Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography

Definitions

• Resin for resist composition negative resist composition and method for forming resist pattern
• the present invention relates to a resin for a resist composition, a negative resist composition, and a method for forming a resist pattern.
• negative resist compositions used in processes using i-line or KrF excimer laser light (248 nm) as light sources include acid generators and alkali-soluble resins such as novolak resins and polyhydroxystyrene.
• a chemically amplified negative resist containing a combination of an amino resin such as a melamine resin and a urea resin is used (for example, Patent Document 1).
• a resin composition having improved transparency to an ArF excimer laser for example, a resin component having a carboxyl group, an alcohol
• Negative resist compositions containing a crosslinking agent having a hydrophilic hydroxyl group and an acid generator have been proposed.
• a type in which the fatty acid component is changed to insoluble by dissolving the fatty acid component into alkali by reacting the alcohol component with an alcoholic hydroxyl group by the action of an acid generated from an acid generator for example, Non-patent documents 1-3, patent document 2, etc.
• Patent Document 2 Japanese Patent Application Laid-Open No. 2000-206694
• Non Patent Literature 1 Journal of Photopolymer Science and Technology (J. Photopolym. Sci. Tech.), Vol. 10, No. 4, pp. 579-584 (1997) : Job Photopolym. Sci. Tech., Vol. 11, No. 3, pp. 507-512 (1998)
• Non-Patent Literature 3 SPIE Advances in Resist Technology and Processing XIV, Vol. 333J, p417-424 (1998)
• Non-Patent Document 4 SPIE Advances in Resist technology and Processing XIX, Vol. 4690, p94-100 (2002)
• the present invention has been made in view of the above circumstances, and has as its object to provide a technique capable of suppressing swelling of a resist pattern.
• the present invention employs the following configurations.
• the first aspect (aspect) of the present invention is a structural unit (al) containing an alicyclic group having a fluorinated hydroxyalkyl group, and a structural unit derived from an acrylate ester, wherein a hydroxyl group And a structural unit (a2) containing an alicyclic group.
• a second aspect (aspect) of the present invention comprises (A) the resin for a resist composition according to the first aspect of the present invention, (B) an acid generator component which generates an acid upon exposure, and (C) ) It is a negative resist composition containing a crosslinking agent component.
• a third aspect of the present invention is to apply the negative resist composition of the second aspect of the present invention onto a substrate, pre-beta, and selectively expose, and then perform PEB (post-exposure heating). ), And alkali-developed to form a resist pattern.
• the "structural unit” refers to a monomer unit constituting a polymer (resin).
• Acrylic acid force-derived structural unit means a structural unit formed by cleavage of an ethylenic double bond of acrylic acid.
• the “structural unit derived from an acrylate ester” means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
• the “acrylic acid ester derived structural unit” is a concept including a compound in which a hydrogen atom at the ⁇ -position is substituted with another substituent such as an alkyl group.
• the term “carbon atom at the ⁇ -position” refers to a carboxyl group unless otherwise specified. Is the carbon atom to which is bound.
• the “structural unit from which acrylic acid power is also derived” is a structural unit in which the hydrogen atom bonded to the ⁇ -position carbon atom is replaced by another substituent such as an alkyl group, or a hydrogen atom is substituted for the oc-position carbon atom.
• alkyl group refers to a linear group unless otherwise specified. , A cyclic or branched alkyl group.
• Exposure is a concept that encompasses not only irradiation of light but also irradiation of radiation such as electron beam irradiation.
• a technique capable of suppressing swelling of a resist pattern can be provided.
• the resin for a resist composition of the present invention comprises a structural unit (al) containing an alicyclic group having a fluorinated hydroxyalkyl group and a structural unit derived from an acrylate ester. And a structural unit (a2) containing a hydroxyl group-containing alicyclic group.
• the resin for a resist composition of the present invention by having the structural unit (al), the effect of suppressing swelling is improved.
• the alicyclic group has a fluorinated hydroxyalkyl group.
• the fluorinated hydroxyalkyl group is different from the alkyl group having a hydroxy group in that a part of hydrogen atoms of the alkyl group Or, all are substituted by fluorine. In such a group, the hydrogen atom of the hydroxyl group is easily released by fluorination.
• the alkyl group is linear or branched, and the number of carbon atoms is not particularly limited, but is, for example, 1 to 20, preferably 4 to 16.
• the number of hydroxyl groups is not particularly limited, but is usually one.
• a fluorinated alkyl group or a fluorine atom is bonded to the ⁇ -position carbon atom to which the hydroxy group is bonded (here, refers to the ⁇ -position carbon atom of the hydroxyalkyl group). It is preferable that the fluorinated alkyl group and the fluorine atom are bonded to each other.
• the fluorinated alkyl group bonded to the ⁇ -position is preferably one in which all of the hydrogen atoms of the alkyl group are substituted with fluorine.
• the alicyclic group may be monocyclic or polycyclic! /, But is preferably a polycyclic group. Further, an alicyclic hydrocarbon group is preferred. Further, it is preferably saturated. Also, the alicyclic group preferably has 5 to 15 carbon atoms! / ,.
• examples of the monocyclic group include groups in which one hydrogen atom has been removed from a cycloalkane.
• examples of the polycyclic group include groups in which one or two hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane, and the like.
• Examples include groups in which one or two hydrogen atoms have been removed, and it is preferred that two hydrogen atoms have been removed from cyclohexane.
• polycyclic group examples include groups in which one or two hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
• a large number of such polycyclic groups have been proposed as constituents of an acid dissociable, dissolution inhibiting group in, for example, a resin for a positive photoresist composition for an ArF excimer laser process!
• the force can be appropriately selected and used.
• a group obtained by removing two hydrogen atoms from norbornane is particularly preferable.
• the structural unit (al) is preferably a structural unit derived from acrylic acid, and the alicyclic group is bonded to an ester group [—c (o) o—] of an atalylic acid ester.
• Preferred is a structure (a structure in which a hydrogen atom of a carboxyl group is substituted with the alicyclic group).
• R is a hydrogen atom, an alkyl group, a fluorinated alkyl group, or a fluorine atom, and m, n, and p are each independently an integer of 1 to 5.
• R is a hydrogen atom, an alkyl group, a fluorinated alkyl group, or a fluorine atom.
• a lower alkyl group having 5 or less carbon atoms is preferable, such as 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. And the like, and a methyl group is preferred.
• the fluorinated alkyl group is preferably a group in which one or more hydrogen atoms of a lower alkyl group having 5 or less carbon atoms are substituted with a fluorine atom.
• Specific examples of the alkyl group are the same as those described above.
• the hydrogen atom substituted with a fluorine atom may be a part of the hydrogen atoms constituting the alkyl group or all of them.
• R a hydrogen atom or an alkyl group is preferred, a hydrogen atom or a methyl group is particularly preferred, and a hydrogen atom is most preferred.
• n, m, and p are each preferably 1.
• the structural unit (al) can be used alone or as a mixture of two or more.
• the effect of suppressing swelling is improved by including the structural unit ( a2 ). Further, the effect of improving the etching resistance can be obtained.
• the hydroxyl group (alcoholic hydroxyl group) iS (B) of the constituent unit (a2) is acted upon by the action of the acid generated from the acid generator to produce ( C) Reacts with the cross-linking agent, whereby the resin for resist composition changes into a property of being soluble in an alkali developer to a property of being insoluble.
• the hydroxyl group-containing alicyclic group is preferably bonded to an ester group (-C (O) O-) of an acrylate ester.
• another substituent may be bonded to the ⁇ -position (the carbon atom at the ⁇ -position) instead of a hydrogen atom.
• the substituent preferably includes an alkyl group, a fluorinated alkyl group, and a fluorine atom.
• the hydroxyl group-containing alicyclic group is a group in which a hydroxyl group is bonded to an alicyclic group.
• the number of hydroxyl groups is preferably, for example, one to three, more preferably one. Further, an alkyl group having 1 to 4 carbon atoms may be bonded to the alicyclic group.
• the alicyclic group may be monocyclic or polycyclic! /, But is preferably a polycyclic group. Also
• an alicyclic hydrocarbon group is preferably saturated.
• the alicyclic group preferably has 5 to 15 carbon atoms.
• examples of the monocyclic group include groups in which one hydrogen atom has been removed from a cycloalkane.
• examples of the polycyclic group include groups obtained by removing one hydrogen atom from bicycloalkane, tricycloalkane, tetracycloalkane, and the like.
• a group excluding one hydrogen atom is preferred, and a cyclohexyl group is preferred.
• polycyclic groups include groups in which one hydrogen atom has been removed from polycycloalkanes such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
• a large number of such polycyclic groups have been proposed as constituents of an acid dissociable, dissolution inhibiting group in, for example, a resin for a positive photoresist composition for an ArF excimer laser process!
• the force can be appropriately selected and used.
• a cyclohexyl group, an adamantyl group, a norbornyl group, and a tetracyclododele group are industrially available and readily preferred.
• a cyclohexyl group and an adamantyl group are preferred, and an adamantyl group is particularly preferred.
• a structural unit represented by the following general formula (2) is preferable.
• R is a hydrogen atom, an alkyl group, a fluorinated alkyl group or a fluorine atom, and q is an integer of 1-3.
• R is a hydrogen atom, an alkyl group, a fluorinated alkyl group, or a fluorine atom bonded to the ⁇ -position, and is the same as described in the general formula (1).
• R is most preferably a hydrogen atom! / ,.
• q is preferably a force 1 which is an integer of 1 to 3.
• the bonding position of the hydroxyl group is not particularly limited, but is preferably bonded to the 3-position of the adamantyl group.
• the structural unit (a2) can be used alone or as a mixture of two or more.
• the structural unit having an alcoholic hydroxyl group in the side chain (a 3) is described Te Nitsu ⁇ .
• a structural unit derived from acrylic acid and having no cyclic structure, and having an alcohol in a side chain in addition to the structural unit (al) and the structural unit (a2), a structural unit derived from acrylic acid and having no cyclic structure, and having an alcohol in a side chain. It preferably has a structural unit (a3) having a hydroxyl group.
• the structural unit (a3) is clearly distinguished from the structural unit (a2) by not having a cyclic structure.
• the resin for a resist composition having the structural unit (a3) is blended into a negative resist composition, the hydroxyl group of the structural unit (a3) and the hydroxyl group of the hydroxyalkyl group of the structural unit (a3) are changed to ( The action of the acid generated from the acid generator (B) reacts with the cross-linking agent (C), whereby the resin for resist composition changes to a property soluble in an alkali developer to a property insoluble in an alkali developer.
• phrases "having an alcoholic hydroxyl group in the side chain” includes, for example, structural units having a hydroxyalkyl group bonded thereto.
• the hydroxyalkyl group may be bonded, for example, to the ⁇ -position carbon atom of the main chain (the portion where the ethylenic double bond of acrylic acid is cleaved), or may be substituted with a hydrogen atom of the carboxyl group of acrylic acid.
• the structural unit (a3) which may form an ester it is preferable that at least one of these is present and both are present.
• the structural unit (a3) is preferably represented by the following general formula (3).
• R 1 is a hydrogen atom, an alkyl group, fluorinated alkyl group, a fluorine atom or a hydroxy Shiarukiru group
• R 2 represents a hydrogen atom, an alkyl group or hydroxyalkyl group der, is, and, the R 2 At least one is a hydroxyalkyl group.
• R 1 hydroxyalkyl group, preferably a lower hydroxyalkyl group of not more than 10 carbon atoms, more preferably a lower hydroxyalkyl group having 2 to 8 carbon atoms, and most preferably a hydroxymethyl group, or It is a hydroxyethyl group.
• the number and the bonding position of the hydroxyl group are not particularly limited, but are usually one, and it is preferable that the hydroxyl group is bonded to the terminal of the alkyl group.
• the alkyl group is preferably a lower alkyl group of not more than 10 carbon atoms, more preferably a lower alkyl group having 2 to 8 carbon atoms, most preferably Echiru group, a methylation group.
• the fluorinated alkyl group is preferably a carbon number of 5 or less lower alkyl group (preferably Echiru group, a methyl group) in which part or all of the hydrogen atoms are substituted with fluorine groups.
• R 2 an alkyl group, hydroxyalkyl group, are similar to those for R 1.
• the structural unit (a3) specifically, a structural unit derived from ⁇ - (hydroxyalkyl) acrylic acid, a structural unit derived from a- (hydroxyalkyl) acrylic acid, and ( ( ⁇ -alkyl) acrylic acid hydroxyalkyl ester power Structural unit derived.
• the structural unit (a3) is a-(hydro) from the viewpoint of improving the effect and improving the film density. It is preferable to include a constitutional unit derived from an (xyalkyl) alkyl acrylate ester. And, among them, a (hydroxymethyl) acrylate ester or ⁇ (hydroxymethyl) -acrylate is also preferred.
• a structural unit derived from the structural unit (a3) hydroxyalkyl (acrylate) is preferable.
• a structural unit derived from a-methyl-acrylic acid hydroxyethyl ester or ⁇ -methyl-acrylic acid hydroxymethyl ester is preferable.
• the structural unit (a3) can be used alone or in combination of two or more.
• the resin for a resist composition of the present invention in addition to the structural unit (al) and the structural unit ( a2 ), the resin is derived from an acrylic acid ester containing a monocyclic or polycyclic group containing ratatotone.
• U which preferably has the structural unit (a4)
• the structural unit (a3) may be used in combination.
• the rataton-containing monocyclic or polycyclic group of the structural unit (a4) enhances the adhesion of the resist film to the substrate or increases the hydrophilicity with the developer. It is effective because it can be raised. In addition, the effect of suppressing swelling is improved.
• rataton here refers to one ring including a -O-C (O)-structure, which is counted as one eye ring. Therefore, when only a rataton ring is used, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of its structure.
• the structural unit (a4) is not particularly limited as long as it has a rataton ring having both the ester structure (—O—C (O) —) and a ring structure. Can be used
• examples of the ratatone-containing monocyclic group include groups excluding one ⁇ -petit rataton force hydrogen atom.
• examples of the rataton-containing polycyclic group include a bicycloalkane, a tricycloalkane, and a tetracycloalkane having a rataton ring, in which one hydrogen atom is excluded.
• groups excluding one ratatotone-containing tricycloalkane hydrogen atom having the following structural formula are advantageous in terms of industrial availability, and the like.
• those having a norbornane rataton are preferable among those which are a rataton-containing polycyclic group, and the like.
• another substituent may be bonded to the ⁇ -position (the carbon atom at the ⁇ -position) instead of a hydrogen atom.
• the substituent preferably includes an alkyl group, a fluorinated alkyl group, or a fluorine atom.
• examples of the structural unit (a4) include structural units represented by the following general formulas (a4-1) to (a4-5).
• R is the same as described above.
• R ′ is each independently a hydrogen atom, an alkyl group, or an alkoxy group having 1 to 5 carbon atoms, and m is an integer of 0 or 1.
• R ′ in the general formulas (a4-1) to (a4-5) is the same as the alkyl group of R in the structural unit (al).
• R ′ is preferably a hydrogen atom in view of industrial availability.
• the units represented by general formulas (a4-2) to (a4-3) are most preferable.
• one type may be used alone, or two or more types may be used in combination.
• the structural units (al) to (a4) are preferably selected from, for example, four types of combinations as described below.
• the structural unit (al) is a structural unit represented by the general formula (1)
• R in the general formula (1) is a hydrogen atom.
• a hydrogen atom is preferably bonded to the ⁇ -position (carbon atom to which a carboxyl group is bonded) of the structural unit (a2). The reason is that the dissolution contrast is improved.
• the selection is made to include a combination of the structural unit (al), the structural unit (a2), and the structural unit (a3).
• the structural unit (al) is a structural unit represented by the general formula (1), and that R in the general formula (1) is a hydrogen atom.
• R in the general formula (1) is a hydrogen atom.
• a hydrogen atom be bonded to the ⁇ -position of the structural unit (a2). The reason is that the dissolution contrast becomes better.
• the selection is made to include a combination of the structural unit (al), the structural unit (a2), and the structural unit (a4).
• the structural unit (al) is a structural unit represented by the general formula (1), and R in the general formula (1) is a hydrogen atom.
• a hydrogen atom is preferably bonded to the ⁇ -position of the structural unit (a2), and a hydrogen atom is preferably bonded to the a-position of the structural unit (a4).
• the selection is made to include a combination of the structural unit (al), the structural unit (a2), the structural unit (a3), and the structural unit (a4).
• the structural unit (al) is a structural unit represented by the general formula (1), and R in the general formula (1) is a hydrogen atom.
• a hydrogen atom is preferably bonded to the ⁇ -position of the structural unit (a2), and a hydrogen atom is preferably bonded to the a-position of the structural unit (a4).
• At least two of the structural unit (al) and the structural unit (a2) are essential.
• the ratio of each structural unit in the resin is in the following numerical range. Is preferably satisfied.
• the proportion of the structural unit (al) is preferably 20 to 80 mol%, more preferably 30 to 70 mole 0/0, and most preferably 35 to 55 mole 0/0.
• the proportion of the structural unit (a2) is preferably 20 to 80 mole 0/0, more preferably 30 to 70 mol%, and most preferably 35 to 55 mole 0/0.
• the proportion of the structural unit (al) is preferably 20 to 80 mol%, more preferably from 3 0 to 70 mole 0/0, and most preferably 35 to 55 mole 0/0.
• the proportion of the structural unit (a2) is preferably 10 to 70 mole 0/0, more preferably 10 to 50 mol%, more preferably from 20 to 40 mole 0/0.
• the proportion of the structural unit (a3) is preferably 10 to 70 mole 0/0, more preferably 10 to 40 mol%, and most preferably 15 to 35 mole 0/0.
• the effect of suppressing swelling is improved.
• the structural unit (a2) and the structural unit (a3) in a well-balanced manner, an appropriate contrast is obtained and the resolution is improved. Further, etching resistance is improved. A better exposure latitude can be obtained.
• the proportion of the structural unit (a2) is preferably 14 to 70 mole 0/0, more preferably 15 to 50 mol%, and most preferably from 30 to 50 mole 0/0.
• the proportion of the structural unit (a4) is preferably 1 to 70 mol 0/0, more preferably 3 to 50 mol%, and most preferably 5 to 20 mol%.
• the proportion of the structural unit (al) is preferably 10 to 85 mol%, more preferably from 2 0 to 70 mole 0/0, and most preferably 25 to 50 mole 0/0.
• the proportion of the structural unit (a2) is preferably 10 to 80 mole 0/0, more preferably 20 to 70 mol%, and most preferably from 30 to 50 mole 0/0.
• the proportion of the structural unit (a3) is preferably 4 to 70 mol%, more preferably 7 to 50 mol%, and most preferably 10 to 30 mole 0/0.
• the proportion of the structural unit (a4) is preferably 1 to 70 mol 0/0, more preferably 3 to 50% by mole, and most preferably 5 to 20% by mole.
• the resin for a resist composition may have another copolymerizable structural unit other than the structural units selected from the structural units (al) to (a4). al) to structural unit (a4) It is preferable that the resin is a resin having a structural unit selected from the main components as a main component.
• the main component is preferably such that the total of the constituent units for which these forces are also selected is 70 mol% or more, preferably 80 mol% or more, and particularly preferably 100%.
• the resist composition for ⁇ of the present invention the structural units (al) to the structural units of (a4) (al) and the structural unit (a2) is required and that it has.
• the weight average molecular weight (Mw; weight average molecular weight in terms of polystyrene by gel permeation chromatography) of the resin for a resist composition is preferably from 2000 to 30,000, more preferably from 2000 to 10,000, and most preferably. Is between 3000 and 8000. This range is preferable from the viewpoint of suppressing swelling and thereby suppressing microbridges. Also, high resolution point power is preferred. The lower the molecular weight, the better the properties tend to be.
• the resin for a resist composition can be obtained, for example, by subjecting a monomer for deriving each structural unit to radical polymerization by a conventional method.
• the resin for a resist composition of the present invention is preferably used for a negative resist composition.
• the negative resist composition of the present invention contains (A) the resin for a resist composition of the present invention, (B) an acid generator component that generates an acid upon exposure, and (C) a crosslinking agent component.
• the components (A) are as described above.
• the component (A) can be used alone or in combination of two or more.
• the content of the component (A) may be adjusted according to the resist film thickness to be formed.
• the component (B) can be used without particular limitation from known acid generators used in conventional chemically amplified resist compositions.
• Such acid generators include, for example, rhodium salt-based acid generators such as odonium salts and sulfo-dum salts, oxime sulfonate-based acid generators, bisalkyl or bisarylsulfol-diazomethanes, Various types are known, such as diazomethane acid generators such as poly (bissulfol) diazomethanes and nitrobenzylsulfonates, iminosulfonate acid generators, and disulfone acid generators.
• rhodium salt-based acid generators such as odonium salts and sulfo-dum salts
• oxime sulfonate-based acid generators such as oxime sulfonate-based acid generators, bisalkyl or bisarylsulfol-diazomethanes
• diazomethane acid generators such as poly (bissulfol) diazomethanes
• the acid salt-based acid generator include trifluoromethanesulfonate or nonafluorobutanesulfonate of di-fluorodominium, trifluoromethanesulfonate or nonafluorobenoble of bis (4-tert-butylphenyl) iodenum.
• oxime sulfonate-based acid generator examples include: a (methylsulfo-roximino) -phenylacetonitrile, at- (methylsulfo- luximino) -p-methoxyphenylacetonitrile, ⁇ - (trifluoromethyl) Sulfo-Roxyimino) -Furea-ceto-tolyl, ⁇ - (Trifluoromethylsulfo-Roxyimino) -p-Methoxyphenyl-acetonitrile, at- (Ethylsulfonyloxyminino) -p-Methoxyphenylacetonitrile, ⁇ - (Propylsulfo-roximinino) p-methylphenyl-acetonitrile, ⁇ (methylsulfo-roximinino) ⁇ -bromo-phenylacetonitrile and the like. Of these, ⁇ (methylsulfo-roxi
• bisalkyl or bisarylsulfol-diazomethanes include bis (isopropylsulfol) diazomethane, bis ( ⁇ toluenesulfol) diazomethane, and bis (1 , 1-dimethylethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, bis (2,4 dimethylphenylsulfol) diazomethane and the like.
• poly (bissulfonyl) diazomethanes examples include, for example, 1,3 bis (phenylsulfol-diazomethylsulfol) propane having the following structure (digestion compound ⁇ , decomposition point 135 ° C) ), 1,4-bis (phenylsulfol-diazomethylsulfol) butane (compound B, decomposition point 147 ° C), 1,6-bis (phenylsulfol-l-diazomethylsulfol) hexane (Compound C, melting point 132 ° C, decomposition point 145 ° C), 1,10 bis (phenylsulfol-diazomethylsulfol) decane (disulfide compound D, decomposition point 147 ° C), 1,2 bis (Cyclohexylsulfol-l-diazomethylsulfol) ethane (I-conjugated product E
• an aluminum salt having a fluorinated alkyl sulfonate ion as the component (B) is used as the component (B). It is preferable to use.
• one type of acid generator may be used alone, or two or more types may be used in combination. May be used.
• the content of the component (B) is 0.5 to 30 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the component (A). With the above range, the pattern can be sufficiently formed. In addition, a uniform resist solution is obtained, and storage stability is improved.
• the component (C) is not particularly limited, and may be arbitrarily selected from crosslinker components used in chemically-amplified negative-type resist compositions known so far. it can.
• an amino group-containing compound such as melamine, acetoguanamine, benzoguanamine, urea, ethylene urea, or glycol peryl is reacted with formaldehyde or formaldehyde and lower alcohol, and the hydrogen atom of the amino group is replaced with a hydroxymethyl group or a lower alkoxymethyl group. Substituted products are included.
• melamine-based products use melamine-based cross-linking agents
• urea-based products use urea-based cross-linking agents
• ethylene-urea-based products use ethylene-urea-based cross-linking agents
• peryl crosslinking agents With peryl crosslinking agents!
• Specific examples include hexamethoxymethyl melamine, bismethoxymethyl urea, bismethoxymethyl bismethoxyethylene urea, tetramethoxymethyldaricol peril, and tetrabutoxymethyl glycol peril.
• the component (C) is particularly preferably at least one selected from a melamine-based crosslinking agent, a urea-based crosslinking agent, an ethyleneurea-based crosslinking agent, and a glycolperyl-based crosslinking agent. Particularly preferred are glycol-peryl crosslinking agents.
• the glycol peryl-based cross-linking agent includes glycol peryl substituted at the N-position with a hydroxyalkyl group or lower alkoxyalkyl group as a cross-linking group, or at the N-position. Glycol peryl substituted with a hydroxyalkyl group and a lower alkoxyalkyl group which are cross-linking groups are preferred!
• examples of the glycoluril-based crosslinking agent include, for example, mono-, di-, tri- or tetrahydroxymethyldaricol-peryl, mono-, di-, tri- and / or tetramethoxymethyl-dalichol-peryl, mono-, di-, tri- And Z or tetraethoxymethyldaricol peril, mono, di, tri and Z or tetrapropoxymethyl iridyl glycol peryl, mono, di, tri and Z or tetrabutoxy methyl iridyl glycol peril and the like.
• “Mono, di, tri and / or tetra” means that one or more of the mono, di, tri and tetra is required. Is preferably a tri- ⁇ tetra-isomer.
• This crosslinking agent can be obtained, for example, as a commercial product “Mx270” (product name, manufactured by Sanwa Chemical Co., Ltd.). These are mostly tri- and tetra-forms, and are mixtures of monomers, dimers and trimers.
• the compounding amount of the component (C) is 3 to 15 parts by mass, preferably 5 to 10 parts by mass, per 100 parts by mass of the component (A).
• the component (A) can be made alkali-insoluble.
• the amount is 15 parts by mass or less, a decrease in resolution can be prevented.
• the negative resist composition of the present invention further comprises a nitrogen-containing organic compound (D) (hereinafter referred to as component (D)) as an optional component in order to improve the resist pattern shape, the stability with time of storage, and the like. ) Can be blended.
• component (D) nitrogen-containing organic compound
• component (D) a wide variety of components have already been proposed, any known one may be used arbitrarily, and aliphatic amines, particularly secondary aliphatic amines ⁇ tertiary aliphatic amines, are preferred. .
• At least one of the hydrogen atoms of ammonia NH has at least 12 carbon atoms.
• Amines alkylamines or alkylalcoholamines substituted with an alkyl or hydroxyalkyl group below. Specific examples thereof include monoalkylamines such as n-hexylamine, n-butylamine, n-octylamine, n-norylamine, and n-decylamine; getylamine, di-n-propylamine, di-n-butylamine, di-n-octylamine.
• Dicyclohexylamine and the like trimethylamine, triethylamine, tri- n -propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-ptylamine, tri-n-octylamine, Trialkylamines such as tri-n-no-lamine, tri-n-de-lamine and tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di- n -o Kutanolamine, tree n —Alkyl alcoholamines such as octanolamine and the like.
• Component (D) is generally used in an amount of 0.015.0 parts by mass with respect to 100 parts by mass of component (A).
• alkyl alcoholamines and trialkylamines are preferred, and alkyl alcoholamines are most preferred.
• alkyl alcoholamines an alkyl alcohol amine such as triethanolamine / triisopropanolamine is most preferable.
• an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof as an optional component.
• component (E) (hereinafter referred to as component (E)).
• the component (D) and the component (E) can be used in combination, or one of them can be used.
• organic carboxylic acid for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
• Phosphorus oxo acids or derivatives thereof include phosphoric acid, phosphoric acid such as di-n-butyl phosphate and diphenyl phosphate, and derivatives such as esters thereof, phosphonic acid, dimethyl phosphonate, and phosphonic acid.
• phosphoric acid such as di-n-butyl phosphate and diphenyl phosphate
• derivatives such as esters thereof, phosphonic acid, dimethyl phosphonate, and phosphonic acid.
• -N-butyl ester Hue- Derivatives such as phosphonic acids and their esters such as diphosphonic acid, diphenyl phosphonate and dibenzyl phosphonate, and derivatives such as phosphinic acids and esters thereof such as phosphinic acid and phenylphosphinic acid.
• phosphonic acid is particularly preferred.
• the component (E) is used in an amount of 0.01 to 5.0 parts by mass per 100 parts by mass of the component (A).
• the negative resist composition of the present invention can be produced by dissolving the constituent materials of the negative resist composition of the present invention in an organic solvent.
• the constituent materials of the negative resist composition of the present invention are (A) the resin for a resist composition of the present invention, (B) an acid generator component that generates an acid upon exposure, and (C) a crosslinking agent component. .
• the constituent material of the negative resist composition of the present invention contains at least one of the (D) nitrogen-containing organic compound and the (E) component in addition to the components (A) to (C).
• any one can be used as long as it can dissolve each component to be used and can form a uniform solution.
• the above can be appropriately selected and used.
• ratatones such as ⁇ -butyrolatatone, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monomonoacetate, diethylene glycol, and diethylene glycol Monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate, such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and polyhydric alcohols and derivatives thereof, Cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EL); methyl acetate; ethyl acetate; butyl acetate; methyl pyruvate; Acid Echiru, methyl methoxypropionate, and the like esters such as ethoxy
• organic solvents may be used alone or as a mixed solvent of two or more. Further, a mixed solvent obtained by mixing propylene glycol monomethyl ether acetate (PGMEA) and a polar solvent is preferable.
• the mixing ratio may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 1: 9 to 9: 1, more preferably 2: 1 to 9: 1. : 8 to 8: preferably in the range of 2! / ,.
• the mass ratio of PGMEA: EL is preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3! / ,.
• a mixed solvent of at least one selected from PGMEA and EL and ⁇ -petit mouth rataton is also preferable.
• the mixing ratio of the former and the latter is preferably 70: 30-95: 5.
• propylene glycol monomethyl ether PGME
• PGME propylene glycol monomethyl ether
• the amount of the organic solvent used is not particularly limited, it is a concentration that can be applied to a substrate or the like and is appropriately set according to a coating film thickness.
• the solid content concentration of the resist composition is 2 to 20 mass %, Preferably in the range of 5 to 15% by mass.
• the negative resist composition of the present invention may contain other optional components in addition to the above-mentioned components, and if necessary, improve the performance of a miscible additive such as a resist film.
• a surfactant, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, and the like for improving the application of the resin and the coatability can be appropriately added and contained.
• the negative resist composition of the present invention is not particularly limited, but is suitable for processes using an ArF excimer laser as an exposure light source.
• the process requires high resolution, and in the negative resist composition of the present invention, various properties such as resolution are improved by suppressing swelling. This is because such strict requirements can be met.
• Another reason is that a structure having high transparency to an ArF excimer laser can be obtained.
• the method of forming a resist pattern comprises applying the negative resist composition of the present invention onto a substrate, pre-betaing (PAB), selectively exposing, subjecting to PEB (heating after exposure), and developing an alkaline image to form a resist pattern.
• PAB pre-betaing
• the method of forming a resist pattern according to the present invention can be performed, for example, as follows. That is, first, the negative resist composition is applied on a substrate such as silicon wafer with a spinner or the like. Next, the negative resist composition is applied with a prebeta at a temperature of 80 to 150 ° C. for 40 to 120 hectares, preferably 60 to 90 hectares. Next, the pre-stressed resist film is selectively exposed to ArF excimer laser light through a desired mask pattern using, for example, an ArF exposure device. Then, PEB (post-exposure bake) is applied to the selectively exposed resist film at a temperature of 80 to 150 ° C. for 40 to 120 seconds, preferably 60 to 90 seconds.
• PEB post-exposure bake
• an alkali developer of the resist film subjected to the PEB e.g. 0.1 to 10 weight 0/0 tetramethylammonium - development processing using Umuhidorokishido solution.
• an organic or inorganic antireflection film can be provided between the substrate and the coating layer of the resist composition.
• the wavelength used for the exposure is not particularly limited.
• the resist composition according to the present invention is effective for ArF excimer laser as described above.
• LER Lie Edge Roughness
• HEMA hydroxyethyl methacrylate
• AdOHA adamantanol acrylate
• NBLA norbornane ratatone acrylate
• NMR Nuclear Magnetic Resonance
• the obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 19.8 g of a white solid (yield 86.8%).
• the results of proton nuclear magnetic resonance spectrum ⁇ H-NMR) and infrared absorption spectrum (IR) were as follows.
• Synthesis example 7 7.87 g of NBHFAA, 3.51 g of HEMA, 6.60 g of AdOHA, and 0.58 g of dimethyl azobisisoacetate as a polymerization initiator were dissolved in 200 ml of THF (tetrahydrofuran). Next, the solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C., and then cooled to room temperature. Next, the reaction solution was concentrated by an evaporator, and then the concentrated solution was dissolved in THF (120 ml) and poured into heptane (1000 ml) to precipitate a resin, followed by filtration. The obtained resin was dried in a dryer at 40 ° C. for 24 hours to obtain 14.9 g of a white solid (yield: 85.7%).
• the results of proton nuclear magnetic resonance spectrum ⁇ H-NMR) and infrared absorption spectrum (IR) were as follows.
• NBHFAA 12.66 g, HEM AO. 6 g, and AdOHAl. 03 g, and a polymerization initiator 0.35 g of dimethyl azobisisoacetate was dissolved in 100 ml of THF (tetrahydrofuran). Next, this solution was subjected to nitrogen publishing for about 10 minutes, stirred for 4 hours while heating using an oil bath at 70 ° C, and then cooled to room temperature. Next, after concentrating the reaction solution with an evaporator, the concentrated solution was dissolved in 60 ml of THF, and poured into 2000 ml of heptane to precipitate a resin, which was filtered. The obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 10.63 g of a white solid (yield: 74.3%).
• the chemical formula of the obtained resin is as shown in the following chemical formula (7). Its mass average molecular weight (Mw) was 3,800, and dispersity (MwZMn) was 1.37. This is referred to as resin 11.
• the chemical formula of the obtained resin is as shown in the following chemical formula (8). Its mass average molecular weight (Mw) was 9,700 and the degree of dispersion (MwZMn) was 1.76. This is referred to as resin 12.
• the amount of the solvent used was adjusted so that the resist solid content concentration was about 8% by mass.
• Binderl ⁇ M x270 (product name, manufactured by Sanwa Chemical Co., Ltd.)
• Binder2 ⁇ E6301 (Product name, manufactured by Sanwa Chemical Co., Ltd.)
• Organic anti-reflective coating composition “AR-19” (trade name, manufactured by Shipley) is applied on an 8-inch silicon wafer using a spinner, baked on a hot plate at 215 ° C for 60 seconds, and dried. As a result, an organic antireflection film having a film thickness shown in Table 3 was formed. Then, the negative resist composition manufactured as described above is applied on an antireflection film using a spinner, pre-betaed (PAB) on a hot plate under the conditions shown in Table 3, and dried to obtain the composition shown in Table 3. A resist layer having a thickness was formed.
• PAB pre-betaed
• PEB treatment was performed under the conditions shown in Table 3, followed by paddle development at 23 ° C with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds, followed by washing with water for 20 seconds and drying to form a resist pattern. Formed.
• the exposure amount (sensitivity) at which the width of the line and space was formed at 1: 1 was obtained.
• the exposure amount (sensitivity) at which the line and space width was 1: 1 in a 160 nm line and space pattern (L & S) was determined.
• Example 1 200 nm 90 ° C / 60 seconds 100/60 seconds Silicon A 8 8 r> m
• Example 2 200 nm 90 ⁇ : / 60 sec. At 100/60 sec.
• Example 3 200 nm 90 ° C / 60 sec. 100 ° C / 60 sec.
• Example 6 200 nm 80 ° C / 60 sec. 100 ° C No. 60 sec.
• Example 7 200 nm 80 ° C / 60 seconds 100 ° C / 60 seconds Silicon wafer 82 nm
• Example 8 200nm 80 ⁇ C / 60sec 100 ° C / 60sec Silicon layer 82nm
• Example 9 200 nm 80. C / 60 sec 100 ° C / 60 sec Silicon wafer 8 2 nm
• Example 1 1 200nm 803 ⁇ 4 / 60sec 10CTC / 60sec Silicon wafer & 2nm
• Comparative Example 2 300 nm 1 10 t / 60 sec nO ° C / 60 sec Silicon wafer 8 2 nm
• Sensitivity is the sensitivity at which an L & S pattern of 1400 nm 1: 1 is obtained
• the resist pattern had a good rectangularity without any practical problem.
• the precipitated resin was taken out, dissolved in 150 ml of THF, and poured into 2,000 ml of heptane to precipitate the resin, followed by filtration.
• the obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 19.8 g of a white solid (yield: 86.8%).
• the obtained resin is represented by the chemical formula (4). Its mass average molecular weight (Mw) was 7,500, and its dispersion (MwZMn) was 2.15.
• the precipitated resin was taken out, dissolved in 150 ml of THF, and poured into 2000 ml of heptane to precipitate the resin, followed by filtration.
• the obtained resin was dried in a drier at 40 ° C. for 24 hours to obtain 14.9 g of a white solid (yield: 73.8%).
• the obtained resin is represented by the chemical formula (4). Its mass average molecular weight (Mw) was 6,500 and the degree of dispersion (MwZMn) was 1.92.
• the obtained resin is represented by the following chemical formula (10). Its mass average molecule
• the dispersity (MwZMn) was 2.23.
• the obtained resin is represented by the following chemical formula (11). Its mass average molecular weight (Mw) was 5,600 and its dispersion (MwZMn) was 2.24.
• the obtained resin is represented by the following chemical formula (13). Its mass average molecular weight (Mw) was 3000 and the degree of dispersion (MwZMn) was 1.83.
• Synthesis example 1 7 40 20 30 10 ⁇ 6000 2.23 (Fiber 17)
• Example 1 Silicon 200nm 80/60 Qin. C / 60 seconds wafer 82nm
• Example 1 Silicon 200nm 80/60 sec 100 "C / 60sec wafer 82nm
• Example 1 Silicon 200nm 80. C / 60sec 100 / 60sec wafer 82nm
• Example 15 5 Silicon 200nm 80 ⁇ / 60 sec 100. C / 60 sec ⁇ Ah 82nm
• Example 16 Silicon / 200 nm 80/60 sec 100/60 sec
• Example 1 Silicon 200 nm 80/60 sec 100. C / 60 sec.
• Example 20 Silicon 200 nm 80/60 seconds 100/60 seconds
• ARC_29 ⁇ Product name, organic anti-reflective coating made by Brew Science Inc.
• Example 1 2 1 4 OnmL S 42mJ / cm 2 Example 1 3 1 2 OnmL S 29mJ / cm e Example 1 4 1 50 rim and S 26mJ / cm 2 Example 1 5 1 2 OnmL S 29 mJ / cm 2 Example 1 6 1 2 Onm LS ⁇ 32 mJ / cm a Example 1 7 1 3 OnmL S ⁇ 32 mJ / om 2 Example 1 8 1 2 OnmL S ⁇ 32 mJ / cm 2 Example 1 9 1 2 OnmL SO 30mJ / cm 2 Example 20 1 3 OnmL S o 35mJ / cm 2 From the results shown in Table 8, it was confirmed that in Examples according to the present invention, swelling was suppressed and a fine resist pattern could be formed.

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