JP2000194143A - Method for forming pattern of luminous body deposited film - Google Patents

Abstract

(57) [Problem] To obtain an insulating film having heat resistance. SOLUTION: The heat resistance of the photosensitive resin film is improved by irradiating the photosensitive resin film pattern after the exposure with ultraviolet rays while heating the film pattern within a heat resistance temperature of the film pattern ± 10 ° C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for forming an insulating film, and more particularly to a method for forming a cathode insulating film for a self-luminous display.

[0002]

2. Description of the Related Art In recent years, displays are mounted on various devices such as mobile phones, electronic organizers, digital cameras, computers, and car navigation systems. Displays include a cathode ray tube (CRT) and liquid crystal (LC
D), plasma and the like are widely used. These displays are characterized by cost, high viewing angle, weight, power consumption, display size, and the like.

For example, a cathode ray tube display is a self-luminous display and has high visibility such as a viewing angle and a color tone, but has a limit in weight reduction and is not suitable for portable equipment. In addition, liquid crystal displays have become
An FT-type display can provide a high viewing angle, but has a problem in that it is not self-luminous and requires a backlight to be used in a dark place, resulting in high power consumption. Further, a plasma display or the like enables the manufacture of a large-sized display, but has a problem that the production cost is high and the yield is poor because study of production process conditions is still insufficient.

Devices that require a small display such as a PDA, such as an electronic organizer and a notebook personal computer, are presumed to be portable, and their power saving and weight reduction are required. A car navigation system is a device that is premised on being mounted on a vehicle and is required to be reduced in size and cost.
The displays described above for such devices are not always suitable. Thus, an organic electroluminescence (EL) display has been newly developed as a self-luminous display. Since the organic EL display is a self-luminous type, it has advantages such as reduced power consumption, small size, light weight, and high visibility.

An organic EL display has a transparent ITO substrate on a glass substrate, and a luminous body (organic EL) on the transparent ITO substrate.
And electrodes are arranged, and electricity is supplied between the ITO substrate and the metal electrode on the light emitting body. The luminous bodies are separated by an insulating film at appropriate intervals, and an image is projected by the color of the energized luminous body area. Since an insulating film is deposited on an ITO substrate by heating, heat resistance of the film is required. Further, as described above, the organic EL display is used as a portable device or an in-vehicle device, and is required to have heat resistance as a product in order to cope with a high temperature condition such as a temperature rise in a vehicle.

Conventionally, as described in JP-A-8-315981, a photosensitive resin composition containing an alkali-soluble resin, an acid generator and a crosslinking agent has been used for a cathode insulating film for an organic EL display. Have been After exposing the photosensitive resin composition film to form a pattern, an insulating film is formed through a step of developing with an alkaline solution. From the ease of development, a weight average molecular weight in terms of monodisperse polystyrene of 3,000 as measured by gel permeation chromatography using a 254 nm UV detector of an alkali-soluble resin and tetrahydrofuran as an eluent was used.
The following are used.

However, an insulating film containing such a low-molecular-weight resin has a heat resistance of at most about 100 ° C., and it has not been able to sufficiently cope with an increasing demand for heat resistance. By the way, as a method for improving heat resistance, it is known that a resin in a photosensitive resin composition has a high molecular weight and a certain photosensitizer or an acid generator is used. In addition, methods for heating and irradiating the obtained pattern with ultraviolet light have been widely studied. For example, according to the May 1987 issue of the monthly Semiconductor World, a pattern obtained by using a photosensitive resin composition such as a photoresist is irradiated with ultraviolet rays while increasing the temperature, whereby curing proceeds and heat resistance is obtained. There is a knowledge that it will be. Actually, for curing, a method has been adopted in which the temperature is raised from a temperature near the heat resistant temperature of the resin composition to finally increase the heat resistant temperature to +20 to 30 ° C. However, even when this method was employed in a cathode insulating film for an organic EL display, heat resistance was not improved.

[0008]

Under such prior art, the present inventors have conducted intensive studies to obtain a heat-resistant cathode insulating film (hereinafter sometimes simply referred to as an insulating film). Was found to improve the heat resistance of the insulating film and obtain a good pattern profile by irradiating it with ultraviolet light under certain conditions, thereby completing the present invention.

[0009]

Thus, according to the present invention, a photosensitive resin composition is applied on a substrate, a resin film obtained by film formation is exposed in a pattern, developed, and then developed. In a method for forming a luminous body deposited film pattern in which a luminous body is vapor-deposited on a substrate having the obtained film pattern, ultraviolet irradiation is performed while heating the photosensitive resin film pattern after exposure, and the heating conditions are as follows. (Heat resistance temperature of film pattern -10 ° C) ≤ heating start temperature <heat resistance temperature of the film pattern, heat resistance temperature of the film pattern ≤ heating end temperature ≤ (heat resistance temperature of the film pattern + 10 ° C), and from the start of heating. A method for forming a pattern of a luminous body vapor-deposited film is provided, comprising a step in which the temperature before completion is within a range of a heat-resistant temperature of the film pattern ± 10 ° C.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (1) Photosensitive resin composition The photosensitive resin composition used in the present invention is obtained by dissolving at least an alkali-soluble phenol resin, a compound capable of generating an acid upon irradiation with activating radiation, and a crosslinking agent in an organic solvent. .

<Alkali-Soluble Phenolic Resin> In the present invention, the alkali-soluble phenol resin may be used alone or in combination of two or more. Specific examples of the alkali-soluble phenolic resin include:
For example, condensation reaction products of phenols and aldehydes, condensation reaction products of phenols and ketones, vinylphenol polymers, isopropenylphenol polymers, hydrogenation reaction products of these phenolic resins, etc. Can be used in combination.

Specific examples of the phenol used here include phenol, ortho-cresol, meta-cresol,
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-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, -Propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-t-butyl-5-methylphenol, thymol, isothymol and the like are exemplified. Of these, ortho-cresol, meta-cresol, para-cresol, 2,3-dimethylphenol,
Preferred examples include 3,4-dimethylphenol, 3,5-dimethylphenol, 2,5-dimethylphenol, 2,3,5-trimethylphenol, and 2,3,6-trimethylphenol. These can be used alone or in combination of two or more.

Specific examples of aldehydes include formalin, paraformaldehyde, trioxane, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde,
p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde,
Examples thereof include o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, and terephthalaldehyde. Of these, formalin, paraformaldehyde and hydroxybenzaldehydes are preferred. These compounds may be used alone or in combination of two or more.

Specific examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone and the like. These compounds may be used alone or in combination of two or more. These condensation reaction products can be obtained by a conventional method, for example, by reacting a phenol with an aldehyde or a ketone in the presence of an acidic catalyst.

The vinylphenol-based polymer is selected from a homopolymer of vinylphenol and a copolymer with a component copolymerizable with vinylphenol, and the isopropenylphenol-based polymer is a copolymer of isopropenylphenol. It is a homopolymer or a copolymer of isopropenylphenol with a copolymerizable component. Specific examples of components copolymerizable with vinyl phenol and isopropenyl phenol include acrylic acid, methacrylic acid, styrene,
Examples thereof include maleic anhydride, maleic imide, vinyl acetate, acrylonitrile, and derivatives thereof. The copolymer is obtained by a well-known method. The hydrogenation reaction product of the phenolic resin is obtained by a conventional method, for example, by dissolving the phenolic resin in an organic solvent and performing hydrogenation in the presence of a homogeneous or heterogeneous catalyst.

Among the above, it is particularly preferable to use meta-cresol and para-cresol in combination and use a novolak resin obtained by subjecting these to condensation reaction with formaldehyde, formalin or paraformaldehyde, whereby the sensitivity controllability of the resist can be expected. Furthermore, when using meta-cresol and para-cresol in combination, the charged weight ratio during the synthesis of both resins is 3/7 to 7/3, preferably 4/6 to 6/4, and more preferably 4/6 to 5/5. Is good.

The weight average molecular weight of the alkali-soluble phenol resin used in the present invention is measured by GPC (gel permeation chromatography) under the following conditions. Apparatus: SC8020 (manufactured by TOSO) Column: TSKGEL G3000HX manufactured by TOSO
L and G2000HXL1000 manufactured by the same company one by one. Temperature: 38 ° C. Solvent: THF Flow rate: 1.0 ml / min. Sample: 0.1 ml of a sample having a concentration of 0.05 to 0.6% by weight
Injection

The molecular weight of the sample is measured under the above conditions, and the molecular weight of the sample is calculated using a molecular weight constitution curve prepared from a monodisperse polystyrene standard sample. Further, the molecular weight of the wax is calculated by conversion using a conversion formula derived from the Mark-Houwink viscosity formula.

As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical C
o. Or Tory Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 1
0 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10
⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and it is appropriate to use at least about 10 standard polystyrene samples.

The weight average molecular weight in terms of monodisperse polystyrene (hereinafter simply referred to as average molecular weight) measured under the above conditions is usually 1,000 to 5,000, preferably 2,
000-3,500. If the average molecular weight is too low, even if a cross-linking reaction of the exposed part occurs, the molecular weight does not increase, so that it is easy to dissolve during the development time, and if it is too high, the unexposed part easily dissolves during the development time, and in any case, good It is difficult to form a pattern.

As a method of controlling the molecular weight and the molecular weight distribution, a resin is crushed and solidified with an organic solvent having an appropriate solubility.
Examples of the method include liquid extraction, dissolving the resin in a good solvent and dropping it in a poor solvent, or solid-liquid or liquid-liquid extraction by dropping a poor solvent.

<Compound that Generates an Acid by Irradiation with Activating Radiation> The resist composition of the present invention includes a compound described above and a compound that generates an acid by irradiation with activating radiation (hereinafter referred to as PAG). Is included). The PAG used here is not particularly limited as long as it generates a Bronsted acid or a Lewis acid when exposed to activating radiation. Onium salts, halogenated organic compounds,
Quinonediazide compound, α, α'-bis (sulfonyl)
Known compounds such as diazomethane compounds, α-carbonyl-α′-sulfonyldiazomethane compounds, sulfone compounds, organic acid ester compounds, organic acid amide compounds, and organic acid imide compounds can be used.

Examples of the onium salt include diazonium salts, ammonium salts, iodonium salts such as diphenyliodonium triflate, sulfonium salts such as triphenylsulfonium triflate, phosphonium salts, arsonium salts and oxonium salts.

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

Specifically, tris (2,3-dibromopropyl) phosphate, tris (2,3-dibromo-3)
-Chloropropyl) phosphate, tetrabromochlorobutane, 2- [2- (3,4dimethoxyphenyl) ethenyl] -4,6-bis (trichlorormethyl) -S-triazine, hexachlorobenzene, hexabromobenzene, hexabromo Cyclododecane, 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-dichloromethane of tetrachlorobisphenol A Propyl) ether, bis (2,3-dibromopropyl) ether of tetrabromobisphenol A, tetrachlorobisphenol S, tetrabromobisphenol S, bis (chloroethyl) ether of tetrachlorobisphenol S, bis (bromoethyl) of tetrabromobisphenol S Ether, bis (2,3-dichloropropyl) ether of bisphenol S, bis (2,3-dibromopropyl) ether of bisphenol S, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4- Hydroxy-3,
5-dibromophenyl) propane, 2,2-bis (4-
Halogen flame retardants such as (2-hydroxyethoxy) -3,5-dibromophenyl) propane;

Dichlorodiphenyltrichloroethane, pentachlorophenol, 2,4,6-trichlorophenyl 4-nitrophenyl ether, 2,4-dichlorophenyl 3'-methoxy-4'-nitrophenyl ether, 2,4-dichlorophenoxyacetic acid, 4,5,6,7
-Tetrachlorophthalide, 1,1-bis (4-chlorophenyl) ethanol, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethanol, 2,4,
4 ', 5-tetrachlorodiphenyl sulfide, 2,
Organic chloro-based pesticides such as 4,4 ', 5-tetrachlorodiphenyl sulfone are exemplified.

Specific examples of the quinonediazide compound include:
1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,1-naphthoquinonediazide-4-sulfonic acid Ester, 2,1-benzoquinonediazide-5
Sulfonic acid esters of quinonediazide derivatives such as sulfonic acid esters, 1,2-benzoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride, 1,2-
Sulfonic acids of quinonediazide derivatives such as naphthoquinone-2-diazide-5-sulfonic acid chloride, 1,2-naphthoquinone-1-diazide-6-sulfonic acid chloride and 1,2-benzoquinone-1-diazide-5-sulfonic acid chloride Chloride and the like.

The α, α'-bis (sulfonyl) diazomethane compound has an unsubstituted, symmetrically or asymmetrically substituted alkyl, alkenyl, aralkyl, aromatic or heterocyclic group. α, α'-
Bis (sulfonyl) diazomethane and the like can be mentioned.

Specific examples of the α-carbonyl-α-sulfonyldiazomethane compound include an unsubstituted, symmetrically or asymmetrically substituted alkyl, alkenyl, aralkyl, aromatic or heterocyclic group. Has α
-Carbonyl-α-sulfonyldiazomethane and the like. Specific examples of the sulfone compound include a sulfone compound and a disulfone compound having an unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aralkyl group, aromatic group, or heterocyclic group. Examples of the organic acid ester include a carboxylic acid ester, a sulfonic acid ester, and a phosphoric acid ester.Examples of the organic acid amide include a carboxylic acid amide, a sulfonic acid amide, and a phosphoric acid amide. Examples thereof include carboxylic imide, sulfonic imide, and phosphoric imide.

In addition, compounds described in the general formula (II) or (III) in columns 9 to 10 of JP-A-7-199467 and specific examples thereof, ie, cyclohexylmethyl (2-oxocyclohexyl) ) Sulfonium trifluoromethanesulfonate, dicyclohexyl (2
-Oxocyclohexyl) sulfonium trifluoromethanesulfonate, 2-oxocyclohexyl (2-norbornyl) sulfonium trifluoromethanesulfonate, 2-cyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate And naphthyl, diphenyliodonium trifluoromethanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, phenyl paratoluenesulfonate and the like.

The amount of the PAG to be added is 1 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts of the alkali-soluble resin. If the amount of PAG used is out of the range, the pattern shape tends to deteriorate.

<Crosslinking Agent> The crosslinking agent is a compound capable of crosslinking an alkali-soluble resin in the presence of an acid, for example, an acid generated by exposure. Examples of such a crosslinking agent include well-known crosslinking compounds such as an alkoxymethylated urea resin, an alkoxymethylated melamine resin, an alkoxymethylated urone resin, and an alkoxymethylated amino resin such as an alkoxymethylated glycoluril resin. be able to. Examples of suitable alkoxymethylated amino resins include methoxymethylated amino resins, ethoxymethylated amino resins, n-propoxymethylated amino resins,
Examples thereof include an n-butoxymethylated amino resin, preferably a methoxymethylated amino resin, and particularly preferably a methoxymethylated urea resin. In the present invention, when a methoxymethylated urea resin is used as a crosslinking agent, a negative radiation-sensitive resin composition having particularly excellent resolution can be obtained.

Suitable commercial products of alkoxymethylated amino resins include PL-1170 and PL-117.
4, UFR65, CYMEL300, CYMEL303
(Manufactured by Mitsui Cytec), BX-4000, Nikarac MW-30, MX290 (manufactured by Sanwa Chemical Co., Ltd.) and the like. These crosslinking agents can be used alone or in combination of two or more. The compounding amount of the crosslinking agent in the present invention is as follows.
The amount is usually 3 to 60 parts by weight, preferably 5 to 40 parts by weight, more preferably 5 to 30 parts by weight, per 100 parts by weight. In this case, if the compounding amount of the crosslinking agent is less than 3 parts by weight, it is difficult for the crosslinking reaction to proceed sufficiently, and as a resist, the residual film ratio tends to decrease, the pattern tends to swell or meander, and the resist tends to have 60 parts by weight. If the number exceeds the above range, the resolution as a resist tends to decrease.

<Additives> Additives for general resist compositions such as dyes and surfactants for preventing reflection of exposure light can be included. As the dye, as a compound having such a cure, a cyanovinylstyrene-based compound described in JP-A-3-25446 or a compound described in JP-A-63-25446 can be used.
1-cyano-2- (4-dialkylaminophenyl) ethylenes described in JP-A-286843 and JP-A-58-1
79441, p- (halogen-substituted phenylazo) -dialkylaminobenzenes;
No. 838, 1-alkoxy-4- (4′-N,
N-dialkylaminophenylazo) benzenes, dialkylamino compounds represented by formulas [1] to [9] described in JP-A-54-95688, nitrile compounds represented by formulas [10] to [15], 1,2-dicyanoethylene, 9
-Cyanoanthracene, 9-anthrylmethylenemalononitrile, N-ethyl-3-carbazolylmethylenemalononitrile, 2- (3,3-dicyano-2-propenylidene) -3-methyl-1,3-thiazoline and the like Oil yellow # 10 commercially available as a general dye
1, oil yellow # 103, oil yellow # 11
7, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-50
5 (manufactured by Orient Chemical Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170)
B), malachite green (CI42000), methylene blue (CI52015) and the like.

Particularly preferred dyes include 1-cyano-2- (4-dialkylaminophenyl) ethylenes, and specifically, 1-carboxy-1-cyano-
2- (4-di-n-hexylaminophenyl) ethylene,
Carboxyl at the 1-position such as 1-carboxy-1-cyano-2- (4-di-n-butylaminophenyl) ethylene, 1-carboxy-1-cyano-2- (4-di-n-heptylaminophenyl) ethylene 1-cyano-2 having a group
-(4-Dialkylaminophenyl) ethylenes, Oil Yellow # 101, Oil Yellow # 103, and Oil Yellow # 107 are preferable in that they are excellent in forming a reverse tapered pattern profile.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenol ether Polyoxyethylene aryl ethers such as polyethylene glycol dilaurate, ethylene glycol distearate, etc .;
01, EF303, EF352 (manufactured by Shin-Akita Kasei), Megafax F171, F172, F173, F177
(Dai Nippon Ink Co., Ltd.), Florade FC430, FC4
31 (Sumitomo 3M), Asahi Guard AG71
0, Surflon S-382, SC-101, SC-1
02, SC-103, SC-104, SC-105, S
Fluorinated surfactants such as C-106 (manufactured by Asahi Glass Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); acrylic acid or methacrylic acid (co) polymer Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK). The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solid content of the composition.

In addition to these, the photosensitive resin composition of the present invention may contain, if necessary, compatible additives such as a storage stabilizer, a sensitizer, and a plasticizer. These can be used instead of those added to a general resist composition for semiconductor production.

<Organic solvent> Specific examples of the solvent for the photosensitive resin composition include ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone;
Alcohols such as propyl alcohol, isopropyl alcohol, n-butyl alcohol and cyclohexanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dioxane; alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; formic acid Esters such as propyl, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, and ethyl lactate; cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, Cellosolve acetates such as butyl cellosolve acetate;

Propylene glycols such as propylene glycol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; trichloroethylene Halogenated hydrocarbons; aromatic hydrocarbons such as toluene and xylene; polar solvents such as dimethylacetamide, dimethylformamide and N-methylacetamide. These may be used alone or in combination of two or more. May be used.

<Developer> The above-described photosensitive resin composition is applied on a substrate described later, and after the solvent is removed by drying, an ultraviolet light source is used as an exposure source for forming a pattern to obtain a desired insulating film. Examples include far ultraviolet rays, KrF excimer laser light, X-rays, and electron beams. As a method for applying the photosensitive resin composition to the substrate, spin coating is particularly recommended.

After exposure, the film is developed with an alkaline developer. An aqueous alkali solution is usually used as the developer, and specific examples thereof include an aqueous solution of an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium silicate, and ammonia; an aqueous solution of a primary amine such as ethylamine and propylamine; Aqueous solutions of secondary amines such as diethylamine and dipropylamine; aqueous solutions of tertiary amines such as trimethylamine and triethylamine; aqueous solutions of alcoholamines such as diethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide; Quaternary ammonium hydrochloride such as trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide Such as an aqueous solution of Sid and the like. If necessary, a water-soluble organic solvent such as methanol, ethanol, propanol, and ethylene glycol, a surfactant, and a resin dissolution inhibitor may be added to the aqueous alkali solution.

(2) Curing Step In the present invention, the film pattern obtained by exposure is cured by irradiating ultraviolet rays under heating conditions before vapor deposition of the luminous body. The heating conditions in the curing step are as follows:
(Heat-resistant temperature of the film pattern-10 ° C.) ≦ heating start temperature <heat-resistant temperature of the film pattern, preferably (heat-resistant temperature of the film pattern−3 ° C.) ≦ heating start temperature ≦ (heat-resistant temperature of the film pattern-10 ° C), and the heating end temperature is as follows: heat resistant temperature of the film pattern ≤ heating end temperature ≤ (heat resistant temperature of the film pattern + 10 ° C), preferably (heat resistant temperature of the film pattern-2 ° C) ≤ heating end temperature. ≤ (heat-resistant temperature of the film pattern + 5 ° C). Further, the temperature from the start to the end of heating is the heat resistant temperature of the film pattern ±
It is in the range of 10 ° C. Within this temperature range, the heat resistance of the insulating film is improved while maintaining a good pattern profile. The heating temperature is based on the surface temperature of the hot plate when heating with a hot plate, and based on the indoor temperature of the oven when heating with an oven. The irradiation dose of the ultraviolet irradiation is 5 to 1000 mW, preferably 5 to 800 mW. From the viewpoint of uniform improvement of the heat resistance of the entire pattern, it is preferable to irradiate a small irradiation dose for a certain period of time from the start of UV irradiation, and then increase the irradiation dose and irradiate again for a certain period of time (irradiation time is the The total is preferably in the range described below, and both the dose and the temperature are within the above range), and the dose difference is usually 300 mW or more,
Preferably, it is 500 mW or more. Within this range,
Heat resistance is improved and pattern deterioration such as line width change does not occur.

The heat resistant temperature is 4 μm on a silicon substrate.
The resist film was molded to form a 15 μm line-and-space pattern, and heated on a hot plate at 110 ° C. to 5 ° C. for 5 minutes in air, and the state of the pattern was measured using a scanning electron microscope. Observation using
This is the temperature at the time when the shape of the pattern top is drooped and rounded, and the inverted tapered shape cannot be maintained.

The heating method is not particularly limited, and examples thereof include a method of directly heating the substrate from the bottom using a hot plate and a method of heating the entire substrate from the surroundings using an oven. The usual method is to place a substrate on which a pattern is formed when a hot plate or the like reaches an ultraviolet irradiation temperature and irradiate the substrate with ultraviolet light.

The irradiation time of the ultraviolet ray is to improve the heat resistance (curing).
10 to 60 seconds, preferably 20 to 40 seconds from the viewpoint of the efficiency of
Seconds. The heating is preferably continued until the end of the irradiation of the ultraviolet rays. However, the heating may be stopped, interrupted, or intermittent as long as the temperature is within the specified range of the present invention.

In order to return the temperature to room temperature after the irradiation of ultraviolet rays, the temperature lowering rate is arbitrarily set in consideration of the strain of the substrate and the shrinkage time of the resin which is a main component of the insulating film with the substrate. For example, an ITO substrate has a thickness of 10 cm ² and a thickness of 4.0 μm,
When the resin that is the main component of the insulating film is a novolak resin (average molecular weight of about 3000) obtained by condensing m-cresol / p-cresol = 6/4 (weight ratio of charged compound during resin synthesis) and formaldehyde. 0.5 ° C./sec to 10 ° C./sec on the cooling plate, preferably 1 ° C./sec.
The temperature is returned to room temperature at a rate of 2 to 5 ° C./sec, and the luminous body is deposited.

(3) Substrate The substrate used in the present invention is not particularly limited, but is generally a so-called ITO substrate.

(4) Light Emitting Element Deposition A light emitting element is deposited on the insulating film obtained by the above-described method. In this step, the luminous body may be deposited on the insulating film in some cases. Although the light emitter is not required on the insulating film, its removal is not essential. The method of vapor deposition is not particularly limited,
In general, a method is employed in which a vacuum is applied to about 10 ⁻⁶ Torr, and the luminous body is heated and vapor-deposited on the substrate while rotating the substrate.

(5) Light Emitting Material The light emitting material used in the present invention is an organic EL compound, for example, Arq (tris (8-quinolinolate) aluminum (III)) or NPD ((N, N'-dinaphthalene-1).
-Yl) -N, N'-diphenyl-benzidine) and the like.

[0050]

The present invention will be more specifically described below with reference to synthesis examples and working examples. The parts and percentages in each example are based on weight unless otherwise specified. <Synthesis Example 1> Production of alkali-soluble resin In a 2 liter flask equipped with a cooling tube and a stirrer,
420 g of m-cresol, 280 g of p-cresol, 3
350 g of 7% formalin and 2.4 of oxalic acid dihydrate
g, and the mixture was reacted for 2 hours while maintaining the temperature at 95 to 100 ° C. Thereafter, water is distilled off at 100 to 105 ° C. over 2 hours, and while heating to 180 ° C., 10 mmHg
After the pressure was reduced to remove unreacted monomers and water, the mixture was returned to room temperature and collected to obtain 420 g of a novolak resin. The weight average molecular weight of this novolak resin measured by the above-described method and conditions was 3,000.

<Examples 1 to 3> 100 parts of the novolak resin competed in Synthesis Example 1 and 2- [2-
(3,4-dimethoxyphenyl) ethenyl] -4,6-
Bis (trichloromethyl) -S-triazine 2.0 As a cross-linking agent, 3.0 parts of "Cymer 303" (trade name, manufactured by Mitsui Cytec Co., Ltd., hexamethylmethoxymelamine), silicon-based surfactant "KP-341" (product) 0.1 part (produced by Shin-Etsu Silicone Co., Ltd.) was dissolved in 180 parts of propylene glycol monoethyl acetate, and then filtered through a 0.1 μm Teflon filter (polytetrafluoroethylene filter) to prepare a photosensitive resin composition. .

Using a coater, the previously obtained photosensitive resin composition was applied on an ITO substrate, and prebaked at 90 ° C. for 90 seconds to form a resin film having a thickness of 4.0 μm. This wafer is placed in a parallel light aligner (PLA5
01F manufactured by Canon Inc.)
After exposure at about 200 mJ / cm ³ for 2 minutes, 110
Post exposure bake at 60 ° C. for 60 seconds (Post Exposur
e Banking) was performed. Next, a 2.38% aqueous solution of tetramethylammonium hydroxide at 23 ° C.,
The pattern was developed by a paddle method for a minute to form an insulating film pattern. When the heat resistance of this pattern was measured under the conditions described above, it was 100 ° C.

Next, in order to improve heat resistance, the substrate on which the pattern was formed was placed on a hot plate heated to 90 ° C. (heating start temperature) and irradiated with 11 mW ultraviolet rays. During the irradiation, the temperature was continuously increased.
After 520 seconds, 588 mW ultraviolet rays are irradiated for 15 seconds,
The ultraviolet irradiation and heating were stopped (the temperature of the hot plate at this time was 100 ° C. (heating end temperature)), the substrate was immediately removed from the hot plate, and placed on a cooling plate at a rate of 3 ° C./sec. The temperature was returned to room temperature (about 25 ° C.). When the heat resistance of the obtained cured insulating film was measured under the above conditions, it was found that the heat resistance was dramatically improved to 150 ° C.

Similarly, the heating and ultraviolet irradiation conditions for improving the heat resistance were as follows. In all cases, the heating end temperature was 100 ° C. (1) Starting temperature: 95 ° C., maximum temperature: 105 ° C. (2) Starting temperature: 95 ° C., maximum temperature: 110 ° C. The heat resistance of each of the obtained cured insulating films was 150 ° C.

<Comparative Examples 1 to 4> The insulating film pattern obtained in Example 1 was treated in the same manner as in Example 1 except that the temperature at the time of ultraviolet irradiation for curing was set as follows. The temperature was measured. (1) Starting temperature 60 ° C, maximum temperature 70 ° C, ending temperature 6
0 ° C (2) Starting temperature 60 ° C, maximum temperature 100 ° C, ending temperature 100 ° C (3) Starting temperature 100 ° C, maximum temperature 110 ° C, ending temperature 100 ° C (4) Starting temperature 95 ° C, maximum temperature 120 ° C, end temperature 110 ° C As a result, in each case, the rise in heat-resistant temperature was less than 5 ° C.

[0056]

The heat resistance of the insulating film can be improved by heating and irradiating the insulating film with ultraviolet light under specific conditions.

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Claims (4)

[Claims] Claims: 1. A photosensitive resin composition is applied on a substrate,
After exposing the resin film obtained by film formation in a pattern form, developing, and then, in a pattern forming method of a luminous body deposited film in which a luminous body is vapor-deposited on a substrate having the obtained film pattern, UV irradiation is performed while heating the photosensitive resin film pattern, and the heating condition is (heat-resistant temperature of the film pattern-10 ° C.) ≦ heating start temperature <heat-resistant temperature of the film pattern, heat-resistant temperature of the film pattern ≦ heating. A light-emitting process characterized in that: end temperature ≦ (heat-resistant temperature of the film pattern + 10 ° C.), and a temperature from the start of heating to before the end is within the heat-resistant temperature of the film pattern ± 10 ° C. Method for forming a pattern of a body-deposited film. 2. The method according to claim 1, wherein the irradiation amount of the ultraviolet rays is 5 to 1000 mW. 3. The photosensitive resin has a thickness of 300 nm to 200 nm.
And a novolak resin having a weight average molecular weight of 1,000 to 5,000 in terms of monodisperse polystyrene, as measured by gel permeation chromatography using a tetrahydrofuran as an eluent using a UV detector having a wavelength in the range of The method for forming a pattern of a luminous body deposited film according to the above. 4. A novolak resin comprising m-cresol and p
The method according to claim 3, wherein the resin is obtained by subjecting cresol to a condensation reaction with formaldehyde.