JP2008116747A - Positive photosensitive composition, method for producing patterned film and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive composition which permits thorough dissolution of the photosensitive composition in its exposed part in a developer and can provide a patterned film excellent in pattern profile, and a method for producing a patterned film and a semiconductor device using the same. <P>SOLUTION: The positive photosensitive composition comprises a condensate of an alkoxysilane (A), an organic compound (B) which insolubilizes the positive photosensitive composition in a developer and has a higher hydrophobicity than the condensate of the alkoxysilane (A), and a catalyst (C) which decomposes the organic compound (B) upon irradiation with light or radiation to solubilize the positive photosensitive composition in a developer, wherein when the photosensitive composition 1 is selectively exposed with light or radiation, the photosensitive composition 1A in its exposed part becomes soluble in a developer. The method for producing a patterned film 1C and the semiconductor device using the same are also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a positive-type photosensitive composition having photosensitivity, and more specifically, by developing after exposure, the photosensitive composition in an exposed portion can be removed and a pattern film is formed. The present invention relates to a positive-type photosensitive composition that can be used, a pattern film manufacturing method using the same, 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.

  In Patent Document 1 below, as an example of a photosensitive resin composition used for pattern formation, (1) an alkali-soluble siloxane polymer, (2) a compound that generates a reaction accelerator by light, and (3) a solvent are mainly used. A photosensitive resin composition as a component is disclosed. In Patent Document 1, (1) an alkali-soluble siloxane polymer obtained by removing water and a catalyst from a reaction solution obtained by hydrolyzing and condensing alkoxysilane with water and a catalyst is used as the alkali-soluble siloxane polymer. Yes.

Further, Patent Document 1 discloses a pattern forming method in which the photosensitive resin composition is applied onto a substrate, dried, exposed through a mask, and subsequently developed. In the pattern forming method described in Patent Document 1, specifically, a photosensitive resin composition layer made of a photosensitive resin composition is formed, and the photosensitive resin composition layer is exposed through a mask. In the exposed portion, the crosslinking reaction of the alkoxysilane condensate was advanced to cure the photosensitive resin composition layer.
Japanese Patent Laid-Open No. 06-148895

  Conventionally, a photosensitive resin composition called a negative type as described in Patent Document 1 has been mainly used to form a fine pattern. That is, the photosensitive resin composition described in Patent Document 1, as described above, proceeds with the crosslinking reaction of the siloxane polymer in the exposed portion and is cured to form a pattern, which is not a positive type but a negative type. It was a photosensitive resin composition.

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

  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 the exposure, the photosensitive resin composition in the unexposed area is cured by heat treatment, if 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.

  An object of the present invention is to provide a pattern film having an excellent pattern shape, in which the photosensitive composition in the exposed area can be sufficiently dissolved in a developer by developing after exposure in view of the current state of the prior art described above. It is an object of the present invention to provide a positive photosensitive composition, a method for producing a pattern film using the positive photosensitive composition, and a semiconductor element.

  The present invention relates to an alkoxysilane condensate (A), a compound that insolubilizes a positive photosensitive composition in a developer, and an organic compound (B) having a higher hydrophobicity than the alkoxysilane condensate (A); And a catalyst (C) that decomposes the organic compound (B) by irradiation with light or radiation and solubilizes the positive photosensitive composition in the developer.

  In a specific aspect of the positive photosensitive composition according to the present invention, the catalyst (C) is anatase-type titanium oxide particles.

  In another specific aspect of the positive photosensitive composition according to the present invention, the organic compound (B) is an organic polymer and / or an organic siloxane compound.

  In still another specific aspect of the positive photosensitive composition according to the present invention, the catalyst (C) is mixed in a proportion of 1 to 20% by weight in 100% by weight of the positive photosensitive composition.

  The method for producing a patterned film according to the present invention comprises a step of forming a photosensitive composition layer comprising a positive photosensitive composition constituted according to the present invention on a substrate, and light or radiation depending on the pattern to be formed. Selectively exposing the photosensitive composition layer to solubilize the photosensitive composition layer in the exposed portion in a developer; and solubilizing the photosensitive composition layer in the exposed portion in the developer; And developing the composition layer with a developer to obtain a pattern film.

  The semiconductor device according to the present invention 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 a positive photosensitive composition constituted according to the present invention. It is set as the film | membrane formed using.

  In the positive photosensitive composition according to the present invention, the alkoxysilane condensate (A) is a compound that insolubilizes the positive photosensitive composition in the developer, and is more hydrophobic than the alkoxysilane condensate (A). The organic compound (B) having a high molecular weight and a catalyst (C) that decomposes the organic compound (B) by irradiation with light or radiation and solubilizes the positive photosensitive composition in the developer. By selectively exposing the photosensitive composition with light or radiation using, the photosensitive composition can be made soluble in the exposed area, and the photosensitive composition can remain insoluble in the unexposed area. Therefore, when it develops after exposing, the photosensitive composition of an exposed part can fully be removed, and the pattern film excellent in the pattern shape which consists of the photosensitive composition of an unexposed part can be obtained.

  When the catalyst (C) is anatase-type titanium oxide particles, the photosensitive composition in the exposed area is more effectively soluble in the developer by selectively exposing the photosensitive composition with light or radiation. Can be. Therefore, when it develops after exposing, the more excellent pattern film by pattern shape can be obtained.

  When the organic compound (B) is an organic polymer and / or an organic siloxane compound, the photosensitive composition can be made more insoluble by a developer before exposure.

  When the catalyst (C) is mixed in an amount of 1 to 20% by weight in 100% by weight of the positive photosensitive composition, the photosensitive composition in the exposed area is sufficiently soluble in the developer by exposure. Can do.

  In the method for producing a patterned film according to the present invention, a step of forming a photosensitive composition layer composed of a positive photosensitive composition constituted according to the present invention on a substrate, and light or radiation depending on the pattern to be formed. A step of selectively exposing the photosensitive composition layer and making the photosensitive composition layer in the exposed portion soluble in a developer, so that the photosensitive composition layer is insoluble in the exposed portion and unexposed. The photosensitive composition layer can be solubilized in the part, and a patterned latent image can be formed.

  Furthermore, in the present invention, since the photosensitive composition layer in the exposed portion is solubilized in the developer, the photosensitive composition layer is further developed with the developer to obtain a pattern film. By development using a developing solution such as alkali, the photosensitive composition layer in the exposed area is sufficiently removed, and a pattern film having an excellent pattern shape composed of the photosensitive composition layer 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 composition of the present invention. Since it is a formed film, the shape of the film is excellent.

  Details of the present invention will be described below.

  In order to achieve the above-mentioned problems, the inventors of the present application are a compound that insolubilizes the positive-side photosensitive composition and the alkoxysilane condensate (A) and the alkoxysilane condensate (A). By using a highly hydrophobic organic compound (B) and a catalyst (C) that decomposes the organic compound (B) by irradiation with light or radiation and solubilizes the positive photosensitive composition in the developer, By developing after selectively exposing the photosensitive composition, the photosensitive composition in the exposed area can be sufficiently removed, and the photosensitive composition in the unexposed area remains, and the pattern shape is excellent. The inventors have found that a patterned film can be obtained, and have reached the present invention.

  The positive photosensitive composition according to the present invention is an alkoxysilane condensate (A) and a compound that insolubilizes the positive photosensitive composition in a developer, and is more hydrophobic than the alkoxysilane condensate (A). The organic compound (B) having a high molecular weight and a catalyst (C) that decomposes the organic compound (B) by irradiation with light or radiation and solubilizes the positive photosensitive composition in the developer. The alkoxysilane condensate (A) alone is soluble in the developer.

  The alkoxysilane condensate (A) comprises a condensate obtained by condensing alkoxysilane. As the condensate (A) of alkoxysilane, at least one kind is used, and therefore, a condensate (A) of two or more kinds of alkoxysilane may be used.

  As the alkoxysilane condensate (A), an alkoxysilane condensate obtained by condensing an alkoxysilane represented by the following formula (1) is preferably used.

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

The alkoxy group R ₂ and the hydrolyzable group R ₃ other than the alkoxy group are usually hydrolyzed by heating in the temperature range of room temperature (25 ° C.) to 100 ° C. in the presence of excess water without catalyst. It is a group that can be decomposed to form a silanol group, or a group that can be further condensed to form a siloxane bond.

Examples of the alkoxy group R _2, is not particularly limited, specifically, methoxy group, an ethoxy group, an alkoxy group having 1 to 6 carbon atoms such as a propoxy group.

The hydrolyzable group R ₃ other than the alkoxy group is not particularly limited, specifically, chlorine, halogeno group such as bromine, an amino group, and a hydroxyl group or a carboxyl group.

The non-hydrolyzable organic group R ₁ 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 (A), it is sufficient that at least one alkoxysilane is used, and therefore two or more alkoxysilanes may be used.

  In 100% by weight of the positive photosensitive composition, the alkoxysilane condensate (A) is preferably mixed in a proportion of 5 to 90% by weight. If the alkoxysilane condensate (A) is less than 5% by weight, the substrate may be exposed when the pattern film is formed, and if it exceeds 90% by weight, uneven coating may occur.

  The above-mentioned alkoxysilane condensate (A), organic compound (B), and catalyst (C) are mixed to form a positive photosensitive composition.

  The organic compound (B) is a compound that insolubilizes the positive photosensitive composition in the developer, and has higher hydrophobicity than the alkoxysilane condensate (A). By mixing the organic compound (B) with the alkoxysilane condensate (A), the positive photosensitive composition becomes insoluble in the developer before irradiation with light or radiation.

  In the photosensitive composition, a catalyst (C) that decomposes the organic compound (B) upon irradiation with light or radiation and solubilizes the positive photosensitive composition in the developer is further mixed. When the object is irradiated with light or radiation, the photosensitive composition in the exposed area can be made soluble in the developer.

  The organic compound (B) is a compound that insolubilizes the positive photosensitive composition in the developer, has higher hydrophobicity than the alkoxysilane condensate (A), and is decomposed by the catalyst (C). If it is, it will not specifically limit, However, An organic polymer and / or an organosiloxane compound are used preferably. Of these, organic polymers are more preferably used.

  Specific examples of the organic polymer that is a compound that insolubilizes the positive photosensitive composition in the developer and has higher hydrophobicity than the alkoxysilane condensate (A) include polypropylene, polyethylene, and polyphenol, and more preferably. Used.

  Specific examples of an organic siloxane compound that is a compound that insolubilizes a positive photosensitive composition in a developer and has a higher hydrophobicity than the condensate (A) of alkoxysilane include polydimethylsiloxane and carbinol (hydroxy) terminated. Polydimethylsiloxane, vinyl-terminated polydimethylsiloxane, N-ethylaminoisobutyl-terminated polydimethylsiloxane, aminoethylaminopropylmethoxysiloxane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, ( 3,3,3-trifluoropropyl) trimethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, H- perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H- perfluorooctyl triethoxysilane methoxypropane silane, and the like.

  The organic compound (B) is preferably mixed in a proportion of 0.01 to 20 parts by weight in 100% by weight of the positive photosensitive composition. If the organic compound (B) is less than 0.01 parts by weight, the hydrophobicity of the positive photosensitive composition may not be sufficiently increased, and if it exceeds 20 parts by weight, uneven coating may occur.

  The catalyst (C) decomposes the organic compound (B) by irradiation with light or radiation and solubilizes the positive photosensitive composition in the developer. When the positive photosensitive composition is irradiated with light or radiation, the photosensitive composition in the exposed area can be made soluble in the developer by the action of the catalyst (C).

  Although it does not specifically limit as said catalyst (C), For example, the hydrolysis condensate of an titanium alkoxide, anatase type titanium oxide particle, etc. are mentioned. Anatase-type titanium oxide particles are preferably used because the photosensitive composition in the exposed area can be effectively solubilized by irradiation with light or radiation.

  Examples of the hydrolysis condensate of titanium alkoxide include condensates such as tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, and the like.

  It is preferable that the catalyst (C) is mixed in a proportion of 1 to 20% by weight in 100% by weight of the positive photosensitive composition. When the catalyst (C) is mixed at a ratio of 1 to 20% by weight, the photosensitive composition in the exposed portion can be effectively solubilized by irradiation with light or radiation.

  In the present invention, an appropriate solvent may be further added. By adding a solvent, a positive photosensitive composition that can be easily applied can be provided.

  Although it does not specifically limit as said solvent, Aromatic hydrocarbon compounds, such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, diethylbenzene; Cyclohexane, cyclohexene, dipentene, n-pentane, isopentane, n-hexane, isohexane, Saturated or unsaturated hydrocarbon compounds such as 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, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibu 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, ethylcyclohexane, methylcyclohexane, p-menthane, o Menthane, m-menthane; ethers such as dipropyl ether and dibutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone and cycloheptanone; Examples thereof include esters such as ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl acetate cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, and butyl stearate. These solvents may be used independently and 2 or more types may be used together.

  What is necessary is just to select the mixing | blending ratio of the said solvent suitably so that it may apply uniformly, for example, when a positive photosensitive composition is applied on a board | substrate and a photosensitive composition layer is formed. Preferably, the positive photosensitive 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 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.

  In the method for producing a patterned film according to the present invention, the positive photosensitive composition is used. For example, as shown in FIG. 1A, a photosensitive composition layer made of a positive photosensitive composition is formed on a substrate. The process of forming 1 is performed. Next, using the photomask 3 corresponding to the pattern, the photosensitive composition layer 1 is selectively exposed with light or radiation to make the photosensitive composition layer 1A in the exposed portion soluble in the developer ( FIG. 1B is performed. The process of making the photosensitive composition layer 1A in the exposed area soluble in the developer and then developing the photosensitive composition layer 1A in the exposed area with the developer to obtain a pattern film 1C (FIG. 1 (c)) Done.

  Although the process of forming the said photosensitive composition layer is not specifically limited, For example, the method of providing the said positive photosensitive composition on the board | substrate 2 shown in FIG. 1, and forming the photosensitive composition layer 1 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 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 positive photosensitive composition, it is preferably heat-treated 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.

  The photosensitive composition layer 1 is formed on the substrate 2, and the photosensitive composition layer is covered with a photomask and irradiated with light in a pattern. Thereby, an organic compound (B) is decomposed | disassembled by the effect | action of a catalyst (C), and 1 A of photosensitive composition layers of an exposure part can be made soluble in a developing solution. 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 type and blending amount of the photocatalyst (C). The irradiation energy of light is generally in the range of 10 to 1000 mJ / cm ² , although it depends on the type of catalyst (C) and the amount of blending. If it is less than 10 mJ / cm ² , the solubility of the photosensitive composition in the developer may not be sufficiently improved. Moreover, when larger than 1000 mJ / cm < ² >, there exists a possibility that exposure time may become long and the manufacturing efficiency per time of a pattern film | membrane may fall.

  In the present invention, the photosensitive composition layer may be heat-treated as necessary after exposure. The temperature of the heat treatment is preferably in the range of 150 to 350 ° C.

  By developing the photosensitive composition layer after exposure using a developer, the photosensitive composition layer in the exposed portion is dissolved and removed in the developer, and the unexposed portion remains on the substrate. As a result, a pattern is formed. This pattern is called a positive pattern because the exposed portion is removed. In the method for producing a patterned film of the present invention, the photosensitive composition in the exposed area can be sufficiently removed, so that good resolution can be obtained.

  Here, the development includes the operation of immersing the photosensitive composition layer 1A in the exposed area and the photosensitive composition layer 1B in the unexposed area in a developer such as an alkaline aqueous solution, as well as the photosensitive composition layer 1A, Various operations for treating the photosensitive composition layers 1A and 1B with a developing solution, such as an operation of washing the surface of 1B with a developing solution or an operation of spraying the developing solution onto the surface of the photosensitive composition layers 1A and 1B, are included. Shall be.

  In addition, a developing solution melt | dissolves the photosensitive composition of an exposure part, when the photosensitive composition is selectively exposed with a light ray or a radiation, but does not melt | dissolve the photosensitive composition of an unexposed part. The developer 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.

  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 preferably in the range of 10 seconds to 5 minutes because development can be efficiently performed and production efficiency is increased. After development, the pattern film is preferably washed with distilled water to remove the aqueous alkali solution remaining on the film.

  The positive photosensitive composition according to the present invention is suitably used for forming a pattern film in various apparatuses. However, the positive photosensitive composition is preferably used for an insulating protective film of an electronic device. It is done. By using a pattern film composed of the photosensitive composition 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.

  Moreover, the positive 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 cross-sectional view schematically showing a semiconductor device including a passivation film and an interlayer insulating film constituted by using the positive 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 by using the positive photosensitive composition according to the present invention.

  The film | membrane formed using the positive photosensitive composition which concerns on this invention is used for various uses. Here, the “film formed using a positive photosensitive composition” is a film obtained by introducing a cross-linked structure by applying energy such as heat, light or radiation to the positive photosensitive composition. It means that there is.

  The positive 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 of an organic EL element, an interlayer protective film of an IC chip, and an insulating layer of a sensor.

  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.

(Examples 1-8)
[Preparation of Alkoxysilane Condensate (A)]
100 parts by weight of phenyltriethoxysilane as an alkoxysilane, 200 parts by weight of PGMEA, 10 parts by weight of water, and 2 parts by weight of hydrochloric acid were mixed and heated and stirred at 70 ° C. for 120 minutes. Furthermore, after reacting at 120 ° C. for 3 hours, the mixture was allowed to cool to obtain a solution containing the condensate (A) of phenyltriethoxysilane (containing 20% by weight of the condensate (A) in 100% by weight of the solution).

  The obtained phenyltriethoxysilane condensate (A) had a polystyrene-reduced weight average molecular weight of 1000 as measured by gel permeation chromatography. This confirmed that the condensate (A) of phenyltriethoxysilane was obtained.

  The resulting phenyltriethoxysilane condensate (A) alone was soluble in a developer (2.38% aqueous solution of tetramethylammonium hydroxide).

(Preparation of photosensitive composition)
10 parts by weight of polypropylene having a weight average molecular weight of 5000 as the organic compound (B) was added to 100 parts by weight of the solution containing the condensate (A) of phenyltriethoxysilane. Anatase TiO ₂ fine particles (manufactured by Ishihara Sangyo Co., Ltd., trade name: photocatalytic titanium oxide) were added so that the concentration in 100% by weight of the photosensitive composition was as shown in Table 1 below. Got.

  The obtained photosensitive composition was insoluble in a developer (a 2.38% aqueous solution of tetramethylammonium hydroxide) before irradiation with light or radiation.

(Comparative Example 1)
In 500 parts by weight of the solution containing the phenyltriethoxysilane condensate (A) obtained in the examples, a sulfonium salt photoacid generator (Naphtalide camphorsulfate, CAS No. 83697-56-7) that generates an acid upon irradiation with light. , Manufactured by Midori Chemical Co., Ltd., trade name: NAI-106), 5 parts by weight were mixed and dissolved to prepare a photosensitive composition.

  The obtained photosensitive composition was soluble in a developer (a 2.38% aqueous solution of tetramethylammonium hydroxide) before irradiation with light or radiation.

(Evaluation of Examples and Comparative Examples)
[Formation of Pattern Film Using Photosensitive Composition of Example]
Each photosensitive composition was 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 having a thickness of 0.5 μm. 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 immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide and developed to obtain a pattern film.

[Formation of Pattern Film Using Photosensitive Composition of Comparative Example]
The photosensitive composition was 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 having a thickness of 0.5 μm. 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 heated in a hot air oven at 80 ° C. for 5 minutes. Thereafter, the coating film was dipped in a 2.38% aqueous solution of tetramethylammonium hydroxide and developed to obtain a pattern film.

[Evaluation of pattern film]
About the pattern film obtained using each photosensitive composition of an Example and a comparative example, the formation state and pattern shape of a positive type pattern were evaluated on the following evaluation criteria.

Criteria for evaluating the formation state of the positive pattern ○: The coating film in the exposed area was completely dissolved and a good positive pattern was formed. Δ: The coating film in the exposed area was almost dissolved, and the positive pattern was almost satisfactory. X: The exposed coating film was not dissolved and a positive pattern was not formed.
Evaluation criteria for pattern shape ○: The surface was uniform and the pattern film had a good shape. Δ: The surface was slightly non-uniform, but the pattern film had a good shape. Table 1 below shows the results of uniform or no pattern formation.

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

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive composition layer 1A ... Photosensitive composition layer 1B ... Photosensitive composition layer 1C ... Pattern film 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 (6)

  An alkoxysilane condensate (A) and a compound that insolubilizes the positive photosensitive composition in a developer, an organic compound (B) having a higher hydrophobicity than the alkoxysilane condensate (A), and light or A positive photosensitive composition comprising: a catalyst (C) that decomposes the organic compound (B) upon irradiation with radiation and solubilizes the positive photosensitive composition in a developer.   The positive photosensitive composition of Claim 1 whose said catalyst (C) is anatase type titanium oxide particle.   The positive photosensitive composition according to claim 1 or 2, wherein the organic compound (B) is an organic polymer and / or an organic siloxane compound.   4. The positive type according to claim 1, wherein the catalyst (C) is mixed at a ratio of 1 to 20% by weight in 100% by weight of the positive photosensitive composition. 5. Photosensitive composition. Forming a photosensitive composition layer comprising the positive photosensitive composition according to any one of claims 1 to 4 on a substrate;
Selectively exposing the photosensitive composition layer with light or radiation according to a pattern to be formed, and making the photosensitive composition layer in an exposed portion soluble in a developer;
And a step of making the photosensitive composition layer of the exposed portion soluble in a developer and then developing the photosensitive composition layer with the developer to obtain a pattern 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 uses the positive photosensitive composition according to any one of claims 1 to 4. A semiconductor element, which is a formed film.

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