WO1998049601A1 - Composition de photoresine positive pour photomasque - Google Patents

Composition de photoresine positive pour photomasque Download PDF

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Publication number
WO1998049601A1
WO1998049601A1 PCT/JP1998/001964 JP9801964W WO9849601A1 WO 1998049601 A1 WO1998049601 A1 WO 1998049601A1 JP 9801964 W JP9801964 W JP 9801964W WO 9849601 A1 WO9849601 A1 WO 9849601A1
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Prior art keywords
solvent
photomask
resist composition
compound
film
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PCT/JP1998/001964
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English (en)
Japanese (ja)
Inventor
Takeyoshi Kato
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Nippon Zeon Co., Ltd.
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Publication of WO1998049601A1 publication Critical patent/WO1998049601A1/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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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 photoresist composition used for producing a photomask, and more particularly to a photomask composition having excellent adhesion to a light-shielding film or an interference film. It relates to a positive resist composition. Further, the present invention relates to a positive resist composition for producing a photomask having excellent adhesion to a light-shielding film or an interference film and excellent storage stability. Further, the present invention relates to a method for producing a photomask using a positive resist composition having such excellent characteristics. Background technology>
  • a photomask is a component in which a pattern of an electronic circuit is formed of a light-shielding material on a transparent substrate.
  • the photomask is formed on a substrate on which a resist film is formed by a photolithography technique. It is used as a master for selectively irradiating light to the device to project a pattern image of an electronic circuit.
  • Photomasks are used, for example, in the manufacture of semiconductor devices, magnetic bubble memory devices, semiconductor integrated circuits (LSI), liquid crystal displays (LCD), print substrates (PWB), and the like.
  • a material obtained by dissolving a photosensitive polymer material called a resist in an organic solvent is applied onto a substrate having a layer to be processed formed on a surface thereof.
  • the organic solvent is evaporated in a pre-bake to form a resist film.
  • an unnecessary portion of the resist film is dissolved and removed using a developing solution, and the resist pattern is formed on the substrate.
  • etching is performed on the resist pattern by immersing it in a solution of an acid or the like that dissolves the layer to be added on the substrate. Finally, remove the unnecessary registry.
  • the photomask is used as an original for partially irradiating the resist film with light.
  • a notation forming method includes a mask pattern transfer method that irradiates ultraviolet rays, electron beams, X-rays, and the like in a pattern through a photomask.
  • a drawing method by beam scanning such as an electronic lion.
  • the drawing method is a sequential process, the throughput is low, but the creation and modification of the pattern can be performed quickly and easily, so that the photo mask (including the reticle), This is useful for manufacturing ASICs (Application Spectrified Circuits), etc., or for prototyping devices at the research and development stages.
  • a mask pattern is formed using an electron beam lithography system or a laser lithography system.
  • a hard mask used for LSI, LCD, PWB and the like and suitable for miniaturization will be described as an example.
  • a light-shielding film made of a thin metal film is formed on a transparent substrate such as a transparent glass plate to form a mask substrate. Chrome is generally used as the metal thin film material.
  • an interference film of a chromium oxide is formed on the metal chromium film.
  • a radiation-sensitive resist film is formed on the light-shielding film or the interference film on the mask substrate.
  • an electron beam lithography system or a laser lithography system scans the resist film with an electron beam or laser beam to form a pattern. Forming structure.
  • a resist pattern is formed by developing using a developing solution compatible with the used resist. In this case, development is performed using the difference in solubility or the difference in dissolution rate between the exposed portion and the unexposed portion with respect to the developer.
  • the light shielding film is etched. Etching of a metal chromium film is mainly performed by etching, and an aqueous solution of ammonium nitrate ammonium is generally used as an etching solution. After the etching, the unnecessary resist film is peeled off. As a result, a photomask in which an electronic circuit pattern (mask turn) formed of a light-shielding film is formed on a transparent substrate can be obtained.
  • PMMA polymethyl methacrylate
  • polymethyl styrene polymethyl styrene
  • an organic solvent is used as a developer.
  • PMMA has the disadvantage that it has high resolution but low sensitivity, and also has problems such as deterioration of working environment and difficulty in waste liquid treatment because it uses an organic solvent for the developer. ing.
  • a positive resist composition in which a soluble phenol resin and a quinone diazide sulfonate-based photosensitizer are dissolved in a solvent has good sensitivity and resolution, and also has an aqueous alkaline composition. Since development with a developer is possible, research and development for use as a resist for photomask manufacturing is underway. However, in general, this positive resist composition has poor adhesion to a metal chromium film (light-shielding film) or a chromium oxide film (thickness film), so that the development step and the etching step For example, there was a problem that the resist film was peeled off. This positive resist composition has poor adhesion especially to a chromium oxide film, but is not suitable for metal chromium oxide. The same is true for the film film because its surface is oxidized to chromium oxide. Invention disclosure>
  • An object of the present invention is to provide a positive resist composition containing an alkali-soluble phenol resin, a quinone diazide sulfonate, and a solvent, which has excellent adhesion to a light-shielding film or an interference film.
  • An object of the present invention is to provide a positive resist composition for producing a photomask.
  • Another object of the present invention is to provide a positive resist composition for producing a photomask, which has excellent adhesion to a light-shielding film or an interference film and excellent storage stability.
  • a positive electrode containing an alkali-soluble phenol resin, a quinone diazide sulfonate, and a solvent In the resist composition, a linear, branched or cyclic ketone compound having 6 to 8 carbon atoms may be used alone or in combination with another solvent.
  • this positive resist composition exhibited excellent properties immediately after production, but had insufficient storage stability such as precipitation of components when stored for a long period of time.
  • the specific ketone compound and the lactone compound are used in combination as a solvent.
  • a positive resist composition having excellent adhesion to a light-shielding film or an interference film and excellent storage stability can be obtained. Therefore, this positive resist composition is suitable when long-term storage is required.
  • the present invention has been completed based on these findings.
  • a photoresist for producing a photomask comprising an alkali-soluble phenol resin (A), a quinone diazide sulfonate (B), and a solvent (C).
  • the solvent (C) contains a linear, branched or cyclic ketone compound having 6 to 8 carbon atoms (C-type positive-type photomask; A resist composition is provided.
  • the solvent (C) contains a ketone compound (C and a lactone compound (C.) together with a photoresist type resist composition for producing a photomask. Things are provided.
  • a resist film is formed by applying a positive resist composition on the light-shielding film or the interference film of the transparent substrate on which the light-shielding film or the light-shielding film and the interference film are formed. Then, the resist film is irradiated with a radiation beam to draw a pattern, developed with an alkaline developer, and then etched to remove the mask and the pattern.
  • an alkali-soluble phenol resin (A), a quinone diazide sulfonate (B), and a positive resist composition are provided in the method for producing a photomask to be formed.
  • a linear, branched or cyclic ketone compound containing a solvent (C) and having 6 to 8 carbon atoms (a poly-type resist composition containing C) is used.
  • a method for producing a photomask characterized by this is provided.
  • the solvent (C) is converted into a ketone compound (C and In particular, it preferably contains a lactone compound (c 2 ).
  • alkali-soluble phenol resin used in the present invention examples include, for example, condensation reaction products of phenols and aldehydes (novolak resin), phenols Reaction products of phenols and ketones, vinylphenol-based polymers, isopropenylphenol-based polymers, and hydrogenation reaction products of these phenolic resins Things. Of these, novolak resin is particularly preferred.
  • phenols used in the production of novolak resin include phenol, ⁇ —cresole, m—cresole, and p—cresole. 1, 3, 5 — xylenol, 2, 5 — xylenol, 2, 3 — xylenol, 3, 4 — xylenol, 2, 3, 5 — Tri-methyl phenol, 2, 3 — dimethyl phenol, 2, 5 — dimethyl phenol, 3, 5 — dimethyl phenol Le, 2—Echinoref Enor, 3—Echinoref Enor, 4—Echinoref Enorno, 2—Pro Pinolev Enorno, 3—Propyrno Nor, 4—Propyr ⁇ Nor, 2, 3, 5 — Tri-Echinolev Enole, 3, 5 — Detjynolev Enole, 2, 5 — Diechinolev Enole, 2 — tert — Butino Phenol, 3-tert-butylphenol, 4-tert-
  • aldehydes include formaldehyde, acetate aldehyde, propionaldehyde, n-butyl aldehyde, isobutyl aldehyde, and trimethyl aldehyde.
  • Aliphatic or cycloaliphatic aldehydes such as furyl crolein; benzaldehyde, o—tolualdehyde, m—tonoraldehyde, p—tolualdehyde, p —Echilbenzaldehyde, 2, 4 — Dimethylbenzaldehyde, 2, 5 — Dimethylbenzaldehyde, 3, 4 1 or 3,5 — Dimethyl norbenzanoledide, phenylase tonanoredeh De, o — hydroxybenzaldehyde, m — hydroxybenzaldehyde, p — hydroxybenzaldehyde, kay skin aldehyde, o — anisaldehyde, m — anisaldehyde, p — anisaldehyde, etc.
  • Aromatic aldehydes and the like. These aldehydes may be used alone or in combination of two or more. Among these, low molecular weight aliphatic saturated aldehydes such as formaldehyde and acetate aldehyde; o—hydroxy benzyl aldehyde, m—hydroxy benzyl aldehyde, and p—hydroxy benzyl aldehyde, etc. Drokishibenzaldehydes are preferred.
  • the condensation reaction between phenols and aldehydes can be carried out according to a conventional method.
  • the vinylphenol-based polymer is selected from a homopolymer of vinylphenol and a copolymer of a component copolymerizable with vinylphenol.
  • Specific examples of copolymerizable components include acrylic acid, methacrylic acid, styrene, maleic anhydride, maleic acid imide, vinyl acetate, and acrylonitrile. Examples thereof include lil and derivatives thereof.
  • Isopropyl vinyl polymer is selected from homopolymers of isopropyl vinyl and copolymers of components copolymerizable with isopropenyl vinyl.
  • copolymerizable components include acrylic acid, methacrylic acid, styrene, maleic anhydride, maleic acid imide, vinyl acetate, and acrylic acid. And the like, and derivatives thereof.
  • the hydrogenation reaction product of the phenolic resin can be produced by any known hydrogenation reaction. Specifically, it can be obtained by dissolving a phenol resin in an organic solvent and introducing hydrogen in the presence of a homogeneous or heterogeneous hydrogenation catalyst.
  • These alcohol-soluble phenol resins can be used as they are, but may be separated by a known means to control the molecular weight and the molecular weight distribution.
  • the resin is pulverized and extracted one by one with an organic solvent having an appropriate solubility, or the resin is dissolved in a good solvent and dissolved in a poor solvent. Or a poor solvent is dropped to perform solid-liquid or liquid-liquid extraction.
  • Each of these alcohol soluble resins can be used alone, but if necessary, two or more of them may be used in combination. Further, in the present invention, among these, phenols and aldehydes are obtained by polycondensation in the presence of an acid catalyst. Alkali-soluble phenol resin is preferred. Furthermore, phenolic phenolic resin obtained by polycondensing phenols containing m- and p-cresols with aldehydes is preferred. . This phenolic box resin is a phenol, other than m- and p-cresols, and 3,5-xylenol or phenol. A combination of 2, 3, and 5 trimethylphenol may be used.
  • the cre- novolak resin has an m-cresol content of 50 mol% or less (usually 5 to 50 mol%, preferably 10 to 45 mol%) in the constituent parts. Mol%) is preferred. If the content of m-cresol is too large, the residual film ratio after development may decrease.
  • the quinone diazide sulfonate used in the present invention functions as a photosensitizer.
  • examples of such quinone diazide sulfonates include 1,2 naphthoquinone diazide-15 sulfonate and 1,2 naphthoquinone diazide-14 sulfonate.
  • 1,2 naphthoquinone diazide 5-sulfonate and 1,2 naphthoquinone diazide 4-sulfonate are preferred, and 1,2-naphthoquinone diazide. DO-4 sulfonate is more preferred.
  • the method for producing these quinonediazidosulfonates is not particularly limited, but quinodiazidosulfonide halides (preferably quinonediazidosulfonate chlorides) are used in accordance with conventional methods.
  • quinodiazidosulfonide halides preferably quinonediazidosulfonate chlorides
  • a solvent such as aceton, dioxane, tetrahydrofuran, etc.
  • Inorganic bases such as aluminum, sodium bicarbonate, sodium hydroxide, and potassium hydroxide, or trimethylamine, tritylamine, trib mouth Pyramine, diisopropylamine, tributylamine, pyrrolidine, pyridin, pyrazine, monolefolin, pyridin, dicyclohexylurea It can be obtained by reacting with polyphenols in the presence of an organic base such as mine.
  • the polyphenols used herein are those having two or more, preferably three or more, and more preferably four or more phenolic hydroxyl groups in the molecule. It is a droxy compound.
  • phenols examples include 2,3,4-trihydroxybenzophenone, 24,4'-trihydroxybenzobenzonone, and 234-4'-telephenol. Trahydroxybenzofenon, 2 4 2'4 'Tetrahydroxybenzofenon, 23,4,2'4' —Pont of hydroxybenzofenon, etc.
  • Polyhydroxybenzophenones gallic esters such as methyl gallate, ethyl gallate, and propyl gallate; 22-bis (4-hydroxybenzoyl) pun, 2,2-bis ( 2 4—Polyhydroxybisphenylalkanes such as dihydroxyphenyl) phenyl; tris (4—hydroxyphenyl) methane, 1,1,1,1 tris ( 4-Hydroxy-1 31-Methylphenyl) ethane, 1 1 1—Tris (4 ⁇ Hydroxy — 2 — methyl phenyl) ethane, 111 — tris (4 — hydroxyphenyl) ethane, 111 — bis (4 — hydroxy 13 — methyl) 4- (hydroxyphenyl) ethane, bis (4-hydroxy-13-methyl-phenyl) -12-hydroxy 4-phenyloxymethane, etc.
  • Lisphenylalkanes 1 1, 2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2—Tetrakis (3—Methenol 14-hydroxyphenyl) Ethan, 1,1,1,3,3—Tetrakis (4—Hi (Drokinphenyl) phenolic alcohols such as prono and phenol; a, a, a ', a'-tetrakis (4-hydroxy) Droxifanil) 1-3 xylene, a, a, a ', a'-Tetrakis (4-hydroxyxeninole) 14-1 xylene HI, a, a ', a'-tetra dry (methyl) 1-4 (hydroxy phenyl) 13-poly (hydroxy) 2,6-bis (2,4-dihydroxybenzil) -r- ⁇ -cresole, 2,6-bis (2,4-dihydro) Loxy 1 3 — Methynorbenzil) 1 ⁇
  • shaku 1 and! ⁇ 2 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and R 3 to R 6 are mutually independent. And an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.
  • the ratio (average esterification rate) of the quinonediazidesulfonic acid esterified hydroxyl groups of the hydroxyl groups of these polyphenols is particularly limited. Usually, it is not less than 65%, preferably not less than 70%, expressed as mol% of the quinonediazidesulfonic acid compound relative to the hydroxyl group of polyphenols, The upper limit is usually 100%, preferably 90%. If the ratio of this esterification is too low, the pattern shape and the resolution may be deteriorated.
  • the quinonediazide sulfonate used as a photosensitizer in the present invention can be used alone or in combination of two or more.
  • the compounding amount of the photosensitizer is usually 1 to 100 parts by weight, preferably 3 to 40 parts by weight, based on 100 parts by weight of the alkali-soluble phenol resin. If the amount is too small, it is difficult to form a pattern. If the amount is too large, the sensitivity is reduced and development residue tends to occur.
  • the positive resist composition for producing a photomask according to the present invention is intended to improve the adhesion to a light-shielding film or an interference film formed on a mask substrate, particularly to a metal chromium film or a chromium oxide film.
  • a linear, branched or cyclic ketone compound having 6 to 8 carbon atoms (C ⁇ ) is used as a solvent. Further, when the storage stability of the port-shaped record Soo Bok composition is required, Quai tons of compound (C ⁇ and La click tons compound (c 2) used together with.
  • the ketone compound (c can be used alone as a solvent, but if necessary, another solvent (c 3 ) may be used in combination. Preferably, it is at least 50% by weight, based on the total solvent content, and at least 80% by weight. More preferred. Therefore, the compound ij (c) is a ketone compound (c is preferably 50 to 100% by weight, more preferably 80 to 100% by weight, and the other solvent (C 3 ) preferably comprises 0 to 50% by weight, more preferably 0 to 20% by weight.
  • the ratio of the lactone compound (c 2 ) is preferably based on the total amount of the solvent components. From 1 to 50% by weight, more preferably from 1 to 30% by weight, particularly preferably from 5 to 20% by weight, so that the composition of the solvent (C) is preferably
  • the ketone compound (C 50 to 99% by weight, the lactone compound (C 2 ) 1 to 50% by weight, and the other solvent (C 3 ) 0 to 49% by weight are more preferable.
  • the proportion of the ketone compound (C) in the solvent (C) component is too small, the adhesion to the light-shielding film and the interference film is reduced, and the resist film is peeled off during development and during etching.
  • the ratio of the lactone compound (c 2 ) is too small, the etchant is more likely to penetrate between the resist film and the light-shielding film or the interference film.
  • the storage stability of the positive resist composition is reduced, a large number of fine particles are generated during long-term storage, which become foreign matter on the substrate at the time of drawing, resulting in a mask pattern.
  • the proportion of each solvent component is within the above range, the balance between adhesion and storage stability becomes good.
  • Ketone compounds (C is a linear, branched or cyclic C 6-8 Is a ketone compound. Specific examples of such ketone compounds include 2—hexanone, 3—hexanone, 2—heptanone, 3—heptanone, and 4-heptanone.
  • Linear ketones such as 2-octanenon, 3-octanenone, 4-octanenone; 3-methyl 2-pentanonone, 4-methanone Chinore 1 2 — Pentanone, 3 — Etchinore 1 2 — Pentanone, 2,4 -Dimethylinole 3 — Pentannon, 2 — Methyl 3 — Pentanone, 3 ⁇ Methyl 2-Hexanone, 5-Methyl 2-Hexanone, 2-Methylenol 3-Hexanone, 4-Methylenol 3-Hexanone, 5-Methyl 1 3- Hexanone, 3 — ethyl 2-, hexanone, 4-ethylinone 2-hexanone, 2, 5 — dimethinol 1 3 — hexanone, 3, 5 — dime Lou 2 — Hexanone, 4, 5 — Dimethyl 2 — Hexanone, 2 — Methyl 3 —
  • La click tons (c 2), 7 - Puchiro la click tons, 7 - Ba Le b La click tons, 7 - Power Pro la click tons, 7 - Ca pli b La Saturated lactones 7—Lactones; croctactone, single angelica lactone, / 3—unsaturated angelic lactones 7— Lactones; (5—valerolactone, 5—caprolactone, etc. S—lactones; S—propiolactone, 3—butyrolactone Tonto, etc. / S-Lactones; (5-Norolactones, etc. 5-Norrelactones, etc.
  • 5-Lactones £ 1 Such as lactolactone, ⁇ -oprolactone, etc., etc. Among them, saturated 7—lactons ⁇ unsaturated 7—lactos 7-Lactones are preferred, and saturated 7-Lactones are particularly preferred.Saturated 7-Lactones are preferred, and 7-Lactone is preferred. Especially preferred.
  • C 3 Other usable solvents (C 3 ) include, for example, ketones such as acetone, methylethyl ketone, cyclopentanone, and the like; ⁇ —propylanolone, is ⁇ — Propinoleanol alcohol, n — butanol alcohols such as butanol alcohol, cyclohexano alcohol, etc .; ethyl alcohol glycol methyl ether, ethylene glycol alcohol jet alcohol, dioxan Ethers such as ethylene glycol monomethyl ether, ethyl alcohol, etc., etc .; propanol formate, butyl formate, propyl acetate, butyl acetate, propionate Esters such as methyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, and ethyl lactate Cerro Sorupuasete one door, Celloso-nolebutest
  • a phenol compound can be added for the purpose of improving the sensitivity of the positive resist composition.
  • phenolic compounds include phenols disclosed in WO96 / 22563 and a, a'-monosubstituted phenols.
  • Resin-based phenols such as obtained resins; p-vinyl phenol, p-isophenol phenol, etc .; phenol; biphenol , 4,4 '— Hydroxy dino-tinole, 4,4'-Dihydroquinone zof Bisphenol A (manufactured by Honshu Chemical Industry Co., Ltd.), Bisphenol C (manufactured by Honshu Chemical Industry Co., Ltd.), Bisphenol E (manufactured by Honshu Chemical Industry Co., Ltd.), bisphenol ⁇ Knore F (Honshu Chemical Co., Ltd.), Bisphenol AP (Honshu Chemical Co., Ltd.), Bisphenol M (Mitsui Petrochemical Co., Ltd.), Bisphenol P (manufactured by Mitsui Petrochemical Industries, Ltd.), bisphenol Z (manufactured by Honshu Chemical Industries), 1, 1-bis (4—hydroxy phenol) 9, 9—bis (4—hydroxyphenyl) fluorene, 1,1bis (5—methyl-2—hydroxyphenyl) me
  • the amount of these phenolic compounds varies depending on the composition, molecular weight, molecular weight distribution, and type and amount of other additives of the soluble polyphenol resin. 1
  • the upper limit is usually 50 parts by weight, preferably 30 parts by weight, more preferably 20 parts by weight, and the lower limit is usually 100 parts by weight based on 100 parts by weight of the resin. Parts by weight, preferably 2 parts by weight, more preferably 3 parts by weight.
  • the positive resist composition of the present invention optionally contains a surfactant, a storage stabilizer, a sensitizer, a striation inhibitor, a plasticizer, and other additives as necessary. It can be done.
  • the positive resist composition of the present invention can be developed with an alkaline developer.
  • an aqueous inorganic alkaline solution that is, an aqueous solution of an alkaline inorganic compound is preferable.
  • aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium gayate, ammonia, mixtures thereof, and pH buffers Agents, surfactants, and compatible low-grade alcohols.
  • an organic developer such as ethanolamine may be used, if necessary. It can also be.
  • a photomask is prepared by a photolithography technique using the positive resist composition.
  • a light-shielding film or a light-shielding film and an interference film are formed on a transparent substrate to form a mask substrate.
  • a transparent glass plate is used as the transparent substrate.
  • Chrome is used as a material for forming the light-shielding film.
  • silicon, iron oxide, molybdenum sulfide, or the like may be used.
  • the interference film serves to reduce the reflectance of the light-shielding film, and usually uses chromium oxide, and is formed as a chromium oxide film on the surface of a metal chromium film (two-layer type). .
  • a three-layer type in which the interference film is also provided on the back surface of the metal chromium film can be used.
  • a positive resist composition is applied on the light-shielding film or the interference film of the mask substrate to form a resist film. Coating, drying, prebaking and the like of the positive resist composition can be carried out according to a conventional method.
  • the resist film is irradiated with a radiation beam to draw a pattern.
  • an electron beam lithography system and a laser lithography system are used for writing with a radiation beam, and an electron beam or a laser beam is scanned based on a mask pattern, and the resist film is formed on the resist film.
  • the pattern is drawn.
  • development is carried out by an ordinary method such as immersion development using an alkaline developer. In this way, a resist pattern is formed.
  • post baking or desmating surface treatment with oxygen plasma or the like
  • Etching is a step of transferring the resist pattern formed by the resist pattern forming method to the underlying light-shielding film or the light-shielding film and the interference film.
  • Etchin There are two types of driving methods: jet etching using a liquid, and dry etching using a gas. ⁇ Etching is generally performed using ammonium cerium nitrate (Kodak specification). Etching is performed by dipping or spraying. As the dry etching gas, a carbon halide gas such as carbon tetrachloride or a chlorine-based gas is used.
  • the resist film is peeled off.
  • the resist film can be removed by a chemical method using an acid obtained by adding hydrogen peroxide or ozone to an organic solvent or concentrated sulfuric acid, or a physical method using an oxygen plasma or a UV-ozone-assisting treatment. .
  • a combination of chemical and physical methods can be applied. Thereby, a photomask on which the mask pattern of the light-shielding film is formed can be obtained.
  • the photomask may be a reticle (a mask for a reduction exposure apparatus).
  • the substrate surface was observed with an optical microscope, and the presence or absence of peeling of the line pattern of the resist film was observed.
  • the adhesion was evaluated according to the following criteria.
  • the cross section of the pattern was observed with a scanning electron microscope to determine the extent of penetration of the etching solution into the interface between the resist film and the chromium oxide film (side etch amount). It was measured. The smaller the side etch amount, the greater the adhesion of the resist film.
  • Polyphenols are 2,3,4,4'-tetrahydroxybe Using 1,2-naphthoquinonediazide-14-sulfonate chloride in dioxane, an amount corresponding to 87.5 mol% of this hydroxyl group was obtained using benzophenone. And dissolved in a solution to make a 10% solution. While controlling the temperature to 250 ° C, 12-naphthoquinone diazide 4 — 1.2 equivalents of sulfonic acid chloride was added for 30 minutes. Then, the reaction was completed by maintaining the reaction temperature for 2 hours. The precipitated salt was separated by filtration and poured into a 10% equivalent of a 0.2% aqueous solution of oxalic acid of the reaction solution. The precipitated solid was filtered, washed with ion-exchanged water, and dried to obtain quinone diazide sulfonate.
  • This resist solution was spin-coated on a silicon wafer coated with 800-ounce-thick chromium oxide, and then heated on a 110 ° C hot plate. Then, the resist film was baked for 90 seconds to form a resist film having a thickness of 50,000 angstroms.
  • an acceleration voltage of 20 kV was applied to the resist film formed on the silicon wafer using an electron beam lithography system ELS-3300 (a pencil beam type manufactured by Elionix Inc.). Irradiation was performed at an energy of 9 ⁇ C / cm 2 , and 11 lines with a line width of 10 11 and a space of 0 lines were drawn.
  • a resist solution was prepared and a pattern was formed in the same manner as in Examples 1 to 3, except that the solvent was changed to the solvent shown in Table 2.
  • Table 2 shows the results. O 98/49601
  • a 500- ⁇ -thick metal chromium film is formed on a square glass substrate (commonly called 409), and a 300- A chromium oxide film was formed to create a two-layer mask substrate.
  • the solution was heated for 90 seconds on a hot plate at 110 ° C.
  • a resist film having a thickness of 5,000 ⁇ was formed.
  • Drawing was performed on this resist film in the same manner as in Examples 1 to 3. Further, development and etching were performed in the same manner as in Examples 1 to 3. Then, the substrate was immersed in N-methylpyrrolidone at 35 ° C for 180 seconds, rinsed with pure water, and the resist film was peeled off. In this way, a photomask was created.
  • a positive resist composition containing an alkali-soluble phenol resin, a quinone diazide sulfonic acid ester, and a solvent, which has an adhesive property with a light-shielding film or an interference film.
  • An excellent positive resist composition for producing a photomask is provided.
  • a positive resist composition for producing a photomask which has excellent adhesion to a light-shielding film or an interference film and excellent storage stability.
  • the positive resist composition for producing a photomask of the present invention not only has excellent resist characteristics such as sensitivity, resolution, pattern cross-sectional shape, and remaining film ratio, particularly in an electron beam lithography method, Because of its excellent adhesion to the light-shielding film and the interference film, peeling and side-etching of the resist film in the developing step and the etching step are suppressed. Furthermore, the positive resist composition of the present invention has excellent storage stability, and can be mass-produced. In addition, since an aqueous inorganic developer can be used, there is no problem of deteriorating the working environment due to evaporation of the organic solvent, and waste liquid treatment is easy.

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  • Materials For Photolithography (AREA)

Abstract

L'invention concerne une composition de photorésine positive permettant de préparer un photomasque, qui contient une résine phénolique soluble dans les alcalis (A), un ester quinonediazidesulfonique (B) et un solvant (C), caractérisée par le fait que le solvant (C) contient un composé cétonique linéaire, ramifié ou cyclique (C1) renfermant 6 à 8 atomes de carbone. L'invention concerne également un procédé permettant de préparer un photomasque au moyen de ladite composition de photorésine positive.
PCT/JP1998/001964 1997-04-30 1998-04-30 Composition de photoresine positive pour photomasque WO1998049601A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP9/126530 1997-04-30
JP12653097 1997-04-30
JP13426697 1997-05-08
JP9/134266 1997-05-08

Publications (1)

Publication Number Publication Date
WO1998049601A1 true WO1998049601A1 (fr) 1998-11-05

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Application Number Title Priority Date Filing Date
PCT/JP1998/001964 WO1998049601A1 (fr) 1997-04-30 1998-04-30 Composition de photoresine positive pour photomasque

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Country Link
WO (1) WO1998049601A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002341521A (ja) * 2001-05-17 2002-11-27 Sumitomo Chem Co Ltd 感放射線性樹脂組成物
WO2013047195A1 (fr) * 2011-09-30 2013-04-04 Hoya株式会社 Ebauche de moule, moule maître, moule de copie et procédé de fabrication d'ébauche de moule

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JPH04362645A (ja) * 1991-06-11 1992-12-15 Sumitomo Chem Co Ltd ポジ型レジスト組成物
JPH0534919A (ja) * 1991-04-26 1993-02-12 Sumitomo Chem Co Ltd ポジ型レジスト組成物
JPH07209861A (ja) * 1994-01-18 1995-08-11 Nippon Kayaku Co Ltd ポジ型感放射線性樹脂組成物
JPH07225477A (ja) * 1993-05-06 1995-08-22 Nippon Kayaku Co Ltd ポジ型感放射線性樹脂組成物
JPH0844054A (ja) * 1994-07-26 1996-02-16 Tokyo Ohka Kogyo Co Ltd ポジ型レジスト組成物
JPH08305014A (ja) * 1995-05-09 1996-11-22 Sumitomo Chem Co Ltd ポジ型レジスト組成物
JPH09160231A (ja) * 1995-12-11 1997-06-20 Tokyo Ohka Kogyo Co Ltd ポジ型ホトレジスト塗布液
JPH09211845A (ja) * 1996-02-02 1997-08-15 Tokyo Ohka Kogyo Co Ltd ポジ型ホトレジスト塗布液
JPH1010711A (ja) * 1996-06-19 1998-01-16 Mitsubishi Chem Corp 感放射線性塗布組成物
JPH1069075A (ja) * 1996-08-29 1998-03-10 Tokyo Ohka Kogyo Co Ltd ポジ型レジスト組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0534919A (ja) * 1991-04-26 1993-02-12 Sumitomo Chem Co Ltd ポジ型レジスト組成物
JPH04362645A (ja) * 1991-06-11 1992-12-15 Sumitomo Chem Co Ltd ポジ型レジスト組成物
JPH07225477A (ja) * 1993-05-06 1995-08-22 Nippon Kayaku Co Ltd ポジ型感放射線性樹脂組成物
JPH07209861A (ja) * 1994-01-18 1995-08-11 Nippon Kayaku Co Ltd ポジ型感放射線性樹脂組成物
JPH0844054A (ja) * 1994-07-26 1996-02-16 Tokyo Ohka Kogyo Co Ltd ポジ型レジスト組成物
JPH08305014A (ja) * 1995-05-09 1996-11-22 Sumitomo Chem Co Ltd ポジ型レジスト組成物
JPH09160231A (ja) * 1995-12-11 1997-06-20 Tokyo Ohka Kogyo Co Ltd ポジ型ホトレジスト塗布液
JPH09211845A (ja) * 1996-02-02 1997-08-15 Tokyo Ohka Kogyo Co Ltd ポジ型ホトレジスト塗布液
JPH1010711A (ja) * 1996-06-19 1998-01-16 Mitsubishi Chem Corp 感放射線性塗布組成物
JPH1069075A (ja) * 1996-08-29 1998-03-10 Tokyo Ohka Kogyo Co Ltd ポジ型レジスト組成物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002341521A (ja) * 2001-05-17 2002-11-27 Sumitomo Chem Co Ltd 感放射線性樹脂組成物
WO2013047195A1 (fr) * 2011-09-30 2013-04-04 Hoya株式会社 Ebauche de moule, moule maître, moule de copie et procédé de fabrication d'ébauche de moule
CN103828022A (zh) * 2011-09-30 2014-05-28 Hoya株式会社 模具坯、母模具、复制模具和模具坯的制造方法

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