Photo-patternable hybrid organic semiconductor polymers for organic thin film transistors

Abstract

A polymer blend comprising at least one organic semiconductor (OSC) polymer such that: the at least one OSC polymer is a diketopyrrolopyrrole-fused thiophene polymeric material, the fused thiophene is beta-substituted, the at least one OSC polymer has a first portion and a second portion, and at least one of the first portion or the second portion comprises at least one UV-curable side chain.

Description

background 1. Technical Field

[0002] The present disclosure relates to photo-patternable heterotype organic semiconducting polymers as semiconducting 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 a critical component in OTFTs, significantly impacting device performance.

[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 developer solvents, which can severely damage the OSC layer and significantly degrade device performance.

[0006] The present disclosure proposes improved photo-patternable heterotype organic semiconducting polymers 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, wherein the at least one OSC polymer is a diketopyrrolopyrrole-fused thiophene polymeric material, wherein the fused thiophene is beta-substituted, and wherein the at least one OSC polymer comprises a first portion and a second portion, wherein at least one of the first portion or the second portion comprises at least one UV-curable side chain.

[0008] In one aspect that may be combined with any other aspect or embodiment, the at least one UV-curable side chain 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 statin, a cinnamate, a coumarin, a fluorosulfate, a silyl ether, or a combination thereof.

[0009] In one aspect that may be combined with any other aspect or embodiment, only the first portion comprises at least one UV-curable side chain.

[0010] In one aspect that may be combined with any other aspect or embodiment, the first portion and the second portion each comprise at least one UV-curable side chain.

[0011] In one aspect that may be combined with any other aspect or embodiment, the polymer blend further comprises: at least one cross-linking agent, wherein the at least one cross-linking agent 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 statin, a cinnamate, a coumarin, a fluorosulfate, a silyl ether, or a combination thereof.

[0012] 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%.

[0013] 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%.

[0014] 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%.

[0015] In one aspect that may be combined with any other aspect or embodiment, the at least one OSC polymer comprises repeating units of Formula 1 or Formula 2, or a salt, isomer, or analog thereof:

[0016]

[0017]

[0018] 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 an integer greater than or equal to 0; 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 both be 0; (v) if either 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.

[0019] In one aspect that may be combined with any other aspect or embodiment, for the first moiety, R5 and R7 are hydrogen, and R6 and R8 are substituted or unsubstituted C4 or higher alkenyl.

[0020] In one aspect that may be combined with any other aspect or embodiment, for the first and second moieties, R5 and R7 are hydrogen, and R6 and R8 are substituted or unsubstituted C4 or higher alkenyl.

[0021] In one aspect that may be combined with any other aspect or embodiment, at least one of R5, R6, R7, and R8 comprises 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 statin, a cinnamate, a coumarin, a fluorosulfate, a silyl ether, or a combination thereof.

[0022] In one aspect that may be combined with any other aspect or embodiment, at least one of R1, R2, R3, and R4 comprises 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 statin, a cinnamate, a coumarin, a fluorosulfate, a silyl ether, or a combination thereof.

[0023] In one aspect that may be combined with any other aspect or embodiment, the at least one UV-curable side chain comprises at least one of: (A) a polymer selected from:

[0024]

[0025] wherein n is an integer greater than or equal to 2, or (B) is a small molecule selected from the following:

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034] or, (C) a combination thereof.

[0035] 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.

[0036] In one aspect that may be combined with any other aspect or embodiment, the at least one photoinitiator comprises at least one cationic photoinitiator.

[0037] 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-benzoyloxime) (HRCURE-OXE01); 2,2-dimethoxy-1,2-diphenylethan-1-one (BDK); benzoyl peroxide (BPO); hydroxyacetophenone (HAP); 2-hydroxy-2-methylphenylacetone (1173). ; 2-Methyl-4'-(methylthio)-2-morpholinopropiophenone (907); 2-Benzyl-2-(dimethylamino)-4'-morpholinopropylphenyl ketone (IHT-PI910); 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 (DMB); 2,2-dimethoxybenzoyl 2-Methyl-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-trimethylbenzoylethoxyphenylphosphine oxide (TEPO); bis(4-tert-butylphenyl)iodonium perfluorobutanesulfonate; bis(4-tert-butylphenyl)iodonium p-methyl Benzenesulfonate; bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; tert-Butoxycarbonylmethoxyphenyldiphenylsulfonium trifluoromethanesulfonate; (4-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; diphenyliodonium hexafluorophosphate; diphenyliodonium 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-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.

[0038] In some embodiments, a polymer blend comprises: at least one organic semiconductor (OSC) polymer, wherein the at least one OSC polymer comprises a structure of Formula 7:

[0039]

[0040] Wherein, in Formula 7: Acceptor 1 and Acceptor 2 are each an electron withdrawing group; Donor 1 and Donor 2 are electron donating groups; a and b are independently integers greater than or equal to 1; 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, wherein: (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, substituted or unsubstituted (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) one of R1 or R2 and one of R3 or R4 are independently attached to Acceptor 1 and Acceptor 2; (v) one of R5 or R6 and one of R7 or R8 are independently attached to Donor 1 and Donor 2; and (vi) the molecular weight of the at least one OSC polymer is greater than 10,000.

[0041] In one aspect that may be combined with any other aspect or embodiment, Receptor 1 and Receptor 2 are independently selected from the group comprising:

[0042]

[0043]

[0044] A and B may independently be either S or O, and T is a connecting terminal group of at least one of donor 1 or donor 2.

[0045] In one aspect that may be combined with any other aspect or embodiment, Donor 1 and Donor 2 are independently selected from the group consisting of thiophene, benzene, fused thiophene, or combinations thereof.

[0046] In one aspect that may be combined with any other aspect or embodiment, at least one of Acceptor 1, Acceptor 2, Donor 1, or Donor 2 comprises at least one UV-curable side chain.

[0047] In one aspect that may be combined with any other aspect or embodiment, the at least one UV-curable side chain 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 statin, a cinnamate, a coumarin, a fluorosulfate, a silyl ether, or a combination thereof.

[0048] In one aspect that may be combined with any other aspect or embodiment, at least one of R5, R6, R7, and R8 comprises 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 statin, a cinnamate, a coumarin, a fluorosulfate, a silyl ether, or a combination thereof.

[0049] In one aspect that may be combined with any other aspect or embodiment, at least one of R1, R2, R3, and R4 comprises 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 statin, a cinnamate, a coumarin, a fluorosulfate, a silyl ether, or a combination thereof.

[0050] In one aspect that may be combined with any other aspect or embodiment, the at least one UV-curable side chain comprises at least one of: (A) a polymer selected from:

[0051]

[0052] wherein n is an integer greater than or equal to 2, or (B) is a small molecule selected from the following:

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060] or, (C) a combination thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] The present disclosure can be more fully understood through the following detailed description in conjunction with the accompanying drawings, in which:

[0062] Figures 1A to 1E A conventional technique for patterning an organic semiconductor blend using a photoresist is illustrated.

[0063] Figures 2A to 2C Patterning techniques for organic semiconductor blends according to some embodiments are illustrated.

[0064] Figure 3 An exemplary OTFT device according to some embodiments is illustrated.

[0065] Figure 4 An exemplary OTFT device according to some embodiments is illustrated.

[0066] Figure 5A and 5B Photopatterning of hetero-OSC polymers using chlorobenzene for dissolution and washing according to some embodiments is illustrated. DETAILED DESCRIPTION

[0067] The exemplary embodiments illustrated in the accompanying drawings will now be described in detail. Whenever possible, the same reference numerals will be used throughout the drawings to represent the same or similar parts. The components in the drawings are not necessarily drawn to scale, with emphasis instead being placed on illustrating the principles of the exemplary embodiments. It should be understood that this application is not limited to the details or methodologies set forth in the specification or illustrated in the drawings. It should also be understood that the terminology used is for descriptive purposes only and should not be considered limiting.

[0068] 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 the various conditions and parameters are common in the art and will be apparent to those skilled in the art and fall within the spirit and scope of the present disclosure.

[0069] definition

[0070] The term "alkyl" refers to a monovalent branched or unbranched saturated hydrocarbon chain radical having from 1 to 40 carbon atoms. This term is exemplified by groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, or tetradecyl. Alkyl groups can be substituted or unsubstituted.

[0071] 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, arylalkyl, aldehyde, cycloalkyl, cycloalkenyl, acyl, acylamino, acyl halide, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxyl, carboxylalkyl, 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, carboxylalkyl, 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 1-10 independently selected from oxygen, sulfur and NR a The alkyl group as defined above is disconnected from the atom of a is selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl and heterocyclic. Optionally, all substituents may be replaced by alkyl, alkoxy, halogen, CF3, amino, substituted amino, cyano or -S(O) n R SO Substituted, 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 alkylhydroxy group, wherein any hydrogen atom in the alkyl group is replaced by a hydroxy group.

[0072] The term "alkyl" as defined herein also includes cycloalkyl. The term "cycloalkyl" as used herein is a non-aromatic carbon-based ring (i.e., carbocycle) with a monocycle or multiple condensed rings consisting of at least three carbon atoms (in some embodiments, 3 to 20 carbon atoms). Monocyclic cycloalkyl examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc. The cycloalkyl examples of multiple rings include, but are not limited to, adamantyl, bicyclo [2.2.1] heptane, 1,3,3- trimethylbicyclo [2.2.1] hept-2-yl, (2,3,3- trimethylbicyclo [2.2.1] hept-2-yl), or a carbocyclic group fused to an aryl group, such as 1,2- dihydroindane, 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.

[0073] The term "unsubstituted alkyl" is defined herein as an alkyl group consisting solely of carbon and hydrogen.

[0074] 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.

[0075] As used herein, the term "aryl" is any carbon-based aromatic group (i.e., aromatic carbocycle), for example, a carbon-based aromatic group having a single ring (e.g., phenyl) or multiple rings (e.g., biphenyl) or multiple condensed rings (fused rings) (e.g., naphthyl or anthracenyl). These aryl groups may include, but are not limited to, benzene, naphthalene, phenyl, and the like.

[0076] The term "aryl" also includes "heteroaryl", which means a radical derived from an aromatic ring radical having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 carbon atoms and 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 radical is an aromatic ring consisting of at least three carbon atoms and containing at least one heteroatom in the aryl ring. Such heteroaryl radicals may have a single ring (e.g., pyridyl or furyl) or multiple condensed rings (e.g., indolizinyl, benzothiazolyl or benzothienyl). Examples of heteroaryl groups include, but are not limited to, [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.

[0077] Unless the definition of heteroaryl substituent 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, carboxylalkyl, arylthio, heteroarylthio, heterocyclothio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy, 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, carboxylalkyl, 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.

[0078] Aryl groups may be substituted or unsubstituted. Unless otherwise limited in the definition of an 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, hydroxy, keto, thiocarbonyl, carboxyl, carboxylalkyl, 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, carboxylalkyl, 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 from 3 to 30 carbon atoms.

[0079] As used herein, the term "aralkyl" refers to an aryl group having an alkyl or alkylene group, as defined herein, covalently bonded to an aryl group. An example of an aralkyl group is benzyl. An "optionally substituted aralkyl" refers to an optionally substituted aryl group covalently bonded to an optionally substituted alkyl or alkylene group. Examples of such aralkyl groups include benzyl, phenethyl, 3-(4-methoxyphenyl)propyl, and the like.

[0080] The term "heteroaralkyl" refers to a heteroaryl group covalently linked to an alkylene group, wherein heteroaryl and alkylene are as defined herein. "Optionally substituted heteroaralkyl" refers to an optionally substituted heteroaryl group covalently linked to an optionally substituted alkylene group. Examples of such heteroaralkyl groups include 3-pyridylmethyl, quinolin-8-ylethyl, 4-methoxythiazol-2-ylpropyl, and the like.

[0081] 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, and the like. When an alkenyl group is attached to nitrogen, the double bond cannot be located alpha to the nitrogen.

[0082] 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, heterocyclothio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy, 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 with 1, 2 or 3 substituents selected from the group consisting of alkyl, carboxyl, carboxylalkyl, 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.

[0083] The term "cycloalkenyl" refers to a carbocyclic group of 3 to 20 carbon atoms having a single ring or multiple condensed rings and at least one double bond in the ring structure.

[0084] The term "alkynyl" refers to a monovalent radical of an unsaturated hydrocarbon 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 one (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 an alkynyl group is attached to a nitrogen atom, the triple bond cannot be located alpha to the nitrogen atom.

[0085] 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, heterocyclothio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy, 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 with 1, 2 or 3 substituents selected from the group consisting of alkyl, carboxyl, carboxylalkyl, 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.

[0086] 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 to 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.

[0087] 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, 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 also be optionally substituted by 1, 2 or 3 substituents selected from the group consisting of alkyl, carboxyl, carboxylalkyl, 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 1-20 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 groups, or a group selected from carbonyl, carboxyl ester, carboxyl amide and sulfonyl; or (3) an alkylene group as defined above which has 1, 2, 3, 4 or 5 substituents as defined above and is 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.

[0088] The term "alkoxy" refers to the group R-O-, where R is optionally substituted alkyl or optionally substituted cycloalkyl, or R is the group -Y-Z, where Y is optionally substituted alkylene and Z is optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted cycloalkenyl, where alkyl, alkenyl, alkynyl, cycloalkyl, and cycloalkenyl are as defined herein. Typical alkoxy groups are optionally substituted alkyl-O-, including, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, n-hexoxy, 1,2-dimethylbutoxy, trifluoromethoxy, and the like.

[0089] The term "alkylthio" refers to a group R S –S–, where R S As defined for alkoxy.

[0090] The term "aminocarbonyl" refers to the group -C(O)NR N R N , where each R N are independently hydrogen, alkyl, aryl, heteroaryl, heterocyclic, 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 be optionally substituted by 1-3 substituents selected from the following: 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.

[0091] 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 limited by the definition, all substituents may be optionally substituted by 1-3 substituents selected from the following: 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.

[0092] 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, carboxylalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano and -S(O) n R SO Substituted, where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2.

[0093] The term "aryloxy" refers to an aryl-O- group wherein aryl is as defined above and includes optionally substituted aryl groups as also defined above.

[0094] The term "heteroaryloxy" refers to a heteroaryl-O- group.

[0095] The term "amino" refers to a -NH2 group.

[0096] 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 (eg, 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 be optionally substituted by 1 to 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.

[0097] The term "carboxyl" refers to a -C(O)OH group. The term "carboxylalkyl" refers to a -C(O)O-alkyl or -C(O)O-cycloalkyl group, 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 Substituted, where R SO is alkyl, aryl or heteroaryl, and n is 0, 1 or 2.

[0098] 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, carboxylalkyl, arylthio, heteroarylthio, heterocyclothio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy, 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 with 1, 2 or 3 substituents selected from the group consisting of alkyl, carboxyl, carboxylalkyl, 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.

[0099] 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 and double or triple bonds, and can also contain lone pairs of electrons, free radicals or carbon cations. Conjugated cyclic groups can include aromatic and non-aromatic groups simultaneously, and can include polycyclic or heterocyclic groups, such as diketopyrrolopyrroles. Ideally, the conjugated groups are combined in a manner such that the conjugation between the thiophene moieties connected to them continues. In some embodiments, "conjugated groups" are limited to conjugated groups with 3 to 30 carbon atoms.

[0100] The terms "halogen," "halo," or "halide" are used interchangeably and refer to fluorine, bromine, chlorine, and iodine.

[0101] 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) within the ring, wherein the heteroatoms are selected from nitrogen, sulfur, phosphorus and / or oxygen. The heterocyclic group can have a monocyclic or polycondensed ring and includes tetrahydrofuranyl, morpholino, piperidinyl, piperazino, dihydropyrido and the like.

[0102] Unless the definition of a heterocyclyl substituent 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, carboxylalkyl, 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, carboxylalkyl, 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.

[0103] 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 the aryl group is as defined above. The term "heteroarylthio" refers to an -S-heteroaryl group, wherein the heteroaryl group is as defined above, including optionally substituted heteroaryl groups as defined above.

[0104] The term "sulfoxide" refers to a -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 an alkyl, aryl or heteroaryl group. The term "substituted sulfone" refers to -S(O)2R SO Group, where R SO is a substituted alkyl, substituted aryl or substituted heteroaryl as defined herein.

[0105] The term "keto" refers to a -C(O)- group. The term "thiocarbonyl" refers to a -C(S)- group.

[0106] As used herein, the term "room temperature" is 20°C to 25°C.

[0107] 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 products of the disclosed methods. These and other materials are disclosed herein, with the understanding that when combinations, subsets, interactions, groups, etc. of these materials are disclosed without explicitly and specifically disclosing every different individual and collective combination and permutation of these compounds, each of these 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, along with a combination of molecules AD, is disclosed, each of these combinations is contemplated both individually and collectively, even if each combination is not individually recited. 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 reference to A, B, and C; D, E, and F; and the example combination AD. Likewise, any subset or combination of these subsets is also specifically contemplated and disclosed. Thus, for example, the subgroups 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 this 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 that each such combination is specifically contemplated and should be considered disclosed.

[0108] Unless specifically indicated to the contrary, weight percentages of a component are based on the total weight of the formulation or composition in which the component is included.

[0109] 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. Compared to inorganic semiconductors (such as silicon), organic semiconductors offer significant cost savings. Deposition of OSCs from solution enables rapid, large-area fabrication routes, such as various printing methods and roll-to-roll processing.

[0110] Organic thin-film transistors (OTFTs) are of particular interest because their fabrication processes are less complex than conventional silicon-based technologies. For example, OTFTs typically rely on low-temperature deposition and solution processing, and when used with semiconducting conjugated polymers, they 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 for 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.

[0111] Organic semiconductor (OSC) polymers

[0112] 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 can contain both fused thiophene and diketopyrrolopyrrole units. In some examples, the OSC is used for OTFT applications. For example, the OSC polymer can contain repeating units of Formula 1 or Formula 2, or salts, isomers, or analogs thereof:

[0113]

[0114]

[0115] 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 an integer greater than or equal to 3; and (ii) if any one of R1, R2, R3 or R4 is hydrogen, then none of R5, R6, R7 or R8 is hydrogen; (iii) if any one of R5, R6, R7 or R8 is hydrogen, then none of R1, R2, R3 or R4 is hydrogen; (iv) e and f cannot both be 0; (v) if either 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.

[0116] 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 can also help improve solubility.

[0117] In some examples, the OSC polymer may include a first portion and a second portion, such that at least one of the first portion or the second portion includes at least one UV-curable side chain. In some examples, the at least one UV-curable side chain includes at least one of the following: acrylate, epoxide, oxetane, alkene, alkyne, azide, thiol, allyloxysilane, phenol, anhydride, amine, cyanate, isocyanate, silyl hydride, statin, cinnamate, coumarin, fluorosulfate, silyl ether, or a combination thereof. In some examples, only the first portion includes the at least one UV-curable side chain. In some examples, only the second portion includes the at least one UV-curable side chain. In some examples, both the first portion and the second portion include the at least one UV-curable side chain.

[0118] In some instances, such as when the first portion includes the at least one UV-curable side chain, the second portion includes a repeating unit of formula 3-6 or a salt, isomer or analog thereof. In some instances, such as when the second portion includes the at least one UV-curable side chain, the first portion includes a repeating unit of formula 3-6 or a salt, isomer or analog thereof. In some instances, in the first portion, R5 and R7 are hydrogen and R6 and R8 are substituted or unsubstituted C4 or higher alkenyl, and the second portion includes a repeating unit of formula 3-6 or a salt, isomer or analog thereof. In some instances, in the first and second portions, R5 and R7 are hydrogen and R6 and R8 are substituted or unsubstituted C4 or higher alkenyl. In some instances, at least one of R5, R6, R7, and R8 comprises: acrylate, epoxide, oxetane, alkene, alkyne, azide, thiol, allyloxysilane, phenol, anhydride, amine, cyanate, isocyanate, silyl hydride, statin, cinnamate, coumarin, fluorosulfate, silyl ether, or a combination thereof. In some instances, at least one of R1, R2, R3, and R4 comprises: acrylate, epoxide, oxetane, alkene, alkyne, azide, thiol, allyloxysilane, phenol, anhydride, amine, cyanate, isocyanate, silyl hydride, statin, cinnamate, coumarin, fluorosulfate, silyl ether, or a combination thereof.

[0119]

[0120]

[0121] In some examples, the at least one UV-curable side chain comprises at least one of: (A) a polymer selected from:

[0122]

[0123] wherein n is an integer greater than or equal to 2, or (B) is a small molecule selected from the following:

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132] or, (C) a combination thereof.

[0133] In some examples, the OSC polymer may comprise a structure of Formula 7:

[0134]

[0135] Wherein, in Formula 7, Acceptor 1 and Acceptor 2 are each an electron withdrawing group; Donor 1 and Donor 2 are electron donating groups; a and b are independently integers greater than or equal to 1; 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, and wherein: (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 substituted or unsubstituted alkyl, substituted or unsubstituted alkynyl, or C5 or higher 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) one of R1 or R2 and one of R3 or R4 are independently attached to Acceptor 1 and Acceptor 2; (v) one of R5 or R6 and one of R7 or R8 are independently attached to Donor 1 and Donor 2; and (vi) the molecular weight of the at least one OSC polymer is greater than 10,000. Electron-donating groups are functional groups that contribute a portion of their electron density to the conjugated π-system through resonance or inductive effects, thereby making the π-system more nucleophilic. Electron-withdrawing groups have the opposite effect on nucleophilicity as electron-donating groups because they remove electron density from the π-system, making the π-system less nucleophilic.

[0136] In some instances, R1 and R3 are connected to receptor 1 and / or receptor 2. In some instances, R1 and R4 are connected to receptor 1 and / or receptor 2. In some instances, R2 and R3 are connected to receptor 1 and / or receptor 2. In some instances, R2 and R4 are connected to receptor 1 and / or receptor 2. In some instances, R5 and R7 are connected to donor 1 and / or donor 2. In some instances, R5 and R8 are connected to donor 1 and / or donor 2. In some instances, R6 and R7 are connected to donor 1 and / or donor 2. In some instances, R6 and R8 are connected to donor 1 and / or donor 2. In some instances, the connection of R1, R2, R3 and / or R4 to receptor 1 and / or receptor 2 is independently direct or through an intermediate functional group. In some examples, the connection of R5, R6, R7 and / or R8 to Donor 1 and / or Donor 2 is independently direct or through an intermediate functional group.

[0137] In some examples, receptor 1 and receptor 2 are independently selected from the group consisting of:

[0138]

[0139] A and B may independently be either S or O, and T is a connecting terminal group of at least one of donor 1 or donor 2.

[0140] In some instances, Donor 1 and Donor 2 are independently selected from the group consisting of thiophene, benzene, fused thiophene, or a combination thereof. In some instances, at least one of Acceptor 1, Acceptor 2, Donor 1, or Donor 2 comprises at least one UV-curable side chain. In some instances, at least one of R5, R6, R7, and R8 comprises an acrylate, epoxide, oxetane, alkene, alkyne, azide, thiol, allyloxysilane, phenol, anhydride, amine, cyanate, isocyanate, silyl hydride, statin, cinnamate, coumarin, fluorosulfate, silyl ether, or a combination thereof. In some instances, at least one of R1, R2, R3, and R4 comprises an acrylate, epoxide, oxetane, alkene, alkyne, azide, thiol, allyloxysilane, phenol, anhydride, amine, cyanate, isocyanate, silyl hydride, statin, cinnamate, coumarin, fluorosulfate, silyl ether, or a combination thereof.

[0141] 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, 10 mg / mL, 15 mg / mL, 20 mg / mL, 25 mg / mL, 30 mg / mL, 35 mg / mL, 40 mg / mL, or any value therebetween, 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.

[0142] 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 , 15cm 2 V -1 s -1 , 20cm 2 V -1 s -1 , 25cm 2 V -1 s -1 , 30cm 2 V -1 s -1 , 35cm 2 V -1 s -1 , 40cm 2 V -1 s -1 , or any value therebetween, 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 -1In some examples, the hole mobility of OSCs is 2 cm 2 V -1 s -1 or higher.

[0143] In some embodiments, 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 .

[0144] In some examples, the threshold voltage of the OSC polymer in a thin film transistor device is -20 V, -15 V, -10 V, -5 V, -4 V, -3 V, -2 V, -1 V, 0 V, 1 V, 2 V, 3 V, 4 V, 5 V, 10 V, 15 V, 20 V, or any value therebetween, or any range defined by any two of these endpoints. In some examples, the threshold voltage of the OSC polymer in a 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 a thin film transistor device is 2 V.

[0145] The OSC polymers disclosed herein (e.g., having at least one UV-curable side chain) can be directly UV-crosslinked and patterned, thereby achieving improved patterning effects and OFET device performance. For example, compared to conventional photolithography ( Figures 1A to 1E Compared to the hybrid OSC polymers that can be directly UV-cured, the number of patterning steps is reduced to only two (e.g. Figures 2A to 2C Due to the inherent UV patternability of the hetero-OSC polymers disclosed herein, traditional processing steps, such as coating with a compatible photoresist, etching the active material, and stripping the resist, are no longer necessary. This reduction in manufacturing steps has a direct benefit in preventing device performance degradation by avoiding contact with potentially harmful solvents during resist coating and avoiding the aggressive plasma etching atmosphere. Furthermore, this reduction in steps can significantly reduce manufacturing costs, equipment investment, and shorten the manufacturing cycle for OTFT fabrication.

[0146] Due to covalent crosslinking, the disclosed hetero-OSC polymers having at least one UV-curable side chain do not suffer from phase separation issues and exhibit enhanced solvent resistance. Consequently, they are easier to process, resulting in more reproducible solution-processable OSC films. The chemical and physical properties of the hetero-OSC polymers disclosed herein are highly tunable by adjusting the ratios between the different monomers. The crosslinked OSC polymer network formed using the disclosed hetero-OSC polymers having at least one UV-curable side chain facilitates polymer chain alignment at high temperatures, thereby providing OTFT devices fabricated therefrom with higher temperature resistance, longer device lifetimes, and improved weather resistance.

[0147] crosslinking agent

[0148] In some examples, the polymer blend comprises at least one organic semiconductor (OSC) polymer and at least one crosslinker comprising 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 statin, a cinnamate, a coumarin, a fluorosulfate, a silyl ether, or a combination thereof. In some examples, the at least one crosslinker comprises a C=C bond, a thiol, an oxetane, a halide, an azide, or a combination thereof.

[0149] In some instances, the cross-linking agent can be a small molecule or polymer that reacts with the OSC polymer, and the reaction is carried out by a combination of one reaction mechanism or multiple reaction mechanisms, depending on the functional moieties present in the cross-linking agent molecule. For example, a cross-linking agent comprising a thiol group can react with the double bonds in the OSC polymer by thiol-ene click chemistry. In some instances, a cross-linking agent comprising a vinyl group can react with the double bonds in the OSC polymer by addition reaction. In some instances, a cross-linking agent (comprising thiols, vinyl groups, etc., or a combination thereof) can react with the cross-linkable functional groups contained in the side chains of the OSC polymer. For example, these comprise acrylates, epoxides, oxetanes, alkenes, alkynes, azides, thiols, allyloxysilanes, phenols, anhydrides, amines, cyanates, isocyanates, silyl hydrides, statins, cinnamates, coumarins, fluorosulfates, silyl ethers, or a combination thereof.

[0150] 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:

[0151]

[0152] wherein n is an integer greater than or equal to 2, or (B) is a small molecule selected from the following:

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161] or, (C) a combination thereof.

[0162] Photoinitiator

[0163] In some examples, the polymer blend includes at least one OSC polymer, at least one cross-linker, and at least one photoinitiator.

[0164] Photoinitiators are key components of photocurable products. In some instances, 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 by which photoinitiator TPO initiates thiol-ene free radical polymerization is shown below.

[0165]

[0166] In some examples, the photoinitiator includes at least one cationic photoinitiator. Cationic photoinitiators are also known as photoacid generators (PAGs). Once the cationic photoinitiator absorbs UV light, the initiator molecules are converted into strong acid species—Lewis acids or Bronsted acids—that initiate 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 a PAG is shown below.

[0167]

[0168] 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-benzoyloxime) (HRCURE-OXE01); 2,2-dimethoxy-1,2-diphenylethan-1-one (BDK); benzoyl peroxide (BPO); hydroxyacetophenone (HAP); 2-hydroxy-2-methylphenylacetone (1173); 2-methyl-4'-(methylthio)-2-morpholinobenzene Acetone (907); 2-benzyl-2-(dimethylamino)-4'-morpholinopropylphenyl ketone (IHT-PI910); 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 (DMB); 2,2-dimethoxy-2-phenylacetophenone (DMPA); 2-ethylanthraquinone (2-E A); 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-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-butyloxycarbonylmethoxy phenyldiphenylsulfonium trifluoromethanesulfonate; (4-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; diphenyliodonium hexafluorophosphate; diphenyliodonium 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-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.

[0169] Table 1 below shows the structures of representative photoinitiators.

[0170]

[0171]

[0172] Table 1

[0173] Table 2 below shows the structures of representative aryl diazonium salt, diaryliodonium salt, triarylsulfonium salt, and arylferrocenium salt photoinitiators.

[0174]

[0175]

[0176]

[0177]

[0178] Table 2

[0179] additive

[0180] 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 organophosphine, a hydroxylamine, or a combination thereof.

[0181] polymer blends

[0182] In some examples, the performance of devices comprising an OSC polymer can be improved by blending the OSC polymer with a crosslinker. In some examples, the OSC polymer and the crosslinker are blended 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.

[0183] In some examples, the at least one OSC polymer is present in an amount ranging from 1 wt% to 99 wt%, or from 5 wt% to 95 wt%, or from 10 wt% to 90 wt%, or from 25 wt% to 85 wt%, or from 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 any range bounded by any two of these endpoints.

[0184] In some examples, the at least one cross-linking agent is present in an amount ranging from 1 wt % to 99 wt %, or from 5 wt % to 95 wt %, or from 10 wt % to 90 wt %, or from 15 wt % to 85 wt %, or from 20 wt % to 80 wt %, or from 25 wt % to 75 wt %, or from 25 wt % to 65 wt %, or from 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 any range bounded by any two of these endpoints. In some examples, the at least one crosslinking agent comprises a first crosslinking agent present in an amount ranging from 30 wt% to 50 wt% and a second crosslinking agent present in an amount ranging from 0.5 wt% to 25 wt%.

[0185] 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 from 0.2 wt% to 8 wt%, or in a range from 0.3 wt% to 6 wt%, or in a range from 0.4 wt% to 5 wt%, or in a range from 0.5 wt% to 4.5 wt%, or in a range from 0.5 wt% to 4 wt%, or in a range from 0.6 wt% to 3.5 wt%, or in a range from 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 any range bounded by any two of these endpoints.

[0186] 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%.

[0187] In some examples, the at least one antioxidant, lubricant, compatibilizer, leveling agent, or nucleating agent can each independently be present in an amount within the range of 0.05 wt % to 5 wt %, or within the range of 0.1 wt % to 4.5 wt %, or within the range of 0.2 wt % to 4 wt %, or within the range of 0.3 wt % to 3.5 wt %, or within the range of 0.4 wt % to 3 wt %, or within 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 an amount of 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 bounded by any two of these endpoints.

[0188] In some examples, the blend consists of an OSC polymer as described herein. In some examples, the blend includes at least two of the following: an OSC polymer as described herein, a crosslinker, a photoinitiator, and an additive. In some examples, the blend includes at least three of the following: an OSC polymer as described herein, a crosslinker, a photoinitiator, and an additive. In some examples, the blend includes at least four of the following: an OSC polymer as described herein, a crosslinker, a photoinitiator, and an additive.

[0189] OTFT device fabrication

[0190] Applications using OTFT devices require patterning of organic semiconductor materials to prevent undesirably high off-state 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 plasmas during pattern transfer or photoresist removal, as well as aggressive developing solvents, which can severely damage the OSC layer and cause significant degradation in OTFT device performance. In other words, when conjugated organic materials are exposed to light, these materials tend to degrade, and the chemicals used for photolithography can have adverse effects on organic thin film transistors. Therefore, it is not practical to pattern organic semiconductor materials using photolithography.

[0191] 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 thin film 104. Optionally, the thin film 104 can be thermally annealed. The photoresist can be deposited using methods known in the art (e.g., spin coating). For example, the photoresist is converted to a liquid form by dissolving the solid components in a solvent, pouring the liquid photoresist onto the substrate, and then spinning it 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 while removing excess solvent.

[0192] exist Figure 1C In the step of , 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 more cross-linked portions 110 of the photoresist layer 106. The effect of the exposure to UV light is to change the solubility of the photoresist in the subsequent developing 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 1D In the following step, 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 or inorganic solution and dry (plasma) stripping], leaving the desired pattern 118 etched into the thin film layer.

[0193] However, as mentioned above, various aspects of conventional photolithography processes (such as harsh O2 plasma during pattern transfer and aggressive photoresist developer and / or stripper solvents) can severely damage the OSC layer and lead to significant degradation in device performance.

[0194] 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 a blended OSC polymer thin film 204 onto substrate 202. Optionally, thin film 204 can be thermally annealed. In some examples, 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. Thin film 204 is prepared as the polymer blend described above, comprising at least one organic semiconductor (OSC) polymer, and optionally, at least one crosslinker, at least one photoinitiator, and at least one additive.

[0195] In some examples, the blending comprises: dissolving the at least one OSC polymer in a first organic solvent to form a first solution; dissolving the at least one crosslinker 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 the polymer blend. In some examples, the first solution, the second solution, and the third solution can be combined simultaneously. In some examples, the at least one OSC polymer, the at least one crosslinker, and the at least one photoinitiator can be prepared together in a single organic solvent. The weight composition of each component in the polymer blend is provided as described above.

[0196] 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 period of 10 seconds to 10 minutes to remove excess solvent.

[0197] 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 comprises exposing the film to an energy of 10 mJ / cm 2 Up to 600mJ / cm 2 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 instances, 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 as described, upon exposure to UV light is to change the solubility of the film in the subsequent developer solvent solution to form a pattern on top of the substrate.

[0198] exist Figure 2CIn the step of , when the light exposure is complete, the portions of the film 204 not exposed to the UV light 208 are stripped using a predetermined solvent 212, thereby leaving the desired pattern 214 in the film layer. In other words, the more highly cross-linked portions 210 are developed in a solvent to remove the unpatterned areas of the film 204. In some examples, the development includes exposing the unpatterned areas of the film to a solvent for a period ranging from 10 seconds to 10 minutes, the solvent comprising 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.

[0199] 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 period of 10 seconds to 30 minutes.

[0200] 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 ).

[0201] Example

[0202] The embodiments described herein are further illustrated by the following examples.

[0203] Unless otherwise stated, all experimental operations were performed in a fume hood.

[0204] Synthesis of DPP-based methyl acrylate alkyl side chain monomers

[0205] In the first step, 0.895 mmol (millimoles) of dibromoDPP (3,6-bis(5-bromothien-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione), 4.0 equivalents of anhydrous KCO, and 1.36% mmol of BHT (di-tert-butylhydroxytoluene) were weighed into a three-necked round-bottom flask. The flask was then evacuated and filled with N using a Schlenk manifold three times. Subsequently, anhydrous DMF (N,N-dimethylformamide, 18 mL) was added to the flask after the condenser was connected. After the oil bath temperature reached 120°C, the reaction mixture was stirred in the 120°C oil bath for 1 hour. The oil bath was then cooled to 110°C.

[0206] Two point four (2.4) equivalents of methyl bromide alkyl side chain (10-bromodecanyl 10-(methacryloyloxy)decanoate) were dissolved in 4.5 mL of anhydrous DMF and then added dropwise to the reaction mixture. The oil bath was maintained at 110°C for two hours while stirring the reaction mixture. After approximately two hours, the reaction mixture was cooled to room temperature and then poured directly into stirred ice-salt water. The dark solid crude product was obtained by filtration and then dissolved in dichloromethane (DCM). Rapid plug column chromatography was performed using neutral alumina and DCM, and the solvent DCM was removed from the filtered solution to obtain a dark solid. After adding 1.3 mg of BHT to a round-bottom flask, the dark solid was then recrystallized from 100 mL of hexane. The product was finally dried under vacuum.

[0207] Synthesis of heterogeneous OSC polymers

[0208] In the first step, (x+y) mol (mole) linear alkyl side chain FT , x mol linear alkyl side chain DPP monomer, y mol methyl acrylate alkyl side chain DPP monomer, 2% (x+y) Pd (DBA) and 8% (x+y) o-tolylphosphine are weighed in a three-necked round-bottom flask.Then the round-bottom flask is evacuated and filled with N , and three times is operated with the Schleck manifold. Reaction flask is connected with condenser and chlorobenzene (20mL) is added into flask. Through the septum in the 3rd neck in the flask, thermocouple is inserted into the reaction mixture. With the internal temperature of reaction mixture from room temperature heating to 120 ℃ and after internal temperature arrives 120 ℃, stir in oil bath 1 hour.

[0209] When the reaction mixture is still hot, it is poured directly into the 300mL methanol that is stirring. Subsequently, the flask is washed with about 50mL methanol, and then concentrated HCl (aqueous solution) (4mL) is added. The mixture is stirred overnight. Then, using a Buchner funnel and an Erlenmeyer flask with a side arm, the polymer is filtered out from the solution under reduced pressure. The filtrate is discarded. The polymer is transferred to a Soxhlet cannula (the polymer does not exceed half the height of the cannula) and is loaded into a Soxhlet extraction device. Soxhlet extraction of the polymer is carried out with acetone (300mL) for 24 hours. The acetone solution / suspension is then discarded. Soxhlet extraction is then carried out with hexane (300mL) for about 24 hours. The hexane solution / suspension is then discarded. The polymer is then extracted into chloroform (300mL) until no more material dissolves. The polymer is precipitated by pouring the chloroform solution into a stirring beaker with acetone (400mL), stirring to room temperature. The polymer was filtered from the solution under reduced pressure using a Buchner funnel and an Erlenmeyer flask with a sidearm. The filtrate was discarded and the polymer was dried under vacuum.

[0210] Light patterning and result comparison

[0211] A solution of the heterogeneous OSC polymer is prepared in chlorobenzene, stirred in an oil bath at 60-90°C for 1 hour to overnight, and then cooled to room temperature. A crosslinker (1-3 wt% relative to the OSC polymer) [e.g., TRIS (trimethylolpropane tris(3-mercaptopropionate))] and a photoinitiator (1-3 wt% relative to the OSC polymer) [e.g., diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO)] are added to the solution, which is then stirred at room temperature for approximately 5 minutes. The mixture is then filtered using a 0.45 μm PTFE filter.

[0212] The filtered OSC polymer solution is spin-coated onto a glass, glass ceramic or ceramic substrate as a thin film coating at a coating speed of, for example, 500 rpm for 30 seconds, followed by, for example, 1000 rpm for 30 seconds. The glass slide coated with the OSC polymer solution is then pre-baked at 90° C. for 1 minute. The coating is then cured using an Oriel lamp in air under a photomask at an appropriate curing dose (e.g., about 300 mJ / cm 2 ) and the substrate coated with the OSC polymer solution was cured at 365 nm. The substrate coated with the OSC polymer solution was washed twice in two glass cylindrical dishes containing chlorobenzene. The photopatterned OSC polymer film was then dried with nitrogen.

[0213] Figure 5A and 5BThe photopatterning of heterogeneous OSC polymers using chlorobenzene for dissolution and washing according to some embodiments is illustrated. Figure 5A The film was exposed to UV light. During the wash cycle, the unexposed areas dissolved in chlorobenzene. The exposed areas cross-linked to form a network structure that was insoluble in chlorobenzene, thus demonstrating excellent solvent resistance. Figure 5B yes Figure 5A , and illustrates a sharp pattern edge with a resolution of 2 μm. The sharp pattern edge demonstrates excellent photopatterning repeatability, which is a prerequisite for maintaining uniform device performance.

[0214] General fabrication procedures for OTFT devices

[0215] In some embodiments, a bottom-gate, bottom-contact OTFT device can be formed by patterning a gold (Au) or silver (Ag) gate electrode onto a substrate, followed by spin-coating a dielectric onto the substrate and treating it to form a gate dielectric layer. After patterning the Au or Ag source and drain electrodes, an OSC layer can be formed to a thickness of 10 nm to 200 nm using the patterning materials and methods described herein. Finally, an insulator layer is applied. Figure 3 An example of a formed OTFT device is shown.

[0216] OFET device performance

[0217] Bottom-gate, bottom-contact OTFT devices can be formed as follows: some substrates are treated with octadecyltrichlorosilane (OTS) on the SiO2 surface. A solution of OSC polymer [x+y mol linear alkyl side chain FT4, 80% (x+y) mol linear alkyl side chain DPP monomer, 20% (x+y) mol methyl acrylate alkyl side chain DPP monomer] containing a photoinitiator and a crosslinker is spin-coated at 1000 rpm. Gold electrodes are fabricated on the spin-coated OSC layer. OFET device performance is shown in Figure 2. Figure 4 The OFET structure is based on

[0218] The bare SiO2 surface and the OTS-treated surface were tested, where the OTS-treated surface showed a higher mobility (μ h ) (Table 3). Low solution concentration and high solution concentration were tested, wherein low solution concentration showed higher mobility, but high solution concentration showed better I 导通 / I 截止 Charge mobility is a parameter that determines the performance of an OTFT device and indicates how fast electrons or holes move per unit voltage; the higher the mobility, the better the performance. 导通 / I 截止Ratio is another parameter that determines the performance of OTFT devices and represents the on / off current ratio. When the on current is fixed, a higher on / off ratio means a lower off current (lower power consumption); therefore, I 导通 / I 截止 The higher the ratio, the better the performance.

[0219]

[0220] Table 3

[0221] Thus, as proposed herein, improved photo-patternable hetero-organic semiconducting polymers and their use in OSC layers of organic thin film transistors are disclosed. Advantages of photo-patternable hetero-organic semiconducting polymers are disclosed herein.

[0222] As used herein, the terms "approximately," "about," "substantially," and similar terms are intended to have a broad meaning consistent with common and acceptable usage by persons of ordinary skill in the art to which the subject matter of the present disclosure relates. Those skilled in the art who review this disclosure should understand that these terms are intended to allow a description of certain features described and claimed without limiting the scope of such 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.

[0223] As used herein, "optional" or "optionally" is 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. Unless otherwise stated, the indefinite article "a" or "an" and the corresponding definite article "the" as used herein mean at least one, or one or more.

[0224] References to element positions herein (e.g., "top," "bottom," "above," "below," etc.) are intended only to describe the orientation of the elements in the drawings. It should be noted that the orientation of the elements may differ according to other exemplary embodiments, and such variations are intended to be encompassed within the scope of the present disclosure.

[0225] For substantially any plural and / or singular terms used herein, those skilled in the art can convert from the plural to the singular and / or from the singular to the plural, as appropriate, as is appropriate to the context and / or application. For clarity, various singular / plural permutations may be explicitly described herein.

[0226] 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 for which protection is sought. Therefore, the subject matter for which protection is sought is not limited by any content other than the appended claims and their equivalents.

Claims

1. A polymer blend comprising: at least one organic semiconductor (OSC) polymer, in, The at least one organic semiconducting polymer is a diketopyrrolopyrrole-fused thiophene polymeric material, wherein the fused thiophene is beta-substituted, and wherein the at least one organic semiconducting polymer comprises a first portion and a second portion, wherein at least one of the first portion or the second portion comprises at least one UV-curable side chain, Wherein, the at least one UV-curable side chain comprises at least one of the following: acrylate, epoxide, azide, thiol, allyloxysilane, phenol, anhydride, amine, cyanate, isocyanate, silyl hydride, cinnamate, coumarin, fluorosulfate, silyl ether or a combination thereof.

2. The polymer blend of claim 1, wherein Only the first portion comprises at least one UV-curable side chain.

3. The polymer blend of claim 1, wherein Both the first part and the second part comprise the at least one UV-curable side chain.

4. The polymer blend of claim 1 , further comprising: At least one cross-linking agent, wherein the at least one cross-linking agent 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.

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 1 , 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 of claim 1, wherein The at least one organic semiconducting polymer comprises a repeating unit of Formula 1 or Formula 2, or a salt or isomer thereof: Wherein, in Equation 1 and Equation 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 are independently 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 are 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; v. if either 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.

9. The polymer blend of claim 8, wherein For the first part, R5 and R7 are hydrogen, and R6 and R8 are substituted or unsubstituted C4 or higher alkenyl.

10. The polymer blend of claim 8, wherein For the first and second parts, R5 and R7 are hydrogen, and R6 and R8 are substituted or unsubstituted C4 or higher alkenyl groups.

11. The polymer blend of claim 8, wherein At least one of R5, R6, R7 and R8 comprises: 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.

12. The polymer blend of claim 8, wherein At least one of R1, R2, R3 and R4 comprises: 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.

13. The polymer blend of claim 1, wherein: The at least one UV-curable side chain 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.

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

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

16. 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-morpholinopropiophenone (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 (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-phenyldiphenyl Methoxybenzene (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; diphenyliodonium nitrate; diphenyliodonium p-toluenesulfonate; diphenyliodonium trifluoromethanesulfonate Methanesulfonate; (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-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.

17. A polymer blend comprising: at least one organic semiconductor (OSC) polymer, in, The at least one organic semiconducting polymer comprises a structure of Formula 7: Wherein, in formula 7: Acceptor 1 and acceptor 2 are each electron-withdrawing groups; Donor 1 and Donor 2 are electron-donating groups; a and b are independently integers greater than or equal to 1; R1, R2, R3, R4, R5, R6, R7 and R8 are independently 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, in: (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 group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a cycloalkyl group; (ii) if any of R1, R2, R3 or R4 is hydrogen, then R5, R6, R7 or R8 is not hydrogen; (iii) if any of R5, R6, R7 or R8 is hydrogen, then none of R1, R2, R3 or R4 is hydrogen; (iv) one of R1 or R2 and one of R3 or R4 are independently attached to receptor 1 and receptor 2; (v) one of R5 or R6 and one of R7 or R8 are independently linked to Donor 1 and Donor 2; and (vi) the molecular weight of the at least one organic semiconducting polymer is greater than 10,000, wherein at least one of acceptor 1, acceptor 2, donor 1 or donor 2 comprises at least one UV-curable side chain, and Wherein, the at least one UV-curable side chain comprises at least one of the following: acrylate, epoxide, azide, thiol, allyloxysilane, phenol, anhydride, amine, cyanate, isocyanate, silyl hydride, cinnamate, coumarin, fluorosulfate, silyl ether or a combination thereof.

18. The polymer blend of claim 17, wherein Receptor 1 and Receptor 2 are independently selected from the group comprising: A and B are independently any one of S or O, and T is a connecting terminal group of at least one of Donor 1 or Donor 2.

19. The polymer blend of claim 17, wherein Donor 1 and Donor 2 are independently selected from the group consisting of thiophene, benzene, fused thiophene, or a combination thereof.

20. The polymer blend of claim 17, wherein The at least one UV-curable side chain 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.

21. A polymer blend comprising: at least one organic semiconductor (OSC) polymer, in, The at least one organic semiconducting polymer comprises a structure of Formula 7: Wherein, in formula 7: Acceptor 1 and acceptor 2 are each electron-withdrawing groups; Donor 1 and Donor 2 are electron-donating groups; a and b are independently integers greater than or equal to 1; R1, R2, R3 and R4 are independently 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, At least one of R5, R6, R7 and R8 is independently 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, acrylate, epoxide, oxetane, azide, thiol, allyloxysilane, phenol, anhydride, amine, cyanate, isocyanate, silyl hydride, cinnamate, coumarin, fluorosulfate, silyl ether or a combination thereof, in: (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 group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a cycloalkyl group; (ii) if any of R1, R2, R3 or R4 is hydrogen, then R5, R6, R7 or R8 is not hydrogen; (iii) if any of R5, R6, R7 or R8 is hydrogen, then none of R1, R2, R3 or R4 is hydrogen; (iv) one of R1 or R2 and one of R3 or R4 are independently attached to Acceptor 1 and Acceptor 2; (v) one of R5 or R6 and one of R7 or R8 are independently attached to Donor 1 and Donor 2; and (vi) the molecular weight of the at least one organic semiconducting polymer is greater than 10,000, wherein at least one of acceptor 1, acceptor 2, donor 1 or donor 2 comprises at least one UV-curable side chain, and Wherein, the at least one UV-curable side chain comprises at least one of the following: acrylate, epoxide, azide, thiol, allyloxysilane, phenol, anhydride, amine, cyanate, isocyanate, silyl hydride, cinnamate, coumarin, fluorosulfate, silyl ether or a combination thereof.

22. A polymer blend comprising: at least one organic semiconductor (OSC) polymer, in, The at least one organic semiconducting polymer comprises a structure of Formula 7: Wherein, in formula 7: Acceptor 1 and acceptor 2 are each electron-withdrawing groups; Donor 1 and Donor 2 are electron-donating groups; a and b are independently integers greater than or equal to 1; R5, R6, R7 and R8 are independently 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, At least one of R1, R2, R3 and R4 is independently 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, acrylate, epoxide, oxetane, azide, thiol, allyloxysilane, phenol, anhydride, amine, cyanate, isocyanate, silyl hydride, cinnamate, coumarin, fluorosulfate, silyl ether or a combination thereof, in: (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 group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a cycloalkyl group; (ii) if any of R1, R2, R3 or R4 is hydrogen, then R5, R6, R7 or R8 is not hydrogen; (iii) if any of R5, R6, R7 or R8 is hydrogen, then none of R1, R2, R3 or R4 is hydrogen; (iv) one of R1 or R2 and one of R3 or R4 are independently attached to receptor 1 and receptor 2; (v) one of R5 or R6 and one of R7 or R8 are independently linked to Donor 1 and Donor 2; and (vi) the molecular weight of the at least one organic semiconducting polymer is greater than 10,000, wherein at least one of acceptor 1, acceptor 2, donor 1 or donor 2 comprises at least one UV-curable side chain, and Wherein, the at least one UV-curable side chain comprises at least one of the following: acrylate, epoxide, azide, thiol, allyloxysilane, phenol, anhydride, amine, cyanate, isocyanate, silyl hydride, cinnamate, coumarin, fluorosulfate, silyl ether or a combination thereof.

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