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WO1998001791A1 - Composition de photoresine positive - Google Patents

Composition de photoresine positive Download PDF

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Publication number
WO1998001791A1
WO1998001791A1 PCT/JP1997/002373 JP9702373W WO9801791A1 WO 1998001791 A1 WO1998001791 A1 WO 1998001791A1 JP 9702373 W JP9702373 W JP 9702373W WO 9801791 A1 WO9801791 A1 WO 9801791A1
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Prior art keywords
sulfonate
photoresist composition
weight
group
parts
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PCT/JP1997/002373
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English (en)
Japanese (ja)
Inventor
Shoji Kawata
Hirokazu Higashi
Masahiro Nakamura
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Nippon Zeon Co., Ltd.
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Application filed by Nippon Zeon Co., Ltd. filed Critical Nippon Zeon Co., Ltd.
Publication of WO1998001791A1 publication Critical patent/WO1998001791A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides

Definitions

  • the present invention relates to a positive-type photoresist composition containing an alkali-soluble phenol resin and a quinonediazide sulfonate, and more particularly, to a semiconductor device and a magnetic bubble memory.
  • a positive photoresist composition has become more prevalent than a negative photoresist composition. It has become. This is because the negative photoresist composition has high sensitivity, but uses an organic solvent for development, so that the resist pattern swells greatly and has a problem in resolution. It is caused.
  • the photoresist type photoresist composition can be developed with an aqueous alkali solution, so that the resist pattern swells little, has excellent resolution, and has a high semiconductor performance. It is thought that it can sufficiently cope with integration.
  • a positive-type photoresist composition generally used in this field is composed of an alkali-soluble phenol resin such as a novolak resin and a quinonedia disulfonate compound. It is. Since this positive photoresist composition is developed with an aqueous alkali solution, it has a small swelling and is excellent in resolution. In addition, such positive type The resolution of the resist composition has been further improved by improving the performance of the resist composition itself and the sophistication of the exposure machine, and it is now possible to form fine patterns of 0.5 m or less. ing.
  • these sensitizers can exert their performance in i-line (365 nm) exposure at a resist film thickness of about l / t / m or less, but the performance exceeds this.
  • the film thickness of the resist there is a problem that a practical pattern cannot be obtained because the exposure of the exposure light by the photosensitive agent is large.
  • 1,2-naphthoquinone-1 (2) -diazido-6-sulfonate ester of phenol X-norls specifically shown in the examples of the publication is Of the hydroxyl groups esterified with 1,2-naphthoquinone (2) -diazido 6-sulfonate in the total hydroxyl groups of the phenols
  • esterification rate is relatively large, with a charge ratio of 75 to 83%.
  • 1,2-naphthoquinone- (2) -diazide-16-sulfonate ester having a high esterification rate is a resist containing an alkali-soluble phenol resin.
  • Alkali-soluble phenol resins and photosensitizers are used after being uniformly dissolved in the solvent.
  • the obtained solution is applied on a substrate to form a resist film. If the photosensitizer precipitates during storage of the solution, it will not be possible to form a resist film with the specified sensitivity, and the precipitate will remain on the resist film as foreign matter. become. Disclosure of the invention
  • An object of the present invention is to provide a resist composition.
  • the present inventors have conducted intensive studies to solve the problems of the prior art, and as a result, as a photosensitive agent used in combination with an alcohol-soluble phenol resin, a specific esterification ratio of 1, 2 — Naphthoquinone diazide — 6 — sulfonate (ie, 1,2 — naphthoquinone mono (2) -diazido 6 — sulfonate) It is possible to obtain a photoresist composition with excellent storage stability, good pattern shape, and excellent focus tolerance, dimensional accuracy, sensitivity, and resolution. Was found.
  • 1,2-naphthoquinone diazide 6-sulfonate and 1,2-naphthoquinone diazide 5-snorrephonate And / or 1,2-Naphthoquinone diazide 4-sulfonate can be used to improve the effect of inhibiting the dissolution in an alkaline developer and improve the pattern.
  • a phenol compound as a resist property improver By adding a phenol compound as a resist property improver, the pattern shape, heat resistance, sensitivity and the like can be further improved.
  • the present invention has been completed based on these findings.
  • (A) an alkali-soluble phenol resin and (B) quinone diazide sulfonate of phenols are contained as photosensitizers.
  • (B) quinonediazidosulfonate of phenols in the positive resist composition of the present invention contains 10 to 7 of all phenolic hydroxyl groups of the phenols. 0% is the formula (1)
  • Examples of the alcohol-soluble phenol resin used in the present invention include, for example, a condensation reaction product of a phenol compound and an aldehyde, and a phenol compound and a ketone. Products of condensation reaction with phenols, vinylphenol-based polymers, isopropanol-based polymers, and hydrogenation reaction products of these phenolic resins I can do it. These soluble phenol resins can be used alone or in combination of two or more.
  • phenol compound used herein examples include phenol, o—cresol, m—cresol, and p—cresol 2,3—dimethanol. Nore, 2, 5 — dimethyl phenol, 3 4 dimethyl phenol, 3, 5 — dimethyl phenol, 2 dimethyl, 2, 6 — Dimethylinophenol, 2, 3, 5 Trimethylphenol, 2, 3, 6 — Trimethylphenol, 2 t-butylinole, 3 — t-butylinole Knol, 4-t-butylphenol, 2 — Methyl benzo resin, 4 — Methyl benzo resin, 5 — Methyl benzo resin, 4 t-butyl catechol, 2 — Methoxy phenol Nor, 3—Methoxy phenol, 2—Propyl phenol, 3—Propyl phenol, 41 propyl phenol, 2—Iso propyl : L-north, 3—isopropylphenol, 4—isopropylphenol, 2—methoxy
  • phenolic compounds 0-cresol, m-cresol, p-cresol, 2,3—dimethyl phenol, 3, 4 — Dimethyltinole, 3, 5 — Dimethylinole, 2, 5 — Dimethylinole, 2, 3, 5 — Trimethylinole, and 2, 3, 6 — Trimethylinophenol is particularly preferred.
  • Each of these phenol compounds can be used alone or in combination of two or more.
  • aldehydes examples include phormarin, paraform aldehyde, trioxane, acetate aldehyde, propyl aldehyde, benzaldehyde, and phenyl aldehyde.
  • Ketones include, for example, acetone, methylethylketone, jeethylketone, diphenylketone, and the like. These ketones can be used alone or in combination of two or more.
  • the condensation reaction product described above can be prepared by a conventional method, for example, by converting a phenol compound and an aldehyde or a phenol compound and a ketone in the presence of an acid catalyst. It can be obtained by reacting.
  • the vinylphenol-based polymer is selected from a homopolymer of vinylphenol and a copolymer of a component copolymerizable with vinylphenol.
  • Isopropenylphenol-based polymers are selected from isopropanolphenol homopolymers and copolymers of isopropenylphenol with components that can be copolymerized with isopropenylphenol. It is something.
  • Components that can be copolymerized with vinylphenol or isopro-vinylphenol include, for example, acrylic acid, methacrylic acid, styrene, maleic anhydride. Examples include monomers such as acid, maleic acid imide, vinyl acetate, acrylonitrile, and derivatives thereof.
  • the copolymer can be obtained by copolymerizing each component by a well-known method.
  • the hydrogenation reaction product of the phenolic resin is obtained by dissolving the phenolic resin in an organic solvent and performing hydrogenation in the presence of a homogeneous or heterogeneous catalyst according to a conventional method. Obtainable.
  • the weight-average molecular weight in terms of polystyrene is usually from 2,000 to 2,500, preferably from 3,500 to 20,000.
  • the weight average molecular weight of the alkali-soluble phenolic resin is less than 3,500, the pattern shape, resolution, and developability tend to deteriorate, and when it is less than 2,000, it is not practical. It becomes bad.
  • the weight average molecular weight exceeds 200,000, the pattern shape, developability, and sensitivity deteriorate, and when the weight average molecular weight exceeds 25,000, it becomes impractical.
  • soluble phenol resin a resin whose molecular weight and molecular weight distribution are controlled by known means can also be used.
  • Methods for controlling the molecular weight and molecular weight distribution include, for example, (1) crushing the resin and performing solid-liquid extraction with an organic solvent having an appropriate solubility, or (2) dissolving the resin in a good solvent and adding a poor solvent. Or by dissolving the resin in a good solvent and dropping a poor solvent to perform solid-liquid or liquid-liquid extraction.
  • the photosensitizer used in the present invention is a naphthoquinone diazide sulfonate of phenols, and particularly, in the total phenolic hydroxyl group of phenols, Ratio of 1,2-naphthoquinonediazido 6-sulfonate-derived phenolic hydroxyl group esterified by a photosensitive group derived from the above formula (1) (esterification ratio) 1,2—Naphthoquinone diazide 6—sulfonate (10-70%, preferably 20-70%, more preferably 25-65%) B 1).
  • esterification rate of 1,2-naphthoquinonediazide 6—sulfonate (B 1) is too high, the storage stability of the positive-type photoresist composition decreases, Also, there is a tendency that a good pattern shape cannot be obtained, which is not preferable.
  • a compound having a photosensitive group represented by the following formula (2) or (3) is used in combination, the effect of inhibiting dissolution in an alkali developer is improved, It is preferable because a better pattern can be obtained.
  • 1,2 —Naphthoquinone diazide 5 Sulfonate-derived 1,2 —Naphthoquinone diazide esterified with a photosensitive group derived from The acid ester (B2) and the phenolic hydroxyl group of phenols are represented by the formula (3)
  • 1,2-Naphthoquinone diazide 4-ester esterified with a photosensitive group derived from 1,2-naphthoquinone diazide 4-sulfonate represented by At least one species selected from the group consisting of 3) can be used in combination.
  • the esterification ratio of the compounds (B2 and B3) having a photosensitive group represented by the formulas (2) and (3) is not particularly limited, and can be arbitrarily set.
  • the esterification ratio of these compounds is usually from 10 to 90%, preferably from 20 to 80%, more preferably from 30 to 70%.
  • 1,2-Naphthoquinonediazido 6-sulfonate (B1) having a photosensitive group represented by the formula (1) is (A) an alkali-soluble phenolic resin having a weight of 100%. It is usually used in a proportion of 2 to 60 parts by weight, preferably 5 to 50 parts by weight, more preferably 5 to 30 parts by weight based on parts.
  • 1,2—Naphthoquinone diazide 6—Sulfonate (B 1) if too small, the sensitivity, resolution, pattern, focus tolerance, and dimensional accuracy Are not improved, and it is difficult to form a more practical pattern by i-line exposure.
  • 1, 2 — Naphthoquinone diazide 6 — Sulfonate (B 1) is preferred if the proportion is too large, because storage stability tends to decrease and pattern shape tends to deteriorate. Not good.
  • the ratio can be appropriately determined in consideration of the respective esterification rates, the type of phenols to be used, and the parameter A described later, and the weight ratio of the two is usually 1: It is desirable to be within the range of 99 to 99: 1, preferably 5:95 to 95: 5.
  • At least one compounding ratio selected from the group consisting of the sulfonate esters (B3) is usually based on 100 parts by weight of (A) the alkali-soluble phenol resin. It is 2 to 60 parts by weight, preferably 5 to 50 parts by weight, and more preferably 5 to 40 parts by weight.
  • the photosensitive agent having a photosensitive group represented by the above formulas (1) to (3) is a 1,2-naphthoquinonediazidosulfonate of phenols.
  • 1,2-Naphthoquinonediazidosulfonate can be converted to 1,2-naphthoquinonediazidosulfonate according to a conventional method.
  • the compound can be synthesized by reacting a diazide sulfonate halide with a phenol in a solvent in the presence of a base.
  • a base for example, acetone, dioxane, tetrahydrofuran or the like is used.
  • Examples of the base include inorganic bases such as sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, and sodium hydroxide, or trimethylamine, Tritylamine, tripropylamine, diisopropylamine, tributynoleamine, pyrrolidine, pyridin, pyrazine, monolefolin, pirenazine
  • Organic bases such as lysine and dicyclohexylamine are used.
  • the photosensitizer used in the present invention comprises 1,2-naphthoquinonediazidosulfonate halide represented by the formula (1) and phenols represented by the formula (2), based on phenols. And Z or 1,2-naphthoquinonediazidosulfonate halide, which gives a photosensitive group represented by the formula (3), simultaneously reacts with one molecule of X-nors. It is also possible to provide a plurality of types of photosensitive groups by using the above method. That is, 1,2-naphthoquinonediazide-16-sulfonate (B1) accounts for 10% to 70% of all phenolic hydroxyl groups of phenols.
  • 1,2-naphthoquinonediazide 16- represented by the formula (1) is esterified with a photosensitive group derived from sulfonate, the remaining At least a part of the phenolic hydroxyl group is a photosensitive group derived from 1,2-naphthoquinonediazido-5-sulfonate represented by the formula (2) and the formula (3) )),
  • the esterification ratio of this mixed ester is not particularly limited, but is at least 10%, preferably at least 20%, of all the phenolic hydroxyl groups of the phenols. Preferably, if at least 25% is esterified with a photosensitive group derived from 1,2-naphthoquinonediazido 6-sulfonate represented by the above formula (1), the entire mixed ester is obtained.
  • the esterification ratio is usually 90% or less, preferably 80% or less, and more preferably 70% or less, from the viewpoint of the balance of the resist properties.
  • the phenols used for the formation of the photosensitizer are preferably polyvalent phenols having three or more phenolic hydroxyl groups.
  • phenols include 2,3,4 trihydroxybenzofenone, 2,4,4'-trihydroxybenzofenon, 2 , 3,4,4'-Tetrahydroxybenzofenon, 2,4,2 ', 4'-Tetrahydroxybenzofonone, 2,3,4,2 ', 4' — Polyhydroxybenzophenones such as hydroxybenzen hydrophenone; gallic acids such as methyl gallate, ethyl gallate and propyl gallate esters; 2, 2 - bis (4 one human b Doki sheet off d) yl Purono, 0 down, 2, 2 - bis (2, 4 - di arsenide mud key sheet off d sulfonyl) Po Li arsenide mud such as propane Xbis bisphenylalkanes; tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-
  • R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 3 to R 6 are each independently an alkyl group having 1 to 4 carbon atoms. Group.
  • phenols there are also polyhydroxytristriphenylalkanes, polyhydroxycitrates, traxphenylalkanes and polyphenols. Fluorine compounds such as triphenylbenzenes, trimethacrylates by condensation reaction of phenolic compounds with formalin, etc. When polyvalent phenols having 3 or 4 nuclei are used, particularly excellent resist characteristics tend to be obtained.
  • a phenol compound can be added as an optional component in order to improve the resist properties such as pattern shape, heat resistance and sensitivity.
  • the phenol compounds include monophenols such as p-phenylphenol, p-isopropanolphenol, and the like; biphenol , 4,4'-Hydroxy-hydrogen-no-tenor, 4,4'-Hydroxy-hydrogen-zonofen, Bis-funo-nore A (Honshu-Dogaku Kogyo Co., Ltd.) Bisphenol C (manufactured by Honshu Chemical Industry Co., Ltd.), bisphenol (manufactured by Honshu Chemical Industry Co., Ltd.), bisphenol F (manufactured by Honshu Chemical Industry Co., Ltd.), bisphenol Nor A (Honshu Chemical Industry Co., Ltd.), Bisphenol M (Mitsui Petrochemical Co., Ltd.), Bisphenol P (Mitsui Petrochemical Co., Ltd.), Bisphenol Le Z (manufacture
  • Bisphenols such as 1,1,1,1 tris (4-hydroxyphenyl) methane, 1, 1, 1, 1—tris (4—hydr) 1,4-bis (3—methyl-14-hydroxyphenyl) 1-11,4- (4-hydroxyphenyl) meta 1, 1-bis (2,5—dimethyl 4-phenyl) 1 1— (2—hydroxy phenyl) methane, 1, 1—bis (3,5—dimethyloxy) -1 1— (2—hydroxyphenyl) methane, 2,6—vis (5—methyloxy2) — Hydroxybenzil) 1-4-Methylphenol, 2, 6-Bis (4-hydroxylbenzil)-4-1 Methylphenol, 2, 6-Bis ( 3 — Mechinore 4 — Hydroxybenzil) 1-4-methyl phenol, 2, 6-bis (3, 5-dimethyl-4-hydroxybenzene) 1-4-methyl phenol -Trisphenols such as Noren, Trisphenol (Honshu Chemical Industry Co., Ltd.) and Trisphenol-TC (Honshu Chemical Industry Co., Ltd.
  • the phenolic compounds of the component (C) can be used alone or in combination of two or more.
  • Alkali soluble When a resin having a low ratio containing a molecular weight of 10 nuclei or less is selected as a functional phenol resin, it is preferable to use such a phenol compound in combination. Results are often obtained.
  • the blending amount of the phenol compound can be arbitrarily selected, but usually 1 to 40 parts by weight, preferably 100 to 100 parts by weight of the alkali-soluble phenol resin. It is in the range of 3 to 30 parts by weight.
  • the positive resist composition of the present invention is usually used by dissolving it in a solvent in order to form a resist film by applying it to a substrate.
  • Each component such as an alkali-soluble phenol resin, a photosensitizer, and a phenol compound is used after being dissolved in a sufficient amount of a solvent to uniformly dissolve these components.
  • the solvent used in the present invention include ketones such as acetone, methylethylenoketone, cyclopentanone, cyclohexanonone; Non-reactive compounds such as pyranol, isopropyl alcohol, n-butyl alcohol, and hexagonal hexanol; ethylene glycol, etc .; ethylene glycol Ethers such as ethylene glycol, polyethylene glycol, dioxane, etc .; ethylene glycol methanol, etc .; ethylene glycol, ethylene glycol, etc.
  • Alcohols such as propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl dextranate, ethyl butyl butyrate, lactic acid Esters such as chill and ethyl lactate; cellosolve acetate, such as cellosolve acetate, methyl acetate solvent acetate, ethylcellosolone acetate, propylcellosolve acetate, and butylcelle solvent acetate
  • Propylene glycol propylene glycol monomethyl ether acetate, propylene glycol Propylene glycols such as luminoethyl acetate, propylene glycol, and butyl alcohol, etc .
  • Diethylene glycols such as ethyl glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc .; halogenates such as trichloroethylene Aromatic hydrocarbons such as toluene and xylene; polar solvents such as dimethyl acetate, dimethylformamide, and N-methylacetamide; and the like. No. These solvents can be used alone or in combination of two or more.
  • the poly-type photoresist composition of the present invention may contain, for example, styrene and acrylic resin, if necessary, in order to improve developability, storage stability, heat resistance and the like.
  • Acid, copolymer of methacrylic acid or maleic anhydride, copolymer of argenine and maleic anhydride, polyvinyl alcohol, polyvinyl pyrrolidone, Addition of rosin, silver, etc. can be added.
  • the amount of such a polymer to be added is generally 0 to 50 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the alkali-soluble phenol resin. Is within the range.
  • the photoresist composition of the present invention may contain, if necessary, a phase such as a surfactant, a storage stabilizer, a sensitizer, a striation inhibitor, and a plasticizer. Soluble additives can be included.
  • surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; Oxyethylene phenyl ether, polyoxyethylene Polyoxyethylene phenol ethers such as nonyl phenol ethers; polyethylene glycols such as polyethylene glycol, polyester glycolate stearate, etc. Glycol dialkyl esters; trade name EF TOP 31, EF 303, EF 352 (manufactured by Shin-Akita Kasei Co., Ltd.), trade names Megafax F171, F17 2, F177, F177 (manufactured by Dainippon Ink Inc.), trade name Florad FC430, FC4311
  • the amount of these surfactants is 100 parts by weight of the solid content of the positive photoresist composition, usually 2 parts by weight or less, and preferably 1 part by weight or less.
  • the positive photoresist composition of the present invention can use an aqueous alkaline solution as a developing solution in the developing step.
  • aqueous solutions of sodium hydroxide include aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium gayate, and ammonia; ethylamine, propylamine Aqueous solutions of primary amines such as acetylamine, dipropylamine, etc. Aqueous solutions of secondary amines such as getylamine, dipropylamine, etc .; Aqueous solutions of tertiary amines such as trimethylamine, triethylamine, etc.
  • Aqueous solutions of alcohol amines such as ethetylethanolamine, triethanolamine, etc .; tetramethylammonium hydroxide, tetrahydroammonium hydroxide, triglyceride Methinole Hydrochloride Chillammonium Hydro
  • An aqueous solution of a quaternary ammonium hydroxide such as xide, triethylenoxy hydroxymethyl methinoammonium hydroxide, trimethyl ethyl hydroxy shetyl ammonium hydroxide or the like; And so on.
  • the aqueous alkali solution may contain, as necessary, a water-soluble organic solvent such as methanol, ethanol, propanol, and ethylene glycol, a surfactant, and a resin dissolution inhibitor. Etc. can be added.
  • the positive photoresist composition of the present invention has the formula (I)
  • T r is the resist film thickness (im)
  • T (max) is the transmittance (%) of the resist after exposure
  • T (.) Is the resist thickness before exposure. The transmittance (%).
  • the transmittances T ( max ) and T (.) are the transmittance (T (max) ) when the resist composition is applied to a glass substrate to a thickness of 1 m, respectively. This is the transmittance (T (.)) When fully bleached using PLA-501F (manufactured by Canon Inc.) after the cloth is measured using a UV spectrophotometer. You.
  • Parameter ⁇ is the parameter that is most affected by the sensitizer component, and the photo resist composition whose parameter A value falls within the above range is unbalanced by i-line exposure. It is particularly preferable because it gives good register characteristics.
  • the positive photoresist composition of the present invention contains an alkaline soluble phenolic resin, quinone diazide sulfonate, and other optional components. Is used and stored as a resist solution uniformly dissolved in a solvent.
  • the resist solution can be applied to a substrate such as a silicon wafer by a conventional method, and then a solvent can be dried and removed to form a resist film.
  • a coating method at this time spin coating is particularly preferable.
  • Exposure sources used in the exposure process for forming a notch on the resist film thus obtained include ultraviolet light, far ultraviolet light, and KrF excimer laser light. Electron sources such as X-rays, X-rays, and electron beams.
  • Heat treatment post-exposure bake after exposure is preferred because sensitivity, residual film ratio, resolution, and heat resistance can be improved.
  • the weight-average molecular weight of the novolak resin in the following synthesis examples was calculated in terms of polystyrene in the pattern obtained by gel permeation chromatography (GPC) using a UV 254 nm detector. It is the weight average molecular weight (Mw).
  • each of the novolak resins obtained in Synthesis Examples 1, 3, 5, and 7 was used, and 1,2-naphthoquinonediazide 16-sulfonate was used with each of these resins.
  • (B-1), (B-2), (B-3) and (B-4) with the esterification rates shown in Table 1 was synthesized.
  • novolak resin and 1,2-naphthoquinonediazide-6-sulfonic acid chloride (Moles) was dissolved in acetone to give a 10% concentration solution. While controlling the temperature of the solution within the range of 20 to 25 ° C, 1.2 equivalents of 1,2-naphthoquinonediazide-6-sulfonyl chloride Triethylamine was added dropwise over 30 minutes, and the temperature was kept at this temperature for 2 hours to complete the reaction. After the precipitated salt was separated by filtration, the solution was poured into a 10-fold amount of a 0.2% aqueous solution of oxalic acid of the reaction solution.
  • This compound is reacted with 1,2-naphthoquinonediazido 6-sulfonyl chloride to give a sensitizer (B — 5), (B-6) and (B-7) were synthesized.
  • the synthesis method was the same as in Synthesis Examples 9 to 12, and Table 1 shows the amount of 1,2-naphthoquinone diazide-6-sulfonyl chloride used. The number of moles was equivalent to the esterification ratio of each photosensitive agent.
  • This compound is reacted with 1,2-naphthoquinone diazide 6-sulfonyl chloride to give a sensitizer with an esterification rate as shown in Table 1.
  • B-8 and (B-9) were synthesized.
  • the synthesis method was the same as in Synthesis Examples 9 to 12, and the amount of 1,2-naphthoquinonediazide-6-sulfonyl chloride used was as shown in Table 1 for each photosensitizer. The number of moles was equivalent to the esterification rate of
  • each positive photoresist composition (resist solution) shown in Table 1 was prepared.
  • the phenol compounds represented by the following formulas (C-11), (C-12) and (C-13) were used.
  • resist compositions 1 to 20 shown in Table 1 resist solution; solid concentration: 23%) were prepared.
  • Various characteristics were evaluated using the resist solutions 1 to 20 shown in Table 1. Specifically, a resist solution was applied on a silicon wafer with a spinner, and then pre-baked at 90 ° C for 60 seconds to obtain a film thickness of 1.0 ⁇ m and 1 ⁇ m. A 30 ⁇ m resist film was formed.
  • Post Exposure Baking a post exposure bake
  • a positive type pattern was formed by developing with a 2.38% aqueous solution of tetramethylammonium hydroxyride by a paddle method at 23 ° C for 1 minute. .
  • the silicon wafer on which the resist pattern is formed is taken out, observed with an electron microscope, and the sensitivity, resolution, pattern shape, focus tolerance, and dimensional change was evaluated. Parameter A value was measured by the measurement method described above. In addition, the storage stability of each resist solution was evaluated. Each evaluation method is as follows.
  • the exposure energy (unit: msec), which represents the amount of exposure energy that can form 1: 1 lines and spaces of 0.6111, according to design dimensions, was expressed.
  • the minimum pattern size (m) resolved when exposed for the above exposure time was expressed.
  • the silicon wafer on which the resist pattern was formed was cut from the vertical direction of the line-turning pattern, observed with an electron microscope from the cross-sectional direction of the pattern, and evaluated according to the following criteria.
  • ⁇ The film thickness is not reduced, and the pattern sidewall is at 80 degrees to the substrate. It stands up at the above angle.
  • the film was not reduced, and the pattern sidewall was rising at an angle of 70 ° or more and less than 80 ° with respect to the substrate.
  • the focus tolerance is determined according to the following criteria depending on the fluctuation width of the focus. The sex was evaluated.
  • the focus swing is 1.2 m or more.
  • the focus deflection force is less than 1.2 m.
  • the dimensional change rate of the resist pattern is 10% or less.
  • ⁇ The dimensional change rate of the resist pattern is 11 to 15%.
  • the dimensional change rate of the resist pattern is 16% or more.
  • the prepared positive photoresist solution was allowed to stand at 23 ° C., and a precipitate in the solution after three months was observed, and evaluated according to the following criteria.
  • Table 2 shows the evaluation results.
  • the positive photoresist composition of the present invention (Examples 1 to 15) has a sensitivity and a resolution in forming a pattern on a relatively thick resist film. , Pattern shape and focus tolerance Industrial applicability that has been shown to improve
  • the photoresist composition of the present invention has excellent sensitivity, resolution, pattern shape, and focus tolerance, and is excellent in dimensional accuracy.
  • the resist characteristics are highly balanced even under thick film conditions, such as excellent storage stability. Therefore, the positive photoresist composition of the present invention is extremely useful for the production of integrated circuits and the like, for which higher integration is expected to further advance in the future.

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Abstract

Composition de photorésine positive comportant (A) une résine phénolique soluble dans les alcalis et (B) un agent photosensible constitué d'un ester de l'acide quinonediazidesulfonique avec un phénol, caractérisée en ce que le constituant (B) renferme un ester (B1) de l'acide 1,2-naphtoquinonediazide-6-sulfonique avec un phénol, de 10 à 70 % des groupes hydroxyles phénoliques du phénol étant estérifiés par un groupe photosensible répondant à la formule (1) et étant obtenu à partir de l'acide 1,2-naphtoquinonediazide-6-sulfonique.
PCT/JP1997/002373 1996-07-10 1997-07-09 Composition de photoresine positive WO1998001791A1 (fr)

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JP19974896 1996-07-10
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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JP2021170132A (ja) * 2017-04-07 2021-10-28 昭和電工株式会社 樹脂組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7006747B2 (en) 2003-01-17 2006-02-28 3M Innovative Properties Company Optical devices incorporating photo reactive polymers
JP2021170132A (ja) * 2017-04-07 2021-10-28 昭和電工株式会社 樹脂組成物
JP7051818B2 (ja) 2017-04-07 2022-04-11 昭和電工株式会社 感光性樹脂組成物
US11561469B2 (en) 2017-04-07 2023-01-24 Showa Denko K.K. Photosensitive resin composition

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