Compound, preparation method thereof and patterned material

Abstract

The invention provides a compound, a preparation method thereof and a patterned material, the compound has a general formula structure of # imgabs0 #, introduced L0 can be regarded as a rigid structure, so that the compound has a three-dimensional structure instead of a planar structure, pi-pi stacking can be prevented in a solution, and the solubility of the compound in a solvent can be improved; moreover, when the compound is used as a photosensitive material, more protons can be generated due to the increase of solubility, so that the acid production efficiency of the compound is improved.

Description

Technical Field

[0001] The present application relates to the field of semiconductor technology, and particularly to a compound, a preparation method thereof, and a patterning material. Background Art

[0002] The patterning material is one of the key materials for microfabrication in microelectronic processing technology and can transfer an image onto a substrate. The patterning material mainly includes: a photosensitive material, a film-forming resin, a solvent, etc. The photosensitive material, as the main component of the patterning material, can decompose under light irradiation to generate protons, and these protons will react with the corresponding anion structure to produce an acid. During the baking process, the generated acid can act as a catalyst to cause the unstable groups hanging on the polymer to fall off and generate new acid, thereby changing the properties of the polymer and realizing the transfer of the image.

[0003] However, when the photosensitive material is a small molecule, there may be problems such as poor solubility of the photosensitive material in the solvent and reduced acid generation efficiency. Therefore, how to improve the solubility of the photosensitive material in the solvent and improve the acid generation efficiency of the photosensitive material has become an urgent problem to be solved. Summary of the Invention

[0004] The present application provides a compound, a preparation method thereof, and a patterning material, which can improve the solubility of the photosensitive material in the solvent and can also improve the acid generation efficiency of the photosensitive material.

[0005] In a first aspect, an embodiment of the present application provides a compound having a structure represented by the following general formula (I) or general formula (II):

[0006]

[0007] Wherein, L0 is selected from: C, a k-membered monocyclic structure, a C5-C30 spiro ring structure, or a C5-C30 bridged ring structure, 10≥k≥3; R0 is C or S; c≥1; M is a counter ion;

[0008] Each R1 is independently selected from any one of: a halogen, a carboxyl group, an aldehyde group, a carbonyl group, a hydroxyl group, a siloxy group, a basic group, a substituted or unsubstituted C1-C10 aliphatic group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C1-C10 ester group, a substituted or unsubstituted C6-C10 aromatic group, and a substituted or unsubstituted C6-C10 aryloxy group. Each R1 is the same or different, n≥0, and the number of R1s connected to each benzene ring is the same or different;

[0009] The substituents in the substituted C1-C10 aliphatic group, substituted C1-C10 alkoxy group, substituted C1-C10 ester group, substituted C6-C10 aromatic group, and substituted C6-C10 aryloxy group are each independently selected from: halogen, carboxyl group, aldehyde group, carbonyl group, hydroxyl group, ester group, siloxy group, basic group, C1-C10 aliphatic group, C6-C10 aromatic group. That is to say, the substituents in the substituted C1-C10 aliphatic group are each independently selected from: halogen, carboxyl group, aldehyde group, carbonyl group, hydroxyl group, ester group, siloxy group, basic group, C1-C10 aliphatic group, C6-C10 aromatic group; the substituents in the substituted C1-C10 alkoxy group are each independently selected from: halogen, carboxyl group, aldehyde group, carbonyl group, hydroxyl group, ester group, siloxy group, basic group, C1-C10 aliphatic group, C6-C10 aromatic group; the substituents in the substituted C1-C10 ester group are each independently selected from: halogen, carboxyl group, aldehyde group, carbonyl group, hydroxyl group, ester group, siloxy group, basic group, C1-C10 aliphatic group, C6-C10 aromatic group; the substituents in the substituted C6-C10 aromatic group are each independently selected from: halogen, carboxyl group, aldehyde group, carbonyl group, hydroxyl group, ester group, siloxy group, basic group, C1-C10 aliphatic group, C6-C10 aromatic group; the substituents in the substituted C6-C10 aryloxy group are each independently selected from: halogen, carboxyl group, aldehyde group, carbonyl group, hydroxyl group, ester group, siloxy group, basic group, C1-C10 aliphatic group, C6-C10 aromatic group; and the substituents in the substituted C1-C10 aliphatic group, substituted C1-C10 alkoxy group, substituted C1-C10 ester group, substituted C6-C10 aromatic group, and substituted C6-C10 aryloxy group can be the same or different.

[0010] Thus, the introduced L0 can be regarded as a rigid structure, which can make the compound have a three-dimensional structure rather than a planar structure. In this way, π-π stacking can be prevented in the solution, thereby improving the solubility of the compound in the solvent; and when this compound is used as a photosensitive material, due to the increased solubility, more protons can be generated, thereby improving the acid generation efficiency of this compound.

[0011] Further, on the one hand, since the hydroxyl group and the siloxy group have a high adsorption force on the Si substrate, when at least one of the hydroxyl group and the siloxy group is included at the end of the compound, the adhesion of the film layer made of this compound on the surface of the Si substrate can be increased, avoiding the problem that the film layer made of this compound is prone to peeling off. On the other hand, when an alkaline group is included in the compound and the compound is applied to a patterning material, the alkaline group can neutralize the diffused acid, thereby inhibiting the diffusion of the acid, and thus the intensity of photoacid diffusion can be controlled. On the other hand, when the compound contains more aromatic hydrocarbon groups, the number of captured secondary electrons can be increased, causing the compound to generate more acid, thereby improving the light sensitivity of the compound. On the other hand, when the compound contains F elements, the light transmittance of the compound can be increased, and the light reflection of the compound can be reduced, thereby improving the light absorption efficiency of the compound.

[0012] It should be understood that aliphatic groups generally may include: alkyl groups, alkenyl groups, and alkynyl groups; alkyl groups such as but not limited to: methyl, ethyl, propyl, isopropyl, butyl, etc., alkenyl groups such as but not limited to: vinyl, propenyl, isopropenyl, etc., alkynyl groups such as but not limited to: ethynyl, butynyl, etc. Aromatic groups generally may include: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, pyrenyl, perylenyl, anthryl, fluorenyl, etc. The siloxy group may be a group containing a Si-O bond, such as SiH3-O-R3, where R3 is selected from: a substituted or unsubstituted C1-C10 aliphatic group, or a substituted or unsubstituted C6-C10 aromatic group; another example is the structure in SiH3-O-R3 after at least one H on Si is substituted by a C1-C10 aliphatic group or a C6-C10 aromatic group.

[0013] Exemplarily, taking any benzene ring shown by general formula (Ⅰ) and general formula (Ⅱ) as an example, when the value of n is 0, it can be understood that R1 is H, and at this time, there is no substituent on this benzene ring; when the value of n is 1, it can be understood that there is one R1 in this benzene ring, and R1 can be selected from any one of halogen, carboxyl, aldehyde group, carbonyl group, hydroxyl group, siloxy group, basic group, substituted or unsubstituted C1-C10 aliphatic group, substituted or unsubstituted C1-C10 alkoxy group, substituted or unsubstituted C1-C10 ester group, substituted or unsubstituted C6-C10 aromatic group, and substituted or unsubstituted C6-C10 aryloxy group; when the value of n is greater than 1, it can be understood that there are at least two R1s in this benzene ring, and each R1 is the same or different, and each R1 can be selected from any one of halogen, carboxyl, aldehyde group, carbonyl group, hydroxyl group, siloxy group, basic group, substituted or unsubstituted C1-C10 aliphatic group, substituted or unsubstituted C1-C10 alkoxy group, substituted or unsubstituted C1-C10 ester group, substituted or unsubstituted C6-C10 aromatic group, and substituted or unsubstituted C6-C10 aryloxy group. Of course, the number of R1s connected to each benzene ring in general formula (Ⅰ) is the same or different. Similarly, the number of R1s connected to each benzene ring in general formula (Ⅱ) is the same or different. In this way, the number of R1s and the selected groups can be set according to actual needs to meet the requirements of different application scenarios and improve the flexibility of design.

[0014] Exemplarily, when L0 is selected from C, each benzene ring connected to L0 is in the same plane, and only the benzene ring connected to S is in a different plane from other benzene rings. Such a compound has a three-dimensional structure, so the solubility and acid production efficiency of the compound can be increased, and the structure of this compound is relatively simple and easy to manufacture, which can not only improve the manufacturing efficiency but also improve the yield of the compound.

[0015] Alternatively, L0 can be selected from a k-membered saturated monocyclic hydrocarbon structure. At this time, some of the benzene rings connected to L0 are in the same plane and some are in different planes, and only the benzene ring connected to S is in a different plane from some of the other benzene rings. Such a compound also has a three-dimensional structure, and compared with when L0 is selected from C, some of the benzene rings connected to L0 are also twisted, making the three-dimensionality of this compound higher, so the solubility of this compound is higher and the acid production efficiency is also higher. Further, the monocyclic hydrocarbon structure can be selected from: cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclodecane; wherein, the connection sites of L0 with adjacent groups are selected from: the positions where each C in the monocyclic hydrocarbon structure is located.

[0016] Or, L0 can be selected from a spiro ring structure, and L0 is selected from any one of the following spiro ring structures:

[0017]

[0018]

[0019] Among them, the connection site of L0 with adjacent groups is selected from the positions indicated by each *. Since L0 is selected from a spiro structure, and the spiro structure is a structure in which two rings share a carbon atom, the benzene ring connected to L0 has a greater degree of torsion. Such a compound has a higher three-dimensional steric degree, which can further improve the solubility of the compound, and further improve the acid production efficiency of the compound.

[0020] Alternatively, L0 can be selected from a bridged-ring structure, and L0 is selected from any one of the following bridged-ring structures:

[0021]

[0022] Among them, the connection site of L0 with adjacent groups is selected from the positions indicated by each *. And, the bridged-ring structure is a structure in which two rings share two carbon atoms, so the benzene ring connected to L0 has a relatively large degree of torsion. The compound with a bridged-ring structure has a relatively higher three-dimensional steric degree, which can further improve the solubility of the compound, and further improve the acid production efficiency of the compound.

[0023] Exemplarily, each R1 is independently selected from: H or isopropyl, which can make the compound easier to prepare, simplify the preparation process, and improve the preparation efficiency and yield of the compound.

[0024] Exemplarily, M is selected from: monovalent halogen anions, HSO4 - , NO3 - , SO3 - , CIO4 - , or a structure represented by the following general formula:

[0025] R2-(X - ) a ;

[0026] Among them, R2 is selected from: substituted or unsubstituted C1-C10 aliphatic groups, or substituted or unsubstituted C6-C10 aromatic groups, and X - is selected from: monovalent halogen anions, HSO4 - , NO3 - , SO3 - , CIO4 - ; when the compound has the structure shown in general formula (Ⅰ), a = c; when the compound has the structure shown in general formula (Ⅱ), a = 2c.

[0027] That is to say, when the compound has the structure shown in general formula (Ⅰ), M can be selected from anions with a valence of -1 as counterions, such as: monovalent halogen anions, HSO4- , NO3 - , SO3 - , CIO4 - , R2-X - etc., X - can be selected from: monovalent halogen anions, HSO4 - , NO3 - , SO3 - , CIO4 - , at this time, the value of c can be 1, and there is one binding position between the anion and the cation in the compound of this structure. When M is selected from R2-(X - ) c , and when the value of c is greater than 1, there are c binding positions between the anion and the cation in the compound of this structure; as the value of c increases, the number of binding positions between the anion and the cation in the compound also increases. When acid is easily generated at the binding position between the anion and the cation, the increase in the number of binding positions increases the acid-producing sites of the compound, thereby further increasing the acid-producing efficiency of the compound.

[0028] When the compound has the structure shown in the general formula (Ⅱ), M can also be selected from monovalent halogen anions, HSO4 - , NO3 - , SO3 - , CIO4 - , R2-(X - ) 2c etc., X - can be selected from: monovalent halogen anions, HSO4 - , NO3 - , SO3 - , CIO4 - , when the value of c is 1, the compound still has two binding positions between the anion and the cation. As the value of c increases, the binding positions increase accordingly. Therefore, the acid-producing efficiency of the compound of this structure can also be further improved.

[0029] Moreover, when selecting the type of counterion, it can be selected according to factors such as the application scenario and the quality requirements of the patterning process. For example, when the compound is applied to a positive patterning material, the larger the volume of the counterion, the shorter the photoacid diffusion length, and the lower the edge roughness after patterning. Therefore, by selecting the type of counterion, the adjustment of the photoacid diffusion length can be achieved. It should be understood that the positive patterning material can be understood as: after being irradiated with light of a specific wavelength, the unirradiated part of the positive patterning material undergoes crosslinking, while the irradiated part does not undergo crosslinking.

[0030] Exemplarily, when L0 is selected from C, the compound is selected from any one of the structures shown in (1) to (12):

[0031]

[0032]

[0033] When L0 is selected from a monocyclic structure, the compound is selected from any one of the structures shown in (13) to (22):

[0034]

[0035] When L0 is selected from a spiro structure, the compound is selected from any one of the structures shown in (23) to (32):

[0036]

[0037] When L0 is selected from a bridged-ring structure, the compound is selected from any one of the structures shown in (33) to (52):

[0038]

[0039]

[0040] In a second aspect, the embodiments of the present application further provide a method for preparing a compound. This preparation method can be used to prepare the compounds described in the first aspect and any one of the embodiments in the first aspect. The preparation method may include: oxidizing and adding a sulfur in a precursor to obtain a compound; the precursor has a structure shown in the following general formula a1 or a structure shown in the general formula a2:

[0041]

[0042] In this way, L0 can be introduced through the above preparation process, so that the compound has a three-dimensional structure rather than a planar structure, which can prevent π-π stacking in the solution, thereby improving the solubility of the compound in the solvent; and when this compound is used as a photosensitive material, due to the increased solubility, more protons can be generated, thereby improving the acid generation efficiency of this compound.

[0043] Exemplarily, when performing oxidation and addition treatment on sulfur in the precursor, it may specifically include: oxidizing the sulfur in the precursor so that the sulfur in the precursor forms a sulfur-oxygen double bond with oxygen; among them, an acid with relatively strong oxidation ability can be used to oxidize sulfur, such as but not limited to using meta-chloroperoxybenzoic acid (abbreviated as mCPBA) to oxidize sulfur; then, using phenylmagnesium reagent to perform an addition reaction on the sulfur-oxygen double bond, and connecting both the benzene ring and the hydroxyl group to the sulfur atom of the precursor; then, activating the hydroxyl group to make the hydroxyl group fall off from the sulfur atom, and trimethylchlorosilane can be used to activate the hydroxyl group. The addition order of trimethylchlorosilane and Grignard reagent can be designed as: adding trimethylchlorosilane first and then adding Grignard reagent, or adding Grignard reagent first and then adding trimethylchlorosilane. The specific addition order can be designed according to actual needs and is not limited herein.

[0044] Moreover, when the hydroxyl group falls off from the sulfur atom, the sulfur atom is positively charged. If an anionic counterion M is added to the reaction solution at this time, then the anion can combine with the positively charged sulfur atom to obtain a compound having the structure shown in general formula (I) or general formula (II), and the value of c is related to the structure of the counterion M. Based on this, the specific reaction process can be as follows:

[0045] For the structure shown in general formula (I):

[0046]

[0047] For the structure shown in general formula (II):

[0048]

[0049] Exemplarily, when preparing the precursor, the synthesis method can be designed according to the group selected by L0, and specifically, the following synthesis methods can be included:

[0050] Synthesis method 1: When L0 is selected from C, the preparation method of the precursor includes:

[0051] Under acidic conditions, performing a reduction reaction and dehydration cyclization on the lithium in raw material 1 and the carbonyl group in raw material 2 to obtain the precursor; raw material 1 has the structure shown in general formula a3 or the structure shown in general formula a4:

[0052]

[0053] Raw material 2 has the structure shown in the following general formula:

[0054]

[0055] Since Li in raw material 1 has strong reducibility and the carbonyl group has certain activity, Li can reduce the carbonyl group, and then a hydroxyl group is formed on the O in the carbonyl group. Under acidic conditions, this hydroxyl group reacts with the H in the benzene ring of raw material 1 that is not connected to Li to form water and be removed, enabling the C originally connected to the hydroxyl group to connect with the C from which H is removed, achieving dehydration and ring closure, thereby forming a precursor shown by the following general formula structure:

[0056]

[0057] Based on this, for general formula a1: The specific synthesis route is as follows:

[0058]

[0059] For general formula a2: The specific synthesis route is as follows:

[0060]

[0061] Synthesis method two: When L0 is selected from a monocyclic structure, a spirocyclic structure or a bridged-ring structure, the preparation method of the precursor includes:

[0062] Under acidic conditions, the lithium in raw material 1 and the lithium in raw material 3 respectively carry out reduction reactions with two carbonyl groups in raw material 4 and undergo dehydration and ring closure to obtain the precursor; the structure of raw material 1 is the same as that of raw material 1 in the above synthesis method one, and raw material 3 has the structure shown by the following general formula:

[0063]

[0064] Among them, in the obtained precursor, L0 is selected from a k-membered monocyclic structure, a C5-C30 spirocyclic structure or a C5-C30 bridged-ring structure, and L0 is the residue after removing two carbonyl groups from raw material 4.

[0065] Similarly, since Li in raw material 1 and raw material 3 has strong reducibility and the carbonyl group has certain activity, Li can reduce the carbonyl group, and then a hydroxyl group is formed on the O in the carbonyl group. Under acidic conditions, this hydroxyl group reacts with the H in the benzene ring of raw material 1 that is not connected to Li to form water and be removed, enabling the C originally connected to the hydroxyl group to connect with the C from which H is removed, achieving dehydration and ring closure; since there are two carbonyl groups in raw material 4 and each Li reacts with one carbonyl group, the residue after removing two carbonyl groups from raw material 4 can be introduced into the precursor.

[0066] Based on this, taking raw material 4 as cyclohexane with two carbonyl groups as an example, for general formula a1: The specific synthesis route is as follows:

[0067]

[0068] For general formula a2: the specific synthesis route is as follows:

[0069]

[0070] Among them, when the dehydration ring closure is carried out in the above-mentioned synthetic routes, it is carried out under acidic conditions. The acid can be selected according to factors such as the activity of the substituent of the intermediate, such as but not limited to the selection of p-toluenesulfonic acid, as long as the ring closure reaction of the intermediate can proceed normally, it is not limited here.

[0071] For example, the raw material 1 in the above synthesis route can be purchased commercially, or can also be prepared by oneself.

[0072] It should be understood that since the principle of solving the problem of the compound prepared by the preparation method is similar to the principle of solving the problem of the aforementioned compound, the implementation and technical effects of the compound in the preparation method can refer to the implementation and technical effects of the aforementioned compound, and the repeated parts will not be repeated.

[0073] In a third aspect, the present application also provides a patterned material, which may include: a photosensitive material, a film-forming resin, and a solvent, wherein the photosensitive material is the compound described in the first aspect; and the photosensitive material and the film-forming resin are both dissolved in the solvent. In this way, when the compound has good solubility and acid production efficiency, the photosensitive material can be well dissolved in the solvent, and the acid production efficiency of the photosensitive material can also be improved, thereby improving the performance of the patterned material.

[0074] Of course, the patterning material may include other components in addition to the photosensitive material, the film-forming resin and the solvent, and the specific design may be based on actual needs and is not limited here.

[0075] Since the principle of solving the problem by the patterned material is similar to the principle of solving the problem by the aforementioned compound, the implementation and technical effects of the patterned material can refer to the implementation and technical effects of the aforementioned compound, and the repeated parts will not be repeated. BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Figure 1 This is a graph showing the NMR characterization data of compound 1 provided in the examples of the present application;

[0077] Figure 2 The solubility test results provided for the examples of this application;

[0078] Figure 3 The sensitivity test results provided in the embodiments of the present application. DETAILED DESCRIPTION

[0079] To make the objectives, technical solutions, and advantages of this application clearer, the following will further describe this application in detail with reference to the accompanying drawings.

[0080] It should be noted that the same reference numerals in the accompanying drawings of this application represent the same or similar structures, and thus repeated descriptions thereof will be omitted. The words expressing positions and directions described in this application are all illustrated by taking the accompanying drawings as examples, but can also be changed as needed, and all such changes are included within the protection scope of this application. The accompanying drawings of this application are only used to illustrate the relative positional relationship and do not represent the true scale.

[0081] To facilitate the understanding of the technical solutions provided in the embodiments of this application, the following first explains its application scenarios.

[0082] The compounds provided in the embodiments of this application can be applied to patterned materials. Patterned materials are one of the key materials for microfabrication in microelectronic processing technology. Patterned materials mainly include: photosensitive materials, film-forming resins, solvents, etc. As the main component of the patterned material, the photosensitive material can decompose to produce acid (such as H + ) under light irradiation. During the baking process, the generated acid can act as a catalyst to cause the unstable groups hanging on the polymer to fall off and generate new acid, thereby changing the properties of the polymer and realizing the transfer of the image.

[0083] To improve the solubility of the photosensitive material in the solvent and also improve the acid generation efficiency of the photosensitive material, the embodiments of this application provide a compound, which can be used as a photosensitive material. The compound has the structure shown in the following general formula (Ⅰ) or general formula (Ⅱ):

[0084]

[0085] In this way, the introduced L0 can make the compound have a three-dimensional structure rather than a planar structure, which can prevent π-π stacking in the solution, thereby improving the solubility of the compound in the solvent; and when this compound is used as a photosensitive material, due to the increased solubility, more protons can be generated, thereby improving the acid generation efficiency of this compound.

[0086] The following will further describe in detail the compounds with the above structural formulas in this application with specific examples.

[0087] Example: Synthesis of Compound 1

[0088] The molecular structure of Compound 1 is as follows:

[0089]

[0090] The synthesis route of Compound 1 is as follows:

[0091]

[0092] Among them, n-BuLi is butyllithium, THF is tetrahydrofuran, mCPBA is meta-chloroperoxybenzoic acid, HBr is hydrogen bromide, TMSCl is trimethylchlorosilane, NEt3 is triethylamine, and DCM is dichloromethane.

[0093] The specific preparation steps of Compound 1 are as follows:

[0094] 1) Synthesis of intermediate: Add raw material 0 and anhydrous THF to a flask respectively. Under ice bath conditions, stir vigorously and then add butyllithium. Slowly warm up to room temperature and react for several hours to generate raw material 1. Subsequently, dissolve raw material 2 in anhydrous tetrahydrofuran and add it to the above system. React at room temperature for 2 hours. After the reaction is completed, quench the reaction with an aqueous solution or a salt solution, and then extract with dichloromethane and spin dry to obtain the intermediate.

[0095] 2) Synthesis of precursor: Dissolve the intermediate in toluene, add p-toluenesulfonic acid, heat under reflux at 110 °C for 5 hours and then quench the reaction to obtain the precursor.

[0096] 3) Synthesis of Substance 1: Add the precursor and dichloromethane to a flask respectively. Slowly dropwise add mCPBA under ice bath conditions. After the addition is completed, slowly warm up to room temperature and react for 5 hours. After the reaction is completed, quench the reaction with a saturated aqueous sodium bicarbonate solution, then extract with dichloromethane, concentrate the organic phase and separate by column chromatography to obtain Substance 1.

[0097] 4) Synthesis of Substance 2: Add Substance 11 and anhydrous THF to a flask respectively. Add phenylmagnesium reagent under ice bath conditions. After reacting for half an hour, add TMSCl and react at room temperature for 5 hours. After the reaction is completed, quench the reaction with an aqueous HBr solution, then extract with dichloromethane, concentrate the organic phase, and then slurry with methyl tert-butyl ether to obtain Substance 2.

[0098] 5) Synthesis of Compound 1: Add Substance 2, triisopropylbenzenesulfonic acid, and dichloromethane to a flask respectively. Then dropwise add triethylamine. After stirring for 2 hours, extract with dichloromethane. Concentrate the organic phase and then slurry with methyl tert-butyl ether to obtain Compound 1.

[0099] Nuclear magnetic characterization data of Compound 1:

[0100] Figure 1 This is the nuclear magnetic test spectrum of Compound 1 in this application. Combining Figure 1 , the nuclear magnetic standard data of Compound 1 are as follows:

[0101] 11H NMR (500 MHz, CDCl3) δ 8.05 (dt, J = 16.3, 9.4 Hz, 4H), 7.69–7.42 (m, 3H), 7.34 (dt, J = 15.2, 7.3 Hz, 2H), 7.28–7.23 (m, 2H), 7.20 (d, J = 7.6 Hz, 3H), 7.16–7.10 (m, 2H), 7.00–6.95 (m, 3H), 6.83–6.77 (m, 2H), 6.55 (d, J = 8.0 Hz, 1H), 6.46 (d, J = 8.2 Hz, 1H), 4.67 (dt, J = 13.4, 6.7 Hz, 2H), 2.77 (dt, J = 13.8, 6.9 Hz, 1H), 2.63 (dt, J = 13.8, 6.9 Hz, 1H), 1.14 (t, J = 6.7 Hz, 18H), 0.93 (d, J = 6.9 Hz, 6H).

[0102] Example: Synthesis of Compound 2

[0103] Molecular structure of Compound 2:

[0104]

[0105] The synthetic route of Compound 2 is as follows:

[0106]

[0107] The specific preparation steps of Compound 2 are as follows:

[0108] 1) Synthesis of Substance 2: The synthesis principle of Substance 2 is basically similar to that of Substance 2 in Compound 1 above. Specifically, the synthesis process of Substance 2 in Compound 1 above can be referred to, and it will not be elaborated here.

[0109] 3) Synthesis of Compound 2: Add Substance 2, sodium p-toluenesulfonate, dichloromethane and water to the flask respectively. After stirring for 2 hours, extract with dichloromethane. Concentrate the organic phase and then slurry with methyl tert-butyl ether to obtain Compound 2.

[0110] It should be understood that the difference between Compound 2 and Compound 1 lies only in the type of anion, while the structure of the cation is exactly the same. Therefore, the NMR characterization data of Compound 2 can be referred to the NMR characterization data in Compound 1, and it will not be elaborated here.

[0111] Example: Synthesis of Compound 3

[0112] Molecular structure of Compound 3:

[0113]

[0114] The synthetic route of Compound 3 is as follows:

[0115]

[0116] The specific preparation steps of Compound 3 are as follows:

[0117] 1) Synthesis of Substance 2: The synthesis principle of Substance 2 is basically similar to that of Substance 2 in Compound 1 above. Specifically, the synthesis process of Substance 2 in Compound 1 above can be referred to, and details are not described here again.

[0118] 3) Synthesis of Compound 3: Add Substance 2, sodium 2,2-dimethylbenzenesulfonate, dichloromethane and water into the flask respectively. After stirring for 2 hours, extract with dichloromethane. Concentrate the organic phase and then slurry with methyl tert-butyl ether to obtain Compound 3.

[0119] It should be understood that the difference between Compound 3 and Compound 1 lies only in the type of anion, while the structure of the cation is exactly the same. Therefore, the NMR characterization data of Compound 3 can be referred to the NMR characterization data in Compound 1, and details are not described here again.

[0120] Example: Synthesis of Compound 4

[0121] Molecular structure of Compound 4:

[0122]

[0123] The synthesis route of Compound 4 is as follows:

[0124]

[0125] The specific preparation steps of Compound 4 are as follows:

[0126] 1) Synthesis of Substance 2: The synthesis principle of Substance 2 is basically similar to that of Substance 2 in Compound 1 above. Specifically, the synthesis process of Substance 2 in Compound 1 above can be referred to, and details are not described here again.

[0127] 3) Synthesis of Compound 4: Add Substance 2, sodium 2,4,6-trimethylbenzenesulfonate, dichloromethane and water into the flask respectively. After stirring for 2 hours, extract with dichloromethane. Concentrate the organic phase and then slurry with methyl tert-butyl ether to obtain Compound 4.

[0128] It should be understood that the difference between Compound 4 and Compound 1 lies only in the type of anion, while the structure of the cation is exactly the same. Therefore, the NMR characterization data of Compound 4 can be referred to the NMR characterization data in Compound 1, and details are not described here again.

[0129] Example: Synthesis of Compound 5

[0130] Molecular structure of Compound 5:

[0131]

[0132] The synthetic route of Compound 5 is as follows:

[0133]

[0134] The specific preparation steps of Compound 5 are as follows:

[0135] 1) Synthesis of Substance 2: The synthesis principle of Substance 2 is basically similar to that of Substance 2 in Compound 1 above. Specifically, the synthesis process of Substance 2 in Compound 1 above can be referred to, and details are not described here.

[0136] 3) Synthesis of Compound 5: Add Substance 2, biphenyl-p-diphenylsulfonic acid, and dichloromethane to the flask respectively, then dropwise add triethylamine. After stirring for 2 hours, extract with dichloromethane. Concentrate the organic phase and then slurry with methyl tert-butyl ether to obtain Compound 5.

[0137] Based on this, the differences between Compound 1 and Compound 5 above are as follows: the counterions are different. Therefore, by selecting different substances to carry out displacement reactions with Substance 2, compounds with counterions of different volume sizes can be obtained to meet the usage requirements of various application scenarios.

[0138] It should be understood that the difference between Compound 5 and Compound 1 lies only in the types of anions, and the structures of the cations are exactly the same. Therefore, the NMR characterization data of Compound 5 can be referred to the NMR characterization data in Compound 1, and details are not described here.

[0139] Example: Synthesis of Compound 6

[0140] Molecular structure of Compound 6:

[0141]

[0142] The synthetic route of Compound 6 is as follows:

[0143]

[0144] The specific preparation steps of Compound 6 are as follows:

[0145] 1) Synthesis of Substance 3: The synthesis principle of Substance 3 is basically similar to that of the precursor in Compound 1 above. Specifically, the synthesis process of the precursor in Compound 1 above can be referred to, and details are not described here.

[0146] 2) Synthesis of the precursor: The synthesis principle is similar to that of Substance 3 in 1), but the difference is that the reaction raw materials are different. Specifically, the synthesis process of Substance 3 can be referred to, and details are not described here.

[0147] 3) Synthesis of Substance 1 and Substance 2: The synthesis principles of Substance 1 and Substance 2 are similar to those of Substance 1 and Substance 2 in the above Compound 1. Specifically, the synthesis processes of Substance 1 and Substance 2 in the above Compound 1 can be referred to, and will not be elaborated here.

[0148] 4) Synthesis of Compound 6: Add Substance 2, triisopropylbenzenesulfonic acid, and dichloromethane into a flask respectively, then dropwise add triethylamine. After stirring for 2 hours, extract with dichloromethane. Concentrate the organic phase and then slurry with methyl tert-butyl ether to obtain Compound 6.

[0149] The performances of the compounds provided in the embodiments of the present application will be described below in combination with solubility tests and sensitivity tests respectively.

[0150] Among them, the above-prepared Compound 1 is used as an example, and the structural formulas of the comparative examples are as follows:

[0151]

[0152] Solubility test:

[0153] Weigh 10 mg, 20 mg, 30 mg, 40 mg, and 50 mg of the example, as well as 10 mg, 20 mg, 30 mg, 40 mg, and 50 mg of the comparative example respectively, and dissolve them in 1 ml of solvent. The solvent is a mixed solution of propylene glycol methyl ether acetate and propylene glycol monomethyl ether with a molar ratio of 4.4:1. After shaking on a shaker for 24 h, observe the dissolution situation. The dissolution results can be seen as shown in Figure 2 shown and Table 1 shown. Figure 1 The arrows in

[0154] Table 1

[0155]

[0156] From Figure 2 the results shown in

[0157] Moreover, when the addition amount in the examples and comparative examples was 10 mg, the molar amount in the examples was approximately 0.013 mmol, and the molar amount in the comparative examples was approximately 0.018 mmol; when the addition amount in the examples and comparative examples was 20 mg, the molar amount in the examples was approximately 0.026 mmol, and the molar amount in the comparative examples was approximately 0.036 mmol; when the addition amount in the examples and comparative examples was 30 mg, the molar amount in the examples was approximately 0.039 mmol, and the molar amount in the comparative examples was approximately 0.054 mmol; when the addition amount in the examples and comparative examples was 40 mg, the molar amount in the examples was approximately 0.052 mmol, and the molar amount in the comparative examples was approximately 0.072 mmol; when the addition amount in the examples and comparative examples was 50 mg, the molar amount in the examples was approximately 0.065 mmol, and the molar amount in the comparative examples was approximately 0.090 mmol. Combining the results shown in Table 1, it can be found that when the addition amounts in the examples and comparative examples are similar, the corresponding molar amounts are also similar. However, due to the different structures of the examples and comparative examples, even when similar addition amounts are used, the dissolution performance of the examples is still better than that of the comparative examples. From this aspect, the dissolution performance of the compounds in the examples is more excellent.

[0158] Sensitivity test:

[0159] Using the method of controlling variables, the comparative examples and examples were added to the formulation of the patterned material, and light treatment verification was carried out. The results of the light treatment verification are as Figure 3 shown, (a) is the test result of the comparative example, and (b) is the test result of the example. It can be seen from Figure 3 this that compared with the comparative example, the Dose transition range corresponding to the compound in the example is narrower, and the fabricated pattern is clearer and has a higher resolution, indicating that the compound in the example is more sensitive to light and is significantly better than the comparative example; the reason is that compared with the comparative example, the volume of the anion is the same, but the structure of the cation is different. The cation structure in the comparative example is planar and contains fewer aryl structures. The cation structure in the example is three-dimensional due to the presence of a rigid structure and contains more aryl structures. Therefore, the cation structure in the example can effectively improve the photosensitive performance, thereby improving the quality of the fabricated pattern.

[0160] The above is only the specific implementation manner of the present application, but the protection scope of the present application is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present application can easily think of changes or substitutions, which should all be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A compound, characterized in that, The compound has a structure represented by the following general formula (I) or general formula (II): Wherein, L0 is selected from: C, a k-membered monocyclic structure, a C5-C30 spiro ring structure or a C5-C30 bridged ring structure, 10≥k≥3; R0 is C or S; c≥1; M is a counter ion; Each R1 is independently selected from: halogen, carboxyl, aldehyde group, carbonyl group, hydroxyl group, siloxy group, basic group, substituted or unsubstituted C1-C10 aliphatic group, substituted or unsubstituted C1-C10 alkoxy group, substituted or unsubstituted C1-C10 ester group, substituted or unsubstituted C6-C10 aromatic group, and substituted or unsubstituted C6-C10 aryloxy group. Each of the R1s is the same or different, n≥0, and the number of the R1s connected to each benzene ring is the same or different; The substituents in the substituted C1-C10 aliphatic group, substituted C1-C10 alkoxy group, substituted C1-C10 ester group, substituted C6-C10 aromatic group, and substituted C6-C10 aryloxy group are independently selected from: halogen, carboxyl, aldehyde group, carbonyl group, hydroxyl group, ester group, siloxy group, basic group, C1-C10 aliphatic group, C6-C10 aromatic group.

2. The compound according to claim 1, wherein L0 is selected from C; each benzene ring connected to L0 is in the same plane, and only the benzene ring connected to S is in a different plane from the other benzene rings.

3. The compound according to claim 1, wherein L0 is selected from: a k-membered saturated monocyclic hydrocarbon structure.

4. The compound according to claim 3, wherein, The monocyclic hydrocarbon structure is selected from: cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclodecane; Wherein, the connection site of L0 to the adjacent group is selected from: the positions where each C in the monocyclic hydrocarbon structure is located.

5. The compound according to claim 1, characterized in that, L0 is selected from any one of the following spiro ring structures: Wherein, the connection site of L0 to the adjacent group is selected from the positions indicated by each *.

6. The compound according to claim 1, characterized in that, L0 is selected from any one of the following bridged ring structures: Wherein, the connection site of L0 to the adjacent group is selected from the positions indicated by each *.

7. The compound according to any one of claims 1-6, characterized in that, Each of the R1s is independently selected from: H or isopropyl.

8. The compound according to any one of claims 1-7, characterized in that, M is selected from: monovalent halogen anions, HSO4 - , NO3 - , SO3 - , CIO4 - , or a structure represented by the following general formula: R2-(X - ) a ; Among them, R2 is selected from: a substituted or unsubstituted C1-C10 aliphatic group, or a substituted or unsubstituted C6-C10 aromatic group, X - is selected from: the monovalent halogen anion, HSO4 - , NO3 - , SO3 - , CIO4 - ; when the compound has the structure shown in the general formula (Ⅰ), a = c; when the compound has the structure shown in the general formula (Ⅱ), a = 2c.

9. The compound according to any one of claims 1-8, characterized in that, The compound is selected from any one of the structures shown in (1) to (52):

10. A method for preparing a compound as claimed in any one of claims 1-9, characterized in that, Including: Oxidizing and adding a phenyl group to the sulfur in the precursor to obtain the compound; the precursor has a structure represented by the following general formula a1 or general formula a2:

11. The method according to claim 10, wherein Oxidizing and adding a phenyl group to the sulfur in the precursor includes: Oxidizing the sulfur in the precursor to form a sulfur-oxygen double bond; Performing an addition reaction between phenylmagnesium reagent and the sulfur-oxygen double bond to introduce a benzene ring and a hydroxyl group onto the sulfur atom in the precursor; Activating the hydroxyl group to cause the hydroxyl group to fall off from the sulfur atom.

12. The method according to claim 10 or 11, characterized in that, The preparation method of the precursor includes: Under acidic conditions, performing a reduction reaction between the lithium in raw material 1 and the carbonyl in raw material 2 and dehydrating and cyclizing to obtain the precursor; raw material 1 has a structure represented by the following general formula a3 or general formula a4: Raw material 2 has a structure represented by the following general formula: Wherein, in the obtained precursor, L0 is selected from C.

13. The method according to claim 10 or 11, characterized in that, The preparation method of the precursor includes: Under acidic conditions, the lithium in raw material 1 and the lithium in raw material 3 are respectively subjected to a reduction reaction with two carbonyl groups in raw material 4 and dehydration and ring closure to obtain the precursor; the raw material 1 has a structure represented by the following general formula a3 or a structure represented by the following general formula a4: The raw material 3 has a structure represented by the following general formula: Wherein, in the obtained precursor, L0 is selected from: a k-membered monocyclic structure, a C5-C30 spiro ring structure or a C5-C30 bridged ring structure, and L0 is the residue after removing the two carbonyl groups from raw material 4.

14. A patterned material, characterized in that, Including: A photosensitive material, a film-forming resin and a solvent, wherein the photosensitive material is the compound according to any one of claims 1-9; both the photosensitive material and the film-forming resin are dissolved in the solvent.

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