CN100503666C - Hyperbranched polymer, process for producing the same and resist composition containing the hyperbranched polymer - Google Patents

Abstract

A hyperbranched polymer suitable as a polymer material for use in nanofabrication whose leading part is played by photolithography. There is provided a hyperbranched polymer characterized by having at its polymer molecular end an acid decomposable group, such as p-tert-butoxystyrene, bonded to a core moiety formed by living radical polymerization of chloromethylstyrene, etc.

Description

Hyperbranched polymer and manufacture method thereof and the resist composition that contains this hyperbranched polymer

Technical field

It is suitable to the hyperbranched polymer and the manufacture method thereof of macromolecular material that acts on the photoetch method nanometer processing that is the center to the present invention relates to, and contains the resist composition of this hyperbranched polymer as the fine pattern that can form super LSI manufacturing usefulness of the base polymer of anticorrosive additive material.

Technical background

In recent years, for the photoetch method that comes into one's own as Micrometer-Nanometer Processing Technology,, realized that super LSI's is highly integrated owing to the short wavelengthization of light source constantly develops miniaturization.Therefore, in the resist composition, the exploitation of base polymer that each light source is had transparent chemical structure is in continuous development.For example, for KrF excimer laser (wavelength 248nm), proposed to contain with PHS (polycarboxylated styrene) is the resist composition of the polymkeric substance of basic framework, for ArF excimer laser (wavelength 193nm), proposed to contain the resist composition of the polymkeric substance of ester ring type structure, or, proposed to contain the resist composition (with reference to No. 00/17712 communique of WO) of the polymkeric substance of having introduced fluorine atom (perfluor structure) for F2 excimer laser (wavelength 157nm).

But, when using the thinner submicroscopic patterns of the required from now on ratio 50nm of above-mentioned polymer formation, be the concavo-convex problem that more and more becomes of the pattern sidewalls of index with the line edge roughness.At FrancoCerrina, Vac.Sci.Tech.B, 19, point out in 62890 (2001), for the resist in the past based on PMMA (polymethylmethacrylate) and PHS (polycarboxylated styrene) being carried out electron rays, Extreme Ultraviolet (EUV) exposure, the pattern that formation is thinner than 50nm, surface smoothing is controlled at nanometer level becomes problem.

According to Toru Yamaguti, Jpn.J.Appl.Phys., 38,7114 (1999), the concavo-convex of pattern sidewalls is by due to the aggregate of the polymkeric substance that constitutes resist, proposed numerous report for the technology of the elements collection that suppresses polymkeric substance.

For example, at Toru Yamaguti, Jpn.J.Appl.Phys. in 38,7114 (1999), as the means of the surface smoothing that improves eurymeric electron rays resist, has reported that it is effective introducing crosslinking structure in linear polymer.

In addition, as comparing with linear molecule, the example of the branching type polymkeric substance that line edge roughness improves is opened the spy and to be disclosed in the 2000-347412 communique straight chain amphyl main chain branch in conjunction with chain polymkeric substance, but does not reach the formation pattern thinner than 50nm.

In addition, Alexander R.Trimble, Proceedings of SPIE, 3999,1198, the polyester of the branching type that is constituted by the amphyl with carboxyl is disclosed in (2000), but poor to the adherence of substrate.

Show 2000-00516 communique, special table 2000-514479 communique, KrzysztofMatyjaszewski the spy, Macromolecules 29,1079 (1996) and Jean M.J.Frecht, J.Poly.Sci., 36, in 955 (1998), for as becoming the high score branching of the high molecular styrene derivatives of etching method main body, reported that the active free radical polymerization that utilizes 1-chloro-4-methyl-benzene can control the degree of branching, weight-average molecular weight.

But practical situation are up to the present required for resist, and the molecular designing that is used to give the processibility that exposure produces does not still have report, expects its rapid exploitation.

Summary of the invention

The object of the present invention is to provide can with act on the photoetch method be the center nanometer processing polymer materials the manufacture method that makes hyperbranched polymer that surface smoothing and alkali-soluble improve, this hyperbranched polymer, contain the resist composition of this hyperbranched polymer.

In order to solve above-mentioned problem, present inventors have carried out research with keen determination repeatedly, and its result obtains following opinion.That is, find with highly branched (branch) structure to be the hyperbranched polymer that core, molecular end have sour decomposability group, its intermolecular entanglement of seeing in linear polymer is few, compares with the molecular structure that main chain is crosslinked, and the swelling that solvent produces is also little.Its formation that found that the big molecular aggregate that becomes the surfaceness of pattern sidewalls reason is inhibited.Find in addition, hyperbranched polymer is generally spherical-like morphology, if there is sour decomposability group on the sphere polymers surface, in photoetch method, owing to the effect of the acid that is produced by light acid propellant at exposed portion causes decomposition reaction, thereby the generation hydrophilic group, its result can become the structure that has the globular micelle shape of a plurality of hydrophilic groups in the periphery of polymer molecule.It found that, is dissolved in the alkali aqueous solution this polymer high efficiency, is removed with alkaline solution, therefore can form fine pattern, suitable base resin as anticorrosive additive material.

The present invention is that finish on the basis with present inventor's above-mentioned experience.That is, the invention provides a kind of hyperbranched polymer, it is characterized in that: have sour decomposability group at the polymer molecule end.

The present invention also provides a kind of hyperbranched polymer, it is characterized in that: have sour decomposability group in the molecular end that makes styrene derivatives carry out the hyperbranched polymer that living free radical polymerization obtains.

In the present invention, the core in the above-mentioned hyperbranched polymer is a monomeric homopolymer shown in the following formula (1), or monomer shown in the following formula (1) and at least a monomeric multipolymer chosen from following formula (2)～(5).

Structural formula (1)

(in the formula (1), the carbonatoms that Y represents to contain hydroxyl or carboxyl is 1～10 alkylidene group.Z represents halogen atom).

(in formula (2)～(5), R ¹Expression hydrogen atom or carbonatoms are 1～3 alkyl.

R ², R ³Expression hydrogen atom, carbonatoms are that 1～30 straight chain shape, branch-like or cyclic alkyl or carbonatoms are 6～30 aryl, R ², R ³Can be same to each other or different to each other.

R ⁴The expression hydrogen atom; Carbonatoms is 1～40 straight chain shape, branch-like or cyclic alkyl; Trialkylsilkl (wherein the carbonatoms of each alkyl is 1～6); Oxoalkyl group (wherein the carbonatoms of alkyl is 4～20); Or (the R wherein of the group shown in the following formula (6) ⁵For straight chain shape, branch's chain or cyclic carbonatoms are 1～10 alkyl, R ⁶, R ⁷Represent that independently of each other hydrogen atom, straight chain shape, branch's chain or cyclic carbonatoms are 1～10 alkyl, or work as R ⁶, R ⁷When expression straight chain shape or branch's catenate carbonatoms are 1～10 alkyl, can form ring mutually together).N represents 0～10 integer).

The present invention also provides a kind of manufacture method of hyperbranched polymer, it is characterized in that comprising: make the monomer shown in the above-mentioned formula (1) carry out active free radical polymerization separately or make monomer shown in the above-mentioned formula (1) and be selected from above-mentioned formula (2)～at least a kind of monomer of (5) and carry out the operation of active free radical polymerization; By polymkeric substance that obtains in this operation and the compound that contains sour decomposability group are reacted, in this polymkeric substance, introduce the operation of sour decomposability group.

The present invention also provides a kind of manufacture method of hyperbranched polymer, it is characterized in that comprising: make the monomer shown in the following formula (1) carry out living free radical polymerization, the hyperbranched polymer synthesis procedure of synthesis of super branched polymkeric substance; Make this synthetic hyperbranched polymer and the compound reaction that contains sour decomposability group, introduce the sour decomposability group of sour decomposability group at the end of this hyperbranched polymer and introduce operation.

Structural formula (1)

(in the formula (1), the carbonatoms that Y represents to contain hydroxyl or carboxyl is 1～10 alkylidene group.Z represents halogen atom).

The present invention also provides the resist that contains above-mentioned hyperbranched polymer composition.

According to the present invention, the variety of issue that can solve in the past can be provided, can be with the hyperbranched polymer of macromolecular material that acts on the photoetch method nanometer processing that is the center, and the base polymer that contains the corresponding anticorrosive additive material of suitable nano level and electron rays, far ultraviolet rays yue (DUN) and Extreme Ultraviolet (EUV) light source that reaches as the surface smoothing requirement, can form the resist composition of hyperbranched polymer of the fine pattern of super LSI manufacturing usefulness.

According to the present invention, can provide the base polymer of the anticorrosive additive material that makes surface smoothing and alkali-soluble raising.According to the present invention, can also provide light sensitivity, elching resistant, film-forming properties excellence, the base polymer of the anticorrosive additive material that the pollution that metal catalyst etc. produce is few.

Embodiment

(manufacture method of hyperbranched polymer and hyperbranched polymer)

Hyperbranched polymer of the present invention has sour decomposability group at the end of the core segment of highly branched (branch) structure.

Hyperbranched polymer of the present invention has sour decomposability group in the molecular end that makes styrene derivatives carry out the hyperbranched polymer that living free radical polymerization obtains.

Hyperbranched polymer of the present invention can adopt the manufacture method preparation of hyperbranched polymer of the present invention.

The manufacture method of hyperbranched polymer of the present invention comprises the synthesis procedure and the sour decomposability group introducing operation of core, comprises other operations as required.

Below pass through explanation, can make the details of hyperbranched polymer of the present invention become clearer the manufacture method of hyperbranched polymer of the present invention.

The synthesis procedure of-core-

As the monomer of the core that forms hyperbranched polymer of the present invention, if can carry out active free radical polymerization, then there is no particular restriction, can suitably select according to purpose.For example, preferably use the monomer shown in above-mentioned formula (1)～(5).

As the styrene derivatives that can use in the present invention, if can carry out active free radical polymerization, then there is no particular restriction, can suitably select according to purpose.For example, preferably use the monomer shown in the said structure formula (1).

Core in the hyperbranched polymer of the present invention is more preferably monomeric homopolymer shown in the above-mentioned formula (1), or monomer shown in the above-mentioned formula (1) and at least a monomeric multipolymer chosen from following formula (2)～(5).

In the core of hyperbranched polymer of the present invention, monomeric formation molar percentage is 5～100% shown in the above-mentioned formula (1), and is preferred 20～100%, more preferably 50～100%.

In the above-mentioned formula (1), the carbonatoms that Y represents to contain hydroxyl or carboxyl is 1～10, preferred carbonatoms is 1～8, more preferably carbonatoms is 1～6 straight chain shape, branch-like or cyclic alkylidene group, can enumerate for example methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, hexylidene, cyclohexylidene etc. and these groups in conjunction with got involved in the group that forms or these groups-O-,-CO-,-COO-group.Wherein, preferred carbonatoms is 1～8 alkylidene group, and more preferably carbonatoms is 1～8 straight-chain alkyl-sub-, further preferred methylene radical, ethylidene ,-OCH ₂-base ,-OCH ₂CH ₂-base.

Z represents halogen atoms such as fluorine, chlorine, bromine, iodine.Wherein preferred chlorine atom, bromine atoms.

As the monomer shown in the operable above-mentioned formula (1) among the present invention, for example can enumerate 1-chloro-4-methyl-benzene, brooethyl vinylbenzene, right-(1-chloroethyl) vinylbenzene, bromine (4-ethenylphenyl) phenylmethane, 1-bromo-1-(4-ethenylphenyl) propane-2-ketone, 3-bromo-3-(4-ethenylphenyl) propyl alcohol etc.Wherein preferred 1-chloro-4-methyl-benzene, brooethyl vinylbenzene, right-(1-chloroethyl) vinylbenzene.

In above-mentioned formula (2)～(5), R ¹Expression hydrogen atom or carbonatoms are 1～3 alkyl.Wherein preferred hydrogen atom and methyl.

R ², R ³The expression hydrogen atom; Carbonatoms is 1～30, preferably carbonatoms is 1～20, more preferably carbonatoms is 1～10 straight chain shape, branch-like, cyclic alkyl; Or carbonatoms is 6～30, preferred carbonatoms is 6～20, more preferably carbonatoms is 6～10 aryl, R ², R ³Can be same to each other or different to each other.As straight chain shape, branch-like, cyclic alkyl, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, cyclohexyl etc., as aryl, can enumerate phenyl, 4-aminomethyl phenyl, naphthyl etc.Wherein preferred hydrogen atom, methyl, ethyl, phenyl.

R ⁴The expression hydrogen atom; Carbonatoms is 1～40, preferably carbonatoms is 1～30, more preferably carbonatoms is 1～20 straight chain shape, branch-like or cyclic alkyl; Trialkylsilkl (wherein the carbonatoms of each alkyl is 1～6, is preferably 1～4); Oxoalkyl group (wherein the carbonatoms of alkyl is 4～20, is preferably 4～10); Or (the R wherein of the group shown in the above-mentioned formula (6) ⁵The expression hydrogen atom; Or straight chain shape, branch's chain or cyclic carbonatoms are 1～10, preferred carbonatoms is 1～8, more preferably carbonatoms is 1～6 alkyl, R ⁶, R ⁷Represent hydrogen atom independently of each other; Or straight chain shape, branch's chain or cyclic carbonatoms are 1～10, preferred carbonatoms is 1～8, more preferably carbonatoms is 1～6 alkyl, or can form ring mutually together).

At above-mentioned R ⁴In, as straight chain shape, branch-like or cyclic alkyl, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, cyclopentyl, cyclohexyl, suberyl, triethyl カ Le PVC Le base, 1-ethyl norcamphyl, 1-methylcyclohexyl, adamantyl, 2-(2-methyl) adamantyl, tert-pentyl etc.

At above-mentioned R ⁴In, as trialkylsilkl, the carbonatoms that can enumerate each alkyl such as trimethyl silyl, triethylsilyl, dimethyl tertiary butyl silyl is 1～6 group.As oxoalkyl group, can enumerate 3-oxo cyclohexyl etc.

As the group shown in the formula (6), can enumerate 1-methoxy ethyl, 1-ethoxyethyl group, 1-positive propoxy ethyl, 1-isopropoxy ethyl, 1-n-butoxy ethyl, 1-isobutoxy ethyl, 1-sec-butoxy ethyl, 1-tert.-butoxy ethyl, uncle's 1-pentyloxy ethyl, 1-oxyethyl group n-propyl, 1-cyclohexyloxy ethyl, methoxy-propyl, ethoxycarbonyl propyl, 1-methoxyl group-1-methyl-ethyl, 1-oxyethyl group-straight chain shape or branch-like acetal radicals such as 1-methyl-ethyl; Cyclic acetal such as tetrahydrofuran base, THP trtrahydropyranyl base etc., wherein preferred especially ethoxyethyl group, butoxyethyl group, ethoxycarbonyl propyl, THP trtrahydropyranyl.

In the formula (5), n represents 0～10 integer, preferred 0～7 integer, more preferably 0～4 integer.

As the monomer shown in the formula (2), preferred R in formula (2) ¹Be hydrogen atom or methyl, R ²And R ³Be 1～6 the straight chain or the monomer of branch's alkyl for hydrogen atom or carbonatoms independently of each other.As monomeric concrete example shown in the formula (2), can enumerate vinylbenzene, alpha-methyl styrene, vinyl toluene, dimethyl styrene, ethyl styrene, t-butyl styrene, styryl phenyl etc.Wherein optimization styrene, alpha-methyl styrene, vinyl toluene.

As the monomer shown in the formula (3), preferred R in formula (3) ¹Be hydrogen atom or methyl, R ²For hydrogen atom or carbonatoms are 1～6 straight chain or branch's alkyl, R ⁴For hydrogen atom or carbonatoms are that straight chain shape, branch-like, cyclic alkyl, each alkyl of 1～12 are the trialkylsilkl of carbonatoms 1～6 or the group shown in the above-mentioned formula (6) (R wherein ⁵For straight chain shape, branch's chain or cyclic carbonatoms are 1～6 alkyl, R ⁶, R ⁷Represent that separate hydrogen atom or straight chain shape, branch's chain or cyclic carbonatoms are 1～6 alkyl, or mutually combine form ring) monomer.As monomeric concrete example shown in the formula (3), can enumerate hydroxy styrenes, Alpha-Methyl hydroxy styrenes, methoxy styrene, tert.-butoxy vinylbenzene, cyclohexyloxy vinylbenzene, trimethylsiloxy vinylbenzene, 4-(1-methoxy ethoxy) vinylbenzene, 4-(1-ethoxy ethoxy) vinylbenzene, tetrahydro-pyran oxy vinylbenzene etc.Wherein preferred hydroxy styrenes, methoxy styrene, tert.-butoxy vinylbenzene, 4-(1-ethoxy ethoxy) vinylbenzene, tetrahydro-pyran oxy vinylbenzene.

As the monomer shown in the formula (4), preferred R in formula (4) ¹Be hydrogen atom or methyl, R ⁴For hydrogen atom or carbonatoms the group (R wherein of 1～12 straight chain shape, branch-like, cyclic alkyl or above-mentioned formula (6) expression ⁵For straight chain shape, branch's chain or cyclic carbonatoms are 1～6 alkyl, R ⁶, R ⁷Represent that separate hydrogen atom or straight chain shape, branch's chain or cyclic carbonatoms are 1～6 alkyl, or mutually combine form ring) monomer.As monomeric concrete example shown in the formula (4), preferred vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl propenoate, butyl acrylate, tert-butyl acrylate, methacrylic tert-butyl acrylate, vinylformic acid diamantane ester, methacrylic acid diamantane ester, vinylformic acid 2-(2-methyl) diamantane ester, methacrylic acid 2-(2-methyl) diamantane ester etc.Wherein preferred vinylformic acid, methacrylic acid, tert-butyl acrylate, methacrylic tert-butyl acrylate, vinylformic acid 2-(2-methyl) diamantane ester, methacrylic acid 2-(2-methyl) diamantane ester.

As the monomer shown in the formula (5), preferred R in formula (5) ⁴For hydrogen atom or carbonatoms are 1～12 straight chain shape, branch-like, cyclic alkyl, n is 1～5 monomer.As the monomeric concrete example shown in the formula (5), can enumerate the compound shown in the following formula (a1)～(g1):

Deng.Wherein, preferred (a1), (d1), (e1), (g1).

When the core of hyperbranched polymer of the present invention is the monomer shown in the formula (1) and at least a kind of monomeric multipolymer choosing from formula (2)～(5), the amount of above-mentioned formula (1) is preferably 20～90 moles of % in whole monomers of formation core, more preferably 50～80 moles of %.If contain the monomer shown in the formula (1) with this amount, core becomes suppressing the favourable spherical-like morphology of intermolecular entanglement, and is therefore preferred.

The core of hyperbranched polymer of the present invention can carry out active free radical polymerization by making the monomer shown in the above-mentioned formula (1), or at least a kind of monomer that makes above-mentioned formula (1) and be selected from above-mentioned formula (2)～(5) carries out living free radical polymerization and synthesizes.Specifically, by in the chlorobenzene equal solvent, making starting monomer reaction 0.1～30 hour under 0～200 ℃, can make the core of hyperbranched polymer of the present invention usually.

Y-Z key shown in the above-mentioned formula (1) in the monomer by transition metal complex reversibly free radical dissociate, stop by suppressing 2 molecules, active free radical polymerization is carried out.

For example, when using 1-chloro-4-methyl-benzene as the monomer shown in the formula (1), when using copper (I valency) bipyridyl complexes as catalyzer, formation adds adult to chlorine atom in the 1-chloro-4-methyl-benzene as intermediate under the state that copper (I valency) complex compound is oxidized to copper (II valency), break away from side at the chlorine atom and produce methylene radical (with reference to Jean M.J.Frecht, J.Poly.Sci., 36,955 (1998)).

The two key reactions of the ethylenic of this free radical intermediate and other 1-chloro-4-methyl-benzene form 2 aggressiveness shown in the following formula (9).At this moment, the primary carbon (1) that intramolecularly generates, secondary carbon (2) therefore further react with the two keys of the ethylenic of other 1-chloro-4-methyl-benzenes separately owing to have chloro as substituting group.Below carry out polymerization with 1-chloro-4-methyl-benzene one by one in the same manner.

In addition, in 4 aggressiveness shown in the following formula (10), primary carbon (1) and (2), secondary carbon (3) and (4) are owing to have chloro as substituting group, separately further with other the two keys reactions of ethylenic of 1-chloro-4-methyl-benzene.Below similarly react repeatedly, generate highly branched polymer.

If increase the copper complex formazan amount as catalyzer this moment, then the degree of branching further improves.With respect to the monomeric total amount of above-mentioned formula (1) that forms core, the consumption of preferred catalyst is 0.1～60 mole of %, more preferably uses 1～40 mole of %.If use catalyzer with this amount, can obtain to have the hyperbranched polymer core of aftermentioned preferred branched degree.

(9) (2 aggressiveness)

(10) (4 aggressiveness)

Above-mentioned formula (1) can adopt and above-mentioned formula (1) shown in monomeric homopolymerization identical method with the a kind of monomeric multipolymer that is selected from above-mentioned formula (2)～(5) at least, makes by using transition metal complex to carry out active free radical polymerization.

As the monomer of the core segment that constitutes hyperbranched polymer of the present invention,, can also use the monomer in addition of monomer shown in formula (1)～(5) if for to have the structure of free-radical polymerised unsaturated link(age).

As operable comonomer, can enumerate monomer shown below.Compound for example with free-radical polymerised unsaturated link(age) for choosing the styrenic beyond above-mentioned and esters of acrylic acid, methyl acrylic ester and allylic cpd, vinyl ethers, the vinyl ester etc.

As the concrete example of styrenic, can enumerate benzyl vinylbenzene, trifluoromethyl styrene, acetoxy-styrene, chloro-styrene, dichlorostyrene, trichlorobenzene ethene, tetrachlorobenzene ethene, pentachlorobenzene ethene, bromstyrol, Dowspray 9, iodobenzene ethene, fluorobenzene ethene, trifluorostyrene, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene, vinyl naphthalene etc.

Concrete example as esters of acrylic acid, can enumerate vinylformic acid chloroethene ester, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2,2-dimethyl hydroxyl propyl ester, vinylformic acid 5-hydroxyl pentyl ester, trimethylolpropane acrylates, glycidyl acrylate, benzyl acrylate, phenyl acrylate, vinylformic acid naphthalene ester etc.

Concrete example as methyl acrylic ester, can enumerate benzyl methacrylate, methacrylic acid benzyl chloride ester, 2-hydroxyethyl methacrylate, methacrylic acid 4-hydroxyl butyl ester, methacrylic acid 5-hydroxyl pentyl ester, methacrylic acid 2,2-dimethyl-3-hydroxy propyl ester, glycidyl methacrylate, phenyl methacrylate, methacrylic acid naphthalene ester etc.

As the concrete example of allyl ester class, can enumerate allyl acetate, pineapple aldehyde, allyl octanoate, lauric acid allyl ester, palmitinic acid allyl ester, stearic acid allyl ester, phenylformic acid allyl ester, acetoacetic acid allyl ester, lactic acid allyl ester, allyloxyethanol etc.

Concrete example as vinyl ethers, can enumerate the hexyl vinyl ether, the octyl group vinyl ether, decave, the ethylhexyl vinyl ether, the methoxy ethyl vinyl ether, the ethoxyethyl group vinyl ether, the chloroethyl vinyl ether, 1-methyl-2,2-dimethyl propyl vinyl ether, 2-ethyl-butyl vinyl ether, the hydroxyethyl vinyl ether, the glycol ether vinyl ether, the dimethyl aminoethyl vinyl ether, the diethylamino ethyl vinyl ether, butyl amino-ethyl vinyl ether, benzyl vinyl ether, the tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, Vinyl toluene base ether, the vinyl chloride phenyl ether, vinyl-2,4 dichloro benzene base ether, vinyl naphthyl ether, vinyl anthryl ether etc.

As the concrete example of vinyl ester, can enumerate vinyl butyrate, isopropylformic acid vinyl acetate, vinyl trimethylacetic acid ester, vinyl diethylacetic acid ester, valeric acid vinyl acetate, vinyl caproate, vinyl chloroacetate, dichloro acetic acid vinyl acetate, vinyl methoxyacetic acid ester, vinyl butoxy acetic acid ester, vinyl benzene yl acetate, etheric acid vinyl acetate, lactic acid vinyl acetate, vinyl-beta-phenyl butyric ester, vinyl cyclohexane carboxylic acid ester etc.

Optimization styrene class wherein, wherein preferred benzyl vinylbenzene, chloro-styrene, vinyl naphthalene.

In hyperbranched polymer of the present invention, the monomeric formation molar percentage that forms core is 10～90%, and is preferred 20～80%, more preferably 30～70%.If the monomeric formation molar percentage that constitutes core is in this scope, owing to have appropriate hydrophobicity for developing solution, the dissolving of unexposed portion is inhibited, and is therefore preferred.

As the monomer that constitutes core, when using the monomer beyond the monomer shown in above-mentioned formula (1)～(5), monomeric amount shown in above-mentioned formula (1)～(5) is preferably 40～90 moles of % in whole monomers of formation core, more preferably 50～80 moles of %.If use the monomer shown in above-mentioned formula (1)～(5) with this amount, in the spherical-like morphology that keeps core, give functions such as substrate adherence, second-order transition temperature rising, therefore preferred.Monomer shown in core Chinese style (1)～(5) and the monomeric amount outside it can be according to purposes, and the inlet amount ratio during by polymerization is regulated.

-sour decomposability group introducing operation-

In hyperbranched polymer of the present invention, can introduce sour decomposability group in polymer ends by making as mentioned above core that can the synthetic hyperbranched polymer and containing the compound reaction of sour decomposability group.

In the present invention, so-called sour decomposability group is meant the group that decomposes under the effect of acid (preferably utilizing the acidic light acid propellant of luminous energy).Preferably be decomposed into the group of hydrophilic group.As above-mentioned sour decomposability group, the preferred group of from following formula (I)～(IV) and following formula (7), choosing.

Wherein, R ^{1 '}And R ^{2 '}Expression and R ¹And R ²The identical group of record.Wherein preferred hydrogen atom, carbonatoms are 1～3 straight chained alkyl, preferred especially hydrogen atom and methyl.R ⁸The expression hydrogen atom; Carbonatoms is 3～40, preferably carbonatoms is 3～30, more preferably carbonatoms is 3～20 straight chain shape, branch-like or cyclic alkyl; Trialkylsilkl (wherein the carbonatoms of each alkyl is 1～6); Oxoalkyl group (wherein the carbonatoms of alkyl is 4～20); Or the group of above-mentioned formula (6) expression.Wherein preferred carbonatoms is 3～40 straight chain shape or branch-like alkyl, special preferred tertiary alkyl.

At above-mentioned R ⁸In, as straight chain shape, branch-like or cyclic alkyl (preferred tertiary alkyl), can enumerate propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, cyclopentyl, cyclohexyl, suberyl, triethyl カ Le PVC Le base, 1-ethyl norcamphyl, 1-methylcyclohexyl, adamantyl, 2-(2-methyl) adamantyl, tert-pentyl etc.Wherein preferred tertiary butyl, 1-methylcyclohexyl, adamantyl, 2-(2-methyl) adamantyl.

At above-mentioned R ⁸In, as trialkylsilkl, the carbonatoms that can enumerate each alkyl such as trimethyl silyl, triethylsilyl, dimethyl tertiary butyl silyl is 1～6 group.As oxoalkyl group, can enumerate 3-oxo cyclohexyl etc.

R ⁹And R ¹⁰The expression hydrogen atom; Straight chain shape, branch's chain or cyclic carbonatoms are 1～10 alkyl; Or carbonatoms is 6～30 aryl, R ⁹And R ¹⁰Can be same to each other or different to each other, can form ring mutually together.

At above-mentioned R ⁹And R ¹⁰In, as the straight chain shape, branch's chain or cyclic carbonatoms are 1～10 alkyl, carbonatoms is the example of 6～30 aryl, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, cyclopentyl, the 1-methylcyclopentyl, cyclohexyl, the 1-methylcyclohexyl, adamantyl, triethyl カ Le PVC Le base, 1-ethyl norcamphyl, the 1-methylcyclohexyl, adamantyl, 2-(2-methyl) adamantyl, tert-pentyl, phenyl, the 2-aminomethyl phenyl, the 2-isopropyl phenyl, the 2-tert-butyl-phenyl, phenyl methyl, 1-phenylethyl etc.In addition, at above-mentioned R ⁹And R ¹⁰In, as R ⁹And R ¹⁰Form the example of ring together, can enumerate cyclopropane ring, tetramethylene ring, pentamethylene ring, cyclohexane ring etc.Wherein preferable methyl, phenyl, pentamethylene ring, cyclohexane ring etc.

G represents that halogen atom, hydrogen atom, cyano group, straight chain shape, branch's chain or cyclic carbonatoms are that 1～10 alkyl, carbonatoms are 6～30 aryl, alkyl carbonyl oxy (wherein the carbonatoms of alkyl is 1～10), alkoxyl group (wherein the carbonatoms of alkyl is 1～10), phenoxy group, thioether group, amino.Wherein preferred hydrogen atom, halogen atom, alkyl, aryl, alkyl carbonyl oxy, phenoxy group, preferred especially hydrogen atom, chlorine atom, bromine atoms, methyl carbonyl oxygen base, phenyl, phenoxy group.

In above-mentioned G, halogen atom can be enumerated chlorine atom, bromine atoms etc., as alkyl, aryl, can enumerate methyl, ethyl, propyl group, cyclohexyl, allyl group, phenyl etc.In addition, in above-mentioned G,, methyl carbonyl oxygen base, ethyl oxy carbonyl etc. can be enumerated,, methyl thioether group, ethyl thioether base, phenyl thioether group etc. can be enumerated as thioether group as alkyl carbonyl oxy.In addition, in above-mentioned G,, can enumerate methylamino, dimethylamino, trimethylammonium amino, ethylamino, diethylamino, triethyl amino, phenyl amino etc. as amino.Wherein preferred chlorine atom, methyl, phenyl, methyl carbonyl oxygen base, phenyl thioether group, phenyl amino.

In said units (II), m represents 0～10 integer, preferred 0～7 integer, more preferably 0～4 integer.In said units (I)～(IV), a, b, c, d represent the integer more than or equal to 1, preferred 1～20 integer, more preferably 1～10 integer.

In the formula (7), X represents that Sauerstoffatom, sulphur atom, nitrogen-atoms or carbonatoms are 1～6 straight chain shape or branch-like alkyl or interatomic bond.Preferred oxygen atom wherein.W represents that hydrogen atom, carbonatoms are 1～10 straight chain shape, branch's chain or cyclic alkyl; Phenyl; Carbonatoms is that 7～20 alkoxyl phenyl, carbonatoms are 2～10 the alkoxy carbonyl or the group of following formula (8) expression.Wherein, preferred carbonatoms is that 7～20 alkoxyl phenyl, carbonatoms are the group of 2～10 alkoxy carbonyl, following formula (8) expression.

-R ¹¹-COO-R ^{8 '}Formula (8)

In the formula (8), R ¹¹Expression carbonatoms 1～40, preferred carbonatoms 1～30, more preferably straight chain shape, branch-like, cyclic alkylidene group or the carbonatoms of carbonatoms 1～20 are 6～30, preferred carbonatoms is 6～20, more preferably carbonatoms is 6～10 arylidene.R ¹¹Can contain ehter bond or ester bond.R ^{8 '}Represent group same as described above.

In above-mentioned formula (7),, for example can enumerate tert.-butoxy phenyl, right-(1-methoxy ethoxy) phenyl, right-(1-ethoxy ethoxy) phenyl, tetrahydrofuran oxygen base phenyl, tetrahydro-pyran oxy phenyl etc. as alkoxyl phenyl.

In above-mentioned formula (7),, can enumerate for example methoxycarbonyl, ethoxy carbonyl, tert-butoxycarbonyl, cyclohexyl-carbonyl, phenyloxycarbonyl etc. as alkoxy carbonyl.

In above-mentioned formula (8), as R ¹¹, can enumerate methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, cyclopentylidene, cyclohexylidene, phenylene, naphthylidene ,-C ₆H ₄OCH ₂-,-C ₆H ₈OCH ₂-,-C ₆H ₅O-etc.

Therefore, as the group shown in the above-mentioned formula (7), can enumerate tert.-butoxy carbonyl oxygen base, tert-butoxycarbonyl methoxyl group, to tert-butoxycarbonyl methoxyl group phenoxy group, uncle's pentyloxy carbonyl oxygen base, tert-pentyloxy carbonyl methoxyl group, 1-ethoxy ethoxy carbonyl methoxyl group, 2-tetrahydro-pyran oxy carbonyl methoxyl group, 2-tetrahydrofuran oxygen base carbonyl methoxyl group etc.Wherein preferred tertiary butoxy carbonyl methoxyl group, to tert-butoxycarbonyl methoxyl group phenoxy group.

As the concrete example of the compound that contains sour decomposability group, can enumerate the compound shown in the following formula (i)～(iv).Wherein preferred formula (i), the compound shown in (iv).

Wherein, R ^{1 '}, R ^{2 '}, R ⁸, R ⁹, R ¹⁰, m is identical with the content of above definition.

As the concrete example of the compound shown in the formula (i), can enumerate tert-butyl acrylate, the methacrylic tert-butyl acrylate, vinylformic acid 1-methyl cyclohexane ester, methacrylic acid 1-methyl cyclohexane ester, vinylformic acid diamantane ester, methacrylic acid diamantane ester, vinylformic acid 2-(2-methyl) diamantane ester, methacrylic acid 2-(2-methyl) diamantane ester, vinylformic acid triethyl カ Le PVC Le ester, vinylformic acid 1-ethyl norborneol ester, vinylformic acid 1-methyl cyclohexane ester, the vinylformic acid tetrahydropyrans ester, the methacrylic acid tetrahydropyrans ester, vinylformic acid trimethyl silyl ester, vinylformic acid dimethyl tertiary butyl silicomethane ester.Wherein preferred tert-butyl acrylate, methacrylic tert-butyl acrylate, vinylformic acid 2-(2-methyl) diamantane ester, methacrylic acid 2-(2-methyl) diamantane ester, vinylformic acid tetrahydropyrans ester, methacrylic acid tetrahydropyrans ester.

As the concrete example of the compound of formula shown in (ii), can enumerate said structure formula (d1), (g1).Wherein preferred (d1), (g1).

As formula (iii) shown in the concrete example of compound, can enumerate the compound shown in following formula (15)～(17).Wherein preferred (15), (16).

As formula (iv) shown in the concrete example of compound, can enumerate tert.-butoxy vinylbenzene, Alpha-Methyl tert.-butoxy vinylbenzene, 4-(1-methoxy ethoxy) vinylbenzene, 4-(1-ethoxy ethoxy) vinylbenzene, tetrahydro-pyran oxy vinylbenzene, adamantyl oxygen base vinylbenzene, 4-(2-methyl-2-adamantyl oxygen base) vinylbenzene, 4-(1-methyl cyclohexane oxygen base) vinylbenzene, trimethylsiloxy vinylbenzene, dimethyl tertiary butyl siloxy-vinylbenzene, tetrahydro-pyran oxy vinylbenzene.Wherein, preferred tertiary butyl phenyl ether ethene, 4-(1-ethoxy ethoxy) vinylbenzene, tetrahydro-pyran oxy vinylbenzene, 4-(2-methyl-2-adamantyl oxygen base) vinylbenzene.

If have the structure of free-radical polymerised unsaturated link(age), the monomer beyond also can using shown in (I)～(IV) as sour decomposability group.

As operable comonomer, can enumerate monomer shown below.The compound of choosing the styrenic beyond above-mentioned and esters of acrylic acid, methyl acrylic ester and allylic cpd, vinyl ethers, vinyl ester, the crotonate class etc. for example with free-radical polymerised unsaturated link(age).

As the concrete example of styrenic, can enumerate benzyl vinylbenzene, trifluoromethyl styrene, acetoxy-styrene, chloro-styrene, dichlorostyrene, trichlorobenzene ethene, tetrachlorobenzene ethene, pentachlorobenzene ethene, bromstyrol, Dowspray 9, iodobenzene ethene, fluorobenzene ethene, trifluorostyrene, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene, vinyl naphthalene etc.

Concrete example as esters of acrylic acid, can enumerate vinylformic acid chloroethene ester, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2,2-dimethyl hydroxypropyl acrylate, vinylformic acid 5-hydroxyl pentyl ester, trimethylolpropane acrylates, glycidyl acrylate, benzyl acrylate, phenyl acrylate, vinylformic acid naphthalene ester etc.

Concrete example as methyl acrylic ester, can enumerate benzyl methacrylate, methacrylic acid benzyl chloride ester, 2-hydroxyethyl methacrylate, methacrylic acid 4-hydroxyl butyl ester, methacrylic acid 5-hydroxyl pentyl ester, methacrylic acid 2,2-dimethyl-3-hydroxy propyl ester, glycidyl methacrylate, phenyl methacrylate, methacrylic acid naphthalene ester etc.

As the concrete example of allyl ester class, can enumerate allyl acetate, pineapple aldehyde, allyl octanoate, lauric acid allyl ester, palmitinic acid allyl ester, stearic acid allyl ester, phenylformic acid allyl ester, acetoacetic acid allyl ester, lactic acid allyl ester, allyloxyethanol etc.

Concrete example as vinyl ethers, can enumerate the hexyl vinyl ether, the octyl group vinyl ether, decave, the ethylhexyl vinyl ether, the methoxy ethyl vinyl ether, the ethoxyethyl group vinyl ether, the chloroethyl vinyl ether, 1-methyl-2,2-dimethyl propyl vinyl ether, 2-ethyl-butyl vinyl ether, the hydroxyethyl vinyl ether, the glycol ether vinyl ether, the dimethyl aminoethyl vinyl ether, the diethylamino ethyl vinyl ether, butyl amino-ethyl vinyl ether, benzyl vinyl ether, the tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, Vinyl toluene base ether, the vinyl chloride phenyl ether, vinyl-2,4 dichloro benzene base ether, vinyl naphthyl ether, vinyl anthryl ether etc.

As the concrete example of vinyl ester, can enumerate vinyl butyrate, isopropylformic acid vinyl acetate, vinyl trimethylacetic acid ester, vinyl diethylacetic acid ester, valeric acid vinyl acetate, vinyl caproate, vinyl chloroacetate, dichloro acetic acid vinyl acetate, vinyl methoxyacetic acid ester, vinyl butoxy acetic acid ester, vinyl benzene yl acetate, etheric acid vinyl acetate, lactic acid vinyl acetate, vinyl-beta-phenyl butyric ester, vinyl cyclohexane carboxylic acid ester etc.

As the concrete example of crotonate class, can enumerate butyl crotonate, the own ester of Ba Dousuan, glycerine list crotonate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dimethyl maleate, dibutyl fumarate, maleic anhydride, maleimide, vinyl cyanide, methacrylonitrile, Malaysia acyl cyanide etc.

Wherein, optimization styrene class, esters of acrylic acid, methyl acrylic ester, crotonate class, wherein preferred benzyl vinylbenzene, chloro-styrene, vinyl naphthalene, benzyl acrylate, phenyl acrylate, vinylformic acid naphthalene ester, benzyl methacrylate, phenyl methacrylate, methacrylic acid naphthalene ester, butyl crotonate, the own ester of Ba Dousuan, maleic anhydride.

In hyperbranched polymer of the present invention, the formation molar percentage of at least a kind the repeating unit of choosing from the above-mentioned formula (I)～(IV) that forms sour decomposability group is 10～90%, and is preferred 20～80%, more preferably 30～70%.If in this scope, in developing procedure,, exposed portion is removed owing to being dissolved in the alkaline solution efficiently, and therefore preferred.

In hyperbranched polymer of the present invention, the formation molar percentage that forms the group shown in the above-mentioned formula (7) of sour decomposability group is 10～50%, and is preferred 20～50%, more preferably 30～50%.If in this scope, in developing procedure,, exposed portion is removed owing to being dissolved in the alkaline solution efficiently, and therefore preferred.

As sour decomposability group, when the monomer that uses shown in above-mentioned formula (I)～(IV) and the formula (7) in addition, with respect to the whole repeating units that constitute sour decomposability group, repeating unit is preferably 30～90 moles of % shown in above-mentioned formula (I)～(IV) and the formula (7), more preferably 50～70 moles of %.If in this scope, because the alkali dissolution efficiently of exposed portion is not hindered, given functions such as elching resistant, wettability, second-order transition temperature rising, therefore preferred.Amount at repeating unit shown in all acid decomposability group Chinese style (I)～(IV) and the formula (7) and the repeating unit beyond this can be according to purpose, and the inlet amount ratio when utilizing core to introduce is regulated.

Above-mentioned sour decomposability group can by any one or they in following two methods and with introducing.

＜the first method 〉

First method is introduced the method for sour decomposability group shown in (I)～(IV) for using above-mentioned formula (i)～(iv) as the compound that contains sour decomposability group.

As catalyzer, use and the identical transition metal complex catalyst of catalyzer that in the core of hyperbranched polymer is synthetic, uses, copper (I valency) bipyridyl complexes for example, there to be a plurality of halocarbons in above-mentioned core ends serves as to cause point, by addition polymerization is the straight chain shape with the active free radical polymerization of two keys of at least a kind of compound shown in the above-mentioned formula (i)～(iv).Specifically, usually under 0～200 ℃, in the chlorobenzene equal solvent, by making at least a kind of compound reaction shown in core and the above-mentioned formula (i)～(iv) 0.1～30 hour, introduce the sour decomposability group shown in (I)～(IV), can make hyperbranched polymer of the present invention.

As an example, introduce the reaction formula of sour decomposability group shown in reaction formula 1 at the core of the hyperbranched polymer that forms with 1-chloro-4-methyl-benzene.

Reaction formula 1

In the formula, y is the integer more than or equal to 1, and j, k, 1 are respectively the number more than or equal to 1, R ¹And R ⁸As defined above.

The group that G represents in the group shown in above-mentioned (I)～(IV) can be introduced for the known reactions of halocarbon by the sour decomposability group of introducing.

＜the second method 〉

Second method be to use in the following reaction formula 2 A-X-W (wherein, A is for producing the group of negatively charged ion kind, positively charged ion kind, free radical kind by the disengaging of A on X) conduct contains the compound of sour decomposability group, the method for the sour decomposability group shown in can drawing-in system (7).Specifically, usually under-78～150 ℃, in the chlorobenzene equal solvent, by making core and A-X-W reaction 0.5～30 hour, the sour decomposability group shown in the drawing-in system (7) can be made hyperbranched polymer of the present invention.A plurality of halocarbons that can exist with the synthetic core ends are reflecting point, introduce by the known reaction for halocarbon.For example, adopt by the chloro of 1-chloro-4-methyl-benzene synthetic core ends existence and the following substitution reaction of X-W base.

Reaction formula 2-C-Cl+A-X-W →-C-X-W

In above-mentioned reaction formula 2, A is for producing the group of negatively charged ion kind, positively charged ion kind, free radical kind on X by the disengaging of A.

Above-mentioned hyperbranched polymer preferably is made of sour decomposability group shown in the core of monomer shown in monomeric homopolymer shown in the above-mentioned formula (1) or the above-mentioned formula (1) and a kind the multipolymer of choosing from monomer shown in above-mentioned formula (2)～(5) and above-mentioned formula (I), (II), (III) or (7) at least.

Above-mentioned hyperbranched polymer also preferably by the core of monomer shown in monomeric homopolymer shown in the above-mentioned formula (1) or the above-mentioned formula (1) and at least a kind the multipolymer of choosing from monomer shown in above-mentioned formula (2)～(4) and above-mentioned formula (I), (III) or the sour decomposability group (IV) constitute.

Above-mentioned hyperbranched polymer is also preferably by constituting with the core of at least a kind the multipolymer of choosing from monomer shown in above-mentioned formula (2), (4) or (5) and the sour decomposability group shown in the above-mentioned formula (IV).

The introducing of sour decomposability group ratio in the hyperbranched polymer of the present invention, with respect to the number of monomers shown in the above-mentioned formula (1) of the core segment that constitutes hyperbranched polymer, be preferably greater than and equal 0.05, more preferably greater than equaling 0.1, further be preferably greater than and equal 0.15, further be preferably greater than and equal 0.2, further be preferably greater than and equal 0.3, further be preferably greater than and equal 0.5, further be preferably greater than and equal 0.6, preferably smaller or equal to 20, be more preferably less than and equal 15, further preferably smaller or equal to 10, further preferably smaller or equal to 7, further preferably smaller or equal to 5.Preferred 0.05～20, more preferably 0.1～20, further preferred 0.3～20, further preferred 0.3～15, further preferred 0.5～10, most preferably 0.6～5.If in this scope, in developing procedure, can carry out forming the efficient alkali dissolution removal of favourable exposed portion and the dissolving inhibition of unexposed portion for fine pattern, therefore preferred.

In hyperbranched polymer of the present invention, the sour decomposability group that constitutes hyperbranched polymer can convert acidic-groups such as carboxyl or phenol hydroxyl to by using the part decomposition reaction of catalyzer after being incorporated into core.

As the concrete example of above-mentioned catalyzer, can enumerate acid catalysts such as hydrochloric acid, sulfuric acid, phosphoric acid, bromination hydracid, tosic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, formic acid, or alkaline catalystss such as sodium hydroxide, potassium hydroxide.Preferred acid catalyzer, more preferably hydrochloric acid, tosic acid, acetic acid, trifluoroacetic acid, formic acid.

Forming being selected from least a kind of repeating unit in the above-mentioned formula (I)～(IV) of sour decomposability group, has R in the hyperbranched polymer of the present invention ⁸For the formation molar percentage of the repeating unit of the acidic-group of hydrogen atom is 0～70%, preferred 0～60%, more preferably 0～50%.If it is in this scope, favourable for the ISOization of resist in the exposure process, therefore preferred.

In the above-mentioned formula (7) that forms sour decomposability group, R in the hyperbranched polymer of the present invention ⁸For the formation molar percentage of the group of hydrogen atom is 0～40%, preferred 0～30%, more preferably 0～20%.If it is in this scope, favourable for the ISOization of resist under the situation that the dissolving that does not hinder unexposed portion suppresses, therefore preferred.

Here, the introducing of above-mentioned sour decomposability group ratio is by measuring resultant ¹H-NMR calculates with respect to monomeric molar ratio computing shown in the above-mentioned formula (1) with the integrated value of the proton of feature in the sour decomposability group, or use following mathematical expression (a)～(c) any one calculate.

$R=\frac{\mathrm{Cm}\×(\mathrm{AW}-\mathrm{CW})}{\mathrm{CW}\×\mathrm{Am}}$ Mathematical expression (a)

$R=\frac{\mathrm{Cm}\×(\mathrm{BW}-\mathrm{CW})}{\mathrm{CW}\×(\mathrm{Bm}-X-1)}$ Mathematical expression (b)

$R=\frac{s}{r}+\frac{\{r\×\mathrm{Cm}+(100-r-s)\×\mathrm{Dm}+s\×\mathrm{Em}\}\×(\mathrm{AW}-\mathrm{CW})}{r\×\mathrm{Am}\×\mathrm{CW}}$ Mathematical expression (c)

R: sour decomposability group is with respect to the monomeric introducing mol ratio shown in the formula 1 that constitutes core segment

Am: monomeric molecular-weight average with sour decomposability group

Bm: the molecular-weight average of molecule with sour decomposability group of dehalogenation

Cm: the monomeric molecular-weight average shown in the formula 1 of formation core segment

Dm: constitute beyond the formula 1 of core segment and the monomeric molecular-weight average of anacidity decomposability group

Bm: constitute core segment and have the monomeric molecular-weight average of sour decomposability group

AW: the weight-average molecular weight of having introduced the hyperbranched polymer of sour decomposability group

BW: the weight-average molecular weight of the hyperbranched polymer of dehalogenation

CW: the weight-average molecular weight of core segment

X: the nucleidic mass of the halogen that in the monomer that constitutes core segment, exists

R: monomeric mole % shown in the formula 1 of formation core segment

S: constitute core segment and have the monomeric mole % of sour decomposability group

The degree of branching of core (Br) is preferably 0.1～0.9 in the above-mentioned hyperbranched polymer, and more preferably 0.3～0.7, more preferably 0.4～0.5, most preferably be 0.5.If the degree of branching of core segment is in this scope, the entanglement between polymer molecule is few, and the surfaceness of pattern sidewalls is suppressed, and is therefore preferred.

Here, the above-mentioned degree of branching can be passed through the mensuration resultant ¹H-NMR, as described below trying to achieve.That is, use occurs at the 4.6ppm place-CH ₂Than H2 °, (A) calculates the integration of the proton at Cl position by following mathematical expression than the integration of the proton at H1 ° and the CHCl position that occurs at the 4.8ppm place.If-CH ₂Cl position and CHCl position both carry out polymerization, and branching improves, and then the Br value is near 0.5.

Mathematical expression (A)

The weight-average molecular weight of core is preferably 300～100000 in the hyperbranched polymer of the present invention, and is also preferred 500～80000, and more preferably 1000～100000, further preferred 1000～50000, most preferably 5000～50000.If the molecular weight of core is in this scope, core becomes spherical-like morphology, and introduces the solvability that can guarantee in the reaction in reaction solvent at sour decomposability group, and is therefore preferred.Film-forming properties excellence in addition is in the core of above-mentioned molecular weight ranges has been derived the hyperbranched polymer of sour decomposability group, favourable for the dissolving that suppresses unexposed portion, therefore preferred.

The weight-average molecular weight of hyperbranched polymer of the present invention (Mw) is preferred 500～150000, and more preferably 2000～150000, further preferred 1000～100000, further preferred 2000～60000, most preferably 6000～60000.The resist that contains the hyperbranched polymer of above-mentioned weight-average molecular weight less than 500, film-forming properties is poor, can not be applied on the substrate, the intensity of the processing graphic pattern that forms in the etching procedure is low and can not keep shape sometimes, and elching resistant reduces sometimes in etching work procedure.If above-mentioned weight-average molecular weight less than 2000, the intensity of processing graphic pattern is low, can't keep shape sometimes, if surpass 150000, the size of polymer molecule can produce detrimentally affect to surfaceness sometimes.

Here, above-mentioned weight-average molecular weight (Mw) can be carried out GPC and measure and try to achieve by the tetrahydrofuran solution of modulation 0.05 weight % under 40 ℃ of temperature.Can use tetrahydrofuran (THF) as mobile solvent, use vinylbenzene as reference material.

If use transition metal complex as the synthetic hyperbranched polymer of the present invention of catalyzer, the hyperbranched polymer that obtains contains transition metal sometimes.Its amount also kind, the amount because of the catalyzer that uses is different, and the amount with 5～7ppm is contained in the hyperbranched polymer usually.At this moment, preferably the metal from catalyzer that contains in the hyperbranched polymer of the present invention is removed, made its amount reach not enough 100ppb, preferred not enough 80ppb, more preferably not enough 60ppb.If the amount of metal from catalyzer is more than the 100ppb, the metallic element that irradiates light is sneaked in exposure process absorbs and the resist light sensitivity is reduced, and it is unfavorable sometimes turnout to be produced.And then adopting O ₂Plasmas etc. carry out in the operation that resist that dry type polishing handled dry-etching removes, and the metallic element of sneaking into adheres to by plasma or is diffused on the substrate, and it is various unfavorable to bring sometimes in back operation.The metallic element amount can be measured with ICPMAS (for example Hitachi's system P-6000 type MIP-MS).As the means of removing, can enumerate and for example use ion-exchange membrane (for example Japanese マ イ Network ロ リ ス (strain) system, プ ロ テ go CP) and メ Application Block レ Application film (for example ミ リ Port ァ society system, ミ リ Port ァ Off イ Le -) separately or also with carrying out filtering means.Can pressurize during filtration, if for example make the flow velocity of polymers soln reach 0.5～10ml/ branch, because favourable to the metallic element removal effect, therefore preferred.

The solvability of hyperbranched polymer of the present invention in alkali aqueous solution for example can be by using the electron rays describing device, for the part irradiation 50～5000mJ/cm of the prescribed level of the test portion film of film forming specific thickness on silicon chip ²Electron rays, perhaps use discharge tubular type UV irradiation equipment, be 0～200mJ/cm for the part illumination wavelength 245nm energy of the prescribed level of the test portion film of film forming specific thickness on silicon chip ²Ultraviolet ray, it be impregnated in the alkali aqueous solution, with the washing of digital micro-analysis sem observation, dried state, perhaps measure washing, dried thickness with the made membrane determinator, estimate.

The surfaceness of plane of exposure for example can be measured according to the method for rapids refined husband, No. 2475, academic dissertation of Waseda University's examination, " about nanostructure instrumentation and its research of using in device-technology of adopting atomic force microscope ", pp99-107 (1996) record forever.Specifically, use electron rays describing device or discharge tubular type UV irradiation equipment, measure for 30% the surface that in above-mentioned alkali aqueous solution, demonstrates deliquescent electron rays or ultraviolet exposure amount.Evaluation test portion for adopting the method identical with the deliquescent record in alkali aqueous solution to make can use atomic force microscope, according to the acquiring method mensuration as 10 mean roughness of the JIS B0601-1994 of the index of surfaceness.

Adopt hyperbranched polymer of the present invention that the manufacture method of hyperbranched polymer of the present invention obtains owing to have the structure of highly branched (branch) at core, therefore the intermolecular entanglement that can see in the wire polymer is few, and compare with the molecular structure that main chain is crosslinked, the swelling that solvent produces is also little, and the formation of big molecular aggregate that therefore becomes the reason of surfaceness is inhibited.In addition, because hyperbranched polymer of the present invention has sour decomposability group in molecular end, therefore in photoetch method, owing to the effect of the acid that is produced by light acid propellant at exposed portion produces decomposition reaction, produce hydrophilic group, consequently become the structure that the molecule periphery has the micellelike of a plurality of hydrophilic groups, can be dissolved in efficiently in the alkali aqueous solution, form fine pattern, can be advantageously used for the base resin of following resist composition.

(resist composition)

Resist composition of the present invention contains the hyperbranched polymer of the invention described above at least, acid diffusion inhibitor (sour trapping agent), tensio-active agent, other compositions and the solvent that can contain light acid propellant and contain as required.

The use level of the hyperbranched polymer of the invention described above is preferably 4～40 weight % with respect to the total amount of resist composition, more preferably 4～20 weight %.

As above-mentioned light acid propellant, if utilize the irradiation of ultraviolet ray, X ray, electron rays etc. to produce acid, then there is no particular restriction, can from known light acid propellant, suitably select, can enumerate for example salt, sulfonium salt, the triaizine compounds that contains halogen, sulphones, sulfonate compound, aromatic sulphonic acid ester cpds, the imido sulfonate compound of N-hydroxyl etc. according to purpose.

As above-mentioned salt, can enumerate for example diaryl group iodized salt, triaryl

Salt, triarylsulfonium salt etc.As above-mentioned diaryl group iodized salt, can enumerate for example phenylbenzene iodine fluoroform sulphonate, 4-p-methoxy-phenyl phenyl-iodide hexafluoro antimonate, 4-p-methoxy-phenyl phenyl-iodide fluoroform sulphonate, two (4-tert-butyl-phenyl) iodine a tetrafluoro borate, two (4-tert-butyl-phenyl) iodine hexafluorophosphate, two (4-tert-butyl-phenyl) iodine hexafluoro antimonate, two (4-tert-butyl-phenyl) iodine fluoroform sulphonate etc.As above-mentioned triaryl

Salt can be enumerated for example triphenyl

Liu Fu phosphonium salt, triphenyl

Fluoroborate, triphenyl

Hexafluoro antimonate etc.As above-mentioned triarylsulfonium salt, can enumerate for example triphenylsulfonium six fluorine phosphonium salts, triphenylsulfonium hexafluoro antimonate, phenylbenzene-4-sulfo-Phenoxyphenyl sulfonium hexafluoro antimonate, phenylbenzene-4-sulfo-Phenoxyphenyl sulfonium five fluorine hydroxyl stibnates etc.

As above-mentioned sulfonium salt; can enumerate for example triphenylsulfonium hexafluorophosphate; the triphenylsulfonium hexafluoro antimonate; the triphenylsulfonium fluoroform sulphonate; 4-p-methoxy-phenyl phenylbenzene sulfonium hexafluoro antimonate; 4-p-methoxy-phenyl phenylbenzene sulfonium fluoroform sulphonate; p-methylphenyl phenylbenzene sulfonium fluoroform sulphonate; 2; 4,6-trimethylphenyl phenylbenzene sulfonium fluoroform sulphonate; 4-tert-butyl-phenyl phenylbenzene sulfonium fluoroform sulphonate; 4-phenyl thio-phenyl phenylbenzene sulfonium hexafluorophosphate; 4-phenyl thio-phenyl phenylbenzene sulfonium hexafluoro antimonate; 1-(2-naphthoyl methyl) チ オ ラ ニ ウ system hexafluoro antimonate; 1-(2-naphthoyl methyl) チ オ ラ ニ ウ system fluoroform sulphonate; 4-hydroxyl-1-naphthyl dimethyl sulfonium hexafluoro antimonate; 4-hydroxyl-1-naphthyl dimethyl sulfonium fluoroform sulphonate etc.

As the above-mentioned triaizine compounds that contains halogen, can enumerate for example 2-methyl-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2,4,6-three (trichloromethyl)-1,3, the 5-triazine, 2-phenyl-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-chloro-phenyl-)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-p-methoxy-phenyl)-4,6-two (trichloromethyl)-1,3,5-triazines, 2-(4-methoxyl group-1-naphthyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(benzo [d] [1,3] dioxolane-5-yl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-methoxyl-styrene)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(3,4,5-trimethoxy styryl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(3, the 4-dimethoxy-styryl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(2, the 4-dimethoxy-styryl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(2-methoxyl-styrene)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-butyl phenyl ether vinyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-amyl phenyl ether vinyl)-4,6-two (trichloromethyl)-1,3,5-triazines etc.

As above-mentioned sulphones; for example can enumerate diphenyl disulfoxide, two pairs of toluene two sulfones, two (phenyl sulfonyl) diazomethane, two (4-chloro-phenyl-alkylsulfonyl) diazomethane, two (p-methylphenyl alkylsulfonyl) diazomethane, two (4-tert-butyl-phenyl alkylsulfonyl) diazomethane, two (2,4-xylyl alkylsulfonyl) diazomethane, two (cyclohexyl alkylsulfonyl) diazomethane, (benzoyl) (phenyl sulfonyl) diazomethane, phenyl sulfonyl methyl phenyl ketone etc.

As above-mentioned aromatic sulphonic acid ester cpds; can enumerate for example α-benzoyl benzyl p-toluenesulfonic esters (common name benzoin tosylate), β-benzoyl-beta-hydroxyphenyl ethyl p-toluenesulfonic esters (common name alpha-hydroxymethyl benzoin tosylate), 1; 2; 3-benzene three basic three methanesulfonates, 2,6-dinitrobenzene benzyl p-toluenesulfonic esters, 2-nitrobenzyl p-toluenesulfonic esters, 4-nitrobenzyl p-toluenesulfonic esters etc.

As the imido sulfonate compound of above-mentioned N-hydroxyl, can enumerate for example N-(phenyl sulfonyloxy) succinimide, N-(trifluoromethyl sulfonyloxy) succinimide, N-(rubigan sulfonyloxy) succinimide, N-(cyclohexyl sulfonyloxy) succinimide, N-(1-naphthyl sulfonyloxy) succinimide, N-(benzyl sulfonyloxy) succinimide, N-(10-camphor sulfonyloxy) succinimide, N-(trifluoromethyl sulfonyloxy) phthalic imidine, N-(trifluoromethyl sulfonyloxy)-5-norbornylene-2,3-dicarboxyl imide, N-(trifluoromethyl sulfonyloxy) naphthalimide, N-(10-camphor sulfonyloxy) naphthalimide etc.

As above-mentioned light acid propellant, preferred sulfonium salt, particularly triphenylsulfonium fluoroform sulphonate; Sulphones, particularly two (4-tert-butyl-phenyl alkylsulfonyl) diazomethane, two (cyclohexyl alkylsulfonyl) diazomethanes.

Above-mentioned light acid propellant can separately or mix more than 2 kinds and use.There is no particular restriction as the use level of above-mentioned light acid propellant, can suitably select according to purpose, with respect to hyperbranched polymer 100 weight parts of the invention described above, preferred 0.1～30 weight part, more preferably 0.1～10 weight part.

In addition, as above-mentioned acid diffusion inhibitor, if have the diffusion phenomena of acid in the resist tunicle that control produces from acid-producing agent by exposure, have and suppress in the territory, non-exposed area the not composition of the effect of preferred chemical reaction, then there is no particular restriction, can from known material, suitably select, can enumerate the nitrogenous compound that for example same intramolecularly has 1 nitrogen-atoms according to purpose, same intramolecularly has the compound of 2 nitrogen-atoms, polyamine compounds or polymkeric substance with 3 above nitrogen-atoms, the compound that contains amido, carbamide compound, nitrogen-containing heterocycle compound etc.

Have the nitrogenous compound of 1 nitrogen-atoms as above-mentioned at same intramolecularly, can enumerate for example single (ring) alkylamine, two (ring) alkylamine, three (ring) alkylamine, aromatic amine etc.As above-mentioned list (ring) alkylamine, can enumerate for example normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, hexahydroaniline etc.As above-mentioned two (ring) alkylamine, can enumerate for example Di-n-Butyl Amine, two n-amylamines, two normal hexyl Amines, two positive heptyl amices, two n-octyl amine, two positive nonyl amines, two n-Decylamines, cyclohexyl methyl amine etc.As above-mentioned three (ring) alkylamine, can enumerate triethylamine, Tri-n-Propylamine, tri-n-butylamine, tri-n-amyl amine, three normal hexyl Amines, three positive heptyl amices, tri-n-octyl amine, tri-n-nonylamine, three n-Decylamines, cyclohexyl dimethyl amine, methyl bicyclic hexyl amine, tricyclohexyltin amine etc.As above-mentioned aromatic amine, can enumerate for example aniline, methylphenylamine, N, accelerine, 2-aminotoluene, 3-monomethylaniline, 4-monomethylaniline, 4-N-methyl-p-nitroaniline, pentanoic, triphenylamine, naphthylamines etc.

As the above-mentioned nitrogenous compound that has 2 nitrogen-atoms at same intramolecularly, can enumerate for example quadrol, N, N, N ', N '-Tetramethyl Ethylene Diamine, tetramethylene-diamine, hexamethylene-diamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 4,4 '-diamino benzophenone, 4,4 '-diamino-diphenyl amine, 2,2-two (4-aminophenyl) propane, 2-(3-aminophenyl)-2-(4-aminophenyl) propane, 2-(4-aminophenyl)-2-(3-hydroxy phenyl) propane, 2-(4-aminophenyl)-2-(4-hydroxy phenyl) propane, 1,4-two [1-(4-aminophenyl)-1-methylethyl] benzene, 1,3-two [1-(4-aminophenyl)-1-methylethyl] benzene, two (2-dimethyl aminoethyl) ether, two (2-diethylamino ethyl) ether etc.

As above-mentioned polyamine compounds or polymkeric substance, can enumerate polymkeric substance of for example polymine, polyallylamine, N-(2-dimethyl aminoethyl) acrylamide etc. with 3 above nitrogen-atoms.

As the above-mentioned compound that contains amido, can enumerate for example N-tert-butoxycarbonyl two n-octyl amine, N-tert-butoxycarbonyl two positive nonyl amines, N-tert-butoxycarbonyl two n-Decylamines, N-tert-butoxycarbonyl dicyclohexyl amine, N-tert-butoxycarbonyl-1-adamantanamines, N-tert-butoxycarbonyl-N-methyl isophthalic acid-adamantanamines, N, N-two tert-butoxycarbonyls-1-adamantanamines, N, N-two tert-butoxycarbonyls-N-methyl isophthalic acid-adamantanamines, N-tert-butoxycarbonyl-4,4 '-diaminodiphenyl-methane, N, N '-two tert-butoxycarbonyl hexamethylene-diamine, N, N, N ', N '-four tert-butoxycarbonyl hexamethylene-diamine, N, N '-two tert-butoxycarbonyl-1,7-diamino heptane, N, N '-two tert-butoxycarbonyl-1,8-diamino octane, N, N '-two tert-butoxycarbonyl-1,9-diamino nonane, N, N '-two tert-butoxycarbonyl-1, the 10-diamino decane, N, N '-two tert-butoxycarbonyl-1,12-diamino dodecane, N, N '-two tert-butoxycarbonyl-4,4 '-diaminodiphenyl-methane, N-tert-butoxycarbonyl benzoglyoxaline, N-tert-butoxycarbonyl-2-tolimidazole, N-tert-butoxycarbonyl-2-Phenylbenzimidazole, methane amide, the N-methylformamide, N, dinethylformamide, ethanamide, the N-methylacetamide, N,N-dimethylacetamide, propionic acid amide, benzamide, pyrrolidone, N-Methyl pyrrolidone etc.

As above-mentioned carbamide compound, can enumerate for example urea, methylurea, 1,1-dimethyl urea, 1,3-dimethyl urea, 1,1,3,3-tetramethyl-urea, 1,3-diphenyl urea, three normal-butyl thiocarbamides etc.

As above-mentioned nitrogen-containing heterocycle compound, can enumerate for example imidazoles, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzoglyoxaline, 2-Phenylbenzimidazole, pyridine, the 2-picoline, the 4-picoline, the 2-ethylpyridine, the 4-ethylpyridine, the 2-phenylpyridine, the 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, niacinamide, quinoline, the 4-hydroxyquinoline, oxine, acridine, piperazine, 1-(2-hydroxyethyl) piperazine, pyrazine, pyrazoles, pyridazine, quinoxaline, purine, tetramethyleneimine, piperidines, 3-piperidines-1, the 2-propylene glycol, morpholine, the 4-methylmorpholine, 1, the 4-lupetazin, 1,4-diazabicyclo [2.2.2] octane etc.

Above-mentioned acid diffusion inhibitor can separately or mix more than 2 kinds and use.As the use level of above-mentioned acid diffusion inhibitor, there is no particular restriction, can suitably select according to purpose, with respect to above-mentioned light acid propellant 100 weight parts, preferred 0.1～1000 weight part, more preferably 0.5～10 weight part.

In addition, as above-mentioned tensio-active agent, if demonstrate the composition that coating, striped, development etc. is had the improvement effect, then there is no particular restriction, can suitably select according to purpose from known material, for example can enumerating, the nonionic of Voranol EP 2001, polyxyethylated allyl ethers, sorbitan fatty(acid)ester, polyoxyethylene sorbitan fatty acid ester is that tensio-active agent, fluorine are that tensio-active agent, silicon are tensio-active agent etc.

As above-mentioned Voranol EP 2001, can enumerate for example polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether etc.As above-mentioned polyxyethylated allyl ethers, can enumerate for example polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether etc.As above-mentioned sorbitan fatty(acid)ester, can enumerate for example Span 20, sorbitan-monopalmityl ester, anhydrosorbitol monostearate, dehydrating sorbitol monooleate, anhydrosorbitol trioleate, anhydrosorbitol tristearate etc.Nonionic as above-mentioned polyoxyethylene sorbitan fatty acid ester is a tensio-active agent, can enumerate for example polyoxyethylene sorbitan mono-laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate etc.As above-mentioned fluorine is tensio-active agent, can enumerate for example エ Off ト ッ プ EF301, EF303, EF352 (new autumn fields changes into (strain) system), メ ガ Off ァ ッ Network F171, F173, F176, F189, R08 (big Japanese ink chemical industry (strain) system), Off ロ ラ-De FC430, FC431 (Sumitomo ス リ-worker's system (strain) system), ァ サ ヒ ガ-De AG710, サ-Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass (strain) system) etc.As above-mentioned silicon is tensio-active agent, can enumerate for example organosiloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system) etc.

Above-mentioned tensio-active agent can separately or mix more than 2 kinds and use.There is no particular restriction as the use level of above-mentioned tensio-active agent, can suitably select according to purpose, with respect to hyperbranched polymer 100 weight parts of the invention described above, preferred 0.0001～5 weight part, more preferably 0.0002～2 weight part.

As above-mentioned other compositions, can enumerate sensitizing agent for example, dissolve control agent, have additive, alkali soluble resin, dyestuff, pigment, bonding auxiliary agent, defoamer, stablizer, anti-clouding agent of acid dissociation group etc.

As above-mentioned sensitizing agent, if demonstrate the energy that absorbs radioactive rays, give light acid propellant with this transmission ofenergy, thereby the effect that the growing amount that makes acid increases, material with the apparent light sensitivity raising effect that makes the resist composition, then there is no particular restriction, for example can enumerate acetophenones, Benzophenones, naphthalene class, biacetyl, eosin, rose-red, pyrene class, anthracene class, phenothiazines etc.These sensitizing agents can separately or mix more than 2 kinds and use.

As above-mentioned dissolving control agent, if the material of the better control of dissolving contrast gradient when becoming resist and dissolution rate, then there is no particular restriction, can enumerate for example polyketone, poly-spiroketal etc.These dissolving control agents can separately or mix more than 2 kinds and use.

As above-mentioned additive with acid dissociation group, if to anti-dry etching, pattern form, the further materials that improve such as cementability with substrate, then there is no particular restriction, can enumerate for example 1-adamantanecarboxylic acid tert-butyl ester, 1-adamantanecarboxylic acid tert-butoxycarbonyl methyl esters, 1,3-adamantane acid di tert butyl carbonate, the 1-adamantane acetic acid tert-butyl ester, 1-adamantane acetic acid tert-butoxycarbonyl methyl esters, 1,3-diamantane oxalic acid di tert butyl carbonate, the Septochol tert-butyl ester, Septochol tert-butoxycarbonyl methyl esters, Septochol 2-ethoxy ethyl ester, Septochol 2-cyclohexyloxy ethyl ester, Septochol 3-oxo cyclohexyl, the Septochol tetrahydropyrans ester, Septochol メ バ ロ ノ ラ Network ト Application ester, the lithocholic acid tert-butyl ester, lithocholic acid tert-butoxycarbonyl methyl esters, lithocholic acid 2-ethoxy ethyl ester, lithocholic acid 2-cyclohexyloxy ethyl ester, lithocholic acid 3-oxo cyclohexyl, the lithocholic acid tetrahydropyrans ester, lithocholic acid メ バ ロ ノ ラ Network ト Application ester etc.These dissolving control agents can separately or mix more than 2 kinds and use.

As above-mentioned alkali soluble resin, if the material that the alkali-soluble of resist composition of the present invention is improved, then there is no particular restriction, can enumerate for example poly-(4-hydroxy styrenes), partial hydrogenation poly-(4-hydroxy styrenes), poly-(3-hydroxy styrenes), poly-(3-hydroxy styrenes), 4-hydroxy styrenes/3-hydroxy styrenes multipolymer, 4-hydroxy styrenes/styrol copolymer, novolac resin, polyvinyl alcohol, polyacrylic acid etc., Mw is generally 1000-1000000, is preferably 2000-100000.These alkali soluble resins can separately or mix more than 2 kinds and use.

Above-mentioned dyestuff or pigment can make the sub-image of exposed portion visual, and the influence of the halation when making exposure relaxes.In addition, above-mentioned bonding auxiliary agent can improve the cementability with substrate.

As above-mentioned solvent, as long as can dissolve mentioned component etc., there is no particular restriction, can from the solvent can being used safely in the resist composition, suitably select, can enumerate for example ketone, cyclic ketone, propylene-glycol monoalky lether acetic ester, 2 hydroxy propanoic acid alkyl ester, 3-alkoxypropan acid alkyl ester, other solvents etc.

As above-mentioned ketone, can enumerate for example methyl iso-butyl ketone (MIBK), methyl ethyl ketone, 2-butanone, 2 pentanone, 3-methyl-2-butanone, methyl-n-butyl ketone, 4-methyl-2 pentanone, 3-methyl-2 pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, methyln-hexyl ketone etc.As above-mentioned cyclic ketone, can enumerate for example pimelinketone, cyclopentanone, 3-methyl-cyclopentanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanon, isophorone etc.As above-mentioned propylene-glycol monoalky lether acetic ester, can enumerate for example propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol list positive propyl ether acetic ester, propylene glycol list isopropyl ether acetic ester, propylene glycol mono-n-butyl ether acetic ester, propylene glycol list ethyl isobutyl ether acetic ester, the secondary butyl ether acetic ester of propylene glycol list, propylene glycol list uncle butyl ether acetic ester etc.As above-mentioned 2 hydroxy propanoic acid alkyl ester, can enumerate for example 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2 hydroxy propanoic acid n-propyl, 2 hydroxy propanoic acid isopropyl ester, the positive butyl ester of 2 hydroxy propanoic acid, 2 hydroxy propanoic acid isobutyl ester, the secondary butyl ester of 2 hydroxy propanoic acid, the 2 hydroxy propanoic acid tert-butyl ester etc.As above-mentioned 3-alkoxypropan acid alkyl ester, can enumerate for example 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate etc.

As above-mentioned other solvent, can enumerate for example n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, hexalin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diglyme, diethyl carbitol, the glycol ether di-n-propyl ether, the glycol ether di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, the ethylene glycol propyl ether acetic ester, propylene glycol, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, 2-hydroxy-2-methyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl-butyrate, 3-methoxyl group butylacetic acid ester, 3-methyl-3-methoxyl group butylacetic acid ester, 3-methyl-3-methoxyl group butyl propionic ester, 3-methyl-3-methoxyl group butyl butyric ester, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, methyl aceto acetate, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, gamma-butyrolactone, toluene, dimethylbenzene, caproic acid, sad, octane, decane, the 1-octanol, 1 nonyl alcohol, benzylalcohol, jasmal, ethyl benzoate, oxalic acid diethyl ester, ethyl maleate, ethylene carbonate, Texacar PC etc.These solvents can separately or mix more than 2 kinds and use.

Resist composition of the present invention carries out patterned process thereby can develop after exposure becomes pattern-like.Resist composition of the present invention reaches nano level electron rays, far ultraviolet rays yue (DUV) and extreme ultraviolet line (EUV) light source owing to can tackle the surface smoothing requirement, can form the fine pattern that super LSI makes usefulness, therefore is adapted at using in the various fields.Resist composition of the present invention is dissolved in the alkaline developer by exposure and heating, waits by washing to exist dissolving residual on plane of exposure hardly, can obtain almost vertical edge.

Embodiment

(embodiment 1A)

-hyperbranched polymer synthetic-

In the 50mL reaction vessel, pack into as the 1-chloro-4-methyl-benzene 21mmol of reaction monomers, as 2 of catalyzer, 2-dipyridyl 2.1mmol, cupric chloride (I) 1.1mmol and as the chlorobenzene 8mL of solvent, with argon gas with in the reaction vessel displacement after, under 115 ℃ of temperature, stir polyreaction 1 hour.In this reaction solution, add tetrahydrofuran (THF) 50mL, after polymkeric substance dilution dissolving, catalyzer is removed by the activated alumina filtration.After filtrate concentrated, add methyl alcohol 200mL, make polymer precipitation, unreacted monomer and reaction solvent are removed by removing top clear liquor.Carry out repeatedly then 2 times with sedimentary polymer dissolution in tetrahydrofuran (THF) 20mL, add methyl alcohol 500mL and make its reppd operation, synthetic polymer 1 (yield 75%).It more than is above-mentioned hyperbranched polymer synthesis procedure.

For the polymkeric substance 1 that obtains, the mensuration weight-average molecular weight as described below (Mw) and the degree of branching (Br).The results are shown in table 1A.

The mensuration of＜weight-average molecular weight (Mw) 〉

The weight-average molecular weight of hyperbranched polymer (Mw) is carried out GPC and is measured and try to achieve by the tetrahydrofuran solution of modulation 0.05 quality % under 40 ℃ of temperature.Mobile solvent uses tetrahydrofuran (THF).Reference material uses vinylbenzene.

＜the degree of branching 〉

The degree of branching of hyperbranched polymer is passed through the mensuration resultant ¹H-NMR, as described below trying to achieve.That is, use 4.6ppm place occurs-CH ₂Than H2 °, (A) calculates the integration of the proton at Cl position by following mathematical expression than the integration of the proton at the CHCl position of H1 ° and 4.8ppm place appearance.If-CH ₂Cl position and two places, CHCl position carry out polymerization, and branching improves, and then the Br value is near 0.5.

Mathematical expression (A)

In the 50mL reaction vessel, pack into then 1g as the above-mentioned polymkeric substance 1 of stock polymer, 6.5mmol as the compound that contains sour decomposability group to tert.-butoxy vinylbenzene, as 2 of catalyzer, 2-dipyridyl 3.2mmol and 1.6mmol cupric chloride (I), 8mL are as the chlorobenzene of solvent, with argon gas with in the reaction vessel displacement after, under 125 ℃ of temperature, stir polyase 13 0 minute.In this reaction solution, add tetrahydrofuran (THF) 50mL, after polymkeric substance dilution dissolving, catalyzer is removed by the activated alumina filtration.After filtrate concentrated, add methyl alcohol 200mL, make polymer precipitation, unreacted monomer and reaction solvent are removed by removing top clear liquor.Carry out repeatedly then 2 times with sedimentary polymer dissolution in tetrahydrofuran (THF) 20mL, add methyl alcohol 500mL and make its reppd operation, the introducing of target compound shown in the synthetic following formula hyperbranched polymer of sour decomposability group.More than be that above-mentioned sour decomposability group is introduced operation.

The introducing that obtains addition amount (introducing amount) mensuration as described below of the sour decomposability group in the hyperbranched polymer of sour decomposability group.The results are shown in table 1A.

The addition amount of＜sour decomposability group (introducing amount) 〉

The addition amount of acid decomposability group is passed through the mensuration resultant ¹H-NMR calculates with the integrated value and the ratio that constitutes unitary styrene derivatives number as hyperbranched polymer of feature proton in the sour decomposability group.

N=is more than or equal to 1 number, and m=is more than or equal to 1 number.

(embodiment 2A)

-hyperbranched polymer synthetic-

In embodiment 1, be 5 times except making the catalytic amount in the above-mentioned hyperbranched polymer synthesis procedure, temperature of reaction is 125 ℃, the reaction times is to carry out outside the polymerization in 30 minutes, similarly to Example 1 synthetic polymer 2 (yield 77%).Measure the weight-average molecular weight (Mw) and the degree of branching (Br) of polymkeric substance 2 similarly to Example 1.The results are shown in table 1A.

The polymkeric substance 2 as stock polymer is 1g in the above-mentioned sour decomposability group introducing operation except making, make as contain sour decomposability group compound be 65mmol to tert.-butoxy vinylbenzene, making the reaction times is outside 3 hours, carry out similarly to Example 1 with to the cinnamic polymerization of tert.-butoxy, refining, synthetic introducing as object the hyperbranched polymer of sour decomposability group.

Measure the addition amount (introducing amount) of sour decomposability group similarly to Example 1.The results are shown in table 1A.

(embodiment 3A)

-hyperbranched polymer synthetic-

In embodiment 1, be 4 times except making the catalytic amount in the above-mentioned hyperbranched polymer synthesis procedure, temperature of reaction is 125 ℃, the reaction times is outside 1 hour, similarly to Example 1 synthetic polymer 3 (yield 78%).

Measure the weight-average molecular weight (Mw) and the degree of branching (Br) of polymkeric substance 3 similarly to Example 1.The results are shown in table 1A.

The polymkeric substance 3 as stock polymer is 1g in the above-mentioned sour decomposability group introducing operation except making, make as contain sour decomposability group compound be 65mmol to ethoxy ethoxy vinylbenzene, making the reaction times is outside 3 hours, carry out similarly to Example 1 with to the cinnamic polymerization of ethoxy ethoxy, refining, synthetic introducing as object the hyperbranched polymer of sour decomposability group.

Measure the addition amount (introducing amount) of sour decomposability group similarly to Example 1.The results are shown in table 1A.

(embodiment 4A)

In the 50mL reaction vessel, pack into 1g as the polymkeric substance 3 of stock polymer, 13.0mmol as the quinhydrones tertbutyl ether of the compound that contains sour decomposability group and the NaH of 13.0mmol, adding was carried out polyreaction 5 hours as the tetrahydrofuran (THF) 30mL of solvent under 70 ℃ of temperature, backflow.In reactant, add methyl alcohol 200mL, the polymkeric substance of separating out separated, wash, drying by decant, the introducing of target compound shown in the synthetic following formula hyperbranched polymer of sour decomposability group.More than be that above-mentioned sour decomposability group is introduced operation.

Measure the addition amount (introducing amount) of sour decomposability group similarly to Example 1.The results are shown in table 1A.

(embodiment 5A)

In embodiment 4, except above-mentioned sour decomposability group is introduced in the operation as the 4-hydroxyphenoxy tert-butyl acetate that contains the compound of sour decomposability group is 65mmol, reaction times is outside 3 hours, carry out similarly to Example 4 and the polymerization of 4-hydroxyphenoxy tert-butyl acetate, refining, synthetic introducing as target compound the hyperbranched polymer of sour decomposability group.

Measure the addition amount (introducing amount) of sour decomposability group similarly to Example 1. the results are shown in table 1A.

Table 1A

(embodiment 6A～10A)

The modulation of-resist composition-

With the introducing of embodiment 1～5 each 10 quality % of hyperbranched polymer of sour decomposability group, the propylene glycol methyl ether acetate solution that contains 0.1 quality % light acid propellant (PAG1～3) mix the resist composition of modulation embodiment 6～10 by the combination shown in the table 1A.

Each the resist composition that obtains is spun onto on the silicon chip, under 90 ℃, carries out thermal treatment in 1 minute so that solvent evaporation, make the film of thick 300nm, as estimating test portion.

The evaluation method of＜alkali-soluble 〉

Solvability in alkali aqueous solution is by using electron rays describing device (Network レ ス テ ッ Network society system, CABL9000), partly shines 50～5000mJ/cm for the test portion film of film forming thick about 300nm on silicon chip at the square of long 30 μ m * wide 30 μ m ²Electron rays, after carrying out thermal treatment in 90 seconds under 120 ℃, flooding 4 minutes under 25 ℃, in as Tetramethylammonium hydroxide (TMAH) the 2.4 quality % aqueous solution of alkaline agent, observe washing, dried state with digital microscope (キ-worker's Application ス society system, VH-6300VH), estimate with following benchmark.The results are shown in table 2A.

[metewand]

Zero: the state of no dissolution residual substance on the plane of exposure.

△: the state that has dissolution residual substance.

*: a large amount of states that exist of dissolution residual substance.

The measuring method of＜surfaceness 〉

The method that the surfaceness of plane of exposure is put down in writing according to rapids refined husband forever, No. 2475, academic dissertation of Waseda University's examination, " about nanostructure instrumentation and its research of using in device-technology of adopting atomic force microscope ", pp99-107 (1996), use electron rays describing device (Network レ ス テ ッ Network society system, CABL9000), measure for 30% the surface that in above-mentioned alkali aqueous solution, demonstrates deliquescent electron rays exposure.Test portion film to film forming thick about 300nm on silicon chip carries out the electron rays irradiation in the square part of long 30 μ m * wide 30 μ m, after carrying out thermal treatment in 90 seconds under 120 ℃, dipping under 25 ℃, in Tetramethylammonium hydroxide (TMAH) the 2.4 quality % aqueous solution 4 minutes, with washing, dry surface as estimating test portion.

For the evaluation test portion that obtains, use atomic force microscope (society of Shimadzu Seisakusho Ltd. system, SPM-9500J3), measure according to acquiring method as 10 mean roughness of the JIS B0601-1994 of surfaceness index.The results are shown in table 2A.

Table 2A

(embodiment 1B)

-hyperbranched polymer synthetic-

In the 50mL reaction vessel, pack into as the 1-chloro-4-methyl-benzene 21mmol of reaction monomers, as 2 of catalyzer, 2-dipyridyl 13.1mmol, cupric chloride (I) 6.6mmol and as the chlorobenzene 8mL of solvent, with argon gas with in the reaction vessel displacement after, under 115 ℃ of temperature, stir polyreaction 30 minutes.In this reaction solution, add tetrahydrofuran (THF) 50mL, after polymkeric substance dilution dissolving, catalyzer is removed by the activated alumina filtration.After filtrate concentrated, add methyl alcohol 200mL, make polymer precipitation, unreacted monomer and reaction solvent are removed by removing top clear liquor.Carry out repeatedly then 2 times with sedimentary polymer dissolution in tetrahydrofuran (THF) 20mL, add methyl alcohol 500mL and make its reppd operation, synthetic core segment A (yield 60%).

Then, in the 50mL reaction vessel, pack into 1g as the core segment A of stock polymer, as contain the tert-butyl acrylate 33mmol of the compound of sour decomposability group, as 2 of catalyzer, 2-dipyridyl 4.1mmol and cupric chloride (I) 2.1mmol, as the chlorobenzene 13mL of solvent, with argon gas with in the reaction vessel displacement after, under 125 ℃ of temperature, stir polyase 13 0 minute.In this reaction solution, add tetrahydrofuran (THF) 50mL, after the polymkeric substance dilution dissolving that generates, catalyzer is removed by the activated alumina filtration.After filtrate concentrated, add methyl alcohol 200mL, make polymer precipitation, unreacted monomer and reaction solvent are removed by removing top clear liquor.Carry out repeatedly then 2 times with sedimentary polymer dissolution in tetrahydrofuran (THF) 20mL, add methyl alcohol 500mL and make its reppd operation, the introducing of object shown in the synthetic following formula hyperbranched polymer＜1 of sour decomposability group.

J, k, 1 are the number more than or equal to 1.

For the core segment A that obtains, the mensuration weight-average molecular weight as described below (Mw) and the degree of branching (Br).

That is, the weight-average molecular weight of core segment A (Mw) is carried out GPC and is measured and try to achieve by the tetrahydrofuran solution of modulation 0.05 weight % under 40 ℃ of temperature.Mobile solvent uses tetrahydrofuran (THF).Reference material uses vinylbenzene.The degree of branching of core segment A is calculated according to above-mentioned mathematical expression (A).The results are shown in table 1B.

In addition, hyperbranched polymer＜1〉weight-average molecular weight (Mw) adopt with the same method of the weight-average molecular weight (Mw) of core segment A and measure.And then calculate the introducing ratio of sour decomposability group according to above-mentioned mathematical expression (a).The results are shown in table 1B.

The modulation of-resist composition-

Making contains hyperbranched polymer＜1 that 10 weight % have introduced sour decomposability group 〉, 0.5 weight % is as the propylene glycol methyl ether acetate solution of the triphenylsulfonium fluoroform sulphonate of light acid propellant, strainer with 0.45 μ m filters, modulation resist composition.

Each the resist composition that obtains is spun onto on the silicon chip, under 90 ℃, carries out thermal treatment in 1 minute so that solvent evaporation, make the film of thick 300nm, as estimating test portion.

The evaluation method of＜alkali-soluble 〉

Solvability in alkali aqueous solution is being grown rectangular segment irradiation 50～5000mJ/cm of 3 μ m * wide 50 μ m by using electron rays describing device (Network レ ス テ ッ Network society system, CABL9000) for the test portion film of film forming thick about 300nm on silicon chip ²Electron rays, after carrying out thermal treatment in 4 minutes under 100 ℃, flooding 2 minutes under 25 ℃, in as Tetramethylammonium hydroxide (TMAH) the 2.4 weight % aqueous solution of alkaline agent, observe washing, dried state with digital microscope (キ-エ Application ス society system, VH-6300VH), estimate with following benchmark.The results are shown in table 2B.

[metewand]

◎: do not have dissolution residual substance on the plane of exposure fully, the edge is vertical state.

◎-zero: do not have dissolution residual substance on the plane of exposure fully, the state that the edge slightly tilts.

Zero: the state that does not almost have dissolution residual substance on the plane of exposure.

*: the state that has dissolution residual substance.

The measuring method of＜surfaceness 〉

The method that the surfaceness of plane of exposure is put down in writing according to rapids refined husband forever, No. 2475, academic dissertation of Waseda University's examination, " about nanostructure instrumentation and its research of using in device-technology of adopting atomic force microscope ", pp99-107 (1996), use electron rays describing device (Network レ ス テ ッ Network society system, CABL9000), measure for 30% the surface that in above-mentioned alkali aqueous solution, demonstrates deliquescent electron rays exposure.Test portion film to film forming thick about 300nm on silicon chip carries out the electron rays irradiation in the square part of long 30 μ m * wide 30 μ m, after carrying out thermal treatment in 4 minutes under 100 ℃, dipping under 25 ℃, in Tetramethylammonium hydroxide (TMAH) the 2.4 weight % aqueous solution 2 minutes, with washing, dry surface as estimating test portion.

For the evaluation test portion that obtains, use atomic force microscope (society of Shimadzu Seisakusho Ltd. system, SPM-9500J3), measure according to acquiring method as 10 mean roughness of the JIS B0601-1994 of surfaceness index.The results are shown in table 2B.

(embodiment 2B)

-hyperbranched polymer synthetic-

Except making the catalytic amount (2,2-dipyridyl and cupric chloride (I)) in the above-mentioned hyperbranched polymer molecule core synthesis procedure is 0.8 times, and temperature of reaction is 125 ℃ carries out outside the polymerization, with the similarly synthetic core segment B (yield 77%) of embodiment 1B.In addition, similarly measure the weight-average molecular weight (Mw) and the degree of branching (Br) of core segment B with embodiment 1B.The results are shown in table 1B.

Secondly, the core segment B as stock polymer is 1g in the above-mentioned sour decomposability group introducing operation except making, and making catalytic amount (2,2-dipyridyl and cupric chloride (I)) is 0.8 times, making the reaction times is to carry out outside the polymerization in 3 hours, with embodiment 1B synthesis of super branched polymkeric substance＜2 similarly 〉.

With embodiment 1B hyperbranched polymer＜2 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to mathematical expression (a) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

The modulation of-resist composition-

Hyperbranched polymer＜2 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 3B)

-hyperbranched polymer synthetic-

Temperature of reaction in making above-mentioned hyperbranched polymer molecule core synthesis procedure is 125 ℃ carries out the polymerization, with the similarly synthetic core segment C (yield 78%) of embodiment 1B.In addition, similarly measure the weight-average molecular weight (Mw) and the degree of branching (Br) of core segment C with embodiment 1B.The results are shown in table 1B.

Secondly, introduce except making above-mentioned sour decomposability group that the core segment C as stock polymer is 1g in the operation, making the reaction times is to carry out outside the polymerization in 3 hours, with embodiment 1B synthesis of super branched polymkeric substance＜3 similarly 〉.

With embodiment 1B hyperbranched polymer＜3 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to mathematical expression (a) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

The modulation of-resist composition-

Hyperbranched polymer＜3 of having introduced sour decomposability group except use 〉, similarly modulate the resist composition with embodiment 1B, make then and estimate test portion.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 4B)

-hyperbranched polymer synthetic-

Synthetic core segment B as stock polymer in above-mentioned sour decomposability group introducing operation is 1g among the embodiment 2B except making, making as the methacrylic tert-butyl acrylate that contains the compound of sour decomposability group is that 33mmol carries out outside the polymerization, with hyperbranched polymer＜4 of object shown in the similarly synthetic following formula of embodiment 2B 〉.

With embodiment 1B hyperbranched polymer＜4 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to mathematical expression (a) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

J, k, 1 are the number more than or equal to 1.

The modulation of-resist composition-

Hyperbranched polymer＜4 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 5B)

-hyperbranched polymer synthetic-

Synthetic core segment B as stock polymer in above-mentioned sour decomposability group introducing operation is 1g among the embodiment 2B except making, making as monomer shown in the formula (15) that contains the compound of sour decomposability group is that 33mmol carries out outside the polymerization, with hyperbranched polymer＜5 of object shown in the similarly synthetic following formula of embodiment 2B 〉.

With embodiment 1B hyperbranched polymer＜5 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to mathematical expression (a) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

J, k, 1 are the number more than or equal to 1.

The modulation of-resist composition-

Hyperbranched polymer＜5 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 6B)

-hyperbranched polymer synthetic-

Synthetic core segment B as stock polymer in above-mentioned sour decomposability group introducing operation is 1g among the embodiment 2B except making, making as monomer shown in the formula (15) that contains the compound of sour decomposability group is that 33mmol carries out outside the polymerization, with hyperbranched polymer＜6 of object shown in the similarly synthetic following formula of embodiment 2B 〉.

With embodiment 1B hyperbranched polymer＜6 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to mathematical expression (a) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

J, k, 1 are the number more than or equal to 1.

The modulation of-resist composition-

Hyperbranched polymer＜6 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 7B)

-hyperbranched polymer synthetic-

Synthetic core segment B as stock polymer in above-mentioned sour decomposability group introducing operation is 1g among the embodiment 2B except making, making as monomer shown in the formula (16) that contains the compound of sour decomposability group is that 33mmol carries out outside the polymerization, with hyperbranched polymer＜7 of object shown in the similarly synthetic following formula of embodiment 2B 〉.

With embodiment 1B hyperbranched polymer＜7 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to mathematical expression (a) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

J, k, 1 are the number more than or equal to 1.

The modulation of-resist composition-

Hyperbranched polymer＜7 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 8B)

-hyperbranched polymer synthetic-

Synthetic core segment B as stock polymer in above-mentioned sour decomposability group introducing operation is 1g among the embodiment 2B except making, making as monomer shown in the formula (17) that contains the compound of sour decomposability group is that 33mmol carries out outside the polymerization, with hyperbranched polymer＜8 of object shown in the similarly synthetic following formula of embodiment 2B 〉.

With embodiment 1B hyperbranched polymer＜8 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to mathematical expression (a) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

J, k, 1 are the number more than or equal to 1.

The modulation of-resist composition-

Hyperbranched polymer＜8 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 9B)

-hyperbranched polymer synthetic-

Except synthetic among the 1g embodiment 2B is introduced in the operation core segment B as stock polymer at above-mentioned sour decomposability group, is mixed as the tert-butyl acrylate 18mmol of the compound that contains sour decomposability group and the monomer 18mmol shown in the formula (15) and carry out the polymerization, hyperbranched polymer＜9 of similarly synthesizing object shown in the following formula with embodiment 2B 〉.

With embodiment 1B hyperbranched polymer＜9 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to mathematical expression (a) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

In the formula, A ₁, A ₂, A ₃The part and the B of above-mentioned sour decomposability group ₁, B ₂Any one connection of part.J, k, 1 are the number more than or equal to 1.

The modulation of-resist composition-

Hyperbranched polymer＜9 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 10B)

-hyperbranched polymer synthetic-

In the 50mL reaction vessel, pack into 1g as core segment B, the 13.0mmol of stock polymer as the quinhydrones tertbutyl ether of the compound that contains sour decomposability group and the NaH of 13.0mmol, adding was carried out polyreaction 5 hours as the tetrahydrofuran (THF) 30mL of solvent under 70 ℃ of temperature, backflow.In reactant, add methyl alcohol 200mL, the polymkeric substance of separating out separated, wash, drying by decant, the introducing of target compound shown in the synthetic following formula hyperbranched polymer＜10 of sour decomposability group.

With embodiment 1B hyperbranched polymer＜11 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to mathematical expression (b) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment. the results are shown in table 1B.

The modulation of-resist composition-

Hyperbranched polymer＜10 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 11B)

-hyperbranched polymer synthetic-

In embodiment 10B, except above-mentioned sour decomposability group is introduced in the operation as the 4-hydroxyphenoxy tert-butyl acetate that contains the compound of sour decomposability group is 65mmol, reaction times is outside 3 hours, similarly carry out and the polymerization of 4-hydroxyphenoxy tert-butyl acetate, refining with embodiment 10B, the introducing of target compound shown in the synthetic following formula hyperbranched polymer＜11 of sour decomposability group.

With embodiment 1B hyperbranched polymer＜11 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to mathematical expression (b) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

The modulation of-resist composition-

Hyperbranched polymer＜11 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 12B)

-hyperbranched polymer synthetic-

1g in the 50mL reaction vessel, pack into as synthetic hyperbranched polymer＜2 among the embodiment 2B of stock polymer 〉, 2,2-dipyridyl 4.1mmol, cupric chloride (I) 2.1mmol, hydrogenation tri-n-butyl tin 6.3mmol and as the chlorobenzene 13ml of solvent, stir down for 60 ℃ in temperature, reacted 24 hours.Through refining with same filtration of embodiment 1B and precipitation, hyperbranched polymer＜12 of object shown in the synthetic following formula 〉.

J, k, 1 are the number more than or equal to 1.

Similarly measure hyperbranched polymer＜12 of dehalogenation with embodiment 1B〉weight-average molecular weight (Mw).The results are shown in table 1B.

(embodiment 13B)

-hyperbranched polymer synthetic-

In the 50mL reaction vessel, pack into as the 1-chloro-4-methyl-benzene 21mmol of reaction monomers, as 2 of catalyzer, 2-dipyridyl 10.5mmol, cupric chloride (I) 5.3mmol and as the chlorobenzene 8mL of solvent, with argon gas with in the reaction vessel displacement after, under 125 ℃ of temperature, stir polyreaction 30 minutes.

Then, do not make with extra care, in identical reaction vessel, splash into, under 125 ℃ of temperature, stir polyase 13 0 minute as the tert-butyl acrylate 105mmol that contains the compound of sour decomposability group, as the chlorobenzene 32mL of solvent.In this reaction solution, add tetrahydrofuran (THF) 50mL, after the polymkeric substance dilution dissolving that generates, catalyzer is removed by the activated alumina filtration.After filtrate concentrated, add methyl alcohol 200mL, make polymer precipitation, unreacted monomer and reaction solvent are removed by removing top clear liquor.Carry out repeatedly then 2 times with sedimentary polymer dissolution in tetrahydrofuran (THF) 20mL, add methyl alcohol 500mL and make its reppd operation, synthetic introducing as object hyperbranched polymer＜13 of sour decomposability group.

This is that above-mentioned hyperbranched polymer molecule core synthesis procedure and above-mentioned sour decomposability group are introduced the example that operation is carried out continuously.

With embodiment 1B hyperbranched polymer＜13 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw).In addition, the addition amount of sour decomposability group is passed through the mensuration resultant ¹H-NMR calculates with the integrated value and the ratio that constitutes unitary styrene derivatives number as core segment of feature proton in the sour decomposability group.The results are shown in table 1B.

The modulation of-resist composition-

Hyperbranched polymer＜13 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 14B)

-hyperbranched polymer synthetic-

1-chloro-4-methyl-benzene as reaction monomers in making above-mentioned hyperbranched polymer molecule core synthesis procedure is that 18mmol, vinylbenzene are that 2mmol carries out the polymerization, with the similarly synthetic core segment D (yield 76%) of embodiment 2B.In addition, similarly measure the weight-average molecular weight (Mw) of core segment D with embodiment 1B.The results are shown in table 1B.

Then, introduce except making above-mentioned sour decomposability group that the core segment D as stock polymer is that 1g carries out the polymerization in the operation, with embodiment 2B synthesis of super branched polymkeric substance＜14 similarly 〉.

With embodiment 1B hyperbranched polymer＜14 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to above-mentioned mathematical expression (c) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

The modulation of-resist composition-

Hyperbranched polymer＜14 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 15B)

-hyperbranched polymer synthetic-

1-chloro-4-methyl-benzene as reaction monomers in making above-mentioned hyperbranched polymer molecule core synthesis procedure is that 18mmol, tert-butyl acrylate are that 2mmol carries out the polymerization, with the similarly synthetic core segment E (yield 77%) of embodiment 2B.Tert-butyl acrylate also is sour decomposability group.In addition, similarly measure the weight-average molecular weight (Mw) of core segment E with embodiment 1B.The results are shown in table 1B.

Then, introduce except making above-mentioned sour decomposability group that the core segment E as stock polymer is that 1g carries out the polymerization in the operation, with embodiment 2B synthesis of super branched polymkeric substance＜15 similarly 〉.

With embodiment 1B hyperbranched polymer＜15 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to above-mentioned mathematical expression (c) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

The modulation of-resist composition-

Hyperbranched polymer＜15 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 16B)

-hyperbranched polymer synthetic-

1-chloro-4-methyl-benzene as reaction monomers in making above-mentioned hyperbranched polymer molecule core synthesis procedure is that 16mmol, vinylbenzene are that 2mmol, tert.-butoxy vinylbenzene are that 2mmol carries out the polymerization, with the similarly synthetic core segment F (yield 80%) of embodiment 2B.Tert.-butoxy vinylbenzene also is sour decomposability group.In addition, similarly measure the weight-average molecular weight (Mw) of core segment F with embodiment 1B.The results are shown in table 1B.

Then, introduce except making above-mentioned sour decomposability group that the core segment F as stock polymer is that 1g carries out the polymerization in the operation, with embodiment 2B synthesis of super branched polymkeric substance＜16 similarly 〉.

With embodiment 1B hyperbranched polymer＜16 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to mathematical expression (c) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

The modulation of-resist composition-

Hyperbranched polymer＜16 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 17B)

-hyperbranched polymer synthetic-

Synthetic core segment D as stock polymer in above-mentioned sour decomposability group introducing operation is 1g among the embodiment 14B except making, making as the tert.-butoxy vinylbenzene that contains the compound of sour decomposability group is that 33mmol carries out outside the polymerization, with similarly synthetic hyperbranched polymer＜17 as object of embodiment 2B 〉.

With embodiment 1B hyperbranched polymer＜17 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to mathematical expression (c) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

The modulation of-resist composition-

Hyperbranched polymer＜17 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 18B)

-hyperbranched polymer synthetic-

Synthetic core segment E as stock polymer in above-mentioned sour decomposability group introducing operation is 1g among the embodiment 15B except making, making as the tert.-butoxy vinylbenzene that contains the compound of sour decomposability group is that 33mmol carries out outside the polymerization, with similarly synthetic hyperbranched polymer＜18 as object of embodiment 2B 〉.

With embodiment 1B hyperbranched polymer＜18 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to mathematical expression (c) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

The modulation of-resist composition-

Hyperbranched polymer＜18 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 19B)

-hyperbranched polymer synthetic-

Synthetic core segment F as stock polymer in above-mentioned sour decomposability group introducing operation is 1g among the embodiment 16B except making, making as the tert.-butoxy vinylbenzene that contains the compound of sour decomposability group is that 33mmol carries out outside the polymerization, with similarly synthetic hyperbranched polymer＜19 as object shown in the following formula of embodiment 2B 〉.

With embodiment 1B hyperbranched polymer＜19 of sour decomposability group of similarly having measured the introducing that obtains〉weight-average molecular weight (Mw), calculate introducing ratio according to mathematical expression (c) with respect to the sour decomposability group of number of monomers shown in the formula 1 that constitutes core segment.The results are shown in table 1B.

The modulation of-resist composition-

Hyperbranched polymer＜19 of having introduced sour decomposability group except use 〉, the resist composition similarly modulated with embodiment 1B.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 20B)

The modulation of-resist composition-

Except using 10 weight % to introduce the hyperbranched polymer of sour decomposability group〉2,0.5 weight % two (cyclohexyl alkylsulfonyl) diazomethane, similarly modulate the resist composition with embodiment 1B as light acid propellant.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

(embodiment 21B)

The modulation of-resist composition-

Except using 10 weight % to introduce hyperbranched polymer＜2 of sour decomposability group 〉, 0.5 weight % two (tertiary butyl alkylsulfonyl) diazomethane, similarly modulate the resist composition with embodiment 1B as light acid propellant.

In addition, similarly estimate alkali-soluble, measure surfaceness with embodiment 1B.It the results are shown in table 2B.

Table 1B

Table 2B

(embodiment 1C)

-hyperbranched polymer synthetic-

In the 1000mL reaction vessel, pack into as the 1-chloro-4-methyl-benzene 630mmol of reaction monomers, as 2 of catalyzer, 2-dipyridyl 315mmol, cupric chloride (I) 157.5mmol and as the chlorobenzene 480mL of solvent, with argon gas with in the reaction vessel displacement after, under 125 ℃ of temperature, stir polyreaction 27 minutes.In this reaction solution, add tetrahydrofuran (THF) 100mL, after polymkeric substance dilution dissolving, catalyzer is removed by the activated alumina filtration.After filtrate concentrated, add methyl alcohol 700mL, make polymer precipitation, unreacted monomer and reaction solvent are removed by removing top clear liquor.In the polymkeric substance of drying under reduced pressure, add then tetrahydrofuran (THF) and methanol mixed solvent (ratio of mixture 8: 2mL/mL) 600mL, carry out agitator treating.Carry out this washing operation repeatedly 2 times, the core segment G (yield 77%) of synthetic weight-average molecular weight (Mw) 2000, the degree of branching 0.47.

Then, in the 1000mL reaction vessel, pack into 16.2g as the core segment G of stock polymer, as contain the tert-butyl acrylate 76mmol of the compound of sour decomposability group, as 2 of catalyzer, 2-dipyridyl 53mmol and cupric chloride (I) 26mmol, as the chlorobenzene 400mL of solvent, with argon gas with in the reaction vessel displacement after, under 125 ℃ of temperature, stir polymerization 5 hours.In this reaction solution, add tetrahydrofuran (THF) 100mL, after the polymkeric substance dilution dissolving that generates, catalyzer is removed by the activated alumina filtration.After filtrate concentrated, add methyl alcohol 750mL, make polymer precipitation, unreacted monomer and reaction solvent are removed by removing top clear liquor.Carry out repeatedly then 2 times with sedimentary polymer dissolution in tetrahydrofuran (THF) 50mL, add methyl alcohol 500mL and make its reppd operation, the introducing of synthetic object hyperbranched polymer＜20 of sour decomposability group.

Then, the 0.5g that in the 50mL reaction vessel, packs into＜20, the 10N hydrochloric acid of 0.75mL, 25mL De diox, 85 ℃ of following heated and stirred of temperature 60 minutes, sour decomposability group is partly decomposed.This reaction solution is injected among the water 250mL, makes polymer precipitation.Then, top clear liquor is removed, made repeatedly in the sedimentary polymer dissolution Dao diox, water carries out reppd operation, the introducing shown in the synthetic following formula hyperbranched polymer of carboxyl＜21.

P, q, r, s, t, u are the number more than or equal to 1.

The hyperbranched polymer that obtains＜21〉weight-average molecular weight measure by above-mentioned GPC and ask for.The composition of the hyperbranched polymer that obtains in addition, is by measuring ¹H-NMR is calculated by the integrated value of the proton of feature in the sour decomposability group.The results are shown in table 1C.

The removal of the copper that contains in-the polymkeric substance-

Adjustment contains 7.5 weight % hyperbranched polymer＜21〉propylene glycol methyl ether acetate (PEGMEA) solution, handle the removal of carrying out copper by ion-exchange membrane and メ Application Block ラ Application film and handle.At first will be positioned at the upper strata 3 of the films that the system プ ロ テ of Japanese マ イ Network ロ リ ス Zhu Shi commercial firm go CP are cut into diameter 47mm circle as ion-exchange membrane, be positioned at lower floor aperture 0.05 μ m, 1 of the diameter 47mm membrane filter of ミ リ Port ァ society system overlapping, make strainer, with flow velocity 4ml/ branch polymers soln 10ml is flow through by pressure filtration, carry out metal removal.The copper residual quantity of having carried out the test portion of removal processing is shaped on machine metal reference liquid as reference material by using CONOSTAN society, uses the system P-6000 type MIP-MS of Hitachi society (copper limit of detection 50ppb) to carry out quantitatively.The results are shown in table 1C.

The modulation of-resist composition-

Making contains 4 weight % and has carried out copper and remove hyperbranched polymer＜21 of handling 〉, 0.04 weight % is as propylene glycol methyl ether acetate (PEGMEA) solution of the triphenylsulfonium fluoroform sulphonate of light acid propellant, strainer with fine pore 0.45 μ m filters, modulation resist composition.

The resist composition that obtains is spun onto on the silicon chip, under 90 ℃, carries out thermal treatment in 1 minute so that the film that obtains thick 100nm is made in solvent evaporation.

The evaluation of-alkali-soluble-

Alkali dissolution is by using discharge tubular type UV irradiation equipment (ァ ト-Zhu Shi commercial firm system, DF-245 type De Na Off イ ッ Network ス), for the test portion film of film forming thick about 100nm on silicon chip rectangular segment illumination wavelength 245nm, the energy 0～200mJ/cm at long 10mm * wide 3mm ²Ultraviolet ray, after carrying out thermal treatment in 4 minutes under 100 ℃, flooding 2 minutes under 25 ℃, in as Tetramethylammonium hydroxide (TMAH) the 2.4 weight % aqueous solution of alkaline agent, measure washing, dried thickness with the made membrane determinator F20 of Filmetrics Zhu Shi commercial firm, estimate with following benchmark.

The unexposed portion exposed portion

Zero: thickness reduces 0～less than 30% 0: thickness reduces 100%

△: thickness reduces 30～less than, 50% △: thickness reduces less than 100～90%

*: thickness minimizing 50～100% *: thickness reduces less than 90%

In addition, at dipping under 25 ℃, in Tetramethylammonium hydroxide (TMAH) the 2.4 weight % aqueous solution after 2 minutes, reduce ultraviolet ray (254nm) irradiation dose that reaches 100% minimum as the thickness of sensitometry exposed portion.The results are shown in table 2C.

The mensuration of-surfaceness-

The surfaceness reference of plane of exposure is the method for rapids refined husband, No. 2475, academic dissertation of Waseda University's examination, " about nanostructure instrumentation and its research of using in device-technology of adopting atomic force microscope ", pp99-107 (1996) record forever, use discharge tubular type UV irradiation equipment (ァ ト-Zhu Shi commercial firm system, DF-245 type De Na Off イ ッ Network ス), measure for 30% the surface that in above-mentioned alkali aqueous solution, demonstrates deliquescent ultraviolet ray (245nm) exposure.Test portion film to film forming thick about 500nm on silicon chip carries out uviolizing at the rectangular segment of long 10mm * wide 3mm, after carrying out thermal treatment in 4 minutes under 100 ℃, dipping under 25 ℃, in Tetramethylammonium hydroxide (TMAH) the 2.4 quality % aqueous solution 2 minutes, with washing, dry surface as estimating test portion.

For the evaluation test portion that obtains, use atomic force microscope (society of Shimadzu Seisakusho Ltd. system, SPM-9500J3), measure according to acquiring method as 10 mean roughness of the JIS B0601-1994 of surfaceness index.The results are shown in table 2C.

(embodiment 2C)

-hyperbranched polymer synthetic-

Hyperbranched polymer＜20 of the 8.0g embodiment 1C that in the 50mL reaction vessel, packs into record 〉, the 10N hydrochloric acid of 12.0mL, 400mL De diox, 85 ℃ of following heated and stirred of temperature 65 minutes, sour decomposability group is partly decomposed.By the refining and copper removal processing same, synthetic hyperbranched polymer＜22 of having introduced carboxyl〉with embodiment 1C.The results are shown in table 1C.

The modulation of-resist composition-

Except using hyperbranched polymer＜22 〉, similarly modulate the resist composition with embodiment 1C, make then and estimate test portion.

In addition, similarly estimate alkali-soluble, measure light sensitivity and surfaceness with embodiment 1C.It the results are shown in table 2C.

(embodiment 3C)

-hyperbranched polymer synthetic-

In the 500mL reaction vessel, pack into as the 1-chloro-4-methyl-benzene 210mmol of reaction monomers, as 2 of catalyzer, 2-dipyridyl 105mmol, cupric chloride (I) 52.5mmol and as the chlorobenzene 160mL of solvent, with argon gas with in the reaction vessel displacement after, under 125 ℃ of temperature, stir polyreaction 40 minutes.In this reaction solution, add tetrahydrofuran (THF) 100mL, after polymkeric substance dilution dissolving, catalyzer is removed by the activated alumina filtration.After filtrate concentrated, add methyl alcohol 200mL, make polymer precipitation, unreacted monomer and reaction solvent are removed by removing top clear liquor.In the polymkeric substance of drying under reduced pressure, add then tetrahydrofuran (THF) and methanol mixed solvent (ratio of mixture 7: 3mL/mL) 200mL, carry out agitator treating.Carry out this washing operation repeatedly 2 times, the core segment H (yield 70%) of synthetic weight-average molecular weight (Mw) 4000, the degree of branching 0.50.

Then, in the 1000mL reaction vessel, pack into 13.1g as the core segment H of stock polymer, as contain the tert-butyl acrylate 62mmol of the compound of sour decomposability group, as 2 of catalyzer, 2-dipyridyl 42.9mmol and cupric chloride (I) 21.5mmol, as the chlorobenzene 327mL of solvent, with argon gas with in the reaction vessel displacement after, under 125 ℃ of temperature, stir polymerization 5 hours.By with same refining of embodiment 1C, the introducing of synthetic object hyperbranched polymer＜23 of sour decomposability group.

Then, the 0.5g that in the 50mL reaction vessel, packs into＜23, the 10N hydrochloric acid of 0.5mL, 25mL De diox, 90 ℃ of following heated and stirred of temperature 60 minutes, sour decomposability group is partly decomposed.By the refining and copper removal processing same, synthetic hyperbranched polymer＜24 of having introduced carboxyl〉with embodiment 1C.The results are shown in table 1C.

The modulation of-resist composition-

Except using hyperbranched polymer＜24 〉, similarly modulate the resist composition with embodiment 1C, make then and estimate test portion.

In addition, similarly estimate alkali-soluble, measure light sensitivity and surfaceness with embodiment 1C.It the results are shown in table 2C.

(embodiment 4C)

-hyperbranched polymer synthetic-

Hyperbranched polymer＜23 of the 12.0g embodiment 3C that in the 50mL reaction vessel, packs into record 〉, the 10N hydrochloric acid of 24.0mL, 600mL De diox, 90 ℃ of following heated and stirred of temperature 60 minutes, sour decomposability group is partly decomposed.By the refining and copper removal processing same, synthetic hyperbranched polymer＜25 of having introduced carboxyl〉with embodiment 1C.The results are shown in table 1C.

The modulation of-resist composition-

Except using hyperbranched polymer＜25 〉, similarly modulate the resist composition with embodiment 1C, make then and estimate test portion.

In addition, similarly estimate alkali-soluble, measure light sensitivity and surfaceness with embodiment 1C.It the results are shown in table 2C.

(embodiment 5C)

-hyperbranched polymer synthetic-

In the 1000mL reaction vessel, pack into 14.7g as the core segment H of stock polymer, as contain the tert-butyl acrylate 63mmol of the compound of sour decomposability group, as 2 of catalyzer, 2-dipyridyl 24.1mmol and cupric chloride (I) 12.1mmol, as the chlorobenzene 366mL of solvent, with argon gas with in the reaction vessel displacement after, under 125 ℃ of temperature, stir polyase 13 hour.By with same refining of embodiment 1C, the introducing of synthetic object hyperbranched polymer＜26 of sour decomposability group.

Then, the 12.0g that in the 1000mL reaction vessel, packs into＜26, the 10N hydrochloric acid of 54mL, 600mL De diox, 90 ℃ of following heated and stirred of temperature 60 minutes, sour decomposability group is partly decomposed.By the refining and copper removal processing same, synthetic hyperbranched polymer＜27 of having introduced carboxyl〉with embodiment 1C.The results are shown in table 1C.

The modulation of-resist composition-

Except using hyperbranched polymer＜27 〉, similarly modulate the resist composition with embodiment 1C, make then and estimate test portion.

In addition, similarly estimate alkali-soluble, measure light sensitivity and surfaceness with embodiment 1C.It the results are shown in table 2C.

(embodiment 6C)

-hyperbranched polymer synthetic-

Hyperbranched polymer＜26 of the 0.6g embodiment 5C that in the 50mL reaction vessel, packs into record 〉, the 10N hydrochloric acid of 2.4mL, 30mL De diox, 90 ℃ of following heated and stirred of temperature 60 minutes, sour decomposability group is partly decomposed.By the refining and copper removal processing same, synthetic hyperbranched polymer＜28 of having introduced carboxyl〉with embodiment 1C.The results are shown in table 1C.

The modulation of-resist composition-

Except using hyperbranched polymer＜28 〉, similarly modulate the resist composition with embodiment 1C, make then and estimate test portion.

In addition, similarly estimate alkali-soluble, measure light sensitivity and surfaceness with embodiment 1C.It the results are shown in table 2C.

(embodiment 7C)

-hyperbranched polymer synthetic-

Hyperbranched polymer＜26 of the 0.6g embodiment 5C that in the 50mL reaction vessel, packs into record 〉, the 10N hydrochloric acid of 2.7mL, 30mL De diox, 90 ℃ of following heated and stirred of temperature 60 minutes, sour decomposability group is partly decomposed.By the refining and copper removal processing same, synthetic hyperbranched polymer＜29 of having introduced carboxyl〉with embodiment 1C.The results are shown in table 1C.

The modulation of-resist composition-

Except using hyperbranched polymer＜29 〉, similarly modulate the resist composition with embodiment 1C, make then and estimate test portion.

In addition, similarly estimate alkali-soluble, measure light sensitivity and surfaceness with embodiment 1C.

It the results are shown in table 2C.

Table 1C

Table 2C

By above result as can be known, the resist composition that uses hyperbranched polymer of the present invention has excellent solvability and surface smoothing in electron rays etching method or photoetch method.Shown in special embodiment 1B, 2B as table 2B, the 12B～15B, contain to introduce ratio and introduced the resist of the polymkeric substance of tert-butyl acrylate more than 1, it is vertical that the edge becomes, and surfaceness is minimum, and it suits to form submicroscopic patterns as can be known.In addition, result from table 1C, 2C, particularly the result of embodiment 2C and 7C can see, used and had the sour decomposability group that constitutes by tert-butyl acrylate and vinylformic acid, in the future the copper of the auto-polymerization catalyzer resist composition of removing the hyperbranched polymer that reaches the ppb level has high light sensitivity, can fully satisfy desired light sensitivity in the etching method of high-throughput.

The suitable base resin that reaches the nano level anticorrosive additive material corresponding as the surface smoothing requirement of hyperbranched polymer of the present invention with electron rays, far ultraviolet rays yue (DUV) and Extreme Ultraviolet (EUV) light source.

Resist composition of the present invention can form the fine pattern that super LSI makes usefulness, can tackle the formation of the also thin submicroscopic patterns of essential from now on ratio 50nm.

Claims (15)

1. hyperbranched polymer, it is characterized in that: have sour decomposability group at the polymer molecule end, core in the described hyperbranched polymer is a monomeric homopolymer shown in the following formula (1), or monomer shown in the following formula (1) and at least a monomeric multipolymer from following formula (2)～(5), chosen

Formula (1)

In the formula (1), the carbonatoms that Y represents to contain or do not contain hydroxyl or carboxyl is 1～10 alkylidene group, and Z represents halogen atom,

In formula (2)～(5), R ¹Expression hydrogen atom or carbonatoms are 1～3 alkyl; R ², R ³Expression hydrogen atom, carbonatoms are that 1～30 straight chain shape, branch-like or cyclic alkyl or carbonatoms are 6～30 aryl, R ², R ³Be same to each other or different to each other; R ⁴The expression hydrogen atom, carbonatoms is 1～40 straight chain shape, branch-like or cyclic alkyl, trialkylsilkl, the carbonatoms of each alkyl is 1～6 in the described trialkylsilkl, oxoalkyl group, the carbonatoms of alkyl is 4～20 in the described oxoalkyl group, or the group shown in the following formula (6), n represents 0～10 integer

R wherein ⁵For straight chain shape, branch's chain or cyclic carbonatoms are 1～10 alkyl, R ⁶, R ⁷Represent hydrogen atom independently of each other, straight chain shape, branch's chain or cyclic carbonatoms are 1～10 alkyl, or work as R ⁶, R ⁷When expression straight chain shape or branch's catenate carbonatoms are 1～10 alkyl, form ring mutually together or do not form ring.

2. the described hyperbranched polymer of claim 1, the sour decomposability group in the wherein said hyperbranched polymer is at least a group that is selected from following formula (I)～(IV) and formula (7),

In formula (I)～(IV), R ^{1 '}And R ^{2 '}Respectively with R ¹, R ²Definition identical; R ⁸The expression hydrogen atom, carbonatoms is 3～40 straight chain shape, branch-like or cyclic alkyl, trialkylsilkl, the carbonatoms of each alkyl is 1～6 in the described trialkylsilkl, oxoalkyl group, the carbonatoms of alkyl is 4～20 in the described oxoalkyl group, or the radicals R shown in the above-mentioned formula (6) ⁹And R ¹⁰The expression hydrogen atom, straight chain shape, branch's chain or cyclic carbonatoms are 1～10 alkyl, or carbonatoms is 6～30 aryl, R ⁹And R ¹⁰Be same to each other or different to each other R ⁹And R ¹⁰Form ring mutually together or do not form ring; G represents halogen atom, hydrogen atom, straight chain shape, branch's chain or cyclic carbonatoms are 1～10 alkyl, and carbonatoms is 6～30 aryl, alkyl carbonyl oxy, the carbonatoms of alkyl is 1～10 in the described alkyl carbonyl oxy, alkoxyl group, the carbonatoms of alkyl is 1～10 in the described alkoxyl group, phenoxy group, thioether group, amino or cyano group; M represents 0～10 integer, and a, b, c and d represent the integer more than or equal to 1 respectively,

—X—W (7)

In the formula (7), X represents that Sauerstoffatom, sulphur atom, nitrogen-atoms, carbonatoms are 1～6 straight chain shape or branch's chain alkylidene group or interatomic bond, W represents that hydrogen atom, carbonatoms are that 1～10 straight chain shape, branch-like or cyclic alkyl, phenyl, carbonatoms are that 7～20 alkoxyl phenyl, carbonatoms are 2～10 the alkoxy carbonyl or the group of following formula (8) expression

—R ¹¹—COO—R ⁸’ (8)

In the formula (8), R ¹¹The expression carbonatoms is that 1～30 straight chain shape, branch-like, cyclic alkylidene group or carbonatoms are 6～30 arylidene, contains or do not contain ehter bond or ester bond, R ^{8 '}With R ⁸The record content identical.

3. the described hyperbranched polymer of claim 2, wherein said hyperbranched polymer is made of the sour decomposability group shown in core and above-mentioned formula (I), (II), (III) or (7), and described core is monomer shown in monomeric homopolymer shown in the above-mentioned formula (1) or the above-mentioned formula (1) and is selected from monomeric at least a kind multipolymer shown in above-mentioned formula (2)～(5).

4. the described hyperbranched polymer of claim 2, wherein said hyperbranched polymer by core and above-mentioned formula (I), (III) or the sour decomposability group (IV) constitute, described core is monomer shown in monomeric homopolymer shown in the above-mentioned formula (1) or the above-mentioned formula (1) and is selected from monomeric at least a kind multipolymer shown in above-mentioned formula (2)～(4).

5. the described hyperbranched polymer of claim 2, the weight-average molecular weight Mw of wherein said hyperbranched polymer is 500～150000.

6. each described hyperbranched polymer of claim 1～5, the monomeric unit of core that wherein constitutes above-mentioned hyperbranched polymer is with respect to the monomeric unit that constitutes above-mentioned hyperbranched polymer, and its content is 10～90 moles of %.

7. each described hyperbranched polymer of claim 1～5, the monomer shown in the wherein above-mentioned formula (1) is a 1-chloro-4-methyl-benzene.

8. each described hyperbranched polymer of claim 1～5, wherein the weight-average molecular weight Mw of hyperbranched polymer is 2000～150000.

9. each described hyperbranched polymer of claim 2～5, it is characterized in that: at least a kind of repeating unit that constitutes the above-mentioned formula of being selected from of sour decomposability group (I)～(IV) is with respect to the monomeric unit that constitutes above-mentioned hyperbranched polymer, and its content is 10～90 moles of %.

10. each described hyperbranched polymer of claim 2～5 is characterized in that: constitute the group shown in the above-mentioned formula (7) of sour decomposability group with respect to the monomeric unit that constitutes above-mentioned hyperbranched polymer, its content is 10～50 moles of %.

11. each described hyperbranched polymer of claim 2～5 is characterized in that: at least a kind of repeating unit that is selected from above-mentioned formula (I)～(IV) that constitutes sour decomposability group, R ⁸For the repeating unit of hydrogen atom with respect to the monomeric unit that constitutes above-mentioned hyperbranched polymer, its content is 0～70 mole of %.

12. the manufacture method of hyperbranched polymer is characterized in that comprising: make the monomer shown in the following formula (1) carry out active free radical polymerization separately or make monomer shown in the following formula (1) and be selected from following formula (2)～at least a kind of monomer of (5) and carry out the operation of active free radical polymerization; By polymkeric substance that obtains in this operation and the compound that contains sour decomposability group are reacted, in this polymkeric substance, introduce the operation of sour decomposability group,

Formula (1)

In the formula (1), the carbonatoms that Y represents to contain or do not contain hydroxyl or carboxyl is 1～10 alkylidene group, and Z represents halogen atom,

In formula (2)～(5), R ¹Expression hydrogen atom or carbonatoms are 1～3 alkyl; R ², R ³Expression hydrogen atom, carbonatoms are that 1～30 straight chain shape, branch-like or cyclic alkyl or carbonatoms are 6～30 aryl, R ², R ³Be same to each other or different to each other; R ⁴The expression hydrogen atom, carbonatoms is 1～40 straight chain shape, branch-like or cyclic alkyl, trialkylsilkl, the carbonatoms of each alkyl is 1～6 in the described trialkylsilkl, oxoalkyl group, the carbonatoms of alkyl is 4～20 in the described oxoalkyl group, or the group shown in the following formula (6), n represents 0～10 integer

R wherein ⁵For straight chain shape, branch's chain or cyclic carbonatoms are 1～10 alkyl, R ⁶, R ⁷Represent hydrogen atom independently of each other, straight chain shape, branch's chain or cyclic carbonatoms are 1～10 alkyl, or work as R ⁶, R ⁷When expression straight chain shape or branch's catenate carbonatoms are 1～10 alkyl, form ring mutually together or do not form ring.

13. the manufacture method of hyperbranched polymer is characterized in that comprising: make the monomer shown in the following formula (1) carry out living free radical polymerization, the hyperbranched polymer synthesis procedure of synthesis of super branched polymkeric substance; Make this synthetic hyperbranched polymer and the compound reaction that contains sour decomposability group, introduce the sour decomposability group of sour decomposability group at the end of this hyperbranched polymer and introduce operation,

Formula (1)

In the formula (1), the carbonatoms that Y represents to contain or do not contain hydroxyl or carboxyl is 1～10 alkylidene group, and Z represents halogen atom.

14. the resist composition, it contains each described hyperbranched polymer of claim 1～11.

15. the described resist composition of claim 14, it also contains light acid propellant.