WO2005116762A1 - Composition de résine et procédé pour former un motif de masque - Google Patents

Composition de résine et procédé pour former un motif de masque Download PDF

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Publication number
WO2005116762A1
WO2005116762A1 PCT/JP2005/008004 JP2005008004W WO2005116762A1 WO 2005116762 A1 WO2005116762 A1 WO 2005116762A1 JP 2005008004 W JP2005008004 W JP 2005008004W WO 2005116762 A1 WO2005116762 A1 WO 2005116762A1
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Prior art keywords
group
resist composition
component
resist
formula
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PCT/JP2005/008004
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English (en)
Japanese (ja)
Inventor
Yusuke Nakagawa
Shinichi Hidesaka
Kazuhiko Nakayama
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Tokyo Ohka Kogyo Co., Ltd.
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Publication of WO2005116762A1 publication Critical patent/WO2005116762A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

Definitions

  • the present invention relates to a resist composition and a method for forming a resist pattern.
  • This application was filed on May 31, 2004, filed in Japanese Patent Application No. 2004-161880, filed in July 9, 2004, filed in Japanese Patent Application No. 2004-203115, and filed on September 6, 2004.
  • Priority is claimed based on Japanese Patent Application No. 2004-259059, the content of which is incorporated herein by reference.
  • miniaturization has rapidly progressed due to advances in lithography technology.
  • the wavelength of light from an exposure light source is shortened.
  • the KrF excimer laser (248 nm) has been introduced in the past, when ultraviolet light represented by g-line and i-line was mainly used.
  • one of the resist materials that satisfies the conditions of high resolution that can reproduce patterns with fine dimensions is a base resin whose alkali solubility changes by the action of acid, and an acid generator that generates acid by exposure.
  • a chemically amplified resist composition containing is known!
  • the chemically amplified resist composition includes a negative composition containing a crosslinking agent and an alkali-soluble resin as a base resin, and a positive composition containing a resin whose alkali solubility increases by the action of an acid. There is.
  • Acid generators used in such chemically amplified resist compositions include oxidized salt acid generators such as odonium salts and sulfo-dum salts, oxime sulfonate-based acid generators, bis Diazomethane acid generators such as alkyl or bisarylsulfol-diazomethanes, poly (bissulfol) diazomethanes, nitrobenzylsulfonates, iminosulfonate-based acid generators, and disulfonate-based acid generators Many kinds are known Yes.
  • oxidized salt acid generators such as odonium salts and sulfo-dum salts
  • oxime sulfonate-based acid generators such as oxime sulfonate-based acid generators
  • bis Diazomethane acid generators such as alkyl or bisarylsulfol-diazomethanes
  • a so-called salt-based acid generator having a high acid generating ability is mainly used (for example, see Patent Document 1).
  • Patent Document 1 JP-A-7-234511
  • the cross-sectional shape of the resist pattern may be in a so-called skirted shape (the lower end portion is tapered ( taper)) and a good rectangular pattern may not be obtained.
  • a so-called oxime sulfonate-based acid generator is used, an effect of improving the pattern shape can be obtained.
  • the acid generator While using an oxime sulfonate-based acid generator, the effect of improving the pattern shape can be obtained, when the resist composition is coated on a substrate to form a resist coating film, the acid generator is used. There is a problem that is deposited.
  • the present invention has been made in view of the above circumstances, and it is an object of the present invention to reduce the precipitation of an acid generator during coating in a resist composition containing an oxime sulfonate-based acid generator.
  • the present invention employs the following configurations.
  • the resist composition of the present invention is characterized in that a base resin component (A) and an oxime sulfonate-based acid generator (B) are dissolved in an organic solvent (C) containing methyl n-amyl ketone.
  • the resist composition of the present invention is prepared, the composition is applied on a substrate, pre-betaed, selectively exposed, and then subjected to PEB (heating after exposure), Developing to form a resist pattern.
  • a resist composition of the present invention is prepared, the composition is applied on a substrate, pre-betaed, selectively exposed, and then heated after exposure (PEB). Resist pattern to form a resist pattern And a narrowing step of narrowing the pattern size of the obtained resist pattern by heat treatment.
  • (meth) acrylate refers to one or both of methacrylate and acrylate.
  • the “structural unit” refers to a monomer unit that can constitute a polymer. What is the structural unit derived from (meth) acrylate ester
  • precipitation of an acid generator during coating of a resist composition containing an oxime sulfonate-based acid generator can be reduced.
  • the resist composition of the present invention is a composition in which a base resin component (A) and an oxime sulfonate-based acid generator (B) are dissolved in an organic solvent (C) containing methyl n-amyl ketone.
  • a base resin component (A) and an oxime sulfonate-based acid generator (B) are dissolved in an organic solvent (C) containing methyl n-amyl ketone.
  • the base resin component (A) means a component having a property of forming a resist film when a resist composition is coated on a substrate or the like.
  • a resin component such as (meth) acrylic resin is used.
  • the component (A) one or more alkali-soluble resins or alkalis commonly used as base resins for chemically amplified resists are used. Fats that can be soluble can be used.
  • the former resin can be used for producing a so-called negative resist composition, and the latter resin can be used for producing a so-called positive resist composition.
  • a crosslinking agent is usually added to the resist composition together with the acid generator component. Then, when an acid is generated from the acid generator component by exposure during the formation of the resist pattern, a strong acid acts, and as a result, crosslinking occurs between the component (A) and the crosslinking agent, and It becomes insoluble in Lucari.
  • the cross-linking agent for example, usually, an amino-based cross-linking agent such as melamine, urea, or glycolperyl having a methylol group or an alkoxymethyl group is used.
  • the component (A) is usually an alkali-insoluble component having any acid dissociable, dissolution inhibiting group. Dissociates the acid dissociable, dissolution inhibiting group, whereby the component (A) becomes alkali-soluble.
  • the resist composition of the present invention is preferably of a positive type.
  • the component (A) of the present invention is not particularly limited as long as it can be used as a base resin component of the resist composition as described above.
  • the composition unit derived from (meth) acrylate ester is 80 mol% or more. Preferably, it contains 90 mol% or more (100 mol% is most preferable).
  • the component (A) is a structural unit having a (meth) acrylic acid having an acid dissociable, dissolution inhibiting group and capable of inducing a (meth) acrylic acid. Or (al) units).
  • the component (A) is preferably composed of a combination of at least one selected unit and an (al) unit.
  • (a4) an acid dissociable, dissolution inhibiting group of (al) unit, a rataton unit of (a2) unit, and an alcoholic hydroxyl group-containing polycyclic group of (a3) unit.
  • structural unit containing a (hereinafter, (a 4) or (as a 4) units) [0013] (a2), (a3) and Z or (a4) can be appropriately combined depending on required characteristics and the like. Other components may be combined as necessary.
  • the component (A) contains (al) and (a2), whereby the resolution and the resist pattern shape are improved. Further, it is preferable that the total of these two types of structural units accounts for 40 mol% or more, more preferably 60 mol% or more of the component (A).
  • the units (al) to (a4) A plurality of different units may be used in combination.
  • the structural unit derived from the (meth) acrylic ester such as the (al) to (a4) units contained in the component (A)
  • the structural unit derived from methacrylic acid ester is derived.
  • the presence of both the structural unit and the structural unit derived from the acrylate ester results in less surface roughness during etching, less line edge roughness, excellent resolution, and excellent focus. This is preferable in that a positive resist composition having a wide depth range is obtained.
  • the surface roughness during the etching refers to a surface roughness of the resist pattern (deterioration of the profile shape) due to the influence of the above-mentioned solvent, or a surface roughness different from the conventional surface roughness that is meant by dry etching resistance.
  • surface roughness during etching means that after developing and forming a resist pattern, the etched resist pattern appears as a distortion around the hole pattern in the contact hole pattern, and the side surface in the line and space pattern. Means that appear as line edge roughness such as uneven unevenness.
  • Line edge roughness occurs in a resist pattern after development.
  • the line edge roughness appears as a distortion around the hole in the hole resist pattern, and appears as uneven unevenness on the side surface in the line and space pattern.
  • the structural unit derived from methacrylic acid ester can be improved by the presence of a structural unit derived from an ester ester derived from a lylic acid ester.
  • the component (A) contains a structural unit derived from a methacrylate ester and a structural unit derived from an acrylate ester.
  • the form and conditions are not particularly limited, and can be selected as needed.
  • the component (A) may be a copolymer (A1): a copolymer containing a structural unit derived from methacrylic acid ester and a structural unit derived from acrylate. ! / Mixed resin (A2): Mixed resin of a polymer containing at least a constituent unit derived from methacrylate ester and a polymer containing at least a constituent unit derived from acrylate ester, May be included.
  • the above component (A) may be mixed with another resin component.
  • the component (A) be one of the copolymer (A1) and the mixed resin (A2), and that both!
  • copolymer (A1) and the mixed resin (A2) may be used in combination of two or more different types! /.
  • the component (A) contains a structural unit also derived from methacrylic acid ester and a structural unit derived from acrylate ester, the structural unit derived from methacrylic acid ester and acrylic acid against the total mole number of Esuteruka ⁇ et the induced structural units, meta 10-85 moles of structural units derived from acrylic acid ester 0/0, preferably 20 to 80 mol%, also induced an acrylate ester force 15-90 mole 0/0 configuration unit that, preferably be used so as to be 20-8 0 mol%.
  • Methacrylic acid ester power If too many structural units are derived, the effect of improving surface roughness is reduced, and if there are too many structural units derived from acrylate, resolution may be reduced. Next, the units (al) to (a4) will be described in detail.
  • the (al) unit is a structural unit derived from a (meth) acrylate ester having an acid dissociable, dissolution inhibiting group.
  • the acid dissociable, dissolution inhibiting group in (al) has an alkali dissolution inhibiting property that renders the entire component (A) alkali-insoluble before exposure, and after exposure, the action of the acid generated by the component (B) occurs.
  • Any material can be used without particular limitation as long as it can dissociate and change the entire component (A) to alkali solubility.
  • a group forming a cyclic or chain tertiary alkyl ester, a tertiary alkoxycarbon group, or a chain alkoxyalkyl group with a carboxyl group of (meth) acrylic acid is widely known. ing. In the present invention, these groups can also be preferably used.
  • the acid dissociable, dissolution inhibiting group in (al) is preferably a structural unit represented by the following general formula (AI-1).
  • AI-1 the acid dissociable, dissolution inhibiting group is easily dissociated by the action of an acid having a relatively low protective energy. It is not clear whether this is the case or not, but the effect of improving the resist pattern shape is further improved by combination with an oxime sulfonate-based acid generator.
  • R represents a methyl group or a hydrogen atom
  • X represents an acid dissociable group containing a monocyclic or polycyclic alicyclic group in which a lower alkyl group is bonded to one of the carbon atoms on the ring skeleton.
  • the carbon atom which is a dissolution inhibiting group and to which the alkyl group is bonded is bonded to an oxygen atom adjacent to X. Shows a group that matches.
  • the lower alkyl group is a lower alkyl group having 1 to 5 carbon atoms, which may be any of a straight-chain or branched group. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n -butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Industrially, a methyl group or an ethyl group is preferred.
  • X has a monocyclic or polycyclic alicyclic group.
  • These cyclic groups may have a lower alkyl group (either linear or branched, preferably 1 to 5 carbon atoms) other than the lower alkyl group on the ring. . Preferred and embodiments of these cyclic groups are the same as those described above.
  • R represents a methyl group or a hydrogen atom
  • R 11 represents a lower alkyl group.
  • R represents a methyl group or a hydrogen atom
  • R 12 represents a lower alkyl group.
  • R 11, R 12 are each of 1 to 5 carbon atoms lower the Methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc., which are preferably linear or branched alkyl groups.
  • a methyl group or an ethyl group is preferred.
  • the acid dissociation-suppressing group in the structural unit (al) is preferably a group having a monocyclic or polycyclic alicyclic group, particularly a polycyclic alicyclic group. It is preferable to have one.
  • the alicyclic group may be either saturated or unsaturated, but is preferably saturated.
  • the alicyclic group is preferably a monocyclic or polycyclic hydrocarbon group. The hydrocarbon group may be substituted with a fluorine atom or a fluorinated alkyl group, or may be unsubstituted. Is also good.
  • the monocyclic alicyclic group (hereinafter sometimes referred to as a monocyclic group) may or may not be substituted with a fluorine atom or a fluorinated alkyl group. And a group from which hydrogen atoms have been removed.
  • the cycloalkane has 3 or more carbon atoms, preferably 5 to 8, and particularly preferred cycloalkane is cyclohexane, cyclopentane, and more preferably cyclohexane.
  • the polycyclic alicyclic group may or may not be substituted with a fluorine atom or a fluorinated alkyl group.
  • examples thereof include groups in which one hydrogen atom has been removed from tricycloalkane, tetracycloalkane, and the like.
  • Specific examples include groups obtained by removing one hydrogen atom from polycycloalkane, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
  • Such a polycyclic group can be used by appropriately selecting the neutrality proposed for a large number of ArF resists.
  • an adamantyl group, a norbornyl group, and a tetracyclododele group are industrially preferable.
  • a monomer suitable as a constituent unit of the component (A) of the present invention in particular, a monomer unit suitable as a constituent unit (al) is represented by the following general formula.
  • the compound represented by the above general formula (AI-2) and the compound represented by the following general formula (AI-4) are substantially the same. [0029] [Formula 1]
  • R is a hydrogen atom or a methyl group, and R 1 is a lower alkyl group.
  • R is a hydrogen atom or a methyl group, and R 2 and R 3 are each independently a lower alkyl group.
  • R is a hydrogen atom or a methyl group, and R 4 is a tertiary alkyl group.
  • R is a hydrogen atom or a methyl group.
  • R is a hydrogen atom or a methyl group, and R 5 is a methyl group.
  • R is a hydrogen atom or a methyl group, and R 6 is a lower alkyl group.
  • R is a hydrogen atom or a methyl group.
  • R is a hydrogen atom or a methyl group, and R 7 is a lower alkyl group.
  • R 6 to R 7 are each preferably a lower linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, and a propyl group. Isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. Industrially, a methyl group or an ethyl group is preferred.
  • R 4 is a tertiary alkyl group such as a tert-butyl group or a tert-amyl group, and the case where R 4 is a tert-butyl group is industrially preferable.
  • the structural units represented by the general formulas (AI-4) to (AI-6) are more preferable among the above-mentioned units because they can form a pattern having excellent high resolution.
  • the (a2) unit is a structural unit derived from a (meth) acrylate ester having a rataton unit. Since it has rataton units, it can improve the adhesion between the resist film and the substrate, Is effective for increasing the hydrophilicity of
  • the unit (a2) in the present invention preferably has a rataton unit, and is preferably a unit that can be copolymerized with other constituent units of the component (A).
  • examples of the monocyclic rataton unit include a group excluding one ⁇ -petit mouth rataton force hydrogen atom.
  • examples of the polycyclic rataton unit include groups excluding one hydrogen atom from a rataton-containing polycycloalkane hydrogen atom.
  • a ring containing the -o-c (o) structure is counted as the first ring. That is, when the ring structure is only one ring containing a -OC (O) structure, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of its structure.
  • a monomer unit suitable as (a2) is represented by the following general formula.
  • R is a hydrogen atom or a methyl group
  • R is a hydrogen atom or a methyl group
  • ⁇ -butyrolataton ester of (meth) acrylic acid having an ester bond on the ⁇ -carbon as shown in the general formula ( ⁇ -3), or the general formula ( ⁇ -1) or the general formula ( ⁇ ⁇ Norbornane ratatone ester strength as shown in 2) Especially preferred because it is industrially available.
  • the (a3) unit is a structural unit derived from (meth) acrylate ester having an alcoholic hydroxyl group-containing polycyclic group.
  • the hydroxyl group in the alcoholic hydroxyl group-containing polycyclic group is a polar group. For this reason, by having this, the hydrophilicity of the entire component (A) with the developer is increased, and the alkali solubility in the exposed area is improved. Therefore, it is preferable that the component (A) has the component (a3) because the resolution is improved.
  • the polycyclic group which should contain an alcoholic hydroxyl group is preferably a polycyclic alicyclic group, and more preferably an alicyclic hydrocarbon group which may have a substituent. Preferably, there is.
  • the polycyclic group may be saturated or unsaturated, but is preferably saturated.
  • the same polycyclic alicyclic hydrocarbon group as exemplified above can be appropriately selected and used.
  • the alcoholic hydroxyl group-containing polycyclic group in (a3) is not particularly limited.
  • a hydroxyl group-containing adamantyl group is preferably used.
  • the dry etching resistance is increased, and the verticality of the pattern cross-sectional shape is increased. It is preferable because it has an effect.
  • n is an integer of 1 to 3.
  • the unit (a3) preferably has an alcoholic hydroxyl group-containing polycyclic group as described above and is copolymerizable with other constituent units of the component (A).
  • a structural unit represented by the following general formula ( ⁇ -2) is preferable.
  • R is a hydrogen atom or a methyl group.
  • the (a4) unit is different from the acid dissociable, dissolution inhibiting group of the (al) unit, the rataton unit of the (a2) unit, and the alcoholic hydroxyl group-containing polycyclic group of the (a3) unit. It is a structural unit containing a polycyclic group.
  • the polycyclic group “different from the acid-dissociable, dissolution-inhibiting group, the lactone unit, and the alcoholic hydroxyl group-containing polycyclic group” is the polycyclic group of the (a4) unit in the component (A).
  • the polycyclic group in the unit (a4) is selected so as not to overlap with the structural units used as the units (al) to (a3) in one component (A). It suffices if there is no particular limitation.
  • the polycyclic group is more preferably an alicyclic hydrocarbon group which is preferably an alicyclic group and may have a substituent.
  • the polycyclic group may be saturated or unsaturated, but is preferably saturated.
  • the same polycyclic alicyclic hydrocarbon group as exemplified in the above (al) unit can be used, and a conventional ArF positive resist material has been used. Many are known!
  • a structural unit containing at least one or more polycyclic groups selected from tricyclodecanyl group, adamantyl group, tetracyclododele group, isobutyl group, and the like is easily available commercially. Preferred in such points ⁇ .
  • the unit (a4) has a polycyclic group as described above and is copolymerizable with other constituent units of the component (A).
  • R is a hydrogen atom or a methyl group
  • R is a hydrogen atom or a methyl group
  • the amount of the unit (a2) is 20 to 60 mol%, preferably 30 to 50 mol%, based on the total of the constituent units constituting the component (A), the resolution and the adhesion are excellent, and thus it is preferable.
  • (a3) When using the unit, the total of the structural units constituting the component (A), (a3) an amount force from 5 to 50 mole 0/0 units, preferably 10 to 40 mole 0/0 If there is, the resist pattern shape is excellent and preferable.
  • (A4) When using the unit, the total of the structural units constituting the component (A), the amount of (a4) units, 1 to 30 mol 0/0, is preferably 5 to 20 mol 0/0 Also, the isolated pattern power is also excellent, as the resolution of the semi-dense pattern is excellent.
  • Each amount of (al) to (a4) units may be arbitrarily determined according to the required characteristics. However, among these, among the components (A), the content power of each of the structural units (al) to (a4) (& 1) 20 to 60 mol%, (& 2) 20 to 60 mol%, and (& 3) ) 5 to 50 mol% Dea Ru ternary, or (al) 25 to 50 mole 0/0, (a2) 25 to 50 mole 0/0, (a3) 10 to 30 mole 0/0, ⁇ And (a4) a positive resist composition using a quaternary copolymer in an amount of 3 to 25 mol% is preferable since a resist pattern having excellent sensitivity and profile shape can be formed.
  • the component (A) is composed of (al) and, if necessary, a monomer corresponding to each of the structural units (a2), (a3) and Z or (a4), such as azobisisobutymouth-tolyl (AIBN). It can be easily produced by copolymerization by known radical polymerization using a suitable radical polymerization initiator. Also, HS—CH—CH—CH—C (CF) —OH
  • the copolymer into which 32 has been introduced can also be used as the component (A).
  • the mass average molecular weight (Mw; value by gel permeation chromatography in terms of polystyrene, the same applies hereinafter) of the component (A) is not particularly limited.
  • the Mw of the component (A) is usually 2,000 to 30,000, 2,000 to 20,000 for the negative type, preferably 4,000 to 15,000, and 5,000 to 30,000 for the positive type, and more preferably ⁇ 8000. ⁇ 20000. If necessary, it may have a molecular weight other than the above.
  • the degree of dispersion (MwZMn) is preferably 1 to 3 force S, and most preferably 1 to 2.5.
  • the component (A) one or more kinds can be used.
  • the resist composition of the present invention essentially contains an oxime sulfonate-based acid generator (B). As a result, it is possible to reduce the skirting phenomenon of the resist pattern, to improve the pattern shape, and to approach the rectangular shape.
  • the "oxime sulfonate-based acid generator” is a compound having at least one structure represented by the following general formula (B-1), It has the property of generating acids.
  • R 21 represents an organic group
  • R 22 represents a monovalent organic group or a cyano group.
  • the organic group R 21 is preferably an alkyl group, Ariru group. These alkyl groups and aryl groups may have a substituent.
  • Each of these alkyl groups and aryl groups preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and most preferably 1 to 6 carbon atoms.
  • the alkyl group is preferably a partially or fully fluorinated alkyl group
  • the aryl group is preferably a partially or fully fluorinated aryl group.
  • R 22 is a cyano group or the same concept as R 21 .
  • the partially or completely fluorinated alkyl group means a partially fluorinated alkyl group or a completely fluorinated alkyl group.
  • a partially or fully fluorinated aryl group refers to a partially or fully fluorinated aryl group.
  • R 21 is preferably Ri that forces an alkyl group or a fluorinated alkyl group having 1 to 4 carbon atoms.
  • R 22 is more preferably a cyano group, an alkyl group having 1 to 8 carbon atoms, or a partially or fully fluorinated alkyl group.
  • oxime sulfonate-based acid generator examples include ⁇ - ( ⁇ -toluenesulfo-loxyimino) -benzyl cyanide, ⁇ - ( ⁇ -toluenebenzenesulfo-loxyimino) -benzylyl-oxide, ⁇ - (4-Nitrobenzenesulfo-roximino) -benzyl cyanide, ⁇ - (4-Nitro-2-trifluoromethylbenzenesulfo-roxyimino) -benzylcyanide, a- (benzenesulfo-roxyimino) -4 -Brozen benzyl cyanide, a-(Benzenesulfo-roxyimino)-2,4-dichlorobenzylazide, ⁇ -(benzenesulfo-roxyimino)-2, 6-Dichlorobenzylazide, ⁇ -(
  • CH 3 -C -OS02- (CH2) 3CH3
  • component (B) containing the above general formula (B-1) a component represented by the following general formula (B-16) or (B-17) is more preferable.
  • R 31 is a partially or completely halogenated alkyl group or a halogenated alkyl group.
  • R 32 is an aryl group.
  • R 33 is a partially or completely halogenated alkyl group. Or a halogenated alkyl group.
  • R 34 is a partially or completely halogenated alkyl group or a halogenated alkyl group.
  • R 35 is an aryl group.
  • R 36 is a partially or completely halogenated alkyl group.
  • p is an integer of 2 to 3.
  • R 31 is preferably a partially fluorinated carbon atom having 1 to 10 (more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms).
  • the ⁇ partially fluorinated '' means that the hydrogen atom of the alkyl group is fluorinated by 50% or more, preferably 70% or more, more preferably 90% or more by fluorination, It is preferable to Of these, partially fluorinated alkyl groups are preferred.
  • the substituted or unsubstituted alkyl group or halogenated alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the halogenated alkyl group is preferably a fluorinated alkyl group!
  • R 33 is preferably a partially fluorinated alkyl group having 1 to 10 carbon atoms (more preferably 1 to 8 carbon atoms, most preferably 1 to 6 carbon atoms) or a fluorinated alkyl group having 1 to 10 carbon atoms (More preferably 2 to 8 carbon atoms, most preferably 3 to 6 carbon atoms).
  • the above ⁇ partially fluorinated '' means that the hydrogen atom of the alkyl group is fluorinated by 50% or more, preferably 70% or more, more preferably 90% or more. However, it is preferable because the strength of the generated acid is increased. Most preferably, it is a fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted.
  • R 34 is preferably a partially fluorinated alkyl group having 1 to 10 carbon atoms (more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms) or Carbon number 1 to: a fluorinated alkyl group of L0 (more preferably 1 to 8 carbon atoms, most preferably 1 to 6 carbon atoms).
  • the ⁇ partially fluorinated '' means that the hydrogen atom of the alkyl group is fluorinated by 50% or more, preferably 70% or more, more preferably 90% or more by fluorination, It is preferable to Of these, partially fluorinated alkyl groups are preferred.
  • R 35 is a phenyl group, a biphenylyl group, a fluorenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, a heteroaryl group, and is an alkyl group having 1 to 10 carbon atoms. Alternatively, it may be replaced by a halogenated alkyl group or an alkoxy group. Of these, a fluorenyl group is preferred.
  • the substituted or unsubstituted alkyl group or halogenated alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the halogenated alkyl group is preferably a fluorinated alkyl group!
  • R db is preferably a partially fluorinated alkyl group having 1 to 10 carbon atoms (more preferably 1 to 8 carbon atoms, most preferably 1 to 6 carbon atoms) or a fluorinated alkyl group having 1 to 10 carbon atoms. (More preferably 2 to 8 carbon atoms, most preferably 3 to 6 carbon atoms).
  • the above ⁇ partially fluorinated '' means that the hydrogen atom of the alkyl group is fluorinated by 50% or more, preferably 70% or more, more preferably 90% or more. However, it is preferable because the strength of the generated acid is increased. Most preferably, it is a fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted.
  • the aforementioned p is preferably 2.
  • the amount of component (B) is 0.01 to 20 parts by mass, preferably 100 parts by mass, per 100 parts by mass of component (A).
  • It is 0.05 to 15 parts by mass, more preferably 0.1 to 10 parts by mass.
  • the amount is 0.01 part by mass or more, a pattern can be formed, and when the amount is 20 parts by mass or less, it is more preferable from the viewpoint of reducing precipitation during coating.
  • component (B) one or more kinds can be used.
  • the component (C) contains methyl n-amyl ketone (2-heptanone).
  • the content of methyl n-amyl ketone in the component (C) is not particularly limited, but is usually 10 to 60% by mass, preferably 15 to 55% by mass, and more preferably 20 to 50% by mass.
  • the content is not particularly limited, but is usually 10 to 60% by mass, preferably 15 to 55% by mass, and more preferably 20 to 50% by mass.
  • precipitation of the oxime sulfonate-based acid generator can be suppressed.
  • the use of a solvent having a higher polarity than that of methyl n-amyl ketone described below can reduce the amount of dimethyl acetate after development. It is assumed that the after-development is caused by other components such as the component (A) rather than the component (B), and is considered to be different from the precipitation of the component (B) described above.
  • the defetat after the development can be reduced by further mixing the following specific solvent.
  • the defetat refers to scum and general defects in the resist pattern that are detected, for example, when observed from directly above the developed resist pattern using a surface defect observation device (trade name “KLA”) manufactured by KLA Tencor. It is.
  • KLA surface defect observation device
  • the component (C) preferably contains, in addition to methyl n-amyl ketone, a solvent having a relatively high polarity as compared with methyl n-amyl ketone.
  • a solvent having a relatively high polarity and a solvent may be selected and used as necessary.
  • the component (C) further comprises It is preferable to contain at least one selected from lenglycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and ethyl lactate (EL).
  • PMEA lenglycol monomethyl ether acetate
  • PGME propylene glycol monomethyl ether
  • EL ethyl lactate
  • the solvent is preferably propylene glycol monomethyl ether acetate (PGME A).
  • the compounding amount of the highly polar solvent is 40 to 90% by mass, preferably 50 to 80% by mass in the component (C).
  • the amount to be equal to or more than the lower limit it is possible to reduce the amount of defetate after development, and by adjusting the amount to be equal to or less than the upper limit, it is possible to balance with methyl n-amyl ketone.
  • Precipitation of the oxime sulfonate-based acid generator during coating can be preferably reduced.
  • the component (C) one or more arbitrary known organic solvents may be arbitrarily compounded as other solvents for the resist composition within a range that does not impair the effects of the present invention. be able to.
  • the amount of the component (C) used is not particularly limited, and can be appropriately set according to the coating film thickness so as to be a concentration that can be applied to a support such as a substrate.
  • the component (C) is used so that the solids concentration of the resist composition is in the range of 2 to 20% by mass, preferably 5 to 15% by mass.
  • a nitrogen-containing organic compound (D) (hereinafter, referred to as a component (D)) can be blended.
  • component (D) various types have already been proposed, and any of known components may be used.
  • component (D) amines, particularly secondary lower aliphatic amines ⁇ tertiary lower aliphatic amines, are preferred.
  • component (D) examples include trimethylamine, getylamine, triethylamine, and diethylamine.
  • Alkylamines such as n-propylamine, tri-n-propylamine, tripentylamine, tri-n-heptylamine, tree n-octylamine, di-n-heptylamine, di-n-octylamine, tri-n-dodecylamine, diethanol
  • alkyl alcohols such as amine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tree-n-octanolamine.
  • secondary or tertiary aliphatic amines having an alkyl group having 7 to 15 carbon atoms are preferred.
  • the aliphatic amine is hardly diffused in the formed resist pattern, so that it can be evenly distributed.
  • alkylamines such as tree n-octylamine and tree n-dodecylamine are particularly preferred.
  • the amount of the component (D) is not particularly limited, but is preferably usually in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the component (A).
  • the resist composition of the present application further includes an optional component for the purpose of preventing sensitivity deterioration that may be caused by blending with the component (D), improving the resist pattern shape, and the stability over time.
  • An organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof (E) (hereinafter, referred to as a component (E)) can be contained.
  • the component (D) and the component (E) may be used in combination, or one of them may be used.
  • organic carboxylic acid for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitably used.
  • Examples of phosphorus oxo acids or derivatives thereof include phosphoric acid such as phosphoric acid, di-n-butyl phosphate and diphenyl phosphate, and derivatives thereof such as phosphonic acid, dimethyl phosphonate, and phosphonic acid.
  • Phosphonic acids such as -di-n-butyl ester, phenylphosphonic acid, diphenylphosphonic acid ester, dibenzylphosphonic acid ester and derivatives thereof, and phosphinic acids such as phosphinic acid and phenylphosphinic acid And derivatives thereof such as esters, among which phosphonic acid is particularly preferred.
  • the resist composition of the present invention comprises the component (A), the component (B), and other optional additives (eg, y-butyrolane, a surfactant, a dye, a dissolution inhibitor, and the like). It can be produced by dissolving in the component (C).
  • additives eg, y-butyrolane, a surfactant, a dye, a dissolution inhibitor, and the like.
  • the method for forming a resist film and a resist pattern using the resist composition of the present invention can be arbitrarily selected as necessary, and can be performed, for example, as follows.
  • a positive resist composition is applied on a substrate such as silicon wafer using a spin coater or the like, and a pre-beta is applied at a temperature of 80 to 150 ° C. for 40 to 120 seconds, preferably 60 to 90 seconds, A resist film is formed.
  • a pre-beta is applied at a temperature of 80 to 150 ° C. for 40 to 120 seconds, preferably 60 to 90 seconds
  • a resist film is formed.
  • an ArF excimer laser beam is selectively exposed through a desired mask pattern using, for example, an ArF exposure apparatus.
  • PEB post-exposure bake
  • this is developed using an alkali developing solution, for example, an aqueous solution of 0.1 to 10% by mass of tetramethylammonium hydroxide.
  • an alkali developing solution for example, an aqueous solution of 0.1 to 10% by mass of tetramethylammonium hydroxide.
  • an organic or inorganic antireflection film may be provided between the substrate and the coating layer of the resist composition.
  • Other films or the like may be provided as necessary.
  • the wavelength used for exposure is not particularly limited, and can be selected as necessary.
  • Exposure can be performed using radiation such as sky ultraviolet rays, EB (electron beam), X-rays, and soft X-rays.
  • the present invention is effective for an ArF excimer laser.
  • the resist composition of the present invention is preferably applied to a substrate having a nitrogen-containing layer. That is, the resist composition of the present invention is suitable as a composition for a substrate having a nitrogen-containing layer.
  • a footing phenomenon is particularly likely to occur in a resist pattern in contact with the nitrogen-containing layer, but this phenomenon can be reduced by applying the present invention.
  • the nitrogen-containing layer is usually provided on a substrate as an insulating layer, a metal layer, or the like according to the purpose of use, and is a layer containing nitrogen.
  • Silicon nitride (SiN) A layer of tri-silicon nitride (Si N) or the like may be used.
  • the metal layer is made of titanium nitride (TiN)
  • the nitrogen-containing layer is, for example, a layer formed on a substrate such as a silicon substrate by vapor deposition or the like.
  • a substrate having such a nitrogen-containing layer is called, for example, a “nitrogen-containing substrate”.
  • the resist composition of the present invention provides a substrate provided with an antireflection film [an organic antireflection film (an antireflection film made of an organic compound) or an inorganic antireflection film (an antireflection film made of an inorganic compound)]. It is also preferable to be applied to It is particularly preferable that the resist composition of the present invention is provided thereon on an organic antireflection film.
  • organic anti-reflection film for example, AR46 (product name: manufactured by Shipley, organic anti-reflection film) and the like can be mentioned.
  • AR46 product name: manufactured by Shipley, organic anti-reflection film
  • the use of AR46 tends to cause tailing, but this can be suppressed by applying the present invention.
  • the resist composition of the present invention may be used in a method of forming a resist pattern performing a thermal flow step as needed.
  • the thermal flow process can be performed after forming the resist pattern as described above.
  • the thermal flow process can be performed, for example, as follows. That is, the resist pattern after the development process is heated at least once, preferably two to three times to soften and flow the resist, so that the pattern size of the resist pattern (for example, the hole pattern hole diameter ⁇ ⁇ ⁇ ⁇ line and (Space width of space) is reduced from the size immediately after development.
  • a suitable heating temperature depends on the composition of the resist composition and the like, and is not particularly limited. It is preferably 80 to 180 ° C, more preferably 95 to 165 ° C, and still more preferably 110 to 150 ° C. Heating temperature within this range Thus, there is an advantage that the control of the pattern size is easy.
  • a suitable heating time is not particularly limited as long as it is within a range in which a desired pattern size that does not hinder the throughput can be obtained. Judging from the ordinary semiconductor device manufacturing line process, the heating time per heating is preferably 10 to 300 seconds, more preferably 20 to 240 seconds, and still more preferably about 30 to 180 seconds. preferable.
  • the resist composition of the present invention has the advantage that, even when the thermal flow process is performed, the precipitation of the component (B) can be preferably suppressed.
  • U which is preferable in that deterioration such as gasification does not easily occur.
  • the resist composition of the present invention is suitable for a thermal flow process.
  • a positive resist composition having the following composition was produced.
  • R force S methyl group R 1 is a methyl group Structural unit represented by general formula (AI-4) (al) ⁇ ⁇ -40 mol%
  • Each of the following acid generators 1 to 3 was used in an amount of 5 parts by mass, 10 parts by mass, or 20 parts by mass with respect to 100 parts by mass of the component (II).
  • the types and amounts of the acid generators are shown in Tables 1-3.
  • Acid generator 1 Acid generator represented by the general formula ( ⁇ -14)
  • Acid generator 2 Acid generator represented by the general formula ( ⁇ -15)
  • Acid generator 3 Acid generator represented by general formula ( ⁇ -31)
  • the solid concentration of the resist composition is adjusted to 12% by mass.
  • Triethanolamine was used in an amount of 0.25 part by mass based on the component ( ⁇ ).
  • a positive resist composition was produced in the same manner as in Example except that in the component (C), methyl ⁇ -amyl ketone was replaced by ethyl lactate.
  • Tables 1-3 show the types and amounts of acid generators.
  • a substrate was coated with each of the positive resist compositions of Examples 11 to 18 and Comparative Examples 11 to 18 using a spin coater, and a pre-beta was applied for 60 seconds at a temperature of 130 ° C to form a resist film. Formed. The thickness of the resist coating was 3000 A (angstrom). Then, the number of acid generator precipitates was visually determined. The measurement was performed on two substrates for each resist composition, and the average value was obtained. The results are shown in Tables 1-3. Although the number of precipitates was measured by an expert, the places where the Can be confirmed
  • the resist composition containing the oxime sulfonate-based acid generator of the present invention can achieve a reduction in the precipitation of the acid generator during coating.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

Est décrite une composition de résine qui se caractérise du fait qu’elle est obtenue par dissolution d’un composant de résine de base (A) et d'un générateur d'acide sulfonate d'oxime (B) dans un solvant organique (C) contenant une méthyl n-amyl cétone.
PCT/JP2005/008004 2004-05-31 2005-04-27 Composition de résine et procédé pour former un motif de masque WO2005116762A1 (fr)

Applications Claiming Priority (6)

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JP2004-161880 2004-05-31
JP2004161880 2004-05-31
JP2004-203115 2004-07-09
JP2004203115 2004-07-09
JP2004-259065 2004-09-06
JP2004259065A JP2006047940A (ja) 2004-05-31 2004-09-06 レジスト組成物、レジストパターンの形成方法

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0667433A (ja) * 1992-05-22 1994-03-11 Ciba Geigy Ag 高感度の高解像度ｉ−線ホトレジスト
JPH1090901A (ja) * 1996-07-24 1998-04-10 Tokyo Ohka Kogyo Co Ltd 化学増幅型レジスト組成物及びそれに用いる酸発生剤
JP2000347392A (ja) * 1999-06-02 2000-12-15 Sumitomo Chem Co Ltd 化学増幅ネガ型レジスト組成物
JP2002184763A (ja) * 2000-12-15 2002-06-28 Sharp Corp 半導体装置の製造方法
JP2002196497A (ja) * 2000-10-20 2002-07-12 Fuji Photo Film Co Ltd サーマルフロー用化学増幅型ポジレジスト組成物及びパターン形成方法
JP2002302979A (ja) * 2001-04-09 2002-10-18 Maruichi Kk 排水トラップ
JP2003167357A (ja) * 2001-12-03 2003-06-13 Tokyo Ohka Kogyo Co Ltd 微細レジストパターン形成方法
JP2004026804A (ja) * 2002-03-29 2004-01-29 Jsr Corp スルホニル構造を有する化合物、それを用いた感放射線性酸発生剤、ポジ型感放射線性樹脂組成物、及びネガ型感放射線性樹脂組成物
JP2004103055A (ja) * 2002-09-05 2004-04-02 Sony Corp カートリッジ収納用ケース
WO2004104702A1 (fr) * 2003-05-20 2004-12-02 Tokyo Ohka Kogyo Co., Ltd. Composition de resine photosensible positive a amplification chimique et procede de formation d'un motif en resine photosensible
JP2004347852A (ja) * 2003-05-22 2004-12-09 Tokyo Ohka Kogyo Co Ltd 化学増幅型ポジ型ホトレジスト組成物およびレジストパターンの形成方法
JP2005070153A (ja) * 2003-08-28 2005-03-17 Tokyo Ohka Kogyo Co Ltd リフトオフ用レジスト材料及びリフトオフ用レジストパターンの形成方法
JP2005157255A (ja) * 2003-10-22 2005-06-16 Tokyo Ohka Kogyo Co Ltd 電子線又はｅｕｖ用レジスト組成物

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0667433A (ja) * 1992-05-22 1994-03-11 Ciba Geigy Ag 高感度の高解像度ｉ−線ホトレジスト
JPH1090901A (ja) * 1996-07-24 1998-04-10 Tokyo Ohka Kogyo Co Ltd 化学増幅型レジスト組成物及びそれに用いる酸発生剤
JP2000347392A (ja) * 1999-06-02 2000-12-15 Sumitomo Chem Co Ltd 化学増幅ネガ型レジスト組成物
JP2002196497A (ja) * 2000-10-20 2002-07-12 Fuji Photo Film Co Ltd サーマルフロー用化学増幅型ポジレジスト組成物及びパターン形成方法
JP2002184763A (ja) * 2000-12-15 2002-06-28 Sharp Corp 半導体装置の製造方法
JP2002302979A (ja) * 2001-04-09 2002-10-18 Maruichi Kk 排水トラップ
JP2003167357A (ja) * 2001-12-03 2003-06-13 Tokyo Ohka Kogyo Co Ltd 微細レジストパターン形成方法
JP2004026804A (ja) * 2002-03-29 2004-01-29 Jsr Corp スルホニル構造を有する化合物、それを用いた感放射線性酸発生剤、ポジ型感放射線性樹脂組成物、及びネガ型感放射線性樹脂組成物
JP2004103055A (ja) * 2002-09-05 2004-04-02 Sony Corp カートリッジ収納用ケース
WO2004104702A1 (fr) * 2003-05-20 2004-12-02 Tokyo Ohka Kogyo Co., Ltd. Composition de resine photosensible positive a amplification chimique et procede de formation d'un motif en resine photosensible
JP2004347852A (ja) * 2003-05-22 2004-12-09 Tokyo Ohka Kogyo Co Ltd 化学増幅型ポジ型ホトレジスト組成物およびレジストパターンの形成方法
JP2005070153A (ja) * 2003-08-28 2005-03-17 Tokyo Ohka Kogyo Co Ltd リフトオフ用レジスト材料及びリフトオフ用レジストパターンの形成方法
JP2005157255A (ja) * 2003-10-22 2005-06-16 Tokyo Ohka Kogyo Co Ltd 電子線又はｅｕｖ用レジスト組成物

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