JP2007187721A - Photosensitive composition and semiconductor element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition used for forming an interlayer insulation film or the like of a semiconductor element and for forming a thick film pattern with irradiation of radiation or the like, has photosensitiveness, and enables a development without using a crosslinking agent, and to provide the semiconductor element using the photosensive composition. <P>SOLUTION: The photosensitive composition contains at least one component (A) selected from a group consisting of a silane compound denoted by formula (1) (in formula (1), X denotes a hydrolytic group, Ra denotes a non-hydrolytic organic group, and m denotes an integer of 1-4), a hydrolyzate of the silane compound and a condensate of hydrolyzate; at least one component (B) selected from a group consisting of a compound denoted by formula (2) (in formula (2), R1-R6 denote hydrogen atoms, a polarity group or 1-10 carbon organic group, and n denotes an integer of ≥1) and a compound denoted by formula (3) (in formula (3), R7 and R8 are hydrogen atoms, a polarity group or 1-10 carbon organic group, and l denotes an integer of ≥2) and a component (C) generating acid or salt by irradiation with an optical beam or radiation. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive composition used for forming, for example, an interlayer insulating film of a semiconductor element, and more specifically, a photosensitive composition into which a crosslinked structure is introduced by irradiation with radiation or the like, and the photosensitive composition. The present invention relates to a semiconductor element using an object.

  In manufacturing a semiconductor device, a liquid crystal display device, a printed circuit board, or the like, various components including a protective film and an interlayer insulating film are formed by a pattern forming method. In recent years, a pattern forming method using a photolithography technique has been widely used, and attempts have been made to shorten the wavelength of light for exposure.

  In the following Patent Document 1, 10 to 90% by weight of a poly (silsesquioxane) compound represented by the following structural formula (X), and a compound that can generate a strong acid upon irradiation with actinic rays or radiation 0.01 to A photosensitive composition containing 20% by weight and 5 to 60% by weight of a crosslinking agent is disclosed.

In the formula (X), R ₁ and R ₂ are the same or different organic groups, n is the degree of polymerization, and R ₁ and R ₂ are preferably phenolic hydroxyl groups.

  Since the said photosensitive composition of patent document 1 uses the said specific poly (silsesquioxane) compound (X), when a fine pattern can be formed using light of a short wavelength. Has been.

However, in the photosensitive composition described in Patent Document 1, as described above, not only the poly (silsesquioxane) compound (X) and a photoacid generator that generates an acid by irradiation with light, but also an alkali. In order to form an insoluble part, the crosslinking agent which bridge | crosslinks poly (silsesquioxane) compound (X) is contained. That is, a crosslinking agent comprising an aliphatic alcohol such as 2,5-dimethyl-2,5-hexanediol, erythritol or pentaerythritol, a methylol-containing melamine compound or an alkyl ether-containing melamine compound, and the like, with respect to 100 parts by weight of the resin component, About 5 to 95 parts by weight were blended.
Japanese Patent Laid-Open No. 10-268520

  In the field of electronic components such as semiconductor devices, it is preferable that the photosensitive composition for obtaining a thin film pattern contains as little impurities as possible. That is, if impurities such as the crosslinking agent remain, the obtained thin film pattern may be colored, or the mechanical strength and electrical characteristics of the thin film pattern may be deteriorated. In addition, the cross-linking agent may be volatilized by heating or the like in a later manufacturing process, which may change the characteristics of the thin film pattern.

  By the way, in recent years, with the high integration of elements, pattern miniaturization is further advanced. Therefore, there is a demand for a photosensitive composition that can form a finer pattern using light having a short wavelength. On the other hand, such a photosensitive composition is required to be able to form a thick film pattern depending on the case and to be free from cracks even when the film thickness is increased.

  The object of the present invention is to provide a film pattern that has photosensitivity, can be developed without using a crosslinking agent, and can be formed by irradiation with radiation, etc. It is providing a photosensitive element and a semiconductor element using the photosensitive composition.

  The photosensitive composition according to the present invention includes at least one component selected from the group consisting of a silane compound represented by the following formula (1), a hydrolyzate of the silane compound, and a condensate of the hydrolyzate. (A), at least one component (B) selected from the group consisting of a compound represented by the following formula (2) and a compound represented by the following formula (3), and an acid by irradiation with light or radiation Or a compound (C) that generates a base.

  In the above formula (1), X represents a hydrolyzable group, Ra represents a non-hydrolyzable organic group, and m represents an integer of 1 to 4. When m is an integer of 2 to 4, a plurality of X may be the same or different. When m is 1 or 2, the plurality of Ras may be the same or different.

In the above formula _(2), R 1 ~R ₆ represents a hydrogen atom, a polar group or an organic group having 1 to 10 carbon atoms, n represents an integer of 1 or more. R _{1 to} R ₆ may be the same or different. When n is an integer of 2 or more, the plurality of R ₁ may be the same or different, and the plurality of R ₂ may be the same or different.

In the above formula (3), _{R 7} and _{R 8} represents a hydrogen atom, a polar group or an organic group having 1 to 10 carbon atoms, l is an integer of 2 or more. R ₇ and R ₈ may be the same or different. The plurality of R ₇ may be the same or different, and the plurality of R ₈ may be the same or different.

  On the specific situation with the photosensitive composition concerning this invention, the component (B) is included in the ratio of 2-250 weight part with respect to 100 weight part of component (A).

  In another specific aspect of the photosensitive composition according to the present invention, the contact angle of water on the surface of the coating film is 60 degrees or less when coated and dried on the substrate to form a coating film.

  A 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 film is formed using a photosensitive composition configured according to the present invention. Film.

  The photosensitive composition according to the present invention includes at least one selected from the group consisting of the silane compound represented by the above formula (1), a hydrolyzate of the silane compound, and a condensate of the hydrolyzate. Component (A), at least one component (B) selected from the group consisting of the compound represented by formula (2) and the compound represented by formula (3), and light or radiation. And a compound (C) that generates an acid or a base upon irradiation.

  Therefore, the component (A) and the component (B) are excellent in reactivity, and the compound (C) generates an acid or a base upon irradiation with light or radiation, so that the photosensitive composition quickly crosslinks, Insoluble in developer. Therefore, it is not necessary to use a crosslinking agent for crosslinking, and development is possible in a short time. Accordingly, coloring due to the use of the crosslinking agent, deterioration of characteristics, and the like can be effectively suppressed.

  In the present invention, since the component (B) is a linear or cyclic compound and has a siloxane bond, not only a fine pattern can be formed, but also a thick film pattern can be formed. Even if a film having a thickness is formed, cracks or the like hardly occur.

  When the component (B) is contained at a ratio of 2 to 250 parts by weight with respect to 100 parts by weight of the component (A), a thicker film pattern can be formed. Even if comprised, generation | occurrence | production of a crack etc. can be suppressed effectively.

  When the contact angle of water on the surface of the coating film is 60 degrees or less when coated and dried on the substrate to form a coating film, patterning can be performed with a development time of 5 minutes or less.

  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. In this invention, since this film | membrane is a film | membrane formed using the photosensitive composition comprised according to this invention, the coloring by use of a crosslinking agent, the deterioration of a characteristic, etc. are suppressed in this film | membrane. Further, even when the gate insulating film, the passivation film, or the interlayer insulating film is thick, cracks and the like hardly occur, and the reliability of the semiconductor element is excellent.

  Details of the present invention will be described below.

  The photosensitive composition according to the present invention includes at least one selected from the group consisting of the silane compound represented by the above formula (1), a hydrolyzate of the silane compound, and a condensate of the hydrolyzate. Component (A), at least one component (B) selected from the group consisting of the compound represented by formula (2) and the compound represented by formula (3), and light or radiation. And a compound (C) that generates an acid or a base upon irradiation.

  The said component (A) contained in a photosensitive compound bridge | crosslinks rapidly with an acid or a base.

  In the silane compound represented by the above formula (1), X represents a hydrolyzable group, Ra represents a non-hydrolyzable organic group, and m represents an integer of 1 to 4. In addition, when m is an integer of 2 to 4, a plurality of X may be the same or different, and when m is 1 or 2, a plurality of Ra may be the same or different. May be.

  The hydrolyzable group X is usually hydrolyzed to form a silanol group by heating within the temperature range of room temperature (25 ° C.) to 100 ° C. without catalyst in the presence of excess water. Or a group that can be further condensed to form a siloxane bond.

  Specific examples of the hydrolyzable group X include an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group. The hydrolyzable group X may be a halogen such as chlorine or bromine, an amino group, a hydroxyl group, or a carboxyl group.

  Examples of the non-hydrolyzable organic group Ra 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 silane compound represented by the above formula (1) include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyl-tri-n-propoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, ethyl-tri-n-propoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyl-tri-n-propoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltri Propoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltripropoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltripropoxysilane Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltripropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltripropoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecyltripropoxysilane, tetradecyltrimethoxysilane , Tetradecyltriethoxysilane, tetradecyltripropoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, hexadecyltripropoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltripropoxysilane, eicosyldecyltri Methoxysilane, eicosyltriethoxysilane, eicosyltripropoxysila , 6-chlorohexyltrimethoxysilane, 6,6,6-trifluorohexyltrimethoxysilane; benzyltrimethoxysilane, 4-chlorobenzyltrimethoxysilane, 4-bromobenzyltri-n-propoxysilane; dodecyltrichlorosilane, Dodecyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxysilane), β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ -Glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrieth Sisilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. It is done. These silane compounds may be used alone or in combination of two or more.

  The photosensitive composition according to the present invention includes, as the component (A), a silane compound represented by the above formula (1), a hydrolyzate of the silane compound, and a condensate of the hydrolyzate. It suffices that at least one selected from the group consisting of these is contained, and therefore two or more may be contained.

  The photosensitive composition according to the present invention includes at least one component (B) selected from the group consisting of the compound represented by the above formula (2) and the compound represented by the above formula (3). It is out. The compound represented by the above formula (2) and the compound represented by the above formula (3) are linear or cyclic compounds and have a siloxane bond. When the photosensitive composition contains the component (B), a thick film pattern can be formed, and cracks and the like are hardly generated even when a thick film is formed.

  The photosensitive composition may contain only one of the compound represented by the above formula (2) and the compound represented by the above formula (3) as the component (B). , Both compounds may be included. Furthermore, the photosensitive composition may contain two or more compounds represented by the above formula (2) as the component (B), and two compounds represented by the above formula (3). The above may be included. In the case where the photosensitive composition contains two or more compounds as the component (B), the content ratio is not particularly limited.

In Formula (2) and Formula (3) described above, R _{1 to} R ₈ each represent a hydrogen atom, a polar group, or an organic group having 1 to 10 carbon atoms. Specific examples of R _{1 to} R ₈ include a hydrogen atom, a hydroxyl group, an amino group, a substituted amino group, a halogeno group, an alkoxy group, an acyl group, a fatty acid group, an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a substituted alkyl group. , Substituted phenyl group, vinyl group and the like.

  Specific examples of the compound represented by the above formula (2) include 1,1,3,3-tetramethyl-1,3-dichlorodisiloxane, 1,1,3,3-tetramethyldisiloxane, , 3-bis (dichloromethyl) -1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxytetramethyldisiloxane, 1,3-diethynyl-1,1,3,3-tetramethyldisiloxane 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxytetramethyldisiloxane, 1,3-bis (acetoxymethyl) tetramethyldisiloxane, 1,3-dichloro Tetraisopropyldisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-dichlorotrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,5,5,5-heptamethyltrisiloxane, heptamethyl-3- (3-hydroxypropyl) trisiloxane, 1,7-dichloro-1,1,3,3,5,5,7, 7-octamethyltetrasiloxane, 1,1,1,3,5,7,7-octamethyltetrasiloxane, 1,7-diacetoxyoctamethyltetrasiloxane, 1,7-dihydroxyoctamethyltetrasiloxane, commercially available Silicone oils and the like.

  Specific examples of the compound represented by the above formula (3) include dodecamethylcyclohexasiloxane, 1,3,5,7,9-pentaethoxy-1,3,5,7,9-pentamethylcyclopenta. Siloxane, decamethylcyclopentasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, octaphenylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetra Phenylcyclotetrasiloxane, 1,3,5,7-tetrabutoxy-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetraisopropoxy-1,3,5,7- Tetramethylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrapropoxycyclotetrasiloxane, 1,3,5,7- Trakis (3,3,3-trifluoropropyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetraethoxy-1,3,5,7-tetramethylcyclotetra Siloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, octamethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, 1,3,5-trimethyl-1,3 , 5-trivinylcyclotrisiloxane, hexamethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and the like.

  In this invention, it is preferable to contain a component (B) in 2-250 weight part with respect to 100 weight part of components (A). If the component (B) is less than 2 parts by weight, cracks are likely to occur when the film thickness is increased, and if the component (B) exceeds 250 parts by weight, patterning may be difficult.

  The compound (C) is a compound that generates an acid or a base upon irradiation with light or radiation.

Although it does not specifically limit as a compound (C) which generate | occur | produces an acid by irradiation of the said light ray or a radiation, For example, onium salt etc. are mentioned. More specifically, salts of diazonium, phosphonium and iodonium such as BF ₄ ⁻ , PF ₆ ⁻ , SBF ₆ ⁻ and ClO ₄ ^— , and other organic halogen compounds, organic metals, and organic halides can be used. More specifically, the acid-generating compound includes triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethane antimonate, triphenylsulfonium benzosulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate. Sulfonium salt compounds such as dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, iodonium salts such as diphenyliodonium trifluoromethanesulfonate, N-hydroxy Succinimide trifluoromethanesulfonate, etc. It is below. Only 1 type may be used for the compound (C) which generate | occur | produces an acid by irradiation of the said light ray or a radiation, and 2 or more types may be used together.

  As the compound (C) that generates an acid upon irradiation with light or radiation, preferably, at least one compound selected from the group consisting of a more reactive onium salt, diazonium salt, and sulfonic acid ester is used. .

  The content ratio of the compound (C) that generates the acid is preferably in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight in total of the component (A) and the component (B). If the acid generating compound (C) is less than 0.01 parts by weight, the sensitivity may not be sufficient, and it may be difficult to form a pattern. If it exceeds 10 parts by weight, the photosensitive composition is made uniform. It becomes difficult to apply, and a residue may easily occur after development.

  In addition to the compound (C) which is a photosensitive agent, 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 are preferably used.

  The compound (C) that generates a base upon irradiation with light or radiation is not particularly limited, and examples thereof include cobaltamine complexes, o-acyloximes, carbamic acid derivatives, formamide derivatives, quaternary ammonium salts, tosylamines, carbamates, An amine imide compound etc. can be mentioned. Specifically, 2-nitrobenzylcarbamate, 2,5-dinitrobenzylcyclohexylcarbamate, N-cyclohexyl-4-methylphenylsulfonamide, 1,1-dimethyl-2-phenylethyl-N-isopropylcarbamate and the like are preferable. Used.

  As the compound (C) that generates a base upon irradiation with light or radiation, an amine imide compound that generates a base upon irradiation with light or radiation is more preferably used. Such an amine imide compound is not particularly limited as long as it generates a base when irradiated with light or radiation. Examples of such amine imide compounds include compounds represented by the following formula (4) or (5).

In the above formula (4) and ^(5), the ^{R 1, R 2, R 3} , independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, 1 to 8 carbon atoms An alkylidene group, a cycloalkyl group having 4 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, a phenoxyalkyl group having 1 to 6 carbon atoms, a phenyl group, an electron donating group and / or an electron withdrawing group substituted. Examples thereof include a benzyl group substituted with a phenyl 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 1 to 6 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 above formula (4) 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, JP-A-2003-35949, and generally Are available. Ar ² in the above formula (5) is an aromatic group.

  The amine imide compound has higher base generation efficiency when irradiated with light or radiation than a compound that generates a primary or secondary amine. Therefore, it is desirable to include an amine imide compound because the exposure time can be shortened and the manufacturing process can be shortened.

  Only 1 type may be used for the compound (C) which generate | occur | produces a base by the said irradiation of a light ray or a radiation, and 2 or more types may be used together. In addition, it is preferable that the content rate of the compound (C) which generate | occur | produces a base is the range of 0.01-10 weight part with respect to a total of 100 weight part of the said component (A) and the said component (B). If the compound (C) generating the base is less than 0.01 parts by weight, the sensitivity may be lowered, and it may be difficult to form a thin film pattern. If it exceeds 10 parts by weight, the photosensitive composition is uniformly applied. In some cases, a residue is likely to occur after development.

  In order to obtain an optimal resist shape, two or more types of the compound (C) that generates an acid upon irradiation with light or radiation and the compound (C) that generates a base upon irradiation with light or radiation are used. May be used in combination.

  In the present invention, an appropriate solvent may be added in addition to the component (A), the component (B), and the compound (C). By adding a solvent, a photosensitive composition that can be easily applied can be provided.

  The solvent is not particularly limited as long as it can dissolve the component (A) and the component (B), but aromatic hydrocarbon compounds such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, and diethylbenzene; cyclohexane, Saturated or unsaturated such as cyclohexene, dipentene, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane Hydrocarbon compounds: diethyl ether, di-n-propyl ether, di-isopropyl ether, dibutyl ether, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glyco Didiethyl 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 cyclohexane Sun, methylcyclohexane, p-menthane, o-menthane, m-menthane; ethers such as dipropyl ether, 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, stearin And esters such as butyl acid. These solvents may be used alone or in combination of two or more.

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

  If necessary, other additives may be further added to the photosensitive 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.

  When the photosensitive composition of the present invention is coated and dried on a substrate, the contact angle of water on the surface of the coating film is preferably 60 degrees or less. When the contact angle of water is 60 degrees or less, development within 5 minutes is possible.

  As a method for forming a pattern using the photosensitive composition according to the present invention, for example, as shown in FIG. 1 (a), a step of forming a photosensitive composition layer 1 made of the photosensitive composition according to the present invention. Next, a step of selectively exposing the photosensitive composition layer 1 using a photomask 3 corresponding to the pattern to form a patterned latent image 1A (FIG. 1B), And a step of developing the formed photosensitive layer 1B with an alkaline aqueous solution (FIG. 1C). Here, development means an operation of immersing the photosensitive layer 1B on which a latent image is formed in an alkaline aqueous solution, an operation of washing the surface of the photosensitive layer 1B with an alkaline aqueous solution, or an alkaline aqueous solution on the surface of the photosensitive layer 1B. It includes various operations for treating the photosensitive layer 1B with an alkaline aqueous solution, such as a spraying operation. 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 composition layer is not specifically limited, For example, the method of providing the photosensitive composition which concerns on this invention on the board | substrate 2 shown in FIG. 1, and forming the photosensitive composition layer 1 is mentioned. It is done. 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 a substrate to which the photosensitive 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 composition layer varies depending on the use, but 10 nm to 10 μm is a standard. When the photosensitive composition layer coated on the substrate uses a solvent to dissolve the photosensitive resin, it is desirable 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 composition layer is formed on a substrate, heat-treated as necessary, and then the photosensitive composition layer is covered with a photomask and irradiated with light 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 sensitizer. The irradiation energy of light depends on the desired film thickness and the type of sensitizer, but generally 10 to 1000 mJ / cm ² is used. When it is less than 10 mJ / cm ² , the silicon-containing polymer is not sufficiently exposed. On the other hand, if it is larger than 1000 mJ / cm ² , the exposure time may be long, and the production efficiency per pattern time may be reduced.

  In the exposed part of the photosensitive composition layer irradiated with light in the pattern shape, as described above, the crosslinking of the component (A) and the component (B) is caused by the action of the acid or base generated from the compound (C) by exposure. proceed. Therefore, the exposed portion becomes insoluble in the developer as a result of the progress of crosslinking. By developing the photosensitive composition layer after exposure using a developer, the unexposed portion of the photosensitive composition layer is dissolved and removed in the developer, and the exposed portion remains on the substrate. As a result, a film pattern is formed. This film pattern is called a negative pattern because the unexposed part is removed.

  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 composition layer and the type of solvent, but is generally 10 seconds to 5 minutes. After development, the film pattern is preferably washed with distilled water to remove the aqueous alkali solution remaining on the film.

  In addition, although the photosensitive composition concerning this invention is used suitably for forming a film pattern in various apparatuses, the said film pattern is used suitably for the insulation protective film of an electronic device. By using a film pattern formed using the photosensitive 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 an electronic device 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.

  The photosensitive 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 sectional view schematically showing a semiconductor element provided with a passivation film and an interlayer insulating film made of the photosensitive 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 composition according to the present invention.

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

  The photosensitive 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.

(Used compounds)
・ Ingredient (A)
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, the ethanol produced | generated by the condensation reaction with water was removed using the evaporator. After completion of the reaction, the flask was left to reach room temperature to prepare a component (A) which is a silicon-containing polymer mixture.

・ Ingredient (B) 1
1,3,5,7-tetramethylcyclotetrasiloxane was used.

・ Ingredient (B) 2
1,7-dihydroxyoctamethyltetrasiloxane was used.

・ Compound (C)
A sulfonium salt photoacid generator (Naphtalimide camphorsulfate (CAS No. 83697-56-7), manufactured by Midori Chemical Co., Ltd., trade name: NAI-106) was used.

(Examples 1-5 and Comparative Example 1)
The said component (A) and the component (B) 1 or the component (B) 2 were mix | blended with the composition shown in following Table 1.

  Next, a total of 100 parts by weight of component (A) and component (B) is taken out, 5 parts by weight of compound (C) is added to and mixed with 100 parts by weight, and then propylene glycol monomethyl ether acetate as a solvent. It was dissolved in 400 parts by weight to prepare a photosensitive composition.

  A photosensitive composition was also prepared by dissolving 95 parts by weight of component (B) and 5 parts by weight of compound (B) in 400 parts by weight of propylene glycol monomethyl ether acetate as a solvent. In this photosensitive composition, The film could not be formed in the pattern formation described later.

(Pattern formation)
The photosensitive compositions of Examples 1 to 5 and Comparative Example 1 were spin-coated on a silicon wafer having a thickness of 0.75 mm at a rotation speed of 1000 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 . After irradiation, the coating film was heated in a hot air oven at 80 ° C. for 5 minutes. Thereafter, the coating film was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide and developed.

  As a result, the coating film was dissolved in the portion not irradiated with ultraviolet rays, and a pattern of L / S 10 μm derived from the photomask was formed. Next, after firing at 250 ° C. for 1 hour, the occurrence of cracks was confirmed.

(Evaluation of Examples and Comparative Examples)
(1) Maximum value of thickness of crack-free film When forming a coating film, the thickness was changed to form patterns having different thicknesses. In the formed pattern, the maximum thickness at which cracks did not occur was determined. Regarding the film thickness, the reflectance was measured using E-3000 manufactured by Otsuka Electronics Co., Ltd., and the result was fitted to calculate the film thickness.

(2) Contact angle The contact angle of water on the surface of the coating film coated and dried on the substrate was determined using a static contact angle meter.

(3) Development time The time required for development was evaluated. Note that a 2.38% aqueous solution of tetramethylammonium hydroxide was used as the developer.

  The results are shown in Table 1 below.

  When Examples 1 to 5 and Comparative Example 1 are compared, it can be seen that the maximum film thickness without cracks is increased by mixing Compound (B) 1 or Compound (B) 2. Comparing Examples 1 to 4, it can be seen that as the mixing ratio of compound (B) 1 is increased, the maximum crack-free film thickness increases, and even when a thick film is formed, the generation of cracks can be suppressed. .

(A)-(c) is sectional drawing of each process for demonstrating the film | membrane pattern formation method which concerns on this invention. BRIEF DESCRIPTION OF THE DRAWINGS Front sectional drawing which shows a semiconductor element provided with the passivation film and interlayer insulation film which consist of a photosensitive composition concerning this invention.

Explanation of symbols

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

Claims (4)

At least one component (A) selected from the group consisting of a silane compound represented by the following formula (1), a hydrolyzate of the silane compound, and a condensate of the hydrolyzate, and the following formula (2) At least one component (B) selected from the group consisting of a compound represented by formula (3) and a compound represented by the following formula (3), and a compound (C) that generates an acid or a base upon irradiation with light or radiation: A photosensitive composition comprising:

In the above formula (1), X represents a hydrolyzable group, Ra represents a non-hydrolyzable organic group, and m represents an integer of 1 to 4. When m is an integer of 2 to 4, a plurality of X may be the same or different. When m is 1 or 2, the plurality of Ras may be the same or different.

In the above formula _(2), R 1 ~R ₆ represents a hydrogen atom, a polar group or an organic group having 1 to 10 carbon atoms, n represents an integer of 1 or more. R ₁ to R ₆ may be different may be the same. When n is an integer of 2 or more, the plurality of R ₁ may be the same or different, and the plurality of R ₂ may be the same or different.

In the above formula (3), _{R 7} and _{R 8} represents a hydrogen atom, polar group or an organic group having 1 to 10 carbon atoms, l represents an integer of two or more. R ₇ and R ₈ may be the same or different. The plurality of R ₇ may be the same or different, and the plurality of R ₈ may be the same or different.   The photosensitive composition of Claim 1 which contains the said component (B) in the ratio of 2-250 weight part with respect to 100 weight part of said components (A).   The photosensitive composition of Claim 1 or 2 whose contact angle of water of this coating-film surface is 60 degrees or less when it is applied and dried on a base material and it is set as a coating film.   It comprises 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 is formed using the photosensitive composition according to any one of claims 1 to 3. A semiconductor element characterized by being a film.

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