WO2016133115A1 - Procédé de formation de film auto-organisé, procédé de formation de motif et composition de formation de film auto-organisé - Google Patents

Procédé de formation de film auto-organisé, procédé de formation de motif et composition de formation de film auto-organisé Download PDF

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Publication number
WO2016133115A1
WO2016133115A1 PCT/JP2016/054567 JP2016054567W WO2016133115A1 WO 2016133115 A1 WO2016133115 A1 WO 2016133115A1 JP 2016054567 W JP2016054567 W JP 2016054567W WO 2016133115 A1 WO2016133115 A1 WO 2016133115A1
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WIPO (PCT)
Prior art keywords
self
polymer
forming
film
pattern
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PCT/JP2016/054567
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English (en)
Japanese (ja)
Inventor
裕之 小松
智博 小田
岳彦 成岡
永井　智樹
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Jsr株式会社
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Priority to JP2017500706A priority Critical patent/JPWO2016133115A1/ja
Publication of WO2016133115A1 publication Critical patent/WO2016133115A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching

Definitions

  • the present invention relates to a method for forming a self-assembled film, a pattern forming method, and a composition for forming a self-assembled film.
  • the pattern formation method of this invention it is a schematic diagram which shows an example of the state after forming a coating film in the area
  • the pattern formation method of this invention it is a schematic diagram which shows an example of the state after forming a self-organization film
  • the formation method of the self-assembled film preferably further includes a step of heating the coating film (hereinafter also referred to as “heating step”). Moreover, you may provide the process (henceforth a "stationary process") which leaves the said coating film before the said heating process or simultaneously with the said heating process.
  • Examples of the heating method in the heating step include a method of heating with an oven, a hot plate, or the like.
  • the lower limit of the temperature of the heating step is preferably 40 ° C, more preferably 100 ° C, further preferably 150 ° C, and particularly preferably 200 ° C.
  • 300 degreeC is preferable, 280 degreeC is more preferable, 260 degreeC is further more preferable, 240 degreeC is especially preferable.
  • the lower limit of the heating step time is preferably 1 minute, more preferably 3 minutes, and even more preferably 5 minutes.
  • the upper limit of the time is preferably 120 minutes, more preferably 60 minutes, still more preferably 30 minutes, and particularly preferably 20 minutes.
  • the method for forming the self-assembled film may include a step of annealing the formed self-assembled film 103 in order to improve the phase separation structure of the self-assembled film 103.
  • the annealing method include a method of heating with an oven, a hot plate, or the like.
  • 80 ° C is preferred, 100 ° C is more preferred, and 150 ° C is still more preferred.
  • 400 degreeC is preferable, 350 degreeC is more preferable, and 300 degreeC is further more preferable.
  • the lower limit of the heating time is usually 30 seconds, preferably 1 minute, more preferably 2 minutes, and even more preferably 3 minutes.
  • the upper limit of the heating time is preferably 120 minutes, more preferably 90 minutes, and even more preferably 60 minutes.
  • the block copolymer can be synthesized by forming the blocks in a desired order by living anion polymerization, living radical polymerization, or the like.
  • a polystyrene block, a poly (meth) acrylic acid ester block, other blocks other than these and the like are connected while being polymerized in a desired order, and then synthesized by adding methanol or the like to stop the polymerization.
  • styrene is first used in an appropriate solvent using an anionic polymerization initiator.
  • a polystyrene block is synthesized by polymerizing.
  • the polymerization is stopped by adding methanol or the like.
  • the method for synthesizing each block include a method in which a solution containing a monomer is dropped into a reaction solvent containing an anionic polymerization initiator to cause a polymerization reaction.
  • anionic polymerization initiator used for the polymerization examples include alkyl lithium, alkyl magnesium halide, sodium naphthalene, alkylated lanthanoid compounds, and the like.
  • alkyl lithium when polymerizing using styrene and / or (meth) acrylic acid ester as a monomer, it is preferable to use an alkyl lithium compound.
  • the lower limit of the weight average molecular weight (Mw) by gel permeation chromatography (GPC) of the block copolymer is preferably 1,000, more preferably 8,000, still more preferably 20,000, 000 is particularly preferred.
  • the upper limit of the Mw of the block copolymer is preferably 150,000, more preferably 100,000, still more preferably 80,000, and particularly preferably 70,000.
  • GPC gel permeation chromatography
  • the lower limit of the ratio (Mw / Mn) between the Mw and the number average molecular weight (Mn) of the block copolymer is usually 1.
  • the upper limit of Mw / Mn of the block copolymer is usually 5, preferably 3, more preferably 2, more preferably 1.5, and particularly preferably 1.2.
  • Mw / Mn of the block copolymer By setting Mw / Mn of the block copolymer in the above range, a better phase separation structure can be formed.
  • the polymer can contain two or more kinds of polymers depending on the desired phase separation structure, but two kinds are preferred.
  • a polymer constituting the polymer for example, an acrylic polymer, a styrene polymer, a vinyl acetal polymer, a urethane polymer, a urea polymer, an imide polymer, an amide polymer, Examples thereof include novolak type phenol polymers and ester polymers.
  • the polymer may be a homopolymer synthesized from one type of monomer or a copolymer synthesized from a plurality of types of monomers.
  • the polymer preferably includes a styrene polymer and an acrylic polymer, and more preferably includes only a styrene polymer and an acrylic polymer.
  • radical polymerization initiator examples include azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropylpropylene). Pionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), azo radical polymerization initiators such as dimethyl 2,2′-azobisisobutyrate; benzoyl peroxide, t-butyl hydroperoxide And peroxide radical polymerization initiators such as cumene hydroperoxide. Of these, AIBN and dimethyl 2,2'-azobisisobutyrate are preferred, and AIBN is more preferred. These radical polymerization initiators can be used alone or in combination of two or more.
  • the lower limit of Mw / Mn of each polymer in the polymer is usually 1.
  • the upper limit of Mw / Mn of the polymer is usually 5, preferably 3 and more preferably 2.
  • the compound [B1] is a compound having an aromatic ring, and is preferably a solvent having a boiling point at 1 atm of 150 ° C. to 300 ° C. and a surface tension at 25 ° C. of 29 mN / m to 60 mN / m.
  • the lower limit of the content of the [B1] compound in the [B] solvent is preferably 30% by mass, more preferably 50% by mass, further preferably 55% by mass, and particularly preferably 60% by mass.
  • the upper limit of the content is preferably 99.9% by mass, more preferably 99% by mass, still more preferably 90% by mass, particularly preferably 80% by mass, still more particularly preferably 75% by mass, and most preferably 70% by mass. preferable.
  • [B1] compounds are preferably ether solvents, hydrocarbon solvents and alcohol solvents, such as anisole, isopropylbenzene, t-butylbenzene, trimethylbenzene, propylene glycol monophenyl ether and combinations thereof. More preferred are anisole, 1,3,5-trimethylbenzene and combinations thereof.
  • a compound can be used individually by 1 type or in combination of 2 or more types.
  • the solvent may contain a solvent other than the [B1] compound.
  • the other solvent is a compound having no aromatic ring, and examples thereof include ketone solvents, ester solvents, amide solvents, aprotic polar solvents, alcohol solvents and the like.
  • phase separation of the [A] polymer proceeds better.
  • a self-assembled film 103 having a better phase separation structure can be formed, and as a result, a self-assembled film with fewer defects in a regular arrangement structure can be obtained.
  • the reason why the phase separation is improved by the [C] polymer is not necessarily clear.
  • the difference in surface free energy between the atmosphere and the [A] polymer is Although it tends to promote phase separation in a substantially horizontal direction due to its large size, the difference in surface free energy from the [A] polymer is reduced by applying the [C] polymer, so that the substantially horizontal direction is reduced. Since phase separation is suppressed, it can be considered that phase separation in a substantially vertical direction is effectively performed as a result.
  • the [C] polymer is unevenly distributed in the region 104 above the self-assembled film 103.
  • the lower limit of the value obtained by subtracting the surface free energy of the polymer [C] from the surface free energy of the polymer is preferably 1 mN / m, more preferably 3 mN / m, still more preferably 5 mN / m, and 7 mN / m. m is particularly preferable, and 9 mN / m is further particularly preferable.
  • the upper limit of the value obtained by subtracting the surface free energy of the [C] polymer from the surface free energy of the polymer is preferably 20 mN / m, more preferably 18 mN / m, still more preferably 15 mN / m, and 13 mN / m.
  • the polymer may have a structural unit other than the structural unit (I) (hereinafter also referred to as “structural unit (II)”).
  • structural unit (II) include structural units derived from (meth) acrylic acid esters, structural units derived from styrene compounds, and the like.
  • styrene compound examples include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, ⁇ -methylstyrene, 4-hydroxystyrene, 4- (t-butoxy) styrene, and the like.
  • a structural unit derived from tetrahydrofurfuryl (meth) acrylate and a structural unit derived from styrene and tetrahydrofurfuryl (meth) acrylate More preferably.
  • the lower limit of the Mw of the [C] polymer is preferably 1,000, more preferably 5,000, still more preferably 8,000, and particularly preferably 10,000.
  • the upper limit of the Mw of the polymer is preferably 100,000, more preferably 60,000, still more preferably 40,000, and particularly preferably 30,000.
  • This step is a step of removing a part of the phase separation structure of the self-assembled film 103.
  • the pre-pattern 106 can also be removed simultaneously with or separately from the partial phase. As shown in FIGS. 6 and 7, the block phase (I) 103a and the pre-pattern 106 of the self-assembled film 103 are removed by etching using the difference in the etching rate of each block phase phase-separated by self-assembly. can do.
  • Pre-pattern removal process This step is a step of removing the pre-pattern 106 as shown in FIGS. By removing the pre-pattern 106, a finer and more complicated pattern can be formed. As a method for removing the pre-pattern 106, a method for removing a part of the phase separation structure described above can be applied. Moreover, this process may be performed simultaneously with the said removal process, and may be performed before or after a removal process.

Abstract

La présente invention concerne un procédé de formation de film auto-organisé comprenant une étape de formation d'un film de revêtement sur un substrat au moyen d'une composition de formation de film auto-organisé qui contient un solvant et au moins un type d'un premier polymère qui peut former une structure à séparation de phases par le biais d'une auto-organisation, le solvant contenant un composé contenant un noyau aromatique. Il est préférable qu'un procédé de formation de film auto-organisé comprenne en outre une étape de chauffage du film de revêtement. Il est préférable que le solvant contienne le composé contenant un noyau aromatique dans une proportion de 80% en masse au maximum et de 50% en masse au minimum. Il est préféré que la composition de formation de film auto-organisé contienne en outre un second polymère présentant une énergie libre de surface inférieure à celle du premier polymère et que le second polymère soit réparti de manière inégale au-dessus du film auto-organisé.
PCT/JP2016/054567 2015-02-20 2016-02-17 Procédé de formation de film auto-organisé, procédé de formation de motif et composition de formation de film auto-organisé WO2016133115A1 (fr)

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JP2017500706A JPWO2016133115A1 (ja) 2015-02-20 2016-02-17 自己組織化膜の形成方法、パターン形成方法及び自己組織化膜形成用組成物

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JP2015032199 2015-02-20
JP2015-032199 2015-02-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018100384A (ja) * 2016-12-21 2018-06-28 東京応化工業株式会社 相分離構造形成用樹脂組成物、及び、相分離構造を含む構造体の製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6896447B2 (ja) * 2017-02-14 2021-06-30 株式会社Ｓｃｒｅｅｎホールディングス 基板処理方法

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JP2005054118A (ja) * 2003-08-06 2005-03-03 Daikin Ind Ltd 非付着性多重表面構造
JP2005146023A (ja) * 2003-11-11 2005-06-09 Daicel Chem Ind Ltd 発色性ポリマー構造体からなる塗膜、塗膜形成方法、及び塗料
JP2008036491A (ja) * 2006-08-03 2008-02-21 Nippon Telegr & Teleph Corp <Ntt> パターン形成方法及びモールド
JP2013166932A (ja) * 2012-02-10 2013-08-29 Rohm & Haas Electronic Materials Llc ブロックコポリマーおよびそれに関連する方法
JP2013209515A (ja) * 2012-03-30 2013-10-10 Tokyo Ohka Kogyo Co Ltd 組成物及びパターン形成方法
JP2013212569A (ja) * 2012-03-09 2013-10-17 Tokyo Ohka Kogyo Co Ltd ブロックコポリマーを含む層のパターン形成方法、及び下地剤
JP2014011245A (ja) * 2012-06-28 2014-01-20 Institute Of Physical & Chemical Research 微細パターン形成方法、現像液
JP2015170723A (ja) * 2014-03-06 2015-09-28 Jsr株式会社 パターン形成方法及び自己組織化組成物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005054118A (ja) * 2003-08-06 2005-03-03 Daikin Ind Ltd 非付着性多重表面構造
JP2005146023A (ja) * 2003-11-11 2005-06-09 Daicel Chem Ind Ltd 発色性ポリマー構造体からなる塗膜、塗膜形成方法、及び塗料
JP2008036491A (ja) * 2006-08-03 2008-02-21 Nippon Telegr & Teleph Corp <Ntt> パターン形成方法及びモールド
JP2013166932A (ja) * 2012-02-10 2013-08-29 Rohm & Haas Electronic Materials Llc ブロックコポリマーおよびそれに関連する方法
JP2013212569A (ja) * 2012-03-09 2013-10-17 Tokyo Ohka Kogyo Co Ltd ブロックコポリマーを含む層のパターン形成方法、及び下地剤
JP2013209515A (ja) * 2012-03-30 2013-10-10 Tokyo Ohka Kogyo Co Ltd 組成物及びパターン形成方法
JP2014011245A (ja) * 2012-06-28 2014-01-20 Institute Of Physical & Chemical Research 微細パターン形成方法、現像液
JP2015170723A (ja) * 2014-03-06 2015-09-28 Jsr株式会社 パターン形成方法及び自己組織化組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018100384A (ja) * 2016-12-21 2018-06-28 東京応化工業株式会社 相分離構造形成用樹脂組成物、及び、相分離構造を含む構造体の製造方法
JP7008403B2 (ja) 2016-12-21 2022-01-25 東京応化工業株式会社 相分離構造形成用樹脂組成物、及び、相分離構造を含む構造体の製造方法

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TW201638166A (zh) 2016-11-01

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