthio, hydroxy, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocycloxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -SO2-alkyl, -SO2-aryl and -SO2-heteroaryl, thioalkyl, vinyl ether. Unless otherwise limited by the definition, all substituents may optionally be substituted by 1, 2 or 3 substituents selected from the group consisting of alkyl, carboxyl, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano and -S(O). n R SO , where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2; or (2) is replaced by 1 to 10 independently selected from oxygen, sulfur and NR a The alkyl group as defined above is disconnected from the atom of ais selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl and heterocyclic. Optionally, all substituents may also be replaced by alkyl, alkoxy, halogen, CF3, amino, substituted amino, cyano or -S(O). n R SO Substitution, where R SO is an alkyl, aryl or heteroaryl group, and n is 0, 1 or 2; or (3) an alkyl group as defined above having 1, 2, 3, 4 or 5 substituents as defined above and interrupted by 1 to 10 atoms as defined above. For example, the alkyl group may be an alkylhydroxyl group, wherein any hydrogen atom in the alkyl group is replaced by a hydroxyl group.

[0063] The term "alkyl" defined herein also includes cycloalkyl. The term "cycloalkyl" used herein is a non-aromatic carbon-based ring (i.e., carbocycle) with a monocyclic or polycondensed ring consisting of at least three carbon atoms (in some embodiments, 3 to 20 carbon atoms). The example of the cycloalkyl of a monocyclic ring includes but is not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc. The example of the cycloalkyl of multiple rings includes but is not limited to adamantyl, bicyclo [2.2.1] heptane, 1,3,3- trimethyl bicyclo [2.2.1] hept-2-yl, (2,3,3- trimethyl bicyclo [2.2.1] hept-2-yl), or a carbocyclic group fused to an aryl, such as 1,2- indane, etc. The term cycloalkyl also includes heterocycloalkyl, wherein at least one carbon atom in the carbon atoms of the ring is replaced by a heteroatom, such as but not limited to nitrogen, oxygen, sulfur or phosphorus.

[0064] The term "unsubstituted alkyl" is defined herein as an alkyl group consisting solely of carbon and hydrogen.

[0065] The term "acyl" refers to the group -C(O)R CO , where R CO is hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted heterocyclyl, optionally substituted aryl and optionally substituted heteroaryl.

[0066] The term "aryl" as used herein is any carbon-based aromatic group (i.e., aromatic carbocycle), for example, a carbon-based aromatic group having a single ring (such as phenyl) or multiple rings (such as biphenyl) or multiple condensed rings (condensed rings) (such as naphthyl or anthracenyl). These aryl groups may include, but are not limited to, benzene, naphthalene, phenyl, etc.

[0067] The term "aryl" also includes "heteroaryl", which means a group derived from: an aromatic ring group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 carbon atoms and having 1, 2, 3 or 4 heteroatoms selected from oxygen, nitrogen, sulfur and phosphorus in at least one ring (i.e., fully unsaturated). In other words, a heteroaryl group is an aromatic ring consisting of at least three carbon atoms and containing at least one heteroatom in the aromatic ring group. Such heteroaryl groups can have a monocyclic ring (e.g., pyridyl or furyl) or multiple condensed rings (e.g., indolizine, benzothiazolyl or benzothienyl). Examples of heteroaryl groups include, but are not limited to, the following: [1,2,4]oxadiazole, [1,3,4]oxadiazole, [1,2,4]thiadiazole, [1,3,4]thiadiazole, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine, quinolizine, isoquinoline, quinoline, 2,3-naphthyridine, naphthylpyridine, quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline, phenanthridine, acridine, phenanthroline, isothiazole, phenazine, isoxazole, phenoxazine, phenothiazine, imidazolidine, imidazoline, triazole, oxazole, thiazole, 1,5-naphthyridine, and the like, as well as N-oxide and N-alkoxy derivatives of nitrogen-containing heteroaryl compounds, such as pyridine-N-oxide derivatives.

[0068] Unless the definition of heteroaryl substituents is otherwise limited, the heteroaryl group may be optionally substituted with 1 to 5 substituents (typically 1 to 3 substituents) selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxyl, carboxyalkyl, arylthio, heteroarylthio, heterocyclicthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocycloxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -SO2-alkyl, -SO2-aryl and -SO2-heteroaryl. Unless otherwise limited by the definition, all substituents may be optionally substituted by 1-3 substituents selected from the group consisting of alkyl, carboxyl, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(O). n R SO , where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2.

[0069] The aryl group may be substituted or unsubstituted. Unless otherwise limited in the definition of the aryl substituent, the aryl group may be optionally substituted with 1 to 5 substituents (typically 1 to 3 substituents) selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, aldehyde, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, ester, halogen, hydroxyl, keto, thiocarbonyl, carboxyl, carboxylalkyl, arylthio, heteroarylthio, heterocyclicthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclic, heterocyclicoxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -SO2-alkyl, -SO2-aryl and -SO2-heteroaryl. Unless otherwise limited by the definition, all substituents may be optionally substituted by 1-3 substituents selected from the group consisting of alkyl, carboxyl, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(O). n R SO , where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2. In some embodiments, the term "aryl" is limited to substituted or unsubstituted aromatic and heteroaromatic rings having 3 to 30 carbon atoms.

[0070] As used herein, the term "aralkyl" is an aryl group having an alkyl or alkylene group as defined herein covalently attached to the aryl group. An example of an aralkyl group is benzyl. "Optionally substituted aralkyl" refers to an optionally substituted aryl group covalently attached to an optionally substituted alkyl or alkylene group. Examples of such aralkyl groups include benzyl, phenethyl, 3-(4-methoxyphenyl)propyl, and the like.

[0071] The term "heteroaralkyl" refers to a heteroaryl group covalently attached to an alkylene group, wherein heteroaryl and alkylene are as defined herein. "Optionally substituted heteroaralkyl" refers to an optionally substituted heteroaryl group covalently attached to an optionally substituted alkylene group. Examples of such heteroaralkyl groups include: 3-pyridylmethyl, quinolin-8-ylethyl, 4-methoxythiazol-2-ylpropyl, and the like.

[0072] The term "alkenyl" refers to a monovalent group of a branched or unbranched unsaturated hydrocarbon radical typically having 2 to 40 carbon atoms, more typically 2 to 10 carbon atoms, and even more typically 2 to 6 carbon atoms, and having 1-6 (typically 1) double bonds (vinyl). Typical alkenyl groups include ethenyl or vinyl, CH=CH2, 1-propenyl or allyl (-CH2CH=CH2), isopropenyl (-C(CH3)=CH2), bicyclo[2.2.1]heptene, etc. When the alkenyl group is attached to nitrogen, the double bond cannot be located in the alpha position of the nitrogen.

[0073] The term "substituted alkenyl" refers to an alkenyl group as defined above having 1, 2, 3, 4 or 5 substituents, typically 1, 2 or 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxyl, carboxyalkyl, arylthio, heteroarylthio, heterocyclicthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocycloxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -SO2-alkyl, -SO2-aryl and -SO2-heteroaryl. Unless otherwise limited by the definition, all substituents may be optionally substituted by 1, 2 or 3 substituents selected from the group consisting of alkyl, carboxyl, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano and -S(O). n R SO , where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2.

[0074] The term "cycloalkenyl" refers to a carbocyclic group of 3 to 20 carbon atoms having a single ring or multiple condensed rings and having at least one double bond in the ring structure.

[0075] The term "alkynyl" refers to a monovalent group of an unsaturated hydrocarbon radical typically having 2 to 40 carbon atoms, more typically 2 to 10 carbon atoms, and even more typically 2 to 6 carbon atoms, and having at least 1, (typically 1-6) sites of acetylene (triple bond) unsaturation. Typical alkynyl groups include ethynyl (-C≡CH), propargyl (or prop-1-yn-3-yl, -CH2C≡CH), and the like. When the alkynyl group is attached to nitrogen, the triple bond cannot be located alpha to the nitrogen.

[0076] The term "substituted alkynyl" refers to an alkynyl group as defined above having 1, 2, 3, 4 or 5 substituents, typically 1, 2 or 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxyl, carboxyalkyl, arylthio, heteroarylthio, heterocyclicthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocycloxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -SO2-alkyl, -SO2-aryl and -SO2-heteroaryl. Unless otherwise limited by the definition, all substituents may be optionally substituted by 1, 2 or 3 substituents selected from the group consisting of alkyl, carboxyl, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano and -S(O). n R SO , where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2.

[0077] The term "alkylene" is defined as a divalent group having a branched or unbranched saturated hydrocarbon chain of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, typically 1-10 carbon atoms, more typically 1, 2, 3, 4, 5 or 6 carbon atoms. The term is exemplified by groups such as methylene (-CH2-), ethylene (-CH2CH2-), propylene isomers (e.g., -CH2CH2CH2- and -CH(CH3)CH2-), and the like.

[0078] The term "substituted alkylene" refers to: (1) an alkylene group as defined above having 1, 2, 3, 4 or 5 substituents selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxyl, carboxyalkyl, arylthio, heteroarylthio, heterocyclicthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclic, heterocyclicoxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -SO2-alkyl, -SO2-aryl and -SO2-heteroaryl. Unless otherwise limited by the definition, all substituents may also be optionally substituted by 1, 2 or 3 substituents selected from the group consisting of alkyl, carboxyl, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano and -S(O). n RSO , where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2; or (2) is replaced by 1 to 20 independently selected from oxygen, sulfur and NR a - an alkylene group as defined above, wherein R a a group selected from hydrogen, optionally substituted alkyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl and heterocyclic, or a group selected from carbonyl, carboxylate, carboxamide and sulfonyl; or (3) an alkylene group as defined above having 1, 2, 3, 4 or 5 substituents as defined above and interrupted by 1 to 20 atoms as defined above. Examples of substituted alkylene groups are chloromethylene (–CH(Cl)–), aminoethylene (–CH(NH2)CH2–), methylaminoethylene (–CH(NHMe)CH2–), 2-carboxypropylene isomers (–CH2CH(CO2H)CH2–), ethoxyethyl (–CH2CH2O–CH2CH2–), ethylmethylaminoethyl (–CH2CH2N(CH3)CH2CH2–), and the like.

[0079] The term "alkoxy" refers to a group R-O-, wherein R is an optionally substituted alkyl or an optionally substituted cycloalkyl, or R is a group -Y-Z, wherein Y is an optionally substituted alkylene, and Z is an optionally substituted alkenyl, an optionally substituted alkynyl, or an optionally substituted cycloalkenyl, wherein alkyl, alkenyl, alkynyl, cycloalkyl, and cycloalkenyl are as defined herein. Typical alkoxy groups are optionally substituted alkyl-O-, for example, including methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, n-hexoxy, 1,2-dimethylbutoxy, trifluoromethoxy, and the like.

[0080] The term "alkylthio" refers to a group R S –S–, where R S As defined for alkoxy.

[0081] The term "aminocarbonyl" refers to the group -C(O)NR N R N , where each R N are independently hydrogen, alkyl, aryl, heteroaryl, heterocyclyl, or two R N The groups are connected to form a heterocyclic group (e.g., morpholino). Unless otherwise limited by the definition, all substituents may also be optionally substituted by 1-3 substituents selected from the following: alkyl, carboxyl, carboxyalkyl, aminocarbonyl, hydroxyl, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(O) n R SO , where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2.

[0082] The term "amido" refers to the group -NR NCO C(O)R, where each R NCO are independently hydrogen, alkyl, aryl, heteroaryl or heterocyclyl. Unless otherwise defined, all substituents may be optionally substituted by 1-3 substituents selected from the group consisting of alkyl, carboxyl, carboxylalkyl, aminocarbonyl, hydroxyl, alkoxy, halogen, CF3, amino, substituted amino, cyano and -S(O) n R SO , where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2.

[0083] The term "acyloxy" refers to the groups -O(O)C-alkyl, -O(O)C-cycloalkyl, -O(O)C-aryl, -O(O)C-heteroaryl and -O(O)C-heterocyclyl. Unless otherwise limited by the definition, all substituents may also be optionally replaced by alkyl, carboxyl, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano and -S(O) n R SO Substitution, where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2.

[0084] The term "aryloxy" refers to an aryl-O- group wherein aryl is as defined above and which includes optionally substituted aryl groups also as defined above.

[0085] The term "heteroaryloxy" refers to a heteroaryl-O- group.

[0086] The term "amino" refers to a -NH2 group.

[0087] The term "substituted amino" refers to the group -NR w R w , where each R w are independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, carboxyalkyl (e.g., benzyloxycarbonyl), aryl, heteroaryl, and heterocyclyl, provided that both R w The group is not simultaneously hydrogen or a group -Y-Z, wherein Y is an optionally substituted alkylene group and Z is an alkenyl, cycloalkenyl or alkynyl group. Unless otherwise limited by the definition, all substituents may also be optionally substituted by 1-3 substituents selected from the group consisting of alkyl, carboxyl, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano and -S(O) n R SO , where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2.

[0088] The term "carboxyl" refers to a -C(O)OH group. The term "carboxylalkyl" refers to a group -C(O)O-alkyl or -C(O)O-cycloalkyl, wherein alkyl and cycloalkyl are as defined herein, and which may be optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, halogen, CF3, amino, substituted amino, cyano and -S(O) n R SO Substitution, where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2.

[0089] The term "substituted cycloalkyl" or "substituted cycloalkenyl" refers to a cycloalkyl or cycloalkenyl group having 1, 2, 3, 4 or 5 substituents, typically 1, 2 or 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxyl, carboxyalkyl, arylthio, heteroarylthio, heterocyclicthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocycloxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -SO2-alkyl, -SO2-aryl and -SO2-heteroaryl. Unless otherwise limited by the definition, all substituents may be optionally substituted by 1, 2 or 3 substituents selected from the group consisting of alkyl, carboxyl, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano and -S(O). n R SO , where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2.

[0090] The term "conjugated group" is defined as a linear, branched or cyclic group or a combination thereof, wherein the p orbitals of the atoms in the group are connected by electron delocalization, and wherein the structure can be described as containing alternating single bonds and double bonds or triple bonds, and can also contain lone pairs of electrons, free radicals or carbocations. Conjugated cyclic groups can include aromatic groups and non-aromatic groups at the same time, and can include polycyclic groups or heterocyclic groups, such as diketopyrrolopyrroles. Ideally, the conjugated groups are combined in a certain way so that the conjugation between the thiophene parts connected to them continues. In some embodiments, "conjugated groups" are limited to conjugated groups with 3 to 30 carbon atoms.

[0091] The terms "halogen," "halo," or "halide" are interchangeable and refer to fluorine, bromine, chlorine, and iodine.

[0092] The term "heterocyclic group" refers to a saturated or partially unsaturated monovalent group having a monocyclic or polycondensed ring and having 1 to 40 carbon atoms and 1 to 10 heteroatoms (typically 1, 2, 3 or 4 heteroatoms) in the ring, wherein the heteroatoms are selected from nitrogen, sulfur, phosphorus and / or oxygen. The heterocyclic group may have a monocyclic or polycondensed ring and includes tetrahydrofuranyl, morpholino, piperidinyl, piperazine, dihydropyrido, and the like.

[0093] Unless the definition of heterocyclyl substituents is otherwise limited, the heterocyclyl group may be optionally substituted with 1, 2, 3, 4 or 5 substituents (typically 1, 2 or 3 substituents) selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxyl, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclyloxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -SO2-alkyl, -SO2-aryl and -SO2-heteroaryl. Unless otherwise limited by the definition, all substituents may be optionally substituted by 1-3 substituents selected from the group consisting of alkyl, carboxyl, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(O). n R SO , where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2.

[0094] The term "thiol" refers to a -SH group. The term "substituted alkylthio" refers to an -S-substituted alkyl group. The term "arylthio" refers to an aryl-S- group, wherein aryl is as defined above. The term "heteroarylthio" refers to an -S-heteroaryl group, wherein heteroaryl is as defined above, including optionally substituted heteroaryl groups as defined above.

[0095] The term "sulfoxide" refers to -S(O)R SO Group, where R SO is alkyl, aryl or heteroaryl. The term "substituted sulfoxide" refers to -S(O)R SO Group, where R SO is a substituted alkyl, substituted aryl or substituted heteroaryl as defined herein. The term "sulfone" refers to -S(O)2R SO Group, where R SO is alkyl, aryl or heteroaryl. The term "substituted sulfone" refers to -S(O)2R SO Group, where R SO is substituted alkyl, substituted aryl or substituted heteroaryl as defined herein.

[0096] The term "keto" refers to a -C(O)- group. The term "thiocarbonyl" refers to a -C(S)- group.

[0097] As used herein, the term "room temperature" is 20°C to 25°C.

[0098] The disclosed compounds, compositions, and components can be used in the disclosed methods and compositions, can be used in conjunction with the disclosed methods and compositions, can be used to prepare the disclosed compositions, or are the products of the disclosed methods. These and other materials are disclosed herein, and it should be understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed without explicitly specifically disclosing each different individual combination and collective combination and arrangement of these compounds, each of them is specifically contemplated and described herein. Thus, if a class of molecules A, B, and C is disclosed and an example of a class of molecules D, E, and F and a combined form of molecules AD is disclosed, each is contemplated individually and collectively even if each is not stated individually. Thus, in this example, each of the following combinations AE, AF, BD, BE, BF, CD, CE, and CF is specifically contemplated and should be considered disclosed by the contents of A, B, and C; D, E, and F; and the example combination AD. Likewise, any subset of the above or combination of these subsets is also specifically contemplated and disclosed. Thus, for example, the subgroups of AE, BF, and CE are specifically contemplated and should be considered disclosed from the disclosure of A, B, and C; D, E, and F; and the exemplary combination AD. This concept applies to all aspects of the disclosure, including, but not limited to, steps in methods of making and using the disclosed compositions. Thus, if there are a variety of additional steps that can be performed, it should be understood that each of these additional steps can be performed by any specific embodiment or combination of embodiments of the disclosed methods, and each such combination is specifically contemplated and should be considered disclosed.

[0099] Unless specifically indicated to the contrary, the weight percentage of a component is based on the total weight of the formulation or composition in which the component is included.

[0100] Organic semiconductors as functional materials can be used in a variety of applications, including, for example, printed electronics, organic transistors [including organic thin film transistors (OTFTs) and organic field effect transistors (OFETs)], organic light emitting diodes (OLEDs), organic integrated circuits, organic solar cells, and disposable sensors. Organic transistors can be used in many applications, including smart cards, security tags, and backplanes for flat panel displays. Organic semiconductors can significantly reduce costs compared to inorganic semiconductors (such as silicon). Deposition of OSCs from solution enables rapid, large-area manufacturing routes, such as various printing methods and roll-to-roll processes.

[0101] Organic thin film transistors are of particular interest because their fabrication processes are less complex than conventional silicon-based technologies. For example, OTFTs generally rely on low temperature deposition and solution processing, which when used with semiconducting conjugated polymers can achieve valuable technical properties, such as compatibility with simple write printing techniques, general low-cost manufacturing methods, and flexible plastic substrates. Other potential applications of OTFTs include flexible electronic paper, sensors, storage devices [e.g., radio frequency identification cards (RFID)], remotely controllable smart tags for supply chain management, large-area flexible displays, and smart cards.

[0102] Organic Semiconductor (OSC) Polymers

[0103] OSC polymers can be used to produce organic semiconductor devices. In some examples, the polymer blend includes an organic semiconductor polymer. In some examples, the OSC polymer has a fully conjugated main skeleton. In some examples, the OSC is a diketopyrrolopyrrole (DPP) fused thiophene polymer material. In some examples, the fused thiophene is β-substituted. The OSC may contain both fused thiophene and diketopyrrolopyrrole units. In some examples, the OSC is used for OTFT applications. For example, the OSC polymer may contain a repeating unit of Formula 1 or Formula 2, or a salt, isomer, or analog thereof:

[0104]

[0105]

[0106] Wherein, in Formula 1 and Formula 2: m is an integer greater than or equal to 1; n is 0, 1 or 2; R1, R2, R3, R4, R5, R6, R7 and R8 can independently be hydrogen, substituted or unsubstituted C4 or higher alkyl, substituted or unsubstituted C4 or higher alkenyl, substituted or unsubstituted C4 or higher alkynyl, or C5 or higher cycloalkyl; a, b, c and d are independently integers greater than or equal to 3; e and f are integers greater than or equal to zero; X ​​and Y are independently a covalent bond, an optionally substituted aryl, an optionally substituted heteroaryl, an optionally substituted fused aryl or fused heteroaryl, an alkyne or an alkene; and A and B can independently be any one of S or O, provided that: (i) at least one of R1 or R2 is R3 or R4; R5 or R6; and R7 or R8 are substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, or cycloalkyl; (ii) if any one of R1, R2, R3 or R4 is hydrogen, then R5, R6, R7 or R8 is not hydrogen; (iii) if any one of R5, R6, R7 or R8 is hydrogen, then R1, R2, R3 or R4 is not hydrogen; (iv) e and f cannot be 0 at the same time; (v) if any one of e or f is 0, then c and d are independently integers greater than or equal to 5; and (vi) the polymer has a molecular weight, wherein the molecular weight of the polymer is greater than 10,000.

[0107] In some embodiments, the OSC polymers defined in Formula 1 or Formula 2 enable simple transistor fabrication at relatively low temperatures, which is particularly important for obtaining large-area, mechanically flexible electronic devices. β-substituted OSC polymers may also help improve solubility.

[0108] In some examples, the OSC polymer may include a repeating unit of Formula 3, Formula 4, or Formula 5, or a salt, isomer, or analog thereof:

[0109]

[0110]

[0111]

[0112] In some examples, the solubility of OSC is 0.5 mg / mL, 1 mg / mL, 2 mg / mL, 3 mg / mL, 4 mg / mL, 5 mg / mL, or any range defined by any two of these endpoints. In some examples, the solubility of OSC at room temperature is 1 mg / mL or higher.

[0113] In some examples, the hole mobility of OSCs is 1 cm 2 V -1 s-1 , 2cm 2 V -1 s -1 , 3cm 2 V -1 s -1 , 4cm 2 V -1 s -1 , 5cm 2 V -1 s -1 , 10cm 2 V -1 s -1 , or any range defined by any two of these endpoints. The hole mobility may be equal to or greater than any of these values. In some examples, the hole mobility of the OSC is 1 cm 2 V -1 s -1 Up to 4cm 2 V -1 s -1 In some examples, the hole mobility of OSCs is 2 cm 2 V -1 s -1 In some examples, the hole mobility of OSCs is 2 cm 2 V -1 s -1 or higher.

[0114] In some examples, the on / off ratio of the OSC polymer is greater than 10 5 In some examples, the on / off ratio of the OSC polymer is greater than 10 6 .

[0115] In some examples, the threshold voltage of the OSC polymer in the thin film transistor device is 1 V, 2 V, 3 V, 4 V, 5 V, 10 V, or any range defined by any two of these endpoints. In some examples, the threshold voltage of the OSC polymer in the thin film transistor device is in the range of 1 V to 3 V. In some examples, the threshold voltage of the OSC polymer in the thin film transistor device is 2 V.

[0116] Crosslinking agent

[0117] In some examples, the polymer blend comprises at least one organic semiconductor (OSC) polymer and at least one cross-linking agent, such that the cross-linking agent comprises at least one of acrylates, epoxides, oxetanes, alkenes, alkynes, azides, thiols, allyloxysilanes, phenols, anhydrides, amines, cyanates, isocyanates, silyl hydrides, cinnamates, coumarins, fluorosulfates, silyl ethers, or combinations thereof. In some examples, the at least one cross-linking agent comprises a C=C bond, a thiol, an oxetanes, a halide, an azide, or a combination thereof.

[0118] In some examples, the crosslinking agent can be a small molecule or polymer that reacts with the OSC polymer, depending on the functional part present in the crosslinking agent molecule, and the reaction is carried out by a combination of a reaction mechanism or multiple reaction mechanisms. For example, a crosslinking agent comprising a thiol group can react with the double bond in the OSC polymer by thiol-ene click chemistry. In some examples, a crosslinking agent comprising vinyl can react with the double bond in the OSC polymer by addition reaction. In some examples, a crosslinking agent (comprising thiol, vinyl, etc. or a combination thereof) can react with the crosslinkable functional group contained in the side chain of the OSC polymer. For example, these crosslinking agents include acrylates, epoxides, oxetanes, alkenes, alkynes, azides, mercaptans, allyloxysilanes, phenols, anhydrides, amines, cyanates, isocyanates, silyl hydrides, cinnamates, coumarins, fluorosulfates, silyl ethers or a combination thereof.

[0119] In one aspect that may be combined with any other aspect or embodiment, the at least one cross-linking agent comprises at least one of: (A) a polymer selected from:

[0120]

[0121] wherein n is an integer greater than or equal to 2, or (B) is a small molecule selected from the following:

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128] or, (C) a combination thereof.

[0129] Photoinitiator

[0130] In some examples, the polymer blend includes at least one OSC polymer, at least one cross-linker, and at least one photoinitiator.

[0131] Photoinitiators are key components of photocurable products. In some examples, the photoinitiator includes at least one free radical photoinitiator. Free radical-based photoinitiators include reactive free radicals that initiate photopolymerization when exposed to UV light. In one example, the mechanism of photoinitiator TPO initiating thiol-ene free radical polymerization is shown below.

[0132]

[0133] In some examples, the photoinitiator includes at least one cationic photoinitiator. Cationic photoinitiators are also referred to as photoacid generators (PAGs). Once the cationic photoinitiator absorbs UV light, the initiator molecule is converted into a strong acid substance, a Lewis acid or a Bronsted acid, that initiates polymerization. Common photoacid generators include aryl diazonium salts, diaryl iodonium salts, triaryl sulfonium salts, and aryl ferrocenium salts. In one example, the mechanism of the polymerization reaction using PAGs is shown below.

[0134]

[0135] In some examples, the at least one photoinitiator includes: 1-hydroxy-cyclohexyl-phenyl-ketone (184); 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (369); diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO); 2-isopropylthioxanthone (ITX); 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime) (HRCURE-OXE01); 2,2-dimethoxy-1,2-diphenylethan-1-one (BDK); benzoyl peroxide (BPO); hydroxyacetophenone (HAP); 2-hydroxy-2-methylphenylpropionone (1173); 2-methyl-4'-(methylthio)-2-morpholinopropionone (907); 2-benzyl-2-(dimethylamino)-4'-morpholinopropylpropionone (IHT-PI 910); ethyl 4-(dimethylamino)benzoate (EDB); methyl o-benzoylbenzoate (OMBB); bis-(2,6-dimethoxybenzoyl)-phenylphosphine oxide (BAPO); 4-benzoyl-4'-methyldiphenyl sulfide (BMS); benzophenone (BP); 1-chloro-4-propoxythioxanthone (CPTX); chlorothioxanthone (CTX); 2,2-diethoxyacetophenone (DEAP); diethylthioxanthone (DETX); 2-dimethylaminoethyl benzoate (DM B); 2,2-dimethoxy-2-phenylacetophenone (DMPA); 2-ethylanthraquinone (2-EA); ethyl p-N,N-dimethyl-dimethylaminobenzoate (EDAB); 2-ethylhexyl dimethylaminobenzoate (EHA); 4,4-bis-(diethylamino)-benzophenone (EMK); methylbenzophenone (MBF); 4-methylbenzophenone (MBP); Michler's ketone (MK); 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone (1) (MMMP ); 4-phenylbenzophenone (PBZ); 2,4,6-trimethyl-benzoyl-ethoxyphenylphosphine oxide (TEPO); bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate; bis(4-tert-butylphenyl)iodonium p-toluenesulfonate; bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; tert-butyloxycarbonylmethoxyphenyldiphenylsulfonium trifluoromethanesulfonate; (4-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; diphenyliodonium hexafluorophosphate; diphenyliodonium nitrate; diphenyliodonium p-toluene Sulfonates; diphenyliodonium triflate; (4-fluorophenyl) diphenylsulfonium triflate; N-hydroxynaphthalimide triflate; N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate; (4-iodophenyl) diphenylsulfonium triflate; (4-methoxyphenyl) diphenylsulfonium triflate; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine; (4-methylthiophenyl) methylphenylsulfonium triflate;1-naphthyldiphenylsulfonium trifluoromethanesulfonate; (4-phenoxyphenyl)diphenylsulfonium trifluoromethanesulfonate; (4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate; triarylsulfonium hexafluoroantimonate mixed at 50% by weight in propylene carbonate; triarylsulfonium hexafluorophosphate mixed at 50% by weight in propylene carbonate; triphenylsulfonium perfluoro-1-butanesulfonate; triphenylsulfonium trifluoromethanesulfonate; tri(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate; tri(4-tert-butylphenyl)sulfonium trifluoromethanesulfonate; aryldiazonium salt; diaryliodonium salt; triarylsulfonium salt; arylferrocenium salt; or a combination thereof. ;

[0136] Table 1 below shows the structures of representative photoinitiators.

[0137]

[0138]

[0139] Table 1

[0140] Table 2 below shows the structures of representative aryl diazonium salt, diaryliodonium salt, triarylsulfonium salt, and arylferrocenium salt photoinitiators.

[0141]

[0142]

[0143]

[0144]

[0145] Table 2

[0146] additive

[0147] In some examples, the polymer blend comprises at least one OSC polymer, at least one crosslinking agent, at least one photoinitiator, and at least one additive, such as an antioxidant (i.e., an oxygen inhibitor), a lubricant, a compatibilizer, a leveling agent, a nucleating agent, or a combination thereof. In some examples, the oxygen inhibitor comprises a phenol, a thiol, an amine, an ether, a phosphite, an organic phosphine, a hydroxylamine, or a combination thereof.

[0148] Polymer blends

[0149] In some examples, the performance of a device comprising an OSC polymer can be improved by blending the OSC polymer with a cross-linking agent. In some examples, the OSC polymer is blended with the cross-linking agent in a solvent. In some examples, the solvent is chloroform, methyl ethyl ketone, toluene, xylene, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2,3,4-tetralin, naphthalene, chloronaphthalene, or a combination thereof. In some examples, a mixture of more than one solvent can be used.

[0150] In some examples, the at least one OSC polymer is present in an amount ranging from 1 wt% to 99 wt%, or in a range of 5 wt% to 95 wt%, or in a range of 10 wt% to 90 wt%, or in a range of 25 wt% to 85 wt%, or in a range of 50 wt% to 80 wt%. In some examples, the at least one OSC polymer is present in an amount of 1 wt%, or 2 wt%, or 3 wt%, or 5 wt%, or 10 wt%, or 15 wt%, or 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 50 wt%, or 60 wt%, or 70 wt%, or 80 wt%, or 90 wt%, or 95 wt%, or 99 wt%, or in any range bounded by any two of these endpoints.

[0151] In some examples, the at least one cross-linking agent is present in an amount ranging from 1 wt % to 99 wt %, or in a range of 5 wt % to 95 wt %, or in a range of 10 wt % to 90 wt %, or in a range of 15 wt % to 85 wt %, or in a range of 20 wt % to 80 wt %, or in a range of 25 wt % to 75 wt %, or in a range of 25 wt % to 65 wt %, or in a range of 25 wt % to 55 wt %. In some examples, the at least one cross-linking agent is present in an amount of 0.1 wt%, or 0.2 wt%, or 0.3 wt%, or 0.5 wt%, or 0.8 wt%, or 1 wt%, or 2 wt%, or 3 wt%, or 5 wt%, or 10 wt%, or 15 wt%, or 20 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt%, or 45 wt%, or 50 wt%, or 55 wt%, or 60 wt%, or 65 wt%, or 70 wt%, or 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%, or 95 wt%, or 99 wt%, or in any range bounded by any two of these endpoints. In some examples, the at least one crosslinking agent comprises a first crosslinking agent and a second crosslinking agent, the first crosslinking agent is present in an amount ranging from 30 wt % to 50 wt %; and the second crosslinking agent is present in an amount ranging from 0.5 wt % to 25 wt %.

[0152] In some examples, the at least one photoinitiator is present in an amount ranging from 0.1 wt % to 10 wt %, or in a range of 0.2 wt % to 8 wt %, or in a range of 0.3 wt % to 6 wt %, or in a range of 0.4 wt % to 5 wt %, or in a range of 0.5 wt % to 4.5 wt %, or in a range of 0.5 wt % to 4 wt %, or in a range of 0.6 wt % to 3.5 wt %, or in a range of 0.7 wt % to 3 wt %. In some examples, the at least one photoinitiator is present in an amount of 0.1 wt%, or 0.2 wt%, or 0.3 wt%, or 0.4 wt%, or 0.5 wt%, or 0.6 wt%, or 0.7 wt%, or 0.8 wt%, or 0.9 wt%, or 1 wt%, or 1.5 wt%, or 2 wt%, or 2.5 wt%, or 3 wt%, or 3.5 wt%, or 4 wt%, or 4.5 wt%, or 5 wt%, or 6 wt%, or 7 wt%, or 8 wt%, or 9 wt%, or 10 wt%, or in any range defined by any two of these endpoints.

[0153] In some examples, the at least one OSC polymer is present in an amount ranging from 1 wt% to 99 wt%; the at least one cross-linking agent is present in an amount ranging from 1 wt% to 99 wt%; and the at least one photoinitiator is present in an amount ranging from 0.1 wt% to 10 wt%. In some examples, the at least one OSC polymer is present in an amount ranging from 50 wt% to 80 wt%; and the at least one cross-linking agent is present in an amount ranging from 25 wt% to 55 wt%.

[0154] In some examples, the at least one antioxidant, lubricant, compatibilizer, leveling agent or nucleating agent can each independently be present in an amount in the following ranges: in the range of 0.05 wt % to 5 wt %, or in the range of 0.1 wt % to 4.5 wt %, or in the range of 0.2 wt % to 4 wt %, or in the range of 0.3 wt % to 3.5 wt %, or in the range of 0.4 wt % to 3 wt %, or in the range of 0.5 wt % to 2.5 wt %. In some examples, the at least one antioxidant, lubricant, compatibilizer, leveling agent or nucleating agent can each independently be present in the following amount: 0.05 wt%, or 0.1 wt%, or 0.2 wt%, or 0.3 wt%, or 0.4 wt%, or 0.5 wt%, or 0.6 wt%, or 0.7 wt%, or 0.8 wt%, or 0.9 wt%, or 1 wt%, or 1.5 wt%, or 2 wt%, or 2.5 wt%, or 3 wt%, or 3.5 wt%, or 4 wt%, or 4.5 wt%, or 5 wt%, or in any range defined by any two of these endpoints.

[0155] In some examples, the blend includes at least two of the following: an OSC polymer described herein, a crosslinker, a photoinitiator, and an additive. In some examples, the blend includes at least three of the following: an OSC polymer described herein, a crosslinker, a photoinitiator, and an additive. In some examples, the blend includes at least four of the following: an OSC polymer described herein, a crosslinker, a photoinitiator, and an additive.

[0156] OTFT device fabrication

[0157] Applications using OTFT devices require patterning of organic semiconductor materials to prevent undesirable high cut-off currents and crosstalk between adjacent devices. As mentioned above, photolithography is a common patterning technique in semiconductor device manufacturing. However, photolithography often involves harsh O2 plasma during pattern transfer or photoresist removal, as well as aggressive developing solvents, which can seriously damage the OSC layer and cause a significant decrease in the performance of the OTFT device. In other words, when conjugated organic materials are exposed to light, these materials tend to degrade, and the chemicals used for photolithography can have an adverse effect on organic thin film transistors. Therefore, it is impractical to pattern organic semiconductor materials using photolithography. In addition, currently available patternable semiconductor polymers with photosensitive side groups require time-consuming molecular design and synthesis. Due to the reduction of effective conjugation in the cross-linked backbone of these cross-linked polymers, these cross-linked polymers can also have an adverse effect on OTFT devices.

[0158] Figures 1A to 1E A conventional technique 100 for patterning an organic semiconductor blend using a photoresist is illustrated. In the first step ( Figure 1A ), depositing the blended OSC polymer film 104 on the substrate 102, and then Figure 1B In the process, a photoresist layer 106 is deposited on the film 104. Optionally, the film 104 can be thermally annealed. The photoresist deposition can be performed using methods known in the art (e.g., spin coating). For example, the photoresist is converted into a liquid form by dissolving the solid components in a solvent, the liquid form of the photoresist is poured onto the substrate, and then it is rotated at high speed on a turntable to produce the desired film. Subsequently, the resulting resist film can be subjected to a post-application baking process (i.e., soft baking or pre-baking) to dry the photoresist when removing excess solvent.

[0159] exist Figure 1C In a step of developing, the photoresist layer 106 is exposed to UV light 112 through a master pattern, referred to as a photomask 108, which is positioned at a distance from the photoresist layer 106, thereby forming a more cross-linked portion 110 of the photoresist layer 106. The effect of the exposure to UV light is to change the solubility of the photoresist in a subsequent developer solvent solution to form a pattern on top of the substrate. Prior to development, the resist layer may be subjected to a post-exposure bake. Figure 1DIn the step of etch 114, the pattern 116 of the photoresist layer is transferred into the thin film 104 by subtractive etching 114 (i.e., O2 plasma dry etching). The patterned photoresist layer 116 "resists" the etching and protects the material covered by the photoresist. When the etching is complete, the photoresist is stripped [e.g., using an organic solution or an inorganic solution and dry (plasma) stripping], leaving the desired pattern 118 etched into the thin film layer.

[0160] However, as described above, various aspects of conventional photolithography processes, such as harsh O 2 plasma during pattern transfer and aggressive photoresist developer and / or stripper solvents, can severely damage the OSC layer and result in significant degradation of device performance.

[0161] Figures 2A to 2C A patterning technique 200 of an organic semiconductor blend according to some embodiments is illustrated. In the first step ( Figure 2A ), depositing the blended OSC polymer thin film 204 on the substrate 202. Optionally, the thin film 204 can be thermally annealed. In some examples, the deposition includes at least one of spin coating, dip coating, spray coating, electrodeposition, meniscus coating, plasma deposition, and roll coating, curtain coating, and extrusion coating.

[0162] The film 204 is prepared as the above-mentioned polymer blend comprising the following substances: at least one organic semiconductor (OSC) polymer, at least one cross-linking agent, at least one photoinitiator, and optionally, at least one additive, wherein the at least one OSC polymer is a diketopyrrolopyrrole-fused thiophene polymer material, wherein the fused thiophene is beta-substituted, and wherein the cross-linking agent includes at least one of the following: acrylates, epoxides, oxetanes, alkenes, alkynes, azides, thiols, allyloxysilanes, phenols, anhydrides, amines, cyanates, isocyanates, silyl hydrides, cinnamates, coumarins, fluorosulfates, silyl ethers or combinations thereof.

[0163] In some examples, blending includes: dissolving the at least one OSC polymer in a first organic solvent to form a first solution; dissolving the at least one cross-linking agent in a second organic solvent to form a second solution; and dissolving the at least one photoinitiator in a third organic solvent to form a third solution; and combining the first solution, the second solution, and the third solution in any suitable order to form a polymer blend. In some examples, the first solution, the second solution, and the third solution may be combined simultaneously. In some examples, the at least one OSC polymer, the at least one cross-linking agent, and the at least one photoinitiator may be prepared together in a single organic solvent. The weight composition of each component in the polymer blend is provided as described above.

[0164] In some examples, after the blended OSC polymer film is deposited over the substrate and before exposing the film to UV light, the film can be heated at a temperature in the range of 50° C. to 200° C. for a time in the range of 10 seconds to 10 minutes to remove excess solvent.

[0165] In the second step ( Figure 2B ), exposing the film 204 to UV light 208 through a photomask 206 to form a more cross-linked portion 210 of the film 204. In some examples, the exposing includes exposing the film to an energy of 10 mJ / cm 2 Up to 600mJ / cm 2 In the range (e.g. 400mJ / cm 2 ) of UV light for a period of time ranging from 1 second to 60 seconds (e.g., 10 seconds). In some examples, the energy of the UV light can be 300 mJ / cm 2 Up to 500mJ / cm 2 The operation time can be in the range of 5 seconds to 20 seconds. Figures 1A to 1E The function of the photoresist described above, is to change the solubility of the film in the subsequent developer solvent solution as a result of exposure to UV light to form a pattern on top of the substrate.

[0166] exist Figure 2C In the step of, when the light exposure is completed, the portion of the film 204 that is not exposed to the UV light 208 is peeled off using a predetermined solvent 212, thereby leaving the desired pattern 214 in the film layer. In other words, the more highly cross-linked portion 210 is developed in a solvent to remove the unpatterned area of ​​the film 204. In some examples, the development includes: exposing the unpatterned area of ​​the film to a solvent for a time ranging from 10 seconds to 10 minutes, and the solvent includes: chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,2,4-trichlorobenzene, dioxane, p-xylene, m-xylene, toluene, cyclopentanone, cyclohexanone, methyl lactate, 2-butanone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, anisole, 1,3,5-trimethylbenzene, decalin, butylbenzene, cyclooctane, 1,2,3,4-tetralin, chloroform or a combination thereof. In some examples, the developer solution includes chlorobenzene, p-xylene, dioxane, or a combination thereof.

[0167] In some examples, after developing the patterned film in a solvent to remove unpatterned areas of the film, the film may be heated at a temperature in a range of 50° C. to 200° C. for a time in a range of 10 seconds to 30 minutes.

[0168] Subsequently, the OTFT device can be completed by the following steps: forming a gate electrode on the substrate; forming a gate dielectric layer on the substrate; forming a patterned source electrode and a drain electrode on the gate dielectric layer; forming an organic semiconductor active layer on the gate dielectric layer; and forming an insulator layer on the patterned organic semiconductor active layer. Figure 3 and 4 ).

[0169] Example

[0170] The embodiments described herein are further illustrated by the following examples.

[0171] Example 1

[0172] Example 1 Based on Figure 3 The OFET structure shown. Figure 5-6D Illustrated are the I and II of the test OFET devices prepared with the formulations shown in Table 3 below. d -V g Curve. The on-off ratio is about 10 4 , and the turn-on voltage is in the range of 0V to 10V. Figure 5 The corresponding data illustrate that the base formulation has high UV patterning efficiency and satisfactory device performance based thereon. Fig. 6A and 6B The importance of the crosslinker C5 is demonstrated; a higher proportion of C5 in the formulation improves the "on" current. Figure 6C and 6D The importance of the photoinitiator is illustrated; a higher proportion of photoinitiator in the formulation improves the "on" current.

[0173]

[0174]

[0175] Table 3

[0176] Example 2

[0177] Example 2 Based on Figure 3 The OFET structure shown. Figure 7A-8 Illustrated are the I and II of the test OFET devices prepared with the formulations shown in Table 4 below. d -V g Curve. The on-off ratio is about 10 4 , and the turn-on voltage is in the range of 0V to 5V. In addition, the “on” current (V g =-15V) is between 400nA and 500nA. Figure 7B Preparations and Fig.7DThe difference between the preparations lies in the solvent used for dissolution, in which Figure 7B The concentration of chlorobenzene in the solvent (20 mg / ml) is Fig.7D The concentration of chlorobenzene in the solvent is twice that of 10 mg / ml. Fig. 7A and 7B And the corresponding data illustrate the robustness of the UV patterning formulation with respect to the purity of the vinyl terminated crosslinker 1 (per Table 4). Fig. 7A and 7D The corresponding data illustrate the importance of solution concentration. The device performance, especially the "on" current, is extremely sensitive to the concentration of the spin-coating solution. Fig. 7A , 7C and 8 and the corresponding data illustrate the high efficiency of the UV patterning formulation. As the amount of vinyl terminated crosslinker 1 is reduced, the "on" current remains high.

[0178]

[0179]

[0180] Table 4

[0181] Example 3

[0182] Example 3 Based on Figure 4 The OFET structure shown. Figures 9A-9C Illustrated are the I and II of the test OFET devices prepared with the formulations shown in Table 5 below. d -V g Curve. The on-off ratio is about 10 3 , and the turn-on voltage is in the range of 6V to 16V. In addition, the “on” current (V g =-15V) is between 800nA and 850nA. Fig. 9A and 9B and corresponding data illustrate functional OFET devices based on cation-based UV-patternable OSC blends. Fig. 9C This shows that photoinitiator is not a necessary component in UV patterning formulations.

[0183]

[0184] Table 5

[0185] Example 4

[0186] Example 4 Based on Figure 4 The OFET structure shown. Figures 10A-10D Illustrated are the I of the test OFET devices prepared with the formulations shown in Table 6 below. d -V gCurve. The on-off ratio is about 10 2 , and the turn-on voltage is in the range of 14V to 17V. In addition, the “on” current (V g =-15V) is between 2.37μA and 3.33μA. As mentioned above, Figures 10A to 10D The corresponding data show that the method disclosed in this article can also be applied to Figure 4 OFET device with the structure shown.

[0187]

[0188] Table 6

[0189] Example 5

[0190] General fabrication procedure of OTFT devices

[0191] In some embodiments, a bottom-gate bottom-contact OTFT device can be formed as follows: a gold (Au) or silver (Ag) gate electrode is patterned onto a substrate, followed by spin coating of a dielectric onto the substrate and processing to obtain a gate dielectric layer. After patterning the Au or Ag source and drain electrodes, the OSC layer can be formed to a thickness of 10 nm to 200 nm by the patterning materials and methods described herein. Finally, an insulator layer is provided. Figure 3 An example of a formed OTFT device is shown.

[0192] Example 6

[0193] Figures 11A to 11D OSC polymer blends are exemplified ( Fig.11A and 11B ) and OSC polymer / crosslinker blends ( Fig. 11C and 11D ) of a confocal laser scanning microscope (CLSM) image. Specifically, Fig.11A and 11B The OSC polymer blend layer before and after development is shown, respectively. Fig. 11C and 11D The OSC polymer / cross-linker blend layer is shown before and after development, respectively.

[0194] Compared to UV-curable OSC polymer blends with each polymer as the doping part, the OSC polymer / cross-linker blends disclosed herein have significantly smoother film surfaces and significantly improved phase separation, resulting in superior and more stable patterning effects and OFET performance.

[0195] Thus, as presented herein, disclosed are improved UV-patternable organic semiconductor / crosslinker polymer blends and their use for OSC layers of organic thin film transistors.

[0196] The advantages of UV-patternable organic semiconductor / crosslinker polymer blends include: (1) Compared with UV-curable OSC polymer blends that use each polymer as a doping part ( Fig.11A and 11B ), the OSC polymer / crosslinker blend disclosed herein ( Fig. 11C and 11D ) has a significantly smoother film surface and significantly improved phase separation, resulting in a more excellent and more stable patterning effect and OFET performance; (2) compared with traditional photolithography ( Figures 1A-1E ), the disclosed patterning method ( Figures 2A-2C ) are less complex and do not require photoresists or aggressive developing solvents, resulting in less damage to the OSC material and better OFET device performance; (3) compared to conventional inkjet printing techniques, the disclosed patterning method provides better resolution (up to several microns) with higher precision and efficiency; (4) compared to UV-curable OSC polymer blends, which require challenging synthetic techniques to incorporate UV-curable functionality into the OSC polymer, the disclosed OSC polymer / cross-linker blends avoid time-consuming synthetic development; and (5) the disclosed UV patterning method is either based on free radical photoinitiators or cationic photoinitiators and can be performed in air, which allows for low-cost OFET devices based on patterned OSC films.

[0197] As used herein, the terms "approximately," "about," "substantially," and similar terms are intended to have a broad meaning consistent with the common and acceptable usage by those of ordinary skill in the art to which the subject matter of the present disclosure relates. Those skilled in the art who review the present disclosure should understand that these terms are intended to allow for a description of certain features described and claimed without limiting the scope of those features to the precise numerical ranges provided. Accordingly, these terms should be interpreted as indicating that insubstantial or minor modifications or alterations of the subject matter described and claimed are considered to be within the scope of the present invention as described in the appended claims.

[0198] As used herein, "optional" or "optionally" etc. are intended to indicate that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not occur. Unless otherwise specified, the indefinite article "a" or "an" and the corresponding definite article "the" used herein mean at least one, or one or more.

[0199] The element positions (e.g., "top", "bottom", "above", "below", etc.) mentioned herein are only used to describe the orientation of the various elements in the drawings. It should be understood that the orientation of the various elements may be different according to other exemplary embodiments, and such changes are intended to be included within the scope of the present disclosure.

[0200] For substantially any plural and / or singular terms used herein, those skilled in the art may appropriately convert from the plural to the singular and / or from the singular to the plural as appropriate as applicable to the context and / or application. For clarity, various singular / plural arrangements may be explicitly described herein.

[0201] It will be apparent to those skilled in the art that various modifications and variations may be made without departing from the spirit or scope of the subject matter claimed. Therefore, the subject matter claimed is not limited by any content other than the attached claims and their equivalents.

Claims

1. A UV-patternable polymer blend as a semiconductor layer in an organic thin film transistor, comprising: at least one organic semiconductor (OSC) polymer and at least one cross-linking agent, in, The at least one OSC polymer is a diketopyrrolopyrrole-fused thiophene polymeric material, wherein the fused thiophene is beta-substituted, and Wherein, the cross-linking agent comprises at least one of the following: epoxide, alkene, thiol or a combination thereof, Wherein, the at least one OSC polymer comprises a repeating unit of Formula 1 or Formula 2, or a salt, isomer or analog thereof: Among them, in formula 1 and formula 2: m is an integer greater than or equal to 1; n is 0, 1, or 2; R1, R2, R3, R4, R5, R6, R7 and R8 may independently be hydrogen, substituted or unsubstituted C4 or higher alkyl, substituted or unsubstituted C4 or higher alkenyl, substituted or unsubstituted C4 or higher alkynyl, or C5 or higher cycloalkyl; a, b, c and d are independently an integer greater than or equal to 3; e and f are integers greater than or equal to zero; X and Y are independently a covalent bond, an optionally substituted aryl, an optionally substituted heteroaryl, an optionally substituted fused aryl or fused heteroaryl, an alkyne, or an alkene; and A and B can be independently any one of S or O, provided that: i. at least one of R1 or R2; one of R3 or R4; one of R5 or R6; and one of R7 or R8 is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, or a cycloalkyl; ii. if any one of R1, R2, R3 or R4 is hydrogen, then R5, R6, R7 or R8 is not hydrogen; iii. if any one of R5, R6, R7 or R8 is hydrogen, then R1, R2, R3 or R4 is not hydrogen; iv.e and f cannot be 0 at the same time; and v. If either e or f is 0, then c and d are independently integers greater than or equal to 5.

2. The polymer blend of claim 1, wherein: The at least one OSC polymer is present in an amount ranging from 1 wt% to 99 wt%; and The at least one cross-linking agent is present in an amount ranging from 1 wt % to 99 wt %.

3. The polymer blend of claim 2, wherein: The at least one OSC polymer is present in an amount ranging from 50 wt% to 80 wt%; and The at least one cross-linking agent is present in an amount ranging from 25 wt % to 55 wt %.

4. The polymer blend of claim 2, wherein: The at least one cross-linking agent includes a first cross-linking agent and a second cross-linking agent, the first cross-linking agent is present in an amount ranging from 30 wt % to 50 wt %; and the second cross-linking agent is present in an amount ranging from 0.5 wt % to 25 wt %.

5. The polymer blend of claim 1, further comprising: At least one photoinitiator, wherein the at least one photoinitiator is present in an amount ranging from 0.1 wt % to 10 wt %.

6. The polymer blend according to claim 5, wherein The at least one photoinitiator is present in an amount ranging from 0.1 wt % to 5.0 wt %.

7. The polymer blend of claim 2, further comprising: At least one of an antioxidant, a lubricant, a compatibilizer, a leveling agent, or a nucleating agent is present in an amount ranging from 0.05 wt % to 5 wt %.

8. The polymer blend according to any one of claims 1 to 7, wherein: The at least one cross-linking agent comprises at least one of the following: (A) a polymer selected from the group consisting of: Where n is an integer greater than or equal to 2, or (B) a small molecule selected from the group consisting of: or, (C)A combination thereof.

9. The polymer blend of claim 5, wherein: The at least one photoinitiator includes at least one free radical photoinitiator.

10. The polymer blend of claim 5, wherein: The at least one photoinitiator comprises at least one cationic photoinitiator.

11. The polymer blend of claim 5, wherein: The at least one photoinitiator comprises: 1-hydroxy-cyclohexyl-phenyl-ketone (184); 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (369); diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO); 2-isopropylthioxanthone (ITX); 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (HRC URE-OXE01); 2,2-dimethoxy-1,2-diphenylethan-1-one (BDK); benzoyl peroxide (BPO); hydroxyacetophenone (HAP); 2-hydroxy-2-methylphenylpropionone (1173); 2-methyl-4'-(methylthio)-2-morpholinopropionone (907); 2-benzyl-2-(dimethylamino)-4'-morpholinopropylphenyl ketone (IHT-PI 910); ethyl 4-(dimethylamino)benzoate (EDB); methyl o-benzoylbenzoate (OMBB); bis-(2,6-dimethoxybenzoyl)-phenylphosphine oxide (BAPO); 4-benzoyl-4'-methyldiphenyl sulfide (BMS); benzophenone (BP); 1-chloro-4-propoxythioxanthone (CPTX); chlorothioxanthone (CTX); 2,2-diethoxyacetophenone (DEAP); diethylthioxanthone Deoxynthone (DETX); 2-dimethylaminoethyl benzoate (DMB); 2,2-dimethoxy-2-phenylacetophenone (DMPA); 2-ethylanthraquinone (2-EA); ethyl p-N,N-dimethyl-dimethylaminobenzoate (EDAB); 2-ethylhexyl dimethylaminobenzoate (EHA); 4,4-bis-(diethylamino)-benzophenone (EMK); methylbenzophenone (MBF); 4-methylbenzophenone (MBP); Michler's ketone (MK); 2-methyl-1-[4(methylthio)phenyl]-2-morpholinopropanone (1) (MMMP); 4-phenylbenzophenone (PBZ); 2,4,6-trimethyl-benzoyl-ethoxyphenylphosphine oxide (TEPO); tert-butyloxycarbonylmethoxyphenyldiphenylsulfonium trifluoromethanesulfonate; N-hydroxynaphthaleneimide trifluoromethanesulfonate; N-hydroxy-5-norbornene-2,3-dicarboximide Fluoro-1-butanesulfonate; 2-(4-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine; (4-methylthiophenyl)methylphenylsulfonium trifluoromethanesulfonate; triarylsulfonium hexafluoroantimonate mixed at 50% by weight in propylene carbonate; triarylsulfonium hexafluorophosphate mixed at 50% by weight in propylene carbonate; aryl diazonium salt; diaryl iodonium salt; triaryl sulfonium salt; aryl ferrocenium salt; or a combination thereof.

12. The polymer blend of claim 5, wherein: The at least one photoinitiator comprises: bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate; bis(4-tert-butylphenyl)iodonium p-toluenesulfonate; bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; (4-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; diphenyliodonium hexafluorophosphate; diphenyliodonium nitrate; diphenyliodonium p-toluenesulfonate; diphenyliodonium trifluoromethanesulfonate; (4-fluorophenyl)diphenylsulfonium trifluoromethanesulfonate; (4-iodonium trifluoromethanesulfonate; (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate; 1-naphthyldiphenylsulfonium trifluoromethanesulfonate; (4-phenoxyphenyl)diphenylsulfonium trifluoromethanesulfonate; (4-phenylthiophenyl)diphenylsulfonium trifluoromethanesulfonate; triphenylsulfonium perfluoro-1-butanesulfonate; triphenylsulfonium trifluoromethanesulfonate; tri(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate; tri(4-tert-butylphenyl)sulfonium trifluoromethanesulfonate; or a combination thereof.

13. The polymer blend of claim 1, wherein: The at least one OSC polymer comprises a repeating unit of Formula 3 or Formula 4, or a salt, isomer or analog thereof:

14. A UV patternable polymer blend as a semiconductor layer in an organic thin film transistor, consisting of: at least one organic semiconductor (OSC) polymer and at least one cross-linking agent, wherein the at least one OSC polymer is a diketopyrrolopyrrole-fused thiophene polymeric material, wherein the fused thiophene is beta-substituted, Wherein, the cross-linking agent comprises at least one of the following: epoxide, alkene, thiol and a combination thereof, Wherein, the at least one OSC polymer comprises a repeating unit of Formula 1 or Formula 2, or a salt, isomer or analog thereof: Among them, in formula 1 and formula 2: m is an integer greater than or equal to 1; n is 0, 1 or 2; R1, R2, R3, R4, R5, R6, R7 and R8 may independently be hydrogen, substituted or unsubstituted C4 or higher alkyl, substituted or unsubstituted C4 or higher alkenyl, substituted or unsubstituted C4 or higher alkynyl, or C5 or higher cycloalkyl; a, b, c and d are independently an integer greater than or equal to 3; e and f are integers greater than or equal to zero; X and Y are independently a covalent bond, an optionally substituted aryl, an optionally substituted heteroaryl, an optionally substituted fused aryl or fused heteroaryl, an alkyne, or an alkene; and A and B can be independently any one of S or O, provided that: i. at least one of R1 or R2; one of R3 or R4; one of R5 or R6; and one of R7 or R8 is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, or a cycloalkyl; ii. if any one of R1, R2, R3 or R4 is hydrogen, then R5, R6, R7 or R8 is not hydrogen; iii. if any one of R5, R6, R7 or R8 is hydrogen, then R1, R2, R3 or R4 is not hydrogen; iv.e and f cannot be 0 at the same time; and v. If either e or f is 0, then c and d are independently integers greater than or equal to 5.

15. The polymer blend of claim 14, wherein The at least one cross-linking agent comprises at least one of the following: (A) a polymer selected from the group consisting of: Where n is an integer greater than or equal to 2, or (B) a small molecule selected from the group consisting of: or, (C)A combination thereof.

16. The polymer blend of claim 14, further comprising at least one photoinitiator.

17. The polymer blend of claim 16, wherein: The at least one photoinitiator comprises: 1-hydroxy-cyclohexyl-phenyl-ketone (184); 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (369); diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO); 2-isopropylthioxanthone (ITX); 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (HRC URE-OXE01); 2,2-dimethoxy-1,2-diphenylethan-1-one (BDK); benzoyl peroxide (BPO); hydroxyacetophenone (HAP); 2-hydroxy-2-methylphenylpropionone (1173); 2-methyl-4'-(methylthio)-2-morpholinopropionone (907); 2-benzyl-2-(dimethylamino)-4'-morpholinopropylphenyl ketone (IHT-PI 910); ethyl 4-(dimethylamino)benzoate (EDB); methyl o-benzoylbenzoate (OMBB); bis-(2,6-dimethoxybenzoyl)-phenylphosphine oxide (BAPO); 4-benzoyl-4'-methyldiphenyl sulfide (BMS); benzophenone (BP); 1-chloro-4-propoxythioxanthone (CPTX); chlorothioxanthone (CTX); 2,2-diethoxyacetophenone (DEAP); diethylthioxanthone Deoxynthone (DETX); 2-dimethylaminoethyl benzoate (DMB); 2,2-dimethoxy-2-phenylacetophenone (DMPA); 2-ethylanthraquinone (2-EA); ethyl p-N,N-dimethyl-dimethylaminobenzoate (EDAB); 2-ethylhexyl dimethylaminobenzoate (EHA); 4,4-bis-(diethylamino)-benzophenone (EMK); methylbenzophenone (MBF); 4-methylbenzophenone (MBP); Michler's ketone (MK); 2-methyl-1-[4(methylthio)phenyl]-2-morpholinopropanone (1) (MMMP); 4-phenylbenzophenone (PBZ); 2,4,6-trimethyl-benzoyl-ethoxyphenylphosphine oxide (TEPO); tert-butyloxycarbonylmethoxyphenyldiphenylsulfonium trifluoromethanesulfonate; N-hydroxynaphthaleneimide trifluoromethanesulfonate; N-hydroxy-5-norbornene-2,3-dicarboximide Fluoro-1-butanesulfonate; 2-(4-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine; (4-methylthiophenyl)methylphenylsulfonium trifluoromethanesulfonate; triarylsulfonium hexafluoroantimonate mixed at 50% by weight in propylene carbonate; triarylsulfonium hexafluorophosphate mixed at 50% by weight in propylene carbonate; aryl diazonium salt; diaryl iodonium salt; triaryl sulfonium salt; aryl ferrocenium salt; or a combination thereof.

18. The polymer blend of claim 16, wherein: The at least one photoinitiator comprises: bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate; bis(4-tert-butylphenyl)iodonium p-toluenesulfonate; bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; (4-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; diphenyliodonium hexafluorophosphate; diphenyliodonium nitrate; diphenyliodonium p-toluenesulfonate; diphenyliodonium trifluoromethanesulfonate; (4-fluorophenyl)diphenylsulfonium trifluoromethanesulfonate; (4-iodonium phenyl) diphenylsulfonium trifluoromethanesulfonate; (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate; 1-naphthyl diphenylsulfonium trifluoromethanesulfonate; (4-phenoxyphenyl) diphenylsulfonium trifluoromethanesulfonate; (4-phenylthiophenyl) diphenylsulfonium trifluoromethanesulfonate; triphenylsulfonium perfluoro-1-butanesulfonate; triphenylsulfonium trifluoromethanesulfonate; tri(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate; tri(4-tert-butylphenyl)sulfonium trifluoromethanesulfonate; or a combination thereof.

19. The polymer blend of claim 14, wherein: The at least one OSC polymer comprises a repeating unit of Formula 3 or Formula 4, or a salt, isomer or analog thereof:

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