KR20050014716A - Radiation Sensitive Resin Composition, Inter Layer Insulating Film and Microlens and Process for Preparing the Same - Google Patents

Abstract

PURPOSE: Provided are a radiation sensitive resin composition which shows high radiation sensitivity, has a development margin capable of forming a satisfactory pattern profile even if it exceeds an optimum development time and can form easily a pattern-type thin film having good adhesion, an interlayered insulating layer using the composition which has high heat resistance and high transmittance, its preparation method, a microlens using the composition which shows high transmittance and satisfactory melt profile, and its preparation method. CONSTITUTION: The radiation sensitive resin composition comprises a copolymer of (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, (a2) an unsaturated compound having an alicyclic epoxy framework represented by the formulas, and (a3) an unsaturated compound other than (a1) and (a2); and a 1,2-naphthoquinonediazidesulfonate compound. Preferably the component (a3) comprises an unsaturated compound having a tricyclo£5.2.1.0¬2,6|decan-8-yl framework and other unsaturated compounds. Preferably the ratio of the copolymer and the 1,2-naphthoquinonediazidesulfonate compound is 100 : 5-100 by weight.

Description

Radiation Sensitive Resin Composition, Inter Layer Insulating Film and Microlens and Process for Preparing the Same}

The present invention relates to a radiation-sensitive resin composition, an interlayer insulating film and a microlens, and a manufacturing method thereof.

In the electronic components such as a thin film transistor (hereinafter, referred to as a "TFT") type liquid crystal display element, a magnetic head element, an integrated circuit element, and a solid-state image sensor, an interlayer insulating film is provided to insulate between wirings arranged in layers. . As a material for forming the interlayer insulating film, it is preferable that there are few process steps for obtaining the required pattern shape and have sufficient flatness, so that the radiation-sensitive resin composition is widely used (Japanese Patent Laid-Open No. 2001-354822 and Japanese Patent). See publication 2001-34743).

Among the electronic components, for example, a TFT type liquid crystal display element is manufactured through a process of forming a transparent electrode film on the interlayer insulating film and forming a liquid crystal alignment film thereon, so that the interlayer insulating film is formed at a high temperature in the process of forming a transparent electrode film. Sufficient resistance to these is required in order to expose them to the conditions or to expose them to the stripping solution of the resist used for pattern formation of the electrode.

In recent years, TFT type liquid crystal display devices have tended to have a large screen, high brightness, high precision, high-speed response, and thinning, and have high sensitivity as a composition for forming an interlayer insulation film used therein, Heat resistance and high transmittance are required.

On the other hand, a microlens having a lens diameter of about 3 to 100 μm as an imaging system of an on-chip color filter such as a facsimile, an electron copier, a solid-state imaging device, or an optical system of an optical fiber connector, or micro Microlens arrays in which lenses are arranged regularly are used.

To form a microlens or microlens array, a resist pattern corresponding to the lens is formed and then subjected to heat treatment to melt flow to use as a lens as it is, or dry etching using a meltflow lens pattern as a mask. Background Art A method of transferring a lens shape to a background is known. The radiation sensitive resin composition is widely used for formation of the said lens pattern (refer Unexamined-Japanese-Patent No. 6-18702 and 6-136239).

By the way, the device in which the microlenses or the microlens array is formed as described above is then coated with a planarization film and an etching resist film in order to remove various insulating films on the bonding pads, which are wiring forming portions, and exposed and developed using a desired mask. The etching resist of the bonding pad portion is removed, and then the planarization film and various insulating films are removed by etching to expose the bonding pad portion. Therefore, solvent resistance and heat resistance are required for the microlens or the microlens array in the coating film forming step and the etching step of the planarization film and the etching resist.

The radiation-sensitive resin composition used to form such a microlens is highly sensitive, and the microlens formed therefrom has a desired radius of curvature and is required to have high heat resistance and high transmittance.

In the interlayer insulating film and the microlens obtained as described above, the developing solution penetrates between the pattern and the substrate and is easily peeled off when the developing time is excessively shorter than the optimum time in the developing step when forming them. The time needs to be tightly controlled and there is a problem in product yield.

As described above, in forming the interlayer insulating film and the microlens from the radiation-sensitive resin composition, the composition is required to have high sensitivity, and even if the developing time has elapsed more than the predetermined time in the developing step during the forming step, no pattern peeling occurs. The interlayer insulating film formed therefrom exhibits good adhesion and high heat resistance, high solvent resistance, high transmittance, and the like, while forming a microlens, a good melt shape (desirable curvature radius), high heat resistance, High solvent resistance and high transmittance are required. However, the radiation sensitive resin composition which can satisfy such a request is not known conventionally.

This invention is made | formed in view of the above points. Therefore, it is an object of the present invention to easily form a patterned thin film having a high radiation sensitivity, having a developing margin such as being able to form a good pattern shape even after the optimum developing time has elapsed in the developing step. It is providing the radiation sensitive composition which can be provided.

Another object of the present invention is to form an interlayer insulating film of high heat resistance and high transmittance when forming an interlayer insulating film, and to use a microlens having high transmittance and a good melt shape when forming an microlens. It is providing the radiation sensitive resin composition which can be formed.

Still another object of the present invention is to provide a method of forming an interlayer insulating film and a microlens using the radiation-sensitive resin composition.

Still another object of the present invention is to provide an interlayer insulating film and a microlens formed by the method of the present invention.

Still other objects and advantages of the present invention will become apparent from the following description.

1 is a schematic diagram of a cross-sectional shape of a microlens.

According to the present invention, the above objects and advantages of the present invention are, firstly,

[A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride

(Hereinafter referred to as `` compound (a1) ''),

(a2) the following formula

Unsaturated compound having an alicyclic epoxy skeleton represented by

(Hereinafter referred to as "compound (a2)") and

(a3) olefinically unsaturated compounds other than the above (a1) and (a2) (hereinafter,

Copolymer of "compound (a3)" (hereinafter referred to as "copolymer [A]"),

And

[B] 1,2-naphthoquinone diazide sulfonic acid ester (hereinafter referred to as "[B] component")

It is achieved by the radiation sensitive resin composition characterized by containing the following.

The objects and advantages of the present invention are second,

(1) forming a coating film of the radiation-sensitive composition on the substrate;

(2) irradiating at least a part of the coating film with radiation;

(3) developing process, and

(4) heating process

It is achieved by a method for forming an interlayer insulating film or microlens, characterized in that it comprises in the order of the substrate.

In addition, the third object and advantage of the present invention,

It is achieved by an interlayer insulating film or microlens formed by the above method.

The radiation-sensitive resin composition of the present invention has a high radiation sensitivity, has a developing margin such that a good pattern shape can be formed even beyond the optimum developing time in the developing step, and can easily form a patterned thin film excellent in adhesion. Can be.

The interlayer insulating film of the present invention formed from the above composition has good adhesion to a substrate, excellent solvent resistance and heat resistance, high transmittance, and low dielectric constant, and thus can be preferably used as an interlayer insulating film of an electronic component.

In addition, the microlens of the present invention formed from the composition has good adhesion to a substrate, excellent solvent resistance and heat resistance, and has a high transmittance and a good melt shape, and can be suitably used as a microlens of a solid-state imaging device.

Hereinafter, the radiation sensitive resin composition of this invention is explained in full detail.

Copolymer [A]

Copolymer [A] can be produced by radical polymerization of compound (a1), compound (a2) and compound (a3) in the presence of a polymerization initiator in a solvent. The copolymer [A] used in the present invention is preferably 5 to 40 based on the sum of the repeating units derived from the compounds (a1), (a2) and (a3) of the structural units derived from the compound (a1). % By weight, particularly preferably 10 to 30% by weight. When this copolymer of the structural unit is less than 5 weight%, it will be hard to melt | dissolve in aqueous alkali solution at the time of a developing process, and the copolymer exceeding 40 weight% tends to become too high in aqueous alkali solution.

As the compound (a1), for example, mono carboxylic acid, dicarboxylic acid, anhydride of dicarboxylic acid, mono [(meth) acryloyloxyalkyl] ester of polyhydric carboxylic acid, carboxyl group and hydroxyl group at both terminals The mono (meth) acrylate of the polymer which has a polycyclic compound, the polycyclic compound which has a carboxyl group, its anhydride, etc. are mentioned.

Specific examples thereof include, for example, acrylic acid, methacrylic acid, crotonic acid and the like as monocarboxylic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like as the dicarboxylic acid;

Anhydrides of the compounds exemplified as the dicarboxylic acids as anhydrides of dicarboxylic acids;

Succinic acid mono [2- (meth) acryloyloxyethyl], monophthalate [2- (meth) acryloyloxyethyl], and the like as mono [(meth) acryloyloxyalkyl] ester of polyhydric carboxylic acid;

Ω-carboxypolycaprolactone mono (meth) acrylate as a mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals;

Polycyclic compound having a carboxyl group and anhydrides thereof as 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5 -Methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept 2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5, 6- dicarboxy bicyclo [2.2.1] hept-2-ene anhydride, etc. are mentioned, respectively. .

Among these, anhydrides of monocarboxylic acid and dicarboxylic acid are preferably used, and acrylic acid, methacrylic acid and maleic anhydride are particularly preferably used in view of copolymerization reactivity, solubility in an aqueous alkali solution and ease of acquisition. These are used alone or in combination.

The copolymer [A] used in the present invention is preferably 10 to 70 based on the sum of the repeating units derived from the compounds (a1), (a2) and (a3). % By weight, particularly preferably 20 to 60% by weight. When this structural unit is less than 10 weight%, there exists a tendency for the heat resistance and surface hardness of the obtained interlayer insulation film and microlens to fall, and when the quantity of this structural unit exceeds 70 weight%, it preserve | saves a radiation sensitive resin composition There exists a tendency for stability to fall.

Compound (a2) having an alicyclic epoxy skeleton is represented by the following formula

It has an alicyclic epoxy skeleton represented by it. As a compound (a2), methacrylic acid ester, acrylic acid ester, styrene, and vinyl ether which have the said alicyclic epoxy skeleton are preferable, and methacrylic acid ester is especially preferable. As a compound (a2) which has an alicyclic epoxy skeleton, the compound represented by a following formula is mentioned as a preferable example.

In formula, R <_1> is a hydrogen atom or a C1-C4 alkyl group, and R <_2> is a C1 or more bivalent hydrocarbon group.

As the compound (a3), for example, an unsaturated compound having a tricyclo [5.2.1.O ^2,6 ] decane-8-yl skeleton (hereinafter referred to as “compound (a3-1)) and alkyl (meth) acrylate Ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid ester having a hydroxyl group, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclounsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, The unsaturated compound (a2) which has an alicyclic epoxy skeleton, another epoxy compound, and another unsaturated compound are mentioned.

The copolymer [A] used in the present invention is preferably 10 to 70 based on the sum of the repeating units derived from the compounds (a1), (a2) and (a3). % By weight, particularly preferably 15 to 50% by weight. When this structural unit is less than 10 weight%, there exists a tendency for the storage stability of a radiation sensitive resin composition to fall, and when it exceeds 70 weight%, it melt | dissolves in aqueous alkali solution in the developing process of forming an interlayer insulation film or a microlens. It is difficult.

In the copolymer [A], the (a3) component is an unsaturated compound which has a (a3-1) tricyclo [5.2.1.0 ^2,6 ] decane-8-yl frame | skeleton, (a3-2) (a1), (a2) And in the copolymer [A1] which consists of olefinically unsaturated compounds other than (a3-1), the structural unit guide | induced from compound (a3-1) is compound (a1), (a2), (a3-1), and ( The content of the repeating units derived from a3-2) is preferably 10 to 50% by weight, particularly preferably 15 to 35% by weight.

As the compound (a3-1), for example, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, tricyclo [5.2.1.O ^2,6 ] decane-8-yloxyethylmethyl Acrylate, tricyclo [5.2.1.O ^2,6 ] decane-8-ylacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl acrylate, and the like.

Of these, tricyclo [5.2.1.0 ^2,6] decane-8-yl methacrylate, tricyclo [5.2.1.0 ^2,6] decane-8-oxyethyl methacrylate is particularly preferred.

As methacrylic acid alkyl ester, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, iso Decyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like;

As alkyl acrylate ester, For example, methyl acrylate, isopropyl acrylate, etc .;

As methacrylic acid cyclic alkylester, For example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, isoboroyl methacrylate, etc .;

As acrylic acid cyclic alkylester, For example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, isoboroyl acrylate, etc .;

As methacrylic acid ester which has a hydroxyl group, for example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol mono Methacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glycoside, 4-hydroxyphenyl methacrylate, and the like;

As acrylic acid ester which has a hydroxyl group, for example, hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxy butyl acrylate, diethylene glycol monoacrylate, 2,3 -Dihydroxypropyl acrylate, 2-acryloxyethyl glycoside, 4-hydroxyphenyl acrylate, and the like;

As methacrylic acid aryl ester, For example, phenyl methacrylate, benzyl methacrylate, etc .;

As acrylic acid aryl ester, For example, phenyl acrylate, benzyl acrylate;

As unsaturated dicarboxylic acid diester, For example, diethyl maleate, diethyl fumarate, diethyl itaconate;

As a bicyclo unsaturated compound, it is bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethyl bicyclo [2.2.1] hept-, for example. 2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept 2-ene, 5,6- [diethoxybicyclo] [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclo Hexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [ 2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2 -Ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicy Chlor [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene and the like;

As a maleimide compound, For example, phenyl maleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimidyl-3- maleimide benzoate, N-succinimidyl-4- maleimide butyrate, N-succinate Imidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like;

As an unsaturated aromatic compound, For example, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene etc .;

As a conjugated diene, it is 1, 3- butadiene, isoprene, 2, 3- dimethyl- 1, 3- butadiene, etc .;

Examples of the unsaturated compound (a2) having an alicyclic epoxy skeleton and another epoxy compound include glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like;

As another unsaturated compound, an acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate is mentioned, for example.

Among these, alkyl (meth) acrylic acid esters, bicyclounsaturated compounds, unsaturated aromatic compounds, conjugated dienes are preferably used, and in particular, styrene, t-butyl methacrylate, p-methoxy styrene, 2-methylcyclohexyl acrylate, 1,3-butadiene and bicyclo [2.2.1] hept-2-ene are preferred in view of copolymerization reactivity and solubility in aqueous alkali solution.

Further, among (a2) and other epoxy compounds, methacrylic acid glycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl Benzyl glycidyl ether and the like are preferably used in terms of increasing copolymerization reactivity and heat resistance and surface hardness of the resulting interlayer insulating film or microlens. These are used alone or in combination.

Preferred specific examples of the copolymer [A] used in the present invention include, for example, methacrylic acid / styrene / tricyclo [5.2.1.O ^2,6 ] decane-8-yl methacrylate / 3,4-epoxy Cyclohexylmethyl methacrylate copolymer, methacrylic acid / styrene / tricyclo [5.2.1.O ^2,6 ] decan-8-yl methacrylate / 3,4-epoxycyclohexylmethylmethacrylate / cyclohexyl Maleimide copolymer, methacrylic acid / styrene / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / 3,4-epoxycyclohexylmethyl methacrylate / 2-hydroxyethyl methacrylate Copolymer, methacrylic acid / styrene / tricyclo [5.2.1.O ^2,6 ] decan-8-yl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / n-lauryl methacrylate air Coalescence is mentioned.

As for the copolymer [A] used by this invention, polystyrene conversion weight average molecular weight (henceforth "Mw") becomes like this. Preferably it is 2 * 10 <^3> -1 * 10 <^5> , More preferably, it is 5 * 10 <^3> -5. It is preferable that it is x10 <^4> . When Mw is less than 2x10 <^3>, development margin may not be enough, the residual film ratio of a film obtained etc. may fall, and the pattern shape, heat resistance, etc. of an interlayer insulation film or microlens obtained may fall. On the other hand, when it exceeds 1 * 10 < ⁵ >, a sensitivity may fall or a pattern shape may fall. Moreover, molecular weight distribution (henceforth "Mw / Mn") becomes like this. Preferably it is 5.0 or less, More preferably, it is 3.0 or less. When Mw / Mn exceeds 5.0, the pattern shape of the interlayer insulation film or microlens obtained may fall. The radiation sensitive resin composition containing said copolymer [A] can form a predetermined pattern shape easily, without developing residue generate | occur | producing at the time of image development.

As a solvent used for manufacture of copolymer [A], alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether pro, for example Cypionate, aromatic hydrocarbon, ketone, ester, etc. are mentioned.

As these specific examples, As alcohol, For example, methanol, ethanol, etc .;

As an ether, For example, tetrahydrofuran etc .;

As glycol ether, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc .;

As ethylene glycol alkyl ether acetate, For example, methyl cellosolve acetate, ethyl cellosolve acetate, etc .;

As diethylene glycol, For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As propylene glycol monoalkyl ether, For example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc .;

As propylene glycol alkyl ether acetate, For example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .;

As propylene glycol alkyl ether propionate, For example, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;

As an aromatic hydrocarbon, For example, toluene, xylene, etc .;

As a ketone, For example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl- 2-pentanane, etc .;

Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and hydroxyacetic acid. Methyl, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate, 3-hydroxypropionic acid propyl, 3-hydroxypropionic acid Butyl, 2-hydroxy-3-methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid propyl, butyl acetate, ethoxyacetic acid, ethyl ethoxyacetate, ethoxyacetic acid propyl Butyl oxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, butoxyacetate Methyl, butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2-ethoxypropionic acid Methyl, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate , 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propyl propionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-Ethoxy Propionate, 3-Propoxy Propionate, 3-Propoxy Propionate, 3-Propoxy Propionate, 3-Propoxy Propionate, 3-Butoxypropionate, 3-Butoxypropion Ethyl, and 3-butoxy-propyl propionate, butyl propionate, 3-butoxy respectively.

Among these, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, and propylene glycol Methyl ether acetate is preferred.

As a polymerization initiator used for manufacture of copolymer [A], what is generally known as a radical polymerization initiator can be used. For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2,2'- azobis- (4-methoxy-2, Azo compounds such as 4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; And hydrogen peroxide and the like. When using a peroxide as a radical polymerization initiator, it can also be set as a redox type initiator by using a peroxide simultaneously with a reducing agent.

In manufacture of copolymer [A], in order to adjust molecular weight, a molecular weight modifier can be used. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan and thioglycolic acid; Xanthogens such as dimethyl xanthogen sulfide and diisopropyl xanthogen disulfide; Tapinene, (alpha) -methylstyrene dimer, etc. are mentioned.

[B] component

As 1,2-naphthoquinone diazide sulfonic-acid ester of the component [B] used by this invention, a condensate of a phenolic compound or an alcoholic compound, and 1,2-naphthoquinone diazide sulfonic-acid halide is preferable, for example. It can be mentioned. As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable.

As said phenolic compound or alcoholic compound, trihydroxy benzophenone, tetrahydroxy benzophenone, pentahydroxy benzophenone, hexahydroxy benzophenone, and (polyhydroxyphenyl) alkane are mentioned, for example.

As specific examples of these, examples of the trihydroxy benzophenone include 2,3,4-trihydroxybenzophenone, 2,4.6-trihydroxybenzophenone, and the like;

As tetrahydroxy benzophenone, it is 2,2 ', 4,4'- tetrahydroxy benzophenone, 2,3,4,3'- tetrahydroxy benzophenone, 2,3,4,4'-, for example. Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone and the like;

As pentahydroxy benzophenone, it is 2,3,4,2 ', 6'- pentahydroxy benzophenone etc .;

As hexahydroxy benzophenone, it is 2,4,6,3 ', 4', 5'-hexahydroxy benzophenone, 3,4,5,3 ', 4', 5'-hexahydroxy benzo, for example. Phenone and the like;

Examples of the (polyhydroxyphenyl) alkane include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxycycloman, 2- [bis {(5-isopropyl-4-hydroxy-2-methyl) phenyl} methyl] phenol, 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6 -Dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1- Methylethyl) benzene, and 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzenebis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3.4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1 -[4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3 , 3,3 ', 3'-tetra Tyl-1,1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan Etc. can be mentioned respectively.

In the condensation reaction, 1,2-naphthoquinone diazide sulfonic acid halide corresponding to the number of OH groups in the phenolic compound or the alcoholic compound is preferably 30 to 85 mol%, more preferably 50 to 70 mol%. Can be used.

As a solvent which can be used at this time, a ketone and a cyclic ether are mentioned, for example. As these specific examples, as a ketone, acetone, methyl ethyl ketone, methyl isoamyl ketone, methyl isobutyl ketone, etc. are mentioned as cyclic ether, for example, 1, 4- dioxane, 1, 3, 5- Trioxane etc. are mentioned, respectively. When using a solvent, the usage-amount becomes like this. Preferably it is 100-500 weight part with respect to a total of 100 weight part of the said specific phenolic compound and 1, 2- naphthoquinone diazide sulfonic-acid halide.

A basic compound can be used as a catalyst. Preferably, triethylamine, tetramethylammonium chloride, tetramethylammonium bromide, pyridine, etc. are mentioned. The use amount of these catalysts is preferably 1 mol or more, more preferably 1.05 to 1.2 mol, with respect to 1 mol of 1,2-naphthoquinone diazide sulfonic acid halide.

The catalyst dropping temperature and the reaction temperature are preferably 0 to 50 ° C, more preferably 0 to 40 ° C, particularly preferably 10 to 35 ° C.

Moreover, reaction time becomes like this. Preferably it is 0.5 to 10 hours, More preferably, it is 1 to 5 hours, Especially 1 to 3 hours are preferable.

After the condensation reaction filtered the precipitate, the filtrate was added to a large amount of 0.1 to 3.0% by weight of a diluted hydrochloric acid aqueous solution to precipitate the reaction product. Thereafter, the precipitate is filtered off, washed with water until the filtrate becomes neutral, and then dried to obtain the component [B].

These [B] components can be used individually or in combination of 2 or more types.

The use ratio of the component [B] is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight based on 100 parts by weight of the copolymer [A]. When this ratio is less than 5 parts by weight, the difference in solubility between the irradiated portion and the unirradiated portion of the radiation to the alkaline aqueous solution serving as the developing solution is small, patterning is difficult, and the heat resistance and solvent resistance of the resulting interlayer insulating film or microlens are insufficient. There may be a case. On the other hand, when this ratio exceeds 100 weight part, the solubility to the said aqueous alkali solution in a radiation part may become inadequate and it may become difficult to develop.

Other ingredients

Although the radiation sensitive resin composition of this invention contains the above-mentioned copolymer [A] and [B] components as an essential component, [C] a thermosensitive acid production compound and [D] at least 1 ethylenic unsaturated as needed. A polymerizable compound having a double bond, an epoxy resin other than the [E] copolymer [A], a [F] surfactant, or a [G] adhesion aid may be contained.

The said (C) thermosensitive acid generating compound can be used in order to improve heat resistance and hardness. Specific examples thereof include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts and phosphonium salts.

Specific examples of the sulfonium salts include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts, and the like.

As these specific examples, as the alkylsulfonium salt, for example, 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbamide) Bonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl 3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate, etc .;

Examples of the benzylsulfonium salts include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate and 4-acetoxyphenylbenzylmethylsulfonium hexa. Fluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro- 4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, etc .;

Examples of the dibenzylsulfonium salts include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, and 4-acetoxyphenyldibenzylsulfonium. Hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3- Methyl-4-hydroxy-5-tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate and the like;

Examples of the substituted benzylsulfonium salt include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p -Chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichloropenzyl-4- Hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Specific examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxybenzyl ) Benzylbenzothianes such as benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, and 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate Zonium salts are mentioned.

Of these, sulfonium salts and benzothiazonium salts are preferably used, and 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetium Methoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothia Zolium hexafluoroantimonate is particularly preferably used.

Examples of these commercially available products include Sun-Aid SI-L85, SI-L110, SI-L145, SI-L150, and SI-L160 (manufactured by Sanshin Kagaku Kogyo Co., Ltd.).

The use ratio of the component [C] is preferably 20 parts by weight or less, and more preferably 5 parts by weight or less based on 100 parts by weight of the copolymer [A]. When the amount of use exceeds 20 parts by weight, precipitates may precipitate in the coating film forming step, which may interfere with the coating film formation.

As a polymeric compound (henceforth "D component") which has at least 1 ethylenically unsaturated double bond which is the said [D] component, For example, monofunctional (meth) acrylate, bifunctional (meth) acrylate, or Trifunctional or more than (meth) acrylate is mentioned preferably.

As said monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isoboroyl (meth) acrylate, 3-methoxybutyl (meth), for example Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, etc. are mentioned. As these commercial items, for example, Alonix M-101, M-111, M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110 S, and TC-120 S (above, Nippon Kaya And Co., Ltd., Biscot 158, Copper 2311 (above, manufactured by Osaka Organic Chemical Industries, Ltd.), and the like.

As said bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxy ethanol fluorene diacrylate, and the like. As such a commercial item, for example, Alonics M-210, M-240, M-6200 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (above, Nippon Kaya) Cu Co., Ltd.), Biscot 260, 312, and 335 HP (above, Osaka Organic Chemical Industries, Ltd. make) etc. are mentioned.

As said trifunctional or more than (meth) acrylate, a trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, a tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol, for example Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned, The commercial item is, for example, Alonics M-309, Copper M-400. , East M-405, East M-450, East M-7100, East M-8030, East M-8060 (above, manufactured by Toa Kosei Co., Ltd.), KAYARAD TMPTA, East DPHA, East DPCA-20, East DPCA- 30, East DPCA-60, East DPCA-120 (above, manufactured by Nippon Kayaku Co., Ltd.), Biscot 295, East 300, East 360, East GPT, East 3PA, East 400 (above, Osaka Organic Kagaku High School ( Note) manufacture) etc. are mentioned.

Of these, trifunctional or higher (meth) acrylates are preferably used, and trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate are particularly preferred. desirable.

These mono-, bi-, or tri- or more (meth) acrylates are used alone or in combination. The use ratio of component [D] is 50 weight part or less with respect to 100 weight part of copolymers [A], More preferably, it is 30 weight part or less.

By containing [D] component in such a ratio, the heat resistance, surface hardness, etc. of the interlayer insulation film or microlens obtained from the radiation sensitive resin composition of this invention can be improved. When this usage amount exceeds 50 weight part, film roughness may arise in the process of forming the coating film of a radiation sensitive resin composition on a board | substrate.

Although epoxy resins other than copolymer [A] which is the said [E] component (henceforth "E component") are not limited as long as they do not affect compatibility, Preferably bisphenol-A epoxy resin and a phenol novolak Epoxy resin, cresol novolac epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, heterocyclic epoxy resin, glycidyl methacrylate (co) polymerized resin Etc. can be mentioned. Among them, bisphenol A epoxy resins, cresol novolac epoxy resins, glycidyl ester epoxy resins, and the like are particularly preferable.

The use ratio of the component [E] is preferably 30 parts by weight or less based on 100 parts by weight of the copolymer [A]. By containing [E] component in such a ratio, the heat resistance, surface hardness, etc. of a protective film or insulating film obtained from the radiation sensitive resin composition of this invention can be improved further. When this ratio exceeds 30 weight part, when forming the coating film of a radiation sensitive resin composition on a board | substrate, the film thickness uniformity of a coating film may become inadequate.

Moreover, although copolymer [A] can also be called "epoxy resin", it differs from [E] component by the point which has alkali solubility.

Surfactant which is the said [F] component can be used for the radiation sensitive resin composition of this invention in order to improve applicability | paintability further. As surfactant, a fluorine-type surfactant, a silicone type surfactant, and a nonionic surfactant are mentioned as a preferable thing, for example.

Specific examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether and octa Ethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1 , 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2, Sodium fluoroalkylbenzenesulfonates in addition to 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane and the like; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodides, fluoroalkylpolyoxyethylene ethers, perfluoroalkylpolyoxyethanols; Perfluoroalkylalkoxylates; Fluorine-based alkyl esters and the like. As such a commercial item, BM-1000, BM-1100 (above, BM Chemie company make), mega pack F142D, copper F172, copper F173, copper F183, copper F178, copper F191, copper F471 (or more, Dai Nippon Ink Chemical Industries, Ltd. ( Note) manufactured), fluoride FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), Supron S-112, copper S-113, copper S-131, East S-141, East S-145, East S-382, East SC-101, East SC-102, East SC-103, East SC-104, East SC-105, East SC-106 (Asahi Glass Production), F-top EF301, copper 303, copper 352 (manufactured by Shinsei Kasei Co., Ltd.), and the like.

As said silicone type surfactant, For example, DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above, Toray Dow Corning What is marketed under brand names, such as a silicone company make, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba Silicone Co., Ltd. make) Can be.

As said nonionic surfactant, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (Meth) acrylic acid copolymer polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be used.

These surfactant can be used individually or in combination of 2 or more types.

These [F] surfactants are used with respect to 100 weight part of copolymers [A], Preferably it is 5 weight part or less, More preferably, it is used in 2 weight part or less. When the usage-amount of [F] surfactant exceeds 5 weight part, when a coating film is formed on a board | substrate, the film roughness of a coating film may arise easily.

In the radiation sensitive resin composition of this invention, in order to improve adhesiveness with a board | substrate, the adhesion | attachment adjuvant which is a [G] component can also be used. As such [G] adhesion adjuvant, a functional silane coupling agent is used preferably. For example, the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group, is mentioned. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxy Silane, (beta)-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned. Such [G] adhesion aid is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the adhesion assistant exceeds 20 parts by weight, a developing residue may easily occur in the developing step.

Radiation-sensitive resin composition

The radiation sensitive resin composition of this invention is manufactured by mixing uniformly the above-mentioned copolymer [A] and [B] components, and the other components added arbitrarily as mentioned above. The radiation sensitive resin composition of the present invention is preferably dissolved in a suitable solvent and used in a solution state. For example, the radiation sensitive resin composition of a solution state can be manufactured by mixing copolymer [A] and [B] component and the other component added arbitrarily at predetermined ratio.

As a solvent used for manufacture of the radiation sensitive resin composition of this invention, it is a thing which melt | dissolves each component of the copolymer [A] and [B] components and the other components arbitrarily mix | blended uniformly, and does not react with each component. Used.

As such a solvent, the same thing as what was illustrated as a solvent which can be used in order to manufacture copolymer [A] mentioned above is mentioned.

Among these solvents, glycol ether, ethylene glycol alkyl ether acetate, ester, and diethylene glycol are preferably used in view of solubility of each component, reactivity with each component, ease of coating film formation, and the like. Among them, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, fulpyrene glycol monomethyl ether acetate, methyl methoxy propionate and ethyl ethoxypropionate can be particularly preferably used.

In addition, a high boiling point solvent may be used in combination with the solvent to increase in-plane uniformity of the film thickness. As a high boiling point solvent which can be used together, it is N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpi, for example. Ralidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, dioxalic acid Ethyl, diethyl maleate, gamma -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate and the like. Among these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

When using a high boiling point solvent together as a solvent of the radiation sensitive resin composition of this invention, the usage-amount is 50 weight% or less with respect to solvent whole quantity, More preferably, it is 40 weight% or less, More preferably, 30 weight% It can be set as follows. When the usage-amount of a high boiling point solvent exceeds this usage-amount, the film thickness uniformity, a sensitivity, and a residual film ratio of a coating film may fall.

In the case where the radiation-sensitive resin composition of the present invention is prepared in a solution state, the ratio of components other than the solvent (ie, the total amount of the copolymer [A] and [B] components and other components optionally added) in the solution is It can set arbitrarily according to a purpose of use, the value of a desired film thickness, etc. Preferably it is 5-50 weight%, More preferably, it is 10-40 weight%, More preferably, it is 15-35 weight%.

The composition solvent thus prepared may be used after being filtered using a Millipore filter having a pore size of about 0.2 μm or the like.

Formation of Interlayer Insulator and Micro Lens

Next, the method of forming the interlayer insulation film and microlens of this invention using the radiation sensitive resin composition of this invention is described. The method of forming the interlayer insulating film or microlens of the present invention

(1) process of forming the coating film of the radiation sensitive resin composition of this invention on a board | substrate,

(2) irradiating at least a part of the coating film with radiation;

(3) developing process, and

(4) heating process

May be included in the order of description.

(1) Process of forming the coating film of the radiation sensitive resin composition of this invention on a board | substrate

In the process of said (1), the solution of the resin composition of this invention is apply | coated to the board | substrate surface, pre-baking is performed, a solvent is removed, and the coating film of a radiation sensitive resin composition is formed.

As a kind of substrate which can be used, a glass substrate, a silicon wafer, and the board | substrate with which the various metal was formed in these surfaces are mentioned, for example.

It does not specifically limit as a coating method of a composition solution, For example, the appropriate method, such as the spray method, the roll coating method, the rotary coating method, the bar coating method, can be employ | adopted. Pre-baking conditions also differ according to the kind of each component, the use ratio, etc. For example, it can be made into about 30 to 15 minutes at 60-110 degreeC.

The film thickness of the coating film formed is a value after pre-baking, for example, when forming an interlayer insulation film, for example, 3-6 micrometers, and when forming a microlens, for example, 0.5-3 micrometers is preferable.

(2) irradiating at least a part of the coating film with radiation

In the process of (2), after irradiating radiation to the formed coating film through the mask which has a predetermined | prescribed pattern, patterning is performed by developing using a developing solution and removing the irradiation part of radiation. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.

As said ultraviolet-ray, g line | wire (wavelength 436 nm), i line | wire (wavelength 365 nm), etc. are mentioned, for example. As far ultraviolet rays, KrF excimer laser etc. are mentioned, for example. As X-ray, a synchrotron radiation etc. are mentioned, for example. As a charged particle beam, an electron beam etc. are mentioned, for example.

Among these, ultraviolet rays are preferable, and radiation including g rays and / or i rays is particularly preferable.

As the exposure amount is preferably set to 50 to In 1,50O J / m ^2, the case of forming the microlens 50 to 2,000 J / m ² In the case of forming the interlayer insulating film.

(3) developing process

As a developing solution used for image development treatment, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propyl Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4, Aqueous solutions of alkali (basic compounds) such as 0] -7-undecene and 1,5-diazabicyclo [4,3,0] -5-nonane can be used. Moreover, the aqueous solution which added water-soluble organic solvents, such as methanol and ethanol, and surfactant in an appropriate quantity to the aqueous solution of said alkali, or the various organic solvent which melt | dissolves the composition of this invention can be used as a developing solution. Moreover, as a developing method, the appropriate methods, such as the liquid immersion method, the dipping method, the oscillation dipping method, the shower method, can be used. The development time at this time depends on the composition of the composition. For example, it can be made into 30 to 120 second.

In addition, since the peeling will generate | occur | produce in the pattern formed when the developing time exceeds about 20-25 second from the optimal value, the radiation-sensitive resin composition of this invention was known conventionally. In this case, even if the excess time is 30 seconds or more from the optimum development time, good pattern formation is possible and there is an advantage in product yield.

(4) heating process

(3) The thin film patterned after the developing step carried out as described above is preferably rinsed by, for example, running water washing, and preferably irradiated with radiation on the entire surface by a high pressure mercury lamp (post exposure). By performing the decomposition | decomposition process of the 1, 2- quinonediazide compound which remain | survives in this thin film by this, and heat-processing (post-baking) this thin film with a heating apparatus, such as a hotplate and oven, hardening process of this thin film Can be done. The exposure amount in the said post-exposure process becomes like this. Preferably it is about 2,00-5,00 J / m <^2> . In addition, the baking temperature in this hardening process is 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, it can be set as 5 to 30 minutes, when carrying out heat processing on a hotplate, for example, and 30 to 90 minutes when carrying out heat processing in an oven. At this time, the step baking method which performs two or more heating processes, etc. can be used.

In this way, a patterned thin film corresponding to the desired interlayer insulating film or microlens can be formed on the surface of the substrate.

The interlayer insulating film and the microlens formed as described above are excellent in adhesion, heat resistance, solvent resistance, transparency, and the like, as will be apparent from the examples described later.

Interlayer insulation film

The interlayer insulating film of the present invention formed as described above has good adhesion to a substrate, is excellent in solvent resistance and heat resistance, has a high transmittance, and can be suitably used as an interlayer insulating film for electronic components.

Microlens

The microlenses of the present invention formed as described above have good adhesion to the substrate, excellent solvent resistance and heat resistance, and high transmittance and good melt shape, and can be suitably used as microlenses of solid-state imaging devices. have.

The microlens of the present invention has a semiconvex lens shape as shown in Fig. 1A.

Example

Although a synthesis example and an Example are shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

Synthesis Example of Copolymer [A]

Synthesis Example 1

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 22 parts by weight of methacrylic acid, 5 parts by weight of styrene, 28 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and 45 parts by weight of 3,4-epoxycyclohexylmethylmethacrylate And 5 parts by weight of α-methylstyrene dimer were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70 ° C., and the temperature was maintained for 4 hours to obtain a polymer solution containing a copolymer [A-1].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-1] was 8,000 and the molecular weight distribution (Mw / Mn) was 2.3. In addition, solid content concentration of the polymer solution obtained here was 29.8 weight%.

Synthesis Example 2

To the flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added. 18 parts by weight of methacrylic acid, 5 parts by weight of styrene, 17 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 40 parts by weight of 3,4-epoxycyclohexylmethylmethacrylate 20 parts by weight of cyclohexylmaleimide and 3 parts by weight of α-methylstyrene dimer were added thereto, and after nitrogen substitution, gentle stirring was started. The temperature of the solution was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer [A-2].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-2] was 11,000, and molecular weight distribution (Mw / Mn) was 2.1. In addition, the solid content concentration of the polymer solution obtained here was 31.5 weight%.

Synthesis Example 3

6 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 15 parts by weight of methacrylic acid, 5 parts by weight of styrene, 20 parts by weight of tricyclo [5.2.1.O ^2,6 ] decane-8-yl methacrylate, 3,4-epoxycyclohexylmethylmethacrylate 40 Part by weight, 20 parts by weight of 2-hydroxyethyl methacrylate and 3 parts by weight of α-methylstyrene dimer were added, and after nitrogen replacement, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4.5 hours to obtain a polymer solution containing a copolymer [A-3].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-3] was 13,000, and the molecular weight distribution (Mw / Mn) was 2.2. In addition, the solid content concentration of the polymer solution obtained here was 32.7 weight%.

Synthesis Example 4

8.5 parts by weight of 2,2'-azobis (2.4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 15 parts by weight of methacrylic acid, 5 parts by weight of styrene, 30 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and 40 parts by weight of 3,4-epoxycyclohexylmethylmethacrylate , 10 parts by weight of n-lauryl methacrylate and 3 parts by weight of α-methylstyrene dimer were added thereto, and after nitrogen substitution, gentle stirring was started. The temperature of the solution was raised to 70 ° C., and the temperature was maintained for 4.5 hours to obtain a polymer solution containing a copolymer [A-4].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-4] was 8,000 and the molecular weight distribution (Mw / Mn) was 1.8. In addition, the solid content concentration of the polymer solution obtained here was 31.5 weight%.

Synthesis Example 5

8.5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 15 parts by weight of methacrylic acid, 5 parts by weight of styrene, 30 parts by weight of tricyclo [5.2.1.O ^2,6 ] decane-8-yl methacrylate, 3,4-epoxycyclohexylmethylmethacrylate 20 Parts by weight, 20 parts by weight of p-vinylbenzyl glycidyl ether, 10 parts by weight of n-lauryl methacrylate and 3 parts by weight of α-methylstyrene dimer were added, and after nitrogen replacement, gently stirring was started. The temperature of the solution was raised to 70 ° C., and the temperature was maintained for 4.5 hours to obtain a polymer solution containing a copolymer [A-5].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-5] was 8,500 molecular weight distribution (Mw / Mn) of 2.2. In addition, solid content concentration of the polymer solution obtained here was 31.7 weight%.

Synthesis Example 6

8.5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 15 parts by weight of methacrylic acid, 5 parts by weight of styrene, 30 parts by weight of tricyclo [5.2.1.O ^2,6 ] decane-8-yl methacrylate, 3,4-epoxycyclohexylmethylmethacrylate 20 By weight, 20 parts by weight of glycidyl methacrylate, 10 parts by weight of n-lauryl methacrylate, and 3 parts by weight of α-methylstyrene dimer were added to replace the nitrogen, followed by gentle stirring. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4.5 hours to obtain a polymer solution containing a copolymer [A-6].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-6] was 9,000, and molecular weight distribution (Mw / Mn) was 2.5. In addition, the solid content concentration of the polymer solution obtained here was 31.9 weight%.

Synthesis Example of Component

Synthesis Example 7

36.41 g of 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxycycloman in a flask equipped with a stirrer, a dropping lot and a thermometer under light shielding (100 mmol), 1,2-naphthoquinonediazide-5-sulfonic acid chloride 85.49 g (300 mmol), and 735 mL of acetone were added and dissolved homogeneously. Subsequently, 33.37 g (330 mmol) of triethylamine was added dropwise for 30 minutes while maintaining the temperature of the solution at 20 to 30 ° C, followed by reacting at the same temperature for 2 hours.

The precipitate was removed by the filtrate, the filtrate was poured into an excess of 1% by weight aqueous hydrochloric acid solution to precipitate the product, the filtrate was separated, washed with water until the filtrate was neutral, and dried at 40 ° C. in a vacuum dryer for one day. [B-1] (2-Methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxycycloman (1.0 mole) and 1,2-naphtho Condensate of quinonediazide-5-sulfonic acid chloride (3.0 mol)).

Synthesis Examples 8 to 12

In Synthesis Example 7, the kind and amount of the specific phenol compound and 1,2-naphthoquinone diazide-5-sulfonic acid chloride were used in the same manner as in Synthesis Example 7, except that the amounts of the 1,2-naphthoquinonediazide-5-sulfonic acid chlorides were as described in Table 1. 2] to [B-6].

<Example 1>

[Manufacture of a radiation sensitive resin composition]

As a component [A] synthesized in Synthesis Example 1, the amount of the solution containing polymer [A-1] corresponding to 100 parts by weight of the polymer [A-1] (solid content), and as the component [B], Synthesis Example 10 20 parts by weight of [B-4] synthesized in the above was dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration was 30% by weight, and then filtered through a membrane filter having a diameter of 0.2 µm to obtain a solution of the radiation-sensitive resin composition (S- 1) was prepared.

<Examples 2 to 16>

[Manufacture of a radiation sensitive resin composition]

In Example 1, it carried out similarly to Example 1 except having used the kind and quantity as shown in Table 2 as component [A] and [B], and the solution of a radiation sensitive resin composition (S-2 ) To (S-16).

<Examples 1 to 16, Comparative Examples 1 and 2>

<Performance evaluation as an interlayer insulation film>

The various characteristics as an interlayer insulation film were evaluated as follows using the radiation sensitive resin composition manufactured as mentioned above. In addition, the composition used by the comparative examples 1 and 2 is a commercial item (made by Tokyo Oka Corporation) of the composition of both m / p-cresol novolak and a 1, 2- naphthoquinone diazide-5-sulfonic acid ester.

[Evaluation of sensitivity]

After applying the composition shown in Table 2 using a spinner on a silicon substrate, it pre-baked on a hot plate for 2 minutes at 90 degreeC, and formed the coating film of 3.0 micrometers in film thicknesses. After exposure by changing exposure time with Canon PLA-501F exposure machine (ultra-high pressure mercury lamp) through the pattern mask which has a predetermined | prescribed pattern in the obtained coating film, the tetramethylammonium hydroxide of the density shown in Table 3 was exposed. It developed by 25 degreeC and the liquid immersion method for 90 second with aqueous solution (developing solution). Flowing water was washed for 1 minute with ultrapure water, and dried to form a pattern on the wafer. The exposure amount required for complete dissolution of the space pattern of the line and space (10 to 1) of 3.0 mu m was measured. This value is shown in Table 3 as the sensitivity. When this value is 100 J / m <^2> or less, it can be said that a sensitivity is favorable.

[Evaluation of Development Margin]

After applying the composition shown in Table 2 using a spinner on a silicon substrate, it pre-baked on a hot plate for 2 minutes at 90 degreeC, and formed the coating film of 3.0 micrometers in film thicknesses. In the "[evaluation of sensitivity]" using the Canon-made PLA-501F exposure machine (ultra-high pressure mercury lamp) through the mask which has a pattern of a line and space (10: 1) of 3.0 micrometers in the obtained coating film, It exposed at the exposure amount corresponding to the value of the measured sensitivity, and developed by 25 degreeC and 90 second immersion in the tetramethylammonium hydroxide aqueous solution of the density | concentration shown in Table 3. Subsequently, flowing water was washed with ultrapure water for 1 minute, dried, and a pattern was formed on the wafer. At this time, the developing time required for the line width to be 3 m is shown in Table 3 as the optimum developing time. In addition, the time from the optimum development time to the time when the development of the line / pattern of 3.0 µm was peeled off was measured and shown in Table 3 as the development margin. When this value is 30 seconds or more, the development margin can be said to be good.

[Evaluation of solvent resistance]

After applying the composition shown in Table 2 using a spinner on a silicon substrate, it was pre-baked on a hot plate for 2 minutes at 950 degreeC, and the coating film with a film thickness of 3.0 micrometers was formed. The obtained coating film was exposed so that the accumulated irradiation amount might be 3,000 J / m ² with a Canon PLA-501 F exposure machine (ultra high pressure mercury lamp), and the silicon substrate was heated at 220 ° C. in a clean oven for 1 hour to obtain a cured film. . The film thickness (T1) of the obtained cured film was measured. Then, the silicon substrate on which the cured film was formed was immersed in dimethyl sulfoxide for 20 minutes at a temperature controlled at 70 ° C., and then the film thickness t1 of the cured film was measured, and the film thickness change rate by immersion {| t1-T1 | / T1} × 100 [%] was calculated. The results are shown in Table 3. When this value is 5% or less, it can be said that solvent resistance is favorable.

In the evaluation of the solvent resistance, since the patterning of the film to be formed is unnecessary, the irradiation step and the developing step were omitted, and only the coating film forming step, the post-baking step and the heating step were used for evaluation.

[Evaluation of Heat Resistance]

In the same manner as the above evaluation of the solvent resistance, a cured film was formed, and the film thickness (T2) of the obtained cured film was measured. Subsequently, after further baking this cured film board | substrate at 240 degreeC in the clean oven for 1 hour, the film thickness (t2) of this cured film is measured, and the film thickness change rate by further baking {| t2-T2 | / T2} × 100 [%] was calculated. The results are shown in Table 3. When this value is 5% or less, it can be said that heat resistance is favorable.

[Evaluation of transparency]

In evaluation of said solvent resistance, the cured film was formed on the glass substrate similarly except having used the glass substrate "Corning 7059 (made by Corning Corporation)" instead of the silicon substrate. The light transmittance of the glass substrate which has this cured film was measured with the wavelength of the range of 400-800 nm using the spectrophotometer "150-20 type double beam (the Hitachi Seisakusho Corporation)." The value of the minimum light transmittance at that time is shown in Table 3.

When this value is 90% or more, it can be said that transparency is favorable.

<Examples 17-32, Comparative Examples 3, 4>

<Evaluation as a micro lens>

Using the radiation sensitive resin composition prepared as described above, various characteristics as microlenses were evaluated as follows. In addition, evaluation of heat resistance and transparency should refer to the result in performance evaluation as said interlayer insulation film.

In addition, the composition used by the comparative examples 3 and 4 is a commercial item (made by Tokyo Oka Corporation) of the composition of m / p-cresol novolak and 1,2-naphthoquinone diazide-5-sulfonic acid ester in all.

[Evaluation of sensitivity]

After applying the composition shown in Table 4 using a spinner on the silicon substrate, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm. The exposure time was changed by the Nikon Corporation NSR 1755i7A reduced projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a predetermined | prescribed pattern to the obtained coating film, and it exposed and changed into tetramethyl of the density shown in Table 5. It developed by 25 degreeC and the liquid immersion method in aqueous ammonium hydroxide solution. Rinse with water and dry to form a pattern on the wafer. The exposure time required for the space line width of the 0.8 mu m line and space pattern (1 to 1) to be 0.8 mu m was measured. This value is shown in Table 5 as the sensitivity. When this value is 2,50 J / m <^2> or less, it can be said that a sensitivity is favorable.

[Evaluation of Development Margin]

After applying the composition shown in Table 4 using a spinner on a silicon substrate, it was pre-baked on a hot plate for 2 minutes at 90 degreeC, and the coating film with a film thickness of 3.0 micrometers was formed. It corresponds to the value of the sensitivity measured by said "[evaluation of sensitivity]" with the Nikon Corporation NSR 1755i7A reduction projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a predetermined | prescribed pattern in the obtained coating film. It exposed at the exposure amount, and it developed by 25 degreeC and the liquid immersion method for 1 minute (development method description) with the tetramethylammonium hydroxide aqueous solution of the density | concentration shown in Table 5. Rinse with water and dry to form a pattern on the wafer. The development time required for the space line width of the 0.8 mu m line and space pattern (1 vs. 142) to 0.8 mu m is shown in Table 5 as the optimum development time. In addition, the time (development margin) until peeling of the pattern of 0.8 micrometers in width | variety when image development was continued by the optimum image development time was measured, and it shows in Table 5 as image development margin. When this value is 30 seconds or more, the development margin can be said to be good.

[Evaluation of solvent resistance]

After applying the composition of Table 4 using a spinner on a silicon substrate, it pre-baked on a hot plate for 2 minutes at 90 degreeC, and formed the coating film of 3.0 micrometers in film thicknesses. It exposed to the obtained coating film so that accumulated irradiation amount might be 3,000 J / m <^2> by Canon's PLA-501F exposure machine (super high pressure mercury lamp), and this silicon substrate was heated at 220 degreeC in the clean oven for 1 hour, and the cured film was obtained. The film thickness (T3) of the obtained cured film was measured. After the silicon substrate on which the cured film was formed was immersed in isopropyl alcohol temperature controlled at 50 ° C. for 10 minutes, the film thickness t3 of the cured film was measured and the film thickness change rate by immersion {| t3-T3 | / T3 } × 100 [%] was calculated. The results are shown in Table 5. When this value is 5% or less, solvent resistance can be said to be favorable.

In addition, since the patterning of the film to form is unnecessary in evaluation of solvent resistance, the irradiation process and the development process were skipped, and only the coating film formation process, the post-baking process, and the heating process were performed and used for evaluation.

[Formation of Micro Lens]

After applying the composition shown in Table 4 using a spinner on a silicon substrate, it pre-baked on a hot plate for 2 minutes at 90 degreeC, and formed the coating film of 3.0 micrometers in film thicknesses. Through the pattern mask having a 4.0 µm dot and 2.0 µm space pattern on the obtained coating film, the NSR1755i7A reduced projection exposure machine (NA = 0.50, λ = 365 nm) manufactured by Nikon Corporation Exposure was carried out at an exposure amount corresponding to the value, and development was carried out by an aqueous solution of 25 ° C. for 1 minute in an aqueous tetramethylammonium hydroxide solution having a concentration described as the developer concentration in the evaluation of sensitivity in Table 5 (development method described). Rinse with water and dry to form a pattern on the wafer. Then, it exposed by the Canon Co., Ltd. product PLA-501F exposure machine (ultra high pressure mercury lamp) so that accumulated irradiation amount might be 3, OOJ / m <^2> . Thereafter, the plate was heated at 160 ° C. for 10 minutes and further heated at 230 ° C. for 10 minutes to meltflow the pattern to form a microlens.

Table 5 shows the dimensions (diameter) and the cross-sectional shape of the bottom portion (surface in contact with the substrate) of the formed microlenses. It can be said that the dimension of a microlens bottom part exceeds 4.0 micrometers and is less than 5.0 micrometers. Moreover, when this dimension becomes 5.0 micrometers or more, it is a state in which adjacent lenses contact, and it is not preferable. In addition, in the schematic diagram shown in FIG. 1, a cross-sectional shape is favorable when it is a semi-convex lens shape as shown in (a), and is bad when it is a substantially trapezoidal shape like (b).

The present invention provides a radiation sensitive resin composition containing a copolymer of an unsaturated compound having the above-described composition and 1,2-naphthoquinone diazide sulfonic acid ester, thereby providing high radiation sensitivity in an electronic component such as an interlayer insulating film or a microlens. In addition, it is possible to easily form a patterned thin film having a developing margin such that a good pattern shape can be formed even after the optimum developing time has elapsed in the developing step.

Claims (8)

[A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) the following formula Unsaturated compounds having an alicyclic epoxy skeleton represented by (a3) copolymers of unsaturated compounds other than the above (a1) and (a2), and [B] 1,2-naphthoquinone diazide sulfonic acid ester A radiation-sensitive resin composition comprising a. A radiation sensitive resin composition according to claim 1, wherein the component (a3) comprises an unsaturated compound having a tricyclo [5.2.1.0 ^2,6 ] decane-8-yl skeleton and another unsaturated compound. The radiation sensitive resin composition of Claim 1 or 2 which is for forming an interlayer insulation film. (1) process of forming the coating film of the radiation sensitive resin composition of Claim 1 on a board | substrate, (2) irradiating at least a part of the coating film with radiation; (3) developing process, and (4) heating process Method for forming an interlayer insulating film, characterized in that it comprises in the order of the substrate. An interlayer insulating film formed by the method of claim 4. The radiation sensitive resin composition of Claim 1 or 2 for microlens formation. (1) Process of forming the coating film of the radiation sensitive resin composition of Claim 1 on a board | substrate, (2) irradiating at least a part of the coating film with radiation; (3) developing process, and (4) heating process Method for forming a microlens, characterized in that it comprises in order. A microlens formed by the method of claim 7.