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WO1999062964A1 - COPOLYMERE α-CHLOROACRYLATE DE METHYLE/α-METHYLSTYRENE PURIFIE ET COMPOSITION DE PROTECTION CONTRE UN FAISCEAU D'ELECTRONS COMPRENANT CE COPOLYMERE - Google Patents

COPOLYMERE α-CHLOROACRYLATE DE METHYLE/α-METHYLSTYRENE PURIFIE ET COMPOSITION DE PROTECTION CONTRE UN FAISCEAU D'ELECTRONS COMPRENANT CE COPOLYMERE Download PDF

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Publication number
WO1999062964A1
WO1999062964A1 PCT/JP1999/002999 JP9902999W WO9962964A1 WO 1999062964 A1 WO1999062964 A1 WO 1999062964A1 JP 9902999 W JP9902999 W JP 9902999W WO 9962964 A1 WO9962964 A1 WO 9962964A1
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WIPO (PCT)
Prior art keywords
methyl
methylstyrene
copolymer
methyl acrylate
acidic water
Prior art date
Application number
PCT/JP1999/002999
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English (en)
Japanese (ja)
Inventor
Kakuei Ozawa
Nobunori Abe
Original Assignee
Nippon Zeon Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Zeon Co., Ltd. filed Critical Nippon Zeon Co., Ltd.
Priority to KR1020007013692A priority Critical patent/KR20010052543A/ko
Publication of WO1999062964A1 publication Critical patent/WO1999062964A1/fr

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Classifications

    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/001—Removal of residual monomers by physical means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

Definitions

  • the present invention relates to a purified methyl-methacrylate acrylate ' ⁇ -methylstyrene copolymer and an electron beam resist composition containing the same, and more particularly to a resist for microfabrication of semiconductor devices and photomasks.
  • Electron beam resist composition having high sensitivity and excellent dry etching resistance suitable as a composition, a polymer suitable as a photosensitive resin component thereof, a method for producing the polymer, and the electron beam resist composition. The method of forming the butterflies.
  • a resist is applied to the surface of a silicon wafer to form a photosensitive film, and the photosensitive film is irradiated with light (ultraviolet rays, electron beams, X-rays, etc.) through a photomask to form a latent image. Then, it is developed to obtain an image by a lithographic technique that forms a negative or positive image.
  • a photomask is a component in which a pattern of an electronic circuit is formed of a material that does not transmit light on a transparent substrate, and serves as an original when an electronic circuit is printed.
  • the substrate to which an electronic circuit is to be printed is a silicon wafer when the semiconductor element such as a semiconductor integrated circuit (LSI) is a semiconductor element, but is a glass substrate or a print substrate (PWB) when a liquid crystal display panel (LCD) is used. In this case, it becomes a resin substrate. Formed on a plane like this The technology for transferring the resulting pattern onto a flat substrate is called lithography.
  • 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.
  • Chromium is used as the material for forming the light-shielding film, but silicon, iron oxide, molybdenum silicide, etc. are also used.
  • the interference film plays a role in lowering the reflectance of the light-shielding film, and usually uses chromium oxide, and is formed as a chromium oxide film on the surface of the chromium metal film (two-layer film). A three-layer type in which a thin film is also provided on the back of the chromium metal film is also used.
  • the resist composition is formed by applying a resist composition on the light-shielding film or the interference film of the mask substrate.
  • the application, drying, and pre-pressing of the resist composition are performed by photolithography technology. This can be done according to the usual method.
  • a resist composition usually contains a resin component that changes the solubility in a developing solution used in a subsequent developing step by exposure.
  • an appropriate photosensitive component is added to impart photosensitivity to the resist composition.
  • the resist film is irradiated with a radiation beam to draw a pattern.
  • electron beam lithography equipment The drawing apparatus is used, and an electron beam or a laser is scanned based on the mask pattern data, and a pattern is drawn on the resist film.
  • development is performed by an ordinary method such as immersion development using an organic solvent-based developer or an alkaline developer.
  • a negative or positive resist pattern is formed by the resist film portion that is not dissolved in the developing solution.
  • post baking and descum surface treatment with oxygen plasma or the like can be performed as necessary.
  • the 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.
  • etching methods wet etching using a liquid and dry etching using a gas. ⁇
  • a cerium nitrate ammonium-based etchant (Kodak specification) is generally used.
  • Etching is performed by a dipping method or a spray method.
  • dry etching a halogenated carbon such as carbon tetrachloride or a chlorine-based etching gas is used.
  • the remaining resist film is removed.
  • the resist film can be stripped by a chemical method using an organic solvent, concentrated sulfuric acid plus hydrogen peroxide or ozone, or a physical method using oxygen plasma or UV-ozone ashesing. It is also possible to apply a combination of technical methods. As a result, a photomask in which the mask pattern of the light-shielding film is formed can be obtained.
  • the conventional etching process is a method in which the chromium layer is corroded and dissolved with an etching chemical ( ⁇ ⁇ ⁇ ⁇ ⁇ Etch etching) was the mainstream.
  • ⁇ ⁇ ⁇ ⁇ Etch etching an etching chemical
  • side etching occurs, it is difficult to control the dimensions when forming a fine pattern.
  • the dry etching method that has recently been widely used, Since side etching does not occur, pattern dimensional control is easy, and it is particularly suitable for forming fine patterns.
  • Japanese Patent Publication No. 8-36636 discloses a copolymer of ⁇ -methyl acrylate and ⁇ -methylstyrene ( ⁇ -methyl acrylate / ⁇ -methylstyrene copolymer). It has been reported that electron beam registries containing (polymer) as a resin component have high sensitivity and excellent dry etching resistance. That is, in the copolymer, since the ⁇ -methyl acrylate unit has a highly sensitive ⁇ -chloro group at the ⁇ -position, the main chain scission efficiency by irradiation with radiation is excellent. On the other hand, ⁇ -methylstyrene unit contributes to dry etching resistance due to the protective stability of the benzene ring.
  • This publication does not disclose a specific method for producing an ⁇ -methyl methyl acrylate ⁇ ⁇ -methylstyrene copolymer.
  • a method in which the copolymer separated from the reaction mixture is dissolved in an organic solvent, and the resulting solution is dropped into a non-solvent and precipitated.
  • a method of recovering a purified copolymer has been adopted.
  • a sufficiently highly purified copolymer can be obtained by such a reprecipitation method.
  • the electron beam resist composition containing the methyl acrylate / ⁇ -methylstyrene copolymer had a serious problem that foreign matter was generated in the dry etching process and defects were likely to occur in the photomask.
  • an electron beam resist composition containing a monomethyl acrylate / ⁇ -methylstyrene copolymer is applied on a mask substrate to form a resist film, and then an electron beam Draw a pattern by scanning. Next, development is performed to form a resist pattern. It was found that when dry etching was performed after the development process, a large number of foreign substances were generated in the resist film forming the pattern.
  • An object of the present invention is to provide an electron beam resist composition containing a methyl methyl acrylate ⁇ -methylstyrene copolymer as a resin component, wherein the electron beam resist composition does not generate foreign matter during dry etching. It is to provide things.
  • Another object of the present invention is to provide a method for forming a pattern using an electron beam resist composition containing a methyl methyl acrylate ⁇ -methylstyrene copolymer as a resin component, the method comprising the steps of: Foreign matter is generated on
  • the object of the present invention is to provide a pattern forming method that does not require the use of a pattern.
  • the inventors of the present invention have conducted intensive studies to solve the problems of the prior art, and as a result, obtained as a result of copolymerization of ⁇ -methyl methyl acrylate and ⁇ -methylstyrene.
  • ⁇ -Methylstyrene copolymer was washed with acidic water with ⁇ ⁇ 6 or less to suppress the generation of foreign substances during dry etching.
  • a-methyl methacrylate and ⁇ -methylstyrene copolymer obtained by copolymerizing a-methyl methacrylate and ⁇ -methylstyrene, and purifying and recovering by a conventional method is probably treated by dry etching. It is presumed to contain small amounts of impurities (residues such as catalysts and emulsifiers, oligomers, etc.) that sometimes become foreign substances. It is presumed that these impurities are efficiently removed by washing with acidic water having ⁇ 6 or less. Alternatively, it can be considered that the copolymer itself has undergone some modification by washing with an acidic water having ⁇ 6 or less, and has been modified so that foreign matter is not generated even by dry etching.
  • the present invention is not limited in any way by these putative mechanisms. It was impossible to predict from the prior art that foreign matter during dry etching treatment was extremely significantly suppressed by washing the copolymer with an acidic water having ⁇ 6 or less. It is. The present invention has been completed based on these findings.
  • the weight average molecular weight is 100,000 to 3,000,000, the ratio of ⁇ -methyl acrylate units to ⁇ -methylstyrene units, m: n is 10: 90 to 90: Purified ⁇ -methyl methyl acrylate by washing the ⁇ -methyl methyl acrylate copolymer 'with ⁇ -methylstyrene copolymer of ⁇ ⁇ ⁇ ⁇ 6 or less —A methylstyrene copolymer is provided.
  • the ⁇ -methyl methyl acrylate- ⁇ -methylstyrene copolymer obtained by copolymerizing ⁇ -methyl methyl acrylate and ⁇ -methylstyrene is less than ⁇ 6.
  • the present invention provides a method for producing a purified methyl ⁇ -methyl acrylate / ⁇ -methylstyrene copolymer which is washed with acidic water.
  • an ⁇ -methyl methyl acrylate- ⁇ -methylstyrene copolymer obtained by copolymerization of ⁇ -methyl methyl acrylate and ⁇ -methylstyrene is obtained by ⁇ ⁇
  • a method for forming a pattern on a substrate by lithography using an electron beam resist composition containing a methyl monoacrylate methyl a-methylstyrene copolymer containing a methyl monoacrylate methyl a-methylstyrene copolymer.
  • -As a copolymer of methyl acrylate and a-methylstyrene.
  • A- Copolymer of methyl acrylate and -methylstyrene The purified ⁇ -methyl methyl acrylate / ⁇ -methylstyrene copolymer is washed with acidic water with ⁇ 6 or less, and the purified ⁇ -chloromethyl acrylate ⁇ ⁇ -methylstyrene copolymer is used.
  • a method for forming a pattern is provided. BEST MODE FOR CARRYING OUT THE INVENTION
  • ⁇ -Methyl acrylate / ⁇ -methylstyrene copolymer ⁇ -Methyl chloroacrylate / ⁇ -methylstyrene copolymer can be obtained by the usual method using ⁇ -methyl chloroacrylate and ⁇ -methylstyrene. Can be obtained by copolymerizing
  • Examples of the polymerization method include a radical polymerization method using ⁇ , a'-azobisisobutyronitrile as a catalyst, an anion polymerization method using sodium naphthene or butyllithium as a catalyst, Examples thereof include a cationic polymerization method using a metal halide as a catalyst, and a polymer modification method in which ⁇ -chloroacrylic acid ⁇ ⁇ -methylstyrene copolymer is synthesized by reacting diazomethane.
  • the radical polymerization method includes a solution polymerization method in which a monomer and a catalyst are reacted in an organic solvent, a bulk polymerization method in which only a monomer is polymerized by heating without a catalyst, and a method in which a monomer is emulsified in an aqueous medium containing an emulsifier. After that, there is an emulsion polymerization method in which a catalyst acts to carry out polymerization.
  • a copolymer obtained by any of the polymerization methods can be used, but in order to obtain a copolymer having a high molecular weight, a radical polymerization method is preferable, and among them, an emulsion polymerization method is more preferable. .
  • the molecular weight of a-methyl methyl acrylate / a-methylstyrene copolymer is measured by gel permeation chromatography (GPC) when used as a resin component of an electron beam resist composition.
  • the weight-average molecular weight in terms of monodisperse polystyrene is usually 10 000 to 3 000, preferably 0 0 000 to 2 000, and more preferably Preferably, they are 30, 00 00 to 1, 00 00, and 00 0. If the weight average molecular weight of the copolymer is too small, the reduction of the resist film during development tends to increase. Conversely, if the weight average molecular weight is too large, the coatability is poor and the uniformity of the coating film is affected. coming out.
  • the degree of dispersion (MwD) of the copolymer by GPC analysis is usually 1 to 4, preferably 1 to 2.5 when expressed as a ratio of weight average molecular weight (Mw) to Z number average molecular weight (Mn). Degree.
  • the ratio (m: n) of the a-methyl acrylate unit to the a-methylstyrene unit is usually 10:90 to 90:10, preferably 30:70 to 70: 30.
  • a copolymer having high sensitivity and excellent dry etching resistance can be obtained.
  • the weight average molecular weight, the degree of dispersion, the ratio of each monomer unit and the like of the copolymer do not substantially change even after the washing treatment with acidic water.
  • the ⁇ -methyl methyl acrylate / ⁇ -methylstyrene copolymer obtained by copolymerization of ⁇ -methyl methyl acrylate and para-methylstyrene is purified by a reprecipitation method, if necessary. After the treatment, wash with acidic water with ⁇ 6 or less.
  • Washing with acidic water is carried out by dissolving the ⁇ -methylmethyl acrylate ⁇ ⁇ -methylstyrene copolymer obtained by copolymerization of ⁇ -methyl methyl acrylate and para-methylstyrene in a suitable organic solvent. It is preferable to carry out the treatment by bringing the solution into contact with acidic water.
  • the organic solvent those which can dissolve the copolymer such as dichloromethane and chloroform are preferable and have low compatibility with water.
  • the contact between the copolymer solution and the acidic water can be suitably performed by mixing and stirring the two. If phase separation between the organic solvent and water occurs after washing, separate the aqueous phase.
  • the aqueous phase can be separated, for example, by leaving the mixed solution to separate into an organic solvent layer and an aqueous layer, and then removing the aqueous layer by decantation or the like.
  • the copolymer can be recovered from the organic solvent layer by, for example, pouring the organic solvent layer into a non-solvent such as alcohol and precipitating the copolymer. In the case where the phase separation between the organic solvent and water does not occur. In the case where the phase separation is insufficient, the mixture may be poured into a non-solvent to precipitate the copolymer.
  • a copolymer can also be precipitated by pouring a non-solvent into the organic solvent layer. The precipitated copolymer is filtered and dried according to a conventional method, and recovered as a purified copolymer.
  • the acid used to prepare the acidic water include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; and carboxylic acids such as formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid, oxalic acid, and malonic acid. Acids; sulfonic acids such as methanesulfonic acid, trifluorenesulfonic acid, and ⁇ -toluenesulfonic acid; and the like, and these can be used alone or in combination of two or more.
  • inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid
  • carboxylic acids such as formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid, oxalic acid, and malonic acid.
  • Acids; sulfonic acids such as methanesulfonic acid, trifluorenesulfonic acid, and ⁇ -toluene
  • volatile acids for example, hydrochloric acid, etc.
  • low-boiling acids for example, nitric acid, formic acid, acetic acid, trifluoroacetic acid, etc. having a boiling point of 0 to 120 ° C.
  • the acid used for the acidic water is an acid having a high boiling point or a non-volatile acid
  • the acid may remain in the copolymer after the washing treatment and deteriorate the storage stability of the electron beam resist composition.
  • volatile acids and acids having a low boiling point are preferred because they hardly remain in the copolymer and do not cause a problem in storage stability.
  • the upper limit of the pH of the acidic water used for washing is less than 6, preferably less than 5, and more preferably less than 4. If the pH of the acidic water is 6 or more, the influence of the emulsifier used in the emulsion polymerization This makes it difficult to separate the organic solvent layer from the aqueous layer.
  • the lower limit of the pH of the acidic water is preferably 1 or more. If the pH of the acidic water is less than 1, hydrolysis of the ester portion of the ⁇ -methyl methyl acrylate unit of the copolymer is likely to occur, which is not preferable. Washing with acidic water may be performed once or may be repeated two or more times, but is usually about 1 to 4 times.
  • washing with water having ⁇ 6 to 8, preferably ⁇ 6.5 to 7.5 can be performed.
  • the remaining water in the copolymer is obtained by washing with water. Can prevent cleavage of the ester bond in the copolymer, and can enhance long-term storage.
  • An electron beam resist composition containing a purified methyl acrylate / ⁇ -methylstyrene copolymer obtained by washing with acidic water is prepared by dissolving the purified copolymer in a solvent.
  • a solvent those generally used as a solvent for the resist composition can be used.
  • ketones such as acetone, methylethylketone, getylketone, cyclohexanone, and cyclopentyne
  • ethers such as ethylene glycol dimethyl ether, ethylene glycol dimethyl ether, and dioxane
  • Alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether
  • Esters such as ethyl propionate, methyl butyrate, ethyl butyrate, ethyl lactate, and getyl malonate
  • 2-oxypropionate 2-ethyl ethyl oxypropionate
  • 2-methoxypropyl Oxycarboxylates such as methyl acrylate, 2-
  • diethylene glycols and aromatic compounds are preferred because of their excellent solubility of ⁇ -chloroacrylic acid / ⁇ -methylstyrene copolymer, and particularly, diethylene glycol dimethyl ether, anisol, And ⁇ -dichloromouth benzene is preferred.
  • These solvents can be used alone or in combination of two or more.
  • a solvent for the resist as described above can be used.
  • xylene, butyl acetate, amyl acetate, getyl ketone, methyl ethyl ketone, getyl malonate, diethylene glycol dimethyl ether, anisol and the like are preferable.
  • These solvents can be used alone or in combination of two or more as a developer.
  • the pattern forming method using the resist composition of the present invention it is possible to perform a treatment with a rinse solution after development.
  • a rinse solution Usually, xylene, butyl acetate, isopropyl alcohol, methyl isobutyl ketone, and the like are preferably used as the rinse solution. These solvents may be used alone or in combination as a rinse liquid. Can be used.
  • the electron beam resist composition of the present invention can be used as a resist for forming a photomask or the like of a semiconductor element by the above-mentioned lithography technique.
  • the electron beam resist composition of the present invention is suitable as a resist for manufacturing a photomask having no shape defect, since generation of foreign matter during dry etching is suppressed.
  • the pH of the acidic water was measured by the following method.
  • Test solution volume 100 ml
  • the GPC analysis of the 15 copolymer was performed under the following conditions.
  • HLC 8120GPC (Tosoh Corporation)
  • Sample 0.1 ml injection of a sample having a concentration of 0.05 to 0.6% by weight.
  • a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample was used.
  • the weight average molecular weight is measured as follows.
  • the column Stabilize the column in a heating chamber at 40 ° C, flow THF at a temperature of 1 m / min as a solvent through the column at this temperature, and use a sample concentration of 0.05 to 0.1 wt.
  • the THF sample solution of the copolymer adjusted to 50% is injected in a range of 50 to 200 a1 for measurement.
  • the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodispersed polystyrene standard samples and the number of counts.
  • standard polystyrene samples for preparing a calibration curve for example, the molecular weights of Tosoh I. Co., Ltd.
  • the weight average molecular weight in terms of polystyrene of the copolymer (A-1) determined by GPC analysis was 338,000, and the polydispersity was 2.1.
  • copolymers (A-1) to ( ⁇ -3) obtained in the above Synthesis Examples 1 to 3 were respectively dissolved in the solvents shown in Table 1, and the resulting solutions were each dissolved in a solvent having a pore size of 0.
  • the mixture was filtered through a filter (1) to prepare a resist solution.
  • This resist solution is applied to the surface of a glass substrate with a 5-inch chrome film, and prebaked with a hot plate at 18 O: for 3 minutes to form a resist film having a thickness of 0.5 m. did.
  • the substrate on which the resist film was formed was replaced with an MR IE type dry etchant. Processed on an 8 g device.
  • the electron beam resist composition which does not generate
  • a highly purified methyl methyl acrylate / ⁇ -methylstyrene copolymer which does not generate foreign matter during dry etching, and a method for producing the same.
  • a pattern forming method in which a foreign substance is not generated during a dry etching process.
  • the resist composition for an electron beam of the present invention can be suitably used for fine processing of a semiconductor device, a photomask, and the like.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

Cette invention concerne un copolymère α-chloroacrylate de méthyle/α-méthylstyrène purifié qui est obtenu en copolymérisant un α-chloroacrylate de méthyle avec un α-méthylstyrène. On obtient ainsi un copolymère α-chloroacrylate de méthyle/α-méthylstyrène qui possède un poids moléculaire moyen en poids de 10.000 à 3.000.000 et dans lequel le rapport m : n entre les unités de α-chloroacrylate de méthyle et les unités de α-méthylstyrène varie de 10 : 90 à 90 : 10. Le copolymère est ensuite rincé en utilisant une eau acide dont le pH est inférieur à 6. Cette invention concerne également un procédé de production de ce copolymère purifié, une composition de protection contre un faisceau d'électrons comprenant ce copolymère, ainsi qu'un procédé de formation d'un diagramme à l'aide de cette composition de protection contre un faisceau d'électrons.
PCT/JP1999/002999 1998-06-04 1999-06-04 COPOLYMERE α-CHLOROACRYLATE DE METHYLE/α-METHYLSTYRENE PURIFIE ET COMPOSITION DE PROTECTION CONTRE UN FAISCEAU D'ELECTRONS COMPRENANT CE COPOLYMERE WO1999062964A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020007013692A KR20010052543A (ko) 1998-06-04 1999-06-04 정제 α- 클로로아크릴산메틸·α-메틸스티렌 공중합체 및이것을 함유하는 전자선 레지스트 조성물

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP10/155480 1998-06-04
JP15548098 1998-06-04
JP29585598 1998-10-16
JP10/295855 1998-10-16

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JP2016012104A (ja) * 2014-06-30 2016-01-21 大日本印刷株式会社 ポジ型レジスト組成物及びその製造方法、並びに、当該ポジ型レジスト組成物を用いたレジストパターンの製造方法
WO2016132722A1 (fr) * 2015-02-20 2016-08-25 日本ゼオン株式会社 Polymère, et composition de réserve de type positive
JP2017119744A (ja) * 2015-12-28 2017-07-06 日本ゼオン株式会社 重合体およびポジ型レジスト組成物
WO2017163825A1 (fr) * 2016-03-25 2017-09-28 日本ゼオン株式会社 Procédé de production d'un copolymère
JPWO2016132724A1 (ja) * 2015-02-20 2017-11-30 日本ゼオン株式会社 重合体およびポジ型レジスト組成物
WO2018155214A1 (fr) * 2017-02-21 2018-08-30 日本ゼオン株式会社 Polymère et solution de réserve de type positif
JPWO2017130870A1 (ja) * 2016-01-29 2018-11-22 日本ゼオン株式会社 重合体、ポジ型レジスト組成物、およびレジストパターン形成方法
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