A chemically amplified photoresist based on silsesquioxane and its preparation method and application

Abstract

The application discloses a kind of based on silsesquioxane chemical amplification type photoresist, including incomplete condensation poly silyl silsesquioxane, photoacid generator and organic solvent, the incomplete condensation poly silyl silsesquioxane is cage type poly silyl silsesquioxane, it is one or more compounds shown in formula (1);The sensitivity and stability of the present application based on silsesquioxane chemical amplification type photoresist compared with prior art significantly improve, can be used in electron beam lithography, deep ultraviolet lithography or extreme ultraviolet lithography, with important application value and broad market prospect.(R1SiO 1.5 ) l (R2SiO 1.5 ) m (R3SiO 1.5 ) n‑l‑m (H2O) 1.5n‑x (1).

Description

Technical Field

[0001] This invention relates to a photoresist, its preparation method, and its application, specifically to a silsesquioxane-based chemically amplified photoresist, its preparation method, and its application. Background Technology

[0002] Hydrogen silsesquioxane (HSQ) photoresist is currently the most commonly used negative electron beam photoresist. Compared to polymer-based photoresists, this inorganic silicon-based photoresist has higher etching resistance, mechanical strength, and a smaller molecular volume, resulting in superior resolution and line edge roughness. The disadvantages of HSQ photoresist are: its sensitivity is an order of magnitude lower than that of chemically amplified photoresist (CAR), which exacerbates the low throughput problem of electron beam lithography (EBL); secondly, HSQ photoresist has poor stability, exhibiting significant gelation after 30 hours at room temperature.

[0003] Extreme ultraviolet (EUV) lithography is currently the most advanced lithography technology. Traditional deep ultraviolet (DUV) chemical amplification photoresists are difficult to apply directly to EUV lithography due to their large molecular volume and low etching resistance. Highly resistant chromogenic (HSQ) photoresists exhibit high etching resistance, high mechanical strength, and small molecular volume, making them a potential candidate for EUV lithography applications. However, due to their poor sensitivity and stability, HSQ is currently mainly used in electron beam lithography (US9917057B2, CN101625522A, CN111564363B), with limited applications in EUV or DUV lithography.

[0004] Therefore, improving the sensitivity and stability of HSQ photoresist while retaining its excellent resolution is an important optimization direction for HSQ photoresist, and also an important way to increase the throughput of electron beam lithography and expand the application of extreme ultraviolet lithography. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing technologies by providing an incompletely condensed silsesquioxane-type photoresist composition, and to improve the sensitivity and stability of the photoresist through formulation improvements.

[0006] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows:

[0007] A chemically amplified photoresist based on silsesquioxane, the photoresist comprising incompletely condensed polysilsesquioxane, a photoacid generator and an organic solvent, wherein the incompletely condensed polysilsesquioxane is one or more of the compounds shown in formula (1).

[0008] (R1SiO 1.5 ) l (R2SiO 1.5 ) m(R3SiO 1.5 ) n-l-m (H2O) 1.5n-x (1)

[0010] In formula (1), R1 and R2 are each independently H, the group shown in formula A, the group shown in formula B, or the following groups that are not substituted or are substituted by one or more substituents A: C1-C 20 Alkyl, C3-C 30 cycloalkyl, C4-C 30 Silyl, C6-C 30 Aromatic group, C3-C 30 Heterocyclic groups or C5-C 30 The heteroaryl group, or a group containing one or more of the above-mentioned groups selected from O, S, N, Si, and P atoms in the carbon chain, wherein the substituent A includes a halogen atom, hydroxyl group, mercapto group, trifluoromethyl group, C1-C14 group, etc. 20 Branched or straight-chain alkyl groups, C1-C 20 Branched or straight-chain alkoxy groups, C3-C 20 Branched or straight-chain cycloalkyl groups, C6-C 30 Aromatic group, C5-C 30 One or more of the heteroaryl groups; the C3-C 30 Cycloalkyl groups include monocyclic or polycyclic cycloalkyl groups;

[0011] Preferably, R1 is H, a group represented by formula A, a group represented by formula B, or one of the following groups that is unsubstituted or substituted by one or more substituents A: C1-C8 alkyl, C3-C 12 cycloalkyl, C6-C 12 Aromatic group, or any of the above-mentioned groups containing O, S, N, or Si atoms in the carbon chain, wherein the C3-C 12 The cycloalkyl group includes monocyclic or polycyclic cycloalkyl groups, wherein the substituent A is preferably a halogen atom, a C1-C5 alkyl group, a trifluoromethyl group, a hydroxyl group, or a mercapto group; the polycyclic cycloalkyl group can be adamantane, norbornane, etc.

[0012] Preferably, R2 is H, a group represented by formula A, a group represented by formula B, or one of the following groups that is unsubstituted or substituted by one or more substituents A: C1-C8 alkyl, C3-C 12 cycloalkyl, C6-C 12 Aromatic group, or any of the above-mentioned groups containing O, S, N, or Si atoms in the carbon chain, wherein the C3-C 12 The cycloalkyl group includes a monocyclic or polycyclic cycloalkyl group, and the substituent A is preferably a halogen atom, a C1-C5 alkyl group, a trifluoromethyl group, a hydroxyl group or a mercapto group;

[0013] In formula (1), R3 is the group shown in formula A or the group shown in formula B;

[0014]

[0015] Indicates a connection key;

[0016] In formula A or formula B, K1 is 0, or is an unsubstituted or substituted group B of the following groups: C1-C 20 Alkylene, C3-C 30 Cycloalkylene, C6-C 30 The substituent B is a C1-C1 substituent, or any of the above-mentioned groups containing oxygen or silicon atoms in the carbon chain. 10 Alkyl or C1-C 10 The alkoxy group, the C3-C 30 Cycloalkyl groups include monocyclic or polycyclic cycloalkyl groups;

[0017] K1 is preferably 0, C1-C8 alkylene, or C3-C 12 Cycloalkylene, phenylene, or other groups containing oxygen or silicon atoms in the carbon chain, wherein the C3-C 12 Cycloalkyl groups include monocyclic or polycyclic cycloalkyl groups;

[0018] K2 can be 0, ester, carbonate, or amide; preferably K2 can be 0 or ester.

[0019] K1 being 0 means K1 does not exist; K2 being 0 means K2 does not exist; K1 and K2 can both be 0, meaning neither exists, which means R4 is directly connected to a silicon atom, or R5 is directly connected to an ethylene atom.

[0020] R4 is C1-C 20 olefin group, C5-C 30 Cycloolefin group, C1-C 20 The alkynyl group, wherein the cycloolefinic group comprises a monocyclic or polycyclic cycloolefinic group;

[0021] R4 is preferably C1-C 10 olefin group, C5-C 12 Cycloolefin or C1-C 10 The alkynyl group, wherein the cycloolefinic group comprises a monocyclic or polycyclic cycloolefinic group;

[0022] R5 is C2-C 20 The epoxy group, or any of the above-mentioned groups containing oxygen or sulfur atoms in the carbon chain; preferably, R5 is a C2-C9 epoxy group; the epoxy group includes monocyclic or polycyclic epoxy groups;

[0023] In the formula (1), l represents the number of R1s in the incompletely condensed polysilsesquioxane, and l is an integer from 0 to 20; preferably an integer from 0 to 14; l of 0 represents that R1s do not exist.

[0024] m represents the number of R2 molecules in the incompletely condensed polysilsesquioxane, where m is an integer from 0 to 20; preferably an integer from 0 to 14; m = 0 indicates that R2 is not present.

[0025] n represents the total number of R1, R2, and R3 in the incompletely condensed polysilsesquioxane, and n is an integer from 7 to 20; preferably an integer from 7 to 14.

[0026] nlm is an integer greater than or equal to 1;

[0027] In equation (1), R1 and R2 may not exist, but R3 must exist.

[0028] R1 and R2 can be the same substituent or different substituents. When R1 and R2 are the same substituent, l and m in equation (1) can be combined.

[0029] Similarly, R1 and R3 can be the same substituent or different substituents. R2 and R3 can also be the same substituent or different substituents. All three substituents, R1, R2, and R3, can be the same, but in this case, they must all be R3, representing either the group shown in Formula A or the group shown in Formula B.

[0030] x represents the number of water molecules generated during the preparation of incompletely condensed polysilsesquioxane, and x is an integer from 9 to 29; preferably an integer from 9 to 20.

[0031] 3n-2x represents the number of silicon-hydroxyl (Si-OH) groups in the incompletely condensed polysilsesquioxane. 3n-2x is an integer greater than or equal to 1, preferably ranging from 2 to 6.

[0032] Furthermore, in the incompletely condensed polysilsesquioxane, the ratio of Si-OH to Si element is preferably 5-45%, and more preferably 10-30%.

[0033] In the incompletely condensed polysilsesquioxane, when neither R1 nor R2 exists, or when neither R1 nor R2 is H, the content of silane-hydrogen groups (Si-H) in the incompletely condensed polysilsesquioxane is 0, and the content of organic groups (the ratio of the number of silicon-organic groups to the total number of silicon-organic groups and silane-hydrogen bonds) is 100%.

[0034] In this invention, the organic group content in the incompletely condensed polysilsesquioxane is preferably 30% to 100%, more preferably 50% to 100%.

[0035] In this invention, the incompletely condensed polysilsesquioxane is a cage-type polysilsesquioxane.

[0036] Furthermore, preferably, the chemical formula of the incompletely condensed polysilsesquioxane is one or more of the following cage-like structural formulas: wherein the R6 group is selected from any one of the R1, R2, and R3 groups, and for any cage-like structure, at least one of the R6 groups is R3, and R6 cannot be all R1 or R2; the definitions of the R1, R2, and R3 groups are as described above:

[0037]

[0038]

[0039] It should be noted that incompletely condensed polysilsesquioxanes are mixtures of molecules with various cage-like structures. Different cage-like structures have different molecular weights. Generally, the average molecular weight of the incompletely condensed polysilsesquioxane is used to infer the possible cage-like structure. However, actual polymers are mixtures of cage-like structures with different molecular weights, and the proportions of these structures vary, resulting in different average molecular weights. The chemical structural formulas above are the closest to the average molecular weight of a particular polymer, but they do not necessarily mean that the polymer contains only one type of cage-like structure.

[0040] Furthermore, for each cage-like molecular structure, the substituent R6 can be one of the R1, R2, or R3 groups, and the content of each R1, R2, or R3 group in the structure can be determined through raw material input and product testing. However, it is impossible to determine the specific position of each R1, R2, or R3 group in the cage-like molecular structure.

[0041] Furthermore, in the cage-like structure of the incompletely condensed polysilsesquioxane, the R6 group is selected from any one of the R1, R2, and R3 groups, and at least one R6 group is R3; R6 cannot be all R1 or R2; R1 and R2 are preferably one of the following groups: H, C1-C8 alkyl, C6-C 10 Aromatic group,

[0042] R3 is preferably selected from one of the following groups:

[0043]

[0044] The present invention also provides a method for preparing incompletely condensed polysilsesquioxanes, wherein the method comprises one of the following:

[0045] (i) When R1, R2, and R3 are not groups shown in formula B, the method is as follows: the silane raw materials shown in formula (2) to formula (4) are mixed in a molar ratio of 1:m:(nlm) and slowly added dropwise to concentrated acid. Under the action of concentrated acid, a hydrolysis-condensation reaction is carried out to obtain the incompletely condensed polysilsesquioxane shown in formula (1).

[0046] The concentrated acid is concentrated sulfuric acid, fuming sulfuric acid, concentrated hydrochloric acid, or concentrated nitric acid; preferably concentrated hydrochloric acid.

[0047]

[0048] In equations (2) to (4), R1 to R3 are defined as described above, R 10 Selected from one of the following groups: Preferred R 10 for

[0049] The ratio of the amount of the concentrated acid to the total amount of the silane raw materials shown in formulas (2) to (4) is 1 to 20:1. Further, when the concentrated acid is concentrated hydrochloric acid or concentrated nitric acid, the ratio of the amount of the concentrated acid to the total amount of the silane raw materials shown in formulas (2) to (4) is preferably 1 to 2:1. When the concentrated acid is concentrated sulfuric acid or fuming sulfuric acid, the ratio of the amount of the concentrated acid to the total amount of the silane raw materials shown in formulas (2) to (4) is preferably 15 to 20:1.

[0050] The temperature of the hydrolysis-condensation reaction is 0–60°C, preferably 0°C.

[0051] The preferred steps for the hydrolysis-condensation reaction are as follows:

[0052] The silane raw materials shown in formulas (2) to (4) are added in a molar ratio of 1:m:(nlm) and dissolved in organic solvent A. Then, the above raw material solution is slowly added dropwise to a mixture of concentrated acid and organic solvent A to carry out a hydrolysis and condensation reaction. The addition time is usually 1-6 hours, and stirring is continued for 1-24 hours after the addition is completed.

[0053] The organic solvent A is typically one or more of tetrahydrofuran, hexane, cyclohexane, benzene, toluene, and ethylene glycol dimethyl ether; preferably hexane.

[0054] The volume of organic solvent A used to dissolve silane raw materials is usually 0.5 to 3 mL / mmol, calculated as the total amount of silane raw materials shown in formulas (2) to (4); the volume of organic solvent A used to mix with concentrated acid is usually 0.1 to 5 mL / mmol, calculated as the amount of concentrated acid.

[0055] After the hydrolysis-condensation reaction, the reaction solution is post-treated to obtain the incompletely condensed polysilsesquioxane shown in formula (1). The post-treatment method of the reaction solution is usually as follows: after the reaction is completed, the solution is washed with water until neutral, then concentrated and crystallized, filtered to remove the crystallized material, and the solvent is evaporated to obtain the incompletely condensed polysilsesquioxane shown in formula (1).

[0056] Furthermore, the preferred post-treatment method for the reaction solution is as follows: after the reaction is completed, deionized water is added to wash until the system is neutral, and then the organic phase is obtained by separation. After drying the organic phase, it is distilled under reduced pressure until crystals are generated. Then, centrifugation is used to remove insoluble crystalline substances. After further distillation under reduced pressure to remove the solvent, the incompletely condensed polysilsesquioxane shown in formula (1) is obtained (if no crystals are generated during the concentration process, the centrifugation step is omitted).

[0057] (ii) When any of the groups R1, R2, and R3 is a group shown in Formula B, taking R3 as an example, the method is as follows: the silane raw materials shown in Formula (2), Formula (3), and Formula (5) are mixed in a molar ratio of 1:m:(nm / lm) and slowly added dropwise to concentrated acid. Under the action of concentrated acid, a hydrolysis condensation reaction is carried out. After the reaction is completed, the mixture is washed with water until neutral. Then, it is concentrated and crystallized. After centrifugation to remove the crystallized material, the solvent is evaporated to obtain an intermediate product. Then, under the catalysis of Karstedt catalyst, the intermediate product is subjected to a hydrosilylation reaction with the vinyl compound shown in Formula (6) to prepare the incompletely condensed polysilsesquioxane shown in Formula (1).

[0058] When R1 or R2 is a group as shown in Formula B, the feeding method can be changed accordingly.

[0059] The concentrated acid is concentrated sulfuric acid, fuming sulfuric acid, concentrated hydrochloric acid, or concentrated nitric acid; preferably concentrated hydrochloric acid.

[0060]

[0061] In equations (5) and (6), K1, K2, and R5 are defined as described above, and R... 10 Selected from one of the following groups: Preferred R 10 for

[0062] The ratio of the amount of the concentrated acid to the total amount of the silane raw materials shown in formulas (2), (3), and (5) is 1 to 20:1.

[0063] The temperature of the hydrolysis-condensation reaction is 0–60°C, preferably 0°C.

[0064] The preferred steps for the hydrolysis-condensation reaction are as follows: the silane raw materials shown in formulas (2), (3), and (5) are added in a molar ratio of 1:m:(nlm) and dissolved in organic solvent A. Then, the above raw material solution is slowly added dropwise to a mixture of concentrated acid and organic solvent A to carry out the hydrolysis-condensation reaction. The addition time is usually 1-6 hours, and stirring is continued for 1-24 hours after the addition is completed.

[0065] The organic solvent A is typically one or more of tetrahydrofuran, hexane, cyclohexane, benzene, toluene, and ethylene glycol dimethyl ether; preferably hexane.

[0066] The volumetric amount of organic solvent A used to dissolve silane raw materials is usually 0.5 to 3 mL / mmol, calculated as the amount of silane raw materials shown in formulas (2), (3), and (5); the volumetric amount of organic solvent A used to mix with concentrated acid is usually 0.1 to 5 mL / mmol, calculated as the amount of concentrated acid.

[0067] After the hydrolysis-condensation reaction, the reaction solution is post-treated to obtain the intermediate product. The post-treatment method of the reaction solution is usually as follows: add deionized water to wash until the system is neutral, then separate the liquid to obtain the organic phase, dry the organic phase and distill under reduced pressure until crystals are formed, then centrifuge to remove insoluble substances, and further distill under reduced pressure to remove the solvent to obtain the intermediate product (if no crystals are formed during the concentration process, the centrifugation step is omitted).

[0068] The temperature of the hydrosilylation reaction is 60-90℃, preferably 80-90℃.

[0069] The preferred steps of the hydrosilylation reaction are:

[0070] The intermediate product, the raw material shown in formula (6), and the Karstedt catalyst are dissolved in organic solvent B and stirred at 80-90°C for a reaction time of 3-9 hours.

[0071] The molar ratio of the vinyl compound shown in formula (6) to the silane bonds in the intermediate is 0.1 to 1.2:1.

[0072] The content of silanol groups (Si-H) in the incompletely condensed polysilsesquioxane product is related to the molar ratio of silanol bonds in the vinyl compound to those in the intermediate product. When the molar ratio of silanol bonds in the vinyl compound to those in the intermediate product is 1:1, it indicates that the content of silanol groups (Si-H) in the incompletely condensed polysilsesquioxane product is 0, and the content of organic groups (the ratio of the number of silicon-organic groups to the total number of silicon-organic groups and silanol bonds) is 100%. However, when the silanol bond content of the target product is 0, slightly more vinyl compound can be added to ensure complete reaction of the silanol bonds.

[0073] When the molar ratio of the vinyl compound to the silane bond in the intermediate product is less than 1:1, the content of silane groups (Si-H) in the incompletely condensed polysilsesquioxane product is greater than 0, and the specific content can be estimated based on the amount of feed.

[0074] The organic solvent B is typically one or more of tetrahydrofuran, hexane, cyclohexane, benzene, and toluene; preferably toluene.

[0075] The amount of the organoplatinum complex in the Karstedt catalyst is typically 10-30 ppm of the total mass of the intermediate product and the vinyl compound shown in formula (6); the amount of the organic solvent B is typically 0.5-5 mL / g of the total mass of the intermediate product and the raw material shown in formula (6).

[0076] After the hydrosilylation reaction, the resulting reaction solution b is post-treated to obtain the incompletely condensed polysilsesquioxane shown in formula (1). The post-treatment method of reaction solution b is usually as follows: after the hydrosilylation reaction is completed, diatomaceous earth is added to adsorb the Karstedt catalyst, then the mixture is filtered, the filtrate is collected, and then the solvent and unreacted raw materials are removed by vacuum distillation of the filtrate to obtain the incompletely condensed polysilsesquioxane shown in formula (1).

[0077] Furthermore, in the photoresist of the present invention, the content of incompletely condensed polysilsesquioxane is 1-20% by mass percentage, the content of photoacid generator is 0.01-4%, and the balance is organic solvent.

[0078] The preferred content of incompletely condensed polysilsesquioxane is 1-10%, the content of photoacid-producing agent is 0.1-1%, and the balance is organic solvent.

[0079] The photo-induced acid-producing agent is a thionium salt or an iodonium salt, composed of cations and anions, wherein the anion is selected from one of the following structures: The cation is selected from one of the following structures:

[0080]

[0081] The organic solvent is selected from one or more of methyl ethyl ketone, methyl isobutyl ketone, ethyl lactate, tetrahydrofuran, propylene glycol monomethyl ether acetate, toluene, chloroform, hexane, ethyl acetate, 1,4-dioxane, and pyridine; preferably methyl isobutyl ketone.

[0082] The photoresist is generally prepared by the following method: at room temperature, incompletely condensed polysilsesquioxane, photoacid generator and organic solvent are added in sequence according to the formula ratio. The mixture is ultrasonicated in the dark for 0.5 to 1 hour to make it fully dissolved. Then, a 0.1 μm pore size filter is used to filter out suspended particulate impurities, and the filtrate is collected to obtain the desired photoresist composition.

[0083] The photoresist provided by this invention can be applied to electron beam lithography, deep ultraviolet lithography, or extreme ultraviolet lithography.

[0084] Furthermore, the method for applying the photoresist includes the following steps:

[0085] 1) Spin-coat the photoresist solution onto the substrate surface;

[0086] 2) Use appropriate exposure light sources to perform exposure processing on specific areas;

[0087] 3) Exposure followed by baking is performed using a hot plate;

[0088] 4) Develop the pattern using a developer solution;

[0089] 5) Fixing with fixer.

[0090] In step 1), the substrate is a silicon wafer, germanium, a silicon wafer with graphene or graphene oxide covering its surface, or other semiconductor materials.

[0091] In step 3), the baking temperature after exposure is 40-200℃, and the time is 30-120 seconds.

[0092] In step 4), the developing solution is selected from one of the following: 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, 10% TMAH aqueous solution, 25% TMAH aqueous solution, 1% NaOH + 4% NaCl aqueous solution, acetone, methyl isobutyl ketone, and butanone; the developing time is 30-240 seconds.

[0093] When the developer in step 4) is selected from one of 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, 10% TMAH aqueous solution, 25% TMAH aqueous solution, or 1% NaOH + 4% NaCl aqueous solution, the fixing solution in step 5) is water, and the fixing time is 15-60 seconds; when the developer in step 4) is selected from one of acetone, methyl isobutyl ketone, or butanone, the fixing solution in step 5) is isopropanol, and the fixing time is 15-60 seconds.

[0094] The present invention also provides the application of the incompletely condensed polysilsesquioxane in the preparation of chemically amplified photoresists.

[0095] Compared with existing technologies, the advantages of this invention are as follows: In this invention, in the photoresist composition, incompletely condensed polysilsesquioxane is used as the film-forming resin. Furthermore, the incompletely condensed polysilsesquioxane used in this invention has a cage-like molecular structure. Compared to random polysilsesquioxane molecules, the cage-like molecular volume is smaller, and this smaller molecular volume can result in higher resolution. Cage-like polysilsesquioxane also exhibits higher rigidity than random polysilsesquioxane, which can prevent the collapse of the photolithographic pattern.

[0096] Furthermore, compared to conventional cage-like polysilsesquioxanes, the incompletely condensed polysilsesquioxane of this invention has a large number of incompletely dehydrated and condensed silanol structures. These silanol structures undergo dehydration and condensation during photolithography, thereby improving the sensitivity of the photoresist. However, the content of silanol structures cannot be too high, as excessive silanol content will reduce the stability of the photoresist.

[0097] The incompletely condensed polysilsesquioxane used in this invention has been modified with unsaturated organic groups, and thioonium or iodonium salts have been introduced as photoacid-generating agents. Under the action of electron beam lithography and photoacids, these unsaturated carbon-carbon double bonds undergo cross-linking reactions, thereby significantly improving the sensitivity of the photoresist. Simultaneously, the introduction of thioonium or iodonium salts facilitates the binding of hydroxyl ions in the environment, preventing the cross-linking and deterioration reactions of the polysilsesquioxane caused by hydroxyl ions, thus significantly improving the stability of the photoresist. The photoresist of this invention significantly improves sensitivity while maintaining good stability, possessing significant application value and broad market prospects. Attached Figure Description

[0098] Figure 1 This is a schematic diagram of a photoresist imaging method, where 1 is an incompletely condensed silsesquioxane-type photoresist film, 2 is the substrate, and 3 is the exposure light source.

[0099] Figure 2 The image shows the 1H NMR spectrum of the incompletely condensed polysilsesquioxane A from Example 1.

[0100] Figure 3 The image shows the carbon NMR spectrum of the incompletely condensed polysilsesquioxane A in Example 1.

[0101] Figure 4 The image shows the 1H NMR spectrum of the incompletely condensed polysilsesquioxane B in Example 2.

[0102] Figure 5 The image shows the carbon NMR spectrum of the incompletely condensed polysilsesquioxane B in Example 2.

[0103] Figure 6 The image shows the 1H NMR spectrum of the incompletely condensed polysilsesquioxane C in Example 3.

[0104] Figure 7 The image shows the carbon NMR spectrum of the incompletely condensed polysilsesquioxane C in Example 3.

[0105] Figure 8 The image shows the 1H NMR spectrum of the incompletely condensed polysilsesquioxane D in Example 4.

[0106] Figure 9 The image shows the carbon NMR spectrum of the incompletely condensed polysilsesquioxane D in Example 4.

[0107] Figure 10 The image shows the 1H NMR spectrum of the incompletely condensed polysilsesquioxane E in Example 5.

[0108] Figure 11 The image shows the carbon NMR spectrum of the incompletely condensed polysilsesquioxane E in Example 5.

[0109] Figure 12 The image shows the 1H NMR spectrum of the incompletely condensed polysilsesquioxane F from Example 6.

[0110] Figure 13 The image shows the carbon NMR spectrum of the incompletely condensed polysilsesquioxane F in Example 6.

[0111] Figure 14 This is a SEM image of the thin film after RA exposure treatment of the photoresist composition in Example 7.

[0112] Figure 15 This is a SEM image of the thin film after RB exposure treatment of the photoresist composition in Example 8.

[0113] Figure 16 This is a SEM image of the thin film after RC exposure treatment of the photoresist composition in Example 9.

[0114] Figure 17 This is a SEM image of the thin film after RD exposure treatment of the photoresist composition in Example 10.

[0115] Figure 18 This is an optical microscope image of the thin film after RE exposure treatment of the photoresist composition in Example 11.

[0116] Figure 19 This is an optical microscope image of the thin film after RF exposure treatment of the photoresist composition in Example 12.

[0117] Figure 20 The image shows the silicon NMR spectrum of random polysilsesquioxane G in Example 14.

[0118] Figure 21The image shows the silicon NMR spectrum of the incompletely condensed polysilsesquioxane A in Example 1. Detailed Implementation

[0119] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the scope of protection of this invention.

[0120] Example 1

[0121] The structure and synthetic route of an incompletely condensed polysilsesquioxane A are as follows:

[0122]

[0123] 5.2 ml (30 mmol, 1 molar equivalent) of triethoxysilane and 7.6 ml (36 mmol, 1.2 molar equivalent) of trimethoxy(4-vinylphenyl)silane were dissolved in 60 ml of hexane to obtain a monomer mixture solution. 7.1 ml (37% by mass) of concentrated hydrochloric acid (82.5 mmol, 2.75 molar equivalent) was added to 200 ml of hexane, and the mixture was stirred at 0 °C for 0.5 h. Subsequently, the monomer mixture solution was added dropwise over 2 h to the continuously stirred 0 °C mixture of concentrated hydrochloric acid and hexane. After the addition was completed, stirring was continued at 0 °C for 3 h.

[0124] After the hydrolysis-condensation reaction was completed, the reaction solution was washed with deionized water (3 × 200 ml), and then the organic phase was obtained by separation. The organic phase was dried with anhydrous magnesium sulfate, and the magnesium sulfate solid was removed by filtration. The solvent was then gradually evaporated under reduced pressure until a large amount of crystals formed. After filtration to remove the crystals, the solvent was completely evaporated to obtain 1.4 g of incompletely condensed polysilsesquioxane A with a molecular weight of 1.2 kDa and a molecular weight distribution of 1.09. The 1H NMR spectrum is shown below. Figure 2 As shown, the carbon NMR spectrum is as follows: Figure 3 As shown in the figure. Its molecular structure, estimated based on molecular weight, is shown in Formula A. However, actual polysilsesquioxanes are mixtures of various cage-like molecular structures, and only the content ratio of substituents can be determined, not their specific substitution positions. The following molecular structures are all estimates and will not be elaborated further.

[0125] Example 2

[0126] The structure and synthetic route of an incompletely condensed polysilsesquioxane B are as follows:

[0127]

[0128] 2.3 ml (15 mmol, 1 molar equivalent) of trimethoxyvinylsilane and 10.3 ml (45 mmol, 3 molar equivalent) of trimethoxy(p-chlorobenzyl)silane were dissolved in 60 ml of hexane to obtain a monomer mixture solution. 6.5 ml of concentrated hydrochloric acid aqueous solution (75 mmol, 5 molar equivalent) was added to 200 ml of hexane, and the mixture was stirred at 0 °C for 0.5 h. Subsequently, the monomer mixture solution was added dropwise over 2 h to the continuously stirred 0 °C concentrated hydrochloric acid and hexane mixture. After the addition was completed, stirring was continued at 0 °C for 6 h.

[0129] After the hydrolysis-condensation reaction was completed, the reaction solution was washed with deionized water (3 × 200 ml), and then the organic phase was obtained by separation. The organic phase was dried with anhydrous magnesium sulfate, and the magnesium sulfate solid was removed by filtration. The solvent was then gradually evaporated under reduced pressure until a large amount of crystals formed. After filtration to remove the crystals, the solvent was completely evaporated to obtain 2.0 g of incompletely condensed polysilsesquioxane B with a molecular weight of 1.8 kDa and a molecular weight distribution of 1.21. The 1H NMR spectrum is shown below. Figure 4 As shown, the carbon NMR spectrum is as follows: Figure 5 As shown.

[0130] Example 3

[0131] The structure and synthetic route of an incompletely condensed polysilsesquioxane C are as follows:

[0132]

[0133] 4.4 ml (24 mmol, 1.3 molar equivalent) of triethoxysilane, 3.9 ml (18 mmol, 1 molar equivalent) of trimethoxy(p-chlorobenzyl)silane, and 4.4 ml (18 mmol, 1 molar equivalent) of trimethoxy(7-octenyl)silane were dissolved in 60 ml of hexane to obtain a monomer mixture solution. 10.5 ml of concentrated hydrochloric acid aqueous solution (120 mmol, 6.6 molar equivalent) was added to 200 ml of hexane, and the mixture was stirred at 0 °C for 0.5 h. Subsequently, the monomer mixture solution was added dropwise over 3 h to the continuously stirred 0 °C mixture of concentrated hydrochloric acid and hexane. After the addition was completed, stirring was continued at 0 °C for 2 h.

[0134] After the hydrolysis-condensation reaction was completed, the reaction solution was washed with deionized water (3 × 200 ml), and then the organic phase was obtained by separation. The organic phase was dried with anhydrous magnesium sulfate, and the magnesium sulfate solid was removed by filtration. The solvent was then gradually evaporated under reduced pressure until a large amount of crystals formed. After filtration to remove the crystals, the solvent was completely evaporated to obtain 1.2 g of incompletely condensed polysilsesquioxane C, with a molecular weight of 1.1 kDa and a molecular weight distribution of 1.15. The 1H NMR spectrum is shown below. Figure 6 As shown, the carbon NMR spectrum is as follows: Figure 7 As shown.

[0135] Example 4

[0136] The structure and synthetic route of an incompletely condensed polysilsesquioxane D are as follows:

[0137]

[0138] 5.2 ml (30 mmol, 1 molar equivalent) of triethoxysilane and 6.4 ml (30 mmol, 1 molar equivalent) of 5-(trimethoxysilyl)bicyclo[2.2.1]hept-2-ene were dissolved in 60 ml of hexane to obtain a monomer mixture solution. 5.2 ml of concentrated hydrochloric acid aqueous solution (60 mmol, 2 molar equivalent) was added to 200 ml of hexane and stirred at 0 °C for 0.5 h. Then, the monomer mixture solution was added dropwise over 1 h to the continuously stirred 0 °C concentrated hydrochloric acid and hexane mixture. After the addition was complete, stirring was continued at 0 °C for 4 h.

[0139] After the hydrolysis-condensation reaction was completed, the reaction solution was washed with deionized water (3 × 200 ml), and then the organic phase was obtained by separation. The organic phase was dried with anhydrous magnesium sulfate, and the magnesium sulfate solid was removed by filtration. The solvent was then gradually evaporated under reduced pressure until a large amount of crystals formed. After filtration to remove the crystals, the solvent was completely evaporated to obtain 1.9 g of incompletely condensed polysilsesquioxane D with a molecular weight of 1.4 kDa and a molecular weight distribution of 1.31. The 1H NMR spectrum is shown below. Figure 8 As shown, the carbon NMR spectrum is as follows: Figure 9 As shown.

[0140] Example 5

[0141] The structure and synthetic route of an incompletely condensed polysilsesquioxane E are as follows:

[0142]

[0143] 10.4 mL (60 mmol, 1 molar equivalent) of triethoxysilane was dissolved in 60 mL of hexane to obtain a monomer mixture solution. 6.5 mL of concentrated hydrochloric acid aqueous solution (75 mmol, 1.25 molar equivalent) was added to 200 mL of hexane, and the mixture was stirred at 0 °C for 0.5 h. Subsequently, the monomer mixture solution was added dropwise over 2 h to the continuously stirred 0 °C concentrated hydrochloric acid and hexane mixture. After the addition was complete, stirring was continued at 0 °C for 3 h.

[0144] After the hydrolysis-condensation reaction was completed, the reaction solution was washed with deionized water (3 × 200 ml), and then the organic phase was obtained by separation. The organic phase was dried with anhydrous magnesium sulfate and the magnesium sulfate solid was removed by filtration. The solvent was then gradually evaporated under reduced pressure until a large amount of crystals were formed. After filtration to remove the crystals, the solvent was completely evaporated to obtain 1.9 g of intermediate 1.

[0145] 1.9 g of intermediate 1 and 2.44 g of 6-vinyl-3-oxatricyclo[3.2.1.0] were added. 2,4 Octane and 90 μL of 0.1 wt% Karstedt catalyst (in toluene) were dissolved in 6 mL of toluene and reacted at 80 °C for 6 h. The catalyst was then adsorbed using diatomaceous earth. The reaction solution was filtered, and the filtrate was further distilled under reduced pressure to remove the solvent and unreacted monomers, yielding 1.3 g of incompletely condensed polysilsesquioxane D with a molecular weight of 1.4 kDa and a molecular weight distribution of 1.24. The 1H NMR spectrum is shown below. Figure 10 As shown, the carbon NMR spectrum is as follows: Figure 11 As shown.

[0146] Example 6

[0147]

[0148] The structure and synthetic route of an incompletely condensed polysilsesquioxane F are as follows:

[0149] 10.4 mL (60 mmol, 1 molar equivalent) of triethoxysilane was dissolved in 60 mL of hexane to produce the intermediate. 15.6 mL of concentrated hydrochloric acid aqueous solution (180 mmol, 3 molar equivalent) was added to 200 mL of hexane, and the mixture was stirred at 0 °C for 0.5 h. Subsequently, the above monomer mixture was added dropwise over 4 h to the continuously stirred 0 °C concentrated hydrochloric acid and hexane mixture. After the addition was complete, stirring was continued at 0 °C for 3 h.

[0150] After the hydrolysis-condensation reaction was completed, the reaction solution was washed with deionized water (3 × 200 ml), and then the organic phase was obtained by separation. The organic phase was dried with anhydrous magnesium sulfate and the magnesium sulfate solid was removed by filtration. The solvent was then gradually evaporated under reduced pressure until a large amount of crystals were formed. After filtration to remove the crystals, the solvent was completely evaporated to obtain 2.5 g of intermediate 2.

[0151] 2.5 g of intermediate 2, 2.92 g of 4-vinylcyclohexene oxide, and 110 μL of 0.1 wt% Karstedt catalyst (in toluene) were dissolved in 7 mL of toluene and reacted at 80 °C for 6 h. The reaction solution was then filtered through diatomaceous earth, and the filtrate was further distilled under reduced pressure to remove the solvent and unreacted monomers, yielding 1.9 g of incompletely condensed polysilsesquioxane F with a molecular weight of 1.0 kDa and a molecular weight distribution of 1.22. Its 1H NMR spectrum is shown below. Figure 12 As shown, the carbon NMR spectrum is as follows: Figure 13 As shown.

[0152] Example 7

[0153] The modulation and imaging methods of an incompletely condensed silsesquioxane A photoresist composition RA are as follows:

[0154] In a clean 20ml glass bottle, 10mg of diphenyliodotrifluoromethanesulfonate and 1.99g of methyl isobutyl ketone were added, followed by sonication for 0.5h to ensure complete dissolution of the photoacid-generating agent. Then, in a 1ml glass bottle, 25mg of incompletely condensed silsesquioxane A, 250mg of the above photoacid-generating agent solution, and 225mg of methyl isobutyl ketone were added, and the photoresist solution was sonicated for 0.5h to ensure thorough mixing. The photoresist solution was then filtered through a 0.1-micron filter. The photoresist solution was spin-coated onto a silicon wafer at 3000 rpm to obtain a 98nm thick film. Photolithography testing was then performed.

[0155] like Figure 1 As shown, using a FEI Nova Nano SEM field emission scanning electron microscope and an NPGS electron beam exposure system, at a voltage of 20 kV, and with a current of 1 μC / cm 2 Up to 100 μC / cm 2 Fifty different dosages of incompletely condensed silsesquioxane A photoresist film were exposed. After exposure, the film was baked at 100°C for 60 seconds, followed by development with 10% (w / w) tetramethylammonium hydroxide (TMAH) solution for 1 minute and fixing with water for 30 seconds. The difference between the film thickness and the original thickness in the 50 exposed areas was measured using a surface profilometer, yielding a sensitivity of 7.9 μC / cm for the incompletely condensed silsesquioxane A photoresist under these conditions. 2 The contrast ratio γ = 4.09.

[0156] Subsequently, at a voltage of 20kV and a temperature of 15μC / cm 2 At the specified dosage, the photoresist film was exposed using different exposure cycles, while the post-baking, developing, and fixing conditions remained the same as described above. For example... Figure 14 As shown, its resolution is 16nm.

[0157] Example 8

[0158] The modulation and imaging methods of an incompletely condensed silsesquioxane B photoresist composition RB are as follows:

[0159] In a clean 20ml glass bottle, 10mg of triphenylsulfonium trifluoromethanesulfonate and 1.99g of methyl isobutyl ketone were added, followed by sonication for 0.5h to ensure complete dissolution of the photoacid-generating agent. Then, in a 1ml glass bottle, 25mg of incompletely condensed silsesquioxane B, 250mg of the above photoacid-generating agent solution, and 225mg of methyl isobutyl ketone were added, and the photoresist solution was sonicated for 0.5h to ensure thorough mixing. The photoresist solution was then filtered through a 0.1-micron filter. The photoresist solution was spin-coated onto a silicon wafer at 3000 rpm to obtain a 105nm thick film. Photolithography testing was then performed.

[0160] Using a FEI NovaNano SEM field emission scanning electron microscope and an NPGS electron beam exposure system, at a voltage of 20 kV, and with a current of 1 μC / cm 2 Up to 100 μC / cm 2 Fifty different dosages of incompletely condensed silsesquioxane B photoresist films were exposed. After exposure, the films were baked at 100°C for 60 seconds, followed by development with methyl isobutyl ketone for 1 minute and fixing with isopropanol for 30 seconds. The difference between the film thickness and the original thickness in the 50 exposed areas was measured using a surface profilometer, yielding a sensitivity of 22.4 μC / cm for the incompletely condensed silsesquioxane B photoresist under these conditions. 2 The contrast ratio γ = 2.07.

[0161] Subsequently, at a voltage of 20kV and a temperature of 50μC / cm 2 At the specified dosage, the photoresist film was exposed using different exposure cycles, while the post-baking, developing, and fixing conditions remained the same as described above. For example... Figure 15 As shown, its resolution is 26nm.

[0162] Example 9

[0163] The modulation and imaging methods of an incompletely condensed silsesquioxane C photoresist composition RC are as follows:

[0164] In a clean 20ml glass bottle, 10mg of triphenylsulfonium-1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate and 1.99g of methyl isobutyl ketone were added, followed by sonication for 0.5h to ensure complete dissolution of the photoacid-generating agent. Then, in a 1ml glass bottle, 25mg of incompletely condensed silsesquioxane C, 250mg of the above photoacid-generating agent solution, and 225mg of methyl isobutyl ketone were added, and the photoresist solution was sonicated for 0.5h to ensure thorough mixing. The photoresist solution was then filtered through a 0.1-micron filter. The photoresist solution was spin-coated onto a silicon wafer at 3000 rpm to obtain a 111nm thick film. Photolithography tests were then performed.

[0165] Using a FEI NovaNano SEM field emission scanning electron microscope and an NPGS electron beam exposure system, at a voltage of 20 kV, and with a current of 1 μC / cm 2 Up to 100 μC / cm 2 Fifty different dosages of incompletely condensed silsesquioxane C photoresist films were exposed. After exposure, the films were baked at 100°C for 60 seconds, followed by development with 10% (w / w) tetramethylammonium hydroxide (TMAH) solution for 1 minute and fixing with water for 30 seconds. The difference between the film thickness and the original thickness in the 50 exposed areas was measured using a surface profilometer, yielding a sensitivity of 31.6 μC / cm for the incompletely condensed silsesquioxane C photoresist under these conditions. 2 The contrast ratio γ = 1.53.

[0166] Subsequently, at a voltage of 20kV and a temperature of 50μC / cm 2 At specific dosages, photoresist films were exposed using different exposure cycles. After exposure, they were baked at 100°C for 60 seconds, followed by development with acetone solution for 1 minute and fixing with isopropanol for 30 seconds. Figure 16 As shown, its resolution is 48nm.

[0167] Example 10

[0168] The modulation and imaging methods of an incompletely condensed silsesquioxane D photoresist composition are as follows:

[0169] In a clean 20ml glass bottle, 10mg of triphenylsulfonium-1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate and 1.99g of methyl isobutyl ketone were added, followed by sonication for 0.5h to ensure complete dissolution of the photoacid-generating agent. Then, in a 1ml glass bottle, 25mg of incompletely condensed silsesquioxane D, 250mg of the above photoacid-generating agent solution, and 225mg of methyl isobutyl ketone were added, and the photoresist solution was sonicated for 0.5h to ensure thorough mixing. The photoresist solution was then filtered through a 0.1-micron filter. The photoresist solution was spin-coated onto a silicon wafer at 3000 rpm to obtain a film 89nm thick. Photolithography tests were then performed.

[0170] Using a FEI NovaNano SEM field emission scanning electron microscope and an NPGS electron beam exposure system, at a voltage of 20 kV, and with a current of 1 μC / cm 2 Up to 100 μC / cm 2Fifty different dosages of incompletely condensed silsesquioxane C photoresist films were exposed. After exposure, the films were baked at 100°C for 60 seconds, followed by development with 10% (w / w) tetramethylammonium hydroxide (TMAH) solution for 1 minute and fixing with water for 30 seconds. The difference between the film thickness and the original thickness in the 50 exposed areas was measured using a surface profilometer, yielding a sensitivity of 4.3 μC / cm for the incompletely condensed silsesquioxane D photoresist under these conditions. 2 The contrast ratio γ = 5.10.

[0171] Subsequently, at a voltage of 20kV and a temperature of 12μC / cm 2 At different exposure cycles, the photoresist film was exposed to different dosages, then baked at 100°C for 60 seconds, followed by development with 25% (mass fraction) tetramethylammonium hydroxide (TMAH) solution for 4 minutes, and then fixed with water for 60 seconds. Figure 17 As shown, its resolution is 28nm.

[0172] Example 11

[0173] The modulation and imaging methods of an incompletely condensed silsesquioxane E photoresist composition RE are as follows:

[0174] In a clean 20ml glass bottle, 10mg of triphenylsulfonium trifluoromethanesulfonate and 1.99g of methyl isobutyl ketone were added, followed by sonication for 0.5h to ensure complete dissolution of the photoacid-generating agent. Then, in a 1ml glass bottle, 25mg of incompletely condensed silsesquioxane E, 250mg of the above photoacid-generating agent solution, and 225mg of methyl isobutyl ketone were added, and the photoresist solution was sonicated for 0.5h to ensure thorough mixing. The photoresist solution was then filtered through a 0.1-micron filter. The photoresist solution was spin-coated onto a silicon wafer at 3000 rpm to obtain a 95nm thick film. Photolithography testing was then performed.

[0175] A 254nm contact alignment deep ultraviolet lithography machine was used, with a wavelength of 254nm and a concentration of 1mJ / cm². 2 Up to 20 mJ / cm 2 Twenty-five different doses of incompletely condensed silsesquioxane E photoresist film were exposed. After exposure, the film was baked at 100°C for 60 seconds, followed by development with 10% (w / w) tetramethylammonium hydroxide (TMAH) solution for 1 minute and fixing with water for 30 seconds. The difference between the film thickness and the original thickness in the 25 exposed areas was measured using a surface profilometer, and the sensitivity of the incompletely condensed silsesquioxane E photoresist under these conditions was found to be 14.7 mJ / cm. 2 The contrast ratio γ = 3.07.

[0176] Subsequently, at 20 mJ / cm 2At the specified dosage, the photoresist film was exposed using different exposure cycles, while the post-baking, developing, and fixing conditions remained the same as described above. For example... Figure 18 As shown, its resolution is 1.5 μm.

[0177] Example 12

[0178] The following is a method for modulation and imaging RF of an incompletely condensed silsesquioxane F photoresist composition:

[0179] In a clean 20ml glass bottle, 10mg of triphenylsulfonium trifluoromethanesulfonate and 1.99g of methyl isobutyl ketone were added, followed by sonication for 0.5h to ensure complete dissolution of the photoacid-generating agent. Then, in a 1ml glass bottle, 25mg of incompletely condensed silsesquioxane F, 250mg of the above photoacid-generating agent solution, and 225mg of methyl isobutyl ketone were added, and the photoresist solution was sonicated for 0.5h to ensure thorough mixing. The photoresist solution was then filtered through a 0.1-micron filter. The photoresist solution was spin-coated onto a silicon wafer at 3000 rpm to obtain a 121nm thick film. Photolithography testing was then performed.

[0180] A 254nm contact alignment deep ultraviolet lithography machine was used, with a wavelength of 254nm and a concentration of 1mJ / cm². 2 Up to 20 mJ / cm 2 Twenty-five different doses of incompletely condensed silsesquioxane F photoresist film were exposed. After exposure, the film was baked at 100°C for 60 seconds, followed by development with methyl ethyl ketone (MEK) for 1 minute and fixing with isopropanol for 30 seconds. The difference between the film thickness and the original thickness in the 25 exposed areas was measured using a surface profilometer, yielding a sensitivity of 7.7 mJ / cm² for the incompletely condensed silsesquioxane F photoresist under these conditions. 2 The contrast ratio γ = 1.84.

[0181] Subsequently, at 13 mJ / cm 2 At the specified dosage, the photoresist film was exposed using different exposure cycles, while the post-baking, developing, and fixing conditions remained the same as described above. For example... Figure 19 As shown, its resolution is 1.2 μm.

[0182] Example 13

[0183] Stability verification of incompletely condensed silsesquioxane photoresist compositions:

[0184] The stability of the photoresist composition shown in Example 7 was verified by placing the prepared photoresist composition at room temperature and atmospheric environment and observing whether gel substances were generated in the photoresist composition. The photoresist composition was spin-coated into films for photolithography performance testing at 1 day, 7 days and 180 days.

[0185] Experimental results showed that no gel material was formed after 180 days of storage at room temperature and atmospheric conditions; the sensitivity data after 1 day, 7 days, and 180 days were 7.9, 7.8, and 8.2 μC / cm, respectively. 2 The contrast ratios were 4.09, 4.02, and 3.87, demonstrating good stability.

[0186] Example 14

[0187] To compare the performance advantages of incompletely condensed cage-like silsesquioxanes, a random polysilsesquioxane G was prepared. Its structure, synthesis route, modulation method, and imaging method are as follows:

[0188]

[0189] 5.2 ml (30 mmol, 1 molar equivalent) of triethoxysilane and 7.6 ml (36 mmol, 1.2 molar equivalent) of trimethoxy(4-vinylphenyl)silane were dissolved in 20 ml of ethylene glycol dimethyl ether to obtain a monomer mixed solution. 0.4 ml of hydrochloric acid aqueous solution (pH=1, 0.04 mmol, 1.3 × 10⁻⁶) was added to the 20 ml of ethylene glycol dimethyl ether. -3 (Molar equivalent), and then the above solution was added dropwise over 0.5 h to a continuously stirred monomer mixture at 0 °C. After the addition was completed, stirring was continued at 0 °C for 6 h. After the reaction was complete, the solution was concentrated, and the original solvent in the reaction system was replaced by adding MIBK solvent multiple times, and then it was prepared into a 10 wt% concentration solution. 68 g of a 10 wt% solution of random polysilsesquioxane G was obtained, with a molecular weight of 1.3 kDa and a molecular weight distribution of 1.93. The NMR silicon spectrum of random polysilsesquioxane G is shown below. Figure 20 As shown. The NMR silicon spectrum of the incompletely condensed polysilsesquioxane A in Example 1 is shown below. Figure 21 As shown.

[0190] Figure 20 and Figure 21 The comparison shows that Figure 21 In the middle, the peak shape of the cage-like molecules is sharp, while Figure 20 The silicon spectra of random polysilsesquioxanes exhibit broad peak distribution, indicating that cage-like polysilsesquioxanes have higher regularity and smaller molecular volume, which in turn leads to higher resolution. Cage-like polysilsesquioxanes also exhibit higher rigidity compared to random polysilsesquioxanes, preventing the collapse of photolithographic patterns.

[0191] In a clean 20ml glass bottle, 10mg of triphenylsulfonium trifluoromethanesulfonate and 1.99g of methyl isobutyl ketone were added, followed by sonication for 0.5h to ensure complete dissolution of the photoacid-generating agent. Then, in a 1ml glass bottle, 100mg of a 10wt% solution of random polysilsesquioxane G and 100mg of the aforementioned photoacid-generating agent solution were added, and the photoresist solution was sonicated for 0.5h to ensure thorough mixing. The photoresist solution was then filtered through a 0.1-micron filter. The photoresist solution was spin-coated onto a silicon wafer at 3000 rpm to obtain a 108nm thick film. Photolithography testing was then performed.

[0192] Using a FEI NovaNano SEM field emission scanning electron microscope and an NPGS electron beam exposure system, at a voltage of 20 kV, and with a current of 1 μC / cm 2 Up to 100 μC / cm 2 Fifty different dosages of atactic polysilsesquioxane E photoresist film were used for exposure. After exposure, the film was developed with 10% (w / v) tetramethylammonium hydroxide (TMAH) solution for 1 min and fixed with water for 30 s. The difference between the film thickness and the original thickness of the 50 exposed areas was measured using a surface profilometer, and the sensitivity of atactic polysilsesquioxane G photoresist under these conditions was found to be 18.9 μC / cm. 2 The contrast ratio γ = 2.13.

[0193] Subsequently, at a voltage of 20kV and a temperature of 37μC / cm 2 At a given dose, the photoresist film was exposed with different exposure cycles, and developed using a 25% (mass fraction) tetramethylammonium hydroxide (TMAH) solution. A resolution of 56 nm was obtained.

[0194] The incompletely condensed cage-like polysilsesquioxane A and random polysilsesquioxane G have similar elemental compositions. Experimental results show that the photoresist prepared by random polysilsesquioxane G is weaker than that of cage-like polysilsesquioxane A in terms of sensitivity, contrast, and resolution, demonstrating that the cage structure is beneficial to improving photolithography performance. Table 1 shows the performance comparison data of Example 1 and Example 14.

[0195] Table 1. Performance Comparison of Cage-type Silsesquioxane Photoresist and Random Silsesquioxane Photoresist

[0196]

[0197] Example 15

[0198] To characterize the effect of the content of organic groups on performance, following the method described in Example 1, the ratio of triethoxysilane and trimethoxy(4-vinylphenyl)silane monomers was varied to prepare incompletely condensed polysilsesquioxane H with a styrene group content of 9% and incompletely condensed polysilsesquioxane I with a styrene group content of 100%. The stability, sensitivity, and contrast of the incompletely condensed cage-like polysilsesquioxanes A, H, and I were characterized.

[0199]

[0200] In a 10 ml glass bottle, 0.5 g of incompletely condensed polysilsesquioxane A and 4.5 g of methyl isobutyl ketone were added. The solution was sonicated for 0.5 h to ensure thorough mixing. The solution was then filtered through a 0.1 μm filter. Solutions of incompletely condensed silsesquioxanes H and I were prepared using the same method. The three solutions were placed under identical environmental conditions, and the gelation time was observed. Table 2 shows the gelation time data for solutions A, H, and I.

[0201] Table 2 shows the gelation time of incompletely condensed polysilsesquioxane A, H, and I solutions under the same environmental conditions.

[0202]

[0203] In a clean 20ml glass bottle, 10mg of triphenylsulfonium trifluoromethanesulfonate and 1.99g of methyl isobutyl ketone were added, followed by sonication for 0.5h to ensure complete dissolution of the photoacid generator. Then, in a 1ml glass bottle, 25mg of incompletely condensed polysilsesquioxane H, 250mg of the above photoacid generator solution, and 225mg of methyl isobutyl ketone were added, and the photoresist solution was sonicated for 0.5h to ensure thorough mixing. The photoresist solution was then filtered through a 0.1-micron filter. The photoresist solution was spin-coated onto a silicon wafer at 3000 rpm to obtain a 97nm thick film. After completion, the film was exposed using a FEI Nova NanoSEM field emission scanning electron microscope and an NPGS electron beam exposure system at 20kV with a temperature of 1μC / cm². 2 Up to 100 μC / cm 2 Fifty different dosages of incompletely condensed polysilsesquioxane H photoresist films were exposed. After exposure, development was performed using a 10% (w / w) tetramethylammonium hydroxide (TMAH) solution. The difference between the film thickness and the original thickness in the 50 exposed areas was measured using a surface profilometer to obtain the sensitivity and contrast data of the incompletely condensed polysilsesquioxane H photoresist under these conditions. I photoresist films were prepared using the same method and photolithographic tests were performed. Table 3 shows the sensitivity and contrast data of A, H, and I photoresists.

[0204] Table 3 Sensitivity contrast of incompletely condensed polysilsesquioxane A, H, and I photoresists

[0205]

[0206] Experimental results show that increasing the organic group content of incompletely condensed polysilsesquioxane can effectively improve the stability of the material; sensitivity and contrast data show that the addition of organic groups significantly improves the sensitivity of the photoresist, while the contrast performance is slightly reduced.

[0207] Example 16

[0208] To characterize the effect of Si-OH group content on performance, following the method described in Example 4, only the stirring time was changed to 5 h and 3 h, respectively, to sequentially prepare incompletely condensed polysilsesquioxanes J and K with different Si-OH contents. The stability, sensitivity, and contrast data of the incompletely condensed cage-like polysilsesquioxanes D, J, and K were compared.

[0209]

[0210] In a 10 ml glass bottle, 0.5 g of incompletely condensed polysilsesquioxane D and 4.5 g of methyl isobutyl ketone were added. The solution was sonicated for 0.5 h to ensure thorough mixing. The solution was then filtered through a 0.1 μm filter. Solutions of incompletely condensed silsesquioxanes J and K were prepared using the same method. The three solutions were placed under identical environmental conditions, and the gelation time was observed. Table 4 shows the gelation time data for solutions D, J, and K.

[0211] Table 4. Gel time of incompletely condensed polysilsesquioxane D, J, and K solutions under environmental conditions.

[0212]

[0213] a: The Si-OH content is expressed as the ratio of the amount of Si-OH to the amount of Si element.

[0214] In a clean 20ml glass bottle, 10mg of triphenylsulfonium trifluoromethanesulfonate and 1.99g of methyl isobutyl ketone were added, followed by sonication for 0.5h to ensure complete dissolution of the photoacid generator. Then, in a 1ml glass bottle, 25mg of incompletely condensed polysilsesquioxane J, 250mg of the above photoacid generator solution, and 225mg of methyl isobutyl ketone were added, and the photoresist solution was sonicated for 0.5h to ensure thorough mixing. The photoresist solution was then filtered through a 0.1-micron filter. The photoresist solution was spin-coated onto a silicon wafer at 3000 rpm to obtain a 101nm thick film. After completion, an FEI NovaNano SEM field emission scanning electron microscope and an NPGS electron beam exposure system were used at 20kV with a temperature of 1μC / cm². 2 Up to 100 μC / cm 2 Fifty different dosages of incompletely condensed polysilsesquioxane J photoresist films were exposed. After exposure, development was performed using a 10% (w / w) tetramethylammonium hydroxide (TMAH) solution. The difference between the film thickness and the original thickness in the 50 exposed areas was measured using a surface profilometer to obtain the sensitivity and contrast data of the incompletely condensed polysilsesquioxane J photoresist under these conditions. K photoresist films were prepared using the same method and photolithographic tests were performed. Table 5 shows the sensitivity and contrast data of D, J, and K photoresists.

[0215] Table 5. Sensitivity and contrast ratios of incompletely condensed polysilsesquioxane D, J, and K photoresists.

[0216]

[0217] a: The Si-OH content is expressed as the ratio of the amount of Si-OH to the amount of Si element.

[0218] Experimental results show that increasing the Si-OH group content of incompletely condensed polysilsesquioxane leads to a significant decrease in material stability. Sensitivity and contrast data indicate that the addition of Si-OH groups significantly improves the sensitivity of the photoresist, while decreasing its contrast performance. A suitable Si-OH group content is needed to achieve both good stability and good sensitivity. Excessive Si-OH group content will reduce stability, while excessively low content will decrease sensitivity.

[0219] Example 17

[0220] The synthetic routes, key reaction parameters, and key properties of a series of incompletely condensed polysilsesquioxanes are shown in Tables 6-9, where the same serial number represents the same incompletely condensed polysilsesquioxane. The incompletely condensed polysilsesquioxanes shown in Table 6 do not contain the group shown in Formula B, and their preparation method is consistent with Examples 1-4, only changing the monomer type, monomer feed ratio, amount of concentrated hydrochloric acid, and dropping / stirring time. The performance parameters of the photoresist prepared using the incompletely condensed polysilsesquioxanes prepared in Table 6 (process reference Example 7) are shown in Table 7. The incompletely condensed polysilsesquioxanes shown in Table 8 contain the group shown in Formula B, and their preparation method is consistent with Examples 5-6, only changing the monomer type, monomer feed ratio, amount of concentrated hydrochloric acid, and dropping / stirring time. The performance parameters of the photoresist prepared using the incompletely condensed polysilsesquioxanes prepared in Table 8 are shown in Table 9. The photoresist and photolithography performance characterization methods in Tables 7 and 9 are the same as in Example 7, except that the type of incompletely condensed polysilsesquioxane is changed.

[0221]

[0222] Table 6. Key reaction parameters for a series of incompletely condensed polysilsesquioxanes (excluding the group shown in formula B).

[0223]

[0224]

[0225] a: This molar amount indicates that the substituent is R. a The molar amount of the monomer.

[0226] b: This molar amount indicates that the substituent is R. b The molar amount of the monomer.

[0227] c: This molar amount indicates that the substituent is R. c The molar amount of the monomer.

[0228] Table 7 Key performance parameters of a series of incompletely condensed polysilsesquioxanes (excluding the group shown in formula B)

[0229]

[0230]

[0231] A: Some photoresists are too sensitive, and even when exposed using the minimum exposure dose of the lithography machine, the photoresist film is still retained, so contrast data cannot be obtained.

[0232]

[0233] Table 8 Key reaction parameters for a series of incompletely condensed polysilsesquioxanes (containing the group shown in formula B) a

[0234]

[0235] a: The amount of Karstedt catalyst used in the hydrosilylation reaction is 20 ppm, and the amount of solvent (toluene) used in the hydrosilylation reaction is 1.3 ml / g based on the total mass of the reactants.

[0236] b: TES is an abbreviation for triethoxysilane.

[0237] c: This molar amount indicates that the substituent is R. d The molar amount of the trialkoxysilane monomer.

[0238] d: This molar amount indicates that the substituent is R. e The molar amount of the vinyl epoxy monomer.

[0239] Table 9. Key performance parameters of a series of incompletely condensed polysilsesquioxanes (containing the groups shown in Formula B)

[0240]

[0241]

[0242] A: Due to the excessively high sensitivity, even when using the minimum exposure dose of the lithography machine for exposure, some film remains, making it impossible to obtain contrast data.

[0243] The specific embodiments described above illustrate the technical solution and beneficial effects of the present invention in detail. It should be understood that the above description is only the most preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, additions, and equivalent substitutions made within the scope of the principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A photoresist based on silsesquioxane chemical amplification, characterized in that... The photoresist comprises an incompletely condensed polysilsesquioxane, a photoacid generator, and an organic solvent, wherein the incompletely condensed polysilsesquioxane is a cage-type polysilsesquioxane; and the incompletely condensed polysilsesquioxane is one or more of the compounds shown in formula (1). ； (1) In formula (1), R1 and R2 are each independently H, the group shown in formula A, the group shown in formula B, or the following groups that are not substituted or are substituted by one or more substituents A: C1-C 20 Alkyl, C3-C 30 cycloalkyl, C4-C 30 Silyl, C6-C 30 Aromatic group, C3-C 30 Heterocyclic groups or C5-C 30 The heteroaryl group, or a group containing one or more of the above-mentioned groups selected from O, S, N, Si, and P atoms in the carbon chain, wherein the substituent A includes a halogen atom, hydroxyl group, mercapto group, trifluoromethyl group, C1-C14 group, etc. 20 Branched or straight-chain alkyl groups, C1-C 20 Branched or straight-chain alkoxy groups, C3-C 20 Branched or straight-chain cycloalkyl groups, C6-C 30 Aromatic group, C5-C 30 One or more of the heteroaryl groups; the C3-C 30 Cycloalkyl groups include monocyclic or polycyclic cycloalkyl groups; In formula (1), R3 is the group shown in formula B; ； AB Indicates a connection key; In formula A or formula B, K1 is absent, or is an unsubstituted or substituted group B of the following groups: C1-C 20 Alkylene, C3-C 30 Cycloalkylene, C6-C 30 The substituent B is a C1-C1 substituent, or any of the above-mentioned groups containing oxygen or silicon atoms in the carbon chain. 10 Alkyl or C1-C 10 The alkoxy group, the C3-C 30 Cycloalkyl groups include monocyclic or polycyclic cycloalkyl groups; K2 is absent, or is an ester group, carbonate group, or amide group; R4 is C1-C 20 olefin group, C5-C 30 Cycloolefin or C1-C 20 The alkynyl group, wherein the cycloolefinic group comprises a monocyclic or polycyclic cycloolefinic group; R5 is C2-C 20 Epoxy groups; the epoxy groups include monocyclic or polycyclic epoxy groups; In the formula (1), l represents the number of R1s in the incompletely condensed polysilsesquioxane, and l is an integer from 0 to 20; m represents the number of R2 molecules in the incompletely condensed polysilsesquioxane, where m is an integer from 0 to 20. n represents the total number of R1, R2, and R3 in the incompletely condensed polysilsesquioxane, and n is an integer from 7 to 20; x represents the number of water molecules generated during the preparation of incompletely condensed polysilsesquioxane, and x is an integer from 9 to 29; nlm is an integer greater than or equal to 1; 3n-2x represents the number of silicon-hydroxyl (Si-OH) groups in the incompletely condensed polysilsesquioxane, where 3n-2x is an integer greater than or equal to 1.

2. The photoresist based on silsesquioxane chemical amplification as described in claim 1, characterized in that... In formula (1), R1 is H, the group shown in formula A, the group shown in formula B, or the following groups that are not substituted or are substituted by one or more substituents A: C1-C8 alkyl, C3-C 12 cycloalkyl, C6-C 12 Aromatic group, or any of the above-mentioned groups containing O, S, N, or Si atoms in the carbon chain, wherein the C3-C 12 The cycloalkyl group includes a monocyclic or polycyclic cycloalkyl group, wherein the substituent A is a halogen atom, a C1-C5 alkyl group, a trifluoromethyl group, a hydroxyl group, or a mercapto group; R2 is H, a group represented by formula A, a group represented by formula B, or one of the following groups that is unsubstituted or substituted by one or more substituents A: C1-C8 alkyl, C3-C 12 cycloalkyl, C6-C 12 Aromatic group, or any of the above-mentioned groups containing O, S, N, or Si atoms in the carbon chain, wherein the C3-C 12 The cycloalkyl group includes a monocyclic or polycyclic cycloalkyl group, wherein the substituent A is a halogen atom, a C1-C5 alkyl group, a trifluoromethyl group, a hydroxyl group, or a mercapto group; K1 is absent, or is a C1-C8 alkylene group, or a C3-C4 alkylene group. 12 Cycloalkylene, phenylene, or any group containing oxygen or silicon atoms in the carbon chain; K2 is absent or is an ester group; R4 is C1-C 10 olefin group, C5-C 12 Cycloolefin or C1-C 10 Alkyne group; R5 is a C2-C9 epoxy group; l is an integer between 0 and 14; m is an integer between 0 and 14; n is an integer between 7 and 14; x is an integer between 9 and 20; 3n-2x is an integer from 2 to 6.

3. The photoresist based on silsesquioxane chemical amplification as described in claim 1, characterized in that... In the incompletely condensed polysilsesquioxane, the ratio of the amount of Si-OH to the amount of Si element is 5~45%.

4. The photoresist based on silsesquioxane chemical amplification as described in claim 1, characterized in that... In the incompletely condensed polysilsesquioxane, the content of organic groups in the incompletely condensed polysilsesquioxane is 30% to 100%; the content of organic groups refers to the ratio of the number of silicon-organic groups to the total number of silicon-organic groups and silicon-hydrogen bonds.

5. The photoresist based on silsesquioxane chemical amplification as described in claim 1, characterized in that... The chemical formula of the incompletely condensed polysilsesquioxane is one or more of the following cage-like structural formulas: wherein the R6 group is selected from any one of the R1, R2, and R3 groups, and for any cage-like structure, at least one of the R6 groups is R3, and R6 cannot be all R1 or R2. ； ； ； ； 。 6. The photoresist based on silsesquioxane chemical amplification as described in claim 5, characterized in that... R1 and R2 are each independently one of the following groups: H, C1-C8 alkyl, C6-C 10 Aromatic group, , , , , , , , , , , , , , , , , , , , ; R3 is selected from one of the following groups: , , , , , , .

7. The silsesquioxane-based chemically amplified photoresist as described in any one of claims 1 to 6, characterized in that... The incompletely condensed polysilsesquioxane is prepared by the following method: When any one of R1, R2, and R3 is a group shown in Formula B, taking R3 as an example, the method is as follows: the silane raw materials shown in Formula (2), Formula (3), and Formula (5) are mixed in a molar ratio of 1:m:(nlm) and slowly added dropwise to concentrated acid. Under the action of concentrated acid, a hydrolysis condensation reaction is carried out. After the reaction is completed, the mixture is washed with water until neutral. Then, it is concentrated and crystallized. After centrifugation to remove the crystallized material, the solvent is evaporated to obtain an intermediate product. Then, under the catalysis of Karstedt catalyst, the intermediate product is subjected to a hydrosilylation reaction with the vinyl compound shown in Formula (6) to prepare the incompletely condensed polysilsesquioxane shown in Formula (1). The concentrated acid mentioned is concentrated sulfuric acid, fuming sulfuric acid, concentrated hydrochloric acid, or concentrated nitric acid; （5） （6） In equation (5), R 10 Selected from one of the following groups: , , , ; The ratio of the amount of the concentrated acid to the total amount of the silane raw materials shown in formulas (2), (3), and (5) is 1 to 20:

1.

8. The silsesquioxane-based chemically amplified photoresist as described in any one of claims 1 to 6, characterized in that... The photoresist contains, by mass percentage, 1-20% incompletely condensed polysilsesquioxane, 0.01-4% photoacid generator, and the remainder is organic solvent.

9. The photoresist based on silsesquioxane chemical amplification as described in claim 8, characterized in that... The photo-induced acid-producing agent is a thionium salt or an iodonium salt, composed of cations and anions, wherein the anion is selected from one of the following structures: , The cation is selected from one of the following structures: ； 。 10. The application of the silsesquioxane-based chemically amplified photoresist as described in any one of claims 1 to 6 in electron beam lithography, deep ultraviolet lithography, or extreme ultraviolet lithography.

11. The application of incompletely condensed polysilsesquioxanes in the preparation of chemically amplified photoresists, characterized in that... The incompletely condensed polysilsesquioxane is a cage-type polysilsesquioxane; the incompletely condensed polysilsesquioxane is one or more of the compounds shown in formula (1); ； (1) In formula (1), R1 and R2 are each independently H, the group shown in formula A, the group shown in formula B, or the following groups that are not substituted or are substituted by one or more substituents A: C1-C 20 Alkyl, C3-C 30 cycloalkyl, C4-C 30 Silyl, C6-C 30 Aromatic group, C3-C 30 Heterocyclic groups or C5-C 30 The heteroaryl group, or a group containing one or more of the above-mentioned groups (O, S, N, Si, P atoms) in the carbon chain, wherein the substituent A includes a halogen atom, hydroxyl group, mercapto group, trifluoromethyl group, C1-C14 group, etc. 20 Branched or straight-chain alkyl groups, C1-C 20 Branched or straight-chain alkoxy groups, C3-C 20 Branched or straight-chain cycloalkyl groups, C6-C 30 Aromatic group, C5-C 30 One or more of the heteroaryl groups; the C3-C 30 Cycloalkyl groups include monocyclic or polycyclic cycloalkyl groups; In formula (1), R3 is the group shown in formula A or the group shown in formula B; ； AB Indicates a connection key; In formula A or formula B, K1 is absent, or is an unsubstituted or substituted group B of the following groups: C1-C 20 Alkylene, C3-C 30 Cycloalkylene, C6-C 30 The substituent B is a C1-C1 substituent, or any of the above-mentioned groups containing oxygen or silicon atoms in the carbon chain. 10 Alkyl or C1-C 10 The alkoxy group, the C3-C 30 Cycloalkyl groups include monocyclic or polycyclic cycloalkyl groups; K2 is absent, or is an ester group, carbonate group, or amide group; R4 is C1-C 20 olefin group, C5-C 30 Cycloolefin group, C1-C 20 The alkynyl group, wherein the cycloolefinic group comprises a monocyclic or polycyclic cycloolefinic group; R5 is C2-C 20 The epoxy group, or any of the above-mentioned groups containing oxygen or sulfur atoms in the carbon chain; the epoxy group includes monocyclic or polycyclic epoxy groups; In the formula (1), l represents the number of R1s in the incompletely condensed polysilsesquioxane, and l is an integer from 0 to 20; m represents the number of R2 molecules in the incompletely condensed polysilsesquioxane, where m is an integer from 0 to 20. n represents the total number of R1, R2, and R3 in the incompletely condensed polysilsesquioxane, and n is an integer from 7 to 20; x represents the number of water molecules generated during the preparation of incompletely condensed polysilsesquioxane, and x is an integer from 9 to 29; nlm is an integer greater than or equal to 1; 3n-2x represents the number of silicon-hydroxyl (Si-OH) groups in the incompletely condensed polysilsesquioxane, where 3n-2x is an integer greater than or equal to 1.

12. A photoresist based on silsesquioxane chemical amplification, characterized in that... The photoresist comprises an incompletely condensed polysilsesquioxane, a photoacid generator, and an organic solvent, wherein the incompletely condensed polysilsesquioxane is a cage-type polysilsesquioxane; and the incompletely condensed polysilsesquioxane is one or more of the compounds shown in formula (1). ； (1) In formula (1), R1 and R2 are each independently H, the group shown in formula A, or the following groups that are not substituted or are substituted by one or more substituents A: C1-C 20 Alkyl, C3-C 30 cycloalkyl, C4-C 30 Silyl, C6-C 30 Aromatic group, C3-C 30 Heterocyclic groups or C5-C 30 The heteroaryl group, or a group containing one or more of the above-mentioned groups selected from O, S, N, Si, and P atoms in the carbon chain, wherein the substituent A includes a halogen atom, hydroxyl group, mercapto group, trifluoromethyl group, C1-C14 group, etc. 20 Branched or straight-chain alkyl groups, C1-C 20 Branched or straight-chain alkoxy groups, C3-C 20 Branched or straight-chain cycloalkyl groups, C6-C 30 Aromatic group, C5-C 30 One or more of the heteroaryl groups; the C3-C 30 Cycloalkyl groups include monocyclic or polycyclic cycloalkyl groups; In formula (1), R3 is the group shown in formula A; ； A Indicates a connection key; In formula A, K1 is absent, or is an unsubstituted or substituted group B, and belongs to the following groups: C1-C 20 Alkylene, C3-C 30 Cycloalkylene, C6-C 30 The substituent B is a C1-C1 substituent, or any of the above-mentioned groups containing oxygen or silicon atoms in the carbon chain. 10 Alkyl or C1-C 10 The alkoxy group, the C3-C 30 Cycloalkyl groups include monocyclic or polycyclic cycloalkyl groups; K2 is absent, or is an ester group, carbonate group, or amide group; R4 is C1-C 20 olefin group, C5-C 30 Cycloolefin or C1-C 20 The alkynyl group, wherein the cycloolefinic group comprises a monocyclic or polycyclic cycloolefinic group; In the formula (1), l represents the number of R1s in the incompletely condensed polysilsesquioxane, and l is an integer from 0 to 20; m represents the number of R2 molecules in the incompletely condensed polysilsesquioxane, where m is an integer from 0 to 20. n represents the total number of R1, R2, and R3 in the incompletely condensed polysilsesquioxane, and n is an integer from 7 to 20; x represents the number of water molecules generated during the preparation of incompletely condensed polysilsesquioxane, and x is an integer from 9 to 29; nlm is an integer greater than or equal to 1; 3n-2x represents the number of silicon-hydroxyl groups (Si-OH) in the incompletely condensed polysilsesquioxane, where 3n-2x is an integer greater than or equal to 1; The incompletely condensed polysilsesquioxane is a cage-type polysilsesquioxane, prepared by the following method: The silane raw materials shown in formulas (2) to (4) are mixed in a molar ratio of l:m:(nlm) and slowly added dropwise to concentrated acid. Under the action of concentrated acid, a hydrolysis-condensation reaction is carried out to obtain the incompletely condensed polysilsesquioxane shown in formula (1). The concentrated acid mentioned is concentrated sulfuric acid, fuming sulfuric acid, concentrated hydrochloric acid, or concentrated nitric acid; ； （2） （3） （4） In equations (2) to (4), R 10 Selected from one of the following groups: , , , ; The ratio of the amount of the concentrated acid to the total amount of the silane raw materials shown in formulas (2) to (4) is 1 to 20:

1.

13. The photoresist based on silsesquioxane chemical amplification as described in claim 12, characterized in that... In formula (1), R1 is H, the group shown in formula A, or the following groups that are not substituted or are substituted by one or more substituents A: C1-C8 alkyl, C3-C 12 cycloalkyl, C6-C 12 Aromatic group, or any of the above-mentioned groups containing O, S, N, or Si atoms in the carbon chain, wherein the C3-C 12 The cycloalkyl group includes a monocyclic or polycyclic cycloalkyl group, wherein the substituent A is a halogen atom, a C1-C5 alkyl group, a trifluoromethyl group, a hydroxyl group, or a mercapto group; R2 is H, a group represented by formula A, or one of the following groups that is unsubstituted or substituted by one or more substituents A: C1-C8 alkyl, C3-C 12 cycloalkyl, C6-C 12 Aromatic group, or any of the above-mentioned groups containing O, S, N, or Si atoms in the carbon chain, wherein the C3-C 12 The cycloalkyl group includes a monocyclic or polycyclic cycloalkyl group, wherein the substituent A is a halogen atom, a C1-C5 alkyl group, a trifluoromethyl group, a hydroxyl group, or a mercapto group; K1 is absent, or is a C1-C8 alkylene group, or a C3-C4 alkylene group. 12 Cycloalkylene, phenylene, or any group containing oxygen or silicon atoms in the carbon chain; K2 is absent or is an ester group; R4 is C1-C 10 olefin group, C5-C 12 Cycloolefin or C1-C 10 Alkyne group; l is an integer between 0 and 14; m is an integer between 0 and 14; n is an integer between 7 and 14; x is an integer between 9 and 20; 3n-2x is an integer from 2 to 6.

14. The photoresist based on silsesquioxane chemical amplification as described in claim 12, characterized in that... R1 and R2 are each independently one of the following groups: H, C1-C8 alkyl, C6-C 10 Aromatic group, , , , , , , , , , , , , 、; R3 is selected from one of the following groups: , , , , , , , , .

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