EP1364254A2 - Antireflex-schicht zur verwendung in der mikrolithographie - Google Patents

Antireflex-schicht zur verwendung in der mikrolithographie

Info

Publication number
EP1364254A2
EP1364254A2 EP01995153A EP01995153A EP1364254A2 EP 1364254 A2 EP1364254 A2 EP 1364254A2 EP 01995153 A EP01995153 A EP 01995153A EP 01995153 A EP01995153 A EP 01995153A EP 1364254 A2 EP1364254 A2 EP 1364254A2
Authority
EP
European Patent Office
Prior art keywords
group
ethylenically unsaturated
polymer
unsaturated compound
carbon atoms
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP01995153A
Other languages
English (en)
French (fr)
Inventor
Larry L. Berger
Michael Karl Crawford
Roger Harquail French
Robert Clayton Wheland
Frederick Claus Zumsteg, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1364254A2 publication Critical patent/EP1364254A2/de
Withdrawn legal-status Critical Current

Links

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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography

Definitions

  • Patent 5,655,627 discloses a process for generating a negative tone resist image by coating a silicon wafer with a copolymer resist solution of pentafluoropropyl methacrylate-t-butyl methacrylate in a solvent, and then exposing at 193 nm and developing with a carbon dioxide critical fluid.
  • resist compositions that satisfy the myriad of requirements for single layer photoresists that include optical transparency at 193 nm and/or 157 nm, plasma etch resistance, and solubility in an aqueous base developer.
  • Representative comonomers having structure H include, but are not limited to:
  • the fluorine-containing copolymer has just two comonomers (the two recited comonomers and having no additional unrecited comonomers).
  • the mole percentages of the two comonomers in the copolymer can range from 90%, 10% to 10%, 90% for the fluoromonomer (first recited monomer) and the second comonomer, respectively.
  • the mole percentages of the two comonomers are in the range from 60%, 40% to 40%, 60% for the fluoromonomer (first recited monomer) and the second comonomer, respectively.
  • the fluorine-containing copolymers of this invention can be comprised of any integral number without limit of additional comonomers beyond the two recited comonomers (i.e., (i) at least one ethylenically unsaturated compound containing at least one fluorine atom covalently attached to an ethylenically unsaturated carbon atom; and (ii) at least one unsaturated compound selected from the group of structures H-N) for some embodiments.
  • Representative additional comonomers can include, but are not limited to, acrylic acid, methacrylic acid, t-butyl acrylate, t-butyl methacrylate, t-amyl acrylate, t-amyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylene, vinyl acetate, itaconic acid, and vinyl alcohol.
  • the mole percentage of the second recited comonomer ranges from about 20 mole % to about 80 mole %, preferably ranges from about 30 mole % to about 70 mole %, more preferably ranges from about 40 mole % to about 70 mole %, and still most preferably is about 50 to about 70 mole %.
  • Summation of the mole percentages of all other comonomers constituting the copolymer represents a balance that when added to the mole percentage of the second recited comonomer totals 100%.
  • the sum of the mole percentages of all other comonomers present in the copolymer except for the second recited comonomer broadly is in the range from about 80 mole % to about 20 mole %.
  • the sum of the mole percentages of all other comonomers is in the range from about 70 mole % to about 30 mole %.
  • a suitable ratio of the fluoromonomer (first recited monomer) to the additional comonomer can broadly range from 5:95 to 95:5..
  • the fluorine-containing copolymer contains additional comonomers having functionality of acid groups or protected acid groups in sufficient amounts necessary for developability, the functionality can be present or absent in the second recited comonomer without limitation.
  • a given fluorine-containing copolymer, comprised of a repeat unit derived from a comonomer having at least one fluorine atom attached to an ethylenically unsaturated carbon atom, of the ARC composition(s) of this invention can be prepared by free radical polymerization.
  • Polymers may be prepared by bulk, solution, suspension or emulsion polymerization techniques known to those skilled in the art using free radical initiators, such as azo compounds or peroxides.
  • a given fluorine-containing copolymer, containing only repeat units derived from all cyclic comonomers and totally lacking a repeat unit derived from a comonomer that has one or more fluorine atom(s) attached to an ethylenically unsaturated carbon atom(s), of the ARC composition(s) of this invention can also be prepared by free radical polymerization, but in addition can be prepared by other polymerization methods, including vinyl- addition polymerization and ring-opening methathesis polymerization (ROMP). Both of the latter polymerization methods are known to those skilled in the art.
  • Ring-opening metathesis polymerization is disclosed in references 1) and 2) supra using ruthenium and irridium catalysts; and also in 5) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100; and 6) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem. Int. Ed. Engl. 1995, 34, 2039.
  • fluorine-containing bipolymers of the resist compositions of this invention where the bipolymer contains a fluoromonomer (e.g., TFE) and a cyclic olefin (e.g., norbornene) appear to be alternating or approximately alternating bipolymers having a structure, but not limited to, the one shown below:
  • a fluoromonomer e.g., TFE
  • a cyclic olefin e.g., norbornene
  • the invention includes these alternating or approximately alternating copolymers but is not in any manner limited to just alternating copolymer structures.
  • the polymer (b) is a branched polymer containing protected acid groups, said polymer comprising one or more branch segment(s) chemically linked along a linear backbone segment.
  • the branched polymer can be formed during free radical addition polymerization of at least one ethylenically unsaturated macromer component and at least one ethylenically unsaturated comonomer.
  • the ethylenically unsaturated macromer component has a number average molecular weight (M n ) between a few hundred and 40,000 and the linear backbone segment resulting from the polymerization has a number average molecular weight (M n ) between about 2,000 and about 500,000.
  • the weight ratio of the linear backbone segment to the branch segment(s) is within a range of about 50/1 to about 1/10, and preferably within the range of about 80/20 to about 60/40.
  • the macromer component has a number average molecular weight (M n ) from 500 to about 40,000 and more typically of about 1 ,000 to about 15,000.
  • M n number average molecular weight
  • such an ethylenically unsaturated macromer component can have a number average molecular weight (M n ) equivalent to there being from about 2 to about 500 monomer units used to form the macromer component and typically between 30 and 200 monomer units.
  • Suitable hydrophilic polar groups include, but are not limited to protic groups such as hydroxy (OH), amino (NH2), ammonium, amido, imido, urethane, ureido, or mercapto; or carboxylic (CO2H), sulfonic, sulfinic, phosphoric, or phosphoric acids or salts thereof.
  • protic groups such as hydroxy (OH), amino (NH2), ammonium, amido, imido, urethane, ureido, or mercapto; or carboxylic (CO2H), sulfonic, sulfinic, phosphoric, or phosphoric acids or salts thereof.
  • compatibilizing groups are present in the branch segment(s).
  • the protected acid groups (described infra) produce carboxylic acid groups after exposure to UV or other actinic radiation and subsequent post-exposure baking (i.e., during deprotection).
  • the branched polymer present in the photosensitive compositions of this invention typically will contain between about 3% to about 40% by weight of monomer units containing protected acid groups, preferably between about 5% to about 50%, and more preferably between about 5% to about 20%.
  • the branch segments of such a preferred branched polymer typically contain between 35% to 100% of the protected acid groups present.
  • Such a branched polymer when completely unprotected (all protected acid groups converted to free acid groups) has an acid number between about 20 and about 500, preferably between about 30 and about 330, and more preferably between about 30 and about 130, and analogously the ethylenically unsaturated macromer component preferably has an acid number of about 20 and about 650, more preferably between about 90 and about 300 and the majority of the free acid groups are in the branch segments.
  • the branched polymer comprises one or more branch segments chemically linked along a linear backbone segment wherein the branched polymers have a number average molecular weight (M n ) of about 500 to 40,000.
  • the branched polymer contains at least 0.5% by weight of branch segments.
  • the branch segments also known as polymer arms, typically are randomly distributed along the linear backbone segment.
  • the "polymer arm” or branch segment is a polymer or oligomer of at least two repeating monomer units, which is attached to the linear backbone segment by a covalent bond.
  • the branch segment, or polymer arm can be incorporated into the branched polymer as a macromer component, during the addition polymerization process of a macromer and a comonomer.
  • a PAG is utilized having a hydroxy group, it is possible, as illustrated in some of the examples, to covalently link (tether) a PAG (or other photoactive components) to a branched polymer comprised of ITA comonomer or the like via this type of ester linkage (or other covalent linkages, such as amide, etc.).
  • Each constituent linear backbone segment and/or branch segment of the branched polymer of this invention may contain a variety of functional groups.
  • a "functional group” is considered to be any moiety capable of being attached to a backbone segment or a branch segment by a direct valence bond or by a linking group.
  • -COOR24 -OR 24 ; -SR24 wherein R 24 can be hydrogen, alkyl group having 1 to 12 carbon atoms; cycloalkyl group of 3-12 carbon atoms; aryl, alkaryl or aralkyl group having 6 to 14 carbon atoms; a heterocyclic group containing 3 to 12 carbon atoms and additionally containing an S, O, N or P atom; or -OR27 where R 27 can be alkyl of 1-12 carbon atoms, aryl, alkaryl or aralkyl group having 6 to 14 carbon atoms; -CN; -N R 25 R26 or
  • the fluorine-containing graft copolymer is further comprised of a repeat unit derived from at least one unsaturated compound selected from the group consisting of structures shown for polymer (a) above.
  • the fluorinated polymers, ARCs, and processes of this invention that include a fluoroalcohol functional group may have the structure:
  • CH 2 CHOCH 2 CH 2 ⁇ CH 2 C(CF 3 ) 2 ⁇ H
  • (c2) a fluorine-containing copolymer comprising a repeat unit derived from at least one ethylenically unsaturated compound characterized in that at least one ethylenically unsaturated compound is cyclic or polycyclic, at least one ethylenically unsaturated compound contains at least one fluorine atom covalently attached to an ethylenically unsaturated carbon atom, and at least one ethylenically unsaturated compound is comprised of a fluoroalcohol functional group having the structure:
  • each of R 40 , R 41 , R 42 , and R 43 independently is hydrogen atom, a halogen atom, a hydrocarbon group containing from 1 to 10 carbon atoms, a hydrocarbon group substituted with O, S, N, P or halogen and having 1 to 12 carbons atoms, for example, an alkoxy group, a carboxylic acid group, a carboxylic ester group or a functional group containing the structure:
  • Rf and Rf' are as describe above;
  • R 44 is a hydrogen atom or an acid- or base-labile protecting group;
  • v is the number of repeat units in the polymer;
  • w is 0-4; at least one of the repeat units has a structure whereby at least one of R 40 , R 41 , R 42 , and R 43 contains the structure C(Rf)(Rf')OR 44 , for example, R 0, R 4" l, and R 42 are a hydrogen atom and
  • R 43 is CH 2 OCH 2 C(CF 3 ) 2 OCH 2 CO 2 C(CH 3 ) 3 wherein CH 2 CO 2 C(CH 3 ) 3 is an acid or base labile protecting group or R 43 is
  • an ethylenically unsaturated compound undergoes free radical polymerization to afford a polymer having a repeat unit that is derived from the ethylenically unsaturated compound.
  • the components in the antireflective layer and resist compositions must contain sufficient functionality for development following imagewise exposure to UV light.
  • the functionality is acid or protected acid such that aqueous development is possible using a basic developer such as sodium hydroxide solution, potassium hydroxide solution, or ammonium hydroxide solution.
  • the polymers in the antireflective layer and resist compositions of this invention are typically acid-containing materials comprised of at least one fluoroalcohol-containing monomer of structural unit:
  • a critical fluid is one or more substances heated to a temperature near or above its critical temperature and compressed to a pressure near or above its critical pressure.
  • Critical fluids in this invention are at least at a temperature that is higher than 15°C below the critical temperature of the fluid and are at least at a pressure higher than 5 atmosphers below the critical pressure of the fluid.
  • Carbon dioxide may be used for the critical fluid in the present invention.
  • Various organic solvents can also be used as developer in this invention. These include, but are not limited to, halogenated solvents and non-halogenated solvents. Halogenated solvents are typical and fluorinated solvents are more typical.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP01995153A 2000-11-29 2001-11-21 Antireflex-schicht zur verwendung in der mikrolithographie Withdrawn EP1364254A2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US25398000P 2000-11-29 2000-11-29
US253980P 2000-11-29
PCT/US2001/043437 WO2002044816A2 (en) 2000-11-29 2001-11-21 Antireflective layer for use in microlithography

Publications (1)

Publication Number Publication Date
EP1364254A2 true EP1364254A2 (de) 2003-11-26

Family

ID=22962450

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01995153A Withdrawn EP1364254A2 (de) 2000-11-29 2001-11-21 Antireflex-schicht zur verwendung in der mikrolithographie

Country Status (7)

Country Link
EP (1) EP1364254A2 (de)
JP (1) JP2004537059A (de)
KR (1) KR20040012692A (de)
CN (1) CN1545644A (de)
AU (1) AU2002225666A1 (de)
TW (1) TW561310B (de)
WO (1) WO2002044816A2 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4400572B2 (ja) * 2003-11-19 2010-01-20 ダイキン工業株式会社 レジスト積層体の形成方法
US7671348B2 (en) 2007-06-26 2010-03-02 Advanced Micro Devices, Inc. Hydrocarbon getter for lithographic exposure tools
CN101989046B (zh) * 2009-08-06 2013-05-29 中芯国际集成电路制造(上海)有限公司 图形转移方法和掩模版制作方法
KR101247830B1 (ko) * 2009-09-15 2013-03-26 도오꾜오까고오교 가부시끼가이샤 보호막 형성용 재료 및 포토레지스트 패턴 형성 방법
WO2020114970A1 (en) * 2018-12-04 2020-06-11 Solvay Specialty Polymers Italy S.P.A. Fluoropolymer having alicyclic repeating units
EP4073586B1 (de) * 2019-12-12 2023-12-20 Solvay Specialty Polymers Italy S.p.A. Verfahren zum entfernen einer fluorpolymerabhebeschicht

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3979553B2 (ja) * 1998-06-12 2007-09-19 東京応化工業株式会社 反射防止膜形成用塗布液組成物およびこれを用いたレジスト材料
US6593058B1 (en) * 1998-09-23 2003-07-15 E. I. Du Pont De Nemours And Company Photoresists, polymers and processes for microlithography
KR100571470B1 (ko) * 1998-10-27 2006-04-17 이 아이 듀폰 디 네모아 앤드 캄파니 마이크로리소그래피를 위한 포토레지스트 및 방법
JP2000249804A (ja) * 1999-02-24 2000-09-14 Asahi Glass Co Ltd 反射防止性基材およびそれを用いた物品
EP1240554A2 (de) * 1999-11-17 2002-09-18 E.I. Du Pont De Nemours And Company Nitril/fluoroalkohol-polymer enthaltende photoresiste und die damit verbundenen verfahren für die mikrolithographie

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0244816A2 *

Also Published As

Publication number Publication date
WO2002044816A3 (en) 2003-09-12
WO2002044816A2 (en) 2002-06-06
JP2004537059A (ja) 2004-12-09
AU2002225666A1 (en) 2002-06-11
CN1545644A (zh) 2004-11-10
TW561310B (en) 2003-11-11
KR20040012692A (ko) 2004-02-11

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