WO2010084918A1 - Application d'une résine de benzocyclobutène à des techniques d'estampage et procédé de formation de motifs utilisant cette technique - Google Patents

Application d'une résine de benzocyclobutène à des techniques d'estampage et procédé de formation de motifs utilisant cette technique Download PDF

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Publication number
WO2010084918A1
WO2010084918A1 PCT/JP2010/050719 JP2010050719W WO2010084918A1 WO 2010084918 A1 WO2010084918 A1 WO 2010084918A1 JP 2010050719 W JP2010050719 W JP 2010050719W WO 2010084918 A1 WO2010084918 A1 WO 2010084918A1
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WO
WIPO (PCT)
Prior art keywords
benzocyclobutene resin
pattern
forming
mold
imprinting
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PCT/JP2010/050719
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English (en)
Japanese (ja)
Inventor
和広 青葉
淳子 片山
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日産化学工業株式会社
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Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Publication of WO2010084918A1 publication Critical patent/WO2010084918A1/fr

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    • 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
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping

Definitions

  • the present invention relates to a pattern forming method by thermal imprinting using a benzocyclobutene resin.
  • Nanoimprint lithography is a technique in which a mold on which a predetermined pattern is formed is pressed against a substrate on which a resin layer is formed, and the pattern of the mold is transferred to the resin layer.
  • thermoplastic resin which is a thermoplastic resin
  • thermal cycle nanoimprint Since the resin layer is deformed by pressing the mold, and then the resin layer is cooled and solidified, it is called “thermal cycle nanoimprint”.
  • thermal cycle nanoimprint has a problem of low throughput and a problem that a pattern size changes due to a temperature difference because it takes time to raise and cool the resin layer.
  • polyimide resins and acrylic resins are generally known as passivation films for organic materials used in multichip modules, liquid crystal display elements, and the like, and semiconductor elements such as LSIs.
  • semiconductor elements such as LSIs.
  • benzocyclobutene resins having good optical, electrical characteristics and process resistance has been studied in place of those resins (see Patent Document 2).
  • the benzocyclobutene resin is used by forming a resin layer on a plate made of silicon or glass and patterning the formed resin layer.
  • a patterning method for the benzocyclobutene resin layer dry etching using a plasma etching apparatus and negative photosensitive benzocyclobutene resin blended composition to which a photoreactive agent is added are etched using an etchant such as an organic solvent. Wet etching is generally used.
  • a layer of photoresist, metal, or the like is formed as a mask material on the benzocyclobutene resin layer formed on the substrate, and the mask material is exposed so that the portion where the benzocyclobutene resin layer is removed is exposed.
  • Patterning is performed, a high frequency is applied to the electrode in an etching gas atmosphere such as O 2 or CF 4 to generate plasma, and the generated plasma is reacted with benzocyclobutene resin in the mask material opening to be gasified, and the benzocyclo in the opening Generally, the butene resin is removed and patterned.
  • a negative photosensitive benzocyclobutene resin layer is formed on a substrate by containing a photosensitizer such as a bisazide compound, and the negative photosensitive benzocyclobutene resin layer is patterned.
  • a photosensitizer such as a bisazide compound
  • the exposed portion is cured by photoreaction, and the unexposed benzocyclobutene resin portion is removed with an organic solvent or the like and patterned (see Patent Document 3).
  • a method of forming a pattern by wet etching without using a photosensitive benzocyclobutene resin there is a method of forming a pattern by wet etching without using a photosensitive benzocyclobutene resin.
  • a photoresist layer is formed on a B-staged benzocyclobutene resin layer formed on a substrate, the photoresist layer is patterned, and then the benzocyclobutene is formed using the formed photoresist pattern as a mask.
  • This is a method in which a butene resin layer is wet-etched with an organic solvent, and finally a photoresist pattern that is no longer needed is removed to form a pattern (see Patent Document 4).
  • the method of forming a photoresist layer on the benzocyclobutene resin layer and performing plasma etching or wet etching has a complicated process, and when plasma etching is performed, the etching selectivity between the mask material and the benzocyclobutene resin is 1 to Since the thickness is about 1.5, it is necessary to increase the thickness of the mask material such as photoresist by about 1.5 to 2 times in consideration of the film reduction during plasma etching, which increases the exposure time and decreases the resolution of the photoresist There are disadvantages such as.
  • the benzocyclobutene resin layer is etched isotropically in the lateral direction (film surface direction) and in the vertical direction (film depth direction), so a vertical pattern with a high aspect ratio is obtained. There is a drawback that it is difficult.
  • the present invention has been made based on the above circumstances, and the problem to be solved is to provide a method for forming a pattern of a layer containing a benzocyclobutene resin using a thermal imprint lithography technique. It is to be. That is, a pattern of a layer containing a benzocyclobutene resin, which can easily form a benzocyclobutene resin pattern without using a photosensitive benzocyclobutene, a resist, a developer, or the like, and has little or no dimensional change. It is to provide a forming method.
  • R 1 independently represents an alkyl group having 1 to 6 carbon atoms, a vinyl group or a phenyl group
  • R 2 independently represents an alkyl group having 1 to 6 carbon atoms or a methoxy group.
  • R 3 each independently represents an alkyl group having 1 to 6 carbon atoms
  • k and m each independently represent 0 or 1
  • n represents an integer of 1 to 3.
  • a desired pattern can be easily formed without using a wet etching mask such as a resist and an etching solution.
  • a wet etching mask such as a resist and an etching solution.
  • the layer on which the pattern is formed by the pattern forming method according to the present invention does not use the photosensitive benzocyclobutene resin, the light transmittance is high and the transparency is excellent.
  • the cross-sectional SEM image of the mold for imprint is shown.
  • the cross-sectional SEM image of the sample used for the method of Example 11 is shown.
  • the present invention relates to divinylsiloxane-bisbenzocyclobutene represented by the above formula (1), For example, the following formula (2): Forming a layer containing a benzocyclobutene resin obtained by polymerizing divinylsiloxane-bisbenzocyclobutene represented by A step of forming a pattern on the layer containing the benzocyclobutene resin by pressing a mold against the layer containing the benzocyclobutene resin while heating and pressing, and after cooling, the benzocyclobutene resin on which the pattern is formed Having a step of releasing the containing layer from the mold,
  • the heating temperature is 150 ° C. to 350 ° C.
  • the benzocyclobutene resin is, for example, a B-staged benzocyclobutene resin.
  • the B-staging means a semi-cured state (cured intermediate state). The resin in this state softens when heated, and swells, melts, or dissolves when touched with a certain solvent.
  • the benzocyclobutene resin is in such a state, it becomes easy to form a desired pattern using the imprint apparatus.
  • the B-staged benzocyclobutene resin is a prepolymer.
  • the uncured state of the thermosetting resin is expressed as A stage
  • the final stage of the curing process of the thermosetting resin is expressed as C stage.
  • the B stage is a state that is neither the A stage nor the C stage.
  • the weight average molecular weight of the benzocyclobutene resin is usually 50,000 to 500,000, and 100,000 to 400,000.
  • the weight average molecular weight is a value obtained by using gel as a standard sample by gel permeation chromatography (GPC).
  • the layer containing the benzocyclobutene resin is formed, for example, by applying a film forming composition for imprinting containing the benzocyclobutene resin and an organic solvent capable of dissolving the benzocyclobutene resin on the substrate and evaporating the organic solvent. Is done.
  • organic solvent examples include alkyl aromatics such as toluene, xylene and mesitylene, cyclic ketones such as cyclopentanone and cyclohexanone, ethers such as diethyl ether, dipropylene glycol dimethyl ether and tetrahydrofuran (THF), butyl acetate, 1 -Methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO).
  • a known coating method such as a spin coating method, a dip method, or a spray method can be employed for coating on the substrate.
  • the pressurization is performed under conditions of, for example, 1 MPa to 10 MPa.
  • the heating temperature if it exceeds 350 ° C., the benzocyclobutene resin is decomposed, so it is necessary to heat at 350 ° C. or less.
  • a temperature lower than 150 ° C. for example, 120 ° C.
  • the cooling after the step of forming the pattern does not necessarily have to be lowered to room temperature. This is because the mold release may be performed at a temperature higher than room temperature. In this specification, 23 ° C. is regarded as room temperature.
  • the mold is a “mold” made of a material such as quartz, silicon, silicon carbide (SiC), nickel, tantalum or the like having an uneven pattern formed on the surface.
  • a mold which has been surface-treated by applying a commercially available release agent (for example, OPTOOL (registered trademark) HD) or a thin film formed on the surface can be used. By performing such treatment on the mold in advance, the benzocyclobutene resin can be easily released from the mold.
  • the step of releasing from the mold may further include a step of heating the substrate at a temperature of 250 ° C. to 350 ° C., if necessary.
  • a heating step curing (crosslinking) of the benzocyclobutene resin proceeds and a three-dimensional polymer is formed. Since the benzocyclobutene resin is decomposed at a temperature exceeding 350 ° C., it is necessary to heat at 350 ° C. or less.
  • Example 5 to Example 7 4 ml of benzocyclobutene resin solution (manufactured by The Dow Chemical Company, trade name: CYCLOTENE [registered trademark] 3022-63) was applied onto a 4-inch silicon substrate at 1500 rpm for 30 seconds using a spin coater, and hot Bake on plate for 90 seconds at 90 ° C. Thereafter, the 4-inch silicon substrate was cut into chips of about 3 cm square size, and samples used in Examples 5 to 7 were obtained. A benzocyclobutene resin layer is formed on the obtained sample (chip).
  • Example 8 to Example 11 A resin solution obtained by diluting 4 ml of a benzocyclobutene resin solution (manufactured by The Dow Chemical Company, trade name: CYCLOTENE [registered trademark] 3022-35) 10 times with mesitylene (1,3,5-trimethylbenzene) This resin solution was applied onto a 4-inch silicon substrate using a spin coater at 3000 rpm for 30 seconds, and baked on a hot plate at 90 ° C. for 90 seconds. Thereafter, the 4-inch silicon substrate was cut into chips of about 3 cm square size, and samples used in Examples 8 to 11 were obtained. A benzocyclobutene resin layer is formed on the obtained sample (chip).
  • CYCLOTENE registered trademark
  • Example 12 and Example 13 4 ml of benzocyclobutene resin solution (manufactured by The Dow Chemical Company, trade name: CYCLOTENE [registered trademark] 3022-35) was applied onto a 4-inch silicon substrate at 2000 rpm for 30 seconds using a spin coater, and hot Bake on plate for 90 seconds at 90 ° C. Thereafter, the 4-inch silicon substrate was cut into chips of about 3 cm square size, and samples used in Examples 12 and 13 were obtained. A benzocyclobutene resin layer is formed on the obtained sample (chip).
  • benzocyclobutene resin solution manufactured by The Dow Chemical Company, trade name: CYCLOTENE [registered trademark] 3022-35
  • a pattern was formed on the benzocyclobutene resin layer using an imprint apparatus (LTNIP-5000, manufactured by RISOTEC JAPAN CO., LTD.). That is, the prepared sample (chip) is placed in an imprint apparatus, a pattern is formed by pressing the mold against the benzocyclobutene resin layer under predetermined heating and pressing conditions (described in Table 1), and after cooling Then, the sample (chip) was taken out from the imprint apparatus, and the pattern-formed benzocyclobutene resin layer was released from the mold at about room temperature, and the results of Comparative Example 1 and Examples 1 to 4 were obtained. .
  • the mold used was made of quartz and surface-treated with a release agent (OPTOOL (registered trademark) HD) in advance.
  • a pattern was formed on the benzocyclobutene resin layer by the same method as described above using an imprint apparatus (NM-0801HB, manufactured by Meisho Kiko Co., Ltd.). That is, the prepared sample (chip) is placed in an imprint apparatus, and a pattern is formed by pressing the mold against the benzocyclobutene resin layer under predetermined heating and pressing conditions (described in Table 2). Then, the sample (chip) was taken out from the imprint apparatus, and the benzocyclobutene resin layer on which the pattern was formed was released from the mold at about room temperature, and the results of Examples 5 to 13 were obtained.
  • the mold used was made of silicon and surface-treated with a release agent (OPTOOL (registered trademark) HD) in advance.
  • FIG. 1 shows a cross-sectional SEM image of the mold (silicon mold) used to obtain the results of Examples 5 to 13
  • FIG. 2 shows a cross-sectional SEM image of the sample of Example 11 on which the pattern was formed.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Theoretical Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention porte sur un procédé de formation d'un motif de résine de benzocyclobutène utilisant une technique lithographique par estampage à chaud, et spécifiquement sur un procédé de formation d'un motif par estampage comprenant les étapes suivantes: formation sur un substrat d'une couche de résine de benzocyclobutène obtenu par polymérisation de divinylsiloxane-bisbenzocyclobutène; pression d'un moule contre la couche de résine de benzocyclobutène chauffée pour y former un motif; et extraction du moule après refroidissement de la couche de résine présentant un motif. Ce procédé utilise une température comprise entre 150 et 350˚C.
PCT/JP2010/050719 2009-01-21 2010-01-21 Application d'une résine de benzocyclobutène à des techniques d'estampage et procédé de formation de motifs utilisant cette technique WO2010084918A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009011099A JP2012061599A (ja) 2009-01-21 2009-01-21 ベンゾシクロブテン樹脂のインプリント技術への適用及び当該技術によるパターン形成方法
JP2009-011099 2009-01-21

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015187909A1 (fr) * 2014-06-04 2015-12-10 Dow Corning Corporation Procede d'impression de composition silicone durcissable de type thermofusible pour dispositifs optiques
CN108516986A (zh) * 2018-05-16 2018-09-11 西南科技大学 苯并环丁烯官能化的四（二甲基硅氧基）硅烷及其制备方法和包含其树脂的制备方法

Citations (6)

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JPH09241419A (ja) * 1996-03-06 1997-09-16 Hitachi Ltd 無溶剤組成物ならびに多層配線基板、およびそれらの製造方法
JPH11507601A (ja) * 1995-06-07 1999-07-06 ザ デクスター コーポレイション 型押し可能な膜
JP2000500617A (ja) * 1995-11-22 2000-01-18 シーメンス アクチエンゲゼルシヤフト 垂直方向に集積された半導体素子及びその製法
JP2002530505A (ja) * 1998-11-24 2002-09-17 ザ ダウ ケミカル カンパニー 架橋性マトリックス前駆体および気孔発生体を含有する組成物、並びにそれから製造された多孔質マトリックス
JP2004500719A (ja) * 2000-03-30 2004-01-08 エイブイエックス　コーポレイション 電子デバイス及び電子デバイスの作製方法
JP2008310944A (ja) * 2007-05-16 2008-12-25 Fujifilm Corp モールド構造体及びそれを用いたインプリント方法、並びに磁気記録媒体及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11507601A (ja) * 1995-06-07 1999-07-06 ザ デクスター コーポレイション 型押し可能な膜
JP2000500617A (ja) * 1995-11-22 2000-01-18 シーメンス アクチエンゲゼルシヤフト 垂直方向に集積された半導体素子及びその製法
JPH09241419A (ja) * 1996-03-06 1997-09-16 Hitachi Ltd 無溶剤組成物ならびに多層配線基板、およびそれらの製造方法
JP2002530505A (ja) * 1998-11-24 2002-09-17 ザ ダウ ケミカル カンパニー 架橋性マトリックス前駆体および気孔発生体を含有する組成物、並びにそれから製造された多孔質マトリックス
JP2004500719A (ja) * 2000-03-30 2004-01-08 エイブイエックス　コーポレイション 電子デバイス及び電子デバイスの作製方法
JP2008310944A (ja) * 2007-05-16 2008-12-25 Fujifilm Corp モールド構造体及びそれを用いたインプリント方法、並びに磁気記録媒体及びその製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015187909A1 (fr) * 2014-06-04 2015-12-10 Dow Corning Corporation Procede d'impression de composition silicone durcissable de type thermofusible pour dispositifs optiques
CN106462056A (zh) * 2014-06-04 2017-02-22 道康宁公司 用于光学器件的热熔型可固化有机硅组合物的压印工艺
US9853193B2 (en) 2014-06-04 2017-12-26 Dow Corning Corporation Imprinting process of hot-melt type curable silicone composition for optical devices
CN108516986A (zh) * 2018-05-16 2018-09-11 西南科技大学 苯并环丁烯官能化的四（二甲基硅氧基）硅烷及其制备方法和包含其树脂的制备方法
CN108516986B (zh) * 2018-05-16 2020-11-17 西南科技大学 苯并环丁烯官能化的四(二甲基硅氧基)硅烷及其制备方法和包含其树脂的制备方法

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TW201031690A (en) 2010-09-01

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