WO2000057249A1 - Revelateur de reserve et procede de formation d'un motif de reserve utilisant celui-ci - Google Patents

Revelateur de reserve et procede de formation d'un motif de reserve utilisant celui-ci Download PDF

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Publication number
WO2000057249A1
WO2000057249A1 PCT/JP2000/001640 JP0001640W WO0057249A1 WO 2000057249 A1 WO2000057249 A1 WO 2000057249A1 JP 0001640 W JP0001640 W JP 0001640W WO 0057249 A1 WO0057249 A1 WO 0057249A1
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WO
WIPO (PCT)
Prior art keywords
resist
developer
forming
resist pattern
copolymer
Prior art date
Application number
PCT/JP2000/001640
Other languages
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.
Publication of WO2000057249A1 publication Critical patent/WO2000057249A1/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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/325—Non-aqueous compositions

Definitions

  • the present invention relates to a resist developer and a method for forming a resist pattern using the same.
  • the present invention relates to a resist developer and a method for forming a resist pattern using the same. More specifically, the present invention relates to a resist developing solution capable of forming a resist pattern having good dimensional accuracy in which a pattern dimensional difference between an end portion and a central portion of a substrate is suppressed in forming a resist pattern by an electron beam, and The present invention relates to a method for efficiently developing a resist pattern by a paddle method and forming a resist pattern with good dimensional accuracy.
  • a resist is applied to the surface of a silicon wafer to form a photosensitive film, and a latent image is formed by irradiating light or ionizing radiation, and then developed to form a negative or positive image.
  • An image is obtained by the lithography technique to be formed.
  • Lithography equipment used in this technology is roughly classified into a mask pattern transfer method using light or X-rays, and a drawing method using beam scanning of electrons or ions. The latter drawing method is widely used in the manufacture of mask patterns and circuit patterns such as ASIC.
  • a developing method a method of immersing a substrate in a bath filled with a developing solution (dipping method), a method of spraying a developing solution onto a substrate (spraying method), and a method using a surface tension of the substrate are used.
  • a method of placing a developer on the substrate surface is generally used.
  • the dipping method and the spraying method are relatively insensitive to the temperature difference of the developer, and can perform stable development processing.
  • the dip method since the developer is stored in a tank and used, the composition of a developer containing a low-boiling solvent changes little by little.
  • the spray method the development state changes depending on the spray conditions, so it takes time to study the conditions and the management of the conditions is strict.
  • the amount of developing solution used can be kept to a minimum, and therefore, especially when processing large substrates or a large number of substrates, development using the paddle method, which has less impact on the environment, is advantageous. is there.
  • the paddle method is a method in which an amount sufficient to hold the substrate with its surface tension, that is, a small amount of a developing solution is applied to the substrate to perform development processing. Therefore, in this method, generally, the thickness of the developing solution layer held on the substrate by surface tension becomes thinner toward the edge of the substrate. For this reason, the degree of temperature change of the developing solution accompanying volatilization of the developing solution is large at the edge of the substrate and small at the center of the substrate. As a result, there is a problem that the developing characteristics are different between the central portion and the end portion of the substrate, resulting in a difference in pattern dimensions. The larger the size of the substrate and the finer the pattern, the larger the difference in pattern dimension.
  • a polymer compound such as PMMA (polymethyl methacrylate) and poly- ⁇ -methylstyrene is generally used.
  • Organic solvent is used as a developing solution.
  • a developer for resist materials for example, a developer for a positive-type radiation resist material containing a copolymer having monomethylstyrene units and (meth) acrylate units has a boiling point of 7%. It has been proposed to use fatty acid esters at 0 to 180 ° C. (Japanese Patent Application Laid-Open No. 61-24949), but in this case, the boiling point is actually 150 ° C. It has only been confirmed that high-contrast development can be achieved using a developing solution at or below ° C.
  • a cyclic ether compound having a four-membered ring or more and six-membered ring or less which is a good solvent for the copolymer is used as a developer for a resist material containing an ⁇ -methylstyrene-based copolymer. It has been proposed to use a mixed solvent composed of a copolymer and a poor solvent (Japanese Patent Application Laid-Open No. Sho 61-22941). Also in this case, the boiling point of the cyclic ether compound is 150 ° C. or less. Disclosure of the birthplace
  • a first object of the present invention is to provide a resist pattern having good dimensional accuracy in which a pattern dimensional difference between an end portion and a central portion of a substrate is suppressed in forming a resist pattern using an electron beam.
  • a second object is to provide a resist developer which can be formed, and to provide a method for forming a resist pattern with good dimensional accuracy by using the developer to efficiently develop by a paddle method. It is in.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, by using a developer containing a high boiling point organic solvent having a boiling point at normal pressure higher than a certain value as a developing solution, It has been found that the first object can be achieved, and that the second object can be achieved by performing development processing by a paddle method using the developer containing the high boiling point organic solvent.
  • the present invention has been completed based on such findings.
  • a first object of the present invention is to develop a resist material containing a copolymer of a styrene-based monomer and an acryl-based monomer in the formation of a resist pattern by an electron beam.
  • a resist developer which comprises an organic solvent having a boiling point at normal pressure higher than 180 ° C.
  • a second object of the present invention is to form a latent image by irradiating an electron beam to a photosensitive film made of a resist material containing a copolymer of a styrene monomer and an acrylic monomer.
  • the above-mentioned resist developing solution is subjected to development by a paddle method, and the above-mentioned resist developing solution is developed by a method of forming a resist pattern.
  • the resist developer of the present invention is used for forming a resist pattern by an electron beam.
  • a resist material for forming the resist pattern a copolymer of a styrene-based monomer and an acrylic monomer is used. Is used, this is an electron beam! It is suitable for pattern formation by H.
  • the structural unit ratio (based on moles) of this copolymer is the structural unit derived from a styrene monomer and the structural unit derived from an acrylic monomer. The order is usually 80 Z 20 to 20 Z 80, preferably 75 25 to 25 Z 75, more preferably 70 Z 30 to 30 Z 70.
  • the styrene monomer is a monomer having a styrene structure, and specific examples thereof are styrene, 4-methylstyrene, 4-propylstyrene, 4-isopropylstyrene, 4-butylstyrene, 4-isobutylstyrene, and 3,4-dimethylstyrene.
  • Styrene such as len, 4-ethyl-13-methylstyrene, 4-hydroxyquinstyrene, 4-hydroxy-13-methylstyrene, 4-methoxystyrene, its 4-substituted product, or its 3-, 4-substituted product ⁇ -methylstyrene, 4-methyl-1-methylstyrene, 4-propyl-1-methylstyrene, 4-isopropyl-1-methylstyrene, 4-butyl-1-methylstyrene, 4-isobutyl-1- ⁇ -methylstyrene, 3,4-dimethyl-1-methylstyrene ⁇ -methylstyrene, 4-ethyl-3-methyl-1- ⁇ -methylstyrene, 4-hydroxy Monomethylstyrene such as 1-methylstyrene, 4-hydroxy-1-methyl-1-methylstyrene, 4-methoxy-1- ⁇ -methylstyrene, 4-substituted product thereof, or
  • styrenic monomers may be used alone or in combination of two or more.
  • ⁇ -methylstyrene compounds ⁇ -methylstyrene, 4-substituted products thereof, Or its 3- or 4-substitution
  • ⁇ -methylstyrene compounds ⁇ -methylstyrene, 4-substituted products thereof, Or its 3- or 4-substitution
  • the acryl-based low molecular weight is an atalylic acid derivative, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, pill (meth) acrylate, and (meth) acrylic acid. Isopropyl acid, butyl (meth) acrylate, etc.
  • (Meth) alkyl acrylate (meth) acrylic acid such as phenyl (meth) acrylate, 4-methacrylic acid 4-chlorophenyl; benzyl (meth) acrylate, benzyl (meth) acrylate, 3,4-dimethyl (meth) acrylate
  • Aralkyl (meth) acrylates such as benzyl; ⁇ -haloacryls such as methyl monochloroacrylate, ethylethyl monochloroacrylate, propyl monobromoacrylate, isopropyl ⁇ -chloroacrylate, and butyl monobromoacrylate Alkyl acrylates;
  • Aryl monohaloacrylates such as phenyl monochloroacrylate; benzyl aralkyls such as benzyl ⁇ 2-bromoacrylate and 3,4-dimethylbenzyl ⁇ -chloroacrylate; monocyanoacrylic Methyl acrylate,
  • acryl-based monomers may be used alone or in combination of two or more.
  • the haloacrylate ester-based compounds (na-halo) are preferred because of their high sensitivity.
  • the copolymer is prepared by charging each of the above monomers so as to be a polymer in the ratio of each of the structural units described above, and polymerizing the monomers by solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, or the like. And obtained by
  • the weight average molecular weight of the copolymer is not particularly limited, but the weight average molecular weight in terms of polystyrene (hereinafter sometimes referred to as Mw) calculated by gel permeation chromatography (GPC) using tetrahydrofuran is 50, Preferred are those with a force of 0,000, 1,000,000.
  • the resist material is a solution obtained by dissolving the above copolymer in an organic solvent such as methyl phenyl ether, diethylene glycol dimethyl ether, or o-dichlorobenzene. It can contain various additives commonly used in resist materials for forming a resist pattern, such as a surfactant.
  • the method for preparing the resist material is not particularly limited.
  • the above-mentioned copolymer of a styrene-based monomer and an acrylic-based monomer, and various additives used as needed are added to the above-mentioned appropriate organic solvent.
  • the desired resist material can be prepared by dissolving and then, if necessary, filtering by using a membrane filter or the like.
  • the resist developer of the present invention contains an organic solvent having a boiling point at normal pressure higher than 180 ° C, but has a boiling point at normal pressure in the range of 185-250 ° C. Those containing an organic solvent having a melting point of 30 ° C. or lower are preferred. Further, the developer may contain L as one kind of the organic solvent, or L as two or more kinds.
  • a developer containing two or more kinds of organic solvents is preferable because the ratio of the remaining film and the resolution can be well balanced.
  • a combination having a boiling point difference of 100 ° C. or less, preferably 80 ° C. or less is particularly preferable because there is no change in pattern dimension.
  • the developing solution of the present invention is used as a liquid at a temperature in a developing process. Therefore, even if a certain substance alone is solid at the development processing temperature, it can be used as a developer as long as it becomes liquid at the development processing temperature when mixed with another organic solvent.
  • organic solvent having a boiling point at normal pressure higher than 180 ° C. include the following. The number in parentheses after the compound name is the boiling point at normal pressure (in units). Where the decimal places are rounded or truncated values. If the boiling point has a range, the upper limit is described.
  • Halogenated hydrocarbons 1,2,4-trichlorobenzene benzene (210), 1-chloronaphthalene (259), 0-bromobenzene (224), 1-bromonaphthalene (281), 1-chloro Mouth octane (182), black mouth decane (223), etc.
  • Ketones acetonylacetone (191), holon (197), acetofenone (202), isophorone (215), and the like.
  • Ethers dihexyl ether (226), butyl phenyl ether (210), n-pentyl phenyl ether (214), isopentyl phenyl ether (225), benzyl ethyl ether (189) , Diphenyl ether (258), dibenzyl ether (298), veratrol (206), 1,2-dibutoxetane (203), diethylene glycol getyl ether (18
  • esters 2-ethylhexyl acetate (198), benzyl acetate (213), isopentyl butyrate (184), isopentyl isovalerate (194), methyl benzoate (199), ethyl benzoate (213) ), Propyl benzoate (231), butyl benzoate (250), isopentyl benzoate (262), benzyl benzoate (324), ethyl ethyl cinnamate (271), a-peptirolactone (20
  • Fatty acids valeric acid (185), cabronic acid (205), 2-ethylbutyric acid (190), caprylic acid (239), 2-ethylhexanoic acid (227), oleic acid (360), etc. .
  • Nitrile group-containing compounds benzonitrile (191), ⁇ -tolunitrinole (233), lactonitrile (184), ethylene cyanohydrin (220), adiponitrile (295) and the like.
  • Nitro group-containing compounds nitrobenzene (210), 0-nitroanisole (277) and the like.
  • esters, amides, sulfoxidesulfones are preferred, and particularly esters having a boiling point at normal pressure of 185 ° C to 250 ° C and a melting point of 30 ° C or less, Amides and sulfoxide'sulfones are preferred.
  • an organic solvent having a boiling point at normal pressure of 180 ° C. or lower can be mixed with the developer of the present invention as long as the effects of the present invention are not impaired.
  • the amount may be 25% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less based on the whole developer. Even if an organic solvent having a boiling point at normal pressure of 180 ° C or lower is mixed with a solvent having a boiling point at normal pressure of 150 ° C or higher, the effect of the present invention is hardly impaired. Absent.
  • the method for developing the above-mentioned resist material using the developing solution of the present invention is not particularly limited. However, as described in the method for forming a resist pattern of the present invention described below, if the development processing is performed by a paddle method, , To maximize its effect.
  • a resist material containing a copolymer of the styrene-based monomer and the acryl-based monomer is applied on a substrate such as a silicon wafer by a spinner or the like. Then, it is dried to form a photosensitive film. Next, after irradiating the photosensitive film with an electron beam to form a latent image, the substrate is usually rotated at a speed of 100 to 500 rotations per minute, usually at a temperature of 10 to 30 ° C., preferably 1 to 30 ° C.
  • the developer of the present invention at 5 to 25 ° C.
  • the substrate is dripped until spread on the substrate (usually 0.5 to 30 seconds, preferably 1 to 15 seconds), and the surface tension is applied to the substrate. And load the developer.
  • the rotation of the substrate is stopped, or the rotation is reduced to a low speed of 50 rotations per minute or less, usually for 0.5 to 30 minutes, preferably for 1 to 15 minutes, about 10 to 30 ° C,
  • the development is preferably carried out at a temperature in the range of 15 to 25 ° C.
  • the rinsing liquid preferably has a boiling point at normal pressure of 150 ° C. or lower, more preferably 120 ° C. or lower.
  • the developing step and the rinsing step are alternately repeated about 2 to 10 times. Can also be.
  • UPE high density polyethylene
  • the electron beam irradiator J BX-700 OMV [manufactured by JEOL Ltd.] was used to adjust the amount of electron beam irradiation on the resist film formed on the blanks at an accelerating voltage of 20 kV to form a 132 mm square Draw a 1.0 m line & space pattern. After pattern drawing, a developer having the composition shown in Table 1 was dropped on the substrate for 3 seconds at 23 ° C while rotating the substrate at a speed of 120 rotations per minute, so that the developer spread over the entire substrate surface. .
  • the rotation was stopped at the same time as the supply of the developing solution was stopped, and while maintaining the temperature, the developing solution was left for 180 seconds in a state where the developing solution was held at a surface tension on the substrate to perform development.
  • methyl isobutyl ketone (boiling point 118 ° C) was dropped as a rinsing liquid for 20 seconds while rotating the substrate at 300 rpm to rinse the substrate.
  • the rinse liquid was dried and removed by a nitrogen stream to obtain a positive resist pattern.
  • the pattern dimensions were measured using an electronic scanning microscope, and the difference between the maximum value and the minimum value was determined. The value obtained by dividing this difference by the pattern dimension (pattern dimension difference rate) was used as an index of pattern dimension variation. Results obtained using each developer are shown in Table 1.
  • the resist pattern formed by developing with the developing solution of the present invention has a smaller pattern and deviation than the resist pattern formed by developing with the developing solution of the comparative example.
  • the dimensional difference ratio is small.
  • the components are hardly volatilized and the composition change is small. Therefore, if the developing solution of the present invention is used, the developing treatment by the paddle method can be performed on the substrate. It is possible to obtain a resist pattern having good dimensional stability, in which a pattern dimensional difference is suppressed. Also, with this developer, the composition of the developer is stable for a long period of time even when the developer is stored in a tank as in the dip method, so that it is expected that a good resist pattern can be continuously obtained.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

L'invention concerne un révélateur de réserve contenant un solvant organique ayant un point d'ébullition supérieur à 180 °C sous une pression normale, conçu pour développer un matériau de réserve contenant un polymère d'un monomère de styrène et un monomère acrylique et servant à former un motif de réserve à l'aide d'un faisceau électronique. L'invention concerne également un procédé permettant de former un motif de réserve par formation d'une image latente sur un film photosensible fait dudit matériau de réserve par application d'un faisceau électronique et exécution du développement au moyen d'un agitateur à palettes faisant appel audit révélateur. L'utilisation du révélateur de réserve permet de former un motif de réserve sur un substrat avec suppression d'erreur dimensionnelle de motif et bonne stabilité dimensionnelle même par développement par paire au moyen d'un agitateur à palettes.
PCT/JP2000/001640 1999-03-19 2000-03-17 Revelateur de reserve et procede de formation d'un motif de reserve utilisant celui-ci WO2000057249A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7471599A JP2000267297A (ja) 1999-03-19 1999-03-19 レジスト現像液および現像方法
JP11/74715 1999-03-19

Publications (1)

Publication Number Publication Date
WO2000057249A1 true WO2000057249A1 (fr) 2000-09-28

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WO (1) WO2000057249A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI281101B (en) 2000-02-28 2007-05-11 Mitsubishi Electric Corp Developing process, process for forming pattern and process for preparing semiconductor device using same
JP5629520B2 (ja) * 2010-07-28 2014-11-19 富士フイルム株式会社 パターン形成方法及びこの方法に用いられる有機系処理液
JP7215005B2 (ja) * 2018-07-23 2023-01-31 日本ゼオン株式会社 重合体及びその製造方法、ポジ型レジスト組成物、並びにレジストパターン形成方法
US20230063003A1 (en) * 2020-01-17 2023-03-02 Zeon Corporation Copolymer, positive resist composition, and method of forming resist pattern

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5983159A (ja) * 1982-11-02 1984-05-14 Nec Corp レジスト像の形成方法
US5268260A (en) * 1991-10-22 1993-12-07 International Business Machines Corporation Photoresist develop and strip solvent compositions and method for their use
JPH06242617A (ja) * 1993-02-18 1994-09-02 Toagosei Chem Ind Co Ltd ポジ型電子線レジストのパターン形成方法
JPH086261A (ja) * 1994-04-21 1996-01-12 Toray Ind Inc 感放射線レジスト用現像液
JPH08160635A (ja) * 1994-12-12 1996-06-21 Ricoh Co Ltd ドライフィルムレジスト用現像液およびそのリンス液
JP2000039717A (ja) * 1998-07-24 2000-02-08 Fujitsu Ltd レジストパターンの形成方法および半導体装置の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5983159A (ja) * 1982-11-02 1984-05-14 Nec Corp レジスト像の形成方法
US5268260A (en) * 1991-10-22 1993-12-07 International Business Machines Corporation Photoresist develop and strip solvent compositions and method for their use
JPH06242617A (ja) * 1993-02-18 1994-09-02 Toagosei Chem Ind Co Ltd ポジ型電子線レジストのパターン形成方法
JPH086261A (ja) * 1994-04-21 1996-01-12 Toray Ind Inc 感放射線レジスト用現像液
JPH08160635A (ja) * 1994-12-12 1996-06-21 Ricoh Co Ltd ドライフィルムレジスト用現像液およびそのリンス液
JP2000039717A (ja) * 1998-07-24 2000-02-08 Fujitsu Ltd レジストパターンの形成方法および半導体装置の製造方法

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