JP2008015187A - Positive photosensitive resin composition, method for producing thin film pattern, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition which allows curing reaction to proceed in an unexposed portion and interrupts the progress of curing reaction in an exposed portion by reliable neutralization of an acid and a base, when selectively exposed to light through a photomask and heat-treated, so that a thin film pattern excellent in pattern profile can be obtained, a method for producing a thin film pattern using the same, and a semiconductor device. <P>SOLUTION: The positive photosensitive resin composition comprises a condensate of an alkoxysilane, an acid generator (A) which generates an acid upon irradiation with light or radiation, molecular weight is in the extent of 150 to 1000 and a thermal base generator (B) which generates a base by the action of heat. The method for producing a thin film pattern 1C using the same and the semiconductor device are also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a positive photosensitive resin composition having photosensitivity, and more specifically, a positive photosensitive resin composition capable of forming a thin film pattern by alkali development or the like, and a thin film pattern using the same The present invention relates to a manufacturing method and a semiconductor element.

  In manufacturing electronic devices such as semiconductors, a passivation film, a gate insulating film, and the like are formed by a fine pattern forming method. For forming these films, for example, a photosensitive resin composition containing an alkoxysilane condensate or the like is used.

As an example of a film formed using such a photosensitive resin composition, the following Patent Document 1 discloses a general formula (1) with respect to 1 mol of a unit composition represented by the general formula (1) R ₂ SiO. 2) An optical material comprising a silica-based film containing 1 to 20 mol of a unit composition represented by RSiO _1.5 is disclosed. When obtaining an optical material composed of a silica-based coating, a coating liquid containing a siloxane polymer obtained by hydrolysis and partial condensation of a specific silane compound is used, and the coating liquid is used for improving curability. A film hardening agent or the like is contained.

  In Patent Document 1, an acid and a base catalyst can be used as a film curing agent, and the acid or base used in the reaction can be left in the film as it is. Patent Document 1 describes that a compound that generates an acid or a base by heat and a compound that generates an acid or a base by light can be added to the coating solution.

Further, Patent Document 1 shows a specific example of a pattern forming method in the case where the coating solution contains a compound that generates an acid or a base by light. In Patent Document 1, after exposure through a desired mask, heating is performed, and an exposed portion is increased in molecular weight by an action of an acid or a basic compound generated by exposure from an unexposed portion. It is described that the difference in the solubility of the developer with respect to the portion is widened and the effect of improving the resolution contrast is obtained.
JP 07-258604 A

  Conventionally, a photosensitive resin composition called a negative type as described in Patent Document 1 has been mainly used to form a fine pattern. In Patent Document 1, as described above, a specific example of the pattern forming method is shown. However, this forming method proceeds with the crosslinking reaction of the siloxane polymer in the exposed portion to cure, and is not a positive type but a negative type. The type photosensitive resin composition was used.

  In recent years, in order to form a fine pattern, development of a positive photosensitive resin composition is strongly demanded instead of a negative photosensitive resin composition.

  When forming a fine pattern using a positive photosensitive resin composition, the photosensitive resin composition is exposed according to the pattern to be formed, as in the case of a negative photosensitive resin composition. Before or after exposure, the photosensitive resin composition in the unexposed area is cured by heat treatment or the like as necessary to form a patterned latent image. Next, by developing the photosensitive resin composition with a developer and removing the uncured photosensitive resin composition in the exposed area, a thin film pattern composed of the photosensitive resin composition in the unexposed area can be obtained. it can.

  In the positive photosensitive resin composition, it has been strongly demanded that the photosensitive resin composition in the exposed portion can be surely dissolved in the developer. However, in the conventional positive photosensitive resin composition, when developed, the photosensitive resin composition in the exposed area may not be sufficiently dissolved in the developer, and the photosensitive resin composition remains in the exposed area. Tended to be. As a result, the pattern film formed tends to be inferior in pattern shape.

  Patent Document 1 merely describes that the coating solution contains an acid and a base catalyst, an acid, or a compound that generates a base as a film curing agent. That is, Patent Document 1 only describes that the curability can be improved by using an acid and a base catalyst, or an acid or a compound that generates a base, and what kind of these compounds is used. Patent Document 1 does not particularly describe whether to use them in combination.

  An object of the present invention is to allow a curing reaction to proceed in an unexposed area when selectively exposed and heat-treated using, for example, a photomask in view of the current state of the prior art described above, and exposure. A positive photosensitive resin composition capable of reliably neutralizing an acid and a base in a part and sufficiently suppressing the progress of a curing reaction and obtaining a thin film pattern having an excellent pattern shape, and A thin film pattern manufacturing method and a semiconductor element are provided.

  The positive photosensitive resin composition according to the present invention comprises an alkoxysilane condensate, an acid generator (A) that generates an acid upon irradiation with light or radiation, a molecular weight in the range of 150 to 1000, and a heat. And a thermal base generator (B) that generates a base by the action of.

  In a specific aspect of the positive photosensitive resin composition according to the present invention, the acid generator (A) and the thermal base generator (B) are 0.5 to 2 in molar ratio (A) / (B). It is contained in the range of 0.0.

  In another specific aspect of the positive photosensitive resin composition according to the present invention, the acid generator (A) and the thermal base generator (B) are (A) based on 100 parts by weight of the alkoxysilane condensate. ) And (B) in a total amount of 0.4 to 30 parts by weight.

  In still another specific aspect of the positive photosensitive resin composition according to the present invention, the acid generator (A) is composed of at least one compound selected from the group consisting of an onium salt, a diazonium salt, and a sulfonic acid ester.

  In still another specific aspect of the positive photosensitive resin composition according to the present invention, the thermal base generator (B) is selected from the group consisting of dialkylamines, trialkylamines, aromatic amines, and amine imide compounds. At least one compound.

  In the method for producing a thin film pattern according to the present invention, a step of forming a photosensitive resin composition layer comprising a positive photosensitive resin composition configured according to the present invention on a substrate, and a light beam depending on the pattern to be formed. Alternatively, the photosensitive resin composition layer is selectively exposed with radiation, an acid is generated from the acid generator (A) in the exposed area, and the photosensitive resin composition layer is heat-treated, and heat is generated in the exposed area and the unexposed area. A base is generated from the base generator (B), thereby neutralizing the acid generated from the acid generator (A) and the base generated from the thermal base generator (B) in the exposed portion to form a pattern-like latent. The method includes a step of forming an image and a step of developing a photosensitive resin composition layer on which the latent image is formed with a developer to form a thin film pattern after forming a patterned latent image.

  The semiconductor device according to the present invention includes at least one film selected from the group consisting of a gate insulating film, a passivation film, and an interlayer insulating film, and the positive photosensitive resin composition in which the film is configured according to the present invention. It is a film formed using an object.

  The positive photosensitive resin composition according to the present invention comprises an alkoxysilane condensate, an acid generator (A) that generates an acid upon irradiation with light or radiation, a molecular weight in the range of 150 to 1000, and a heat. And a thermal base generator (B) that generates a base by the action of, for example, by irradiating the photosensitive resin composition with light or radiation using, for example, a photomask, the acid generator (A) in the exposed area. The base can be generated from the thermal base generator (B) in the exposed part and the unexposed part by heat-treating the photosensitive resin composition.

  Therefore, in the exposed area, a neutralization reaction between the acid generated from the acid generator (A) and the base generated from the thermal base generator (B) occurs, so that the curing reaction of the photosensitive resin composition hardly proceeds. . On the other hand, in the unexposed area, the photosensitive resin composition can be sufficiently cured by the base generated from the thermal base generator (B). Therefore, if it develops after exposure and heat processing, the photosensitive resin composition of an exposed part can be removed, and the thin film pattern excellent in the pattern shape which consists of the photosensitive resin composition of an unexposed part can be obtained.

  Furthermore, in this invention, the thermal base generator which has a molecular weight in the range of 150-1000 is used as a thermal base generator (B) which generate | occur | produces a base by the effect | action of a heat | fever.

  As described above, a base is generated from the thermal base generator (B) by heat-treating the photosensitive resin composition, and the heat treatment is performed at a relatively high temperature. Therefore, if the molecular weight of the thermal base generator (B) is small, the thermal base generator (B) is volatilized by heat treatment, and a sufficient amount of base may not be generated from the thermal base generator (B). It was. In this case, the neutralization reaction between the acid generated from the acid generator (A) and the base generated from the thermal base generator (B) does not sufficiently occur in the exposed area, and the acid generator (A) in the exposed area. The curing reaction of the photosensitive resin composition tended to proceed due to the acid generated from. On the other hand, in the present invention, since the thermal base generator (B) having a molecular weight in the range of 150 to 1000 is used, a sufficient base is generated without volatilization of the thermal base generator (B) by heat treatment. be able to. Moreover, the usage-amount of a thermal base generator (B) can also be reduced.

  When the acid generator (A) and the thermal base generator (B) are contained in a molar ratio (A) / (B) in the range of 0.5 to 2.0, the exposed portion is exposed to an acid by exposure. The acid generated from the generator (A) and the base generated from the thermal base generator (B) by heat treatment can be appropriately neutralized. Therefore, since the curing of the photosensitive resin composition is more difficult to proceed in the exposed portion, a more excellent thin film pattern can be obtained due to the pattern shape.

  The acid generator (A) and the thermal base generator (B) are combined in a total amount of (A) and (B) in the range of 0.4 to 30 parts by weight with respect to 100 parts by weight of the alkoxysilane condensate. In the case where it is contained, the curing reaction of the photosensitive resin composition can be advanced more efficiently. Furthermore, in the obtained thin film pattern, the residue resulting from an acid generator (A) and a heat base generator (B) is hard to produce.

  When the acid generator (A) is composed of at least one compound selected from the group consisting of onium salts, diazonium salts and sulfonic acid esters, the acid generator (A ) Can generate an acid more efficiently.

  When the thermal base generator (B) is composed of at least one compound selected from the group consisting of dialkylamines, trialkylamines, aromatic amines and amine imide compounds, the photosensitive resin composition is heat treated. By doing so, a base can be more efficiently generated from the thermal base generator (B).

  In the method for producing a thin film pattern according to the present invention, a step of forming a photosensitive resin composition layer comprising a positive photosensitive resin composition configured according to the present invention on a substrate, and a light beam depending on the pattern to be formed. Alternatively, the photosensitive resin composition layer is selectively exposed with radiation, an acid is generated from the acid generator (A) in the exposed area, and the photosensitive resin composition layer is heat-treated, and heat is generated in the exposed area and the unexposed area. A base is generated from the base generator (B), thereby neutralizing the acid generated from the acid generator (A) and the base generated from the thermal base generator (B) in the exposed portion to form a pattern-like latent. A step of forming an image, so that the cross-linking reaction of the alkoxysilane condensate does not sufficiently proceed in the exposed area, and the cross-linking reaction of the alkoxysilane condensate sufficiently proceeds in the unexposed area. Bets can be, it is possible to form a patterned latent image.

  Further, in the present invention, after the pattern-like latent image is formed, the photosensitive resin composition layer on which the latent image is formed is further developed with a developer to obtain a thin film pattern. The photosensitive resin composition layer in the exposed area is removed by development using a developing solution such as the above, and a thin film pattern having an excellent pattern shape made of the photosensitive resin composition in the unexposed area can be obtained.

  The semiconductor element according to the present invention includes at least one film selected from the group consisting of a gate insulating film, a passivation film, and an interlayer insulating film, and the film uses the positive photosensitive resin composition of the present invention. Therefore, the film is excellent in shape.

  Details of the present invention will be described below.

  In order to achieve the above-mentioned problems, the present inventors have made extensive studies on a positive photosensitive resin composition containing a condensate of alkoxysilane used for pattern formation. As a result, an acid that generates an acid upon irradiation with light or radiation is obtained. The photosensitive resin composition was exposed and heat-treated by containing a generator (A) and a thermal base generator (B) having a molecular weight in the range of 150 to 1000 and generating a base by the action of heat. Later, by developing, it was found that the photosensitive resin composition in the exposed area was sufficiently removed, and a thin film pattern having an excellent pattern shape was obtained, and the present invention was achieved.

  The positive photosensitive resin composition according to the present invention comprises an alkoxysilane condensate, an acid generator (A) that generates an acid upon irradiation with light or radiation, and a thermal base generator that generates a base by the action of heat. (B).

  The alkoxysilane condensate comprises a condensate obtained by condensing alkoxysilane. At least one kind of alkoxysilane condensate is contained, and therefore, a condensate of two or more kinds of alkoxysilanes may be contained.

  In this invention, it is preferable to contain the condensate of the alkoxysilane obtained by condensing the alkoxysilane represented by following formula (1).

Si (X) _p (Y) _q (Z) _4-pq Formula (1)
In the above formula (1), X represents hydrogen or a non-hydrolyzable organic group having 1 to 30 carbon atoms, Y represents an alkoxy group, Z represents a hydrolyzable group other than an alkoxy group, p represents an integer of 0 to 3, q represents an integer of 1 to 4, and p + q ≦ 4. When p is 2 or 3, the plurality of X may be the same or different. When q is 2 to 4, a plurality of Y may be the same or different. When p + q ≦ 2, the plurality of Z may be the same or different.

  The alkoxy group Y and the hydrolyzable group Z other than the alkoxy group are usually hydrolyzed by heating in the temperature range of room temperature (25 ° C.) to 100 ° C. without catalyst in the presence of excess water. A group capable of forming a silanol group, or a group capable of further condensation to form a siloxane bond.

  Although it does not specifically limit as said alkoxy group Y, Specifically, C1-C6 alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned.

  Although it does not specifically limit as hydrolyzable group Z other than the said alkoxy group, Specifically, halogeno groups, such as chlorine and a bromine, an amino group, a hydroxyl group, or a carboxyl group etc. are mentioned.

  The non-hydrolyzable organic group X is not particularly limited, and examples thereof include an organic group having 1 to 30 carbon atoms that hardly causes hydrolysis and is a stable hydrophobic group. As the organic group having 1 to 30 carbon atoms which is a stable hydrophobic group, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group, pentyl group, decyl group, dodecyl group, tetradecyl group, Alkyl groups having 1 to 30 carbon atoms such as hexadecyl group, octadecyl group and eicosyl group, and alkyl halide groups such as fluorinated, chlorinated and brominated alkyl groups (for example, 3-chloropropyl group, 6-chloropropyl group) , 6-chlorohexyl group, 6,6,6-trifluorohexyl group, etc.), aromatic substituted alkyl groups such as halogen-substituted benzyl groups (for example, benzyl group, 4-chlorobenzyl group, 4-bromobenzyl group, etc.) ), Aryl groups (eg phenyl group, tolyl group, mesityl group, naphthyl group, etc.), vinyl groups and epoxy groups Group, an organic group containing an amino group, and the like organic group containing a thiol group.

  Specific examples of the alkoxysilane include, for example, triphenylethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triethylmethoxysilane, ethyldimethylmethoxysilane, methyldiethylmethoxysilane, ethyldimethylethoxysilane, methyldiethyl. Ethoxysilane, phenyldimethylmethoxysilane, phenyldiethylmethoxysilane, phenyldimethylethoxysilane, phenyldiethylethoxysilane, methyldiphenylmethoxysilane, ethyldiphenylmethoxysilane, methyldiphenylethoxysilane, ethyldiphenylethoxysilane, tert-butoxytrimethylsilane, butoxy Trimethylsilane, dimethylethoxysilane, methoxydimethylvinylsilane , Ethoxydimethylvinylsilane, diphenyldiethoxysilane, phenyldiethoxysilane, dimethyldimethoxysilane, diacetoxymethylsilane, diethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxymethylsilane, diethoxydimethylsilane Diacetoxymethylvinylsilane, diethoxymethylvinylsilane, diethoxydiethylsilane, dimethyldipropoxysilane, dimethoxymethylphenylsilane, methyltrimethoxysilane, methyltriethoxysilane, methyl-tri-n-propoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyl-tri-n-propoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyl-tri-n Propoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltripropoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyl Tripropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltripropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltripropoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecyltripropoxysilane, tetra Decyltrimethoxysilane, tetradecyltriethoxysilane, tetradecyltripropoxysilane, hex Sadecyltrimethoxysilane, hexadecyltriethoxysilane, hexadecyltripropoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltripropoxysilane, eicosyldecyltrimethoxysilane, eicosyltriethoxysilane, eicosyltripropoxy Silane, 6-chlorohexyltrimethoxysilane, 6,6,6-trifluorohexyltrimethoxysilane, benzyltrimethoxysilane, 4-chlorobenzyltrimethoxysilane, 4-bromobenzyltri-n-propoxysilane, phenyltrimethoxy Silane, phenyltriethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-amino Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, N-β-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltri Methoxysilane, triethoxysilane, trimethoxysilane, triisopropoxysilane, tri-n-propoxysilane, triacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraiso Examples include propoxysilane and tetraacetoxysilane. An alkoxysilane condensate obtained by condensing these alkoxysilanes is more preferably used. In constituting the alkoxysilane condensate, it is sufficient that at least one alkoxysilane is used, and therefore two or more alkoxysilanes may be used.

  The positive photosensitive resin composition according to the present invention contains an acid generator (A) that generates an acid upon irradiation with light or radiation.

Although it does not specifically limit as said acid generator (A), For example, onium salt etc. are mentioned. More specifically, diazonium, phosphonium, and iodonium salts such as BF ₄ ⁻ , PF ₆ ⁻ , SBF ₆ ⁻ , and ClO ₄ ^— , and other organic halogen compounds, organic metals, and organic halides can be used. .

  The acid generator (A) is not particularly limited, but is triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethaneantimonate, triphenylsulfonium benzosulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfone. Nart, sulfonium salt compounds such as dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, iodonium salts such as diphenyliodonium trifluoromethanesulfonate, N- Hydroxysuccinimide trifluoromethanesulfonate, etc. And the like. These acid generators (A) may be used alone or in combination of two or more.

  Since an acid is efficiently generated by irradiation with light or radiation, at least one compound selected from the group consisting of an onium salt, a diazonium salt and a sulfonic acid ester is more preferably used as the acid generator (A).

  In addition to the acid generator (A) that is a photosensitizer, a sensitizer may be further added in order to further increase sensitivity.

  The sensitizer is not particularly limited. Specifically, benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, Anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2- Chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-t rt-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis ( 5,7-dimethoxycarbonylcoumarin) and coronene, and the like are preferable.

  In addition to the acid generator (A) that generates an acid upon irradiation with light or radiation, the positive photosensitive resin composition according to the present invention has a molecular weight in the range of 150 to 1,000, and a base by the action of heat. It further contains a thermal base generator (B) that generates

  In addition to the acid generator (A) that generates an acid upon irradiation with light or radiation, the present invention is characterized by a thermal base generator that has a molecular weight in the range of 150 to 1000 and generates a base by the action of heat ( B) is further contained. As will be described in detail later, by this configuration, a patterned latent image can be formed by exposing the photosensitive resin composition layer to light or radiation through a photomask and further heat-treating it. And after forming a pattern-like latent image, it develops with a developing solution and a thin film pattern excellent in pattern shape can be obtained by removing an exposure part. Furthermore, by performing exposure and heat treatment, the acid generated from the thermal acid generator (A) and the base generated from the thermal base generator (B) are surely prevented without volatilizing the thermal base generator (B). Can be neutralized.

  The thermal base generator (B) has a molecular weight in the range of 150 to 1000. When the molecular weight of the thermal base generator (B) is less than 150, the thermal base generator (B) is volatilized by the heat treatment and does not generate a sufficient amount of base, and a relatively large amount of thermal base generator ( B) must be used, and a residue tends to occur after development. When the molecular weight of the thermal base generator (B) exceeds 1000, the reactivity of the thermal base generator (B) is remarkably reduced or developability is lowered.

  The thermal base generator (B) is not particularly limited, and examples thereof include ammonium such as monoalkyltrimethylammonium chloride, monoalkylbenzyldimethylammonium chloride, dialkylethylmethylammonium ethosulphate, dialkyldimethylammonium chloride, and alkyldiammonium chloride. Salts; amines such as monoalkylamines, dialkylamines, trialkylamines, aromatic amines, alkanolamines; diamino compounds having two nitrogen atoms in the same molecule; diaminos having three or more nitrogen atoms A polymer, an amide group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound and the like can be mentioned and preferably used.

  Examples of the compound or polymer as the thermal base generator (B) include monoalkylamines such as n-decylamine, hexadecylamine, octadecylamine; di-n-pentylamine, di-n-hexylamine. , Di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine and other dialkylamines; tri-n-butylamine, tri-n-pentylamine, tri-n-hexyl Trialkylamines such as amine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine and tri-n-decylamine; aromatic amines such as diphenylamine, triphenylamine and 1-naphthylamine Can be mentioned. Examples of the diamino compound having two nitrogen atoms in the same molecule include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2 -(3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4 -Hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene and the like Can be mentioned. Examples of the diamino polymer having 3 or more nitrogen atoms include polymers of polyethyleneimine, polyallylamine, and dimethylaminoethylacrylamide.

  Examples of the nitrogen-containing heterocyclic compound include imidazoles such as 4-methyl-2-phenylimidazole; pyridines such as 2-phenylpyridine, 4-phenylpyridine and N-methyl-4-phenylpyridine. be able to. These thermal base generators (B) may be used alone or in combination of two or more.

  Since the base is efficiently generated by the heat treatment, the thermal base generator (B) is more preferably at least one compound selected from the group consisting of dialkylamines, trialkylamines, aromatic amines, and amine imide compounds. Used.

  As the amine imide compound, an amine imide compound represented by the following general formula (2) or (3) can be used.

In the above formulas (2) and (3), R ¹ , R ² and R ³ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkylidene having 1 to 8 carbon atoms. Group, a cycloalkyl group having 4 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, a phenoxyalkyl group having 7 to 12 carbon atoms, a phenyl group, an electron donating group and / or an electron withdrawing group And a benzyl group substituted with a group, a benzyl group, an electron donating group and / or an electron withdrawing group. As a C1-C8 alkyl group, the alkyl group which has a substituent other than a linear alkyl group, for example, an isopropyl group, an isobutyl group, t-butyl group etc. are included. Among these substituents, from the viewpoint of ease of synthesis, solubility of amine imide, etc., an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 8 carbon atoms, and a phenoxyalkyl group having 7 to 12 carbon atoms. Is preferred. R ⁴ independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a cycloalkyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group. Ar ¹ in the general formula (2) is an aromatic group, and such an amine imide compound is known prior to the filing of the present application as disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-35949. Are available. In the general formula (3), Ar ² is an aromatic group.

Specific examples of Ar ¹ that is an aromatic group in the general formula (2) described above include aromatic groups represented by the following formulas (4) to (16).

In the above formulas (4) to (16), R ^{5 to} R ²⁸ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, carbon An alkylidene group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 6 carbon atoms, and a dialkylamino group having 1 to 3 carbon atoms , Morpholino group, mercapto group, hydroxyl group, hydroxyalkyl group having 1 to 6 carbon atoms, halogen such as fluorine, chlorine and bromine, ester group having 1 to 6 carbon atoms, carbonyl group having 1 to 6 carbon atoms, aldehyde group, cyano Group, trifluoromethyl group, cyano group, nitro group, benzoyl group, phenyl group, electron-donating group and / or electron-withdrawing group substituted phenyl group, electron-donating group and / or electron-withdrawing group A conversion to benzyl group. Moreover, U to Z in the above-described formulas (4) to (16) are any of carbon, nitrogen, oxygen, and sulfur atoms.

Specific examples of Ar ² that is the aromatic group in the general formula (3) described above include aromatic groups represented by the following formulas (17) to (25).

In the above formulas (17) to (25), R ^{29 to} R ³⁶ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, carbon An alkylidene group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 6 carbon atoms, and a dialkylamino group having 1 to 3 carbon atoms , Morpholino group, mercapto group, hydroxyl group, hydroxyalkyl group having 1 to 6 carbon atoms, halogen such as fluorine, chlorine and bromine, ester group having 1 to 6 carbon atoms, carbonyl group having 1 to 6 carbon atoms, aldehyde group, cyano Group, trifluoromethyl group, cyano group, nitro group, phenyl group, electron donating group and / or electron withdrawing group substituted phenyl group, electron donating group and / or electron withdrawing group substituted Is Jill group. In the above formulas (17) to (25), W is any one of carbon, nitrogen, nitrogen substituted with an alkyl group having 1 to 6 carbon atoms, oxygen, and sulfur. One of carbon, nitrogen, oxygen, and sulfur atoms.

  The amine imide compound can be synthesized by a known method. Methods for synthesizing amine imide compounds are described in, for example, Encyclopedia of Polymer Science and Engineering, John Wiley & Sons Ltd. (1985), Volume 1, p740. Specifically, an amine imide compound can be obtained from a reaction of a corresponding carboxylic acid ester with a halogenated hydrazine and sodium alkoxide or a reaction of a carboxylic acid ester with hydrazine and an epoxy compound. In view of the ease of synthesis and safety, an amine imide compound obtained from the reaction of the corresponding carboxylic acid ester with hydrazine and an epoxy compound is preferred. The synthesis temperature and synthesis time are not particularly limited as long as the starting materials to be used are not decomposed, and generally an amine imide compound can be obtained under conditions of stirring at a temperature of 0 to 100 ° C. for 30 minutes to 7 days. it can.

  As an example of a method for synthesizing the amine imide compound, p-nitrobenzoic acid methyl ester, N, N-dimethylhydrazine, and phenylglycidyl ether are added to tert-butanol, and the mixture is stirred at 50 ° C. for 10 hours, and further room temperature. After stirring for 48 hours, a white precipitate is formed, and then the white precipitate is filtered off, washed twice with ethyl acetate, and dried in a vacuum dryer to obtain an amine imide compound.

  As another example of the method for synthesizing the amine imide compound, p-cyanobenzoic acid methyl ester, N, N-dimethylhydrazine and phenylglycidyl ether are added to tert-butanol and stirred at 50 ° C. for 72 hours. Furthermore, after removing tert-butanol from the reaction solution obtained by stirring at room temperature for 48 hours, white amine imide compound can be obtained by adding 10 g of ethyl acetate and performing recrystallization.

  In the positive photosensitive resin composition according to the present invention, the acid generator (A) and the thermal base generator (B) are (A) and (B) based on 100 parts by weight of the alkoxysilane condensate. It is preferable to contain in the range of 0.4-30 weight part by the total amount of. More preferably, the total amount of (A) and (B) is in the range of 0.5 to 20 parts by weight.

  If the total amount of the acid generator (A) and the thermal base generator (B) is less than 0.4 parts by weight, the sensitivity may not be sufficient and the formation of a thin film pattern may be difficult. When the total amount of the acid generator (A) and the thermal base generator (B) exceeds 30 parts by weight, it becomes difficult to uniformly apply the positive photosensitive resin composition, and a residue is generated after development. There is.

  The compounding amount of the acid generator (A) and the thermal base generator (B) is such that the acid generated from the acid generator (A) and the base generated from the thermal base generator (B) are neutralized in the exposed area. Can be adjusted as appropriate. Preferably, the acid generator (A) and the thermal base generator (B) have a molar ratio (A) / (B) of the acid generator (A) to the thermal base generator (B) of 0.5 to 2. It is preferable to contain in the range of 0.0. More preferably, the molar ratio (A) / (B) is in the range of 0.6 to 1.8.

  When the molar ratio (A) / (B) exceeds 2.0, too much acid is generated from the acid generator (A), and the photosensitive resin composition is easily cured in the exposed area. On the other hand, when the molar ratio (A) / (B) is less than 0.5, too much base is generated from the thermal base generator (B), and the photosensitive resin composition is easily cured in the exposed area.

  In the present invention, in addition to the alkoxysilane condensate, the acid generator (A), and the thermal base generator (B), an appropriate solvent may be further added. By adding a solvent, a positive photosensitive resin composition that can be easily applied can be provided.

  The solvent is not particularly limited as long as it can dissolve the alkoxysilane condensate, but is an aromatic hydrocarbon compound such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, diethylbenzene; cyclohexane, cyclohexene, dipentene, n Saturated or unsaturated hydrocarbon compounds such as pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane; diethyl Ether, di-n-propyl ether, di-isopropyl ether, dibutyl ether, ethylpropyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol Ethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether , Ethylene glycol methyl ethyl ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl cyclohexa , Methylcyclohexane, p-menthane, o-menthane, m-menthane; ethers such as dipropyl ether and dibutyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, Ketones such as cyclohexanone and cycloheptanone; ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, stearic acid Examples include esters such as butyl. These solvents may be used independently and 2 or more types may be used together.

  What is necessary is just to select the compounding ratio of the said solvent suitably so that it may apply uniformly, for example, when a positive photosensitive resin composition is applied on a board | substrate and a photosensitive resin composition layer is formed. Preferably, the positive photosensitive resin composition has a solid concentration of 0.5 to 60% by weight, more preferably about 2 to 40% by weight.

  If necessary, other additives may be further added to the positive photosensitive resin composition according to the present invention. Such additives include fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, UV absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, plasticizers, plasticizers. Examples include accelerators and sagging inhibitors.

  The method for producing a thin film pattern according to the present invention includes a step of forming a photosensitive resin composition layer 1 made of a positive photosensitive resin composition according to the present invention, as shown in FIG. The photosensitive resin composition layer 1 is selectively exposed using the photomask 3 corresponding to the pattern, and an acid is generated from the acid generator (A) in the photosensitive resin composition layer 1A of the exposed portion, In addition, the exposed photosensitive resin composition layer 1A and the unexposed photosensitive resin composition layer 1B are heat-treated to generate a base from the thermal base generator (B) to form a patterned latent image (FIG. 1 (b)) and a step of developing the photosensitive resin composition layer 1A in the exposed portion where the latent image is formed with an alkaline aqueous solution to obtain a thin film pattern composed of the photosensitive resin composition layer in the unexposed portion (FIG. 1 (c)).

  Here, the development is not only an operation of immersing the exposed and unexposed photosensitive resin composition layers 1A and 1B in which a latent image is formed in an alkaline aqueous solution, but also the photosensitive resin composition layers 1A and 1B. Various operations for treating the photosensitive resin composition layers 1A, 1B with an alkaline aqueous solution, such as an operation of washing the surface of the photosensitive resin composition layer 1A, 1B with an alkaline aqueous solution or an operation of spraying the alkaline aqueous solution onto the surface of the photosensitive resin composition layer 1A, 1B. Shall be. The developing solution is not limited to an alkaline aqueous solution, and an acidic aqueous solution or various solvents may be used. Examples of the solvent include the various solvents described above. Examples of the acidic aqueous solution include oxalic acid, formic acid, acetic acid and the like.

  Although the process of forming the said photosensitive resin composition layer is not specifically limited, For example, the positive photosensitive resin composition which concerns on this invention is provided on the board | substrate 2 shown in FIG. 1, and the photosensitive resin composition layer 1 is provided. The method of forming is mentioned. As a specific method in this case, a general coating method can be used, for example, dip coating, roll coating, bar coating, brush coating, spray coating, spin coating, extrusion coating. Work, gravure coating, etc. can be used. As the substrate on which the positive photosensitive resin composition is applied, a silicon substrate, a glass substrate, a metal plate, a plastics plate, or the like is used depending on the application. The thickness of the photosensitive resin composition layer varies depending on the use, but 10 nm to 10 μm is a standard. When the photosensitive resin composition layer coated on the substrate uses a solvent to dissolve the photosensitive resin, it is preferable to heat-treat the solvent to dry the solvent. The heat treatment temperature is generally 40 ° C. to 200 ° C., and is appropriately selected according to the boiling point and vapor pressure of the solvent.

  A photosensitive resin composition layer is formed on a substrate, the photosensitive resin composition layer is covered with a photomask, and light is irradiated in a pattern. Thereby, a latent image having a necessary pattern shape can be formed. What is necessary is just to use the common thing marketed as a photomask.

The light source for irradiating light rays such as ultraviolet rays and visible rays, or radiation is not particularly limited, and an ultrahigh pressure mercury lamp, a deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer laser, etc. can be used. . These light sources are appropriately selected according to the photosensitive wavelength of the acid generator (A) or sensitizer. The irradiation energy of light is generally in the range of 10 to 1000 mJ / cm ² , although depending on the desired film thickness and the type of acid generator (A) or sensitizer. When it is less than 10 mJ / cm ² , the alkoxysilane condensate is not sufficiently exposed. Moreover, when larger than 1000 mJ / cm < ² >, there exists a possibility that exposure time may become long and there exists a possibility that the manufacturing efficiency per time of a thin film pattern may fall.

  In the present invention, the photosensitive resin composition layer is heat-treated by the heat treatment step for drying the solvent, or the photosensitive resin composition layer is heat-treated before, after or simultaneously with the exposure. Preferably, the photosensitive composition layer is heat-treated after exposure. By heat-treating the photosensitive resin composition, a base is generated from the thermal base generator (B).

  The temperature of the heat treatment can be appropriately selected according to the thermal base generator (B) to be used, but is preferably in the range of 80 to 300 ° C. In the present invention, since the thermal base generator (B) having a molecular weight in the range of 150 to 1000 is used, the thermal base generator (B) does not volatilize by heat treatment, and the thermal base generator (B) is reliably And a sufficient amount of base can be generated.

  In the exposed portion of the photosensitive resin composition layer irradiated with light in the pattern shape, the neutralization reaction between the acid generated from the acid generator (A) by exposure and the base generated from the thermal base generator (B) by heat treatment And the cross-linking of the alkoxysilane condensate hardly proceeds. On the other hand, in the unexposed area, crosslinking of the alkoxysilane condensate proceeds by the action of the base generated from the thermal base generator (B) by heat treatment. Therefore, the unexposed portion becomes insoluble in the developer as a result of the progress of crosslinking.

  By developing the exposed photosensitive resin composition layer using a developer, the exposed portion of the photosensitive resin composition layer is dissolved and removed in the developer, and the unexposed portion remains on the substrate. As a result, a thin film pattern 1C is formed. This thin film pattern is called a positive pattern because the exposed portion is removed. That is, this positive photosensitive resin composition was generated from the acid generator (A) in the exposed portion by neutralizing the base generated from the base generator in the exposed portion with the acid generated from the thermal acid generator. It prevents the acid from acting.

  As the developer, an explosion-proof facility is unnecessary, and the burden on the facility due to corrosion or the like is small, so an alkaline aqueous solution is preferably used. For example, alkaline aqueous solutions, such as tetramethylammonium hydroxide aqueous solution, sodium silicate aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, are mentioned. The time required for development depends on the thickness of the photosensitive resin composition layer and the type of solvent, but is preferably in the range of 10 seconds to 5 minutes because development can be efficiently performed and production efficiency is increased. The thin film pattern obtained after development is preferably washed with distilled water to remove the alkaline aqueous solution remaining on the thin film.

  In addition, although the photosensitive resin composition which concerns on this invention is used suitably for forming a film | membrane pattern in various apparatuses, the said film | membrane pattern is used suitably for the insulation protective film of an electronic device. By using a film pattern formed using the photosensitive resin composition according to the present invention as an insulating protective film of an electronic device, the shape stability of the obtained insulating protective film can be effectively increased. Examples of such an insulating protective film for electronic devices include a TFT protective film for protecting a thin film transistor (TFT) in a liquid crystal display element and a protective film for protecting a filter in a color filter.

  In addition, the photosensitive resin composition according to the present invention is more preferably used to constitute an interlayer insulating film or a passivation film of a semiconductor element.

  FIG. 2 is a front cross-sectional view schematically showing a semiconductor element including a passivation film and an interlayer insulating film made of the photosensitive resin composition according to the present invention.

  In the semiconductor element 11 shown in FIG. 2, a gate electrode 13 is provided at the center of the upper surface of the substrate 12. A gate insulating film 14 is formed on the upper surface of the substrate 12 so as to cover the gate electrode 13. A source electrode 15 and a drain electrode 16 are provided on the gate insulating film 14. A semiconductor layer 17 is formed on the gate insulating film 14 so as to cover part of the source electrode 15 and part of the drain electrode 16. Further, a passivation film 18 is formed so as to cover the portion of the source electrode 15 and the drain electrode 16 that are not covered with the semiconductor layer 17 and the semiconductor layer 17. In the semiconductor element 11, the gate insulating film 14 and the passivation film 18 are films formed using the photosensitive resin composition according to the present invention.

  The film | membrane formed using the photosensitive resin composition is used for various uses. Here, the “film formed using the photosensitive resin composition” is a film obtained by introducing energy such as heat, light or radiation to the photosensitive resin composition and introducing a crosslinked structure. Means.

  The photosensitive resin composition according to the present invention can be widely used as an insulating protective film for various electronic devices such as a TFT protective film for organic EL elements, an interlayer protective film for IC chips, and an insulating layer for sensors.

  Hereinafter, the present invention will be clarified by giving examples and comparative examples of the present invention. In addition, this invention is not limited to a following example.

(Materials used)
[Condensate of alkoxysilane]
To a 100 ml flask equipped with a condenser, 5 g of phenyltriethoxysilane, 10 g of triethoxysilane, 0.5 g of oxalic acid, 5 ml of water and 50 ml of propylene glycol monomethyl ether acetate were added. The solution was stirred using a semicircular type mechanical stirrer and reacted at 70 ° C. for 6 hours with a mantle heater. Subsequently, ethanol and residual water produced by the condensation reaction with water were removed using an evaporator. After completion of the reaction, the flask was left to reach room temperature to prepare an alkoxysilane condensate.

[Photoacid generator (A)]
(A1) Sulfonate (Midori Chemical Co., Ltd., trade name: NAI-101)
(A2) Sulphonium salt (trade name: NDS-165, manufactured by Midori Chemical Co., Ltd.)

[Heat base generator (B)]
(B1) Tri-n-butylamine (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 185.35)
(B2) Octadecylamine (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 269.51)
(B3) Tri-n-octylamine (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 353.68)
(B4) Di-n-decylamine (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 297.57)
(B5) Triphenylamine (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 245.32)
(B6) Tri-n-propylamine (Wako Pure Chemical Industries, molecular weight 143.27)
(B7) Amineimide compound: 1,1,1-trimethyl-2- (hydroxymethylbenzoyl) amineimide

Synthesis method:
11.8 g of 1,1,1-trimethylhydrazinium-p-toluenesulfonic acid was dissolved in 70 ml of tert-butanol, and 2.6 g of sodium methylate was added at room temperature with stirring. Next, a solution of 8.0 g of p-hydroxymethylbenzoate dissolved in 35 ml of tert-butanol was added dropwise at room temperature over 30 minutes. This was heated to 55 ° C. and stirred for 68 hours to produce a precipitate. The obtained precipitate was filtered, washed with tert-butanol and dried under reduced pressure at 60 ° C., and the residue was recrystallized from ethyl acetate / methanol (volume ratio 9/1) to obtain 2.3 g of the desired compound (yield). Rate 78.0%). The molecular weight of the obtained compound was 208.26.
(B8) Tridodecylamine (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 5211.952)
(B9) Amine polymer (made by Nippon Shokubai Co., Ltd., trade name: NK-100PM, average molecular weight 20,000, amine value (number of moles of amine contained in 1 g of solid) average 2.55 mmol / g)

(Preparation of photosensitive resin compositions of Examples and Comparative Examples)
The alkoxysilane condensate, the photoacid generator (A), and the thermal base generator (B) are mixed in the blending ratio shown in Table 1 below, and then dissolved in 500 parts by weight of tetrahydrofuran as a solvent. A photosensitive resin composition was prepared.

(Evaluation of Examples and Comparative Examples)
As a base material, a glass substrate having aluminum deposited on the surface layer was used, and the photosensitive resin compositions of Examples and Comparative Examples were spin-coated on the glass substrate at a rotational speed of 1500 rpm. After coating, it was dried in a hot air oven at 80 ° C. to form a coating film.

Next, ultraviolet rays having a wavelength of 365 nm are applied to the coating film through a photomask having a predetermined pattern (USHIO Inc., Spot Cure SP-5), and the irradiation energy is 500 mJ / cm ² . It was irradiated for 5 seconds with an ultraviolet illuminance of 100 mW / cm ² .

  Next, the coating film was heat-treated in a hot air oven at 150 ° C. for 5 minutes. Thereafter, the coating film was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide and developed to form a thin film pattern.

  About the thin film pattern obtained as mentioned above, the pattern shape was evaluated on the following evaluation criteria.

[Evaluation criteria for pattern shape]
○: A good pattern is formed. Δ: A pattern is formed only partially. ×: A pattern is not formed. The results are shown in Table 1 below.

(A)-(c) is sectional drawing of each process for demonstrating the method of forming a thin film pattern using the positive photosensitive resin composition which concerns on this invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a front sectional view showing a semiconductor element including a passivation film and an interlayer insulating film made of a positive photosensitive resin composition according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive resin composition layer 1A ... Photosensitive resin composition layer 1B ... Photosensitive resin composition layer 1C ... Thin film pattern 2 ... Substrate 3 ... Photomask 11 ... Semiconductor element 12 ... Substrate 13 ... Gate electrode 14 ... Gate insulation Film 15 ... Source electrode 16 ... Drain electrode 17 ... Semiconductor layer 18 ... Passivation film

Claims (7)

  An alkoxysilane condensate, an acid generator (A) that generates acid upon irradiation with light or radiation, and a thermal base generator (B) that has a molecular weight in the range of 150 to 1000 and generates a base by the action of heat. And a positive photosensitive resin composition.   The positive type according to claim 1, comprising the acid generator (A) and the thermal base generator (B) in a molar ratio (A) / (B) in the range of 0.5 to 2.0. Photosensitive resin composition.   With respect to 100 parts by weight of the alkoxysilane condensate, the acid generator (A) and the thermal base generator (B) are combined in a total amount of (A) and (B) of 0.4 to 30 wt. The positive photosensitive resin composition according to claim 1, which is contained in a range of parts.   The positive photosensitive resin according to any one of claims 1 to 3, wherein the acid generator (A) comprises at least one compound selected from the group consisting of an onium salt, a diazonium salt, and a sulfonic acid ester. Composition.   The thermal base generator (B) is composed of at least one compound selected from the group consisting of dialkylamines, trialkylamines, aromatic amines, and amine imide compounds. The positive photosensitive resin composition according to Item. Forming a photosensitive resin composition layer comprising the positive photosensitive resin composition according to any one of claims 1 to 5 on a substrate;
Depending on the pattern to be formed, the photosensitive resin composition layer is selectively exposed with light or radiation, an acid is generated from the acid generator (A) in an exposed portion, and the photosensitive resin composition layer is formed. Heat treatment is performed to generate a base from the thermal base generator (B) in the exposed area and the unexposed area, thereby generating an acid generated from the acid generator (A) in the exposed area and the thermal base generator (B). Forming a patterned latent image by neutralizing the generated base;
A method of producing a thin film pattern, comprising: forming the pattern latent image; and developing the photosensitive resin composition layer on which the latent image is formed with a developer to obtain a thin film pattern. .   A positive photosensitive resin composition according to claim 1, comprising at least one film selected from the group consisting of a gate insulating film, a passivation film, and an interlayer insulating film. A semiconductor element, characterized in that it is a film formed by

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