TWI314249B - Radiation-sensitive resin composition - Google Patents

Description

1314249 IX. Description of the Invention: Technical Field of the Invention The present invention relates to a radiation sensitive resin composition used as a photoresist material in the field of lithography, and more particularly to a radiation sensitive resin composition. It is possible to form a photoresist pattern having a reverse cross-sectional shape and excellent heat resistance, and which does not cause abnormalities such as protrusions on the side walls. Further, the present invention relates to a radiation sensitive resin composition which has the above-described characteristics and has storage stability, and has a large limit (allowable range) of heating temperature in the heating portion after exposure. The radiation sensitive resin composition of the present invention is suitable for use as an electrical or insulating barrier material for forming a barrier layer in an organic organic electroluminescence display panel (hereinafter referred to as "organic EL display device") or by pulling up (lift) The cross section formed by the -off method is a reverse-cone shape resist material for pattern formation. [Prior Art]

In the lithography technique using a photoresist material, it is required that the cross section can form a photoresist material having a reverse tapered shape of the resist pattern. Specifically, there are, for example, a case where a pattern is formed by a lift-up method, or a case where an insulating wall of an organic EL display element is formed. The pulling-up method is applied, for example, to formation of a conductor pattern, formation of a heating element for a heating head, correction of a white defect of a photomask, and the like. When the photoresist pattern is used to form a conductor pattern by the lift-up method, a conductor pattern is formed on the substrate by the following series of steps: (1) a step of forming a photoresist film on the substrate, and (2) making the photoresist a film for pattern exposure, development, to form a negative photoresist pattern (negative image), (3) a step of vapor-depositing the metal on the substrate including the surface of the negative photoresist pattern to form a vapor deposited film, (4) A step of immersing the entire substrate f 1314249 in a solution to dissolve the negative photoresist pattern. In the above step (4), the negative resist pattern is removed together with the vapor deposited film thereon, and only the deposited film on the substrate remains in a pattern. In the above step (2), as shown in FIG. 1, when a negative resist pattern 2 having a reverse tapered shape is formed on the substrate 1, a metal vapor deposited film is formed on the substrate in the next step (3). And the vapor deposition film 3 and the vapor deposition film 3' are formed independently on the substrate 1 and on the negative resist pattern 2, respectively. At this time, if the negative resist pattern 2 is removed by the step (4), the vapor deposited film 3' on the upper surface thereof is also removed together, and only the pattern of the vapor deposited film 3 remains on the substrate 1. On the other hand, in the case where the outline of the resist pattern is a rectangular or a tapered shape or a skirt shape, in the above step (3), since the metal vapor deposited film is formed on the entire surface of the substrate, the side of the resist pattern is also formed. Since the vapor deposition film is formed, the vapor deposition film on the substrate and the vapor deposition film on the photoresist pattern are continuously formed. For example, as shown in FIG. 5, the cross-sectional shape of the photoresist pattern 52 formed on the substrate 51 is a tapered shape, the metal deposition film 53 is formed on the entire surface of the substrate, and the side of the photoresist pattern is also formed with steam. Coating. Therefore, if the photoresist pattern 52 is removed by the step (4), not only the vapor deposited film formed on the upper surface but also the vapor deposited film formed on the substrate continuously formed thereon is partially or completely removed. The pattern formed by the lift-up method is not only a photoresist pattern of a typical reverse cone shape cross section but also a photoresist pattern having a suspended cross section of the protruding portion 43 on the substrate 41 as shown in FIG. 42. In the present invention, the "inverse tapered shape" also includes a case where the cross-sectional shape is suspended. In the organic EL display device, it is also required that the photoresist film for forming an electrically insulating partition wall can form a resist pattern profile having a reverse tapered shape. The organic EL display element 1314249 has a high brightness due to its own light-emitting type, so the viewing angle is not limited. The panel can be thinned, and the low-voltage driving 'fast response speed' can be RGB (red, blue, green) and the 3 primary colors are fully colored. Characteristics such as chemistry. However, the organic EL material cannot be subjected to an etching treatment because of its low resistance to an organic solvent. Therefore, it is difficult to form a matrix structure as a display element by microfabrication using a lithography technique. Therefore, the main use of the organic EL display element is as a backlight for a liquid crystal display. In recent years, there have been new proposals for the formation technology of display elements using organic EL materials. Specifically, it is proposed (i) to form a plurality of strip patterns composed of indium tin oxide (ITO) on a transparent substrate as a first display electrode (anode), and then to be fully coated on the substrate. a negative photoresist composition, a photoresist film is formed, (Hi) is exposed through a strip mask that is positive with a strip pattern of ITO, and then subjected to post-exposure heat treatment (post exposure baking; PEB) and then image formation 'To form a strip-shaped negative resist pattern, (iv) sequentially deposit an organic EL material (hole transport material and electron transport material) on the substrate, (v) then vapor-deposit a metal such as aluminum to manufacture The method of the organic EL display element is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. In the organic EL display device, the 'negative photoresist pattern' is a task for achieving an electrically insulating partition wall. That is, as shown in Fig. 2, a strip-shaped patterned ITO film (anode) 22 is formed on the transparent substrate 2, and then a strip-shaped negative resist pattern 23 orthogonal thereto is formed. When the negative resist pattern has a reverse cross-sectional shape and the organic EL material is vapor-deposited thereon, the vapor-deposited film 24 of the strip-shaped organic EL material orthogonal to the ιτ film 22 is formed independently on the substrate 21. Even if the allowable range of the heating temperature is small even when the negative resist pattern is 1314249 and heated, it is difficult to obtain a well-shaped resist pattern. In the past, there has been proposed a negative-type photoresist composition containing at least one component which is exposed by light or crosslinked by exposure and subsequent heat treatment, an alkali-soluble resin, and a compound which absorbs light, and an alkaline aqueous solution. It is used as a developing solution (Japanese Unexamined Patent Publication No. Hei 5-1 652 1 8). If the negative photoresist composition is used, a resist pattern having a reverse cone shape suitable for the lift-up method can be formed.

However, the above retarder-shaped resist pattern has a problem that heat resistance is insufficient. When the metal deposition film is formed by the lift-up method, it is carried out at a high temperature. The electrically insulating partition wall in the organic EL display element must withstand the vapor deposition or metal evaporation process of the organic EL material under high temperature conditions to maintain its shape. In particular, in the case of vapor-depositing an organic EL material, the limit (permissible range) of the sublimation temperature is enlarged, and it is required to improve the heat resistance of the electrically insulating partition wall formed by the photoresist pattern. In addition, the organic EL display element is required to have durability against high temperature conditions such as temperature rise in the machine or in the vehicle as much as possible in order to be used in a portable device or a vehicle-mounted device. However, a photoresist pattern having low heat resistance cannot meet this requirement. Therefore, a photoresist material having a reverse-cone shape and a heat-resistant pattern can be formed, and various proposals are made. For example, there is a proposal (i) of a radiation-sensitive resin composition for forming a partition wall of an EL display element, which comprises an alkali-soluble resin, a melamine, and a trihalomethyl triad or a key salt [JP-2002-83687] No. 1 1 93 5 57], (ii) using a bisphenol compound containing a methylol group and a polycondensation of a phenol compound and an aldehyde 1314249 function. Further, since the above-mentioned photoresist materials are all chemical-line-amplified negative-type radiation-sensitive resin compositions, they are prone to interlocking chemical reactions' without sufficient preservation stability. Further, the "radiosensitive linear resin composition" does not necessarily have sufficient heat resistance for the higher-temperature baking necessary for the improvement of the durability of the organic EL display element. That is, the shape of the resist pattern is liable to change when the processing temperature of the post-exposure heat treatment (PEB) is raised. [Summary of the Invention]

An object of the present invention is to provide a radiation-sensitive resin composition which can form a photoresist pattern having a reverse-cone shape in cross section, excellent heat resistance, and no abnormal shape such as protrusions on the side walls. Another object of the present invention is to provide a radiation sensitive resin composition which is excellent in storage stability and excellent in storage stability, and has a large heating temperature limit (allowable range) at the time of heat treatment after exposure. The inventors of the present invention conducted intensive efforts to achieve the above object, and as a result, the alkali-soluble resin can be crosslinked by irradiation with an active radiation or irradiation with activating radiation and subsequent heat treatment in an alkali-soluble resin U). The component (b) and the compound for absorbing active radiation (the sensitized radiation-sensitive resin composition of ruthenium is used as the base by using 30 to 80% by weight of polyvinyl phenol and 20 to 70% by weight of novolak resin) The soluble resin U) and the compound (c) which uses the bis-azide compound as the radiation-absorbing radiation can provide a cross-sectional shape having a reverse cone shape, excellent heat resistance, and no protrusion or the like on the side wall. A radiation-sensitive resin composition of a photoresist pattern having an abnormal shape. -11- • 1314249 Further, in the radiation-sensitive resin composition of the present invention, it has been found that by adding a nitrogen-containing basic compound such as triethanolamine, the storage stability of the radiation-sensitive resin composition can be remarkably improved, and the exposure can be improved. The limit of the heating temperature of the post heat treatment (PEB). The radiation-sensitive resin composition of the present invention is used as a negative-type photoresist material by increasing the molecular weight of the alkali-soluble resin in the exposed region by the action of the crosslinking component and extremely lowering the dissolution rate in the alkali developing solution. Based on this knowledge, the present invention has finally been completed. Accordingly, the present invention provides a radiation sensitive resin composition comprising a % alkali-soluble resin (a), a component capable of crosslinking an alkali-soluble resin by irradiation of actinic radiation or irradiation of actinic radiation, and subsequent heat treatment (b) And an active radiation-absorbing compound (c), wherein (1) the alkali-soluble resin (a) contains -30 to 80% by weight of polyvinyl phenol and 20 to 70% by weight of novolac resin, and (2) absorption activity The radiation-emitting compound (c) is a diazide compound. [Embodiment] The best mode for carrying out the invention 1 - Alkali-soluble resin · In the present invention, as the alkali-soluble resin, a resin composition containing a polyvinylphenol and a novolak resin is used. The proportion of the polyvinyl phenol in the alkali-soluble resin is 30 to 80% by weight, preferably 35 to 75% by weight, more preferably 40 to 70% by weight. Therefore, the ratio of the novolac resin is from 2 to 70% by weight, preferably from 25 to 65% by weight, more preferably from 30 to 60% by weight. If the proportion of the polyvinyl phenol is too large, the side wall of the resist pattern is liable to cause a sudden shape abnormality. Further, if the proportion of the polyvinyl phenol becomes too large, the light 1314249 resist pattern is easily peeled off from the substrate. If the proportion of the polyvinyl phenol is too small, the heat resistance becomes insufficient. When the blending ratio of the polyvinyl phenol and the novolac resin is within the above range, a radiation-sensitive resin composition having a reverse tapered shape, an abnormal shape of the side wall, excellent heat resistance, and a substrate can be obtained. The suppressed photoresist pattern is peeled off. The polyvinyl phenol may, for example, be a homopolymer of a vinyl phenol, a copolymer of a vinyl phenol and a monomer copolymerizable therewith, or the like. As the monomer copolymerizable with the vinyl phenol, for example, isopropenylphenol, acrylic acid, methacrylic acid, styrene, maleic anhydride, decylamine maleate or vinyl acetate is preferable. As the polyvinyl alcohol, a homopolymer of a vinyl phenol is preferred, and a homopolymer of a vinyl phenol is more preferred. The average molecular weight of polyvinylphenol is the weight average molecular weight (Mw) in terms of monodisperse polystyrene measured by gel permeation chromatography (GPC).

Generally speaking, it is 3000 to 20000, preferably 4000 to 15000, more preferably 5 to 10,000. When the average molecular weight of the polyvinyl phenol is too low, even if the crosslinking reaction is carried out in the exposed region, the molecular weight does not sufficiently increase, and it becomes easy to be dissolved in the alkali developing solution, and the heat resistance is also lowered. When the average molecular weight of the polyvinyl phenol is too large, the difference in solubility between the exposed region and the unexposed region in the alkali developing solution becomes small, so that it is difficult to obtain a good resist pattern. As the novolak resin, those widely used in the technical field of photoresist can be used. The novolac resin can be obtained, for example, by reacting a phenol with an aldehyde or a ketone in the presence of an acidic catalyst (e.g., oxalic acid). As the phenol, for example, phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3, 5-dimethyl 1314249 phenol, 2,4-dimethyl phenol, 2,6-dimethyl phenol, 2,3,5-trimethyl phenol, 2,3,6-trimethyl phenol, 2- Third butyl phenol, 3-deca-butyl phenol, 4-tert-butyl phenol, 2-methyl resorcinol, 4-methyl resorcinol, 5-methyl resorcinol, 4 - t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 2- Methoxy-5-methylphenol, 2-t-butyl-5-methylphenol, thymol, iso-thymol, and the like. These may be used singly or in combination of two or more. As the aldehyde, for example, formaldehyde, formalin, polyoxymethylene, trioxane, % acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, (X-phenylpropanal, β-phenylpropanal, ortho-hydroxyl group) Benzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-methylbenzaldehyde, m-methylbenzene. aldehyde, p-methylbenzaldehyde, pair B Benzobenzaldehyde, p-n-butylbenzaldehyde, terephthalaldehyde, etc. As the ketone, for example, acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone or the like may be used. Each may be used alone or in Two or more combinations are used.

Among the above, from the viewpoint of sensitivity control, a novolac resin obtained by a condensation reaction of m-cresol and p-cresol with formaldehyde, formalin or polyoxymethylene is particularly preferable. The weight ratio of m-cresol to p-cresol is usually 80:20 to 20:80, preferably 70:30 to 50:50 °. The average molecular weight of the novolac resin is the monodisperse polystyrene measured by GPC. The converted weight average molecular weight is usually from 1,000 to 10,000, preferably from 2,000 to 7,000, more preferably from 2,500 to 6,000. When the average molecular weight of the resin is too low, even if the crosslinking reaction occurs in the exposed portion, the effect of increasing the molecular weight is small, and it is easily dissolved in the alkali developing solution. When the average molecular weight of the novolac resin -14 to 1314249 is too high, the difference in solubility between the exposed portion and the unexposed portion in the alkali developing solution becomes small, so that it is difficult to obtain a good resist pattern. The weight average molecular weight of the polyvinyl phenol and the novolac resin can be controlled to a desired range by adjustment of the synthesis conditions. Further, for example, (1) a resin obtained by synthesis is pulverized, a solid-liquid extraction method is performed in an organic solvent having an appropriate solubility, and (2) a resin obtained by the synthesis is dissolved in a good solvent, and is dropped. In a weak solvent, or by dropping into a weak solvent, the weight average molecular weight can be controlled by a solid-liquid or liquid-liquid extraction method or the like.

The weight average molecular weight measurement by GPC was carried out under the following conditions using a GPC measuring apparatus of SC8020 (manufactured by TOSO Co., Ltd.). Column: A combination of TSKGELG3000HXL and G200HXL1000 manufactured by TOSO Co., Ltd., temperature: 3 8 °C, solvent: tetrahydrofuran, flow rate: 1.0 ml/min, sample: 0.1 ml of a sample having a concentration of 0.05 to 0.6% by weight was injected. 2. Cross-linking component: The crosslinking component used in the present invention is a component capable of crosslinking an alkali-soluble resin by irradiation of actinic radiation or irradiation of actinic radiation and subsequent heat treatment. By the action of the crosslinking component, the molecular weight of the alkali-soluble resin in the exposed region is increased, and the dissolution rate in the alkali developing solution is extremely lowered. Therefore, the radiation sensitive resin composition of the present invention has a function as a negative photoresist material which can be imaged by an alkali developing solution. The crosslinking component may be, for example, a photopolymerization initiator (for example, a diphenyl ketone derivative, a benzoin derivative, a benzoin ether derivative, etc.) which generates a radical by irradiation of an actinic radiation 1314249. a compound having an unsaturated hydrocarbon group polymerized by the radical (for example, pentaerythritol tetra(meth)acrylate, etc., and optionally, a combination of a sensitizer for improving photoreaction efficiency, and (2) A compound which crosslinks an alkali-soluble resin by a compound which generates an acid by irradiation of actinic radiation (hereinafter referred to as "photoacid generator") and an acid generated by light as a catalyst (acidic substance) The combination of hereinafter referred to as "acid cross-linking agent", which is a cross-linking type chemically amplified photoresist which is excellent in compatibility with an alkali-soluble resin and which is excellent in sensitivity when combined with a % alkali-soluble resin. It is preferably a crosslinking component formed by a combination of a photoacid generator and an acid crosslinking agent. <Photoacid generator> A compound which generates an acid by actinic radiation, as long as it is exposed by actinic radiation Energy production The substance of the Bronsted acid or the Lewis acid can be used without particular limitation, and a key salt, a halogenated organic compound, a quinonediazide compound, a hydrazine compound, an organic acid ester compound, an organic acid decylamine compound, or an organic compound can be used. It is a well-known person such as a bismuth imino compound, etc. These photoacid generators are selected from the spectral sensitivity surface according to the wavelength of the exposure light source of the pattern. As the fiber salt, for example, a diazo salt, an ammonium salt, a diphenyl group a mirror salt, a scaly salt, an arsenic salt, an oxo salt, or the like of an iodine salt such as a iodine-containing trifluoromethanesulfonate or a triphenylsulfonium trifluoromethanesulfonate. The halogenated organic compound may be, for example, Halogen-containing oxadiazole-based compound, halogen-containing triple-trap compound, halogen-containing acetophenone-based compound, halogen-containing benzophenone-based compound, halogen-containing fluorene-based compound, halogen-containing lanthanide compound A halogen-containing thiazole compound, a halogen-containing oxazole-based-16-1314249 compound, a halogen-containing triazole-based compound, a halogen-containing pyridone compound, another halogen-containing heterocyclic compound, and a halogen-containing compound. fat a hydrocarbon compound, a dentate-containing aromatic hydrocarbon compound, a sulfenium halide compound, etc. Specific examples of the halogenated organic compound include, for example, ginseng (2,3-dibromopropyl)phosphate and ginseng (2,3-di). Bromo-3-chloropropyl)phosphate, tetrabromochlorobutane, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)_s_ Tri-trap, 2-[2-(4-methoxyphenyl)vinyl]-4,6-bis(trichloromethyl)_8_three

Well, hexachlorobenzene, hexabromobenzene, hexabromocyclodecane, hexabromocyclododecane, hexabromobiphenyl, allyltribromophenyl ether, tetrachlorobisphenol A, tetrabromobisphenol a, four Bis(chloroethyl)ether of chlorobisphenol A, bis(bromoethyl)ether of tetrabromobisphenol A, bis(2,3-dichloropropyl)ether of biguanide, double of bisphenol A 2,3-dichloropropyl)ether, bis(2,3-dichloropropyl)ether of tetrachlorobisphenol A, bis(2,3-dibromopropyl)ether of tetrabromobisphenol A, four Chlorobisphenol S, tetrabromobisphenol S, bis(chloroethyl)ether of tetrachlorobisphenols, bis(bromoethyl)ether of tetrabromobisphenol S, double (2,3-di) of bisphenol 5 Chloropropyl)ether, bis(2,3-dibromopropyl)ether of bisphenol S, ginseng (2,3-dibromopropyl)isocyanurate, 2,2-bis(4-hydroxy- A halogen-based flame retardant such as 3,5-dibromophenyl)propane or 2,2-bis(4-(2-hydroxyethoxy)-3,5-dibromophenyl)propane. Specific examples of the quinonediazide compound are, for example, 1,2-benzene-containing diazide-4-sulfonate, 1,2-naphthoquinonediazide-4-sulfonate, and 1,2-naphthoquinone. a quinonediazide derivative such as a diazide-5-sulfonate, a 2,1-naphthoquinonediazide-4-sulfonate or a 2,1-benzoquinonediazide-5-sulfonate Sulfonate; 1,2-benzoquinone-2-diazide-4-propionic acid chloride 1, 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride, i,2-naphthoquinone -2-Diazide-5-sulfonic acid chloride, 1,2-naphthoquinone-1-diazide_6-sulfonic acid chloride ' 1,2-benzoquinone-1 -diazide-5-sulfonate a quinonediazide derivative of acid chloride or the like -17-, a sulfonate chloride of 1314249 or the like. Specific examples of the milled compound are, for example, an unsubstituted, symmetrical or asymmetric substituted alkyl, alkenyl, aralkyl, aromatic or heterocyclic cyclic fluorene compound, diterpene compound, and the like. The organic acid ester is, for example, a carboxylate, a sulfonate, a phosphate or the like. As the organic acid amide, for example, carboxylic acid amide, sulfonic acid decylamine, guanidinium phosphate and the like. The organic acid quinone imide is, for example, a quinone carboxylic acid imide, a sulfonium sulfinimide, a ruthenium phosphate or the like.

Further, for example, it may be cyclohexylmethyl (2-oxocyclohexyl)phosphonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl)phosphonium trifluoromethanesulfonate, 2-oxocyclohexyl group. (2-originyl) fluorinated trifluoromethanesulfonate, 2-cyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl)phosphonium trifluoromethanesulfonate, triphenylsulfonate Fluoromethanesulfonate, diphenyliodopyl trifluoromethanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, phenyl p-toluenesulfonate, and the like. 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, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the alkali-soluble resin. If the proportion of the photoacid generator is too small or too large, the shape of the photoresist pattern is deteriorated. <Acid Crosslinking Agent> The acid crosslinking agent is a compound (acidic substance) capable of crosslinking an alkali-soluble resin in the presence of an acid generated by irradiation (exposure) of actinic radiation. As the acid crosslinking agent, for example, an alkoxymethylated urea resin, an alkoxymethylated melamine resin, an alkoxymethylated urethane resin, an alkoxymethylated glycoluril resin, an alkoxy group A well-known acid crosslinkable compound such as a methylated amine-based resin. -18-.1314249 is preferably one in which active radiation is absorbed in a region of a wavelength of 200 to 500 ηπ. As the bisazido compound, for example, 4,4'-diazidechalcone, 2,6-bis(4'-azidobenzylidene)cyclohexanone, 2,6-bis (4, -azidobenzylidene)_ 4-methylcyclohexanone, 2,6-bis(4'-azidobenzylidene)-4-ethylcyclohexanone, 4,4,-diazidodiphenyl Sodium ethylene-2,2'-disulfonate, 4,4'-diazide diphenyl sulfide '4,4'-diazide benzophenone, 4,4'-diazide diphenyl 2,7-diazidopurine, 4,4'-diazidophenylmethane. As a commercially available diazido compound, for example, trade names BAC-H, BAC-M, BAC-E, DAC, DAz, ST (Na), DazST (51), and DazBA (manufactured by Toyo Kogyo Co., Ltd.) can be used. Na) and so on. The bisazido compound may be used singly or in combination of two or more kinds. The bisazido compound is usually used in an amount of 0.1 to 10 parts by weight, preferably 0. 3 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the alkali-soluble resin. When the ratio of use of the bisazide-based compound is too small, the effect of improving the shape of the side wall of the pattern is small. However, if it is too large, it is difficult to form a cross-sectional shape of the reverse tapered shape, and the heat resistance is also lowered. In general, when the thickness of the photoresist film is thick, since the light is hard to permeate, the use ratio of the bisazide-based compound is preferably small, and in the case of thinness, it is preferably used. The diazide-based compound may also be used in combination with other compounds that absorb active radiation, but in this case, the proportion of the diazide-based compound used in the total amount of the compound that absorbs the active radiation is more than 50% by weight. It is preferably 7% by weight or more, more preferably 90% by weight or more. As another compound which absorbs active radiation, for example, it may be a natural compound such as azo dye 1314249, methine dye, azo methine dye, curcumin or xanthone, or a cyanovinylstyrene compound, -Cyano-2-(4-dialkylaminophenyl)ethene, p-(halo-substituted phenylazo)dialkylaminobenzene, 1-alkoxy-4-(4'-N , N-dialkylaminophenylazo)benzenes, dialkylamino compounds, 1,2-dicyanoethylene, 9-cyanoguanidine, 9-fluorenylmethylenemalononitrile, N -ethyl-3-oxazolylene malononitrile, 2-(3,3-dicyano-2-propylene)_3_methyl-1,3-anthene and the like. 4. Other additives:

A surfactant may be added in order to improve the dispersibility and the like of each component of the radiation sensitive resin composition. As the surfactant, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyethylene oxide hard decyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxidation Polyoxyethylene aryl ethers such as vinyl nonylphenol ether; polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and ethylene glycol distearate; Eptop EF301, EF 303, EF352 (made by New Akita Chemical Co., Ltd.), Megafax F17 1, F172, F173, F177 (made by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (made by Sumitomo 3M), Asahigard AG710, Sarfron S-382, SC-101, SC Fluorinated surfactants such as -102, SC-103, SC-104, SC-105, SC-106 (made by Asahi Glass Co., Ltd.); organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); acrylic or nail Acrylic (co)polymer Polyfro Νο·75, Νο. 95 (manufactured by Kyoeisha Oil Chemical Industry Co., Ltd.). The amount of the surfactant to be added 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 resist composition. -22 - .1314249 5. Organic solvent The radiation sensitive resin composition of the present invention is usually prepared by dissolving each component in an organic solvent and filtering to obtain a solution. The amount of the organic solvent is an amount sufficient to uniformly dissolve or disperse the components. The solid content concentration in the solution is usually from 5 to 50% by weight ', but preferably from about 10 to 40% by weight. The organic solvent used in the present invention may be, for example, an alcohol of n-propyl alcohol, isopropanol, n-butanol or cyclohexanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone a ketone such as cyclohexanone; propyl formate, butyl formate, ethyl acetate, propyl acetate, butyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, methyl butyrate, Esters such as ethyl butyrate, methyl lactate, ethyl lactate, ethyl ethoxypropionate, ethyl pyruvate; cyclic ethers such as tetrahydrofuran and dioxane; methyl cellosolve, ethyl Solicactone for cellosolve, butyl cellosolve, etc.; cellosolve acetate such as ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; ethylene glycol dimethyl Alcohol ethers such as ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; propylene glycol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate, and propylene glycol ^ Propylene glycol such as alcohol monobutyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol II a diethylene glycol such as ethyl ether; a propyl ester such as γ-butyl propionate; a halogenated hydrocarbon such as trichloroethylene; an aromatic hydrocarbon such as toluene or xylene; dimethylacetamide; A polar organic solvent such as dimethylformamide or hydrazine-methylacetamide; or a mixed solvent of two or more of these. 6. Nitrogen-containing basic compound: In the present invention, in order to improve the preservation of the radiation-sensitive resin composition, it is preferred to add a nitrogen-containing basic compound. The nitrogen-containing basic compound may, for example, be an aliphatic primary amine, an aliphatic secondary amine, an aliphatic tertiary amine, an amino alcohol, an aromatic amine, a quaternary ammonium hydroxide or an alicyclic amine. Specific examples of the nitrogen-containing basic compound are, for example, butylamine, hexylamine, ethanolamine, triethanolamine, 2-ethylhexylamine '2-ethylhexyloxypropylamine, methoxypropylamine, diethyl Aminopropylamine, N-methylaniline, N-ethylaniline, N-propylaniline, dimethyl-N-methylaniline, diethyl-N-methylphenylamine, diisopropyl Base-N-dimethylaniline, N-methylaminophenol, N-ethylaminophenol, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl Aminophenol, tetrabutylammonium hydroxide, tetramethylammonium hydroxide, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4 . 3, 0] 壬-5-ene and the like. The nitrogen-containing basic compound is usually used in an amount of 0.01 to 10 parts by weight, preferably 1 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the alkali-soluble resin. If the ratio of use of the nitrogen-containing basic compound is too small, the effect of improving the storage stability is small, and if it is too large, the effect of improving the stability of storage is saturated, and the photoresist characteristics are adversely affected. 7. Method of using a radiation-sensitive resin composition of the present invention The radiation-sensitive resin composition of the present invention is uniformly coated on a substrate by a coating method such as spin coating, and the solvent is dried and removed to form a photoresist film on the substrate. The photoresist film is usually heated at a heating temperature of about 80 to 110 ° C for about 10 to 200 seconds, and is subjected to heat treatment (prebaking) to obtain a photoresist film having a thickness of usually about 0.5 to 5 μm. . In order to form a photoresist pattern, first, a desired light source is used to perform pattern exposure on the photoresist film -24-*1314249. When the radiation sensitive resin composition of the present invention is a crosslinked type chemically amplified photoresist material containing a photoacid generator as a crosslinking component and an acid crosslinking agent, in order to promote a crosslinking reaction, it is usually 1 after exposure. Heat treatment at a temperature of about 130 °C for about 1 to 200 seconds (PEB). The actinic radiation used for the exposure may be, for example, ultraviolet rays, far ultraviolet rays, KrF excimer laser light, X-rays, electron wires or the like. Specific examples of the light source to be exposed are, for example, a bright line spectrum of mercury of 436 nm, 405 nm, 365 nm, 254 nm, or the like, or a KrF excimer laser light source of 248 nm. The substrate ' is not particularly limited, and may be, for example, a tantalum substrate, a glass substrate, an ITO film forming substrate, a chromium film forming substrate, a resin substrate, or the like. The radiation-sensitive resin composition of the present invention has a function of a negative-type photoresist which is not dissolved or hardly dissolved in an alkali developing solution by the action of a crosslinking component in the exposed portion, so that the exposure amount is more than a certain amount, The post-resist film remains on the substrate. The exposure energy of this is called Eth.

The radiation sensitive resin composition of the present invention can be imaged by an alkali developing solution. As the alkali developing solution, an aqueous alkali solution is usually used. The base may, for example, be an inorganic base such as sodium hydroxide, potassium hydroxide, sodium citrate or ammonia; a primary amine such as ethylamine or propylamine; or a secondary amine such as diethylamine or dipropylamine. Amines; tertiary amines such as trimethylamine and triethylamine; alcohol amines such as diethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, triethyl hydroxide A quaternary ammonium hydroxide such as hydroxymethylammonium or trimethylhydroxyethylammonium hydroxide. Further, if necessary, a water-soluble organic solvent such as methanol, ethanol, propanol or ethylene glycol, a surfactant, or a resin -2514249 may be added to the aqueous alkali solution, and the price is A. B. (3) Storage stability: The radiation sensitive resin composition was stored at 5 ° C and 23 t for 3 months, and then the sensitivity (Eth) was measured. The sensitivity of the radiation-sensitive resin composition stored at 5 ° C was used as a standard, and the change in the sensitivity of the radiation-sensitive resin composition stored at 23 ° C was evaluated as A within 5%, and within 5 to 10%. The assessment is B, and more than 10% are evaluated as C. (4) Sensitivity measurement method:

After spin-coating the radiation sensitive resin composition on the wafer, it was baked on a 1 1 (TC hot plate for 90 seconds to form a film having a film thickness of 1.95 μm. A g-line indexer (manufactured by Nikon Corporation) was used. Product name "NSR1505G6E"), the exposure amount is changed at regular intervals, and the pattern of 5 mm square is made to be 100 exposures. After exposure, the exposure section is made by baking on a hot plate (PEB) at 10 ° C for 60 seconds. After the PEB, a 70-second paddle imaging was performed in a 2 to 38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH), and the exposure amount of the portion where the exposed portion of the photoresist film was exposed was used as the sensitivity. (Eth) (5) PEB limit: In the patterning operation, except that the temperature at the time of PEB is changed to 1 〇〇. 〇 and 120 ° C are similarly operated for patterning. By SEM The line width of the line pattern obtained under each PEB temperature condition was measured, and the amount of change in the line width change per 10 ° C was calculated. The line width variation was 1·0 μιη/10 ° (: The following is evaluated as A , will be more than 1_0μπι/10 °C but 2. 〇μπι / 1 〇 °C below the evaluation of B, will exceed 2.0 (im/10 ° C The price is C. -27 - J314249 Example 1 With respect to a polyethylene terephthalate having a weight average molecular weight (Mw) of 5 Å (manufactured by Kyusan Petrochemical Co., Ltd., trade name "Marucaiink S_2P"), 70 parts by weight 2 parts by weight of the alkali-soluble resin composed of 30 parts by weight of the phenolic phenol resin obtained by dehydration condensation of cresol/p-methyl hydrazine with 70/30 (by weight) and formaldehyde Halogen-containing triple well

Photoacid generator (manufactured by Midori Chemical Co., Ltd., trade name "TAZ110"), 20 parts by weight of melamine-based crosslinking agent (acid crosslinking agent: manufactured by Mitsui Scientific Co., Ltd., trade name "Saimel 303"), and 1 part by weight The bis-azido compound (manufactured by Toyo Seiki Co., Ltd., trade name "BAC-M") was dissolved in 290 parts by weight of propylene glycol monomethyl ether acetate (PGMEA). The resulting solution was filtered with a membrane filter made of polytetrafluoroethylene having a pore size of ίμίη to prepare a photoresist solution having a solid content of 30% by weight. The photoresist solution was coated on a tantalum wafer using a spin coater, followed by prebaking on a hot plate at 1 1 ° C for 90 seconds to form a photoresist film having a film thickness of 3 μm. Above the photoresist film, a 20 μm line & gap (L&S) pattern mask was used, and exposed by a parallel light collimator (manufactured by Canon Co., Ltd., trade name "PLA501F"). The exposure amount is such that the line and the gap portion become 1:1 energy. After the exposure, it was baked (PEB) on a hot plate at 110 ° C for 60 seconds to crosslink the exposed portion. After PEB, paddle-type development was carried out for 70 seconds in a 2.38 wt% TMAH aqueous solution to obtain a pattern of L&S. The cross-sectional shape of the pattern is an inverse cone shape. The measurement results are shown in Table 1. Examples 2 and 3 were changed to the polyvinyl phenol and novolac resin shown in Table 1 -28 - .1314249 inch § 〇 ocsτ 06 (n « pq ε 0 inch 09 OCNτ

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V s__) ((NelifIC Bi Yi Jing (lq) 蘅 Hu 粼氍罘 (βφ 罃 ? β OIPA πο) real rose loose pregnancy g搣 _ floating (vwsod) 蘅 ingot ¥ jf ^ sIililiM (s « 1314249 by the table As a result of 1, it is understood that the radiation-sensitive resin composition of the present invention (Examples 1 to 3) has a cross-sectional shape of a reverse cone shape, is excellent in heat resistance, and has no protruding shape abnormality in the pattern side wall. ～6 In the examples 1 to 3, 'the same operation was carried out except that 1 part by weight of triethanolamine was added as a nitrogen-containing basic compound. The results are shown in Table 2. Table 2

EXAMPLES (parts by weight) 4 5 6 Alkali-soluble resin (a) Polyvinylphenol (al) 70 60 40 Novolak resin (a2) 30 40 60 Cross-linking component (b) Photoacid generator (bl) 2 2 2 Acid crosslinker (b2) 20 20 20 Absorbing active radiation compound (C) Bismuth compound 1 1 1 nitrogen basic compound (d) Triethanolamine 0.1 0.1 0.1 Solvent (PGMEA) 290 290 290 light Eye features preserve stability AAA PEB boundary (# m/10°C) AAA

As is apparent from the results of Table 2, the radiation sensitive resin composition of the present invention (Examples 4 to 6) is excellent in storage stability, and the heating temperature after exposure is 1314249. INDUSTRIAL APPLICABILITY The radiation sensitive resin composition of the present invention is selected from a resist pattern of a reverse cone shape profile by selecting a ratio of polyethenyl phenol in an alkali-soluble resin and containing a bisazido compound. The shape of the side wall is good, and even if it is heated by an oven, a sharp heat treatment step of a heat such as a heating plate can maintain the reverse taper shape and exhibit high heat resistance.

Further, according to the present invention, by adding a nitrogen-containing basic compound, it is possible to provide a radiation-sensitive resin composition which is excellent in storage stability in addition to the above characteristics and has a large heating temperature limit (allowable range) after heat treatment after exposure. . The radiation-sensitive resin composition of the present invention can be used as a photoresist material for forming an electrically insulating partition wall in an organic electroluminescence display panel (organic EL display device) or as a reverse tapered shape by a lift-up method. A photoresist material for patterning. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view showing an example of a pattern forming program of the drawing method. Fig. 2 is an explanatory view showing an example of fine processing of the organic EL display panel. Fig. 3 is a cross-sectional view showing an example of the microfabricated organic EL display panel $. Figure 4 is a diagram showing the tone of the photoresist pattern in the shape of a suspension. -32 - 1314249 Fig. 5 is an explanatory view showing an example of a pattern forming program using a lift-up method having a resist pattern having a tapered cross section. [Component Symbol Description]

1 substrate 2 photoresist pattern 3, 3, ruthenium plating film 2 1 substrate 22 ITO film 23 photoresist pattern 24, 24 5 vapor deposition film 25, 25 1 metal deposition film 3 1 transparent substrate 32 ITO film 34a, 34b, 34c vapor deposition film 35 ' 35 5 metal lotus coating 4 1 substrate 42 photoresist pattern 43 overhang 5 1 substrate 52 photoresist pattern 53 metal evaporation film -33-

Claims (1)

1314249 94 1 095 1 No. 1 "Radiation Resin Composition" Patent (Amended on June 22, 2009) X. Patent Application Range: 1. A radiation sensitive resin composition containing an alkali soluble resin (a) a cross-linking component (b) capable of crosslinking an alkali-soluble resin and a compound (c) absorbing active radiation by irradiation of active radiation or irradiation of actinic radiation and subsequent heat treatment, wherein (1) The alkali-soluble resin (a) contains 30 to 80% by weight of polyvinyl phenol and 20 to 70% by weight of novolac resin, and (2) the compound (c) which absorbs active radiation is selected from 4, 4'- Diazol-chalcone, 2,6-bis(4'-azidobenzylidene)cyclohexanone, 2,6-bis(4'-azidobenzylidene)-4-methylcyclohexanone , 2,6-bis(4'-azidobenzylidene)-4-ethylcyclohexanone, 4,4'-diazidodisyl-2,2'-disulfonic acid sodium, 4,4 '-Diazide diphenyl sulfide, 4,4'-diazide benzophenone, 4,4'-diazide diphenyl, 2,7-diazide fluorene and 4,4' - at least one diazide compound of a group consisting of diazidophenylmethane, used in a proportion of 0.5 to 5 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a), and (3) The component (b) is a combination of an acid crosslinking agent which is a photoacid generator which generates an acid by irradiation of actinic radiation and an acid which is obtained by irradiation of actinic radiation as a catalyst to crosslink the alkali-soluble resin. Wherein the use of a photoacid generator is relative to 100 parts by weight of the alkali-soluble resin (a) Example 1~1 0 parts by weight based, and relatively! O. 1 314 249 to 0 parts by weight of a posterior-soluble resin (a) 'that the acid crosslinking agent is 4 ~ 6 0 parts by weight of proportion. 2. The radiation sensitive resin composition of claim 1, wherein the polyvinyl phenol has a weight average molecular weight of 3,000 to 20,000. 3. The radiation sensitive resin composition according to claim 1, wherein the novolac resin is a novolac resin obtained by a condensation reaction of m-cresol and p-cresol with formaldehyde, formalin or polyoxymethylene. 4. For the radiation sensitive linear resin composition of claim 3, the weight ratio of intermediate cresol to p-cresol is 80:20 to 20:80. 5. The radiation sensitive resin composition of claim 1, wherein the novolac resin has a weight average molecular weight of from 1,000 to 10,000. 6 _ The radiation sensitive resin composition according to the first aspect of the patent application, wherein the photoacid generator is a substance capable of generating Bronsted acid or Lewis acid by irradiation with actinic radiation. 7. The radiation sensitive linear resin composition of claim 6, wherein the photoacid generator key salt, the halogenated organic compound, the quinonediazide compound, the hydrazine compound, the organic acid ester compound, the organic acid decylamine compound, Or an organic acid quinone imine compound. 8. The radiation sensitive linear resin composition of claim 1, wherein the acid crosslinking agent is an alkoxymethylated urea resin, an alkoxymethylated melamine resin, an alkoxymethylated aldehyde Resin, alkoxymethylated glycoluril resin, alkoxymethylated amine based resin, alkyl etherified melamine resin, benzoguanamine resin, alkyl etherified benzoguanamine resin, urea resin, alkane Etherified urea resin, urethane-formaldehyde resin, resole phenol 1314249 aldehyde resin type phenol formaldehyde resin, alkyl etherified resol type phenol formaldehyde resin, or epoxy resin. 9. The radiation sensitive linear resin composition of claim 8 wherein the alkoxymethylated melamine resin is a methoxymethylated melamine resin, an ethoxymethylated melamine resin, or a positive C An oxymethylated melamine resin, or a n-butoxymethylated melamine resin. 10. The radiation sensitive resin composition of claim 1, wherein the crosslinking component (b) comprises a weight ratio (photoacid generator: acid crosslinking agent) of from 1:1 to 1:30. Photoacid generator and acid crosslinker. 1 1. The radiation sensitive resin composition of claim 1, further comprising a nitrogen-containing basic compound (d). 12. The radiation sensitive linear resin composition of claim 11, wherein the nitrogen-containing basic compound (d) is an aliphatic primary amine, an aliphatic secondary amine, an aliphatic tertiary amine, an amino alcohol, an aromatic A metal amine, a quaternary ammonium hydroxide, or an alicyclic amine. 1 3 · The radiation-sensitive resin composition of claim 11, wherein the nitrogen-containing basic compound (d) is used in a proportion of 1 part by weight of the alkali-soluble resin (a) 〇.〇1~1 〇 by weight. 14. The radiation sensitive resin composition according to the first aspect of the invention, which is a barrier material for forming a partition wall of an organic EL display device. 1 5 The radiation sensitive resin composition according to the first aspect of the patent application is a photoresist material for forming a pattern having a reverse pyramid shape by a lift-up method.