Organic thin film transistor

Abstract

The present invention provides a compound of formula (I) wherein the core comprises at least one aromatic, heteroaromatic or aliphatic group; each L is a linking group or a covalent bond, preferably a linking group; each SP is a spacer group, preferably selected from alkylene, alkenylene, arylene or heteroarylene, optionally interrupted by one or more heteroatoms, and optionally substituted; each X is a potentially crosslinkable group, preferably a crosslinkable group capable of being activated by actinic radiation; and a is an integer selected from 3 to 20.

Description

[0001] introduction

[0002] This invention provides a compound of formula (I), and a composition comprising the compound of formula (I), polynorbornene, and a photosensitizer, said composition being used to prepare organic electronic devices. This invention also relates to a method for preparing the compound of formula (I) and a method for preparing a composition comprising the compound of formula (I). Furthermore, this invention relates to a structure and a method for preparing the structure, wherein the structure comprises a substrate and the composition of this invention on at least one surface of said substrate. Moreover, this invention relates to an electronic device comprising the above-described structure, particularly a thin-film transistor. Background Technology

[0003] Interest in organic electronic (OE) devices has been growing for many years. OE devices include organic field-effect transistors (OFETs) used in the substrate of display devices and in sensors, such as organic thin-film transistors (TFTs). A conventional TFT consists of multiple material layers, including a gate, a gate dielectric, a semiconductor layer, and source / drain electrodes.

[0004] Many different types of polymers have been successfully used as dielectrics in TFTs, including polycyclic olefin polymers such as polynorbornene. Polynorbornene is attractive because it achieves the desired low dielectric constant without introducing environmentally harmful fluorine atoms into the structure, provides options for introducing additional chemical functionalities into the polymer backbone, such as crosslinking groups and solubility modifiers, and enables greater flexibility in formulating materials to be processed into oTFT devices, including adjusting formulation viscosity, using different solvents as formulation carriers, and achieving orthogonality between the preceding and following layers in the device.

[0005] However, one of the challenges of using polynorbornene polymers as gate dielectrics is that they typically require the addition of photosensitizers to increase the crosslinking rate in order to fix the polymer film via UV curing at 365 nm. The curing of the dielectric layer is necessary to complete the device structure, so it is important that curing be completed within a short timeframe to achieve acceptable overall processing conditions. Various suitable photosensitizers (such as CPTX, DETX, and 7010) are available, and they have successfully reduced the curing time of polynorbornene to an acceptable level.

[0006] However, a drawback of including these photosensitizers in dielectric compositions is that they have been found to lead to low adhesion in the final organic electronic devices. More specifically, the presence of photosensitizers in polycyclic olefin polymer dielectrics has been found to result in low adhesion of the dielectric to ITO (<0.2 N / 2.5 cm) and low adhesion to the underlying TFT stack (<1 N / 2.5 cm). This has been found to be the lowest adhesion in the stack and is a major failure mode for electronic devices (such as substrates) during lamination, bending, and transport / handling. The reason why photosensitizers have this effect is not yet known. Summary of the Invention

[0007] From a first perspective, the present invention provides a compound of formula (I):

[0008]

[0009] in

[0010] The core contains at least one aromatic, heteroaromatic, or aliphatic group;

[0011] Each L represents a linking group or a covalent bond, preferably a linking group;

[0012] Each SP is a spacer group, preferably selected from alkylene, alkenylene, arylene or heteroarylene, which is optionally interrupted by one or more heteroatoms and optionally substituted;

[0013] Each X is a potential crosslinkable group, preferably a crosslinkable group that can be activated by photochemical radiation; and

[0014] a is an integer selected from 3 to 20.

[0015] In another respect, the present invention provides a method for preparing a compound of formula (I), the method comprising: reacting a compound of formula (V) with a compound of formula (VI):

[0016]

[0017] in

[0018] The core contains at least one aromatic, heteroaromatic, or aliphatic group;

[0019] The reaction between each L' and L'' produces L, and each L is a linking group or a covalent bond, preferably a linking group;

[0020] Each SP is a spacer group, preferably selected from alkylene, alkenylene, arylene or heteroarylene, which is optionally interrupted by one or more heteroatoms and optionally substituted;

[0021] Each X is a potential crosslinkable group, preferably a crosslinkable group that can be activated by photochemical radiation; and

[0022] a is an integer selected from 3 to 20.

[0023] In another respect, the present invention provides a composition comprising:

[0024] (i) Compounds of formula (I) as described above;

[0025] (ii) a polycyclic olefin, preferably polynorbornene; and

[0026] (iii) Photosensitizers.

[0027] In another respect, the present invention provides a method for preparing the composition as described above, the method comprising mixing the following in a solvent: (i) a compound of formula (I) as described above; (ii) a polycyclic olefin, preferably polynorbornene; and (iii) a photosensitizer.

[0028] From another perspective, the present invention provides a structure comprising:

[0029] (i) base; and

[0030] (ii) The composition as defined above on at least one surface of the substrate.

[0031] In another respect, the present invention provides a method for preparing the structure described above, the method comprising:

[0032] (i) The composition described above is deposited on at least one surface of the substrate by solution treatment;

[0033] (ii) Drying the composition; and

[0034] (iii) Crosslinking the composition to produce the structure.

[0035] In another respect, the present invention provides an electronic device including the structure described above, preferably a thin-film transistor, as defined above.

[0036] definition

[0037] As used in this article, the term "aromatic" refers to a cyclic planar molecule with 4n+2 π electrons. Aromatic compounds are sometimes referred to as aromatic hydrocarbons.

[0038] As used herein, the term "heteroaromatic" refers to an aromatic compound containing one or more heteroatoms selected from N, O, and S.

[0039] As used herein, the term "aliphatic" refers to non-aromatic organic compounds that contain carbon and hydrogen atoms.

[0040] As used herein, the term "linking group" refers to any group used to indirectly bind two or more components of a molecule together. When two components of a molecule are bound together without a linking group, the two parts of the molecule are directly bonded to each other, i.e., there are no intervening atoms. When two components of a molecule are linked by a linking group, there are intervening atoms between the two components.

[0041] As used herein, the term spacer group refers to any group used to separate two or more components of a molecule. Its function is to increase the distance between two or more components of the molecule.

[0042] As used herein, the term "alkyl" refers to any group comprising carbon and hydrogen. The group may be saturated, straight-chain, branched, or cyclic. Alkyl groups may be substituted or unsubstituted.

[0043] As used herein, the term "alkylene" refers to a divalent group derived from an alkyl group that has had two hydrogen atoms removed. The group may be substituted or unsubstituted. An example of an alkylene group is an ethylene having the formula -C2H4.

[0044] As used herein, the term "alkenyl" refers to a divalent group derived from an alkene that has had two hydrogen atoms removed. The group may be substituted or unsubstituted. An example of an alkenyl group is an vinylene having the formula -CH=CH-.

[0045] As used herein, the term "arylene" refers to a divalent group derived from an aromatic hydrocarbon from which hydrogen atoms have been removed from each of the two carbon atoms. An example of an arylene is the phenylene (C6H4) derived from benzene.

[0046] As used herein, the term "hybrid aryl" refers to an aryl group containing at least one heteroatom. Examples of "heteroatom" include N, S, or O. Hybrid aryl groups are derived from aromatic heterocycles from which hydrogen atoms have been removed from two carbon atoms.

[0047] As used herein, the term "polynorbornene" refers to a polymer comprising at least one repeating unit derived from norbornene, a substituted norbornene, or a cyclic derivative of norbornene. The repeating unit present in the polynorbornene is preferably at least 55% by weight, more preferably at least 70% by weight, and still more preferably at least 95% by weight, derived from the aforementioned norbornene monomer. Other monomeric units that may be present include, for example, olefinic monomers, acrylic monomers, acrylate monomers, styrene, vinyl monomers, and combinations thereof.

[0048] As used herein, the term "hydrocarbon group" refers to a free radical or group containing a carbon backbone, wherein each carbon atom is suitably replaced by one or more hydrogen atoms. A representative example of a hydrocarbon group is C0. 1-25 Alkyl, C 2-24 alkenyl, C 2-24 alkynyl group, C 5-25 cycloalkyl, C 6-24 Aryl or C 7-24 Aryl groups. Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl. Specific examples of alkenyl groups include vinyl, propenyl, butenyl, and hexenyl. Specific examples of ynyl groups include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Specific examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and cyclooctyl. Specific examples of aryl groups include phenyl, biphenyl, naphthyl, and anthraceneyl. Specific examples of aralkyl groups include benzyl, phenethyl, and phenylbutyl.

[0049] As used herein, the term "halogenated hydrocarbon group" refers to a hydrocarbon group in which one or more, but not all, of the hydrogen atoms have been replaced by a halogen (F, CI, Br, or I).

[0050] As used in this article, the term "perhalocarbyl" refers to a hydrocarbon group in which every hydrogen atom has been replaced by a halogen.

[0051] Additionally, as used herein, the terms “hydrocarbon,” “halogenated hydrocarbon,” and “hologenated hydrocarbon” are defined to include a portion in which one or more of the plurality of carbon atoms are substituted by a heteroatom independently selected from O, N, P, or Si. Such heteroatom-containing portions include, for example, ethers, epoxides, glycidyl ethers, alcohols, carboxylic acids, esters, maleimides, amines, imines, amides, phenols, amide-phenols, silanes, siloxanes, phosphine, phosphine oxides, phosphinites, phosphonites, phosphites, phosphonates, phosphinates, and phosphonates.

[0052] As used herein, the phrase “potentially crosslinkable group” refers to a group that does not crosslink under ambient conditions or during the initial formation of the compound itself, but only crosslinks upon specific initiation.

[0053] As used herein, the phrase "a crosslinkable group that can be activated by photochemical radiation" refers to a group that is reactive to photochemical radiation and participates in a crosslinking reaction as a result of that reactivity. Such a group is an example of a potential crosslinkable group.

[0054] As used herein, the term photosensitizer refers to a compound that absorbs light and transfers energy to reactants to promote a chemical reaction. In the case of this application, the chemical reaction is curing.

[0055] As used herein, the term “total dry weight” refers to the total weight of the dried components (i.e., excluding solvents). Detailed Implementation

[0056] This invention provides a compound of formula (I):

[0057]

[0058] in

[0059] The core contains at least one aromatic, heteroaromatic, or aliphatic group;

[0060] Each L represents a linking group or a covalent bond, preferably a linking group;

[0061] Each SP is a spacer group, preferably selected from alkylene, alkenylene, arylene or heteroarylene, which is optionally interrupted by one or more heteroatoms and optionally substituted;

[0062] Each X represents a potential crosslinkable group, preferably a crosslinkable group that can be activated by photochemical radiation; and

[0063] a is an integer selected from 3 to 20.

[0064] Advantageously, the compound of formula (I) can be incorporated into a composition comprising a polycyclic olefin (preferably polynorbornene) and a photosensitizer, and coated onto a substrate to form a dielectric layer. The presence of the compound of formula (I) in the composition improves the adhesion of the dielectric layer to adjacent layers (e.g., ITO and / or semiconductor layers). Therefore, compositions comprising formula (I) are particularly useful in organic electronic devices (such as TFTs) that require a dielectric, and the improved adhesion to the remainder of the TFT stack is particularly beneficial during lamination, bending, transport, and handling.

[0065] Definition of X

[0066] In the preferred compound of formula (I), each X is a group capable of crosslinking via a [2π+2π] photo-cycloaddition reaction. The preferred crosslinkable group has a degree of potentiality. This means that the group does not crosslink under ambient conditions or during the initial formation of the compound itself, but only upon specific initiation, preferably by photochemical radiation.

[0067] Preferably, the crosslinkable groups include maleimide, epoxy, vinyl, acetyl, indole, cinnamic acid ester, or coumarin groups. More preferably, the crosslinkable groups include maleimide groups, such as 3-monoalkylmaleimide or 3,4-dialkylmaleimide.

[0068] Representative examples of suitable crosslinkable groups are those shown below:

[0069] .

[0070] In the above structure, the wavy line indicates the position where the crosslinkable group is attached to the rest of the compound of formula (I).

[0071] In the preferred compound of formula (I), each X is a crosslinkable group of formula (II):

[0072]

[0073] in

[0074] R 1 Selected from H and C 1-6 Alkyl, preferably C 1-6 Alkyl, and more preferably methyl;

[0075] R 2 Selected from H and C 1-6 Alkyl, preferably C 1-6 Alkyl, and more preferably methyl; or

[0076] R 1 and R 2 Together with the carbon atoms they are attached to, they form a ring, wherein the ring optionally fuses with another ring.

[0077] In the diagram depicting formula (II) above, the wavy bond indicates the position where the group is attached to the rest of the molecule.

[0078] In the preferred compound of formula (II), R 1 Selected from H and C 1-6 Alkyl group. In more preferred compounds of formula (II), R 2 Selected from H and C 1-6 Alkyl group. In even more preferred compounds of formula (II), R 1 and R 2 Each is selected from H and C 1-6 alkyl.

[0079] In the more preferred compound of formula (II), R 1 C 1-6 Alkyl group. For example, R 1It can be methyl, ethyl, propyl, butyl, pentyl, or hexyl. However, preferably, R 1 It is methyl.

[0080] In the more preferred compound of formula (II), R 2 C 1-6 Alkyl group. For example, R 2 It can be methyl, ethyl, propyl, butyl, pentyl, or hexyl. However, preferably, R 2 It is methyl.

[0081] In the particularly preferred compound of formula (I), R 1 and R 2 It is methyl.

[0082] The preferred compounds of the present invention are those of formula (Ia):

[0083]

[0084] Wherein, nucleus, L, SP, and a are as defined above with respect to equation (I); and

[0085] R 1 and R 2 Each selected from C 1-6 Alkyl group, preferably methyl group.

[0086] In the compounds of formula (I) and (Ia), the letter "a" indicates the number of arms extending from the core of the compound. In preferred compounds of formula (I) and (Ia), a is 3-12, more preferably 3-6, and even more preferably 3 or 4. Thus, preferred compounds of formula (I) and (Ia) have 3 or 4 arms. The presence of multiple arms increases the number of crosslinks per molecule, which results in a more highly crosslinked film. Typically, this leads to a more robust film with lower solubility and better resistance to process chemicals such as solvents, etchants, etc.

[0087] Definition of nuclear group

[0088] In compounds of formula (I), the core may contain one or more, preferably one, aliphatic group. The preferred aliphatic group is derived from polycarboxylic acids and polyols.

[0089] Preferred polycarboxylic acids include C 4-8The main chain of a dicarboxylic acid, such as 1,5-glutaric acid, 1,6-adipic acid, etc. More preferably, the polycarboxylic acid is substituted with one or more COOH groups, for example, along its main chain. Thus, preferred polycarboxylic acids comprise a total of 3-6, and more preferably 3-4, COOH groups. The presence of multiple COOH groups allows for the formation of multiple arms, and keeps the individual arms spatially separated. Examples of suitable aliphatic cores can be formed from polycarboxylic acids selected from: propanetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, and aconitic acid.

[0090] Preferred polyols include C 3-12 The main chain, for example, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, etc. Further preferred polyols are substituted with one or more OH groups, for example, along their main chain. Thus, preferred polyols contain a total of 3-8 OH groups, more preferably 3-6 OH groups. The presence of multiple OH groups allows for the formation of multiple arms, and keeps these arms spatially separated. Examples of suitable aliphatic cores can be formed from polyols selected from: glycerol, 1,2,4-butanetriol, erythritol, threitol, 1,2,6-hexanetriol, 1,2,10-decanetriol, 1,2,3-hexanetriol, sorbitol, mannitol, and inositol.

[0091] In the preferred compounds of formulas (I) and (Ia), the core comprises at least one aromatic or heteroaromatic group, preferably an aromatic group. Aromatic or heteroaromatic groups are generally preferred because they allow the "arms" of the compound to be spatially separated, avoiding any steric hindrance problems. Aromatic or heteroaromatic cores also tend to improve the compatibility of the compound with the types of solvents preferably used with them.

[0092] In the preferred compounds of formulas (I) and (Ia), the core comprises 1 to 6, more preferably 1 to 4, and still more preferably 1, 2 or 3 aromatic or heteroaromatic groups, preferably aromatic groups.

[0093] Preferably, the nucleus contains 6-24 atoms, preferably carbon atoms. More preferably, the nucleus contains 6-18 atoms, preferably carbon atoms. Particularly preferably, the nucleus contains 6, 12, or 18 atoms, preferably carbon atoms.

[0094] Preferably, the core is not fused. Preferably, the core is not bound by any groups other than the "arms" described above (e.g., C). 1-6 Alkyl, halogen, NO2, etc. are substituted.

[0095] Among the preferred compounds of formulas (I) and (Ia), the nuclear selection is made from the group consisting of the following:

[0096]

[0097] Preferably, the core is (i) or (ii), and most preferably (i).

[0098] In the preferred compounds of formula (I) or (Ia), the selection is made from the group consisting of the following:

[0099]

[0100] The keys terminating with a wavy line indicate the location where the SP is connected to the core. Preferably, the "arms" are distributed around the core, and thus they are spaced apart from each other.

[0101] The particularly preferred compounds of the present invention are compounds of formula (Ib), (Ic) or (Id), and especially compounds of formula (Ib):

[0102]

[0103]

[0104]

[0105] in

[0106] L, SP, a, R 1 and R 2 As defined above with respect to equation (Ia); and

[0107] k+l = a as defined above.

[0108] Definition of spacer group

[0109] In the preferred compounds of formulas (I), (Ia), (Ib), (Ic), and (Id), all spacer groups are identical. The purpose of the spacer groups is to separate the core from one or more crosslinkable groups, and to increase the degree of freedom of the crosslinkable groups, thereby increasing the likelihood of crosslinking. The properties of the spacers can also be used to regulate the solubility of the compound and / or adjust its interaction with polymers mixed with the compound.

[0110] In the preferred compounds, each spacer group is selected from C 3-20 Alkylene and C 3-20 alkenyl groups, and even more preferably C 3-20 Alkylene. In the preferred compounds of formulas (I), (Ia), (Ib), (Ic), and (Id), each spacer group is C. 3-20 Alkylene, more preferably C 4-18 Alkylene, still more preferably C 5-16 Alkylene, and more preferably C 5-14Alkylene. Optionally, the spacer group is substituted, and preferably unsubstituted.

[0111] The particularly preferred compounds of the present invention are those of formula (Ibi):

[0112]

[0113] in

[0114] L, a, R 1 and R 2 As defined above with respect to equations (Ia) and (Ib); and

[0115] n is an integer selected from 3-20, preferably 4-16, more preferably 4-10, and still more preferably 6-8.

[0116] Definition of linking group

[0117] In the preferred compounds of formulas (I), (Ia), (Ib), (Ibi), (Ic), and (Id), each L is a linking group.

[0118] In some preferred compounds of formulas (I), (Ia), (Ib), (Ibi), (Ic), and (Id), the linking group includes C(O)O, C(O), OC(O)O, C(O)NH, O, S, SO2, SO2NH, NH, and NMe. In some particularly preferred compounds of the present invention, the linking group is composed of C(O)O.

[0119] In some preferred compounds of formulas (I), (Ia), (Ib), (Ibi), (Ic), and (Id), the linking group comprises an aromatic or heteroaromatic group, preferably an aromatic group. In such compounds, preferably, each L is a linking group of formula (III):

[0120]

[0121] Each R 3 It is selected from C(O)O, OC(O), C(O), OC(O)O, C(O)NH, O, S, SO2, SO2NH, NH and NMe, and is preferably selected from C(O)O and OC(O).

[0122] Particularly preferred compounds of the present invention are compounds of formulas (Ibii) and (Ibiii):

[0123]

[0124]

[0125] in

[0126] a, n, R 1 and R 2 As defined above with respect to equations (Ia), (Ib), and (Ibi).

[0127] Particularly preferred compounds of the present invention are selected from the compounds shown below:

[0128]

[0129]

[0130] .

[0131] The present invention also relates to a method for preparing a compound of formula (I), the method comprising: reacting a compound of formula (V) with a compound of formula (VI):

[0132]

[0133] in

[0134] The core contains at least one aromatic, heteroaromatic, or aliphatic group;

[0135] The reaction between each L' and L'' produces L, and each L is a linking group or a covalent bond, preferably a linking group;

[0136] Each SP is a spacer group, preferably selected from alkylene, alkenylene, arylene or heteroarylene, which is optionally interrupted by one or more heteroatoms and optionally substituted;

[0137] Each X represents a potential crosslinkable group, preferably a crosslinkable group that can be activated by photochemical radiation; and

[0138] a is an integer selected from 3 to 20.

[0139] Preferably, L' is CO-LG, where LG is a leaving group, such as a halogen, for example, Cl. Preferably, L'' is OH. Thus, the resulting linking group includes esters (COO).

[0140] Technicians will be able to easily select appropriate L' and L'' based on the required L. Similarly, the conditions for carrying out the reaction can be easily determined by synthetic chemists using their synthetic chemistry knowledge.

[0141] The present invention also relates to a composition comprising: (i) a compound of formula (I) as described above; (ii) a polycyclic olefin, preferably polynorbornene; and (iii) a photosensitizer. During device fabrication, the composition also preferably comprises a solvent to facilitate solution handling. Most of the solvent subsequently evaporates during drying, so the final composition present in the device is substantially solvent-free. In the device of the present invention, the composition preferably consists of: (i) a compound of formula (I) as described above; (ii) a polycyclic olefin, preferably polynorbornene; and (iii) a photosensitizer.

[0142] Based on the total dry weight of the composition, the preferred composition of the present invention comprises 1-30% by weight of the compound of formula (I), more preferably 2-20% by weight of the compound of formula (I), and still more preferably 5-10% by weight of the compound of formula (I).

[0143] Based on the total dry weight of the composition, the preferred composition of the present invention comprises 55-98.5% by weight of a polycyclic olefin (preferably polynorbornene), more preferably 70-97.5% by weight of a polycyclic olefin (preferably polynorbornene), and still more preferably 75-90% by weight of a polycyclic olefin (preferably polynorbornene).

[0144] Based on the total dry weight of the composition, the preferred composition of the present invention contains 0.5-15% by weight of photosensitizer, more preferably 1-10% by weight of photosensitizer, and still more preferably 5-10% by weight of photosensitizer.

[0145] Polycyclic olefins

[0146] The polycyclic olefin present in the composition of the present invention is preferably polynorbornene, and more preferably polynorbornene derived from a norbornene monomer of formula (X):

[0147]

[0148] in

[0149] Z is selected from -CH2-, -CH2-CH2-, or -O-;

[0150] z is 0 or an integer from 1 to 5; and

[0151] R 10 R 11 R 12 and R 13 Each of them is independently selected from H, C 1-25 hydrocarbon group, C 1-25 Halogenated hydrocarbon group or C 1-25 Fully halogenated carbon-based.

[0152] Therefore, the preferred polynorbene present in the compositions of the present invention includes repeating units of formula (XI):

[0153]

[0154] in

[0155] Z is selected from -CH2-, -CH2-CH2-, or -O-;

[0156] z is 0 or an integer from 1 to 5; and

[0157] R 10 R 11 R 12 and R 13 Each of them is independently selected from H, C 1-25 hydrocarbon group, C 1-25 Halogenated hydrocarbon group or C 1-25 Fully halogenated carbon-based.

[0158] In the preferred monomer of formula (X) and the repeating unit of formula (XI), Z is -CH2-.

[0159] In other preferred monomers of formula (X) and repeating units of formula (XI), z is 0, 1 or 2, more preferably 0 or 1, and especially preferably 0.

[0160] In the preferred monomer of formula (X) and the repeating unit of formula (XI), R 10 R 11 R 12 and R 13 At least one of them is H, more preferably, R 10 R 11 R 12 and R 13 At least two of them are H, and more preferably, R 10 R 11 R 12 and R 13 At least three of them are H. Optionally, R 10 R 11 R 12 and R 13 Each of them is H.

[0161] In some preferred monomers of formula (X) and repeating units of formula (XI), R 10 R 11 R 12 and R 13 One of them is C 1-25 Alkyl or C 7-24 Aryl group. Preferred C 1-25Alkyl groups include C 4-20 Alkyl, and more preferably C 6-18 Alkyl group. Preferred aralkyl group is -(CH2). 2-6 -Phenyl.

[0162] In some preferred monomers of formula (X) and repeating units of formula (XI), R 10 R 11 R 12 and R 13 One of them contains a crosslinkable group. Representative examples of crosslinkable groups include maleimide, epoxy, vinyl, acetyl, indenyl, cinnamic acid ester, or coumarin groups. More preferably, the crosslinkable group present is a maleimide group, such as 3-monoalkylmaleimide or 3,4-dialkylmaleimide. Preferably, the crosslinkable group is via an alkylene linker (e.g., C... 1-12 (alkylene linker) is attached to norbornene core.

[0163] In some preferred monomers of formula (X) and repeating units of formula (XI), R 10 R 11 R 12 and R 13 One of them is a hydrocarbon group containing a terminal hydroxyl, carboxyl, or oligoethyleneoxy group. Representative examples include terminal hydroxyalkyl, alkylcarbonyloxy (e.g., acetyl), hydroxyoligoethyleneoxy, alkoxyoligoethyleneoxy, or alkylcarbonyloxyoligoethyleneoxy moiety, wherein "oligoethyleneoxy" is -(CH2CH2O). s - where s is 1, 2 or 3.

[0164] The particularly preferred monomers of formula (X) are shown below. The repeating units of the corresponding formula (XI) are also preferred.

[0165]

[0166]

[0167] The preferred polynorbornene present in the compositions of the present invention may contain one or more repeating units of formula (XI). For example, the polycyclic olefin (preferably polynorbornene) may contain two or three different repeating units of formula (XI), and preferably two different repeating units of formula (XI). When more than one type of repeating unit is present in the polymer, those skilled in the art will be able to easily determine the appropriate ratio according to the precise properties required for a given application. Preferred copolymers are random copolymers.

[0168] The preferred polynorbornene present in the compositions of the present invention has an Mw of 5,000 to 500,000, more preferably 30,000 to 400,000, and still more preferably 60,000 to 250,000.

[0169] Suitable polynorbornene can be synthesized using methods known in the art. Alternatively, polynorbornene suitable for use in this invention is commercially available, for example from Sumitomo Bakelite.

[0170] photosensitizer

[0171] The photosensitizer present in the compositions of the present invention is preferably a type II photosensitizer, and more preferably a thioxanthone derivative. These photosensitizers have been found to be the most efficient in shortening the curing time of, for example, polynorbornene. This is thought to be due to the efficient activation of the DMMI group by the excited sensitizer molecules through triplet-triplet energy transfer.

[0172] Preferably, the thioxanone derivative comprises the portion of formula (XII):

[0173]

[0174] in

[0175] Each R is independently selected from H, halogens, and hydrocarbon groups; and

[0176] r is 0 or an integer from 1 to 4. Preferably, R is an integer from 1 to 4.

[0177] Optionally, each R can be C 1-25 Alkyl, C 2-25 alkenyl or C 2-25 The alkynyl group is optionally interrupted by one or more atoms (preferably O).

[0178] Representative examples of suitable photosensitizers include 1-chloro-4-propoxythioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone (DETX) (CAS 82799-44-8), 2-isopropylthioxanthone (CAS 5495-84-1), thioxanthone, CPTX (CAS142770-42-1), and mixtures thereof.

[0179] Photosensitizers suitable for incorporation into the compositions of the present invention are commercially available. Examples include Arkema's Speedcure 7010 and IGM resin's Omnipol-TX.

[0180] solvent

[0181] To facilitate solution handling, the compositions of the present invention further comprise a single solvent or a mixture of two or more solvents. A wide variety of solvents can be used, such as toluene, 3-methylthiophene, cyclopentanone, chlorobenzene, ethylcyclohexane, p-xylene, cyclopentanol, o-xylene, 2-heptanone (MAK), anisole, cumene, cyclohexanone, α-pinene, bromobenzene, n-propylbenzene, cyclohexanol, 3-methylcyclohexanol, p-ethyltoluene, mesitylene, 1,2,4-trimethylbenzene, tert-butylbenzene, diisobutyl ketone, phenethyl ether, 3-methylcyclohexanone, 4-methylcyclohexanone, tert-butylcyclohexane, 1,3-phenylpropanedioxane, 4-methyl anisole, 3-methyl anisole, dihydroindene, 1,2,3-trimethylbenzene, p-cymene, o-dichlorobenzene, diethylbenzene (mixture), 2,6-dimethyl anisole, n-butylbenzene, decahydronaphthalene (mixture), ethyl heptanoate, 2,3-dihydrobenzofuran, 2,5-dimethylbenzene Ethers, 2,4-dimethylanisole, 3,5-dimethylanisole, (-)-fenazine, phenyl acetate, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, methyl benzoate, 3,4-dimethylanisole, NMP, acetophenone, 1,3-diisopropylbenzene, g-butyrolactone, benzyl alcohol, benzyl acetate, tetrahydronaphthalene, veratrine ether, ethyl benzoate, isophorone, acetone, α-pine Oleyl alcohol, methyl phenylacetate, n-hexylbenzene, n-propyl benzoate, 4-phenyl-2-butanone, 2-phenoxyethanol, bicyclohexane, cyclohexylbenzene, 1-methylnaphthalene, 1,4-benzodioxane, ethyl hydrogenated cinnamate, butyl benzoate, 2-pyrrolidone, 4-methoxybenzyl alcohol, 1-methoxynaphthalene, ethyl cinnamate, N-cyclohexylpyrrolidone, diisopropylnaphthalene, dodecylbenzene, and mixtures thereof.

[0182] Some preferred solvents include: organic ketones, such as methyl ethyl ketone (MEK), 2-heptanone (MAK), cyclohexanone, and cyclopentanone; esters, such as ethyl benzoate; ethers, such as butyl phenyl ether, 4-methyl anisole, and propylene glycol methyl ether acetate; and aromatic hydrocarbons, such as cyclohexylbenzene; or mixtures thereof.

[0183] Preferably, the total concentration of polycyclic olefins (preferably polynorbornene) in the solution is 3-30% by weight, based on the total weight of the composition.

[0184] Preferably, the total concentration of the compound of formula (I) in the solution is 0.15-3 by weight, based on the total weight of the composition.

[0185] Preferably, the total concentration of photosensitizer in the solution is 0.3-3% by weight, based on the total weight of the composition.

[0186] The present invention also relates to a method for preparing the composition described above, the method comprising mixing the following in a solvent: (i) a compound of formula (I) as described above; (ii) a polycyclic olefin as described above, preferably polynorbornene; and (iii) a photosensitizer as described above. Preferred solvents are as described above. Any conventional mixing technique may be used.

[0187] Structures and devices

[0188] Compositions of compounds of formula (I) and compounds comprising formula (I) are ideal for the fabrication of structures in electronic devices, and therefore ideal for the fabrication of electronic devices. Therefore, the present invention relates to a structure comprising:

[0189] (i) base; and

[0190] (ii) The composition as defined above on at least one surface of the substrate.

[0191] Preferably, the composition exists in the form of a layer on the substrate.

[0192] Preferably, the substrate is selected from electrode materials, such as Al, Ag, Au, Cr, Ni, Mo, ITO, or other materials patterned with ITO. This invention is particularly advantageous when the electrode material is ITO or other materials patterned with ITO.

[0193] Preferably, the substrate is a semiconductor layer. It can be any conventional semiconductor layer. Preferably, the semiconductor layer comprises a semiconductor polymer.

[0194] A significant advantage of the compositions of the present invention comprising formula (I) is that the adhesion of the composition to a substrate (e.g., ITO) is significantly improved. Preferably, the adhesion of the compositions of the present invention (e.g., the cured compositions) to ITO is at least 5 N / cm, and more preferably at least 5 N / cm when measured by the test methods described in the embodiments herein.

[0195] The deposition and / or formation of layers of the compositions of the present invention on a substrate is preferably performed by solution treatment. Preferred techniques include dip coating, spin coating, slot extrusion coating or slot coating, inkjet printing, letterpress printing, screen printing, doctor blade coating, roller printing, reverse roller printing, offset lithography printing, flexographic printing, web printing, spraying, brushing, or pad printing. Spin coating, flexographic printing, inkjet printing, and slot extrusion coating are preferred. In each technique, the solvent is evaporated after deposition to form, for example, a layer of the composition on the substrate.

[0196] The compositions of the present invention should be coated to a suitable thickness, which will depend on the device being manufactured and the materials used. Those skilled in the art will be able to readily determine the appropriate dry film thickness of the layer formed by the compositions of the present invention.

[0197] The crosslinking of the compositions of the present invention is preferably carried out by exposing the compositions to electromagnetic (photochemical) radiation (such as X-rays, ultraviolet radiation, or visible radiation). For example, photochemical radiation with wavelengths from 11 nm to 700 nm (e.g., 200 to 700 nm) can be used. The dose of photochemical radiation used for exposure is typically 25 to 15,000 mJ / cm. Suitable radiation sources include mercury lamps, mercury / xenon lamps, mercury / halogen lamps, and xenon lamps, argon or xenon laser sources, or X-rays. This exposure to photochemical radiation causes crosslinking in polynorbornene, in compounds of formula (I), and between such compounds. Advantageously, these reactions are carried out with almost no or very few byproducts.

[0198] Optionally, baking may be performed. In some cases, heating the structure to a temperature of, for example, 70-130°C can further promote cross-linking.

[0199] The present invention also relates to a method for preparing a structure as defined above, the method comprising:

[0200] (i) Depositing the composition as defined above onto at least one surface of a substrate by solution treatment;

[0201] (ii) Drying the composition; and

[0202] (iii) Crosslinking the composition to produce the structure.

[0203] Typically, the structure of the present invention is incorporated into an electronic device. Therefore, the present invention also relates to an electronic device comprising the structure described above. This electronic device is preferably an organic electronic device. Preferred devices include organic field-effect transistors (OFETs), such as organic thin-film transistors (OTFTs), organic photovoltaic (OPV) devices, biosensors, and other organic sensors. Particularly preferred devices are OFETs, especially electrolyte-gate controlled TFTs and OTFTs. OFETs and OTFTs can be top-gate or bottom-gate devices.

[0204] Other components or functional layers of the electronic device (such as substrates, gates, sources, drains, and organic semiconductor layers) can be selected from standard materials and can be fabricated and applied to the device using standard methods. The materials and fabrication methods suitable for these components and layers are known to those skilled in the art and are described in the literature. Exemplary deposition methods include the previously described liquid coating method, as well as chemical vapor deposition (CVD) or physical vapor deposition methods.

[0205] The gate, source, and drain of the electronic device of the present invention can be deposited or formed by liquid coating (e.g., spraying, dip coating, web-coating, or spin coating) or by vacuum deposition methods (e.g., physical vapor deposition (PVD), chemical vapor deposition (CVD), or thermal evaporation). Suitable electrode materials and deposition methods are known to those skilled in the art. However, compounds of formula (I) and compositions containing such compounds are particularly suitable for use with metal oxides, such as indium tin oxide (ITO), F-doped ITO, or Al-doped ZnO, especially ITO.

[0206] The invention will now be described with reference to the following non-limiting embodiments.

[0207] Example

[0208] Synthesis of compounds 1 and 2

[0209] Preparation of intermediates

[0210]

[0211] 2,3-Dimethylmaleimide was reacted with a small excess of 6-amino-1-hexanol (1.05 equivalents) in toluene. The reaction mixture was heated under reflux until the reaction was complete. The reaction mixture was evaporated under vacuum to give a colorless oily product (101 wt% yield). ¹H NMR showed the presence of 1.2 wt% toluene, therefore the adjusted yield was 99 wt%. The product was ready for use without further purification.

[0212] Preparation of Compound 1

[0213]

[0214] The intermediate DMMI-C6-OH was dissolved in THF and trimethylamine (1.4 equivalents). Tris(trimethylammonium chloride) (0.4 equivalents) was added dropwise at 0–10 °C, and the reaction mixture was then heated to room temperature. The reaction was completed after 2 hours. The reaction mixture was then filtered to remove Et3N-HCl and then evaporated. The resulting residue was redissolved in DCM and washed with dilute acid to remove residual base. The resulting DCM solution was filtered through silica using 6% ethyl acetate in DCM and then evaporated to an oil. The product, compound 1, was given with a purity of 99.7 wt% and a melting point (mp) of 76–80 °C.

[0215] Preparation of compound 2

[0216] Step (1)

[0217]

[0218] In a Dean-Stark apparatus, 5-hydroxyphthalic acid was reacted with 2.5 equivalents of the intermediate DMMI-C6-OH in toluene containing 5 mol% pTSA and heated under reflux for 72 hours. The resulting mixture was filtered to remove a white solid, which was unreacted 5-hydroxyphthalic acid. The resulting solution contained the product with a purity of 98.6% (as determined by HPLC).

[0219] Step (2)

[0220]

[0221] The product from step (1) was dissolved in THF along with benzene-1,3,5-tricarbonyltrichloro (0.3 equivalents), trimethylamine (1.5 equivalents), and DMAP. The reaction was completed after 2 hours. The reaction mixture was then filtered to remove Et3N-HCl, and the resulting solution was filtered through silica and then evaporated to a viscous, colorless oil. The product, compound 2, was given (88% by weight yield).

[0222] Other compounds and polymers used in the examples are listed in the following table. They are all commercially available.

[0223] Table 1

[0224]

[0225] Test methods

[0226] Solubility is tested by visual inspection. The solution is mixed for 12 hours using a magnetic stirrer. Solutions with a cloudy appearance or undissolved particles are considered insoluble.

[0227] The coating is tested visually. Coating quality is evaluated by examining color changes and dehydration in relation to coating thickness. Film thickness on the substrate is also tested using a stylus profilometer.

[0228] Adhesion testing was conducted in accordance with ASTM D6862-11 (2021). Different materials were tested using a Mecmesin Imperial 1000 adhesion tester equipped with a 50 N load sensor and a compliance value set to 20 N (equivalent to 8 N / cm). Adhesion was determined using a 90° peel test and 25 mm wide Tesa 4965 tape. An initialization cut was made at the peel initiation point and along the side of the tape using a scalpel to eliminate the influence of wider films on adhesion / cohesion.

[0229] Preparation and testing of the compositions of the present invention

[0230] In a laboratory drum or stirrer plate, the components of the compositions shown in Table 2 below are mixed in a sealed amber glass vial at room temperature for 12 hours to produce a homogeneous and stable formulation. In Table 2, all component values ​​are expressed as a weight percentage.

[0231] The composition was coated onto a TAC substrate with a thickness of 0.5–1 µm using spin coating or bar coating. The TAC substrate was coated with SU8 (Nippon Kayaku Co.), indium tin oxide (ITO), or SU8 with a patterned ITO layer applied (referred to as “mixed adhesion” in Table 2 below). All substrates were first treated in a plasma chamber with 500 W oxygen plasma for 30 seconds.

[0232] The coating film was dried on a hot plate at 80°C for 5 minutes, then allowed to cool to room temperature. Next, a 365 nm LED lamp was used at 2-10 J / cm². 2 The total UV dose causes the membrane to crosslink.

[0233] Adhesion tests were performed as described above, and the results are shown in Table 2 below, where CE represents the comparative example. CE1 contains no adhesive additives.

[0234] Table 2:

[0235]

[0236] Solubility: = Soluble and stable preparations, ~ = Soluble but unstable preparations. = Poor solubility. Adhesion strength is expressed in N / cm.

[0237] The results showed that the compositions of the present invention containing compound 1 or 2 achieved much stronger adhesion to substrates (particularly ITO and SU8 with a patterned ITO layer). CE1 contained no compounds of the present invention and did not adhere to ITO or SU8 with a patterned ITO layer, whereas in Example 1, the compositions of the present invention containing compound 1 significantly improved the achieved level of adhesion. Similarly, despite the presence of a UV-sensitive agent (CPTX or Speedcure 7010), Examples 2-6 containing compound 2 also achieved adhesion to both ITO and SU8 with a patterned ITO layer. A range of concentrations of compound 2 showed effective improvement in adhesion.

[0238] Films containing 0-1.5% by weight of the compounds of the present invention were also tested to ensure that curing was still possible. The UV dose was tested at 4 J / cm². 2 Under these conditions, the membrane achieved the same level of curing as the membrane without the compounds of this invention (as demonstrated by solvent resistance testing).

Claims

1. A compound of formula (I): in The core contains at least one aromatic, heteroaromatic, or aliphatic group; Each L represents a linking group or a covalent bond, preferably a linking group; Each SP is a spacer group, preferably selected from alkylene, alkenylene, arylene or heteroarylene, which is optionally interrupted by one or more heteroatoms and optionally substituted; Each X represents a potential crosslinkable group, preferably a crosslinkable group that can be activated by photochemical radiation; and a is an integer selected from 3 to 20.

2. The compound according to claim 1, wherein each X is a group capable of crosslinking via a [2π+2π] photo-cycloaddition reaction.

3. The compound according to claim 1 or 2, wherein each X is a crosslinkable group of formula (II): in R 1 Selected from H and C 1-6 Alkyl groups, preferably methyl groups; R 2 Selected from H and C 1-6 Alkyl, preferably methyl; or R 1 and R 2 Together with the carbon atoms they are attached to, they form a ring, wherein the ring optionally fuses with another ring.

4. The compound according to claim 3, wherein R 1 and R 2 It is a methyl group.

5. The compound according to any one of the preceding claims, wherein the compound is a compound of formula (Ia): The core, L, SP, and a are as defined in claim 1; and R 1 and R 2 As defined in claim 3 or 4.

6. The compound according to any one of the preceding claims, wherein each a is 3-12, more preferably 3-6, and still more preferably 3 or 4.

7. The compound according to any of the preceding claims, wherein the core comprises at least one aromatic or heteroaromatic group, preferably an aromatic group.

8. The compound according to any one of the preceding claims, wherein the core is selected from the group consisting of: The key ending with a wavy line indicates the location where the SP is connected to the core.

9. The compound according to any one of the preceding claims, wherein the compound is a compound of formula (Ib), (Ic), or (Id): in L and SP are as defined in claim 1; R 1 and R 2 As defined in claim 3 or 4; and k+l = a as defined in claim 1, i.e., 3-20, more preferably 3-6, and still more preferably 3 or 4.

10. The compound according to claim 9, wherein the compound is a compound of formula (Ib).

11. The compound according to any of the preceding claims, wherein each spacer group is selected from C 3-20 Alkylene and C 3-20 Alkenyl group.

12. The compound according to any one of the preceding claims, wherein the compound is a compound of formula (Ibi): in L and a are as defined in claim 1; R 1 and R 2 As defined in claim 3 or 4; and n is an integer selected from 3 to 20.

13. The compound according to any of the preceding claims, wherein each L is a linking group consisting of C(O)O.

14. The compound according to any one of claims 1 to 13, wherein each L is a linking group comprising an aromatic or heteroaromatic group, preferably an aromatic group.

15. The compound according to any of the preceding claims, wherein each L is a linking group of formula (III): Each R 3 It is selected from C(O)O, OC(O), C(O), OC(O)O, C(O)NH, O, S, SO2, SO2NH, NH and NMe, and is preferably selected from C(O)O and OC(O).

16. The compound according to any one of the preceding claims, wherein the compound is selected from the structures shown below: 。 17. A method for preparing a compound of formula (I) according to any one of claims 1 to 16, the method comprising: React the compound of formula (V) with the compound of formula (VI): in The core contains at least one aromatic, heteroaromatic, or aliphatic group; The reaction between L' and L'' produces L, and each L is a linking group or a covalent bond, preferably a linking group; Each SP is a spacer group, preferably selected from alkylene, alkenylene, arylene or heteroarylene, which is optionally interrupted by one or more heteroatoms and optionally substituted; Each X represents a potential crosslinkable group, preferably a crosslinkable group that can be activated by photochemical radiation; and a is an integer selected from 3 to 20.

18. A composition comprising: (i) The compound of formula (I) according to any one of claims 1 to 16; (ii) Polycyclic olefins, preferably polynorbornene; (iii) photosensitizers; and (iv) Optional solvent.

19. A method for preparing the composition according to claim 18, the method comprising mixing the following in a solvent: (i) a compound of formula (I) according to any one of claims 1 to 16; (ii) a polycyclic olefin, preferably polynorbornene; and (iii) a photosensitizer.

20. A structure comprising: (i) Base; and (ii) The composition according to claim 18 on at least one surface of the substrate.

21. The structure of claim 20, wherein the composition exists in the form of a layer on the substrate.

22. The structure according to claim 20 or 21, wherein the substrate is selected from ITO or other substrates patterned with ITO.

23. A method for preparing a structure according to any one of claims 20 to 22, the method comprising: (i) Depositing the composition according to claim 18 onto at least one surface of the substrate by solution treatment; (ii) Dry the composition; as well as (iii) Crosslinking the composition to produce the structure.

24. An electronic device comprising a structure according to any one of claims 20 to 22.

25. The electronic device according to claim 24, wherein the electronic device is a thin-film transistor.

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