CN116880125A - Positive photosensitive resin composition, use thereof, and metal patterning method using the same - Google Patents

Positive photosensitive resin composition, use thereof, and metal patterning method using the same Download PDF

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Publication number
CN116880125A
CN116880125A CN202310693308.8A CN202310693308A CN116880125A CN 116880125 A CN116880125 A CN 116880125A CN 202310693308 A CN202310693308 A CN 202310693308A CN 116880125 A CN116880125 A CN 116880125A
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China
Prior art keywords
group
weight
parts
resin composition
positive photosensitive
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CN202310693308.8A
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Chinese (zh)
Inventor
马文杰
晏凯
杨遇春
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Huizhou City Appearance Photosensitive Technology Co ltd
Shenzhen Rongda Photosensitive Science & Technology Co ltd
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Huizhou City Appearance Photosensitive Technology Co ltd
Shenzhen Rongda Photosensitive Science & Technology Co ltd
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Priority to CN202310693308.8A priority Critical patent/CN116880125A/en
Publication of CN116880125A publication Critical patent/CN116880125A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking

Abstract

The invention relates to a positive photosensitive resin composition, which comprises the following components: an alkali-soluble resin, (B) a photosensitive compound, (C) an imidazole compound, (D) a solvent, (E) an adhesion promoter, and (F) a surfactant, wherein the amount of components (B) - (F) is 100 parts by weight based on the component (A), wherein the alkali-soluble resin has a weight average molecular weight of 1,000 to 10,000, preferably 1,000 to 5,000, more preferably 2,000 to 5,000, and most preferably 2,900 to 4,000. The invention also provides a method for patterning the positive photosensitive resin composition and the use of the positive photosensitive resin composition for metal patterning in semiconductor preparation. The resin composition of the present invention improves the adhesion between the resin composition and a substrate.

Description

Positive photosensitive resin composition, use thereof, and metal patterning method using the same
Technical Field
The present invention relates to the field of photoresists, and more particularly, to a positive photosensitive resin composition, particularly a positive photosensitive resin composition containing an imidazole compound, uses thereof, and a metal patterning method using the same.
Background
In recent years, with the rapid development of the manufacture of semiconductor integrated circuit devices, liquid crystal display devices of thin film transistors, or touch panels, photoresists have played an increasingly important role in these fields as key functional materials in the process of fine pattern lithography. In general, after the photoresist is subjected to ultraviolet radiation, a series of chemical reactions occur, so that the dissolution rate of the photoresist in a specific developer before and after exposure changes, and then a series of processes such as development, hardening (making the film denser), wet etching or dry etching or ion implantation, photoresist removal and the like are performed, so that the fine pattern designed by the mask plate is transferred onto a target substrate (substrate). In this photolithographic manufacturing process, pattern transfer by wet etching is one of means for achieving fine processing using a positive photosensitive resin composition. Although having cost and efficiency advantages, the main problems are the following: 1) Patterns of submicron order cannot be etched out accurately; 2) The metal edge is rough or has burr defects after corrosion; 3) The thicker the etch, the greater the lateral etch width of the substrate will be due to the lateral etch problem of wet etching. The adhesion of the photoresist to the substrate surface is therefore decisive for the etching process.
While photoresists currently typically employ the addition of multifunctional organic amines and metal-coordinating amines to improve the adhesion of the photoresist to the substrate. However, such components generally have only a good effect on improving the adhesion of the photoresist to the metal surface, while there is limited improvement in the surface adhesion to a range of hydrophilic substrates such as silicon oxide, silicon nitride.
In addition, polyurethane resins with different etherification degrees are adopted in the prior art to improve the adhesiveness of photoresist on an oxide layer, for example, etherified melamine resin is added into a positive photosensitive resin composition, and the positive photosensitive resin composition of the system has ultrahigh adhesiveness on the surface of a hydrophilic film layer which is not treated by Hexamethyldisilazane (HMDS) under the action of acids such as organic strong acid and the like and is subjected to pre-curing by heating. Because etherified melamine resin is easy to be used as a crosslinking center, and forms crosslinking with organic components of photoresist under the action of acid and temperature, the photoresist cannot be completely stripped after etching, and the problem of residual photoresist occurs.
Commercially available positive photosensitive resin compositions require hexamethyldisilazane treatment of the coated hydrophilic film prior to spin coating to improve surface oleophobicity, i.e., to improve adhesion of the photoresist to the substrate. If the processing is not carried out, the problems of gel bleaching in the developing process or serious undercutting in the wet etching process and the like are easy to occur. HMDS, however, is extremely toxic and can be stored and replaced with a risk of environmental pollution and personal injury.
There is therefore a need for a positive photosensitive resin composition with improved substrate adhesion that allows improved adhesion, i.e., some adhesion between the photoresist film layer and the different hydrophilic substrate/film layers, without the use of HMDS to treat the substrate. However, the adhesion cannot be too strong, and excessive tackifying can cause the problems of wrinkling, cracking, residue after the development of the adhesive film, incapability of completely demolding after etching, reduced placement stability of the photoresist and the like.
Disclosure of Invention
In order to solve the above problems, the present invention provides a positive photosensitive resin composition comprising:
(A) An alkali-soluble resin, 100 parts by weight,
(B) 5 to 50 parts by weight, preferably 10 to 20 parts by weight,
(C) Imidazole compound, 0.5 to 10 parts by weight, preferably 1.0 to 5 parts by weight, more preferably 1.67 to 4 parts by weight,
(D) 150 to 350 parts by weight, preferably 200 to 300 parts by weight,
(E) 1 to 5 parts by weight, preferably 1.5 to 2.5 parts by weight, of an adhesion promoter,
(F) Surfactants, from 0.1 to 0.5 part by weight, preferably from 0.2 to 0.4 part by weight,
wherein the amounts of components (B) - (F) are based on 100 parts by weight of component (A),
wherein the alkali soluble resin has a weight average molecular weight of 1,000 to 10,000, preferably 1,000 to 5,000, more preferably 2,000 to 5,000, most preferably 2,900 to 4,000, wherein the weight average molecular weight is determined according to GB/T21863-2008 using polystyrene as a standard curve.
In another aspect of the present invention, there is provided a method of patterning a photoresist, comprising the steps of:
(i) Uniformly coating the positive photosensitive resin composition on a substrate to form a photoresist film, and baking at 80-120 ℃ for 10-180 seconds to obtain a film thickness of 0.5-15 μm, preferably 1.0-2.5 μm;
(ii) Subjecting the adhesive film obtained in (i) to partial irradiation;
(iii) Developing the photoresist film obtained in (ii) with a developing solution, which is an alkaline solution, and washing with ultrapure water;
(iv) The developed photoresist was baked at a temperature of 100 to 150 c for 1 to 40 minutes to make the hardening more complete.
Still another aspect of the present invention relates to the use of the positive photosensitive resin composition described above for metal patterning in semiconductor manufacturing.
The positive photosensitive resin composition of the present invention can improve the adhesion between the positive photosensitive resin composition and a substrate.
Detailed Description
In the present invention, unless otherwise indicated, all operations are carried out at room temperature and pressure.
Alkali-soluble resin (A)
The alkali-soluble resin (A) includes a novolak resin (A-1) and other novolak resins (A-2). More specifically, the novolak-based polymer may be a copolymer represented by formula (1), and the novolak resin (a-1) and other novolak resins (a-2) are described in detail below:
Wherein m and n represent the degree of polymerization of the respective repeating units, wherein m: n=1:9 to 9:1
Novolak resin (A-1)
The method for producing the novolak resin (A-1) is not particularly limited, and any method capable of obtaining the novolak resin (A-1) having a target weight average molecular weight and molecular weight distribution may be used, wherein the novolak resin (A-1) is preferably a condensate of a phenolic compound with an aldehyde or ketone compound, polyhydroxystyrene and a derivative.
In the present invention, the phenolic compound used for preparing the novolak resin (A-1) may be phenol, o-cresol, m-cresol, p-cresol, 2, 3-xylenol, 2, 5-xylenol, 3, 4-xylenol and other xylenols; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3, 5-trimethylphenol, 2,3, 5-triethylphenol, 2-t-butylphenol, 2-t-butyl-5-methylphenol and other alkylphenols; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol and other alkoxyphenols; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropenylphenol and other isopropenylphenols; phenylphenol, alpha-naphthol, beta-naphthol, and other aryl phenols; bisphenol A, m-benzenediol, p-benzenediol, 4' -dihydroxybiphenyl and other polyhydric phenols, which may be used alone or in combination; phenol, o-cresol, m-cresol, p-cresol, 2, 3-xylenol, 2, 5-di-methylphenol and/or 3, 5-di-methylphenol are preferred, with m-cresol and/or p-cresol being more preferred.
In the present invention, the aldehyde compound used for preparing the novolak resin (a-1) may be formaldehyde, paraformaldehyde, trioxymethylene, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexane formaldehyde, furan-based acrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α -phenylpropionaldehyde, β -phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, among which formaldehyde compounds is preferred particularly for improving heat resistance and economy.
In the present invention, the ketone compound used for preparing the novolak resin (A-1) may be acetone, methyl ethyl ketone, diethyl ketone and benzophenone, and the above compounds may be used alone or in combination. In addition, an appropriate combination of aldehyde compounds and ketone compounds may be used.
In some preferred embodiments of the present invention, the weight average molecular weight of the novolak resin (a-1) is preferably 1,000 to 30,000, more preferably 2,000 to 10,000, most preferably 3000 to 7000, and the dispersity (weight average molecular weight Mw/number average molecular weight Mn) is 1.0 to 8.0, more preferably 3.0 to 7.0.
In the present invention, the acid catalyst used for preparing the novolak resin (a-1) may be phosphoric acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, carboxylic acid, organic phosphoric acid, etc., but the present invention is not limited thereto, and the above-mentioned compounds may be used singly or in combination of plural kinds.
In the method for producing a novolak resin (A-1) of the present invention, the water content is preferably less than 40% by weight in order to improve the productivity. The reaction temperature of the phenol and the aldehyde is preferably 40 ℃ to the reflux temperature, more preferably 60 ℃ to the reflux temperature, and most preferably the reflux temperature. The reaction time should be maintained between 1 hour and 30 hours. In addition, the reaction may be carried out under normal pressure, preferably under conditions of increased pressure or reduced pressure.
The content of the novolak resin (a-1) is 30 to 100 parts by weight, preferably 35 to 90 parts by weight, more preferably 40 to 70 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (a).
Other novolak resins (A-2)
The preparation of the other novolak resin (A-2) is carried out similarly to the preparation of the novolak resin (A-1), except that the other novolak resin (A-2) obtained has a dispersity of 1.0 to 4.0, preferably 1.5 to 3.0, and a weight average molecular weight thereof is preferably 1,000 to 15,000, more preferably 1,000 to 5,000, and most preferably 1,000 to 3,000.
The content of the other novolak resin (a-2) is 0 to 70 parts by weight, preferably 10 to 65 parts by weight, more preferably 30 to 60 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (a).
In some preferred embodiments of the invention, the weight ratio of the two novolac resins is 20:80 to 60:40, preferably 30:70 to 50:50.
In some preferred embodiments of the invention, the weight ratio of the two novolak resins is 50:50.
In some preferred embodiments of the present invention, the alkali soluble resin (a) used in the composition of the present invention has a weight average molecular weight Mw of 1,000 to 10,000, preferably 1,000 to 5,000, more preferably 2,000 to 5,000, more preferably 2,900 to 4,000, most preferably 3,000 to 4,000, as determined according to GB/T21863-2008 using polystyrene as a standard curve.
Photosensitive compound (B)
The photosensitive compound (B) is a photosensitive compound which generates chemical reaction under the irradiation of ultraviolet rays or radiation, and the component (B) is an esterified compound of a 1, 2-naphthoquinone diazide sulfonic acid compound which is conventionally used in the field. In a preferred embodiment of the present invention, the esterified product (B) of 1, 2-naphthoquinone diazide sulfonic acid may be an esterified product formed by reacting 1, 2-naphthoquinone diazide sulfonic acid such as 1, 2-naphthoquinone diazide-4-sulfonate or 1, 2-naphthoquinone diazide-5-sulfonate with a polyhydric phenol compound. The esters of the above 1, 2-naphthoquinone diazide sulfonic acids may be fully or partially esterified. The kind of the aforementioned hydroxyl compound (hereinafter also referred to as b) may be, for example: hydroxybenzophenones (b-1).
In some embodiments of the present invention, the hydroxybenzophenones (b-1) may be 2,3, 4-trihydroxybenzophenone, 2,4 '-trihydroxybenzophenone, 2,4, 6-trihydroxybenzophenone, 2',3, 4-tetrahydroxybenzophenone, 2,3', 4', 6-pentahydroxybenzophenone, 2',3, 4' -pentahydroxybenzophenone, 2',3,4,5' -pentahydroxybenzophenone. The above-mentioned hydroxy compound is preferably 2,3, 4-trihydroxybenzophenone, 2',3, 4-tetrahydroxybenzophenone. The above-mentioned hydroxyl compounds may be used alone or in combination.
The esterified product of the 1, 2-naphthoquinone-diazide sulfonic acid compound as the component (B) of the present invention can be obtained by condensation reaction of a quinone diazide group-containing compound such as 1, 2-naphthoquinone diazide-4 (or 5) -sulfonic acid halide salt with the above-mentioned (B-1) hydroxy compound, and can be completely esterified or partially esterified. The condensation reaction is usually carried out in an organic solvent such as dioxane, N-methylpyrrolidone or dimethylacetamide, preferably in the presence of an alkaline condensing agent such as triethanolamine, an alkali metal carbonate or an alkali metal hydrogencarbonate.
In some preferred embodiments of the present invention, preferably 20 mol% or more, more preferably 20 mol% or more and 80 mol% or less of hydroxyl groups are condensed with 1, 2-naphthoquinone-diazide-4 (or 5) sulfonate based on 100 mol% of the total hydroxyl groups in the hydroxyl compound to form an esterified product, that is, the degree of esterification is preferably 20 to 80%, and if the average degree of esterification is less than 20%, the film residue ratio and clarity in the unexposed region are significantly reduced. If the average degree of esterification is more than 80%, both photosensitivity and solubility are lowered.
In the embodiment of the present invention, the photosensitive compound (B) of the present invention is used in an amount of usually 5 to 50 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). If the proportion of the component (B) is less than the above range, an image completely conforming to the mask plate cannot be obtained, and the film retention rate in the non-exposed region is poor. In contrast, if the ratio exceeds the above-described specific range, both the photosensitivity of the photoresist and the line uniformity are deteriorated, resulting in a decrease in resolution.
Imidazole compounds (C)
In the present invention, an imidazole-based compound is used to improve the adhesion between the positive photosensitive resin composition and the substrate. In addition, the imidazole compound is very advantageous in terms of stability of the resin composition. In the general environment, the imidazole compound does not cause the resin composition to generate cross-linking polymerization, so that the problem of difficult demolding does not exist.
The imidazole compound as the component (C) may be a compound of the following formulas (4) to (9).
Wherein, the liquid crystal display device comprises a liquid crystal display device,
r1 is a hydrogen atom, or an alkyl group having at least 1 polar functional group selected from the group consisting of a hydroxyl group, a carbonyl group, an ester group, an ether group, a thioether group, a carbonate group, a cyano group, and an acetal group and having 2 to 20 carbon atoms;
R 2 、R 3 R is R 4 Each independently is a hydrogen atom, C 1 -C 10 Alkyl, aryl or C 7 -C 10 An arylalkyl group;
R 5 、R 7 、R 9 r is R 13 Each independently is a saturated alkylene group having 1 to 10 carbon atoms;
R 6 r is R 8 Each independently is a hydrogen atom or C 1 -C 15 An alkyl group which may contain at least 1 polar functional group selected from the group consisting of a hydroxyl group, a carbonyl group, an ester group, an ether group, a thioether group, a carbonate group, a cyano group, and an acetal group;
R 10 is C 1 -C 15 An alkyl group which may contain at least 1 polar functional group selected from the group consisting of a hydroxyl group, a carbonyl group, an ester group, an ether group, a thioether group, a carbonate group, a cyano group, and an acetal group;
R 11 saturated or unsaturated C of valence (b+1) 2 -C 10 A hydrocarbon group;
R 12 each independently is a hydrogen atom or C 1 -C 15 Alkyl which may contain at least 1 polar functional group selected from the group consisting of hydroxyl, carbonyl, ester, thioether, carbonate, cyano and acetal groups, 2R 12 Can be bonded to form a ring and can be used for preparing a medicine,
b is 2, 3, 4 or 5.
In some preferred embodiments of the present invention, the imidazole compound (C) is preferably imidazole, 2-methylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-methoxymethylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1-aminoethyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1- (2-hydroxyethyl) imidazole, 1- (carboxymethyl) imidazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole.
In some preferred embodiments of the present invention, the imidazole compound (C) of the present invention is used in an amount of usually 0.5 to 10 parts by weight, preferably 1.0 to 5 parts by weight, more preferably 1.67 to 4 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). Wherein the above-mentioned compounds of the component (C) may be used alone or in combination of 2 or more.
In some preferred embodiments of the present invention, wherein the alkali-soluble resin (A) and the imidazole compound are used in a ratio of 75:1 to 10:1, preferably 60:1 to 25:1.
In some preferred embodiments of the present invention, the ratio of the photosensitive compound to the imidazole compound is from 12:1 to 2.5:1, preferably from 9:1 to 3.75:1.
In a preferred embodiment of the present invention, the amount relationship between the alkali-soluble resin (a) (denoted as m), the imidazole-based compound (C) (denoted as n), and the photosensitive compound (B) (denoted as q) used in the present invention satisfies the formula:
0.080≤n/[mq/(m+q)]≤0.350；
preferably is
0.128≤n/[mq/(m+q)]≤0.307；
More preferably
0.290≤n/[mq/(m+q)]≤0.310；
Wherein m, n and q are the weight parts of the alkali-soluble resin (A), the imidazole compound (C) and the photosensitive compound (B) respectively.
Solvent (D)
The solvent (D) used for the positive photosensitive resin composition of the present invention is an organic solvent which can dissolve the above-mentioned components but does not react with the above-mentioned components.
In some embodiments of the present invention, wherein solvent (D) is, for example, a polyol and its derivatives, esters, ethers, ketones, aromatic hydrocarbons, amides, or combinations thereof.
Specific examples of polyols and their derivatives include ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, or monomethyl, monoethyl, monopropyl, monobutyl or monophenyl ether or analogues thereof, or combinations of the foregoing.
Specific examples of esters include ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, or the like, or a combination of the foregoing.
Examples of ethers include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran or the like, or combinations of the foregoing.
Examples of ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, or analogs thereof, or combinations of the foregoing.
Examples of aromatic hydrocarbons include toluene, xylene or the like, or combinations of the foregoing.
Examples of amides include N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide or the like, or combinations of the foregoing. The solvent (D) is preferably propylene glycol methyl ether acetate, lactic acid, cyclohexanone, propylene glycol monomethyl ether, N-methylpyrrolidone, or a combination of the above solvents. The solvent (D) may be used singly or in combination of plural kinds.
In the present invention, the solvent (D) of the present invention is used in an amount of usually 150 to 350 parts by weight, preferably 200 to 300 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A).
Bonding aid (E)
The adhesion promoter is a component that improves adhesion of the obtained cured film to the substrate. The adhesion promoter is preferably a functional silane coupling agent having a reactive functional group such as styrene, methyl propylene, methyl acryl, vinyl, isocyanate, ethylene oxide, amino, or urea.
Examples of the functional silane coupling agent include vinyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, hydrolysis condensate of 3-3 ethoxysilane-N- (1, 3-dimethyl-butylene) propylamino, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, γ -methacryloxypropyltrimethoxysilane, vinyltriacetoxy silane, vinyltrimethoxysilane, γ -isocyanatopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, and β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.
In some preferred embodiments of the present invention, the resin composition of the present invention may contain a bonding aid, which may be used alone or in combination of two or more thereof, wherein the bonding aid is used in an amount of 1 to 5 parts by weight, preferably 1.5 to 2.5 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).
Surfactant (F)
Other auxiliary agents such as surfactants or the like may be further added to the positive photosensitive resin composition of the present invention.
In some preferred embodiments of the present invention, the surfactant is selected from organofluorine modified surfactants, (poly) siloxane-based surfactants, and other surfactants.
In some preferred embodiments of the present invention, the fluorine-based surfactant is preferably a compound having a fluoroalkyl group and/or a fluoroalkylene group in at least one of a terminal, a main chain, and a side chain, for example, 1, 2-tetrafluoro-n-octyl (1, 2-tetrafluoro-n-propyl) ether, 1, 2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethyleneglycol di (1, 2, 3-hexafluoro-n-pentyl) ether, octaethyleneglycol di (1, 2-tetrafluoro-n-butyl) ether hexapropylene glycol bis (1,1,2,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol bis (1, 2-tetrafluoro-n-butyl) ether, sodium perfluoro-n-dodecanesulfonate, 1,2, 3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9, 10, 10-decafluoro-n-dodecane and/or sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerol tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethylene alcohol, perfluoroalkyl alkoxylates, fluoroalkyl carboxylates, and the like. Commercially available fluorosurfactants are, for example, BM-1000, BM01100 (available from BM CHEMIE); megaface F142D, F, F173, F183, F178, F191, F471, F476 (purchased from Dainippon Ink and Chemicals inc.); surflon S-112, SC-102, SC-103, SC104 (from Asahi nitro); eftop EF301, EF303, EF352 (from new autumn chemical company); ftergent FT-100, FT-110, FT-140A, FT-150, FTX-218, FTX-251 (available from NEOS).
In some preferred embodiments of the invention, commercially available (poly) siloxane-based surfactants are, for example, toray silicone DC PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, DC-57, DC-190 (available from Dow Corning Toray Silicone co., ltd.); organosiloxane polymer KP341 (purchased from more belief chemistry); BYK-310, 320, 322, 323, 330, 333, 377, 378, 3760 (from BYK).
Other surfactants which may be used in the present invention are, for example, ammonium salts and organic amine salts of alkyl diphenyl ether disulfonic acids; ammonium salts and organic amine salts of alkyl diphenyl ether sulfonic acids; ammonium salts and organic amine salts of alkylbenzenesulfonic acids; ammonium salts and organic amine salts of polyoxyethylene alkyl ether sulfuric acid; and ammonium salts and organic amine salts of alkyl sulfuric acid.
In some embodiments of the present invention, the resin composition of the present invention may contain a surfactant, which may be used alone or in combination of two or more thereof, in an amount of 0.1 to 0.5 parts by weight, preferably 0.2 to 0.4 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).
The positive photosensitive resin composition of the present invention is prepared by a method known in the art, specifically, by stirring the above-mentioned novolak resin (a), photosensitive compound (B), imidazole compound (C) and solvent (D) in a stirrer to uniformly mix them into a solution, and optionally adding additives such as a binder aid and a surfactant. The obtained uniform solution is filtered to obtain the positive photosensitive resin composition of the invention.
In another aspect of the present invention, there is provided a method of patterning a photoresist, comprising the steps of:
(i) Uniformly coating the positive photosensitive resin composition on a substrate to form a photoresist film, and baking at 80-120 ℃ for 10-180 seconds to obtain a film thickness of 0.5-15 μm, preferably 1.0-2.5 μm;
(ii) Subjecting the adhesive film obtained in (i) to partial irradiation;
(iii) Developing the photoresist film obtained in (ii) with a developing solution, which is an alkaline solution, and washing with ultrapure water;
(iv) The developed photoresist was baked at a temperature of 100 to 150 c for 1 to 40 minutes to make the hardening more complete.
In the method for forming a pattern of a photoresist of the present invention, the foregoing description of the positive photosensitive resin composition applies equally, and the description is not necessarily repeated here.
In some embodiments of the present invention, a coating film is formed on a substrate using the resin composition of the present invention. More specifically, the solution of the resin composition is applied to the substrate surface, and preferably prebaked to remove the solvent, thereby forming a coating film. Suitable substrates include glass substrates, silicon substrates, sapphire substrates, silicon carbide substrates, compound semiconductor substrates, and substrates obtained by forming various metal thin films or oxide thin films on their surfaces.
As a method of applying the positive photosensitive resin composition to the substrate, a coating method conventionally used in the art may be employed, and for example, a spray coating method, a roll coating method, a spin coating method, a slit coating method, a screen printing method, or the like may be employed, and the positive photosensitive resin composition in a solution state is uniformly spread on the substrate and prebaked via a hot plate. The conditions for the preliminary baking may be adjusted according to the types and the ratios of the components used.
In a preferred embodiment of the present invention, in step (i), the coating film formed therein may be prebaked by heating. The heating method is not particularly limited, and for example, a hot plate may be used to prebake the film, the prebake temperature being 80℃to 120℃and the bake time being 10 seconds to 180 seconds, a photoresist film layer of 0.5 μm to 15 μm, preferably 1.0 to 2.5 μm may be obtained. In another preferred embodiment of the invention, a contact hotplate may also be used for pre-baking.
In a preferred embodiment of the present invention, in step (ii), a portion of the photoresist film formed in step (i) is irradiated with radiation, specifically, the coating film formed in step (i) is irradiated with radiation from a mask having a specific pattern. Preferably, the radiation is ultraviolet, for example, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm); deep ultraviolet light (248 nm for KrF excimer laser, 193nm for ArF excimer laser) or X-rays. Rays comprising g-line, h-line and i-line are preferred. The ultraviolet radiation device can be a (ultra) high pressure mercury lamp or a metal halogen lamp. The exposure amount as a ray was 0.1J/m 2 To 10000J/m 2 。
In a preferred embodiment of the present invention, in step (iii), the coating film irradiated with rays in step (ii) is developed. Specifically, the portion irradiated with the radiation in step (ii) is removed by development with a developer (positive resist). In the present invention, the positive photosensitive resin composition is a photoresist material of novolak resin/ester system of o-naphthoquinone diazide sulfonic acid, and the ester (B) of o-naphthoquinone diazide sulfonic acid is used as photosensitive active ingredient, after patterning ultraviolet exposure to photoresist, small-molecule carboxylic acid can be generated so that the dissolution rate of the exposed area in alkaline developer is greatly increased. Among the suitable developing solutions useful in the present invention are inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, ammonia or the like; primary amines of ethylamine, n-propylamine or analogs thereof; multistage amines of diethylamine, diethylaminoethanol, di-n-propylamine, trimethylamine, triethylamine, methyldiethylamine or analogues thereof; dimethylethanolamine, diethylethanolamine, triethanolamine or similar amino alcohols thereof; quaternary ammonium hydroxides such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, triethylammonium hydroxide, trimethylammonium hydroxide, or the like; aqueous solutions of bases (basic compounds) such as pyrrole, piperidine, 1, 8-diazabicyclo [ 5.4.0 ] -7-undecene, and 1, 5-diazabicyclo [ 4.3.0 ] -5-nonane. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and/or a surfactant to the aqueous solution of the above base, or an aqueous alkali solution containing a small amount of various organic solvents in which the positive photosensitive resin composition of the present invention can be dissolved may be used as a developer.
In a preferred embodiment of the present invention, suitable development methods of the present invention are, for example, spin-coating immersion, dipping, shaking immersion, spraying. The development time in the present invention may be determined according to the dissolution rate of the negative photosensitive resin composition of the present invention in the developing solution, and may be, for example, 30 to 120 seconds.
In some preferred embodiments of the present invention, after developing the photoresist, the patterned coating film is preferably subjected to a cleaning process by running water washing, and then spin-drying the moisture on the surface of the coating film at a high speed. Then, the coating film is subjected to a Hard baking treatment (Hard cake) using a heating device such as a hot plate or an oven. The hard bake temperature is generally 100 to 150 ℃, wherein the heating time using a hot plate is 1 to 60 minutes, and the heating time using an oven is 5 to 40 minutes. After the steps, a pattern corresponding to the mask plate can be formed on the substrate.
The invention also provides the use of the positive photosensitive resin composition of the invention for metal patterning in semiconductor manufacturing.
Advantageously, using the positive photosensitive resin composition of the present invention, adhesion between the resin composition and the substrate can be improved.
Examples
Synthesis of alkali-soluble resin (A-1)
A four-necked flask was equipped with a stirrer, a thermometer, an air-guide tube, and a reflux condenser, and the flask was placed in a constant-temperature oil bath and held stationary with an iron stand. 108g of m-methylphenol, 54g of p-methylphenol, 48g of 37% formaldehyde aqueous solution and 0.71g of oxalic acid dihydrate are weighed, nitrogen is introduced into a reaction bottle under stirring, the reaction solution is heated to 60 ℃ to start condensation reaction, the temperature is slowly increased for 3 hours, and then the reaction solution flows back. After the reflux temperature time was maintained for 8 hours. While stirring was continued, 500mL of methyl isobutyl ketone was added to dissolve the condensate, and then the stirring was stopped to transfer the solution into a separation flask and left to stand, whereby the methyl isobutyl ketone solution (upper layer) was separated from the oxalic acid dihydrate solution (lower layer). After removing the aqueous oxalic acid dihydrate solution, the methyl isobutyl ketone solution was repeatedly washed with pure water 5 times (60 mL of water each time) to completely remove oxalic acid dihydrate, and the reaction solution was distilled in vacuo to remove the methyl isobutyl ketone solvent. When the reaction liquid reached 222 ℃, the system was depressurized to 7mmHg and distilled to remove unreacted monomeric phenol, and when the reaction liquid reached 228 ℃, the distillation was ended, and the reaction liquid was placed in a stainless steel tank under nitrogen protection and cooled until 160.46g of a yellow transparent solid resin (A-1) was obtained, wherein Mw=5000 and Mw/Mn=5.0.
Synthesis of alkali-soluble resin (A-2)
The same procedure as for the synthesis of the alkali-soluble resin (A-1) was carried out, except that the kind of the catalyst used and the reaction time were changed, and the molecular weight distribution were different. Wherein 81.0g of methylphenol, 81.0g of p-methylphenol, 48.0g of aqueous formaldehyde solution, 17.0g of 89.0% aqueous phosphoric acid solution and 7.0g of tartaric acid were weighed out and the reflux temperature was maintained for 10 hours, 129.72g of yellow transparent solid resin (a-2) was obtained, with mw=2000, mw/mn=2.2.
Preparation of photosensitive Compound (B-1)
The hydroxy compounds 2,3, 4-trihydroxybenzophenone (available from national pharmaceutical systems chemical reagent Co., ltd.) can be all esterified with naphthoquinone diazide sulfonic acid by conventional methods. Specifically, 11.5g of 2,3, 4-trihydroxybenzophenone and 36.54g of naphthoquinone-1, 2-diazide-5-sulfonyl chloride (purchased from Shanghai Baishun Biotechnology Co., ltd.) were dissolved in 450ml of an aqueous acetone solution (the volume ratio of acetone to water was 85:15) at room temperature, reacted for 0.5h under stirring, 18.76ml of triethylamine was slowly added dropwise, and the dropwise addition time was controlled to 1h. After the dripping is finished, stirring and reacting for 4 hours, pouring the reacted solution into ultrapure water with the volume of 10 times, repeatedly washing the solution with the ultrapure water until the solution is neutral after the solid is completely separated out, carrying out suction filtration, and drying at the constant temperature of 40 ℃ until the solid product has constant weight, thus obtaining 46.33g of yellow solid.
Preparation of photosensitive Compound B-2
12.3g of 2,2',3, 4-tetrahydroxybenzophenone (from the company of Chemie, inc. of the group of Chinese medicine) and 51.43g of naphthoquinone-1, 2-diazide-5-sulfonyl chloride were dissolved in 450ml of an aqueous acetone solution (the volume ratio of acetone to water: 85:15) at room temperature, and after stirring, 26.41ml of triethylamine was slowly added dropwise, and the dropwise addition time was controlled to 1 hour. After the dripping is finished, stirring and reacting for 4 hours, pouring the reacted solution into ultrapure water with the volume of 10 times, repeatedly washing the solution with the ultrapure water until the solution is neutral after the solid is completely separated out, carrying out suction filtration, and drying at the constant temperature of 40 ℃ until the solid product has constant weight, thus obtaining 58.75g of yellow solid.
Positive photosensitive resin composition
Example 1
100 parts by weight of the novolak resin (A-1) obtained by the synthesis described above, 15 parts by weight of an ester (B-2) of 2,2',3, 4-tetrahydroxybenzophenone and 1, 2-naphthoquinone diazide-5-sulfonic acid, 1.67 parts by weight of 1-vinylimidazole (C), 250 parts by weight of propylene glycol methyl ether acetate (D), 2 parts by weight of a bonding aid (E) and 0.3 part by weight of a surfactant (F) were mixed and stirred uniformly by a shaking stirrer, whereby a positive photosensitive resin composition of example 1 was obtained. The positive photosensitive resin composition obtained was evaluated in the following manner in terms of the photosensitive speed, critical dimension resolution, adhesion and stability.
Example 2
The positive photosensitive resin composition of example 2 was obtained by uniformly mixing and stirring 100 parts by weight of novolak resin (A-2), 15 parts by weight of ester of 2,3, 4-trihydroxybenzophenone with 1, 2-naphthoquinone diazide-5-sulfonic acid (B-1), 1.67 parts by weight of 1-vinylimidazole (C), 250 parts by weight of propylene glycol methyl ether acetate (D), 2 parts by weight of adhesion promoter (E) and 0.3 part by weight of surfactant (F) with a shaking stirrer.
Example 3
The positive photosensitive resin composition of example 3 was obtained by uniformly mixing 30 parts by weight of the novolak resin (A-1), 70 parts by weight of the novolak resin (A-2), 15 parts by weight of the ester of 2,3, 4-trihydroxybenzophenone with 1, 2-naphthoquinone diazide-5-sulfonic acid (B-1), 4 parts by weight of 1-vinylimidazole (C), 250 parts by weight of propylene glycol methyl ether acetate (D), 2 parts by weight of the adhesion promoter (E) and 0.3 parts by weight of the surfactant (F) with a shaking stirrer, and obtaining the positive photosensitive resin composition of example 3, wherein the Mw of the alkali-soluble resin (A) (namely, 30 parts of novolak resin (A-1) was 2900 as measured by using polystyrene as a standard curve according to GB/T21863-2008 after mixing with 70 parts of novolak resin (A-2).
Example 4
50 parts by weight of the novolak resin (A-1) obtained by the synthesis, 50 parts by weight of the novolak resin (A-2), 15 parts by weight of the ester (B-2) of 2,2',3, 4-tetrahydroxybenzophenone with 1, 2-naphthoquinone diazide-5-sulfonic acid, 4 parts by weight of 1-vinylimidazole (C), 250 parts by weight of propylene glycol methyl ether acetate (D), 2 parts by weight of the adhesion promoter (E) and 0.3 part by weight of the surfactant (F) were mixed and stirred uniformly by a shaker, whereby the positive photosensitive resin composition of example 4 was obtained, in which the alkali-soluble resin (A) (i.e., mw as measured by using polystyrene as a standard curve according to GB/T21863-2008 after 50 parts of the novolak resin (A-1) and 50 parts of (A-2) were mixed) was 3500.
Comparative example 1
100 parts by weight of the novolak resin (A-1) obtained by the synthesis, 15 parts by weight of an ester of 2,3, 4-trihydroxybenzophenone and 1, 2-naphthoquinone diazide-5-sulfonic acid (B-1), 250 parts by weight of propylene glycol methyl ether acetate (D), 2 parts by weight of a bonding aid (E) and 0.3 part by weight of a surfactant (F) were mixed and stirred uniformly by a shaking stirrer, whereby a positive photosensitive resin composition of comparative example 1 was obtained.
Comparative example 2
50 parts by weight of the above-mentioned synthetic novolak resin (A-1), 50 parts by weight of the above-mentioned synthetic novolak resin (A-2), 15 parts by weight of an ester of 2,2',3, 4-tetrahydroxybenzophenone with 1, 2-naphthoquinone diazide-5-sulfonic acid (B-2), 250 parts by weight of propylene glycol methyl ether acetate (D), 2 parts by weight of a bonding aid (E) and 0.3 part by weight of a surfactant (F) were uniformly mixed and stirred by a shaking stirrer to obtain a positive photosensitive resin composition of comparative example 1.
Evaluation method
Speed of sensitization test
The positive photosensitive resin composition of the above example was spin-coated on a single crystal silicon substrate by vapor deposition of HMDS on the single crystal silicon substrate at an atmospheric temperature of 115 ℃ for 60sec, and baked with a hot plate at 90 ℃ for 60sec to form a photoresist film layer having a thickness of about 1.3 μm. The photoresist film layer was then subjected to patterned exposure using ultraviolet light of different radiation doses (exposure model number Nikon NSR-2005i9C, manufactured by Nikon corporation). Then, after baking at 115 ℃ for 60 seconds with a hot plate to eliminate standing wave effect formed in the middle of the photoresist film, the photoresist film layer after the above treatment was developed with 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ℃ for 60 seconds to remove the photoresist film layer in the exposed area on the substrate. After the developed photoresist was subjected to running water washing with ultrapure water for 1 minute, the developed film thicknesses of different exposure amounts were measured by an optical film thickness meter (manufactured by Filmetrics F20, youkang), and the corresponding radiation dose of which the film thickness after development was 0 after the exposure amount was used as a comparison value of the speed of the light sensitivity, and a smaller value represents a faster speed of the light sensitivity and a slower speed of the light sensitivity.
Critical dimension resolution evaluation test
The step of photosensitive speed test was repeated, and finally line width measurement was performed by a scanning electron microscope (scanning electron microscope model Hitachi Hightech S8840) for dense 1:1 line width and line spacing pattern areas (Lines & Spaces). The exposure time (optimal exposure amount, eop) at which the measured dimension and the designed dimension of the mask plate agree can be obtained, and the critical dimension resolution is evaluated according to the minimum measurable line width obtained at the respective Eops as a criterion for evaluating the critical dimension resolution, and according to the following criteria:
A：CD≤1.0μm；
B：1.0μm＜CD≤2.0μm；
C：2.0μm＜CD≤5.0μm；
D：CD>5.0μm。
in the case of a, the resolution was evaluated as excellent, in the case of B, as good, in the case of C, as general, and in the case of D, as bad.
Adhesion evaluation test
The positive photosensitive resin composition of the above example was spin-coated on a silica substrate without HMDS treatment, and baked at 100 ℃ for 90 seconds with a hot plate to form a photoresist film layer having a thickness of about 2.0 μm. Then, 10X 10 small grids of 1mm X1 mm are cut on the surface of the test sample by using a hundred grid knife, and the exposed substrate is cut when the hundred grid knife is cut down. After the hundred grids are drawn, a soft brush is used, and the scraps are cleaned by slightly sweeping the grids in the backward direction for several times and then sweeping the grids in the forward direction for several times along each diagonal line of the grids. The tested small grids are firmly stuck by using a 3M hundred-grid adhesive tape, the adhesive tape is pressed down by using a finger or is rubbed by using an eraser to enlarge the contact area and the strength of the adhesive tape and a tested area, then one end of the adhesive tape is grasped by a hand, the adhesive tape is rapidly torn down in the vertical direction (90 degrees), the falling-off phenomenon of the photoresist film on the substrate is observed, and the same test is generally carried out for 2-3 times at the same position by pulling and tearing the adhesive tape. After the above steps are completed, a handle magnifying glass with a magnification of 2 times or 3 times is adopted, the falling-off condition of the photoresist film is observed as a comparison standard of the adhesion, and the adhesion is evaluated according to the following standard:
A: the edge of the scribing is smooth, and no adhesive film falls off at the edge and the crossing point of the scribing;
b: the edges and the crossing points of the scribing lines are provided with small adhesive films which fall off, and the total falling-off area is less than 15 percent;
c: the edges and the crossing points of the scribing lines are provided with flake adhesive films which fall off, and the total falling-off area is 15-65%;
d: the total area of the shedding area exceeds 65 percent.
In the case of a, the adhesion was evaluated as excellent, in the case of B, as good, and in the cases of C and D, as poor.
Development adhesion evaluation test
The positive photosensitive resin composition of the above example was spin-coated on a silica substrate without HMDS treatment, and baked at 100 ℃ for 90 seconds with a hot plate to form a photoresist film layer having a thickness of about 2.0 μm. Then, using the mask plate with the line and the space, the photoresist film layer is subjected to patterning exposure by using ultraviolet light with the optimal exposure dose of each sample. The photoresist film layer after the above treatment was then developed with 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ℃ for 60 seconds to remove the photoresist film layer from the exposed areas on the substrate. After the developed photoresist was subjected to running water washing with ultrapure water for 1 minute and spin-dried, the minimum line width (dense 1:1 line width and line space pattern area, which is free from rinsing after pattern development) remaining on the substrate was determined by a scanning electron microscope as a comparative standard for developing the adhesion, and the adhesion was evaluated according to the following criteria:
A：CD≤1.0μm；
B：1.0μm＜CD≤5.0μm；
C：CD＞5.0μm。
In the case of a, development adhesion was evaluated as excellent, in the case of B, as general, and in the case of C, as poor.
Sensitivity stability assessment test
The critical dimension resolution evaluation test procedure was repeated to find the line widths of the respective examples and comparative examples in the formation of 1:1Exposure time of line-space pattern (optimum exposure amount, E op1 )
Next, each of the photosensitive resin compositions obtained in each of examples and comparative examples was left for 3 months under an ultra clean room atmosphere (temperature: 23.+ -. 0.5 ℃ C., humidity: 45.+ -. 5%) and an optimum exposure time E was obtained by the same procedure as described above op2 . Finally, delta E can be obtained by the following formula op And sensitivity stability was evaluated according to the following criteria.
ΔE op (mJ/cm 2 )＝E op2 -E op1
A：ΔE op ≤30；
B：30＜ΔE op ≤50；
C：50＜ΔE op 。
In the case of a, sensitivity stability was evaluated as excellent, in the case of B, as general, and in the case of C, as poor.
Viscosity stability evaluation test
The resin compositions of the above examples and comparative examples were subjected to a clean room atmosphere (temperature: the mixture was left at 23.+ -. 0.5 ℃ and humidity 45.+ -. 5%) for 3 months, and the viscosity before and after leaving the mixture was measured, and the viscosity was measured using a constant capillary viscometer (Shanghai Haihui glass products Co., ltd.) in a constant temperature water bath at 25 ℃. The viscosity change ratio aη (%) was calculated and obtained as an index of storage stability. The viscosity change rate was set as follows:
A：Δη≤5％；
B：5％＜Δη≤10％；
C：10％＜Δη。
In the case of a, the viscosity stability was evaluated as excellent, in the case of B, as good, and in the case of C, as bad.
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Claims (9)

1. A positive photosensitive resin composition comprising the following components:
(A) An alkali-soluble resin, 100 parts by weight,
(B) 5 to 50 parts by weight, preferably 10 to 20 parts by weight,
(C) Imidazole compound, 0.5 to 10 parts by weight, preferably 1.0 to 5 parts by weight, more preferably 1.67 to 4 parts by weight,
(D) 150 to 350 parts by weight, preferably 200 to 300 parts by weight,
(E) 1 to 5 parts by weight, preferably 1.5 to 2.5 parts by weight, of an adhesion promoter,
(F) Surfactants, from 0.1 to 0.5 part by weight, preferably from 0.2 to 0.4 part by weight,
wherein the amounts of components (B) - (F) are based on 100 parts by weight of component (A),
wherein the weight average molecular weight of the alkali-soluble resin is 1,000 to 10,000, preferably 1,000 to 5,000, more preferably 2,000 to 5,000, and most preferably 2,900 to 4,000.
2. The positive photosensitive resin composition according to claim 1, wherein the imidazole-based compound is a compound selected from the group consisting of formulas (4) to (9),
wherein, in the formulas (4) to (9),
R 1 is a hydrogen atom, or has at least one polar functional group selected from the group consisting of a hydroxyl group, a carbonyl group, an ester group, an ether group, a thioether group, a carbonate group, a cyano group and an acetal group and has a carbon number of 2 to
20, an alkyl group of 20;
R 2 、R 3 r is R 4 Each independently is a hydrogen atom, C 1 -C 10 Alkyl, aryl or C 7 -C 10
An arylalkyl group;
R 5 、R 7 、R 9 r is R 13 Each independently is a saturated alkylene group having 1 to 10 carbon atoms;
R 6 r is R 8 Each independently being a hydrogen atom or C 1 -C 15 An alkyl group which may contain at least 1 polar functional group selected from the group consisting of a hydroxyl group, a carbonyl group, an ester group, an ether group, a thioether group, a carbonate group, a cyano group, and an acetal group;
R 10 is C 1 -C 15 Alkyl groups which may contain a moiety selected from the group consisting of hydroxy, carbonyl, ester, ether, thioether,
At least 1 polar functional group of carbonate group, cyano group, acetal group;
R 11 saturated or unsaturated C of valence (b+1) 2 -C 10 A hydrocarbon group;
R 12 each independently being a hydrogen atom or C 1 -C 15 Alkyl groups which may contain a moiety selected from the group consisting of hydroxy, carbonyl, ester, and,
At least 1 polar functional group of thioether group, carbonate group, cyano group and acetal group, 2R 12 Can be bonded to form a ring and can be used for preparing a medicine,
b is 2, 3, 4 or 5.
3. The positive photosensitive resin composition according to claim 1 or 2, wherein the imidazole-based compound is selected from imidazole, 2-methylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-methoxymethylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-hydroxyethyl) imidazole, 1-aminoethyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1- (carboxymethyl) imidazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, preferably 1-vinylimidazole.
4. A positive photosensitive resin composition according to any one of claims 1-3, wherein the ratio of the alkali-soluble resin (a) to the imidazole-based compound is in the range of 75:1 to 10:1, preferably 60:1 to 25:1.
5. The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the ratio of the photosensitive compound to the imidazole-based compound is in an amount of 12:1 to 2.5:1, preferably 9:1 to 3.75:1.
6. The positive photosensitive resin composition according to any one of claims 1-5, wherein the alkali-soluble resin is a phenolic resin, preferably a combination of two phenolic resins of different molecular weights, more preferably wherein the weight ratio of the two phenolic resins is 20:80 to 60:40, preferably 30:70 to 50:50.
7. The positive photosensitive resin composition according to any one of claims 1 to 6, wherein the amount relationship between the alkali-soluble resin (a) (denoted as m), the imidazole-based compound (C) (denoted as n), and the photosensitive compound (B) (denoted as q) satisfies the formula:
0.080≤n/[mq/(m+q)]≤0.350；
preferably 0.128.ltoreq.n/[ mq/(m+q) ].ltoreq.0.307;
more preferably 0.290.ltoreq.n/[ mq/(m+q) ].ltoreq.0.310.
8. A method of patterning a photoresist comprising the steps of:
(i) Uniformly coating the positive photosensitive resin composition according to any one of claims 1 to 7 on a substrate to form a photoresist film, and baking at 80 to 120 ℃ for 10 to 180 seconds to obtain a film thickness of 0.5 to 15 μm, preferably 1.0 to 2.5 μm;
(ii) Subjecting the adhesive film obtained in (i) to partial irradiation;
(iii) Developing the photoresist film obtained in (ii) with a developing solution, which is an alkaline solution, and washing with ultrapure water;
(iv) The developed photoresist was baked at a temperature of 100 to 150 c for 1 to 40 minutes to make the hardening more complete.
9. Use of the positive photosensitive resin composition according to any one of claims 1 to 7 for metal patterning in semiconductor production.
CN202310693308.8A 2023-06-12 2023-06-12 Positive photosensitive resin composition, use thereof, and metal patterning method using the same Pending CN116880125A (en)

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