CN101464628A - Novel compound and method of producing the same, acid generator, resist composition and method of forming resist pattern - Google Patents

Abstract

The invention relates to a resist composition including a base component (A) which exhibits changed solubility in an alkali developing solution under action of acid and an acid-generator component (B) which generates acid upon exposure. The invention is characterized in: the acid-generator component (B) including an acid generator (B1) consisting of a compound represented by general formula (b1-1) shown below: <R>x-<Q>3-O-<Q>2-<Y>1-<SO3>-<Z>+ ... (b1-1); wherein <R>x represents a hydrocarbon group which may have a substituent exclusive of a nitrogen atom; <Q>2 and <Q>3 each independently represents a single bond or a divalent linkage group; <Y>1 represents an alkylene group or fluorinated alkyl group of 1 to 4 carbon atoms; and <Z>+ represents an organic cation exclusive of an ion represented by general formula (w-1).

Description

New compound and manufacture method thereof, acid agent, resist composition and resist pattern formation method

Technical field

The present invention relates to use new compound and manufacture method, acid agent, resist composition and the resist pattern formation method of acid agent and can conduct be used as new compound and the manufacture method thereof of resist composition with the intermediate use of the compound of acid agent as the resist composition.

The spy that the application requires on Dec 21st, 2007 to propose in Japan is willing to that the spy who proposed in Japan in 2007-No. 330891,2007 12 years 21 days is willing to 2007-No. 331163 and on March 6th, 2008 proposed in Japan spy is willing to 2008-No. 056880 right of priority, quotes its content at this.

Background technology

In photoetching technique, carry out following operation: for example on substrate, form the resist film that forms by anticorrosive additive material, use up, the electron ray isoradial carries out selectivity exposure to this resist film, implement development treatment, thereby on above-mentioned resist film, form the resist pattern of regulation shape.Part after the exposure is called eurymeric to the anticorrosive additive material that the characteristic of dissolving changes in developer solution, the part after the exposure is called minus to the anticorrosive additive material that the characteristic that is insoluble to developer solution changes.

In recent years, in the manufacturing of semiconductor element and liquid crystal display cells, along with the progress of photoetching technique, the miniaturization of pattern development rapidly.

As the method for miniaturization, the wavelength of exposure light source is shortened.Particularly, adopted with g line, i line is the ultraviolet ray of representative in the past, but begins to adopt KrF excimer laser or ArF excimer laser to carry out the batch process of semiconductor element now.In addition, studying the short F of the above-mentioned excimer laser of wavelength ratio ₂Excimer laser, electron ray, EUV (extreme ultraviolet) and X ray etc.

Be accompanied by the short wavelengthization of exposure light source, seek anticorrosive additive material with respect to the sensitivity of exposure light source, photolithographic characteristics such as the exploring degree raising that can reproduce the pattern of fine sizes.As the anticorrosive additive material that satisfies this requirement, known have contain under the effect of acid base material component that the dissolubility to alkaline developer changes and by exposing to the chemical amplification type anti-corrosion agent of acidic acid agent composition.

In the past; base material component as this chemical amplification type anti-corrosion agent; the main resin that adopts, a part of for example using polycarboxylated styrene (PHS) or its hydroxyl by the acid dissociation dissolving suppress the base protection PHS resinoids such as resin, derive and the part of the multipolymer that comes or its carboxyl is suppressed the resin of base protection etc. by the acid dissociation dissolving by (methyl) acrylate.

In addition, " (methyl) acrylate " is meant a side or two sides in the methacrylate of the acrylate of α position and hydrogen atom bonding and α position and methyl bonding." (methyl) acrylates " is meant a side or two sides in the methacrylate of the acrylates of α position and hydrogen atom bonding and α position and methyl bonding." (methyl) acrylic acid " is meant a side or two sides in the methacrylic acid of the acrylic acid of α position and hydrogen atom bonding and α position and methyl bonding.

Up to now, proposed the multiple acid agent that uses in the chemical amplification type anti-corrosion agent, known have for example salt such as salt compounded of iodine, sulfonium salt acid agent etc. (for example with reference to patent documentation 1).

Patent documentation 1: the Jap.P. spy opens communique 2003-No. 241385

As above-mentioned salt acid agent, general now the employing has the salt acid agent of perfluoro alkyl sulfonic acid ion as negative ion portion (acid).

But this salt acid agent compatibility to alkaline developer on its structure is low, and is difficult in that homogeneous distributes in the resist film, might cause harmful effect to photolithographic characteristics such as exploring degree.

In addition, the perfluoroalkyl chain of above-mentioned negative ion portion is because the diffusion of the acid after suppressing exposure, so thinks that the longer the better, is difficult to decomposition but carbon number is 6～10 perfluoroalkyl chain.For this reason, from considering the handling safety aspect of the biosome property accumulated, using carbon number is perfluoro alkyl sulfonic acid ion, for example ninth of the ten Heavenly Stems fluorine butane azochlorosulfonate acid ion etc. below 4.

Therefore, demand has to liken to and is the salt compounds of resist composition with the more useful negative ion portion of acid agent, meanwhile also need be when making this compound useful as intermediates.

Summary of the invention

The present invention is the invention of In view of the foregoing finishing, and its purpose is to provide as the resist composition with the new compound of acid agent and manufacture method, acid agent, resist composition and resist pattern formation method and new compound and the manufacture method thereof that can use as the synthetic intermediate during with the compound of acid agent as the resist composition.

To achieve these goals, the present invention adopts following formation.

Promptly, the 1st mode of the present invention is a kind of resist composition, it is to contain under the effect of acid base material component (A) that the dissolubility to alkaline developer changes and by exposing to the resist composition of acidic acid agent composition (B), it is characterized in that, above-mentioned acid agent composition (B) contains the acid agent (B1) that the compound by following general formula (b1-1) expression forms

In the formula, R ^XBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ²And Q ³Be the linking group of singly-bound or divalent independently respectively; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; Z ⁺Be organic cation, but be not the ion of following general formula (w-1) expression,

In the formula, R ³～R ⁶Maybe can have substituent alkyl for hydrogen atom independently respectively, R ³～R ⁶In at least 1 be above-mentioned alkyl, R ³～R ⁶In at least 2 can be bonded to ring respectively.

The 2nd mode of the present invention is a kind of resist pattern formation method, and it comprises: use the resist composition of above-mentioned the 1st mode to form the operation of resist film on supporter; Operation with above-mentioned resist film exposure; And above-mentioned resist film is carried out alkali develop and form the operation of resist pattern.

The 3rd mode of the present invention is the compound (hereinafter referred to as compound (b1-1)) of following general formula (b1-1) expression.

[in the formula, R ^XBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ²And Q ³Be the linking group of singly-bound or divalent independently respectively; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; Z ⁺Be organic cation, but be not the ion of following general formula (w-1) expression.]

[in the formula, R ³～R ⁶Maybe can have substituent alkyl for hydrogen atom independently respectively, R ³～R ⁶In at least 1 be above-mentioned alkyl, R ³～R ⁶In at least 2 can be bonded to ring respectively.]

The 4th mode of the present invention is a kind of manufacture method of compound, and it comprises: the operation (hereinafter referred to as the manufacture method of compound (b1-1)) that obtains the compound (b1-1) of following general formula (b1-1) expression by the compound (b0-1) and compound (b0-02) reaction of following general formula (b0-02) expression that makes following general formula (b0-1) expression.

Z ⁺ A ^- …(b0—02)

[in the formula, R ^XBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ²And Q ³Be the linking group of singly-bound or divalent independently respectively; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; W ⁺It is the ion of alkali metal ion or following general formula (w-1) expression; Z ⁺Be organic cation, but be not the ion of following general formula (w-1) expression; A ^-It is non-nucleophilicity negative ion.]

[in the formula, R ³～R ⁶Maybe can have substituent alkyl for hydrogen atom independently respectively, R ³～R ⁶In at least 1 be above-mentioned alkyl, R ³～R ⁶In at least 2 can be bonded to ring respectively.]

The 5th mode of the present invention is a kind of acid agent, and its compound by above-mentioned the 3rd mode forms.

The 6th mode of the present invention is a kind of compound, and it is by following general formula (b0-1) expression (hereinafter referred to as compound (b0-1)).

[in the formula, R ^XBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ²And Q ³Be the linking group of singly-bound or divalent independently respectively; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; R ³～R ⁶Maybe can have substituent alkyl for hydrogen atom independently respectively, R ³～R ⁶In at least 1 be above-mentioned alkyl, R ³～R ⁶In at least 2 can be bonded to ring respectively.]

The 7th mode of the present invention is a kind of manufacture method of compound, and it comprises: react the operation (hereinafter referred to as the manufacture method (1) of compound (b0-1)) of the compound (b0-1) that obtains following general formula (b0-1) expression by the compound (1-11) that makes following general formula (1-11) expression, compound (1-12) and the amine or the ammonium salt of following general formula (1-12) expression.

R ^X—Q ³—X ²¹…(1-12)

[in the formula, R ^XBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ²And Q ³Be the linking group of singly-bound or divalent independently respectively; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; R ³～R ⁶Maybe can have substituent alkyl for hydrogen atom independently respectively, R ³～R ⁶In at least 1 be above-mentioned alkyl, R ³～R ⁶In at least 2 can be bonded to ring respectively; X ²¹Be halogen atom; M ⁺Be alkali metal ion.]

The 8th mode of the present invention is a kind of manufacture method of compound, and it comprises: react the operation (hereinafter referred to as the manufacture method (2) of compound (b0-1)) of the compound (b0-1) that obtains following general formula (b0-1) expression by the compound (1-21) that makes following general formula (1-21) expression, compound (1-12) and the amine or the ammonium salt of following general formula (1-12) expression.

R ^X—Q ³—X ²¹ …(1—12)

[in the formula, R ^XBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ²And Q ³Be the linking group of singly-bound or divalent independently respectively; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; R ³～R ⁶Maybe can have substituent alkyl for hydrogen atom independently respectively, R ³～R ⁶In at least 1 be above-mentioned alkyl, R ³～R ⁶In at least 2 can be bonded to ring respectively; R ^{3 '}～R ^{6 '}Maybe can have substituent alkyl for hydrogen atom independently respectively, R ^{3 '}～R ^{6 '}In at least 1 be above-mentioned alkyl, R ^{3 '}～R ^{6 '}In at least 2 can be bonded to ring respectively; X ²¹Be halogen atom.]

The 9th mode of the present invention is a kind of compound, and it is the compound (1-21) by following general formula (1-21) expression.

[in the formula, Q ²It is the linking group of singly-bound or divalent; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; R ^{3 '}～R ^{6 '}Maybe can have substituent alkyl for hydrogen atom independently respectively, R ^{3 '}～R ^{6 '}In at least 1 be above-mentioned alkyl, R ^{3 '}～R ^{6 '}In at least 2 can be bonded to ring respectively.]

The 10th mode of the present invention is a kind of manufacture method of compound, and it comprises: the operation (hereinafter referred to as the manufacture method of compound (1-21)) of reacting the compound (1-21) that obtains following general formula (1-21) expression by compound (1-11) and the ammonium salt that makes following general formula (1-11) expression.

[in the formula, Q ²It is the linking group of singly-bound or divalent; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; R ^{3 '}～R ^{6 '}Maybe can have substituent alkyl for hydrogen atom independently respectively, R ^{3 '}～R ^{6 '}In at least 1 be above-mentioned alkyl, R ^{3 '}～R ^{6 '}In at least 2 can be bonded to ring respectively; M ⁺Be alkali metal ion.]

The 11st mode of the present invention is a kind of manufacture method of compound, and it comprises: the operation (hereinafter referred to as the manufacture method of compound (1-14)) of reacting the compound (1-14) that obtains following general formula (1-14) expression by compound (1-13) and the ammonium salt that makes following general formula (1-13) expression.

[in the formula, R ^cBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ⁴It is the linking group of singly-bound or divalent; N is 0 or 1; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; R ^{3 '}～R ^{6 '}Maybe can have substituent alkyl for hydrogen atom independently respectively, R ^{3 '}～R ^{6 '}In at least 1 be above-mentioned alkyl, R ^{3 '}～R ^{6 '}In at least 2 can be bonded to ring respectively; M ⁺Be alkali metal ion.]

In this instructions and claims, " aliphatics " is the notion relative with aromatic series, is defined as group with aromaticity, compound etc.

" alkylidene " do not having under the situation of specified otherwise, comprises the divalent saturated hydrocarbyl of straight chain shape, a chain and ring-type.

" alkyl " do not having under the situation of specified otherwise, comprises 1 valency saturated hydrocarbyl of straight chain shape, a chain and ring-type." low alkyl group " is that carbon number is 1～5 alkyl.

" structural unit " is meant the monomeric unit (monomeric unit) that constitutes resinous principle (polymkeric substance).

The notion of " exposure " comprises all radiation exposures.

According to the present invention, can provide as the resist composition with the new compound of acid agent and manufacture method, acid agent, resist composition and resist pattern formation method and new compound and the manufacture method thereof that can use as synthetic intermediate during with the compound of acid agent as the resist composition.

Embodiment

＜＜compound (b0-1)〉〉

At first, the compound (b0-1) to the 6th mode of the present invention describes.

The compound of the 6th mode of the present invention (b0-1) is the compound with above-mentioned general formula (b0-1) expression.

In the formula (b0-1), R ^XAlkyl can be an aromatic hydrocarbyl, also can be aliphatic alkyl.

R ^XAromatic hydrocarbyl be alkyl with aromatic ring, the carbon number of this aromatic hydrocarbyl is preferably 3～30, more preferably 5～30, more preferably 5～20, be preferably 6～15 especially, most preferably be 6～12.But this carbon number does not comprise the carbon number in the substituting group.

As aromatic hydrocarbyl, can enumerate specifically that phenyl, biphenyl (biphenyl) base, fluorenes (fluorenyl) base, naphthyl, anthracene (anthryl) base, phenanthryl etc. are removed 1 hydrogen atom by the aromatic hydrocarbon ring and aryl alkyl such as the aryl that obtains, benzyl, phenethyl, 1-naphthyl methyl, 2-naphthyl methyl, 1-naphthyl ethyl, 2-naphthyl ethyl etc.The carbon number of the alkyl chain in the above-mentioned aryl alkyl is preferably 1～4, and more preferably 1～2, be preferably 1 especially.

This aromatic hydrocarbyl can have substituting group.The part of the carbon atom of the aromatic ring that for example constitutes this aromatic hydrocarbyl and had can be replaced by heteroatoms, and the hydrogen atom that is bonded to the aromatic ring that this aromatic hydrocarbyl has also can be substituted base and replace.

As the former example, can enumerate the ring that constitutes above-mentioned aryl carbon atom a part by heteroatomss such as oxygen atom, sulphur atom (but except nitrogen-atoms) replace the heteroaryl that obtains, the part of the carbon atom that constitutes the aromatic hydrocarbon ring in the above-mentioned aryl alkyl is replaced the heteroaryl alkyl that obtains by above-mentioned heteroatoms etc.

As the substituting group of the aromatic hydrocarbyl in the latter's the example, for example can enumerate alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, oxygen atom (=O) etc.

About the substituent alkyl as above-mentioned aromatic hydrocarbyl, preferred carbon number is 1～5 alkyl, most preferable, ethyl, propyl group, normal-butyl, the tert-butyl group.

About the substituent alkoxy as above-mentioned aromatic hydrocarbyl, preferred carbon number is 1～5 alkoxy, further preferred methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, most preferably methoxyl, ethoxy.

About substituent halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom etc., preferred fluorine atom as above-mentioned aromatic hydrocarbyl.

About the substituent haloalkyl as above-mentioned aromatic hydrocarbyl, part or all of hydrogen atom that can enumerate abovementioned alkyl replaced by above-mentioned halogen atom and the group that obtains.

R ^XAliphatic alkyl can be the representative examples of saturated aliphatic alkyl, also can be the unsaturated fatty hydrocarbons base.Aliphatic alkyl can be any in straight chain shape, a chain, the ring-type.

About R ^XAliphatic alkyl, can be that the substituting group that the part that constitutes the carbon atom of this aliphatic alkyl is contained heteroatoms (but except nitrogen-atoms) replaces, also can be that part or all of hydrogen atom that constitutes this aliphatic alkyl contained the substituting group replacement of heteroatoms (but except nitrogen-atoms).

As R ^XIn " heteroatoms ", so long as carbon atom, hydrogen atom and nitrogen-atoms beyond atom get final product, do not have particular restriction, can enumerate for example halogen atom, oxygen atom, sulphur atom etc.

As halogen atom, can enumerate fluorine atom, chlorine atom, iodine atom, bromine atoms etc.

The substituting group that contains heteroatoms (but except nitrogen-atoms) can be the substituting group that is only formed by above-mentioned heteroatoms, also can be to contain the group beyond the above-mentioned heteroatoms or the group of atom.

As the substituting group that replaces a part of carbon atom, specifically for example can enumerate-O-,-C (=O)-O-,-C (=O)-,-O-C (=O)-O-,-S-,-S (=O) ₂-,-S (=O) ₂-O-etc.When aliphatic alkyl is ring-type, also can in ring structure, contain these substituting groups.

As the substituting group that replaces part or all hydrogen atom, for example specifically can enumerate alkoxy, halogen atom, haloalkyl, hydroxyl, oxygen atom (=O) etc.

As above-mentioned alkoxy, preferred carbon number is 1～5 alkoxy, further preferred methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, most preferably methoxyl, ethoxy.

As above-mentioned halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom etc., preferred fluorine atom.

As above-mentioned haloalkyl, can enumerate carbon number and be 1～5 alkyl, for example part or all of the hydrogen atom of alkyl such as methyl, ethyl, propyl group, normal-butyl, the tert-butyl group replaced by above-mentioned halogen atom and the group that obtains.

As aliphatic alkyl, the saturated hydrocarbyl of a preferred straight chain shape or a chain, straight chain shape or the 1 valency unsaturated alkyl of a chain or the aliphatic alkyl (alicyclic group) of ring-type.

As the saturated hydrocarbyl (alkyl) of straight chain shape, preferred carbon number is 1～20, more preferably 1～15, most preferably be 1～10.Particularly, can enumerate for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, pentadecyl, cetyl, isocetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl etc.

As the saturated hydrocarbyl (alkyl) of chain, preferred carbon number is 3～20, more preferably 3～15, most preferably be 3～10.Particularly, can enumerate for example 1-Methylethyl, 1-methyl-propyl, 2-methyl-propyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1-ethyl-butyl, 2-ethyl-butyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl etc.

As unsaturated alkyl, preferred carbon number is 2～10, more preferably 2～5, more preferably 2～4, be preferably 3 especially.As 1 valency unsaturated alkyl of straight chain shape, can enumerate for example vinyl, propenyl (allyl), butenyl group etc.As 1 valency unsaturated alkyl of a chain, can enumerate for example 1-methylpropenyl, 2-methylpropenyl etc.

Preferred especially propenyl in the above-mentioned unsaturated alkyl.

As alicyclic group, can be the monocycle base, also can be many cyclic groups.Its carbon number is preferably 3～30, and more preferably 5～30, more preferably 5～20, be preferably 6～15 especially, most preferably be 6～12.

Particularly, can enumerate the group of for example removing the hydrogen atom more than 1 and obtaining by mononaphthene; Remove group that 1 above hydrogen atom obtains etc. by polynaphthenes such as dicyclo alkane, three cycloalkanes, tetracycloalkanes.More specifically, can enumerate the group of for example removing the hydrogen atom more than 1 and obtaining by mononaphthenes such as cyclopentane, cyclohexanes; Remove 1 above hydrogen atom and group of obtaining etc. by polynaphthenes such as diamantane, norbornane, isoborneol alkane, tristane, Fourth Ring dodecanes.

When alicyclic group does not have in its ring structure when containing heteroatomic substituting group, as alicyclic group, preferred many cyclic groups are further preferably removed 1 above hydrogen atom by polynaphthene and the group that obtains, most preferably remove 1 above hydrogen atom by diamantane and the group that obtains.

When alicyclic group has in its ring structure when containing heteroatomic substituting group, contain heteroatomic substituting group as this, preferred-O-,-C (=O)-O-,-S-,-S (=O) ₂-,-S (=O) ₂-O-.As the object lesson of described alicyclic group, can enumerate for example following formula (L1)～(L5), (S1)～(S4) etc.

[in the formula, Q " be carbon number be 1～5 alkylidene ,-O-,-S-,-O-R ⁹⁴-or-S-R ⁹⁵-, R ⁹⁴And R ⁹⁵Be respectively that carbon number is 1～5 alkylidene independently, m is 0 or 1 integer.]

As Q " alkylidene, can enumerate and above-mentioned R ¹The identical group of alkylidene.

As R ⁹⁴And R ⁹⁵Alkylidene, can enumerate and above-mentioned R ¹The identical group of alkylidene.

About these alicyclic groups, a part that is bonded to the hydrogen atom on the carbon atom that constitutes its ring structure can be substituted base and replace.As this substituting group, for example can enumerate alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, oxygen atom (=O) etc.

As abovementioned alkyl, preferred carbon number is 1～5 alkyl, special preferable methyl, ethyl, propyl group, normal-butyl, the tert-butyl group.

About above-mentioned alkoxy, halogen atom, can enumerate respectively with as replace above-mentioned hydrogen atom part or all substituting group and the identical group of group enumerated.

In the present invention, as R ^X, preferably can have substituent straight chain shape alkyl, maybe can have substituent cyclic group.As this cyclic group, can be to have substituent aromatic hydrocarbyl, also can be to have substituent alicyclic group, further preferably can have substituent alicyclic group.

As above-mentioned aromatic hydrocarbyl, preferably can have substituent naphthyl and maybe can have substituent phenyl.

As having substituent alicyclic group, preferably can have substituent polycycle alicyclic group.As this polycycle alicyclic group, preferably remove 1 above hydrogen atom and the group that obtains, above-mentioned (L2)～(L5), (S3)～(S4) etc., wherein preferred adamantyl by above-mentioned polynaphthene.

Q ²And Q ³Be the linking group of singly-bound or divalent independently respectively.

As the linking group of divalent, for example can enumerate alkylidene, contain heteroatomic group (hereinafter referred to as containing heteroatomic linking group) etc.

" heteroatoms " that contain in the heteroatomic linking group is meant carbon atom and hydrogen atom atom in addition, can enumerate for example oxygen atom, sulphur atom, nitrogen-atoms etc.

About alkylidene as the divalent linking group, can be the straight chain shape, also can be a chain.The carbon number of this alkylidene is preferably 1～12, and more preferably 1～5, be preferably 1～3 especially.

As this alkylidene, specifically can enumerate for example methylene [CH ₂-];-CH (CH ₃)-,-CH (CH ₂CH ₃)-,-C (CH ₃) ₂-,-C (CH ₃) (CH ₂CH ₃)-,-C (CH ₃) (CH ₂CH ₂CH ₃)-,-C (CH ₂CH ₃) ₂-wait the alkyl methylene; Ethylidene [CH ₂CH ₂-];-CH (CH ₃) CH ₂-,-CH (CH ₃) CH (CH ₃)-,-C (CH ₃) ₂CH ₂-,-CH (CH ₂CH ₃) CH ₂-wait the alkyl ethylidene; Trimethylene (positive propylidene) [CH ₂CH ₂CH ₂-];-CH (CH ₃) CH ₂CH ₂-,-CH ₂CH (CH ₃) CH ₂-wait the alkyl trimethylene; Tetramethylene [CH ₂CH ₂CH ₂CH ₂-];-CH (CH ₃) CH ₂CH ₂CH ₂-,-CH ₂CH (CH ₃) CH ₂CH ₂-wait the alkyl tetramethylene; Pentamethylene [CH ₂CH ₂CH ₂CH ₂CH ₂-] etc.

As containing heteroatomic linking group, can enumerate for example oxygen atom (ehter bond;-O-), sulphur atom (thioether bond;-S-) ,-NH-key (H can by substituting groups such as alkyl, acyl group replace), ester bond (C (=O)-O-), amido link (C (=O)-NH-), carbonyl (C (=O)-), carbonic acid ester bond (O-C (=O)-O-) etc. non-hydrocarbons contains heteroatomic linking group; This non-hydrocarbons contains the composition of heteroatomic linking group and above-mentioned alkylidene.As said composition, for example can enumerate-R ⁹¹-O-,-R ⁹²-O-C (=O)-,-C (=O)-O-R ⁹³-(R in the formula ⁹¹～R ⁹³Be alkylidene independently respectively) etc. or their composition.As R in the following formula ⁹¹～R ⁹³Alkylidene, can enumerate and the identical group of enumerating as above-mentioned divalent linking group of alkylidene.

As Q ², preferred carbonyl, singly-bound ,-R ⁹²-O-C (=O)-.

As Q ³, preferred singly-bound, alkylidene, carbonyl.

Preferred especially Q ²Be carbonyl and Q ³Be singly-bound or Q ²Be singly-bound and Q ³Be alkylidene or Q ²For-R ⁹²-O-C (=O)-and Q ³Be carbonyl.

In the formula (b0-1), Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene.

As Y ¹Alkylidene, can enumerate with the alkylidene of enumerating as above-mentioned divalent linking group in carbon number be 1～4 the identical group of alkylidene.As the fluoro alkylidene, can enumerate part or all group that is obtained by the fluorine atom replacement of the hydrogen atom of this alkylidene.

As Y ¹, specifically can enumerate-CF ₂-,-CF ₂CF ₂-,-CF ₂CF ₂CF ₂-,-CF (CF ₃) CF ₂-,-CF (CF ₂CF ₃)-,-C (CF ₃) ₂-,-CF ₂CF ₂CF ₂CF ₂-,-CF (CF ₃) CF ₂CF ₂-,-CF ₂CF (CF ₃) CF ₂-,-CF (CF ₃) CF (CF ₃)-,-C (CF ₃) ₂CF ₂-,-CF (CF ₂CF ₃) CF ₂-,-CF (CF ₂CF ₂CF ₃)-,-C (CF ₃) (CF ₂CF ₃)-;-CHF-,-CH ₂CF ₂-,-CH ₂CH ₂CF ₂-,-CH ₂CF ₂CF ₂-,-CH (CF ₃) CH ₂-,-CH (CF ₂CF ₃)-,-C (CH ₃) (CF ₃)-,-CH ₂CH ₂CH ₂CF ₂-,-CH ₂CH ₂CF ₂CF ₂-,-CH (CF ₃) CH ₂CH ₂-,-CH ₂CH (CF ₃) CH ₂-,-CH (CF ₃) CH (CF ₃)-,-C (CF ₃) ₂CH ₂-;-CH ₂-,-CH ₂CH ₂-,-CH ₂CH ₂CH ₂-,-CH (CH ₃) CH ₂-,-CH (CH ₂CH ₃)-,-C (CH ₃) ₂-,-CH ₂CH ₂CH ₂CH ₂-,-CH (CH ₃) CH ₂CH ₂-,-CH ₂CH (CH ₃) CH ₂-,-CH (CH ₃) CH (CH ₃)-,-C (CH ₃) ₂CH ₂-,-CH (CH ₂CH ₃) CH ₂-,-CH (CH ₂CH ₂CH ₃)-,-C (CH ₃) (CH ₂CH ₃)-etc.

As Y ¹, preferred fluoro alkylidene especially preferably is bonded to the fluoro alkylidene that the carbon atom of adjacent sulphur atom is replaced by fluorine.As such fluoro alkylidene, can enumerate-CF ₂-,-CF ₂CF ₂-,-CF ₂CF ₂CF ₂-,-CF (CF ₃) CF ₂-,-CF ₂CF ₂CF ₂CF ₂-,-CF (CF ₃) CF ₂CF ₂-,-CF ₂CF (CF ₃) CF ₂-,-CF (CF ₃) CF (CF ₃)-,-C (CF ₃) ₂CF ₂-,-CF (CF ₂CF ₃) CF ₂-;-CH ₂CF ₂-,-CH ₂CH ₂CF ₂-,-CH ₂CF ₂CF ₂-;-CH ₂CH ₂CH ₂CF ₂-,-CH ₂CH ₂CF ₂CF ₂-,-CH ₂CF ₂CF ₂CF ₂-etc.

Wherein, preferred-CF ₂-,-CF ₂CF ₂-,-CF ₂CF ₂CF ₂-or CH ₂CF ₂CF ₂-, further preferably-CF ₂-,-CF ₂CF ₂-or-CF ₂CF ₂CF ₂-, especially preferably-CF ₂-.

In the formula (b0-1), R ³～R ⁶Maybe can have substituent alkyl for hydrogen atom independently respectively, R ³～R ⁶In at least 1 be above-mentioned alkyl.

As R ³～R ⁶Alkyl, can enumerate and above-mentioned R ^XIdentical group.

This alkyl can be an aliphatic alkyl, also can be aromatic hydrocarbyl.When this alkyl is aliphatic alkyl,, especially preferably can have substituent carbon number and be 1～12 alkyl as this aliphatic alkyl.

As the substituting group that this alkyl can have, can enumerate with as above-mentioned R ^XThe alkyl substituting group that can have and the identical group of group enumerated, preferred especially hydroxyl.In addition, for example nitrogen-atoms, cyano group (CN), amino (NH of the substituting group that can also have a nitrogen atom ₂), amide group (NH-C (=O)-) etc.

R ³～R ⁶In at least 1 be described alkyl, preferred 2 or 3 is described alkyl.

R ³～R ⁶In at least 2 can be bonded to ring respectively.For example, can be R ³～R ⁶In 2 bondings form 1 ring, also can be R ³～R ⁶In 3 bondings form 1 ring, can also be R ³～R ⁶In each 2 respectively bondings form 2 rings.

As R ³～R ⁶In at least 2 rings (nitrogen atom is as heteroatomic heterocycle) of forming of bonding and the nitrogen-atoms in formula respectively, can be the aliphatics heterocycle, also can be heteroaromatic.In addition, this heterocycle can be a monocycle, also can be many rings.

As (the N of kation portion in the formula (b0-1) ⁺(R ³) (R ⁴) (R ⁵) (R ⁶)) object lesson, can enumerate by amine and derive and the ammonium ion that comes.

Here, " derive and the ammonium ion that comes " and be meant the nitrogen-atoms of amine and the kation that the hydrogen atom bonding forms, nitrogen-atoms and quaternary ammonium ion that the substituting group bonding forms of amine by amine.

The amine of above-mentioned ammonium ion of deriving can be fatty amine, also can be aromatic amine.

As fatty amine, preferred especially ammonia NH ₃At least 1 of hydrogen atom be that alkyl or hydroxyalkyl below 12 replaces amine (alkyl amine or alkyl alcoholamine) or the cyclammonium that obtains by carbon number.

As the object lesson of alkyl amine and alkyl alcoholamine, can enumerate alkyl amines such as n-hexyl amine, n-heptyl amine, n-octylamine, n-nonyl amine, positive decyl amine; Dialkylamines such as diethylamide, di-n-propyl amine, two n-heptyl amine, di-n-octyl amine, dicyclohexyl amine; Trialkylamines such as Trimethylamine, triethylamine, three n-pro-pyl amine, tri-n-butyl amine, three n-hexyl amine, three n-pentyl amine, three n-heptyl amine, three n-octylamine, three n-nonyl amine, three positive decyl amine, three dodecyl amine; Alkyl alcoholamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, two n-octyl alcohol amine, three n-octyl alcohol amine.

As cyclammonium, can enumerate and for example contain nitrogen-atoms as heteroatomic heterogeneous ring compound.As this heterogeneous ring compound, can be monocyclic compound (aliphatics monocycle amine), also can be polycyclic compund (aliphatics polycyclic amines).

As aliphatics monocycle amine, specifically can enumerate piperidines, piperazine etc.

As the aliphatics polycyclic amines, preferred carbon number is 6～10 aliphatics polycyclic amines, specifically can enumerate 1,5-diazo bicyclic [4.3.0]-5-nonene, 1,8-diazo bicyclic [5.4.0]-7-undecylene, hexamethylene tetramine, 1,4-diazo bicyclic [2.2.2] octane etc.

As aromatic amine, can enumerate aniline, pyridine, 4-dimethylaminopyridine (DMAP), pyrroles, indoles, pyrazoles, imidazoles etc.

As quaternary ammonium ion, can enumerate tetramethyl ammonium, tetraethyl ammonium ion, TBuA ion etc.

In the present invention, as (the N of kation portion in the formula (b0-1) ⁺(R ³) (R ⁴) (R ⁵) (R ⁶)), preferred especially R ³～R ⁶In at least 1 be that alkyl and at least 1 are the kation portion of hydrogen atom.

Wherein, preferred R ³～R ⁶In 3 for alkyl and remain 1 and be kation of hydrogen atom (trialkyl ammonium ion) or R ³～R ⁶In 2 for alkyl and remain 1 and be the kation of hydrogen atom (dialkyl ammonium ion).

The preferred independently respectively carbon number of alkyl in trialkyl ammonium ion or the dialkyl ammonium ion is 1～10, more preferably 1～8, most preferably be 1～5.Specifically can enumerate for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl etc.Ethyl most preferably wherein.

In the present invention, compound (b0-1) is preferably the compound of following general formula (b0-1-1) expression, the compound that is preferably following general formula (b0-1-11) especially or (b0-1-12) represents.

[in the formula, R ^X, Q ³, Y ¹, R ³～R ⁶Respectively with above-mentioned general formula (b0-1) in R ^X, Q ³, Y ¹, R ³～R ⁶Identical, n is 0 or 1.]

[in the formula, n, Y ¹, R ³～R ⁶Respectively with above-mentioned general formula (b0-1-1) in n, Y ¹, R ³～R ⁶Identical, R ¹Be alkylidene, R ^bAnd R ^cRespectively independently for having the alkyl of substituting group (but except nitrogen-atoms), Q ⁴Be singly-bound or alkylidene.]

In the formula (b0-1-11), as R ^b, can enumerate and above-mentioned R ^XIdentical group, preferably can have substituent straight chain shape or chain saturated hydrocarbyl, can have substituent alicyclic group, maybe can have substituent aromatic hydrocarbyl.Wherein, the saturated hydrocarbyl of preferred straight chain shape maybe can have substituent alicyclic group.

As R ¹Alkylidene, the alkylidene of a preferred straight chain shape or a chain, the carbon number of this alkylidene is preferably 1～12, more preferably 1～5, be preferably 1～3 especially.As object lesson, can enumerate and the identical group of enumerating as above-mentioned divalent linking group of alkylidene.

As the R in the formula (b0-1-12) ^c, can enumerate and above-mentioned R ^XIdentical group preferably can have substituent alicyclic group and maybe can have substituent aromatic hydrocarbyl.Wherein, preferably in its ring structure, have and contain heteroatomic substituent alicyclic group.

As Q ⁴Alkylidene, can enumerate and the identical group of enumerating as above-mentioned divalent linking group of alkylidene.

N is preferably 1.

As compound (b0-1), the compound of preferred especially following general formula (b0-1-21)～(b0-1-22), (b0-1-31)～(b0-1-35) expression.

[in the formula, d, e, f are respectively 1～10 integer independently, and p is 1～3 integer, and q1～q2 is respectively 1～5 integer independently, and r1 is 0～3 integer, and g is 1～20 integer, R ⁷Be substituting group.]

[in the formula, Q ", d, e, f, p be same as described above respectively, n1～n3 is respectively 0 or 1 independently, v1～v5 is respectively 0～3 integer independently, w1～w5 is respectively 0～3 integer independently, R ⁷Be substituting group.]

As R ⁷Substituting group, can be set forth in above-mentioned R ^XIn the substituting group, substituting group that aromatic hydrocarbyl can have that can have as aliphatic alkyl and the identical group of group enumerated.

Work as R ⁷With symbol (when r1, w1～w5) are integer more than 2, a plurality of R in this compound ⁷Respectively can be identical, also can be different.

Compound of the present invention (b0-1) is a new compound.

Compound of the present invention (b0-1) can be as using at the synthetic intermediate during with the compound (compound of the 3rd mode particularly of the present invention (b1-1)) of acid agent as the resist composition.

Compound of the present invention (b0-1) for example can adopt compound (b0-1) manufacture method (1) of the present invention's the 7th mode described later or compound (b0-1) manufacture method (2) of the present invention's the 8th mode to make.

The manufacture method (1) of＜＜compound (b0-1)〉〉

Then, compound (b0-1) manufacture method (1) to the present invention's the 7th mode describes.

The manufacture method (1) of compound of the present invention (b0-1) comprising: react the compound (b0-1) that obtains following general formula (b0-1) expression by the compound (1-11) that makes following general formula (1-11) expression, compound (1-12) and the amine or the ammonium salt of following general formula (1-12) expression.

R ^X—Q ³--X ²¹ …(1—12)

[in the formula, R ^X, Q ², Q ³, Y ¹, R ³～R ⁶Respectively with above-mentioned general formula (b0-1) in R ^X, Q ², Q ³, Y ¹, R ³～R ⁶Identical; X ²¹Be halogen atom; M ⁺Be alkali metal ion.]

As the M in the formula (1-11) ⁺, can enumerate sodion, potassium ion, lithium ion etc.

As compound (1-11), can use commercially available compound, also can synthesize.

For example, when compound (1-11) be Q in the formula (1-11) ²When being the compound (hereinafter referred to as compound (1-11-1)) of carbonyl, can enumerating and comprise by the compound (0-1) of following general formula (0-1) expression is obtained the operation (forming operation hereinafter referred to as salt) of the compound (0-2) of following general formula (0-2) expression and above-claimed cpd (0-2) is higher than the method that heats the operation (hereinafter referred to as carboxylic acid chemical industry preface) that obtains compound (1-11-1) down of the acid of compound (1-11-1) in acid strength in heating in the presence of the alkali, neutralization.

[in the formula, R ⁰¹Be alkyl, Y ¹, M ⁺The same.]

As R ⁰¹Alkyl, the alkyl of a preferred straight chain shape or a chain specifically can be enumerated methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, hot amyl group etc.

Wherein, preferred carbon number is 1～4 alkyl, most preferable.

As compound (0-1), can use commercially available product.

Form operation about salt, for example can be by compound (0-1) being dissolved, adds alkali in solvent, heat and implement in this solution.

As solvent,, can enumerate for example water, tetrahydrofuran etc. so long as the solvent of energy dissolved compound (0-1) gets final product.

As alkali, the corresponding alkali of M in use and the formula (0-2) as this alkali, can be enumerated alkali metal hydroxides such as NaOH, potassium hydroxide, lithium hydroxide.

About the consumption of alkali, with respect to 1 mole of compound (0-1), be preferably 1～5 mole, more preferably 2～4 moles.

Heating-up temperature is preferably about 20～120 ℃, more preferably about 50～100 ℃.Heat time heating time is according to heating-up temperature etc. and different, and preferred 0.5～12 hour usually, further preferred 1～5 hour.

About the neutralization after the above-mentioned heating, can implement by adding acid such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid in the reactant liquor after above-mentioned heating.

At this moment, preferably make the pH (25 ℃) of the reactant liquor after acid is added 6～8 implement neutralization.In and the time the temperature of reactant liquor be preferably 20～30 ℃, more preferably 23～27 ℃.

After reaction finishes, can separate, make with extra care the compound in the reactant liquor (0-2).Separate, refiningly can utilize existing known method, for example concentrate, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use in them any separately, or be used in combination more than 2 kinds.

In carboxylic acid chemical industry preface, obtain this compound (1-11-1) by forming the compound (0-2) that obtain in the operation is higher than compound (1-11-1) in acid strength heating down of acid at above-mentioned salt.

The value that " acid strength is higher than the acid (the following strong acid that abbreviates as sometimes) of compound (1-11-1) " is meant pKa (25 ℃) less than in the compound (1-11-1)-acid of COOH.By using described strong acid, in the compound (0-2)-COO ^-M ⁺Become-COOH, obtain compound (1-11-1).

As strong acid, can from known acid, suitably select to use pKa less than in the above-claimed cpd (1-11-1)-acid of the pKa of COOH.In the compound (1-11-1)-pKa of COOH can try to achieve with known titrimetry.

As strong acid, specifically can enumerate sulfonic acid such as aryl sulfonic acid, alkyl sulfonic acid, sulfuric acid, hydrochloric acid etc.As aryl sulfonic acid, can enumerate for example p-toluenesulfonic acid.As alkyl sulfonic acid, can enumerate for example methane-sulforic acid, trifluoromethanesulfonic acid etc.As strong acid, to the dissolubility of organic solvent and the viewpoint of refining easiness, preferred especially p-toluenesulfonic acid.

About carboxylic acid chemical industry preface, for example can be by being dissolved in compound (0-2) in the solvent, adding to heat behind the strong acid and implement.

As solvent,, can enumerate for example acetonitrile, MEK etc. so long as the solvent of energy dissolved compound (0-2) gets final product.

About the consumption of strong acid, with respect to 1 mole of compound (0-2), be preferably 0.5～3 mole, more preferably 1～2 mole.

Heating-up temperature is preferably about 20～150 ℃, more preferably about 50～120 ℃.Heat time heating time is according to heating-up temperature etc. and different, and preferred 0.5～12 hour usually, further preferred 1～5 hour.

After reaction finishes, can separate, make with extra care the compound in the reactant liquor (1-11-1).Separate, refiningly can utilize existing known method, for example concentrate, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use in them any separately, or be used in combination more than 2 kinds.

For example, when compound (1-11) be Q in the formula (1-11) ²For-R ¹-O-C (=O)-(in the formula, R ¹With above-mentioned R ⁹²Equally, be alkylidene) compound (hereinafter referred to as compound (1-11-2)) time, can enumerate the method that the compound (0-3) that comprises by making following general formula (0-3) expression and above-claimed cpd (1-11-1) reaction obtain the operation of compound (1-11-2).

HO—R ¹—O—R ² …(0—3)

[in the formula, R ¹Be alkylidene; R ²For having aromatic radical as substituent fat-based, Y ¹For carbon number 1～4 alkylidene or fluoro alkylidene; M ⁺Be alkali metal ion.]

Make the compound (0-3) and the method for compound (1-11-1) reaction not have particular restriction, for example can be by in solvent, compound (0-3) being mixed, dissolve, heats and implement with compound (1-11-1).

As solvent, can enumerate for example toluene, dichloro-benzenes, 1,2-ethylene dichloride, 1,3-propylene dichloride etc.

As heating-up temperature (temperature of reaction), preferred about 20～140 ℃, more preferably about 60～130 ℃.Usually be preferably 1～72 hour, more preferably 6～48 hour according to heating-up temperature etc. and different heat time heating time.

Above-mentioned reaction can be carried out in the presence of acidic catalyst.As acidic catalyst, there is not particular restriction, can enumerate for example sulfonic acid such as aryl sulfonic acid, alkyl sulfonic acid, sulfuric acid, hydrochloric acid etc.As aryl sulfonic acid, can enumerate for example p-toluenesulfonic acid.As alkyl sulfonic acid, can enumerate for example methane-sulforic acid, trifluoromethanesulfonic acid etc.Can use in them any separately, also can share more than 2 kinds.As acidic catalyst, to the dissolubility of organic solvent and the viewpoint of refining easiness, preferred especially p-toluenesulfonic acid.

About the consumption of acidic catalyst, with respect to 1 mole of compound (1-11-1), be preferably 0.1～2 mole, more preferably 0.1～1 mole.

After reaction finishes, can separate, make with extra care the compound in the reactant liquor (1-11-2).Separate, refiningly can utilize existing known method, for example concentrate, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use in them any separately, or be used in combination more than 2 kinds.

As the X in the formula (1-12) ²¹Halogen atom, can enumerate bromine atoms, chlorine atom, iodine atom, fluorine atom etc., from reactive excellent viewpoint, preferred bromine atoms or chlorine atom.

As compound (1-12), can use commercially available product.

As amine or ammonium salt, can use with formula (b0-1) in (the N of kation portion ⁺(R ³) (R ⁴) (R ⁵) (R ⁶)) corresponding material.As the object lesson of this amine, can enumerate above-mentioned conduct the derive amine of ammonium ion and the alkyl amine enumerated, dialkylamine, trialkylamine, aromatic amine etc.As the object lesson of ammonium salt, can enumerate quaternary ammonium salts such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TBAH etc.

As making compound (1-11), compound (1-12) and the method that amine or ammonium salt react, there is not particular restriction, can enumerate the method that compound (1-11), compound (1-12) are contacted with amine or ammonium salt.Adding compound (1-12) and amine or quaternary ammonium compound in the solution that this method for example can obtain by dissolved compound in reaction dissolvent (1-11) implements.

As reaction dissolvent, as long as energy dissolved compound (1-11) and compound (1-12) specifically can be enumerated tetrahydrofuran (THF), acetone, dimethyl formamide (DMF), dimethyl acetamide, dimethyl sulfoxide (DMSO) (DMSO), acetonitrile etc.

About the addition of compound (1-12), with respect to compound (1-11), preferably be about 1～3 equivalent, further preferred 1～2 equivalent.

About the addition of amine or quaternary ammonium compound, with respect to compound (1-11), preferably be about 1～3 equivalent, further preferred 1～2 equivalent.

Temperature of reaction is preferably-20～40 ℃, more preferably 0～30 ℃.Reaction time is preferably 1～120 hour, more preferably 1～48 hour usually according to the reactivity of compound (1-11) and compound (1-12) and temperature of reaction etc. and different.

After reaction finishes, can separate, make with extra care the compound in the reactant liquor (b0-1).Separate, refiningly can utilize existing known method, for example wash, concentrate, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use in them any separately, or be used in combination more than 2 kinds.

In the present invention, compound (b0-1) has N ⁺(R ³) (R ⁴) (R ⁵) (R ⁶) as kation portion, owing to be insoluble in water, therefore can make with extra care by washing.

The structure of the compound that obtains (b0-1) can be passed through ¹H-nuclear magnetic resonance (NMR) spectrometry, ¹³The C-NMR spectrometry, ¹⁹General organic analysis methods such as F-NMR spectrometry, infrared ray absorbing (IR) spectrometry, mass spectrum (MS) method, elemental microanalysis method, X ray crystal diffraction method are confirmed.

The manufacture method (2) of＜＜compound (b0-1), compound (1-21)〉〉

Then, compound (b0-1) manufacture method (2) of the present invention's the 8th mode and the compound (1-21) of the present invention ground 9 modes are described.

The manufacture method (2) of compound of the present invention (b0-1) comprises that compound (1-12) and amine or the ammonium salt by the compound (1-21) that makes following general formula (1-21) expression, following general formula (1-12) expression reacts the operation of the compound (b0-1) that obtains following general formula (b0-1) expression.

R ^X—Q ³—X ²¹ …(1—12)

[in the formula, R ^X, Q ², Q ³, Y ¹, R ³～R ⁶Respectively with above-mentioned general formula (b0-1) in R ^X, Q ², Q ³, Y ¹, R ³～R ⁶Identical; R ^{3 '}～R ^{6 '}Maybe can have substituent alkyl for hydrogen atom independently respectively, R ^{3 '}～R ^{6 '}In at least 1 be above-mentioned alkyl, R ^{3 '}～R ^{6 '}In at least 2 respectively bonding form ring; X ²¹Be halogen atom.]

As the R in the formula (1-21) ^{3 '}～R ^{6 '}, can enumerate respectively and above-mentioned R ³～R ⁶Identical group.

In this manufacture method (2), (N of kation portion in the formula (1-21) ⁺(R ^{3 '}) (R ^{4 '}) (R ^{5 '}) (R ^{6 '})) with formula (b0-1) in (the N of kation portion ⁺(R ³) (R ⁴) (R ⁵) (R ⁶)) can be identical, also can be different, consider the simplification of operation etc., preferably identical.

About making compound (1-21), compound (1-12) and the operation that amine or ammonium salt react, except being replaced with compound (1-21), the compound (1-11) in the above-mentioned manufacture method (1) can use the method identical to implement with above-mentioned manufacture method (1).

The compound (1-21) that uses as parent material in this manufacture method (2) is novel compound.

Compound (1-21) for example can use the manufacture method of compound described later (1-21) to make.

The manufacture method of＜＜compound (1-21)〉〉

Then, the manufacture method to the compound (1-21) of the present invention's the 10th mode describes.

The manufacture method of compound of the present invention (1-21) comprises the operation of reacting the compound (1-21) that obtains following general formula (1-21) expression by compound (1-11) that makes following general formula (1-11) expression and ammonium salt.

In the formula, Q ², Y ¹, R ^{3 '}～R ^{6 '}, M ⁺The same respectively.

As ammonium salt, can enumerate the hydrochloride of abovementioned alkyl amine, dialkylamine, trialkylamine and aromatic amine or bromate etc.

About the reaction of compound (1-11), can similarly implement with existing known salt method of replacing with ammonium salt.For example, in compound (1-11) and ammonium salt is water-soluble, methylene chloride, acetonitrile, methyl alcohol, the chloroform equal solvent, make its reaction by stirring to wait.

Temperature of reaction is preferably about 0 ℃～150 ℃, about more preferably 0 ℃～100 ℃.Reaction time is preferably 0.5～10 hour, more preferably 1～5 hour usually according to the reactivity of compound (1-11) and ammonium salt and temperature of reaction etc. and different.

After reaction finishes, can separate, make with extra care the compound in the reactant liquor (1-21).Separate, refiningly can utilize existing known method, for example concentrate, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use in them any separately, or be used in combination more than 2 kinds.

The structure of the compound that obtains (1-21) can be passed through ¹H-nuclear magnetic resonance (NMR) spectrometry, ¹³The C-NMR spectrometry, ¹⁹Common organic analysis methods such as F-NMR spectrometry, infrared ray absorbing (IR) spectrometry, mass spectrum (MS) method, elemental microanalysis method, X ray crystal diffraction method are confirmed.

The manufacture method of＜＜compound (1-14)〉〉

Then, compound (1-14) manufacture method to the present invention's the 11st mode describes.

The manufacture method of compound of the present invention (1-14) comprises the operation of reacting the compound (1-14) that obtains following general formula (1-14) expression by compound (1-13) that makes following general formula (1-13) expression and ammonium salt.

[in the formula, R ^cFor can having substituent alkyl, but substituting group is not a nitrogen-atoms; Q ⁴It is the linking group of singly-bound or divalent; N is 0 or 1; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; R ^{3 '}～R ^{6 '}Maybe can have substituent alkyl for hydrogen atom independently respectively, R ^{3 '}～R ^{6 '}In at least 1 be above-mentioned alkyl, R ^{3 '}～R ^{6 '}In at least 2 can be bonded to ring respectively; M ⁺Be alkali metal ion.]

In the formula, R ^c, Q ⁴, n, Y ¹, R ^{3 '}～R ^{6 '}, M ⁺The same respectively.

As ammonium salt, can enumerate the hydrochloride of abovementioned alkyl amine, dialkylamine, trialkylamine and aromatic amine or bromate etc.

About the reaction of compound (1-13), can similarly implement with existing known salt method of replacing with ammonium salt.For example, in compound (1-13) and ammonium salt is water-soluble, methylene chloride, acetonitrile, methyl alcohol, the chloroform equal solvent, make its reaction by stirring to wait.

Temperature of reaction is preferably about 0 ℃～150 ℃, about more preferably 0 ℃～100 ℃.Reaction time is preferably 0.5～10 hour, more preferably 1～5 hour usually according to the reactivity of compound (1-13) and ammonium salt and temperature of reaction etc. and different.

After reaction finishes, can separate, make with extra care the compound in the reactant liquor (1-14).Separate, refiningly can utilize existing known method, for example wash, concentrate, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use in them any separately, or be used in combination more than 2 kinds.

In the present invention, compound (1-14) has N ⁺(R ^{3 '}) (R ^{4 '}) (R ^{5 '}) (R ^{6 '}) as kation portion, owing to be insoluble in water, therefore can make with extra care by washing.

The structure of the compound that obtains (1-14) can be passed through ¹H-nuclear magnetic resonance (NMR) spectrometry, ¹³The C-NMR spectrometry, ¹⁹Common organic analysis methods such as F-NMR spectrometry, infrared ray absorbing (IR) spectrometry, mass spectrum (MS) method, elemental microanalysis method, X ray crystal diffraction method are confirmed.

The purposes of＜＜compound (b0-1)〉〉

As mentioned above, compound of the present invention (b0-1) is a new compound, can as synthetic as the resist composition with the compound of acid agent particularly the intermediate the during compound (b1-1) of the present invention's the 3rd mode use.

That is, compound (b0-1) is carried out the salt displacement, with (the N of kation portion of compound (b0-1) ⁺(R ³) (R ⁴) (R ⁵) (R ⁶)) be replaced as for example organic cation such as sulfonium cation, iodide ion and the compound that obtains can produce sour (sulfonic acid) by exposure of suitable kation portion.Described compound can be used as the resist composition and uses with acid agent.

Compound of the present invention (b0-1) is as making the intermediate of acid agent when the compound replacing by above-mentioned salt, and is very useful.That is, because kation portion is N ⁺(R ³) (R ⁴) (R ⁵) (R ⁶), therefore can come easily refining this compound by washing, can expect the raising of final product purity.If kation portion is an alkali metal ion, then washing is refining can make this compound dissolution, is difficult to by washing refining.

In addition, the compound that is made by compound of the present invention (b0-1) by the salt displacement can not only use as acid agent, and this compound mixed the photolithographic characteristics that helps to improve the resist composition behind the resist composition as acid agent, for example improve exploring degree when forming the resist pattern, mask reappearance (for example mask linearity (mask linearity: マ ス Network リ ニ ア リ テ イ) etc.), exposure (EL) allowance, resist pattern form, depth of focus (DOF) etc.

EL holds nargin and is meant when the change exposure is exposed, can be to form the scope of the exposure of resist pattern with the size of deviation in specialized range of target size, promptly obtain the scope of exposure of the resist pattern of faithful to mask pattern, the value that EL holds nargin is big more, the variable quantity of the pattern dimension that produces with the change of exposure is more little, the appearance nargin of operation improves more, thereby preferred.

Infer and produce the reasons are as follows of above-mentioned effect.That is, the negative ion portion of the compound that is made by above-claimed cpd (b0-1) by salt displacement has at " Y ¹-SO ^3-" skeleton on bonding R is arranged ^X-Q ³-O-Q ²-structure.Therefore, compare with the fluoro-alkyl azochlorosulfonate acid ion that uses as negative ion in the past, polarity is big, and is sterically hindered big, becomes huge structure.By inference, compare with the negative ion portion of existing acid agents such as nine fluorine fourth azochlorosulfonate acid ions, the intermolecular interaction that polarity causes greatly with and huge spatial structure can be from chemically and physically suppressing this diffusion of negative ion portion (acid) in resist film.Therefore, suppress the acid that the exposure area produces and spread, thereby poor (the dissolving contrast) to the dissolubility of alkaline developer of unexposed area and exposure area improved, take this exploring degree and the raising of resist pattern form to unexposed area.

Y ¹The substituent alkylidene that can have maybe can to have the alkyl chain of substituent fluoro alkylidene and for example carbon number be that 6～10 the hard-decomposed of perfluoroalkyl chain compared, its decomposability is good, can obtain to consider that the operability of the biosome property accumulated further improves this effect.

As the example that the resist composition is used the compound of acid agent that is used as that compound of the present invention (b0-1) is made as intermediate, can enumerate aftermentioned compound of the present invention (b1-1).

＜＜compound (b1-1)〉〉

Then, the compound (b1-1) to the present invention's the 3rd mode describes.Compound (b1-1) preferably uses as the acid agent of the resist composition of the present invention's the 1st mode.

R in the formula (b1-1) ^X, Y ¹, Q ²And Q ³Respectively with above-mentioned general formula (b0-1) in R ^X, Y ¹, Q ²And Q ³Identical.

As Z ⁺Organic cation, so long as the kation beyond the ion of above-mentioned general formula (w-1) expression gets final product, do not have particular restriction, can suitably use in the past as the kation portion of salt acid agent and known kation.In the described kation portion, as Z ⁺Organic cation, preferred sulfonium cation or iodide ion, preferred especially sulfonium cation.

Particularly, the kation portion that can preferably use following general formula (b '-1), (b '-2), (b-5) or (b-6) represent.

[in the formula, R ¹"～R ³", R ⁵"～R ⁶" represent aryl or alkyl respectively independently; R ¹"～R ³" in any 2 bonding and the sulphur atom Cheng Huan in formula mutually; R ¹"～R ³" at least one the expression aryl, R ⁵"～R ⁶" at least one the expression aryl.]

[in the formula, R ⁴⁰Be hydrogen atom or alkyl, R ⁴¹Be alkyl, acetyl group, carboxyl or hydroxyalkyl, R ⁴²～R ⁴⁶Be alkyl, acetyl group, alkoxy, carboxyl or hydroxyalkyl independently respectively; n ₀～n ₅Be respectively 0～3 integer independently, wherein, n ₀+ n ₁Be below 5, n ₆It is 0～2 integer.]

In the formula (b '-1), R ¹"～R ³" represent aryl or alkyl respectively independently.R ¹"～R ³" in any 2 bonding and the sulphur atom Cheng Huan in formula mutually.

And, R ¹"～R ³" at least one the expression aryl.R ¹"～R ³" in preferred be aryl, most preferably R more than 2 ¹"～R ³" all be aryl.

As R ¹"～R ³" aryl; do not have particular restriction, the substituted aryl of part or all hydrogen atom that can enumerate carbon number for example and be aryl that 6～20 nothing replaces, aryl that this nothings replaces after by replacements such as alkyl, alkoxy, alkoxyalkyl oxygen base, alkoxy carbonyl alkyl oxygen base, halogen atom, hydroxyls ,-(R ⁴')-C (=O)-R ⁵'.R ⁴' be that carbon number is 1～5 alkylidene.R ⁵' be aryl.As R ⁵' aryl, can enumerate and above-mentioned R ¹"～R ³" the identical group of aryl.

As there not being the aryl that replaces, from the cheap synthetic viewpoint of energy, preferred carbon number is 6～10 aryl.Specifically can enumerate for example phenyl, naphthyl.

As the alkyl in the substituted aryl, preferred carbon number is 1～5 alkyl, most preferable, ethyl, propyl group, normal-butyl, the tert-butyl group.

As the alkoxy in the substituted aryl, preferred carbon number is 1～5 alkoxy, most preferably methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy.

As the halogen atom in the substituted aryl, preferred fluorine atom.

As the alkoxyalkyl oxygen base in the substituted aryl, can enumerate for example general formula-O-C (R ⁴⁷) (R ⁴⁸)-O-R ⁴⁹[in the formula, R ⁴⁷, R ⁴⁸Be respectively the alkyl of hydrogen atom or straight chain shape or a chain independently, R ⁴⁹It is alkyl.] expression group.

R ⁴⁷, R ⁴⁸In, the carbon number of alkyl is preferably 1～5, can be the straight chain shape, also can be a chain, preferred ethyl, methyl, most preferable.

R ⁴⁷, R ⁴⁸Preferred at least one side is a hydrogen atom.A preferred especially side is a hydrogen atom, and the opposing party is hydrogen atom or methyl.

As R ⁴⁹Alkyl, preferred carbon number is 1～15, can be in straight chain shape, a chain, the ring-type any.

As R ⁴⁹In straight chain shape, the alkyl of chain, preferred carbon number is 1～5, can enumerate for example methyl, ethyl, propyl group, normal-butyl, the tert-butyl group etc.

As R ⁴⁹In cyclic alkyl, preferred carbon number is 4～15, more preferably carbon number is 4～12, most preferably carbon number is 5～10.Specifically can enumerate by the alkyl of carbon number 1～5, fluorine atom or fluoro-alkyl replaces or polynaphthenes such as unsubstituted mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane are sloughed group behind the hydrogen atom more than 1 etc.As mononaphthene, can enumerate cyclopentane, cyclohexane etc.As polynaphthene, can enumerate diamantane, norbornane, isoborneol alkane (isobornane), tristane, Fourth Ring dodecane etc.Wherein, preferred diamantane is sloughed 1 group behind the above hydrogen atom.

As the alkoxy carbonyl alkyl oxygen base in the substituted aryl, can enumerate for example general formula :-O-R ⁵⁰-C (=O)-O-R ⁵¹[in the formula, R ⁵⁰Be the alkylidene of a straight chain shape or a chain, R ⁵¹It is tertiary alkyl.] expression group.

As R ⁵⁰In straight chain shape, the alkylidene of chain, preferred carbon number is 1～5, can enumerate for example methylene, ethylidene, trimethylene, tetramethylene, 1,1-dimethyl ethylidene etc.

As R ⁵¹In tertiary alkyl, can enumerate 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 1-methyl-1-cyclopentyl, 1-ethyl-1-cyclopentyl, 1-methyl-1-cyclohexyl, 1-ethyl-1-cyclohexyl, 1-(1-adamantyl)-1-Methylethyl, 1-(1-adamantyl)-1-methyl-propyl, 1-(1-adamantyl)-1-methyl butyl, 1-(1-adamantyl)-1-methyl amyl; 1-(1-cyclopentyl)-1-Methylethyl, 1-(1-cyclopentyl)-1-methyl-propyl, 1-(1-cyclopentyl)-1-methyl butyl, 1-(1-cyclopentyl)-1-methyl amyl; 1-(1-cyclohexyl)-1-Methylethyl, 1-(1-cyclohexyl)-1-methyl-propyl, 1-(1-cyclohexyl)-1-methyl butyl, 1-(1-cyclohexyl)-1-methyl amyl, the tert-butyl group, tertiary pentyl, uncle's hexyl etc.

As R ¹"～R ³" aryl, preferred phenyl or naphthyl respectively.

As R ¹"～R ³" alkyl, do not have particular restriction, can enumerate carbon number for example and be the alkyl of 1～10 straight chain shape, a chain or ring-type etc.From the viewpoint of exploring degree excellence, preferred carbon number is 1～5.Specifically can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, n-pentyl, cyclopentyl, hexyl, cyclohexyl, nonyl, decyl etc.Wherein, the excellent and cheap synthetic viewpoint of energy from the exploring degree can preferable methyl.

Work as R ¹"～R ³" in any 2 mutual bondings and the sulphur atom in formula when becoming to encircle, be preferably formed and comprise sulphur atom at 3～10 yuan of interior rings, be preferably formed 5～7 yuan of rings especially.

Work as R ¹"～R ³" in any 2 mutual bondings and the sulphur atom in formula when becoming to encircle, remaining one is preferably aryl.Above-mentioned aryl can be enumerated and above-mentioned R ¹"～R ³" the identical group of aryl.

Object lesson as the kation portion of formula (b '-1) expression, can enumerate triphenylsulfonium, (3,5-3,5-dimethylphenyl) diphenyl sulfonium, (4-(2-Buddha's warrior attendant alkoxy methyl oxygen base)-3,5-3,5-dimethylphenyl) diphenyl sulfonium, (4-(2-Buddha's warrior attendant alkoxy methyl oxygen base) phenyl) diphenyl sulfonium, (4-(tert-butoxycarbonyl methyl oxygen base) phenyl) diphenyl sulfonium, (4-(tert-butoxycarbonyl methyl oxygen base)-3,5-3,5-dimethylphenyl) diphenyl sulfonium, (4-(2-methyl-2-adamantyl oxygen base carbonyl methyl oxygen base) phenyl) diphenyl sulfonium, (4-(2-methyl-2-adamantyl oxygen base carbonyl methyl oxygen base)-3,5-3,5-dimethylphenyl) diphenyl sulfonium, three (4-aminomethyl phenyl) sulfonium, dimethyl (4-hydroxyl naphthyl) sulfonium, one phenyl dimethyl sulfonium, diphenyl monomethyl sulfonium, (4-aminomethyl phenyl) diphenyl sulfonium, (4-methoxyphenyl) diphenyl sulfonium, three (4-tert-butyl group) phenyl sulfonium, diphenyl (1-(4-methoxyl) naphthyl) sulfonium, two (1-naphthyl) phenyl sulfonium, 1-phenyl thiophane (phenyl tetrahydrothiophenium), 1-(4-aminomethyl phenyl) thiophane, 1-(3,5-dimethyl-4-hydroxyphenyl) thiophane, 1-(4-methoxynaphthalene-1-yl) thiophane, 1-(4-ethoxy naphthalene-1-yl) thiophane, 1-(4-n-butoxy naphthalene-1-yl) thiophane, 1-phenyl tetrahydric thiapyran, 1-(4-hydroxyphenyl) tetrahydric thiapyran, 1-(3,5-dimethyl-4-hydroxyphenyl) tetrahydric thiapyran, 1-(4-aminomethyl phenyl) tetrahydric thiapyran etc.

In the formula (b '-2), R ⁵" and R ⁶" represent aryl or alkyl respectively independently.R ⁵" and R ⁶" at least one the expression aryl.Preferred R ⁵" and R ⁶" both are aryl.

As R ⁵" and R ⁶" aryl, can enumerate and R ¹"～R ³" the identical group of aryl.

As R ⁵" and R ⁶" alkyl, can enumerate and R ¹"～R ³" the identical group of alkyl.

Wherein, R most preferably ⁵" and R ⁶" be phenyl.

As the object lesson of the kation portion of formula (b '-2) expression, can enumerate diphenyl iodine, two (4-tert-butyl-phenyl) iodine etc.

The R of general formula (b-5)～(b-6) ⁴⁰～R ⁴⁶In, the preferred carbon number of alkyl is 1～5 alkyl, wherein, and the more preferably alkyl of straight chain shape or chain, special preferable methyl, ethyl, propyl group, isopropyl, normal-butyl or the tert-butyl group.

The preferred carbon number of alkoxy is 1～5 alkoxy, the more preferably alkoxy of straight or branched wherein, preferred especially methoxyl, ethoxy.

In the preferred abovementioned alkyl of hydroxyalkyl-group after individual or a plurality of hydrogen atoms are replaced by hydroxyl, can enumerate methylol, hydroxyethyl, hydroxypropyl etc.

Work as OR ⁴⁰With symbol n ₀When being the integer more than 2, a plurality of OR ⁴⁰Can be identical or different respectively.

Work as R ⁴¹～R ⁴⁶With symbol n ₁～n ₆When being the integer more than 2, a plurality of R ⁴¹～R ⁴⁶Can be identical or different respectively.

n ₀Be preferably 0 or 1.

n ₁Be preferably 0～2.

n ₂And n ₃Preferably be respectively 0 or 1 independently, more preferably 0.

n ₄Be preferably 0～2, more preferably 0 or 1.

n ₅Be preferably 0 or 1, more preferably 0.

n ₆Be preferably 0 or 1.

As Z ⁺The kation portion of preferred formula (b '-1) or (b-5) expression, the kation portion of preferred especially following formula (b '-1-1)～(b '-1-10), (b-5-1)～(b-5-4) expression, more preferably the kation portion of the kation portion of the triphenyl skeletons such as kation portion of formula (b '-1-1)～(b '-1-8) expression or (b '-1-10) expression.

In formula (b '-1-9)～(b '-1-10), R ⁸, R ⁹Be 1～5 alkyl, alkoxy, hydroxyl for having substituent phenyl, naphthyl or carbon number independently respectively, preferably can have substituent phenyl.

U is 1～3 integer, most preferably 1 or 2.

As compound (b1-1), the compound of preferred following general formula (b1-1-1) expression.

[in the formula, R ^X, Y ¹And Z ⁺Respectively with above-mentioned general formula (b1-1) in R ^X, Y ¹And Z ⁺Identical; R ¹Be alkylidene.]

In above-mentioned general formula (b1-1-1), R ^X, Y ¹And Z ⁺Respectively with above-mentioned general formula (b1-1) in R ^X, Y ¹And Z ⁺Identical.

R ¹Alkylidene can be in straight chain shape, chain, the ring-type any, a preferred straight chain shape or a chain, further preferred straight chain shape.

The carbon number of the alkylidene of straight chain shape or chain is preferably 1～12, and more preferably 1～5, more preferably 1～3.As this alkylidene, specifically can enumerate for example methylene [CH ₂-];-CH (CH ₃)-,-CH (CH ₂CH ₃)-,-C (CH ₃) ₂-,-C (CH ₃) (CH ₂CH ₃)-,-C (CH ₃) (CH ₂CH ₂CH ₃)-,-C (CH ₂CH ₃) ₂-wait the alkyl methylene; Ethylidene [CH ₂CH ₂-];-CH (CH ₃) CH ₂-,-CH (CH ₃) CH (CH ₃)-,-C (CH ₃) ₂CH ₂-,-CH (CH ₂CH ₃) CH ₂-wait the alkyl ethylidene; Trimethylene (positive propylidene) [CH ₂CH ₂CH ₂-];-CH (CH ₃) CH ₂CH ₂-,-CH ₂CH (CH ₃) CH ₂-wait the alkyl trimethylene; Tetramethylene [CH ₂CH ₂CH ₂CH ₂-];-CH (CH ₃) CH ₂CH ₂CH ₂-,-CH ₂CH (CH ₃) CH ₂CH ₂-wait the alkyl tetramethylene; Pentamethylene [CH ₂CH ₂CH ₂CH ₂CH ₂-] etc.Wherein, preferred methylene, ethylidene or positive propylidene, preferred especially ethylidene.

As compound (b1-1), the compound of preferred especially following general formula (b1-1-11)～(b1-1-13) expression.

[in the formula, Z ⁺The same, p is 1～3 integer, and q1～q3 is respectively 1～12 integer independently, and r1 is 0～3 integer, and g is 1～20 integer, R ⁷Be substituting group.]

As R ⁷Substituting group, can be set forth in above-mentioned R ^XIn the substituting group that can have as aliphatic alkyl and the identical group of group enumerated.

Work as R ⁷With symbol (r1) when being integer more than 2, a plurality of R in this compound ⁷Can be identical or different respectively.

P is preferably 1 or 2.

Q1～q3 preferably is respectively 1～5 independently, more preferably 1～3.

R1 is preferably 0～2 integer, and more preferably 0 or 1.

G more preferably is 1～15, more preferably 1～10.

Compound of the present invention (b1-1) is a new compound.

Compound of the present invention (b1-1) can use with acid agent as chemical amplification type anti-corrosion agent composition, can be used as acid agent and mixes in the chemical amplification type anti-corrosion agent composition.

The manufacture method of compound of the present invention (b1-1) does not have particular restriction, for example can adopt the manufacture method of The compounds of this invention described later (b1-1) to make.

The manufacture method of＜＜compound (b1-1)〉〉

Then, compound (b1-1) manufacture method to the present invention's the 4th mode describes.

Compound (b1-1) manufacture method of the present invention's the 4th mode comprises that compound (b0-02) reaction by compound (b0-1) that makes following general formula (b0-1) expression and following general formula (b0-02) expression obtains the operation of compound (b1-1).

Z ⁺ A ^- …(b0—02)

[in the formula, R ^XBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ²And Q ³Be the linking group of singly-bound or divalent independently respectively; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; W ⁺It is the ion of alkali metal ion or following general formula (w-1) expression; Z ⁺Be organic cation, but except the ion of following general formula (w-1) expression; A ^-It is non-nucleophilicity negative ion.]

[in the formula, R ³～R ⁶Maybe can have substituent alkyl for hydrogen atom independently respectively, R ³～R ⁶In at least 1 be above-mentioned alkyl, R ³～R ⁶In at least 2 can be bonded to ring respectively.]

In the formula, R ^X, Q ², Q ³, Y ¹, Z ⁺Respectively with above-mentioned general formula (b1-1) in R ^X, Q ², Q ³, Y ¹, Z ⁺Identical.

W ⁺It is the ion (hereinafter referred to as substituted ammonium ion) of alkali metal ion or above-mentioned general formula (w-1) expression.

W ⁺In, as alkali metal ion, can enumerate sodion, potassium ion, lithium ion etc.

In the formula (W-1), R ³～R ⁶Respectively with above-mentioned general formula (b0-1) in R ³～R ⁶Identical.

A ^-It is non-nucleophilicity negative ion.

As this non-nucleophilicity ion, for example can enumerate halogen such as bromide ion, chlorion ion, can form ion, BF that acidity is lower than the acid of compound (b0-1) ₄ ^-, AsF ₆ ^-, SbF ₆ ^-, PF ₆ ^-Or ClO ₄ ^-Deng.

As forming the ion that acidity is lower than the acid of compound (b0-1) among the A-, can enumerate azochlorosulfonate acid ions such as p-toluenesulfonic acid ion, methane-sulforic acid ion, benzene sulfonic acid ion, trifluoromethanesulfonic acid ion.

In compound (b1-1) manufacture method of the present invention's the 4th mode, special preferred compound (b0-1) is the compound (b0-1) of following general formula (b0-1) expression, and compound (b1-1) is the compound (b1-1-1) of following general formula (b1-1-1) expression.

[in the formula, R ^X, Y ¹And W ⁺With the R in the above-mentioned general formula (b0-1) ^X, Y ¹And W ⁺Identical; R ^bWith R ^XIdentical; Z ⁺With the Z in the above-mentioned general formula (b1-1) ⁺Identical; R ¹With the R in the above-mentioned general formula (b0-1-11) ¹Identical.]

Above-claimed cpd (b0-01) for example can be next synthetic with compound (2-1) reaction of following general formula (2-1) expression by the compound (1-3) that makes following general formula (1-3) expression.

[in the formula, R ^X, R ¹, Y ¹, W ⁺The same respectively, X ²²Be halogen atom.]

As X ²²Halogen atom, can enumerate bromine atoms, chlorine atom, iodine atom, fluorine atom etc., from reactive excellent viewpoint, preferred bromine atoms or chlorine atom, preferred especially chlorine atom.

Compound (1-3), (2-1) can use commercially available product respectively, also can synthesize.

For example, the W in compound (1-3) ⁺During for alkali metal ion, as the compound of this compound (following general formula (1-3 ') expression (1-3 ')) preferred synthetic method, compound (1-2) reaction that can enumerate the compound (1-1) that has by making following general formula (1-1) expression and following general formula (1-2) expression obtains the method for the operation of compound (1-3 ').

HO—R ¹—O—R ² …(1—1)

[in the formula, R ¹, Y ¹Same as described above respectively, R ²For having the aromatic series base as substituent fatty group, M ⁺Be alkali metal ion.]

As M ⁺, can enumerate and above-mentioned W ⁺The alkali metal ion that cited alkali metal ion is identical.

R ²For having the aromatic series base as substituent fatty group.

This fatty group can be the representative examples of saturated aliphatic base, also can be the unsaturated aliphatic base.In addition, fatty group can be any in straight chain shape, a chain, the ring-type, also can be their combination.

Fatty group can be the aliphatic alkyl that is only formed by carbon atom and hydrogen atom, also can be that the part that constitutes the carbon atom of this aliphatic alkyl is contained the group after heteroatomic substituting group replaces, also can be that part or all of hydrogen atom that constitute this aliphatic alkyl contained the group after heteroatomic substituting group replaces.

As above-mentioned heteroatoms, so long as the atom beyond carbon atom and the hydrogen atom gets final product, there is not particular restriction, can enumerate for example halogen atom, oxygen atom, sulphur atom, nitrogen-atoms etc.As halogen atom, can enumerate fluorine atom, chlorine atom, iodine atom, bromine atoms etc.

Containing heteroatomic substituting group can only be formed by heteroatoms, also can be to contain the group beyond the heteroatoms or the group of atom.

As the substituting group of the part of alternate c atoms, specifically for example can enumerate-O-,-C (=O)-O-,-C (=O)-,-O-C (=O)-O-,-C (=O)-NH-,-NH-(H can be replaced by substituting groups such as alkyl, acyl groups) ,-S-,-S (=O) ₂-,-S (=O) ₂-O-etc.When fatty group contains cyclic group, can in the ring structure of this cyclic group, contain these substituting groups.

As part or all the substituting group that replaces hydrogen atom, for example specifically can enumerate alkoxy, halogen atom, haloalkyl, hydroxyl, oxygen atom (=O) ,-COOR ⁹⁶,-OC (=O) R ⁹⁷, cyano group etc.

As above-mentioned alkoxy, preferred carbon number is 1～5 alkoxy, further preferred methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, most preferably methoxyl, ethoxy.

As above-mentioned halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom etc., preferred fluorine atom.

As above-mentioned haloalkyl, the group after can enumerating carbon number and be 1～5 alkyl for example part or all of hydrogen atom of alkyl such as methyl, ethyl, propyl group, normal-butyl, the tert-butyl group being replaced by above-mentioned halogen atom.

R ⁹⁶And R ⁹⁷Be respectively that hydrogen atom or carbon number are 1～15 straight chain shape, chain or cyclic alkyl independently.

Work as R ⁹⁶And R ⁹⁷In alkyl when being straight chain shape or chain, its carbon number is preferably 1～10, more preferably 1～5, more preferably 1 or 2.Specifically can enumerate the identical group of 1 valency saturated hydrocarbyl with a straight chain shape described later or a chain.

Work as R ⁹⁶And R ⁹⁷In alkyl when being ring-type, this ring can be a monocycle, also can be many rings.Its carbon number is preferably 3～15, and more preferably 4～12, more preferably 5～10.Specifically can enumerate the identical group of 1 valency saturated hydrocarbyl with ring-type described later.

As aliphatic alkyl, preferred carbon number is that saturated hydrocarbyl, the carbon number of a straight chain shape of 1～30 or a chain is that 1 valency unsaturated alkyl of a straight chain shape of 2～10 or a chain or carbon number are the aliphatic alkyl (alicyclic group) of 3～30 ring-type.

As the saturated hydrocarbyl of straight chain shape, preferred carbon number is 1～20, more preferably 1～15, most preferably be 1～10.Specifically can enumerate for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, pentadecyl, cetyl, isocetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl etc.

As the saturated hydrocarbyl of chain, preferred carbon number is 3～20, more preferably 3～15, most preferably be 3～10.Specifically can enumerate for example 1-Methylethyl, 1-methyl-propyl, 2-methyl-propyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1-ethyl-butyl, 2-ethyl-butyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl etc.

As unsaturated alkyl, preferred carbon number is 2～5, more preferably 2～4, more preferably 3.As 1 valency unsaturated alkyl of straight chain shape, can enumerate for example vinyl, propenyl (allyl), butenyl group etc.As 1 valency unsaturated alkyl of a chain, can enumerate for example 1-methylpropenyl, 2-methylpropenyl etc.

Preferred especially propenyl in the above-mentioned unsaturated alkyl.

As alicyclic group, can be the monocycle base, also can be many cyclic groups.Its carbon number is preferably 3～30, and more preferably 5～30, more preferably 5～20, be preferably 6～15 especially, most preferably be 6～12.For example specifically can enumerate and remove 1 group behind the above hydrogen atom by mononaphthene; Remove 1 group behind the above hydrogen atom etc. by polynaphthenes such as dicyclo alkane, three cycloalkanes, tetracycloalkanes.More specifically, for example can enumerate and remove 1 group behind the above hydrogen atom by mononaphthenes such as cyclopentane, cyclohexanes; Remove 1 group behind the above hydrogen atom etc. by polynaphthenes such as diamantane, norbornane, isoborneol alkane, tristane, Fourth Ring decane.

At R ²In, above-mentioned fatty group can have the aromatic series base as substituting group.

As the aromatic series base, can enumerate phenyl, biphenyl (biphenyl) base, fluorenes (fluorenyl) base, naphthyl, anthracene (anthryl) base, phenanthryl etc. and remove 1 aryl behind the hydrogen atom by the aromatic hydrocarbon ring; Heteroaryl after the part of carbon atom that constitutes the ring of these aryl is replaced by heteroatomss such as oxygen atom, sulphur atom, nitrogen-atoms etc.

It is substituting groups such as 1～10 alkyl, haloalkyl, alkoxy, hydroxyl, halogen atom that these aromatic series bases can have carbon number.The preferred carbon number of alkyl in this substituting group or haloalkyl is 1～8, and more preferably carbon number is 1～4.This haloalkyl is preferably fluoro-alkyl.This halogen atom can be enumerated fluorine atom, chlorine atom, iodine atom, bromine atoms etc., preferred fluorine atom.

In addition, if the R in the compound (1-1) ²Be the aromatic series base, promptly with R ²Adjacent oxygen atom does not pass through fatty group and direct and aromatic rings bonding, and then compound (1-1) can't carry out with the reaction of compound (1-2), can not get compound (1-3).

Compound (1-1), (1-2) can use commercially available product respectively, also can utilize known method to synthesize.

Compound (1-2) for example, can enumerate comprise by with the compound (0-1) of following general formula (0-1) expression heating in the presence of the alkali, neutralization obtain the operation (forming operation) of the compound (0-2) of following general formula (0-2) expression and the acid by above-claimed cpd (0-2) being higher than compound (1-2) in acid strength hereinafter referred to as salt in the presence of heat the method for the operation (hereinafter referred to as carboxylic acid chemical industry preface) that obtains compound (1-2).

[in the formula, R ⁰¹Be alkyl, Y ¹, M ⁺The same.]

As R ⁰¹Alkyl, the alkyl of a preferred straight chain shape or a chain specifically can be enumerated methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, neopentyl etc.Wherein, preferred carbon number is 1～4 alkyl, most preferable.

As compound (0-1), can use commercially available product.

Form operation about salt, for example can be by compound (0-1) being dissolved, adds alkali in solvent, heat and implement in this solution.

As solvent,, can enumerate for example water, tetrahydrofuran etc. so long as the solvent of energy dissolved compound (0-1) gets final product.

As alkali, use with formula (0-2) in the corresponding alkali of M, as this alkali, can enumerate alkali metal hydroxides such as NaOH, potassium hydroxide, lithium hydroxide.

About the consumption of alkali, with respect to 1 mole of compound (0-1), be preferably 1～5 mole, more preferably 2～4 moles.

Heating-up temperature is preferably about 20～120 ℃, more preferably about 50～100 ℃.Heat time heating time is according to heating-up temperature etc. and different, and preferred 0.5～12 hour usually, further preferred 1～5 hour.

About the neutralization after the above-mentioned heating, can implement by adding acid such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid in the reactant liquor after above-mentioned heating.

At this moment, preferably make the pH (25 ℃) of the reactant liquor after acid is added 6～8 implement neutralization.In and the time the temperature of reactant liquor be preferably 20～30 ℃, more preferably 23～27 ℃.

After reaction finishes, can separate, make with extra care the compound in the reactant liquor (0-2).Separate, refiningly can utilize existing known method, for example concentrate, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use in them any separately, or be used in combination more than 2 kinds.

In carboxylic acid chemical industry preface, obtain this compound (1-2) by forming the compound (0-2) that obtain in the operation is higher than compound (1-2) in acid strength heating down of acid at above-mentioned salt.

The value that " acid strength is higher than the acid (the following strong acid that abbreviates as sometimes) of compound (1-2) " is meant pKa (25 ℃) less than in the compound (1-2)-acid of COOH.By using described strong acid, in the compound (0-2)-COO ^-M ⁺Become-COOH, obtain compound (1-2).

As strong acid, from known acid, suitably select to use pKa less than in the above-claimed cpd (1-2)-acid of the pKa of COOH gets final product.In the compound (1-2)-pKa of COOH can try to achieve with known titrimetry.

As strong acid, specifically can enumerate sulfonic acid such as aryl sulfonic acid, alkyl sulfonic acid, sulfuric acid, hydrochloric acid etc.As aryl sulfonic acid, can enumerate for example p-toluenesulfonic acid.As alkyl sulfonic acid, can enumerate for example methane-sulforic acid, trifluoromethanesulfonic acid etc.As strong acid, to the dissolubility of organic solvent and the viewpoint of refining easiness, preferred especially p-toluenesulfonic acid.

About carboxylic acid chemical industry preface, for example can be by being dissolved in compound (0-2) in the solvent, adding to heat behind the strong acid and implement.

As solvent,, can enumerate for example acetonitrile, MEK etc. so long as the solvent of energy dissolved compound (0-2) gets final product.

About the consumption of strong acid, with respect to 1 mole of compound (0-2), be preferably 0.5～3 mole, more preferably 1～2 mole.

Heating-up temperature is preferably about 20～150 ℃, more preferably about 50～120 ℃.Heat time heating time is according to heating-up temperature etc. and different, and preferred 0.5～12 hour usually, further preferred 1～5 hour.

After reaction finishes, can separate, make with extra care the compound in the reactant liquor (1-2).Separate, refiningly can utilize existing known method, for example concentrate, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use in them any separately, or be used in combination more than 2 kinds.

For example, the W in compound (1-3) ⁺During for above-mentioned substituted ammonium ion, the compound of this compound (following general formula (1-3 ") expression (1-3 ")) for example can make by above-claimed cpd (1-3 ') is reacted with ammonium salt.

[in the formula, R ^X, R ¹, Y ¹, R ³～R ⁶Same as described above respectively.]

As the ammonium salt that use this moment, can enumerate the hydrochloride of abovementioned alkyl amine, dialkylamine, trialkylamine and aromatic amine or bromate etc.

About reaction, for example compound (1-3 ') and ammonium salt can be dissolved in water, methylene chloride, acetonitrile, methyl alcohol, chloroform equal solvent and wait and make its reaction by stirring.

Temperature of reaction is preferably about 0 ℃～150 ℃, more preferably 0 ℃～100 ℃.Reaction time is preferably 0.5～10 hour, more preferably 1～5 hour usually according to the reactivity of compound (1-3 '), ammonium salt and temperature of reaction etc. and different.

Method as making compound (1-3) with compound (2-1) reaction does not have particular restriction, can enumerate the method that compound (1-3) is contacted with compound (2-1).This method for example can be implemented by add compound (2-1) to be dissolved with the solution that compound (1-3) obtains in reaction dissolvent in the presence of alkali.

As reaction dissolvent, so long as can dissolve compound (1-3) and the solvent of compound (2-1) gets final product, specifically can enumerate tetrahydrofuran (THF), acetone, dimethyl formamide (DMF), dimethyl acetamide, dimethyl sulfoxide (DMSO) (DMSO), acetonitrile etc. as raw material.

As alkali, can enumerate for example organic bases such as triethylamine, 4-dimethylaminopyridine (DMAP), pyridine; NaOH, K ₂CO ₃, Cs ₂CO ₃Deng inorganic base etc.

About the addition of compound (2-1), with respect to compound (1-3), preferably be about 1～3 equivalent, more preferably 1～2 equivalent.

Temperature of reaction is preferably-20～40 ℃, more preferably 0～30 ℃.Reaction time is preferably 1～120 hour, more preferably 1～48 hour usually according to the reactivity of compound (1-3) and compound (2-1) and temperature of reaction etc. and different.

W in compound (b0-01) ⁺During for above-mentioned substituted ammonium ion, the compound of this compound (following general formula (b0-01 ') expression (b0-01 ')) for example can make with the method that amine or ammonium salt react simultaneously by making above-claimed cpd (1-3 '), above-claimed cpd (2-1).

[in the formula, R ^X, R ¹, Y ¹, W ⁺, X ²²Same as described above respectively.]

Above-claimed cpd (1-3 '), above-claimed cpd (2-1) can similarly react with the above-claimed cpd (1-3) and the situation of above-claimed cpd (2-1) reaction with amine or ammonium salt.

As the amine that uses this moment, can enumerate abovementioned alkyl amine, dialkylamine, trialkylamine and aromatic amine etc., as ammonium salt, can enumerate tetra-alkyl ammonium hydroxides (, being respectively 1～4 alkyl independently for carbon number) such as Tetramethylammonium hydroxide, tetraethyl oxyammonia, tetrabutylammonium hydroxide amine as the alkyl in the tetra-allkylammonium.

In above-mentioned manufacture method, the intermediate of substituted ammonium salts such as above-claimed cpd (1-3 "), compound (b0-01 ') when making compound of the present invention (b1-1) is very useful.That is, because kation portion is N ⁺(R ³) (R ⁴) (R ⁵) (R ⁶), therefore can come easily refining this compound by washing, can expect the raising of final product purity.If kation portion is an alkali metal ion, then washing is refining can make this compound dissolution, is difficult to by washing refining.

Therefore, in manufacture method of the present invention, compound (b1-1) is preferably made by the intermediate that kation portion has an above-mentioned substituted ammonium ion.

Compound (b0-01) can similarly be implemented with existing known salt method of replacing with the reaction of compound (b0-02).For example, compound (b0-01) and compound (b0-02) can be dissolved in water, methylene chloride, acetonitrile, methyl alcohol, the chloroform equal solvent, make its reaction by stirring to wait.

Temperature of reaction is preferably about 0 ℃～150 ℃, about more preferably 0 ℃～100 ℃.Reaction time is according to the reactivity of compound (b0-01) and compound (b0-02) and temperature of reaction etc. and different, and preferred 0.5～12 hour usually, further preferred 1～5 hour.

After reaction finishes, can separate, make with extra care the compound in the reactant liquor (b1-1).Separate, refiningly can utilize existing known method, for example concentrate, solvent extraction, distillation, crystallization, recrystallization, chromatography etc., can use in them any separately, or be used in combination more than 2 kinds.

The structure of the compound that obtains (b1-1) can be passed through ¹H-nuclear magnetic resonance (NMR) spectrometry, ¹³The C-NMR spectrometry, ¹⁹General organic analysis methods such as F-NMR spectrometry, infrared ray absorbing (IR) spectrometry, mass spectrum (MS) method, elemental microanalysis method, X ray crystal diffraction method are confirmed.

＜＜acid agent〉〉

The acid agent of the present invention's the 5th mode is formed by the compound (b1-1) of the invention described above.

This acid agent is a chemical amplification type anti-corrosion agent composition acid agent, for example can be used as the acid agent composition (B) of the resist composition of aftermentioned the present invention the 1st mode.

This acid agent is especially preferably formed by the compound of following general formula (b1-1-1) expression.

＜＜resist composition〉〉

Then, the resist composition to the present invention's the 1st mode describes.

The resist composition of the present invention's the 1st mode contains under the effect of acid base material component (A) (hereinafter referred to as (A) composition) that the dissolubility to alkaline developer changes and by exposing to acidic acid agent composition (B) (hereinafter referred to as (B) composition).

About the resist film that uses described resist composition to form, if when the resist pattern forms, optionally expose, then produce acid by (B) composition, this acid makes (A) composition change to the dissolubility of alkaline developer.Consequently, the exposure portion of this resist film changes the dissolubility of alkaline developer, and unexposed the dissolubility to alkaline developer is constant, therefore develops by alkali, and unexposed dissolved removing when the exposure portion during eurymeric, minus forms the resist pattern.

Resist composition of the present invention can be the negative resist composition, also can be eurymeric resist composition.

＜(A) composition 〉

As (A) composition, can use the organic compound of a kind of base material component that agent is used as chemical amplification type anti-corrosion usually separately or mix use more than 2 kinds.

Here, " base material component " is meant the organic compound with film forming ability, and preferably using molecular weight is organic compound more than 500.Because the molecular weight of this organic compound is more than 500, so film forming ability improves, and easily forms the resist pattern of nanometer level.

Above-mentioned molecular weight be the organic compound more than 500 can roughly be divided into molecular weight at the low molecular weight organic compound of 500 above less thaies 2000 (hereinafter referred to as low molecular compound.) and molecular weight at the high molecular weight resin more than 2000 (macromolecular material).As above-mentioned low molecular compound, adopt non-polymer usually.Under the situation of resin (polymkeric substance, multipolymer),, adopt the matter average molecular weight of the polystyrene conversion that records by GPC (gel permeation chromatography) as " molecular weight ".During hereinafter to be referred as " resin ", refer to that molecular weight is at the resin more than 2000.

As (A) composition, can use the resin that alkali dissolution sexually revises under the effect of acid, also can use the low molecular material that alkali dissolution sexually revises under the effect of acid.

When resist composition of the present invention is the negative resist composition, as (A) composition, can adopt soluble base material component in alkaline developer, in this negative resist composition, also mix crosslinking chemical.

About described negative resist composition, when producing acid by (B) composition, between base material component and crosslinking chemical, producing crosslinkedly under the effect of this acid by exposure, become indissoluble in alkaline developer.Therefore, in the formation of resist pattern, when the resist film that this negative resist composition of coating on substrate is obtained carries out the selectivity exposure, exposure portion becomes indissoluble in alkaline developer, and unexposed portion is still solvable and do not change in alkaline developer, and therefore can develop by alkali forms the resist pattern.

As (A) composition of negative resist composition, usually use in alkaline developer soluble resin (hereinafter referred to as alkali soluble resin.)。

As alkali soluble resin, have by the resin that is selected from least a unit of deriving in α-(hydroxyalkyl) acrylic acid or α-(hydroxyalkyl) acrylic acid lower alkyl esters and can form the few good resist pattern of swelling, so preferred.In addition, α-(hydroxyalkyl) acrylic acid is meant that bonding on the carbon atom with the α position of carboxyl bonding has bonding on the acrylic acid of hydrogen atom and this α position carbon atom that a side or both sides in the alpha-hydroxyalkyl acrylic acid of hydroxyalkyl (hydroxyalkyl of preferred carbon number 1～5) are arranged.

As crosslinking chemical, for example, then can form the few good resist pattern of swelling, so preferred usually if adopt amino class crosslinking chemicals such as glycoluril with methylol or alkoxy methyl.The blending amount of crosslinking chemical is preferably 1～50 mass parts with respect to alkali soluble resin 100 mass parts.

When resist composition of the present invention is eurymeric resist composition,, adopt the base material component that the dissolubility in alkaline developer increases under the effect of acid as (A) composition.Should be insoluble in alkaline developer by (A) composition before exposure, when producing acid by exposure by above-mentioned (B) composition, under the effect of this acid, the dissolubility in alkaline developer increases.Therefore, in the formation of resist pattern, if the resist film that this eurymeric resist composition of coating on substrate is obtained carries out the selectivity exposure, then the dissolubility of exposure portion in alkaline developer changes to solubility from slightly solubility, and unexposed portion does not change, still be the alkali slightly solubility, therefore can develop by alkali forms the resist pattern.

In the resist composition of the present invention, (A) composition is preferably the base material component that the dissolubility in alkaline developer increases under the effect of acid.That is the preferred eurymeric resist of resist composition of the present invention composition.

Should (A) composition can be resinous principle (A1) that the dissolubility in alkaline developer under the effect of acid increases (below be sometimes referred to as (A1) composition.), also can be low molecular compound (A2) that the dissolubility in alkaline developer under the effect of acid increases (below be sometimes referred to as (A2) composition.), also can be their potpourri.Wherein, should preferably contain (A1) composition by (A) composition.

[(A1) composition]

As (A1) composition, usually, can use the resinous principle (substrate resin) of a kind of base material component of using as the chemical amplification type anti-corrosion agent separately or mix more than 2 kinds and use.

In the manner,, preferably contain the structural unit of deriving by acrylate as (A1) composition.

Here, in this instructions and claims, " structural unit of being derived by acrylate " is meant the structural unit that the olefinic double bond fracture of acrylate constitutes.

" acrylate " the acrylate of hydrogen bonding atom, also comprises the carbon atom of α position and the acrylate of substituting group (atom or group beyond the hydrogen atom) bonding on the carbon atom of α position.As substituting group, can enumerate low alkyl group, junior alkyl halides etc.

In addition, do not having under the situation of specified otherwise, the α position (carbon atom of α position) of the structural unit of being derived by acrylate is meant the carbon atom with the carbonyl bonding.

In acrylate,, specifically can enumerate the alkyl of a lower straight shape such as methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, neopentyl or a chain about substituent low alkyl group as the α position.

As junior alkyl halides, the group after part or all hydrogen atom that specifically can enumerate above-mentioned " the substituent low alkyl group of α position " is replaced by halogen atom.As this halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom etc., preferred especially fluorine atom.

In the present invention, the preferred hydrogen atom of group, low alkyl group or junior alkyl halides with the α position bonding of acrylate, more preferably hydrogen atom, low alkyl group or fluoro low alkyl group are from the viewpoint of the easiness of industrial acquisition, most preferably hydrogen atom or methyl.

(A1) composition especially preferably has by containing that acrylate that the acid dissociation dissolving suppresses base is derived and the structural unit (a1) that comes.

(A1) composition also preferably has by the acrylate of the cyclic group that contains lactone and derives and next structural unit (a2) except that structure unit (a1).

(A1) composition is except that structure unit (a1) or structural unit (a1) with (a2), also preferably has by the acrylate that contains the polar group aliphatic alkyl to derive and the structural unit (a3) that comes.Structural unit (a1)

Acid dissociation dissolving in the structural unit (a1) suppresses base and have the alkali dissolution inhibition that makes (A1) composition integral body indissoluble in alkaline developer before dissociating, and under the effect of acid, dissociate and the dissolubility of this (A1) composition integral body in alkaline developer increased, can use the chemical amplification type anti-corrosion agent that proposes up to now to suppress base with the acid dissociation dissolving of substrate resin.Well-known have with (methyl) acrylic acid etc. in carboxyl form the group of the tertiary alkyl ester of ring-type or chain; Acetal type acid dissociation dissolvings such as alkoxyalkyl suppress base etc.

Here, " tertiary alkyl ester " is meant: the hydrogen atom of carboxyl is replaced and the formation ester by the alkyl of chain or ring-type, the structure of the tertiary carbon atom bonding of the oxygen atom of the end of its ketonic oxygen base (-C (O)-O-) and the alkyl of above-mentioned chain or ring-type.This tertiary alkyl ester under the effect of acid, the bond rupture between oxygen atom and the tertiary carbon atom.

In addition, the alkyl of above-mentioned chain or ring-type can have substituting group.

Below, for simplicity, will be called " dissolving of tertiary alkyl ester type acid dissociation suppresses base " by forming the group that tertiary alkyl ester has acid dissociation with carboxyl.

Suppress base as the dissolving of tertiary alkyl ester type acid dissociation, can enumerate aliphatics and prop up the acid dissociation dissolving inhibition base that the dissolving of chain acid dissociation suppresses base, contains alicyclic group.

" aliphatics is propped up chain " is meant the chain structure with aromaticity.

The structure of " aliphatics prop up the dissolving of chain acid dissociation suppress base " is not limited to the group (alkyl) that formed by carbon and hydrogen, but preferred alkyl.In addition, " alkyl " can be saturated also can be unsaturated, preferably saturated usually.

Prop up the dissolving of chain acid dissociation as aliphatics and suppress base, the tertiary alkyl of preferred carbon number 4～8 specifically can be enumerated the tert-butyl group, tertiary pentyl, uncle's heptyl etc.

" alicyclic group " is meant monocycle base or the many cyclic groups with aromaticity.

" alicyclic group " in the structural unit (a1) can have substituting group, also can not have substituting group.As substituting group, can enumerate the low alkyl group, fluorine atom of carbon number 1～5, the fluoro low alkyl group of the carbon number 1～5 after being replaced by fluorine atom, oxygen atom (=O) etc.

" alicyclic group " removed basic ring structure behind the substituting group and is not limited to the group (alkyl) that formed by carbon and hydrogen, but preferred alkyl.In addition, " alkyl " can be saturated also can be unsaturated, preferably saturated usually." alicyclic group " preferred many cyclic groups.

As alicyclic group, for example can enumerate replaced by low alkyl group, fluorine atom or fluoro-alkyl or polynaphthenes such as unsubstituted mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane remove 1 group behind the above hydrogen atom etc.More specifically, can enumerate polynaphthenes such as mononaphthenes such as cyclopentane, cyclohexane or diamantane, norbornane, isoborneol alkane, tristane, Fourth Ring decane and remove 1 group behind the above hydrogen atom etc.

Suppress base as the acid dissociation dissolving that contains alicyclic group, for example can enumerate the group that on the ring skeleton of the alkyl of ring-type, has tertiary carbon atom, specifically can enumerate 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl etc.Perhaps, can be listed below in the structural unit of stating general formula (a1 "-1)～(a1 "-6) expression with the group of the oxygen atom bonding of ketonic oxygen base (-C (O)-O-) such, have alicyclic group such as adamantyl, cyclohexyl, cyclopentyl, norborneol alkyl, tristane base, Fourth Ring dodecyl and with the group of the chain alkylidene with tertiary carbon atom of its bonding.

[in the formula, R represents hydrogen atom, low alkyl group or junior alkyl halides; R ¹⁵, R ¹⁶Expression alkyl (any in straight chain shape, the chain, preferred carbon number is 1～5).]

Among general formula (a1 "-1)～(a1 "-6), the low alkyl group of R or junior alkyl halides with above-mentioned can be identical with the low alkyl group or the junior alkyl halides of the α position bonding of acrylate.

" dissolving of acetal type acid dissociation suppress base " usually with the hydrogen atom replacement of alkali-soluble group ends such as carboxyl, hydroxyl with the oxygen atom bonding.When producing when acid by exposure, under the effect of this acid, the dissolving of acetal type acid dissociation suppresses the bond rupture between the oxygen atom that basic and this acetal type acid dissociation dissolving suppresses basic institute bonding.

Suppress base as the dissolving of acetal type acid dissociation, can enumerate the group of for example following general formula (p1) expression.

[in the formula, R ¹', R ²' representing hydrogen atom or low alkyl group respectively independently, n represents 0～3 integer, Y represents low alkyl group or alicyclic group.]

In the above-mentioned formula, n is preferably 0～2 integer, and more preferably 0 or 1, most preferably 0.

As R ¹', R ²' low alkyl group, can enumerate the group identical, preferable methyl or ethyl, most preferable with the low alkyl group of above-mentioned R.

In the present invention, preferred R ¹', R ²' at least one be hydrogen atom.That is, the acid dissociation dissolving suppresses the group that base (p1) is preferably following general formula (p1-1) expression.

[in the formula, R ¹', n, Y be same as described above.]

As the low alkyl group of Y, can enumerate the group identical with the low alkyl group of above-mentioned R.

As the alicyclic group of Y, can from a large amount of monocycles of proposing the existing ArF resist etc. or polycycle alicyclic group, suitably select to use, for example with above-mentioned " alicyclic group " identical group.

Suppress base as the dissolving of acetal type acid dissociation, can also enumerate the group of following general formula (p2) expression.

[in the formula, R ¹⁷, R ¹⁸Independent respectively is the alkyl or the hydrogen atom of a straight chain shape or a chain, R ¹⁹It is the alkyl of straight chain shape, a chain or ring-type.R ¹⁷And R ¹⁹Can distinguish is the alkylidene of a straight chain shape or a chain independently, R ¹⁷End and R ¹⁹End can be bonded to ring.]

R ¹⁷, R ¹⁸In, the carbon number of alkyl is preferably 1～15, can be in straight chain shape, the chain any, preferred ethyl, methyl, most preferable.

Preferred especially R ¹⁷, R ¹⁸In a side be hydrogen atom, the opposing party is a methyl.

R ¹⁹Be the alkyl of straight chain shape, a chain or ring-type, carbon number is preferably 1～15, can be in straight chain shape, a chain or the ring-type any.

Work as R ¹⁹When being straight chain shape, chain, carbon number is preferably 1～5, more preferably ethyl, methyl, preferred especially ethyl.

Work as R ¹⁹During for ring-type, carbon number is preferably 4～15, carbon number more preferably 4～12, and carbon number most preferably is 5～10.Particularly, can enumerate and replaced by fluorine atom or fluoro-alkyl or polynaphthenes such as unsubstituted mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane are removed 1 group behind the above hydrogen atom etc.Specifically can enumerate polynaphthenes such as mononaphthenes such as cyclopentane, cyclohexane or diamantane, norbornane, isoborneol alkane, tristane, Fourth Ring dodecane and remove 1 group behind the above hydrogen atom etc.Wherein, preferred diamantane is removed 1 group behind the above hydrogen atom.

In addition, in the above-mentioned formula, R ¹⁷And R ¹⁹Can distinguish is the alkylidene (preferred carbon number is 1～5 alkylidene) of a straight chain shape or a chain independently, and R ¹⁹End and R ¹⁷Terminal bonding.

At this moment, by R ¹⁷And R ¹⁹, R ¹⁹The oxygen atom of institute's bonding, this oxygen atom and R ¹⁷The carbon atom of institute's bonding forms cyclic group.As this cyclic group, preferred 4～7 yuan of rings, more preferably 4～6 yuan of rings.As the object lesson of this cyclic group, can enumerate THP trtrahydropyranyl, tetrahydrofuran base etc.

As structural unit (a1), in the preferred structural unit that uses the structural unit that is selected from following general formula (a1-0-1) expression and following general formula (a1-0-2) expression more than a kind.

[in the formula, R represents hydrogen atom, low alkyl group or junior alkyl halides; X ¹The dissolving of expression acid dissociation suppresses base.]

[in the formula, R represents hydrogen atom, low alkyl group or junior alkyl halides; X ²The dissolving of expression acid dissociation suppresses base; Y ²Expression alkylidene, alicyclic group or have the divalent linking group of ehter bond.]

In the general formula (a1-0-1), the low alkyl group of R or junior alkyl halides with above-mentioned can be identical with the low alkyl group or the junior alkyl halides of the α position bonding of acrylate.

X ¹Get final product so long as the acid dissociation dissolving suppresses base, do not have particular restriction, can enumerate for example above-mentioned tertiary alkyl ester type acid dissociation dissolving and suppress base, acetal type acid dissociation dissolving inhibition base etc., the dissolving of preferred tertiary Arrcostab type acid dissociation suppresses base.

In general formula (a1-0-2), R is same as described above.

X ²With the X in the formula (a1-0-1) ¹Identical.

Y ²For alkylidene, alicyclic group or have the divalent linking group of ehter bond.

Work as Y ²When being alkylidene, preferred carbon number is 1～10 alkylidene, and more preferably carbon number is 1～6, and preferred especially carbon number is 1～4, and most preferably carbon number is 1～3.

Work as Y ²When being alicyclic group, the alicyclic group of preferred divalent, as this alicyclic group, can the use and above-mentioned " alicyclic group " middle identical group of group that illustrates of group of sloughing 2 above hydrogen atoms except use.

Work as Y ²When being the alicyclic group of divalent, especially preferably remove 2 groups behind the above hydrogen atom by cyclopentane, cyclohexane, norbornane, isoborneol alkane, diamantane, tristane, Fourth Ring dodecane.

Work as Y ²Be when having the divalent linking group of ehter bond, to be preferably-Y ^a-O-Y ^bThe group of-expression.

At above-mentioned-Y ^a-O-Y ^bIn the group of-expression, Y ^aBe that can to have substituent carbon number be divalent alkyl more than 2.Alkyl can be an aliphatic alkyl, also can be aromatic hydrocarbyl.The preferred aliphat alkyl.As aliphatic alkyl, can enumerate the aliphatic alkyl that contains ring in the aliphatic alkyl, structure of straight chain shape or chain etc.Particularly, with Y ²When being the divalent alicyclic group or Y ²Carbon number is that group more than 2 is identical in the group of enumerating when being alkylidene.In addition, Y ^aCan have substituting group,, work as Y as this substituting group ^aThe carbon number that can enumerate fluorine atom when being the aliphatic alkyl of chain, be replaced by fluorine atom be 1～5 fluoro low alkyl group, oxygen atom (=O) etc., work as Y ^aBe when containing the aliphatic alkyl of ring in the structure, identical with substituting group in above-mentioned " alicyclic group ".

As Y ^a, the aliphatic alkyl of preferred straight chain shape, the alkylidene of further preferred straight chain shape, more preferably carbon number is the alkylidene of 2～5 straight chain shape, most preferably ethylidene.

Y ^bBe that can to have substituent carbon number be divalent alkyl more than 1.As Y ^bAlkyl, can enumerate and above-mentioned Y ^aIn to enumerate the same carbon number of alkyl be the divalent alkyl more than 2 and can have substituent methylene.As the substituting group that methylene can have, can enumerate the identical group of enumerating with the substituting group that can have of substituting group as above-mentioned chain aliphatic alkyl.

As Y ^b, the aliphatic alkyl of a preferred straight chain shape or a chain, preferred especially methylene or alkyl methylene.

The preferred carbon number of alkyl in the alkyl methylene is 1～5 straight chain shape alkyl, and further preferred carbon number is 1～3 straight chain shape alkyl, most preferable.

As structural unit (a1), more specifically, can enumerate the structural unit of following general formula (a1-1)～(a1-4) expression.

[in the formula, the dissolving of X ' expression tertiary alkyl ester type acid dissociation suppresses base, and Y represents that carbon number is 1～5 low alkyl group or alicyclic group; N represents 0～3 integer; Y ²Expression alkylidene, alicyclic group or have the divalent linking group of ehter bond; R is same as described above, R ¹', R ²' represent independently that respectively hydrogen atom or carbon number are 1～5 low alkyl group.]

In the formula, X ' can enumerate and above-mentioned X ¹In illustrative tertiary alkyl ester type acid dissociation dissolving suppress the identical group of base.

As R ¹', R ²', n, Y, respectively with the general formula (p1) described in above-mentioned " dissolving of dissociating property of acetal type suppress base " in R ¹', R ²', n, Y be identical.

As Y ², can enumerate with above-mentioned general formula (a1-0-2) in Y ²Identical group.

Below, enumerate the object lesson of the structural unit of above-mentioned general formula (a1-1)～(a1-4) expression.

As structural unit (a1), can use a kind separately, also can be used in combination more than 2 kinds.

Wherein, the structural unit of preferred formula (a1-1) expression, particularly, more preferably use at least a kind that is selected among (a1-1-1)～(a1-1-6), (a1-1-17)～(a1-1-18), (a1-1-35)～(a1-1-41) and (a1-3-49)～(a1-3-50).

In addition, as structural unit (a1), preferably include especially formula (a1-1-1)～formula (a1-1-4) structural unit following general formula (a1-1-01) expression structural unit or comprise the following general formula (a1-1-02) of the structural unit of formula (a1-1-35)～(a1-1-41).

[in the formula, R represents hydrogen atom, low alkyl group or junior alkyl halides, R ¹¹The expression low alkyl group.]

[in the formula, R represents hydrogen atom, low alkyl group or junior alkyl halides, R ¹²The expression low alkyl group.H represents 1～3 integer.]

In the general formula (a1-1-01), R is same as described above.

R ¹¹Low alkyl group identical with low alkyl group among the R, preferable methyl or ethyl.

In general formula (a1-1-02), R is same as described above.

R ¹²Low alkyl group identical with low alkyl group among the R, preferable methyl or ethyl, most preferably ethyl.H preferred 1 or 2, and most preferably 2.

As structural unit (a1), can use a kind separately, also can be used in combination more than 2 kinds.

(A1) in the composition, the ratio of structural unit (a1) is preferably 10～80 moles of % for the general construction unit with respect to formation (A1) composition, more preferably 20～70 moles of %, further preferred 25～50 moles of %.If more than the lower limit, can easily obtain pattern during then as the resist composition, if below the higher limit, then can reach balance with other structural unit.

Structural unit (a2)

Structural unit (a2) is to be derived and next structural unit by the acrylate of the cyclic group that contains lactone.

Here, the cyclic group that contains lactone is meant that containing one has-cyclic group of the ring (lactonic ring) of O-C (O)-structure.Lactonic ring be can be regarded as a ring, when only lactonic ring being arranged, is called the monocycle base, when also having other ring structures, no matter which kind of structure is this structure be, all is called many cyclic groups.

The lactone cyclic group of structural unit (a2) can improve resist film effectively to the adaptation of substrate or the compatibility of raising and moisture developer solution when forming resist film with (A1) composition.

As structural unit (a2), there is not particular restriction, can use structural unit arbitrarily.

Particularly, as the monocycle base that contains lactone, can enumerate γ-butyrolactone and remove 1 group behind the hydrogen atom.As the many cyclic groups that contain lactone, can enumerate dicyclo alkane, three cycloalkanes, tetracycloalkane and remove 1 group behind the hydrogen atom with lactonic ring.

As the example of structural unit (a2), more specifically, can enumerate the structural unit of following general formula (a2-1)～(a2-5) expression.

[in the formula, R is hydrogen atom, low alkyl group or junior alkyl halides, R ' be hydrogen atom, low alkyl group, carbon number be 1～5 alkoxy or-COOR "; above-mentioned R " be that hydrogen atom or carbon number are the alkyl of 1～15 straight chain shape, a chain or ring-type, m is 0 or 1 integer, A " be that the carbon number that can contain oxygen atom or sulphur atom is 1～5 alkylidene, oxygen atom or sulphur atom.]

R among general formula (a2-1)～(a2-5) is identical with R in said structure unit (a1).

As the low alkyl group of R ', can enumerate with said structure unit (a1) in the identical group of low alkyl group of R.

As R " when being the alkyl of a straight chain shape or a chain, preferred carbon number is 1～10, more preferably carbon number is 1～5.

As R " when being the alkyl of ring-type, preferred carbon number is 3～15, and more preferably carbon number is 4～12, and most preferably carbon number is 5～10.Particularly, can enumerate and replaced by fluorine atom or fluoro-alkyl or polynaphthenes such as unsubstituted mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane are removed 1 group behind the above hydrogen atom etc.Specifically can enumerate polynaphthenes such as mononaphthenes such as cyclopentane, cyclohexane or diamantane, norbornane, isoborneol alkane, tristane, Fourth Ring dodecane and remove 1 group behind the above hydrogen atom etc.

Consider industrial acquisition easiness etc., the preferred hydrogen atom of the R ' among general formula (a2-1)～(a2-5).

As A " the carbon number that can contain oxygen atom or sulphur atom be 1～5 alkylidene, specifically can enumerate methylene, ethylidene, positive propylidene, isopropylidene ,-O-CH ₂-,-CH ₂-O-CH ₂-,-S-CH ₂-,-CH ₂-S-CH ₂-etc.

Below, the concrete structure unit of the above-mentioned general formula of illustration (a2-1)～(a2-5).

As structural unit (a2), be preferably selected from least a kind in the structural unit of above-mentioned general formula (a2-1)～(a2-5) expression, more preferably be selected from least a kind in the structural unit of general formula (a2-1)～(a2-3) expression.Wherein, be preferably selected from the structural unit of chemical formula (a2-1-1), (a2-1-2), (a2-2-1), (a2-2-2), (a2-2-9), (a2-2-10), (a2-3-1), (a2-3-2), (a2-3-9) and (a2-3-10) expression at least a kind.

As structural unit (a2), can use a kind separately, also can be used in combination more than 2 kinds.

(A1) in the composition, the ratio of structural unit (a2) is preferably 5～60 moles of % for the general construction unit with respect to formation (A1) composition, more preferably 10～50 moles of %, more preferably 20～50 moles of %.If more than the lower limit, then can fully obtain to contain the effect that structural unit (a2) is produced, if below the higher limit, then can reach balance with other structural units.

Structural unit (a3)

Structural unit (a3) is to be derived and next structural unit by the acrylate of the aliphatic alkyl that contains polar group.

(A1) composition has structural unit (a3), and therefore the water wettability of (A1) composition improves, and with the compatibility raising of developer solution, the alkali dissolution raising of exposure portion helps to improve the exploring degree.

As polar group, the hydroxyalkyl after a part of hydrogen atom that can enumerate hydroxyl, cyano group, carboxyl, alkyl is replaced by fluorine atom etc., preferred especially hydroxyl.

As aliphatic alkyl, can enumerate carbon number is 1～10 straight chain shape or the alkyl (preferred alkylidene) that props up chain or the aliphatic alkyl (many cyclic groups) of polycycle.As these many cyclic groups, can use from for example in many cyclic groups that the ArF excimer laser is mentioned with resin in a large number with the resist composition, suitably selecting.The carbon number of these many cyclic groups preferred 7～30.

Wherein, the more preferably structural unit of being derived by following acrylate, this acrylate comprise the many cyclic groups of aliphatics of the hydroxyalkyl after a part of hydrogen atom that contains hydroxyl, cyano group, carboxyl or alkyl is replaced by fluorine atom.As these many cyclic groups, can illustration dicyclo alkane, three cycloalkanes, tetracycloalkane etc. remove 2 groups behind the above hydrogen atom etc.Specifically can enumerate polynaphthenes such as diamantane, norbornane, isoborneol alkane, tristane, Fourth Ring dodecane and remove 2 groups behind the above hydrogen atom etc.In these many cyclic groups, industrial preferred diamantane is removed 2 group, norbornanes behind the above hydrogen atom and is removed 2 group, Fourth Ring dodecanes behind the above hydrogen atom and remove 2 groups behind the above hydrogen atom.

As structural unit (a3), when the alkyl in the aliphatic alkyl of polar functionalities is that carbon number is when being the alkyl of a straight chain shape of 1～10 or a chain, the preferred structural unit of deriving by acrylic acid hydroxyethyl ester, when this alkyl is many cyclic groups, the structural unit of the structural unit of preferred following formula (a3-1) expression, (a3-2) expression, the structural unit of (a3-3) expression.

[in the formula, R is the same, and j is 1～3 integer, and k is 1～3 integer, and t ' is 1～3 integer, and 1 is 1～5 integer, and s is 1～3 integer.]

In the formula (a3-1), j is preferably 1 or 2, and more preferably 1.When j is 2,3 and 5 bondings of preferred hydroxyl and adamantyl.When j is 1,3 bondings of preferred hydroxyl and adamantyl.

J is preferably 1,3 bondings of preferred especially hydroxyl and adamantyl.

In the formula (a3-2), k is preferably 1.Cyano group preferably with 5 or 6 bondings of norborneol alkyl.

In the formula (a3-3), t ' is preferably 1.1 is preferably 1.S is preferably 1.Their preferred acrylic acid carboxyl terminals and 2-norborneol alkyl or 3-norborneol are alkyl linked.Fluoroalkyl alcohol preferably with 5 or 6 bondings of norborneol alkyl.

As structural unit (a3), can use a kind separately, also can be used in combination more than 2 kinds.

(A1) in the composition, the ratio of structural unit (a3) is preferably 5～50 moles of % for the general construction unit with respect to formation (A1) composition, more preferably 5～40 moles of %, more preferably 5～25 moles of %.If more than the lower limit, then can fully obtain to contain the effect that structural unit (a3) is produced, if below the higher limit, then can reach balance with other structural units.

Structural unit (a4)

In the scope of not damaging effect of the present invention, (A1) composition can also contain said structure unit (a1)～(a3) in addition other structural units (a4) are arranged.

Structural unit (a4) is not so long as belong to other structural units of said structure unit (a1)～(a3) and get final product, there is not particular restriction, the structural unit that can use the known numerous ArF of being used for excimer laser to use with resin with the resist of (preferred ArF excimer laser with) etc. with, KrF excimer laser.

As structural unit (a4), preference is as the structural unit of being derived by the acrylate of the many cyclic groups of aliphatics that contains non-the dissociating property of acid etc.These many cyclic groups for example can enumerate with said structure unit (a1) in the identical group enumerated, can use known numerous structural unit that uses in, KrF excimer laser resinous principle in the ArF excimer laser with the resist composition of (preferred ArF excimer laser with) etc.

Particularly, if at least a kind of selecting from three ring decyls, adamantyls, Fourth Ring dodecyl, isoborneol alkyl, norborneol alkyl then becomes preferred because of industrial easy acquisition etc.It is that the alkyl of a straight chain shape of 1～5 or a chain is as substituting group that these many cyclic groups can have carbon number.

As structural unit (a4), structure that specifically can the following general formula of illustration (a4-1)～(a4-5).

[in the formula, R is same as described above.]

When containing described structural unit (a4) in (A1) composition, (A1) ratio of the structural unit in the composition (a4) is preferably 1～30 mole of % for the total with respect to the general construction unit that constitutes (A1) composition, more preferably 10～20 moles of %.

In the present invention, (A1) composition preferably contains and has structural unit (a1), (a2) and multipolymer (a3).As this multipolymer, can enumerate by structural unit (a1), (a2) and the multipolymer that (a3) forms, by structural unit (a1), (a2), (a3) and multipolymer of (a4) forming etc.

(A1) composition can use for example known free radical polymerization of the radical polymerization initiator of azoisobutyronitrile (AIBN) and so on to wait polymerization to obtain by the monomer utilization that makes each structural unit of deriving.

When carrying out above-mentioned polymerization, by in (A1) composition, share for example HS-CH ₂-CH ₂-CH ₂-C (CF ₃) ₂The chain-transferring agent that-OH is such can be introduced-C (CF endways ₃) ₂-OH base.The multipolymer of the hydroxyalkyl that a part of hydrogen atom of so having introduced alkyl is replaced by fluorine atom can reduce developing defect and LER (line edge roughness: line sidewall inhomogeneous concavo-convex) effectively.

(A1) the matter average molecular weight (Mw) of composition (the polystyrene conversion benchmark that gel permeation chromatography obtains) does not have particular restriction, and is preferred 2000～50000, and more preferably 3000～30000, most preferably 5000～20000.If the upper limit less than this scope has sufficient dissolubility to the resist solvent when then using as resist, as if the lower limit greater than this scope, then anti-dry corrosion and resist pattern section shape are good.

Dispersion degree (Mw/Mn) is preferably 1.0～5.0, and more preferably 1.0～3.0, most preferably be 1.2～2.5.In addition, Mn represents number-average molecular weight.

[(A2) composition]

As (A2) composition, preferred molecular weight is in 500 above less thaies 2000 and have the low molecular compound that in the explanation of above-mentioned (A1) composition illustrative acid dissociation dissolving suppresses base and hydrophilic group.The a part of hydrogen atom that specifically can enumerate the hydroxyl of the compound with a plurality of phenol skeletons is suppressed compound after base replaces by above-mentioned acid dissociation dissolving.

(A2) composition can be selected use arbitrarily preferably as the g line of amplification type non-chemically or the sensitizer in the i line resist, thermotolerance improving agent and a part of hydrogen atom of the hydroxyl of known low-molecular-weight phenolic compounds is suppressed compound after base replaces by above-mentioned acid dissociation dissolving from these compounds.

As described low-molecular-weight phenolic compounds, can enumerate for example two (4-hydroxy phenyl) methane, two (2,3,4-trihydroxy phenyl) methane, 2-(4-hydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, 2-(2,3,4-trihydroxy phenyl)-2-(2 ', 3 ', 4 '-trihydroxy phenyl) propane, three (4-hydroxy phenyl) methane, two (4-hydroxyls-3,5-3,5-dimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-2,5-3,5-dimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-3,5-3,5-dimethylphenyl)-3,4-dihydroxy benzenes methylmethane, two (4-hydroxyls-2,5-3,5-dimethylphenyl)-3,4-dihydroxy benzenes methylmethane, two (4-hydroxyls-3-aminomethyl phenyl)-3,4-dihydroxy benzenes methylmethane, two (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl)-4-hydroxy phenyl methane, two (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl)-3,4-dihydroxy benzenes methylmethane, 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1,1-two (4-hydroxy phenyl) ethyl] benzene, phenol, metacresol, 2 of the formaldehyde condensation products of phenol such as paracresol or xylenols, 3,4 nucleomes etc.Certainly, be not limited to these.

The acid dissociation dissolving suppresses base and also is not subjected to particular restriction, can enumerate above-mentioned group.

As (A) composition, can use a kind separately, also can share more than 2 kinds.

In the resist composition of the present invention, (A) content of composition can wait according to preformed resist thickness and regulate.

＜(B) composition 〉

(B) composition contain the acid agent (B1) that the compound by above-mentioned general formula (b1-1) expression forms (below, be sometimes referred to as (B1) composition.)。It is identical with the compound (B1) of the invention described above to be somebody's turn to do (B1) composition.

(B1) composition can use to mix more than a kind or 2 kinds and use.

In resist composition of the present invention, (B) content of (B1) composition in the composition is preferably more than the 40 quality %, more than the 70 quality %, also can be 100 quality % more preferably.Most preferably be 100 quality %.If more than the lower limit of this scope, when then using this resist composition to form the resist pattern, exploring degree, Yan Mo Chong Now, line width roughness (LWR), pattern form, exposure (EL) allowance, depth of focus photolithographic characteristics such as (DOF) improve.

(B) in the composition, the acid agent (B2) (hereinafter referred to as (B2) composition) beyond above-mentioned (B1) composition and above-mentioned (B1) composition can be share.

As (B2) composition, so long as the composition beyond above-mentioned (B1) composition gets final product, there is not particular restriction, can use the chemical amplification type anti-corrosion agent acid agent that proposes up to now.

As this acid agent, known up to now have diazomethane class acid agent, nitrobenzyl Sulfonates acid agent, imines Sulfonates acid agent, two sulfone class acid agents etc. such as salt acid agents such as salt compounded of iodine or sulfonium salt, sulfonation oximes acid agent, dialkyl group or diaryl sulphonyl diazomethane class, poly-(disulfonyl) diazomethane class multiple.

As the salt acid agent, can use the compound of for example following general formula (b-1) or (b-2) expression.

[in the formula, R ¹"～R ³", R ⁵"～R ⁶" represent aryl or alkyl respectively independently; R in the formula (b-1) ¹"～R ³" in any 2 bonding and the sulphur atom Cheng Huan in formula mutually; R ⁴" represent the straight chain shape, prop up the alkyl or the fluoro-alkyl of chain or ring-type; R ¹"～R ³" at least one the expression aryl, R ⁵"～R ⁶" at least one the expression aryl.]

R in the formula (b-1) ¹"～R ³" respectively with above-mentioned (b '-1) in R ¹"～R ³" identical.

R ⁴" represent the straight chain shape, prop up the alkyl or the fluoro-alkyl of chain or ring-type

As the alkyl of an above-mentioned straight chain shape or a chain, preferred carbon number is 1～10, and more preferably carbon number is 1～8, and most preferably carbon number is 1～4.

As the alkyl of above-mentioned ring-type, be above-mentioned R ¹" cyclic group of expression, preferred carbon number is 4～15, and more preferably carbon number is 4～10, and most preferably carbon number is 6～10.

As above-mentioned fluoro-alkyl, preferred carbon number is 1～10, and more preferably carbon number is 1～8, and most preferably carbon number is 1～4.

In addition, the rate of fluoridizing of this fluoro-alkyl (ratio of the fluorine atom in the alkyl) is preferably 10～100%, and more preferably 50～100%, the fluoro-alkyl (perfluoroalkyl) after particularly hydrogen atom is all replaced by fluorine atom becomes preferably because of the acid strength grow.

As R ⁴", the most preferably alkyl of straight chain shape or ring-type or fluoro-alkyl.

R in the formula (b-2) ⁵"～R ⁶" respectively with above-mentioned (b '-2) in R ⁵"～R ⁶" identical.

As the R in the formula (b-2) ⁴", can enumerate with following formula (b-1) in R ⁴" identical group.

As formula (b-1), the object lesson of salt acid agent of (b-2) expression can be enumerated the fluoroform sulphonate or the nine fluorine fourth sulfonate of diphenyl iodine, fluoroform sulphonate of two (4-tert-butyl-phenyl) iodine or nine fluorine fourth sulfonate, the fluoroform sulphonate of triphenylsulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of three (4-aminomethyl phenyl) sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of dimethyl (4-hydroxyl naphthyl) sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of one phenyl dimethyl sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate; The fluoroform sulphonate of diphenyl monomethyl sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of (4-aminomethyl phenyl) diphenyl sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of (4-methoxyphenyl) diphenyl sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of three (4-tert-butyl group) phenyl sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of diphenyl (1-(4-methoxyl) naphthyl) sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate, the fluoroform sulphonate of two (1-naphthyl) phenyl sulfonium, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate; The fluoroform sulphonate of 1-phenyl thiophane, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate; The fluoroform sulphonate of 1-(4-aminomethyl phenyl) thiophane, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate; The fluoroform sulphonate of 1-(3,5-dimethyl-4-hydroxy phenyl) thiophane, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate; The fluoroform sulphonate of 1-(4-methoxynaphthalene-1-yl) thiophane, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate; The fluoroform sulphonate of 1-(4-ethoxy naphthalene-1-yl) thiophane, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate; The fluoroform sulphonate of 1-(4-normal-butyl naphthalene-1-yl) thiophane, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate; The fluoroform sulphonate of 1-phenyl tetrahydric thiapyran, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate; The fluoroform sulphonate of 1-(4-hydroxy phenyl) tetrahydric thiapyran, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate; The fluoroform sulphonate of 1-(3,5-dimethyl-4-hydroxy phenyl) tetrahydric thiapyran, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate; The fluoroform sulphonate of 1-(4-aminomethyl phenyl) tetrahydric thiapyran, its seven fluorine propane sulfonic acid salt or its nine fluorine fourth sulfonate etc.

In addition, the salt after the negative ion portion that also can use these salt is replaced by mesylate, positive propane sulfonic acid salt, positive fourth sulfonate, positive hot sulfonate.

In addition, the salt acid agent (kation portion is identical with (b-1) or (b-2)) after can also using negative ion portion among above-mentioned general formula (b-1) or (b-2) to be replaced by the negative ion portion of following general formula (b-3) or (b-4) expression.

[in the formula, X " alkylidene of the carbon number 2～6 that replaced by fluorine atom of at least 1 hydrogen atom of expression; Y ", Z " represent the alkyl of the carbon number 1～10 that at least one hydrogen atom is replaced by fluorine atom respectively independently.]

X " straight chain shape that to be at least one hydrogen atom replaced by fluorine atom or the alkylidene of a chain, the carbon number of this alkylidene is 2～6, and preferred carbon number is 3～5, and most preferably carbon number is 3.

Y ", Z " the straight chain shape that replaced by fluorine atom at least one hydrogen atom independently respectively or the alkyl of a chain, the carbon number of this alkyl is 1～10, preferred carbon number is 1～7, further preferred carbon number is 1～3.

Owing to reason, X such as the dissolubility in the resist solvent is also good " the carbon number or the Y of alkylidene ", Z " the carbon number of alkyl the smaller the better in the scope of above-mentioned carbon number.

X " alkylidene or Y ", Z " alkyl in the number of the hydrogen atom that replaced by fluorine atom many more, the intensity of acid is strong more, and improves in the high-energy light below the 200nm or the transparency under the electron ray, thereby preferred.The ratio of the fluorine atom in this alkylidene or the alkyl i.e. rate of fluoridizing is preferably 70～100%, and more preferably 90～100%, preferably all hydrogen atoms are all replaced perfluorinated alkylidene or the perfluoroalkyl that obtains by fluorine atom.

In addition, also the kation portion with above-mentioned general formula (b-5) or (b-6) expression can be become the sulfonium salt of other negative ion portions beyond the negative ion portion that branch has to be used as the salt acid agent with above-mentioned (B1).

As above-mentioned other negative ion portions, can use the negative ion portion of the salt acid agent that has proposed up to now, can enumerate (the R of negative ion portion of the salt acid agent of for example above-mentioned general formula (b-1) or (b-2) expression ^{4 "}SO ₃ ^-) wait the fluoro-alkyl azochlorosulfonate acid ion; The negative ion portion of above-mentioned general formula (b-3) or (b-4) expression etc.Wherein, preferred fluoro-alkyl azochlorosulfonate acid ion, further preferred carbon number are 1～4 fluoro-alkyl azochlorosulfonate acid ion, and preferred especially carbon number is 1～4 straight chain shape perfluoro alkyl sulfonic acid ion.As object lesson, can enumerate trifluoromethane sulfonic acid ion, seven fluorine n-pro-pyl azochlorosulfonate acid ions, nine fluorine normal-butyl azochlorosulfonate acid ions etc.

In this manual, sulfonation oximes acid agent is meant the compound of the group that has 1 following general formula (B-1) expression at least, has acidic characteristic under the irradiation of radioactive ray.This sulfonation oximes acid agent is usually used in chemical amplification type anti-corrosion agent composition, therefore can select arbitrarily to use.

(in the formula (B-1), R ³¹, R ³²Represent organic group respectively independently.)

R ³¹, R ³²Organic group be the group that contains carbon atom, also can have the atom (for example hydrogen atom, oxygen atom, nitrogen-atoms, sulphur atom, halogen atom (fluorine atom, chlorine atom etc.) etc.) beyond the carbon atom.

As R ³¹Organic group, the alkyl or aryl of preferred straight chain shape, a chain or ring-type.These alkyl, aryl also can have substituting group.As this substituting group, there is not particular restriction, can enumerate for example fluorine atom, carbon number and be the alkyl of 1～6 straight chain shape, a chain or ring-type etc.Here, " have substituting group " and be meant that part or all hydrogen atom of alkyl or aryl is substituted the base replacement.

As alkyl, preferred carbon number is 1～20, and further preferred carbon number is 1～10, and more preferably carbon number is 1～8, and preferred especially carbon number is 1～6, and most preferably carbon number is 1～4.As alkyl, preferred especially partly or entirely by the alkyl of halo (below be sometimes referred to as haloalkyl).In addition, part is meant the alkyl that a part of hydrogen atom is replaced by halogen atom by the alkyl of halo, is meant the alkyl that whole hydrogen atoms are replaced by halogen atom by the alkyl of halo fully.As halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom etc., preferred especially fluorine atom.That is the preferred fluoro-alkyl of haloalkyl.

The preferred carbon number of aryl is 4～20, and more preferably carbon number is 4～10, and most preferably carbon number is 6～10.As aryl, preferred especially partly or entirely by the aryl of halo.In addition, part is meant the aryl that a part of hydrogen atom is replaced by halogen atom by the aryl of halo, all is meant the aryl that whole hydrogen atoms are replaced by halogen atom by the aryl of halo.

As R ³¹, the carbon number of preferred especially unsubstituted is 1～4 alkyl, or carbon number is 1～4 fluoro-alkyl.

As R ³²Organic group, alkyl, aryl or the cyano group of preferred straight chain shape, a chain or ring-type.As R ³²Alkyl, aryl, can enumerate and above-mentioned R ³¹In the identical group of alkyl, aryl enumerated.

As R ³², the carbon number of preferred especially cyano group, unsubstituted is that 1～8 alkyl or carbon number are 1～8 fluoro-alkyl.

As sulfonation oximes acid agent, the compound of further preferred following general formula (B-2) or (B-3) expression.

[in the formula (B-2), R ³³Be the alkyl or the haloalkyl of cyano group, unsubstituted.R ³⁴It is aryl.R ³⁵Be the alkyl or the haloalkyl of unsubstituted.]

[in the formula (B-3), R ³⁶Be the alkyl or the haloalkyl of cyano group, unsubstituted.R ³⁷It is the aromatic hydrocarbyl of divalent or 3 valencys.R ³⁸Be the alkyl or the haloalkyl of unsubstituted.P " be 2 or 3.]

In the above-mentioned general formula (B-2), R ³³The alkyl or the preferred carbon number of haloalkyl of unsubstituted be 1～10, more preferably carbon number is 1～8, most preferably carbon number is 1～6.

As R ³³, preferred haloalkyl, more preferably fluoro-alkyl.

R ³³In being replaced by fluorine more than 50% of hydrogen atom of fluoro-alkyl preferred alkyl, more preferably replaced by fluorine more than 70%, preferably especially replaced by fluorine more than 90%.

As R ³⁴Aryl, can enumerate phenyl, biphenyl (biphenyl) base, fluorenes (fluorenyl) base, naphthyl, anthracene (anthryl) base, phenanthryl etc. and remove 1 group and the part of carbon atom that constitutes the ring of these groups heteroaryl after being replaced by heteroatomss such as oxygen atom, sulphur atom, nitrogen-atoms etc. behind the hydrogen atom by the aromatic hydrocarbon ring.Wherein, preferred fluorenyl.

R ³⁴Aryl can to have carbon number be substituting groups such as 1～10 alkyl, haloalkyl, alkoxy.The preferred carbon number of alkyl in this substituting group or haloalkyl is 1～8, and more preferably carbon number is 1～4.In addition, the preferred fluoro-alkyl of this haloalkyl.

As R ³⁵The alkyl or the haloalkyl of unsubstituted, preferred carbon number is 1～10, more preferably carbon number is 1～8, most preferably carbon number is 1～6.

As R ³⁵, preferred haloalkyl, more preferably fluoro-alkyl.

R ³⁵In being replaced by fluorine more than 50% of hydrogen atom of fluoro-alkyl preferred alkyl, more preferably replaced by fluorine more than 70%, when being replaced by fluorine more than 90%, the intensity of the acid of generation improves, thereby preferred especially.The perfluoroalkyl that replaced by fluorine of hydrogen atom 100% most preferably.

In above-mentioned general formula (B-3), as R ³⁶The alkyl or the haloalkyl of unsubstituted, can enumerate and above-mentioned R ³³The alkyl or the identical group of haloalkyl of unsubstituted.

As R ³⁷Divalent or the aromatic hydrocarbyl of 3 valencys, can enumerate by above-mentioned R ³⁴Aryl further remove group behind 1 or 2 hydrogen atoms.

As R ³⁸The alkyl or the haloalkyl of unsubstituted, can enumerate and above-mentioned R ³⁵The alkyl or the identical group of haloalkyl of unsubstituted.

P " preferred 2.

Object lesson as sulfonation oximes acid agent, can enumerate α-(p-tosyloxy imido grpup)-benzyl prussiate, α-(p-chlorobenzene sulfonyloxy imido grpup)-benzyl prussiate, α-(4-nitrobenzene sulfonyloxy imido grpup)-benzyl prussiate, α-(4-nitro-2-trifluoromethyl phenylsulfonyloxy imido grpup)-benzyl prussiate, α-(phenylsulfonyloxy imido grpup)-4-benzyl chloride base prussiate, α-(phenylsulfonyloxy imido grpup)-2,4-dichloro benzyl prussiate, α-(phenylsulfonyloxy imido grpup)-2,6-dichloro benzyl prussiate, α-(phenylsulfonyloxy imido grpup)-4-methoxy-benzyl prussiate, α-(2-chlorobenzene sulfonyloxy imido grpup)-4-methoxy-benzyl prussiate, α-(phenylsulfonyloxy imido grpup)-thiophene-2-basic acetonitrile, α-(4-dodecyl phenylsulfonyloxy imido grpup)-benzyl prussiate, α-[(p-tosyloxy imido grpup)-4-methoxyphenyl] acetonitrile, α-[(dodecyl phenylsulfonyloxy imido grpup)-4-methoxyphenyl] acetonitrile, α-(tosyloxy imines)-4-thienyl prussiate, α-(sulfonyloxy methyl oxygen base imido grpup)-1-cyclopentenyl acetonitrile, α-(sulfonyloxy methyl oxygen base imido grpup)-1-cyclohexenyl group acetonitrile, α-(sulfonyloxy methyl oxygen base imido grpup)-1-cycloheptenyl acetonitrile, α-(sulfonyloxy methyl oxygen base imido grpup)-1-cyclooctene base acetonitrile, α-(trifluoromethyl sulfonyloxy imido grpup)-1-cyclopentenyl acetonitrile, α-(trifluoromethyl sulfonyloxy imido grpup)-cyclohexyl acetonitrile, α-(ethyl sulfonyloxy imido grpup)-ethyl acetonitrile, α-(sulfonyl propyl oxygen base imido grpup)-propyl group acetonitrile, α-(cyclohexyl sulfonyloxy imido grpup)-cyclopentyl acetonitrile, α-(cyclohexyl sulfonyloxy imido grpup)-cyclohexyl acetonitrile, α-(cyclohexyl sulfonyloxy imido grpup)-1-cyclopentenyl acetonitrile, α-(ethyl sulfonyloxy imido grpup)-1-cyclopentenyl acetonitrile, α-(isopropyl sulfonyloxy imido grpup)-1-cyclopentenyl acetonitrile, α-(normal-butyl sulfonyloxy imido grpup)-1-cyclopentenyl acetonitrile, α-(ethyl sulfonyloxy imido grpup)-1-cyclohexenyl group acetonitrile, α-(n-pro-pyl sulfonyloxy imido grpup)-1-cyclohexenyl group acetonitrile, α-(normal-butyl sulfonyloxy imido grpup)-1-cyclohexenyl group acetonitrile, α-(sulfonyloxy methyl oxygen base imido grpup)-phenylacetonitrile, α-(sulfonyloxy methyl oxygen base imido grpup)-p-methoxyphenyl acetonitrile, α-(trifluoromethyl sulfonyloxy imido grpup)-phenylacetonitrile, α-(trifluoromethyl sulfonyloxy imido grpup)-p-methoxyphenyl acetonitrile, α-(ethyl sulfonyloxy imido grpup)-p-methoxyphenyl acetonitrile, α-(sulfonyl propyl oxygen base imido grpup)-p-aminomethyl phenyl acetonitrile, α-(sulfonyloxy methyl oxygen base imido grpup)-p-bromophenyl acetonitrile etc.

In addition, also can preferably use disclosed sulfonation oximes acid agent in 9-No. 208554 communiques of Japanese patent laid-open ([change 18] of paragraph [0012]～[0014]～[changing 19]), international disclosed sulfonation oximes acid agent in No. 04/074242 pamphlet (the 65th～85 page example 1～40) disclosed.

Preferred example is as follows.

Object lesson as dialkyl group in the diazomethane class acid agent or diaryl sulphonyl diazomethane class, can enumerate two (isopropyl sulphonyl) diazomethane, two (tolysulfonyl) diazomethanes, two (1,1-dimethyl ethyl sulphonyl) diazomethane, two (cyclohexyl sulphonyl) diazomethane, two (2,4-3,5-dimethylphenyl sulphonyl) diazomethane etc.

In addition, also can preferably use disclosed diazomethane class acid agent in 11-No. 035551 communique of Japanese patent laid-open, 11-No. 035552 communique of Japanese patent laid-open, 11-No. 035573 communique of Japanese patent laid-open.

As poly-(disulfonyl) diazomethane class, for example can enumerate in 11-No. 322707 communiques of Japanese patent laid-open disclosed 1,3-two (phenyl sulphonyl dizaomethyl sulphonyl) propane, 1,4-two (phenyl sulphonyl dizaomethyl sulphonyl) butane, 1,6-two (phenyl sulphonyl dizaomethyl sulphonyl) hexane, 1,10-two (phenyl sulphonyl dizaomethyl sulphonyl) decane, 1,2-two (cyclohexyl sulphonyl dizaomethyl sulphonyl) ethane, 1,3-two (cyclohexyl sulphonyl dizaomethyl sulphonyl) propane, 1,6-two (cyclohexyl sulphonyl dizaomethyl sulphonyl) hexane, 1,10-two (cyclohexyl sulphonyl dizaomethyl sulphonyl) decane etc.

(B2) composition can use a kind of above-mentioned acid agent separately, also can be used in combination more than 2 kinds.

The content of (B) composition in the resist composition of the present invention is preferably 1～20 mass parts for being 0.5～30 mass parts with respect to 100 mass parts (A) composition.Can fully carry out pattern in above-mentioned scope forms.And, can obtain uniform solution, storage stability is good, thereby preferred.＜any composition 〉

In order to improve the resist pattern form, to place ageing stability (Japanese original text: draw I

I

The Time stability) etc., resist composition of the present invention can also contain organic compounds containing nitrogen (D) (hereinafter referred to as (D) composition).

About this (D) composition, multiple material has been proposed, from known material, select arbitrarily to use to get final product, wherein, preferred aliphat amine, special preferred aliphat secondary amine, aliphatic tertiary amine.Fatty amine is meant the amine with 1 above fatty group, and the preferred carbon number of this fatty group is 1～12.

As fatty amine, can enumerate ammonia NH ₃At least one hydrogen atom be amine (alkyl amine or alkyl alcoholamine) or cyclammonium after alkyl below 12 or hydroxyalkyl replace by carbon number.

As the object lesson of alkyl amine and alkyl alcoholamine, can enumerate alkyl amines such as n-hexyl amine, n-heptyl amine, n-octylamine, n-nonyl amine, positive decyl amine; Dialkylamines such as diethylamide, di-n-propyl amine, two n-heptyl amine, di-n-octyl amine, dicyclohexyl amine; Trialkylamines such as Trimethylamine, triethylamine, three n-pro-pyl amine, tri-n-butyl amine, three n-pentyl amine, three n-hexyl amine, three n-heptyl amine, three n-octylamine, three n-nonyl amine, three positive decyl amine, three dodecyl amine; Alkyl alcoholamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, two n-octyl alcohol amine, three n-octyl alcohol amine.Wherein, preferred 3 carbon numbers are the trialkylamine that 5～10 alkyl and nitrogen atom bonding form, most preferably three n-pentyl amine.

As cyclammonium, can enumerate and for example contain nitrogen-atoms as heteroatomic heterogeneous ring compound.As this heterogeneous ring compound, can be monocyclic compound (aliphatics monocycle amine), also can be polycyclic compund (aliphatics polycyclic amines).

As aliphatics monocycle amine, specifically can enumerate piperidines, piperazine etc.

As the aliphatics polycyclic amines, preferred carbon number is 6～10, specifically can enumerate 1,5-diazo bicyclic [4.3.0]-5-nonene, 1,8-diazo bicyclic [5.4.0]-7-undecylene, urotropine, 1,4-diazo bicyclic [2.2.2] octane etc.

Except that the above-mentioned material of enumerating, can also preferably use the stearyl diethanolamine.

They may be used alone, two or more kinds can also be used in combination.

(D) composition uses in the scope of 0.01～5.0 mass parts usually with respect to 100 mass parts (A) composition.

For oxyacid and any composition of at least a compound (E) in the derivant (hereinafter referred to as (E) composition) conduct thereof that prevents from that sensitivity from descending, improving the resist pattern form, placing ageing stability etc., in resist composition of the present invention, can also contain to be selected from organic carboxyl acid and phosphorus.

As organic carboxyl acid, preference such as acetate, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid etc.

As the oxyacid and the derivant thereof of phosphorus, can enumerate phosphoric acid, phosphonic acids, phosphinic acids etc., wherein preferred especially phosphonic acids.

As the derivant of the oxyacid of phosphorus, can enumerate ester after for example the hydrogen atom of above-mentioned oxyacid is replaced by alkyl etc., as above-mentioned alkyl, can enumerate carbon number and be 1～5 alkyl, carbon number and be 6～15 aryl etc.

As the derivant of phosphoric acid, can enumerate phosphates such as di(2-ethylhexyl)phosphate n-butyl, di(2-ethylhexyl)phosphate phenylester etc.

As the derivant of phosphonic acids, can enumerate phosphonate esters such as phosphonic acids dimethyl esters, phosphonic acids di-n-butyl ester, phosphonic acids phenylester, phosphonic acids diphenyl, phosphonic acids dibenzyl ester etc.

As the derivant of phosphinic acids, can enumerate phosphinates such as phosphinic acids phenylester etc.

(E) composition can use a kind separately, also can share more than 2 kinds.

As (E) composition, preferred organic carboxyl acid, preferred especially salicylic acid.

(E) composition uses in the ratio that with respect to 100 mass parts (A) composition is 0.01～5.0 mass parts.

As required, in resist composition of the present invention, can also suitably add and have blended adjuvant, for example be used to improve the additivity resin of resist film performance, the surfactant that is used to improve coating, dissolution inhibitor, plastifier, stabilizing agent, colorant, anti hazing agent, dyestuff etc.[organic solvent (S)]

Resist composition of the present invention can be by making material dissolves in organic solvent (S) (below be sometimes referred to as (S) composition).

As (S) composition,, can from the solvent of known chemical amplification type anti-corrosion agent in the past, suitably select for use any more than a kind or 2 kinds so long as the solvent that can dissolve employed each composition and make homogeneous solution gets final product.

Lactone such as γ-butyrolactone for example; Ketones such as acetone, MEK, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, 2-heptanone; Polyalcohols such as ethylene glycol, diglycol, propylene glycol, dipropylene glycol; Ethylene glycol acetate, diglycol monotertiary acetic acid esters, propylene glycol monoacetate or dipropylene glycol monoacetate etc. have the compound of ester bond, above-mentioned polyalcohols or above-mentionedly have a derivant [wherein, preferred propylene glycol monomethyl ether (PGMEA), propylene glycol monomethyl ether (PGME)] that monoalky lether such as the monomethyl ether of the compound of ester bond, single ethylether, single propyl ether, single-butyl ether or single phenyl ether etc. have the polyalcohols such as compound of ehter bond; Cyclic ethers classes such as diox or, ester class such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid methyl esters, ethoxyl ethyl propionate; Fragrant same clan organic solvents such as methyl phenyl ethers anisole, ethyl benzyl ether, tolyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butyl phenylate, ethylbenzene, diethylbenzene, amylbenzene, isopropyl benzene,toluene,xylene, isopropyl toluene, mesitylene etc.

These organic solvents can use separately, and the mixed solvent that also can be used as more than 2 kinds uses.

Wherein, preferred propylene glycol monomethyl ether (PGMEA), propylene glycol monomethyl ether (PGME), EL.

In addition, the mixed solvent that mixes of also preferred PGMEA and polar solvent.Its proportioning (mass ratio) can wait suitably according to the intermiscibility of PGMEA and polar solvent and determine, preferably at 1:9～9:1, more preferably in the scope at 2:8～8:2.

More specifically, when mixing EL as polar solvent, the mass ratio of PGMEA:EL is preferably 1:9～9:1, more preferably 2:8～8:2.When mixing PGME as polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9～9:1, more preferably 2:8～8:2, more preferably 3:7～7:3.

As (S) composition, in addition, also be preferably selected among PGMEA and the EL at least a kind mixed solvent with γ-butyrolactone.At this moment, about blending ratio, the mass ratio of the former with the latter is preferably 70:30～95:5.

(S) consumption of composition does not have particular restriction, for concentration that can coating on substrate etc., suitably sets according to coated film thickness, and is common, with the solid component concentration of resist composition is to use in the scope of 2～20 quality %, preferred 5～15 quality %.

The resist composition of the invention described above is unknown in the past new compositions.

Contain compound of the present invention (b1-1) as acid agent, can improve photolithographic characteristics, the exploring degree when for example improve forming the resist pattern, mask reappearance (for example mask linearity etc.), exposure (EL) allowance, resist pattern form, depth of focus (DOF) etc.

EL holds nargin and is meant when the change exposure is exposed, can be to form the scope of the exposure of resist pattern with the size of deviation in specialized range of target size, promptly obtain the scope of exposure of the resist pattern of faithful to mask pattern, the value that EL holds nargin is big more, the variable quantity of the pattern dimension that produces with the change of exposure is more little, the appearance nargin of operation improves, thereby preferred.

Infer and produce the reasons are as follows of above-mentioned effect.That is, the negative ion portion of above-claimed cpd (b0-1) has at " Y ¹-SO ³-" skeleton on bonding R is arranged ^X-Q ³-O-Q ²-structure.Therefore, compare with the fluoro-alkyl azochlorosulfonate acid ion that uses as negative ion in the past, polarity is big, and is sterically hindered big, becomes huge structure.By inference, compare with the negative ion portion of existing acid agents such as nine fluorine fourth azochlorosulfonate acid ions, the intermolecular interaction that polarity causes greatly with and huge spatial structure can be from chemically and physically suppressing this diffusion of negative ion portion (acid) in resist film.Therefore, suppress the acid that the exposure area produces and spread, thereby poor (the dissolving contrast) to the dissolubility of alkaline developer of unexposed area and exposure area improved, take this exploring degree and the raising of resist pattern form to unexposed area.

Y ¹The substituent alkylidene that can have maybe can to have the alkyl chain of substituent fluoro alkylidene and for example carbon number be that 6～10 the hard-decomposed of perfluoroalkyl chain compared, its decomposability is good, can obtain to consider that the operability of the biosome property accumulated further improves this effect.

＜＜resist pattern formation method〉〉

The operation that the resist pattern formation method of the present invention's the 2nd mode comprises the operation of using resist composition of the present invention to form resist film on supporter, expose above-mentioned resist film and above-mentioned resist film is carried out alkali develop and form the operation of resist pattern.

This resist pattern formation method for example can be carried out as follows.

Promptly, at first on supporter with the resist composition of coating such as spin coater the invention described above, under 80～150 ℃ temperature conditions, prebake conditions (postapply bake:PAB) 40～120 seconds, preferred 60～90 seconds, for example utilize ArF exposure device etc., carry out the selectivity exposure by required mask pattern with the ArF excimer laser after, under 80～150 ℃ temperature conditions, implement 40～120 seconds, preferred 60～90 seconds PEB (heating of exposure back).Then, use alkaline developer, for example 0.1～10 quality % Tetramethylammonium hydroxide (TMAH) aqueous solution is carried out the alkali development treatment to it, preferably uses pure water to carry out water wash, drying.According to circumstances, also can after above-mentioned alkali development treatment, carry out baking processing (back baking).Like this, can obtain the resist pattern of faithful to mask pattern.

As supporter, do not have particular restriction, can use known in the past supporter, for example substrate for electronic device, be formed with this substrate etc. of the wiring pattern of regulation.More specifically, can enumerate metal substrates such as silicon wafer, copper, chromium, iron, aluminium or glass substrate etc.As the material of wiring pattern, can use for example copper, aluminium, nickel, gold etc.

As supporter, can also be the substrate that on aforesaid substrate, is provided with mineral-type and/or organic class film.As the film of mineral-type, can enumerate inorganic antireflection film (inorganic BARC).As the film of organic class, can enumerate organic anti-reflective film (organic BARC).

The wavelength that exposure is adopted is not subjected to particular restriction, can adopt ArF excimer laser, KrF excimer laser, F ₂Excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron ray), X ray, grenz ray isoradial carry out.Above-mentioned resist composition is to KrF excimer laser, ArF excimer laser, EB or EUV, particularly the ArF excimer laser is effective.

The exposure of resist film can be the common exposure of carrying out in inert gases such as air or nitrogen (dry type exposure), also can be immersion exposure.

If adopt immersion exposure, then as mentioned above, in when exposure, be to impregnated under the state of refractive index greater than the solvent (liquid soaks medium) of air refraction in the lens that make inert gases such as being full of air or nitrogen and the part between the resist film on the wafer to expose in the past.

More specifically, immersion exposure is to use refractive index to be full of the resist film that obtains as stated above greater than the solvent (liquid soaks medium) of air refraction and is positioned at exposure device between the lens of below, under this state, by required mask pattern expose (impregnated exposure).

Soak medium as liquid, preferred index is greater than air refraction and less than the solvent of the refractive index of the resist film that is exposed by this impregnated exposure.As the refractive index of described solvent,, there is not particular restriction as long as in above-mentioned scope.

Greater than air refraction and less than the solvent of the refractive index of resist film, can enumerate for example water, fluorine class inert fluid, silicone based solvent, varsol etc. as refractive index.

As the object lesson of fluorine class inert fluid, can enumerate with C ₃HCl ₂F ₅, C ₄F ₉OCH ₃, C ₄F ₉OC ₂H ₅, C ₅H ₃F ₇Be the liquid etc. of principal ingredient Deng fluoride compound, preferred boiling point is 70～180 ℃ a liquid, further preferred 80～160 ℃ liquid.If the boiling point that fluorine class inert fluid has above-mentioned scope then behind end exposure, can be removed liquid with simple method and soak the middle medium that uses, thereby become preferred.

As fluorine class inert fluid, the all-fluoroalkyl compound that the hydrogen atom of special preferred alkyl is all replaced by fluorine atom.As all-fluoroalkyl compound, specifically can enumerate perfluoroalkyl ether compound or perfluoroalkyl amines.

More specifically,, perfluor (2-butyl-tetrahydrofuran) (102 ℃ of boiling points) can be enumerated,, perfluor tri-butylamine (174 ℃ of boiling points) can be enumerated as above-mentioned perfluoroalkyl amines as above-mentioned perfluoroalkyl ether compound.

Embodiment

Below, illustrate in greater detail the present invention by embodiment, but the invention is not restricted to these embodiment.

In following each example, the compound that chemical formula (II) is represented is designated as " compound (II) ", and the compound of other chemical formulations is also explained with the same manner respectively.

[synthesis example 1]

94.1%), 2-benzyl oxyethanol 3.14g, toluene 43.4g compound (II) 4.34g (purity:, add p-toluenesulfonic acid monohydrate 0.47g, refluxed 20 hours down of packing at 105 ℃.With reacting liquid filtering, in the filter thing, add hexane 20g, stir.Refilter, will filter the thing drying, obtain compound (III) 1.41g (yield: 43.1%).

The compound (III) that obtains is carried out NMR to be analyzed.

¹H—NMR(DMSO—d6，400MHz)：δ(ppm)＝4.74—4.83(t，1H，OH)、4.18—4.22(t，2H，H ^a)、3.59—3.64(q，2H，H ^b)。

¹⁹F—NMR(DMSO—d6、376MHz)：δ(ppm)＝—106.6。

The above results confirms: show structure under compound (III) has.

[embodiment 1]

In compound (III) 1.00g and acetonitrile 3.00g, at ice-cooled 1-diamantane formyl chloride 0.82g and the triethylamine 0.397g of dripping down.After dripping end, at room temperature stirred 20 hours, filter.With the filtrate concentrate drying, be dissolved in methylene chloride 30g, wash 3 times.With the organic layer concentrate drying, obtain compound (IV) 0.82g (yield: 41%).

The compound (IV) that obtains is carried out NMR to be analyzed.

¹H-NMR (DMSO-d6,400MHz): δ (ppm)=8.81 (s, 1H, H ^c) 4.37-4.44 (t, 2H, H ^d), 4.17-4.26 (t, 2H, H ^e), 3.03-3.15 (q, 6H, H ^b), 1.61-1.98 (m, 15H, diamantane), 1.10-1.24 (t, 9H, H ^a).

¹⁹F—NMR(DMSO—d6，376MHz)：δ(ppm)＝—106.6。

The above results confirms: show structure under compound (IV) has.

[embodiment 2]

94.1%), 2-benzyl oxyethanol 3.14g, toluene 43.4g compound (II) 4.34g (purity: of packing into, add p-toluenesulfonic acid-hydrate 0.47g, after refluxing 20 hours under 105 ℃, cooling, add triethylamine hydrochloride 3.18g then, at room temperature stirred 3 hours.In reactant liquor, add methylene chloride 31.4g, filter.With the filtrate concentrate drying, obtain compound (VII) 1.31g (yield: 19.8%).

The compound (VII) that obtains is carried out NMR to be analyzed.

¹H—NMR(DMSO—d6、400MHz)：δ(ppm)＝9.20(s，1H，H ^c)、4.80(s，1H，H ^f)、4.19—4.21(t，2H，H ^d)、3.58—3.59(m，2H，H ^e)、3.04—3.10(q，6H，H ^b)、1.13—1.21(t，9H，H ^a)。

¹⁹F—NMR(DMSO—d6，376MHz)：δ(ppm)＝—106.6。

The above results confirms: show structure under compound (VII) has.

[embodiment 3]

In compound (VII) 1.33g and acetonitrile 3.00g, at ice-cooled 1-diamantane formyl chloride 0.82g and the triethylamine 0.397g of dripping down.After dripping end, at room temperature stirred 20 hours, filter.With the filtrate concentrate drying, be dissolved in methylene chloride 30g, wash 3 times.With the organic solvent layer concentrate drying, obtain compound (IV ') 0.86g (yield: 43.1%).

The compound that obtains (IV ') is carried out NMR to be analyzed.Obtain with [embodiment 1] in the identical spectrogram of compound (IV) that obtains.

[embodiment 4]

0.384g is dissolved in methylene chloride 3.84g and water 3.84g with compound (V), adds compound (IV) 0.40g.Stir after 1 hour, handle by separatory and reclaim organic layer, water 3.84g washing 3 times.With the organic layer concentrate drying that obtains, obtain compound (VI) 0.44g (yield 81.5%).

The compound (VI) that obtains is carried out NMR to be analyzed.

¹H-NMR (DMSO-d6,400MHz): δ (ppm)=7.57-7.87 (m, 14H, phenyl), 4.40-4.42 (t, 2H, H ^b), 4.15-4.22 (t, 2H, H ^a), 2.43 (s, 3H, H ^c), 1.60-1.93 (m, 15H, diamantane).

¹⁹F—NMR(DMSO—d6，376MHz)：δ(ppm)＝—106.6。

The above results confirms: show structure under compound (VI) has.

[embodiment 5]

(i)

To the methane-sulforic acid 60.75g difference small addition of oxygen phosphorus 8.53g, 2 that is controlled at below 20 ℃, 5-xylenol 8.81g and diphenyl sulfoxide 12.2g.When temperature was controlled at 15～20 ℃, slaking 30 minutes was warming up to 40 ℃ then, slaking 2 hours.Then, reactant liquor is splashed among the pure water 109.35g that is cooled to below 15 ℃.After dripping end, add methylene chloride 54.68g, after the stirring, reclaim dichloromethane layer.

In another container, pack into 20～25 ℃ hexane 386.86g, the drip dichloromethane layer.After dripping end,, filter, obtain target compound (i) 17.14g (yield 70.9%) 20～25 ℃ of following slakings 30 minutes.

The compound (i) that obtains is carried out NMR to be analyzed.

¹H-NMR (DMSO-d6,600MHz): δ (ppm)=7.61-7.72 (m, 10H, phenyl), 7.14 (s, 2H, H ^c), 3.12 (s, 3H, H ^b), 2.22 (s, 6H, H ^a).

The above results can confirm that compound (i) shows structure under having.

(ii)

4g is dissolved in methylene chloride 79.8g with compound (i).After confirming dissolving, add sal tartari 6.87g, add bromoacetic acid methyl adamantane 3.42g.The reaction down that refluxes was filtered after 24 hours, and washing is carried out partial crystallization with hexane.With the powder drying under reduced pressure that obtains, obtain (ii) 3.98g (yield 66%) of target compound.

The compound that obtains is (ii) carried out NMR to be analyzed.

¹H-NMR (CDCl ₃, 400MHz): δ (ppm)=7.83-7.86 (m, 4H, phenyl), 7.69-7.78 (m, 6H, phenyl), 7.51 (s, 2H, H ^d), 4.46 (s, 2H, H ^c), 2.39 (s, 6H, H ^a), 2.33 (s, 2H, diamantane), 2.17 (s, 2H, diamantane), 1.71-1.98 (m, 11H, diamantane), 1.68 (s, 3H, H ^b), 1.57-1.61 (m, 2H, diamantane).

The above results can confirm that compound shows structure under (ii) having.

With compound (ii) 4.77g be dissolved in methylene chloride 23.83g and water 23.83g, add compound (IV) 3.22g.Stir after 1 hour, handle by separatory and reclaim organic layer, water 3.84g washing 3 times.With the organic layer concentrate drying that obtains, obtain compound (X) 4.98g (yield 87%).

The compound (X) that obtains is carried out NMR to be analyzed.

¹H-NMR (DMSO-d6,400MHz): δ (ppm)=7.76-7.88 (m, 10H, phenyl), 7.62 (s, 2H, phenyl), 4.64 (s, 2H, H ^b), 4.43-4.44 (t, 2H, H ^e), 4.22-4.23 (t, 2H, H ^d), 1.51-2.36 (m, 38H, diamantane+H ^a+ H ^c).

¹⁹F—NMR(DMSO—d6、376MHz)：δ(ppm)＝—106.6。

The above results confirms: show structure under compound (X) has.

[embodiment 6]

Pack in reaction vessel triethylamine hydrochloride 1.99g and acetonitrile 25.00g are to wherein adding compound (VIII) 5.00g.At room temperature stirred 15 hours, and, filtrate under reduced pressure heated up in a steamer desolvate reacting liquid filtering.The material that obtains is dissolved in the methylene chloride (29g) again, with pure water (5.8g) washing 2 times.With the organic phase separatory, be added drop-wise in the hexane (435g), obtain target compound (IX) 1.2g (yield 20%).

The compound (IX) that obtains is carried out NMR to be analyzed.

¹H-NMR (DMSO-d6,400MHz): δ (ppm)=8.81 (brs, 1H, NH), 5.46 (t, 1H, the oxo norborene), 4.97 (s, 1H, oxo norborene), 4.71 (d, 1H, oxo norborene), 4.57 (d, 1H, oxo norborene), 3.09 (q, 6H, NCH ₂), 2.69-2.73 (m, 1H, oxo norborene), 2.06-2.16 (m, 2H, oxo norborene), 1.15 (t, 9H, CH ₃).

¹⁹F—NMR(DMSO—d6，376MHz)：δ(ppm)＝—107.1。

The above results confirms that compound (IX) has said structure.

[embodiment 7]

In compound (III) 2.42g and acetonitrile 7.26g, at ice-cooled 11 phosgene 2.19g and the triethylamine 1.01g of dripping down.

After dripping end, at room temperature stirred 20 hours, filter.With the filtrate concentrate drying, be dissolved in methylene chloride 20g, wash 3 times.With the organic layer concentrate drying, obtain compound (XI) 3.41g (yield: 80.4%).

The compound (XI) that obtains is carried out NMR to be analyzed.

¹H—NMR(DMSO—d6，400MHz)：δ(ppm)＝8.81(s，1H，H ^f)、4.39—4.41(t，2H，H ^d)、4.23—4.39(t，2H，H ^e)、3.06—3.10(q，6H，H ^h)、2.24—2.29(t，2H，H ^c)、1.09—1.51(m，25H，H ^b+H ^g)、0.83—0.89(t，3H，H ^a)。

¹⁹F—NMR(DMSO—d6，376MHz)：δ(ppm)＝—106.8。

The above results confirms that compound (XI) shows structure under having.

[embodiment 8]

1.68g is dissolved in methylene chloride 8.41g and water 8.41g with compound (XII '), adds compound (XI) 2.00g.Stir after 1 hour, handle by separatory and reclaim organic layer, water 3.84g washing 3 times.With the organic layer concentrate drying that obtains, obtain compound (XII) 2.20g (yield 81.5%).

The compound (XII) that obtains is carried out NMR to be analyzed.

¹H-NMR (DMSO-d6,400MHz): δ (ppm)=7.74-7.90 (m, 15H, phenyl), 4.39-4.42 (t, 2H, H ^e), 4.21-4.24 (t, 2H, H ^d), 2.25-2.89 (t, 3H, H ^c), 1.17-1.50 (m, 15H, H ^b), 0.79-0.88 (t, 3H, H ^a).

¹⁹F—NMR(DMSO—d6，376MHz)：δ(ppm)＝—106.8。

The above results confirms that compound (XII) shows structure under having.

[embodiment 9]

Triethylamine hydrochloride 2.50g, compound (XIII) 3.19g, acetonitrile 15.00g were at room temperature stirred 15 hours.With reacting liquid filtering, filtrate under reduced pressure heated up in a steamer desolvate, obtain compound (XIV) 4.01g (yield 95.6%).

The compound (XIV) that obtains is carried out NMR to be analyzed.

¹H—NMR(DMSO—d6，400MHz)：δ(ppm)＝9.20(s，1H，H ^c)、3.02—3.13(q，6H，H ^b)、1.11—1.24(t，9H，H ^a)。

¹⁹F—NMR(DMSO—d6，376MHz)：δ(ppm)＝—106.8。

The above results confirms that compound (XIV) shows structure under having.

[embodiment 10, comparative example 1]

Each composition shown in the table 1 is mixed, dissolves, the resist composition of preparation eurymeric.

[table 1]

The meaning of each abbreviation in the table 1 is as follows.In addition, the numerical value in [] in the table 1 is blending amount (mass parts).

In addition, in the table 1,9.14 weight portions (B)-1 are equimolar amounts with 8.0 mass parts of (B ')-1.

(A)-1: the Mw=7000 of following chemical formula (A)-1 (in the formula, 1/m/n=45/35/20 (mol ratio)) expression, the multipolymer of Mw/Mn=1.8.

(B)-1: the compound (above-claimed cpd (VI)) of following chemical formula (B)-1 expression.

(B ')-1: following chemical formula (B ')-1 compound of representing.

(D)-1: three n-pentyl amine.

(E)-1: salicylic acid.

(S)-1: γ-butyrolactone.

(S)-2:PGMEA/PGME=6/4 (mass ratio).

The resist composition that use obtains carries out following evaluation.

[formation of resist pattern]

On 8 inches silicon wafer, be coated with organic class antireflection film composition " ARC29A " (trade name, Bu Li science (Block リ ユ ワ-サ イ エ Application ス) corporate system) with spin coater, on heating plate, made its drying in 60 seconds, form organic class antireflection film of thickness 82nm at 205 ℃ of following sintering.Then, on this antireflection film, be coated with above-mentioned resist composition respectively, under 110 ℃, 60 seconds condition, carrying out prebake conditions (PAB) processing on the heating plate, drying, the resist film of formation thickness 150nm with spin coater.

Then, at above-mentioned resist film, (NIKON makes to utilize ArF exposure device NSR-S302; NA (opening number)=0.60,2/3 ring illumination), across mask pattern, elective irradiation ArF excimer laser (193nm).Then, under 110 ℃, the back heating (PEB) that exposes under 60 seconds the condition handles, then 23 ℃ down with Tetramethylammonium hydroxide (TMAH) the aqueous solution development of 2.38 quality % 30 seconds, used pure water drip washing then 30 seconds, the water dumping drying.

Consequently, line and the space pattern (hereinafter referred to as the L/S pattern) of live width 120nm, spacing 240nm in arbitrary example, all on above-mentioned resist film, have been formed.

Obtain the suitableeest exposure Eop (mJ/cm of the L/S pattern that forms above-mentioned live width 120nm, spacing 240nm ²).In addition, as the exploring degree, obtain the boundary exploring degree among the above-mentioned Eop.They the results are shown in table 2.

The section shape of the L/S pattern of live width 120nm, the spacing 240nm of the above-mentioned formation of use scanning electron microscope (trade name: S-9220, Hitachi's corporate system) observation.Consequently, the resist pattern form of embodiment 10 is compared with comparative example 1, and the perpendicularity of line sidewall improves, and the rectangularity raising such as is suppressed with the limit (the Japanese original text: the full front of a Chinese gown draws I) of dragging of substrate interface.

[LWR evaluation]

L/S pattern for the live width 120nm, the spacing 240nm that form with above-mentioned Eop, utilize and survey long SEM (scanning electron microscope, accelerating potential 800V, trade name: S-9220, Hitachi's corporate system), length direction along the line is measured the live width at 5 places, calculates the yardstick of 3 times of values (3s) of standard deviation (s) as expression LWR from its result.Its result is as shown in table 2.The value of this 3s is more little, and the roughness of expression live width is more little, obtains the more L/S pattern of homogeneous of width.

[EL holds nargin]

Except changing exposure respectively, adopt and above-mentioned same sequence of operation, forming with live width 120nm, spacing 240nm is the L/S pattern of target size.

At this moment, obtain with target size (live width 120nm) ± exposure when 5% (114nm, 126nm) forms the line of L/S pattern, obtain EL with following formula then and hold nargin (unit: %).Its result is as shown in table 2.

EL hold nargin (%)=(| in E1-E2|/Eop) * 100[formula, the exposure (mJ/cm when E1 represents to form the L/S pattern of live width 114nm ²), the exposure (mJ/cm when E2 represents to form the L/S pattern of live width 126nm ²).]

[table 2]

	Embodiment 10	Comparative example 1
			Eop(mJ/cm 2)	36.0	31.5
Exploring degree (nm)	110	110
			LWR(nm)	8.1	10.4
EL allowance (%)	7.37	5.70

[mask error factor (MEF) evaluation]

With above-mentioned Eop, use with the L/S pattern of live width 130nm, spacing 260nm as the mask pattern of target with the L/S pattern of live width 120nm, spacing 260nm mask as target, form the L/S pattern, obtain the value of MEF by following formula.

MEF＝|CD ₁₃₀-CD ₁₂₀|/|MD ₁₃₀-MD ₁₂₀|

In the following formula, CD ₁₃₀, CD ₁₂₀Be to use respectively with live width 130nm, 120nm is the actual linewidth (nm) of the L/S pattern that forms of the mask pattern of target.MD ₁₃₀, MD ₁₂₀Be respectively the target live width (nm) of this mask pattern, MD ₁₃₀=130, MD ₁₂₀=120.The value of this MEF is represented the faithful to more mask of resist pattern that forms more near 1.

Consequently, embodiment 10 is 2.0, and comparative example 1 is 2.0, and is equal.

[mask linear evaluation]

With above-mentioned Eop, with the L/S of mask pattern than (ratio that live width is wide with the space) stuck-at-: 1, making mask size (live width) is that unit changes with 10nm in the scope of 110～150nm, forms the L/S pattern respectively, measures the size (live width) of the L/S pattern that forms.Its result is as shown in table 3.

As shown in table 3, in embodiment 10, under the Eop of 120nm, even size departs from 120nm, compare with comparative example 1, also can form the L/S pattern of the size of faithful to mask size, prove that the mask reappearance of the resist composition of embodiment 10 is better than the resist composition of comparative example 1.

[table 3]

	Embodiment 10	Comparative example 1
			110nm	93.5	89.5
120nm	121.9	119.9
			130nm	118.8	139.1
140nm	147.4	153.1
			150nm	163.2	167.0

Shown in above-mentioned result, the photolithographic characteristics excellence of the resist composition of embodiment 10.

[embodiment 11～13, comparative example 2]

Each composition shown in the table 4 is mixed, dissolves, the resist composition of preparation eurymeric.

[table 4]

(A)-1 in the table 4, (D)-1, (S)-1, (S)-2 are identical with (A)-1, (D)-1, (S)-1, (S-2) in the table 1, the meaning that other abbreviation is expressed as follows respectively.In addition, the numerical value in [] is blending amount (mass parts).

In addition, the blending amount (total) of (B) composition of embodiment 11～13 and comparative example 2 is respectively equimolar amounts.

(B)-2: the compound (above-claimed cpd (X)) that shows chemical formula (B)-2 expression down.

(B ')-2: following chemical formula (B ')-2 compounds of representing.

The resist composition that use obtains carries out following evaluation.

[formation of resist pattern]

On 8 inches silicon wafer, be coated with organic class antireflection film composition " ARC29A " (trade name, Bu Li scientific company system) with spin coater, on heating plate, made its drying in 60 seconds in 205 ℃ of following sintering, form organic class antireflection film of thickness 89nm.Then, on this antireflection film, be coated with above-mentioned resist composition respectively, under 110 ℃, 60 seconds condition, carrying out prebake conditions (PAB) processing on the heating plate, drying, the resist film of formation thickness 150nm with spin coater.

Then, use spin coater on above-mentioned resist film, to be coated with diaphragm and form, heated 60 seconds down, form the outer diaphragm of thickness 90nm at 90 ℃ with coating fluid " TILC-035 " (trade name, Tokyo Applied Chemistry Industrial Co., Ltd.'s system).

Then, (NIKON makes to utilize ArF liquid immersion exposure apparatus NSR-S609B; NA (opening number)=1.07, σ 0.97), across the mask of sectional hole patterns, to having formed the above-mentioned resist film elective irradiation ArF excimer laser (193nm) of outer diaphragm.

Then, under 105 ℃, the back heating (PEB) that exposes under 60 seconds the condition handles, then 23 ℃ down with Tetramethylammonium hydroxide (TMAH) the aqueous solution development of 2.38 quality % 30 seconds, used pure water drip washing then 30 seconds, the water dumping drying.

Consequently, all having formed bore dia in arbitrary example on above-mentioned resist film is that the contact hole pattern (hereinafter referred to as the DenceCH pattern) that forms is arranged with equidistantly (spacing 180nm) in the hole of 90nm.

Then, to form the suitableeest exposure Eop (mJ/cm of above-mentioned Dence CH pattern ²) to form bore dia be that the contact hole pattern (hereinafter referred to as Iso CH pattern) that forms is arranged with equidistantly (spacing 570nm) in the hole of 90nm.

Photolithographic characteristics in the Iso CH pattern of above-mentioned diameter 90nm is estimated.Its result is as shown in table 5.

[depth of focus (DOF) evaluation]

With above-mentioned Eop, focus is suitably staggered up and down, similarly form the resist pattern with above-mentioned [formation of resist pattern], obtain at target size ± 5% and (promptly can form depth of focus (DOF, the unit: nm) of above-mentioned Iso CH pattern in the scope of 85.5～94.5nm) size changing rate.Its result is as shown in table 5.

[MEF evaluation]

With above-mentioned Eop, adopt the mask pattern that the target size of bore dia is decided to be 61nm, 63nm, 65nm, 67nm, 69nm respectively, form the Iso CH pattern of spacing 57nm.At this moment, obtain with target size (nm) and be transverse axis, be the slope that the longitudinal axis is drawn the straight line that obtains, as MEF with the aperture (nm) of the sectional hole patterns that on resist film, forms with each mask pattern.The value of MEF (slope of straight line) is good more near 1 expression mask reappearance more.The result who obtains is as shown in table 5.

[EL holds the nargin evaluation]

Obtain with target size (bore dia 90nm) ± exposure when 5% (85.5nm, 94.5nm) forms the Iso CH pattern of diameter 90nm, obtain EL by following formula then and hold nargin (unit: %).Its result is as shown in table 5.

EL hold nargin (%)=(| in E1-E2|/Eop) * 100[formula, the exposure (mJ/cm when E1 represents to form the CH pattern of bore dia 85.5nm ²), the exposure (mJ/cm when E2 represents to form the CH pattern of bore dia 94.5nm ²).]

[table 5]

	Embodiment 11	Embodiment 12	Embodiment 13	Comparative example 2
					Eop(mJ/cm 2)	37.1	39.4	42.1	41.7
DOF(nm)	0.15	0.14	0.15	0.14
					MEF	3.03	3.32	2.98	3.52
EL holds nargin (%)	9.5	9.46	9.27	8.58

As shown in table 5, compare with the resist composition of comparative example 2, it is good that MEF, the EL of the resist composition of embodiment 11～13 holds nargin, better on DOF.

The above results confirms: the compound (b0-1) of the present invention's the 6th mode can use as the intermediate of acid agent with compound, and the compound (b1-1) of the present invention's the 3rd mode is can be as the compound of acid agent use.

[embodiment 14～20]

Each composition shown in the table 6 is mixed, dissolves, the resist composition of preparation eurymeric.

[table 6]

(B)-1 in the table 6, (D)-1, (S)-2 are identical with (B)-1, (D)-1, (S)-2 in the table 1, and other abbreviations are expressed as follows the meaning respectively.Numerical value in [] is blending amount (mass parts).

In addition, the blending amount (total amount) of (B) composition of embodiment 14～20 is respectively equimolar amounts.

(A)-2: the Mw=10000 of following chemical formula (A)-2 (in the formula, 1/m/n=30/50/20 (mol ratio)) expression, the multipolymer of Mw/Mn=2.0.

(A)-3: the Mw=10000 of following chemical formula (A)-3 (in the formula, 1/m/n=40/40/20 (mol ratio)) expression, the multipolymer of Mw/Mn=2.0.

The resist composition that use obtains carries out following evaluation.

[formation of resist pattern]

On 12 inches silicon wafer, be coated with organic class antireflection film composition " ARC29A " (trade name, Bu Li scientific company system) with spin coater, on heating plate, made its drying in 60 seconds in 205 ℃ of following sintering, form organic class antireflection film of thickness 70nm.Then, on this antireflection film, be coated with above-mentioned resist composition respectively, under 110 ℃, 60 seconds condition, carrying out prebake conditions (PAB) processing on the heating plate, drying, the resist film of formation thickness 170nm with spin coater.

Then, (NIKON makes to utilize ArF exposure device NSR-S308F; NA (opening number)=0.85, σ=0.95), across mask pattern, to above-mentioned resist film elective irradiation ArF excimer laser (193nm).Then, the back heating (PEB) that exposes under 90 ℃, 60 seconds condition is handled, and develops 30 seconds with Tetramethylammonium hydroxide (TMAH) aqueous solution of 2.38 quality % down at 23 ℃ then, uses pure water drip washing then 30 seconds, the water dumping drying.

Consequently, all having formed bore dia in arbitrary example on above-mentioned resist film is that the Dense CH pattern that forms is arranged with equidistantly (spacing 210nm) in the hole of 110nm.

Then, to form the suitableeest exposure Eop (mJ/cm of above-mentioned Dence CH pattern ²) to form bore dia be that the Iso CH pattern that forms is arranged with equidistantly (spacing 780nm) in the hole of 110nm.

Photolithographic characteristics in each CH pattern of the Dense/Iso of above-mentioned diameter 110nm is estimated.Its result is as shown in table 7.

[depth of focus (DOF) evaluation]

With above-mentioned Eop, focus is suitably staggered up and down, similarly form the resist pattern with above-mentioned [formation of resist pattern], obtain at target size ± 5% and (promptly can form depth of focus (DOF, the unit: nm) of above-mentioned each CH pattern in the scope of 104.5～115.5nm) size changing rate.

[MEF evaluation]

Adopting the target size of bore dia respectively is the mask pattern of unit change with 1nm in the scope of 110nm ± 5nm, with above-mentioned Eop, forms each CH pattern (spacing is Dense:210nm, Iso:780nm).At this moment, obtain with mask size (nm) and be transverse axis, be the slope that the longitudinal axis is drawn the straight line that obtains, as MEF with the aperture (nm) of the sectional hole patterns that on resist film, forms with each mask pattern.The value of MEF (slope of straight line) is good more near 1 expression mask reappearance more.

[CDU (homogeneity of bore dia) evaluation]

To each the CH pattern that obtains, measure the diameter (Dence:54, Iso:26) in hole respectively, obtain 3 times of values (3 σ) of the standard deviation (σ) of calculating by this result.The value of 3 σ that so try to achieve is more little, and the CDU that is formed at each hole on this resist film is high more, means that promptly the deviation of the diameter that is present in the hole in the certain limit is more little.

[circularity evaluation]

Use to survey long SEM (Hitachi's corporate system, ProductName: S-9220) observe hole shape in each CH pattern, estimate by following benchmark.

A: circularity very high (circumferential part of the sectional hole patterns of observing from the sky does not have concavo-convex, and shape is very good).

B: circularity height (circumferential part of the sectional hole patterns of observing from the sky is slightly concavo-convex, and integral body is the high shape of circularity)

[table 7]

As shown in table 7, the resist composition of embodiment 14～20 has excellent photolithographic characteristics (DOF, MEF, CDU, circularity) at Dense/Iso CH pattern two Fang Jun.About the hole shape of CDU and circularity etc., the resist composition of embodiment 15～19 is good especially.

The above results also confirms: the compound (b0-1) of the present invention's the 6th mode can use as the intermediate of acid agent with compound, and the compound (b1-1) of the present invention's the 3rd mode is can be as the compound of acid agent use.

[embodiment 21]

In compound (III) 8.00g and methylene chloride 150.00g, under ice-cooled, drip 1-diamantane acetyl chloride 7.02g and triethylamine 3.18g.After dripping end, at room temperature stirred 20 hours, filter.Filtrate with pure water 54.6g washing 3 times, with the organic layer concentrate drying, is obtained compound (XV) 14.90g (yield: 88.0%).

The compound (XV) that obtains is carried out NMR to be analyzed.

¹H-NMR (DMSO, 400MHz): δ (ppm)=8.81 (brs, 1H, H ^c), 4.40 (t, 2H, H ^d), 4.20 (t, 2H, H ^e), 3.08 (q, 6H, H ^b), 2.05 (s, 2H, H ^f), 1.53-1.95 (m, 15H, diamantane), 1.17 (t, 9H, H ^a).

¹⁹F—NMR(DMSO，376MHz)：δ(ppm)＝—106.90。

The above results confirms that compound (XV) shows structure under having.

[embodiment 22]

Compound (V) 7.04g is dissolved among methylene chloride 70.4g and the water 70.4g, adds compound (XV) 9.27g.Stir after 1 hour, handle by separatory and reclaim organic layer, with 1%HCl aq70.4g washing 1 time, with pure water 70.4g washing 4 times.With the organic layer concentrate drying that obtains, obtain compound (XVI) 11.59g (yield 90.6%).

The compound (XVI) that obtains is carried out NMR to be analyzed.

¹H-NMR (DMSO, 400MHz): δ (ppm)=7.50-7.87 (m, 14H, phenyl), 4.42 (s, 3H, H ^c), 4.23 (s, 2H, H ^b), 2.43 (s, 3H, H ^a), 2.01 (s, 2H, H ^f), 1.94 (s, 2H, diamantane), 1.52-1.61 (m, 13H, diamantane)

¹⁹F—NMR(DMSO，376MHz)：δ(ppm)＝—106.49

The above results confirms that compound (XVI) shows structure under having.

[embodiment 23]

Compound (XX) 21.6g, water 53.0g and methylene chloride 69.7g are at room temperature stirred, to wherein adding compound (IV) 12.9g.Stir after 1 hour, reclaim organic layer, with 1%HCl aq34.9g washing 1 time, with pure water 69.7g washing 2 times by separatory.With the organic layer concentrate drying that obtains, obtain compound (X XI) 9.94g (yield 61.4%).

The compound (X XI) that obtains is carried out NMR to be analyzed.

¹H-NMR (DMSO, 400MHz): δ (ppm)=8.00 (d, 2H, H ^f), 7.75 (t, 1H, H ⁱ), 7.58 (t, 2H, H ^g), 5.30 (s, 2H, H ^e), 4.37-4.44 (t, 2H, H ^a), 4.17-4.26 (t, 2H, H ^b), 3.54 (m, 4H, H ^d), 2.49-2.18 (m, 4H, H ^c), 1.93-1.60 (m, 15H, diamantane)

¹⁹F—NMR(DMSO，376MHz)：δ(ppm)＝—106.2

The above results confirms that compound (XXI) shows structure under having.

[embodiment 24～26]

Each composition shown in the table 8 is mixed, dissolves, prepare the resist composition of eurymeric.

[table 8]

(B)-1 in the table 8, (S)-2 are identical with (B)-1, (S)-2 in the table 1, and other abbreviations are represented the following meaning respectively.Numerical value in [] is blending amount (mass parts).

In addition, the blending amount (total amount) of (B) composition of embodiment 24～26 is respectively equimolar amounts.

(A)-4: the Mw=10000 of following chemical formula (A)-4 (in the formula, 1/m/n=30/50/20 (mol ratio)) expression, the multipolymer of Mw/Mn=2.0.

(A)-5: the Mw=10000 of following chemical formula (A)-5 (in the formula, 1/m/n=30/50/20 (mol ratio)) expression, the multipolymer of Mw/Mn=2.0.

(A)-6: macromolecular compound (A)-6 (synthetic) by aftermentioned reference example 3.

(B)-3: the compound (above-claimed cpd (XVI)) of following chemical formula (B)-3 expression.

(B)-4: the compound (above-claimed cpd (XXI)) of following chemical formula (B)-4 expression.

(D)-2: the stearyl diethanolamine.

[synthesis example of macromolecular compound (A)-6]

[reference example 1]

Sodium hydride (NaH) 4.8g that in the there-necked flask of 1L, packs into, in ice bath, keep 0 ℃ in, add 300g tetrahydrofuran (THF), add 124g compound (1) while stir then, stirred 10 minutes.Then, add 30g compound (2), reacted 12 hours while stir.After reaction finishes,, remove the THF in the filtrate of recovery by concentrating under reduced pressure with the reactant liquor suction filtration.Then, in concentrate, add entry and ethyl acetate extracts, with the ethyl acetate solution concentrating under reduced pressure that obtains, with column chromatography (SiO ₂, heptane: ethyl acetate=8:2) make with extra care, with the fraction concentrating under reduced pressure, and then drying under reduced pressure, obtain compound (3) 12g.

The compound that mensuration obtains (3) ¹H-NMR.Its result is as follows.

1H-NMR (solvent: CDC1 ₃, 400MHz): δ (ppm)=4.09 (s, 2H (H ^a)), 3.75 (t, 2H (H ^b)), 3.68 (t, 2H (H ^c)), 3.03 (brs, 2H (H ^d)), 1.51-2.35 (m, 17H (H ^e))

The above results confirms that compound (3) shows structure under having.

[reference example 2]

Pack in the there-necked flask of 300mL 5g compound (3), 3.04g triethylamine (Et3N) and 10g THF stirred 10 minutes.Then, add 2.09g compound (4) and 10g THF, at room temperature reacted 12 hours.After reaction finishes,, remove the THF in the filtrate of recovery by concentrating under reduced pressure with the reactant liquor suction filtration.Then, in concentrate, add entry and ethyl acetate extracts.To the ethyl acetate solution column chromatography (SiO that obtains ₂, heptane: ethyl acetate=8:2) make with extra care, with the fraction concentrating under reduced pressure, and then drying under reduced pressure, obtain compound (5) 4.9g.

The compound that mensuration obtains (5) ¹H-NMR.Its result is as follows.

¹H-NMR (solvent: CDCl ₃, 400MHz): δ (ppm)=6.15 (s, 1H (H ^a)), 5.58 (s, 1H (H ^b)), 4.35 (t, 2H (H ^c)), 4.08 (s, 2H (H ^d)), 3.80 (t, 2H (H ^e)), 1.51-2.35 (m, 2OH (H ^f))

The above results confirms that compound (5) shows structure under having.

[reference example 3 (synthesizing of macromolecular compound (A)-6)]

Compound (6), the compound (5) of 7.00g (20.83mmo1), 2.83g (11.99mmo1) compound (7) of 6.30g (30.30mmo1) are dissolved in the 64.52g MEK.In this solution, add and pure medicine system V-601 (polymerization initiator) 11.68mmol of light and make its dissolving.Under nitrogen atmosphere gas, spent be added drop-wise among the MEK 26.88g that is heated to 75 ℃ in 6 hours it.After drip finishing,, then, reactant liquor is cooled to room temperature with reactant liquor heated and stirred 1 hour.

It is 30 quality % that this polymer fluid is concentrated into solid constituent, at room temperature is added drop-wise in the normal heptane of 320mL multipolymer is separated out.Then, prepare the THF solution 54g of this multipolymer, be added drop-wise among the normal heptane 320mL multipolymer is separated out.

This multipolymer is disperseed and carry out the washing of multipolymer with the mixed solution of methanol=60/40 (volume ratio), use the mixed solution of methanol=70/30 (volume ratio) to disperse then and carry out the washing of multipolymer, reclaim by filtering.

The multipolymer that so obtains was descended dry 3 days at 40 ℃, obtain 12.0g white powder (yield 74%).

The copolymer sheet that obtains is shown macromolecular compound (A)-6, and its structural formula is as follows.Measure this macromolecular compound (A)-6 ¹³C-NMR (600MHz), the result: it is 1/m/n=52.6/27.5/19.9 that polymkeric substance is formed (ratio of each structural unit in the following structural formula (mol ratio)).The matter average molecular weight (Mw) of measuring the polystyrene standard conversion of trying to achieve by GPC is 5300, and dispersion degree (Mw/Mn) is 1.97.This result proves: the macromolecular compound that obtains (A)-the 6th, the multipolymer of compound (6) and compound (5) and compound (7).

The resist composition that use obtains forms the resist pattern by following sequence of operation, estimates photolithographic characteristics.

[formation of resist pattern]

On 12 inches silicon wafer, be coated with organic class antireflection film composition " ARC29 " (trade name, Bu Li scientific company system) with spin coater, on heating plate, made its drying in 60 seconds in 205 ℃ of following sintering, form organic class antireflection film of thickness 89nm.Then, on this antireflection film, be coated with the eurymeric resist composition of the above-mentioned embodiment that obtains 24～26 respectively with spin coater, handle under 90 ℃, 60 seconds condition, carrying out prebake conditions (PAB) on the heating plate, drying, the resist film of formation thickness 120nm.

Then, use spin coater on above-mentioned resist film, to be coated with diaphragm and form, heated 60 seconds down, form the outer diaphragm of thickness 28nm at 90 ℃ with coating fluid " TSRC-002 " (trade name, Tokyo Applied Chemistry Industrial Co., Ltd.'s system).

Then, at the above-mentioned resist film that has formed outer diaphragm, utilize liquid to soak (NIKON's manufacturing with ArF exposure device NSR-S609B; NA (opening number)=1.07,2/3 ring illumination, 1/4 times of minification, liquid soaks medium: water), across mask pattern (6% shadow tone) elective irradiation ArF excimer laser (193nm).

Then; after using diaphragm to remove liquid " TS-Rememover-S " (trade name, Tokyo Applied Chemistry Industrial Co., Ltd.'s system) to remove outer diaphragm; carrying out PEB under the conditions shown in Table 8 handles; TMAH aqueous solution NMD-W (trade name, Tokyo Applied Chemistry Industrial Co., Ltd.'s system) alkali with 2.38 quality % developed 30 seconds under 23 ℃ then; used pure water drip washing then 25 seconds, the water dumping drying.

Consequently, all having formed diameter in arbitrary example is that 70nm, spacing are the CH pattern of 131nm.The suitableeest exposure Eop (mJ/cm of this moment ²) be that sensitivity is as shown in table 9.

[circularity evaluation]

Use to survey long SEM (Hitachi's corporate system, ProductName: S-9220) observe hole shape in each CH pattern, estimate with the benchmark identical with embodiment 14～20.The result is as shown in table 9.

[table 9]

	Embodiment 24	Embodiment 25	Embodiment 26
				Eop(mJ/cm 2)	31	28	20
Circularity	A	B	B

The result of table 9 confirms: the compound (b0-1) of the present invention's the 6th mode can use as the intermediate of acid agent with compound, and the compound (b1-1) of the present invention's the 3rd mode is can be as the compound of acid agent.

Claims (22)

1. resist composition, it is to contain under the effect of acid base material component (A) that the dissolubility to alkaline developer changes and by exposing to the resist composition of acidic acid agent composition (B), it is characterized in that,

Described acid agent composition (B) contains the acid agent (B1) that the compound by following general formula (b1-1) expression forms,

In the formula, R ^XBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ²And Q ³Be the linking group of singly-bound or divalent independently respectively; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; Z ⁺Be organic cation, but be not the ion of following general formula (w-1) expression,

In the formula, R ³～R ⁶Maybe can have substituent alkyl for hydrogen atom independently respectively, R ³～R ⁶In at least 1 be described alkyl, R ³～R ⁶In at least 2 can be bonded to ring respectively.

2. resist composition according to claim 1, wherein, described acid agent (B1) is formed by the compound of following general formula (b1-1-1) expression,

In the formula, R ^X, Y ¹And Z ⁺Respectively with described general formula (b1-1) in R ^X, Y ¹And Z ⁺Identical; R ¹Be alkylidene.

3. resist composition according to claim 1, wherein, described base material component (A) is the base material component that under the effect of acid the dissolubility of alkaline developer is increased.

4. resist composition according to claim 3, wherein, described base material component (A) contains under the effect of acid the resinous principle (A1) that the dissolubility to alkaline developer increases, and this resinous principle (A1) has by containing that acrylate that the acid dissociation dissolving suppresses base is derived and the structural unit (a1) that comes.

5. resist composition according to claim 4, wherein, described resinous principle (A1) also has by the acrylate of the cyclic group that contains lactone derives and next structural unit (a2).

6. resist composition according to claim 4, wherein, described resinous principle (A1) also has by the acrylate of the aliphatic alkyl that contains polar functionalities derives and next structural unit (a3).

7. resist composition according to claim 1, it also contains organic compounds containing nitrogen (D).

8. resist pattern formation method, it comprises: use each described resist composition in the claim 1～7 to form the operation of resist film on supporter; Operation with described resist film exposure; And described resist film is carried out alkali develop and form the operation of resist pattern.

9. compound, it is by following general formula (b1-1) expression,

In the formula, R ^XBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ²And Q ³Be the linking group of singly-bound or divalent independently respectively; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; Z ⁺Be organic cation, but be not the ion of following general formula (w-1) expression,

In the formula, R ³～R ⁶Maybe can have substituent alkyl for hydrogen atom independently respectively, R ³～R ⁶In at least 1 be described alkyl, R ³～R ⁶In at least 2 can be bonded to ring respectively.

10. compound according to claim 9, it is by following general formula (b1-1-1) expression,

In the formula, R ^X, Y ¹And Z ⁺Respectively with described general formula (b1-1) in R ^X, Y ¹And Z ⁺Identical; R ¹Be alkylidene.

11. the manufacture method of a compound, it comprises: the operation that obtains the compound (b1-1) of following general formula (b1-1) expression by the compound (b0-1) and compound (b0-02) reaction of following general formula (b0-02) expression that makes following general formula (b0-1) expression

Z ⁺ A ^-…(b0-02)

In the formula, R ^XBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ²And Q ³Be the linking group of singly-bound or divalent independently respectively; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; W ⁺It is the ion of alkali metal ion or following general formula (w-1) expression; Z ⁺Be organic cation, but be not the ion of following general formula (w-1) expression; A ^-Be non-nucleophilicity negative ion,

In the formula, R ³～R ⁶Maybe can have substituent alkyl for hydrogen atom independently respectively, R ³～R ⁶In at least 1 be described alkyl, R ³～R ⁶In at least 2 can be bonded to ring respectively.

12. manufacture method according to claim 11, wherein, described compound (b0-1) is the compound (b0-01) of following general formula (b0-01) expression, and described compound (b1-1) is the compound (b1-1-1) of following general formula (b1-1-1) expression,

In the formula, R ^X, Y ¹And W ⁺With the R in the described general formula (b0-1) ^X, Y ¹And W ⁺Identical; Z in Z+ and the described general formula (b1-1) ⁺Identical; R ¹Be alkylidene.

13. an acid agent, it is formed by the described compound of claim 9.

14. acid agent according to claim 13, its compound by following general formula (b1-1-1) expression forms,

In the formula, R ^X, Y ¹And Z ⁺Respectively with described general formula (b1-1) in R ^X, Y ¹And Z ⁺Identical; R ¹Be alkylidene.

15. a compound, it is by following general formula (b0-1) expression,

In the formula, R ^XBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ²And Q ³Be the linking group of singly-bound or divalent independently respectively; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; R ³～R ⁶Maybe can have substituent alkyl for hydrogen atom independently respectively, R ³～R ⁶In at least 1 be described alkyl, R ³～R ⁶In at least 2 can be bonded to ring respectively.

16. compound according to claim 15, it is by following general formula (b0-1-1) expression,

In the formula, R ^X, Q ³, Y ¹, R ³～R ⁶Respectively with described general formula (b0-1) in R ^X, Q ³, Y ¹, R ³～R ⁶Identical, n is 0 or 1.

17. compound according to claim 16, its by following general formula (b0-1-11) or (b0-1-12) expression,

In the formula, n, Y ¹, R ³～R ⁶Respectively with described general formula (b0-1-1) in n, Y ¹, R ³～R ⁶Identical, R ¹Be alkylidene, R ^bAnd R ^cRespectively independently for can have substituent alkyl, but substituting group is not a nitrogen-atoms, Q ⁴Be singly-bound or alkylidene.

18. the manufacture method of a compound, it comprises: react the operation of the compound (b0-1) that obtains following general formula (b0-1) expression by the compound (1-11) that makes following general formula (1-11) expression, compound (1-12) and the amine or the ammonium salt of following general formula (1-12) expression

R ^X—Q ³—X ²¹…(1-12)

In the formula, R ^XBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ²And Q ³Be the linking group of singly-bound or divalent independently respectively; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; R ³～R ⁶Maybe can have substituent alkyl for hydrogen atom independently respectively, R ³～R ⁶In at least 1 be described alkyl, R ³～R ⁶In at least 2 can be bonded to ring respectively; X ²¹Be halogen atom; M ⁺Be alkali metal ion.

19. the manufacture method of a compound, it comprises: react the operation of the compound (b0-1) that obtains following general formula (b0-1) expression by the compound (1-21) that makes following general formula (1-21) expression, compound (1-12) and the amine or the ammonium salt of following general formula (1-12) expression

R ^X—Q ³—X ²¹…(1-12)

In the formula, R ^XBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ²And Q ³Be the linking group of singly-bound or divalent independently respectively; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; R ³～R ⁶Maybe can have substituent alkyl for hydrogen atom independently respectively, R ³～R ⁶In at least 1 be described alkyl, R ³～R ⁶In at least 2 can be bonded to ring respectively; R ^{3 '}～R ^{6 '}Maybe can have substituent alkyl for hydrogen atom independently respectively, R ^{3 '}～R ^{6 '}In at least 1 be described alkyl, R ^{3 '}～R ^{6 '}In at least 2 can be bonded to ring respectively; X ²¹Be halogen atom.

20. a compound, it is by following general formula (1-21) expression,

In the formula, Q ²It is the linking group of singly-bound or divalent; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; R ^{3 '}～R ^{6 '}Maybe can have substituent alkyl for hydrogen atom independently respectively, R ^{3 '}～R ^{6 '}In at least 1 be described alkyl, R ^{3 '}～R ^{6 '}In at least 2 can be bonded to ring respectively.

21. the manufacture method of a compound, it comprises: react the operation of the compound (1-21) that obtains following general formula (1-21) expression by compound (1-11) and the ammonium salt that makes following general formula (1-11) expression,

In the formula, Q ²It is the linking group of singly-bound or divalent; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; R ^{3 '}～R ^{6 '}Maybe can have substituent alkyl for hydrogen atom independently respectively, R ^{3 '}～R ^{6 '}In at least 1 be described alkyl, R ^{3 '}～R ^{6 '}In at least 2 can be bonded to ring respectively; M ⁺Be alkali metal ion.

22. the manufacture method of a compound, it comprises: react the operation of the compound (1-14) that obtains following general formula (1-14) expression by compound (1-13) and the ammonium salt that makes following general formula (1-13) expression,

In the formula, R ^cBe to have substituent alkyl, but substituting group is not a nitrogen-atoms; Q ⁴It is the linking group of singly-bound or divalent; N is 0 or 1; Y ¹Be that carbon number is 1～4 alkylidene or fluoro alkylidene; R ^{3 '}～R ^{6 '}Maybe can have substituent alkyl for hydrogen atom independently respectively, R ^{3 '}～R ^{6 '}In at least 1 be described alkyl, R ^{3 '}～R ^{6 '}In at least 2 can be bonded to ring respectively; M ⁺Be alkali metal ion.