Radiation-sensitive resin composition

专利摘要:
A radiation-sensitive resin composition used as achemically amplified positive tone resist responsive to shortwavelength active radiation such as KrF excimer laser and ArFexcimer laser is disclosed. The resin composition comprises:(A) an acid-dissociable group-containing resin which isinsoluble or scarcely soluble in alkali and becomes alkalisoluble when the acid-dissociable group dissociates, the resincomprising a lactone cyclic structure of the following formula(1),wherein a is an integer from 1-3, b is an integer from 0-9, andR1 represents a monovalent organic group, and (B) a photoacidgenerator. The composition has high transmittance ofradiation, exhibits high sensitivity, resolution, and patternshape, and can produce semiconductors at a high yield withoutproducing resolution defects during microfabrication.
公开号:EP1162506A1
申请号:EP01113944
申请日:2001-06-07
公开日:2001-12-12
发明作者:Yukio Nishimura；Katsuji Douki；Toru Kajita；Tsutomu Shimokawa
申请人:JSR Corp；
IPC主号:G03F7-00

专利说明:
[0001] The present invention relates to a radiation-sensitiveresin composition and, more particularly, to aradiation-sensitive resin composition suitable as achemically-amplified resist useful for microfabricationutilizing various types of radiation, for example, deepultraviolet rays such as a KrF excimer laser or ArF excimerlaser, X-rays such as synchrotron radiation, or chargedparticle rays such as electron beams. Description of the Background Art
[0002] In the field of microfabrication represented byfabrication of integrated circuit devices, a lithographictechnology enabling microfabrication with a line width of 0.20µm or less has been demanded in order to achieve higherintegration.
[0003] A conventional lithographic process utilizes nearultraviolet rays such as i-line as radiation. It is known inthe art that microfabrication with a line width of sub-quartermicron is very difficult using near ultraviolet rays.
[0004] Therefore, use of radiation with a shorter wavelengthhas been studied for enabling microfabrication with a line widthof 0.20 µm or less. As radiation with a shorter wavelength, deepultraviolet rays represented by a line spectrum of a mercury lamp and an excimer laser, X-rays, electron beams, and the likecan be given. Of these, a KrF excimer laser (wavelength: 248nm) and an ArF excimer laser (wavelength: 193 nm) have attractedattention.
[0005] As a radiation-sensitive resin composition applicableto the excimer laser radiation, a number of compositionsutilizing a chemical amplification effect between a componenthaving an acid-dissociable functional group and a componentgenerating an acid (hereinafter called "photoacid generator")which generates an acid upon irradiation (hereinafter called"exposure") has been proposed. Such a composition ishereinafter called a chemically-amplified radiation-sensitivecomposition.
[0006] As the chemically-amplified radiation-sensitivecomposition, Japanese Patent Publication No. 27660/1990discloses a composition comprising a polymer containing at-butyl ester group of carboxylic acid or a t-butylcarbonategroup of phenol and a photoacid generator. This compositionutilizes the effect of the polymer to release a t-butyl estergroup or t-butyl carbonate group by the action of an acidgenerated upon exposure to form an acidic group such as acarboxylic group or a phenolic hydroxyl group, which rendersan exposed area on a resist film readily soluble in an alkalinedeveloper.
[0007] Most of conventional chemically-amplifiedradiation-sensitive compositions use a phenol resin as a baseresin. Deep ultraviolet rays used as radiation for exposure are absorbed due to an aromatic ring in the resin and cannotsufficiently reach the lower layers of the resist film. Becauseof this, the dose of the radiation is greater in the upper layersand is smaller in the lower layers of the resist film. Thiscauses a resist pattern to be thinner in the upper portion andbe thicker toward the lower portion, thereby forming a trapezoidshape after development. No sufficient resolution can beobtained from such a resist film. Such a trapezoid shape formedafter development cannot give a desired dimensional accuracyin the succeeding steps such as an etching step and an ionimplantation step. In addition, if the configuration of theresist pattern is not rectangular on the upper portion, theresist disappears faster during dry etching, making itdifficult to control etching conditions.
[0008] The shape of the resist pattern can be improved byincreasing the radiation transmittance through the resist film.For example, (meth)acrylate resins represented bypolymethylmethacrylate are desirable from the viewpoint ofradiation transmittance due to the superior transparency todeep ultraviolet rays. Japanese Patent Application Laid-openNo. 226461/1992 proposes a chemically-amplifiedradiation-sensitive resin composition using a methacrylateresin. However, in spite of the excellent micro-processingperformance, this composition exhibits only poor dry etchingresistance due to the absence of an aromatic ring, giving riseto difficulty in performing etching with high accuracy. Thiscomposition thus does not have both radiation transmittance and dry etching resistance at the same time.
[0009] A method of introducing an aliphatic ring into the resincomponent in the composition instead of an aromatic ring hasbeen known as a means for improving dry etching resistancewithout impairing radiation transmittance of the resist madefrom a chemically-amplified radiation-sensitive resincomposition. A chemically-amplified radiation-sensitiveresin composition using a (meth)acrylate resin having analicyclic ring is proposed in Japanese Patent ApplicationLaid-open No. 234511/1995, for example.
[0010] This composition, however, comprises groups which arecomparatively easily dissociated with conventional acids (forexample, an acetal functional group such as a tetrahydropyranylgroup) and groups which are comparatively difficult to bedissociated with acids (for example, a t-butyl functional groupsuch as a t-butyl ester group, t-butylcarbonate group) as anacid-dissociable functional group as the resin component. Theresin component possessing the former acid-dissociablefunctional group exhibits excellent basic characteristics asa resist such as superior sensitivity and excellent patternshape, but has a problem of poor storage stability. Inaddition, the resin component possessing the formeracid-dissociable functional group exhibits impaired resistcharacteristics, particularly in terms of sensitivity andpattern shape, in spite of excellent storage stability. Inaddition, inclusion of an alicyclic structure in the resincomponents of this composition increases hydrophobicity of the resin, resulting in poor adhesion to substrates.
[0011] More recently, several chemically amplified radiationsensitive compositions in which resin components having alactone ring structure are used have been proposed. For example,Japanese Patent Applications Laid-open No. 239846/1998, No.274852/1998, No. 12326/1999, and No. 223950/1999 disclosecompositions containing a resin component in which the lactonering structure is bonded at the 2-position (α-position) anda photoacid generator. Japanese Patent Applications Laid-openNo. 90637/1997 and No. 319595/1998 disclose compositionscontaining a resin component in which the lactone ring structureis bonded at the 3-position (β-position) and a photoacidgenerator. Japanese Patent Application Laid-open No.207069/1998 discloses compositions containing a resincomponent in which the lactone ring structure is bonded at the2 or 3-position and a photoacid generator.
[0012] However, most of these chemically amplified radiationsensitive compositions contain a resin component in which thelactone ring structure is bonded mainly at the 2-position, andsome compositions at the 3-position. Although the resincomponents used in conventional chemically amplified radiationsensitive compositions contain a variety of functional groupsmentioned above, these compositions have both merits anddemerits in the performance as a resist. In addition, asindicated in Japanese Patent Application Laid-open No.239846/1998, there are no established design standards for anacid-decomposable functional group protecting a carboxyl group, for example.
[0013] In view of recent progress in the microfabrication ofsemiconductor devices, development of a novel resin componentexhibiting high transmittance of radiation, having excellentbasic properties as a resist, and suitable for use in chemicallyamplified radiation sensitive compositions which can be adaptedto short wavelength radiation represented by a deep ultravioletrays is an important subject.
[0014] Therefore, an object of the present invention is toprovide a radiation-sensitive resin composition usable as achemically amplified positive tone resist, which has hightransmittance of radiation, exhibits superior basic propertiesas a resist such as high sensitivity, resolution, and patternshape, and is capable of producing semiconductors at a highyield without producing resolution defects duringmicrofabrication. SUMMARY OF THE INVENTION
[0015] This object can be solved in the present invention bya radiation-sensitive resin composition comprising: (A) an acid-dissociable group-containing resin which isinsoluble or scarcely soluble in alkali and becomes alkalisoluble when the acid-dissociable group dissociates, the resincomprising a lactone cyclic structure of the following formula(1),
[0016] In the above radiation sensitive resin composition, theresin of component (A) preferably comprises a recurring unitof the following formula (2) and at least one other recurringunit having an alicyclic hydrocarbon skeleton in the main chainand/or side chain,
[0017] In the above radiation sensitive resin composition,the resin of component (A) preferably comprises a recurring unitof the following formula (3) and at least one other recurringunit having an alicyclic hydrocarbon skeleton in the main chainand/or side chain:
[0018] In the above radiation sensitive resin composition, theat least one other recurring unit is selected from the groupconsisting of the recurring unit of the following formula (8),the recurring unit of the following formula (9), and therecurring unit of the following formula (10):
[0019] Other objects, features and advantages of the inventionwill hereinafter become more readily apparent from thefollowing description. DETAILED DESCRIPTION OF THE INVENTIONAND PREFERRED EMBODIMENTSComponent (A)
[0020] The component (A) of the present invention (hereinafterreferred to as "resin (A)", is an acid-dissociable group-containing resin insoluble or scarcely soluble in alkalicontaining the lactone ring structure of the above formula (1)(hereinafter referred to as "lactone ring structure (1)"). Theresin (A) becomes alkali soluble when the acid-dissociablegroup dissociates.
[0021] The following groups are given as examples of themonovalent organic group represented by R¹ in the formula (1) :linear, branched, or cyclic alkyl groups having 1-6 carbon atomssuch as a methyl group, ethyl group, n-propyl group, i-propylgroup, n-butyl group, 2-methylpropyl group, 1-methylpropylgroup, t-butyl group, n-pentyl group, i-pentyl group, andcyclohexyl group; linear, branched, or cyclic hydroxyalkylgroups having 1-6 carbon atoms such as a hydroxymethyl group,1-hydroxyethyl group, 2-hydroxyethyl group,1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group,3-hydroxy-n-propyl group, 1-hydroxy-n-butyl group,2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group,4-hydroxy-n-butyl group, 1-hydroxy-n-pentyl group,2-hydroxy-n-pentyl group, 3-hydroxy-n-pentyl group,4-hydroxy-n-pentyl group, 5-hydroxy-n-pentyl group, and4-hydroxycyclohexyl group; linear, branched, or cyclic alkoxylgroups having 1-6 carbon atoms such as methoxy group, ethoxygroup, n-propoxy group, i-propoxy group, n-butoxy group,2-methylpropoxy group, 1-methylpropoxy group, t-butoxygroup,n-pentyloxy group, and cyclohexyloxy group; a carboxyl group;a cyano group; and linear, branched, or cyclic cyanoalkyl groupshaving 2-7 carbon atoms such as a cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group, 1-cyano-n-propylgroup, 2-cyano-n-propyl group, 3-cyano-n-propyl group,1-cyano-n-butyl group, 2-cyano-n-butyl group, 3-cyano-n-butylgroup, 4-cyano-n-butyl group, 1-cyano-n-pentyl group,2-cyano-n-pentyl group, 3-cyano-n-pentyl group,4-cyano-n-pentyl group, 5-cyano-n-pentyl group, and4-cyanocyclohexyl group.
[0022] Preferable groups represented by R¹ in the formula (1)are a methyl group, methoxy group, n-butoxy group,cyclohexyloxy group, and cyano methyl group, with a methyl groupbeing particularly preferable.
[0023] In the formula (1), 1 is particularly preferable as theinteger a, and 0, 1, or 2 is particularly preferable as theinteger b.
[0024] The lactone ring structure (1) may directly bond to themain chain or side chain of the resin (A) or may bond to themain chain or side chain of the resin (A) through a divalentbonding hand.
[0025] As examples of the divalent bonding hand, substitutedor unsubstituted, linear, branched, or cyclic hydrocarbongroups having 1-5 main chain carbon atoms, substituted orunsubstituted (poly)oxymethylene groups, substituted orunsubstituted, linear or branched oxyalkylene groups having 2-4carbon atoms, or derivatives to which two or more suchoxyalkylene groups are added, -O-, -CO-, -COO-, -R-OCO-,-R-COO-, -OCO-R-COO-, and -COO-R-OCO- (wherein R is asubstituted or unsubstituted, linear or branched divalent hydrocarbon group having 1-4 main chain carbon atoms,hereinafter the same) can be given.
[0026] It is preferable that the lactone ring structure (1) ofthe present invention bonds to the main chain and/or side chain,particularly to the side chain of the resin (A), directly orthrough a substituted or unsubstituted, linear or brancheddivalent cyclic hydrocarbon groups having 1-5 main chain carbonatoms or a group -R-OCO-.
[0027] As an acid-dissociating group in the resin (A), a groupdissociating an acidic functional group in the presence of anacid, particularly an acid-dissociating organic group having20 or less carbon atoms which produces a carboxyl group(hereinafter referred to simply as "acid-dissociating organicgroup") can be given.
[0028] As preferable specific examples of acid-dissociatingorganic groups in the present invention, the groups shown bythe following formula (4) (hereinafter referred to as "anacid-dissociable group (I)"), the groups shown by the followingformula (5) (hereinafter referred to as "an acid-dissociablegroup (II)"), and the like can be given.
[0029] The acid-dissociating organic group (I) dissociates inthe presence of an acid at the bonding site between thecarbonyloxy group and the group -C(R⁴)₃. On the other hand, theacid-dissociating organic group (II) dissociates in thepresence of an acid at the bonding site between the t-butyl groupof the t-butoxycarbonyl group and the oxycarbonyl group.
[0030] As examples of the linear or branched alkyl group having1-4 carbon atoms represented by R⁴ in the formula (4), a methylgroup, ethyl group, n-propyl group, i-propyl group, n-butylgroup, 2-methylpropyl group, 1-methylpropyl group, and t-butylgroup can be given.
[0031] Of these, a methyl group and ethyl group are particularlypreferable.
[0032] As examples of the monovalent alicyclic hydrocarbongroup having 4-20 carbon atoms and the divalent alicyclichydrocarbon group having 4-20 carbon atoms formed by two R⁴sin combination, alicyclic groups derived from a cycloalkanesuch as norbornane, tricyclodecane, tetracyclododecane,adamantane, cyclobutane, cyclopentane, cyclohexane,cycloheptane, or cyclooctane, and groups obtained by replacinghydrogen atoms on these alicyclic groups with one or more linearor branched alkyl groups having 1-4 carbon atoms, such as methylgroup, ethyl group, n-propyl group, i-propyl group, n-butylgroup, 2-methyl propyl group, 1-methyl propyl group, or t-butylgroup, can be given.
[0033] Of these monovalent and divalent alicyclic hydrocarbongroups, groups containing an alicyclic ring derived fromnorbornane, tricyclodecane, tetracyclododecane, oradamantane, groups in which these alicyclic ring-containinggroups are substituted with the above alkyl groups arepreferable.
[0034] As examples of derivatives of the monovalent or divalentalicyclic hydrocarbon groups, groups having one or moresubstituents such as a hydroxyl group; a carboxyl group; alinear or branched hydroxyalkyl group having 1-4 carbon atomssuch as a hydroxymethyl group, 1-hydroxyethyl group,2-hydroxyethyl group, 1-hydroxy-n-propyl group,2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group,1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group,3-hydroxy-n-butyl group, and 4-hydroxy-n-butyl group; a linear or branched alkoxyl group having 1-4 carbon atoms such as amethoxy group, ethoxy group, n-propoxy group, i-propoxy group,n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group,and t-butoxy group; a cyano group; a linear or branchedcyanoalkyl group having 2-5 carbon atoms such as a cyanomethylgroup, 1-cyanoethyl group, 2-cyanoethyl group, 1-cyanopropylgroup, 2-cyanopropyl group, 3-cyanopropyl group, 1-cyanobutylgroup, 2-cyanobutyl group, 3-cyanobutyl group, and4-cyanobutyl group; and the like can be given.
[0035] Of these substituents, a hydroxyl group, carboxyl group,hydroxymethyl group, cyano group, cyanomethyl group, and thelike are preferable.
[0036] As examples of the linear or branched hydrocarbon grouphaving 1-4 carbon atoms in the main chain represented by R⁵ inthe formula (5), methylene group, 1-methyl-1,1-ethylene group,ethylene group, propylene group, 1,1-dimethylethylene group,trimethylene group, tetramethylene group, and the like can begiven.
[0037] As examples of the divalent alicyclic hydrocarbon grouphaving 3-15 carbon atoms represented by R⁵, groups containingan alicyclic ring derived from norbornane, tricyclodecane,tetracyclododecane, adamantane, or cycloalkanes such ascyclopropane, cyclobutane, cyclopentane, cyclohexane,cycloheptane, and cyclooctane; groups in which the above groupcontaining an alicyclic ring is substituted with at least oneof linear or branched alkyl groups having 1-4 carbon atoms suchas a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, andt-butyl group; and the like can be given.
[0038] Of these alicyclic hydrocarbon groups, groups containingan alicyclic ring derived from norbornane, tricyclodecane,tetracyclododecane, or adamantane, groups in which thesealicyclic ring containing groups are substituted with the abovealkyl groups, and the like are preferable.
[0039] As specific preferable examples of the acid-dissociatingorganic group (I), t-butoxycarbonyl group and groups shown bythe following formulas (I-1) to (I-57) can be given.
[0040] Of these acid-dissociating organic groups (I), t-butoxycarbonyl group and the groups shown by the formulas (I-1),(I-2), (I-10), (I-11), (I-13), (I-14), (I-16), (I-17), (I-22),(I-23), (I-34), (I-35), (I-52), or (I-53) are particularlypreferable.
[0041] As examples acid-dissociating organic groups other thanthe acid-dissociating organic group (I) or acid-dissociating organic group (II) (hereinafter referred to as"acid-dissociating organic group (III)"), the following groupscan be given: a (cyclo)alkoxycarbonyl group such amethoxycarbonyl group, ethoxycarbonyl group,n-propoxycarbonyl group, i-propoxycarbonyl group,n-butoxycarbonyl group, 2-methylpropoxycarbonyl group,1-methylpropoxycarbonyl group, n-pentyloxycarbonyl group,n-hexyloxycarbonyl group, n-heptyloxycarbonyl group,n-octyloxycarbonyl group, n-decyloxycarbonyl group,cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group,4-t-butylcyclohexyloxycarbonyl group, cycloheptyloxycarbonylgroup, and cyclooctyloxycarbonyl group; an aryloxycarbonylgroup such as a phenoxycarbonyl group,4-t-butylphenoxycarbonyl group, and 1-naphthyloxycarbonylgroup; an aralkyloxycarbonyl group such as a benzyloxycarbonylgroup, 4-t-butylbenzyloxycarbonyl group,phenethyloxycarbonyl group, and4-t-butylphenethyloxycarbonyl group; a1-(cyclo)alkyloxyethoxycarbonyl group such as a1-methoxyethoxycarbonyl group, 1-ethoxyethoxycarbonyl group,1-n-propoxyethoxycarbonyl group, 1-i-propoxyethoxycarbonylgroup, 1-n-butoxyethoxycarbonyl group,1-(2'-methylpropoxy)ethoxycarbonyl group,1-(1'-methylpropoxy)ethoxycarbonyl group,1-t-butoxyethoxycarbonyl group,1-cyclohexyloxyethoxycarbonyl group, and1-(4'-t-butylcyclohexyloxy)ethoxycarbonyl group; a 1-aryloxyethoxycarbonyl group such as a1-phenoxyethoxycarbonyl group,1-(4'-t-butylphenoxy)ethoxycarbonyl group, and1-(1'-naphthyloxy)ethoxycarbonyl group;a 1-aralkyloxyethoxycarbonyl group such as a1-benzyloxyethoxycarbonyl group,1-(4'-t-butylbenzyloxy)ethoxycarbonyl group,1-phenethyloxyethoxycarbonyl group, and1-(4'-t-butylphenethyloxy)ethoxycarbonyl group; a(cyclo)alkoxycarbonylmethoxycarbonyl group such as amethoxycarbonylmethoxycarbonyl group,ethoxycarbonylmethoxycarbonyl group,n-propoxycarbonylmethoxycarbonyl group,i-propoxycarbonylmethoxycarbonyl group,n-butoxycarbonylmethoxycarbonyl group,2-methylpropoxycarbonylmethoxycarbonyl group,1-methylpropoxycarbonylmethoxycarbonyl group,cyclohexyloxycarbonylmethoxycarbonyl group, and4-t-butylcyclohexyloxycarbonylmethoxycarbonyl group; a(cyclo)alkoxycarbonylmethyl group such as amethoxycarbonylmethyl group, ethoxycarbonylmethyl group,n-propoxycarbonylmethyl group, i-propoxycarbonylmethylgroup, n-butoxycarbonylmethyl group,2-methylpropoxycarbonylmethyl group,1-methylpropoxycarbonylmethyl group, t-butoxycarbonylmethylgroup, cyclohexyloxycarbonylmethyl group, and4-t-butylcyclohexyloxycarbonylmethyl group; an aryloxycarbonylmethyl group such as a phenoxycarbonylmethylgroup, 4-t-butylphenoxycarbonylmethyl group, and1-naphthyloxycarbonylmethyl group; anaralkyloxycarbonylmethyl group such as abenzyloxycarbonylmethyl group,4-t-butylbenzyloxycarbonylmethyl group,phenethyloxycarbonylmethyl group, and4-t-butylphenethyloxycarbonylmethyl group; a2-(cyclo)alkoxycarbonylethyl group such as a2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group,2-n-propoxycarbonylethyl group, 2-i-propoxycarbonylethylgroup, 2-n-butoxycarbonylethyl group,2-(2'-methylpropoxy)carbonylethyl group,2-(1'-methylpropoxy)carbonylethyl group,2-t-butoxycarbonylethyl group, 2-cyclohexyloxycarbonylethylgroup, and 2-(4'-t-butylcyclohexyloxycarbonyl)ethyl group; a2-aryloxycarbonylethyl group such as a 2-phenoxycarbonylethylgroup, 2-(4'-t-butylphenoxycarbonyl)ethyl group, and2-(1'-naphthyloxycarbonyl)ethyl group; a2-aralkyloxycarbonylethyl group such as a2-benzyloxycarbonylethyl group,2-(4'-t-butylbenzyloxycarbonyl)ethyl group,2-phenethyloxycarbonylethyl group, and 2-(4'-t-butylphenethyloxycarbonyl)ethylgroup; atetrahydrofuranyloxycarbonyl group; and atetrahydropyranyloxycarbonyl group.
[0042] Of these acid-dissociable groups (III), groups corresponding to the formula -COOR' (wherein R' represents alinear, branched, or cyclic alkyl group having 1-19 carbonatoms) or the formula -COOCH₂COOR" (wherein R" represents alinear, branched, or cyclic alkyl group having 1-17 carbonatoms) are preferable.
[0043] The resin (A) is not specifically limited as long as theresin contains the lacton ring structure (1) andacid-dissociating groups such as the acid-dissociating organicgroup (I), acid-dissociating organic group (II), andacid-dissociating organic group (III), and is insoluble orscarcely soluble in alkali and becomes alkali soluble when theacid-dissociable group dissociates. The resin (A) may be anaddition polymerization resin, a polyaddition resin, or apolycondensation resin, but preferably is an additionpolymerization resin.
[0044] From the viewpoint of transmittance of radioactive rays,the resin (A) of the present invention preferably does not havean aromatic ring or contains as small an amount of aromatic ringsas possible.
[0045] As a preferable resin (A) of the present invention, anacid-dissociable group-containing resin insoluble or scarcelysoluble in alkali containing the recurring unit represented bythe following formula (2) (hereinafter referred to as"recurring unit (2)") and/or the recurring unit represented bythe following formula (3) (hereinafter referred to as"recurring unit (3)"), and becoming alkali soluble when theacid-dissociable group dissociates, can be given (such a resin (A) being hereinafter referred to as "resin (A1)".
[0046] As examples of the linear or branched hydrocarbon grouphaving 1-5 carbon atoms represented by R³ in the formulas (2)and (3), methylene group, 1-methyl-1,1-ethylene group,ethylene group, propylene group, 1,1-dimethylethylene group,trimethylene group, tetramethylene group, hydroxymethylenegroup, 1-hydroxy-1,1-ethylene group, 1-hydroxy-1,2-ethylenegroup, 2-hydroxy-1,2-ethylene group, 1-hydroxytrimethylenegroup, 2-hydroxytrimethylene group, 3-hydroxytrimethylenegroup, and the like can be given.
[0047] Of these divalent hydrocarbon groups or the derivatives,a methylene group, ethylene group, and 2-hydroxytrimethylenegroup are particularly preferable.
[0048] In the formulas (2) and (3), 1 is particularly preferableas the integer a, and 0, 1, or 2 is particularly preferable asthe integer b.
[0049] Either one or two or more recurring units (2) and therecurring units (3) may be present in the resin (A1). The grouprepresented by R¹ in the recurring unit (2) and the grouprepresented by R¹ in the recurring unit (3) may be either thesame or different. In addition, the group represented by R³in the recurring unit (2) and the group represented by R³ inthe recurring unit (3) may be either the same or different.
[0050] The polymerizable unsaturated monomers produces therecurring unit (2) are compounds represented by the following formula (6) (hereinafter referred to as "(meth)acrylic acidderivatives (α)").
[0051] As examples of polymerizable unsaturated monomers whichprovide the recurring unit (3), compounds shown by the followingformula (7) (hereinafter referred to as "norbornene derivatives(α)") can be given.
[0052] The compounds shown by the following formulas (6-1) to(6-28) can be given as preferable examples of the (meth) acrylicacid derivatives (α).
[0053] Of these (meth)acrylic acid derivatives (α), compoundsshown by the formulas (6-1), (6-2), (6-25), and (6-26) arepreferable.
[0054] The (meth)acrylic acid derivatives (α) can besynthesized by the esterification reaction of4-hydroxymethyl-γ-butyrolactone and (meth)acrylic acidchloride, for example.
[0055] The compounds shown by the following formulas (7-1) to(7-28) can be given as preferable examples of the norbornenederivatives (α).
[0056] The norbornene derivatives (α) can be synthesized by theDiels-Alder reaction of the above (meth)acrylic acidderivatives (α) and cyclopentadiene or the like, for example.
[0057] In addition to the recurring unit (1) and/or the recurringunit (2), the resin (A1) usually comprises one or more otherrecurring units.
[0058] As preferable examples of such other recurring units,the units shown by the following formula (8) (hereinafterreferred to as "recurring unit (8)"), the following formula (9)(hereinafter referred to as "recurring unit (9)"), and thefollowing formula (10) (hereinafter referred to as "recurringunit (10)") can be given.
[0059] The polymerizable unsaturated monomer providing the recurring unit (8) is a compound derived from (meth) acrylic acidby converting the carboxyl group into an acid-dissociatingorganic group (I) (hereinafter referred to as "(meth)acrylicacid derivative (β-1)"). The polymerizable unsaturatedmonomer providing the recurring unit (9) is a compound derivedfrom (meth)acrylic acid by converting the carboxyl group intoan acid-dissociating organic group (II) (hereinafter referredto as "(meth)acrylic acid derivative (β-2)").
[0060] As the acid-dissociable groups A and B in the formula(10), t-butoxycarbonyl group andt-butoxycarbonylmethoxycarbonyl group, as well as the groupscorresponding to -COOR' (wherein R' represents a linear,branched, or cyclic alkyl group having 1-19 carbon atoms) or-COOCH₂COOR" (wherein R" represents a linear, branched, orcyclic alkyl group having 1-17 carbon atoms) among theacid-dissociating organic groups (III), are preferable.Particularly preferable groups are t-butoxycarbonyl group,t-butoxycarbonylmethoxycarbonyl group, and1-methylpropoxycarbonyl group.
[0061] As examples of linear or branched alkyl groups having1-4 carbon atoms represented by X or Y, a methyl group, ethylgroup, n-propyl group, i-propyl group, n-butyl group,2-methylpropyl group, 1-methylpropyl group, t-butyl group, andthe like can be given.
[0062] Of these alkyl groups, a methyl group and ethyl groupare particularly preferable.
[0063] m in the formula (10) is preferably either 0 or 1.
[0064] As examples of polymerizable unsaturated monomersproviding the recurring unit (10), compounds shown by thefollowing formula (11) (hereinafter referred to as "norbornenederivatives (β-1)") can be given.
[0065] The following compounds can be given as examples of thenorbornene derivatives (β-1) having m=0 in the formula (11): 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-n-propoxycarbonylnorbornene, 5-i-propoxycarbonylnorbornene, 5-n-butoxycarbonylnorbornene, 5-(2'-methylpropoxy)carbonylnorbornene, 5-(1'-methylpropoxy)carbonylnorbornene, 5-t-butoxycarbonylnorbornene, 5-cyclohexyloxycarbonylnorbornene, 5-(4'-t-butylcyclohexyloxy)carbonylnorbornene, 5-phenoxycarbonylnorbornene, 5-(1'-ethoxyethoxy)carbonylnorbornene, 5-(1'-cyclohexyloxyethoxy)carbonylnorbornene, 5-t-butoxycarbonylmethoxycarbonylnorbornene, 5-tetrahydrofuranyloxycarbonylnorbornene, 5-tetrahydropyranyloxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, 5-methyl-5-n-propoxycarbonylnorbornene, 5-methyl-5-i-propoxycarbonylnorbornene, 5-methyl-5-n-butoxycarbonylnorbornene, 5-methyl-5-(2'-methylpropoxy)carbonylnorbornene, 5-methyl-5-(1'-methylpropoxy)carbonylnorbornene, 5-methyl-5-t-butoxycarbonylnorbornene, 5-methyl-5-cyclohexyloxycarbonylnorbornene, 5-methyl-5-(4'-t-butylcyclohexyloxy)carbonylnorbornene, 5-methyl-5-phenoxycarbonylnorbornene, 5-methyl-5-(1'-ethoxyethoxy)carbonylnorbornene, 5-methyl-5-(1'-cyclohexyloxyethoxy)carbonylnorbornene, 5-methyl-5-t-butoxycarbonylmethoxycarbonylnorbornene, 5-methyl-5-tetrahydrofuranyloxycarbonylnorbornene, 5-methyl-5-tetrahydropyranyloxycarbonylnorbornene, 5,6-di(methoxycarbonyl)norbornene, 5,6-di(ethoxycarbonyl)norbornene, 5,6-di(n-propoxycarbonyl)norbornene, 5,6-di(i-propoxycarbonyl)norbornene, 5,6-di(n-butoxycarbonyl)norbornene, 5,6-di(2'-methylpropoxycarbonyl)norbornene, 5,6-di(1'-methylpropoxycarbonyl)norbornene, 5,6-di(t-butoxycarbonyl)norbornene, 5,6-di(cyclohexyloxycarbonyl)norbornene, 5,6-di(4'-t-butylcyclohexyloxycarbonyl)norbornene, 5,6-di(phenoxycarbonyl)norbornene, 5,6-di(1'-ethoxyethoxycarbonyl)norbornene, 5,6-di(1'-cyclohexyloxyethoxycarbonyl)norbornene, 5,6-di(t-butoxycarbonylmethoxycarbonyl)norbornene, 5,6-di(tetrahydrofuranyloxycarbonyl)norbornene, and 5,6-di(tetrahydropyranyloxycarbonyl)norbornene.
[0066] The following compounds can be given as examples of thenorbornene derivatives (β-1) having m=1 in the formula (11): 8-methoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-ethoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-n-propoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-i-propoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-n-butoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-(2'-methylpropoxy)carbonyltetracyclo[4.4.0.1^2,5,1^7,10]-dodeca-3-ene, 8-(1'-methylpropoxy)carbonyltetracyclo[4.4.0.1^2,5,1^7,10]-dodeca-3-ene, 8-t-butoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-cyclohexyloxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-(4'-t-butylcyclohexyloxy)carbonyltetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-phenoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-(1'-ethoxyethoxy)carbonyltetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8-(1'-cyclohexyloxyethoxy)carbonyltetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-t-butoxycarbonylmethoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-tetrahydrofuranyloxycarbonyltetracyclo-[4.4.0,1^2,5.1^7,10]dodeca-3-ene, 8-tetrahydropyranyloxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8-methyl-8-i-propoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8-methyl-8-(2'-methylpropoxy)carbonyltetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-methyl-8-(1'-methylpropoxy)[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-methyl-8-t-butoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8-methyl-8-cyclohexyloxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8-methyl-8-(4'-t-butylcyclohexyloxy)carbonyltetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-methyl-8-phenoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8-methyl-8-(1'-ethoxyethoxy)carbonyltetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-methyl-8-(1'-cyclohexyloxyethoxy)carbonyltetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-methyl-8-t-butoxycarbonylmethoxycarbonyltetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-methyl-8-tetrahydrofuranyloxycarbonyltetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-methyl-8-tetrahydropyranyloxycarbonyltetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,9-di(methoxycarbonyl)tetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,9-di(ethoxycarbonyl)tetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8,9-di(n-propoxycarbonyl)tetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8,9-di(i-propoxycarbonyl)tetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8,9-di(n-butoxycarbonyl)tetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8,9-di(2'-methylpropoxycarbonyl)tetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8,9-di(1'-methylpropoxycarbonyl)tetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8,9-di(t-butoxycarbonyl)tetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8,9-di(cyclohexyloxycarbonyl)tetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8,9-di(4'-t-butylcyclohexyloxycarbonyl)tetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,9-di(phenoxycarbonyl)tetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8,9-di(1'-ethoxyethoxycarbonyl)tetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8,9-di(1'-cyclohexyloxyethoxycarbonyl)tetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,9-di(t-butoxycarbonylmethoxycarbonyl)tetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,9-di(tetrahydrofuranyloxycarbonyl)tetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene,and 8,9-di(tetrahydropyranyloxycarbonyl)tetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene.
[0067] Of these norbornene derivativeses (β-1), 5-t-butoxycarbonylnorbornene, 5,6-di(t-butoxycarbonyl)norbornene, 5,6-di(t-butoxycarbonylmethoxycarbonyl)norbornene, 8-t-butoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-methyl-8-t-butoxycarbonyl)tetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene,8-methyl-8-t-butoxycarbonylmethoxycarbonyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene,and the like are preferable.
[0068] The resin (A1) may comprise at least one recurring unitother than the recurring units (8), (9), and (10) (hereinafterreferred to as "other recurring units").
[0069] The following compounds can be given as examples ofmono-functional monomers among the polymerizable unsaturatedmonomers which provide the other recurring units: (meth)acrylatic acid esters having an alicyclic hydrocarbonskeleton such as norbornyl (meth)acrylate, isobornyl(meth)acrylate, tricyclodecanyl (meth)acrylate,tetracyclodecanyl (meth)acrylate, dicyclopentenyl(meth)acrylate, adamantyl (meth)acrylate, adamantylmethyl(meth)acrylate, 1-methyladamantyl (meth)acrylate,cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate,cyclohexyl (meth)acrylate, cyclohexenyl (meth)acrylate, 4-methoxycyclohexyl (meth)acrylate, 2-cyclopropyloxycarbonylethyl (meth)acrylate, 2-cyclopentyloxycarbonylethyl (meth)acrylate, 2-cyclohexyloxycarbonylethyl (meth)acrylate, 2-cyclohexenyloxycarbonylethyl (meth)acrylate, and 2-(4'-methoxycyclohexyl)oxycarbonylethyl (meth)acrylate; (meth)acrylatic acid esters having a carboxyl group-containingalicyclic hydrocarbon skeleton such as 4-carboxycyclohexyl (meth)acrylate, carboxytricyclodecanyl (meth)acrylate, andcarboxytetracyclodecanyl (meth)acrylate; compounds which can introduce an alicyclic hydrocarbon skeletonin the main chain of the resin (A1) such as norbornene (e.g. bicyclo[2.2.1]hept-2-ene), 5-methylnorbornene, 5-ethylnorbornene, 5-hydroxynorbornene. 5-hydroxymethylnorbornene, tetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-methyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-ethyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-hydroxytetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-hydroxymethyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-fluorotetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-fluoromethyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-difluoromethyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-trifluoromethyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-pentafluoroethyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,8-difluorotetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,9-difluorotetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,8-bis(trifluoromethyl)tetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,9-bis(trifluoromethyl)tetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8-methyl-8-trifluoromethyltetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8,8,9-trifluorotetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,8,9-tris (trifluoromethyl) tetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8,8,9,9-tetrafluorotetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,8,9,9-tetrakis(trifluoromethyl)tetracyclo-[4.4.0.1^2,5.1^7,10]odeca-3-ene, 8,8-difluoro-9,9-bis(trifluoromethyl)tetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,9-difluoro-8,9-bis(trifluoromethyl)tetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,8,9-trifluoro-9-trifluoromethyltetracyclo[4.4.0.1^2,5,1^7,10]dodeca-3-ene, 8,8,9-trifluoro-9-trifluoromethoxytetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,8,9-trifluoro-9-pentafluoropropoxytetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-fluoro-8-pentafluoroethyl-9,9-bis(trifluoromethyl)-tetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8,9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracyclo[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-chloro-8,9,9-trifluorotetracyclo[4.4.0.1^2,5.1^7,10]-dodeca-3-ene, 8,9-dichloro-8,9-bis(trifluoromethyl)tetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-(2',2'2'-trifluorocarboethoxy)tetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, 8-methyl-8-(2',2'2'-trifluorocarboethoxy)tetracyclo-[4.4.0.1^2,5.1^7,10]dodeca-3-ene, dicyclopentadiene, tricyclo[5.2.1.0^2,6]deca-8-ene, tricyclo [5.2.1.0^2,6]deca-3-ene, tricyclo[4.4.0.1^2,5]undeca-3-ene, tricyclo[6.2.1.0^1,8]undeca-9-ene, tricyclo[6.2.1.0^1,8]undeca-4-ene, tetracyclo[4.4.0.1^2,5.1^7,10.0^1,6]dodeca-3-ene, 8-methyltetracyclo[4.4.0.1^2,5.1^7,10.0^1,6]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.1^2,5.1^7,12]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.1^2,5.1^7,10.0^1,6]dodeca-3-ene, pentacyclo[6.5.1.1^3,6.0^2,7.0^9,13]pentadeca-4-ene, pentacyclo[7.4.0.1^2,5.1^9,12.0^8,13]pentadeca-3-ene, (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, 2-methylpropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate; α-hydroxymethylacrylic acid esters such as methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, n-propyl α-hydroxymethyl acrylate, and n-butyl α-hydroxymethyl acrylate; vinyl esters such as vinyl acetate,vinyl propionate, and vinyl butyrate; unsaturated nitrylcompounds such as (meth)acrylonitrile, α-chloroacrylonitrile,crotonitrile, maleinitrile, fumaronitrile, mesaconitrile,citraconitrile, and itaconitrile; unsaturated amide compoundssuch as (meth) acrylamide, N,N-dimethyl(meth)acrylamide,crotonamide, maleinamide, fumaramide, mesaconamide,citraconamide, and itaconamide; other nitrogen-containingvinyl compounds such as N-vinyl-ε-caprolactam, N-vinylpyrrolidone, vinylpyridine, and vinylimidazole;unsaturated carboxylic acids (anhydrides) such as(meth)acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride,citraconic acid, citraconic anhydride, and mesaconic acid; carboxyl group-containing esters of unsaturated carboxylicacids such as 2-carboxyethyl (meth)acrylate, 2-carboxypropyl(meth)acrylate, 3-carboxypropyl (meth)acrylate, 4-carboxybutyl (meth)acrylate; and compounds derived from theabove (meth)acrylic acid esters having a carboxylgroup-containing alicyclic hydrocarbon skeleton, the aboveunsaturated carboxylic acids, or the above carboxylgroup-containing unsaturated carboxylic acid esters byconverting the carboxyl groups into the followingacid-dissociable organic groups (hereinafter referred to as"acid-dissociable organic group (IV)").
[0070] The acid-dissociating organic group (IV) includes thegroups obtained by replacing the hydrogen atom on the carboxylgroup with a substituted methyl group, 1-substituted ethylgroup, 1-branched alkyl group, silyl group, germyl group,alkoxycarbonyl group, acyl group, cyclic acid-dissociatinggroup, or the like. The acid-dissociable group (IV) excludesthe groups from which a compound corresponding to (meth) acrylicacid derivatives (β-1) or (meth) acrylic acid derivatives (β-2)is derived when the carboxyl group in (meth)acrylic acid isconverted by the acid-dissociable group (IV).
[0071] As examples of a substituted methyl group, amethoxymethyl group, methylthiomethyl group, ethoxymethylgroup, ethylthiomethyl group, methoxyethoxymethyl group,benzyloxymethyl group, benzylthiomethyl group, phenacylgroup, bromophenacyl group, methoxyphenacyl group,methylthiophenacyl group, α-methylphenacyl group,cyclopropylmethyl group, benzyl group, diphenylmethyl group,triphenylmethyl group, bromobenzyl group, nitrobenzyl group,methoxybenzyl group, methylthiobenzyl group, ethoxybenzylgroup, ethylthiobenzyl group, piperonyl group,methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethylgroup, i-propoxycarbonylmethyl group,n-butoxycarbonylmethyl group, t-butoxycarbonylmethyl group,and the like can be given.
[0072] As examples of a 1-substituted methyl group, a1-methoxyethyl group, 1-methylthioethyl group,1,1-dimethoxyethyl group, 1-ethoxyethyl group,1-ethylthioethyl group, 1,1-diethoxyethyl group,1-phenoxyethyl group, 1-phenylthioethyl group,1,1-diphenoxyethyl group, 1-benzyloxyethyl group,1-benzylthioethyl group, 1-cyclopropylethyl group,1-phenylethyl group, 1,1-diphenylethyl group,1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group,1-n-propoxycarbonylethyl group, 1-i-propoxycarbonylethylgroup, 1-n-butoxycarbonylethyl group,1-t-butoxycarbonylethyl group, and the like can be given.
[0073] As examples of a 1-branched alkyl group, an i-propylgroup, 1-methylpropyl group, t-butyl group,1,1-dimethylpropyl group, 1-methylbutyl group,1,1-dimethylbutyl group, and the like can be given.
[0074] As examples of the silyl group, a trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group,triethylsilyl group, i-propyldimethylsilyl group,methyldi-i-propylsilyl group, tri-i-propylsilyl group,t-butyldimethylsilyl group, methyldi-t-butylsilyl group,tri-t-butylsilyl group, phenyldimethylsilyl group,methyldiphenylsilyl group, triphenylsilyl group, and the likecan be given.
[0075] As examples of the germyl group, a trimethylgermyl group,ethyldimethylgermyl group, methyldiethylgermyl group,triethylgermyl group, i-propyldimethylgermyl group,methyldi-i-propylgermyl group, tri-i-propylgermyl group,t-butyldimethylgermyl group, methyldi-t-butylgermyl group,tri-t-butylgermyl group, phenyldimethylgermyl group,methyldiphenylgermyl group, triphenylgermyl group, and thelike can be given.
[0076] As examples of the alkoxycarbonyl group, amethoxycarbonyl group, ethoxycarbonyl group,i-propoxycarbonyl group, t-butoxycarbonyl group, and the likecan be given.
[0077] As examples of the acyl group, an acetyl group, propionylgroup, butyryl group, heptanoyl group, hexanoyl group, valerylgroup, pivaloyl group, isovaleryl group, lauryloyl group,myristoyl group, palmitoyl group, stearoyl group, oxalyl group,malonyl group, scucinyl group, glutaryl group, adipoyl group,piperoyl group, suberoyl group, azelaoyl group, sebacoyl group,acryloyl group, propioloyl group, methacryloyl group,crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, campholoyl group, benzoyl group, phthaloylgroup, isophthaloyl group, terephthaloyl group, naphthoylgroup, toluoyl group, hydroatropoyl group, atropoyl group,cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group,isonicotinoyl group, p-toluenesulfonyl group, mesyl group, andthe like can be given.
[0078] As examples of the cyclic acid-dissociable group, a3-oxocyclohexyl group, tetrahydropyranyl group,tetrahydrofuranyl group, tetrahydrothiopyranyl group,tetrahydrothiofuranyl group, 3-bromotetrahydropyranyl group,4-methoxytetrahydropyranyl group,2-oxo-4-methyl-4-tetrahydropyranyl group,4-methoxytetrahydrothiopyranyl group,3-tetrahydrothiophene-1,1-dioxide group, and the like can begiven.
[0079] Given as polyfunctional monomers among the polymerizableunsaturated monomers providing the other recurring units arepoly-functional monomers having an alicyclic hydrocarbonskeleton such as 1,2-adamantanediol di(meth)acrylate,1,3-adamantanediol di(meth)acrylate, 1,4-adamantanedioldi(meth)acrylate, and tricyclodecanyldimethyloldi(meth)acrylate, as well as methylene glycoldi(meth)acrylate, ethylene glycol di(meth)acrylate, propyleneglycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 1,8-octanedioldi(meth)acrylate, 1,9-nonanediol di (meth) acrylate,1,4-bis(2-hydroxypropyl)benzene di(meth)acrylate, and 1,3-bis(2-hydroxypropyl)benzene di(meth)acrylate.
[0080] As the resin (A1) in the present invention, the resincontaining a unit having an alicyclic hydrocarbon skeleton inthe main chain and/or the side chain as the recurring unit otherthan the recurring units (2) or (3) is desirable. Particularlypreferable resins are those containing at least one of the unitsselected from the recurring unit (8) having an alicyclichydrocarbon skeleton, the recurring unit (9) having analicyclic hydrocarbon skeleton, and the recurring unit (10).
[0081] The total content of the recurring unit (2) and therecurring unit (3) in the resin (A1) is usually 10-70 mol%,preferably 10-60 mol%, and still more preferably 15-60 mol% ofthe total amount of the recurring units. If the total amountof the above recurring units is less than 10 mol%,developability decreases and undeveloped areas tend to be leftafter development. If the amount exceeds 70 mol%, on the otherhand, resolution capability as a resist tends to decrease.
[0082] The total content of the recurring units (8), (9), and(10) in the resin (A1) is usually 5-70 mol%, preferably 5-60mol%, and still more preferably 10-60 mol% of the total amountof the recurring units. If the total amount of the aboverecurring units is less than 5 mol%, resolution capability anddry etching resistance as a resist tend to decrease. If theamount exceeds 70 mol%, on the other hand, developabilitydecreases and undeveloped areas tend to be left afterdevelopment.
[0083] The content of other recurring units is usually 60 mol% or less, and preferably 50 mol% or less.
[0084] The resin (A1) can be prepared by polymerizing the(meth)acrylic acid derivatives (α) and/or norbornenederivatives (α), preferably together with at least one of thederivatives selected from the group consisting of acrylic acidderivatives (β- 1), (meth)acrylic acid derivatives (β- 2),and norbornene derivatives (β- 1), and optionally withpolymerizable unsaturated monomers which provide the otherrecurring units in an appropriate solvent using a radicalpolymerization initiator such as a hydroperoxide, dialkylperoxide, diacyl peroxide, or azo compound and, as required,in the presence of a chain-transfer agent. When the norbornenederivatives (α), or norbornene or a norbornene derivative isused as a polymerizable unsaturated monomer providing the otherrecurring units, it is desirable to copolymerize maleicanhydride, because copolymerization of maleic anhydride mayincrease the molecular weight of the resin (A1) to a desiredlevel.
[0085] As examples of the solvent used for polymerizing thecomponents, alkanes such as n-pentane, n-hexane, n-heptane,n-octane, n-nonane, and n-decane; cycloalkanes such ascyclohexane, cycloheptane, cyclooctane, decalin, andnorbornane; aromatic hydrocarbons such as benzene, toluene,xylene, ethylbenzene, and cumene; halogenated hydrocarbonssuch as chlorobutanes, bromohexanes, dichloroethanes,hexamethylene dibromide, and chlorobenzene; saturatedcarboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate, and methyl propionate; ethers such astetrahydrofuran, dimethoxyethanes, and diethoxyethanes; andthe like can be given.
[0086] These solvents may be used either individually or incombination of two or more.
[0087] The polymerization is carried out at a temperature ofusually 40-120°C, and preferably 50-90°C for usually 1-48hours, and preferably 1-24 hours.
[0088] The polystyrene-reduced weight average molecular weight(hereinafter referred to as "Mw") of the resin (A) determinedby gel permeation chromatography (GPC) is usually3,000-300,000, preferably 4,000-200,000, and still morepreferably 5,000-100,000. If Mw of the resin (A) is less than3,000, heat resistance as a resist tends to decrease. If Mwexceeds 300,000, developability as a resist tends to decrease.
[0089] The ratio of Mw to the polystyrene-reduced number averagemolecular weight (hereinafter referred to as "Mn") determinedby gel permeation chromatography (GPC) (Mw/Mn) of the resin (A)is usually 1-5, and preferably 1-3.
[0090] It is preferable that the resin (A) contains almost noimpurities such as halogens or metals. The smaller the amountof such impurities, the better are the sensitivity, resolution,process stability, pattern shape, or the like as a resist. Theresin (A) can be purified using, for example, a chemicalpurification method such as washing with water or liquid-liquidextraction or a combination of the chemical purification methodand a physical purification method such as ultrafiltration or centrifugation.
[0091] In the present invention, the resin (A) may be used eitherindividually or in combination of two or more. Component (B)
[0092] The component (B) of the present invention is a photoacidgenerator which generates an acid upon exposure (hereinafterreferred to as "acid generator (B)").
[0093] The acid generator (B) causes an acid-dissociable groupin the resin (A) to dissociate by the action of an acid generatedupon exposure. As a result, an exposed part of the resist filmbecomes readily soluble in an alkaline developer, therebyforming a positive-tone resist pattern.
[0094] As examples of the acid generator (B), onium salts,halogen-containing compounds, diazoketone compounds, sulfonecompounds, sulfonate compounds, and the like can be given.
[0095] Examples of the acid generator (B) are given below. Onium salt compounds:
[0096] As examples of onium salt compounds, iodonium salts,sulfonium salts (including tetrahydrothiophenium salts),phosphonium salts, diazonium salts, and pyridinium salts canbe given.
[0097] Specific examples of onium salt compounds include: diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium naphthalenesulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate, bis(4-t-butylphenyl)iodonium perfluoro-n-octanesulfonate, bis(4-t-butylphenyl)n-dodecylbenzenesulfonate, bis(4-t-butylphenyl)iodonium hexafluoroantimonate, bis(4-t-butylphenyl)iodonium naphthalenesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium 10-camphorsulfonate, 4-hydroxyphenyl·phenyl·methylsulfonium p-toluenesulfonate,cyclohexyl·2-oxocyclohexyl·methylsulfonium trifluoromethanesulfonate, dicyclohexy·2-oxocyclohexylsulfoniumtrifluoromethane sulfonate, 2-oxocyclohexyldimethylsulfoniumtrifluoromethane sulfonate, 4-hydroxyphenyl·benzyl·methylsulfonium p-toluenesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldimethylsulfoniumtrifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfoniumtrifluoromethanesulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldiethylsulfoniumtrifluoromethanesulfonate, 4-nitro-1-naphthyldiethylsulfoniumtrifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfoniumtrifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfoniumtrifluoromethanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-methoxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-ethoxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-n-butoxy-1-naphthyltetrahydrothiopheniumnonafluoro-n-butanesulfonate, 4-n-butoxy-1-naphthyltetrahydrothiopheniumperfluoro-n-octanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-ethoxymethoxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-(1'-methoxyethoxy)-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-(2'-methoxyethoxy)-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-methoxycarbonyloxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-ethoxycarbonyloxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-n-propoxycarbonyloxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-i-propoxycarbonyloxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-n-butoxycarbonyloxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-t-butoxycarbonyloxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-(2'-tetrahydrofuranyloxy)-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-(2'-tetrahydropyranyloxy)-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-benzyloxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 1-(1'-naphthylacetomethyl)tetrahydrothiopheniumtrifluoromethanesulfonate, 4-hydroxy-3,5-dimethylphenyl-1-tetrahydrothiopheniumtrifluoromethanesulfonate, 4-hydroxy-3,5-dimethylphenyl-1-tetrahydrothiopheniumnonafluoro-n-butanesulfonate, and 4-hydroxy-3,5-dimethylphenyl-1-tetrahydrothiopheniumperfluoro-n-octanesulfonate.
[0098] As examples of halogen-containing compounds, haloalkylgroup-containing hydrocarbon compounds, haloalkylgroup-containing heterocyclic compounds, and the like can begiven.
[0099] As specific examples of preferable halogen-containingcompounds, (trichloromethyl)-s-triazine derivatives such asphenylbis(trichloromethyl)-s-triazine,4-methoxyphenylbis(trichloromethyl)-s-triazine, and1-naphthylbis(trichloromethyl)-s-triazine,1,1-bis(4'-chlorophenyl)-2,2,2-trichloroethane, and the likecan be given. Diazoketone compounds:
[0100] As examples of diazoketone compounds,1,3-diketo-2-diazo compounds, diazobenzoquinone compounds,diazonaphthoquinone compounds, and the like can be given.
[0101] As specific examples of preferable diazoketonecompounds, 1,2-naphthoquinonediazido-4-sulfonyl chloride,1,2-naphthoquinonediazido-5-sulfonyl chloride,1,2-naphthoquinonediazido-4-sulfonate or1,2-naphthoquinonediazido-5-sulfonate of2,3,4,4'-tetrahydroxybenzophenone,1,2-naphthoquinonediazido-4-sulfonate or1,2-naphthoquinonediazido-5-sulfonate of1,1,1-tris (4'-hydroxyphenyl)ethane, and the like can be given. Sulfone compounds:
[0102] As examples of sulfone compounds, β-ketosulfone,β-sulfonylsulfone, α-diazo compounds of these compounds, and the like can be given.
[0103] As specific examples of preferable sulfone compounds,4-trisphenacylsulfone, mesitylphenacylsulfone,bis(phenylsulfonyl)methane, and the like can be given. Sulfonate compounds:
[0104] As examples of sulfonate compounds, alkyl sulfonate,alkylimide sulfonate, haloalkyl sulfonate, aryl sulfonate,imino sulfonate, and the like can be given.As specific examples of preferable sulfone compounds,benzointosylate, tris(trifluoromethanesulfonate) ofpyrogallol,nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate,trifluoromethanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide,trifluoromethanesulfonylbicyclo[2.2.1]hepto-2-ene-5,6-dicarbodiimide,nonafluoro-n-butanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide,nonafluoro-n-butanesulfonylbicyclo[2.2.1]hepto-2-ene-5,6-dicarbodiimide,N-hydroxysuccinimidetrifluoromethanesulfonate,1,8-naphthalenedicarboxylic acid imidetrifluoromethanesulfonate, and the like can be given.
[0105] Of the above acid generators (B), the following compoundsare preferable: diphenyliodoniumtrifluoromethanesulfonate,diphenyliodoniumnonafluoro-n-butanesulfonate,bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate,triphenylsulfonium trifluoromethanesulfonate,triphenylsulfonium nonafluoro-n-butanesulfonate,cyclohexyl · 2-oxocyclohexyl-methylsulfoniumtrifluoromethanesulfonate,dicyclohexyl · 2-oxocyclohexylsulfoniumtrifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfoniumtrifluoromethanesulfonate,4-hydroxy-1-naphthyldimethylsulfoniumtrifluoromethanesulfonate,4-hydroxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate,1-(1'-naphthylacetomethyl)tetrahydrothiopheniumtrifluoromethanesulfonate,trifluoromethanesulfonylbicyclo[2.2.1]hepto-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimidetrifluoromethanesulfonate,1,8-naphthalenedicarboxylic acid imidotrifluoromethanesulfonate, and the like.
[0106] In the present invention, the acid generator (B) may beused either individually or in combination of two or more.
[0107] The amount of the acid generator (B) to be used in thepresent invention is usually 0.1-10 parts by weight, andpreferably 0.5-7 parts by weight for 100 parts by weight of theresin (A) from the viewpoint of ensuring sensitivity anddevelopability as a resist. If the amount of the acid generator(B) is less than 0.1 part by weight, sensitivity anddevelopability tend to decrease. If the amount exceeds 10 parts by weight, a rectangular resist pattern may not be obtained dueto decreased radiation transmittance. Additives
[0108] It is preferable to add an acid diffusion controller tothe radiation-sensitive resin composition of the presentinvention. The acid diffusion controller controls diffusionof an acid generated from the acid generator (B) upon exposurein the resist film to hinder unfavorable chemical reactions inthe unexposed area.
[0109] The addition of such an acid diffusion controllerimproves storage stability of the resultingradiation-sensitive resin composition and resolution as aresist. Moreover, the addition of the acid diffusioncontroller prevents the line width of the resist pattern fromchanging due to changes in the post-exposure delay (PED) betweenexposure and development, whereby a composition with remarkablysuperior process stability can be obtained.
[0110] As the acid diffusion controller, organic compoundscontaining nitrogen of which the basicity does not change duringexposure or heating for forming a resist pattern are preferable.
[0111] The following compounds can be given as examples of thenitrogen-containing organic compound: a compound representedby the following formula (12) (hereinafter referred to as"nitrogen-containing compound (a)");
[0112] Examples of the nitrogen-containing compounds (a)include mono(cyclo)alkylamines such as n-hexylamine,n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, andcyclohexylamine; di(cyclo)alkylamines such asdi-n-butylamine, di-n-pentylamine, di-n-hexylamine,di-n-heptylamine, di-n-octylamine, di-n-nonylamine,di-n-decylamine, cyclohexylmethylamine, anddicyclohexylamine; tri(cyclo)alkylamines such as triethylamine, tri-n-propylamine, tri-n-butylamine,tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine,tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine,cyclohexyldimethylamine, dicyclohexylmethylamine, andtricyclohexylamine; aromatic amines such as aniline,N-methylaniline, N,N-dimethylaniline, 2-methylaniline,3-methylaniline, 4-methylaniline, 4-nitroaniline,diphenylamine, triphenylamine, and naphthylamine; and thelike.
[0113] Examples of the nitrogen-containing compound (II)include ethylenediamine,N,N,N',N'-tetramethylethylenediamine,tetramethylenediamine, hexamethylenediamine,4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether,4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine,2,2-bis(4'-aminophenyl)propane,2-(3'-aminophenyl)-2-(4'-aminophenyl)propane,2-(4'-aminophenyl)-2-(3'-hydroxyphenyl)propane,2-(4'-aminophenyl)-2-(4'-hydroxyphenyl)propane,1,4-bis[1'-(4"-aminophenyl)-1'-methylethyl]benzene,1,3-bis[1'-(4"-aminophenyl)-1'-methylethyl]benzene,bis(2-diethylaminoethyl)ether, and the like.
[0114] Examples of the nitrogen-containing compounds (c)include polyethyleneimine, polyallylamine, a polymer of2-dimethylaminoethylacrylamide, and the like.
[0115] Examples of the nitrogen-containing compound (d) includeN-t-butoxycarbonyl di-n-octylamine, N-t-butoxycarbonyl di-n-nonylamine, N-t-butoxycarbonyl di-n-decylamine,N-t-butoxycarbonyl dicyclohexylamine,N-t-butoxycarbonyl-1-adamantylamine, N-t-butoxycarbonyl-N-methyl-1-adamantylamine,N,N-di-t-butoxycarbonyl-1-adamantylamine,N,N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine,N-t-butoxycarbonyl-4,4'-diaminodiphenylmethane,N,N'-di-t-butoxycarbonylhexamethylenediamine,N,N,N'N'-tetra-t-butoxycarbonylhexamethylenediamine,N,N'-di-t-butoxycarbonyl-1,7-diaminoheptane,N,N'-di-t-butoxycarbonyl-1,8-diaminooctane,N,N'-di-t-butoxycarbonyl-1,9-diaminononane,N,N'-di-t-butoxycarbonyl-1,10-diaminodecane,N,N'-di-t-butoxycarbonyl-1,12-diaminododecane,N,N'-di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane,N-t-butoxycarbonylbenzimidazole,N-t-butoxycarbonyl-2-methylbenzimidazole, andN-t-butoxycarbonyl-2-phenylbenzimidazole.
[0116] Examples of the other amide group-containing compoundsinclude formamide, N-methylformamide, N,N-dimethylformamide,acetamide, N-methylacetamide, N,N-dimethylacetamide,propionamide, benzamide, pyrrolidone, N-methylpyrrolidone,and the like.
[0117] Examples of the urea compounds include urea, methylurea,1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea,1,3-diphenylurea, tri-n-butylthiourea, and the like. Examplesof the other nitrogen-containing heterocyclic compounds include: imidazoles such as imidazole, benzimidazole,4-methylimidazole, and 4-methyl-2-phenylimidazole; pyridinessuch as pyridine, 2-methylpyridine, 4-methylpyridine,2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine,4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine,nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline,8-oxyquinoline, and acridine; piperazines such as piperazine,1-(2'-hydroxyethyl)piperazine; pyrazine, pyrazole,pyridazine, quinoxaline, purine, pyrrolidine, piperidine,morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine,1,4-diazabicyclo[2.2.2]octane; and the like.
[0118] Of these nitrogen-containing organic compounds, thenitrogen-containing compounds (a), nitrogen-containingcompounds (b), nitrogen-containing compounds (c), andnitrogen-containing heterocyclic compounds are preferable.
[0119] The acid diffusion controller may be used eitherindividually or in combination of two or more.
[0120] The amount of the acid diffusion controller to be addedis usually 15 parts by weight or less, preferably 10 parts byweight or less, and still more preferably 5 parts by weight orless for 100 parts by weight of the resin (A). If the proportionof the acid diffusion controller exceeds 15 parts by weight,sensitivity as a resist and developability of the exposed areatend to decrease. If the amount is less than 0.001 part by weight,the pattern shape or dimensional accuracy as a resist maydecrease depending on the processing conditions.
[0121] Alicyclic additives which further improve dry etching resistance, pattern shape, adhesion to substrate, or the likemay be added to the radiation-sensitive resin composition ofthe present invention.
[0122] The following compounds can be given as examples of thealicyclic additives: adamantane derivatives such as t-butyl1-adamantanecarboxylate, t-butyl 3-adamantanecarboxylate,di-t-butyl 1,3-adamantanedicarboxylate, t-butyl1-adamantaneacetate, t-butyl 3-adamantaneacetate, di-t-butyl1,3-adamantanediacetate, and2,5-dimethyl-2,5-di(adamantylcarbonyloxy)hexane;deoxycholates such as t-butyl deoxycholate,t-butoxycarbonylmethyl deoxycholate, 2-ethoxyethyldeoxycholate, 2-cyclohexyloxyethyl deoxycholate,3-oxocyclohexyl deoxycholate, tetrahydropyranyldeoxycholate, and mevalonolactone deoxycholate;lithocholates such as t-butyl lithocholate,t-butoxycarbonylmethyl lithocholate, 2-ethoxyethyllithocholate, 2-cyclohexyloxyethyl lithocholate,3-oxocyclohexyl lithocholate, tetrahydropyranyllithocholate, and mevalonolactone lithocholate; and the like.
[0123] These alicyclic additives may be used eitherindividually or in combination of two or more.
[0124] The amount of the alicyclic additives to be added isusually 50 parts by weight or less, and preferably 30 parts byweight or less for 100 parts by weight of the resin (A). If theamount of alicyclic additives exceeds 50 parts by weight, heatresistance as a resist tends to decrease.
[0125] Surfactants which improve applicability,developability, or the like may be added to theradiation-sensitive resin composition of the presentinvention.
[0126] As examples of surfactants, nonionic surfactants suchas polyoxyethylene lauryl ether, polyoxyethylene stearylether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonyl phenyl ether,polyethylene glycol dilaurate, polyethylene glycoldistearate; commercially available products such as KP341(manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No.75, No. 95 (manufactured by Kyoeisha Chemical Co. , Ltd.), FTOPEF301, EF303, EF352 (manufactured by TOHKEM PRODUCTSCORPORATION), MEGAFAC F171, F173 (manufactured by Dainippon Inkand Chemicals, Inc.), Fluorard FC430, FC431 (manufactured bySumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-382, SC-101,SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by AsahiGlass Co., Ltd.); and the like can be given.
[0127] These surfactants may be used either individually or incombination of two or more.
[0128] The amount of surfactants to be added is usually 2 partsby weight or less for 100 parts by weight of the total of theresin (A) and the acid generator (B).
[0129] As other additives, halation inhibitors, adhesionpromoters, storage stabilizers, anti-foaming agents, and thelike can be given. Preparation of composition solution
[0130] The radiation-sensitive resin composition of the presentinvention is prepared as a composition solution by dissolvingthe composition in a solvent so that the total solid contentis 5-50 wt%, and preferably 10-25 wt%, and filtering thecomposition using a filter with a pore diameter of about 0.2µm, for example.
[0131] Examples of solvents used for the preparation of thecomposition solution include: linear or branched ketones suchas 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone,4-methyl-2-pentanone, 3-methyl-2-pentanone,3,3-dimethyl-2-butanone, 2-heptanone, and 2-octanone;cyclic ketones such as cyclopentanone,3-methylcyclopentanone, cyclohexanone,2-methylcyclohexanone, 2,6-dimethylcyclohexanone, andisophorone; propylene glycol monoalkyl ether acetates such aspropylene glycol monomethyl ether acetate, propylene glycolmonoethyl ether acetate, propylene glycol mono-n-propyl etheracetate, propylene glycol mono-i-propyl ether acetate,propylene glycol mono-n-butyl ether acetate, propylene glycolmono-i-butyl ether acetate, propylene glycol mono-sec-butylether acetate, and propylene glycol mono-t-butyl ether acetate;alkyl 2-hydroxypropionates such as methyl2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl2-hydroxypropionate, i-propyl 2-hydroxypropionate, n-butyl2-hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl2-hydroxypropionate, and t-butyl 2-hydroxypropionate; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate,ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, andethyl 3-ethoxypropionate; as well as other solvents such asn-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butylalcohol, cyclohexanol, ethylene glycol monomethyl ether,ethylene glycol monoethyl ether, ethylene glycol mono-n-propylether, ethylene glycol mono-n-butyl ether, diethylene glycoldimethyl ether, diethylene glycol diethyl ether, diethyleneglycol di-n-propyl ether, diethylene glycol di-n-butyl ether,ethylene glycol monomethyl ether acetate, ethylene glycolmonoethyl ether acetate, ethylene glycol mono-n-propyl etheracetate, propylene glycol monomethyl ether, propylene glycolmonoethyl ether, propylene glycol mono-n-propyl ether,toluene, xylene, 2-hydroxy-2-methylethyl propionate,ethoxyethyl acetate, ethyl hydroxyacetate, methyl2-hydroxy-3-methylbutyrate, 3-methoxybutylacetate,3-methyl-3-methoxybutylacetate,3-methyl-3-methoxybutylpropionate,3-methyl-3-methoxybutylbutyrate, ethyl acetate, n-propylacetate, n-butylacetate, methyl acetoacetoate, ethylacetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide,benzyl ethyl ether, di-n-hexyl ether, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, caproicacid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol,benzyl acetate, ethyl benzoate, diethyl oxalate, diethylmaleate, γ-butyrolactone, ethylene carbonate, and propylene carbonate.
[0132] These solvents may be used either individually or incombination of two or more. Among these solvents, linear orbranched ketones, cyclic ketones, propylene glycol monoalkylether acetates, alkyl 2-hydroxypropionates, and alkyl3-alkoxypropionates are preferable. Formation of resist pattern
[0133] The radiation-sensitive resin composition of the presentinvention is particularly useful as a chemically-amplifiedpositive-tone resist.
[0134] In the chemically-amplified positive-tone resist, anacid-dissociable group in the resin (A) dissociates by theaction of an acid generated from the acid generator (B) uponexposure, thereby producing an acidic functional group,preferably a carboxyl group. As a result, solublity of theexposed part of the resist in an alkaline developer increases,whereby the exposed part is dissolved in an alkaline developerand removed to obtain a positive-tone resist pattern.
[0135] A resist pattern is formed from the radiation-sensitiveresin composition of the present invention by applying thecomposition solution to, for example, substrates such as asilicon wafer or a wafer coated with aluminum using anappropriate application method such as rotational coating, castcoating, and roll coating to form a resist film. The resistfilm is then optionally pre-baked (hereinafter called "PB") andexposed to form a predetermined resist pattern. As radiation used for exposure, visible rays, ultraviolet rays, deepultraviolet rays, X-rays, electron beams, or the like isappropriately selected depending on types of the acidgenerator. It is particularly preferable to use an ArF excimerlaser (wavelength: 193 nm) or KrF excimer laser (wavelength:248 nm).
[0136] In the present invention, it is preferable to performpost-exposure bake (hereinafter called "PEB") after exposure.PEB ensures smooth dissociation of the acid-dissociable organicgroup in the resin (A). The heating temperature for PEB isusually 30-200°C, and preferably 50-170°C, although the heatingconditions vary depending on the composition of theradiation-sensitive resin composition.
[0137] In order to bring out latent capability of theradiation-sensitive resin composition of the presentinvention, an organic or inorganic anti-reflection film may beformed on a substrate as disclosed in Japanese PatentPublication No. 12452/1994, for example. Moreover, aprotection film may be formed on the resist film as disclosedin Japanese Patent Publication No. 188598/1993 or the like inorder to prevent the effects of basic impurities or the likein an environmental atmosphere. These techniques may beemployed in combination.
[0138] The exposed resist film is then developed to form apredetermined resist pattern.
[0139] As examples of a developer used for development, it ispreferable to use an alkaline aqueous solution prepared by dissolving at least one of alkaline compounds such as sodiumhydroxide, potassium hydroxide, sodium carbonate, sodiumsilicate, sodium metasilicate, aqueous ammonia, ethylamine,n-propylamine, diethylamine, di-n-propylamine,triethylamine, methyldiethylamine, ethyldimethylamine,triethanolamine, tetramethylammonium hydroxide, pyrrole,piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene,and 1,5-diaza bicyclo-[4.3.0]-5-nonene.
[0140] The concentration of the alkaline aqueous solution isusually 10 wt% or less. If the concentration of the alkalineaqueous solution exceeds 10 wt%, an unexposed area may bedissolved in the developer.
[0141] Organic solvents or the like may be added to the developercontaining an alkaline aqueous solution.
[0142] As examples of organic solvents, linear, branched, orcyclic ketones such as acetone, methyl ethyl ketone, methyli-butyl ketone, cyclopentanone, cyclohexanone,3-methylcyclopentanone, and 2,6-dimethylcyclohexanone;alcohols such as methylalcohol, ethylalcohol,n-propylalcohol, i-propylalcohol, n-butylalcohol,t-butylalcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol,and 1,4-hexanedimethylol; ethers such as tetrahydrofuran anddioxane; esters such as ethyl acetate, n-butyl acetate, andi-amyl acetate; aromatic hydrocarbons such as toluene andxylene; phenol, acetonylacetone, dimethylformamide; and thelike can be given.
[0143] These organic solvents may be used either individually or in combination of two or more.
[0144] The amount of the organic solvents is preferably 100 vol%of the alkaline aqueous solution. If the amount of the organicsolvents exceeds 100 vol%, an exposed area may remainundeveloped due to decreased developability.
[0145] In addition, surfactants or the like may be added to thedeveloper containing the alkaline aqueous solution in anappropriate amount.
[0146] The resist film is generally washed with water afterdevelopment using a developer containing an alkaline aqueoussolution. EXAMPLES
[0147] The embodiments of the present invention will bedescribed in more detail by examples. However, these examplesshould not be construed as limiting the present invention. Inthe examples, part(s) refers to part(s) by weight unlessotherwise indicated.
[0148] Measurement and evaluation of each composition in theexamples and comparative examples were carried out as follows. Mw:
[0149] Mw was measured by gel permeation chromatography (GPC)using GPC columns (manufactured by Tosoh Corp., G2000HXL x 2,G3000HXL x 1, G4000HXL x 1) under the following conditions. Flow rate: 1.0 ml/minute Eluate: tetrahydrofuran Column temperature: 40°C Standard reference material: monodispersed polystyrene
[0150] A solution composition was applied to a quartz plate andthe coating was post-baked on a hot plate at 90°C for 60 secondsto obtain a resist coating with a thickness of 1 µm. Radiationtransmittance of the resist coating was calculated fromabsorbance at a wavelength of 193 nm and was adopted as a standardfor transparency in the deep UV ray region. Sensitivity:
[0151] A solution composition was applied to a silicon waferwith a 520Å thickness Deep UV30 film (manufactured by BrewerScience Corp.) coated on the surface by spin coating andpost-baked on a hot plate under the conditions shown in Table2 to obtain a resist coating with a thickness of 0.4 µm. Thecoating was exposed to radiation through a mask pattern usingan ArF excimer laser exposure apparatus (manufactured by NikonCorp., lens numerical aperture: 0.55, wavelength: 193 nm).After PEB under the conditions shown in Table 2, the resistcoatings were developed in a 2.38 wt% tetramethylammoniumhydroxide aqueous solution (Example 1) or 2.38 x 1/50 wt%tetramethylammonium hydroxide aqueous solution (ComparativeExample 4) at 25°C for 60 seconds. The resist coatings inExamples 8-11 were developed in a 2.38 wt% tetramethylammoniumhydroxide aqueous solution at 25°C for 40 seconds. The resistfilms were then washed with water and dried to obtainpositive-tone resist patterns. An optimum dose at which aline-and-space (1L1S) pattern with a line width of 0.18 µm was formed was taken as sensitivity. Resolution:
[0152] The minimum dimension of the resist pattern resolved atthe optimum dose was taken as the resolution of the resistcoating. Defective development:
[0153] Defective development was evaluated by observing thepresence or absence of the defective development using anoptical microscope and a KLA defect inspection device(manufactured by KLA-TENCOR JAPAN LTD.) by the followingprocedure. Evaluation procedure using KLA defect inspection device:
[0154] The total number of defective clusters and unclustersin one piece of wafer extracted from the difference producedby superposing reference images and pixels was counted by arraymode observation using the KLA defect inspection device of whichthe sensitivity was set to detect defects with a size 0.15 µmor greater. Pattern configuration:
[0155] The length of the bottom (L₁) and top (L₂) of a squarecross-section of a line-and-space (1L1S) pattern with a linewidth of 0.20 µm was measured by a scanning electron microscope.
[0156] The pattern configuration was judged as "Good" when 0.85≦L₂/L₁≦1 was satisfied and the pattern did not have a skirt-likeextension. Synthesis of monomersSynthesis Example 1(a) Oxidation reaction
[0157] A two liter three-necked flask was charged with 202 gof 4,5-diacetoxypentanal, 121 g of distilled water, 606 g ofmethylene chloride, 14 g of potassium dihydrogenphosphate, and2.62 g of 4-benzyloxy-2,2,6,6-tetramethyl-1-piperidinoxy.602 g of 13 wt% aqueous solution of sodium hypochlorite was addeddropwise to the mixture over one hour while vigorously stirringthe reaction mixture and maintaining the temperature at 5-10°C.After the addition, the mixture was stirred for 0.5 hour at thesame temperature. The resulting reaction solution was analyzedby gas chromatography (GPC) to confirm that the conversion rateof aldehyde groups to carboxyl groups was 100%.
[0158] The reaction solution was allowed to stand to separatethe water layer from the methylene chloride layer. The waterlayer was extracted with 300 g of methylene chloride. Aftercombining the methylene chloride layer and the methylenechloride extract, methylene chloride was evaporated to obtain202 g of a crude product. The crude product was purified by vacuumdistillation to obtain 171 g of 4,5-diacetoxypentanoic acid.The yield on the basis of 4,5-diacetoxtpentanal was 74 mol%. (b) Hydrolysis and cyclization reaction
[0159] A 500 ml three-necked flask was charged with 116 g of4,5-diacetoxypentanoic acid obtained in (a) above and 280 g ofan aqueous solution of 25 wt% sodium hydroxide. The mixturewas stirred for three hours while maintaining the temperature at 75-80°C. After cooling to 30°C, the reaction solution wasdropped into a 1 l three-necked flask which contained 490 g of40 wt% sulfuric acid aqueous solution. After the addition, themixture was stirred for three hours while maintaining thetemperature at 75-80°C. The resulting reaction solution wasanalyzed by gas chromatography (GPC) to confirm that theconversion rate of 4,5-diacetoxypentanoic acid to4-hydroxymethyl-γ-butyrolactone was 100%.
[0160] The reaction solution was neutralized with sodiumhydrogencarbonate, extracted with 300 g of methylene chloridethree times. The methylene chloride extracts were combined andmethylene chloride was evaporated to obtain 46 g of a crudeproduct. The crude product was purified by vacuum distillationto obtain 34 g of 4-hydroxymethyl-γ-butyrolactone. The yieldon the basis of 4,5-diacetoxtpentanoic acid was 57 mol%. (c) Methacrylation reaction
[0161] A 1 l three-necked flask was charged with 58 g of4-hydroxymethyl-γ-butyrolactone obtained in (b) above, 500 gof methylene chloride, and 60.6 g of triethylamine . The mixturewas stirred while maintaining the temperature at 0-5°C and 62.5g of methacryloyl chloride was added dropwise over one hour.After the addition, the mixture was stirred for one hour at thesame temperature, allowed to cool to room temperature, andstirred for a further six hours.
[0162] The reaction solution was filtered to separateby-produced triethylamine hydrochloride. 500 g of ethylacetate and 500 g of n-hexane were added to the filtrate. After the addition of 1 l of an aqueous solution of sodium carbonate,the mixture was washed with water. The upper organic layer wasfurther washed twice with 1 l of distilled water and the organicsolvent was evaporated to obtain 82 g of a crude product. Thecrude product was purified by vacuum distillation to obtain 58g of 4-methacryloyloxymethyl-γ-butyrolactone of the previouslydescribed formula (6-2). The yield on the basis of4-hyroyloxymethyl-γ-butyrolactone was 55 mol%. Synthesis Example 2
[0163] 50 g of 4-acryloyloxymethyl-γ-butyrolactone of thepreviously described formula (6-1) was obtained in the samemanner as in Synthesis Example 1, except that 54 g of acryloylchloride was used instead of 62.5 g of methacryloyl chloride.
[0164] 50 g of 4-acryloyloxymethyl-γ-butyrolactone wasdissolved in 200 ml of tetrahydrofuran and 50 ml ofcyclopentadiene was slowly dropped into the solution in a waterbath. After the addition, the mixture was allowed to cool toroom temperature, and stirred for 12 hours. Analysis of thereaction solution by gel chromatography confirmed progress ofthe Diels-Alder reaction. The reaction solution was distilledunder vacuum to obtain 50 g of5-[(4-γ-butyrolactone)methyloxycarbonyl]norbornene of theabove formula (7-1). The yield on the basis of4-acryloyloxymethyl-γ-butyrolactone was 52 mol%. Synthesis Example 3
[0165] 144.17 g of 4-hydroxymethyl-3,3-dimethyl-γ-butyrolactoneand 121.2 g of triethylamine were dissolved in 500 ml of dichloromethane and 100 g of acryloyl chloride wasslowly dropped into the solution in a water bath. After theaddition, the mixture was allowed to cool to room temperature,and stirred for 6 hours. Analysis of the reaction solution bygel chromatography confirmed progress of the esterificationreaction. After separating solid triethylamine hydrochloridein the reaction solution by filtration, the reaction solutionwas transferred to a separating funnel and washed untilneutralized. The organic layer was dehydrated by mixing withmagnesium sulfate. After removing the magnesium sulfate,dichloromethane was evaporated under vacuum to obtain 158 g of(4-methylene-3,3-dimethyl-γ-butyrolactone)acrylate of theabove formula (6-25). The yield on the basis of4-hyroyloxymethyl-3,3-dimethyl-γ-butyrolactone was 80%. Synthesis Example 4
[0166] 144.17 g of 4-hydroxymethyl-3,3-dimethyl-γ-butyrolactoneand 121.2 g of triethylamine were dissolved in500 ml of dichloromethane and 115 g of methacryloyl chloridewas slowly dropped into the solution in a water bath. Afterthe addition, the mixture was allowed to cool to roomtemperature, and stirred for 6 hours. Analysis of the reactionsolution by gel chromatography confirmed progress of theesterification reaction. The reaction product was processed inthe same manner as in Synthesis Example 3 to obtain 161 g of(4-methylene-3,3-dimethyl-γ-butyrolactone)methacrylate ofthe formula (6-26). The yield on the basis of4-hyroyloxymethyl-3,3-dimethyl-γ-butyrolactone was 78%. Synthesis Example 5
[0167] A three-necked flask was charged with 99 g of(4-methylene-3,3-dimethyl-γ-butyrolactone)acrylate. Afterreplacing the internal atmosphere of the flask with nitrogen,the flask was heated to about 50°C. 30 ml of previously preparedcyclopentadiene was slowly dropped into the flask in thenitrogen atmosphere while controlling the temperature below80°C. After the addition, the mixture was stirred for 6 hoursat 60°C and allowed to cool to room temperature. Analysis ofthe reaction solution by gel chromatography confirmed that theconversion rate of the addition reaction of(4-methylene-3,3-dimethyl-γ-butyrolactone)acrylate andcyclopentadiene was 80%. The reaction solution was distilledunder vacuum to obtain 90 g of 5-(4'-methylene-3',3'-dimethyl-γ-butyrolactone)oxycarbonylnorbornene.The yield on the basisof (4-methylene-3,3-dimethyl-γ-butyrolactone)acrylate was65%. Synthesis of resin (A1)Synthesis Example 6
[0168] 25 g of 4-methacryloyloxymethyl-γ-butyrolactone, 25 g of2-methacryloyloxy-2-methyladamantane, and 0.7 g of3-mercaptopropionic acid were dissolved in 50 g oftetrahydrofuran to obtain a homogeneous solution. Afterinjection of nitrogen for 30 minutes, 3 g ofazobisisobutyronitrile was added as an initiator. The mixturewas heated to 65°C and stirred for 4 hours at this temperature. After the reaction, the reaction solution was cooled to roomtemperature and diluted with 50 g of tetrahydrofuran. Thediluted solution was poured into 1,000 ml of n-hexane to causethe resin to precipitate. The precipitated resin was filteredand recovered as white resin powder.
[0169] The resulting resin was confirmed to be a copolymer witha copolymerization molar ratio of the recurring unit (i-1) andrecurring unit (i-2), shown in the following formulas (13), of45:55, and having Mw of 7,500. This resin is referred to as a"resin (A-1)".
[0170] 15 g of 4-methacryloyloxymethyl-γ-butyrolactone, 20 g of2-methacryloyloxy-2-methyladamantane, 15 g of1-methacryloyloxy-3-hydroxyadamantine, and 0.7 g of3-mercaptopropionic acid were dissolved in 50 g oftetrahydrofuran to obtain a homogeneous solution. Afterinjection of nitrogen for 30 minutes, 3 g ofazobisisobutyronitrile was added as an initiator. The mixturewas heated to 65°C and stirred for 4 hours at this temperature. After the reaction, the reaction solution was cooled to roomtemperature and diluted with 50 g of tetrahydrofuran. Thediluted solution was poured into 1,000 ml of n-hexane to causethe resin to precipitate. The precipitated resin was filteredand recovered as white resin powder.
[0171] The resulting resin was confirmed to be a copolymer witha copolymerization molar ratio of the recurring unit (ii-1),recurring unit (ii-2), and recurring unit (ii-3), shown in thefollowing formulas (14), of 30:40:30, and having Mw of 8,100.This resin is referred to as a "resin (A-2)".
[0172] 25 g of 4-methacryloyloxymethyl-γ-butyrolactone, 25 g of2-(2'-methacryloyloxy-2'-propyl)norbornane, and 0.7 g of3-mercaptopropionic acid were dissolved in 50 g oftetrahydrofuran to obtain a homogeneous solution. Afterinjection of nitrogen for 30 minutes, 3 g ofazobisisobutyronitrile was added as an initiator. The mixturewas heated to 65°C and stirred for 4 hours at this temperature.After the reaction, the reaction solution was cooled to room temperature and diluted with 50 g of tetrahydrofuran. Thediluted solution was poured into 1,000 ml of n-hexane to causethe resin to precipitate. The precipitated resin was filteredand recovered as white resin powder.
[0173] The resulting resin was confirmed to be a copolymer witha copolymerization molar ratio of the recurring unit (iii-1)and recurring unit (iii-2), shown in the following formulas(15), of 45:55, and having Mw of 8, 900. This resin is referredto as a "resin (A-3)".
[0174] 15 g of 4-methacryloyloxymethyl-γ-butyrolactone, 15 g of2-(2'-methacryloyloxy-2'-propyl)norbornane, 20 g of1-methacryloyloxy-3-hydroxyadamantine, and 0.7 g of3-mercaptopropionic acid were dissolved in 50 g oftetrahydrofuran to obtain a homogeneous solution. Afterinjection of nitrogen for 30 minutes, 3 g ofazobisisobutyronitrile was added as an initiator. The mixturewas heated to 65°C and stirred for 4 hours at this temperature.After the reaction, the reaction solution was cooled to room temperature and diluted with 50 g of tetrahydrofuran. Thediluted solution was poured into 1,000 ml of n-hexane to causethe resin to precipitate. The precipitated resin was filteredand recovered as white resin powder.
[0175] The resulting resin was confirmed to be a copolymer witha copolymerization molar ratio of the recurring unit (iv-1),recurring unit (iv-2), and recurring unit (iv-3), shown in thefollowing formulas (16), of 30:30:40, and having Mw of 9,200.This resin is referred to as a "resin (A-4)".
[0176] 25 g of 4-methacryloyloxymethyl-γ-butyrolactone, 15 g of2-(2'-methacryloyloxy-2'-propyl)norbornane, 5 g ofnorbornene, 5 g of maleic anhydride, and 0.7 g of3-mercaptopropionic acid were dissolved in 50 g oftetrahydrofuran to obtain a homogeneous solution. Afterinjection of nitrogen for 30 minutes, 3 g ofazobisisobutyronitrile was added as an initiator. The mixturewas heated to 65°C and stirred for 4 hours at this temperature.After the reaction, the reaction solution was cooled to room temperature and diluted with 50 g of tetrahydrofuran. Thediluted solution was poured into 1,000 ml of n-hexane to causethe resin to precipitate. The precipitated resin was filteredand recovered as white resin powder. The resulting resin wasconfirmed to be a copolymer with a copolymerization molar ratioof the recurring unit (v-1), recurring unit (v-2), recurringunit (v-3), and recurring unit (v-4), shown in the followingformulas (17), of 40:30:15:15, and having Mw of 7,500. Thisresin is referred to as a "resin (A-5)".
[0177] 15.5 g of 5-[(4'-γ-butyrolactone)methyloxycarbonyl]-norbornene,23 g of 2-methacryloyloxy-2-methyladamantane, 2.5g of norbornene, and 9 g of maleic anhydride were dissolved in50 g of tetrahydrofuran to obtain a homogeneous solution. Afterinjection of nitrogen for 30 minutes, 3 g ofazobisisobutyronitrile was added as an initiator. The mixturewas heated to 65°C and stirred for 4 hours at this temperature.After the reaction, the reaction solution was cooled to room temperature and diluted with 50 g of tetrahydrofuran. Thediluted solution was poured into 1,000 ml of n-hexane to causethe resin to precipitate. The precipitated resin was filteredand recovered as white resin powder.
[0178] The resulting resin was confirmed to be a copolymer witha copolymerization molar ratio of the recurring unit (vi-1),recurring unit (vi-2), recurring unit (vi-3), and recurringunit (vi-4), shown in the following formulas (18), of22:35:10:33, and having Mw of 7,500. This resin is referred toas a "resin (A-6)".
[0179] 15.5 g of 5-[(4'-γ-butyrolactone)methyloxycarbonyl]-norbornene,23 g of 2-(2'-methacryloyloxy-2'-propyl)-norbornane,2.5 g of norbornene, and 9 g of maleic anhydridewere dissolved in 50 g of tetrahydrofuran to obtain ahomogeneous solution. After injection of nitrogen for 30minutes, 3 g of azobisisobutyronitrile was added as aninitiator. The mixture was heated to 65°C and stirred for 4 hours at this temperature. After the reaction, the reactionsolution was cooled to room temperature and diluted with 50 gof tetrahydrofuran. The diluted solution was poured into 1,000ml of n-hexane to cause the resin to precipitate. Theprecipitated resin was filtered and recovered as white resinpowder.
[0180] The resulting resin was confirmed to be a copolymer witha copolymerization molar ratio of the recurring unit (vii-1),recurring unit (vii-2), recurring unit (vii-3), and recurringunit (vii-4), shown in the following formulas (19), of22:35:10:33, and having Mw of 7,800. This resin is referred toas a "resin (A-7)".
[0181] 23.76 g of (4-methylene-3,3-dimethyl-γ-butyrolactone)-methacrylateand 26.24 g of 2-methacryloyloxy-2-methyladamantanewere dissolved in 150 g of tetrahydrofuran innitrogen atmosphere to obtain a homogeneous solution. 4.12 g of dimethyl azobisisobutanoate and 1.35 g of t-dodecylmercaptanwere added to and dissolved in the mixture while stirring. Themixture was then heated to 70°C and stirred for 4 hours. Afterthe reaction, the reaction solution was allowed to cool to roomtemperature and poured into 1,000 g of methanol to cause theresin to precipitate. The precipitated resin was filtered anddried under vacuum to recover the resin as white resin powder.
[0182] The resulting resin was confirmed to be a copolymer witha copolymerization molar ratio of the recurring unit (viii-1)and recurring unit (viii-2), shown in the following formulas(20), of 49.4:50.6, and having Mw of 12,000. This resin isreferred to as a "resin (A-8)".
[0183] 11.56 g of (4-methylene-3,3-dimethyl-γ-butyrolactone)-methacrylate,22.99 g of 2-methacryloyloxy-2-methyladamantane,and 15.45 g of 1-methacryloyloxy-3-hydroxyadamantanewere dissolved in 150 g of tetrahydrofuran innitrogen atmosphere to obtain a homogeneous solution. 4.01 gof dimethyl azobisisobutanoate and 1.31 g of t-dodecylmercaptan were added to and dissolved in the mixture while stirring. Themixture was then heated to 70°C and stirred for 4 hours. Afterthe reaction, the reaction solution was allowed to cool to roomtemperature and poured into 1,000 g of methanol to cause theresin to precipitate. The precipitated resin was filtered anddried under vacuum to recover the resin as white resin powder.
[0184] The resulting resin was confirmed to be a copolymer witha copolymerization molar ratio of the recurring unit (ix-1),recurring unit (ix-2), and recurring unit (ix-3), shown in thefollowing formulas (21), of 24.2:46.3:29.5, and having Mw of11,700. This resin is referred to as a "resin (A-9)".
[0185] 8.63 g of 5-(4'-methylene-3',3'-dimethyl-γ-butyrolactone)oxycarbonylnorbornene,16.00 g of maleicanhydride, and 25.37 g of 5-t-butoxycarbonylnorbornene weredissolved in 50 g of n-butyl acetate in nitrogen atmosphere toobtain a homogeneous solution. 6.01 g of dimethylazobisisobutanoate was added to and dissolved in the mixturewhile stirring. The mixture was then heated to 70°C and stirred for 6 hours. After the reaction, the reaction solution wasallowed to cool to room temperature, diluted with 100 g oftetrahydrofuran. The diluted solution was poured into 1,000g of n-heptane to cause the resin to precipitate. Theprecipitated resin was filtered and dried under vacuum torecover the resin as white resin powder.
[0186] The resulting resin was confirmed to be a copolymer witha copolymerization molar ratio of the recurring unit (x-1),recurring unit (x-2), and recurring unit (x-3), shown in thefollowing formulas (22), of 9.8:50.4:39.8, and having Mw of7,200. This resin is referred to as a "resin (A-10)".
[0187] 8.15 g of 5-(4'-methylene-3',3'-dimethyl-γ-butyrolactone)oxycarbonylnorbornene,13.61 g of maleicanhydride, 20.98 g of 5-t-butoxycarbonylnorbornene, and 7.26g of 2-methacryloyloxy-2-methyladamantine were dissolved in 50g of n-butyl acetate in nitrogen atmosphere to obtain ahomogeneous solution. 5.68 g of dimethyl azobisisobutanoatewas added to and dissolved in the mixture while stirring. The mixture was then heated to 70°C and stirred for 6 hours. Afterthe reaction, the reaction solution was allowed to cool to roomtemperature, diluted with 100 g of tetrahydrofuran. Thediluted solution was poured into 1,000 g of n-heptane to causethe resin to precipitate. The precipitated resin was filteredand dried under vacuum to recover the resin as white resinpowder.
[0188] The resulting resin was confirmed to be a copolymer witha copolymerization molar ratio of the recurring unit (xi-1),recurring unit (xi-2), recurring unit (xi-3), and recurringunit (xi-4), shown in the following formulas (23), of9.6:46.3:34.4:9.7, and having Mw of 7,200. This resin isreferred to as a "resin (A-11)".
[0189] Each composition solution having components shown inTable 1 was evaluated. The evaluation results are shown in Table3.
[0190] Components other than the resins (A-1) to (A-11) shown in Table 1 are as follows. Other resins
[0191] a-1: t-Butyl methacrylate/methyl methacrylate/methacrylicacid copolymer (copolymerization molar ratio =40/40/20, Mw = 20,000) Acid generator (B)
[0192] B-1: Triphenylsulfonium nonafluoro-n-butanesulfonate B-2: Bis(4-t-butylphenyl)iodoniumnonafluoro-n-butanesulfonate B-3: 4-n-Butoxy-1-naphthyltetrahydrothiopheniumnonafluoro-n-butanesulfonate B-4: 4-n-Butoxy-1-naphthyltetrahydrothiopheniumperfluoro-n-octanesulfonate B-5: 4-Hydroxy-3,5-dimethylphenyl-1-tetrahydrothiopheniumnonafluoro-n-butanesulfonate B-6: 4-Hydroxy-3,5-dimethylphenyl-1-tetrahydrothiopheniumperfluoro-n-octanesulfonate B-7: Nonafluoro-n-butanesulfonylbicyclo[2.2.1]-hepto-2-ene-5,6-dicarbodiimide
[0193] C-1: Tri-n-octylamine C-2: Bis(2-dimethylaminoethyl)ether C-3: N-t-butoxycarbonyl-2-phenylbenzimidazole C-4: N-t-butoxycarbonyldicyclohexylamine
[0194] D-1: t-Butyl deoxycholate D-2: t-Butoxycarbonylmethyl deoxycholate D-3: Di-t-butyl 1,3-adamantanedicarboxylate D-4: 2,5-Dimethyl-2,5-di(adamantylcarbonyloxy)hexane
[0195] E-1: 2-Heptanone E-2: Cyclohexanone E-3: Propylene glycol monomethyl ether acetate E-4: γ-Butyrolactone Resin (parts) Acid Generator (B) (parts) Acid Diffusion Control Agent (parts) Other Additives (parts) Solvent (parts) Example 1 A-1 (90) B-1 (2) C-1 (0.05) D-1 (10) E-1 (430) E-2 (100) Example 2 A-2 (90) B-2 (2) C-2 (0.05) D-1 (10) E-1 (430) E-2 (100) Example 3 A-3 (90) B-1 (2) C-2 (0.05) D-1 (10) E-1 (430) E-2 (100) Example 4 A-4 (90) B-2 (2) C-1 (0.05) D-1 (10) E-1 (430) E-2 (100) Example 5 A-5 (90) B-2 (2) C-1 (0.05) D-1 (10) E-1 (430) E-2 (100) Example 6 A-6 (90) B-1 (2) C-2 (0.05) D-1 (10) E-1 (430) E-2 (100) Example 7 A-7 (90) B-2 (2) C-1 (0.05) D-1 (10) E-1 (430) E-2 (100) Example 8 A-8 (100) B-2 (2) C-3 (0.10) - E-1 (430)B-3 (3)E-2 (100) Example 9 A-9 (95) B-4 (3) C-4 (0.10) D-2 (5) E-1 (430)B-5 (2)E-2 (100) Example 10 A-10 (90) B-5 (3) C-3 (0.10) D-3 (10) E-3 (630) B-7 (2) Example 11 A-11 (90) B-6 (3) C-3 (0.08) D-4 (10) E-3 (630) B-7 (3) C-4 (0.02) Comparative Example 1 a-1 (90) B-1 (2) C-1 (0.05) D-1 (10) E-1 (530) Resist Coating Thickness (µm) Substrate PB PEB Temp. (°C) Time (sec) Temp. (°C) Time (sec) Example 1 0.4 ARC 130 90 140 90 Example 2 0.4 ARC 130 90 140 90 Example 3 0.4 ARC 130 90 140 90 Example 4 0.4 ARC 130 90 140 90 Example 5 0.4 ARC 130 90 140 90 Example 6 0.4 ARC 130 90 140 90 Example 7 0.4 ARC 130 90 140 90 Example 8 0.4 ARC 130 90 130 90 Example 9 0.4 ARC 130 90 130 90 Example 10 0.4 ARC 130 90 130 90 Example 11 0.4 ARC 130 90 130 90 Comparative Example 1 0.4 ARC 130 90 140 90 Radiation Transmittance (193nm, %) Sensitivity (J/m²) Resolution (µm) Resolution Defects Pattern Configuration Example 1 75 79 0.15 0 good Example 2 72 76 0.15 0 good Example 3 68 83 0.15 0 good Example 4 70 84 0.15 0 good Example 5 71 72 0.15 0 good Example 6 71 72 0.15 0 good Example 7 69 75 0.15 0 good Example 8 73 82 0.15 0 good Example 9 71 79 0.15 0 good Example 10 68 83 0.15 0 good Example 11 66 81 0.15 0 good Comparative Example 1 62 150 0.15 45 good
[0196] The radiation-sensitive resin composition of the presentinvention is used as a chemically amplified positive tone resistresponsive to short wavelength active radiation, for example, deep ultraviolet rays represented by KrF excimer laser and ArFexcimer laser. The resin composition has high transmittanceof radiation, exhibits superior basic properties as a resistsuch as high sensitivity, resolution, and pattern shape, andis capable of producing semiconductors at a high yield withoutproducing resolution defects during microfabrication. Theresin composition is expected to be an ideal material in thesemiconductor field in which microfabrication technology willfurther advance in the future.
[0197] Obviously, numerous modifications and variations of thepresent invention are possible in light of the above teachings.It is therefore to be understood that, within the scope of theappended claims, the invention may be practiced otherwise thanas specifically described herein.
[0198] A radiation-sensitive resin composition used as achemically amplified positive tone resist responsive to shortwavelength active radiation such as KrF excimer laser and ArFexcimer laser is disclosed. The resin composition comprises:(A) an acid-dissociable group-containing resin which isinsoluble or scarcely soluble in alkali and becomes alkalisoluble when the acid-dissociable group dissociates, the resincomprising a lactone cyclic structure of the following formula(1),
wherein a is an integer from 1-3, b is an integer from 0-9, andR¹ represents a monovalent organic group, and (B) a photoacidgenerator. The composition has high transmittance ofradiation, exhibits high sensitivity, resolution, and patternshape, and can produce semiconductors at a high yield withoutproducing resolution defects during microfabrication.

权利要求:
Claims (10)
[1]
A radiation-sensitive resin composition comprising:
(A) an acid-dissociable group-containing resin which isinsoluble or scarcely soluble in alkali and becomes alkalisoluble when the acid-dissociable group dissociates, the resincomprising a lactone cyclic structure of the following formula(1),
[2]
The radiation sensitive resin composition accordingto claim 1, wherein the resin of component (A) comprises arecurring unit of the following formula (2) and at least oneother recurring unit having an alicyclic hydrocarbon skeletonin the main chain and/or side chain,
[3]
The radiation-sensitive resin compositionaccording to claim 2, wherein the recurring unit of theformula (2) in the resin of component (A) is a recurring unitobtained form an (meth)acrylic acid derivative represented bythe following formulas (6-1), (6-2), (6-25), or (6-26):
[4]
The radiation sensitive resin composition accordingto claim 2, wherein the at least one other recurring unit isselected from the group consisting of the recurring unit of thefollowing formula (8), the recurring unit of the followingformula (9), and the recurring unit of the following formula(10) :
[5]
The radiation sensitive resin composition accordingto claim 1, wherein the resin of component (A) comprises arecurring unit of the following formula (3) and at least oneother recurring unit having an alicyclic hydrocarbon skeletonin the main chain and/or side chain:
[6]
The radiation sensitive resin composition accordingto claim 5, wherein the at least one other recurring unit isselected from the group consisting of the recurring unit of thefollowing formula (8), the recurring unit of the followingformula (9), and the recurring unit of the following formula(10) :
[7]
The radiation-sensitive resin composition accordingto claim 1, further comprising an acid diffusion controller.
[8]
The radiation-sensitive resin composition accordingto claim 7, wherein the acid diffusion controller is anitrogen-containing organic compound.
[9]
The radiation-sensitive resin composition accordingto claim 1, further comprising an alicyclic additive having anacid-dissociating organic group.
[10]
The radiation-sensitive resin composition accordingto claim 1, further comprising at least one solvent selectedfrom the group consisting of a linear or branched ketone, cyclicketone, propylene glycol monoalkyl ether acetate, alkyl2-hydroxypropionate, and alkyl 3-alkoxypropionate.

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TWI246634B|2006-01-01|

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JP4576737B2|2010-11-10|

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优先权:

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申请号 | 申请日 | 专利标题

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JP2000173708||2000-06-09||

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JP2000173708||2000-06-09||

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JP2001095877||2001-03-29||

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JP2001095877A|JP4576737B2|2000-06-09|2001-03-29|Radiation sensitive resin composition|

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