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WO2008035640A1 - Composition pour la formation d'un film de protection de réserve et procédé de formation de motif de réserve à l'aide de ladite composition - Google Patents

Composition pour la formation d'un film de protection de réserve et procédé de formation de motif de réserve à l'aide de ladite composition Download PDF

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Publication number
WO2008035640A1
WO2008035640A1 PCT/JP2007/067986 JP2007067986W WO2008035640A1 WO 2008035640 A1 WO2008035640 A1 WO 2008035640A1 JP 2007067986 W JP2007067986 W JP 2007067986W WO 2008035640 A1 WO2008035640 A1 WO 2008035640A1
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WIPO (PCT)
Prior art keywords
resist
protective film
forming
composition
group
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PCT/JP2007/067986
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English (en)
Japanese (ja)
Inventor
Keita Ishiduka
Toshikazu Takayama
Satoshi Maemori
Shigeru Yokoi
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Tokyo Ohka Kogyo Co., Ltd.
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Application filed by Tokyo Ohka Kogyo Co., Ltd. filed Critical Tokyo Ohka Kogyo Co., Ltd.
Priority to JP2008535340A priority Critical patent/JP4918095B2/ja
Publication of WO2008035640A1 publication Critical patent/WO2008035640A1/fr

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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20Exposure; Apparatus therefor
    • G03F7/2041Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means

Definitions

  • Resist protective film forming composition and resist pattern forming method using the same
  • the present invention relates to a resist protective film-forming composition for forming a resist protective film provided on a resist film. More specifically, the present invention relates to an ⁇ alkali-soluble polymer, and (b) an ether solvent and an alcohol system. The present invention relates to a resist protective film forming composition containing an organic solvent composed of a mixed solvent with a solvent, and a resist pattern forming method using the resist protective film forming composition.
  • Non-Patent Documents 1 to 3 a liquid immersion lithography process has been reported as a new lithography technique.
  • the resist film is exposed with an immersion medium having a predetermined thickness interposed on at least the resist film in an exposure optical path between an exposure apparatus (lens) and the resist film on the substrate.
  • this is a method of forming a resist pattern.
  • an inert gas such as air or nitrogen has been interposed.
  • the gas in the exposure optical path space is larger than the refractive index of these gases, and a resist film. It is replaced with an immersion medium having a refractive index (n) smaller than the refractive index (for example, pure water or a fluorine-based inert liquid).
  • n refractive index
  • the immersion exposure process achieves high resolution even when a light source with the same exposure wavelength is used, as is the case with exposure light with a shorter wavelength or with a high NA lens. At the same time, it has the advantage that the depth of focus does not decrease.
  • a resist pattern can be formed (see Patent Document 1).
  • the resist protective film is removed at the time of alkali development after immersion exposure by using an alkali-soluble resist protective film. And a technique for simultaneously forming a resist pattern has been proposed (see Patent Document 3).
  • Non-Patent Document 1 “Journal of Vacuum Science & Technology B” (USA), 1999, Vol. 117, No. 6, pages 3306-3309
  • Non-Patent Document 2 "Journal of Vacuum Science & Technology B” (USA), 2001, Vol. 119, No. 6, pages 2353-2356
  • Non-Patent Document 3 "Proceedings of SPI E”, (USA), 2002, 4691, 459-465
  • Patent Document 1 International Publication No. 2004/068242 Pamphlet
  • Patent Document 2 Pamphlet of International Publication No. 2004/074937
  • Patent Document 3 Japanese Patent Laid-Open No. 2005-264131
  • the solvent used in the resist protective film forming material disclosed in Patent Document 3 is mainly alcohol.
  • alcohol when used as a solvent, the resist pattern that can damage the resist film becomes T-top shape, or if the surface of the resist pattern is rough, it may swell. Sometimes.
  • the use of alcohol may be restricted depending on the structure of the polymer (resin) used in the resist composition.
  • the present invention is capable of forming a favorable rectangular resist pattern with little damage to the resist film, and a polymer in the resist composition.
  • the purpose of the present invention is to provide a resist protective film forming composition whose use is not restricted by any structure, and a resist pattern forming method using the resist protective film forming composition. To do.
  • the present inventors have found that the above-mentioned problems can be solved by using an organic solvent composed of a mixed solvent of an ether solvent and an alcohol solvent as a solvent of the composition for forming a resist protective film.
  • the present invention has been completed. Specifically, it is as follows.
  • the present invention relates to a resist protective film-forming composition for forming a resist protective film provided on a resist film, comprising: (a) an alkali-soluble polymer; and (b) an ether solvent and an alcohol solvent. And a composition for forming a resist protective film, which comprises an organic solvent comprising a mixed solvent.
  • the present invention also includes a resist film forming step of forming a resist film on a substrate, and a protective film forming step of forming a resist protective film on the resist film using the resist protective film forming composition described above.
  • Forming a resist pattern comprising: an exposure step of exposing the resist film through the resist protective film; and an image step of developing the resist film after the exposure by removing the resist protective film with a developer.
  • the present invention it is possible to reduce damage to the resist film by using an organic solvent composed of a mixed solvent of an ether solvent and an alcohol solvent.
  • an organic solvent composed of a mixed solvent of an ether solvent and an alcohol solvent.
  • the solubility of the polymer can be improved by using an organic solvent comprising a mixed solvent of an ether solvent and an alcohol solvent.
  • composition for forming a resist protective film according to the present invention includes an immersion exposure process and a dry exposure process. It can be used for both exposure processes.
  • the composition for forming a resist protective film of the present invention comprises an ⁇ alkali-soluble polymer (hereinafter also referred to as ⁇ component), and (b) an organic solvent (hereinafter referred to as a mixed solvent of an ether solvent and an alcohol solvent). (Also referred to as component (b)). The following explains each component o
  • alkali-soluble polymer (a) examples include the following embodiments.
  • a polymer having at least a monomer unit represented by the following general formula (A-1) as a constituent unit can be used as a first embodiment of (a) the alkali-soluble polymer.
  • R is an alkylene group having 1 to 6 carbon atoms or a fluoroalkylene group, and each R is independently a hydrogen atom or a straight chain having 1 to 6 carbon atoms.
  • is an alkylene group having 1 to 2 carbon atoms or an oxygen atom, and ⁇ is an integer of 0 to 3.
  • R specifically, methylene group, ethylene group, ⁇ -propylene group, ⁇ butylene group, ⁇ -pentylene group or other linear alkylene group, 1 methylethylene group, 1-methylpropylene Groups, branched alkylene groups such as 2-methylpropylene group, and the like. Some or all of the hydrogen atoms of these alkylene groups may be substituted with fluorine atoms. Among these, R is more preferably a methylene group.
  • R include, in addition to a hydrogen atom, a methyl group, an ethyl group, and ⁇ -propinole.
  • Group a linear alkyl group such as n-butyl group and n-pentyl group, and a branched alkyl group such as isopropyl group, 1-methylpropyl group and 2-methylpropyl group.
  • Some or all of the hydrogen atoms of these alkyl groups may be substituted with fluorine atoms.
  • a perfluoroalkyl group in which all of the hydrogen atoms of these alkyl groups are replaced with fluorine atoms is preferable, and a trifluoromethyl group is particularly preferable.
  • Z is preferably a methylene group, and n is preferably 0.
  • the alkali-soluble polymer of the first aspect includes a structural unit represented by the above general formula (A-1), the following general formulas (A-2), (A-3), and (A — A copolymer having at least one selected from among the monomer units represented by 4) as a constituent unit may also be used.
  • R represents an alkyle having 1 to 6 carbon atoms.
  • R and R are each an alkyl group having 0 to 6 carbon atoms.
  • the monomer units represented by the general formulas (A-2), (A-3), and (A-4) are represented by the following general formulas (A-5), (A-6), and ( The monomer unit represented by A—7) is preferred.
  • R represents a single bond or a methylene group.
  • R is independently a methyl group or a trifluoromethyl group, and R is carbon.
  • R is a linear or branched alkyl having 5 to 10 carbon atoms.
  • a fluoroalkyl group (provided that a part of the hydrogen atom or fluorine atom of the alkyl group or fluoroalkyl group may be substituted by a hydroxyl group), R Z, and
  • R is -CH C F or one C (CH) CH C (CF) OH.
  • R is C F -CF CF (CF) CF CF CF CF (CF) or one CF CF (CF)
  • CF C (CF) is preferred.
  • the basic characteristics required for the protective film are the ability of the immersion medium to have high resistance to the immersion medium and low compatibility with the resist film provided in the lower layer.
  • the resist film strength can also prevent elution of components into the immersion medium, and can suppress gas permeation of the protective film.
  • the above general formula (A-2), (A By incorporating at least one structural unit selected from the monomer units represented by 3) and (A-4), a protective film with further improved water repellency can be formed.
  • a large amount of the monomer unit represented by the general formula (A-2) as the monomer unit is preferable because the solubility of the copolymer in the ether solvent is improved.
  • a monomer unit represented by the general formula (A-1) and a copolymer essentially including the monomer unit represented by the general formula (A-2) are preferable.
  • a copolymer comprising a monomer unit represented by formula (1) and / or a monomer unit represented by formula (A-4) is more preferred.
  • an alkali-soluble structure composed of an aliphatic cyclic compound having both a fluorine atom or a fluoroalkyl group and an alcoholic hydroxyl group or an oxyalkyl group is used.
  • Polymers having units can be used.
  • a fluorine atom or a fluoroalkyl group and an alcoholic hydroxyl group or an alkyloxy group of the structural unit are bonded to an aliphatic cyclic compound, respectively, and the aliphatic ring constitutes the main chain. It is.
  • fluorine atom or the fluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and the like.
  • a fluorine atom or a trifunoleolomethyl group is preferable.
  • the alcoholic hydroxyl group or alkyloxy group specifically, an alcoholic hydroxyl group, a linear, branched, or cyclic alkyloxyalkylene group or alkyloxy group having 1 to 15 carbon atoms is used. Can be mentioned.
  • alkyloxy group having 1 to 15 carbon atoms include a methyloxy group, an ethyloxy group, a propyloxy group, a butoxy group, and the like, and examples of the alkyloxy group having 1 to 15 carbon atoms include Examples thereof include a methyloxymethyl group, an ethyloxymethyl group, a propoxymethyl group, and a butoxymethyl group.
  • the gen compound is preferably butadiene, which is excellent in transparency and dry etching resistance, and can easily form a polymer having a 5-membered ring or a 6-membered ring.
  • a polymer formed by polymerization is most preferred in the industry.
  • each R is independently a hydrogen atom, or a straight, branched, or
  • 1 and m represent the molar ratio of the structure in parentheses, and each 10 mol% force is 90 mol%.
  • each R is independently linear, branched,
  • a cyclic alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group is a cyclic alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group.
  • R 15 each independently represents a hydrogen atom, a fluorine atom, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group, and at least one of R 1 and R 2
  • the displacement force is a group having a fluorine atom.
  • R is a hydrogen atom or a methyl group, and p is
  • the structural units represented by the general formulas (A-9) and (A-10) are represented by the following structural formulas (A-11) and (A-12), respectively.
  • the structural unit is preferably used.
  • the polymer having the structural units represented by (A-9) and (A-10) is: It may be a copolymer and / or a mixed polymer with the structural unit represented by the general formula (A-13). By using such a copolymer and / or mixed polymer, alkali solubility can be further improved.
  • each R is independently a hydrogen atom or linear or branched.
  • p is a repeating unit as in the general formulas (A-9) and (A-10).
  • C is a methylene group or a fluoromethylene group
  • R is
  • a 18 Linear, branched or cyclic fluoroalkyl group having 1 to 5 carbon atoms, q is an integer of 0 to 3, and p is the same as in general formulas (A-9) and (A-10) It is a repeating unit.
  • part or all of the hydrogen atoms bonded to the carbon atoms constituting the ring skeleton may be substituted with fluorine atoms! /.
  • the structural unit represented by 15) is particularly preferably used.
  • R is a hydrogen atom or a methyl group, and R is a carbon atom of 1
  • R 1 is a group in which some or all of the hydrogen atoms are substituted with fluorine atoms.
  • P is a general formula (A-9) and (A-2)
  • C is a methylene group or a fluoromethylene group
  • R is
  • a 22 A linear, branched, or cyclic fluoroalkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms, and R is a hydrogen atom or a hydrogen atom.
  • part or all of the hydrogen atoms bonded to the carbon atoms constituting the ring skeleton may be substituted with fluorine atoms! /, Or may be! /.
  • the above-mentioned (a) alkali-soluble polymer does not impair the effects of the present invention! / If within the range, the copolymerized polymer obtained by copolymerization or mixing with any other monomer unit It may be a polymer or a mixed polymer.
  • Such (a) alkali-soluble polymer can be synthesized by a known method.
  • the polystyrene equivalent weight average molecular weight (Mw) of this polymer by GPC is not limited to force 2000 force, etc. 80000, 3000 force, etc. More preferred.
  • the blending amount of the alkali-soluble polymer is preferably about 0.1% by mass to 20% by mass with respect to the total amount of the resist protective film forming composition. More preferably, the content is 10% by mass.
  • the organic solvent (b) is not particularly limited as long as it is an organic solvent composed of a mixed solvent of an ether solvent and an alcohol solvent.
  • V and the difference do not contain a fluorine atom! /, Or an organic solvent.
  • the ether solvent preferably has 2 to 16 carbon atoms, more preferably 6 to 12 carbon atoms. By setting the carbon number within the above range, damage to the resist film can be further reduced, and the coating property and drying property of the resist protective film forming composition can be maintained in a good state.
  • ether solvents include linear chains such as dimethyl ether, jetyl ethereol, methinoleethinoreethenole, dipropinoleenotenole, diisopropinoleethenore, dibutyl ether, diisoamyl ether, and the like.
  • examples include branched alkyl ethers. Among these, it is preferable to use at least one selected from diisopropyl ether, dibutyl ether, and diisoamyl ether. These can be used alone or in combination of two or more.
  • ether solvents are non-fluorine solvents, it is possible to provide a composition for forming a resist protective film that has little environmental impact.
  • the boiling point of the ether solvent is preferably 200 ° C. or less from the viewpoint of coating properties and drying properties of the resist protective film forming composition! [0064] Further, the alcohol solvent preferably has 2 to 10 carbon atoms. By making the number of carbons within the above range, it becomes possible to improve the solubility of (a) the alkali-soluble polymer.
  • alkyl alcohols examples include linear, branched, and cyclic alkyl alcohols such as ethanol, propanol, n-butanol, isobutanol, n-pentanol, 4-methyl-2-pentanol, and 2-octanol. Among them, it is preferable to use at least one selected from 4-methyl 2-pentanol and iso-butanol.
  • the boiling point of the alcohol solvent is preferably 200 ° C. or less from the viewpoints of coating properties and drying properties of the resist protective film forming composition.
  • the content ratio of the ether solvent and the alcohol solvent in the organic solvent is preferably 50:50 force, et al. 99: 1 by mass ratio, 60:40 force, et al. 99: 1 is more preferable, and 80:20 to 95: 5 is most preferable.
  • the composition for forming a resist protective film according to the present invention may further contain (c) a crosslinking agent, if necessary, in addition to the components (a) and (b).
  • the crosslinking agent includes a nitrogen-containing compound having an amino group substituted with at least one substituent selected from a hydroxyalkyl group and an alkoxyalkyl group, and a hydrogen atom having a hydroxyalkyl group and an alkoxyalkyl group.
  • nitrogen-containing compounds include, for example, melamine derivatives, urea derivatives, guanamine derivatives, acetoguanamine derivatives, benzoguanamine derivatives, which are substituted with a hydrogen atom of a hydroxyl group, a hydroxyl group or an alkoxymethyl group, or both.
  • Succinamide derivatives, glycoluril derivatives in which the hydrogen atom of the imino group is substituted examples include a tylene urea-based derivative.
  • nitrogen-containing compounds are obtained by, for example, reacting the above-mentioned nitrogen-containing compounds with formalin in boiling water to form methylol, or in addition to this, lower alcohols, specifically methanol, ethanol, n- It can be obtained by reacting with propanol, isopropanol, n-butanol, isobutanol and the like to effect alkoxylation.
  • a preferable cross-linking agent is tetrabutoxymethylated glycoluril.
  • a condensation reaction product of a hydrocarbon compound substituted with at least one substituent selected from a hydroxyl group and an alkyloxy group and a monohydroxymonocarboxylic acid compound may be preferably used. it can.
  • the monohydroxymonocarboxylic acid those in which the hydroxyl group and the carboxyl group are bonded to the same carbon atom or two adjacent carbon atoms are preferred.
  • the blending amount is preferably about 0.5 to 10% by mass with respect to the amount of (a) the alkali-soluble polymer.
  • the resist protective film-forming material according to the present invention may further contain (d) an acidic compound as necessary.
  • an acidic compound By adding this acidic compound, an effect of improving the shape of the resist pattern can be obtained.
  • the resist film is exposed to an atmosphere containing a trace amount of amine before development. Even if it is present (reservation after exposure), the presence of the protective film can effectively suppress the adverse effects of the amine. As a result, it is possible to prevent a large deviation in the size of the resist pattern obtained by subsequent development.
  • Examples of such acidic compounds include at least one selected from the following general formulas (D-l), (D-2), (D-3), and (D-4). .
  • 23 24 is an alkyl group having 1 to 15 carbon atoms or a fluoroalkyl group (a part of hydrogen atoms or fluorine atoms may be substituted with a hydroxyl group, an alkoxy group, a carboxyl group, or an amino group).
  • the compound is preferably a compound such as C 2 F 3 COOH.
  • the blending amount is set to 0.
  • It is preferably about 1 to 10% by mass.
  • the resist protective film-forming composition according to the present invention may further contain (e) an acid generation assistant.
  • This (e) acid generation auxiliary agent means an acid generation agent that does not have a function of generating an acid alone, but generates an acid by the presence of an acid.
  • the acid generation in the resist film Even when acid power S generated from the raw material is diffused into the resist protective film, the acid generated from the acid generation auxiliary agent in the resist protective film compensates for the shortage of acid in the resist film. By doing so, it is possible to suppress the degradation of the resolution of the resist composition and the reduction of the depth of focus, and a finer resist pattern can be formed.
  • Such an acid generation auxiliary agent is preferably an alicyclic hydrocarbon compound having both a carbonyl group and a sulfonyl group in the molecule.
  • such an acid generation auxiliary agent is preferably at least one selected from the compounds represented by the following general formulas (E-1) and (E-2).
  • R to R are each independently a hydrogen atom
  • X is an electrophilic group having a sulfonyl group.
  • the "linear or branched alkyl group having 1 to 10 carbon atoms” means a methyl group, an ethynole group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second group Butyl, tertiary butyl, amyl, isoamyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl And straight-chain or branched saturated hydrocarbon groups such as a group, a decyl group, and an isodecyl group.
  • X is "an electrophilic group having a sulfonyl group".
  • the “electrophilic group having a sulfonyl group” is preferably —O—SO—Y. Where Y is 1 carbon number
  • Y is preferably a fluoroalkyl group.
  • Specific examples of the compounds represented by the general formulas (E-1) and (E-2) include the following: Examples thereof include compounds represented by formulas (E-3) to (E-10).
  • the blending amount of the acid generation auxiliary agent is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the (a) alkali-soluble polymer. Is more preferable. By setting it within such a range, it is possible to improve the pattern shape by effectively generating an acid with respect to the resist film force that does not cause uneven coating and the acid eluted.
  • the protective film-forming composition according to the present invention may further contain an optional (f) surfactant, if desired.
  • this surfactant include “XR-104” (trade name: manufactured by Dainippon Ink & Chemicals, Inc.), but are not limited thereto. By blending such a surfactant, it is possible to further improve the coating properties and the ability to suppress the eluate.
  • the blending amount is (a) an alkali-soluble polymer.
  • the amount is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass.
  • the resist composition is not particularly limited, and any resist composition that can be developed with an aqueous alkali solution, including negative and positive resist compositions, can be used.
  • Such resist compositions include (i) a pod-type resist composition containing a naphthoquinone diazide compound and a nopolac resin, (ii) a compound that generates an acid upon exposure, an alkaline water decomposed by the acid.
  • a positive resist composition containing a compound that increases solubility in a solution and an alkali-soluble resin (iii) a compound that generates an acid upon exposure, an alkali having a group that decomposes with an acid and increases the solubility in an alkaline aqueous solution Power that includes a positive resist composition containing a soluble resin, and (iv) a negative resist composition containing a compound that generates an acid by light, a cross-linking agent, and an alkali-soluble resin, etc. Absent.
  • the method for forming a resist pattern according to the present invention includes a resist film forming step for forming a resist film on a substrate, and a protective film for forming a resist protective film on the resist film using a resist protective film forming composition.
  • This resist pattern can be formed using either a dry exposure process or an immersion exposure process.
  • the “resist film forming step” refers to a step of forming a resist film on a substrate. Specifically, a known resist composition is applied to a substrate such as a silicon wafer by using a known method such as a spinner and then pre-beta (PAB treatment) is performed to form a resist film. Note that the resist film may be formed after providing one layer of an organic or inorganic antireflection film (lower antireflection film) on the substrate.
  • the resist composition is not particularly limited, and any resist composition that can be developed with an alkaline aqueous solution can be used, including negative and positive resists.
  • a resist composition the resist composition as described above can be used.
  • “Protective film forming step” refers to a step of forming a resist protective film. Specifically, the resist protective film forming composition according to the present invention is uniformly applied to the surface of the resist film formed by the above resist film forming process by the same method as in the resist film forming process, beta And a step of forming a resist protective film by curing.
  • the “exposure step” refers to a step of performing exposure at a predetermined wavelength via a mask pattern from above the resist protective film formed in the protective film forming step. At this time, the exposure light passes through the resist protective film and reaches the resist film.
  • the wavelength used for exposure in this case is appropriately selected depending on the characteristics of the resist film, which is not particularly limited.
  • the exposure wavelength is particularly preferably 193 nm.
  • the refractive index of the resist protective film with respect to the exposure wavelength is preferably higher than the refractive index of water at the exposure wavelength!
  • the exposed resist film and resist protective film are subjected to a heat treatment (PEB).
  • PEB heat treatment
  • Developing step refers to a step of developing a resist film after exposure using an alkaline developer composed of an alkaline aqueous solution. Since this developing solution is alkaline, when the resist protective film is formed on the surface of the resist film, the resist protective film is first dissolved, and then the soluble portion of the resist film is dissolved. In addition, post-beta may be performed after development.
  • the same procedure as in the dry exposure process is performed up to the “protective film formation step”. Then, in the “exposure process”, an immersion medium is disposed on the substrate on which the resist protective film is formed, and in this state, the resist film and the resist protective film on the substrate are selectively exposed through the mask pattern. I do. Accordingly, at this time, the exposure light passes through the immersion medium and the resist protective film and reaches the resist film.
  • the exposure light is not particularly limited as in the dry exposure process, and can be performed using radiation such as ArF excimer laser, KrF excimer laser, VUV (vacuum ultraviolet).
  • the immersion medium is not particularly limited as long as it is a liquid having a refractive index larger than that of air and smaller than that of the resist film to be used.
  • immersion media include water (pure water, deionized water), fluorine-based inert liquids, etc., but immersion media having high refractive index characteristics that are expected to be developed in the near future can also be used. is there.
  • fluorinated inert liquids include c HC1 F, C F OCH, C F OC H, C
  • liquids mainly composed of fluorine-based compounds such as HF.
  • fluorine-based compounds such as HF.
  • water pure water, deionized water
  • exposure light eg, F excimer laser
  • the exposed resist film and resist protective film are heated in the same manner as in the dry exposure process, and developed using an alkali developer.
  • a known developing solution can be appropriately selected and used as the alkaline developer.
  • the resist protective film is dissolved and removed simultaneously with the soluble portion of the resist film.
  • post-beta may be performed following the development processing.
  • rinsing is performed using pure water or the like.
  • water rinse for example, while rotating the substrate, water is dropped or sprayed on the surface of the substrate to wash away the developer on the substrate and the resist protective film component and the resist composition dissolved by the developer. Then, drying is performed to obtain a resist pattern in which the resist film is patterned into a shape corresponding to the mask pattern.
  • the removal of the resist protective film and the development of the resist film are realized simultaneously by the development process.
  • the resist protective film formed from the resist protective film-forming composition of the present invention has improved water repellency, so that the amount of the immersion medium that can be easily separated after completion of the exposure is as follows. So-called immersion medium leakage with less is less. [0109]
  • a resist pattern By forming a resist pattern in this manner, it is possible to manufacture a resist pattern with a fine line width, particularly a line 'and' space pattern with a small pitch with a good resolution. Note that the pitch in the line-and-space pattern refers to the total distance of the resist pattern width and the space width in the line width direction of the pattern.
  • the resist pattern formed by such a method has a better rectangular shape as compared with the case where a resist pattern is formed using a conventional resist protective film-forming composition using only an alcohol solvent. .
  • a film-forming composition 2 was prepared.
  • a resist protective film forming composition 4 having a solid content concentration of 1.5% by mass.
  • TArF-7a 128 manufactured by Tokyo Ohka Kogyo Co., Ltd.
  • ARC29 manufactured by Brewer
  • a resist film with a film thickness of 170 nm is formed by heating at 60 ° C for 60 seconds, and the resist protective film forming compositions 1 to 4 are applied to the upper layer, and heated at 90 ° C for 60 seconds.
  • a resist protective film having a thickness of 35 nm was formed.
  • the resist pattern As a result of observing the resist pattern with an SEM (scanning electron microscope), the resist pattern was formed in a good rectangular shape when using the resist protective film forming compositions 1 to 3 of Examples; In contrast, when the resist protective film forming composition 4 of Comparative Example 1 was used, the pattern top portion had a T-top shape.
  • X-2 mass average molecular weight
  • a resist protective film-forming composition 5 having a solid content concentration of 2.5 mass% was prepared.
  • This substrate was subjected to immersion exposure using an exposure machine NSR-S609B (Nikon Corp.), followed by post-exposure heating at 100 ° C for 60 seconds, followed by 2.38% by mass.
  • a resist pattern was formed by developing for 30 seconds using an aqueous solution of tetramethylammonium hydroxide (TMAH) and rinsing.
  • TMAH tetramethylammonium hydroxide
  • the shape of the resist pattern was a good rectangular shape.
  • TARF-7a 128 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is a resist material containing acrylic yarn resin, is applied onto a substrate on which ARC29 (manufactured by Brewer) having a film thickness of 77 nm is formed. Then, a resist film with a thickness of 170 nm is formed, and a resist protective film-forming composition 6 is applied on the upper layer and heated at 90 ° C. for 60 seconds to form a resist film with a thickness of 35 nm. A strike protective film was formed.
  • This substrate was subjected to immersion exposure using an exposure machine NSR-S609B (Nikon Corp.), followed by post-exposure heating at 100 ° C for 60 seconds, followed by 2.38 mass% tetramethyl.
  • the resist pattern was formed by developing for 30 seconds using an aqueous solution of ammonium hydroxide (TMAH) and rinsing.
  • TMAH ammonium hydroxide
  • the shape of the resist pattern was a good rectangular shape.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention concerne une composition pour la formation d'un film de protection de réserve, qui limite l'endommagement d'un film de réserve, qui permet de former un motif de réserve rectangulaire, satisfaisant, et qui peut être utilisée indépendamment de la structure d'une résine utilisée dans une composition de réserve; ainsi qu'un procédé de formation d'un motif de réserve à l'aide de la composition. Plus spécifiquement, l'invention concerne une composition pour la formation d'un film de protection de réserve, qui comprend (a) un polymère alcalino-soluble et (b) un solvant organique comprenant un mélange d'un solvant à base d'éther et un solvant à base d'alcool; ainsi qu'un procédé de formation d'un motif de réserve à l'aide de la composition.
PCT/JP2007/067986 2006-09-20 2007-09-14 Composition pour la formation d'un film de protection de réserve et procédé de formation de motif de réserve à l'aide de ladite composition WO2008035640A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007102228A (ja) * 2005-10-03 2007-04-19 Rohm & Haas Electronic Materials Llc フォトリソグラフィーのための組成物および方法
JP2008268850A (ja) * 2006-12-19 2008-11-06 Shin Etsu Chem Co Ltd パターン形成方法
JP2010134006A (ja) * 2008-12-02 2010-06-17 Shin-Etsu Chemical Co Ltd レジスト保護膜材料及びパターン形成方法
WO2011104127A1 (fr) 2010-02-24 2011-09-01 Basf Se Acides latents et leur utilisation

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JP2006030477A (ja) * 2004-07-14 2006-02-02 Fuji Photo Film Co Ltd 液浸露光用保護膜形成組成物及びそれを用いたパターン形成方法
WO2006035790A1 (fr) * 2004-09-30 2006-04-06 Jsr Corporation Copolymere et composition de formation de film supérieur
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WO2005098541A1 (fr) * 2004-03-31 2005-10-20 Central Glass Company, Limited Composition de revetement superieur
JP2005352384A (ja) * 2004-06-14 2005-12-22 Fuji Photo Film Co Ltd 液浸露光用保護膜形成組成物及びそれを用いたパターン形成方法
JP2006023538A (ja) * 2004-07-08 2006-01-26 Fuji Photo Film Co Ltd 液浸露光用保護膜形成組成物及びそれを用いたパターン形成方法
JP2006030477A (ja) * 2004-07-14 2006-02-02 Fuji Photo Film Co Ltd 液浸露光用保護膜形成組成物及びそれを用いたパターン形成方法
WO2006035790A1 (fr) * 2004-09-30 2006-04-06 Jsr Corporation Copolymere et composition de formation de film supérieur
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007102228A (ja) * 2005-10-03 2007-04-19 Rohm & Haas Electronic Materials Llc フォトリソグラフィーのための組成物および方法
JP2008268850A (ja) * 2006-12-19 2008-11-06 Shin Etsu Chem Co Ltd パターン形成方法
JP2010134006A (ja) * 2008-12-02 2010-06-17 Shin-Etsu Chemical Co Ltd レジスト保護膜材料及びパターン形成方法
WO2011104127A1 (fr) 2010-02-24 2011-09-01 Basf Se Acides latents et leur utilisation

Also Published As

Publication number Publication date
TWI367396B (fr) 2012-07-01
TW200836014A (en) 2008-09-01
JPWO2008035640A1 (ja) 2010-01-28
JP4918095B2 (ja) 2012-04-18

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