Compound for light patterning of small organic molecule semiconductor and preparation method thereof

Abstract

The invention relates to the field of semiconductors, in particular to a compound for light patterning of small organic molecule semiconductors and a preparation method of the compound. The structure of the compound is shown as a formula (1), A is selected from-OCH2CH2-or-CH2-, R1 is selected from one or more of C5-C42 polyhydric alcohol derivative groups, R2 and R3 are respectively and independently selected from one or more of H, halogen and cyano, R4 and R5 are respectively and independently selected from one or more of H, C1-C12 alkyl, C2-C12 alkyl containing ether bonds, sulfydryl, hydroxyl and amino, n is an integer greater than 1, and n is an integer greater than 1. And m is an integer of 4 or more. The compound provided by the invention is used as a photo-crosslinking agent to creatively realize direct photo-crosslinking patterning of small organic molecule semiconductors. Formula (1) # imgabs0 #

Description

Technical Field

[0001] The invention relates to the field of semiconductors, and in particular to a compound used for photo-patterning of organic small molecule semiconductors and a preparation method thereof. Background Art

[0002] Organic small molecule semiconductors are widely used in the field of organic optoelectronics due to their clear molecular structure, easy molecular structure modification, and small differences in synthesis batches. In order to obtain high-performance functional devices and highly integrated circuits, organic small molecule semiconductor materials need to be precisely patterned.

[0003] At present, the patterning of organic small molecule semiconductors in the existing technology mostly adopts the traditional photolithography method, which is complicated to operate and has high processing cost. In addition, some organic small molecule semiconductors are unstable under strong ultraviolet light or high temperature, which ultimately leads to poor results. However, the direct photolithography method of photocrosslinker with simple operation steps and milder conditions can better realize the photopatterning of organic small molecule semiconductors.

[0004] Trifluoromethylphenylbis(aziridine) photocrosslinkers can efficiently generate active carbene intermediates under ultraviolet light irradiation and rapidly bind to adjacent SP 3 The CH bonds undergo efficient insertion reactions, thereby achieving chemical cross-linking to form an insoluble network. After covering the light with a photomask of a specific shape, accurate and high-resolution patterning can be directly achieved by washing away the uncross-linked parts using the difference in solubility before and after cross-linking. Multi-site photocrosslinkers have multiple reaction sites and can react with multiple molecules or multiple functional groups in the same molecule to form a denser cross-linked network. Compared with traditional single-site photocrosslinkers, this dense cross-linking structure can significantly improve the degree of cross-linking of the material, thereby greatly improving the mechanical strength, heat resistance, solubility resistance and other properties of the material.

[0005] At present, there have been many research reports on the direct photolithography patterning of polymer semiconductors and biomacromolecules using trifluoromethylphenylbis(aziridine)-based photocrosslinkers, but there are few reports on the photocrosslinking patterning of organic small molecule semiconductors. Therefore, the development of a multi-site photocrosslinker suitable for direct photolithography of organic small molecule semiconductors is an urgent issue to be solved. Summary of the invention

[0006] The purpose of the present invention is to overcome the problems existing in the above-mentioned prior art and provide a compound for photopatterning of organic small molecule semiconductors and a preparation method thereof. The compound is used as a photocrosslinking agent to successfully realize direct photocrosslinking of organic small molecule semiconductors with high resolution and precision patterning.

[0007] In order to achieve the above object, the present invention provides a compound suitable for a photocrosslinking agent, the structure of which is shown in formula (1):

[0008] Formula (1)

[0009] Wherein, A is selected from -OCH2CH2- or -CH2-, R1 is selected from one or more of C5-C42 polyol derivative groups, R2 and R3 are each independently selected from one or more of H, halogen and cyano, R4 and R5 are each independently selected from one or more of H, C1-C12 alkyl, C2-C12 alkyl containing ether bonds, mercapto, hydroxyl and amino, n is an integer greater than 1, and m is an integer greater than 4.

[0010] The second aspect of the present invention provides a method for preparing the above compound, the method comprising:

[0011] (1) subjecting the compound represented by formula (A) to a first contact reaction with oxalyl chloride to obtain a compound represented by formula (B);

[0012] (2) in the presence of an alkaline agent, subjecting the compound represented by formula (B) to a second contact reaction with a polyol compound to obtain a compound represented by formula (1);

[0013] Formula (A) Formula (B)

[0014] The third aspect of the present invention provides a photocrosslinking agent comprising the above compound.

[0015] The fourth aspect of the present invention provides a method for photo-patterning an organic small molecule semiconductor, which comprises mixing the organic small molecule semiconductor with the above-mentioned photo-crosslinking agent and then spin coating it on the surface of a substrate to form a thin film, covering the surface of the thin film with a photomask template and performing photo-crosslinking, and then using a solvent to clean the uncrosslinked part to obtain a patterned thin film.

[0016] The present invention provides a class of compounds suitable for photocrosslinking agents with a specific structure, which, as photocrosslinking agents, have pioneered the direct photocrosslinking patterning of organic small molecule semiconductors. The compound has good solubility and excellent miscibility with a variety of organic small molecule semiconductors. In addition, the compound has multiple active sites and has higher activity and reaction efficiency in the crosslinking reaction. It also has a wide range of applicability and can directly perform precise and high-resolution photopatterning on a variety of organic small molecule semiconductors. In addition, the preparation method of the compound is simple, the conditions are mild, and the cost is low. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1The hydrogen nuclear magnetic resonance spectrum of the compound represented by formula (1-1) prepared in Example 1;

[0018] Figure 2 The hydrogen nuclear magnetic resonance spectrum of the compound represented by formula (1-2) prepared in Example 2;

[0019] Figure 3 The hydrogen nuclear magnetic resonance spectrum of the compound represented by formula (1-3) prepared in Example 3;

[0020] Figure 4 The hydrogen nuclear magnetic resonance spectrum of the compound represented by formula (1-4) prepared in Example 4;

[0021] Figure 5 The hydrogen nuclear magnetic resonance spectrum of the compound represented by formula (D-1) prepared in Comparative Example 1;

[0022] Figure 6 It is a schematic diagram of the photo-patterning process of the organic small molecule semiconductor in the present invention;

[0023] Figure 7 The absorption spectra before and after development obtained in Test Example 2;

[0024] Figure 8 The absorption spectra before and after development obtained in Test Example 14;

[0025] Fig. 9 This is an example of the photopatterning of an organic small molecule semiconductor obtained in Test Example 8;

[0026] Fig.10 The resolution image of the organic small molecule semiconductor photopatterning obtained in Test Example 1-15;

[0027] in, Fig.10 In FIG. 1 , a to o correspond to test cases 1 to 15, respectively. DETAILED DESCRIPTION

[0028] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0029] In the present invention, The wavy lines in structures such as these indicate where the groups are attached.

[0030] In one aspect, the present invention provides a compound suitable for a photocrosslinking agent, the structure of the compound is shown in formula (1):

[0031] Formula (1)

[0032] Wherein, A is selected from -OCH2CH2- or -CH2-, R1 is selected from one or more of C5-C42 polyol derivative groups, R2 and R3 are each independently selected from one or more of H, halogen and cyano, R4 and R5 are each independently selected from one or more of H, C1-C12 alkyl, C2-C12 alkyl containing ether bonds, mercapto, hydroxyl and amino, n is an integer greater than 1, and m is an integer greater than 4.

[0033] According to the present invention, the compound having a specific structure comprises a plurality of trifluoromethylphenylbis(aziridine) photocrosslinking groups, which, when used as a photocrosslinking agent in direct photolithography of organic small molecule semiconductors, can efficiently generate active carbene intermediates under ultraviolet light irradiation, and rapidly and efficiently react with multiple molecules or multiple reaction sites in the same molecule to form SP 3 The CH bond insertion reaction forms a covalent cross-linked network, which significantly reduces the solubility of the organic small molecule semiconductor. The difference in solubility before and after cross-linking is used to wash away the uncross-linked part and achieve photopatterning.

[0034] According to the present invention, in order to make the above-mentioned compounds better miscible with organic small molecule semiconductors and achieve better chemical crosslinking effect and higher reaction efficiency, thereby performing more accurate and rapid direct photolithography patterning of organic small molecule semiconductors, preferably, A is selected from -OCH2CH2- or -CH2-, R1 is selected from one or more of a tetrahydric alcohol derivative group of C5-C26, a pentahydric alcohol derivative group of C5-C10, a hexahydric alcohol derivative group of C6-C10, an octahydric alcohol derivative group of C15-C21, a nonadecanol derivative group of C36-C42 and a twenty-undecyl alcohol derivative group of C36-C42, R2 and R3 are each independently selected from one or more of H, F, Cl, Br and cyano, R4 and R5 are each independently selected from one or more of H, C1-C12 alkyl, C2-C12 alkyl containing an ether bond, thiol, hydroxyl and amino, n is an integer greater than 1, and m is an integer greater than 4.

[0035] More preferably, A is selected from -OCH2CH2- or -CH2-, and R1 is selected from one or more of the fragments shown in the following formula:

[0036] R2 and R3 are each independently selected from one or more of H, F, Cl, Br and cyano; R4 and R5 are each independently selected from one or more of H, C1-C6 alkyl, C2-C6 alkyl containing ether bond, mercapto, hydroxyl and amino; n is an integer of 1-6, and m is an integer of 4-10.

[0037] Further preferably, A is selected from -OCH2CH2- or -CH2-, R1 is selected from the fragment represented by formula (R1-1) or (R1-4), R2 and R3 are each independently selected from one or more of H, F, Cl, Br and cyano, R4 and R5 are each independently selected from one or more of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, -CH2-O-CH3, -CH2-CH2-O-CH3, -CH2-CH2-O-CH2-CH3, -CH2-O-CH2-CH2-CH3, -CH2-O-CH2-CH2-CH3, thiol, hydroxyl and amino, n is an integer of 1-3, and m is an integer of 4-6.

[0038] According to a particularly preferred embodiment of the present invention, the compound is selected from one or more compounds represented by the following formula:

[0039] Formula (1-1)

[0040] Formula (1-2)

[0041] Formula (1-3)

[0042] Formula (1-4)

[0043] According to the present invention, the compound has excellent solubility and can be easily dissolved in various common organic solvents. This property makes it more convenient to use as a photocrosslinking agent and can be flexibly matched with various organic solvents to meet different application requirements. At the same time, the compound has excellent miscibility with organic small molecule semiconductors and can be fully integrated with a variety of organic small molecule semiconductors to form a uniform and stable blending system, providing a solid foundation for subsequent processing and application.

[0044] According to the present invention, the compound contains a plurality of trifluoromethylphenylbis(aziridine) active groups, and the presence of these active groups makes it have higher reactivity and reaction efficiency in the cross-linking reaction. Compared with the traditional double-ended photocrosslinker, its cross-linking efficiency is significantly improved, and the cross-linking reaction can be completed in a shorter time, forming a denser cross-linking network, and improving the efficiency and effect of chemical cross-linking.

[0045] The second aspect of the present invention provides a method for preparing the above compound, the method comprising:

[0046] (1) subjecting the compound represented by formula (A) to a first contact reaction with oxalyl chloride to obtain a compound represented by formula (B);

[0047] (2) in the presence of an alkaline agent, subjecting the compound represented by formula (B) to a second contact reaction with a polyol compound to obtain a compound represented by formula (1);

[0048] Formula (A) Formula (B)

[0049] According to the present invention, the group selection of the compound represented by formula (A), the compound represented by formula (B) and the polyol compound in the above-mentioned preparation method will be adaptively adjusted according to the compound represented by formula (1) to be prepared, as described above, and the present invention will not be repeated here.

[0050] According to the present invention, the preparation method has short steps, simple operation, and no cumbersome and complicated process, making the entire synthesis process more efficient and convenient. At the same time, the reaction conditions in the preparation method are mild, and no harsh conditions such as extreme temperature and pressure are required, which not only reduces the requirements for equipment, but also improves the safety and stability of the preparation process and reduces costs.

[0051] According to the present invention, in order to make the reaction proceed better and improve the product yield, in the reaction of preparing the compound represented by formula (B) from the compound represented by formula (A), preferably, relative to 1mmol of the compound represented by formula (A), the amount of oxalyl chloride used is at least 3mmol, preferably 8-15mmol, for example, it can be 8mmol, 10mmol, 12mmol and 14mmol and the range between any values ​​thereof.

[0052] According to the present invention, in order to make the compound represented by formula (A) and the compound represented by formula (B) contact more fully and promote the reaction, the solvent and the amount of the first contact reaction can be adjusted. Preferably, the solvent of the first contact reaction is selected from one or more of dichloromethane, chloroform, tetrahydrofuran, dichloroethane, toluene and n-hexane, preferably one or more of dichloromethane, chloroform and tetrahydrofuran.

[0053] Preferably, relative to 1 mmol of the compound represented by formula (A), the amount of the solvent used in the first contact reaction is 3-50 mL, preferably 8-20 mL, for example, it can be 8 mL, 10 mL, 15 mL, 18 mL and 20 mL and any range therebetween.

[0054] According to the present invention, in order to improve the reaction efficiency and obtain better yield and product purity, the conditions of the first contact reaction can be adjusted. Preferably, the conditions of the first contact reaction include: temperature 10-40°C, time 4-16h.

[0055] More preferably, the conditions of the first contact reaction include: temperature 20-30°C (for example, it can be a range between 20°C, 25°C, 28°C and 30°C, and any values ​​thereof), time 6-10h (for example, it can be a range between 6h, 8h, 9h and 10h, and any values ​​thereof).

[0056] According to the present invention, preferably, the first contact reaction is carried out under an inactive gas atmosphere. Preferably, the inactive gas is nitrogen and / or argon.

[0057] According to the present invention, preferably, the specific steps of the first contact reaction may be: adding oxalyl chloride and a solvent into a reactor, cooling to -20°C to 5°C, dissolving the compound represented by formula (A) in the solvent and adding it to the reactor, and performing the first contact reaction after the addition is completed.

[0058] According to the present invention, the post-treatment method of the first contact reaction can be a post-treatment method commonly used in the art, as long as the product of the compound represented by formula (B) can be obtained. For example, the post-treatment method adopted can be: the reaction solution is spin-dried, and a solvent is added and spin-dried again (the purpose is to remove excess oxalyl chloride) to obtain the compound represented by formula (B).

[0059] According to the present invention, in the reaction of preparing the compound represented by formula (1) from the compound represented by formula (B), in order to obtain a better reaction effect, the selection and dosage of the alkaline reagent can be adjusted. Preferably, the alkaline reagent is selected from one or more of triethylamine, pyridine, piperidine, ethylenediamine and diisopropylethylamine, preferably triethylamine and / or pyridine.

[0060] Preferably, relative to 1 mmol of the compound represented by formula (B), the amount of the alkaline agent used is 0.1-50 mmol, preferably 1-10 mmol, for example, it can be 1 mmol, 4 mmol, 8 mmol, 10 mmol, and any value in between.

[0061] According to the present invention, the polyol compound can be selected from the polyol compounds corresponding to the selection of the R1 group described in the first aspect above. Preferably, the polyol compound is selected from one or more polyol compounds of C5-C42.

[0062] More preferably, the polyol compound is selected from one or more of C5-C26 tetrahydric alcohol compounds, C5-C10 pentahydric alcohol compounds, C6-C10 hexahydric alcohol compounds, C15-C21 octahydric alcohol compounds, C36-C42 nonadehydric alcohol compounds and C36-C42 hexonehydric alcohol compounds.

[0063] More preferably, the polyol compound is selected from one or more of the compounds shown in the following formula:

[0064]

[0065] According to a particularly preferred embodiment of the present invention, the polyol compound is selected from the compound represented by formula (Z-1) or formula (Z-4).

[0066] According to the present invention, the amount of the above-mentioned polyol compound can be selected within a wide range. In order to obtain a better reaction effect, preferably, relative to 1mmol of the compound represented by formula (B), the amount of the polyol compound is 0.1-1mmol, preferably 0.15-0.3mmol, for example, it can be 0.15mmol, 0.2mmol, 0.25mmol and 0.3mmol and the range of any values ​​therebetween.

[0067] According to the present invention, in order to make the materials more fully dispersed and contacted, preferably, the solvent of the second contact reaction is selected from one or more of dichloromethane, chloroform, tetrahydrofuran, toluene and pyridine, preferably one or more of dichloromethane, tetrahydrofuran and pyridine.

[0068] Preferably, relative to 1 mmol of the compound represented by formula (B), the amount of the solvent used in the second contact reaction is 1-30 mL, preferably 3-15 mL, for example, 3 mL, 10 mL, 12 mL and 15 mL and any value in between.

[0069] According to the present invention, in order to improve the yield and purity of the compound represented by formula (1) and promote the reaction process, preferably, the conditions of the second contact reaction include: temperature 10-40°C, time 8-30h.

[0070] More preferably, the conditions of the second contact reaction include: temperature 20-30°C (for example, it can be a range between 20°C, 25°C, 28°C and 30°C and any values ​​thereof), time 12-24h (for example, it can be a range between 12h, 18h, 20h and 24h and any values ​​thereof).

[0071] According to the present invention, preferably, the second contact reaction is carried out under an inactive gas atmosphere. Preferably, the inactive gas is nitrogen and / or argon.

[0072] According to the present invention, preferably, the second contact reaction is carried out under light-proof conditions.

[0073] According to the present invention, preferably, the specific steps of the second contact reaction may be: adding the polyol compound, the alkaline reagent and the solvent into the reactor, dissolving the compound represented by formula (B) in the solvent and adding it to the reactor, and performing the second contact reaction after the addition is completed.

[0074] According to the present invention, the post-treatment method of the second contact reaction can be a post-treatment method commonly used in the art, as long as the product of the compound represented by formula (1) can be obtained. For example, the post-treatment method adopted can be: extracting the reaction solution (the extraction solvent can be selected from one or more of dichloromethane, ethyl acetate, saturated copper sulfate aqueous solution and saturated sodium chloride aqueous solution, and the amount used is a conventional amount), collecting the organic phase, adding a desiccant (such as anhydrous sodium sulfate, anhydrous calcium sulfate and anhydrous magnesium sulfate, etc., and the amount used is a conventional amount), drying, suction filtering, and spin drying to obtain the compound represented by formula (1).

[0075] The third aspect of the present invention provides a photocrosslinking agent comprising the above compound.

[0076] The fourth aspect of the present invention provides a method for photo-patterning an organic small molecule semiconductor, which comprises mixing an organic small molecule semiconductor with the above-mentioned photo-crosslinking agent and then spin-coating the mixture on a substrate (e.g., a silicon wafer) to form a thin film, covering the film surface with a photomask and performing photo-crosslinking, and then cleaning the uncrosslinked portion to obtain a patterned film. The basic process of the photo-patterning method is as follows: Figure 6 shown.

[0077] According to the present invention, the compound has wide applicability as a photocrosslinking agent, and can directly pattern a variety of organic small molecule semiconductors accurately and with high resolution, with a resolution of up to micrometer level. Compared with the traditional photolithography patterning method, the photopatterning method is simpler and easier to operate, does not require complex equipment and processes, and is also cheaper in cost, without expensive equipment investment and maintenance costs.

[0078] According to the present invention, in the above-mentioned photopatterning method, the mixing method of the organic small molecule semiconductor and the photocrosslinker can be selected within a wide range. For example, the two can be dissolved and mixed separately in the same container in sequence, the two can be added to the solvent at the same time and dissolved and mixed, or the two can be dissolved separately and then the solutions of the two can be mixed.

[0079] According to the present invention, preferably, the above-mentioned photopatterning method is carried out under light-proof conditions.

[0080] According to the present invention, the above-mentioned photocrosslinking agent can be chemically crosslinked with a variety of organic small molecule semiconductors to achieve direct photolithography. In order to achieve better results, preferably, the organic small molecule semiconductor can be one or more of Y6, Y6-EG and C8-BTBT-C8. (Generally used in the field of organic solar cells), Y6-EG is (Generally used in the field of organic electrochemical transistors), C8-BTBT-C8 is (Generally used in the field of organic field effect transistors).

[0081] According to the present invention, in order to achieve a better chemical cross-linking effect and ensure the accuracy of patterning, the dosage of the organic small molecule semiconductor and the photocross-linking agent can be adjusted. Preferably, the mass ratio of the organic small molecule semiconductor to the photocross-linking agent is 1:0.5-8, preferably 1:1-4, for example, it can be 1:1, 1:2, 1:3 and 1:4 and the range between any values ​​thereof.

[0082] According to the present invention, the solvent for dissolving the above-mentioned organic small molecule semiconductor and the photocrosslinker can be selected from a wide range. The above-mentioned photocrosslinker has good solubility and can be dissolved in most organic solvents. Generally, the solvent is selected according to the properties of the organic small molecule semiconductor. Preferably, the solvent for dissolving the organic small molecule semiconductor and the photocrosslinker is selected from one or more organic solvents, preferably one or more of chloroform, chlorobenzene, toluene, tetrahydrofuran and ethanol, and more preferably chloroform and / or chlorobenzene.

[0083] According to the present invention, in the above-mentioned patterning method, in order to form a thin film in a better state, preferably, the spin coating rotation speed is 500-4000r / min, preferably 1000-3000r / min, for example, it can be 1000r / min, 1500r / min, 2000r / min, 2500r / min and 3000r / min and the range between any values ​​thereof.

[0084] According to the present invention, the photocrosslinking is carried out under ultraviolet light irradiation, and the ultraviolet light is generally selected to have a wavelength of 365nm. Preferably, the power of the ultraviolet light is 300-1000mW / cm 2 , preferably 500-800mW / cm 2 , for example, 500 mW / cm 2 、600mW / cm 2 、700mW / cm 2 and 800mW / cm 2 Preferably, the ultraviolet light irradiation time is more than 0.5 min, preferably 1-5 min, for example, it can be 1 min, 2 min, 3 min, 5 min and other values ​​and the range between any values.

[0085] According to the present invention, preferably, the solvent used to clean the uncrosslinked part is selected from one or more organic solvents, preferably one or more of chloroform, ethanol, ethyl acetate and dichloromethane, more preferably chloroform and / or ethanol.

[0086] According to the present invention, in the above-mentioned operation of cleaning the uncrosslinked part, the cleaning time needs to be adjusted to avoid damage to the pattern due to excessive cleaning. Preferably, the cleaning time is 5-20s, preferably 10-15s, for example, it can be 10s, 12s, 13s and 15s and any range therebetween.

[0087] The present invention provides a class of compounds suitable for photocrosslinking agents with a specific structure, which, as photocrosslinking agents, have pioneered the direct photocrosslinking patterning of organic small molecule semiconductors. The compound has good solubility and excellent miscibility with a variety of organic small molecule semiconductors. In addition, the compound has multiple active sites and has higher activity and reaction efficiency in the crosslinking reaction. It also has a wide range of applicability and can directly perform precise and high-resolution photopatterning on a variety of organic small molecule semiconductors. In addition, the preparation method of the compound is simple, the conditions are mild, and the cost is low.

[0088] The present invention will be described in detail below through examples.

[0089] In the following examples, the devices used are all conventional experimental devices in the art, the experimental operations adopted are all conventional operations in the art, and the raw materials, reagents, etc. used can be obtained commercially. Among them, the compound shown in formula (A-1) was purchased from Shanghai Bid Pharmaceutical Technology Co., Ltd., and the compound shown in formula (A-2) was synthesized according to the document (Angew. Chem. Int. Ed. 2023, 62, e202304708); Y6 was synthesized according to the document (Joule 3, 1140-1151, April 17, 2019), Y6-EG was synthesized according to the document (Adv. Energy Mater. 2021, 11, 2003141), and C8-BTBT-C8 was purchased from Admas-beta.

[0090] Example 1

[0091] This example is used to illustrate the preparation of the compound represented by formula (1-1).

[0092]

[0093] The specific steps are as follows:

[0094] (1) Under nitrogen atmosphere, 9 mmol of oxalyl chloride and 5 mL of dichloromethane were added to the reactor, the temperature was lowered to 0°C, 0.9 mmol of the compound represented by formula (A-1) was added to 10 mL of dichloromethane and dissolved and then added dropwise to the reactor, and the reaction was carried out at 25°C for 6 hours. The reaction solution was spin-dried and then 10 mL of dichloromethane was added and spin-dried again to remove excess oxalyl chloride, to obtain the compound represented by formula (B-1).

[0095] (2) Under nitrogen atmosphere, add 0.2 mmol of the compound represented by formula (Z-1), 0.9 mmol of triethylamine and 5 mL of dichloromethane to the reactor. Dissolve 0.9 mmol of the compound represented by formula (B-1) in 5 mL of dichloromethane and add dropwise to the reactor, and react for 12 hours at 25°C in the dark. Extract the reaction solution with 50 mL of dichloromethane and 150 mL of saturated sodium chloride aqueous solution, collect the organic phase, add anhydrous sodium sulfate to dry, filter with suction, and spin dry to obtain the compound represented by formula (1-1).

[0096] The H NMR spectrum of the compound represented by formula (1-1) is as follows Figure 1 As shown, 1 HMR (600MHz, CDCl3) δ = 7.41 (d, J = 7.9Hz, 8H), 7.20 (d, J = 7.9Hz, 8H), δ = 5.26 (s, 8H), 4.41 (s, 8H).

[0097] Example 2

[0098] This example is used to illustrate the preparation of the compound represented by formula (1-2).

[0099]

[0100] The specific steps are as follows:

[0101] (1) Under nitrogen atmosphere, 9 mmol of oxalyl chloride and 5 mL of dichloromethane were added to the reactor, the temperature was lowered to 0°C, 0.9 mmol of the compound represented by formula (A-2) was added to 10 mL of dichloromethane and dissolved and then added dropwise to the reactor, and the reaction was carried out at 20°C for 6 hours. The reaction solution was spin-dried and then 10 mL of dichloromethane was added and spin-dried again to remove excess oxalyl chloride, to obtain the compound represented by formula (B-2).

[0102] (2) Under nitrogen atmosphere, add 0.2 mmol of the compound represented by formula (Z-1), 0.9 mmol of triethylamine and 5 mL of dichloromethane to the reactor. Dissolve 0.9 mmol of the compound represented by formula (B-1) in 5 mL of dichloromethane and add dropwise to the reactor, and react for 12 hours at 30°C in the dark. Extract the reaction solution with 50 mL of dichloromethane and 150 mL of saturated sodium chloride aqueous solution, collect the organic phase, add anhydrous sodium sulfate to dry, filter with suction, and spin dry to obtain the compound represented by formula (1-2).

[0103] The H NMR spectrum of the compound represented by formula (1-2) is as follows Figure 2 As shown, 1 HMR (400MHz, CDCl3) δ = 7.12 (d, J = 8.6Hz, 8H), 6.90 (d, J = 8.8Hz, 8H), δ = 4.43 (t, J = 4.4Hz, 8H), 4.39 (s, 8H), 4.10 (t, J = 4.6Hz, 8H), 3.82 (m, 16H).

[0104] Example 3

[0105] This example is used to illustrate the preparation of the compound represented by formula (1-3).

[0106]

[0107] The specific steps are as follows:

[0108] (1) Under nitrogen atmosphere, 13 mmol of oxalyl chloride and 5 mL of dichloromethane were added to the reactor, the temperature was lowered to 0°C, 0.9 mmol of the compound represented by formula (A-1) was added to 10 mL of dichloromethane and dissolved and then added dropwise to the reactor, and the reaction was carried out at 30°C for 8 hours. The reaction solution was spin-dried and then 10 mL of dichloromethane was added and spin-dried again to remove excess oxalyl chloride, to obtain the compound represented by formula (B-1).

[0109] (2) Under nitrogen atmosphere, add 0.2 mmol of the compound represented by formula (Z-4) and 5 mmol of pyridine to the reactor. Dissolve 1.3 mmol of the compound represented by formula (B-1) in 5 mL of dichloromethane and add dropwise to the reactor, and react at 20°C in the dark for 24 hours. Extract the reaction solution with 50 mL of ethyl acetate, 150 mL of saturated copper sulfate aqueous solution and 150 mL of saturated sodium chloride aqueous solution, collect the organic phase, add anhydrous sodium sulfate to dry, filter with suction, and spin dry to obtain the compound represented by formula (1-3).

[0110] The H NMR spectrum of the compound represented by formula (1-3) is as follows Figure 3 As shown, 1 HMR (600MHz, CDCl3) δ = 7.39 (d, J = 7.9 Hz, 12H), 7.18 (d, J = 8.0 Hz, 12H), δ = 5.23 (s, 12H), 4.30 (s, 12H), 3.47 (s, 4H).

[0111] Example 4

[0112] This example is used to illustrate the preparation of the compound represented by formula (1-4).

[0113]

[0114] The specific steps are as follows:

[0115] (1) Under nitrogen atmosphere, 13 mmol of oxalyl chloride and 5 mL of dichloromethane were added to the reactor, the temperature was lowered to 0°C, 1.3 mmol of the compound represented by formula (A-2) was added to 10 mL of dichloromethane and dissolved and then added dropwise to the reactor, and the reaction was carried out at 25°C for 6 hours. The reaction solution was spin-dried and then 10 mL of dichloromethane was added and spin-dried again to remove excess oxalyl chloride, to obtain the compound represented by formula (B-2).

[0116] (2) Under nitrogen atmosphere, add 0.2 mmol of the compound represented by formula (Z-4) and 5 mmol of pyridine to the reactor. Dissolve 1.3 mmol of the compound represented by formula (B-2) in 5 mL of dichloromethane and add dropwise to the reactor, and react at 25°C in the dark for 24 hours. Extract the reaction solution with 50 mL of ethyl acetate, 150 mL of saturated copper sulfate aqueous solution and 150 mL of saturated sodium chloride aqueous solution, collect the organic phase, add anhydrous sodium sulfate to dry, filter with suction, and spin dry to obtain the compound represented by formula (1-4).

[0117] The H NMR spectrum of the compound represented by formula (1-4) is as follows Figure 4 As shown, 1 HMR (600MHz, CDCl3) δ = 7.11 (d, J = 8.4Hz, 12H), 6.89 (d, J = 8.6Hz, 12H), δ = 4.41 (t ,J=4.1Hz,8H),4.30(s,12H),4.09(t,J=4.4Hz,8H),3.82(m,24H),3.47(m,4H).

[0118] Comparative Example 1

[0119] This comparative example is used to illustrate the preparation of a traditional double-terminal photocrosslinker.

[0120]

[0121] The specific steps are as follows:

[0122] Under nitrogen atmosphere, 2.86 mmol of the compound represented by formula (A-1) and 8 mL of dichloromethane were added to the reactor, the temperature was lowered to 0°C, 1.19 mmol of oxalyl chloride was dissolved in 5 mL of dichloromethane and added dropwise to the reactor, and the mixture was reacted at 25°C for 10 h. The reaction solution was spin-dried to obtain the compound represented by formula (D-1).

[0123] The H NMR spectrum of the compound represented by formula (D-1) is as follows Figure 5 As shown, 1HMR (600MHz, CDCl3) δ = 7.43 (d, J = 8.4Hz, 4H), 7.21 (d, J = 8.1Hz, 4H), 5.30 (s, 4H).

[0124] Test Example 1-15

[0125] The compounds obtained in Examples 1-4 and Comparative Example 1 were used as photocrosslinkers for photopatterning of organic small molecule semiconductors. The specific steps are as follows:

[0126] (1) Dissolve the organic small molecule semiconductor in chloroform to prepare a 20 mg / mL solution; dissolve the photocrosslinker in chloroform to prepare a 100 mg / mL solution. Mix the two solutions to prepare a mixed solution with a certain mass ratio of the organic small molecule semiconductor and the photocrosslinker.

[0127] (2) Take 30 μL of the mixed solution and add it dropwise to the center of the silicon wafer at a spin coating speed of 2000 r / min. After the spin coating is completed, a thin film with a thickness of about 100 nm is formed on the surface of the silicon wafer.

[0128] (3) Select a photomask with a predetermined pattern and cover it on the film. Open the wavelength to 365nm and the power to 600mW / cm 2 The ultraviolet LED lamp is used for ultraviolet irradiation, and the light evenly covers the entire film area and lasts for 2 minutes.

[0129] (4) After the irradiation, the silicon wafer with the thin film is immersed in chloroform for cleaning for 10 seconds. After taking out the silicon wafer, it is blown dry with nitrogen gas to obtain the patterning result on the silicon wafer.

[0130] The organic small molecule semiconductors and photocrosslinkers used in Test Examples 1-15 and their mass ratios are shown in Table 1.

[0131] To further determine the crosslinking efficiency, the films of Test Example 2 and Test Example 14 before and after development (i.e., step 4) were tested for UV-visible absorption spectra using a UNICO UV-4802 UV-visible spectrophotometer, as shown in FIG. Figure 7 and Figure 8 As shown. The molar extinction coefficient of test example 2 is 57%, and the molar extinction coefficient of test example 14 is 7%. Molar extinction coefficient = peak absorbance after development / peak absorbance before development.

[0132] The light patterning images obtained in Test Example 8 are as follows: Fig. 9 shown.

[0133] The resolution images of the light patterning obtained in Test Examples 1-15 are as follows: Fig.10 As shown in a to o.

[0134] Table 1

[0135]

[0136]

[0137] pass Figure 7 and Figure 8 It can be seen that the molar extinction coefficient of the multi-terminal photocrosslinker prepared in Example 1 can reach 57% after development, while the molar extinction coefficient of the double-terminal photocrosslinker prepared in Comparative Example 1 is only 7% after development. Since the absorption intensity of the compound can be used as the basis for the quantification of the substance (the more organic small molecule semiconductors remain in the film after development, the higher the absorbance retention), the retention of the film after development can be expressed by the molar extinction coefficient. The higher the crosslinking efficiency of the photocrosslinker, the better the film retention and the larger the molar extinction coefficient. It can be seen that the film retention after development of Example 1 using the technical solution of the present invention is significantly better than that of Comparative Example 1.

[0138] pass Fig. 9 and Fig.10 It can be seen that test examples 1-12 using the compounds provided in Examples 1-4 as photocrosslinkers can achieve direct and precise lithography of organic small molecule semiconductors, and the resolution reaches the micron level. However, test examples 13-15 using the traditional double-ended photocrosslinker prepared in Comparative Example 1 have limited molecular weight and good solubility of organic small molecule semiconductors. At the same time, during the crosslinking process, the traditional double-ended photocrosslinker has only two crosslinking sites, making it difficult to form a continuous crosslinking network, resulting in no obvious change in the solubility of the crosslinked organic small molecule semiconductor. After development, the retention rate of the organic small molecule semiconductor in the obtained film is low, which directly leads to the material being unsuitable for direct lithography.

[0139] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A compound suitable for a photocrosslinking agent, characterized in that: The structure of the compound is shown in formula (1): Formula (1) Wherein, A is selected from -OCH2CH2- or -CH2-, R1 is selected from one or more of C5-C42 polyol derivative groups, R2 and R3 are each independently selected from one or more of H, halogen and cyano, R4 and R5 are each independently selected from one or more of H, C1-C12 alkyl, C2-C12 alkyl containing ether bonds, mercapto, hydroxyl and amino, n is an integer greater than 1, and m is an integer greater than 4.

2. The compound according to claim 1, wherein A is selected from -OCH2CH2- or -CH2-, R1 is selected from one or more of a C5-C26 tetrahydric alcohol derivative group, a C5-C10 pentahydric alcohol derivative group, a C6-C10 hexahydric alcohol derivative group, a C15-C21 octahydric alcohol derivative group, a C36-C42 nonadecanol derivative group and a C36-C42 heneconol derivative group, R2 and R3 are each independently selected from one or more of H, F, Cl, Br and cyano, R4 and R5 are each independently selected from one or more of H, C1-C12 alkyl, C2-C12 alkyl containing an ether bond, mercapto, hydroxyl and amino, n is an integer greater than 1, and m is an integer greater than 4; Preferably, A is selected from -OCH2CH2- or -CH2-, and R1 is selected from one or more of the fragments shown in the following formula: R2 and R3 are each independently selected from one or more of H, F, Cl, Br and cyano, R4 and R5 are each independently selected from one or more of H, C1-C6 alkyl, C2-C6 alkyl containing ether bond, thiol, hydroxyl and amino, n is an integer of 1-6, and m is an integer of 4-10; More preferably, A is selected from -OCH2CH2- or -CH2-, R1 is selected from the fragment represented by formula (R1-1) or (R1-4), R2 and R3 are each independently selected from one or more of H, F, Cl, Br and cyano, R4 and R5 are each independently selected from one or more of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, -CH2-O-CH3, -CH2-CH2-O-CH3, -CH2-CH2-O-CH2-CH3, -CH2-O-CH2-CH2-CH3, -CH2-O-CH2-CH2-CH3, thiol, hydroxyl and amino, n is an integer of 1-3, and m is an integer of 4-6.

3. The compound according to claim 1 or 2, wherein The compound is selected from one or more compounds represented by the following formula: Formula (1-1) Formula (1-2) Formula (1-3) Formula (1-4) 4. A method for preparing the compound according to any one of claims 1 to 3, comprising: (1) subjecting the compound represented by formula (A) to a first contact reaction with oxalyl chloride to obtain a compound represented by formula (B); (2) in the presence of an alkaline agent, subjecting the compound represented by formula (B) to a second contact reaction with a polyol compound to obtain a compound represented by formula (1); Formula (A) Formula (B) 5. The method according to claim 4, wherein: The amount of oxalyl chloride used is at least 3 mmol, preferably 8-15 mmol, relative to 1 mmol of the compound represented by formula (A); Preferably, the solvent for the first contact reaction is selected from one or more of dichloromethane, chloroform, tetrahydrofuran, dichloroethane, toluene and n-hexane, preferably one or more of dichloromethane, chloroform and tetrahydrofuran; Preferably, the amount of the solvent used in the first contact reaction is 3-50 mL, preferably 8-20 mL, relative to 1 mmol of the compound represented by formula (A); Preferably, the conditions of the first contact reaction include: temperature 10-40°C, time 4-16h; more preferably, the conditions of the first contact reaction include: temperature 20-30°C, time 6-10h.

6. The method according to claim 4 or 5, wherein: The alkaline agent is selected from one or more of triethylamine, pyridine, piperidine, ethylenediamine and diisopropylethylamine, preferably triethylamine and / or pyridine; Preferably, relative to 1 mmol of the compound represented by formula (B), the amount of the alkaline agent used is 0.1-50 mmol, preferably 1-10 mmol; Preferably, relative to 1 mmol of the compound represented by formula (B), the amount of the polyol compound is 0.1-1 mmol, preferably 0.15-0.3 mmol; Preferably, the solvent for the second contact reaction is selected from one or more of dichloromethane, chloroform, tetrahydrofuran, toluene and pyridine, preferably one or more of dichloromethane, tetrahydrofuran and pyridine; Preferably, relative to 1 mmol of the compound represented by formula (B), the amount of the solvent used in the second contact reaction is 1-30 mL, preferably 3-15 mL; Preferably, the conditions of the second contact reaction include: temperature 10-40°C, time 8-30h; more preferably, the conditions of the second contact reaction include: temperature 20-30°C, time 12-24h.

7. The method according to any one of claims 4 to 6, wherein: The polyol compound is selected from one or more polyol compounds of C5-C42; Preferably, the polyol compound is selected from one or more of C5-C26 tetrahydric alcohol compounds, C5-C10 pentahydric alcohol compounds, C6-C10 hexahydric alcohol compounds, C15-C21 octahydric alcohol compounds, C36-C42 nonadecahydric alcohol compounds and C36-C42 hexonedecahydric alcohol compounds; More preferably, the polyol compound is selected from one or more of the compounds represented by the following formula: More preferably, the polyol compound is selected from the compound represented by formula (Z-1) or formula (Z-4).

8. A photocrosslinking agent comprising the compound according to any one of claims 1 to 3.

9. A method for photopatterning an organic small molecule semiconductor, the method comprising: The organic small molecule semiconductor is mixed with the photocrosslinking agent described in claim 8 and then spin-coated on the surface of a substrate to form a thin film, a photomask is covered on the surface of the thin film and photocrosslinked, and then the uncrosslinked part is cleaned to obtain a patterned thin film.

10. The method according to claim 9, wherein: The mass ratio of the organic small molecule semiconductor to the photocrosslinking agent is 1:0.5-8, preferably 1:1-4.

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