Compounds for organic small molecule semiconductor photopatterning and methods of making the same

Abstract

The present application relates to the field of semiconductors, and in particular to a compound for organic small-molecule semiconductor photo patterning and a preparation method thereof. The structure of the compound is shown in 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 an ether bond, mercapto, hydroxyl and amino, n is an integer of 1 or more, and m is an integer of 4 or more. The compound provided by the present application initiatively realizes direct photo crosslinking patterning of organic small-molecule semiconductors as a photo crosslinking agent. Formula (1)

Description

Technical Field

[0001] This invention relates to the field of semiconductors, and more specifically to a compound for optical patterning of organic small molecule semiconductors and its preparation method. Background Technology

[0002] Organic small-molecule semiconductors are widely used in the field of organic optoelectronics due to their well-defined molecular structures, ease of modification, and minimal batch-to-batch variability. To obtain high-performance functional devices and highly integrated circuits, precise patterning of organic small-molecule semiconductor materials is required.

[0003] Currently, most existing technologies for patterning organic small molecule semiconductors employ traditional photolithography methods. These methods are complex, costly, and prone to instability under strong ultraviolet light or high temperatures, ultimately leading to poor results. In contrast, direct photolithography using photocrosslinking agents, with its simpler operation and milder conditions, can better achieve the photolithographic patterning of organic small molecule semiconductors.

[0004] Trifluoromethylphenyl bisacrylidine photocrosslinking agents can efficiently generate active carbene intermediates under ultraviolet light irradiation and rapidly react with neighboring SPs. 3 CH bonds undergo efficient insertion reactions, resulting in chemical cross-linking and the formation of an insoluble network. After covering the network with a photomask of a specific shape and applying light, the difference in solubility before and after cross-linking allows for the direct washing away of uncross-linked portions, achieving precise and high-resolution patterning. Multi-site photocrosslinking agents possess multiple reaction sites, enabling them to react with multiple molecules or multiple functional groups within the same molecule, thus forming a denser cross-linked network. Compared to traditional single-site photocrosslinking agents, this dense cross-linked structure significantly enhances the degree of cross-linking in materials, resulting in substantial improvements in mechanical strength, heat resistance, and solvent resistance.

[0005] While there are numerous research reports on the direct photolithographic patterning of polymer semiconductors and biomacromolecules using trifluoromethylphenyl bisacrylidine photocrosslinking agents, there are few reports on the photocrosslinking patterning of small organic molecule semiconductors. Therefore, developing a multi-site photocrosslinking agent suitable for direct photolithography of small organic molecule semiconductors is an urgent problem to be solved. Summary of the Invention

[0006] The purpose of this invention is to overcome the problems existing in the prior art and provide a compound for photo-patterning of organic small molecule semiconductors and its preparation method. This compound, as a photocrosslinking agent, successfully achieves high-resolution and precise patterning of organic small molecule semiconductors through direct photocrosslinking.

[0007] To achieve the above objectives, the present invention provides a compound suitable for photocrosslinking agents, the structure of which is shown in formula (1):

[0008] Equation (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 bond, mercapto, hydroxyl and amino, n is an integer of 1 or more, and m is an integer of 4 or more.

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

[0011] (1) The compound shown in formula (A) was reacted with oxalyl chloride in the first contact reaction to obtain the compound shown in formula (B);

[0012] (2) In the presence of an alkaline reagent, the compound shown in formula (B) is reacted with a polyol compound in a second contact reaction to obtain the compound shown in formula (1);

[0013] Formula (A) Formula (B)

[0014] A third aspect of the present invention provides a photocrosslinking agent comprising the above-described compounds.

[0015] The fourth aspect of the present invention provides a method for photo-patterning organic small molecule semiconductors. The method includes mixing organic small molecule semiconductors with the above-mentioned photocrosslinking agent and spin-coating them onto the surface of a substrate to form a thin film, covering the surface of the thin film with a photomask and performing photocrosslinking, and then cleaning the uncrosslinked parts with a solvent to obtain a patterned thin film.

[0016] This invention provides a class of compounds with specific structures suitable for photocrosslinking, which innovatively enable direct photocrosslinking patterning of small organic molecule semiconductors. These compounds exhibit good solubility and excellent miscibility with a variety of small organic molecule semiconductors. Furthermore, they possess multiple active sites, resulting in higher activity and reaction efficiency in the crosslinking reaction. They also possess broad applicability, enabling precise and high-resolution photocrosslinking of various small organic molecule semiconductors. Moreover, the preparation method of these compounds is simple, mild, and inexpensive. Attached Figure Description

[0017] Figure 1The 1H NMR spectrum of the compound of formula (1-1) obtained in Example 1;

[0018] Figure 2 The 1H NMR spectrum of the compound of formula (1-2) obtained in Example 2;

[0019] Figure 3 The 1H NMR spectrum of the compound of formula (1-3) obtained in Example 3;

[0020] Figure 4 The 1H NMR spectrum of the compound of formula (1-4) obtained in Example 4;

[0021] Figure 5 The 1H NMR spectrum of the compound of formula (D-1) prepared in Comparative Example 1 is shown.

[0022] Figure 6 This is a schematic diagram of the optical patterning process of organic small molecule semiconductors in this invention;

[0023] Figure 7 The absorption spectra before and after development were obtained in test example 2;

[0024] Figure 8 The absorption spectra before and after development were obtained in test example 14;

[0025] Figure 9 Examples of optical patterning of organic small molecule semiconductors obtained in Test Example 8;

[0026] Figure 10 The resolution image of the organic small molecule semiconductor optical pattern obtained in Test Examples 1-15;

[0027] in, Figure 10 In the text, a to o correspond to test cases 1-15 respectively. Detailed Implementation

[0028] The endpoints and any values ​​of the ranges disclosed herein 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 the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0029] In this invention, In structures with wavy lines, the wavy lines indicate the connection positions of the functional groups.

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

[0031] Equation (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 bond, mercapto, hydroxyl and amino, n is an integer of 1 or more, and m is an integer of 4 or more.

[0033] According to the present invention, the above-mentioned compound having a specific structure contains a plurality of trifluoromethylphenylbisacrylidine photocrosslinking groups. When used as a photocrosslinking agent in the direct photolithography of organic small molecule semiconductors, it can efficiently generate an active carbene intermediate under ultraviolet light irradiation and rapidly and efficiently react with multiple molecules or multiple reaction sites within the same molecule via SP. 3 The CH bond insertion reaction leads to the formation of 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, thereby achieving optical patterning.

[0034] According to the present invention, in order to enable the above-mentioned compounds to be more miscible with organic small molecule semiconductors and achieve better chemical crosslinking effect and higher reaction efficiency, thereby enabling more precise and rapid direct photolithographic patterning of organic small molecule semiconductors, preferably, A is selected from -OCH2CH2- or -CH2-, R1 is selected from one or more of the following: tetrahydric alcohol derivatives of C5-C26, pentahydric alcohol derivatives of C5-C10, hexahydric alcohol derivatives of C6-C10, octahydric alcohol derivatives of C15-C21, nonadecyl alcohol derivatives of C36-C42, and dodecyl alcohol derivatives 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 ether bond, mercapto, hydroxyl, and amino, n is an integer of 1 or more, and m is an integer of 4 or more.

[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 groups; R4 and R5 are each independently selected from one or more of H, C1-C6 alkyl groups, C2-C6 alkyl groups containing ether bonds, mercapto groups, hydroxyl groups, and amino groups; n is an integer from 1 to 6; and m is an integer from 4 to 10.

[0037] More preferably, A is selected from -OCH2CH2- or -CH2-, R1 is selected from the fragment shown in formula (R1-1) or formula (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-CH2-CH3, mercapto, hydroxyl and amino, n is an integer from 1 to 3, and m is an integer from 4 to 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] Equation (1-1)

[0040] Equation (1-2)

[0041] Equation (1-3)

[0042] Equation (1-4)

[0043] According to the present invention, the above-mentioned compound exhibits excellent solubility, readily dissolving in various common organic solvents. This characteristic makes it more convenient to use as a photocrosslinking agent, allowing for flexible combination with various organic solvents to meet different application requirements. Simultaneously, the compound demonstrates excellent miscibility with small organic molecule semiconductors, enabling it to fully integrate with multiple small organic molecule semiconductors to form a uniform and stable blend system, providing a solid foundation for subsequent processing and applications.

[0044] According to the present invention, the above-mentioned compound contains a plurality of trifluoromethylphenyl bisacrylidine active groups, the presence of which gives it higher reactivity and efficiency in the crosslinking reaction. Compared with traditional double-ended photocrosslinking agents, its crosslinking efficiency is significantly improved, enabling the crosslinking reaction to be completed in a shorter time, forming a denser crosslinking network, and improving the efficiency and effect of chemical crosslinking.

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

[0046] (1) The compound shown in formula (A) was reacted with oxalyl chloride in the first contact reaction to obtain the compound shown in formula (B);

[0047] (2) In the presence of an alkaline reagent, the compound shown in formula (B) is reacted with a polyol compound in a second contact reaction to obtain the compound shown in formula (1);

[0048] Formula (A) Formula (B)

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

[0050] According to the present invention, the above-described preparation method is concise and simple to operate, without cumbersome and complex procedures, making the entire synthesis process more efficient and convenient. Furthermore, the reaction conditions in this preparation method are mild, requiring no extreme temperatures, pressures, or other harsh conditions, which not only reduces equipment requirements but also improves the safety and stability of the preparation process and lowers costs.

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

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

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

[0054] According to the present invention, in order to improve 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 and time 4-16h.

[0055] More preferably, the conditions for the first contact reaction include: a temperature of 20-30°C (e.g., values ​​such as 20°C, 25°C, 28°C, and 30°C, and any range thereof), and a time of 6-10 hours (e.g., values ​​such as 6 hours, 8 hours, 9 hours, and 10 hours, and any range thereof).

[0056] According to the present invention, preferably, the first contact reaction is carried out in a non-reactive gas atmosphere. Preferably, the non-reactive gas is nitrogen and / or argon.

[0057] According to the present invention, preferably, the specific steps of the first contact reaction can be as follows: adding oxalyl chloride and solvent to the reactor, cooling to -20°C to 5°C, dissolving the compound shown in formula (A) in the solvent and adding it to the reactor, and then carrying out the first contact reaction after the addition is complete.

[0058] According to the present invention, the post-treatment of the first contact reaction can be a post-treatment method commonly used in the art, as long as it can yield the product of the compound shown in formula (B). For example, the post-treatment method can be: to evaporate the reaction solution to dryness, and then add a solvent to evaporate it to dryness again (the purpose of which is to remove excess oxalyl chloride) to obtain the compound shown in formula (B).

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

[0060] Preferably, the amount of the basic reagent used is 0.1-50 mmol relative to 1 mmol of the compound shown in formula (B), preferably 1-10 mmol, for example, values ​​such as 1 mmol, 4 mmol, 8 mmol and 10 mmol and any range between these values.

[0061] According to the present invention, the polyol compound may 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 the following: tetrahydric compounds of C5-C26, pentahydric compounds of C5-C10, hexahydric compounds of C6-C10, octahydric compounds of C15-C21, nonadecylhydric compounds of C36-C42, and twentiethylhydric compounds of C36-C42.

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

[0064]

[0065] According to a particularly preferred embodiment of the present invention, the polyol compound is selected from compounds 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 better reaction effect, preferably, the amount of the polyol compound is 0.1-1 mmol, more preferably 0.15-0.3 mmol, relative to 1 mmol of the compound shown in formula (B). For example, it can be 0.15 mmol, 0.2 mmol, 0.25 mmol and 0.3 mmol and any range between these values.

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

[0068] Preferably, the amount of solvent used in the second contact reaction is 1-30 mL, more preferably 3-15 mL, relative to 1 mmol of the compound shown in formula (B), for example, values ​​such as 3 mL, 10 mL, 12 mL and 15 mL and any range between these values.

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

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

[0071] According to the present invention, preferably, the second contact reaction is carried out in a non-reactive gas atmosphere. Preferably, the non-reactive gas is nitrogen and / or argon.

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

[0073] According to the present invention, preferably, the specific steps of the second contact reaction can be: adding the polyol compound, the alkaline reagent and the solvent to the reactor, dissolving the compound shown in formula (B) in the solvent and adding it to the reactor, and then carrying out 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 commonly used post-treatment method in the art, as long as the product of the compound shown in formula (1) can be obtained. For example, the post-treatment method 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 conventional), collecting the organic phase, adding a drying agent (e.g. anhydrous sodium sulfate, anhydrous calcium sulfate and anhydrous magnesium sulfate, etc., and the amount used is conventional), drying, filtering, and evaporating to obtain the compound shown in formula (1).

[0075] A third aspect of the present invention provides a photocrosslinking agent comprising the above-described compounds.

[0076] A fourth aspect of this invention provides a method for photo-patterning organic small molecule semiconductors. The method includes mixing the organic small molecule semiconductor with a photocrosslinking agent and spin-coating it onto a substrate (e.g., a silicon wafer) to form a thin film; covering the surface of the thin film with a photomask and performing photocrosslinking; and then cleaning the uncrosslinked portions to obtain a patterned thin film. The basic flow of this photo-patterning method is as follows: Figure 6 As shown.

[0077] According to the present invention, the above-mentioned compound has wide applicability as a photocrosslinking agent, enabling precise and high-resolution patterning of various small organic molecule semiconductors, with a resolution down to the micrometer level. Compared with traditional photolithography patterning methods, the above-mentioned photopatterning method is simpler and easier to operate, requires no complex equipment and processes, and is also less expensive, eliminating the need for costly equipment investment and maintenance.

[0078] According to the present invention, in the above-described optical patterning method, the mixing method of the organic small molecule semiconductor and the photocrosslinking agent can be selected within a wide range. For example, they can be dissolved and mixed separately in the same container, or they can be added to the solvent at the same time to dissolve and mix, or they can be dissolved separately and then their solutions can be mixed.

[0079] According to the present invention, preferably, the above-described optical patterning method is performed under light-protected conditions.

[0080] According to the present invention, the above-mentioned photocrosslinking agent can chemically crosslink with a variety of organic small molecule semiconductors to achieve direct photolithography. For better results, preferably, the organic small molecule semiconductor can be one or more of Y6, Y6-EG, and C8-BTBT-C8. Wherein, Y6 is... (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 better chemical crosslinking effect and ensure the accuracy of patterning, the amount of organic small molecule semiconductor and photocrosslinking agent can be adjusted. Preferably, the mass ratio of the organic small molecule semiconductor to the photocrosslinking 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 any range between these values.

[0082] According to the present invention, the solvent for dissolving the above-mentioned organic small molecule semiconductor and the photocrosslinking agent can be selected from a wide range. The above-mentioned photocrosslinking agent 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 photocrosslinking agent 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 order to form a thin film with better properties in the above patterning method, the spin coating speed is preferably 500-4000 r / min, more preferably 1000-3000 r / min, for example, it can be 1000 r / min, 1500 r / min, 2000 r / min, 2500 r / min and 3000 r / min and any range between these values.

[0084] According to the present invention, the photocrosslinking is carried out under ultraviolet light irradiation, and the ultraviolet light is generally selected with a wavelength of 365 nm. Preferably, the power of the ultraviolet light is 300-1000 mW / cm². 2 The preferred value is 500-800mW / cm. 2 For example, it can be 500mW / cm 2 600mW / cm 2 700mW / cm 2 and 800mW / cm 2 The value range is defined as follows: The ultraviolet light irradiation time is preferably 0.5 min or more, more preferably 1-5 min, for example, it can be 1 min, 2 min, 3 min, and 5 min, or any value range thereof.

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

[0086] According to the present invention, in the above-described cleaning of the uncrosslinked portions, the cleaning time needs to be adjusted to avoid over-cleaning and damage to the pattern. Preferably, the cleaning time is 5-20 seconds, more preferably 10-15 seconds, for example, it can be 10 seconds, 12 seconds, 13 seconds, and 15 seconds, or any value between these values.

[0087] This invention provides a class of compounds with specific structures suitable for photocrosslinking, which innovatively enable direct photocrosslinking patterning of small organic molecule semiconductors. These compounds exhibit good solubility and excellent miscibility with a variety of small organic molecule semiconductors. Furthermore, they possess multiple active sites, resulting in higher activity and reaction efficiency in the crosslinking reaction. They also possess broad applicability, enabling precise and high-resolution photocrosslinking of various small organic molecule semiconductors. Moreover, the preparation method of these compounds is simple, mild, and inexpensive.

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

[0089] In the following examples, all apparatus used are conventional experimental apparatus in the art, all experimental operations performed are conventional operations in the art, and all raw materials and reagents used are commercially available. Specifically, the compound shown in formula (A-1) was purchased from Shanghai Bied Pharmaceutical Technology Co., Ltd.; the compound shown in formula (A-2) was synthesized according to the literature (Angew. Chem. Int. Ed. 2023, 62, e202304708); Y6 was synthesized according to the literature (Joule 3, 1140-1151, April 17, 2019); Y6-EG was synthesized according to the literature (Adv. Energy Mater. 2021, 11, 2003141); and C8-BTBT-C8 was purchased from Admas-Beta.

[0090] Example 1

[0091] This example illustrates the preparation of the compound shown in formula (1-1).

[0092]

[0093] The specific steps are as follows:

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

[0095] (2) Under a nitrogen atmosphere, 0.2 mmol of the compound shown in formula (Z-1), 0.9 mmol of triethylamine, and 5 mL of dichloromethane were added to the reactor. 0.9 mmol of the compound shown in formula (B-1) was dissolved in 5 mL of dichloromethane and added dropwise to the reactor. The reaction was carried out at 25°C in the dark for 12 h. The reaction solution was extracted with 50 mL of dichloromethane and 150 mL of saturated sodium chloride aqueous solution. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and evaporated to dryness to obtain the compound shown in formula (1-1).

[0096] The proton NMR spectrum of the compound shown in 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 illustrates the preparation of the compounds shown in formulas (1-2).

[0099]

[0100] The specific steps are as follows:

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

[0102] (2) Under a nitrogen atmosphere, 0.2 mmol of the compound shown in formula (Z-1), 0.9 mmol of triethylamine, and 5 mL of dichloromethane were added to the reactor. 0.9 mmol of the compound shown in formula (B-1) was dissolved in 5 mL of dichloromethane and added dropwise to the reactor. The reaction was carried out at 30°C in the dark for 12 h. The reaction solution was extracted with 50 mL of dichloromethane and 150 mL of saturated sodium chloride aqueous solution. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and evaporated to dryness to obtain the compound shown in formula (1-2).

[0103] The proton NMR spectrum of the compound shown in 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 illustrates the preparation of the compounds shown in formulas (1-3).

[0106]

[0107] The specific steps are as follows:

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

[0109] (2) Under a nitrogen atmosphere, 0.2 mmol of the compound shown in formula (Z-4) and 5 mmol of pyridine were added to the reactor. 1.3 mmol of the compound shown in formula (B-1) was dissolved in 5 mL of dichloromethane and added dropwise to the reactor. The reaction was carried out at 20 °C in the dark for 24 h. The reaction solution was extracted with 50 mL of ethyl acetate, 150 mL of saturated copper sulfate aqueous solution and 150 mL of saturated sodium chloride aqueous solution. The organic phase was collected, dried with anhydrous sodium sulfate, filtered, and evaporated to dryness to obtain the compound shown in formula (1-3).

[0110] The proton NMR spectra of the compounds shown in formula (1-3) are 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 illustrates the preparation of the compounds shown in formulas (1-4).

[0113]

[0114] The specific steps are as follows:

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

[0116] (2) Under a nitrogen atmosphere, 0.2 mmol of the compound shown in formula (Z-4) and 5 mmol of pyridine were added to the reactor. 1.3 mmol of the compound shown in formula (B-2) was dissolved in 5 mL of dichloromethane and added dropwise to the reactor. The reaction was carried out at 25 °C in the dark for 24 h. The reaction solution was extracted with 50 mL of ethyl acetate, 150 mL of saturated copper sulfate aqueous solution and 150 mL of saturated sodium chloride aqueous solution. The organic phase was collected, dried with anhydrous sodium sulfate, filtered, and evaporated to dryness to obtain the compound shown in formula (1-4).

[0117] The proton NMR spectra of the compounds shown in formula (1-4) are 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 illustrates the preparation of a conventional two-end photocrosslinking agent.

[0120]

[0121] The specific steps are as follows:

[0122] Under a nitrogen atmosphere, 2.86 mmol of the compound shown in formula (A-1) and 8 mL of dichloromethane were added to the reactor. The mixture was cooled to 0 °C, and 1.19 mmol of oxaloyl chloride was dissolved in 5 mL of dichloromethane and added dropwise to the reactor. The reaction was carried out at 25 °C for 10 h. The reaction solution was evaporated to dryness to obtain the compound shown in formula (D-1).

[0123] The proton NMR spectrum of the compound shown in 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 photocrosslinking agents for the 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 solution of 20 mg / mL; dissolve the photocrosslinking agent in chloroform to prepare a solution of 100 mg / mL. Mix the two solutions to prepare a blend solution of organic small molecule semiconductor and photocrosslinking agent in a certain mass ratio.

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

[0128] (3) Select a photomask with a predetermined pattern and cover it on the thin film. Turn on the photomask with a wavelength of 365nm and a power of 600mW / cm. 2 The film is irradiated with ultraviolet light by ultraviolet LEDs, and the light evenly covers the entire film area for 2 minutes.

[0129] (4) After irradiation, immerse the silicon wafer with the thin film in chloroform for cleaning for 10 seconds. After removing the silicon wafer, dry it with nitrogen gas to obtain the patterned result on the silicon wafer.

[0130] Table 1 shows the organic small molecule semiconductors and photocrosslinking agents used in Test Examples 1-15, as well as their respective mass ratios.

[0131] To further determine the crosslinking efficiency, UV-Vis absorption spectra of the films before and after development (i.e., step 4) in Test Example 2 and Test Example 14 were measured using a UNICO UV-4802 UV-Vis spectrophotometer, as shown below. Figure 7 and Figure 8 As shown. The molar extinction coefficient of Test Example 2 was 57%, and that of Test Example 14 was 7%. The molar extinction coefficient is defined as: peak absorbance after development / peak absorbance before development.

[0132] The light patterned image obtained from Test Example 8 is as follows: Figure 9 As shown.

[0133] The light-patterned resolution images obtained from Test Examples 1-15 are as follows: Figure 10 As shown in Figures 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 by Example 1 can reach 57% after development, while the molar extinction coefficient of the double-terminal photocrosslinker prepared by Comparative Example 1 is only 7% after development. Since the absorption intensity of the compound can be used as the basis for quantitative analysis of the substance (the more organic small molecule semiconductors remain in the film after development, the higher the absorbance retention), the molar extinction coefficient can be used to represent the retention of the film after development. 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 Figure 9 and Figure 10 As can be seen, Test Examples 1-12, which use the compounds provided in Examples 1-4 as photocrosslinking agents, can achieve direct and precise photolithography of small organic molecule semiconductors with a resolution down to the micrometer level. However, Test Examples 13-15, which use the traditional double-ended photocrosslinking agent prepared in Comparative Example 1, suffer from limited molecular weight and good solubility of the small organic molecule semiconductors. Furthermore, during the crosslinking process, the traditional double-ended photocrosslinking agent only has two crosslinking sites, making it difficult to form a continuous crosslinking network. This results in minimal change in the solubility of the crosslinked small organic molecule semiconductors. After development, the retention rate of the small organic molecule semiconductors in the obtained film is low, directly rendering the material unsuitable for direct photolithography.

[0139] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A compound suitable for use in a photocrosslinker, characterized in that, The structure of the compound is shown in formula (1): Formula (1) ; Wherein, A is selected from -OCH2CH2- or -CH2-, and R1 is selected from... , and One or more of the following, R2 and R3 are H, R4 and R5 are each independently selected from one or more of H and C1-C6 alkyl groups, n is an integer from 1 to 6, and m is one or more of 4, 6 and 8.

2. The compound of claim 1, wherein, R4 and R5 are each independently selected from one or more of H and C1-C3 alkyl groups.

3. The compound of claim 1, wherein, R4 and R5 are each independently selected from one or more of H, methyl, ethyl, n-propyl, and isopropyl.

4. The compound of claim 1, wherein, The compound is selected from one or more compounds shown in the following formula: Formula (1-1) , Formula (1-2) , Equation (1-3) , Formula (1-4) .

5. A method for preparing the compound according to any one of claims 1-4, the method comprising: (1) The compound shown in formula (A) is reacted with oxalyl chloride in the first contact reaction to obtain the compound shown in formula (B); (2) In the presence of an alkaline reagent, the compound shown in formula (B) is reacted with a polyol compound in a second contact reaction to obtain the compound shown in formula (1); Formula (A) , Formula (B) .

6. The method of claim 5, wherein, The amount of oxalyl chloride used is at least 3 mmol relative to 1 mmol of the compound shown in formula (A).

7. The method of claim 6, wherein, The amount of oxalyl chloride used is 8-15 mmol relative to 1 mmol of the compound shown in formula (A).

8. The method of claim 5, wherein, The solvent for the first contact reaction is selected from one or more of dichloromethane, trichloromethane, tetrahydrofuran, dichloroethane, toluene, and n-hexane.

9. The method of claim 8, wherein, The solvent for the first contact reaction is selected from one or more of dichloromethane, trichloromethane, and tetrahydrofuran.

10. The method of claim 5, wherein, The amount of solvent used in the first contact reaction is 3-50 mL relative to 1 mmol of the compound shown in formula (A).

11. The method of claim 10, wherein, The amount of solvent used in the first contact reaction is 8-20 mL relative to 1 mmol of the compound shown in formula (A).

12. The method of claim 5, wherein, The conditions for the first contact reaction include: temperature 10-40℃ and time 4-16h.

13. The method of claim 12, wherein, The conditions for the first contact reaction include: temperature 20-30℃ and time 6-10h.

14. The method according to claim 5, wherein, The alkaline reagent is selected from one or more of triethylamine, pyridine, piperidine, ethylenediamine, and diisopropylethylamine.

15. The method of claim 14, wherein, The alkaline reagent is triethylamine and / or pyridine.

16. The method of claim 5, wherein, The amount of the basic reagent used is 0.1-50 mmol relative to 1 mmol of the compound shown in formula (B).

17. The method of claim 16, wherein, The amount of the basic reagent used is 1-10 mmol relative to 1 mmol of the compound shown in formula (B).

18. The method according to claim 5, wherein, The amount of the polyol compound used is 0.1-1 mmol relative to 1 mmol of the compound shown in formula (B).

19. The method of claim 18, wherein, The amount of the polyol compound used is 0.15-0.3 mmol relative to 1 mmol of the compound shown in formula (B).

20. The method of claim 5, wherein, The solvent for the second contact reaction is selected from one or more of dichloromethane, trichloromethane, tetrahydrofuran, toluene, and pyridine.

21. The method of claim 20, wherein, The solvent for the second contact reaction is selected from one or more of dichloromethane, tetrahydrofuran, and pyridine.

22. The method of claim 5, wherein, The amount of solvent used in the second contact reaction is 1-30 mL relative to 1 mmol of the compound shown in formula (B).

23. The method of claim 22, wherein, The amount of solvent used in the second contact reaction is 3-15 mL relative to 1 mmol of the compound shown in formula (B).

24. The method of claim 5, wherein, The conditions for the second contact reaction include: temperature 10-40℃ and time 8-30h.

25. The method according to claim 24, wherein, The conditions for the second contact reaction include: temperature 20-30℃ and time 12-24h.

26. The method of claim 5, wherein, The polyol compound is selected from one or more of , and .

27. A photocrosslinking agent comprising the compound of any one of claims 1-4.

28. A method of optical patterning of an organic small molecule semiconductor, the method comprising: Organic small molecule semiconductors are mixed with the photocrosslinking agent described in claim 27 and spin-coated onto the substrate surface to form a thin film. A photomask is then covered on the surface of the thin film and photocrosslinking is performed. The uncrosslinked parts are then cleaned to obtain a patterned thin film.

29. The method of claim 28, wherein, The mass ratio of the organic small molecule semiconductor to the photocrosslinking agent is 1:0.5-8.

30. The method of claim 29, wherein, The mass ratio of the organic small molecule semiconductor to the photocrosslinking agent is 1:1-4.

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