Negative-type photosensitive resin composition and method of forming resist pattern

Abstract

A negative-type photosensitive resin composition and a method of forming a resist pattern are provided. The negative-type photosensitive resin composition includes a novolac resin (A), polysiloxane (B), a photoacid generator (C), a crosslinking agent (D) and a solvent (E). The polysiloxane (B) is formed by polycondensing specific silane monomer. The negative-type photosensitive resin composition can form inverted trapezoid pattern and have great developing resistance.

Description

[Technical Field]

[0001] This invention relates to a negative photosensitive resin composition and a method for forming a photoresist pattern, and particularly to a negative photosensitive resin composition and a method for forming an inverted trapezoidal pattern with good developability. [Previous Technology]

[0002] The lift-off method is a known method used to create metal circuit patterns such as aluminum, copper, and tantalum on semiconductor substrates.

[0003] For example, in the peel-off method, a photoresist composition is first coated onto a substrate, and then exposed and developed using a photomask to form a photoresist pattern on the substrate. Next, a metal layer can be formed on the photoresist pattern and the substrate using methods such as sputtering and vapor deposition. Then, the photoresist pattern and the metal layer on the photoresist pattern can be simultaneously peeled off to form a metal circuit pattern on the substrate.

[0004] In the peel-off process, since the metal circuit pattern is formed using a photoresist pattern as a photomask, the accuracy of the metal circuit pattern is affected by the shape of the photoresist pattern. Therefore, it is necessary to provide a photoresist composition suitable for the peel-off process to form particularly fine metal circuit patterns with high precision.

[0005] In the peel-off method, the ideal shape of the photoresist pattern is one in which the lower portion of the photoresist pattern (i.e., the portion in contact with the substrate) interlocks inward. This shape is called a microgroove. During the formation of the aforementioned metal layer, the microgroove facilitates the penetration of the metal layer between the photoresist patterns, resulting in good adhesion between the formed rectangular or conical metal circuit pattern and the substrate. This allows the photoresist pattern to be easily peeled off from the substrate, and the shape of the metal circuit pattern is not adversely affected when the photoresist pattern is peeled off.

[0006] In order to make the peeling method more effective in the production of photoresist patterns for metal circuits, there is an urgent need to provide a negative photosensitive resin composition that can form inverted trapezoidal patterns and has good development resistance. [Summary of the Invention]

[0007] One aspect of the present invention is to provide a negative photosensitive resin composition, which is used to form an inverted trapezoidal pattern and has better developability.

[0008] Another aspect of the present invention is to provide a method for forming a photoresist pattern, which involves forming a photoresist pattern from a negative photosensitive resin composition as described above.

[0009] According to one aspect of the present invention, a negative photosensitive resin composition is provided, comprising a phenolic varnish resin (A), a polysiloxane (B), a photoacid generator (C), a crosslinking agent (D), and a solvent (E). The polysiloxane (B) is formed by polycondensation of a silane monomer as shown in formula (I): Si(Y1)a(OY2)4-a(I).

[0010] In the above formula (I), Y1 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aromatic group having 6 to 15 carbon atoms, an alkyl group having an anhydride group, an alkyl group having an epoxy group, or an alkoxy group having an epoxy group, Y2 independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an aromatic group having 6 to 15 carbon atoms, and a represents an integer from 0 to 3.

[0011] According to one embodiment of the present invention, at least one of Y1 in the above formula (I) represents an alkyl group having an anhydride group, an alkyl group having an epoxy group, or an alkoxy group having an epoxy group.

[0012] According to one embodiment of the present invention, the above-mentioned silane monomer comprises a first silane monomer and a second silane monomer, wherein the Y1 of the first silane monomer represents an alkyl group having an anhydride group, an alkyl group having an epoxy group, or an alkoxy group having an epoxy group, and the Y1 of the second silane monomer represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aromatic group having 6 to 15 carbon atoms.

[0013] According to one embodiment of the present invention, based on a total amount of silane monomer used of 1 mol, the amount of the first silane monomer used is 0.01 mol to 0.20 mol.

[0014] According to one embodiment of the present invention, the above-mentioned photoacid generator (C) comprises an onium salt compound, a triazine compound, a sulfonic acid compound, a sulfonate compound, a sulfadiazine compound, or a combination thereof.

[0015] According to one embodiment of the present invention, the amount of phenolic varnish resin (A) used is 100 parts by weight, the amount of polysiloxane (B) used is 10 to 200 parts by weight, the amount of photoacid generator (C) used is 1 to 30 parts by weight, the amount of crosslinking agent (D) used is 1 to 50 parts by weight, and the amount of solvent (E) used is 100 to 1000 parts by weight.

[0016] According to another aspect of the present invention, a method for forming a photoresist pattern is provided. The method includes coating the above-mentioned negative photosensitive resin composition on a substrate; and processing the negative photosensitive resin composition to form a photoresist pattern.

[0017] According to one embodiment of the present invention, the above processing steps include heating treatment, exposure treatment and development treatment.

[0018] According to one embodiment of the present invention, the above-mentioned exposure process includes irradiating the negative photosensitive resin composition with ultraviolet light rays, wherein the wavelength of the ultraviolet light rays is 240 nm to 500 nm.

[0019] According to one embodiment of the present invention, the above-described developing process includes the use of an alkaline developing agent.

Implementation Method

[0020] The manufacture and use of embodiments of the present invention will be discussed in detail below. However, it will be understood that the embodiments provide many applicable inventive concepts that can be implemented in a wide variety of specific situations. The specific embodiments discussed are for illustrative purposes only and are not intended to limit the scope of the invention.

[0021] This invention provides a negative photosensitive resin composition comprising phenolic varnish resin (A), polysiloxane (B), photoacid generating agent (C), crosslinking agent (D), and solvent (E). The phenolic varnish resin (A), polysiloxane (B), photoacid generating agent (C), crosslinking agent (D), and solvent (E) will be described in detail below.

[0022] Phenolic varnish resin (A)

[0023] The phenolic varnish resin (A) used in this invention can be obtained by polycondensation of cresol-type aromatic hydroxyl compounds and aldehydes.

[0024] In some embodiments, the above-mentioned cresol aromatic hydroxyl compounds include, but are not limited to, cresol compounds such as m-cresol, p-cresol, or o-cresol; and xylenol compounds such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, and 3,4-xylenol. The aforementioned cresol aromatic hydroxyl compounds may be used alone or in combination.

[0025] Without affecting the physical properties of the negative photosensitive resin composition, the phenolic varnish resin (A) of the present invention can also be obtained by polycondensation of other types of aromatic hydroxyl compounds and aldehyde compounds.

[0026] In some embodiments, the other types of aromatic hydroxyl compounds mentioned above include, but are not limited to, phenol; alkyl phenols such as m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, and 6-tert-butyl-3-methylphenol; alkoxy phenols such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, and m-propoxyphenol; and isopropenyl phenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, and 2-ethyl-4-isopropenylphenol. phenol compounds; aryl phenol compounds such as phenyl phenol; polyhydroxyphenol compounds such as 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, and pyrogallol.

[0027] In some embodiments, the aldehyde compound that undergoes polycondensation with the above-mentioned cresol-based aromatic hydroxyl compounds includes, but is not limited to, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furylacrolein, 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, and cinnamaldehyde. Preferably, the aldehyde compound is formaldehyde. Furthermore, the aldehyde compounds may be used alone or in combination.

[0028] The above-mentioned phenolic varnish resin (A) is preferably prepared by the following method: a condensation reaction is carried out under normal pressure in the presence of catalysts such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid and / or inorganic acids, and unreacted monomers are removed by dehydration.

[0029] Polysiloxane (B)

[0030] There is no particular limitation on the type of polysiloxane (B), as long as it achieves the purpose of this invention. Polysiloxane (B) can be formed by polymerization [i.e., hydrolysis and partial condensation] of a mixture, wherein the mixture may contain silane monomer, polysiloxane prepolymer, or a combination of silane monomer and polysiloxane prepolymer.

[0031] The polysiloxane (B) of the present invention is formed by polycondensation of a silane monomer as shown in the following formula (I): Si(Y1)a(OY2)4-a(I).

[0032] In formula (I), Y1 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aromatic group having 6 to 15 carbon atoms, an alkyl group having an anhydride group, an alkyl group having an epoxy group, or an alkoxy group having an epoxy group, Y2 independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an aromatic group having 6 to 15 carbon atoms, and a represents an integer from 0 to 3.

[0033] When Y1 represents an alkyl group having 1 to 10 carbon atoms, Y1 can be methyl, ethyl, n-propyl, isopropyl, n-butyl, tributyl, n-hexyl, or n-decyl. Alternatively, Y1 can also be an alkyl group having other substituents, such as trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3-mercaptopropyl, or 3-isocyanate propyl.

[0034] When the aforementioned Y1 represents an alkenyl group having 2 to 10 carbon atoms, Y1 may be a vinyl group. Alternatively, Y1 may be an alkenyl group having substituents, such as 3-propenyloxypropyl or 3-methpropenyloxypropyl.

[0035] When the aforementioned Y1 represents an aromatic group having 6 to 15 carbon atoms, Y1 can be phenyl, tolyl, or naphthyl. Alternatively, Y1 can be an aromatic group having other substituents, such as p-hydroxyphenyl, 1-(p-hydroxyphenyl)ethyl, 2-(p-hydroxyphenyl)ethyl, or 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl.

[0036] When the aforementioned Y 1 represents an alkyl group having an anhydride group, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and the anhydride group is a group formed by intramolecular dehydration of a dicarboxylic acid, wherein the dicarboxylic acid may be succinic acid or glutaric acid. Specific examples of the alkyl group having an anhydride group may be groups having the structures shown in the following formulas (I-1) to (I-3): (I-1)(I-2)(I-3).

[0037] When Y1 represents an alkyl group having an epoxy group, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and the epoxy group can be a group formed by intramolecular dehydration of a diol, wherein specific examples of the diol can be propylene glycol, butanediol or pentanediol. Specific examples of the alkyl group having an epoxy group can be oxetanylpentyl or 2-(3,4-epoxycyclohexyl)ethyl.

[0038] When Y1 in the above-mentioned case represents an alkoxy group having an epoxy group, the alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms. Specific examples of the alkoxy group having an epoxy group may be glycidoxypropyl or 2-oxetanylbutoxy.

[0039] When Y2 represents an alkyl group having 1 to 6 carbon atoms, specific examples of Y2 may be methyl, ethyl, n-propyl, isopropyl, or n-butyl; when Y represents an acetyl group having 1 to 6 carbon atoms, specific examples of Y2 may be acetyl; when Y2 represents an aromatic group having 6 to 15 carbon atoms, specific examples of Y2 may be phenyl.

[0040] When the aforementioned 'a' represents 2 or 3, the multiple Y1s may be the same or different. When 'a' represents 0 or 2, the multiple Y2s may be the same or different.

[0041] When a represents 0, a silane monomer having the structure shown in formula (I) can be a tetrafunctional silane monomer (i.e., a silane monomer having four hydrolyzable groups); when a represents 1, a silane monomer having the structure shown in formula (I) can be a trifunctional silane monomer (i.e., a silane monomer having three hydrolyzable groups); when a represents 2, a silane monomer having the structure shown in formula (I) can be a difunctional silane monomer (i.e., a silane monomer having two hydrolyzable groups); when a represents 3, a silane monomer having the structure shown in formula (I) can be a monofunctional silane monomer (i.e., a silane monomer having one hydrolyzable group). The aforementioned hydrolytic groups represent groups that can undergo hydrolysis and are bonded to silicon, and specific examples of hydrolytic groups may be alkoxy, acyloxy, or phenoxy groups.

[0042] Specific examples of the above-mentioned tetrafunctional silane monomers may be silane monomers such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, or tetraphenoxysilane.

[0043] Specific examples of the above-mentioned trifunctional silane monomers may be methyltrimethoxysilane (MTMS), methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, and n-butyltriethoxysilane. ethoxysilane), n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryoyloxypropyltrimethoxysilane, 3-methylacryloyloxypropyltrimethoxysilane (MPTMS), 3-methylacryloyloxypropyltriethoxysilane, phenyltrimethoxysilane (PTMS), phenyltriethoxysilane;PTES), p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane [pentyltrimethoxysilane], trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane thoxysilane), 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-epoxypropylbutoxypropyl Triphenoxysilane (2-oxetanylbutoxypropyltriphenoxysilane), or commercially available products, such as 2-oxetanylbutoxypropyltrimethoxysilane (TMSOX-D), 2-oxetanylbutoxypropyltriethoxysilane (TESOX-D), or 3-(triphenoxysilyl)propylsuccinic anhydride manufactured by Toa Synthetic Laboratories;Shin-Etsu Chemical manufactures 3-(trimethoxysilyl)propyl succinic anhydride (model X-12-967); WACKER manufactures 3-(triethoxysilyl)propyl succinic anhydride (model GF-20), 3-(trimethoxysilyl)propyl glutaric anhydride (model TMSG), 3-(triethoxysilyl)propyl glutaric anhydride, or 3-(triphenoxysilyl)propyl glutaric anhydride.

[0044] Specific examples of the above-mentioned difunctional silane monomers may be dimethyldimethoxysilane (DMDMS), dimethyldiethoxysilane, dimethyldiacetyloxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, diisopropoxy-di(2-oxetanylbutoxypropyl)silane (DIDOS), di(3-oxetanylpentyl)dimethoxysilane, and (di-n-butoxysilyl)di(propylsuccinic anhydride). Silane monomers such as (dimethoxysilyl)di(ethyl succinic anhydride) or (dimethoxysilyl)di(ethyl succinic anhydride)[(dimethoxysilyl)di(ethyl succinic anhydride)].

[0045] Specific examples of the above-mentioned monofunctional silane monomers may be trimethylmethoxysilane, tri-n-butylethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, di(2-oxetanylbutoxypentyl)-2-oxetanylpentylethoxysilane, tri(2-oxetanylpentyl)methoxysilane, and phenoxysilyltripropylsuccinic anhydride. Silane monomers such as methyl methoxysilyldiethyl succinic anhydride or methyl methoxysilyldiethyl succinic anhydride.

[0046] When the negative photosensitive resin composition does not contain polysiloxane (B), it is impossible to form an inverted trapezoidal pattern and has poor developability.

[0047] In some embodiments, at least one of Y1 in formula (I) above represents an alkyl group having an anhydride group, an alkyl group having an epoxy group, or an alkoxy group having an epoxy group. When the polysiloxane (B) of the present invention is formed by polycondensation of a silane monomer having the structure shown in formula (I), and at least one of Y1 in formula (I) represents an alkyl group having an anhydride group, an alkyl group having an epoxy group, or an alkoxy group having an epoxy group, the resulting negative photosensitive resin composition can form an inverted trapezoidal pattern and has better developability.

[0048] The amount of phenolic varnish resin (A) used is 100 parts by weight, and the amount of polysiloxane (B) used is 10 parts by weight to 200 parts by weight, preferably 30 parts by weight to 180 parts by weight, and even more preferably 50 parts by weight to 150 parts by weight. When the amount of polysiloxane (B) used is within the aforementioned range, the resulting negative photosensitive resin composition can form a better inverted trapezoidal pattern.

[0049] In some embodiments, the silane monomer shown in formula (I) comprises a first silane monomer and a second silane monomer, wherein the Y1 of the first silane monomer represents an alkyl group having an anhydride group, an alkyl group having an epoxy group, or an alkoxy group having an epoxy group, and the Y1 of the second silane monomer represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aromatic group having 6 to 15 carbon atoms. In the foregoing embodiments, based on a total amount of silane monomer used of 1 mol, the amount of the first silane monomer used is 0.01 mol to 0.20 mol, preferably 0.02 mol to 0.18 mol, and more preferably 0.03 mol to 0.15 mol. When the amount of the first silane monomer used is within the foregoing range, the resulting negative photosensitive resin composition can have better developability.

[0050] The above-mentioned polysiloxane prepolymer may include a polysiloxane prepolymer having the structure shown in formula (I-4): (I-4).

[0051] In formula (I-4), A1, A2, A3 and A4 independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aromatic group having 6 to 15 carbon atoms, respectively. A5 and A6 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acetyl group having 1 to 6 carbon atoms, or an aromatic group having 6 to 15 carbon atoms, respectively. i represents an integer from 1 to 1000.

[0052] When A1, A2, A3, and A4 independently represent alkyl groups having 1 to 10 carbon atoms, specific examples of A1, A2, A3, and A4 may be methyl, ethyl, or n-propyl, etc.; when A1, A2, A3, and A4 independently represent alkenyl groups having 2 to 6 carbon atoms, specific examples of A1, A2, A3, and A4 may be vinyl, acryloxypropyl, or methacryloxypropyl, etc.; when A1, A2, A3, and A4 independently represent aromatic groups having 6 to 15 carbon atoms, specific examples of A1, A2, A3, and A4 may be phenyl, tolyl, or naphthyl, etc. Any of the aforementioned alkyl, alkenyl, and aromatic groups may selectively have substituents.

[0053] When A5 and A6 respectively independently represent alkyl groups having 1 to 6 carbon atoms, specific examples of A5 and A6 may be methyl, ethyl, n-propyl, isopropyl, or n-butyl, etc.; when A5 and A6 respectively independently represent acetyl groups having 1 to 6 carbon atoms, specific examples of A5 and A6 may be acetyl; when A5 and A6 respectively independently represent aromatic groups having 6 to 15 carbon atoms, specific examples of A5 and A6 may be phenyl. Any of the alkyl, acetyl, and aromatic groups mentioned above may also selectively have substituents.

[0054] When i represents an integer from 1 to 1000, the multiple A1s may be the same or different, and the multiple A3s may be the same or different. i is preferably an integer from 3 to 300, and more preferably an integer from 5 to 200.

[0055] Specific examples of polysiloxane prepolymers having the structure shown in formula (I-4) may be 1,1,3,3-tetramethyl-1,3-dimethoxydisiloxane, 1,1,3,3-tetramethyl-1,3-diethoxydisiloxane, 1,1,3,3-tetraethyl-1,3-diethoxydisiloxane, or polysiloxanes terminated with silanol manufactured by Gelest Corporation. Polydimethylsiloxane (PM2.5) is available in the following molecular weights: DM-S12 (molecular weight 400 to 700), DMS-S15 (molecular weight 1500 to 2000), DMS-S21 (molecular weight 4200), DMS-S27 (molecular weight 18000), DMS-S31 (molecular weight 26000), DMS-S32 (molecular weight 36000), DMS-S33 (molecular weight 43500), DMS-S35 (molecular weight 49000), DMS-S38 (molecular weight 58000), DMS-S42 (molecular weight 77000), or PDS-9931 (molecular weight 1000 to 1400).

[0056] The polysiloxane prepolymers having the structure shown in formula (I-4) can be used alone or in combination of multiple types.

[0057] The aforementioned silane monomer can be used in combination with polysiloxane prepolymer, and there is no particular limitation on the mixing ratio of the two. In some embodiments, the molar ratio of silicon atoms in the silane monomer to the polysiloxane prepolymer is preferably 100:0.01 to 50:50.

[0058] In some embodiments, the mixture described above may also selectively contain silicon dioxide particles. There is no particular limitation on the average particle size of the silicon dioxide particles, and the average particle size may be from 2 nm to 250 nm, preferably from 5 nm to 200 nm, and more preferably from 10 nm to 100 nm.

[0059] In some specific examples, the silicon dioxide particles may be manufactured by Catashoku Kasei Co., Ltd., under the model names OSCAR 1132 (particle size 12 nm, dispersant is methanol), OSCAR 1332 (particle size 12 nm, dispersant is n-propanol), OSCAR 105 (particle size 60 nm, dispersant is γ-butyrolactone), or OSCAR 106 (particle size 120 nm, dispersant is diacetone alcohol), etc.; or manufactured by Fuso Chemical Co., Ltd., under the model names Quartron PL-1-IPA (particle size 13 nm, dispersant is isopropyl ketone), Quartron PL-1-TOL (particle size 13 nm, dispersant is toluene), Quartron PL-2L-PGME (particle size 18 nm, dispersant is propylene glycol monomethyl ether), or Quartron Commercial products include PL-2L-MEK (18nm particle size, with methyl ethyl ketone as dispersant); and products manufactured by Nissan Chemical Co., Ltd., with models such as IPA-ST (12nm particle size, with isopropanol as dispersant), EG-ST (12nm particle size, with ethylene glycol as dispersant), IPA-ST-L (45nm particle size, with isopropanol as dispersant), or IPA-ST-ZL (100nm particle size, with isopropanol as dispersant). The aforementioned silicon dioxide particles can be used alone or in combination.

[0060] The aforementioned silicon dioxide particles can be used in combination with silane monomers and / or polysiloxane prepolymers, and there are no particular limitations on the mixing ratio. In some embodiments, the molar ratio of silicon atoms in the silicon dioxide particles to that in the polysiloxane prepolymer is preferably 1% to 50%.

[0061] In the above polymerization reaction (i.e., hydrolysis reaction and partial condensation reaction), the mixture is first added to the solvent and water, wherein the mixture may contain silane monomers, polysiloxane prepolymers and / or silica particles, and the mixture may selectively contain a catalyst. Then, it is heated and stirred at 50°C to 150°C. After 0.5 hours to 120 hours, the byproducts (alcohols or water, etc.) are removed by distillation.

[0062] There are no particular limitations on the solvent used in the aforementioned polymerization reaction, and the solvent may be the same as or different from the solvent (E) described later in this invention. Based on the total amount of silane monomer, polysiloxane prepolymer and / or silica particles used being 100 grams, the amount of solvent used is 15 grams to 1200 grams, preferably 20 grams to 1100 grams, and more preferably 30 grams to 1000 grams.

[0063] The amount of hydrolyzable groups in the silane monomer, polysiloxane prepolymer and / or silica particles is 1 mole, and the amount of water used in the above polymerization reaction (i.e., the water used for hydrolysis) is 0.5 to 2 moles.

[0064] There are no particular limitations on the catalyst used in the above polymerization reaction, but it is preferably an acid catalyst or a basic catalyst. Specific examples of acid catalysts may include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polybasic carboxylic acid or their anhydrides, or ion-exchange resins, etc. Specific examples of alkaline catalysts may include diethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, sodium hydroxide, potassium hydroxide, silanes containing amine and alkoxy groups, or ion exchange resins.

[0065] The total amount of silane monomer, polysiloxane prepolymer and / or silica particles used is 100 grams, and the amount of catalyst used in the polymerization reaction is 0.005 grams to 15 grams, preferably 0.01 grams to 12 grams, and even more preferably 0.05 grams to 10 grams.

[0066] From a stability point of view, the polysiloxane (B) of the present invention preferably does not contain byproducts (e.g., alcohols or water) and catalysts. Therefore, the mixture after polymerization can be selectively purified to obtain polysiloxane (B). The purification method is not particularly limited, but preferably involves adding a hydrophobic solvent to the mixture after polymerization to dilute and form a mixed solution. The mixed solution is then transferred to a separation funnel. The organic layer is then washed several times with water, and then concentrated using a rotary evaporator to remove alcohols or water. Furthermore, the catalyst can be removed using an ion exchange resin.

[0067] Photoacid generator (C)

[0068] The photoacid generator (C) is a compound that generates acid upon irradiation with light. In this invention, the photoacid generator (C) serves as a catalyst for the polymerization reaction of the phenolic varnish resin (A) with the crosslinking agent (D) described below. Specifically, the photoacid generator (C) is, for example, an onium salt compound, a triazine compound, a sulfonic acid compound, a sulfonamide compound, or a combination of the above compounds.

[0069] In some embodiments, the onium salt compound comprises iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, pyridinium salt, or the like. Specific examples of onium salt compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, and 4-t-butylphenyldiphenylsulfonium p-toluenesulfonate. p-toluenesulfonate), 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate, or combinations thereof.

[0070] In addition, the onium salt compound can also be cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, dicyclohexyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, (2-oxocyclohexyl)(2-norbornyl)sulfonium trifluoromethanesulfonate, 2-cyclohexylsulfonylcyclohexanone, dimethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, N-hydroxy succinimide trifluoromethanesulfonate, phenyl p-toluenesulfonate, or combinations thereof.

[0071] In some embodiments, the triazine compound comprises a compound having the following formula (C1): (C1).

[0072] In formula (C1), Rd 15 preferably represents *-L x1-Rd x1, where L x1 represents a single bond or a divalent linking group; Rd x1 represents an aromatic cyclic hydrocarbon group or an aromatic heterocyclic group. Specifically, the divalent linking group represented by L x1 may be, for example, -CO-, -O-, -SO-, -SO 2-, -NRA-, alkenyl (preferably a straight-chain or branched group with 1 to 6 carbon atoms), alkenyl (preferably a straight-chain or branched group with 2 to 6 carbon atoms), alkynyl (preferably a straight-chain or branched group with 2 to 6 carbon atoms), and a divalent linking group combining the aforementioned groups. The aforementioned alkenyl, alkenyl, and alkynyl groups may also have substituents, wherein the substituents may include halogen atoms (preferably fluorine atoms) and hydroxyl groups, etc. The aforementioned RA includes hydrogen atoms or alkyl groups with 1 to 6 carbon atoms. L x1 preferably represents a single bond or an alkenyl group, more preferably a single bond or an alkenyl group having 2 to 4 carbon atoms.

[0073] The aromatic cyclic hydrocarbon group represented by Rd ​​x1 includes phenyl and naphthyl groups; while the aromatic heterocyclic group represented by Rd ​​x1 includes pyrrole group, furan group, thiophene group, indole group, benzofuran group, and benzothiophene furan group, preferably furan group. The aromatic cyclic hydrocarbon group and aromatic heterocyclic group represented by Rd ​​x1 may further have substituents, wherein the substituents may include alkyl (e.g., having 1 to 15 carbon atoms), cycloalkyl (e.g., having 3 to 15 carbon atoms), aryl (e.g., having 6 to 14 carbon atoms), alkoxy (e.g., having 1 to 15 carbon atoms), halogen atoms, and hydroxyl groups.

[0074] In some specific examples, the triazine compound having the formula (C1) comprises:

[0075] The sulfonium compound is, for example, a β-ketosulfone compound, a β-sulfonyl sulfone compound, or an α-diazo compound of the above. Specific examples of sulfonium compounds include 4-trisphenacyl sulfone, mesityl phenacyl sulfone, bis(phenacylsulfonyl)methane, or combinations thereof.

[0076] The sulfonic acid compound is, for example, an alkylsulfonic acid ester, a haloalkylsulfonic acid ester, an arylsulfonic acid ester, or an iminosulfonate. Specific examples of sulfonic acid compounds include benzoin tosylate, pyrogallol tris(trifluoromethanesulfonate), o-nitrobenzyl trifluoromethanesulfonate, o-nitrobenzyl p-toluenesulfonate, or combinations thereof.

[0077] Specific examples of sulfonylimide compounds include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, and N-(trifluoromethylsulfonyloxy)naphthalenedimethylimide. naphthylimide (NAI-105) or a combination of the above compounds.

[0078] When the photoacid generator (C) is a triazine compound or an onium salt compound, the resulting negative photosensitive resin composition can form a better inverted trapezoidal pattern.

[0079] The amount of phenolic varnish resin (A) used is 100 parts by weight, and the amount of photoacid generator (C) used is 1 to 30 parts by weight, preferably 1.5 to 29 parts by weight, and even more preferably 2 to 28 parts by weight.

[0080] Bridging agent (D)

[0081] The crosslinking agent (D) is a compound that promotes the formation of covalent bonds or ionic bonds between linear molecules, enabling linear molecules to bond together and form a polymer network. It is noteworthy that phenolic varnish resin (A) can react with the crosslinking agent (D) under the catalysis of the aforementioned photoacid generator (C) to form a polymer with a high degree of crosslinking.

[0082] The crosslinking agent (D) is, for example, alkoxymethylated urea resin, alkoxymethylated melamine resin, alkoxymethylated uronresin, alkoxymethylated glycoluryl resin, or alkoxymethylated amino resin.

[0083] In addition, the crosslinking agent (D) is, for example, alkyl etherified melamine resin, benzoguanamine resin, alkyl etherified benzoguanamine resin, urea resin, alkyl etherified urea resin, urethane formaldehyde resins, resol-type phenol-formaldehyde resin, alkyl etherified resol-type phenol-formaldehyde resin, or epoxy resin.

[0084] Among the above-mentioned crosslinking agent (D), alkoxymethylated amino resin is preferred. Specific examples of alkoxymethylated amino resin include methoxymethylated amino resin, ethoxymethylated amino resin, n-propoxymethylated amino resin, n-butoxymethylated amino resin, or combinations of the above compounds. For example, commercially available products of alkoxymethylated amino resins include PL-1170, PL-1174, UFR 65, CYMEL 300, CYMEL 303 (manufactured by Sumitomo Cytec), BX-4000, NIKALAC MW-30, MX-290, MW-30HM, MS-11, MS-001, MX-750 or MX-706 (manufactured by Sanwa Chemicals) or combinations of the above compounds.

[0085] The aforementioned crosslinking agent (D) is preferably CYMEL 303, NIKALAC MW-30, PL-1170 or a combination of the above compounds.

[0086] In some embodiments, based on the amount of phenolic varnish resin (A) used being 100 parts by weight, the amount of crosslinking agent (D) used is typically 1 to 50 parts by weight, preferably 7 to 45 parts by weight, and even more preferably 10 to 40 parts by weight.

[0087] Solvent (E)

[0088] The solvent (E) used in this invention refers to a solvent that does not react with the above-mentioned organic components, but readily dissolves other organic components.

[0089] In some embodiments, the solvent (E) described above may include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether, etc. Poly(alkylene glycol) monoalkyl ethers; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, or propylene glycol ethyl ether acetate, etc.; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, or tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, or 3-heptanone, etc.; methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate (ethyl lactate) and other lactic acid esters. Classes; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methyl-3-methoxybutyl acetate, methyl 3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, Other esters such as n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, or ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene or xylene; carboxylic acids and amines such as N-methylpyrrolidone, N,N-dimethylformamide, or N,N-dimethylacetamide.

[0090] The solvent (E) described above can be used alone or in combination. Preferred solvents are propylene glycol monoethyl ether, propylene glycol methyl ether acetate, or ethyl lactate.

[0091] In some embodiments, based on the amount of phenolic varnish resin (A) used being 100 parts by weight, the amount of solvent (E) used is typically 100 parts by weight to 1000 parts by weight, preferably 150 to 900 parts by weight, and more preferably 200 to 800 parts by weight.

[0092] Additives (F)

[0093] The negative photosensitive resin composition of the present invention may be selectively further supplemented with additives (F), specifically, additives (F) are, for example, adhesion auxiliary agents, leveling agents, diluents or sensitizers or the like.

[0094] Adhesion aids may be, for example, silane compounds to increase the adhesion property between the negative photosensitive resin composition and the substrate. Specific examples of silane compounds include: vinyltrimethoxysilane, vinyltriethoxysilane, and 3-(methyl)acryloyloxypropyltrimethoxysilane. MPTMS), vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane methoxysilane), 3-glycidoxypropyldimethylmethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 1,2-bis-(trimethoxysilyl)ethane, or combinations thereof.

[0095] In some embodiments, based on the amount of phenolic varnish resin (A) used being 100 parts by weight, the amount of adhesion promoter used is typically 0 to 2 parts by weight, preferably 0.001 to 1 part by weight, and even more preferably 0.005 to 0.8 parts by weight.

[0096] The leveling agent may include fluorinated or silicone surfactants. Specific examples of fluorinated surfactants include commercially available Flourate FC-430, FC-431 (manufactured by 3M), F top EF122A, 122B, 122C, 126, BL20 [manufactured by Tochem Products Co., Ltd.] or combinations thereof. Specific examples of silicone surfactants include commercially available SF-8427, SH29PA [manufactured by Dow Corning Toray Silicone Co., Ltd.] or combinations thereof.

[0097] In some embodiments, based on the amount of phenolic varnish resin (A) used being 100 parts by weight, the amount of surfactant used is generally from 0 parts by weight to 1.2 parts by weight, preferably from 0.025 parts by weight to 1.0 parts by weight, and even more preferably from 0.050 parts by weight to 0.8 parts by weight.

[0098] Specific examples of diluents include commercially available RE801, RE802 [manufactured by Teikoku Ink] or similar substances, or combinations of the above compounds.

[0099] In some specific examples, the sensitizer includes commercially available TPPA-1000P, TPPA-100-2C, TPPA-1100-3C, TPPA-1100-4C, TPPA-1200-24X, TPPA-1200-26X, TPPA-1300-235T, TPPA-1600-3M6C, and TPPA-MF (manufactured by Honshu Chemical Industry, Japan), or combinations of the above compounds. TPPA-600-3M6C or TPPA-MF are preferred as the sensitizer. The sensitizer can be used alone or in combination.

[0100] In some embodiments, based on the amount of phenolic varnish resin (A) used being 100 parts by weight, the amount of sensitizer used is typically from 0 parts by weight to 20 parts by weight, preferably from 0.5 parts by weight to 18 parts by weight, and even more preferably from 1.0 parts by weight to 15 parts by weight.

[0101] Additive (F) can be used alone or in combination. In addition, other additives may be added as needed, such as plasticizers or stabilizers or similar substances.

[0102] Method for forming photoresist patterns

[0103] The method for forming a photoresist pattern using the negative photosensitive resin composition of the present invention is not limited to conventional methods. First, the negative photosensitive resin composition is coated on a substrate to form a thin film with a desired thickness. In some embodiments, the substrate may be silicon (Si), silicon dioxide (SiO2), silicon nitride (SiN), silicon oxynitride (SiON), titanium nitride (TiN), tungsten silicon (WSi), borophosphosilicate glass (BPSG), spin-on glass (SOG), a metal substrate (e.g., gold, titanium, tungsten, copper, nickel, iron, tantalum, zinc, cobalt, lead, etc.), or an organic antireflective film. In some embodiments, the coating method may be spin coating, roll coating, flow coating, impregnation coating, spray coating, blade coating, or other suitable coating methods.

[0104] Next, the substrate to which the coated film is applied is subjected to a processing step. In some embodiments, the processing step includes a heat treatment, an exposure treatment, and a development treatment. In some specific examples, the heat treatment includes pre-baking at a temperature of about 60°C to about 150°C for about 1 minute to about 10 minutes, preferably at a temperature of about 80°C to about 120°C for about 1 minute to about 5 minutes.

[0105] In some specific examples, the exposure process includes using a light source such as ultraviolet light, far ultraviolet light, or an electron beam, and passing it through a specific photomask to obtain the desired pattern. In the aforementioned specific examples, the wavelength of the light source is from about 200 nm to about 500 nm, and the exposure intensity is from about 1 mJ / cm² to 1000 mJ / cm², preferably from about 10 mJ / cm² to 800 mJ / cm². Next, post-exposure baking (PEB) is performed on a hot plate, for example, baking at a temperature of about C to about 150°C for about 1 minute to about 5 minutes, preferably baking at a temperature of about 80°C to about 120°C for about 1 minute to about 3 minutes.

[0106] In some specific examples, the developing process includes developing the film for about 0.1 minutes to about 60 minutes, preferably about 0.5 minutes to about 10 minutes, using an alkaline developer, such as tetramethylammonium hydroxide (TMAH). The developing process can be performed by conventional methods, such as dip, immersion, or spraying, to form the desired pattern on the substrate. Then, after forming a metal film using sputtering or vapor deposition, the photoresist pattern and the metal layer on the photoresist pattern can be peeled off to form a metal circuit on the substrate.

[0107] The following examples illustrate the application of the present invention, but they are not intended to limit the present invention. Those skilled in the art can make various modifications and refinements without departing from the spirit and scope of the present invention.

[0108] Preparation of phenolic varnish resin (A)

[0109] Synthesis Example A-1

[0110] A nitrogen inlet, stirrer, heater, condenser, and thermometer were installed on a 1000 mL four-necked reaction flask. After introducing nitrogen into the reaction flask, 0.70 moles of m-cresol (o-cresol), 0.30 moles of p-cresol (p-cresol), 0.65 moles of formaldehyde, and 0.020 moles of oxalic acid (catalyst) were added to the reaction flask. Next, the mixture was slowly stirred to raise the temperature of the reaction solution to 100°C, and a polycondensation reaction was carried out at this temperature for about 6 hours. Then, the reaction solution was heated to 180°C and dried under reduced pressure at 10 mmHg to remove the solvent, yielding phenolic varnish resin (A-1).

[0111] Synthetic Examples A-2 to A-4

[0112] Synthetic Examples A-2 to A-4 were prepared using the same method as Synthetic Example A-1, except that the types and amounts of raw materials and reaction conditions were changed in Synthetic Examples A-2 to A-4. The formulations and reaction conditions of Synthetic Examples A-2 to A-4 are shown in Table 1 below, and will not be repeated here.

[0113] Table 1 Synthesis example Composition (moles) Reaction temperature (°C) Polymerization time (hours) Aromatic hydroxyl compounds Aldehydes catalyst o-Cresol m-Cresol p-Cresol 2,5-Xylene formaldehyde oxalic acid A-1 0.70 0.30 0.65 0.020 100​​ 6 A-2 0.05 0.30 0.65 0.80 0.015 95 6 A-3 0.35 0.60 0.05 0.70 0.020 100 6 A-4 0.05 0.30 0.60 0.05 0.75 0.020 100 6

[0114] Preparation of polysiloxane (B)

[0115] Synthetic Example B-1

[0116] In a 500 mL three-necked flask, add 0.30 moles of methyltrimethoxysilane (hereinafter referred to as MTMS), 0.65 moles of phenyltrimethoxysilane (hereinafter referred to as PTMS), 0.05 moles of 3-(triethoxysilyl)propylsuccinic anhydride (hereinafter referred to as GF-20), and 200 g of propylene glycol monoethyl ether (hereinafter referred to as PGEE). While stirring at room temperature, add an aqueous solution of oxalic acid (0.40 g oxalic acid / 75 g water) over 30 minutes. Then, immerse the flask in a 30°C oil bath and stir for 30 minutes. Next, raise the oil bath temperature to 120°C over 30 minutes. When the solution temperature drops to 105°C, continue heating and stirring.

[0117] After polymerization for 6 hours, the solvent is removed by distillation to obtain polysiloxane (B-1).

[0118] Synthetic Examples B-2 to B-9 ​​

[0119] Synthetic Examples B-2 to B-9 were prepared using the same method as the polysiloxane preparation method of Synthetic Example B-1, except that the types and amounts of raw materials used in the polysiloxane resin and the polymerization conditions were changed in Synthetic Examples B-2 to B-9. The formulations and reaction conditions of Synthetic Examples B-2 to B-9 are shown in Table 2 below, and will not be repeated here. The compound abbreviations in Table 2 correspond to the compound names shown in Table 3. Synthesis example Composition Reaction temperature (°C) Polymerization time (hours) Silane monomer / polysiloxane (mol) Solvent (g) Catalyst (g) MTMS DMDMS PTMS PTES GF-20 TMSG TMSOX-D ECETES TESOX-D PGEE DAA water oxalic acid B-1 0.30 0.65 0.05 200 75 0.40 105 6 B-2 0.40 0.40 0.20 100 100 75 0.40 110 ​​​​​​​​​​​​​5 B-3 0.55 0.35 0.10 200 75 0.35 105 6 B-4 0.65 0.30 0.05 200 75 0.45 110 6 B-5 0.60 0.30 0.10 200 75 0.40 110 5 B-6 0.34 0.65 0.01 200 75 0.40 105 6 B-7 0.30 0.50 0.20 200 75 0.40 105 6 B-8 0.30 0.45 0.25 200 75 0.40 105 6 B-9 0.45 0.40 0.15 100 100 75 0.40 105 6

[0120] Table 2

[0121] Table 3 Abbreviation compound MTMS Methyltrimethoxysilane DMDMS Dimethyldimethoxysilane PTMS ​​​​​​​​​​​​​​​​​​​​Phenyltrimethoxysilane PTES Phenyltriethoxysilane GF-20 3-(triethoxysilyl)propyl succinic anhydride TMSG 3-(trimethoxysilyl)propylglutaric anhydride TMSOX-D 2-Oxetanylbutoxypropyltrimethoxysilane ECETES 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane TESOX-D 2-Oxetanylbutoxypropyltriethoxysilane PGEE Propylene glycol monoethyl ether DAA 4-Hydroxy-4-methyl-2-pentanone (Diacetone alcohol)

[0122] Example 1

[0123] In a 500 mL three-necked flask, 100 parts by weight of phenolic varnish resin (A-1), 10 parts by weight of polysiloxane (B-1), 1.0 part by weight of 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine (hereinafter referred to as photoacid generator (C-1)), 1.0 part by weight of Cymel-303 (hereinafter referred to as crosslinking agent (D-1)), and 100 parts by weight of propylene glycol methyl ether acetate (PGMEA; hereinafter referred to as solvent (E-1)) were added. After stirring evenly with a shaker, the negative photosensitive resin composition of Example 1 was obtained. The obtained negative photosensitive resin composition was evaluated using the pattern evaluation and development resistance evaluation methods described below, and the results are shown in Table 4. The compounds corresponding to the numbers in Table 4 are shown in Table 5.

[0124] Examples 2 to 13 and Comparative Examples 1 to 2

[0125] Examples 2 to 13 and Comparative Examples 1 to 2 were prepared using the same method as the negative photosensitive resin composition of Example 1. The difference was that the types and amounts of raw materials in Examples 2 to 13 and Comparative Examples 1 to 2 were changed, and their formulations and evaluation results are shown in Table 4, which will not be repeated here. The compounds corresponding to the numbers in Table 4 are shown in Table 5.

[0126] Table 4 Ingredients Example Comparative example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1 2 Phenolic varnish resin (A) (parts by weight) A-1 100 100 ​​​​ 100 100 100 100 A-2 100 100 100 100 100 100 A-3 100 100 A-4 100 100 Polysiloxane (B) (parts by weight) B-1 10 ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ 200 B-2 100 B-3 30 B-4 50 B-5 80 ​ B-6 100 100 5 250 250 B-7 120 B-8 100 B-9 150 ​ Photoacid generator (C) (parts by weight) C-1 1.0 25 10 15 15 25 25 15 10 C-2 5.0 15 30 10 25 10 C-3 10 Crosslinking agent (D) (parts by weight) D-1 1 30​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ 30 30 35 35 35 30 D-2 10 40 40 40 40 30 D-3 20 50 Solvent (E) (parts by weight) E-1 100 500 400 500 500 500 500 500 500 500 E-2 ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​300 600 600 600 600 E-3 800 Additives (F) (parts by weight) F-1 1 F-2 2 Pattern Evaluation ◎​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ ○ ◎ ○ ◎ ○ ○ ◎ ◎ ◎ ○ ○ ○ ◎ X X Developability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ ◎ ○ X X

[0127] Table 5 serial number compound C-1 2,4-Bis(trichloromethyl)-6-p-methoxystyryl-s-triazine (TAZ-110) C-2 N-hydroxyimine trifluoromethanesulfonate (N-Hydroxynaphthalimide Trifluoromethanesulfonate, NAI-105) C-3 Triphenylsulfonium trifluoromethanesulfonate D-1 CYMEL 303 D-2 NIKALAC MW-30 D-3 PL-1170 E-1 Propylene glycol monomethyl ether acetate (PGMEA) E-2 Ethyl lactate (EL) E-3 Propylene glycol monoethyl ether (PGEE) F-1 Surfactant: Trade name SF8427; manufactured by Dow Corning Silicone. F-2 Adhesion aid: 3-epoxypropoxypropyltrimethoxysilane

[0128] Evaluation Method

[0129] Pattern Evaluation

[0130] The negative photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 2 were spin-coated onto a glass substrate and pre-baked at 100°C for 90 seconds to obtain a pre-baked coating of approximately 4.0 μm. This pre-baked coating, positioned between lines and spaces, was irradiated with 80 mJ / cm² ultraviolet light (exposure machine model AG500-4N; manufactured by M&R Nano Technology) and then pre-baked at 110°C for 2 minutes. It was then developed with a 2.38% TMAH aqueous solution at 23°C for 1 minute to remove the exposed portions. Subsequent SEM inspection was performed, as shown in the schematic diagram in Figure 1, observing the angle θ between the photoresist pattern 120 and the substrate 110. The pattern was evaluated based on the angle θ, with the following evaluation criteria: ◎: θ ≦ 75°. ○: 75° < θ ≦ 85°. △: 85° < θ ≦ 110°. ╳: θ > 110°.

[0131] Developability

[0132] The negative photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 2 were spin-coated onto a glass substrate and pre-baked at 100°C for 90 seconds to obtain a pre-baked coating of approximately 4.0 μm. This pre-baked coating, positioned between lines and space, was irradiated with 80 mJ / cm² ultraviolet light (exposure machine model AG500-4N; manufactured by M&R Nano Technology), and then pre-baked at 110°C for 2 minutes. The thickness of the pre-coated film after exposure (i.e., the film thickness before development) was measured. Then, it was developed with a 2.38% TMAH aqueous solution at 23°C for 1 minute to remove the exposed portions. After rinsing with pure water, the pattern array can be obtained. Measure the film thickness of the pattern array (i.e., the film thickness after development), calculate the film thickness ratio before and after development using the following formula (VII), and evaluate it according to the following criteria: (VII) ◎: 98% ≤ film thickness ratio. ○: 95% ≤ film thickness ratio < 98%. △: Partial pattern peeling. ╳: Complete pattern peeling.

[0133] According to Table 4, when the negative photosensitive resin composition does not contain a specific polysiloxane (B), the photoresist pattern formed is poorly evaluated (i.e., an inverted trapezoidal pattern cannot be formed) and the developability is poor. When the polysiloxane (B) in the negative photosensitive resin composition contains a first silane monomer (i.e., at least one of Y1 in the silane monomer of formula (I) represents an alkyl group having an anhydride group, an alkyl group having an epoxy group, or an alkoxy group having an epoxy group), the photoresist pattern formed is better evaluated and has better developability. When the total amount of silane monomer used is 1 mol and the amount of the first silane monomer used is 0.01 mol to 0.20 mol, the resulting negative photosensitive resin composition has better developability.

[0134] It should be added that although the present invention uses specific compounds, compositions, reaction conditions, processes, analytical methods or specific instruments as examples to illustrate the negative photosensitive resin composition and photoresist pattern formation method of the present invention, it is clear to anyone with ordinary knowledge in the art to which the present invention pertains that the present invention is not limited thereto. Without departing from the spirit and scope of the present invention, the negative photosensitive resin composition and photoresist pattern formation method of the present invention may also be carried out using other compounds, compositions, reaction conditions, processes, analytical methods or instruments.

[0135] Although the present invention has been disclosed above with reference to several embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field to which the present invention pertains may make various modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims. [Simplified Explanation of the Diagram]

[0136] A better understanding of the features disclosed herein will be achieved by reading the following detailed description in conjunction with the accompanying drawings. It should be noted that, as is standard practice in the industry, many features are not drawn to scale. In fact, for clarity of discussion, the dimensions of many features can be arbitrarily scaled. Figure 1 is a schematic diagram illustrating a photoresist pattern and substrate according to some embodiments of the present invention. [Biomaterial Storage]

[0138] Domestic storage information (please note in order of storage institution, date, and number): None. International storage information (please note in order of storage country, institution, date, and number): None.

Claims

1. A negative photosensitive resin composition comprising: a phenolic varnish resin (A); a polysiloxane (B), wherein the polysiloxane (B) is formed by polycondensation of a silane monomer as shown in formula (I): Si(Y1)a(OY2)4-a (I) In formula (I), Y1 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aromatic group having 6 to 15 carbon atoms, an alkyl group having an anhydride group, an alkyl group having an epoxy group, or an alkoxy group having an epoxy group; Y2 independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an aromatic group having 6 to 15 carbon atoms; and a represents an integer from 0 to 3; a photoacid generator (C); a crosslinking agent (D); and a solvent (E), wherein the phenolic varnish resin (A) is used as the base. The amount used is 100 parts by weight, the amount used of the polysiloxane (B) is 10 to 200 parts by weight, the amount used of the photoacid generator (C) is 1 to 30 parts by weight, the amount used of the crosslinking agent (D) is 1 to 50 parts by weight, and the amount used of the solvent (E) is 100 to 1000 parts by weight.

2. The negative photosensitive resin composition as claimed in claim 1, wherein at least one of the Y1 in formula (I) represents an alkyl group having an anhydride group, an alkyl group having an epoxy group, or an alkoxy group having an epoxy group.

3. The negative photosensitive resin composition as claimed in claim 1, wherein the silane monomer comprises: a first silane monomer, wherein the Y1 of the first silane monomer represents an alkyl group having an anhydride group, an alkyl group having an epoxy group, or an alkoxy group having an epoxy group; and a second silane monomer, wherein the Y1 of the second silane monomer represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aromatic group having 6 to 15 carbon atoms.

4. The negative photosensitive resin composition as described in claim 3, wherein the total amount of the silane monomer used is 1 mol, and the amount of the first silane monomer used is from 0.01 mol to 0.20 mol.

5. The negative photosensitive resin composition as claimed in claim 1, wherein the photoacid generator (C) comprises an onium salt compound, a triazine compound, a sulfonic acid compound, a sulfonate compound, a sulfadiazine compound, or a combination thereof.

6. A method for forming a photoresist pattern, comprising: coating a negative photosensitive resin composition as described in any one of claims 1 to 5 onto a substrate; and performing a processing step on the negative photosensitive resin composition to form the photoresist pattern.

7. The method for forming a photoresist pattern as described in claim 6, wherein the processing steps include a heating process, an exposure process, and a development process.

8. The method for forming a photoresist pattern as claimed in claim 7, wherein the exposure process includes irradiating the negative photosensitive resin composition with an ultraviolet ray, and the wavelength of the ultraviolet ray is from 240 nm to 500 nm.

9. The method for forming a photoresist pattern as described in claim 7, wherein the developing process includes using an alkaline developer.

Images