WO2010095698A1 - 重合体及び感放射線性組成物並びに単量体 - Google Patents
重合体及び感放射線性組成物並びに単量体 Download PDFInfo
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- WO2010095698A1 WO2010095698A1 PCT/JP2010/052477 JP2010052477W WO2010095698A1 WO 2010095698 A1 WO2010095698 A1 WO 2010095698A1 JP 2010052477 W JP2010052477 W JP 2010052477W WO 2010095698 A1 WO2010095698 A1 WO 2010095698A1
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- 0 *S([N-]S(*)(=O)=O)(=O)=O Chemical compound *S([N-]S(*)(=O)=O)(=O)=O 0.000 description 7
- WNTGVOIBBXFMLR-UHFFFAOYSA-N C(C1)CC2CC1CCC2 Chemical compound C(C1)CC2CC1CCC2 WNTGVOIBBXFMLR-UHFFFAOYSA-N 0.000 description 1
- GWZSONAXKINSCO-UHFFFAOYSA-N C1C=C2CCCC1C2 Chemical compound C1C=C2CCCC1C2 GWZSONAXKINSCO-UHFFFAOYSA-N 0.000 description 1
- UVFIXEGOSUKAPD-UHFFFAOYSA-N FC(F)(F)[S+]1c(cccc2)c2-c2c1cccc2 Chemical compound FC(F)(F)[S+]1c(cccc2)c2-c2c1cccc2 UVFIXEGOSUKAPD-UHFFFAOYSA-N 0.000 description 1
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- C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- 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
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- 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
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- G03F7/004—Photosensitive materials
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Definitions
- the present invention relates to a polymer, a radiation-sensitive composition and a monomer using the polymer as an acid-dissociable group-containing polymer. More specifically, the present invention relates to various kinds of radiation such as KrF excimer laser, ArF excimer laser, F 2 excimer laser, EUV (extreme) far ultraviolet rays, synchrotron radiation, etc., X-rays, electron beam, etc.
- the present invention relates to a radiation-sensitive composition, a polymer, and a monomer that are used as a chemically amplified resist suitable for microfabrication.
- Lithography using an electron beam or EUV light is positioned as a next-generation or next-generation pattern forming technology, and a positive resist with high sensitivity and high resolution is desired.
- high sensitivity is a very important issue for shortening the wafer processing time.
- nano edge roughness is designed when the pattern is viewed from directly above because the resist pattern and the edge of the substrate interface vary irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. This refers to the deviation that occurs between the dimensions and the actual pattern dimensions.
- a chemically amplified resist using an acid-catalyzed reaction is mainly used from the viewpoint of high sensitivity.
- a phenolic polymer (hereinafter referred to as “phenolic acid-decomposable polymer”), which is insoluble or hardly soluble in an aqueous alkali solution and becomes soluble in an aqueous alkaline solution by the action of an acid, and an acid A chemically amplified resist composition comprising a generator is effectively used.
- sulfonic acid generator compounds that generate sulfonic acid upon irradiation with actinic rays or radiation using a phenolic acid-decomposable polymer copolymerized with an acid-decomposable acrylate monomer
- sulfonic acid generator compounds that generate sulfonic acid upon irradiation with actinic rays or radiation using a phenolic acid-decomposable polymer copolymerized with an acid-decomposable acrylate monomer
- the present invention has been made in view of the above circumstances, and is effectively sensitive to X-rays such as KrF excimer lasers, ArF excimer lasers, EUV (extreme) deep ultraviolet rays, synchrotron radiation, and electron beams, and nanoedges.
- X-rays such as KrF excimer lasers, ArF excimer lasers, EUV (extreme) deep ultraviolet rays, synchrotron radiation, and electron beams, and nanoedges.
- a radiation-sensitive composition, a polymer, and a monomer that are excellent in roughness, sensitivity, and resolution, and that can form a chemically amplified positive resist film capable of forming a fine pattern with high accuracy and stability.
- a polymer comprising a repeating unit represented by the following general formula (1).
- R 1 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group
- R 2 is a substituted or unsubstituted aryl group having 6 to 22 carbon atoms
- Y is a carbon atom.
- X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y.
- R 1 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group
- R 3 is an alkyl group having 1 to 4 carbon atoms
- Y is a carbon atom
- X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y
- h is an integer of 0 to 3.
- R 4 is a hydrogen atom or a methyl group
- R 5 is a monovalent organic group
- i represents an integer of 0 to 3
- j represents an integer of 0 to 3.
- R 6 represents a hydrogen atom or a methyl group
- R 7 represents a monovalent organic group
- k represents an integer of 0 to 3
- l represents an integer of 0 to 3.
- R 8 represents a hydrogen atom or a methyl group
- R 9 represents a monovalent organic group
- m represents an integer of 0 to 3
- n represents an integer of 0 to 3.
- 0 ⁇ m + n ⁇ 5 is satisfied.
- a radiation sensitive composition comprising an acid dissociable group-containing polymer (A) and a radiation sensitive acid generator (B), The radiation-sensitive composition, wherein the acid dissociable group-containing polymer (A) is the polymer according to any one of [1] to [3].
- M + Z ⁇ (b1) M + represents a monovalent onium cation, and Z ⁇ represents a monovalent anion represented by the following general formula (b1-Z-1) or (b1-Z-2). .
- R 41 and R 42 each independently a fluorine atom or an alkyl group having 1 to 20 carbon atoms substituted with at least one fluorine atom? or, R 41 and R 42 are bonded to each other to form a cyclic structure of at least one carbon number of 1 to 20 substituted by a fluorine atom.
- R 43 , R 44 and R 45 are each independently an alkyl group having 1 to 20 carbon atoms substituted with at least one fluorine atom, or , R 43 , R 44 , and R 45 are bonded to each other to form a C 1-20 cyclic structure substituted with at least one fluorine atom, and the remaining one is at least An alkyl group having 1 to 20 carbon atoms substituted with one fluorine atom;
- R 10 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group
- R 11 is a substituted or unsubstituted aryl group having 6 to 22 carbon atoms
- Y is It is a carbon atom
- X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y.
- R 10 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group
- R 11 is a substituted or unsubstituted aryl group having 6 to 22 carbon atoms
- Y is It is a carbon atom
- X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y.
- the radiation-sensitive composition of the present invention is sensitive to X-rays such as KrF excimer laser, ArF excimer laser, EUV (extreme) far ultraviolet rays, synchrotron radiation, and electron beam, and nano edge roughness, sensitivity.
- X-rays such as KrF excimer laser, ArF excimer laser, EUV (extreme) far ultraviolet rays, synchrotron radiation, and electron beam, and nano edge roughness, sensitivity.
- a chemically amplified positive resist film that is excellent in resolution and capable of forming a fine pattern with high accuracy and stability can be formed.
- the said radiation sensitive composition can be easily obtained by using the polymer of this invention as an acid dissociable group containing polymer.
- polymer (I) includes a repeating unit represented by the following general formula (1) [hereinafter referred to as “repeating unit (1)”]. It is characterized by that.
- This polymer (I) is an alkali-insoluble or hardly-alkaline-soluble polymer, and is a polymer that becomes readily alkali-soluble by the action of an acid. Therefore, it can be suitably used as an acid-dissociable group-containing polymer in the radiation-sensitive composition.
- R 1 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group
- R 2 is a substituted or unsubstituted aryl group having 6 to 22 carbon atoms
- Y is a carbon atom.
- X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y.
- the carbon number of the alicyclic hydrocarbon group formed by X and Y is not particularly limited, but is preferably 5 to 25, more preferably 5 to 20, and still more preferably 5 to 15.
- the alicyclic hydrocarbon group may be monocyclic or polycyclic. Specific examples of the structure of the alicyclic moiety include the following structures (a-1) to (a-50).
- the alicyclic hydrocarbon group formed by X in the general formula (1) together with Y is preferably a group having a monocyclo, bicyclo, tricyclo, or tetracyclo structure.
- alicyclic hydrocarbon group examples include, for example, a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group; adamantyl group, noradamantyl group Group, decalin residue (decalinyl group), tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group and the like.
- a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group
- adamantyl group noradamanty
- a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group; an adamantyl group, a decalin residue, a norbornyl group, and the like are preferable.
- a cycloalkyl group having 5 to 15 carbon atoms is preferable.
- the alicyclic hydrocarbon group may be substituted or unsubstituted.
- substituents include, for example, methyl group, ethyl group, propyl group, hydroxyl group, carboxyl group, halogen atom (fluorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group) Etc.), alkyloxycarbonyl groups and the like.
- Examples of the aryl group having 6 to 22 carbon atoms of R 2 include groups derived from the following structures (x-1) to (x-3).
- R 2 is a group derived from the following (x-2) (ie, a naphthyl group)
- the bonding position for bonding to Y in the general formula (1) is either the 1-position or the 2-position. May be.
- a group R 2 is derived from the following (x-3) (i.e., an anthryl group), then bonding positions that bind to Y in the general formula (1) is the 1-position, 2-position and 9-position Either may be sufficient.
- the aryl group may be substituted.
- substituents include, for example, methyl group, ethyl group, propyl group, hydroxyl group, carboxyl group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group) , Butoxy group and the like), alkyloxycarbonyl group and the like.
- the repeating unit (1) is a repeating unit represented by the following general formula (1-1) [hereinafter referred to as “repeating unit (1-1)”. ].
- R 1 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group
- R 3 is an alkyl group having 1 to 4 carbon atoms
- Y is a carbon atom
- X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y
- h is an integer of 0 to 3.
- Examples of the alkyl group having 1 to 4 carbon atoms of R 3 in the general formula (1-1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, -Methylpropyl group, t-butyl group and the like.
- h is an integer of 0 to 3, and more preferably 0 or 1.
- the repeating unit (1) can be obtained, for example, by using a compound represented by the following general formula (M-1) as a monomer.
- R 10 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group
- R 11 is a substituted or unsubstituted aryl group having 6 to 22 carbon atoms
- Y is It is a carbon atom
- X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y.
- the “aryl group of R 11 ” and the “alicyclic hydrocarbon group formed by X and Y” in the general formula (M-1) are respectively “the aryl group of R 2 ” in the general formula (1). And the description of “alicyclic hydrocarbon group which X forms with Y” can be applied as it is.
- the compound represented by the general formula (M-1) (the monomer of the present invention) is CH 2 ⁇ C (R) C ( ⁇ O) X (wherein R is a hydrogen atom, a methyl group, a fluorine atom) Or a trifluoromethyl group and X is a halogen atom.) And a compound that can be subjected to a substitution reaction with X in the compound.
- R is a hydrogen atom, a methyl group, a fluorine atom
- X is a halogen atom.
- the following is a production example of the compound (1-1a) capable of forming the repeating unit represented by the general formula (1-1).
- the compound (1-1a) is represented by the following general formula (1-r1): It can be produced by a reaction between a compound represented by the formula (1-phenylcyclohexanol) and a compound represented by the following general formula (1-r2) (methacrylic acid chloride).
- the polymer (I) of the present invention may be composed of only the repeating unit (1).
- the repeating unit represented by the following general formula (2) [ Hereinafter, it is referred to as “repeating unit (2)”. ]
- a repeating unit represented by the following general formula (3) [hereinafter referred to as “repeating unit (3)”.
- a repeating unit represented by the following general formula (4) [hereinafter referred to as “repeating unit (4)”. ]
- a repeating unit represented by the following general formula (5) [hereinafter referred to as “repeating unit (5)”. ] May be further included.
- R 4 is a hydrogen atom or a methyl group
- R 5 is a monovalent organic group
- i represents an integer of 0 to 3
- j represents an integer of 0 to 3.
- 0 ⁇ i + j ⁇ 5 is satisfied.
- R 6 represents a hydrogen atom or a methyl group
- R 7 represents a monovalent organic group
- k represents an integer of 0 to 3
- l represents an integer of 0 to 3.
- 0 ⁇ k + 1 ⁇ 5 is satisfied.
- R 8 represents a hydrogen atom or a methyl group
- R 9 represents a monovalent organic group
- m represents an integer of 0 to 3
- n represents an integer of 0 to 3.
- 0 ⁇ m + n ⁇ 5 is satisfied.
- R a represents a hydrogen atom or a methyl group
- R b represents a monovalent organic group
- r represents an integer of 0 to 3
- s represents an integer of 0 to 3.
- Examples of the monovalent organic group represented by R 5 in the general formula (2) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, and a 1-methyl group.
- a linear or branched alkyl group having 1 to 12 carbon atoms such as propyl group and t-butyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methyl
- a methyl group, an ethyl group, an n-butyl group, and a t-butyl group are preferable.
- i is an integer of 0 to 3, and is more preferably 1 or 2.
- j in the general formula (2) is an integer of 0 to 3, and more preferably 0 to 2.
- repeating unit (2) represented by the general formula (2) include repeating units represented by the following formulas (2-1) to (2-4).
- this repeating unit (2) when repeating unit (2) is contained in polymer (I), this repeating unit (2) may be contained only 1 type and may be contained 2 or more types.
- k in the general formula (3) is an integer of 0 to 3, and is more preferably 1 or 2.
- l in the general formula (3) is an integer of 0 to 3, and is more preferably 0 or 1.
- repeating unit (3) represented by the general formula (3) include repeating units represented by the following formulas (3-1) and (3-2).
- this repeating unit (3) when repeating unit (3) is contained in polymer (I), this repeating unit (3) may be contained only 1 type and may be contained 2 or more types.
- n in the general formula (4) is an integer of 0 to 3, and more preferably 0 or 1.
- repeating unit (4) represented by the general formula (4) include repeating units represented by the following formulas (4-1) and (4-2).
- this repeating unit (4) may be contained only 1 type and may be contained 2 or more types.
- r in the general formula (5) is an integer of 0 to 3, and more preferably 1 or 2.
- s in the general formula (5) is an integer of 0 to 3, and more preferably 0 or 1.
- repeating unit (5) represented by the general formula (5) include repeating units represented by the following formulas (5-1) and (5-2).
- this repeating unit (5) may be contained only 1 type, and may be contained 2 or more types.
- Each repeating unit represented by the formulas (2-1) to (2-3) can be obtained by using a corresponding hydroxystyrene derivative as a monomer. Furthermore, it can also obtain by using as a monomer the compound from which a hydroxy styrene derivative is obtained by hydrolyzing.
- the monomer used for generating each repeating unit represented by the above formulas (2-1) to (2-3) p-acetoxystyrene, p- (1-ethoxyethoxy) styrene and the like are preferable. .
- each of the repeating units represented by the formulas (2-1) to (2-3) may be formed by a side chain hydrolysis reaction after forming a polymer. it can.
- each of the formulas (2-4), (3-1), (3-2), (4-1), (4-2), (5-1) and (5-2) The repeating unit can be obtained by using a corresponding monomer.
- Each repeating unit represented by the formula (2-4), (3-1), (3-2), (4-1), (4-2), (5-1) and (5-2) Monomers used to produce p-isopropenylphenol, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacryl Amide, 5-hydroxynaphthalen-1-yl methacrylate, 5-hydroxynaphthalen-1-yl acrylate and the like are preferable.
- the polymer (I) of the present invention includes a repeating unit derived from a non-acid dissociable compound (hereinafter also referred to as “repeating unit (6)”), It may further contain a repeating unit derived from the acid dissociable compound (hereinafter also referred to as “repeating unit (7)”).
- the non-acid dissociable compound include styrene, ⁇ -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, isobornyl acrylate, tricyclodecanyl (meth) acrylate, and tetracyclodone.
- Examples thereof include decenyl (meth) acrylate and compounds represented by the following formulas (b-1) to (b-4).
- Compounds are preferred.
- this repeating unit (6) when the said repeating unit (6) is contained in polymer (I), this repeating unit (6) may be contained only 1 type and may be contained 2 or more types.
- Examples of the acid dissociable compound include compounds represented by the following general formulas (c-1) and (c-2).
- each R 12 independently represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
- each R 13 is independently of each other a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a group derived therefrom. Or any two R 13 's bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom together with the carbon atoms to which each is bonded.
- the remaining one R 13 is a linear or branched alkyl group having 1 to 4 carbon atoms, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom. Show.
- Examples of the linear or branched alkyl group having 1 to 4 carbon atoms in R 13 of the general formulas (c-1) and (c-2) include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples include -propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like.
- Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms in R 13 include norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, Examples thereof include groups consisting of alicyclic rings derived from cycloalkanes such as cyclooctane.
- Examples of the group derived from this alicyclic hydrocarbon group include the above-mentioned monovalent alicyclic hydrocarbon groups such as methyl, ethyl, n-propyl, i-propyl, n- Groups substituted with one or more linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms such as butyl group, 2-methylpropyl group, 1-methylpropyl group and t-butyl group Etc.
- the alicyclic hydrocarbon group of R 13 is a group composed of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane, or cyclohexane, or an alicyclic ring thereof.
- a group obtained by substituting a group consisting of the above alkyl group is preferred.
- any two R 13 's are bonded to each other and formed together with the carbon atom to which each R 13 is bonded (the carbon atom bonded to the oxygen atom).
- the hydrogen group include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group.
- examples of the group derived from a divalent alicyclic hydrocarbon group formed by bonding R 13 to each other include the above-described divalent alicyclic hydrocarbon group such as a methyl group, an ethyl group, and the like.
- Linear, branched or cyclic alkyl having 1 to 4 carbon atoms such as n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group and t-butyl group
- Examples include groups substituted with one or more groups or one or more groups.
- a cyclopentylene group, a cyclohexylene group, a group obtained by substituting the divalent alicyclic hydrocarbon group with the alkyl group, and the like are preferable.
- repeating unit (7) examples include repeating units represented by the following general formulas (7-1) to (7-8).
- R 14 each independently represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group
- R 15 each independently represents a carbon number of 1 to 4 linear or branched alkyl groups are represented.
- this repeating unit (7) when the said repeating unit (7) is contained in polymer (I), this repeating unit (7) may be contained only 1 type and may be contained 2 or more types.
- the content of the repeating unit (1) in the polymer (I) of the present invention is preferably 1 mol% or more when the total of all repeating units in the polymer (I) is 100 mol%, More preferably, it is 5 to 70 mol%, still more preferably 5 to 50 mol%. When this content is 1 mol% or more, when the polymer (I) is used as an acid-dissociable group-containing polymer in the radiation-sensitive composition, it can be excellent in nano edge roughness. .
- the total content of the repeating units (2) to (5) is preferably 1 mol% or more when the total of all repeating units in the polymer (I) is 100 mol%, Preferably it is 5 to 95 mol%, more preferably 5 to 80 mol%.
- the total content of the repeating units (1) to (5) is preferably 10% by mole or more when the total of all the repeating units in the polymer (I) is 100% by mole, The amount is preferably 40 to 100 mol%, more preferably 50 to 100 mol%.
- the total content is 10 mol% or more, when the polymer (I) is used as an acid-dissociable group-containing polymer in the radiation-sensitive composition, it should have excellent nano edge roughness. Can do.
- the content of the repeating unit (6) is usually 80 mol% or less, preferably 0 to 60 mol%, when the total of all repeating units in the polymer (I) is 100 mol%. .
- this content is 80 mol% or less, when this polymer (I) is used as an acid-dissociable group-containing polymer in a radiation-sensitive composition, the resolution performance and the performance of nanoedge roughness It can be excellent in balance.
- the content of the repeating unit (7) is usually 60 mol% or less, preferably 0 to 50 mol%, when the total of all repeating units in the polymer (I) is 100 mol%. .
- the total content of the repeating units (6) and (7) is 90 mol% or less, preferably 0 to 0 when the total of all the repeating units in the polymer (I) is 100 mol%. 80 mol%.
- this content is 90 mol% or less, when this polymer (I) is used as an acid-dissociable group-containing polymer in a radiation-sensitive composition, the resolution performance and the performance of nanoedge roughness It can be excellent in balance.
- the method for synthesizing the polymer (I) in the present invention is not particularly limited, and can be obtained by, for example, known radical polymerization or anionic polymerization. Further, the side chain hydroxystyrene unit in the repeating units (2) to (4) is obtained by subjecting the obtained polymer (I) to hydrolysis of an acetoxy group or the like in the presence of a base or an acid in an organic solvent. Can be obtained.
- the radical polymerization is carried out, for example, by stirring and heating necessary monomers such as the compound (M-1) in a suitable organic solvent in a nitrogen atmosphere in the presence of a radical polymerization initiator. can do.
- radical polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy). -2,4-dimethylvaleronitrile) 2,2'-azobismethylbutyronitrile, 2,2'-azobiscyclohexanecarbonitrile, cyanomethylethylazoformamide, 2,2'-azobis (2,4-dimethyl) Azo compounds such as methyl propionate) and 2,2'-azobiscyanovaleric acid; benzoyl peroxide, lauroyl peroxide, 1,1'-bis- (t-butylperoxy) cyclohexane, 3,5,5-trimethyl Organic peroxides such as hexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate And hydrogen peroxide, and the like.
- the reaction temperature in the radical polymerization is not particularly limited, and is appropriately selected depending on the type of initiator and the like (eg, 50 to 200 ° C.). In particular, when an azo initiator or a peroxide initiator is used, a temperature at which the half life of the initiator is about 10 minutes to about 30 hours is preferable, and more preferably, the half life of the initiator is about 30 minutes to about 10 hours. Temperature.
- the reaction time varies depending on the type of initiator and the reaction temperature, but the reaction time during which 50% or more of the initiator is consumed is desirable, and in many cases is about 0.5 to 24 hours.
- a necessary monomer such as the compound (M-1) is stirred at a predetermined temperature in a suitable organic solvent in a nitrogen atmosphere in the presence of an anionic polymerization initiator. It can be carried out by maintaining the above.
- anionic polymerization initiator examples include n-butyllithium, s-butyllithium, t-butyllithium, ethyllithium, ethylsodium, 1,1-diphenylhexyllithium, 1,1-diphenyl-3-methylpentyllithium.
- Organic alkali metals such as
- the reaction temperature in the anionic polymerization is not particularly limited and is appropriately selected depending on the kind of the initiator.
- the temperature is preferably ⁇ 100 to 50 ° C., more preferably ⁇ 78 to 30 ° C.
- the reaction time varies depending on the type of initiator and the reaction temperature, but the reaction time during which 50% or more of the initiator is consumed is desirable, and in many cases is about 0.5 to 24 hours.
- examples of the acid used for the hydrolysis reaction include p-toluenesulfonic acid and its hydrate, methane Organic acids such as sulfonic acid, trifluoromethanesulfonic acid, malonic acid, succinic acid, 1,1,1-fluoroacetic acid; inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, hydrobromic acid; or pyridinium p-toluenesulfonate, ammonium Examples thereof include salts such as p-toluenesulfonate and 4-methylpyridinium p-toluenesulfonate.
- examples of the base include inorganic bases such as potassium hydroxide, sodium hydroxide, sodium carbonate, and potassium carbonate; organic bases such as triethylamine, N-methyl-2-pyrrolidone, piperidine, and tetramethylammonium hydroxide.
- inorganic bases such as potassium hydroxide, sodium hydroxide, sodium carbonate, and potassium carbonate
- organic bases such as triethylamine, N-methyl-2-pyrrolidone, piperidine, and tetramethylammonium hydroxide.
- organic solvent used for the polymerization or hydrolysis examples include ketones such as acetone, methyl ethyl ketone, and methyl amyl ketone; ethers such as diethyl ether and tetrahydrofuran (THF); methanol, ethanol, propanol, and the like.
- Alcohols such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated alkyls such as chloroform, bromoform, methylene chloride, methylene bromide, and carbon tetrachloride; Esters such as ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cellosolves; dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, etc. Protic polar solvents, and the like.
- acetone, methyl amyl ketone, methyl ethyl ketone, tetrahydrofuran, methanol, ethanol, propanol, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable.
- the polymer (I) has a polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC), preferably from 1500 to 100,000, more preferably from 1500 to 40000. More preferably, it is 2000 to 25000. Further, the ratio (Mw / Mn) of Mw of the polymer (I) and polystyrene-equivalent number average molecular weight (hereinafter also referred to as “Mn”) measured by GPC is usually 1 to 5, more preferably 1 To 4, more preferably 1 to 3.
- Radiation sensitive composition The radiation sensitive composition of the present invention is characterized by containing an acid dissociable group-containing polymer (A) and a radiation sensitive acid generator (B).
- the acid-dissociable group-containing polymer is a polymer that is insoluble in alkali or hardly soluble in alkali and easily soluble in alkali by the action of an acid (hereinafter referred to as “polymer”).
- polymer The term “alkali insoluble or alkali insoluble” as used herein refers to the alkali development conditions employed when a resist pattern is formed from a resist film formed from a radiation-sensitive composition containing the polymer (A).
- alkali insoluble or alkali insoluble refers to the alkali development conditions employed when a resist pattern is formed from a resist film formed from a radiation-sensitive composition containing the polymer (A).
- a 100 nm-thick film using only the polymer (A) is developed instead of the resist film, 50% or more of the initial film thickness of the film remains after development.
- description of the above-mentioned polymer (I) is applicable as it is.
- the radiation-sensitive composition of the present invention contains a compound having the acid dissociable group [the polymer (A)], it has excellent sensitivity. From this point of view, this radiation-sensitive composition effectively responds to X-rays such as KrF excimer laser, ArF excimer laser, and EUV (ultra-far) ultraviolet rays, synchrotron radiation, and electron beams in the lithography process. Therefore, it is possible to form a chemically amplified positive resist film having low roughness, excellent sensitivity and resolution, and capable of forming a fine pattern with high accuracy and stability.
- X-rays such as KrF excimer laser, ArF excimer laser, and EUV (ultra-far) ultraviolet rays, synchrotron radiation, and electron beams in the lithography process. Therefore, it is possible to form a chemically amplified positive resist film having low roughness, excellent sensitivity and resolution, and capable of forming a fine pattern with high accuracy and stability.
- the acid generator (B) is contained in the radiation-sensitive composition when the radiation-sensitive composition of the present invention is irradiated with an electron beam or radiation in a lithography process. It is a substance that generates acid. And the acid dissociable group in the polymer already mentioned above will dissociate by the action of the acid generated from the acid generator (B).
- the acid generator (B) is, for example, at least one selected from the group consisting of an onium salt, a diazomethane compound, and a sulfonimide compound from the viewpoint of good acid generation efficiency, heat resistance, and the like. preferable. In addition, these may be used individually by 1 type and may be used in combination of 2 or more type.
- M + Z ⁇ (b1) As said onium salt, what is represented by the following general formula (b1) is preferable.
- M + is a monovalent onium cation, and Z ⁇ is a monovalent anion.
- onium salts examples include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.
- onium cation of S or an onium cation of I that is, a sulfonium cation or an iodonium cation is preferable.
- Examples of the M + monovalent onium cation in the general formula (b1) include those represented by the following general formula (b1-M-1) and the following general formula (b1-M-2).
- R 31 , R 32 , and R 33 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms that may be substituted, or Or an aryl group having 6 to 18 carbon atoms which may be substituted, or any two of R 31 , R 32 and R 33 are bonded to each other to form a cyclic structure together with the sulfur atom in the formula. And the remaining one is an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 18 carbon atoms.
- R 34 and R 35 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, or Or an aryl group having 6 to 18 carbon atoms, or R 34 and R 35 are bonded to each other to form a cyclic structure together with an iodine atom in the formula.
- Examples of the unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms in the general formulas (b1-M-1) and (b1-M-2) include a methyl group, an ethyl group, and n-propyl. Group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like.
- this alkyl group includes halogen atoms such as fluorine, chlorine, bromine and iodine, hydroxyl groups, thiol groups, and hetero atoms (for example, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, etc.) ) May be substituted with a substituent such as an organic group.
- Examples of the unsubstituted aryl group having 6 to 18 carbon atoms in the general formulas (b1-M-1) and (b1-M-2) include a phenyl group and a naphthyl group.
- the aryl group includes a halogen atom such as fluorine, chlorine, bromine and iodine, a hydroxyl group, a thiol group, an alkyl group, and a hetero atom (for example, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, It may be substituted with a substituent such as an organic group containing a silicon atom).
- the monovalent onium cation moiety represented by M + in the general formula (b1) is described in, for example, Advances in Polymer Sciences, Vol. 62, p. 1-48 (1984).
- examples of the monovalent anion represented by Z ⁇ in the general formula (b1) include anions represented by the following general formulas (b1-Z-1) to (b1-Z-4). Among these, anions represented by the following general formula (b1-Z-1) or (b1-Z-2) are preferable.
- R 41 and R 42 are each independently a fluorine atom or an alkyl group having 1 to 20 carbon atoms substituted with at least one fluorine atom, Alternatively, R 41 and R 42 are bonded to each other to form a cyclic structure having 1 to 20 carbon atoms that is substituted with at least one fluorine atom.
- R 43 , R 44 and R 45 are each independently an alkyl group having 1 to 20 carbon atoms substituted with at least one fluorine atom, Alternatively, R 43, R 44, and any two of R 45 are bonded to each other, and form a cyclic structure of at least one fluorine atom carbon number of 1 to 20 substituted by, remaining one, An alkyl group having 1 to 20 carbon atoms substituted with at least one fluorine atom; Further, in the general formulas (b1-Z-3) and (b1-Z-4), R 46 and R 47 are each independently a fluorine atom or an optionally substituted carbon atom having 1 to 12 carbon atoms. Indicates a hydrogen group. n represents an integer of 1 to 10.
- Examples of the alkyl group having 1 to 20 carbon atoms substituted with at least one fluorine atom in the general formulas (b1-Z-1) and (b1-Z-2) include, for example, a methyl group, an ethyl group, and an n-propyl group And a group in which at least one hydrogen atom in an alkyl group such as i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like is substituted with a fluorine atom. it can.
- Specific onium salts include, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfoniumbenzenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium n-octanesulfonate, Triphenylsulfonium 4-trifluoromethylbenzenesulfonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium perfluorobenzenesulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.
- Examples include compounds represented by the following formulas (2x-1) to (2x-43).
- triphenylsulfonium trifluoromethanesulfonate triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium 10-camphorsulfonate, (4-hydroxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-hydroxy) Phenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tris (4-methoxyphenyl) sulfonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) diphenylsulfonium trifluoromethane Sulfonate, (4-fluorophenyl) diphenylsulfonium nonafluoro-n- Tansulfonate, (4-fluor
- diazomethane compound examples include bis (trifluoromethanesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] decane-7-sulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane and the like can be mentioned.
- diazomethane compounds bis (cyclohexylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4] .5] decane-7-sulfonyl) diazomethane is preferred.
- sulfonimide compound examples include N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy)- 7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy- 2,3-dicarboximide; N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bi Chlo [2.2.1] heptane-5,6-oxy-2,
- N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide N- (10-camphorsulfonyloxy) succinimide N-[(5-methyl-5-carboxymethylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] succinimide is preferred.
- the amount of the acid generator (B) is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the polymer (A). . There exists a possibility that a sensitivity and developability may fall that the compounding quantity of this acid generator (B) is less than 0.1 mass part. On the other hand, if the blending amount exceeds 50 parts by mass, the transparency to radiation, pattern shape, heat resistance, etc. may be reduced.
- the radiation sensitive composition of the present invention includes an acid diffusion control agent (hereinafter referred to as “acid diffusion control agent (C)”. It is preferable to further contain.
- the acid diffusion controller (C) controls the diffusion phenomenon in the resist film (resist film) of the acid generated from the acid generator (B) by exposure, and has an action of suppressing undesired chemical reaction in the non-exposed region It is an ingredient.
- the storage stability of the resulting radiation-sensitive composition is improved and the resolution of the resist film to be formed is reduced. It can be improved sufficiently. Furthermore, it is possible to suppress changes in the line width of the resist pattern due to fluctuations in the holding time (PED) from the exposure to the heat treatment after the exposure, thereby obtaining a radiation-sensitive composition having extremely excellent process stability. It is done.
- a nitrogen-containing organic compound or a photosensitive basic compound is preferably used as the acid diffusion controller (C).
- the nitrogen-containing organic compound include a compound represented by the following general formula (7) (hereinafter, referred to as “nitrogen-containing compound (i)”), a compound having two nitrogen atoms in the same molecule (hereinafter, “ Nitrogen-containing compound (ii) ”), polyamino compounds and polymers having three or more nitrogen atoms (hereinafter collectively referred to as“ nitrogen-containing compound (iii) ”), amide group-containing compounds, urea compounds, nitrogen-containing compounds Examples include heterocyclic compounds.
- each R 16 is independently of each other a hydrogen atom, a linear, branched or cyclic alkyl group which may be substituted, an aryl group which may be substituted, or a substituent. Represents an aralkyl group which may be substituted.
- nitrogen-containing compound (i) examples include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; -Butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc.
- mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine;
- Di (cyclo) alkylamines triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octyl Amine, tri-n-nonylamine, tri-n-decylamine, cyclo Tri (cyclo) alkylamines such as xyldimethylamine, methyldicyclohexylamine, tricyclohexylamine; substituted alkylamines such as triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3 -Methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,4,6-tri-tert-butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisoprop
- nitrogen-containing compound (ii) examples include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diamino.
- nitrogen-containing compound (iii) for example, polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer and the like are preferable.
- Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt -Butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, (S)- ( ⁇ )-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl-4-hydroxy Piperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxycar Nilpiperazine, N, N-di-t-butoxycarbonyl-1-adamanty
- urea compound examples include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butyl. Thiourea and the like are preferable.
- nitrogen-containing heterocyclic compound examples include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2.
- -Imidazoles such as methyl-1H-imidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenyl Pyridines such as pyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, 2,2 ′: 6 ′, 2 ′′ -terpyridine; piperazine, 1- (2- Of piperazines such as hydroxyethyl) piperazine Or pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidine ethanol, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine 3- (N-morpholino
- the photosensitive basic compound is a component that decomposes in the exposed region and loses basicity, and remains in the unexposed portion without being decomposed. Since such a photosensitive basic compound can effectively use an acid generated in an exposed portion (that is, an exposed region), compared with a non-photosensitive basic compound, sensitivity can be further improved. .
- the type of the photosensitive basic compound is not particularly limited as long as it has the above properties. Specifically, for example, compounds represented by the following general formulas (8-1) and (8-2) can be preferably used.
- R 17 to R 21 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent.
- These are an alkyl group of formula 1 to 10, an alicyclic hydrocarbon group which may have a substituent, or an aryl group which may have a substituent.
- Z ⁇ is OH ⁇ , R 22 O ⁇ , or R 22 COO —
- R 22 is a monovalent organic group.
- Examples of the alkyl group having 1 to 10 carbon atoms which may have a substituent of R 17 to R 21 in the general formulas (8-1) and (8-2) include a methyl group, an ethyl group, and n- Examples thereof include a butyl group, a tert-butyl group, and a trifluoromethyl group.
- the alkyl group includes a hydroxyl group, a carboxyl group, a halogen atom (fluorine atom, bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, etc.), alkyloxycarbonyl group.
- Examples of the alicyclic hydrocarbon group which may have a substituent in R 17 to R 21 include the structures of the general formulas (a-1) to (a-50).
- the alicyclic hydrocarbon group includes a hydroxyl group, a carboxyl group, a halogen atom (fluorine atom, bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, etc.), It may be substituted with a substituent such as an alkyloxycarbonyl group (such as t-butoxycarbonylmethyloxy group).
- examples of the halogen atom in R 17 to R 21 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- examples of the alkyl group having 1 to 10 carbon atoms which may have a substituent of R c and R d of —OSO 2 —R c group and —SO 2 —R d in R 17 to R 21 include, for example, , Methyl group, ethyl group, n-butyl group, tert-butyl group, trifluoromethyl group and the like.
- the alkyl group includes a hydroxyl group, a carboxyl group, a halogen atom (fluorine atom, bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, etc.), alkyloxycarbonyl group. It may be substituted with a substituent such as (t-butoxycarbonylmethyloxy group and the like). Further, examples of the alicyclic hydrocarbon group which may have a substituent in R c and R d include the structures of the general formulas (a-1) to (a-50).
- the alicyclic hydrocarbon group includes a hydroxyl group, a carboxyl group, a halogen atom (fluorine atom, bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, etc.), It may be substituted with a substituent such as an alkyloxycarbonyl group (such as t-butoxycarbonylmethyloxy group).
- examples of the aryl group which may have a substituent in R c and R d include the structures of the general formulas (x-1) to (x-3).
- the aryl group includes a hydroxyl group, a carboxyl group, a halogen atom (fluorine atom, bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, etc.), alkyloxycarbonyl group. It may be substituted with a substituent such as (t-butoxycarbonylmethyloxy group and the like).
- R c and R d are each preferably a cyclohexyl group, a phenyl group, a methyl group, or a trifluoromethyl group.
- R 17 to R 21 are preferably a hydrogen atom or a tert-butyl group.
- R 17 to R 19 may all be the same or a part or all of them may be different.
- R 20 and R 21 may be the same or different.
- Each Z ⁇ in the general formulas (8-1) and (8-2) is OH ⁇ , R 22 O ⁇ , or R 22 COO — .
- Examples of the monovalent organic group for R 22 include an alkyl group which may have a substituent and an aryl group which may have a substituent.
- Z ⁇ is preferably OH ⁇ , CH 3 COO ⁇ , and compounds (Z-1) to (Z-5) represented by the following formulae.
- a specific example of the photosensitive basic compound is a triphenylsulfonium compound [compound represented by the general formula (8-1)], the anion portion (Z ⁇ ) of which is OH ⁇ , CH 3. COO ⁇ , and the compound (Z-2) or (Z-3) are exemplified.
- the said acid diffusion control agent (C) may be used individually by 1 type, and may be used in combination of 2 or more type.
- the amount of the acid diffusion controller (C) is preferably 30 parts by mass or less, more preferably 0.001 to 30 parts by mass, and still more preferably 100 parts by mass of the polymer (A). 0.005 to 15 parts by mass.
- the compounding amount of the acid diffusion controller (C) exceeds 15 parts by mass, the sensitivity of the formed resist film and the developability of the exposed part may be deteriorated.
- the blending amount is less than 0.001 part by mass, the pattern shape and dimensional fidelity of the formed resist film may be lowered depending on the process conditions.
- the radiation-sensitive composition of the present invention is obtained by dissolving the polymer (A), the acid generator (B), and the acid diffusion controller (C) in a solvent. Is preferred. That is, it is preferable to further contain a solvent as another component. Moreover, various additives, such as surfactant, a sensitizer, and an aliphatic additive, can further be mix
- the solvent examples include linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionate, alkyl 3-alkoxypropionate, and ⁇ -butyrolactone. At least one selected from the group consisting of
- the amount of the solvent in the radiation-sensitive composition of the present invention is preferably such that the total solid concentration in the composition is 1 to 70% by mass, more preferably 1 to 15% by mass. More preferably, the amount is 1 to 10% by mass.
- the radiation-sensitive composition of the present invention comprises a polymer (A), an acid generator (B), an acid diffusion controller (C), and other components (excluding the solvent) as required, with a total solid content concentration.
- A polymer
- B acid generator
- C acid diffusion controller
- other components excluding the solvent
- a total solid content concentration can be prepared by uniformly dissolving in a solvent so that is in the above range.
- the surfactant is a component having an action of improving coating properties, striations, developability and the like.
- examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate.
- nonionic surfactants such as polyethylene glycol distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no.
- surfactants may be used individually by 1 type, and may be used in combination of 2 or more type. Further, the blending amount of the surfactant is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of the polymer (A).
- the sensitizer absorbs radiation energy and transmits the energy to the acid generator (B), thereby increasing the amount of acid produced.
- the apparent sensitivity of the radiation-sensitive composition It has the effect of improving sensitivity.
- Examples of such sensitizers include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines, and the like.
- these sensitizers may be used individually by 1 type, and may be used in combination of 2 or more type.
- the blending amount of the sensitizer is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer (A).
- the latent image in the exposed area can be visualized, and the influence of halation during exposure can be mitigated.
- substrate can be improved by mix
- the alicyclic additive is a component having a function of further improving dry etching resistance, pattern shape, adhesion to a substrate, and the like.
- Examples of such alicyclic additives include 1-adamantane carboxylic acid, 2-adamantanone, 1-adamantane carboxylic acid t-butyl, 1-adamantane carboxylic acid t-butoxycarbonylmethyl, 1-adamantane carboxylic acid ⁇ .
- the blending amount of the alicyclic additive is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymer (A). When the blending amount of the alicyclic additive exceeds 20 parts by mass, the heat resistance of the formed resist film may be lowered.
- additives other than the above include alkali-soluble polymers, low-molecular alkali solubility control agents having an acid-dissociable protective group, antihalation agents, storage stabilizers, antifoaming agents, and the like. .
- the radiation-sensitive composition of the present invention is useful as a material capable of forming a chemically amplified positive resist film.
- the acid dissociable group in the polymer is eliminated by the action of the acid generated from the acid generator by exposure, and the polymer becomes alkali-soluble. That is, an alkali-soluble site is generated in the resist film.
- This alkali-soluble portion is an exposed portion of the resist, and this exposed portion can be dissolved and removed by an alkali developer. In this way, a positive resist pattern having a desired shape can be formed. This will be specifically described below.
- a resist film is formed using the radiation-sensitive composition of the present invention.
- the radiation-sensitive composition for example, as described above, after adjusting the total solid content concentration, a composition filtered with a filter having a pore diameter of about 0.2 ⁇ m can be used.
- a resist film is formed by applying this radiation-sensitive composition onto a substrate such as a silicon wafer or a wafer coated with aluminum by an appropriate application means such as spin coating, cast coating, or roll coating. To do. Thereafter, in some cases, heat treatment (hereinafter referred to as “PB”) may be performed in advance at a temperature of about 70 to 160 ° C.
- PB heat treatment
- the resist film is exposed so that a predetermined resist pattern is formed.
- radiation that can be used for this exposure include (extreme) far ultraviolet rays such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), EUV (extreme ultraviolet light, wavelength 13.5 nm, etc.), and synchro Examples include X-rays such as tron radiation, and charged particle beams such as electron beams.
- exposure conditions, such as exposure amount can be suitably selected according to the compounding composition of a radiation sensitive composition, the kind of additive, etc. This exposure can also be immersion exposure.
- PEB heat processing
- the radiation-sensitive composition in order to maximize the potential of the radiation-sensitive composition, it is used, for example, as disclosed in Japanese Patent Publication No. 6-12452 (Japanese Patent Laid-Open No. 59-93448).
- An organic or inorganic antireflection film can also be formed on the substrate.
- a protective film can be provided on the resist film as disclosed in, for example, Japanese Patent Laid-Open No. 5-188598. These techniques can be used in combination.
- a predetermined resist pattern is formed by developing the exposed resist film.
- the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propylamine.
- An alkaline aqueous solution in which at least one alkaline compound such as [4.3.0] -5-nonene is dissolved is preferable.
- the concentration of the alkaline aqueous solution is preferably 10% by mass or less. When the concentration of the alkaline aqueous solution exceeds 10% by mass, the unexposed area may be dissolved in the developer.
- the developer is preferably pH 8 to 14, more preferably pH 9 to 14.
- an organic solvent can be added to the developer composed of the alkaline aqueous solution.
- the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n-propyl Alcohols such as alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol and 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane And esters such as ethyl acetate, n-butyl acetate and i-amyl acetate; aromatic hydrocarbons such as toluene and
- the blending amount of the organic solvent is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution.
- the blending amount of the organic solvent exceeds 100 parts by volume, the developability is lowered, and there is a possibility that the remaining development in the exposed part increases.
- an appropriate amount of a surfactant or the like can be added to the developer composed of an alkaline aqueous solution.
- it can also wash with water and can be dried.
- EB electron beam
- part is based on mass unless otherwise specified.
- the obtained copolymer had an Mw of 11000, an Mw / Mn of 2.3, and a content ratio of each repeating unit derived from p-hydroxystyrene and the compound (M-1-1) as a result of 13 C-NMR analysis. It was a copolymer having a (molar ratio) of 65:35. Hereinafter, this copolymer is referred to as a polymer (A-1).
- Example 6> After dissolving 5.4 g of p-acetoxystyrene, 4.6 g of the compound (M-1-2) obtained in Example 2, 0.4 g of AIBN and 0.1 g of t-dodecyl mercaptan in 10 g of propylene glycol monomethyl ether, The polymerization was carried out for 16 hours under a nitrogen atmosphere while maintaining the reaction temperature at 70 ° C. After the polymerization, the reaction solution was dropped into 500 g of n-hexane to coagulate and purify the resulting copolymer.
- the obtained copolymer had Mw of 10,000, Mw / Mn of 2.3, and the content ratio of each repeating unit derived from p-hydroxystyrene and the compound (M-1-2) as a result of 13 C-NMR analysis. It was a copolymer having a (molar ratio) of 64:36. Hereinafter, this copolymer is referred to as a polymer (A-2).
- Example 7 After dissolving 5.5 g of p-acetoxystyrene, 4.5 g of the compound (M-1-1) obtained in Example 1 and 1.0 g of AIBN in 15 g of propylene glycol monomethyl ether, the reaction temperature was changed under a nitrogen atmosphere. The polymerization was carried out for 16 hours while maintaining at 70 ° C. After the polymerization, the reaction solution was dropped into 500 g of n-hexane to coagulate and purify the resulting copolymer.
- the resulting copolymer, Mw is 4000, Mw / Mn is 2.4, 13 C-NMR analysis results, the content ratio of the repeating units derived from p- hydroxystyrene and Compound (M-1-1) It was a copolymer having a (molar ratio) of 65:35.
- this copolymer is referred to as a polymer (A-3).
- Example 8> After dissolving 5.1 g of p-acetoxystyrene, 4.9 g of the compound (M-1-3) obtained in Example 3, 0.3 g of AIBN and 0.1 g of t-dodecyl mercaptan in 10 g of propylene glycol monomethyl ether, The polymerization was carried out for 16 hours under a nitrogen atmosphere while maintaining the reaction temperature at 70 ° C. After the polymerization, the reaction solution was dropped into 500 g of n-hexane to coagulate and purify the resulting copolymer.
- the obtained copolymer had Mw of 10,000, Mw / Mn of 2.3, and the content ratio of each repeating unit derived from p-hydroxystyrene and the compound (M-1-3) as a result of 13 C-NMR analysis. It was a copolymer having a (molar ratio) of 65:35. Hereinafter, this copolymer is referred to as a polymer (A-4).
- Example 9 After dissolving 5.5 g of p-acetoxystyrene, 4.5 g of the compound (M-1-4) obtained in Example 4, 0.3 g of AIBN and 0.1 g of t-dodecyl mercaptan in 10 g of propylene glycol monomethyl ether, The polymerization was carried out for 16 hours under a nitrogen atmosphere while maintaining the reaction temperature at 70 ° C. After the polymerization, the reaction solution was dropped into 500 g of n-hexane to coagulate and purify the resulting copolymer.
- the obtained copolymer had an Mw of 11000, an Mw / Mn of 2.3, and a content ratio of each repeating unit derived from p-hydroxystyrene and the compound (M-1-4) as a result of 13 C-NMR analysis. It was a copolymer having a (molar ratio) of 66:34. Hereinafter, this copolymer is referred to as a polymer (A-5).
- Example 10> After dissolving 4.8 g of the compound represented by the following general formula (b-1), 5.2 g of the compound (M-1-1) obtained in Example 1, and 0.4 g of AIBN in 30 g of methyl ethyl ketone, Under the atmosphere, the reaction temperature was maintained at 78 ° C., and polymerization was performed for 6 hours. After the polymerization, the reaction solution was dropped into 500 g of methanol to solidify and purify the resulting copolymer, and the obtained solid was dried at 50 ° C. under reduced pressure overnight.
- C Acid diffusion controller
- C-1 Tri-n-octylamine
- C-2 Triphenylsulfonium salicylate
- C-3 Nt-butoxycarbonyl-2-phenylbenzimidazole
- D Solvent
- D-1 Ethyl lactate
- D-2 Propylene glycol monomethyl ether acetate
- D-3 Cyclohexanone
- the obtained copolymer had an Mw of 11000, an Mw / Mn of 2.1, and, as a result of 13 C-NMR analysis, the content ratio (moles) of each repeating unit derived from p-hydroxystyrene and the compound (M-2). The ratio) was a 65:35 copolymer.
- this copolymer is referred to as “polymer (A-7)”.
- (D) solvent D-1): ethyl lactate (D-2): propylene glycol monomethyl ether acetate
- Sensitivity (L / S)
- a pattern [a so-called line-and-space pattern (1L1S)] composed of a line portion having a line width of 150 nm and a space portion (that is, a groove) having an interval of 150 nm formed by adjacent line portions is 1: 1.
- the exposure amount formed in the line width was set as the optimum exposure amount, and the sensitivity was evaluated based on the optimum exposure amount.
- FIG. 1 is a plan view schematically showing the shape of a line and space pattern.
- FIG. 2 is a cross-sectional view schematically showing the shape of the line and space pattern. However, the unevenness shown in FIGS. 1 and 2 is exaggerated from the actual.
- Nano-edge roughness Line-and-space pattern (1L1S) with a design line width of 150 nm is scanned with a scanning electron microscope for semiconductors (high resolution FEB measuring device, trade name “S-9220”, manufactured by Hitachi, Ltd.) ).
- high resolution FEB measuring device trade name “S-9220”, manufactured by Hitachi, Ltd.
- FIG. 1 and FIG. 2 the line width and the design line at the most conspicuous portion of the unevenness generated along the lateral surface 2a of the line part 2 of the resist film formed on the silicon wafer 1 are shown.
- the difference “ ⁇ CD” from the width of 150 nm was measured by CD-SEM (manufactured by Hitachi High-Technologies Corporation, “S-9220”) to evaluate nanoedge roughness.
- the radiation-sensitive compositions of Examples 11 to 26 containing the polymers (A-1) to (A-6) are Comparative Examples 1 and 2 containing the polymer (A-7). Compared to other radiation-sensitive compositions, it is more sensitive to electron beams or extreme ultraviolet rays, has low roughness and excellent sensitivity and resolution, and can form fine patterns with high accuracy and stability. It was confirmed that a positive chemically amplified positive resist film could be formed.
- the radiation-sensitive composition of the present invention is not only excellent in the resolution of the line and space pattern at the time of pattern formation, but also excellent in nano edge roughness, and thus is useful for fine pattern formation by EB, EUV or X-ray. . Therefore, the radiation-sensitive composition of the present invention is extremely useful as a composition capable of forming a chemically amplified resist for manufacturing semiconductor devices, which is expected to be further miniaturized in the future.
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Abstract
Description
KrFエキシマレーザー光、電子線、或いはEUV光を用いたリソグラフィープロセスに適したレジストとしては、高感度化の観点から主に酸触媒反応を利用した化学増幅型レジストが用いられており、ポジ型レジストにおいては主成分として、アルカリ水溶液には不溶又は難溶性で、酸の作用によりアルカリ水溶液に可溶となる性質を有するフェノール性ポリマー(以下、「フェノール性酸分解性重合体」という)、及び酸発生剤からなる化学増幅型レジスト組成物が有効に使用されている。
[1]下記一般式(1)で表される繰り返し単位を含むことを特徴とする重合体。
[2]前記一般式(1)で表される繰り返し単位が、下記一般式(1-1)で表される繰り返し単位である前記[1]に記載の重合体。
[3]更に、下記一般式(2)~(5)で表される繰り返し単位のうちの少なくとも1種を含む前記[1]又は[2]に記載の重合体。
[4]酸解離性基含有重合体(A)と、感放射線性酸発生剤(B)と、を含有する感放射線性組成物であって、
前記酸解離性基含有重合体(A)が、前記[1]乃至[3]のいずれかに記載の重合体であることを特徴とする感放射線性組成物。
[5]前記感放射線性酸発生剤(B)が、下記一般式(b1)で表されるオニウム塩である前記[4]に記載の感放射線性組成物。
M+Z- (b1)
〔一般式(b1)において、M+は1価のオニウムカチオンを示し、Z-は下記一般式(b1-Z-1)又は(b1-Z-2)で表される1価のアニオンを示す。〕
〔一般式(b1-Z-2)において、R43、R44、及びR45は、相互に独立に、少なくとも1つのフッ素原子で置換された炭素数1~20のアルキル基であるか、或いは、R43、R44、及びR45のいずれか2つが相互に結合して、少なくとも1つのフッ素原子で置換された炭素数1~20の環状構造を形成しており、残りの1つが、少なくとも1つのフッ素原子で置換された炭素数1~20のアルキル基である。〕
[6]下記一般式(M-1)で表されることを特徴とする単量体。
[7]下記一般式(M-1)で表される化合物の製造方法。
また、本発明の重合体は、酸解離性基含有重合体として用いることにより、前記感放射線性組成物を容易に得ることができる。
[1]重合体
本発明における重合体〔以下、「重合体(I)」という〕は、下記一般式(1)で表される繰り返し単位〔以下、「繰り返し単位(1)」という〕を含むことを特徴とする。
この重合体(I)は、アルカリ不溶性又はアルカリ難溶性の重合体であって、酸の作用によりアルカリ易溶性となる重合体である。そのため、感放射線性組成物における酸解離性基含有重合体として好適に使用することができる。
これらのなかでも、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデカニル基、及びシクロドデカニル基等のシクロアルキル基;アダマンチル基、デカリン残基、ノルボルニル基等が好ましい。特に、炭素数5~15のシクロアルキル基であることが好ましい。
また、このアリール基は、置換されていてもよい。置換基の具体例としては、例えば、メチル基、エチル基、プロピル基、ヒドロキシル基、カルボキシル基、ハロゲン原子(フッ素原子、塩素原子、臭素原子等)、アルコキシ基(メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等)、アルキルオキシカルボニル基等を挙げることができる。
また、一般式(1-1)におけるhは、0~3の整数であり、0又は1であることがより好ましい。
以下は、上記一般式(1-1)で表した繰り返し単位を形成可能な化合物(1-1a)の製造例であり、この化合物(1-1a)は、下記一般式(1-r1)で表される化合物(1-フェニルシクロヘキサノール)と、下記一般式(1-r2)で表される化合物(メタクリル酸クロライド)との反応により製造することができる。
また、一般式(2)におけるiは、0~3の整数であり、1又は2であることがより好ましい。
更に、一般式(2)におけるjは、0~3の整数であり、0~2であることがより好ましい。
尚、繰り返し単位(2)が重合体(I)に含まれている場合、この繰り返し単位(2)は1種のみ含まれていてもよいし、2種以上含まれていてもよい。
また、一般式(3)におけるkは、0~3の整数であり、1又は2であることがより好ましい。
更に、一般式(3)におけるlは、0~3の整数であり、0又は1であることがより好ましい。
尚、繰り返し単位(3)が重合体(I)に含まれている場合、この繰り返し単位(3)は1種のみ含まれていてもよいし、2種以上含まれていてもよい。
また、一般式(4)におけるmは、0~3の整数であり、1又は2であることがより好ましい。
更に、一般式(4)におけるnは、0~3の整数であり、0又は1であることがより好ましい。
尚、繰り返し単位(4)が重合体(I)に含まれている場合、この繰り返し単位(4)は1種のみ含まれていてもよいし、2種以上含まれていてもよい。
また、一般式(5)におけるrは、0~3の整数であり、1又は2であることがより好ましい。
更に、一般式(5)におけるsは、0~3の整数であり、0又は1であることがより好ましい。
尚、繰り返し単位(5)が重合体(I)に含まれている場合、この繰り返し単位(5)は1種のみ含まれていてもよいし、2種以上含まれていてもよい。
前記式(2-1)~(2-3)で表される各繰り返し単位を生成するために用いられる単量体としては、p-アセトキシスチレン、p-(1-エトキシエトキシ)スチレン等が好ましい。これらの単量体を用いた場合には、重合体とした後、側鎖の加水分解反応により、式(2-1)~(2-3)で表される各繰り返し単位を生成することができる。
前記式(2-4)、(3-1)、(3-2)、(4-1)、(4-2)、(5-1)及び(5-2)で表される各繰り返し単位を生成するために用いられる単量体としては、p-イソプロペニルフェノール、4-ヒドロキシフェニルアクリレート、4-ヒドロキシフェニルメタクリレート、N-(4-ヒドロキシフェニル)アクリルアミド、N-(4-ヒドロキシフェニル)メタクリルアミド、5-ヒドロキシナフタレン-1-イルメタクリレート、5-ヒドロキシナフタレン-1-イルアクリレート等が好ましい。
前記非酸解離性化合物としては、例えば、スチレン、α-メチルスチレン、4-メチルスチレン、2-メチルスチレン、3-メチルスチレン、イソボロニルアクリレート、トリシクロデカニル(メタ)アクリレート、テトラシクロドデセニル(メタ)アクリレート、下記式(b-1)~(b-4)で表される化合物等が挙げられる。これらのなかでも、スチレン、α-メチルスチレン、4-メチルスチレン、2-メチルスチレン、3-メチルスチレン、トリシクロデカニルアクリレート、下記式(b-1)~(b-4)で表される化合物が好ましい。
尚、前記繰り返し単位(6)が重合体(I)に含まれている場合、この繰り返し単位(6)は1種のみ含まれていてもよいし、2種以上含まれていてもよい。
また、各R13は、相互に独立に、炭素数1~4の直鎖状若しくは分岐状のアルキル基、又は炭素数4~20の1価の脂環式炭化水素基若しくはそれから誘導される基を示すか、或いは、いずれか2つのR13が相互に結合して、それぞれが結合している炭素原子とともに炭素数4~20の2価の脂環式炭化水素基若しくはそれから誘導される基を形成し、残りの1つのR13が、炭素数1~4の直鎖状若しくは分岐状のアルキル基、又は炭素数4~20の1価の脂環式炭化水素基若しくはそれから誘導される基を示す。
また、この脂環式炭化水素基から誘導される基としては、上述の1価の脂環式炭化水素基を、例えば、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、2-メチルプロピル基、1-メチルプロピル基、t-ブチル基等の炭素数1~4の直鎖状、分岐状又は環状のアルキル基の1種以上或いは1個以上で置換した基等を挙げることができる。
これらのなかでも、R13の脂環式炭化水素基は、ノルボルナン、トリシクロデカン、テトラシクロドデカン、アダマンタン、シクロペンタン又はシクロヘキサンに由来する脂環族環からなる基や、これらの脂環族環からなる基を前記アルキル基で置換した基等が好ましい。
更に、R13が相互に結合して形成された2価の脂環式炭化水素基から誘導される基としては、上述の2価の脂環式炭化水素基を、例えば、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、2-メチルプロピル基、1-メチルプロピル基、t-ブチル基等の炭素数1~4の直鎖状、分岐状又は環状のアルキル基の1種以上或いは1個以上で置換した基等を挙げることができる。
これらのなかでも、シクロペンチレン基、シクロヘキシレン基や、この2価の脂環式炭化水素基を前記アルキル基で置換した基等が好ましい。
また、前記繰り返し単位(2)~(5)の含有量の合計は、重合体(I)における全繰り返し単位の合計を100モル%とした場合に、1モル%以上であることが好ましく、より好ましくは5~95モル%、更に好ましくは5~80モル%である。この含有量の合計が95モル%を超える場合には、重合体(I)を感放射線性組成物における酸解離性基含有重合体として用いた際に、ナノエッジラフネスが悪化することがある。
更に、前記繰り返し単位(1)~(5)の含有量の合計は、重合体(I)における全繰り返し単位の合計を100モル%とした場合に、10モル%以上であることが好ましく、より好ましくは40~100モル%、更に好ましくは50~100モル%である。この含有量の合計が10モル%以上である場合には、重合体(I)を感放射線性組成物における酸解離性基含有重合体として用いた際に、ナノエッジラフネスに優れるものとすることができる。
更に、前記繰り返し単位(7)の含有量は、重合体(I)における全繰り返し単位の合計を100モル%とした場合に、通常60モル%以下であり、好ましくは0~50モル%である。この含有量が60モル%以下である場合には、この重合体(I)を感放射線性組成物における酸解離性基含有重合体として用いた際に、解像性能とナノエッジラフネスとの性能バランスに優れるものとすることができる。
また、前記繰り返し単位(6)及び(7)の含有量の合計は、重合体(I)における全繰り返し単位の合計を100モル%とした場合に、90モル%以下であり、好ましくは0~80モル%である。この含有量が90モル%以下である場合には、この重合体(I)を感放射線性組成物における酸解離性基含有重合体として用いた際に、解像性能とナノエッジラフネスとの性能バランスに優れるものとすることができる。
尚、この重合の際には、必要に応じて、2,2,6,6-テトラメチル-1-ピペリジニルオキシ、沃素、メルカプタン、スチレンダイマー等の重合助剤を添加することもできる。
また、反応時間は、開始剤の種類や反応温度により異なるが、開始剤が50%以上消費される反応時間が望ましく、多くの場合0.5~24時間程度である。
また、反応時間は、開始剤の種類や反応温度により異なるが、開始剤が50%以上消費される反応時間が望ましく、多くの場合0.5~24時間程度である。
更に、塩基としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム等の無機塩基;トリエチルアミン、N-メチル-2-ピロリドン、ピペリジン、テトラメチルアンモニウムヒドロキシド等の有機塩基等が挙げられる。
これらのなかでも、アセトン、メチルアミルケトン、メチルエチルケトン、テトラヒドロフラン、メタノール、エタノール、プロパノール、酢酸エチル、酢酸ブチル、乳酸エチル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等が好ましい。
また、重合体(I)のMwと、GPCで測定したポリスチレン換算数平均分子量(以下、「Mn」ともいう)との比(Mw/Mn)は、通常1~5であり、より好ましくは1~4、更に好ましくは1~3である。
本発明の感放射線性組成物は、酸解離性基含有重合体(A)と、感放射線性酸発生剤(B)と、を含有することを特徴とする。
前記酸解離性基含有重合体は、アルカリ不溶性又はアルカリ難溶性であって、且つ酸の作用によりアルカリ易溶性となる重合体(以下、「重合体(A)」ともいう。)である。尚、ここでいう「アルカリ不溶性又はアルカリ難溶性」とは、重合体(A)を含有する感放射線性組成物から形成されたレジスト被膜からレジストパターンを形成する際に採用されるアルカリ現像条件下で、当該レジスト被膜の代わりに重合体(A)のみを用いた膜厚100nmの被膜を現像した場合に、当該被膜の初期膜厚の50%以上が現像後に残存する性質を意味する。
また、この重合体(A)については、前述の重合体(I)の説明をそのまま適用することができる。
前記酸発生剤(B)は、リソグラフィープロセスにおいて、本発明の感放射線性組成物に電子線や放射線等を照射したときに、感放射線性組成物内で酸を発生する物質である。そして、酸発生剤(B)から発生した酸の作用によって、既に上述した重合体中の酸解離性基が解離することになる。
M+Z- (b1)
〔一般式(b1)において、M+は1価のオニウムカチオンであり、Z-は1価のアニオンである。〕
また、このアルキル基は、フッ素、塩素、臭素、ヨウ素等のハロゲン原子、ヒドロキシル基、チオール基、及び、ヘテロ原子(例えば、ハロゲン原子、酸素原子、窒素原子、硫黄原子、リン原子、ケイ素原子等)を含む有機基等の置換基により置換されていてもよい。
また、このアリール基は、フッ素、塩素、臭素、ヨウ素等のハロゲン原子、ヒドロキシル基、チオール基、アルキル基、及び、ヘテロ原子(例えば、ハロゲン原子、酸素原子、窒素原子、硫黄原子、リン原子、ケイ素原子等)を含む有機基等の置換基により置換されていてもよい。
R47SO3 - (b1-Z-4)
また、一般式(b1-Z-2)において、R43、R44、及びR45は、相互に独立に、少なくとも1つのフッ素原子で置換された炭素数1~20のアルキル基であるか、或いは、R43、R44、及びR45のいずれか2つが相互に結合して、少なくとも1つのフッ素原子で置換された炭素数1~20の環状構造を形成しており、残りの1つが、少なくとも1つのフッ素原子で置換された炭素数1~20のアルキル基である。
更に、一般式(b1-Z-3)及び(b1-Z-4)において、R46及びR47は、相互に独立に、フッ素原子、又は置換されていても良い炭素数1~12の炭化水素基を示す。nは、1~10の整数を示す。
これらのジアゾメタン化合物のなかでも、ビス(シクロヘキシルスルホニル)ジアゾメタン、ビス(3,3-ジメチル-1,5-ジオキサスピロ[5.5]ドデカン-8-スルホニル)ジアゾメタン、ビス(1,4-ジオキサスピロ[4.5]デカン-7-スルホニル)ジアゾメタンが好ましい。
本発明の感放射線性組成物は、前記重合体(A)及び酸発生剤(B)以外に、酸拡散制御剤(以下、「酸拡散制御剤(C)」ともいう)を更に含有することが好ましい。
酸拡散制御剤(C)は、露光により酸発生剤(B)から生じる酸の、レジスト膜(レジスト被膜)中における拡散現象を制御し、非露光領域における好ましくない化学反応を抑制する作用を有する成分である。
本発明の感放射線性組成物においては、この酸拡散制御剤(C)が配合されることにより、得られる感放射線性組成物の貯蔵安定性が向上すると共に、形成されるレジスト膜の解像度を十分に向上させることができる。更には、露光後から露光後の加熱処理までの引き置き時間(PED)の変動に起因するレジストパターンの線幅変化を抑えることができ、プロセス安定性に極めて優れた感放射線性組成物が得られる。
前記含窒素有機化合物としては、例えば、下記一般式(7)で表される化合物(以下、「含窒素化合物(i)」という)、同一分子内に窒素原子を2個有する化合物(以下、「含窒素化合物(ii)」という)、窒素原子を3個以上有するポリアミノ化合物や重合体(以下、これらをまとめて「含窒素化合物(iii)」という)、アミド基含有化合物、ウレア化合物、含窒素複素環化合物等を挙げることができる。
また、前記R17~R21における置換基を有してもよい脂環式炭化水素基としては、前記一般式(a-1)~(a-50)の構造等が挙げられる。尚、この脂環式炭化水素基は、ヒドロキシル基、カルボキシル基、ハロゲン原子(フッ素原子、臭素原子等)、アルコキシ基(メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、t-ブトキシ基等)、アルキルオキシカルボニル基(t-ブトキシカルボニルメチルオキシ基等)等の置換基により置換されていてもよい。
更に、前記R17~R21におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
また、Rc及びRdにおける置換基を有してもよい脂環式炭化水素基としては、前記一般式(a-1)~(a-50)の構造等が挙げられる。尚、この脂環式炭化水素基は、ヒドロキシル基、カルボキシル基、ハロゲン原子(フッ素原子、臭素原子等)、アルコキシ基(メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、t-ブトキシ基等)、アルキルオキシカルボニル基(t-ブトキシカルボニルメチルオキシ基等)等の置換基により置換されていてもよい。
更に、Rc及びRdにおける置換基を有してもよいアリール基としては、前記一般式(x-1)~(x-3)の構造等が挙げられる。尚、このアリール基は、ヒドロキシル基、カルボキシル基、ハロゲン原子(フッ素原子、臭素原子等)、アルコキシ基(メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、t-ブトキシ基等)、アルキルオキシカルボニル基(t-ブトキシカルボニルメチルオキシ基等)等の置換基により置換されていてもよい。
特に、Rc及びRdは、それぞれ、シクロヘキシル基、フェニル基、メチル基、トリフルオロメチル基であることが好ましい。
前記R22の1価の有機基としては、例えば、置換基を有してもよいアルキル基、置換基を有してもよいアリール基を挙げることができる。
特に、前記Z-としては、OH-、CH3COO-、及び下記式で表される化合物(Z-1)~(Z-5)であることが好ましい。
本発明の感放射線性組成物は、前記重合体(A)、酸発生剤(B)及び酸拡散制御剤(C)を、溶剤に溶解させたものであることが好ましい。即ち、その他の成分として溶剤を更に含有することが好ましい。
また、本発明の感放射線性組成物には、その他の成分として、必要に応じて、界面活性剤、増感剤、脂肪族添加剤等の各種の添加剤を更に配合することができる。
このような界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンn-オクチルフェニルエーテル、ポリオキシエチレンn-ノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート等のノニオン系界面活性剤のほか、以下商品名で、KP341(信越化学工業社製)、ポリフローNo.75、同No.95(共栄社化学社製)、エフトップEF301、同EF303、同EF352(トーケムプロダクツ社製)、メガファックF171、同F173(大日本インキ化学工業社製)、フロラードFC430、同FC431(住友スリーエム社製)、アサヒガードAG710、サーフロンS-382、同SC-101、同SC-102、同SC-103、同SC-104、同SC-105、同SC-106(旭硝子社製)等を挙げることができる。これらの界面活性剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
また、界面活性剤の配合量は、重合体(A)100質量部に対して、0.001~2質量部であることが好ましい。
このような増感剤としては、例えば、カルバゾール類、アセトフェノン類、ベンゾフェノン類、ナフタレン類、フェノール類、ビアセチル、エオシン、ローズベンガル、ピレン類、アントラセン類、フェノチアジン類等を挙げることができる。尚、これらの増感剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
また、増感剤の配合量は、重合体(A)100質量部に対して、0.1~10質量部であることが好ましい。
このような脂環族添加剤としては、例えば、1-アダマンタンカルボン酸、2-アダマンタノン、1-アダマンタンカルボン酸t-ブチル、1-アダマンタンカルボン酸t-ブトキシカルボニルメチル、1-アダマンタンカルボン酸α-ブチロラクトンエステル、1,3-アダマンタンジカルボン酸ジ-t-ブチル、1-アダマンタン酢酸t-ブチル、1-アダマンタン酢酸t-ブトキシカルボニルメチル、1,3-アダマンタンジ酢酸ジ-t-ブチル、2,5-ジメチル-2,5-ジ(アダマンチルカルボニルオキシ)ヘキサン等のアダマンタン誘導体類;デオキシコール酸t-ブチル、デオキシコール酸t-ブトキシカルボニルメチル、デオキシコール酸2-エトキシエチル、デオキシコール酸2-シクロヘキシルオキシエチル、デオキシコール酸3-オキソシクロヘキシル、デオキシコール酸テトラヒドロピラニル、デオキシコール酸メバロノラクトンエステル等のデオキシコール酸エステル類;リトコール酸t-ブチル、リトコール酸t-ブトキシカルボニルメチル、リトコール酸2-エトキシエチル、リトコール酸2-シクロヘキシルオキシエチル、リトコール酸3-オキソシクロヘキシル、リトコール酸テトラヒドロピラニル、リトコール酸メバロノラクトンエステル等のリトコール酸エステル類;アジピン酸ジメチル、アジピン酸ジエチル、アジピン酸ジプロピル、アジピン酸ジn-ブチル、アジピン酸ジt-ブチル等のアルキルカルボン酸エステル類や、3-〔2-ヒドロキシ-2,2-ビス(トリフルオロメチル)エチル〕テトラシクロ[4.4.0.12,5.17,10]ドデカン等を挙げることができる。これらの脂環族添加剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
本発明の感放射線性組成物は、化学増幅型ポジ型レジスト膜を成膜可能な材料として有用である。
前記化学増幅型ポジ型レジスト膜においては、露光により酸発生剤から発生した酸の作用によって、重合体中の酸解離性基が脱離し、重合体がアルカリ可溶性となる。即ち、レジスト膜に、アルカリ可溶性部位が生じる。このアルカリ可溶性部位は、レジストの露光部であり、この露光部はアルカリ現像液によって溶解、除去することができる。このようにして所望の形状のポジ型のレジストパターンを形成することができる。以下、具体的に説明する。
この露光に使用することができる放射線としては、例えば、KrFエキシマレーザー(波長248nm)、ArFエキシマレーザー(波長193nm)、EUV(極紫外線、波長13.5nm等)等の(極)遠紫外線、シンクロトロン放射線等のX線、電子線等の荷電粒子線等を挙げることができる。また、露光量等の露光条件は、感放射線性組成物の配合組成や添加剤の種類等に応じて適宜選定することができる。尚、この露光は、液浸露光とすることもできる。
また、現像液は、pH8~14であることが好ましく、より好ましくはpH9~14である。
尚、アルカリ性水溶液からなる現像液で現像した後は、水で洗浄して乾燥することもできる。
<実施例1>
1-フェニルシクロヘキサノール15.9g、メタクリル酸クロライド12.2g、及び1,4-ジアザビシクロ[2.2.2]オクタン13.12gを塩化メチレン200gに溶解させた後、塩化メチレン還流下、6時間反応させた。反応終了後、反応母液に酢酸エチルを加え、有機層を水で洗浄した。その後、展開溶媒に酢酸エチル/n-ヘキサン=1/1(体積比)の混合溶媒を用いて、シリカゲルカラムクロマトグラフィーを行うことにより、目的とする化合物を得た(収率60%)。
1H-NMR(400MHz、溶媒DMSO-d6、内部標準TMS):δ(ppm)=1.11~1.82(8.0H)、1.85~1.90(3.0H)、2.30~2.45(2.0H)、5.58~6.10(2.0H)、7.15~7.23(1H)、7.23~7.35(4.0H)
1-p-トルイルシクロヘキサノール17.2g、メタクリル酸クロライド12.2g、及び1,4-ジアザビシクロ[2.2.2]オクタン13.12gを塩化メチレン200gに溶解させた後、塩化メチレン還流下、6時間反応させた。反応終了後、反応母液に酢酸エチルを加え、有機層を水で洗浄した。その後、展開溶媒に酢酸エチル/n-ヘキサン=1/1(体積比)の混合溶媒を用いて、シリカゲルカラムクロマトグラフィーを行うことにより、目的とする化合物を得た(収率62%)。
1H-NMR(400MHz、溶媒DMSO-d6、内部標準TMS):δ(ppm)=1.16~1.82(8.0H)、1.82~1.95(3.0H)、2.31~2.31(3.0H)、2.19~2.45(2.0H)、5.58~6.15(2.0H)、7.01~7.30(4H)
1-(ナフタレン-1-イル)シクロヘキサノール20.4g、メタクリル酸クロライド12.2g、及び1,4-ジアザビシクロ[2.2.2]オクタン13.12gを塩化メチレン200gに溶解させた後、塩化メチレン還流下、6時間反応させた。反応終了後、反応母液に酢酸エチルを加え、有機層を水で洗浄した。その後、展開溶媒に酢酸エチル/n-ヘキサン=1/1(体積比)の混合溶媒を用いて、シリカゲルカラムクロマトグラフィーを行うことにより、目的とする化合物を得た(収率55%)。
1H-NMR(400MHz、溶媒CDCl3、内部標準TMS):δ(ppm)=1.11~2.2(11.0H)、2.90~3.20(2.0H)、5.50~6.30(2.0H)、7.30~7.95(6.0H)、8.43~8.65(1.0H)
1-p-トルイルシクロペンタノール15.9g、メタクリル酸クロライド12.2g、及び1,4-ジアザビシクロ[2.2.2]オクタン13.12gを塩化メチレン200gに溶解させた後、塩化メチレン還流下、6時間反応させた。反応終了後、反応母液に酢酸エチルを加え、有機層を水で洗浄した。その後、展開溶媒に酢酸エチル/n-ヘキサン=1/1(体積比)の混合溶媒を用いて、シリカゲルカラムクロマトグラフィーを行うことにより、目的とする化合物を得た(収率54%)。
1H-NMR(400MHz、溶媒DMSO-d6、内部標準TMS):δ(ppm)=1.52~1.90(7.0H)、1.90~2.10(2.0H)、2.15~2.26(3.0H)、2.26~2.40(2.0H)、5.50~6.10(2.0H)、7.00~7.31(4.0H)
<実施例5>
p-アセトキシスチレン5.5g、実施例1で得られた化合物(M-1-1)4.5g、アゾビスイソブチロニトリル(以下、「AIBN」という)0.4g、及びt-ドデシルメルカプタン0.1gを、プロピレングリコールモノメチルエーテル10gに溶解したのち、窒素雰囲気下、反応温度を70℃に保持して、16時間重合させた。重合後、反応溶液を500gのn-ヘキサン中に滴下して、生成共重合体を凝固精製した。次いで、この共重合体に、再度プロピレングリコールモノメチルエーテル7.5gを加えたのち、更に、メタノール15g、トリエチルアミン4.0g及び水1.0gを加えて、沸点にて還流させながら、8時間加水分解反応を行った。反応後、溶剤及びトリエチルアミンを減圧留去し、得られた共重合体をアセトン10gに溶解したのち、100gの水中に滴下して凝固させ、生成した白色粉末をろ過して、減圧下50℃で一晩乾燥した。
得られた共重合体は、Mwが11000、Mw/Mnが2.3、13C-NMR分析の結果、p-ヒドロキシスチレン及び化合物(M-1-1)に由来する各繰り返し単位の含有比(モル比)が65:35の共重合体であった。以下、この共重合体を、重合体(A-1)とする。
p-アセトキシスチレン5.4g、実施例2で得られた化合物(M-1-2)4.6g、AIBN0.4g、及びt-ドデシルメルカプタン0.1gを、プロピレングリコールモノメチルエーテル10gに溶解したのち、窒素雰囲気下、反応温度を70℃に保持して、16時間重合させた。重合後、反応溶液を500gのn-ヘキサン中に滴下して、生成共重合体を凝固精製した。次いで、この共重合体に、再度プロピレングリコールモノメチルエーテル7.5gを加えたのち、更に、メタノール15g、トリエチルアミン4.0g及び水1.0gを加えて、沸点にて還流させながら、8時間加水分解反応を行った。反応後、溶剤及びトリエチルアミンを減圧留去し、得られた共重合体をアセトン10gに溶解したのち、100gの水中に滴下して凝固させ、生成した白色粉末をろ過して、減圧下50℃で一晩乾燥した。
得られた共重合体は、Mwが10000、Mw/Mnが2.3、13C-NMR分析の結果、p-ヒドロキシスチレン及び化合物(M-1-2)に由来する各繰り返し単位の含有比(モル比)が64:36の共重合体であった。以下、この共重合体を、重合体(A-2)とする。
p-アセトキシスチレン5.5g、実施例1で得られた化合物(M-1-1)4.5g、及びAIBN1.0gを、プロピレングリコールモノメチルエーテル15gに溶解したのち、窒素雰囲気下、反応温度を70℃に保持して、16時間重合させた。重合後、反応溶液を500gのn-ヘキサン中に滴下して、生成共重合体を凝固精製した。次いで、この共重合体に、再度プロピレングリコールモノメチルエーテル7.5gを加えたのち、更に、メタノール15g、トリエチルアミン4.0g及び水1.0gを加えて、沸点にて還流させながら、8時間加水分解反応を行った。反応後、溶剤及びトリエチルアミンを減圧留去し、得られた共重合体をアセトン10gに溶解したのち、100gの水中に滴下して凝固させ、生成した白色粉末をろ過して、減圧下50℃で一晩乾燥した。
得られた共重合体は、Mwが4000、Mw/Mnが2.4、13C-NMR分析の結果、p-ヒドロキシスチレン及び化合物(M-1-1)に由来する各繰り返し単位の含有比(モル比)が65:35の共重合体であった。以下、この共重合体を、重合体(A-3)とする。
p-アセトキシスチレン5.1g、実施例3で得られた化合物(M-1-3)4.9g、AIBN0.3g、及びt-ドデシルメルカプタン0.1gを、プロピレングリコールモノメチルエーテル10gに溶解したのち、窒素雰囲気下、反応温度を70℃に保持して、16時間重合させた。重合後、反応溶液を500gのn-ヘキサン中に滴下して、生成共重合体を凝固精製した。次いで、この共重合体に、再度プロピレングリコールモノメチルエーテル7.5gを加えたのち、更に、メタノール15g、トリエチルアミン4.0g及び水1.0gを加えて、沸点にて還流させながら、8時間加水分解反応を行った。反応後、溶剤及びトリエチルアミンを減圧留去し、得られた共重合体をアセトン10gに溶解したのち、100gの水中に滴下して凝固させ、生成した白色粉末をろ過して、減圧下50℃で一晩乾燥した。
得られた共重合体は、Mwが10000、Mw/Mnが2.3、13C-NMR分析の結果、p-ヒドロキシスチレン及び化合物(M-1-3)に由来する各繰り返し単位の含有比(モル比)が65:35の共重合体であった。以下、この共重合体を、重合体(A-4)とする。
p-アセトキシスチレン5.5g、実施例4で得られた化合物(M-1-4)4.5g、AIBN0.3g、及びt-ドデシルメルカプタン0.1gを、プロピレングリコールモノメチルエーテル10gに溶解したのち、窒素雰囲気下、反応温度を70℃に保持して、16時間重合させた。重合後、反応溶液を500gのn-ヘキサン中に滴下して、生成共重合体を凝固精製した。次いで、この共重合体に、再度プロピレングリコールモノメチルエーテル7.5gを加えたのち、更に、メタノール15g、トリエチルアミン4.0g及び水1.0gを加えて、沸点にて還流させながら、8時間加水分解反応を行った。反応後、溶剤及びトリエチルアミンを減圧留去し、得られた共重合体をアセトン10gに溶解したのち、100gの水中に滴下して凝固させ、生成した白色粉末をろ過して、減圧下50℃で一晩乾燥した。
得られた共重合体は、Mwが11000、Mw/Mnが2.3、13C-NMR分析の結果、p-ヒドロキシスチレン及び化合物(M-1-4)に由来する各繰り返し単位の含有比(モル比)が66:34の共重合体であった。以下、この共重合体を、重合体(A-5)とする。
下記一般式(b-1)で表される化合物4.8g、実施例1で得られた化合物(M-1-1)5.2g、AIBN0.4g、を、メチルエチルケトン30gに溶解したのち、窒素雰囲気下、反応温度を78℃に保持して、6時間重合させた。重合後、反応溶液を500gのメタノール中に滴下して、生成共重合体を凝固精製し、得られた固体を減圧下50℃で一晩乾燥した。
得られた共重合体は、Mwが8000、Mw/Mnが2.1、13C-NMR分析の結果、一般式(b-1)で表される化合物及び化合物(M-1-1)に由来する各繰り返し単位の含有比(モル比)が50:50の共重合体であった。以下、この共重合体を、重合体(A-6)とする。
(1)Mw及びMn
東ソー(株)社製GPCカラム(G2000HXL2本、G3000HXL1本、G4000HXL1本)を用い、流量:1.0ミリリットル/分、溶出溶剤:テトラヒドロフラン、カラム温度:40℃の分析条件で、単分散ポリスチレンを標準とするゲルパーミエーションクロマトグラフィー(GPC)により測定した。また、分散度Mw/Mnは測定結果より算出した。
(2)13C-NMR分析
各樹脂の13C-NMR分析は、日本電子(株)製「JNM-EX270」を用い、測定した。
<実施例11~26>
表1に示す仕込み量にて、(A)重合体、(B)酸発生剤、(C)酸拡散制御剤、(D)溶剤を混合し、得られた混合液を孔径200nmのメンブランフィルターでろ過することにより、実施例11~26の各組成物溶液(感放射線性組成物)を調製した。
(A)重合体
(A-1):実施例5で得られた前記重合体(A-1)
(A-2):実施例6で得られた前記重合体(A-2)
(A-3):実施例7で得られた前記重合体(A-3)
(A-4):実施例8で得られた前記重合体(A-4)
(A-5):実施例9で得られた前記重合体(A-5)
(A-6):実施例10で得られた前記重合体(A-6)
(B)酸発生剤
(B-1):トリフェニルスルホニウムトリフルオロメタンスルホネート
(B-2):トリフェニルスルホニウムノナフルオロ-n-ブタンスルホネート
(B-3):トリフェニルスルホニウム1,1,2,2-テトラフルオロ-2-(テトラシクロ[4.4.0.12,5.17,10]ドデカン-8-イル)エタンスルホネート
(B-4):トリフェニルスルホニウム1,1-ジフルオロ-2-(ビシクロ[2.2.1]ヘプタン-2-イル)エタンスルホネート
(B-5):下記式(2x-16)で表される化合物
(B-6):下記式(2x-43)で表される化合物
(B-7):下記式(2x-19)で表される化合物
(B-8):下記式(2x-31)で表される化合物
(B-9):下記式(2x-21)で表される化合物
(C-1):トリ-n-オクチルアミン
(C-2):トリフェニルスルホニウムサリチレート
(C-3):N-t-ブトキシカルボニル-2-フェニルベンズイミダゾール
(D)溶剤
(D-1):乳酸エチル
(D-2):プロピレングリコールモノメチルエーテルアセテート
(D-3):シクロヘキサノン
(1)重合体(A-7)の合成
p-アセトキシスチレン109.6g、下記式(M-2)で表される化合物(単量体)90.4g、AIBN6.8g及びt-ドデシルメルカプタン2.6gを、プロピレングリコールモノメチルエーテル200gに溶解したのち、窒素雰囲気下、反応温度を70℃に保持して、16時間重合させた。重合後、反応溶液を10000gのn-ヘキサン中に滴下して、生成共重合体を凝固精製した。次いで、この共重合体に、再度プロピレングリコールモノメチルエーテル150gを加えたのち、更に、メタノール300g、トリエチルアミン80g及び水15gを加えて、沸点にて還流させながら、8時間加水分解反応を行った。反応後、溶剤及びトリエチルアミンを減圧留去し、得られた共重合体をアセトン200gに溶解したのち、2000gの水中に滴下して凝固させ、生成した白色粉末をろ過して、減圧下50℃で一晩乾燥した。
得られた共重合体は、Mwが11000、Mw/Mnが2.1、13C-NMR分析の結果、p-ヒドロキシスチレンと化合物(M-2)に由来する各繰り返し単位の含有比(モル比)が65:35の共重合体であった。以下、この共重合体を、重合体(A-7)とする。
表1に示す仕込み量にて、(A)重合体、(B)酸発生剤、(C)酸拡散制御剤、(D)溶剤を混合し、得られた混合液を孔径200nmのメンブランフィルターでろ過することにより、比較例1~2の各組成物溶液(感放射線性組成物)を調製した。
(A)重合体
(A-7):前記重合体(A-7)
(B)酸発生剤
(B-1):トリフェニルスルホニウムトリフルオロメタンスルホネート
(B-7):前記式(2x-19)で表される化合物
(C)酸拡散制御剤
(C-1):トリ-n-オクチルアミン
(C-2):トリフェニルスルホニウムサリチレート
(D)溶剤
(D-1):乳酸エチル
(D-2):プロピレングリコールモノメチルエーテルアセテート
東京エレクトロン社製のクリーントラックACT-8内で、シリコンウエハー上に各組成物溶液(実施例11~26及び比較例1~2の各感放射線性組成物)をスピンコートした後、表2に示す条件でPB(加熱処理)を行い、膜厚60nmのレジスト(感放射線性組成物)被膜を形成した。その後、簡易型の電子線描画装置(日立製作所社製、型式「HL800D」、出力;50KeV、電流密度;5.0アンペア/cm2)を用いてレジスト被膜に電子線を照射した。電子線の照射後、表2に示す条件でPEBを行った。その後、2.38%テトラメチルアンモニウムヒドロキシド水溶液を用い、23℃で1分間、パドル法により現像した後、純水で水洗し、乾燥して、レジストパターンを形成した。このようにして形成したレジストについて下記の要領で評価を行った。実施例11~26及び比較例1~2の各感放射線性組成物の評価結果を表2に示す。
線幅150nmのライン部と、隣り合うライン部によって形成される間隔が150nmのスペース部(即ち、溝)と、からなるパターン〔いわゆる、ライン・アンド・スペースパターン(1L1S)〕を1対1の線幅に形成する露光量を最適露光量とし、この最適露光量により感度を評価した。
図1は、ライン・アンド・スペースパターンの形状を模式的に示す平面図である。また、図2は、ライン・アンド・スペースパターンの形状を模式的に示す断面図である。但し、図1及び図2で示す凹凸は、実際より誇張している。
設計線幅150nmのライン・アンド・スペースパターン(1L1S)のラインパターンを、半導体用走査電子顕微鏡(高分解能FEB測長装置、商品名「S-9220」、日立製作所社製)にて観察した。観察された形状について、図1及び図2に示すように、シリコンウエハー1上に形成したレジスト膜のライン部2の横側面2aに沿って生じた凹凸の最も著しい箇所における線幅と、設計線幅150nmとの差「ΔCD」を、CD-SEM(日立ハイテクノロジーズ社製、「S-9220」)にて測定することにより、ナノエッジラフネスを評価した。
ライン・アンド・スペースパターン(1L1S)について、最適露光量により解像されるラインパターンの最小線幅(nm)を解像度とした。
Claims (7)
- 更に、下記一般式(2)~(5)で表される繰り返し単位のうちの少なくとも1種を含む請求項1又は2に記載の重合体。
- 酸解離性基含有重合体(A)と、感放射線性酸発生剤(B)と、を含有する感放射線性組成物であって、
前記酸解離性基含有重合体(A)が、請求項1乃至3のいずれかに記載の重合体であることを特徴とする感放射線性組成物。 - 前記感放射線性酸発生剤(B)が、下記一般式(b1)で表されるオニウム塩である請求項4に記載の感放射線性組成物。
M+Z- (b1)
〔一般式(b1)において、M+は1価のオニウムカチオンを示し、Z-は下記一般式(b1-Z-1)又は(b1-Z-2)で表される1価のアニオンを示す。〕
〔一般式(b1-Z-2)において、R43、R44、及びR45は、相互に独立に、少なくとも1つのフッ素原子で置換された炭素数1~20のアルキル基であるか、或いは、R43、R44、及びR45のいずれか2つが相互に結合して、少なくとも1つのフッ素原子で置換された炭素数1~20の環状構造を形成しており、残りの1つが、少なくとも1つのフッ素原子で置換された炭素数1~20のアルキル基である。〕
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KR20110127153A (ko) | 2011-11-24 |
JPWO2010095698A1 (ja) | 2012-08-30 |
US20100310987A1 (en) | 2010-12-09 |
US20130053526A1 (en) | 2013-02-28 |
US8809476B2 (en) | 2014-08-19 |
TWI503334B (zh) | 2015-10-11 |
KR101626637B1 (ko) | 2016-06-01 |
TW201035120A (en) | 2010-10-01 |
JP5737174B2 (ja) | 2015-06-17 |
US8334087B2 (en) | 2012-12-18 |
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