Positive photosensitive resin composition and method for preparing cured pattern

Abstract

The present invention belongs to the field of photosensitive resin compositions, and specifically discloses a positive photosensitive resin composition and a method for preparing a cured pattern. The positive photosensitive resin composition comprises (A) an alkali-soluble resin polymer; (B) a crosslinking compound, wherein the crosslinking compound is selected from at least two of a first crosslinking compound, a second crosslinking compound, and a third crosslinking compound; and (C) a phenolic diazonaphthoquinone sulfonate, wherein the phenolic diazonaphthoquinone sulfonate comprises a first phenolic diazonaphthoquinone sulfonate and a second phenolic diazonaphthoquinone sulfonate. The method for preparing the cured pattern is to coat the above positive photosensitive resin composition on a substrate, and after baking, exposure, development, and curing, a cured pattern is obtained. The present invention has a good development rate during the development process after exposure in the process of preparing the cured pattern, and has a high dark film retention rate after development and forms a cured pattern that is completely free of cracks.

Description

Technical Field

[0001] The present invention relates to the technical field of photosensitive resin compositions, and particularly relates to a positive photosensitive resin composition and a method for preparing a cured pattern. Background Art

[0002] In recent years, with the miniaturization and high performance of various electronic devices such as personal computers, digital cameras, and mobile phones, the requirements for further miniaturization, thinning, and high density of semiconductor elements have also been rapidly increasing. Therefore, it is desired to develop a photosensitive insulating material that can cope with the increase in the substrate area during the process of improving productivity and that is fine and has a high aspect ratio on the substrate in high-density mounting technologies such as chip scale package or chip level package (CSP) or three-dimensional stacking.

[0003] In high-density mounting technologies such as three-dimensional stacking, as a photosensitive insulating material capable of forming a pattern on a substrate, it is required to have more excellent heat resistance (such as coefficient of thermal expansion), mechanical properties (such as fracture strength, elongation at break, etc.). As an insulating layer material having such characteristics, an alkali-soluble resin polymer has been developed.

[0004] In the existing improvement of the development of positive resin compositions, if the amount of photoacid generator used is increased, free acid will be generated during the subsequent heat curing process of the resin, which will corrode the metal substrate; if the amount of small molecule dissolution promoter used is increased, cracks are likely to appear in the film during curing after development. Summary of the Invention

[0005] The purpose of the present invention is to overcome the defects of the above-mentioned existing technologies and provide a positive photosensitive resin composition and a method for preparing a cured pattern that can effectively solve the cracking problem during the curing process.

[0006] To achieve the above purpose and other related purposes, the present invention provides the following technical solutions.

[0007] In a first aspect, the present invention provides a positive photosensitive resin composition, which comprises:

[0008] (A) An alkali-soluble resin polymer;

[0009] (B) A crosslinking compound for adjusting the internal stress distribution after resin curing, thereby improving the mechanical properties. The crosslinking compound is selected from at least two of a first crosslinking compound, a second crosslinking compound, and a third crosslinking compound. The first crosslinking compound is selected from ether compounds of melamine or ether compounds of glycoluril. The second crosslinking compound is selected from epoxy group-containing compounds. The third crosslinking compound is selected from vinyl ether compounds;

[0010] And (C) phenolic diazonaphthoquinone sulfonate ester compounds are used to inhibit the alkali dissolution rate of the resin before exposure and increase the alkali dissolution rate after exposure, without significantly affecting the copper substrate. The phenolic diazonaphthoquinone sulfonate ester compounds include a first phenolic diazonaphthoquinone sulfonate ester compound and a second phenolic diazonaphthoquinone sulfonate ester compound; the degree of esterification of the first phenolic diazonaphthoquinone sulfonate ester compound is 10% to 90%, such as 85%; the degree of esterification of the second phenolic diazonaphthoquinone sulfonate ester compound is 0 or 30 to 90%, such as 67%;

[0011] Further, the mass ratio of (A) the alkali-soluble resin polymer, (B) the crosslinking compound, and (C) the phenolic diazonaphthoquinone sulfonate ester compound is 100:(3 to 15):(20 to 35); such as 100:10:25 or 100:10:20 or 100:15:20.

[0012] Preferably, the mass ratio of (B) the crosslinking compound and (C) the phenolic diazonaphthoquinone sulfonate ester compound is 1:(1 to 2.5), such as 1:2 or 1:1.3;

[0013] Further, the crosslinking compound further includes at least one of the following technical features:

[0014] a1) The first crosslinking compound is selected from at least one of the following general structural formulas,

[0015]

[0016] Among them, in formula B-1, R1, R2, R3, and R4 are each independently selected from C1-C6 alkyl groups; in formula B-2, R5, R6, R7, R8, R9, and R 10 are each independently selected from C1-C6 alkyl groups;

[0017] a2) The second crosslinking compound is selected from at least one of the following general structural formulas,

[0018]

[0019] Among them, in formula B-3, R 11 and R 12 are each independently selected from a hydrogen atom or a C1-C6 alkyl group; in formula B-4, M is a C5-C7 cycloalkyl group; in formula B-5, R 13 、R 14 and R 15 are each independently selected from an epoxy group structure or a C1-C6 alkyl group, and at least one of R 13 、R 14 and R 15 is an epoxy group structure;

[0020] a3) The third crosslinking compound is selected from at least one of the following general structural formulas,

[0021]

[0022] wherein in formula B-6, R 13 is an alkylene group having 1 to 6 carbon atoms, and 1 ≤ m ≤ 5; in formula B-7, N is a cycloalkyl group having 5 to C 10 ;

[0023] Furthermore, the crosslinking compound further includes at least one of the following technical features:

[0024] b1) The first crosslinking compound is specifically selected from at least one of the following structures

[0025]

[0026] b2) The second crosslinking compound is specifically selected from at least one of the following structures

[0027]

[0028] b3) The third crosslinking compound is specifically selected from at least one of the following structures

[0029]

[0030] Furthermore, the phenolic diazonaphthoquinone sulfonate ester also includes at least one of the following technical features:

[0031] c1) The first phenolic diazonaphthoquinone sulfonate ester is an ester of a phenolic resin and 2,1,4-diazonaphthoquinone sulfonyl chloride, and the phenolic resin is a polymer selected from one or more of the following phenol structures,

[0032] wherein a, b, c, and d are all positive integers greater than or equal to 3 and less than or equal to 10, and the dashed line represents a bonding bond;

[0033] c2) The second phenolic diazonaphthoquinone sulfonate ester is an ester of α,α,α''-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene and 2,1,5-diazonaphthoquinone sulfonyl chloride.

[0034] Furthermore, the alkali-soluble resin polymer is selected from the following general structural formulas,

[0035]

[0036] wherein X1 is selected from at least one of a benzene ring structure and a siloxane structure, and Y1 is selected from at least one of a benzene ring structure and a polyether structure; the R 15 and R 16independently selected from a hydrogen atom, a C1-C6 alkyl group, and an acetal structure; 0 ≤ p ≤ 2, 0 ≤ q ≤ 2, and p + q > 0.

[0037] Furthermore, the alkali-soluble resin polymer further includes at least one of the following technical features:

[0038] d1) X1 is selected from at least one of the following structures

[0039]

[0040] wherein the dotted line represents a bonding bond;

[0041] d2) Y1 is selected from at least one of the following structures

[0042]

[0043] wherein the dotted line represents a bonding bond.

[0044] Furthermore, it further includes a solvent.

[0045] Preferably, the solvent is selected from at least one of anisole, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol, γ-butyrolactone, N-methylpyrrolidone, or ethyl lactate.

[0046] The second aspect of the present invention provides a method for preparing a cured pattern. The above positive photosensitive resin composition is coated on a substrate and then baked, exposed, developed, and cured to obtain a cured pattern.

[0047] Furthermore, it further includes at least one of the following technical features:

[0048] e1) The baking temperature is 80-120 °C, such as 120 °C;

[0049] e2) The baking time is 1-10 minutes, such as 3 minutes;

[0050] e3) The exposure uses a 200W ultraviolet mercury lamp exposure machine;

[0051] e4) The developer uses a 2.38% aqueous solution of tetramethylammonium hydroxide;

[0052] e5) The curing temperature is 160-400 °C, such as 350 °C;

[0053] e6) The curing time is 1 to 3 hours, such as 1.5 hours;

[0054] e7) The thickness of the cured film is 5 to 20 um, such as 7 um.

[0055] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0056] In the present invention, two or more different crosslinking compounds are used, and at the same time, two different phenolic diazonaphthoquinone sulfonate compounds are combined. During the development process after exposure in the preparation process of the cured pattern, there is a good development rate, and after development, the dark film retention rate is high, and a completely crack-free cured pattern is formed. Detailed implementation manners

[0057] Unless otherwise specified, implied from the context or in accordance with the convention of the prior art, all parts and percentages in this application are based on weight, and the test and characterization methods used are synchronized with the filing date of this application. Where applicable, any patents, patent applications or published content referred to in this application are incorporated herein by reference in their entirety, and their equivalent family patents are also incorporated by reference. In particular, the definitions of synthetic techniques, products and processing designs, polymers, comonomers, initiators or catalysts in the art disclosed in these documents. If the definition of a specific term disclosed in the prior art is inconsistent with any definition provided in this application, the definition of the term provided in this application shall prevail.

[0058] The numerical ranges in this application are approximate values. Therefore, unless otherwise specified, they may include values outside the ranges. The numerical ranges include all values from the lower limit value to the upper limit value increased by 1 unit, provided that there is an interval of at least 2 units between any lower value and any higher value. For example, if it is stated that a component, physical or other property (such as molecular weight, melt index, etc.) is from 100 to 1000, it means that all individual values are explicitly listed, such as 100, 101, 102, etc., and all sub-ranges, such as 100 to 166, 155 to 170, 198 to 200, etc. For ranges containing values less than 1 or fractions greater than 1 (such as 1.1, 1.5, etc.), 1 unit is appropriately regarded as 0.0001, 0.001, 0.01 or 0.1. For ranges of single digits less than 10 (such as 1 to 5), 1 unit is usually regarded as 0.1. These are merely specific examples of what is intended to be expressed, and all possible combinations of the values between the lowest and highest values listed are considered to be clearly recited in this application. The numerical ranges in this application particularly provide the calcium filler content, stirring temperature, and various characteristics and properties of these components.

[0059] When referring to the use of chemical compounds, unless otherwise specified, the singular form includes all isomeric forms, and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively). Additionally, unless otherwise specified, nouns preceded by "a", "an", or "the" also include their plural forms.

[0060] The terms "comprising", "including", "having", and their derivatives do not exclude the presence of any other components, steps, or processes, regardless of whether or not they are disclosed in the present application. To eliminate any doubt, unless otherwise specified, all compositions in the present application using the terms "comprising", "including", or "having" may contain any additional additives, excipients, or compounds. In contrast, the term "consisting essentially of" excludes any other components, steps, or processes from the scope described below any such term, except for those necessary for the operating performance. The term "consisting of" does not include any components, steps, or processes not specifically described or listed. Unless otherwise specified, the term "or" refers to the individual members listed or any combination thereof.

[0061] Embodiment

[0062] The embodiments of the present invention will be described in detail below. These embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation manners and specific operation procedures are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0063] The following are various components used in the examples and comparative examples

[0064] 1. Alkali-soluble resin polymer A

[0065] Synthesis of alkali-soluble resin polymer A1

[0066] Dissolve 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (9.16 g, 0.025 mol), 2,2-bis(4-hydroxy-3-aminophenyl)propane (6.46 g, 0.025 mol), 4,4-chlorocarbonylphenylether (7.08 g, 0.024 mol), and isophthaloyl chloride (4.87 g, 0.024 mol) in N,N-dimethylformamide (200 g), and react at -20 to 50 °C for 12 to 24 hours. After filtration, precipitation in a precipitant prepared with a 1:1 mixture of water and methanol, and drying, a quaternary copolymer of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane-4,4-chlorocarbonylphenylether-2,2-bis(4-hydroxy-3-aminophenyl)propane-isophthaloyl chloride, resin polymer A1 (24.56 g, molecular weight 19000) is obtained.

[0067] Measurement of the dissolution rate (ADR) of alkali-soluble resin polymer A1: The alkali-soluble resin polymer A1 was immersed in an aqueous solution of 2.38% tetramethylammonium hydroxide (TMAH), and the measured ADR was

[0068] Synthesis of alkali-soluble resin polymer A2

[0069] 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (9.16 g, 0.025 mol), 2,2-bis(4-hydroxy-3-aminophenyl)propane (9.16 g, 0.025 mol), 4,4-chlorocarbonylphenyl ether (6.79 g, 0.023 mol), and isophthaloyl chloride (4.67 g, 0.023 mol) were dissolved in N,N-dimethylformamide (180 g), and the reaction was carried out at -20 to 50 °C for 12 to 24 hours. After filtration, precipitation was carried out in a precipitant prepared by mixing water and methanol in a 1:1 ratio, and after drying, a quaternary copolymer of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane-4,4-chlorocarbonylphenyl ether-2,2-bis(4-hydroxy-3-aminophenyl)propane-isophthaloyl chloride, resin polymer A2 (25.29 g, molecular weight 23000), was obtained.

[0070] Measurement of the dissolution rate (ADR) of alkali-soluble resin polymer A2: The alkali-soluble resin polymer A2 was immersed in an aqueous solution of 2.38% TMAH, and the measured ADR was

[0071] Synthesis of alkali-soluble resin polymer A3

[0072] 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (18.13 g, 0.05 mol), 2,2-bis(4-hydroxy-3-aminophenyl)propane (12.92 g, 0.05 mol), 4,4'-biphenylene ether dianhydride (31.02 g, 0.1 mol), and N,N-dimethylformamide diethyl acetal (29.44, 0.2 mol) were dissolved in N-methylpyrrolidone (230 g), and the reaction was carried out at -20 to 50 °C for 12 to 24 hours. After filtration, precipitation was carried out in a precipitant prepared by mixing water and methanol in a 1:1 ratio, and after drying, a ternary copolymer of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane-4,4'-biphenylene ether dianhydride-2,2-bis(4-hydroxy-3-aminophenyl)propane, resin polymer A3 (60.83 g, molecular weight 10300), was obtained.

[0073] Measurement of the dissolution rate (ADR) of alkali-soluble resin polymer A3: The alkali-soluble resin polymer A3 was immersed in an aqueous solution of 2.38% TMAH, and the measured ADR was

[0074] Synthesis of alkali-soluble resin polymer A4

[0075] Dissolve 4,4'-diaminodiphenyl ether (7.01 g, 0.035 mol), 1,3-bis(3-aminopropyl)tetramethyldisiloxane (3.73 g, 0.015 mol), 4,4'-biphenylene ether dianhydride (15.51 g, 0.05 mol), and N,N-dimethylformamide dimethyl acetal (12.51 g, 0.085 mol) in γ-butyrolactone (220 g), and react at -20 to 50 °C for 12 to 24 hours. After filtration, precipitation in a precipitant prepared from water and methanol in a 1:1 ratio, and drying, a terpolymer of 4,4'-diaminodiphenyl ether-4,4'-biphenylene ether dianhydride-1,3-bis(3-aminopropyl)tetramethyldisiloxane, resin polymer A4 (24.67 g, molecular weight 9500) is obtained.

[0076] Measurement of the dissolution rate (ADR) of alkali-soluble resin polymer A4: Immerse alkali-soluble resin polymer A4 in an aqueous solution of 2.38% TMAH, and the measured ADR is

[0077] 2. Crosslinking compound B

[0078] First crosslinking compound B1: Tetramethoxymethyl glycoluril

[0079]

[0080] Second crosslinking compound B2: Bisphenol A diglycidyl ether

[0081]

[0082] Third crosslinking compound B3: Diethylene glycol divinyl ether

[0083]

[0084] 3. Phenolic diazonaphthoquinone sulfonate C

[0085] First phenolic diazonaphthoquinone sulfonate C1; Esterification product of p-cresol-formaldehyde novolak resin and 2,1,4-diazonaphthoquinone sulfonyl chloride, with an esterification degree of 85%.

[0086] Second phenolic diazonaphthoquinone sulfonate C2: Esterification product of α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene and 2,1,5-diazonaphthoquinone sulfonyl chloride, with an esterification degree of 67%.

[0087] 4. Solvent

[0088] γ-Butyrolactone

[0089] Example 1

[0090] A positive photosensitive resin composition comprising the following components in parts by mass:

[0091]

[0092] Method for preparing a cured pattern:

[0093] Fully dissolve the components of the above positive photosensitive resin composition to prepare a colloid with a solid content of 30%. Spin-coat the above colloid on a 4-inch silicon wafer, adjust the rotation speed, and bake it on a contact hot plate at 120 °C for 3 minutes to form a photosensitive film with a specific film thickness. Use a UV mercury lamp exposure machine with a power of 200 W for pattern exposure, develop it in a 2.38% TMAH solution, and cure it at a heating rate of 5 °C per minute from room temperature through 180 °C for 0.5 hour and 350 °C for 1 hour. Then cool it at a rate of 2 °C per minute to 200 °C and then at a rate of 5 °C per minute to room temperature to obtain a 7-μm cured film. Measure the development The film retention rate is 94%, completely free of residues and completely free of cracking. The specific results are shown in Table 1.

[0094] Example 2

[0095] A positive photosensitive resin composition comprising the following components in parts by mass:

[0096]

[0097] Method for preparing a cured pattern:

[0098] Fully dissolve the components of the above positive photosensitive resin composition to prepare a colloid with a solid content of 30%. Spin-coat the above colloid on a 4-inch silicon wafer, adjust the rotation speed, and bake it on a contact hot plate at 120 °C for 3 minutes to form a photosensitive film with a specific film thickness. Use a UV mercury lamp exposure machine with a power of 200 W for pattern exposure, develop it in a 2.38% TMAH solution, and cure it at a heating rate of 5 °C per minute from room temperature through 180 °C for 0.5 hour and 350 °C for 1 hour. Then cool it at a rate of 2 °C per minute to 200 °C and then at a rate of 5 °C per minute to room temperature to obtain a 7-μm cured film. Measure the development The film retention rate is 89%, completely free of residues and completely free of cracking. The specific results are shown in Table 1.

[0099] Example 3

[0100] A positive photosensitive resin composition comprising the following components in parts by mass:

[0101]

[0102] Method for preparing a cured pattern:

[0103] Fully dissolve each component of the above positive photosensitive resin composition to prepare a colloid with a solid content of 30%. Spin-coat the above colloid on a 4-inch silicon wafer, adjust the rotation speed, and bake it on a contact hot plate at 120 °C for 3 minutes to form a photosensitive film with a specific film thickness. Use a UV mercury lamp exposure machine with a power of 200 W for pattern exposure, develop it in a 2.38% TMAH solution, and cure it at a heating rate of 5 °C per minute from room temperature through 180 °C for 0.5 hours and 350 °C for 1 hour, then cool it to 200 °C at a rate of 2 °C per minute and then cool it to room temperature at a rate of 5 °C per minute to obtain a cured film with a thickness of 7 μm, and measure the development rate Among them, the film retention rate is 91%, the residue is less than 1 / 4 of the opening area, and there is no cracking at all. The specific results are shown in Table 1.

[0104] Example 4

[0105] A positive photosensitive resin composition comprising the following components in parts by mass:

[0106]

[0107] Preparation method of the cured pattern:

[0108] Fully dissolve each component of the above positive photosensitive resin composition to prepare a colloid with a solid content of 30%. Spin-coat the above colloid on a 4-inch silicon wafer, adjust the rotation speed, and bake it on a contact hot plate at 120 °C for 3 minutes to form a photosensitive film with a specific film thickness. Use a UV mercury lamp exposure machine with a power of 200 W for pattern exposure, develop it in a 2.38% TMAH solution, and cure it at a heating rate of 5 °C per minute from room temperature through 180 °C for 0.5 hours and 350 °C for 1 hour, then cool it to 200 °C at a rate of 2 °C per minute and then cool it to room temperature at a rate of 5 °C per minute to obtain a cured film with a thickness of 7 μm, and measure the development The film retention rate is 90%, there is no residue at all, and there is no cracking at all. The specific results are shown in Table 1.

[0109] Example 5

[0110] A positive photosensitive resin composition comprising the following components in parts by mass:

[0111]

[0112] Preparation method of the cured pattern:

[0113] The components of the positive photosensitive resin composition are fully dissolved to obtain a colloid with a solid content of 30%. The colloid is spin-coated on a 4-inch silicon wafer, the rotation speed is adjusted, and the photosensitive film with a specific film thickness is formed after baking at 120°C for 3 minutes on a contact hot plate. The pattern is exposed using a UV mercury lamp exposure machine with a power of 200W, and developed in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 350°C for 1 hour at a heating rate of 5°C per minute from room temperature, the temperature is lowered to 200°C at a rate of 2°C per minute, and then lowered to room temperature at 5°C per minute to obtain a 7um cured film. The development rate is measured. The film retention rate was 88%, with no residue and no cracking. The specific results are shown in Table 1.

[0114] Example 6

[0115] A positive photosensitive resin composition comprises the following components in parts by weight:

[0116]

[0117] Preparation method of curing pattern:

[0118] The components of the positive photosensitive resin composition are fully dissolved to obtain a colloid with a solid content of 30%. The colloid is spin-coated on a 4-inch silicon wafer, the rotation speed is adjusted, and it is baked on a contact hot plate at 120°C for 3 minutes to form a photosensitive film of a specific film thickness. A UV mercury lamp exposure machine with a power of 200W is used for pattern exposure, and it is developed in a TMAH 2.38% solution. After curing at a heating rate of 5°C per minute from room temperature to 180°C for 0.5 hours and 350°C for 1 hour, it is cooled to 200°C at a rate of 2°C per minute, and then cooled to room temperature at 5°C per minute to obtain a 7um cured film. Measured development rate The film retention rate was 87%, with no residue and no cracking. The specific results are shown in Table 1.

[0119] Example 7

[0120] A positive photosensitive resin composition comprises the following components in parts by weight:

[0121]

[0122] Preparation method of curing pattern:

[0123] The components of the positive photosensitive resin composition are fully dissolved to obtain a colloid with a solid content of 30%. The colloid is spin-coated on a 4-inch silicon wafer, the rotation speed is adjusted, and the photosensitive film with a specific film thickness is formed after baking at 120°C for 3 minutes on a contact hot plate. The pattern is exposed using a UV mercury lamp exposure machine with a power of 200W, and developed in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 350°C for 1 hour at a heating rate of 5°C per minute from room temperature, the temperature is lowered to 200°C at a rate of 2°C per minute, and then lowered to room temperature at 5°C per minute to obtain a 7um cured film. The development rate is measured. The film retention rate was 91%, with no residue and no cracking. The specific results are shown in Table 1.

[0124] Example 8

[0125] A positive photosensitive resin composition comprises the following components in parts by weight:

[0126]

[0127] Preparation method of curing pattern:

[0128] The components of the positive photosensitive resin composition are fully dissolved to obtain a colloid with a solid content of 30%. The colloid is spin-coated on a 4-inch silicon wafer, the rotation speed is adjusted, and the photosensitive film with a specific film thickness is formed after baking at 120°C for 3 minutes on a contact hot plate. The pattern is exposed using a UV mercury lamp exposure machine with a power of 200W, and developed in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 350°C for 1 hour at a heating rate of 5°C per minute from room temperature, the temperature is lowered to 200°C at a rate of 2°C per minute, and then lowered to room temperature at 5°C per minute to obtain a 7um cured film. The development rate is measured. The film retention rate was 89%, with no residue and no cracking. The specific results are shown in Table 1.

[0129] Example 9

[0130] A positive photosensitive resin composition comprises the following components in parts by weight:

[0131]

[0132] Preparation method of curing pattern:

[0133] The components of the positive photosensitive resin composition are fully dissolved to obtain a colloid with a solid content of 30%. The colloid is spin-coated on a 4-inch silicon wafer, the rotation speed is adjusted, and the photosensitive film with a specific film thickness is formed after baking at 120°C for 3 minutes on a contact hot plate. The pattern is exposed using a UV mercury lamp exposure machine with a power of 200W, and developed in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 350°C for 1 hour at a heating rate of 5°C per minute from room temperature, the temperature is lowered to 200°C at a rate of 2°C per minute, and then lowered to room temperature at 5°C per minute to obtain a 7um cured film. The development rate is measured. The film retention rate is 83%, there is absolutely no residue, and there is absolutely no cracking. The specific results are shown in Table 1.

[0134] Example 10

[0135] A positive photosensitive resin composition comprises the following components in parts by weight:

[0136]

[0137] Preparation method of curing pattern:

[0138] The components of the positive photosensitive resin composition are fully dissolved to obtain a colloid with a solid content of 30%. The colloid is spin-coated on a 4-inch silicon wafer, the rotation speed is adjusted, and the photosensitive film with a specific film thickness is formed after baking at 120°C for 3 minutes on a contact hot plate. The pattern is exposed using a UV mercury lamp exposure machine with a power of 200W, and developed in a TMAH 2.38% solution. After curing at a heating rate of 5°C per minute from room temperature to 180°C for 0.5 hours and 350°C for 1 hour, the temperature is lowered to 200°C at a rate of 2°C per minute, and then lowered to room temperature at a rate of 5°C per minute to obtain a 7um cured film. The measured development rate is The film retention rate was 87%, with no residue and no cracking. The specific results are shown in Table 1.

[0139] Comparative Example 1

[0140] A positive photosensitive resin composition comprises the following components in parts by weight:

[0141]

[0142] Preparation method of curing pattern:

[0143] Fully dissolve each component of the above positive photosensitive resin composition to prepare a colloid with a solid content of 30%. Spin-coat the above colloid on a 4-inch silicon wafer, adjust the rotation speed, and bake it on a contact hot plate at 120 °C for 3 minutes to form a photosensitive film with a specific film thickness. Use a UV mercury lamp exposure machine with a power of 200 W for pattern exposure, develop it in a 2.38% TMAH solution, heat it from room temperature at a heating rate of 5 °C per minute through 180 °C for 0.5 hours and 350 °C for 1 hour for curing, then cool it to 200 °C at a rate of 2 °C per minute, and then cool it to room temperature at a rate of 5 °C per minute to obtain a cured film with a thickness of 7 μm, and measure the development rate The film retention rate is 81%, the residue is less than 1 / 4 of the opening area, and the crack is less than 1 / 3 of the opening spacing. The specific results are shown in Table 1.

[0144] Comparative Example 2

[0145] A positive photosensitive resin composition, comprising the following components in parts by mass:

[0146]

[0147] Preparation method of the cured pattern:

[0148] Fully dissolve each component of the above positive photosensitive resin composition to prepare a colloid with a solid content of 30%. Spin-coat the above colloid on a 4-inch silicon wafer, adjust the rotation speed, and bake it on a contact hot plate at 120 °C for 3 minutes to form a photosensitive film with a specific film thickness. Use a UV mercury lamp exposure machine with a power of 200 W for pattern exposure, develop it in a 2.38% TMAH solution, heat it from room temperature at a heating rate of 5 °C per minute through 180 °C for 0.5 hours and 350 °C for 1 hour for curing, then cool it to 200 °C at a rate of 2 °C per minute, and then cool it to room temperature at a rate of 5 °C per minute to obtain a cured film with a thickness of 7 μm, and measure the development The film retention rate is 81%, there is no residue at all, and the crack is greater than 1 / 3 of the opening spacing. The specific results are shown in Table 1.

[0149] Comparative Example 3

[0150] A positive photosensitive resin composition, comprising the following components in parts by mass:

[0151]

[0152]

[0153] Preparation method of the cured pattern:

[0154] Dissolve each component of the above positive photosensitive resin composition sufficiently to prepare a colloid with a solid content of 30%. Spin-coat the above colloid on a 4-inch silicon wafer, adjust the rotation speed, and bake it on a contact hot plate at 120 °C for 3 minutes to form a photosensitive film with a specific film thickness. Use a UV mercury lamp exposure machine with a power of 200 W for pattern exposure, develop it in a 2.38% TMAH solution, heat from room temperature to 180 °C at a heating rate of 5 °C per minute, cure at 180 °C for 0.5 hour and 350 °C for 1 hour, then cool to 200 °C at a rate of 2 °C per minute, and further cool to room temperature at a rate of 5 °C per minute to obtain a cured film with a thickness of 7 μm, and measure the development The film retention rate is 81%, there is no residue at all, and the crack is less than 1 / 3 of the opening spacing. The specific results are shown in Table 1.

[0155] Comparative Example 4

[0156] A positive photosensitive resin composition comprising the following components in parts by mass:

[0157]

[0158] Preparation method of the cured pattern:

[0159] Dissolve each component of the above positive photosensitive resin composition sufficiently to prepare a colloid with a solid content of 30%. Spin-coat the above colloid on a 4-inch silicon wafer, adjust the rotation speed, and bake it on a contact hot plate at 120 °C for 3 minutes to form a photosensitive film with a specific film thickness. Use a UV mercury lamp exposure machine with a power of 200 W for pattern exposure, develop it in a 2.38% TMAH solution, heat from room temperature to 180 °C at a heating rate of 5 °C per minute, cure at 180 °C for 0.5 hour and 350 °C for 1 hour, then cool to 200 °C at a rate of 2 °C per minute, and further cool to room temperature at a rate of 5 °C per minute to obtain a cured film with a thickness of 7 μm, and measure the development The film retention rate is 76%, there is no residue at all, and the crack is less than 1 / 3 of the opening spacing. The specific results are shown in Table 1.

[0160] The development rates and film retention rates of the photoresists in the above Examples 1-10 and Comparative Examples 1-4, as well as the residue and cracking results of the photolithography patterns, are shown in Table 1 below.

[0161] Measurement method of the development rate: Immerse the exposed film in a 2.38% aqueous TMAH solution until the bottom substrate is exposed, record the elapsed time as t, then the development rate ADR is the film thickness T / development time t.

[0162] When developing Good, indicated by "○"; Medium, indicated by "△"; Poor, indicated by "×"

[0163] Measurement method of film retention rate: Based on the boundary where the exposed area is just revealed after development, and the residual film thickness T1 at the unexposed area after development, the film retention rate after development is T1 / the original film thickness T.

[0164] Measurement method of residue: Observe under a microscope after curing

[0165] Completely no residue, good, represented by "○"; residue less than 1 / 4 of the opening area, medium, represented by "△"; residue greater than 1 / 4 of the opening area, poor, represented by "×".

[0166] Measurement method of cracking: Observe under a microscope after curing

[0167] Completely no cracking, good, represented by "○"; cracks less than 1 / 3 of the opening spacing, medium, represented by "△"; cracks greater than 1 / 3 of the opening spacing, poor, represented by "×".

[0168] Table 1

[0169]

[0170] Compared with Comparative Example 1, in Example 2 under the same conditions of the alkaline polymer resin, two crosslinking compounds B2 and B3 and two phenolic diazonaphthoquinone sulfonate compounds C1 and C2 were used in Example 2, while one crosslinking compound B2 and one phenolic diazonaphthoquinone sulfonate compound C1 were used in Comparative Example 1. The film retention rate of Example 2 was 89%, and there was no cracking. The film retention rate of Comparative Example 1 was 81%, and cracking with cracks less than 1 / 3 of the opening spacing occurred. Similarly, there were also comparisons between Example 1 and 2 with Comparative Example 2, Example 3 with Comparative Example 1, Example 7 with Comparative Example 3, and Example 9 and 10 with Comparative Example 4. Three crosslinking compounds and two phenolic diazonaphthoquinone sulfonate compounds were used in Example 6, and the effect was also better than that of Comparative Examples 1 - 4.

[0171] It can be seen from Examples 1 - 10 and Comparative Examples 1 - 4 that the film retention rates of Examples 1 - 10 are all higher than those of Comparative Examples 1 - 4, up to 94% at most, and there is no cracking in the lithography patterns of Examples 1 - 10, while there are cracks in the photoresist patterns of Comparative Examples 1 - 4.

[0172] Therefore, by using two or more different crosslinking compounds and simultaneously combining two different phenolic diazonaphthoquinone sulfonate compounds, the prepared positive - type photosensitive resin composition has a good development rate during the development process after exposure, and has a high film retention rate of the dark film after development and forms a cured film without cracking.

Claims

1. A positive photosensitive resin composition, characterized in that, Comprising: (A)An alkali-soluble resin polymer; (B)A crosslinking compound, which comprises at least two of a first crosslinking compound, a second crosslinking compound and a third crosslinking compound; The first crosslinking compound is an ether compound containing melamine or glycoluril, the second crosslinking compound is an epoxy compound containing a benzene structure or an alicyclic hydrocarbon structure or a cyanuric acid structure, and the third crosslinking compound is a vinyl ether compound containing a hydrocarbon structure or an alicyclic hydrocarbon structure; And (C)A phenolic diazonaphthoquinone sulfonate, which comprises a first phenolic diazonaphthoquinone sulfonate and a second phenolic diazonaphthoquinone sulfonate; the esterification degree of the first phenolic diazonaphthoquinone sulfonate is 10% - 90%, and the esterification degree of the second phenolic diazonaphthoquinone sulfonate is 0 or 30 - 90%; a1)The first crosslinking compound is selected from at least one of the following general structural formulas, (B-1), (B-2) Among them, in formula B-1, R1, R2, R3 and R4 are each independently selected from C1-C6 alkyl groups; in formula B-2, R5, R6, R7, R8, R9 and R 10 are each independently selected from C1-C6 alkyl groups; a2)The second crosslinking compound is selected from at least one of the following general structural formulas, (B-3), (B-4), （B-5） Among them, in formula B-3, R 11 and R 12 are each independently selected from a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; in formula B-4, M is a cycloalkyl group having 5 to 7 carbon atoms; in formula B-5, R 13 , R 14 and R 15 are each independently selected from an epoxy group structure or an alkyl group having 1 to 6 carbon atoms, and at least one of R 13 , R 14 and R 15 is an epoxy group structure; a3)The third crosslinking compound is selected from at least one of the following general structural formulas, (B-6), (B-7) In formula B-6, R 16 is an alkylene group selected from C1 to C6, 1 ≤ m ≤ 5; in formula B-7, N is a C5 to C 10 cycloalkyl group; c1)The first phenolic diazonaphthoquinone sulfonate is an ester of a phenolic resin and 2,1,4-diazonaphthoquinone sulfonyl chloride, and the phenolic resin is a polymer selected from one or more of the following phenol structures, , , , , where a, b, c, and d are all positive integers greater than or equal to 3 and less than or equal to 10, and the dashed lines represent bonding keys; c2)The second phenolic diazonaphthoquinone sulfonate is an ester of α,α,α''-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene and 2,1,5-diazonaphthoquinone sulfonyl chloride.

2. The positive photosensitive resin composition according to claim 1, wherein The mass ratio of the (A)alkali-soluble resin polymer, (B)crosslinking compound and (C)phenolic diazonaphthoquinone sulfonate is 100:(3 - 15):(20 - 35).

3. The positive photosensitive resin composition according to claim 1, wherein The crosslinking compound further comprises at least one of the following technical features: b1)The first crosslinking compound is specifically selected from at least one of the following structures 、 、 ； b2)The second crosslinking compound is specifically selected from at least one of the following structures 、 、 、 、 、 ； b3)The third crosslinking compound is specifically selected from at least one of the following structures 、 、 、 、 。 4. The positive photosensitive resin composition according to claim 1, wherein The alkali-soluble resin polymer is selected from the following general structural formula, Among them, the X1 is selected from at least one of a benzene ring structure and a siloxane structure, and the Y1 is selected from at least one of a benzene ring structure and a polyether structure; the R 15 and R 16 are each independently selected from a hydrogen atom, a C1-C6 alkyl group, and an acetal structure; 0 ≤ p ≤ 2, 0 ≤ q ≤ 2, and p + q > 0.

5. The positive photosensitive resin composition according to claim 4, characterized in that, The alkali-soluble resin polymer further comprises at least one of the following technical features: d1)X1 is selected from at least one of the following structures, 、 、 、 、 、 、 、 、 、 、 ， wherein, the dotted line represents a bonding bond; d2)Y1 is selected from at least one of the following structures, 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ， wherein, the dotted line represents a bonding bond.

6. The positive photosensitive resin composition according to any one of claims 1-5, characterized in that It further comprises a solvent.

7. A method for preparing a cured pattern, characterized in that, Coat the positive photoresist composition according to any one of claims 1 - 6 on a substrate, and obtain a cured pattern through baking, exposure, development and curing.

8. The method for preparing a cured pattern according to claim 7, wherein It further comprises at least one of the following technical features: e1)The temperature of the baking is 80 - 120°C; e2)The time of the baking is 1 - 10 min; e3)The exposure uses a 200W ultraviolet mercury lamp exposure machine; e4)The developer uses a 2.38% aqueous solution of tetramethylammonium hydroxide; e5)The temperature of the curing is 160 - 400°C; e6)The time of the curing is 1 - 3 hours; e7)The thickness of the cured film is 5 - 20 um.

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