WO2011004528A1 - Procédé de formation de motif - Google Patents

Procédé de formation de motif Download PDF

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Publication number
WO2011004528A1
WO2011004528A1 PCT/JP2010/002831 JP2010002831W WO2011004528A1 WO 2011004528 A1 WO2011004528 A1 WO 2011004528A1 JP 2010002831 W JP2010002831 W JP 2010002831W WO 2011004528 A1 WO2011004528 A1 WO 2011004528A1
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WO
WIPO (PCT)
Prior art keywords
group
resist film
pattern
resist
cyclic ether
Prior art date
Application number
PCT/JP2010/002831
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English (en)
Japanese (ja)
Inventor
遠藤政孝
笹子勝
Original Assignee
パナソニック株式会社
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 パナソニック株式会社 filed Critical パナソニック株式会社
Publication of WO2011004528A1 publication Critical patent/WO2011004528A1/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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2037—Exposure with X-ray radiation or corpuscular radiation, through a mask with a pattern opaque to that radiation
    • G03F7/2039—X-ray radiation

Definitions

  • the present invention relates to a pattern forming method used in a semiconductor device manufacturing process or the like.
  • a positive chemically amplified resist material having the following composition is prepared.
  • pattern exposure is performed by selectively irradiating the resist film 2 with exposure light composed of extreme ultraviolet rays having a numerical aperture (NA) of 0.25 and a wavelength of 13.5 nm.
  • NA numerical aperture
  • the degree of vacuum at the time of exposure is 1 ⁇ 10 ⁇ 6 Pa.
  • the resist film 2 subjected to pattern exposure is heated at a temperature of 105 ° C. for 60 seconds by a hot plate.
  • the heated resist film 2 is developed with a tetramethylammonium hydroxide developer having a concentration of 2.38 wt%, and the resist film 2 is not exposed as shown in FIG. A resist pattern 2a having a line width of 30 nm is obtained.
  • the conventional pattern formation method using the chemically amplified resist material has a problem that the upper part of the pattern does not dissolve and a so-called overhead shape (T-top shape) occurs.
  • an object of the present invention is to prevent a pattern defect in extreme ultraviolet exposure and to form a fine pattern having a good shape.
  • the inventors of the present application have studied various causes of pattern defects that have a head-shaped shape in extreme ultraviolet exposure, and as a result, in a vacuum (for example, a pressure of 1 ⁇ 10 ⁇ 6 Pa or less) that is an atmosphere of extreme ultraviolet exposure. It has been concluded that the photoacid generator tends to volatilize from the resist film, and the amount of acid necessary for the exposed portion of the resist film is insufficient. The volatilization of the photoacid generator from the resist film is more because the volatilization ratio in the photoacid generator increases as the resist film used for forming a fine pattern by extreme ultraviolet exposure becomes thinner (about 50 nm or less). Become prominent.
  • the inventors of the present invention have obtained the following knowledge as a result of intensive studies to prevent volatilization of the photoacid generator in extreme ultraviolet exposure. That is, at least a part of the acid leaving group bonded to the main polymer in the positive chemically amplified resist material is a cyclic ether group forming an acetal bond substituted with a hydrogen atom of a carboxyl group, or a positive type In addition to the main polymer, a polymer having a cyclic ether group that forms an acetal bond in which at least a part of the acid leaving group is substituted with a hydrogen atom of a carboxyl group is added to the chemically amplified resist material. .
  • the cyclic ether group that forms an acetal bond substituted with the hydrogen atom of the carboxyl group is easily decomposed by an acid, the dissolution of the exposed portion of the resist film in the developer proceeds smoothly, and the pattern has a head-on shape. Can be prevented. Therefore, a good pattern can be formed when a resist film having a thickness of 50 nm or less in which acid deficiency is remarkable during extreme ultraviolet exposure is used.
  • the present invention is made based on the above-described knowledge, and specifically, is realized by the following configuration.
  • the first pattern forming method includes a step of forming a resist film having a film thickness of 50 nm or less from a positive chemically amplified resist material on a substrate, and exposure light comprising extreme ultraviolet rays on the resist film.
  • the pattern exposure is performed by selectively irradiating, the step of heating the resist film subjected to the pattern exposure, and development on the heated resist film to form a resist pattern from the resist film.
  • the chemically amplified resist material is a cyclic ether group that forms an acetal bond in which at least a part of the acid leaving group bonded to the main polymer is substituted with a hydrogen atom of a carboxyl group.
  • the positive chemically amplified resist material is a cyclic ether in which at least part of the acid leaving group bonded to the main polymer forms an acetal bond in which a hydrogen atom of a carboxyl group is substituted. It is a group.
  • This cyclic ether group is easily decomposed by the acid generated in the exposed portion of the resist film and becomes alkali-soluble. Therefore, in the case of a resist film having a film thickness of 50 nm or less using extreme ultraviolet light as the exposure light, Even if a part of the acid generator volatilizes, the decrease of the volatilized photoacid generator can be compensated. As a result, pattern defects such as a head shape can be prevented, and a pattern having a good shape can be formed.
  • the cyclic ether group forming an acetal bond substituted with a hydrogen atom of the carboxyl group may be about 10% or more and about 50% or less of the acid leaving groups in the chemically amplified resist material.
  • the amount is too small, the effect is difficult to be obtained, and when the amount is too large, the solubility becomes too high, which may affect the unexposed portion of the resist film. More preferably, it is about 20% or more and about 40% or less.
  • a second pattern forming method includes a step of forming a resist film having a film thickness of 50 nm or less from a positive chemically amplified resist material on a substrate, and exposure light comprising extreme ultraviolet rays on the resist film.
  • the pattern exposure is performed by selectively irradiating, the step of heating the resist film subjected to the pattern exposure, and development on the heated resist film to form a resist pattern from the resist film
  • the chemically amplified resist material includes a main polymer and a polymer that is a cyclic ether group that forms an acetal bond in which at least a part of the acid leaving group is substituted with a hydrogen atom of a carboxyl group.
  • the second pattern forming method similarly to the first pattern forming method, pattern defects such as a head-up shape can be prevented and a pattern having a good shape can be formed.
  • the main polymer contains a polymer in which at least a part of the acid leaving group is a cyclic ether group forming an acetal bond substituted with a hydrogen atom of a carboxyl group, so that the solubility control in the resist film can be controlled. It can be done easily.
  • the ratio of the polymer, which is a cyclic ether group forming an acetal bond substituted with a hydrogen atom of a carboxyl group according to the present invention, to the main polymer may be about 10 wt% or more and about 50 wt% or less. However, the present invention is not limited to this range.
  • the remainder of the acid leaving group includes a t-butyl group, a t-butyloxycarbonyl group, 1-
  • An ethoxyethyl group, a methoxymethyl group, a 2-methyladamantyl group, or a 2-ethyladamantyl group can be used.
  • a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, or a 2-2H-pyranyl group can be used as the cyclic ether group.
  • the wavelength of the extreme ultraviolet light may be 13.5 nm.
  • the higher the degree of vacuum during extreme ultraviolet exposure the greater the volatilization amount of the photoacid generator.
  • the present invention is applicable even when the degree of vacuum is as high as 1 ⁇ 10 ⁇ 8 Pa or less.
  • a pattern defect in extreme ultraviolet exposure can be prevented and a fine pattern having a good shape can be obtained.
  • FIG. 1A to FIG. 1D are cross-sectional views showing respective steps of the pattern forming method according to the first embodiment of the present invention.
  • 2A to 2D are cross-sectional views showing respective steps of the pattern forming method according to the second embodiment of the present invention.
  • FIG. 3A to FIG. 3D are cross-sectional views showing respective steps of the conventional pattern forming method.
  • a positive chemically amplified resist material having the following composition is prepared.
  • pattern exposure is performed by selectively irradiating the resist film 102 with exposure light composed of extreme ultraviolet rays having a numerical aperture (NA) of 0.25 and a wavelength of 13.5 nm.
  • NA numerical aperture
  • the degree of vacuum at the time of exposure is set to 1 ⁇ 10 ⁇ 6 Pa.
  • the resist film 102 subjected to pattern exposure is heated at a temperature of 105 ° C. for 60 seconds by a hot plate.
  • the heated resist film 102 is developed with a tetramethylammonium hydroxide developer having a concentration of 2.38 wt%, and the resist film 102 is not exposed as shown in FIG. And a resist pattern 102a having a line width of 30 nm is obtained.
  • At least a part of the acid leaving group (t-butyl group) bonded to the main polymer is added to the chemically amplified resist material constituting the resist film 102 by hydrogen of a carboxyl group. It is a cyclic ether group (2-tetrahydropyranyl group) that forms an acetal bond substituted with an atom.
  • This 2-tetrahydropyranyl group is easily decomposed by the acid generated in the exposed portion of the resist film 102 and becomes alkali-soluble, so that the decrease in the volatilized photoacid generator can be compensated. As a result, pattern defects such as a head-up shape are prevented, and the resist pattern 102a having a good shape can be formed.
  • a positive chemically amplified resist material having the following composition is prepared.
  • pattern exposure is performed by selectively irradiating the resist film 202 with exposure light composed of extreme ultraviolet rays having a numerical aperture (NA) of 0.25 and a wavelength of 13.5 nm.
  • NA numerical aperture
  • the degree of vacuum at the time of exposure is set to 1 ⁇ 10 ⁇ 6 Pa.
  • the resist film 202 subjected to pattern exposure is heated at a temperature of 105 ° C. for 60 seconds by a hot plate.
  • the heated resist film 202 is developed with a tetramethylammonium hydroxide developer having a concentration of 2.38 wt%, and the resist film 202 is not exposed as shown in FIG. A resist pattern 202a having a line width of 30 nm is obtained.
  • the chemically amplified resist material constituting the resist film 202 is carboxylated.
  • a polymer containing a cyclic ether group (2-tetrahydrofuranyl group) that forms an acetal bond substituted with a hydrogen atom of the group is added. Since the 2-tetrahydrofuranyl group is easily decomposed by an acid generated in the exposed portion of the resist film 202 and becomes alkali-soluble, a decrease in the volatilized photoacid generator can be compensated. As a result, pattern defects such as a head-up shape can be prevented, and the resist pattern 202a having a good shape can be formed.
  • an additive polymer containing a cyclic ether group that forms an acetal bond substituted with a hydrogen atom of a carboxyl group as an acid leaving group is included. Therefore, the solubility can be easily controlled.
  • a t-butyl group is used as the acid leaving group contained in the main polymer.
  • the t-butyl group is not limited to this, and the t-butyloxycarbonyl group, 1-ethoxyethyl group, methoxy group is not limited thereto.
  • a methyl group, a 2-methyladamantyl group or a 2-ethyladamantyl group can be used.
  • a 2-tetrahydropyranyl group is used as the cyclic ether group
  • a 2-tetrahydrofuranyl group is used as the cyclic ether group.
  • a 2-2H-pyranyl group can be used.
  • the chemically amplified resist material and the exposure conditions used in each of the above embodiments are examples, and can be appropriately changed as long as the effects of the present invention can be obtained.
  • the pattern forming method according to the present invention can prevent a pattern defect in extreme ultraviolet exposure and obtain a fine pattern having a good shape, and is useful for a pattern forming method used in a semiconductor device manufacturing process or the like. .

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

Selon l'invention, un film de résist (102) ayant une épaisseur de film de 50 nm ou moins, est formé, à partir d'un matériau de résist à amplification chimique de type positif, sur un substrat (101). Ultérieurement, le film de résist (102) est irradié par une lumière d'exposition comprenant une lumière ultraviolette extrême d'une manière sélective pour obtenir une exposition de motif. Le film de résist (102) qui a été soumis à l'exposition de motif est chauffé, et le film de résist chauffé (102) est développé pour former un motif de résist (102a) à partir du film de résist (102). Dans le matériau de résist à amplification chimique, au moins certains des groupes partants acides qui sont liés au polymère principal sont des groupes éther cycliques chacun capable de former une liaison acétal qui est substituée par un atome d'hydrogène contenu dans un groupe carboxyle.
PCT/JP2010/002831 2009-07-09 2010-04-20 Procédé de formation de motif WO2011004528A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-162836 2009-07-09
JP2009162836A JP2011017921A (ja) 2009-07-09 2009-07-09 パターン形成方法

Publications (1)

Publication Number Publication Date
WO2011004528A1 true WO2011004528A1 (fr) 2011-01-13

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WO (1) WO2011004528A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101570447B1 (ko) * 2010-03-11 2015-11-19 후지필름 가부시키가이샤 포지티브형 감광성 수지 조성물, 경화막의 형성 방법, 경화막, 액정 표시 장치, 및 유기 ｅｌ 표시 장치
JP5589101B2 (ja) * 2012-03-30 2014-09-10 富士フイルム株式会社 感光性樹脂組成物、これを用いたパターンの製造方法
KR102000492B1 (ko) * 2012-03-30 2019-07-16 후지필름 가부시키가이샤 감광성 수지 조성물, 이것을 사용한 패턴의 제조 방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000008525A1 (fr) * 1998-08-07 2000-02-17 Clariant International Ltd. Composition radiosensible du type a amplification chimique
JP2000089464A (ja) * 1998-09-08 2000-03-31 Matsushita Electric Ind Co Ltd パターン形成方法
JP2003075998A (ja) * 2001-06-22 2003-03-12 Matsushita Electric Ind Co Ltd パターン形成方法
JP2006276688A (ja) * 2005-03-30 2006-10-12 Fuji Photo Film Co Ltd 化学増幅型レジスト組成物及びそれを用いたパターン形成方法
JP2007101715A (ja) * 2005-09-30 2007-04-19 Fujifilm Corp パターン形成方法及びそれに用いるレジスト組成物
JP2008151953A (ja) * 2006-12-15 2008-07-03 Tokyo Ohka Kogyo Co Ltd 厚膜用化学増幅型ポジ型ホトレジスト組成物及び厚膜レジストパターンの製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000008525A1 (fr) * 1998-08-07 2000-02-17 Clariant International Ltd. Composition radiosensible du type a amplification chimique
JP2000089464A (ja) * 1998-09-08 2000-03-31 Matsushita Electric Ind Co Ltd パターン形成方法
JP2003075998A (ja) * 2001-06-22 2003-03-12 Matsushita Electric Ind Co Ltd パターン形成方法
JP2006276688A (ja) * 2005-03-30 2006-10-12 Fuji Photo Film Co Ltd 化学増幅型レジスト組成物及びそれを用いたパターン形成方法
JP2007101715A (ja) * 2005-09-30 2007-04-19 Fujifilm Corp パターン形成方法及びそれに用いるレジスト組成物
JP2008151953A (ja) * 2006-12-15 2008-07-03 Tokyo Ohka Kogyo Co Ltd 厚膜用化学増幅型ポジ型ホトレジスト組成物及び厚膜レジストパターンの製造方法

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