KR100869458B1 - Resist composition - Google Patents

Abstract

The present invention provides a resist composition containing (A) an alkali-soluble resin, (B) a component that crosslinks the alkali-soluble resin by heat treatment followed by irradiation of active light or irradiation with active light, and (C) a compound that absorbs active light, (A) Alkali-soluble resin is a resin composition containing 30 to 95 weight% of polyvinylphenol and 5 to 70 weight% of novolak resin, It is related with the resist composition characterized by the above-mentioned. Moreover, it is related with the pattern formation method using the said resist composition.

Description

Resist Composition {RESIST COMPOSITION}

The present invention relates to a resist composition used in the field of photolithography, and more particularly, to a resist composition whose cross section is capable of forming an inverse tapered or overhanged resist pattern, and in which the heat resistance of the resist pattern is remarkably improved. will be. The resist composition of the present invention is particularly suitable for applications such as a negative resist for pattern formation by a lift-off method, a photoresist for manufacturing an electrically insulating partition wall of an organic electroluminescent display panel, and the like.

In photolithography techniques using a resist, there is a case where a resist material capable of forming a resist pattern profile having an inverse taper shape or an overhang shape in cross section is required. Specifically, the case of forming a pattern by the lift-off method, or the case of forming the electrically insulating partition of an organic electroluminescent display panel, etc. are mentioned.

The lift-off method is applied to, for example, the formation of a semiconductor pattern, the formation of a heating element for a thermal head, the correction of white defects in a photomask, and the like. For example, in the case of forming a conductor pattern by a lift-off method, (1) a resist film is formed on a substrate, and (2) the resist film is exposed and developed in a pattern shape to form a negative resist pattern (negative image). And (3) depositing a metal on the entire surface of the substrate including the negative resist pattern phase to form a deposited film, and (4) swelling and dissolving the negative resist pattern on the substrate by immersing the entire substrate in a solution. To form a conductor pattern. In the step (4), the deposited film on the negative resist pattern is also removed, and the deposited film on the substrate remains in a pattern shape.

In the step (2), as shown in Fig. 1, a negative resist pattern 2 having an inverse taper shape in cross section is formed on the substrate 1, and a metal deposition film is formed on the entire surface of the substrate in the next step (3). On the lower surface, the deposition film 3 and the deposition film 3 'are formed on the substrate 1 and on the negative resist pattern 2, respectively. Then, when the negative resist pattern 2 is removed in step (4), the deposited film 3 'on it is also removed, leaving only the pattern of the deposited film 3 on the substrate 1.

In the case where the resist pattern profile has a rectangular, forward tapered, triangular, or the like cross-sectional shape, when the metal deposition film is formed on the entire surface of the substrate in the step (3), the deposition film is also formed on the side of the resist pattern. The deposited film on the resist pattern is formed continuously. Therefore, when the resist pattern is removed in step (4), not only the vapor deposition film formed thereon but also the vapor deposition film on the substrate continuous thereto is partially or completely removed. In the pattern formation by the lift haute method, not only the resist pattern of the reverse tapered cross section, but also the resist pattern 42 which is an overhang cross section which has the overhang part 43 on the board | substrate 41 as shown in FIG.

The photoresist for producing an electrically insulating partition wall of an organic electroluminescent display panel also needs to be able to form a resist pattern profile having an inverse taper shape or an overhang shape. The organic electro luminescence (hereinafter referred to as `` organic EL '') display is self-luminous and has no limitation on viewing angle, high brightness, thin panel, low voltage operation, fast response, RGB (Red / Green / Blue) It is possible to make full colors using three primary colors. However, organic EL materials have a problem in that they are low in resistance to organic solvents and cannot be etched, making it difficult to form matrix structures as display elements by microfabrication using photolithography techniques. Therefore, the use of the organic EL display as a backlight for a liquid crystal display is mainly used.

Therefore, Japanese Patent Laid-Open No. 8-315981 proposes a new proposal regarding a technology for forming a display element using an organic EL material. Specifically, for example, (1) a plurality of stripe-shaped patterns of indium tin oxide (ITO) are formed on a transparent substrate to form a first display electrode (anode), and (2) a negative type on the entire surface of the substrate from above. A resist composition is applied to form a resist film, (3) exposed through a stripe-shaped photomask orthogonal to the stripe-shaped pattern of ITO, post exposure baking (PEB), and then developed to form a stripe negative resist pattern. (4) An organic EL material (hole transporting material and electron transporting material) is sequentially deposited on the substrate, and (5) and a metal such as aluminum is deposited thereon to manufacture an organic EL display panel.

In this organic EL display panel, the negative resist pattern serves as an electrically insulating partition. That is, as shown in Fig. 2, an ITO film (anode 22) patterned in a stripe shape is formed on the transparent substrate 21, and then a stripe negative resist pattern 23 orthogonal to this is formed. do. If the cross section of the negative resist pattern is in an inverse taper shape or an overhang shape, when the organic EL material is deposited from above, the vapor deposition film 24 of the stripe organic EL material orthogonal to the ITO film 22 on the substrate 21 is independent. Is formed. Even if an organic EL material is deposited on the negative resist pattern, the deposition film 24 'is independent of the deposition film 24 on the substrate.

When metals such as aluminum are deposited from above, independent metal deposition films 25 and 25 'are formed on the deposition film 24' and the organic EL material on the deposition film 24 of the organic EL material on the substrate and on the negative resist pattern, respectively. The metal deposition film 25 formed on the deposition film 24 of the organic EL material becomes a second display electrode (cathode). Adjacent second display electrodes (cathodes) are divided electrically by a negative resist pattern. The ITO film (anode 22) and the metal vapor deposition film (cathode 25) are not shorted by the vapor deposition film 24 of the organic EL material.

When the organic EL material is deposited, the organic EL material of each RGB color is sequentially deposited using a deposition mask. As shown in Fig. 3, the organic EL material of each color on the transparent substrate 31 and the ITO film 32 is shown. Vapor deposition films 34a (R), 34b (G) and 34c (B) are formed. When the negative resist pattern is covered with the deposition mask, a deposition film of an organic EL material is hardly formed thereon. When metals such as aluminum are deposited from above, metal deposition films 35 and 35 'are formed independently on the deposition film of each color of organic EL material and on the negative resist pattern, respectively.

In the organic EL display panel having such a structure, the evaporation portion of the organic EL material in which the first display electrode and the second display electrode cross each other and is sandwiched between the two electrodes becomes a light emitting portion. The negative resist pattern is not removed and remains as an electrically insulating partition.

Conventionally, a method of using a positive photoresist made of a novolak resin and a quinonediazide compound, and forming an inverse tapered resist pattern by an image reversal method is known. However, this image reversal method is complicated to operate, and the tolerance of the heating temperature at the time of heat treatment (amine diffusion and heating) is narrow, making it difficult to obtain a good shape resist pattern.

Japanese Laid-Open Patent Publication No. 5-165218 contains at least one component (A) which crosslinks by exposure or heat treatment following exposure, (B) alkali-soluble resin, and (C) a compound that absorbs the light to be exposed. And also the negative resist composition which uses alkaline aqueous solution as a developing solution is proposed. By using this negative resist composition, the resist pattern of the reverse taper shape or the overhang shape suitable for the lift-off method can be formed.

However, formation of the metal vapor deposition film by the lift-off method is performed at high temperature. The electrically insulating partition wall of the organic EL display panel must maintain its shape in order to withstand the deposition of the organic EL material or the deposition of the metal under high temperature conditions. In particular, in the case of depositing an organic EL material, in order to widen the margin (allowability) of the sublimation temperature, it is required to improve the heat resistance of the electrically insulating partition wall made of a resist pattern. In addition, since the organic EL display panel is used in a portable device, a vehicle-mounted device, or the like, it is required to have durability that can withstand high temperature conditions such as temperature rise in a car. By the way, the conventional resist pattern of the reverse taper shape or the overhang cross section has a problem that heat resistance is not enough yet.

It is an object of the present invention to provide a resist composition capable of forming a resist pattern having an inverse taper shape or an overhang shape in cross section, and capable of forming a resist pattern with significantly improved heat resistance.

Another object of the present invention is to provide a method of forming a resist pattern on a substrate using such a resist composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, the component which bridge | crosslinks alkali-soluble resin by the heat processing following (A) alkali-soluble resin, (B) irradiation of actinic light (exposure) or irradiation of actinic light (crosslinking component ) And (C) a resist composition containing a compound that absorbs actinic light (exposure light), wherein (A) an alkali-soluble resin is used in combination with a polyvinylphenol and a novolak resin in a specific ratio to It was found that the resist pattern can be formed, the peeling resistance of the resist pattern to the substrate is good, and the heat resistance of the resist pattern is remarkably improved. The resist composition of the present invention is suitably used as a negative resist because the molecular weight of the alkali-soluble resin in the exposure region increases due to the action of the crosslinking component, and the dissolution rate is extremely lowered with respect to the alkaline developer.                 

Moreover, as a crosslinking component (B), the compound (B1) which produces | generates an acid by irradiation of actinic light, and the compound (B2) which bridge | crosslinks alkali-soluble resin using this acid as a catalyst are used together, and it is a compound (B1) The heat resistance of a resist pattern can be improved further by increasing the ratio of the compound (B2) with respect to.

Alkali development is possible for the resist composition of this invention, and can form the negative resist pattern of a reverse taper shape or an overhang cross section. Although the resist composition of the present invention is suitably applied to the lift-off method or the like, the cross-sectional shape of the resist pattern can be varied in various ways by adjusting the exposure amount as desired, and therefore, the resist composition can be used as a conventional etching resist. The present invention has been accomplished according to these knowledge.

According to the present invention, there is provided a resist composition containing (A) an alkali-soluble resin, (B) a component that crosslinks the alkali-soluble resin by a heat treatment subsequent to irradiation with active light or irradiation with active light, and (C) a compound that absorbs active light. As a resist composition, (A) alkali-soluble resin is a resin composition containing 30 to 95 weight% of polyvinylphenol and 5 to 70 weight% of novolak resin.

Moreover, according to this invention, the pattern formation method including the process of forming the resist film which consists of said resist composition on a board | substrate, exposing this resist film in pattern shape, and developing with alkaline developing solution is provided.

1 is an explanatory diagram showing an example of a pattern forming step by the lift-off method.                 

2 is an explanatory diagram showing an example of microfabrication of an organic EL display panel.

3 is a cross-sectional view showing an example of an organic EL display panel finely processed.

Fig. 4 is a cross sectional view showing a resist pattern having an overhang cross section.

1. (A) Alkali-soluble resin

In the present invention, a resin composition containing 30 to 95% by weight of polyvinylphenol and 5 to 70% by weight of novolak resin is used as the alkali-soluble resin. Conventionally, as an alkali-soluble resin, the novolak resin which addition-condensed m-cresol / p-cresol (weight ratio 80: 20-20: 80) and formaldehyde is used (for example, Unexamined-Japanese-Patent No. 5-165218). Example 2). When novolak resin is used as the alkali-soluble resin, a reverse tapered resist pattern can be obtained, but the heat resistance of the obtained resist pattern is not sufficient, so that the cross-sectional shape of the reverse tapered resist pattern collapses at a temperature of about 120 to 130 ° C. There was a problem.

The present inventors have found that even a resist composition using a novolak resin as an alkali-soluble resin can improve the heat resistance temperature to about 150 ° C by performing ultraviolet irradiation while heating a resist pattern formed on a substrate. However, the heat-resistant temperature exceeding this may be required for vapor deposition of an organic EL material. On the other hand, a resist composition using polyvinylphenol as an alkali-soluble resin has a problem that the resist pattern is easily peeled off from the substrate after forming the resist pattern, and in the technical field of depositing a metal or an organic EL material on the resist pattern, It was hard to use.

The inventors of the present invention have found that, by surprisingly using polyvinylphenol and a novolak resin together as an alkali-soluble resin, the heat resistance temperature can be remarkably improved while suppressing peeling of the resist pattern from the substrate.

As polyvinylphenol, the homopolymer of vinylphenol, the copolymer of vinylphenol, and the monomer copolymerizable with this is mentioned. Examples of the monomer copolymerizable with vinylphenol include isopropenylphenol, acrylic acid, methacrylic acid, styrene, maleic anhydride, maleic acid imide, and vinyl acetate. Among these, the homopolymer of vinylphenol is preferable and the homopolymer of p-vinylphenol is especially preferable.

The average molecular weight of the polyvinylphenol is a weight average molecular weight (Mw) in terms of single-dispersed polystyrene measured by gel permeation chromatography (GPC), and is usually 3,000 to 20,000, preferably 4,000 to 15,000, more preferably 5,000 to 10,000. If the weight average molecular weight of the polyvinyl phenol is too low, the molecular weight does not sufficiently increase even when the exposure region crosslinks, so that it is well dissolved in the alkaline developer and the effect of improving heat resistance is lowered. If the weight average molecular weight of the polyvinyl phenol is too large, the difference in solubility in the alkaline developer in the exposed region and the unexposed region becomes small, so that it is difficult to obtain a good resist pattern.

As a novolak resin, what is widely used in the technical field of a resist can be used. The novolak resin can be obtained, for example, by reacting phenols with aldehydes or ketones in the presence of an acidic catalyst (eg, oxalic acid).                 

Examples of the phenols include phenol, orthocresol, metacresol, paracresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, 2-methylresol Sinol, 4-methylresolcinol, 5-methylresolcinol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propyl Phenol, 2-isopropylphenol, 2-methoxy-5-methylphenol, 2-t-butyl-5-methylphenol, thymol, isothymol and the like. These can be used individually or in combination of 2 types or more, respectively.

As the aldehydes, for example, formaldehyde, formalin, paraformaldehyde, trioxane, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-aldehyde Oxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde Aldehydes and the like. Acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone, etc. are mentioned as ketones. These can be used individually or in combination of 2 types or more, respectively.

Among the above-mentioned contents, the novolak resin which used metacresol and paracresol together and condensed these and formaldehyde, formalin, or paraformaldehyde is especially preferable from a viewpoint of the sensitivity controllability of a resist. The injection weight ratio of metacresol and paracresol is usually 80:20 to 20:80, preferably 70:30 to 50:50. It is also preferable to use 3,5-dimethylphenol (ie, 3,5-xylenol). In this case, the injection weight ratio of cresols (total amount of metacresol and paracresol) and 3,5-xyleneol is usually 50:50 to 80:20, preferably 60:40 to 70:30.

The average molecular weight of the novolak resin is usually from 1,000 to 10,000, preferably from 2,000 to 7,000, more preferably from 2,500 to 6,000 in terms of the weight average molecular weight in terms of monodisperse polystyrene measured by GPC. If the weight average molecular weight of the novolak resin is too low, even if a crosslinking reaction occurs in the exposed portion, the effect of increasing the molecular weight is small, so that it is easily dissolved in the alkaline developer. If the weight average molecular weight of the novolak resin is too high, the difference in solubility in the alkaline developer of the exposed portion and the unexposed portion is small, and it is difficult to obtain a good resist pattern.

The weight average molecular weight of polyvinyl phenol and a novolak resin can be controlled to a desired range by adjusting synthetic conditions. In addition, for example, (1) a method of pulverizing the resin obtained by the synthesis and solid-liquid extraction with an organic solvent having a suitable solubility, and (2) a solvent obtained by dissolving the resin obtained by the synthesis in a well-soluble solvent and insoluble The weight average molecular weight can be controlled by dropwise addition of a solvent which is added dropwise or insoluble, and extraction by solid-liquid or liquid-liquid extraction.

The weight average molecular weight was measured by GPC using SC8020 (manufactured by TOSO Corporation) as a GPC measuring apparatus under the following conditions.

Column: each one combination of TSKGEL G3000HXL and G200HXL1000 manufactured by TOSO                 

Temperature: 38 ℃

Solvent: Tetrahydrofuran

Flow rate: 1.0ml / min

Sample: 0.1 ml of a sample with a concentration of 0.05-0.6 wt%

When the ratio of polyvinylphenol and novolak resin is expressed by weight ratio, it is usually in the range of 30:70 to 95: 5, preferably 35:65 to 95: 5, and more preferably 40:60 to 90:10. . The higher the proportion of polyvinylphenol, the better the heat resistance of the resist pattern, but easily peels off the substrate. When the ratio of novolak resin increases, the problem of peeling of the resist pattern from a board | substrate will be solved, but heat resistance will fall. Therefore, the balance of heat resistance and peeling resistance becomes favorable because a quantum ratio exists in the said range.

2. (B) crosslinking component

(B) crosslinking component used by this invention is a component which bridge | crosslinks alkali-soluble resin by the heat processing following irradiation of an actinic light or irradiation of an actinic light. By the action of the (B) crosslinking component, the molecular weight of the alkali-soluble resin in the exposure region increases, and the dissolution rate in the alkaline developer is extremely lowered. Then, the resist composition of this invention functions as a negative resist which can be developed with alkaline developing solution.

(B) As a crosslinking component, (1) A compound which has a photoinitiator which generate | occur | produces a radical by irradiation of an actinic light (for example, a benzophenone derivative, a benzoin derivative, a benzoin ether derivative etc.), and the unsaturated hydrocarbon group superposed | polymerized by this radical. [For example, pentaerythritol tetra (meth) acrylate, etc.], a combination of a sensitizer for enhancing the efficiency of the photoreaction if necessary, and (2) a compound which generates an acid by irradiation with active light (hereinafter referred to as "mine And a compound (crosslinking substance: hereinafter referred to as a "sensitizer") that crosslinks an alkali-soluble resin using an acid generated by light as a catalyst. Among these, the photoacid generator (B1) and the crosslinking agent (B2) of (2) are excellent in terms of excellent compatibility with alkali-soluble resins, and in combination with alkali-soluble resins, can provide a highly sensitive crosslinked chemically amplified resist. Preferred is a crosslinking component consisting of a combination of

<Mine generator>

The compound which generates an acid by actinic light is not particularly limited as long as it is a substance that generates brested acid or a Lewis acid when exposed by activating radiation. However, onium salts, halogenated organic compounds, quinonediazide compounds, α, α Known ones such as' -bis (sulfonyl) diazomethane compounds, α-carbonyl-α'-sulfonyl diazomethane compounds, sulfone compounds, organic acid ester compounds, organic acid amide compounds, and organic acid imide compounds can be used. have. Among these, aromatic sulfonic acid esters, aromatic iodonium salts, aromatic sulfonium salts, aromatic compounds having a halogenated alkyl residue and the like are preferable. It is preferable to select these photoacid generators from a viewpoint of spectral sensitivity according to the wavelength of the light source which exposes a pattern.

Examples of the onium salts include iodonium salts such as diazonium salts, ammonium salts and diphenyl iodonium triplates, and sulfonium salts such as triphenylsulfonium triplates, phosphonium salts, arsonium salts, and oxonium salts.

Examples of the halogenated organic compound include halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds, halogen-containing thiazole compounds And halogen-containing oxazole-based compounds, halogen-containing triazole-based compounds, halogen-containing 2-pyrone-based compounds, other halogen-containing heterocyclic compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, sulfenyl halide compounds and the like. .

Specific examples of the halogenated organic compound include tris (2,3-dibromopropyl) phosphate, tris (2,3-dibromo-3-chloropropyl) phosphate, tetrabromochlorobutane, 2- [2- (3 , 4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloroγmethyl) -S-triazine, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromocyclododecene Hexabromobiphenyl, allyltribromophenyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis (chloroethyl) ether of tetrachlorobisphenol A, bis (bromoethyl) ether of tetrabromobisphenol A, Bis (2,3-dichloropropyl) ether of bisphenol A, bis (2,3-dibromopropyl) ether of bisphenol A, bis (2,3-dichloropropyl) ether of tetrachlorobisphenol A, tetrabromobisphenol Bis (2,3-dibromopropyl) ether of A, tetrachlorobisphenol S, tere Labromobisphenol S, bis (chloroethyl) ether of tetrachlorobisphenol S, bis (bromoethyl) ether of tetrabromobisphenol S, bis (2,3-dichloropropyl) ether of bisphenol S, bis (of bisphenol S) 2,3-dibromopropyl) ether, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, Halogen flame retardants such as 2,2-bis (4- (2-hydroxyethoxy) -3,5-dibromophenyl) propane; Dichlorodiphenyltrichloroethane, pentachlorophenol, 2,4,6-trichlorophenyl, 4-nitrophenylether, 2,4-dichlorophenyl, 3'-methoxy-4'-nitrophenylether, 2,4 -Dichlorophenoxyacetic acid, 4,5,6,7-tetrachlorophthalide, 1,1-bis (4-chlorophenyl) ethanol, 1,1-bis (4-chlorophenyl) -2,2,2 Organic chloro-based pesticides such as -trichloroethanol, 2,4,4'5-tetrachlorodiphenyl sulfide, 2,4,4 ', 5-tetrachlorodiphenyl sulfone and the like.

Specific examples of the quinone diazide compound include 1,2-benzoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester, and 1,2-naphthoquinone diazide-5-sulfonic acid ester Sulfonic acid esters of quinonediazide derivatives such as 2,1-naphthoquinonediazide-4-sulfonic acid ester and 2,1-benzoquinonediazide-5-sulfonic acid ester; 1,2-benzoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-5- Sulfonic acid chlorides of quinonediazide derivatives such as sulfonic acid chloride, 1,2-naphthoquinone-1-diazide-6-sulfonic acid chloride, 1,2-naphthoquinone-1-diazide-5-sulfonic acid chloride and the like Can be.

As the α, α'-bis (sulfonyl) diazomethane-based compound, α, α'-bis having an unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group, aromatic group or heterocyclic group (Sulfonyl) diazomethane etc. are mentioned.

Specific examples of the α-carbonyl-α-sulfonyldiazomethane-based compound include α-carbonyl- having an unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group, aromatic group or heterocyclic group. (alpha)-sulfonyl diazomethane etc. are mentioned.

As a specific example of a sulfone compound, the sulfone compound, disulfone compound, etc. which have an unsubstituted, symmetrically or asymmetrically substituted alkyl group, an alkenyl group, an aralkyl group, an aromatic group, or a heterocyclic group are mentioned.

Examples of the organic acid esters include carboxylic acid esters, sulfonic acid esters, and phosphoric acid esters. Examples of the organic acid amides include carboxylic acid amides, sulfonic acid amides, and phosphoric acid amides. Examples of the organic acid imides include carboxylic acid imides and sulfonic acid imides. And imide phosphate.

In addition, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, 2-oxocyclohexyl (2-norbor Yl) sulfonium trifluoromethanesulfonate, 2-cyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, di Phenyl iodonium trifluoromethanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, a phenyl paratoluene sulfonate, etc. are mentioned.

The photoacid generator is usually used in an amount of 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. If the ratio of the photoacid generator is too small or too large, the shape of the resist pattern may be deteriorated.                 

<Crosslinking system>

A crosslinking agent is a compound (subduction material) which can crosslink alkali-soluble resin in presence of the acid generate | occur | produced by irradiation of actinic light (exposure). As such a crosslinking agent, well-known acid crosslinking compounds, such as an alkoxy methylation urea resin, the alkoxy methylation melamine resin, the alkoxy methylation uron resin, the alkoxy methylation glycoluril resin, the alkoxy methylation amine resin, etc. are mentioned, for example. Alkyl etherified melamine resin, benzoguanamine resin, alkyl etherified benzoguanamine resin, free ia resin, alkyl ether free urea resin, urethane-formaldehyde resin, resol type phenol formaldehyde resin, alkyl ether resol type phenol form Aldehyde resin, an epoxy resin, etc. are mentioned.

Among these, an alkoxy methylated amine resin is preferable and methoxymethylated amino resin, ethoxymethylated amino resin, n-propoxymethylated amino resin, n-butoxymethylated amino resin, etc. are mentioned as a specific example. Among these, methoxymethylated amino resins such as hexamethoxymethylmelamine and the like are particularly preferable from the viewpoint of good resolution. As a commercial item of the alkoxy methylation amino resin, PL-1170, PL-1174, UFR65, CYMEL300, CYMEL303 (above, Mitsui Cytech Co., Ltd.), BX-4000, NikarakMW-30, MX290 (above, Sangwa Chemical Co., Ltd. make) Etc. can be mentioned.

These crosslinking agents can be used individually or in combination of 2 types or more, respectively. The crosslinking agent is usually used in an amount of 0.5 to 60 parts by weight, preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. When the amount of the crosslinking agent used is too small, the crosslinking reaction is difficult to proceed sufficiently, and the residual film ratio of the resist pattern after development using the alkaline developer is lowered or deformation such as swelling or meandering of the resist pattern occurs well. If the amount of the crosslinking agent is too large, the resolution may be lowered.

<Ratio of photoacid generator and crosslinking agent>

As a crosslinking component (B) from the viewpoint of heat resistance improvement of a resist pattern, the combination of a photo-acid generator (B1) and a crosslinking agent (B2) is preferable. The weight ratio (B1: B2) of the photoacid generator (B1) and the crosslinking agent (B2) is usually 1: 1 to 1:30, preferably 1: 2 to 1:25, and more preferably 1: 3 to 1: 1. 20. By having a quantum ratio in the above range, higher heat resistance than conventional levels can be achieved.

As a result of further studies, the present inventors found that the weight ratio (B1: B2) of the photoacid generator (B1) and the crosslinking agent (B2) is preferably 1: 4 to 1:30, more preferably 1: 5 to 1:25, It was found that the heat resistance of the resist pattern is further remarkably improved as the lower limit of the ratio of the crosslinking agent (B2) to the photoacid generator (B1) is particularly preferably set to 1: 6 to 1:20. In most cases, the high heat resistance can be sufficiently achieved in the weight ratio B1: B2 of 1: 7 to 1:15. In this case, the use ratio of the photoacid generator (B1) with respect to 100 weight part of alkali-soluble resin becomes like this. Preferably it is 1-10 weight part, More preferably, it is 2-8 weight part, and also with respect to 100 weight part of alkali-soluble resin It is preferable to make the usage-amount of a crosslinking agent (B2) into 4 to 60 weight part, More preferably, to 8-50 weight part, and to raise the minimum of each use ratio.

3. (C) Compounds That Absorb Active Light                 

If the resist composition contains a compound that absorbs actinic light, a resist pattern having an inverse taper shape or an overhang shape in cross section can be obtained in order to absorb light going in the depth direction of the resist film during exposure. The shape of the resist pattern is also affected by reflecting light exposed by a substrate, an ITO film formed on the substrate, or the like. Therefore, (C) component is needed also for the reflection prevention of exposure light. In particular, a resist composition using a combination of a photoacid generator and a crosslinking agent as the component (B) is a crosslinking chemically amplified resist, because an acid generated by irradiation of light diffuses in the resist film and causes a crosslinking reaction to a region where light is not reached. It becomes important to control the shape of a resist pattern by having (C) component which absorbs actinic light.

As (C) component, what is necessary is just to select the compound which has an absorption region in the wavelength range according to the wavelength of an exposure light source. However, when (C) component is a compound with low solubility with respect to alkaline developing solution, since this (C) component tends to remain on a board | substrate after image development, it is alkaline by giving acidic residues, such as a phenolic hydroxyl group, a carboxyl group, a sulfonyl group, etc. The compound which raised the solubility to a developing solution is preferable. In addition, for the purpose of solving the problem of residue generation, it is preferable to select a compound having a higher absorbance and to obtain sufficient absorbance with a small amount of addition. When the formed resist pattern is exposed to high temperature in a post-exposure baking (PEB) or sputtering process, the component (C) is preferably a compound having low sublimability because the component (C) sublimes to contaminate the apparatus.

As (C) component used by this invention, what is called an azo dye is preferable. Examples of the azo dyes include azobenzene derivatives, azonaphthalene derivatives, azobenzene or azonaphthalene substituents of arylpyrrolidone, and heterocyclic aryl azo compounds such as pyrazolone, benzpyrazolone, pyrazole, imidazole, thiazole, and the like. Can be.

These aryl azo compounds can be appropriately selected from the length of the conjugated system, the type of the substituent, etc. in order to set the absorption wavelength to a desired region. For example, an aryl azo compound having an absorption region set to a short wavelength by substituting an electron withdrawing group such as a sulfonic acid (metal salt) group, a sulfonic acid ester group, a sulfonic group, a carboxyl group, a cyano group, a (substituted) aryl or an alkylcarbonyl group, or a halogen may be used. Can be. Also, an aryl azo compound in which the absorption wavelength is set to a long wavelength region by substituting an electron donor such as an amino group, a hydroxy group, an alkoxy group, or an aryloxy group substituted with (substituted) alkyl, (substituted) aryl or polyoxyalkylene, etc. You may. Substituents include groups that lower the solubility in alkaline developers, such as amino groups, and groups that increase the solubility in alkaline developers, such as carboxyl groups and hydroxy groups, and thus, the types of substituents of the arylazo compound so that the sensitivity of the resist composition of the present invention becomes a practical level. It is desirable to select appropriately.

In the case of an azo dye, by selecting a compound structure and a substituent group, various compounds which absorb an actinic light in the wide wavelength range of 200-500 nm can be used. The selection of the length and the substituent of such a conjugated system is also suitable for compounds other than azo dyes. As a compound corresponding mainly to the light source of a 300-400 nm wavelength range, the styrene derivative obtained by condensing a (substituted) benzaldehyde and the compound which has an active methylene group is mentioned. Examples of the substituent of the benzaldehyde include an alkylamino group substituted with hydroxy, alkoxy or halogen, polyoxyalkyleneamino group, hydroxy group, halogen, alkyl group, alkoxy group, alkyl or arylcarbonyl group. As a compound which has an active methylene group, 1, 3- diketones, such as acetonitrile, (alpha)-cyanoacetic acid ester, (alpha) -cyano ketones, malonic acid ester, acetoacetic acid ester, etc. are mentioned, for example.

As (C) component, methine dyes obtained by condensation of arylpyrazolone and arylaldehyde, arylbenzotriazoles, natural compounds such as azomethine dyes obtained as condensates of amines and aldehydes, curcumin, xanthone, and the like can also be used. have. The developing characteristic can also be adjusted using the compound which absorbs exposure light, such as quinonediazide sulfonic-acid esterified material and bisazide compound of the dye which has an arylhydroxy group, and changes solubility to alkaline developing solution, or crosslinks.

Moreover, as (C) component, for example, cyano vinyl styrene-based compound, 1-cyano-2- (4-dialkylaminophenyl) ethylene, p- (halogen substituted phenylazo) -dialkylaminobenzene, 1- Alkoxy-4- (4'-N, N-dialkylaminophenylazo) benzenes, dialkylamino compounds, 1,2-dicyanoethylene, 9-cyanoanthracene, 9-anthrylmethylenemalononitrile, N -Ethyl-3-carbazolyl methylenemalononitrile, 2- (3,3-dicyano-2-propenylidene) -3-methyl-1,3-thiazoline and the like can be used.

Among the commercially available dyes, those useful as the (C) component include, for example, oil yellow # 101, oil yellow # 103, oil yellow # 117, oil pink # 312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (above, Oriento Chemical Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (CI42000), Methylene blue (CI52015), and the like.

Specific examples of the 1-cyano-2- (4-dialkylaminophenyl) ethylenes include 1-carboxy-1-cyano-2- (4-di-n-hexylaminophenyl) ethylene and 1-carboxy. A carboxyl group is placed in the first position such as 1-cyano-2- (4-di-n-butylaminophenyl) ethylene, 1-carboxy-1-cyano-2- (4-di-n-heptylaminophenyl) ethylene, and the like. 1-cyano-2- (4-dialkylaminophenyl) ethylene which has is mentioned.

These 1-cyano-2- (4-dialkylaminophenyl) ethylenes, oil yellow # 101, oil yellow # 103, oil yellow # 107, etc. are excellent in the formation property of a reverse taper-type resist pattern profile. Particularly preferred.

In the case where the cross section forms an inverse tapered or overhanged resist pattern, the amount of the component (C) may be appropriately determined depending on the thickness of the resist composition, the type of the component (C), and the like. Since light is difficult to transmit through, it is relatively at least, and when thin, it is used relatively much. The component (C) is usually used in an amount of 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, and particularly preferably 1 to 8 parts by weight with respect to 100 parts by weight of the alkali-soluble resin.

4. Other additives

Surfactant can be added to a resist composition for the purpose of the improvement of the dispersibility of each component of a resist composition, etc. As surfactant, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc .; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene nonyl phenol ether and the like; Polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and ethylene glycol distearate; F-top EF301, EF303, EF352 (made by Shinkoda Chemical Co., Ltd.), megafax F171, F172, F173, F177 (made by Dainippon Ink Corporation), prolad FC430, FC431 (made by Sumitomo 3M Corporation), Asahi Guard AG710, West Fluorine surfactants such as Pron S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.); Organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.); Acrylic acid type or methacrylic acid type (co) polymer Polyfloor No.75, No.95 (made by Kyoisha Oil & Chemical Co., Ltd.) is mentioned. The compounding quantity of these surfactant is normally 2 weight part or less, Preferably it is 1 weight part or less per 100 weight part of solid content of a resist composition.

5. Organic Solvent

Although the resist composition of this invention can also be used as a powder as desired, it is normally used to use it as the resist solution obtained by melt | dissolving and filtering each component in the organic solvent. The organic solvent is used in an amount sufficient to dissolve or disperse each component uniformly. Solid content concentration in a resist solution is 5-50 weight% normally, Preferably it is about 10-40 weight%.

As an organic solvent, For example, Alcohol, such as n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, cyclohexyl alcohol, etc .; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and the like; Esters such as propyl formate, butyl formate, ethyl acetate, propyl acetate, butyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate, ethyl ethoxypropionate, and ethyl pyruvate Ryu; Cyclic ethers such as tetrahydrofuran, dioxane and the like; Cellosol classes such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and the like; Cellosolve acetates such as ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, and the like; Alcohol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like; Propylene glycols such as propylene glycol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate, propylene glycol monobutyl ether and the like; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and the like; lactones such as γ-butyrolactone; Halogenated hydrocarbons such as trichloroethylene; Aromatic hydrocarbons such as toluene, xylene and the like; Polar organic solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, and the like; 2 or more types of these mixed solvents are mentioned.

6. How to use resist composition

The resist composition of this invention is apply | coated uniformly on a board | substrate by the apply | coating method, such as spin coating, and when a solvent is dried and removed, a resist film is formed on a board | substrate. Then, the resist film is generally heat treated (prebaked) for about 10 to 200 seconds at a temperature of about 80 to 110 ° C. In this way, a resist film with a thickness of generally about 0.5 to 5 mu m is obtained. In order to form a pattern, first, it exposes in a pattern shape on a resist film using a desired light source. When the resist composition of the present invention is a crosslinking type chemically amplified resist containing a photoacid generator and a crosslinking agent as the component (B), it is usually 10 to 200 at a temperature of about 100 to 130 ° C after exposure for the purpose of promoting the crosslinking reaction. For about a second, post exposure baking (PEB) is performed.

Examples of the active light used for exposure include ultraviolet rays, far ultraviolet rays, KrF excimer laser light, X-rays, electron beams, and the like. Specific examples of the light source to be exposed include mercury bright spectrums such as 436 nm, 405 nm, 365 nm, and 254 nm, KrF excimer laser light sources of 248 nm, and the like. Examples of the substrate include, but are not particularly limited to, a silicon substrate, a glass substrate, an ITO film forming substrate, a chromium film forming substrate, a resin substrate, and the like.

In the resist composition of the present invention, since the exposed portion is substantially insolubilized with respect to the alkaline developer by the action of the crosslinking component to function as a negative resist, when the exposure amount is a certain amount or more, the resist film starts to remain on the substrate after development. The exposure energy at this time is called Eth. A resist pattern having an inverse tapered or overhanging cross section can be obtained at an exposure amount of which Eth is usually about 2 times or less. When the exposure amount is increased, the cross-sectional shape of the resist pattern is shortly forward tapered.

The resist composition of the present invention can be developed with an alkaline developer. As alkaline developing solution, aqueous alkali solution is used normally. As alkali, Inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia; Primary amines such as ethylamine, propylamine and the like; Secondary amines such as diethylamine, dipropylamine and the like; Tertiary amines such as trimethylamine, triethylamine and the like; Alcohol amines such as diethyl ethanol amine and triethanol amine; Quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, and the like. In addition, if necessary, a water-soluble organic solvent such as methyl alcohol, ethyl alcohol, propyl alcohol, ethylene glycol, a surfactant, a dissolution inhibitor of a resin, and the like may be added to the aqueous alkali solution.

When the resist pattern obtained by development is used for the lift-off method, various films, such as a metal vapor deposition film, are formed in the whole surface of a board | substrate from above. Thereafter, the resist pattern is removed together with the film formed thereon, leaving a film such as a metal deposited film formed on the substrate. When manufacturing an organic electroluminescent display panel, organic electroluminescent material is vapor-deposited from the resist pattern obtained by image development, and metals, such as aluminum, are then deposited. In this case, the resist pattern is left without being removed.

When ultraviolet rays are irradiated while heating the resist pattern formed on the substrate before such a deposition process, the heat resistance of the resist pattern can be further improved. Specifically, the whole substrate is placed on a hot plate, and the ultraviolet rays are irradiated at an irradiation dose of about 5 to 1000 mW while heating to a temperature of about 70 to 120 ° C. The irradiation time of ultraviolet rays is usually about 20 to 40 seconds.                 

Example

Next, an Example and a comparative example are given and this invention is demonstrated further more concretely. The measuring method of a characteristic is as follows.

(1) heat resistance

The board | substrate with which the resist pattern was formed is put on a hotplate for 300 second, and the temperature which can hold | maintain an inverse taper type resist pattern is measured. Specifically, the shape of the resist pattern is observed with a scanning electron microscope while heating at intervals of 110 ° C. to 5 ° C. for 300 seconds, and the temperature at the point when the top shape of the resist pattern becomes round and becomes unable to maintain the reverse taper shape is measured. .

(2) peeling resistance

It is visually observed whether a resist pattern is formed on a board | substrate after image development, and what cannot be confirmed is evaluated as poor peeling resistance (x), and what can be confirmed is good peeling resistance (O).

Example 1

90 parts by weight of polyp-vinylphenol having a weight average molecular weight of 6,000 and m-cresol / p-cresol at an injection ratio of 70/30 (weight ratio) to 10 parts by weight of a novolak resin having a weight average molecular weight of 4,000 obtained by dehydration of formaldehyde. 1 part by weight of a triazine-based photoacid generator (manufactured by Midori Chemical Co., Ltd., TAZ106), and 3 parts by weight of a melamine-based resin crosslinking agent [reducing substance: Mitsui Cytec, Cymel 303] 5 parts by weight of a dye [Oriento Chemical Industries, Ltd., Oil Yellow] was dissolved in polyethylene glycol monomethyl ether, filtered through a membrane filter made of polytetrafluoroethylene having a hole diameter of 0.1 µm, and a resist solution having a solid content concentration of 34% by weight. To prepare.

A resist solution is applied on a ITO substrate on which a ITO film is formed on a glass substrate by a spin coater, and then prebaked at 90 ° C. for 90 seconds to form a resist film having a film thickness of 4 μm. It exposes by exposure amount 200mJ / cm <2> using the test reticle of parallel light aligner (Pan501, PLA501F) from this resist film. 60 seconds of post-exposure baking (PEB) is performed. Subsequently, it is developed by the paddle method for 23 degreeC and 70 second using 2.38 weight% of tetramethylammonium hydroxide aqueous solution, and the resist pattern (L / S = 20 micrometers reverse taper shape) is formed. Table 1 shows the measurement results.

Examples 2-4

A resist pattern was formed on a substrate in the same manner as in Example 1 except that the use ratio of polyvinylphenol and novolak resin was changed as shown in Table 1. Table 1 shows the measurement results.

Comparative Example 1

A resist pattern was formed on a substrate in the same manner as in Example 1 except that the polyvinylphenol used in Example 1 was used alone as the alkali-soluble resin. Table 1 shows the measurement results.

Comparative Example 2

A resist pattern was formed on a substrate in the same manner as in Example 1 except that the novolak resin used in Example 1 was used alone as the alkali-soluble resin. Table 1 shows the measurement results.

Alkali soluble resin Heat resistance Peeling resistance PVP (part) NVK (part) Heat-resistant temperature (℃) Comparative Example 1 100 0 Not measurable × Example 1 90 10 250 O Example 2 80 20 235 O Example 3 60 40 200 O Example 4 50 50 180 O Comparative Example 2 0 100 120 O  PVP: Polyvinylphenol, NVK: Novolak resin

As can be seen from the experimental results shown in Table 1, when polyvinylphenol and novolak resin are used in combination at a specific ratio as the alkali-soluble resin (Examples 1 to 4), the heat resistance and the peeling resistance of the resist pattern are highly balanced. It can be seen that. Moreover, all of these resist patterns have a reverse taper shape in cross section.

Example 5

A resist solution was prepared in the same manner as in Example 3 except that 1 part by weight of the triazine-based photoacid generator was changed to 3 parts by weight and 3 parts by weight of the melamine resin crosslinking agent, respectively, to form a resist pattern. As a result, the heat resistance temperature of the resist pattern is improved from 200 deg. C to 300 deg. This resist pattern also has good peeling resistance (O).

Example 6

A resist solution was prepared in the same manner as in Example 4 except that 1 part by weight of the triazine-based photoacid generator was changed to 3 parts by weight and 3 parts by weight of the melamine resin crosslinker, respectively, to form a resist pattern. As a result, the heat resistance temperature of the resist pattern is improved from 180 ° C to 270 ° C of Example 4. This resist pattern also has good peeling resistance (O).

According to the present invention, there is provided a resist composition in which a cross section can form a resist pattern having an inverse taper shape or an overhang shape, and the heat resistance of the resist pattern is remarkably improved. The resist composition of the present invention is particularly suitable for applications such as a negative resist for pattern formation by a lift-off method, a photoresist for manufacturing an electrically insulating partition wall of an organic electroluminescent display panel.

Claims (18)

A resist composition containing (A) an alkali-soluble resin, (B) a component that crosslinks the alkali-soluble resin by heat treatment subsequent to irradiation of active light or irradiation of active light, and (C) a compound that absorbs active light, the resist composition comprising (A) An alkali-soluble resin is a resin composition containing 30 to 95 weight% of polyvinylphenol and 5 to 70 weight% of novolak resin. The resist composition according to claim 1, wherein the novolak resin is a novolak resin obtained by dehydrating condensation of formaldehyde and paracresol with formaldehyde at an injection weight ratio of 80:20 to 20:80. The novolak resin according to claim 1, wherein the novolak resin is a novolak resin obtained by dehydrating and condensing cresols containing methacresol and paracresol and 3,5-dimethylphenol with formaldehyde at an injection weight ratio of 50:50 to 80:20. Resist composition, characterized in that. The crosslinking agent (B2) according to claim 1, wherein the crosslinking component (B) is a photoacid generator (B1) that generates an acid by irradiation with active light and an acid generated by light as a catalyst. A resist composition comprising a combination. 5. The photoacid generator (B1) according to claim 4, wherein the photoacid generator (B1) is an onium salt, a halogenated organic compound, a quinonediazide compound, an α, α'-bis (sulfonyl) diazomethane compound, an α-carbonyl-α'-sulphate. A resist composition comprising at least one compound selected from the group consisting of a ponyl diazomethane compound, a sulfone compound, an organic acid ester compound, an organic acid amide compound, and an organic acid imide compound. The resist composition according to claim 4, wherein the use ratio of the photoacid generator (B1) is 0.1 to 10 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). The crosslinking agent (B2) is an alkoxymethylated amino resin, an alkoxymethylated urea resin, an alkoxymethylated melamine resin, an alkoxymethylated uron resin, an alkoxymethylated glycoluril resin, an alkyletherized melamine resin, a benzoguanamine resin or an alkylether. At least one member selected from the group consisting of benzoguanamine resins, urea resins, alkyl etherified urea resins, urethane-formaldehyde resins, resol type phenol formaldehyde resins, alkyl etherified resol type phenol formaldehyde resins and epoxy resins. Resist composition to be. The resist composition according to claim 4, wherein the use ratio of the crosslinking agent (B2) is 0.5 to 60 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). The resist composition according to claim 4, wherein the weight ratio of the photoacid generator (B1) and the crosslinking agent (B2) is 1: 1 to 1:30. The resist composition according to claim 4, wherein the weight ratio of the photoacid generator (B1) and the crosslinking agent (B2) is 1: 4 to 1:30. The resist composition according to claim 1, wherein the crosslinking component (B) is a combination of a photoinitiator which generates a radical by irradiation of active light and a compound having an unsaturated hydrocarbon group polymerized by the radical. The styrene derivative, methine dye, azomethine dye, curcumin, xanthone according to claim 1, wherein the compound (C) absorbing actinic light is obtained by dehydrating and condensing azo dye, unsubstituted or substituted benzaldehyde and a compound having an active methylene group. Quinonediazidesulfonic acid esters of dyes having arylhydroxy groups, bisazide compounds, cyanovinylstyrene compounds, 1-cyano-2- (4-dialkylaminophenyl) ethylenes, p- (halogen substituted phenylazo) -Dialkylaminobenzenes, 1-alkoxy-4- (4'-N, N-dialkylaminophenylazo) benzenes, dialkylamino compounds, 1,2-dicyanoethylene, 9-cyanoanthracene, 9 With anthrylmethylenemalononitrile, N-ethyl-3-carbazolylmethylenemalononitrile and 2- (3,3-dicyano-2-propenylidene) -3-methyl-1,3-thiazoline At least one resist composition selected from the group consisting of. The resist composition according to claim 1, wherein the use ratio of the compound (C) that absorbs the actinic light is 0.1 to 15 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). The resist composition of claim 1, further comprising an organic solvent in an amount sufficient to dissolve or disperse each component uniformly. (A) To 100 parts by weight of alkali-soluble resin containing 30 to 95% by weight of polyvinylphenol and 5 to 70% by weight of novolak resin, (B1) 0.1-10 weight part of photo-acid generators which generate | occur | produce an acid by irradiation of actinic light, (B2) 0.5 to 60 parts by weight of a crosslinking agent that crosslinks an alkali-soluble resin using an acid generated by light as a catalyst, and (C) The resist composition containing 0.1-15 weight part of compounds which absorb actinic light, and the weight ratio of a photo-acid generator (B1) and a crosslinking agent (B2) is 1: 4-1: 30. Claim 16 was abandoned upon payment of a setup registration fee. Alkali-soluble resin containing (A) 30-95 weight% of polyvinyl phenols and 5-70 weight% of novolak resins, (B) Alkali-soluble resin by heat processing following irradiation of an actinic light or irradiation of an actinic light And forming a resist film comprising a resist composition containing a component to be crosslinked and a compound (C) absorbing actinic light, and exposing the resist film in a pattern shape and then developing with an alkali developer. . Claim 17 was abandoned upon payment of a registration fee. 17. The resist tape according to claim 16, wherein after the development, the exposure energy Eth when the resist film starts to remain on the substrate is exposed and developed at an exposure amount of 2 times or less (2Eth), and then a resist tapered in cross section is formed. Pattern formation method. Claim 18 was abandoned upon payment of a set-up fee. The method of claim 16, further comprising irradiating the resist pattern with ultraviolet rays while heating the resist pattern after forming the resist pattern.

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