Positive photoresist composition and application thereof

Abstract

The invention provides a positive photoresist composition and application thereof. The positive photoresist composition comprises a combination of photosensitive resin, a photosensitizer, a sensitizer and silane coupling agent modified nano silicon dioxide, the silane coupling agent has a structure as shown in a formula I. Through the specific design of the silane coupling agent modified nano silicon dioxide and the mutual compounding of the silane coupling agent modified nano silicon dioxide with other components, the heat resistance of the positive photoresist composition is remarkably improved, so that a formed photoresist cured film has relatively high film residue rate and excellent adhesive force, the peeling phenomenon is avoided, the reliability is good, and the application prospect is wide. Therefore, the product yield of the electronic device is effectively improved.

Description

Technical Field

[0001] The invention belongs to the technical field of photoresist materials, and in particular relates to a positive photoresist composition and application thereof. Background Art

[0002] Photoresist is one of the key electronic chemicals used in large-scale integrated circuit processing. Based on the solubility of the photosensitive part during exposure and development, photoresist can be divided into positive and negative. The exposed part of the positive photoresist is dissolved by the developer to form a pattern; conversely, the unexposed part of the negative photoresist is dissolved by the developer, while the exposed part remains undissolved to form a pattern. The main components of photoresist include resin and photosensitive material, among which the photosensitive material (PAC) will undergo a chemical reaction after being irradiated with light, affecting the solubility of the adhesive layer in the developer; however, the use of PAC makes positive photoresist have problems such as low transmittance and extremely poor heat resistance, resulting in outgassing and volume shrinkage of the formed film layer during subsequent processing, poor adhesion, and easy peeling, affecting product yield. Therefore, improving the heat resistance and adhesion of positive photoresist to improve product reliability and yield is a problem that needs to be solved in this field. Summary of the Invention

[0003] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a positive photoresist composition and its application. By designing a silane coupling agent-modified nano-silica with a specific structure and compounding it with other components, the positive photoresist composition has significantly improved heat resistance, residual film rate and adhesion, avoids peeling, and has high reliability, thereby effectively improving the yield of electronic devices.

[0004] To achieve this object, the present invention adopts the following technical solutions:

[0005] In a first aspect, the present invention provides a positive photoresist composition, comprising a photosensitive resin, a photosensitizer, a sensitizer, and a combination of silane coupling agent-modified nano-silica; the silane coupling agent has a structure as shown in Formula I:

[0006]

[0007] In Formula I, Y1 and Y2 are each independently selected from O or S.

[0008] In Formula I, A is selected from any one of C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10) linear or branched alkylene groups.

[0009] In Formula I, R1, R2, and R3 are each independently selected from any one of hydrogen, C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10) straight chain or branched chain alkyl, and C6-C12 (e.g., C6, C8, C9, C10, C12, etc.) aryl.

[0010] In formula I, R4 is selected from any one of C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10) linear or branched alkyl, C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10) alkoxy.

[0011] In Formula I, R5 and R6 are each independently selected from any one of C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10) linear or branched alkyl groups.

[0012] Among the present invention, adopt the silane coupling agent with structure shown in formula I to carry out modification treatment to nano silicon dioxide, form the bonding layer of organic material-silane coupling agent-inorganic material, make the hydrophobicity and the degree of organization of described silane coupling agent modified nano silicon dioxide improve, its compatibility in positive photoresist composition is significantly improved, and can bring into play the effect of excellent improvement high temperature aging resistance.Through the design of specific silane coupling agent modified nano silicon dioxide and the mutual composite with other components, thereby introduce siloxane group and chemical bonds such as *-OS-*, *-SO-*, *-OO-*, *-SS-*, can produce free radical, be conducive to the free radical polymerization of resin in the exposure process, be conducive to hard film, make described positive photoresist composition have the heat resistance / high temperature resistance that significantly promotes, the residual film rate and the adhesive force of the photoresist cured film formed significantly promote, avoid peeling (peeling) phenomenon, excellent reliability, effectively improve the product yield of electronic device.

[0013] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0014] In the present invention, the expression of chemical elements, unless otherwise specified, includes the concept of isotopes with the same chemical properties. For example, hydrogen (H) includes 1 H (hydrogen), 2 H (deuterium, D), 3 H (tritium, T), etc.; carbon (C) includes 12 C. 13 C, etc.

[0015] In the present invention, the expression "Ca-Cb" means that the number of carbon atoms in the group is ab; unless otherwise specified, the number of carbon atoms in the group generally does not include the number of carbon atoms in the substituent.

[0016] In the present invention, “each independently” means that when there are multiple subjects, they may be the same or different.

[0017] In the present invention, the C1-C10 straight chain or branched chain alkyl group can be a C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 straight chain or branched chain alkyl group, illustratively including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, neohexyl, 2-ethylhexyl, n-octyl, n-heptyl, n-nonyl, n-decyl, etc.

[0018] The C1-C10 straight chain or branched chain alkylene group may be a straight chain or branched chain alkylene group of C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10, and a specific example thereof may be a divalent group formed by losing one H from the aforementioned straight chain or branched chain alkyl group.

[0019] The C1-C10 alkoxy group can be a straight chain or branched chain alkoxy group of C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10, and a specific example thereof can be a monovalent group formed by connecting the aforementioned straight chain or branched chain alkyl group to an O atom.

[0020] The C6-C12 aryl group may be an aryl group of C6, C9, C10, C12, etc., including a monocyclic aryl group and a condensed ring aryl group, illustratively including but not limited to: phenyl, naphthyl, biphenyl, etc.

[0021] Preferably, the A is selected from any one of C1-C6 straight chain alkylene groups.

[0022] Preferably, R1, R2, and R3 are each independently selected from any one of hydrogen and C1-C6 linear or branched alkyl, more preferably any one of hydrogen and C1-C3 linear or branched alkyl.

[0023] Preferably, R4 is selected from any one of C1-C6 alkoxy groups, more preferably any one of C1-C3 alkoxy groups.

[0024] Preferably, R5 and R6 are each independently selected from any one of C1-C6 linear or branched alkyl groups, more preferably any one of C1-C3 linear or branched alkyl groups.

[0025] Preferably, the silane coupling agent is selected from any one or a combination of at least two of the following compounds:

[0026]

[0027] Preferably, the silane coupling agent modified nano-silica is prepared by the following method, which comprises:

[0028] Mixing nano-silica with a solvent and treating the mixture under acidic conditions to obtain a first dispersion;

[0029] The first dispersion liquid and the silane coupling agent are mixed and reacted to obtain the silane coupling agent modified nano-silica.

[0030] Preferably, the particle size of the nano-silica is 1-100 nm, for example, it can be 1 nm, 5 nm, 10 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm, 60 nm, 80 nm, 90 nm or 100 nm.

[0031] Preferably, the solvent comprises a combination of water and an alcohol solvent.

[0032] Preferably, the alcohol solvent includes any one of methanol, ethanol, n-propanol, and isopropanol, or a combination of at least two thereof, with ethanol being more preferred.

[0033] Preferably, the mass ratio of water to alcohol solvent in the solvent is 1:(0.5-10), for example, it can be 1:0.8, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:6, 1:7, 1:8, 1:9, etc., and more preferably 1:(0.5-5).

[0034] Preferably, the mass ratio of the nano-silica to the solvent is 1:(1-100), for example, it can be 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, 1:85, 1:90 or 1:95, and more preferably 1:(10-80).

[0035] Preferably, the pH value of the acidic condition is 3.5-4.5, for example, it can be 3.6, 3.7, 3.8, 3.9, 4.1, 4.2, 4.3 or 4.4.

[0036] As a preferred technical solution of the present invention, nano-silica is mixed with a solvent and then treated under acidic conditions with a pH value of 3.5-4.5, which is conducive to the oxygen of the silica combining with more hydrogen to form attached hydroxyl groups.

[0037] Preferably, glacial acetic acid is used to adjust the mixture of nano-silica and solvent to be acidic.

[0038] Preferably, the treatment method is stirring treatment.

[0039] Preferably, the treatment temperature is 15-40°C, for example, 18°C, 20°C, 22°C, 25°C, 28°C, 30°C, 32°C, 35°C or 38°C, and more preferably normal temperature / room temperature.

[0040] Preferably, the treatment time is 10-120 min, for example, it can be 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min or 110 min.

[0041] Preferably, the mass ratio of the nano-silica to the silane coupling agent is 1:(1-22), for example, it can be 1:1.2, 1:1.5, 1:1.8, 1:1.9, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20 or 1:21, etc.

[0042] As a preferred technical solution of the present invention, the reaction is carried out under alkaline conditions to improve the hydrolysis activity of hydroxyl and alkoxy groups.

[0043] Preferably, the pH value of the reaction is 9.5-10.5, for example, it can be 9.6, 9.7, 9.8, 9.9, 10, 10.1, 10.2, 10.3 or 10.4.

[0044] Preferably, the reaction method comprises: adjusting the pH value of the first dispersion to 9.5-10.5, adding a silane coupling agent thereto for reaction to obtain the silane coupling agent-modified nano-silica.

[0045] Preferably, the pH value of the first dispersion is adjusted to 9.5-10.5 using ammonia water.

[0046] Preferably, the reaction is carried out in a protective atmosphere.

[0047] Preferably, the protective atmosphere includes nitrogen atmosphere and / or argon atmosphere.

[0048] Preferably, the reaction temperature is 60-95°C, for example, 62°C, 65°C, 68°C, 70°C, 72°C, 75°C, 78°C, 80°C, 82°C, 85°C, 88°C, 90°C, 92°C or 94°C, etc.

[0049] Preferably, the reaction time is 4-16 h, for example, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h or 15 h.

[0050] Preferably, the reaction further comprises a post-treatment step after completion.

[0051] Preferably, the post-treatment comprises washing and drying.

[0052] As a preferred technical solution, the silane coupling agent modified nano-silica is prepared by the following method, which includes the following steps:

[0053] (1) mixing nano-silica with a solvent, adjusting the pH value to 3.5-4.5 with glacial acetic acid, and stirring at room temperature for 10-120 minutes to obtain a first dispersion; the solvent comprises water and ethanol in a mass ratio of 1: (0.5-10);

[0054] (2) adjusting the pH value of the first dispersion to 9.5-10.5 with ammonia water, stirring for 10-120 minutes, evacuating, filling with a protective atmosphere, and then adding a silane coupling agent, reacting at 60-95° C. for 4-16 hours, and post-treating to obtain the silane coupling agent-modified nano-silica; the mass ratio of the silane coupling agent to the nano-silica in step (1) is (1-22):1.

[0055] As a preferred technical solution of the present invention, the degree of organization of the silane coupling agent-modified nano-silica is relatively high. The contact angle test shows that the hydrophobicity of the nano-silica is increased from 4.58° to 42.37° (silane coupling agent-modified nano-silica), and the compatibility with the components in the positive photoresist composition is better.

[0056] In the present invention, the photosensitive resin includes any one or a combination of at least two of polyimide, polyimide precursor resin, polyamic acid-polyimide copolymer, polyamic acid ester-polyimide copolymer, polyisoimide-polyamic acid copolymer, and polyisoimide.

[0057] Preferably, the polyimide precursor resin includes polyamic acid ester and / or polyamic acid.

[0058] Preferably, the polyimide precursor resin (polyamic acid and / or polyamic acid ester) can be prepared by methods well known in the art, illustratively including any one of the following routes: route (1) directly polymerizing a diamine with a dianhydride to obtain polyamic acid, which is then subjected to an esterification reaction to obtain polyamic acid ester; route (2) reacting a dianhydride with an alcohol to obtain a dicarboxylic acid diester, which is then reacted with thionyl chloride to obtain a diacyl chloride diester, which is then polymerized with a diamine compound to obtain polyamic acid ester; route (3) reacting a dianhydride with an alcohol to obtain a dicarboxylic acid diester, which is then reacted with a diamine compound in the presence of a dehydrating agent such as cyclohexylcarbodiimide to obtain polyamic acid ester.

[0059] For example, the diamine includes but is not limited to any one or a combination of at least two of the following compounds:

[0060]

[0061] Exemplarily, the dianhydride includes but is not limited to: any one of the dianhydride diphenyl ether dianhydride, 4,4'-(hexafluoroisopropylene) diphthalic anhydride, bisphenol A diether dianhydride, diphenylmethanol dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, hydrogenated pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and cyclobutane tetracarboxylic dianhydride, or a combination of at least two thereof.

[0062] Preferably, based on 100 parts by mass of the photosensitive resin, the mass of the silane coupling agent-modified nano-silica is 0.1-5 parts, for example, it can be 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts, etc., more preferably 0.2-2 parts.

[0063] Preferably, the photosensitizer is a compound containing a diazonaphthoquinone group.

[0064] Preferably, the structure of the diazonaphthoquinone group is Represents the attachment site of the group.

[0065] Preferably, the photosensitizer includes but is not limited to any one or a combination of at least two of the following compounds:

[0066] D1 represents a diazonaphthoquinone group, further preferably

[0067] Preferably, based on 100 parts by mass of the photosensitive resin, the mass of the photosensitizer is 0.1-40 parts, for example, it can be 0.2 parts, 0.5 parts, 0.8 parts, 1 parts, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts or 38 parts, etc.

[0068] Preferably, the sensitizer is a polyphenol compound.

[0069] In the present invention, the polyphenol compound is a compound containing at least two (eg, two, three, four, five, six) phenolic hydroxyl groups in its molecular structure.

[0070] Preferably, the sensitizer includes but is not limited to any one or a combination of at least two of the following compounds:

[0071]

[0072] Preferably, based on 100 parts by mass of the photosensitive resin, the mass of the sensitizer is 0.1-40 parts, for example, it can be 0.2 parts, 0.5 parts, 0.8 parts, 1 parts, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts or 38 parts, etc.

[0073] Preferably, the positive photoresist composition further comprises a leveling agent.

[0074] Preferably, the leveling agent includes any one or a combination of at least two of a fluorine-containing surfactant, a polyethylene glycol-containing surfactant, and a silicone-containing surfactant; the leveling agent can improve the uniformity of the film and improve the unevenness of the film caused by surface tension.

[0075] Preferably, based on 100 parts by mass of the photosensitive resin, the mass of the leveling agent is 0.01-5 parts, for example, it can be 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts.

[0076] Preferably, the positive photoresist composition further comprises a solvent.

[0077] Preferably, the solvent includes any one or a combination of at least two of γ-butyrolactone, butyl lactate, propylene glycol methyl ether, propylene glycol methyl ether acetate, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and benzyl alcohol.

[0078] Preferably, based on 100 parts by mass of the photosensitive resin, the mass of the solvent is 100-1500 parts, for example, it can be 200 parts, 300 parts, 400 parts, 500 parts, 600 parts, 700 parts, 800 parts, 900 parts, 1000 parts, 1100 parts, 1200 parts, 1300 parts or 1400 parts, etc.

[0079] In a preferred technical solution, the positive photoresist composition comprises the following components in parts by mass:

[0080]

[0081] It should be noted that the positive photoresist composition provided by the present invention may further include any other additives that are added in the art, including but not limited to: any one or a combination of at least two of a curing accelerator, a dispersant, and a colorant.

[0082] In a second aspect, the present invention provides a photoresist cured film, which is prepared by the positive photoresist composition as described in the first aspect.

[0083] In a third aspect, the present invention provides a use of the positive photoresist composition as described in the first aspect and the photoresist cured film as described in the second aspect in a semiconductor device or a flat panel display device.

[0084] Compared with the prior art, the present invention has the following beneficial effects:

[0085] In the positive photoresist composition provided by the present invention, the heat resistance of the positive photoresist composition is significantly improved by designing a specific silane coupling agent-modified nano-silica and compounding it with other components. The formed photoresist cured film has a high residual film rate and excellent adhesion, avoids peeling, has good reliability, and thus effectively improves the product yield of electronic devices. DETAILED DESCRIPTION

[0086] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0087] In one embodiment, the silane coupling agent has a structure shown in Formula I, wherein Y1 and Y2 are O, and can be prepared by the following synthetic route A:

[0088]

[0089] wherein A, R1, R2, R3, R4, R5, and R6 have the same definitions as in Formula I; Hal1 is selected from halogen, preferably Cl, Br, or I, and further preferably Cl.

[0090] In one embodiment, the reaction in Synthesis Scheme A is carried out in the presence of a catalyst, which preferably comprises FeCl 3 .

[0091] In one embodiment, the silane coupling agent has a structure shown in Formula I, wherein Y1 and Y2 are S, and can be prepared by the following synthetic route B:

[0092]

[0093] In one embodiment, the reaction in Synthesis Route B is carried out under alkaline conditions, which are preferably provided by sodium hypochlorite and / or triethylamine.

[0094] The following preparation examples are used to describe in detail the specific preparation methods of the silane coupling agents of the present invention, but the preparation methods of the silane coupling agents are not limited to these preparation examples. In the following preparation examples 1-3, the prepared silane coupling agents were tested by mass spectrometry (MS) and elemental analysis to confirm the product structures.

[0095] Preparation Example 1

[0096] Silane coupling agent A1, structure is The preparation method is as follows:

[0097] (1) Take 3 g of tert-butyl hydroperoxide, add 5 g of n-hexane to extract the tert-butyl hydroperoxide, add 3 g of anhydrous magnesium sulfate and stir thoroughly, filter, and distill off the n-hexane to obtain anhydrous tert-butyl hydroperoxide;

[0098] (2) Add 15 mL of anhydrous toluene and 0.08 g of ferric chloride to a three-necked flask, evacuate, and fill with nitrogen. Under magnetic stirring, inject anhydrous tert-butyl hydroperoxide into the three-necked flask. After a pre-reaction at 40°C for 30 min, inject 8 g of 3-chloropropyltrimethoxysilane and continue the reaction for 8 h to obtain a crude product of 1-tert-butylperoxy-3-(trimethoxysilyl)propane.

[0099] (3) The crude product of 1-tert-butylperoxy-3-(trimethoxysilyl)propane was washed with 200 mL of 10% sodium hydroxide solution, centrifuged, and filtered. After cooling and crystallization, the product was filtered. 45 mL of methanol was added and distilled in a 37°C water bath to obtain 1-tert-butylperoxy-3-(trimethoxysilyl)propane, i.e., silane coupling agent A1.

[0100] Preparation Example 2

[0101] Silane coupling agent A2, structure is The preparation method is as follows:

[0102] (1) Take 5 g of tert-butyl mercaptan and 5 g of γ-mercaptopropyltrimethoxysilane, add 100 g of methanol as solvent, control the temperature at 45 ° C, and stir for 8 h; then add hydrogen peroxide solution (50 mL, H2O2 concentration of 30%) and triethylamine to the system, adjust the pH to 10, and continue stirring for 8 h. At this time, the alkaline condition is conducive to the reaction in the direction of disulfide bonds;

[0103] (2) After the reaction is completed, the product is repeatedly washed with 10% sodium hydroxide solution, filtered, and distilled under reduced pressure to obtain a crude product. The crude product is further cooled and crystallized to remove impurities, filtered, and distilled under reduced pressure again to obtain the target product, silane coupling agent A2.

[0104] Preparation Example 3

[0105] Silane coupling agent A3, structure is (tert-Butylpropyltriethoxysilane disulfide), the preparation method is as follows:

[0106] (1) Take 5 g of tert-butyl mercaptan and 5 g of γ-mercaptopropyltriethoxysilane, add 100 g of methanol as solvent, control the temperature at 45 ° C, and stir for 12 h; then add hydrogen peroxide solution (50 mL, H2O2 concentration of 30%) and triethylamine to the system to adjust the pH to 10, and continue stirring for 12 h. At this time, the alkaline conditions are conducive to the reaction in the direction of disulfide bonds;

[0107] (2) After the reaction is completed, the product is repeatedly washed with 10% sodium hydroxide solution, filtered, and distilled under reduced pressure to obtain a crude product. The crude product is further cooled and crystallized to remove impurities, filtered, and distilled under reduced pressure again to obtain the target product, silane coupling agent A3.

[0108] Preparation Example 4

[0109] Silane coupling agent modified nano-silica S1, nano-silica was modified with silane coupling agent A1, the method is as follows:

[0110] 1 part by mass of nano-silica (average particle size of 5 nm) was added to a three-necked flask, followed by 50 parts of solvent (a 1:2 mixture of water and ethanol). The flask was ultrasonically shaken for 30 minutes, the pH was adjusted to 4.5 with glacial acetic acid, and stirred at room temperature for 1 hour to obtain a first dispersion. The pH of the first dispersion was adjusted to 10.5 with aqueous ammonia and stirred for another 1 hour. The flask was then evacuated and filled with high-purity nitrogen. Silane coupling agent A1 was added in an amount equal to the mass of the nano-silica. The mixture was reacted in an 80°C water bath for 8 hours. The product was cooled to room temperature, washed multiple times with methanol and then centrifuged with water. The resulting product was then vacuum dried for 24 hours to obtain silane coupling agent-modified nano-silica S1.

[0111] Preparation Example 5

[0112] The silane coupling agent modified nano-silica S2 is different from Preparation Example 4 only in that the silane coupling agent A1 is replaced by the silane coupling agent A2 of equal mass, and the types, amounts and parameters of other materials are the same as those in Preparation Example 4 to obtain the silane coupling agent modified nano-silica S2.

[0113] Preparation Example 6

[0114] The silane coupling agent-modified nano-silica S3 differs from Preparation Example 4 only in that the silane coupling agent A1 is replaced by the silane coupling agent A3, and the mass ratio of nano-silica to the silane coupling agent A3 is 1:5. The types, amounts, and parameters of other materials are the same as those in Preparation Example 4, to obtain the silane coupling agent-modified nano-silica S3.

[0115] Comparative Preparation Example 1

[0116] The silane coupling agent modified nano-silica SD1 differs from Preparation Example 4 only in that the silane coupling agent A1 is replaced with an equal mass of A171 vinyltrimethoxysilane, and the types, amounts and parameters of other materials are the same as those in Preparation Example 4 to obtain the silane coupling agent modified nano-silica SD1.

[0117] In the following specific implementations of the present invention, the material information involved is as follows:

[0118] (1) Photosensitive resin: Homemade polyimide precursor resin, the synthesis method is as follows:

[0119] Under nitrogen protection, 5 g of 2.2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 30 mL of N-methylpyrrolidone (NMP), cooled to 0°C, and a mixture of 4 g of 3,3,4,4-diphenyl ether tetraanhydride and 15 g of NMP was added to the system. The reaction was carried out at 0°C for 5 h, and the temperature was raised to 65°C. 3 g of N,N-dimethylformamide dimethyl acetal was added to the reaction system, and the reaction was maintained at 60°C for 3 h. The temperature was lowered to room temperature, and the reaction solution was introduced into 300 mL of deionized water. The precipitate was filtered and dried in vacuo for 24 h to obtain a polyimide precursor resin with a molecular weight of 8500 (Malvern Viscotek gel chromatography instrument, D6000M column).

[0120] (2) Photosensitizer: PAC435, Shenyang Jingfan New Materials.

[0121] (3) Sensitizer: TMTP, Shenyang Jingfan New Materials.

[0122] (4) Leveling agent: Efka 3777, Shanghai Huiyan New Materials.

[0123] Example 1

[0124] A positive photoresist composition comprises the following components in parts by mass:

[0125]

[0126]

[0127] The preparation method of the positive photoresist composition is as follows: all components are mixed according to the formula amount and fully dissolved to obtain the positive photoresist composition.

[0128] Example 2

[0129] A positive photoresist composition is provided, which differs from Example 1 only in that the silane coupling agent-modified nano-silica S1 is replaced by the silane coupling agent-modified nano-silica S2 of equal mass; the types and amounts of other materials are the same as those in Example 1.

[0130] Example 3

[0131] A positive photoresist composition is provided, which differs from Example 1 only in that the silane coupling agent-modified nano-silica S1 is replaced by the silane coupling agent-modified nano-silica S3 of equal mass; the types and amounts of other materials are the same as those in Example 1.

[0132] Comparative Example 1

[0133] A positive photoresist composition is provided, which differs from Example 1 only in that the silane coupling agent-modified nano-silica S1 is replaced with silane coupling agent-modified nano-silica SD1 of equal mass; the types and amounts of other materials are the same as those in Example 1.

[0134] Comparative Example 2

[0135] A positive photoresist composition is provided, which differs from Example 1 only in that the silane coupling agent-modified nano-silica S1 is replaced by the silane coupling agent A1 of equal mass; the types and amounts of other materials are the same as those in Example 1.

[0136] Comparative Example 3

[0137] A positive photoresist composition is provided, which differs from Example 1 only in that the silane coupling agent-modified nano-silica S1 is replaced by a silane coupling agent A2 of equal mass; the types and amounts of other materials are the same as those in Example 1.

[0138] Comparative Example 4

[0139] A positive photoresist composition comprises the following components in parts by mass:

[0140]

[0141] The preparation method of the positive photoresist composition is as follows: all components are mixed according to the formula amount and fully dissolved to obtain the positive photoresist composition.

[0142] Comparative Example 5

[0143] A positive photoresist composition is provided, which differs from Example 1 only in that the silane coupling agent-modified nano-silica S1 is not added; the types and amounts of other materials are the same as those in Example 1.

[0144] The performance test of the positive photoresist composition is as follows:

[0145] (1) Post-baking residual film rate test

[0146] The positive photoresist composition to be tested was applied to a 4-inch square glass substrate using a spin coating method and pre-baked at 120°C for 200 seconds to remove most of the solvent, forming a film of approximately 5 μm. Maskless exposure was performed using a UV exposure machine (center exposure dose of 80 mJ). The coated glass substrate was then placed in a 250°C clean oven under nitrogen protection (oxygen concentration <5 ppm) and cured for 60 minutes. The film thickness before and after curing was measured using a step profiler. The film thickness before curing was t1, and the film thickness after curing was t2. The post-bake residual film rate = 100% × t2 / t1.

[0147] (2) Adhesion test (100-grid cross-cut method)

[0148] The positive photoresist composition to be tested was spin-coated onto a 4-inch square glass substrate and pre-baked at 120°C for 200 seconds to remove most of the solvent, forming a film approximately 5 μm thick. The resulting film was then cured for 60 minutes in a clean oven at 250°C under nitrogen (oxygen concentration <5 ppm). After curing, the cross-cuts were cross-checked according to ISO-2409 and observed using an OM microscope to detect any peeling. Grade 0 indicates the best adhesion, while grade 5 indicates the worst.

[0149] (3) Peeling test

[0150] The positive photoresist composition to be tested was spin-coated onto a 4-inch square glass substrate and pre-baked at 120°C for 170 seconds to remove most of the solvent, forming a film approximately 2.2 μm thick. After exposure using a stepper, the film was developed (developer: 2.38% tetramethylammonium hydroxide aqueous solution, 55 seconds, temperature 24°C). The coated glass substrate was then cured for 60 minutes in a clean oven at 250°C under nitrogen protection (oxygen concentration <5 ppm). The resulting cured film was observed for peeling under an OM microscope.

[0151] The test results are shown in Table 1:

[0152] Table 1

[0153] Post-baking residual film rate (%) Adhesion peeling Example 1 87.07 Level 0 none Example 2 87.36 Level 0 none Example 3 86.28 Level 0 none Comparative Example 1 85.09 Level 1 none Comparative Example 2 84.60 Level 0 none Comparative Example 3 84.11 Level 0 none Comparative Example 4 81.28 Level 2 have Comparative Example 5 82.36 Level 3 have

[0154] The performance test results in Table 1 indicate that the present invention, through the design of a silane coupling agent-modified nano-silica comprising the specific structures *-OO-* and *-SS-* and its combination with other components, results in a positive photoresist composition having significantly improved heat resistance, a significantly increased post-bake residual film rate, significantly improved adhesion, and no peeling. This is because, compared to conventional commercially available silane coupling agents, the *-OO-* and *-SS-* in the silane coupling agent structure of the present invention can generate free radicals, which facilitate free radical polymerization of the resin during exposure, promote film hardening, improve adhesion to a certain extent, avoid peeling, and also contribute to improved heat resistance, thereby enhancing properties such as the post-bake residual film rate.

[0155] Comparison of Examples 1-3 with Comparative Examples 1-5 shows that, compared with Comparative Example 5 in which no modifier was added, the post-baking residual film rate and adhesion of Examples 1-3 were significantly improved, there was no peeling phenomenon, and the heat resistance and reliability were excellent. Comparative Example 1 used a common commercially available silane coupling agent to modify the nano-silica. Although the performance was improved compared to Comparative Example 5, the adhesion and residual film rate were still significantly insufficient. The addition of a single coupling agent in Comparative Examples 2-3 also helped to improve the performance, but the improvement effect was not significant. In Comparative Example 4, the silane coupling agent and nano-silica were added separately. The nano-silica without the silane coupling agent compound had poor compatibility with the system, resulting in solid particles remaining on the film surface after film formation, thereby affecting the performance of the film.

[0156] The applicant declares that the present invention uses the above-described embodiments to illustrate the positive photoresist composition and its applications. However, the present invention is not limited to the above-described embodiments, and it does not mean that the present invention must rely on the above-described embodiments in order to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacements for various raw materials in the product of the present invention, addition of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A positive photoresist composition, characterized in that The positive photoresist composition comprises a combination of a photosensitive resin, a photosensitizer, a sensitizer and silane coupling agent modified nano-silica; The silane coupling agent has a structure as shown in Formula I: Wherein, Y1 and Y2 are each independently selected from O or S; A is selected from any one of C1-C10 straight or branched chain alkylene; R1, R2, and R3 are each independently selected from any one of hydrogen, C1-C10 linear or branched alkyl, and C6-C12 aryl; R4 is selected from any one of C1-C10 straight or branched alkyl and C1-C10 alkoxy; R5 and R6 are each independently selected from any one of C1-C10 straight-chain or branched alkyl groups.

2. The positive photoresist composition according to claim 1, characterized in that A is selected from any one of C1-C6 straight chain alkylene groups; Preferably, R1, R2, and R3 are each independently selected from any one of hydrogen, C1-C6 linear or branched alkyl; Preferably, the R4 is selected from any one of C1-C6 alkoxy groups; Preferably, R5 and R6 are each independently selected from any one of C1-C6 straight chain or branched chain alkyl groups; Preferably, the silane coupling agent is selected from any one or a combination of at least two of the following compounds:

3. The positive photoresist composition according to claim 1 or 2, characterized in that The silane coupling agent modified nano-silica is prepared by the following method, which comprises: Mixing nano-silica with a solvent and treating the mixture under acidic conditions to obtain a first dispersion; mixing the first dispersion and the silane coupling agent and reacting them to obtain the silane coupling agent-modified nano-silica; Preferably, the solvent comprises a combination of water and an alcohol solvent; Preferably, the pH value of the acidic condition is 3.5-4.5; Preferably, the treatment temperature is 15-40°C; Preferably, the treatment time is 10-120 min; Preferably, the mass ratio of the nano-silica to the silane coupling agent is 1:(1-22); Preferably, the pH value of the reaction is 9.5-10.5; Preferably, the reaction temperature is 60-95°C; Preferably, the reaction time is 4-16 hours.

4. The positive photoresist composition according to claim 1, characterized in that The photosensitive resin includes any one or a combination of at least two of polyimide, polyimide precursor resin, polyamic acid-polyimide copolymer, polyamic acid ester-polyimide copolymer, polyisoimide-polyamic acid copolymer, and polyisoimide, preferably polyimide precursor resin; Preferably, the polyimide precursor resin includes polyamic acid ester and / or polyamic acid.

5. The positive photoresist composition according to claim 1, characterized in that Based on 100 parts by mass of the photosensitive resin, the mass of the silane coupling agent modified nano-silica is 0.1-5 parts, preferably 0.2-2 parts.

6. The positive photoresist composition according to claim 1, characterized in that The photosensitizer is a compound containing a diazonaphthoquinone group; Preferably, based on 100 parts by mass of the photosensitive resin, the mass of the photosensitizer is 0.1-40 parts by mass.

7. The positive photoresist composition according to claim 1, characterized in that The sensitizer is a polyphenol compound; Preferably, based on 100 parts by mass of the photosensitive resin, the mass of the sensitizer is 0.1-40 parts by mass.

8. The positive photoresist composition according to claim 1, characterized in that The positive photoresist composition further includes a leveling agent; Preferably, the leveling agent comprises any one or a combination of at least two of a fluorine-containing surfactant, a surfactant containing a polyethylene glycol structure, and a surfactant containing a siloxane structure; Preferably, based on 100 parts by mass of the photosensitive resin, the mass of the leveling agent is 0.01-5 parts by mass.

9. The positive photoresist composition according to claim 1, characterized in that The positive photoresist composition further includes a solvent; Preferably, the solvent comprises any one or a combination of at least two of γ-butyrolactone, butyl lactate, propylene glycol methyl ether, propylene glycol methyl ether acetate, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and benzyl alcohol; Preferably, based on 100 parts by mass of the photosensitive resin, the mass of the solvent is 100-1500 parts by mass.

10. A photoresist cured film, characterized in that: The photoresist cured film is prepared by the positive photoresist composition according to any one of claims 1 to 9.

11. Use of the positive photoresist composition according to any one of claims 1 to 9 and the photoresist cured film according to claim 9 in a semiconductor device or a flat panel display device.

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