CN101528653B

CN101528653B - Radiation-sensitive composition

Info

Publication number: CN101528653B
Application number: CN200780040498.2A
Authority: CN
Inventors: 越后雅敏; 小黑大
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2006-11-02
Filing date: 2007-11-01
Publication date: 2013-09-11
Anticipated expiration: 2027-11-01
Also published as: CN101528653A; JP2008116677A; JP5109338B2; CN108008600B; CN108008600A

Abstract

The present invention discloses a radiation-sensitive composition containing a resist compound having a high sensitivity, a high resolution, a high etching resistance, and a low outgas which forms a resist pattern with a good shape. Further described is a method of forming a resist pattern using the radiation-sensitive composition. Still further described are a novel composition for forming a photoresist under coat film which is excellent in optical properties and etching resistance and contains substantially no sublimable substance and an under coat film formed by the composition. Still further described are a radiation-sensitive composition containing a solvent and a cyclic compound having a specific structure, for example, a cyclic compound (A) having a molecular weight of 700 to 5000 which is synthesized by the condensation reaction of a compound having 2 to 59 carbon atoms and 1 to 4 formyl groups (aldehyde compound (A1)) with a compound having 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl groups (phenol compound (A2)), and a cyclic compound for use in the radiation-sensitive composition.

Description

Radiation-ray sensitive composition

Technical field

The present invention relates to as sour proliferous type on-macromolecular class anticorrosive additive material and the ring compound of representing with the specific chemical structure formula, contain the radiation-ray sensitive composition of this ring compound and be used to form the composition of lower membrane and use the formation method of resist pattern of said composition and the formation method of lower membrane.

Background technology

Existing general anticorrosive additive material is for forming the high score subclass material of amorphous film.For example, make the resist film by the solution that is coated with polymer anticorrosive additive materials such as polymethylmethacrylate, the polycarboxylated styrene with acid dissociation reactive group or poly-alkylmethacrylate at substrate, to this film irradiation ultraviolet radiation, far ultraviolet rays yue, electron rays, extreme ultraviolet (EUV), X ray etc., form the linear figure of the degree of 45-100nm again.

But, high score subclass resist since molecular weight greatly to 10,000-100,000 degree, and molecular weight distribution is also wide, therefore in the photolithography of using high score subclass resist, produces coarsely on the Micropicture surface, is difficult to control dimension of picture, yield rate reduces.Therefore, in the photolithography of using high score subclass resist in the past, limited in miniaturization.In order to make finer figure, various low-molecular-weight anticorrosive additive materials are disclosed.

For example, proposed to use with the eurymeric resist composition of low-molecular-weight multinuclear polyphenolic substance as main component, this multinuclear polyphenolic substance has at least one phenolic hydroxyl group introduces the structure (with reference to patent documentation 1) that acid dissociation functional group is arranged, or use with the negative resist composition (with reference to patent documentation 2) of low-molecular-weight multinuclear polyphenolic substance as the alkali-developable of main component, thermotolerance becomes insufficient, the shortcoming of the shape variation of the resist pattern that obtains but they exist.

Candidate as low-molecular-weight anticorrosive additive material, proposed to use with the eurymeric resist composition of low-molecular-weight ring-type polyphenolic substance as main component, this ring-type polyphenolic substance has at least one phenolic hydroxyl group introducing the structure (with reference to patent documentation 3-10 and non-patent literature 1,2) of acid dissociation functional group is arranged, or uses with the negative resist composition (with reference to non-patent literature 3) of low-molecular-weight ring-type polyphenolic substance as the alkali-developable of main component.

Because the molecular weight of these low-molecular-weight ring-type polyphenolic substances is little, therefore the resist pattern that molecular size is little, resolving power is high, roughness is little is given in expectation.In addition, lower molecular weight ring-type polyphenolic substance keeps the low-molecular-weight while can give high heat resistance by have upright and outspoken ring texture thing at its skeleton.

But, now disclosed low-molecular-weight ring-type polyphenolic substance have that elching resistant is low, ease tolerance is many, the problem of the shape difference etc. of poorly soluble, the resist pattern that obtains of employed safety solvent in the semiconductor preparing process, expect the improvement of low-molecular-weight ring-type polyphenolic substance.

In addition, consider the homogeneity of solids component of eurymeric resist composition to the resolving power of resist pattern, the influence of roughness, the low-molecular-weight ring-type polyphenolic substance that expectation will have an acid dissociation functional group as homogeneity high, it is desirable to the eurymeric resist composition as single component.But, with the eurymeric resist composition of low-molecular-weight ring-type polyphenol as single component, be 100% owing to usually make the introducing rate of acid dissociation functional group, at this moment, the susceptibility step-down, and the low-molecular-weight ring-type polyphenol of high sensitive type did not also disclose so far.

Patent documentation 1: the spy opens the 2005-369761 communique

Patent documentation 2: the spy opens the 2005-326838 communique

Patent documentation 3: the spy opens flat 11-153863 communique

Patent documentation 4: the spy opens flat 11-322656 communique

Patent documentation 5: the spy opens the 2002-328473 communique

Patent documentation 6: the spy opens the 2003-321423 communique

Patent documentation 7: the spy opens the 2005-170902 communique

Patent documentation 8: the spy opens the 2006-276459 communique

Patent documentation 9: the spy opens the 2006-276742 communique

Patent documentation 10: the spy opens the 2007-8875 communique

Non-patent literature 1:Seung Wook Chang et al., " " Materials for Future Lithography " ", Proc.SPIE, Vol.5753, p.1

Non-patent literature 2:Daniel Bratton et al., " " Molecular Glass Resists for Next Generation Lithography " ", Proc.SPIE, Vol.6153,61531D-1

Non-patent literature 3:T.Nakayama, M.Nomura, K.Haga, M.Ueda:Bull.Chem.Soc.Jpn., 71,2979 (1998)

Summary of the invention

The objective of the invention is to:

(1) provide high sensitive, very high resolution, high elching resistant, low ease tolerance and the good radiation-ray sensitive composition that contains the resist compound of shape of the resist pattern that obtains, and the formation method of using the resist pattern of this radiation-ray sensitive composition;

(2) provide the good radiation-ray sensitive composition that contains the resist compound of the shape of the resist pattern that obtains and the formation method of using the resist pattern of this radiation-ray sensitive composition;

And (3) provide that optical characteristics and elching resistant are good and that do not have sublimate in fact, the composition that is used to form new photoresist material lower membrane and the lower membrane that is formed by said composition, and the formation method of having used the resist pattern of this lower membrane.

The present invention relates to:

(1) a kind of ring compound, wherein, this ring compound shown in following formula (1),

[Chemical formula 1]

(in the formula, L independently for be selected from by singly-bound, carbonatoms are the alkylidene group of the straight chain shape of 1-20 or chain, cycloalkylidene that carbonatoms is 3-20, carbonatoms is 6-24 arylidene ,-O-,-OC (=O)-,-OC (=O) O-,-N (R ⁵)-C (=O)-,-N (R ⁵)-C (=O) O-,-S-,-SO-,-SO ₂-and their group of forming arbitrarily in the organic group of divalence; R ¹Be the alkyl of 1-20 for being selected from by carbonatoms independently, carbonatoms is the cycloalkyl of 3-20, carbonatoms is the aryl of 6-20, carbonatoms is the alkoxyl group of 1-20, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, carboxyl, carbonatoms is the alkyl silane of 1-20, and the functional group in the group formed of their derivative, be the substituent methyl of 2-20 for being selected from by carbonatoms perhaps, carbonatoms is that the 1-of 3-20 replaces ethyl, carbonatoms is that the 1-of 4-20 replaces n-propyl, carbonatoms is the 1-branched-chain alkyl of 3-20, carbonatoms is the silyl of 1-20, carbonatoms is the acyl group of 2-20, carbonatoms is the 1-substituted alkoxy alkyl of 2-20, carbonatoms is the cyclic ethers base of 2-20, carbonatoms is the acid dissociation functional group in the carbalkoxy of 2-20 and the group that alkoxycarbonyl alkyl is formed, perhaps is hydrogen atom; R ' is the alkyl of 2-20 for carbonatoms independently or is that the carbonatoms shown in the following formula is the aryl of 6-24 or their derivative:

[Chemical formula 2]

R ⁴Be functional group in the alkyl silane of 1-20 and the group that their derivative is formed for being selected from by carbonatoms is the alkyl (but for the tertiary butyl) of 1-20, cycloalkyl that carbonatoms is 3-20, carbonatoms is 6-20 aryl, alkoxyl group, cyano group, nitro, heterocyclic radical, halogen, carboxyl, carbonatoms that carbonatoms is 1-20; R ⁵For hydrogen or carbonatoms are the alkyl of 1-10; M is the integer of 1-4; P is the integer of 0-5.）；

(2) a kind of radiation-ray sensitive composition, wherein, this radiation-ray sensitive composition contains above-mentioned (1) described ring compound and solvent;

(3) a kind of composition that is used to form lower membrane, wherein, this composition that is used to form lower membrane contains above-mentioned (2) described radiation-ray sensitive composition;

(4) preparation method of a kind of ring compound B0, wherein, reaction as the fs, to make acid dissociation functional group introduce reagent be 2-59 with carbonatoms and have reactive functional groups and the aldehyde compound A1b of 1-4 formyl radical reaction, to synthesize the aldehyde compound A1c that introducing has acid dissociation functional group; As the reaction of subordinate phase, carry out the condensation reaction of aldehyde compound A1c and phenolic compound A2;

(5) preparation method of a kind of ring compound B0, wherein, reaction as the fs, to carry out carbonatoms be 2-59 and have 1-2 carboxyl or the aldehyde compound A1d of ester group and 1-4 formyl radical and the condensation reaction of phenolic compound A2, is the ring compound A0 of 800-5000 with the molecular weight that has 1-8 carboxyl in the synthetic molecules; As the reaction of subordinate phase, have the ring compound A0 and the reaction with compound A-13 of halo methyl ether base of carboxyl;

(6) a kind of lower membrane, wherein, this lower membrane is formed by above-mentioned (3) described composition that is used to form lower membrane;

And the formation method of (7) a kind of resist pattern, wherein, this method comprises: use above-mentioned (2) described radiation-ray sensitive composition to form the operation of resist film at substrate; Operation with described resist film exposure; And the operation of described resist film being developed to form resist pattern.

Can provide by the present invention:

(1) the good radiation-ray sensitive composition that contains the resist compound of shape of high sensitive, very high resolution, high elching resistant, the low resist pattern that escapes tolerance and obtain, and the formation method of using the resist pattern of this radiation-ray sensitive composition;

The radiation-ray sensitive composition that contains the resist compound that the shape of the resist pattern that (2) obtains is good and the formation method of using the resist pattern of this radiation-ray sensitive composition;

And (3) optical characteristics and elching resistant are good and that do not have sublimate in fact, the composition that is used to form new photoresist material lower membrane and the lower membrane that is formed by said composition, and the formation method of having used the resist pattern of this lower membrane.

Embodiment

Below explain the present invention.

[ring compound]

The present invention relates to the ring compound as anticorrosive additive material.

Ring compound of the present invention is the ring compound shown in the following formula (1).

[chemical formula 3]

(in the formula, L independently for be selected from by singly-bound, carbonatoms are the alkylidene group of the straight chain shape of 1-20 or chain, cycloalkylidene that carbonatoms is 3-20, carbonatoms is 6-24 arylidene ,-O-,-OC (=O)-,-OC (=O) O-,-N (R ⁵)-C (=O)-,-N (R ⁵)-C (=O) O-,-S-,-SO-,-SO ₂-and their group of forming arbitrarily in the organic group of divalence; R ¹Be the alkyl of 1-20 for being selected from by carbonatoms independently, carbonatoms is the cycloalkyl of 3-20, carbonatoms is the aryl of 6-20, carbonatoms is the alkoxyl group of 1-20, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, carboxyl, carbonatoms is the alkyl silane of 1-20, and the functional group in the group formed of their derivative, be the substituent methyl of 2-20 for being selected from by carbonatoms perhaps, carbonatoms is that the 1-of 3-20 replaces ethyl, carbonatoms is that the 1-of 4-20 replaces n-propyl, carbonatoms is the 1-branched-chain alkyl of 3-20, carbonatoms is the silyl of 1-20, carbonatoms is the acyl group of 2-20, carbonatoms is the 1-substituted alkoxy alkyl of 2-20, carbonatoms is the cyclic ethers base of 2-20, carbonatoms is the acid dissociation functional group in the carbalkoxy of 2-20 and the group that alkoxycarbonyl alkyl is formed, perhaps is hydrogen atom; R ' is the alkyl of 2-20 for carbonatoms independently or is that the carbonatoms shown in the following formula is the aryl of 6-24 or their derivative;

R ⁴Be the alkyl (but for the tertiary butyl) of 1-20 for being selected from by carbonatoms, carbonatoms is the cycloalkyl of 3-20, carbonatoms is the aryl of 6-20, carbonatoms is the alkoxyl group of 1-20, cyano group, nitro, heterocyclic radical, halogen, carboxyl, carbonatoms is the alkyl silane of 1-20, and the functional group in the group formed of their derivative, be the substituent methyl of 2-20 for being selected from by carbonatoms perhaps, carbonatoms is that the 1-of 3-20 replaces ethyl, carbonatoms is that the 1-of 4-20 replaces n-propyl, carbonatoms is the 1-branched-chain alkyl of 3-20, carbonatoms is the silyl of 1-20, carbonatoms is the acyl group of 2-20, carbonatoms is the 1-substituted alkoxy alkyl of 2-20, carbonatoms is the cyclic ethers base of 2-20, carbonatoms is the acid dissociation functional group in the carbalkoxy of 2-20 and the group that alkoxycarbonyl alkyl is formed; R ⁵For hydrogen or carbonatoms are the alkyl of 1-10; M is the integer of 1-4; P is the integer of 0-5.）

Ring compound as shown in the above-mentioned formula (1) preferably lists following compound.

[chemical formula 5]

[chemical formula 6]

[chemical formula 7]

[chemical formula 8]

(above-mentioned formula (1-1), (1-1-1), (1-2) and (1-2-1) separately in, X ₂Be hydrogen or halogen atom; m ₃Integer for 1-2; m ₄Be 1; R ⁴, p is same as described above).

Above-mentioned ring compound is owing to the thermotolerance height, have amorphism, thereby film-forming properties is good, does not have sublimability, and alkali-developable, elching resistant etc. are good, are suitable as anticorrosive additive material, especially are suitable as the main component (base material) of anticorrosive additive material.Further, it is shocking when having the benzene structure, lower to the optical extinction coefficient of the light of 193nm, and to have the high advantage of specific refractory power, be suitable as the lower membrane material.

In addition, above-mentioned ring compound, aspect preparation, also because can be by being that the phenols of the various aldehydes of representative and Resorcinol, pyrogallol etc. is as raw material with the aromatic aldehyde with industrial preparation, non-metallic catalyst by hydrochloric acid etc. carries out dehydration condensation, thereby preparation efficiently, thereby the practicality of above-mentioned ring compound is also extremely good.

Further, above-mentioned ring compound owing to be insoluble in general employed propylene glycol methyl ether acetate (PGMEA), dissolves in propylene glycol monomethyl ether (PGME) or pimelinketone during as solvent, thereby can also suppress to mix when forming the multilayer resist.

Ring compound among the present invention can obtain cis body and trans body, can be any structure or mixture.As the resist composition of radiation-ray sensitive composition the time, only have under any one the situation of structure in cis body and the trans body, become the pure substance compound, and the homogeneity height of the composition in the resist film, thereby preferred.Only had any one the method for ring compound of structure in cis body and the trans body, for example can use: utilizing column chromatography or the separation carried out of preparation liquid-liquid chromatography (preparative liquid chromatography) or in the preparation, known method such as optimization such as reaction solvent and temperature of reaction are carried out.

In the present invention, in the above-mentioned ring compound, preferred following epoxy compounds.

(a) ring compound shown in the following formula (2).

[chemical formula 9]

(in the formula, R ^7ABe straight chain shape alkyl, halogen atom, cyano group, hydroxyl, alkoxyl group or the ester group of 1-12 for hydrogen atom, carbonatoms independently.）

By having said structure, can obtain high refractive index and suitable optical extinction coefficient to the light of 193nm.

As R ^7A, can enumerate: hydrogen atom; Carbonatoms is the straight chained alkyl of 1-10, as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, neo-pentyl, hexyl, heptyl, octyl group, nonyl, decyl etc.; Halogen atom; Cyano group; Hydroxyl; Alkoxyl group or ester group.

Wherein, especially hydrogen atom, propyl group, amyl group can obtain high refractive index and suitable optical extinction coefficient to the light of 193nm, thereby be especially in use in when using in the composition that forms lower membrane preferred.

(b) ring compound shown in the following formula (3).

[Chemical formula 1 0]

(in the formula, R ^7BBe the straight chain shape alkyl of 1-6 independently for carbonatoms.）

R ^7BFor carbonatoms is the straight chained alkyl of 1-6, as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, neo-pentyl, hexyl etc., be preferably trans body.

Wherein, especially propyl group can obtain high refractive index and suitable optical extinction coefficient to the light of 193nm, thereby preferred.

Above-mentioned ring compound (a) and (b), can by carbonatoms be 6-24 aromatic aldehyde, obtain with the condensation reaction that contains the compound of Resorcinol or pyrogallol.

Above-mentioned ring compound can prepare by known method.For example, can obtain by following method: at organic solvent (as toluene, methyl alcohol, ethanol etc.) in, at thioacetic acid or β-Qiu Jibingsuan, and acid catalyst (hydrochloric acid, sulfuric acid or tosic acid) existence under, use molar ratio as 1:(1 to excessive) carbonyl compound (as aromatic aldehyde etc.) and phenols (as Resorcinol, pyrogallol etc.), 60-150 ℃ of degree of reacting 0.5-20 hour down, after reaction finishes, in reaction solution, add toluene and be heated to 60-80 ℃, stir after 0.5-2 hour, cool to room temperature, filter then and separate, make its drying at last.

The molecular weight of above-mentioned ring compound is preferably more than 400 below 2000, more preferably more than 600 below 2000, more preferably more than 800 below 1500.In the time of in above-mentioned scope, can obtain that film-forming properties is good, elching resistant is good and distillation composition few anticorrosive additive material, especially lower membrane material.

(c) be selected from the ring compound of each compound shown in following formula (4-0) or (4).

[Chemical formula 1 1]

[Chemical formula 1 2]

(formula (4-0) and formula (4) separately in, X ₂Be hydrogen or halogen atom; L ₁Organic group for the divalence of the alkyl that is selected from straight chain shape that singly-bound, carbonatoms are 1-4 or a chain; l ₁Be 0 or 1; M is the integer of 1-4; m ₃Integer for 1-2; m ₄Be 1.）

(d) be selected from the ring compound in the group of being formed by each compound shown in the following formula (5) or be selected from ring compound in the group of being formed by each compound shown in the following formula (6).

[Chemical formula 1 3]

[Chemical formula 1 4]

(in formula (5), (6), R ¹Same as described above.But, at least one R wherein ¹Be acid dissociation functional group.）

Above-mentioned acid dissociation functional group can select use aptly from the acid dissociation functional group that proposes in the employed hydroxy styrenes resinoid of chemical amplification type anti-corrosion agent composition that is used for KrF or ArF, (methyl) acrylic resin etc.Preferably for example can enumerate: substituent methyl, 1-replace ethyl, 1-replaces n-propyl, 1-branched-chain alkyl, silyl, acyl group, 1-substituted alcoxyl methyl, cyclic ethers base and carbalkoxy etc.Above-mentioned acid dissociation functional group does not preferably have bridging property functional group.

The molecular weight of ring compound (d) is preferably 800-5000, more preferably 800-2000, more preferably 1000-2000.In the time of in above-mentioned scope, resist can keep necessary film-forming properties, and resolving power is improved.

As substituent methyl, be generally the substituent methyl that carbonatoms is 2-20, be preferably the substituent methyl that carbonatoms is 4-18, more preferably carbonatoms is the substituent methyl of 6-16.Can enumerate for example substituting group shown in methoxymethyl, methylthiomethyl, ethoxyl methyl, n-propoxymethyl, isopropoxy methyl, n-butoxy methyl, tert.-butoxy methyl, 2-methyl-prop oxygen ylmethyl, ethylmercapto group methyl, methoxy ethoxy methyl, phenoxymethyl, 1-cyclopentyloxy methyl, 1-cyclohexyloxy methyl, benzyl sulphomethyl, phenacyl, 4-bromobenzene formyl methyl, 4-methoxybenzoyl methyl, piperonyl and the following formula (7) etc.

[Chemical formula 1 5]

(in the formula, R ²Be the alkyl of 1-4 for carbonatoms.Be the alkyl of 1-4 as carbonatoms, can enumerate methyl, ethyl, sec.-propyl, n-propyl, the tertiary butyl, normal-butyl etc.）

Replace ethyl as 1-, being generally carbonatoms is the 1-replacement ethyl of 3-20, and being preferably carbonatoms is the 1-replacement ethyl of 5-18, and more preferably carbonatoms is the replacement ethyl of 7-16.Can enumerate for example 1-methoxy ethyl, 1-methylmercaptoethyl, 1,1-dimethoxy-ethyl, 1-ethoxyethyl group, 1-ethylmercapto group ethyl, 1,1-diethoxy ethyl, positive propoxy ethyl, isopropoxy ethyl, n-butoxy ethyl, tert.-butoxy ethyl, 2-methyl propoxy-ethyl, 1-phenoxy group ethyl, 1-phenyl thio-ethyl, 1,1-two phenoxy group ethyls, 1-cyclopentyloxy ethyl, 1-cyclohexyloxy ethyl, 1-phenylethyl, 1, the substituting group shown in 1-diphenyl-ethyl and the following formula (8) etc.

[Chemical formula 1 6]

(in the formula, R ²Same as described above.）

Replace n-propyl as 1-, being generally carbonatoms is the 1-replacement n-propyl of 4-20, and being preferably carbonatoms is the 1-replacement n-propyl of 6-18, and more preferably carbonatoms is the 1-replacement n-propyl of 8-16.Can enumerate for example 1-methoxyl group n-propyl and 1-oxyethyl group n-propyl etc.

As the 1-branched-chain alkyl, being generally carbonatoms is the 1-branched-chain alkyl of 3-20, and being preferably carbonatoms is the 1-branched-chain alkyl of 5-18, and more preferably carbonatoms is the 1-branched-chain alkyl of 7-16.Can enumerate for example sec.-propyl, sec-butyl, the tertiary butyl, 1,1-dimethyl propyl, 1-methyl butyl, 1,1-dimethylbutyl, 2-methyl adamantane base and 2-ethyl adamantyl etc.

As silyl, be generally the silyl that carbonatoms is 1-20, be preferably the silyl that carbonatoms is 3-18, more preferably carbonatoms is the silyl of 5-16.Can enumerate for example trimethyl silyl, ethyl dimetylsilyl, methyl diethylsilane base, triethylsilyl, t-butyldimethylsilyl, tertiary butyl diethylsilane base, t-butyldiphenylsilyl, tri-tert silyl and triphenyl silyl etc.

As acyl group, be generally the acyl group that carbonatoms is 2-20, be preferably the acyl group that carbonatoms is 4-18, more preferably carbonatoms is the acyl group of 6-16.Can enumerate for example ethanoyl, phenoxy group ethanoyl, propionyl, butyryl radicals, oenanthyl, caproyl, pentanoyl, pivaloyl, isovaleryl, lauroyl, diamantane acyl group (アダマ Application チ Le カ Le ボニ Le base), benzoyl and naphthoyl etc.

As 1-substituted alcoxyl ylmethyl, being generally carbonatoms is the 1-substituted alcoxyl ylmethyl of 2-20, and being preferably carbonatoms is the 1-substituted alcoxyl ylmethyl of 4-18, and more preferably carbonatoms is the 1-substituted alcoxyl ylmethyl of 6-16.Can enumerate for example 1-cyclopentyl methoxymethyl, 1-cyclopentyl ethoxyl methyl, 1-cyclohexyl methoxymethyl, 1-cyclohexyl ethoxyl methyl, 1-ring octyl group methoxymethyl and 1-adamantyl methoxymethyl etc.

As the cyclic ethers base, being generally carbonatoms is the cyclic ethers base of 2-20, and being preferably carbonatoms is the cyclic ethers base of 4-18, and more preferably carbonatoms is the cyclic ethers base of 6-16.Can enumerate for example THP trtrahydropyranyl, tetrahydrofuran base, tetrahydrochysene sulfo-pyranyl, tetrahydrochysene thio-furan base, 4-methoxyl group THP trtrahydropyranyl and 4-methoxyl group tetrahydrochysene sulfo-pyranyl etc.

As carbalkoxy, be generally the carbalkoxy that carbonatoms is 2-20, be preferably the carbalkoxy that carbonatoms is 4-18, more preferably carbonatoms is the carbalkoxy of 6-16.Can enumerate methoxycarbonyl for example, ethoxycarbonyl, the positive third oxygen carbonyl, isopropyl oxygen carbonyl, positive butoxy carbonyl, tertbutyloxycarbonyl or the acid dissociation functional group during for the n=0 shown in the following formula (9) etc.

As alkoxycarbonyl alkyl, be generally the alkoxycarbonyl alkyl that carbonatoms is 2-20, be preferably the alkoxycarbonyl alkyl that carbonatoms is 4-18, more preferably carbonatoms is the alkoxycarbonyl alkyl of 6-16.Can enumerate methoxycarbonyl methyl for example, ethoxycarbonylmethyl group, the positive third oxygen carbonyl methyl, isopropyl oxygen carbonyl methyl, n-butoxy carbonyl methyl or the acid dissociation functional group during for the described n=1-4 of following formula (9) etc.

[Chemical formula 1 7]

(in the formula, R ²For hydrogen or carbonatoms are the straight or branched alkyl of 1-4; N is the integer of 0-4.）

In these acid dissociation functional groups, preferred substituent methyl, 1-replace ethyl, 1-substituted alcoxyl methyl, cyclic ethers base, carbalkoxy and alkoxycarbonyl alkyl, substituent methyl, 1-replace ethyl, carbalkoxy and alkoxycarbonyl alkyl, more preferred because susceptibility is high, further preferably have the acid dissociation functional group that is selected from the structure in the aromatic nucleus that cycloalkanes, lactone and carbonatoms that carbonatoms is 3-12 are 6-12.Being the cycloalkanes of 3-12 as carbonatoms, can be monocycle, also can be many rings, is preferably many rings.Concrete example, can enumerate mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane etc., more specifically, can enumerate the mononaphthene of cyclopropane, tetramethylene, pentamethylene, hexanaphthene etc., the polynaphthene of diamantane, norbornane, iso-borneol alkane, tristane, Fourth Ring decane etc.Wherein, be preferably diamantane, three cycloalkanes, tetracycloalkane, be preferably diamantane, three cycloalkanes especially.Carbonatoms is that the cycloalkanes of 3-12 also can have substituting group.As lactone, the carbonatoms that can enumerate butyrolactone or have a lactone group is the cycloalkyl of 3-12.Be the aromatic nucleus of 6-12 as carbonatoms, can enumerate phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, pyrene ring etc., be preferably phenyl ring, naphthalene nucleus, be preferably naphthalene nucleus especially.

Especially be selected from the acid dissociation functional group in the group of being formed by each group shown in the following formula (10), preferred because resolving power is high.

[Chemical formula 1 8]

(in the formula, R ⁵For hydrogen or carbonatoms are the straight or branched alkyl of 1-4; R ⁶Be straight or branched alkyl, cyano group, nitro, heterocyclic radical, halogen, the carboxyl of 1-4 for hydrogen, carbonatoms; n ₁Integer for 0-4; n ₂Integer for 1-5; n ₀Integer for 0-4.）

In addition, in the scope of not damaging effect of the present invention, the R of acid dissociation functional group ¹Also can be to contain the repeating unit shown in the following formula (11) and following formula (12) or R ¹(R ¹Same as described above) shown in the substituting group of end group.

[Chemical formula 1 9]

[Chemical formula 2 0]

In formula (11) and/or (12), R ¹Same as described above.L is singly-bound, methylene radical, ethylidene or carbonyl.n ₅Be the integer of 0-4, n ₆Be the integer of 1-3, x is the integer of 0-3, and satisfies 1 ≦ n ₅+ n ₆≦ 5.A plurality of n ₅, n ₆, x can be the same or different.R ³For being selected from the substituting group in the group of being formed by halogen atom, alkyl, cycloalkyl, aryl, aralkyl, alkoxyl group, aryloxy, alkenyl, acyl group, carbalkoxy, alkanoyloxy, aryl acyloxy, cyano group and nitro.As halogen atom, can enumerate chlorine atom, bromine atoms and iodine atom; As alkyl, can enumerate the alkyl that carbonatoms is 1-4, as methyl, ethyl, propyl group, n-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl etc.; As cycloalkyl, can enumerate cyclohexyl, norborneol alkyl, adamantyl etc.; As aryl, can enumerate phenyl, tolyl, xylyl, naphthyl etc.; As aralkyl, can enumerate benzyl, hydroxybenzyl, dihydroxy benzyl etc.; As alkoxyl group, can enumerate the alkoxyl group that carbonatoms is 1-4, as methoxyl group, oxyethyl group, hydroxyl-oxethyl, propoxy-, hydroxyl propoxy-, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy etc.; As aryloxy, can enumerate phenoxy group etc.; As alkenyl, can enumerate the alkenyl that carbonatoms is 2-4, as vinyl, propenyl, allyl group, butenyl etc.; As acyl group, can enumerate the aliphatic acyl radical that carbonatoms is 1-6 (as formyl radical, ethanoyl, propionyl, butyryl radicals, pentanoyl, isovaleryl, pivaloyl etc.) and aromatic acyl (as benzoyl, toluyl etc.); As carbalkoxy, can enumerate the carbalkoxy that carbonatoms is 2-5, as methoxycarbonyl, ethoxycarbonyl, the third oxygen carbonyl, isopropyl oxygen carbonyl, positive butoxy carbonyl, isobutyl boc, secondary butoxy carbonyl, tertbutyloxycarbonyl etc.; As alkanoyloxy, can enumerate acetoxyl group, propionyloxy, butyryl acyloxy, isobutyl acyloxy, penta acyloxy, isoamyl acyloxy, trimethyl acetoxyl etc.; As aryl acyloxy, can enumerate benzoyloxy etc.A plurality of R ³Can be the same or different.

The method of introducing acid dissociation functional group at least one phenolic hydroxyl group of ring compound A is known.For example shown below, can introduce acid dissociation functional group at least one phenolic hydroxyl group of ring compound A.Be used for to introduce the compound of acid dissociation functional group, can be with known method synthetic or can easily obtain, can enumerate for example active carboxylic acid derivative's compound, as acyl chlorides, acid anhydrides, two carbonic ethers etc.; Haloalkane; Vinyl alkyl ethers, dihydropyrane, halogenated carboxylic acid alkane ester etc., but not special restriction.

For example, can be dissolved or suspended in the non-protonic solvent (as acetone, tetrahydrofuran (THF) (THF), propylene glycol methyl ether acetate etc.) by making ring compound A.Then, add vinyl alkyl ethers (as ethyl vinyl ether etc.) or dihydropyrane, in the presence of acid catalyst (as tosic acid pyridinium salt etc.), under normal pressure, 20-60 ℃, reacted 6-72 hour, with basic cpd neutralization reaction liquid, add to separate out white solid in the distilled water after, with the white solid that distilled water wash separates, drying obtains ring compound d.

In addition, ring compound A is dissolved or suspended in the non-protonic solvent (as acetone, THF, propylene glycol methyl ether acetate etc.); Then, add haloalkane (as chloromethyl ethyl ether etc.) or halogenated carboxylic acid alkane ester (as bromoacetic acid methyl adamantane ester etc.), in the presence of alkaline catalysts (as salt of wormwood etc.), under normal pressure, 20-110 ℃, reacted 6-72 hour; With acid (example hydrochloric acid etc.) neutralization reaction liquid, add to separate out white solid in the distilled water after, with the white solid that distilled water wash separates, drying obtains ring compound d.

In the present invention, so-called acid dissociation functional group refers to division in the presence of acid and produces the characteristic group of alkali-soluble group.As the alkali-soluble group, can enumerate phenolic hydroxyl group, carboxyl, sulfonic group, hexafluoroisopropanol base etc., be preferably phenolic hydroxyl group and carboxyl, be preferably phenolic hydroxyl group especially.In order to form the more figure of high sensitive very high resolution, described acid dissociation functional group preferably has the character that dissociative reaction takes place chainly in the presence of acid.

Ring compound A can by be selected from the group of being formed by aromatic carbonyl A1 more than one, obtain with more than one the condensation reaction that is selected from the group of being formed by phenolic compound A2.

Aromatic carbonyl A1; except being the aromatic nucleus of phenyl aldehyde; be the phenyl aldehyde of 10-24 for having the substituent carbonatoms that contains at least one alicyclic ring or aromatic nucleus; for example can enumerate: cyclopropyl-phenyl formaldehyde, cyclobutyl phenyl aldehyde, cyclopentyl phenyl aldehyde, phenylcyclohexane formaldehyde, phenyl phenyl aldehyde, naphthaldehyde, adamantyl phenyl aldehyde, norcamphyl phenyl aldehyde, hydroxy propionyl group phenyl aldehyde etc.; be preferably phenylcyclohexane formaldehyde, phenyl phenyl aldehyde, more preferably phenylcyclohexane formaldehyde.In the scope of not damaging effect of the present invention, aromatic carbonyl A1 also can have straight or branched alkyl that carbonatoms is 1-4, cyano group, hydroxyl, halogen etc.Aromatic carbonyl A1 can be used alone or in combination of two or more.

As the example of phenolic compound A2, can enumerate phenol, pyrocatechol, Resorcinol, Resorcinol, pyrogallol etc., be preferably Resorcinol, pyrogallol, more preferably Resorcinol.In the scope of not damaging effect of the present invention, phenolic compound A2 also can have straight or branched alkyl that carbonatoms is 1-4, cyano group, hydroxyl, halogen etc.Phenolic compound A2 also can be used alone or in combination of two or more.

Ring compound A can prepare by known method.For example, can obtain by following method: in organic solvent (as methyl alcohol, ethanol etc.), in the presence of acid catalyst (hydrochloric acid, sulfuric acid or tosic acid etc.), use molar ratio to be 1:(0.1-10) aromatic carbonyl A1 and phenolic compound A2,60-150 ℃ of down reaction about 0.5-20 hour, after the filtration, with alcohols (as methyl alcohol etc.) washing after washing, filter then and separate, make its drying at last.Also can use basic catalyst (sodium hydroxide, hydrated barta or 1,8-diazabicyclo [5.4.0], 11 carbon-7-alkene etc.) by replacing acid catalyst, similarly obtain by reaction.Further, ring compound A also can become dihalide by make above-mentioned aromatic carbonyl A1 with hydrogen halide or halogen gas, makes dihalide and phenolic compound A2 behind the segregation react to prepare.

In order to reduce the kish amount of ring compound A, also can make with extra care as required.In addition, general if when acid catalyst and promotor are residual, the stability in storage of radiation-ray sensitive composition reduces; When perhaps basic catalyst was residual, general, the susceptibility of radiation-ray sensitive composition can reduce, and therefore also can carry out reducing its content is the refining of purpose.Refining can being undertaken by known method, as long as not modification of ring compound A, just there is no particular limitation, for example can enumerate: the method that water washs, the method for washing with acidic aqueous solution, the method for washing with alkaline aqueous solution, method that spent ion exchange resin is handled, the method handled with silica dioxide gel column chromatography instrument etc.More preferably the two or more combinations of these process for purification are carried out.Can be according to the kind of the amount of the metal that should remove, acidic cpd and/or basic cpd and kind, refining ring compound A etc., from acidic aqueous solution, alkaline aqueous solution, ion exchange resin and silica dioxide gel column chromatography instrument, suitably select best method.For example as acidic aqueous solution, can enumerate hydrochloric acid, nitric acid, aqueous acetic acid that concentration is 0.01-10mol/L, as alkaline aqueous solution, can enumerate the ammonia soln that concentration is 0.01-10mol/L, as ion exchange resin, can enumerate Zeo-karb, for example Amberlyst 15J-HG Dry of オ Le ガノ system etc.Can also carry out drying after refining.Drying can be undertaken by known method, and there is no particular limitation, under the condition of not modification of ring compound A, can enumerate the method for vacuum-drying, warm air drying etc.

Ring compound d, preferably under normal pressure, below 100 ℃, be preferably below 120 ℃, more preferably below 130 ℃, more preferably below 140 ℃, be preferably below 150 ℃ especially, sublimability is low.So-called sublimability is low, and to be preferably loss of weight when having kept 10 minutes under the temperature of defined in thermogravimetric analysis be below 10%, be preferably below 5%, more preferably below 3%, more preferably below 1%, be preferably below 0.1% especially.By making sublimability low, the pollution of the exposure apparatus that the ease gas in the time of can preventing by exposure causes.In addition, can give good graphics shape with low line edge roughness (LER).

Ring compound d satisfies: be preferably F＜3.0(F and represent total atom number/(total carbon atom number-total oxygen atomicity)), F＜2.5 more preferably.By satisfying above-mentioned condition, make that anti-dry etching is good.

Ring compound d is selected from propylene glycol methyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, methyl-phenoxide, butylacetate, ethyl propionate and ethyl lactate, and, demonstrating for ring compound d in the solvent of maximum dissolving power, under 23 ℃, more than the preferred dissolution 1 weight %, more preferably dissolve more than the 3 weight %, more than the further preferred dissolution 5 weight %, the solvent of the ring compound d that special preferred dissolution 10 weight % are above.By satisfying above-mentioned condition, make the use of safety solvent in the semiconductor fabrication operation become possibility.

Ring compound d can form amorphous film by spin coating.In addition, can be applicable in the general semiconductor preparing process.

The amorphous film of ring compound d dissolution rate to the TMAH aqueous solution of 2.38 quality % under 23 ℃ is preferably

Below, more preferably

More preferably

For

When following, be insoluble to alkaline-based developer, can become resist.In addition, have

During above dissolution rate, the situation that has resolving power to improve.Infer that this is because the small surperficial position of described ring compound d is dissolved, has reduced the cause of LER.In addition, reduce the effect of defective in addition.

The acid dissociation functional group of ring compound d dissociates and the ring compound A0 that generates, also preferably has the character that forms amorphous film by spin coating.The amorphous film of ring compound A0 dissolution rate to the TMAH aqueous solution of 2.38 quality % under 23 ℃ is preferably

More than, more preferably

More preferably

For

When above, can be dissolved in alkaline-based developer, become resist.In addition, have

During following dissolution rate, the situation that also has resolving power to improve.Infer that this is because by the caused deliquescent variation of being dissociated by the acid dissociation functional group of described ring compound d, make the big cause of contrast change at interface that is dissolved in the exposure portion of alkaline-based developer and is not dissolved in the unexposed portion of alkaline-based developer.In addition, has the effect that reduces LER, reduces defective.

The solids component of radiation-ray sensitive composition can be by spin coating to form amorphous film.The solids component of spin coating radiation-ray sensitive composition and the amorphous film that the forms dissolution rate to the TMAH aqueous solution of 2.38 quality % under 23 ℃ is preferably Below.By to irradiation KrF excimer laser, extreme ultraviolet, electron rays or X ray isoradial on the described amorphous film, be exposed to desired figure, the dissolution rate at the TMAH aqueous solution of relative 2.38 quality % under 23 ℃ of the amorphous film after the heating under 20-250 ℃ is preferably as required

More than.By satisfying above-mentioned condition, make yield rate good, can give good graphics shape.

The second-order transition temperature of ring compound d is preferably more than 100 ℃, more preferably more than 120 ℃, more preferably more than 140 ℃, is preferably especially more than 150 ℃.By making second-order transition temperature in above-mentioned scope, in semiconductor lithography method technology, have the thermotolerance that to keep graphics shape, and can give the performance of very high resolution etc.

By the differential scanning calorimetric analysis of the second-order transition temperature of ring compound d and the crystallization thermal value of obtaining is preferably not enough 20J/g.And (Tc)-(second-order transition temperature) is preferably more than 70 ℃, more preferably more than 80 ℃, more preferably more than 100 ℃, is preferably especially more than 130 ℃.The not enough 20J/g of crystallization thermal value and (Tc)-(second-order transition temperature) be that above-mentioned scope is when interior, by the spin coating radiation-ray sensitive composition, form amorphous film easily, and can keep the necessary film-forming properties of resist for a long time, can improve resolving power.

In the present invention, described crystallization thermal value, Tc and second-order transition temperature can be determined as follows by the DSC/TA-50WS that uses Shimadzu Seisakusho Ltd.'s system and carry out the differential scanning calorimetric analysis and obtain.The about 10mg of sample is added in the aluminum non-tight container, and (50ml/min) is that 20 ℃/min is warming up to more than the fusing point with heat-up rate in stream of nitrogen gas.After the quenching, (30ml/min) is that 20 ℃/min is warming up to more than the fusing point with heat-up rate in stream of nitrogen gas again.And then after the quenching, (30ml/min) is that 20 ℃/min is warming up to 400 ℃ with heat-up rate in stream of nitrogen gas again.To count second-order transition temperature (Tg) in the temperature of mid point (specific heat becomes in half) that the zone of discontinuous part appears in baseline, the temperature of the exothermal peak that occurs will subsequently be counted Tc.Area by exothermal peak and baseline area surrounded is obtained thermal value, counts the crystallization thermal value.

(e) ring compound shown in following formula (13-0) or the formula (13).

[Chemical formula 2 1]

[Chemical formula 2 2]

(in formula (13-0) and (13), R ^3ACan enumerating substituent methyl that carbonatoms is 2-20,1-that carbonatoms is 3-20, to replace ethyl, carbonatoms be that the 1-of 4-20 replaces 1-branched-chain alkyl that n-propyl, carbonatoms are 3-20, silyl that carbonatoms is 1-20, acyl group that carbonatoms is 2-20,1-substituted alkoxy alkyl that carbonatoms is 2-20, cyclic ethers base that carbonatoms is 2-20, carbalkoxy that carbonatoms is 2-20 and the alkoxycarbonyl alkyl of carbonatoms 2-20; X ₂, L ₁, l ₁, identical in m and the above-mentioned formula (4-0).）

As carbonatoms be the substituent methyl of 2-20,1-that carbonatoms is 3-20 to replace ethyl, carbonatoms be that the 1-of 4-20 replaces 1-branched-chain alkyl that n-propyl, carbonatoms are 3-20, silyl that carbonatoms is 1-20, acyl group that carbonatoms is 2-20,1-substituted alkoxy alkyl that carbonatoms is 2-20, cyclic ethers base that carbonatoms is 2-20, carbalkoxy that carbonatoms is 2-20 and the alkoxycarbonyl alkyl of carbonatoms 2-20, can similarly enumerate at above-mentioned R ¹The middle acid dissociation functional group that illustrated.

Above-mentioned ring compound e more preferably is selected from the compound of each compound shown in the following formula (14).

[Chemical formula 2 3]

(in the formula, R ^3A, X ₂, L ₁, l ₁Same as described above.）

Above-mentioned ring compound e is preferably the compound that is selected from each compound shown in the following formula (15) especially.

[Chemical formula 2 4]

(in the formula, X ₂, R ^3ASame as described above.）

R ^3AMore preferably have and be selected from the acid dissociation functional group of structure that cycloalkanes, lactone and carbonatoms that carbonatoms is 3-20 are the aromatic nucleus of 6-12.Being the cycloalkanes of 3-20 as carbonatoms, can be that monocycle also can be many rings, is preferably many rings.Concrete example, can enumerate mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane etc., more specifically, can enumerate the mononaphthene of cyclopropane, tetramethylene, pentamethylene, hexanaphthene etc., the polynaphthene of diamantane, norbornane, iso-borneol alkane, tristane, Fourth Ring decane etc.Wherein, be preferably diamantane, three cycloalkanes, tetracycloalkane, be preferably diamantane, three cycloalkanes especially.Carbonatoms is that the cycloalkanes of 3-20 also can have substituting group.As lactone, the carbonatoms that can enumerate butyrolactone or have a lactone group is the cycloalkyl of 3-20.Be the aromatic nucleus of 6-12 as carbonatoms, can enumerate phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, pyrene ring etc., be preferably phenyl ring, naphthalene nucleus, be preferably naphthalene nucleus especially, more preferably the acid dissociation functional group shown in the following formula (16).By having this acid dissociation functional group, can improve resolving power and the LER of the resist pattern that obtains.

[Chemical formula 2 5]

(in the formula, R ⁵, R ⁶, n ₀, n ₁, n ₂Same as described above.）

Ring compound e also can obtain by the ring compound A0 with carboxyl and the dehydration condensation with compound of alcoholic extract hydroxyl group.

Ring compound e also can obtain by ring compound A0a and the transesterification reaction with compound of alcoholic extract hydroxyl group, and this ring compound A0a is that the carboxyl substituted by the ring compound A0 with carboxyl is that the ester bond shown in the following formula (17) obtains.Transesterification reaction is known.As the compound with alcoholic extract hydroxyl group, can use any alcohol in primary alconol, secondary alcohol, the tertiary alcohol, more preferably secondary alcohol, the tertiary alcohol are preferably the tertiary alcohol especially.

[Chemical formula 2 6]

(in the formula, R ^3BFor carbonatoms is that straight chain shape alkyl, the carbonatoms of 1-20 is that the alkyl of the chain of 3-20, cycloalkyl or the carbonatoms that carbonatoms is 3-20 are the aryl of 6-20.）

Be the straight chain shape alkyl of 1-20 as carbonatoms, preferred carbonatoms is 1-12, can enumerate methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-octyl, dodecyl etc. particularly.

Be the alkyl of the chain of 3-20 as carbonatoms, preferred carbonatoms is 3-10, can enumerate sec.-propyl, the tertiary butyl, isopentyl, neo-pentyl etc. particularly, wherein is preferably the tertiary butyl.

Be the cycloalkyl of 3-20 as carbonatoms, preferred carbonatoms is 6-14.In addition, the cycloaliphatic ring that contains in the cycloalkyl can be that monocycle also can be many rings, more preferably many rings.Can enumerate particularly: mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane etc., more specifically, can enumerate: the mononaphthene of cyclopropane, tetramethylene, pentamethylene, hexanaphthene etc., the polynaphthene of diamantane, norbornane, iso-borneol alkane, tristane, Fourth Ring decane etc.Wherein, be preferably diamantane, three cycloalkanes, tetracycloalkane, be preferably diamantane, three cycloalkanes especially.

Be the aryl of 6-20 as carbonatoms, can enumerate phenyl, tolyl, xylyl, naphthyl etc.

Ring compound e can obtain by the ring compound A0 with carboxyl and the reaction with compound A-13 of halogen methyl ether base.For example, ring compound B0 can obtain by following method: make the ring compound A0 with carboxyl be dissolved or suspended in non-protonic solvent (as acetone, THF, propylene glycol methyl ether acetate etc.) in, then, add the compound A-13 with halogen methyl ether base, be the 0.5-4 equivalent at the carboxyl with respect to the ring compound A0 with carboxyl, be preferably the 0.9-1.1 equivalent, more preferably the alkaline catalysts of 1.0 equivalents is (as pyridine, triethylamine, the diazabicyclo undecylene, salt of wormwood etc.) under the existence, at normal pressure, 0-110 ℃ was reacted 1-72 hour down, thereafter, wash after washing with alcohols (as methyl alcohol etc.), filter then and separate, make its drying at last.This compound also can carry out the refining of column chromatography etc. as required.

The molecular weight of ring compound e is 800-5000, is preferably 1000-2500, more preferably 1500-2000.When above-mentioned scope, can keep the necessary film-forming properties of resist, and can improve resolving power.

[radioactivity responsive type composition and the ring compound that is used for said composition]

The present invention relates to contain in the ring compound of formula (1) and formula (a) ~ (e) any one ring compound and the radioactive rays sensing composition of solvent.

In addition; relate to above-mentioned radiation-ray sensitive composition; in said composition; ring compound is for being the ring compound of 700-5000 by the synthetic molecular weight of the condensation reaction of aldehyde compound A1 and phenolic compound A2; wherein said aldehyde compound A1 is that carbonatoms is 2-59 and the compound with 1-4 formyl radical, and described phenolic compound A2 is that carbonatoms is 6-15 and the compound with 1-3 phenolic hydroxyl group.

(radiation-ray sensitive composition A)

Preferred above-mentioned radiation-ray sensitive composition has following feature among the present invention: at this radiation-ray sensitive composition, ring compound is that at least one phenolic hydroxyl group introducing that has at described ring compound has the structure of acid dissociation functional group and the ring compound B that molecular weight satisfies 800-5000.

Namely, preferred radiation-ray sensitive composition has following feature among the present invention: this radiation-ray sensitive composition contains the solids component of 1-80 weight % and the solvent of 20-99 weight %, wherein, described radiation-ray sensitive composition contains ring compound B, and the 50-99.999 weight % of the described ring compound B gross weight that is solids component, wherein said ring compound B satisfies: (a) have at least one phenolic hydroxyl group of ring compound A and introduce the structure that acid dissociation functional group is arranged, described ring compound A is to be the phenyl aldehyde of 7-24 by any one the carbonatoms that do not have in hydroxyl and the tertiary butyl, with carbonatoms be the condensation reaction of 6-15 and the compound with 1-3 phenolic hydroxyl group and synthetic; (b) molecular weight is 800-5000.

In addition, preferred radiation-ray sensitive composition has following feature among the present invention: this radiation-ray sensitive composition contains the solids component of 1-80 weight % and the solvent of 20-99 weight %, wherein, described radiation-ray sensitive composition contains the ring compound B as solids component, and more than the 50 weight % of the described ring compound B gross weight that is solids component, wherein said ring compound B satisfies: (a) have at least one phenolic hydroxyl group of ring compound A and introduce the structure that acid dissociation functional group is arranged, described ring compound A is to be the phenyl aldehyde of 10-24 by having the substituent carbonatoms that contains alicyclic ring or aromatic nucleus, with carbonatoms be the condensation reaction of 6-15 and the compound with 1-3 phenolic hydroxyl group and synthetic; (b) molecular weight is 800-5000.

In the radiation-ray sensitive composition of the present invention, the content of ring compound B is more than the 50 weight % of solids component gross weight.

Ring compound B has the structure that acid dissociation functional group is arranged at least one phenolic hydroxyl group introducing of ring compound A, and molecular weight is 800-5000, wherein said ring compound A is for being the phenyl aldehyde of 10-24 by having the substituent carbonatoms that contains alicyclic ring or aromatic nucleus, or do not have the phenyl aldehyde that any one carbonatoms in hydroxyl and the tertiary butyl is 7-24 (below, aromatic carbonyl A1 respectively calls oneself), with carbonatoms be the condensation reaction of 6-15 and the compound with 1-3 phenolic hydroxyl group (below, be called phenolic compound A2) and synthetic.

Ring compound A can be by being selected from more than one compounds in the group of being made up of aromatic carbonyl A1, obtaining with the condensation reaction that is selected from more than one compounds in the group of being made up of phenolic compound A2.

Aromatic carbonyl A1 is the phenyl aldehyde of 7-24 for any one the carbonatoms that does not have in hydroxyl and the tertiary butyl; or to have the substituent carbonatoms that contains alicyclic ring or aromatic nucleus be the phenyl aldehyde of 10-24; can enumerate for example phenyl aldehyde; tolyl aldehyde; dimethylbenzaldehyde; ethylbenzene formaldehyde; propylbenzene formaldehyde; butylbenzene formaldehyde except the tertiary butyl; the ethyl-methyl phenyl aldehyde; the isopropyl methyl phenyl aldehyde; diethylbenzaldehyde; aubepine; naphthaldehyde; anthraldehyde; cyclopropyl-phenyl formaldehyde; the cyclobutyl phenyl aldehyde; the cyclopentyl phenyl aldehyde; phenylcyclohexane formaldehyde; the phenyl phenyl aldehyde; the naphthyl phenyl aldehyde; the adamantyl phenyl aldehyde; the norcamphyl phenyl aldehyde; the hydroxy propionyl group phenyl aldehyde; isopropyl benzene formaldehyde; n-propylbenzene formaldehyde; bromobenzaldehyde and dimethylaminobenzaldehyde etc.; be preferably isopropyl benzene formaldehyde; n-propylbenzene formaldehyde; bromobenzaldehyde and dimethylaminobenzaldehyde; phenylcyclohexane formaldehyde; phenyl phenyl aldehyde, more preferably phenylcyclohexane formaldehyde; 4-isopropyl benzene formaldehyde and 4-n-propylbenzene formaldehyde.

In the scope of not damaging effect of the present invention, aromatic carbonyl A1 also can have straight or branched alkyl that carbonatoms is 1-4, cyano group, halogen etc.Aromatic carbonyl A1 can be used alone or in combination of two or more.

As the example of phenolic compound A2, can enumerate phenol, pyrocatechol, Resorcinol, Resorcinol, pyrogallol etc., be preferably Resorcinol, pyrogallol, more preferably Resorcinol.In the scope of not damaging effect of the present invention, phenolic compound A2 also can have straight or branched alkyl that carbonatoms is 1-4, cyano group, hydroxyl, halogen etc.Phenolic compound A2 can be used alone or in combination of two or more.

About ring compound A, as about as described in as described in the formula (4), (5) and (6).

More preferably use two or more aromatic carbonyl A1 and/or two or more phenolic compound A2.By using two or more aromatic carbonyl A1 and/or two or more phenolic compound A2, can improve the solvability of the semi-conductor safety solvent of ring compound A that obtains.

Ring compound A can form amorphous film by spin coating.In addition, go in the general semiconductor preparing process.

The amorphous film of ring compound A dissolution rate to Tetramethylammonium hydroxide (TMAH) aqueous solution of 2.38 quality % under 23 ℃ is preferably

More than, more preferably

More preferably

For

When above, can be dissolved in alkaline-based developer, become resist.In addition, have During following dissolution rate, the situation that also has resolving power to improve.In addition, has the effect that reduces LER, reduces defective.

Described acid dissociation functional group selects use aptly in the acid dissociation functional group that can propose in the employed hydroxy styrenes resinoid of chemical amplification type anti-corrosion agent composition that is used for KrF or ArF, (methyl) acrylic resin etc.Preference as: substituent methyl, 1-replace ethyl, 1-replaces n-propyl, 1-branched-chain alkyl, silyl, acyl group, 1-substituted alcoxyl methyl, cyclic ethers base and carbalkoxy etc.Described acid dissociation functional group does not preferably have bridging property functional group.

The molecular weight of ring compound B is 800-5000, is preferably 800-2000, more preferably 1000-2000.In the time of in above-mentioned scope, resist can keep necessary film-forming properties, and resolving power is improved.

Ring compound among the present invention can obtain cis body and trans body, can be any structure or mixture.As the resist composition of radiation-ray sensitive composition the time, only have under any one the situation of structure in cis body and the trans body, become the pure substance compound, and the homogeneity height of the composition in the resist film, thereby preferred.Only had any one the method for ring compound of structure in cis body and the trans body, for example can use: utilizing column chromatography or the preparation separation carried out of liquid-liquid chromatography or in the preparation, known method such as optimization such as reaction solvent and temperature of reaction are carried out.

In a kind of mode of the present invention, ring compound B is preferably the compound shown in the following formula (18).

[Chemical formula 2 7]

(in the formula, R ⁴Be functional group in the alkyl silane of 1-20 and the group that their derivative is formed for being selected from by hydrogen atom, carbonatoms are the alkyl (still, removing the tertiary butyl) of 1-20, cycloalkyl that carbonatoms is 3-20, carbonatoms is 6-20 aryl, alkoxyl group, cyano group, nitro, heterocyclic radical, halogen, carboxyl, carbonatoms that carbonatoms is 1-20; L, R ¹, R ⁵, identical in p and the above-mentioned formula (1), at least one R ¹Be acid dissociation functional group.）

Above-mentioned ring compound B is preferably the compound shown in following formula (19), (19-0), more preferably the compound shown in formula (19-1), the formula (10-0-1).

[Chemical formula 2 8]

(in the formula, L, R ¹, R ⁴, p is same as described above.）

[Chemical formula 2 9]

(in the formula, R ¹, R ⁴, p, m be same as described above.）

[chemical formula 30]

(in the formula, R ¹, R ⁴, p, m ₃, m ₄Same as described above.）

[chemical formula 31]

(in the formula, R ¹, R ⁴, p is same as described above.）

Above-mentioned ring compound B more preferably is selected from the compound of the compound shown in following formula (20) or the formula (21).

[chemical formula 32]

[chemical formula 33]

(in the formula, R ¹Identical with described formula (18).）

In formula (20) and the formula (21), R ¹Be that to replace ethyl, carbonatoms be that the 1-of 4-20 replaces acid dissociation functional group or the hydrogen atom in 1-branched-chain alkyl that n-propyl, carbonatoms are 3-20, silyl that carbonatoms is 1-20, acyl group that carbonatoms is 2-20,1-substituted alkoxy alkyl that carbonatoms is 2-20, cyclic ethers base that carbonatoms is 2-20, carbalkoxy that carbonatoms is 2-20 and the group that alkoxycarbonyl alkyl is formed, R for the substituent methyl of 2-20,1-that carbonatoms is 3-20 for being selected from by carbonatoms independently ¹In at least one be preferably acid dissociation functional group.

About be selected from by substituent methyl, carbonatoms be the 1-of 3-20 replace ethyl, carbonatoms be the 1-of 4-20 replace in 1-branched-chain alkyl that n-propyl, carbonatoms are 3-20, silyl that carbonatoms is 1-20, acyl group that carbonatoms is 2-20,1-substituted alkoxy alkyl that carbonatoms is 2-20, cyclic ethers base that carbonatoms is 2-20, carbalkoxy that carbonatoms is 2-20 and the group that alkoxycarbonyl alkyl is formed acid dissociation functional group as mentioned above.

In these acid dissociation functional groups, be preferably substituent methyl, 1-replacement ethyl, 1-substituted alcoxyl methyl, cyclic ethers base, carbalkoxy and alkoxycarbonyl alkyl, substituent methyl, 1-replace ethyl, carbalkoxy and alkoxycarbonyl alkyl because more preferred for high sensitive, further preferably have the acid dissociation functional group that is selected from the structure in the aromatic nucleus that cycloalkanes, lactone and carbonatoms that carbonatoms is 3-12 are 6-12.Being the cycloalkanes of 3-12 as carbonatoms, can be that monocycle also can be many rings, more preferably many rings.Concrete example can be enumerated mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane etc.; More specifically, can enumerate the mononaphthene of cyclopropane, tetramethylene, pentamethylene, hexanaphthene etc., the polynaphthene of diamantane, norbornane, iso-borneol alkane, tristane, Fourth Ring decane etc.Wherein, be preferably diamantane, three cycloalkanes, tetracycloalkane, be preferably diamantane, three cycloalkanes especially.Carbonatoms is that the cycloalkanes of 3-12 also can have substituting group.As lactone, the carbonatoms that can enumerate butyrolactone or have a lactone group is the cycloalkyl of 3-12.Be the aromatic nucleus of 6-12 as carbonatoms, can enumerate phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, pyrene ring etc., be preferably phenyl ring, naphthalene nucleus, be preferably naphthalene nucleus especially.

Especially the acid dissociation functional group resolving power height shown in the following formula (22), thus preferred.

[chemical formula 34]

With respect to total constituting atom number of described ring compound B, the ratio of halogen atom number is preferably 0.1-60%, 0.1-40% more preferably, and more preferably 0.1-20% is preferably 0.1-10% especially, most preferably is 1-5%.In the time of in above-mentioned scope, to the susceptibility rising of radioactive rays, and can keep film-forming properties.In addition, can improve the safety solvent solvability.

With respect to total constituting atom number of described ring compound B, the ratio of nitrogen-atoms number is preferably 0.1-40%, 0.1-20% more preferably, and more preferably 0.1-10% is preferably 0.1-5% especially.In the time of in above-mentioned scope, the line edge roughness of the resist pattern that can reduce to obtain, and can keep film-forming properties.In addition, as nitrogen-atoms, be preferably the nitrogen-atoms that is contained in secondary amine or the tertiary amine, more preferably be contained in the nitrogen-atoms in the tertiary amine.

In the present invention, so-called acid dissociation functional group refers to division in the presence of acid and produces the characteristic group of alkali-soluble group.As the alkali-soluble group, can enumerate phenolic hydroxyl group, carboxyl, sulfonic group, hexafluoroisopropanol base etc., preferred phenolic hydroxyl group and carboxyl, preferred especially phenolic hydroxyl group.In order to form the more figure of high sensitive very high resolution, described acid dissociation functional group preferably has the character that causes dissociative reaction in the presence of acid chainly.

The ring compound B of formula (20) or formula (21) has film-forming properties, thermotolerance, anti-dry etching, low ease gas simultaneously owing to be low-molecular weight compound, thereby preferred resist composition as radiation-ray sensitive composition.The radiation-ray sensitive composition that contains the ring compound B of formula (20) ~ formula (21) has good resolving power, susceptibility, low line edge roughness.

Ring compound B of the present invention, except can be himself being that main component forms the positive radiation line sensitive compositions, can be not as main component, and improve susceptibility or improve the additive of elching resistant and add radiation-ray sensitive composition to as for example being used for.At this moment, ring compound B can be used with the 1-49.999 weight % of solids component gross weight.

Ring compound B can form amorphous film by spin coating.In addition, go in the general semiconductor preparing process.

In the scope of not damaging effect of the present invention, also can be in the non-acid dissociation of at least one phenolic hydroxyl group introducing functional group of ring compound B.So-called non-acid dissociation functional group refers to not divide, do not produce the characteristic group of alkali-soluble group in the presence of acid.For example can enumerate: not the decomposition that is caused by the effect of acid, be selected from functional group in the group of being formed by the alkyl silane of the alkoxyl group of the aryl of the cycloalkyl of the alkyl of C1-20, C3-20, C6-20, C1-20, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, carboxyl, C1-20, their derivative etc.

Also can introduce diazido naphthoquinones ester group (Na Off トキノ Application ジアジ De エステ Le base) at least one phenolic hydroxyl group of ring compound B of the present invention.Introduced the compound of diazido naphthoquinones ester group at least one phenolic hydroxyl group of ring compound B, except forming the positive radiation line sensitive compositions as main component with himself, can be used as acidogenic agent or additive and add in the radiation-ray sensitive composition.

Also can introduce the acidic product acidic functionality by the irradiation radioactive rays at least one phenolic hydroxyl group of ring compound B.Introduced the ring-type polyphenolic substance of acidic product acidic functionality by the irradiation radioactive rays at least one phenolic hydroxyl group of ring compound B, except forming the positive radiation line sensitive compositions as main component with himself, can be used as acidogenic agent or additive and add in the radiation-ray sensitive composition.

The amorphous film of ring compound B dissolution rate to the TMAH aqueous solution of 2.38 quality % under 23 ℃ is preferably

Below, more preferably

More preferably

For

During above dissolution rate, the situation that has resolving power to improve.Infer that this is because the small surperficial position of described ring compound B is dissolved, has reduced the cause of LER.In addition, reduce the effect of defective in addition.

The acid dissociation functional group of ring compound B dissociates and the ring compound A that generates, also preferably has the character that forms amorphous film by spin coating.The amorphous film of ring-type polyphenolic substance A dissolution rate to the TMAH aqueous solution of 2.38 quality % under 23 ℃ is preferably

More than, more preferably

More preferably

For

During following dissolution rate, the situation that also has resolving power to improve.Infer that this is because by the caused deliquescent variation of being dissociated by the acid dissociation functional group of described ring compound B, make the big cause of contrast change at interface that is dissolved in the exposure portion of alkaline-based developer and is not dissolved in the unexposed portion of alkaline-based developer.In addition, has the effect that reduces LER, reduces defective.

The solids component of radiation-ray sensitive composition can be by spin coating to form amorphous film.The solids component of spin coating radiation-ray sensitive composition and the amorphous film that the forms dissolution rate to the TMAH aqueous solution of 2.38 quality % under 23 ℃ is preferably

Below.By described amorphous film is shone KrF excimer laser, extreme ultraviolet, electron rays or X ray isoradial, be exposed to desired figure, the dissolution rate at the TMAH aqueous solution of relative 2.38 quality % under 23 ℃ of the amorphous film after the heating under 20-250 ℃ is preferably as required

In radiation-ray sensitive composition of the present invention, preferably contain the solids component of 1-80 weight % and the solvent of 20-99 weight %, more preferably contain the solids component of 1-50 weight % and the solvent of 50-99 weight %, further preferably contain the solids component of 2-40 weight % and the solvent of 60-98 weight %, especially preferably contain the solids component of 2-10 weight % and the solvent of 90-98 weight %.The amount of ring compound B is more than the 50 weight % of solids component gross weight, is preferably more than the 65 weight %, more preferably more than the 81 weight %.During for above-mentioned mix proportions, can obtain very high resolution, line edge roughness diminishes.

Composition of the present invention preferably contains more than one acidogenic agent C, this acidogenic agent C by radioactive rays irradiation and produce acid directly or indirectly, described radioactive rays are for being selected from any one the radioactive rays in visible rays, ultraviolet ray, excimer laser, electron rays, extreme ultraviolet (EUV), X ray and the ionic fluid.The usage quantity of acidogenic agent is preferably the solids component gross weight (summation of the solids component that is free to use among ring-type polyphenolic substance B, acidogenic agent C, lower molecular weight dissolution accelerator D, sour diffusion control agent E and other the composition F etc., below same) 0.001-50 weight %, more preferably 1-40 weight %, more preferably 3-30 weight %.By in above-mentioned scope, using acidogenic agent, can obtain the graph outline of high sensitive and low edge roughness.In the present invention, as long as can produce acid in system, the production method of acid is just unqualified.Use excimer laser if replacement g line, i line etc. are ultraviolet, can carry out finer processing; In addition, if use electron rays, extreme ultraviolet, X ray, ionic fluid as high-energy rays, can carry out finer processing.

As described acidogenic agent C, be preferably at least a compound that is selected from the group of being formed by the compound shown in the following formula (23-1)-(23-8).

[chemical formula 35]

(in the formula (23-1), R ¹³Can be the same or different, be hydrogen atom respectively independently, straight chain shape, chain or cyclic alkyl, straight chain shape, chain or cyclic alkoxy, hydroxyl, or halogen atom; X ^-Be azochlorosulfonate acid ion or the halide ions with alkyl, aryl, haloalkyl or halogenated aryl.）

Compound shown in the above-mentioned formula (23-1), be preferably and be selected from by trifluoromethanesulfonic acid triphenyl sulfonium salt, the positive fourth sulfonic acid of nine fluorine triphenyl sulfonium salt, the positive fourth sulfonic acid of nine fluorine diphenylmethyl phenyl sulfonium salt, the positive hot sulfonic acid triphenyl sulfonium salt of perfluor, trifluoromethanesulfonic acid phenylbenzene-4-aminomethyl phenyl sulfonium salt, trifluoromethanesulfonic acid two-2,4,6-trimethylphenyl sulfonium salt, trifluoromethanesulfonic acid phenylbenzene-4-tert.-butoxy phenyl sulfonium salt, the positive fourth sulfonic acid phenylbenzene of nine fluorine-4-tert.-butoxy phenyl sulfonium salt, trifluoromethanesulfonic acid phenylbenzene-4-hydroxy phenyl sulfonium salt, two (4-the fluorophenyl)-4-hydroxy phenyl sulfonium salts of trifluoromethanesulfonic acid, the positive fourth sulfonic acid phenylbenzene of nine fluorine-4-hydroxy phenyl sulfonium salt, two (4-the hydroxy phenyl)-phenyl sulfonium salts of trifluoromethanesulfonic acid, trifluoromethanesulfonic acid three (4-p-methoxy-phenyl) sulfonium salt, trifluoromethanesulfonic acid three (4-fluorophenyl) sulfonium salt, tosic acid triphenyl sulfonium salt, Phenylsulfonic acid triphenyl sulfonium salt, tosic acid phenylbenzene-2,4,6-trimethylphenyl sulfonium salt (ジ Off エニ Le-2,4,6-トリメチ Le Off エニ Le-p-ト Le エ Application ス Le ホネ one ト), 2-trifluoromethyl Phenylsulfonic acid phenylbenzene-2,4,6-trimethylphenyl sulfonium salt, 4-trifluoromethyl Phenylsulfonic acid phenylbenzene-2,4,6-trimethylphenyl sulfonium salt, 2,4-difluoro Phenylsulfonic acid phenylbenzene-2,4,6-trimethylphenyl sulfonium salt, phenyl-hexafluoride sulfonic acid phenylbenzene-2,4,6-trimethylphenyl sulfonium salt, trifluoromethanesulfonic acid phenylbenzene naphthyl sulfonium salt, tosic acid phenylbenzene-4-hydroxy phenyl sulfonium salt, 10-camphorsulfonic acid triphenyl sulfonium salt, 10-camphorsulfonic acid phenylbenzene-4-hydroxy phenyl sulfonium salt and encircle at least a in the group that 1,3-perfluoropropane disulfonyl imines forms.

[chemical formula 36]

(in the formula (23-2), R ¹⁴Can be the same or different, be hydrogen atom respectively independently, straight chain shape, chain or cyclic alkyl, straight chain shape, chain or cyclic alkoxy, hydroxyl or halogen atom; X ^-Same as described above.）

By the compound shown in the above-mentioned formula (23-2), be preferably and be selected from by two (4-tert-butyl-phenyl) iodine fluoroform sulphonate, the positive fourth sulfonate of two (4-tert-butyl-phenyl) iodine nine fluorine, the positive hot sulfonate of two (4-tert-butyl-phenyl) iodine perfluor, two (4-tert-butyl-phenyl) iodine tosilate, two (4-tert-butyl-phenyl) iodobenzene sulfonate, two (4-tert-butyl-phenyl) iodo-2-trifluoromethyl benzene sulfonate, two (4-tert-butyl-phenyl) iodo-4-trifluoromethyl benzene sulfonate, two (4-tert-butyl-phenyl) iodo-2,4-difluoro benzene sulfonate, two (4-tert-butyl-phenyl) iodine phenyl-hexafluoride sulfonate, two (4-tert-butyl-phenyl) iodo-10-camsilate, phenylbenzene iodine fluoroform sulphonate, the positive fourth sulfonate of phenylbenzene iodine nine fluorine, the positive hot sulfonate of phenylbenzene iodine perfluor, phenylbenzene iodine tosilate, phenylbenzene iodobenzene sulfonate, phenylbenzene iodo-10-camsilate, phenylbenzene iodo-2-trifluoromethyl benzene sulfonate, phenylbenzene iodo-4-trifluoromethyl benzene sulfonate, phenylbenzene iodo-2,4 difluorobenzene sulfonate, phenylbenzene iodine phenyl-hexafluoride sulfonate, two (4-trifluoromethyl) iodine fluoroform sulphonate, the positive fourth sulfonate of two (4-trifluoromethyl) iodine nine fluorine, the positive hot sulfonate of two (4-trifluoromethyl) iodine perfluor, two (4-trifluoromethyl) iodine tosilate, at least a in the group that two (4-trifluoromethyl) iodobenzene sulfonate and two (4-trifluoromethyl) iodo-10-camsilate is formed.

[chemical formula 37]

(in the formula (23-3), Q is alkylidene group, arylidene or alkylene oxide group; R ¹⁵Be alkyl, aryl, haloalkyl or halogenated aryl.）

By the compound shown in the above-mentioned formula (23-3), be preferably and be selected from the succinimide by N-(trifluoromethyl sulfonyloxy), N-(trifluoromethyl sulfonyloxy) phthalic imidine, N-(trifluoromethyl sulfonyloxy) xenyl maleimide, N-(trifluoromethyl sulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl imide, N-(trifluoromethyl sulfonyloxy) naphthalimide, N-(10-camphor sulfonyloxy) succinimide, N-(10-camphor sulfonyloxy) phthalic imidine, N-(10-camphor sulfonyloxy) xenyl maleimide, N-(10-camphor sulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl imide, N-(10-camphor sulfonyloxy) naphthalimide, N-(octane sulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl imide, N-(octane sulfonyloxy) naphthalimide, N-(tolysulfonyl oxygen base) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl imide, N-(tolysulfonyl oxygen base) naphthalimide, N-(2-trifluoromethyl phenylsulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl imide, N-(2-trifluoromethyl phenylsulfonyloxy) naphthalimide, N-(4-trifluoromethyl phenylsulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl imide, N-(4-trifluoromethyl phenylsulfonyloxy) naphthalimide, N-(perfluor phenylsulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl imide, N-(perfluor phenylsulfonyloxy) naphthalimide, N-(1-naphthalene sulfonyl oxygen base) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl imide, N-(1-naphthalene sulfonyl oxygen base) naphthalimide, N-(nine fluorine normal butane sulfonyloxies) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl imide, N-(nine fluorine normal butane sulfonyloxies) naphthalimide, N-(perfluor octane sulfonyloxy) two ring [2.2.1] heptan-5-alkene-2, at least a in the group that 3-dicarboxyl imide and N-(perfluor octane sulfonyloxy) naphthalimide is formed.

[chemical formula 38]

(in the formula (23-4), R ¹⁶Can be the same or different, be respectively straight chain, side chain or the cyclic alkyl that replaces arbitrarily independently, any aryl that replaces, the heteroaryl that replaces or the aralkyl of replacement arbitrarily arbitrarily.）

By the compound shown in the above-mentioned formula (23-4), be preferably and be selected from least a in the group of being formed by phenylbenzene two sulfones, two (4-aminomethyl phenyl) two sulfones, dinaphthyl two sulfones, two (4-tert-butyl-phenyl) two sulfones, two (4-hydroxy phenyl) two sulfones, two (3-hydroxyl naphthyl) two sulfones, two (4-fluorophenyl) two sulfones, two (2-fluorophenyl) two sulfones and two (4-trifluoromethyl) two sulfones.

[chemical formula 39]

(in the formula (23-5), R ¹⁷Can be the same or different, be respectively straight chain, straight chain or the cyclic alkyl that replaces arbitrarily independently, any aryl that replaces, the heteroaryl that replaces or the aralkyl of replacement arbitrarily arbitrarily.）

By the compound shown in the above-mentioned formula (23-5), be preferably and be selected from by α-(sulfonyloxy methyl oxygen base imino-) phenylacetonitrile, α-(sulfonyloxy methyl oxygen base imino-)-4-p-methoxy-phenyl acetonitrile, α-(trifluoromethyl sulfonyloxy imino-) phenylacetonitrile, α-(trifluoromethyl sulfonyloxy imino-)-4-p-methoxy-phenyl acetonitrile, α-(ethyl sulfonyloxy imino-)-4-p-methoxy-phenyl acetonitrile, at least a in the group that α-(sulfonyl propyl oxygen base imino-)-4-aminomethyl phenyl acetonitrile and α-(sulfonyloxy methyl oxygen base imino-)-4-bromophenyl acetonitrile is formed.

[chemical formula 40]

In the formula (23-6), R ¹⁸Can be the same or different, respectively independently for having chlorine atom more than 1 and the haloalkyl of the bromine atoms more than 1.The preferred 1-5 of the carbonatoms of haloalkyl.

[chemical formula 41]

[chemical formula 42]

Formula (23-7) and (23-8) in, R ¹⁹And R ²⁰Be the alkyl of 1-3 for carbonatoms independently respectively, as methyl, ethyl, n-propyl, sec.-propyl etc., cycloalkyl, as cyclopentyl, cyclohexyl etc., carbonatoms is the alkoxyl group of 1-3, as methoxyl group, oxyethyl group, propoxy-etc., perhaps aryl, as phenyl, tolyl, naphthyl etc., be preferably the aryl that carbonatoms is 6-10.L ¹⁹And L ²⁰Independent of having the organic group of 1,2-diazido naphthoquinones respectively.As the preferred example of the organic group with 1,2-diazido naphthoquinones, can enumerate 1 particularly; 2-diazido naphthoquinones alkylsulfonyl is as 1,2-diazido naphthoquinones-4-alkylsulfonyl, 1; 2-diazido naphthoquinones-5-alkylsulfonyl, 1,2-diazido naphthoquinones-6-alkylsulfonyl etc.Preferred especially 1,2-diazido naphthoquinones-4-alkylsulfonyl and 1,2-diazido naphthoquinones-5-alkylsulfonyl.P is the integer of 1-3, and q is the integer of 0-4, and 1 ≦ p+q ≦ 5.J ¹⁹Be group, carbonyl, ester group, amide group or the ether shown in the polymethylene of singly-bound, carbonatoms 1-4, ring alkylidene group, phenylene, the following formula (23-7-1); Y ¹⁹Be hydrogen atom, alkyl or aryl; X ²⁰Be the group shown in the following formula (23-8-1) independently of one another.

[chemical formula 43]

[chemical formula 44]

(in the formula (23-8-1), Z ²²Be alkyl, cycloalkyl or aryl independently of one another; R ²²Be alkyl, cycloalkyl or alkoxyl group; R is the integer of 0-3.）

As other acidogenic agent, can enumerate disulfonyl basic weight n-formyl sarcolysine alkanes, as two (p-toluenesulfonyl) diazomethane, two (2,4-3,5-dimethylphenyl alkylsulfonyl) diazomethane, two (tertiary butyl alkylsulfonyl) diazomethane, two (normal-butyl alkylsulfonyl) diazomethane, two (isobutyl-alkylsulfonyl) diazomethane, two (sec.-propyl alkylsulfonyl) diazomethane, two (n-propyl alkylsulfonyl) diazomethane, two (cyclohexyl alkylsulfonyl) diazomethane, two (sec.-propyl alkylsulfonyl) diazomethane, 1,3-two (cyclohexyl alkylsulfonyl azido-methyl alkylsulfonyl) propane, 1,4-two (phenyl sulfonyl azido-methyl alkylsulfonyl) butane, 1,6-two (phenyl sulfonyl azido-methyl alkylsulfonyl) hexane, 1,10-two (cyclohexyl alkylsulfonyl azido-methyl alkylsulfonyl) decane etc.; The pyrrolotriazine derivatives that contains halogen, as 2-(4-p-methoxy-phenyl)-4,6-two (trichloromethyl)-1,3,5-triazine, 2-(4-methoxyl group naphthyl)-4,6-two (trichloromethyl)-1,3,5-triazines, three (2, the 3-dibromopropyl)-1,3,5-triazine, three (2,3-dibromopropyl) isocyanuric acid ester etc.

In the above-mentioned acidogenic agent, preferably have the acidogenic agent of aromatic nucleus, more preferably formula (23-1) or (23-2) shown in acidogenic agent.The X that further preferably has formula (23-1) or formula (23-2) ^-For having the acidogenic agent of the azochlorosulfonate acid ion that contains aryl or halogenated aryl, the acidogenic agent that especially preferably has the azochlorosulfonate acid ion that contains aryl, preferred especially: tosic acid phenylbenzene (trimethylammonium) phenyl sulfonium salt, tosic acid triphenyl sulfonium salt, trifluoromethanesulfonic acid triphenyl sulfonium salt, nine fluorine methylsulfonic acid triphenyl sulfonium salts.By using this acidogenic agent, can reduce LER.

Above-mentioned acidogenic agent C can independent or two or more uses.

Lower molecular weight dissolution accelerator D, when low for crossing in the solvability of the developing solution of the alkali of ring compound B etc., have the composition that improves its solvability and suitably increase the effect of the dissolution rate of ring compound B when developing, can in the scope of not damaging effect of the present invention, use.As this dissolution accelerator, can enumerate for example low-molecular-weight phenolic compound, for example can enumerate bisphenols, three (hydroxy phenyl) methane etc.These dissolution accelerators can use in independent or two or more mixing.The blended amount of dissolution accelerator, can suit according to the kind of employed described ring compound B to regulate, the summation of ring compound B and low molecular melting vulkacit D is the 50-99.999 weight % of the gross weight of solids component, be preferably 60-99 weight %, more preferably 70-99 weight %, more preferably 80-99 weight %.

Lower molecular weight dissolution accelerator D is preferably the compound that is selected among the above-mentioned ring compound A.Ring compound A is lower molecular weight, has high heat resistance, amorphism simultaneously, and with the affinity height of ring compound B, can form uniform resist film, can give performances such as very high resolution, low LER.As the ring compound A of lower molecular weight dissolution accelerator D, more preferably identical with ring compound A for the manufacture of ring compound B.The affinity of ring compound B and lower molecular weight dissolution accelerator D further increases, and can form more uniform resist film, can give performances such as very high resolution, low LER.

In the present invention, also can be in radiation-ray sensitive composition fusion acid diffusion control agent E, described sour diffusion control agent E has diffusion in resist film of acid that inhibition produces by acidogenic agent by radiation exposure, stop in the effect of the chemical reaction of not expecting of unexposed area etc.By using so sour diffusion control agent E, resolving power is improved, can suppress simultaneously the line width variation by the caused resist pattern of change of storage period of electron rays pre-irradiation, electron rays postradiation storage period, technology stability is extremely excellent.And by using sour diffusion control agent E, the storage stability of radiation-ray sensitive composition is improved.As so sour diffusion control agent E, can enumerate electron rays radiation decomposability basic cpds such as the basic cpd of nitrogen atom, alkaline sulfonium compound, alkaline iodine compound.The agent of acid diffusion control can independent or two or more uses.

As above-mentioned sour diffusion control agent, for example can enumerate organic compounds containing nitrogen, by exposing basic cpd that causes decomposition etc. to the open air.As above-mentioned organic compounds containing nitrogen, for example can enumerate the compound shown in the following general formula (24) (below, be called " nitrogenous compound I ".), in a part, have two nitrogen-atoms diamino compounds (below, be called " nitrogenous compound II ".), have the polyamino compound of three above nitrogen-atoms or polymkeric substance (below, be called " nitrogenous compound III ".), amide-containing compound, carbamide compound and nitrogen-containing heterocycle compound etc.And above-mentioned sour diffusion control agent can be used alone, also can two or more and usefulness.

[chemical formula 45]

In the above-mentioned general formula (24), R ⁶¹, R ⁶²And R ⁶³Be hydrogen atom independently of one another, straight chain shape, chain or cyclic alkyl, aryl or aralkyl.In addition, abovementioned alkyl, aryl or aralkyl can not be substituted, and can be replaced by other functional group such as hydroxyl yet.At this, as above-mentioned straight chain shape, chain or cyclic alkyl, for example can enumerate that carbon atom is 1-15, be preferably the group of 1-10, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, n-hexyl, uncle's hexyl (テキシ Le base), n-heptyl, n-octyl, positive ethylhexyl, n-nonyl, positive decyl etc. particularly.In addition, as above-mentioned aryl, the group that carbonatoms is 6-12 can be enumerated, phenyl, tolyl, xylyl, cumyl, 1-naphthyl etc. can be enumerated particularly.Further, the group that as above-mentioned aralkyl, can to enumerate carbonatoms be 7-19, be preferably 7-13 can be enumerated benzyl, α-Jia Jibianji, styroyl, menaphthyl etc. particularly.

As above-mentioned nitrogenous compound I, for example can enumerate particularly: single (ring) alkanamine class, as normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-dodecane amine, hexahydroaniline etc., two (ring) alkanamine class, as Di-n-Butyl Amine, two n-amylamines, two normal hexyl Amines, two positive heptyl amices, two n-octyl amine, two positive nonyl amines, two n-Decylamines, methyl n-dodecane amine, two dodecyl methylamines, the cyclohexyl methylamine, dicyclohexyl amine etc., three (ring) alkanamine class, as triethylamine, Tri-n-Propylamine, tri-n-butylamine, tri-n-amyl amine, three normal hexyl Amines, three positive heptyl amices, tri-n-octyl amine, tri-n-nonylamine, three n-Decylamines, the dimethyl n n-Laurylamine, two dodecyl methylamines, the dicyclohexyl methylamine, tricyclohexyltin amine etc., the alkanol amine, as monoethanolamine, diethanolamine, trolamine etc., aromatic amine, as aniline, methylphenylamine, N, accelerine, 2-aminotoluene, the 3-monomethylaniline, the 4-monomethylaniline, the 4-N-methyl-p-nitroaniline, pentanoic, triphenylamine, naphthalidine etc.

As above-mentioned nitrogenous compound II, can enumerate for example quadrol particularly, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N, N ', N '-four (2-hydroxypropyl) quadrol, tetramethylene-diamine, hexamethylene-diamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 4,4 '-diaminobenzophenone, 4,4 '-diamino-diphenylamine, two (4-aminophenyl) propane of 2,2-, 2-(3-aminophenyl)-2-(4-aminophenyl) propane, 2-(4-aminophenyl)-2-(3-hydroxy phenyl) propane, 2-(4-aminophenyl)-2-(4-hydroxy phenyl) propane, 1, two [1-(4-the aminophenyl)-1-methylethyl] benzene of 4-, two [1-(4-aminophenyl)-1-methylethyl] benzene of 1,3-etc.

As above-mentioned nitrogenous compound III, can enumerate particularly, for example polymkeric substance of polymine, many arylamine, N-(2-dimethylaminoethyl) acrylamide etc.

As above-mentioned amide-containing compound, can enumerate particularly, for example methane amide, N-methylformamide, N, dinethylformamide, ethanamide, N-methylacetamide, N,N-dimethylacetamide, propionic acid amide, benzamide, pyrrolidone, N-Methyl pyrrolidone etc.

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

As above-mentioned nitrogen-containing heterocycle compound, for example can enumerate particularly, imidazoles, as imidazoles, benzoglyoxaline, 4-methylimidazole, 4-methyl-2-phenylimidazole, 2-Phenylbenzimidazole etc., pyridines, as pyridine, the 2-picoline, the 4-picoline, the 2-ethylpyridine, the 4-ethylpyridine, the 2-phenylpyridine, the 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, niacinamide, quinoline, 8-oxygen quinoline, acridine etc., and pyrazine, pyrazoles, pyridazine, quinoxaline, purine, tetramethyleneimine, piperidines, morpholine, the 4-methylmorpholine, piperazine, 1, the 4-lupetazin, 1,4-diazabicylo [2.2.2] octane etc.

In addition, cause the basic cpd of decomposition as above-mentioned by exposure, can enumerate iodine compound shown in the sulfonium compound shown in the following formula (25-1) for example and the following general formula (25-2) etc.

[chemical formula 46]

[chemical formula 47]

Above-mentioned general formula (25-1) and (25-2) in, R ⁷¹, R ⁷², R ⁷³, R ⁷⁴And R ⁷⁵Represent that independently of one another hydrogen atom, carbonatoms are the alkyl of 1-6, alkoxyl group, hydroxyl or the halogen atom that carbonatoms is 1-6.Z ^-Be HO ^-, R-COO ^-Negatively charged ion shown in (still, R represents that carbonatoms is that the alkyl of 1-6, aryl or the carbonatoms that carbonatoms is 1-6 are the alkaryl of 1-6) or the following general formula (25-3).

[chemical formula 48]

Cause the basic cpd of decomposition as above-mentioned by exposure, for example can enumerate particularly: hydroxide triphenyl sulfonium salt (triphenylsulfonium hydroxide), acetic acid triphenyl sulfonium salt, Whitfield's ointment triphenyl sulfonium salt, hydroxide phenylbenzene-4-hydroxy phenyl sulfonium salt, acetic acid phenylbenzene-4-hydroxy phenyl sulfonium salt, Whitfield's ointment phenylbenzene-4-hydroxy phenyl sulfonium salt, two (4-tert-butyl-phenyl) salt compounded of iodine (bis (4-t-butylphenyl) iodonium hydroxide) of hydroxide, two (4-tert-butyl-phenyl) salt compounded of iodine of acetic acid, two (4-tert-butyl-phenyl) salt compounded of iodine of hydroxide, two (4-tert-butyl-phenyl) salt compounded of iodine of acetic acid, two (4-tert-butyl-phenyl) salt compounded of iodine of Whitfield's ointment, hydroxide 4-tert-butyl-phenyl-4-hydroxy phenyl salt compounded of iodine, acetic acid 4-tert-butyl-phenyl-4-hydroxy phenyl salt compounded of iodine, Whitfield's ointment 4-tert-butyl-phenyl-4-hydroxy phenyl salt compounded of iodine etc.

The blended amount of acid diffusion control agent E is preferably the 0-10 weight % of solids component gross weight, more preferably 0.001-5 weight %, 0.001-3 weight % more preferably.The blended amount of described sour diffusion control agent E is in the above-mentioned scope time, can prevent the reduction of resolving power, variation such as graphics shape, size naturalness.And even elongated from the storage period that electron rays irradiation begins till the radiation exposure post-heating, the shape of graphic design portion can variation yet.In addition, the blended amount of described sour diffusion control agent E is 10 weight % when following, can prevent the reduction of the development etc. in susceptibility, territory, non-exposed area.In addition, by using so sour diffusion control agent, the storage stability of resist composition is improved, and resolving power is improved, can suppress simultaneously the line width variation by the caused resist pattern of change of storage period of electron rays pre-irradiation, electron rays postradiation storage period, thus make fusion the radiation-ray sensitive composition of described sour diffusion control agent E become the extremely excellent material of technology stability.

In the scope of not damaging purpose of the present invention, can be as required in resist composition of the present invention, add one or more various additives as other composition F, as the oxygen acid or derivatives thereof of dissolving control agent, sensitizer, tensio-active agent and organic carboxyl acid or phosphorus etc.

[1] dissolving control agent

The dissolving control agent is when the solvability of the developing solution of the alkali of ring compound B etc. is too high, has the solvability of control ring-type compd B and the composition of the effect that dissolution rate when making development moderately reduces.As such dissolving control agent, be preferably the material that chemical transformation can not take place in the operation of baking that resist is filmed, radiation exposure, development etc.

As the dissolving control agent, can enumerate for example aromatic hydrocarbon based, as naphthalene, phenanthrene, anthracene, acenaphthene etc., ketone, as methyl phenyl ketone, benzophenone, phenyl napthyl ketone etc., the sulfone class is as methyl phenyl sulfone, sulfobenzide, dinaphthyl sulfone etc.These dissolving control agents can independent or two or more uses simultaneously.

The blended amount of dissolving control agent can suit according to the kind of employed ring compound B to regulate, and for the ring compound of per 100 weight parts, is preferably below 30 weight parts, more preferably below 10 weight parts.

[2] sensitizer

Sensitizer is, has the energy of the radioactive rays that absorb irradiation and this transmission ofenergy is given acidogenic agent C, increased the effect of the growing amount of acid thus, and can improve the composition of the apparent susceptibility of resist.As such sensitizer, for example can enumerate: benzophenone, di-acetyl class, pyrene class, phenothiazines, fluorenes class etc., but there is no particular limitation.

These sensitizers can independent or two or more uses simultaneously.The blended amount of sensitizer is below 30 weight parts for the ring compound of per 100 weight parts preferably, more preferably below 10 weight parts.

[3] tensio-active agent

Tensio-active agent is the composition of effect with development etc. of the coating that improves resist composition of the present invention, grain, resist.As such tensio-active agent, can be in anionic, cationic, non-ionic type or the both sexes any one.Preferred surfactants is nonionic surface active agent.Nonionic surface active agent is good with the affinity of the solvent of the preparation that is used for radiation-ray sensitive composition, has more effect.As examples of nonionic surfactants, can enumerate the higher fatty acid diester class of polyethylene oxide senior alkyl ethers, polyethylene oxide senior alkyl phenyl ethers, polyoxyethylene glycol etc., there is no particular limitation.As commercially available product, can enumerate following with trade(brand)name, as エ Off ト Star プ (ジエ system コ society system), メガ Off ア Star Network (big Japanese イ Application キ chemical industry society system), Off ロラ one De (Sumitomo スリ one エ system society system), アサヒガ one De, サ one Off ロ Application (above is Asahi Glass society system), ペ Port one Le (chemical industry society of eastern nation system), chemical industry society of KP(SHIN-ETSU HANTOTAI system), Port リ Off ロ one (oil chemistry industry society of common prosperity society system) etc.

The blended amount of tensio-active agent, for the ring compound of per 100 weight parts, as the effective constituent of tensio-active agent, be preferably below 2 weight parts.

[4] the oxygen acid or derivatives thereof of organic carboxyl acid or phosphorus

To prevent the susceptibility deterioration, the shape, shelf-stability etc. that perhaps improve resist pattern are purpose, can further contain the organic carboxyl acid as composition arbitrarily, the oxygen acid or derivatives thereof of phosphorus in the resist composition of the present invention.And, can with sour diffusion control agent and usefulness, also can use separately.As organic carboxyl acid, suitable for example has: propanedioic acid, citric acid, oxysuccinic acid, succsinic acid, phenylformic acid, Whitfield's ointment etc.Oxygen acid or derivatives thereof as phosphorus, can enumerate phosphoric acid or derivatives thereof (as its ester etc.), as phosphoric acid, phosphoric acid di-n-butyl, diphenyl phosphate etc., phosphonic acids or derivatives thereof (as its ester etc.), as phosphonic acids, dimethyl phosphonate, phosphonic acids di-n-butyl, phenyl-phosphonic acid, phosphonic acid diphenyl ester, phosphonic acids dibenzyl ester etc., phospho acid or derivatives thereof (as its ester etc.) as phospho acid, phenyl phosphinic acid etc., wherein is preferably phosphonic acids especially.

The oxygen acid or derivatives thereof of organic carboxyl acid or phosphorus can use separately or two or more use simultaneously.The blended amount of the oxygen acid or derivatives thereof of organic carboxyl acid or phosphorus is preferably the 0-50 weight % of solids component gross weight, 0-20 weight % more preferably, and more preferably 0-5 weight % is preferably 0-1 weight % especially.

[5] additive of other beyond the oxygen acid or derivatives thereof of above-mentioned dissolving control agent, sensitizer, tensio-active agent and organic carboxyl acid or phosphorus

In the scope of not damaging purpose of the present invention, can be as required further additive beyond one or more above-mentioned dissolving control agents of fusion, sensitizer and the tensio-active agent in radiation-ray sensitive composition of the present invention.As such additive, can enumerate for example dyestuff, pigment and bonding auxiliary agent etc.For example, when fusion dyestuff or pigment, can make the latent image visibleization of exposure portion, the influence of the halation when relaxing exposure, thereby preferred.In addition, during the bonding auxiliary agent of fusion, can improve the cementability with substrate, thus preferred.Further, as other additive, antihalation agent, storage-stable agent, defoamer, Improvement in Shape agent etc. can be enumerated, 4-hydroxyl-4 '-methyl chalcone etc. can be enumerated particularly.

Radiation-ray sensitive composition of the present invention is prepared by following method usually: being dissolved in each composition in the solvent in use and forming uniform solution, is that the strainer etc. of 0.2 μ m degree filters with for example aperture afterwards as required.

As employed described solvent in the preparation of radiation-ray sensitive composition of the present invention, for example can enumerate: the ethylene glycol monoalkyl ether acetate class, as the ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, glycol monomethyl n-propyl ether acetic ester, glycol monomethyl n-butyl ether acetic ester etc., the ethylene glycol monoalkyl ether class, as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether etc., the propylene-glycol monoalky lether acetate esters, as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol list positive propyl ether acetic ester, propylene glycol mono-n-butyl ether acetic ester etc., the propylene-glycol monoalky lether class, as propylene glycol monomethyl ether, dihydroxypropane single-ether etc., lactic acid ester, as methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, lactic acid n-pentyl ester etc., the alphatic carboxylic acid ester class, as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate etc., other ester class, as 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-methoxyl group-2 Methylpropionic acid methyl esters, acetic acid 3-methoxyl group butyl ester, acetic acid 3-methyl-3-methoxyl group butyl ester, 3-methoxyl group-3-methylpropanoic acid butyl ester, 3-methoxyl group-3 Methylbutanoic acid butyl ester, methyl acetoacetate, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester etc., aromatic hydrocarbons, as toluene, dimethylbenzene etc., ketone, as 2-heptanone, the 3-heptanone, dipropyl ketone, pimelinketone etc., amides, as N, dinethylformamide, the N-methylacetamide, N, the N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone etc., lactone, as gamma lactone etc., but special the restriction not.These solvents can independent or two or more uses simultaneously.

In the scope of not damaging purpose of the present invention, radiation-ray sensitive composition of the present invention can contain the resin that dissolves in the alkaline aqueous solution.As the resin that dissolves in the alkaline aqueous solution, can enumerate: resol, polyethylene phenols, polyacrylic acid, polyvinyl alcohol, phenylethylene-maleic anhydride resin, and the polymkeric substance that contains vinylformic acid, vinyl alcohol or vinylphenol as monomeric unit, or their derivative etc.Dissolve in the blended amount of the resin of the alkaline aqueous solution, can regulate aptly according to the kind of employed resist compound, for the above-mentioned ring compound B of per 100 weight parts, be preferably 30 weight parts following, more preferably 10 weight parts following, more preferably 5 weight parts following, be preferably 0 weight part especially.

(radiation-ray sensitive composition B)

The present invention relates to radiation-ray sensitive composition; this radiation-ray sensitive composition contains ring compound B0 and solvent; described ring compound B0 has the aldehyde compound A1c of acid dissociation functional group and condensation reaction that carbonatoms is 6-15 and the phenolic compound with 1-3 phenolic hydroxyl group and synthetic by introducing; and the molecular weight of described ring compound B0 is 700-5000, and wherein carbonatoms is that 2-59 and the aldehyde compound A1 with 1-4 formyl radical are the aldehyde compound A1c with acid dissociation functional group.About each prerequisite of the synthetic method of ring compound B0, identical with the preparation method's about ring compound B0 described later (1) narration.

Ring compound B0 also can obtain by the ring compound A0 with carboxyl and the reaction with compound A-13 of halo methyl ether base.The carboxyl of ring compound A0 is high with the reactivity of the halogen of the compound A-13 with halo methyl ether base, therefore can when suppressing side reaction (as the reaction of the phenolic hydroxyl group of ring compound A0 and the halogen of the compound A-13 with halo methyl ether base etc.), react, thereby can obtain with high yield optionally introducing the ring compound B0 that acid dissociation functional group is arranged, productivity height at carboxyl.

Ring compound A0 with carboxyl for by carbonatoms be 2-59 and have 1-2 carboxyl or the aldehyde of ester group and 1-4 formyl radical (below; be called aldehyde compound A1d), with carbonatoms be the condensation reaction of 6-15 and the compound with 1-3 phenolic hydroxyl group (below, be called phenolic compound A2) and the molecular weight that has 1-8 carboxyl in synthetic, the molecule is the ring compound A0 of 800-5000.

There is no particular limitation for aldehyde compound A1d, for example can enumerate: have 1-2 carboxyl or ester group the fatty aldehyde compound, have 1-2 carboxyl or ester group alicyclic aldehyde cpd, have the aromatic aldehyde compound of 1-2 carboxyl or ester group etc.

As the fatty aldehyde compound with 1-2 carboxyl, can enumerate Ra-CHO(Ra is the substituent 1-2 of having carboxyl of 1-20 or the alkyl of ester group for also having carbonatoms), OHC-Rb-CHO(Rb is that also can to have carbonatoms be the substituent 1-2 of having carboxyl of 1-20 or the alkylidene group of ester group), Rc-(CHO) ₃(Rc is the organic group of the trivalent that also can have the substituent 1-2 of having carboxyl that carbonatoms is 2-20 or ester group), Rd-(CHO) ₄(Rd is for also having the organic group of tetravalence that carbonatoms is the substituent 1-2 of having the carboxyl of 2-20) etc.In the literary composition, so-called substituting group is the functional group that is selected from the group of being made up of alkyl, cycloalkyl, aryl, alkoxyl group, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, carboxyl, alkyl silane, their derivative.

As alicyclic aldehyde cpd, can enumerate: carboxyl hexahydrobenzaldehyde (カ Le ボキシシ Network ロヘキサ Application カ Le ボア Le デヒ De); also can have carbonatoms is the substituent carboxyl hexahydrobenzaldehyde of 2-20; carboxyl ring octyl group formaldehyde; carboxyl norborneol alkyl formaldehyde; carboxyl adamantyl formaldehyde; carboxyl furfural (カ Le ボキシ Off Le Off ラ one Le); carboxyl diformyl hexanaphthene; carboxyl diformyl cyclooctane (カ Le ボキシジホ Le ミ Le シ Network ロオ Network タ Application); carboxyl diformyl norbornane; carboxyl diformyl diamantane; carboxyl three formyl radical hexanaphthenes; carboxyl three formyl radical cyclooctane; carboxyl three formyl radical norbornanes; carboxyl three formyl radical diamantane; carboxyl three formyl radical hexanaphthenes; carboxyl tetramethyl acyl group cyclooctane; carboxyl tetramethyl acyl group norbornane; carboxyl tetramethyl acyl group diamantane etc.In the literary composition, so-called substituting group is the functional group that is selected from the group of being made up of alkyl, cycloalkyl, aryl, alkoxyl group, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, alkyl silane, their derivative.

As the aromatic aldehyde compound, can enumerate: carboxyl benzaldehyde; the carboxyl toluic aldehyde; also can have carbonatoms is the substituent carboxyl benzaldehyde of 2-20; the carboxyl aubepine; the carboxyl naphthaldehyde; carboxyl anthracene aldehyde; carboxyl biphenyl aldehyde; carboxyl formyl radical fluorenes; the carboxyl formyl biphenyl; carboxyl formyl radical anthracene; carboxyl formyl radical phenanthrene; carboxyl formyl radical thiodiphenylamine (カ Le ボキシホ Le ミ Le Off エノチアザ Application); carboxyl formyl radical pyrene; carboxyl formyl radical benzopyrene; carboxyl formyl radical benzo two indenes; carboxyl formyl radical benzo naphthalene; carboxyl formyl radical acenaphthylene; carboxyl formyl radical naphthacene; carboxyl formyl radical pentacene; carboxyl formyl radical three adjacent inferior benzene; carboxyl formyl radical pyridine; carboxyl formyl radical ovalene; the carboxyl diformyl-benzenes; carboxyl diformyl toluene; carboxyl diformyl dimethylbenzene; carboxyl diformyl naphthalene; carboxyl diformyl biphenyl; carboxyl diformyl terphenyl; carboxyl diformyl anthracene; carboxyl diformyl phenanthrene; carboxyl diformyl pyrene; carboxyl diformyl benzo two indenes; non-that alkene of carboxyl diformyl (カ Le ボキシジホ Le ミ Le Off エ Na レ Application); carboxyl diformyl acenaphthylene; non-that alkene of carboxyl diformyl; carboxyl diformyl naphthacene; carboxyl diformyl pentacene; carboxyl diformyl three adjacent inferior benzene; carboxyl diformyl pyridine; carboxyl diformyl imidazoles; carboxyl diformyl furans; carboxyl diformyl thiazole; carboxyl diformyl flavones; carboxyl diformyl isoflavones; carboxyl three formyl radical benzene; carboxyl three formyl radical toluene; carboxyl three formyl radical dimethylbenzene; carboxyl front three acyl-naphthaline; carboxyl three formyl radical biphenyl; carboxyl three formyl radical terphenyls; carboxyl three formyl radical anthracenes; carboxyl three formyl radical phenanthrene; carboxyl three formyl radical pyrenes; carboxyl three formyl radical benzos two indenes; non-that alkene of carboxyl three formyl radicals; carboxyl three formyl radical acenaphthylenes; non-that alkene of carboxyl three formyl radicals; carboxyl front three acyl group naphthacene; carboxyl three formyl radical pentacenes; carboxyl three formyl radicals three adjacent inferior benzene; carboxyl front three acyl pyridine ketone quinoline (カ Le ボキシトリホ Le ミ Le ピリトリ Application); carboxyl three formyl imidazoles; carboxyl three formyl radical furans; carboxyl three formyl radical thiazoles; carboxyl three formyl radical flavones; carboxyl three formyl radical isoflavones; carboxyl tetramethyl acyl group benzene; carboxyl tetramethyl acyl-naphthaline; carboxyl tetramethyl acyl group biphenyl; carboxyl tetramethyl acyl group terphenyl; carboxyl tetramethyl acyl group anthracene; carboxyl tetramethyl acyl group phenanthrene; carboxyl tetramethyl acyl group pyrene; carboxyl tetramethyl acyl group benzo two indenes; non-that alkene of carboxyl tetramethyl acyl group; carboxyl tetramethyl acyl group acenaphthylene; non-that alkene of carboxyl tetramethyl acyl group; carboxyl tetramethyl acyl group naphthacene; carboxyl tetramethyl acyl group pentacene; the inferior benzene of carboxyl tetramethyl acyl group neighbours; carboxyl tetramethyl acyl pyridine ketone alkane (カ Le ボキシテトラホ Le ミ Le ピリテトラ Application); carboxyl tetramethyl acylimidazole; carboxyl tetramethyl acyl group furans; carboxyl tetramethyl acyl group thiazole; carboxyl tetramethyl acyl group flavones; carboxyl tetramethyl acyl group isoflavones etc.In the literary composition, so-called substituting group is the functional group that is selected from the group of being made up of alkyl, cycloalkyl, aryl, alkoxyl group, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, carboxyl, alkyl silane, their derivative.

Further, as the aldehyde cpd that contains heterocycle, can enumerate: carboxyl furfural, carboxyl cigarette aldehyde, carboxyl 2-tetrahydrofuran (THF) formaldehyde, 2 thiophene carboxaldehyde etc.

As the aldehyde cpd with 1-2 ester group, can enumerate: 1-2 carboxyl of the aldehyde cpd of the above-mentioned 1-2 of a having carboxyl and alcohols dehydration condensation and the compound with the such ester bond of described formula (17) that obtains.

In the formula (17), be the straight chain shape alkyl of 1-20 as carbonatoms, preferred carbonatoms is 1-12, can enumerate particularly: methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-octyl, dodecyl etc.

Be the alkyl of the chain of 3-20 as carbonatoms, preferred carbonatoms is 3-10, and can enumerate particularly: sec.-propyl, the tertiary butyl, isopentyl, neo-pentyl etc. are preferably the tertiary butyl in them.

Be the cycloalkyl of 3-20 as carbonatoms, preferred carbonatoms is 6-14.In addition, the cycloaliphatic ring that contains in the cycloalkyl can also can be many rings for monocycle, more preferably many rings.Can enumerate particularly: mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane etc., more specifically, can enumerate: the mononaphthene of cyclopropane, tetramethylene, pentamethylene, hexanaphthene etc., the polynaphthene of diamantane, norbornane, iso-borneol alkane, tristane, Fourth Ring decane etc.Wherein, be preferably diamantane, three cycloalkanes, tetracycloalkane, be preferably diamantane, three cycloalkanes especially.

Aldehyde compound with 1-2 ester group can obtain or obtain so that known method is synthetic with reagent.For example, can obtain by following method: the aldehyde compound with 1-2 carboxyl is dissolved or suspended in the organic solvent (as acetone etc.), and adds alkali (as salt of wormwood etc.); Afterwards, add the compound shown in the following formula (27) of aldehyde compound with 1-2 carboxyl and 0.5-4 equivalent, 0-100 ℃ of reaction 1-72 hour down, remove lixiviating (as salt of wormwood etc.) by filtering to wait, and desolventizing.This compound also can be made with extra care (as with column chromatography etc.) as required.

[chemical formula 49]

(in the formula, X is halogen atom; R ^3ASame as described above.）

As halogen atom, can enumerate fluorine, chlorine, bromine, iodine, be preferably chlorine, bromine, iodine, more preferably bromine, iodine, more preferably bromine.

In these, consider from the aspect of elching resistant, be preferably the aromatic aldehyde that has 1-2 carboxyl or ester group and have 1-4 formyl radical; From considering forming the favourable aspect of Micropicture, more preferably have 1-2 carboxyl or ester group and have the aromatic aldehyde of 1-2 formyl radical; From can high yield, the aspect consideration of high purity ground preparation aromatic aldehyde itself and ring compound A, more preferably have 1-2 carboxyl or ester group and have the aromatic aldehyde of 1 formyl radical.

As the aromatic aldehyde compound with 1-2 carboxyl or ester group, be preferably the compound shown in following general formula (28-0) or (28).

[chemical formula 50]

(in the formula, X ₂Be hydrogen or halogen, be preferably hydrogen, fluorine, chlorine, bromine, iodine, more preferably hydrogen, chlorine, bromine, iodine, more preferably hydrogen, bromine, iodine are preferably bromine especially; M is the integer of 1-4; L ₁, l ₁And R ^3ASame as described above.）

[chemical formula 51]

(in the formula, X ₂, L ₁, l ₁, R ^3ASame as described above.）

In addition, the preferred compound of following formula (28-1)-(28-4) shown in separately that use.

[chemical formula 52]

(in the formula, m, X ₂, R ^3ASame as described above.）

[chemical formula 53]

(in the formula, m, R ^3ASame as described above.）

[chemical formula 54]

(in the formula, R ^3ASame as described above.）

[chemical formula 55]

(in the formula, R ^3ASame as described above.）

Aldehyde compound A1d may be used singly or in combination of two or more, when using separately, and the homogeneity height of the solids component of resist film, thereby preferred.

As the example of phenolic compound A2, can enumerate: phenol, pyrocatechol, Resorcinol, Resorcinol, pyrogallol etc. are preferably Resorcinol, pyrogallol, more preferably Resorcinol.In the scope of not damaging effect of the present invention, phenolic compound A2 also can have to be selected from and replaces ethyl, 1-by halogen atom, alkyl, cycloalkyl, aryl, aralkyl, alkoxyl group, alkenyl, carboxyl, acyl group, carbalkoxy, alkanoyloxy (ア Le キロイ Le オキシ yl), aryl acyloxy, cyano group, nitro, heterocyclic radical, alkyl silane, substituent methyl, 1-and replace substituting group in the group that n-propyl, 1-branched-chain alkyl, silyl, 1-substituted alkoxy alkyl, cyclic ethers base and alkoxycarbonyl alkyl form etc.There is no particular limitation for the purity of phenolic compound A2, is generally more than the 95 weight %, is preferably more than the 99 weight %.Phenolic compound A2 can be used alone or in combination of two or more, when using separately, and the homogeneity height of the solids component of resist film, thereby preferred.

Ring compound A0 with carboxyl, for example, can obtain by following method: in organic solvent (as methyl alcohol, ethanol, acetonitrile etc.), in the presence of acid catalyst (hydrochloric acid, sulfuric acid or tosic acid etc.), use molar ratio to be 1:(0.1-10) aldehyde compound A1d and phenolic compound A2,60-150 ℃ of following 0.5-20 hour degree of reaction, after the filtration, with the alcohols washing after washing of methyl alcohol etc., filter then and separate, make its drying at last.As required, also can make with extra care by column chromatography etc.

As reaction solvent, the situation of the alcohols that has used methyl alcohol, ethanol etc. is arranged; Or as aldehyde compound A1d, used the situation of the fatty aldehyde compound with ester group etc.; The situation of the state that the carboxyl of part or all of the ring compound Aa with carboxyl after reaction finishes is esterified.At this moment, in order to make the ester hydrolysis, add as the sodium hydroxide of alkali etc., and stirred about 0.5-20 hour down at 10-100 ℃.Afterwards, this solution is transferred in the separating funnel, added as the diethyl ether of organic solvent etc. and separatory, remove its water layer, acid with hydrochloric acid etc. neutralizes, and reclaims by the solid matter filtration of will separate out etc., obtains having the ring compound A0 of nonesterified carboxyl thus.

The molecular weight of ring compound A0 is 700-5000, is preferably 1000-2500, more preferably 1500-2000.When above-mentioned scope, resist can keep necessary film-forming properties, and resolving power is improved.

Ring compound among the present invention can obtain cis body and trans body, can be any structure or mixture.As the resist composition of radiation-ray sensitive composition the time, only have under any one the situation of structure in cis body and the trans body, become the pure substance compound, and the homogeneity height of the composition in the resist film, thereby preferred.Only had any one the method for ring compound of structure in cis body and the trans body, can use: utilizing column chromatography or the preparation separation carried out of liquid-liquid chromatography or in the preparation, known method such as optimization such as reaction solvent and temperature of reaction are carried out.

Above-mentioned ring compound A0 with carboxyl is preferably and is selected from each compound shown in following formula (29-0) or the formula (29).

[chemical formula 56]

[chemical formula 57]

(formula (29-0) and (29) separately in, X ₂Be hydrogen or halogen atom; L ₁Organic group for the divalence of the alkylidene group that is selected from straight chain shape that singly-bound, carbonatoms are 1-4 or a chain; l ₁Be 0 or 1; M is the integer of 1-4; m ₃Integer for 1-2; m ₄Be 1.）

Above-mentioned ring compound A0 with carboxyl more preferably is selected from the compound of each compound shown in the compound shown in the following formula (30) or the following formula (31).

[chemical formula 58]

[chemical formula 59]

(in formula (30), (31), X ₂Same as described above.）

There is no particular limitation to have the compound A-13 of halo methyl ether base, for example have 1-2 halogenated methyl fatty compounds, have 1-2 halogenated methyl alicyclic compound, have the aromatics of 1-2 halogenated methyl etc., preferably can enumerate the compound shown in the following formula (32).

[chemical formula 60]

(in the formula, R ₈For carbonatoms is that straight chain shape alkyl, the carbonatoms of 1-20 is that the alkyl of the chain of 3-20, cycloalkyl or the carbonatoms that carbonatoms is 3-20 are the aryl of 6-20; X ₁Be halogen; l ₂Be 1 or 2.）

Be the straight chain shape alkyl of 1-20 as carbonatoms, preferred carbonatoms is 1-12, can enumerate particularly: methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-octyl, dodecyl etc.

Be the alkyl of the chain of 3-20 as carbonatoms, preferred carbonatoms is 3-10, can enumerate particularly: sec.-propyl, the tertiary butyl, isopentyl, neo-pentyl etc.

As halogen, can enumerate fluorine, chlorine, bromine, iodine, be preferably chlorine, bromine, iodine, more preferably bromine, iodine, more preferably bromine.

l ₂Be 1 or 2, more preferably 1.

Compound A-13 with halo methyl ether base, for example can obtain by following method: alcohols (as hexalin etc.) is dissolved in the organic solvent of normal hexane etc., add Paraformaldehyde 96, being blown into respect to alcohols is the hydrogen halide (as hydrogen chloride gas etc.) of 2.0-3.0 equivalent, reacts under 0-100 ℃; Reaction separates resultant by underpressure distillation, thereby obtains the compound A-13 with halo methyl ether base as target product after finishing.

Be preferably the compound shown in the following formula (32-1) as the compound A-13 with halo methyl ether base.

[chemical formula 61]

(in the formula, X, R ⁵, R ⁶, n ₀, n ₁, n ₂With identical in described formula (22) and the formula (27).）

Ring compound B0 can obtain by the ring compound A0 with carboxyl and the reaction with compound A-13 of halo methyl ether base.For example, can obtain by following method: make the ring compound A0 with carboxyl be dissolved or suspended in non-protonic solvent (as acetone, THF, propylene glycol methyl ether acetate etc.) in, then, add the compound A-13 with halo methyl ether base, (carboxyl with respect to the ring compound A0 with carboxyl is the 0.5-4 equivalent at alkaline catalysts, be preferably the 0.9-1.1 equivalent, the pyridine of 1.0 equivalents more preferably, triethylamine, the diaza-bicyclo undecylene, salt of wormwood etc.) under the existence, at normal pressure, 0-110 ℃ was reacted 1-72 hour down, thereafter, after the washing of alcohols such as methyl alcohol, washing, filter and separate, make its drying then.This compound can carry out the refining of column chromatography etc. as required.

The molecular weight of ring compound B0 is 800-5000, is preferably 1000-2500, more preferably 1500-2000.In the time of in above-mentioned scope, resist can keep necessary film-forming properties, and resolving power is improved.

Above-mentioned ring compound B0 is preferably the compound that is selected from each compound shown in following formula (33-0) or (33).

[chemical formula 62]

(in the formula, R ^3A, X ₂, L ₁, l ₁, m, m ₃, m ₄With identical in the above-mentioned formula (13-0).）

[chemical formula 63]

(in the formula, R ^3A, X ₂, L ₁, l ₁With identical in the above-mentioned formula (13).）

Above-mentioned ring compound B0 is the compound shown in the following formula (34) more preferably.

[chemical formula 64]

(in the formula, R ^3A, X ₂, L ₁, l ₁Same as described above.）

Above-mentioned ring compound B0 is preferably the compound shown in the following formula (35) especially.

[chemical formula 65]

(in the formula, R ^3A, X ₂Same as described above.）

R ^3AMore preferably have and be selected from the acid dissociation functional group of structure that cycloalkanes, lactone and carbonatoms that carbonatoms is 3-20 are the aromatic nucleus of 6-12.Being the cycloalkanes of 3-20 as carbonatoms, can be that monocycle also can be many rings, more preferably many rings.Concrete example, can enumerate mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane etc., more specifically, can enumerate the mononaphthene of cyclopropane, tetramethylene, pentamethylene, hexanaphthene etc., the polynaphthene of diamantane, norbornane, iso-borneol alkane, tristane, Fourth Ring decane etc.Wherein, be preferably diamantane, three cycloalkanes, tetracycloalkane, be preferably diamantane, three cycloalkanes especially.Carbonatoms is that the cycloalkanes of 3-12 also can have substituting group.As lactone, the carbonatoms that can enumerate butyrolactone or have a lactone group is the cycloalkyl of 3-12.Be that the aromatic nucleus of 6-12 can be enumerated phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, pyrene ring etc. as carbonatoms, be preferably phenyl ring, naphthalene nucleus, be preferably naphthalene nucleus especially.

Especially more preferably the acid dissociation functional group shown in the following formula (36).By having this acid dissociation functional group, can improve resolving power and the LER of the resist pattern that obtains.

[chemical formula 66]

(in the formula, R ⁵, R ⁶, n ₀, n ₁, n ₂Same as described above.）

Ring compound B0 also can obtain by the ring compound A0 with carboxyl and the dehydration condensation with compound of alcoholic extract hydroxyl group.

Ring compound B0 also can obtain by ring compound A0a and the transesterification reaction with compound of alcoholic extract hydroxyl group, and this ring compound A0a is that the carboxyl substituted by the ring compound A0 that will have carboxyl is that the ester bond shown in the described formula (17) obtains.Transesterification reaction is known.As the compound with alcoholic extract hydroxyl group, can use any alcohol in primary alconol, secondary alcohol, the tertiary alcohol, more preferably secondary alcohol, the tertiary alcohol are preferably the tertiary alcohol especially.

Compound A-13 with halo methyl ether base can obtain by following method, for example alcohols (as hexalin etc.) is dissolved in the organic solvent of normal hexane etc., add Paraformaldehyde 96, being blown into respect to alcohols is the hydrogen halide (as hydrogen chloride gas etc.) of 2.0-3.0 equivalent, reacts under 0-100 ℃; Reaction separates resultant by underpressure distillation, thereby obtains the compound A-13 with halo methyl ether base as target product after finishing.

In order to reduce the kish amount of ring compound B0, also can make with extra care as required.In addition, general if when acid catalyst and promotor are residual, the stability in storage of radiation-ray sensitive composition reduces; When perhaps basic catalyst was residual, general, the susceptibility of radiation-ray sensitive composition can reduce, and therefore also can carry out reducing its content is the refining of purpose.Refining can being undertaken by known method, as long as not modification of ring compound B0, just there is no particular limitation, for example can enumerate: the method that water washs, the method for washing with acidic aqueous solution, the method for washing with alkaline aqueous solution, method that spent ion exchange resin is handled, the method handled with silica dioxide gel column chromatography instrument etc.More preferably the two or more combinations of these process for purification are carried out.

Can be according to the kind of the amount of the metal that should remove, acidic cpd and/or basic cpd and kind, refining ring compound B0 etc., from acidic aqueous solution, alkaline aqueous solution, ion exchange resin and silica dioxide gel column chromatography instrument, suitably select best method.For example as acidic aqueous solution, can enumerate hydrochloric acid, nitric acid, aqueous acetic acid that concentration is 0.01-10mol/L, as alkaline aqueous solution, can enumerate the ammonia soln that concentration is 0.01-10mol/L, as ion exchange resin, can enumerate Zeo-karb, for example オ Le ガノ Amberlyst 15J-HG processed Dry etc.Can also carry out drying after refining.Drying can be undertaken by known method, and there is no particular limitation, under the condition of not modification of ring compound B0, can enumerate the method for vacuum-drying, warm air drying etc.

With respect to total constituting atom number of described ring compound B0, the ratio of halogen atom number is preferably 0.1-60%, 0.1-40% more preferably, and more preferably 0.1-20% is preferably 0.1-10% especially, most preferably is 0.1-5%.In the time of in above-mentioned scope, to the susceptibility rising of radioactive rays, and can keep film-forming properties.In addition, can improve the safety solvent solvability.

With respect to total constituting atom number of described ring compound B0, the ratio of nitrogen-atoms number is preferably 0.1-40%, 0.1-20% more preferably, and more preferably 0.1-10% is preferably 0.1-5% especially.In the time of in above-mentioned scope, the line edge roughness of the resist pattern that can reduce to obtain, and can keep film-forming properties.In addition, as nitrogen-atoms, be preferably the nitrogen-atoms that is contained in secondary amine or the tertiary amine, more preferably be contained in the nitrogen-atoms in the tertiary amine.

The solids component of radiation-ray sensitive composition of the present invention and ring compound B0 can form amorphous film by spin coating.In addition, can be applicable in the general semiconductor preparing process.

The amorphous film of ring compound B0 dissolution rate to Tetramethylammonium hydroxide (TMAH) aqueous solution of 2.38 quality % under 23 ℃ is preferably Below, more preferably More preferably

For

During above dissolution rate, the situation that has resolving power to improve.Infer that this is because the small surperficial position of described ring compound B0 is dissolved, has reduced the cause of LER.In addition, reduce the effect of defective in addition.

The acid dissociation functional group of ring compound B0 dissociates and the ring compound that generates, also preferably has the character that forms amorphous film by spin coating.The amorphous film of ring compound A3 dissolution rate to the TMAH aqueous solution of 2.38 quality % under 23 ℃ is preferably More than, more preferably

More preferably

For

During following dissolution rate, the situation that also has resolving power to improve.Infer that this is because by the caused deliquescent variation of being dissociated by the acid dissociation functional group of described ring compound B0, make the big cause of contrast change at interface that is dissolved in the exposure portion of alkaline-based developer and is not dissolved in the unexposed portion of alkaline-based developer.In addition, has the effect that reduces LER, reduces defective.

The solids component of spin coating radiation-ray sensitive composition and the amorphous film that the forms dissolution rate to the TMAH aqueous solution of 2.38 quality % under 23 ℃ is preferably Below.By irradiation KrF excimer laser, extreme ultraviolet, electron rays or X ray isoradial, be exposed to desired figure, the dissolution rate at the TMAH aqueous solution of relative 2.38 quality % under 23 ℃ of the amorphous film after the heating under 20-250 ℃ is preferably as required

The second-order transition temperature of ring compound B0 is preferably more than 100 ℃, more preferably more than 120 ℃, more preferably more than 140 ℃, is preferably especially more than 150 ℃.By making second-order transition temperature in above-mentioned scope, in semiconductor lithography method technology, have the thermotolerance that to keep graphics shape, and can give the performance of very high resolution etc.

By the differential scanning calorimetric analysis of the second-order transition temperature of ring compound B0 and the crystallization thermal value of obtaining is preferably not enough 20J/g.And (Tc)-(second-order transition temperature) is preferably more than 70 ℃, more preferably more than 80 ℃, more preferably more than 100 ℃, is preferably especially more than 130 ℃.The not enough 20J/g of crystallization thermal value and (Tc)-(second-order transition temperature) be that above-mentioned scope is when interior, by the spin coating radiation-ray sensitive composition, form amorphous film easily, and can keep the necessary film-forming properties of resist for a long time, can improve resolving power.

Ring compound B0 of the present invention, except can be himself being that main component forms the positive radiation line sensitive compositions, can be not as main component, and improve susceptibility or improve the additive of elching resistant and add radiation-ray sensitive composition to as for example being used for.At this moment, ring compound B0 can be used with the 1-50 weight % of solids component gross weight.

In radiation-sensitive resist composition of the present invention, preferably contain the solids component of 1-80 weight % and the solvent of 20-99 weight %, more preferably contain the solids component of 1-50 weight % and the solvent of 50-99 weight %, further preferably contain the solids component of 2-40 weight % and the solvent of 60-98 weight %, especially preferably contain the solids component of 2-10 weight % and the solvent of 90-98 weight %.The amount of ring compound B0 is preferably more than the 50 weight % of solids component gross weight, 60-95 weight % more preferably, and more preferably 65-90 weight % is preferably 70-85 weight % especially.During for above-mentioned mix proportions, can obtain very high resolution, line edge roughness diminishes.As solvent, can similarly use with described radiation-ray sensitive composition A in identical solvent.

In the scope of not damaging effect of the present invention, also can at least one phenolic hydroxyl group of ring compound B0, introduce non-acid dissociation functional group.So-called non-acid dissociation functional group refers to not divide, do not produce the characteristic group of alkali-soluble group in the presence of acid.For example can enumerate: not the decomposition that is caused by the effect of acid, be selected from functional group in the group of being formed by the alkyl silane of the alkoxyl group of the aryl of the cycloalkyl of the alkyl of C1-20, C3-20, C6-20, C1-20, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, carboxyl, C1-20, their derivative etc.

Also can introduce diazido naphthoquinones ester group at least one phenolic hydroxyl group of ring compound B0 of the present invention.Introduced the compound of diazido naphthoquinones ester group at least one phenolic hydroxyl group of ring compound B0, except forming the positive radiation line sensitive compositions as main component with himself, can be used as acidogenic agent or additive and add in the radiation-ray sensitive composition.

Also can introduce the acidic product acidic functionality by the irradiation radioactive rays at least one phenolic hydroxyl group of ring compound B0.Introduced the ring-type polyphenolic substance of acidic product acidic functionality by the irradiation radioactive rays at least one phenolic hydroxyl group of ring compound B0, except forming the positive radiation line sensitive compositions as main component with himself, can be used as acidogenic agent or additive and add in the radiation-ray sensitive composition.

Composition of the present invention preferably contains more than one acidogenic agent C, this acidogenic agent C by radioactive rays irradiation and produce acid directly or indirectly, described radioactive rays are for being selected from any one the radioactive rays in visible rays, ultraviolet ray, excimer laser, electron rays, extreme ultraviolet (EUV), X ray and the ionic fluid.The usage quantity of acidogenic agent C is preferably the solids component gross weight (summation of the solids component of ring-type polyphenolic substance B0, acidogenic agent C, lower molecular weight dissolution accelerator D, sour diffusion control agent E and other any composition F etc., below same) 0.001-50 weight %, 1-40 weight % more preferably, further preferred 3-30 weight %.By in above-mentioned scope, using acidogenic agent, can obtain the graph outline of high sensitive and low edge roughness.In the present invention, as long as can produce acid in system, the production method of acid is just unqualified.Use excimer laser if replacement g line, i line etc. are ultraviolet, can carry out finer processing; In addition, if use electron rays, extreme ultraviolet, X ray, ionic fluid as high-energy rays, can carry out finer processing.

The usage quantity of above-mentioned acidogenic agent C is preferably the 15-25 weight % of solids component gross weight especially.By in above-mentioned scope, using above-mentioned acidogenic agent C, can obtain high sensitive.

In the scope of not damaging purpose of the present invention, radiation-ray sensitive composition of the present invention can contain the resin that dissolves in the alkaline aqueous solution.As the resin that dissolves in the alkaline aqueous solution, can enumerate: resol, polyethylene phenols, polyacrylic acid, polyvinyl alcohol, phenylethylene-maleic anhydride resin, and the polymkeric substance that contains vinylformic acid, vinyl alcohol or vinylphenol as monomeric unit, or their derivative etc.Dissolve in the blended amount of the resin of the alkaline aqueous solution, can regulate aptly according to the kind of employed resist compound, for the above-mentioned ring compound B0 of per 100 weight parts, be preferably 30 weight parts following, more preferably 10 weight parts following, more preferably 5 weight parts following, be preferably 0 weight part especially.

(radiation-ray sensitive composition C)

The present invention relates to the radioactive rays sensing composition, this radioactive rays sensing composition contains any one and the solvent in described formula (1) and the ring compound (a) ~ (e).

In addition; the present invention relates to above-mentioned radiation-ray sensitive composition; wherein, ring compound for be 2-59 and the compound with 1-4 formyl radical (aldehyde compound A1) by carbonatoms with carbonatoms be the condensation reaction of 6-15 and the compound with 1-3 phenolic hydroxyl group (phenolic compound A2) synthetic, molecular weight is the ring compound A of 700-5000.

Namely, preferred radiation-ray sensitive composition has following feature among the present invention: this radiation-ray sensitive composition contains the solids component of 1-80 weight % and the solvent of 20-99 weight %, wherein said radiation-ray sensitive composition contains ring compound A, and described ring compound A is for being that the phenyl aldehyde of 7-24 and condensation reaction that carbonatoms is 6-15 and the compound with 1-3 phenolic hydroxyl group are synthetic by not having any one carbonatoms in hydroxyl and the tertiary butyl, and the molecular weight of described ring compound A is 700-5000.

In addition, preferred radiation-ray sensitive composition has following feature among the present invention: this radiation-ray sensitive composition contains the solids component of 1-80 weight % and the solvent of 20-99 weight %, wherein, described radiation-ray sensitive composition contains ring compound A, acidogenic agent C, acid crosslinking agent G and sour diffusion control agent E, wherein said ring compound A is for synthetic by having the condensation reaction that phenyl aldehyde that the substituent carbonatoms that contains alicyclic ring or aromatic nucleus is 10-24 and carbonatoms be 6-15 and the compound with 1-3 phenolic hydroxyl group, and molecular weight is 700-5000; Described acidogenic agent C by be selected from the group of being formed by visible rays, ultraviolet ray, excimer laser, electron rays, extreme ultraviolet (EUV), X ray and ionic fluid any one radioactive rays irradiation and produce acid directly or indirectly.

Radiation-ray sensitive composition of the present invention contains the ring-type polyphenolic substance.The content of ring compound A is more than the 50 weight % of solids component gross weight.

Ring compound A for by have the substituent carbonatoms that contains alicyclic ring or aromatic nucleus be the phenyl aldehyde of 10-24 or do not have the phenyl aldehyde that any one carbonatoms in hydroxyl and the tertiary butyl is 7-24 (below, be called aromatic carbonyl A1) with carbonatoms be the condensation reaction of 6-15 and the compound with 1-3 phenolic hydroxyl group (below, be called phenolic compound A2) and synthetic, molecular weight is the ring compound of 700-5000.

Described ring compound A has advantages such as film-forming properties, thermotolerance, alkali-developable, elching resistant be good.

Ring compound A can obtain by the condensation reaction that is selected from more than one compounds in the group that more than one compounds in the group of being made up of aromatic carbonyl A1 and phenolic compound A2 form.

Aromatic carbonyl A1 is that to have the substituent carbonatoms that contains alicyclic ring or aromatic nucleus be the phenyl aldehyde of 10-24; or any one the carbonatoms that does not have in hydroxyl and the tertiary butyl is the phenyl aldehyde of 7-24; for example can enumerate: phenyl aldehyde; tolyl aldehyde; dimethylbenzaldehyde; trimethylbenzaldehyde; ethylbenzene formaldehyde; propylbenzene formaldehyde; butylbenzene formaldehyde except the tertiary butyl; the ethyl-methyl phenyl aldehyde; the isopropyl methyl phenyl aldehyde; diethylbenzaldehyde; aubepine; cyclopropyl-phenyl formaldehyde; the cyclobutyl phenyl aldehyde; the cyclopentyl phenyl aldehyde; phenylcyclohexane formaldehyde; the phenyl phenyl aldehyde; naphthaldehyde; the adamantyl phenyl aldehyde; the norcamphyl phenyl aldehyde; the hydroxy propionyl group phenyl aldehyde; isopropyl benzene formaldehyde; n-propylbenzene formaldehyde; bromobenzaldehyde and dimethylaminobenzaldehyde etc.; be preferably isopropyl benzene formaldehyde; n-propylbenzene formaldehyde; bromobenzaldehyde and dimethylaminobenzaldehyde; phenylcyclohexane formaldehyde; phenyl phenyl aldehyde, more preferably 4-isopropyl benzene formaldehyde; phenylcyclohexane formaldehyde and 4-n-propylbenzene formaldehyde.

In the scope of not damaging effect of the present invention, aromatic carbonyl A1 also can have straight or branched alkyl that carbonatoms is 1-4, cyano group, hydroxyl, halogen etc.Aromatic carbonyl A1 can be used alone or in combination of two or more.

Among the ring compound A in the present invention, also can introduce the crosslinking reaction group, described crosslinking reaction group causes crosslinking reaction by the chemical reaction of visible rays, ultraviolet ray, excimer laser, electron rays, extreme ultraviolet (EUV), X ray and ion beam irradiation or initiation thus.For example introduce and undertaken by ring compound A and crosslinking reaction group introducing reagent is reacted under alkaline catalysts.As the crosslinking reaction group, can enumerate carbon-to-carbon unsaturated bond, epoxy group(ing), azido-, halogenophenyl and chloromethyl.Introduce reagent as the crosslinking reaction group, can enumerate carboxylic acid derivative (as acid, acyl chlorides, acid anhydrides, two carbonic ethers etc.) with such crosslinking reaction group and haloalkane etc.The resist composition that contains the ring compound A with crosslinking reaction group also can be used as the soluble on-macromolecular class of very high resolution, high heat resistance and solvent radiation-ray sensitive composition.

Ring compound A of the present invention, except can be himself being that main component forms the positive radiation line sensitive compositions, can be not as main component, and add radiation-ray sensitive composition to as the additive that for example is used for improving susceptibility or improving elching resistant.At this moment, ring compound A can be used with the 1-49.999 weight % of solids component gross weight.

By irradiation KrF excimer laser, extreme ultraviolet, electron rays or X ray, ring compound A can be as the material that is used for the eurymeric resist that becomes the compound that is insoluble in alkaline-based developer.Consider that this is by to ring compound A irradiation KrF excimer laser, extreme ultraviolet, electron rays or X ray, and cause the condensation reaction between the compound, thereby become the cause of the compound that is insoluble in alkaline-based developer.The LER of the resist pattern that obtains thus is very little.

In the scope of not damaging effect of the present invention, also can be in the non-acid dissociation of at least one phenolic hydroxyl group introducing functional group of ring compound A.So-called non-acid dissociation functional group refers to not divide, do not produce the characteristic group of alkali-soluble group in the presence of acid.For example can enumerate: not the decomposition that is caused by the effect of acid, be selected from functional group in the group of being formed by the alkyl silane of the alkoxyl group of the aryl of the cycloalkyl of the alkyl of C1-20, C3-20, C6-20, C1-20, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, carboxyl, C1-20, their derivative etc.

Also can introduce diazido naphthoquinones ester group at least one phenolic hydroxyl group of ring compound A of the present invention.Introduced the compound of diazido naphthoquinones ester group at least one phenolic hydroxyl group of ring compound A, divided by forming beyond the minus positive radiation line sensitive compositions as main component with himself, can be used as himself to be that positive radiation line sensitive compositions, acidogenic agent or the additive of main component adds in the radiation-ray sensitive composition.

Also can introduce the acidic product acidic functionality by the irradiation radioactive rays at least one phenolic hydroxyl group of ring compound A.Introduced the ring-type polyphenolic substance of acidic product acidic functionality by the irradiation radioactive rays at least one phenolic hydroxyl group of ring compound A, except forming the minus positive radiation line sensitive compositions as main component with himself, can be used as himself to be that positive radiation line sensitive compositions, acidogenic agent or the additive of main component adds in the radiation-ray sensitive composition.

Ring compound A can prepare by known method.For example, can obtain by following method: in organic solvent (as methyl alcohol, ethanol etc.), in the presence of acid catalyst (hydrochloric acid, sulfuric acid or tosic acid etc.), use molar ratio to be 1:(0.1-10) aromatic carbonyl A1 and phenolic compound A2,60-150 ℃ of down reaction about 0.5-20 hour, after the filtration, with the alcohols washing after washing of methyl alcohol etc., filter then and separate, make its drying at last.Also can use basic catalyst (sodium hydroxide, hydrated barta or 1,8-diazabicyclo [5.4.0], 11 carbon-7-alkene etc.) by replacing acid catalyst, similarly obtain by reaction.Further, ring-type polyphenolic substance A also can become dihalide by make above-mentioned aromatic carbonyl A1 with hydrogen halide or halogen gas, makes dihalide and phenolic compound A2 behind the segregation react to prepare.

Above-mentioned ring compound more preferably uses two or more aromatic carbonyl A1 and/or two or more phenolic compound A2 to prepare.By using two or more aromatic carbonyl A1 and/or two or more phenolic compound A2, can improve the solvability of the semi-conductor safety solvent of ring compound A that obtains.

In order to reduce the kish amount of ring compound A, can make with extra care as required.In addition, general if when acid catalyst and promotor are residual, the stability in storage of radiation-ray sensitive composition reduces; When perhaps basic catalyst was residual, general, the susceptibility of radiation-ray sensitive composition can reduce, and therefore can carry out reducing its content is the refining of purpose.Refining can being undertaken by known method, as long as not modification of ring compound A, just there is no particular limitation, for example can enumerate: the method that water washs, the method for washing with acidic aqueous solution, the method for washing with alkaline aqueous solution, method that spent ion exchange resin is handled, the method handled with silica dioxide gel column chromatography instrument etc.More preferably the two or more combinations of these process for purification are carried out.Can be according to the kind of the amount of the metal that should remove, acidic cpd and/or basic cpd and kind, refining ring compound A etc., from acidic aqueous solution, alkaline aqueous solution, ion exchange resin and silica dioxide gel column chromatography instrument, suitably select best method.For example as acidic aqueous solution, can enumerate hydrochloric acid, nitric acid, aqueous acetic acid that concentration is 0.01-10mol/L; As alkaline aqueous solution, can enumerate the ammonia soln that concentration is 0.01-10mol/L; As ion exchange resin, can enumerate Zeo-karb, for example オ Le ガノ Amberlyst15J-HG Dry processed etc.Can also carry out drying after refining.Drying can be undertaken by known method, and there is no particular limitation, can enumerate the method for vacuum-drying, warm air drying etc. under the condition of not modification of ring compound A.

Ring compound A, preferably under normal pressure, below 100 ℃, be preferably below 120 ℃, more preferably below 130 ℃, more preferably below 140 ℃, be preferably below 150 ℃ especially, sublimability is low.So-called sublimability is low, and to be preferably loss of weight when having kept 10 minutes under the temperature of defined in thermogravimetric analysis be below 10%, be preferably below 5%, more preferably below 3%, more preferably below 1%, be preferably below 0.1% especially.By making sublimability low, the pollution of the exposure apparatus that the ease gas in the time of can preventing by exposure causes.In addition, can give good graphics shape with low LER.

Ring compound A satisfies: be preferably F＜3.0(F and represent total atom number/(total carbon atom number-total oxygen atomicity)), F＜2.5 more preferably.By satisfying above-mentioned condition, make that anti-dry etching is good.

Ring compound A is selected from propylene glycol methyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, methyl-phenoxide, butylacetate, ethyl propionate and ethyl lactate, and, demonstrating in the solvent of maximum dissolving power with respect to ring-type polyphenolic substance A, under 23 ℃, more than the preferred dissolution 1 weight %, more preferably dissolve more than the 3 weight %, more than the further preferred dissolution 5 weight %, the dissolving of the ring compound A that special preferred dissolution 10 weight % are above.By satisfying above-mentioned condition, make the use of safety solvent in the semiconductor fabrication operation become possibility.

The second-order transition temperature of ring compound A is preferably more than 100 ℃, more preferably more than 120 ℃, more preferably more than 140 ℃, is preferably especially more than 150 ℃.By making second-order transition temperature in above-mentioned scope, in semiconductor lithography method technology, have the thermotolerance that to keep graphics shape, and can give the performance of very high resolution etc.

By the differential scanning calorimetric analysis of the second-order transition temperature of ring compound A and the crystallization thermal value of obtaining is preferably not enough 20J/g.And (Tc)-(second-order transition temperature) is preferably more than 70 ℃, more preferably more than 80 ℃, more preferably more than 100 ℃, is preferably especially more than 130 ℃.The not enough 20J/g of crystallization thermal value and (Tc)-(second-order transition temperature) be that above-mentioned scope is when interior, by the spin coating radiation-ray sensitive composition, form amorphous film easily, and can keep the necessary film-forming properties of resist for a long time, can improve resolving power.

The molecular weight of ring compound A is 700-5000, is preferably 800-2000, more preferably 900-1500.In the time of in above-mentioned scope, resist can keep necessary film-forming properties, and resolving power is improved.

In a kind of mode of the present invention, ring compound A be preferably following formula (37), (37-1) or (37-2) shown in compound.

[chemical formula 67]

(in the formula, R ⁴Be functional group in the alkyl silane of 1-20 and the group that their derivative is formed for being selected from alkyl (still, removing the tertiary butyl) that hydrogen atom, carbonatoms are 1-20, cycloalkyl that carbonatoms is 3-20, aryl that carbonatoms is 6-20, alkoxyl group, cyano group, nitro, heterocyclic radical, halogen, carboxyl, carbonatoms that carbonatoms is 1-20; L is same as described above; P is the integer of 0-5.）

[chemical formula 68]

[chemical formula 69]

(above-mentioned formula (37-1) and (37-2) in, X ₂Be hydrogen or halogen atom; M is the integer of 1-4; m ₃Integer for 1-2; m ₄Be 1; R ⁴, p is same as described above.）

Ring compound A is the compound shown in the following formula (38) more preferably.

[chemical formula 70]

(in the formula, R ⁴, p is same as described above.）

Ring compound A is the compound shown in the following formula (39) more preferably.

[chemical formula 71]

In addition, ring compound A is the compound shown in the following formula (40) more preferably, more preferably the compound shown in the following formula (41).

[chemical formula 72]

(in the formula, R ⁷Be straight chain shape alkyl, halogen atom, cyano group, hydroxyl, alkoxyl group or the ester group of 1-12 for hydrogen atom, carbonatoms independently.）

[chemical formula 73]

In addition, only otherwise damage effect of the present invention, the organic group that the hydrogen atom of the hydroxyl in the above-mentioned formula also can be contained the end group shown in the repeating unit shown in the following formula (42-1) and hydrogen atom or the following formula (42-2) replaces.

[chemical formula 74]

[chemical formula 75]

Formula (42-1) and/or (42-2) in, L is singly-bound, methylene radical, ethylidene or carbonyl.A plurality of L can be the same or different.n ₅Be the integer of 0-4, n ₆Be the integer of 1-3, x is the integer of 0-3, and satisfies 1 ≦ n ₅+ n ₆≦ 5.A plurality of n ₅, n ₆, x can be the same or different.R ³For being selected from the substituting group in the group of being formed by halogen atom, alkyl, cycloalkyl, aryl, aralkyl, alkoxyl group, aryloxy, alkenyl, acyl group, carbalkoxy, alkanoyloxy, aryl acyloxy, cyano group and nitro.As halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms and iodine atom; As alkyl, can enumerate the alkyl that carbonatoms is 1-4, as methyl, ethyl, propyl group, n-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl etc.; As cycloalkyl, can enumerate cyclohexyl, norcamphyl, adamantyl etc.; As aryl, can enumerate phenyl, tolyl, xylyl, naphthyl etc.; As aralkyl, can enumerate benzyl, hydroxybenzyl, dihydroxy benzyl etc.; As alkoxyl group, can enumerate the alkoxyl group that carbonatoms is 1-4, as methoxyl group, oxyethyl group, hydroxyl-oxethyl, propoxy-, hydroxyl propoxy-, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy etc.; As aryloxy, can enumerate phenoxy group etc.; As alkenyl, can enumerate the alkenyl that carbonatoms is 2-4, as vinyl, propenyl, allyl group, butenyl etc.; As acyl group, can enumerate the aliphatic acyl radical that carbonatoms is 1-6 (as formyl radical, ethanoyl, propionyl, butyryl radicals, pentanoyl, isovaleryl, pivaloyl etc.) and aromatic acyl (as benzoyl, toluyl etc.); As carbalkoxy, can enumerate the carbalkoxy that carbonatoms is 2-5, as methoxycarbonyl, ethoxycarbonyl, the third oxygen carbonyl, isopropyl oxygen carbonyl, positive butoxy carbonyl, isobutyl boc, secondary butoxy carbonyl, tertbutyloxycarbonyl etc.; As alkanoyloxy, can enumerate acetoxyl group, propionyloxy, butyryl acyloxy, isobutyl acyloxy, penta acyloxy, isoamyl acyloxy, trimethyl acetoxyl etc.; As aryl acyloxy, can enumerate benzoyloxy etc.A plurality of R ³Can be the same or different.

With respect to total constituting atom number of described ring compound A, the ratio of halogen atom number is preferably 0.1-60%, 0.1-40% more preferably, and more preferably 0.1-20% is preferably 0.1-10% especially, most preferably is 1-5%.In the time of in above-mentioned scope, to the susceptibility rising of radioactive rays, and can keep film-forming properties.In addition, can improve the safety solvent solvability.

With respect to total constituting atom number of described ring compound A, the ratio of nitrogen-atoms number is preferably 0.1-40%, 0.1-20% more preferably, and more preferably 0.1-10% is preferably 0.1-5% especially.In the time of in above-mentioned scope, the line edge roughness of the resist pattern that can reduce to obtain.In addition, as nitrogen-atoms, be preferably the nitrogen-atoms that is contained in secondary amine or the tertiary amine, more preferably be contained in the nitrogen-atoms in the tertiary amine.

Ring compound A can form amorphous film by spin coating.In addition, can be applicable in the general semiconductor preparing process.

More than, more preferably

More preferably

For

When above, be dissolved in alkaline-based developer, can become resist.In addition, have

During following dissolution rate, the situation that also has resolving power to improve.Infer that this is because the deliquescent variation before and after the exposure by ring compound A, make the contrast at interface that is dissolved in the unexposed portion of alkaline-based developer and is not dissolved in the exposure portion of alkaline-based developer become big cause.In addition, has the effect that reduces LER, reduces defective.

The solids component of radiation-ray sensitive composition of the present invention can form amorphous film by spin coating.The solids component of spin coating radiation-ray sensitive composition of the present invention and the amorphous film that the forms dissolution rate to the TMAH aqueous solution of 2.38 quality % under 23 ℃ is preferably

More than, more preferably

More preferably

For

During following dissolution rate, the situation that also has resolving power to improve.Infer that this is because the deliquescent variation before and after the exposure of ring compound A, make the contrast at interface that is dissolved in the unexposed portion of alkaline-based developer and is not dissolved in the exposure portion of alkaline-based developer become big cause.In addition, has the effect that reduces LER, reduces defective.

Part after the radioactive rays exposure of KrF excimer laser, extreme ultraviolet, electron rays or X ray etc. of the solids component of spin coating radiation-ray sensitive composition of the present invention and the amorphous film that forms, the dissolution rate to the TMAH aqueous solution of 2.38 quality % under 23 ℃ are preferably

Below, more preferably

More preferably

For

During above dissolution rate, the situation that has resolving power to improve.Infer that this is because the small surperficial position of described ring compound A is dissolved, has reduced the cause of LER.In addition, reduce the effect of defective in addition.

In radiation-ray sensitive composition of the present invention, preferably contain the solids component of 1-80 weight % and the solvent of 20-99 weight %, more preferably contain the solids component of 1-50 weight % and the solvent of 50-99 weight %, further preferably contain the solids component of 2-40 weight % and the solvent of 60-98 weight %, especially preferably contain the solids component of 2-10 weight % and the solvent of 90-98 weight %.The amount of ring-type polyphenolic substance A is more than the 50 weight % of solids component gross weight, is preferably more than the 65 weight %, more preferably more than the 81 weight %.During for above-mentioned mix proportions, can obtain very high resolution, line edge roughness diminishes.

Composition of the present invention preferably contains more than one acidogenic agent C, this acidogenic agent C by radioactive rays irradiation and produce acid directly or indirectly, described radioactive rays are for being selected from any one the radioactive rays in visible rays, ultraviolet ray, excimer laser, electron rays, extreme ultraviolet (EUV), X ray and the ionic fluid.The usage quantity of acidogenic agent is preferably the solids component gross weight (summation of the solids component that is free to use among ring-type polyphenolic substance A, acidogenic agent C, acid crosslinking agent G, sour diffusion control agent E and other the composition F etc., below same) 0.001-50 weight %, more preferably 1-40 weight %, more preferably 3-30 weight %.By in above-mentioned scope, using acidogenic agent, can obtain the graph outline of high sensitive and low edge roughness.In the present invention, as long as can produce acid in system, the production method of acid is just unqualified.Use excimer laser if replacement g line, i line etc. are ultraviolet, can carry out finer processing; In addition, if use electron rays, extreme ultraviolet, X ray, ionic fluid as high-energy rays, can carry out finer processing.

Described acidogenic agent C is with identical about the described acidogenic agent of radiation-ray sensitive composition A.

Radiation-ray sensitive composition of the present invention preferably contains more than one acid crosslinking agent G.So-called acid crosslinking agent G be in the presence of the acid that is generated by acidogenic agent C, can be at the compound of intramolecularly or intermolecular cross-linking ring compound A.Linking agent G as such for example can enumerate: the compound of the substituting group of that have more than one and crosslinking reaction ring compound A (below, be called the bridging property substituting group).

As such bridging property substituting group, for example can enumerate: (i) hydroxyalkyl or by its substituting group of deriving, as the alkoxyl group (alkyl of C1-C6) of hydroxyl (alkyl of C1-C6), C1-C6, acetoxyl group (alkyl of C1-C6) etc.; (ii) carbonyl or by its substituting group of deriving, as formyl radical, carboxyl (alkyl of C1-C6) etc.; The substituting group that (iii) contains nitrogen-containing group is as dimethylamino methyl, diethylamino methyl, dihydroxy methylamino-methyl, dihydroxy ethyl amino methyl, morpholinyl methyl etc.; The substituting group that (iv) contains glycidyl is as glycidyl ether, Racemic glycidol ester group, Racemic glycidol amino etc.; (the v) substituting group of being derived by aromatic group is as the aryloxy (alkyl of C1-C6) of C1-C6, the aralkoxy (benzyloxymethyl, benzoyloxy methyl etc.) such as (alkyl of C1-C6) of C1-C6; (substituting group that vi) contains the polymerizability unsaturated link(age) is as vinyl, pseudoallyl etc.Bridging property substituting group as acid crosslinking agent G of the present invention is preferably hydroxyalkyl and alkoxyalkyl etc., is preferably alkoxy methyl especially.

As having the substituent acid crosslinking agent G of described bridging property, for example can enumerate: (i) contain the compound of methylol, as contain methylol melamine compound, contain methylol the benzoguanamine compound, contain methylol carbamide compound, contain methylol glycoluril compounds, contain the phenolic compound of methylol etc.; (ii) contain the compound of alkoxyalkyl, as contain alkoxyalkyl melamine compound, contain alkoxyalkyl the benzoguanamine compound, contain alkoxyalkyl carbamide compound, contain alkoxyalkyl glycoluril compounds, contain the phenolic compound of alkoxyalkyl etc.; (iii) contain the compound of carboxymethyl, as contain carboxymethyl melamine compound, contain carboxymethyl the benzoguanamine compound, contain carboxymethyl carbamide compound, contain carboxymethyl glycoluril compounds, contain the phenolic compound of carboxymethyl etc.; (iv) epoxy compounds is as dihydroxyphenyl propane class epoxy compounds, Bisphenol F class epoxy compounds, bisphenol S class epoxy compounds, resol class epoxy compounds, resole class epoxy compounds, polycarboxylated styrene class epoxy compounds etc.

Further, as acid crosslinking agent G, can use compound and the resin introducing described bridging property substituting group in the acidic functionality in the compound with phenolic hydroxyl group and alkali soluble resin and give bridging property.The substituent introducing rate of bridging property under this situation with respect to the total acidic functional group in the compound with phenolic hydroxyl group and the alkali soluble resin, is adjusted to 5-100 mole % usually, is preferably 10-60 mole %, 15-40 mole % more preferably.In the time of in above-mentioned scope, crosslinking reaction is fully carried out, and residual film ratio reduces, and can avoid the swelling phenomenon of figure and bending etc., thereby preferred.

In radiation-ray sensitive composition of the present invention, acid crosslinking agent G is preferably alkoxyalkyl carbamide compound or its resin or alkoxyalkyl glycoluril compounds or its resin.As particularly preferred acid crosslinking agent G, can enumerate the compound shown in the following formula (43) and r-o-methylation melamine compound (acid crosslinking agent G1).

[chemical formula 76]

(in the above-mentioned formula, each R ⁷Represent hydrogen atom, alkyl or acyl group independently; R ⁸-R ¹¹Represent hydrogen atom, hydroxyl, alkyl or alkoxyl group independently of one another; X ²Expression singly-bound, methylene radical or Sauerstoffatom.）

R in the formula (43) ⁷The alkyl or the carbonatoms that are preferably hydrogen atom, carbonatoms and are 1-6 are the acyl group of 2-6.Carbonatoms is the alkyl of 1-6, and more preferably carbonatoms is the alkyl of 1-3, for example can enumerate: methyl, ethyl, propyl group.Carbonatoms is the acyl group of 2-6, and more preferably carbonatoms is the acyl group of 2-4, for example can enumerate: ethanoyl, propionyl.R in the formula (21) ⁸-R ¹¹, more preferably hydrogen atom, hydroxyl, carbonatoms are that alkyl or the carbonatoms of 1-6 are the alkoxyl group of 1-6.Carbonatoms is the alkyl of 1-6, and more preferably carbonatoms is the alkyl of 1-3, for example can enumerate: methyl, ethyl, propyl group.Carbonatoms is the alkoxyl group of 1-6, and more preferably carbonatoms is the alkoxyl group of 1-3, for example can enumerate: methoxyl group, oxyethyl group, propoxy-.X ²Expression singly-bound, methylene radical or Sauerstoffatom are preferably singly-bound or methylene radical.In addition, R ⁷-R ¹¹, X ²Also can on above-mentioned illustrative group, further have substituting group, as alkyl (methyl, ethyl etc.), alkoxyl group (methoxyl group, oxyethyl group etc.), hydroxyl, halogen atom etc.A most R ⁷, R ⁸-R ¹¹Respectively can be identical or different.

As the compound shown in the formula (43-1), can enumerate compound for example shown below etc. particularly.

[chemical formula 77]

As the compound shown in the formula (43-2), for example can enumerate particularly: N, N, N, N-four (methoxymethyl) glycoluril, N, N, N, N-four (ethoxyl methyl) glycoluril, N, N, N, N-four (n-propoxymethyl) glycoluril, N, N, N, N-four (isopropoxy methyl) glycoluril, N, N, N, N-four (n-butoxy methyl) glycoluril and N, N, N, N-four (tert.-butoxy methyl) glycoluril etc.Wherein, be preferably N especially, N, N, N-four (methoxymethyl) glycoluril.

As the compound shown in the formula (43-3), can enumerate compound for example shown below etc. particularly.

[chemical formula 78]

As the r-o-methylation melamine compound, can enumerate for example N, N, N, N, N particularly, N-six (methoxymethyl) trimeric cyanamide, N, N, N, N, N, N-six (ethoxyl methyl) trimeric cyanamide, N, N, N, N, N, N-six (n-propoxymethyl) trimeric cyanamide, N, N, N, N, N, N-six (isopropoxy methyl) trimeric cyanamide, N, N, N, N, N, N-six (n-butoxy methyl) trimeric cyanamide and N, N, N, N, N, N-six (tert.-butoxy methyl) trimeric cyanamide etc.Wherein, preferred especially N, N, N, N, N, N-six (methoxymethyl) trimeric cyanamide.

Described acid crosslinking agent G1, for example can obtain by following method: after making carbamide compound or glycoluril compounds and formalin condensation reaction introduce methylol, further carry out etherificate with the lower alcohols of methyl alcohol, ethanol, propyl alcohol, butanols etc., reclaim compound or its resin of separating out by with the reaction solution cooling then.In addition, described acid crosslinking agent G1 also can be used as commercially available product and obtains, as the CYMEL(trade name, Mitsui サイア Na ミ Star De system), ニカラ Star Network (three and ケミカ Le (strain) system).

In addition, as other particularly preferred acid crosslinking agent G, can enumerate and have 1-6 phenyl ring in the molecule, have two above hydroxyalkyls and/or alkoxyalkyl and this hydroxyalkyl and/or alkoxyalkyl at whole intramolecularly and be combined in amphyl (acid crosslinking agent G2) on described any one phenyl ring.Preferably molecular weight is below 1500, has 1-6 phenyl ring in the molecule, has the amphyl that adds up on any one or a plurality of phenyl ring that plural hydroxyalkyl and/or alkoxyalkyl and this hydroxyalkyl and/or alkoxyalkyl be combined in described phenyl ring.

As the hydroxyalkyl that is incorporated on the phenyl ring, be preferably the hydroxyalkyl that carbonatoms is 1-6, as methylol, 2-hydroxyethyl and 2-hydroxyl-1-propyl group etc.As the alkoxyalkyl that is incorporated on the phenyl ring, be preferably the alkoxyalkyl that carbonatoms is 2-6, be preferably particularly: methoxymethyl, ethoxyl methyl, n-propoxymethyl, isopropoxy methyl, n-butoxy methyl, isobutoxy methyl, sec-butoxy methyl, tert.-butoxy methyl, 2-methoxy ethyl and 2-methoxyl group-1-propyl group.

Below enumerate more preferred example in these amphyls.

[chemical formula 79]

[chemical formula 80]

[chemical formula 81]

[chemical formula 82]

[chemical formula 83]

[chemical formula 84]

In the above-mentioned formula, L ¹-L ⁸Can be the same or different, represent methylol, methoxymethyl or ethoxyl methyl independently of one another.Amphyl with methylol, can by make phenolic compound with corresponding methylol (in the above-mentioned formula, L ¹-L ⁸Compound for hydrogen atom) under alkaline catalysts, reacts and obtain with formaldehyde.At this moment, in order to prevent resinifying or gelation, preferably under the temperature of reaction below 60 ℃, carry out.Particularly, can open flat 6-282067 communique with the spy, the spy opens the method for putting down in writing in flat 7-64285 communique etc. and synthesizes.

Amphyl with alkoxy methyl can obtain by the amphyl with corresponding methylol is reacted under acid catalyst with alcohol.At this moment, in order to prevent resinifying or gelation, preferably under the temperature of reaction below 100 ℃, carry out.Particularly, can synthesize with the method for putting down in writing among EP 632003A1 etc.

The He Cheng amphyl with methylol and/or alkoxy methyl like this, the aspect of the stability when preserving are considered and preferred; Amphyl with alkoxy methyl, the stable aspect when preserving are considered and preferred especially.Acid crosslinking agent G2 can be used singly or in combination of two or more.

In addition, as other particularly preferred acid crosslinking agent G, can enumerate the compound (acid crosslinking agent G3) with at least one Alpha-hydroxy sec.-propyl.As long as have the Alpha-hydroxy sec.-propyl, just there is no particular limitation to its structure.In addition, the hydrogen atom of the hydroxyl in the above-mentioned Alpha-hydroxy sec.-propyl also can be by more than one acid dissociation group (R-COO-group, R-SO ₂-groups etc., R represent to be selected from the group in the group of being made up of by the aromatic hydrocarbyl of 6-12 the alkoxyl group that carbonatoms is the straight chain shape alkyl of 1-12, cyclic hydrocarbon radical that carbonatoms is 3-12, carbonatoms is 1-12,1-branched-chain alkyl that carbonatoms is 3-12 and carbonatoms) replaced.As above-mentioned compound with Alpha-hydroxy sec.-propyl, for example can enumerate: contain in the aromatic series compounds, biphenol compound, naphthalene compound, furan compound etc. of the replacement of at least one Alpha-hydroxy sec.-propyl or non-replacement one or more.For example can enumerate particularly: the compound shown in the following general formula (44-1) (below, be called benzene-like compounds 1), the compound shown in the following general formula (44-2) (below, be called two benzene-like compounds 2), the compound shown in the following general formula (44-3) (below, be called naphthalene compounds 3) and following general formula (44-4) shown in compound (below, be called furfuran compound 4) etc.

[chemical formula 85]

In the above-mentioned general formula (44-1)-(44-4), each A ²Represent Alpha-hydroxy sec.-propyl or hydrogen atom independently, and at least one A ²Be the Alpha-hydroxy sec.-propyl.In addition, in general formula (44-1), R ⁵¹Expression hydrogen atom, hydroxyl, carbonatoms are the alkyl-carbonyl of the straight chain shape of 2-6 or a chain or straight chain shape that carbonatoms is 2-6 or the carbalkoxy of a chain.And then, in the general formula (44-2), R ⁵²Expression singly-bound, carbonatoms be the straight chain shape of 1-5 or a chain alkylidene group ,-O-,-CO-or-COO-.In addition, in the general formula (44-4), R ⁵³And R ⁵⁴Represent that hydrogen atom independent of each other or carbonatoms are the straight chain shape of 1-6 or the alkyl of a chain.

As above-mentioned benzene-like compounds 1, for example can enumerate particularly: Alpha-hydroxy isopropyl benzene class, as the Alpha-hydroxy isopropyl benzene, 1, two (Alpha-hydroxy sec.-propyl) benzene of 3-, 1, two (Alpha-hydroxy sec.-propyl) benzene of 4-, 1,2,4-three (Alpha-hydroxy sec.-propyl) benzene, 1,3,5-three (Alpha-hydroxy sec.-propyl) benzene etc., Alpha-hydroxy isopropyl benzene phenols, as 3-Alpha-hydroxy isopropyl-phenol, 4-Alpha-hydroxy isopropyl-phenol, 3, two (Alpha-hydroxy sec.-propyl) phenol of 5-, 2,4,6-three (Alpha-hydroxy sec.-propyl) phenol etc., Alpha-hydroxy isopropyl phenyl alkyl ketone, as 3-Alpha-hydroxy isopropyl phenyl methyl ketone, 4-Alpha-hydroxy isopropyl phenyl methyl ketone, 4-Alpha-hydroxy isopropyl phenyl ethyl ketone, 4-Alpha-hydroxy isopropyl phenyl n-propyl ketone, 4-Alpha-hydroxy isopropyl phenyl nezukone, 4-Alpha-hydroxy isopropyl phenyl normal-butyl ketone, 4-Alpha-hydroxy isopropyl phenyl tertiary butyl ketone, 4-Alpha-hydroxy isopropyl phenyl n-pentyl ketone, 3, two (Alpha-hydroxy sec.-propyl) acetophenone of 5-, 3, two (Alpha-hydroxy sec.-propyl) Propiophenones of 5-, 2,4,6-three (Alpha-hydroxy sec.-propyl) acetophenone etc., 4-Alpha-hydroxy isopropyl acid alkyl esters, as 3-Alpha-hydroxy isopropyl acid methyl esters, 4-Alpha-hydroxy isopropyl acid methyl esters, 4-Alpha-hydroxy isopropyl acid ethyl ester, 4-Alpha-hydroxy isopropyl acid n-propyl, 4-Alpha-hydroxy isopropyl acid isopropyl ester, the positive butyl ester of 4-Alpha-hydroxy isopropyl acid, the 4-Alpha-hydroxy isopropyl acid tert-butyl ester, 4-Alpha-hydroxy isopropyl acid n-pentyl ester, 3, two (Alpha-hydroxy sec.-propyl) methyl benzoate of 5-, 3, two (Alpha-hydroxy sec.-propyl) ethyl benzoates of 5-, 2,4,6-three (Alpha-hydroxy sec.-propyl) methyl benzoate etc.

In addition, as above-mentioned two benzene-like compounds 2, for example can enumerate particularly: Alpha-hydroxy isopropyl biphenyl class, as 3-Alpha-hydroxy isopropyl biphenyl, 4-Alpha-hydroxy isopropyl biphenyl, two (Alpha-hydroxy sec.-propyl) biphenyl of 3,5-, two (Alpha-hydroxy sec.-propyl) biphenyl of 3,3'-, 3, two (Alpha-hydroxy sec.-propyl) biphenyl of 4'-, two (Alpha-hydroxy sec.-propyl) biphenyl of 4,4'-, 2,4,6-three (Alpha-hydroxy sec.-propyl) biphenyl, 3,3', 5-three (Alpha-hydroxy sec.-propyl) biphenyl, 3,4', 5-three (Alpha-hydroxy sec.-propyl) biphenyl, 2,3', 4,6-four (Alpha-hydroxy sec.-propyl) biphenyl, 2,4,4', 6-four (Alpha-hydroxy sec.-propyl) biphenyl, 3,3', 5,5'-four (Alpha-hydroxy sec.-propyl) biphenyl, 2,3', 4,5', 6-five (Alpha-hydroxy sec.-propyl) biphenyl, 2,2', 4,4', 6,6'-six (Alpha-hydroxy sec.-propyl) biphenyl etc., Alpha-hydroxy isopropyl diphenyl base paraffinic, as 3-Alpha-hydroxy isopropyl diphenyl methylmethane, 4-Alpha-hydroxy isopropyl diphenyl methylmethane, 1-(4-Alpha-hydroxy isopropyl phenyl)-2-diphenylphosphino ethane, 1-(4-Alpha-hydroxy isopropyl phenyl)-2-phenyl-propane, 2-(4-Alpha-hydroxy isopropyl phenyl)-2-phenyl-propane, 1-(4-Alpha-hydroxy isopropyl phenyl)-3-phenyl-propane, 1-(4-Alpha-hydroxy isopropyl phenyl)-4-phenyl butane, 1-(4-Alpha-hydroxy isopropyl phenyl)-5-phenyl pentane, two (the Alpha-hydroxy isopropyl diphenyl methylmethanes of 3,5-, two (Alpha-hydroxy sec.-propyl) ditans of 3,3'-, 3, two (Alpha-hydroxy sec.-propyl) ditans of 4'-, two (Alpha-hydroxy sec.-propyl) ditans of 4,4'-, two (the 4-Alpha-hydroxy isopropyl phenyl) ethane of 1,2-, 1, two (the 4-Alpha-hydroxy propyl group phenyl) propane of 2-, two (the 4-Alpha-hydroxy propyl group phenyl) propane of 2,2-, two (the 4-Alpha-hydroxy propyl group phenyl) propane of 1,3-, 2,4,6-three (Alpha-hydroxy sec.-propyl) ditan, 3,3', 5-three (Alpha-hydroxy sec.-propyl) ditan, 3,4', 5-three (Alpha-hydroxy sec.-propyl) ditan, 2,3', 4,6-four (Alpha-hydroxy sec.-propyl) ditan, 2,4,4', 6-four (Alpha-hydroxy sec.-propyl) ditan, 3,3', 5,5'-four (Alpha-hydroxy sec.-propyl) ditan, 2,3', 4,5', 6-five (Alpha-hydroxy sec.-propyl) ditan, 2,2', 4,4', 6,6'-six (Alpha-hydroxy sec.-propyl) ditan etc., Alpha-hydroxy isopropyl diphenyl base ethers, as 3-Alpha-hydroxy isopropyl diphenyl base ether, 4-Alpha-hydroxy isopropyl diphenyl base ether, two (Alpha-hydroxy sec.-propyl) diphenyl ethers of 3,5-, two (Alpha-hydroxy sec.-propyl) diphenyl ethers of 3,3'-, 3, two (Alpha-hydroxy sec.-propyl) diphenyl ethers of 4'-, 4, two (Alpha-hydroxy sec.-propyl) diphenyl ethers of 4'-, 2,4,6-three (Alpha-hydroxy sec.-propyl) diphenyl ether, 3,3', 5-three (Alpha-hydroxy sec.-propyl) diphenyl ether, 3,4', 5-three (Alpha-hydroxy sec.-propyl) diphenyl ether, 2,3', 4,6-four (Alpha-hydroxy sec.-propyl) diphenyl ether, 2,4,4', 6-four (Alpha-hydroxy sec.-propyl) diphenyl ether, 3,3', 5,5'-four (Alpha-hydroxy sec.-propyl) diphenyl ether, 2,3', 4,5', 6-five (Alpha-hydroxy sec.-propyl) diphenyl ether, 2,2', 4,4', 6,6'-six (Alpha-hydroxy sec.-propyl) diphenyl ether etc., Alpha-hydroxy isopropyl diphenyl base ketone is as 3-Alpha-hydroxy isopropyl diphenyl base ketone, 4-Alpha-hydroxy isopropyl diphenyl base ketone, 3, two (Alpha-hydroxy sec.-propyl) diphenylketones of 5-, 3, two (Alpha-hydroxy sec.-propyl) diphenylketones of 3'-, two (Alpha-hydroxy sec.-propyl) diphenylketones of 3,4'-, two (Alpha-hydroxy sec.-propyl) diphenylketones of 4,4'-, 2,4,6-three (Alpha-hydroxy sec.-propyl) diphenylketone, 3,3', 5-three (Alpha-hydroxy sec.-propyl) diphenylketone, 3,4', 5-three (Alpha-hydroxy sec.-propyl) diphenylketone, 2,3', 4,6-four (Alpha-hydroxy sec.-propyl) diphenylketone, 2,4,4', 6-four (Alpha-hydroxy sec.-propyl) diphenylketone, 3,3', 5,5'-four (Alpha-hydroxy sec.-propyl) diphenylketone, 2,3', 4,5', 6-five (Alpha-hydroxy sec.-propyl) diphenylketone, 2,2', 4,4', 6,6'-six (Alpha-hydroxy sec.-propyl) diphenylketone etc., Alpha-hydroxy isopropyl acid phenyl ester class, as 3-Alpha-hydroxy isopropyl acid phenyl ester, 4-Alpha-hydroxy isopropyl acid phenyl ester, phenylformic acid 3-Alpha-hydroxy sec.-propyl phenyl ester, phenylformic acid 4-Alpha-hydroxy sec.-propyl phenyl ester, two (Alpha-hydroxy sec.-propyl) phenol benzoates of 3,5-, 3-Alpha-hydroxy isopropyl acid 3-Alpha-hydroxy sec.-propyl phenyl ester, 3-Alpha-hydroxy isopropyl acid 4-Alpha-hydroxy sec.-propyl phenyl ester, 4-Alpha-hydroxy isopropyl acid 3-Alpha-hydroxy sec.-propyl phenyl ester, 4-Alpha-hydroxy isopropyl acid 4-Alpha-hydroxy sec.-propyl phenyl ester, phenylformic acid 3, two (Alpha-hydroxy sec.-propyl) phenyl esters of 5-, 2,4,6-three (Alpha-hydroxy sec.-propyl) phenol benzoate, two (Alpha-hydroxy sec.-propyl) the phenylformic acid 3-Alpha-hydroxy sec.-propyl phenyl esters of 3,5-, two (Alpha-hydroxy sec.-propyl) the phenylformic acid 4-Alpha-hydroxy sec.-propyl phenyl esters of 3,5-, 3-Alpha-hydroxy isopropyl acid 3, two (Alpha-hydroxy sec.-propyl) phenyl esters of 5-, 4-Alpha-hydroxy isopropyl acid 3, two (Alpha-hydroxy sec.-propyl) phenyl esters of 5-, phenylformic acid 2,4,6-three (Alpha-hydroxy sec.-propyl) phenyl ester, 2,4,6-three (Alpha-hydroxy sec.-propyl) phenylformic acid 3-Alpha-hydroxy sec.-propyl phenyl ester, 2,4,6-three (Alpha-hydroxy sec.-propyl) phenylformic acid 4-Alpha-hydroxy sec.-propyl phenyl ester, 3, two (Alpha-hydroxy sec.-propyl) phenylformic acid 3 of 5-, two (Alpha-hydroxy sec.-propyl) phenyl esters of 5-, 3-Alpha-hydroxy isopropyl acid 2,4,6-three (Alpha-hydroxy sec.-propyl) phenyl ester, 4-Alpha-hydroxy isopropyl acid 2,4,6-three (Alpha-hydroxy sec.-propyl) phenyl ester, 2,4,6-three (Alpha-hydroxy sec.-propyl) phenylformic acid 3, two (Alpha-hydroxy sec.-propyl) phenyl esters of 5-, 3, two (Alpha-hydroxy sec.-propyl) phenylformic acid 2,4 of 5-, 6-three (Alpha-hydroxy sec.-propyl) phenyl ester, 2,4,6-three (Alpha-hydroxy sec.-propyl) phenylformic acid 2,4,6-three (Alpha-hydroxy sec.-propyl) phenyl ester etc.

Further, as above-mentioned naphthalene compounds 3, for example can enumerate particularly: 1-(Alpha-hydroxy sec.-propyl) naphthalene, 2-(Alpha-hydroxy sec.-propyl) naphthalene, two (Alpha-hydroxy sec.-propyl) naphthalenes of 1,3-, two (Alpha-hydroxy sec.-propyl) naphthalenes of 1,4-, 1, two (Alpha-hydroxy sec.-propyl) naphthalenes of 5-, 1, two (Alpha-hydroxy sec.-propyl) naphthalenes of 6-, two (Alpha-hydroxy sec.-propyl) naphthalenes of 1,7-, two (Alpha-hydroxy sec.-propyl) naphthalenes of 2,6-, 2, two (Alpha-hydroxy sec.-propyl) naphthalenes of 7-, 1,3,5-three (Alpha-hydroxy sec.-propyl) naphthalene, 1,3,6-three (Alpha-hydroxy sec.-propyl) naphthalene, 1,3,7-three (Alpha-hydroxy sec.-propyl) naphthalene, 1,4,6-three (Alpha-hydroxy sec.-propyl) naphthalene, 1,4,7-three (Alpha-hydroxy sec.-propyl) naphthalene, 1,3,5,7-four (Alpha-hydroxy sec.-propyl) naphthalene etc.

In addition, as above-mentioned furfuran compound 4, for example can enumerate particularly: 3-(Alpha-hydroxy sec.-propyl) furans, 2-methyl-3-(Alpha-hydroxy sec.-propyl) furans, 2-methyl-4-(Alpha-hydroxy sec.-propyl) furans, 2-ethyl-4-(Alpha-hydroxy sec.-propyl) furans, 2-n-propyl-4-(Alpha-hydroxy sec.-propyl) furans, 2-sec.-propyl-4-(Alpha-hydroxy sec.-propyl) furans, 2-normal-butyl-4-(Alpha-hydroxy sec.-propyl) furans, the 2-tertiary butyl-4-(Alpha-hydroxy sec.-propyl) furans, 2-n-pentyl-4-(Alpha-hydroxy sec.-propyl) furans, 2,5-dimethyl-3-(Alpha-hydroxy sec.-propyl) furans, 2,5-diethyl-3-(Alpha-hydroxy sec.-propyl) furans, 3, two (Alpha-hydroxy sec.-propyl) furans of 4-, 2,5-dimethyl-3, two (Alpha-hydroxy sec.-propyl) furans of 4-, 2,5-diethyl-3, two (Alpha-hydroxy sec.-propyl) furans of 4-etc.

As above-mentioned acid crosslinking agent G3, be preferably the compound with Alpha-hydroxy sec.-propyl free more than two, more preferably have two above Alpha-hydroxy sec.-propyls described benzene-like compounds 1, have two above Alpha-hydroxy sec.-propyls described two benzene-like compounds 2, have the described naphthalene compounds 3 of two above Alpha-hydroxy sec.-propyls, be preferably the Alpha-hydroxy isopropyl biphenyl class with two above Alpha-hydroxy sec.-propyls, the naphthalene compounds 3 with two above Alpha-hydroxy sec.-propyls especially.

Described acid crosslinking agent G3 can obtain by following method usually: the compound (as 1,3-diacetyl benzene etc.) that makes acetyl-containing and Grignard reagent are (as CH ₃MgBr etc.) reaction, after methylating, the method that is hydrolyzed; The compound (as 1,3-diisopropyl benzene etc.) that perhaps will contain sec.-propyl carries out oxidation with oxygen etc. and after generating superoxide, the method for reducing.

Among the present invention, the mix proportions of acid crosslinking agent G is for being the 0.5-70 weight part with respect to the above-mentioned ring compound A of per 100 weight parts, being preferably 0.5-40 weight part, 1-30 weight part more preferably.The mix proportions of above-mentioned acid crosslinking agent G makes resist film improve the deliquescent inhibition of alkaline-based developer when 0.5 weight part is above, reduces residual film ratio, and can suppress swelling and the crooked generation of figure, thereby preferred; On the other hand, when 70 weight parts are following, can suppress the stable on heating reduction as resist, thus preferred.

In addition, the mix proportions that is selected from least a compound among described acid crosslinking agent G1, acid crosslinking agent G2, the acid crosslinking agent G3 among the above-mentioned acid crosslinking agent G, also there is no particular limitation, can be when forming resist pattern the kind etc. of employed substrate set various scopes.

Under the preferable case, in total acid crosslinking agent component, described alkoxy methyl melamine compound and/or (43-1)-(43-3) shown in compound be 50-99 weight %, be preferably 60-99 weight %, more preferably 70-98 weight %, 80-97 weight % more preferably.By make the alkoxy methyl melamine compound and/or (43-1)-(43-3) shown in compound be more than the 50 weight % of total acid crosslinking agent composition, can improve resolving power, thereby preferred; By being below the 99 weight %, as the figure cross-sectional shape, form rectangular-shaped cross-sectional shape easily, thereby preferred.

In the present invention, also can be at fusion in radiation-ray sensitive composition acid diffusion control agent E, described sour diffusion control agent E has control by radiation exposure and diffusion in resist film of the acid that produced by acidogenic agent, stops the effect of non-undesirable chemical reaction in exposed areas etc.By using so sour diffusion control agent E, the storage stability of resist composition is improved; In addition, when resolving power is improved, can also suppress the line width variation of the resist pattern that the change by storage period of electron rays pre-irradiation, electron rays postradiation storage period causes, thus make fusion the radiation-ray sensitive composition of described sour diffusion control agent E become the extremely excellent material of technology stability.Sour diffusion control agent E as such, can enumerate: electron rays radiation decomposability basic cpd, as the basic cpd of nitrogen atom, alkaline sulfonium compound, alkaline iodine compound etc.The agent of acid diffusion control can be used alone or in combination of two or more.Particularly, can use with about the identical material of the material of the above-mentioned described mistake of radiation-ray sensitive composition A.

The blended amount of acid diffusion control agent E is preferably the 0.001-10 weight % of solids component gross weight, more preferably 0.001-5 weight %, more preferably 0.001-3 weight %.In the time of in above-mentioned scope, can prevent the variation such as reduction, graphics shape, size naturalness of resolving power.And even elongated from the storage period that electron rays irradiation begins till the radiation exposure post-heating, the shape of graphic design portion can variation yet.In addition, the blended amount of described sour diffusion control agent E is 10 weight % when following, can prevent the reduction of the development etc. of susceptibility, unexposed portion.In addition, by using so sour diffusion control agent, the storage stability of resist composition is improved, and resolving power is improved, can suppress simultaneously the line width variation of the resist pattern that caused by the change of storage period of electron rays pre-irradiation, electron rays postradiation storage period, thus make fusion the radiation-ray sensitive composition of described sour diffusion control agent E become the extremely excellent material of technology stability.

In the scope of not damaging purpose of the present invention, the various additives that can be as required add one or more in resist composition of the present invention are as the oxygen acid or derivatives thereof of dissolution accelerator, dissolving control agent, sensitizer, tensio-active agent and organic carboxyl acid or phosphorus etc.

The lower molecular weight dissolution accelerator

The lower molecular weight dissolution accelerator is, cross when low in the solvability of the developing solution of the alkali of ring compound A etc., have the composition that improves its solvability and suitably increase the effect of the dissolution rate of ring compound A when developing, can in the scope of not damaging effect of the present invention, use.As described dissolution accelerator, can enumerate for example low-molecular-weight phenolic compound, for example can enumerate: bisphenols, three (hydroxyphenyl) methane etc.These dissolution accelerators can use in independent or two or more mixing.The blended amount of dissolution accelerator can suit according to the kind of employed described ring compound A to regulate, the summation of ring compound A and lower molecular weight dissolution accelerator becomes the 50-99.999 weight % of the gross weight of solids component, be preferably 60-99 weight %, more preferably 70-99 weight %, the more preferably amount of 80-99 weight %.

About the various additives such as oxygen acid or derivatives thereof of dissolving control agent, sensitizer, tensio-active agent and organic carboxyl acid or phosphorus, can use with about the identical material of the material of the above-mentioned described mistake of radiation-ray sensitive composition A.

The mix proportions of radiation-sensitive resist composition of the present invention (any composition F of ring compound A/ acidogenic agent C/ acid crosslinking agent G/ acid diffusion control agent E/), be the weight % of benchmark in the solid matter, be preferably 3-96.9/0.1-30/3-65/0.01-30/0-93.9,65-96.9/0.1-30/0.3-34.9/0.01-30/0-30 more preferably, 65-96.9/0.1-30/0.3-34.9/0.01-30/0-10 more preferably, further be preferably 65-96.9/0.1-30/0.6-34.9/0.01-30/0-5, most preferably be 65-96.9/0.1-30/0.6-30/0.01-30/0.When adopting above-mentioned mix proportions, the excellent performance of susceptibility, resolving power and alkali-developable etc.

When not containing any composition F, the composition of the total solids material in the radiation-sensitive resist composition of the present invention is preferably: A is that 3-96.9 weight %, C are that 0.1-30 weight %, G are that 0.3-96.9 weight %, E are 0.01-30 weight %, (A+C+G+E=100 weight %); More preferably A is that 65-96.9 weight %, C are that 0.1-32 weight %, G are that 0.3-34.9 weight %, E are 0.01-30 weight %, (A+C+G+E=100 weight %); Further preferred A is that 70-96.9 weight %, C are that 0.1-27 weight %, G are that 0.3-29.9 weight %, E are 0.01-30 weight %, (A+C+G+E=100 weight %); Preferred especially A is that 80-96.9 weight %, C are that 0.1-17 weight %, G are that 0.3-19.9 weight %, E are 0.01-30 weight %, (A+C+G+E=100 weight %); Most preferably being A is that 90-96.9 weight %, C are that 0.1-7 weight %, G are that 0.3-9.9 weight %, E are 0.01-30 weight %, (A+C+G+E=100 weight %); In the time of in above-mentioned scope, the excellent performance of susceptibility, resolving power and alkali-developable etc.

As the described solvent that in the preparation of radiation-ray sensitive composition of the present invention, uses, can use with about the identical material of the material of the above-mentioned described mistake of radiation-ray sensitive composition A.

In the scope of not damaging purpose of the present invention, radiation-ray sensitive composition of the present invention can contain the resin that dissolves in the alkaline aqueous solution.As the resin that dissolves in the alkaline aqueous solution, can enumerate: resol, polyethylene phenols, polyacrylic acid, polyvinyl alcohol, phenylethylene-maleic anhydride resin, and the polymkeric substance that contains vinylformic acid, vinyl alcohol or vinylphenol as monomeric unit, or their derivative etc.Dissolve in the blended amount of the resin of the alkaline aqueous solution, can regulate aptly according to the kind of employed resist compound, with respect to the above-mentioned ring compound A of per 100 weight parts, be preferably 30 weight parts following, more preferably 10 weight parts following, more preferably 5 weight parts following, be preferably 0 weight part especially.

(being used to form composition D and the lower membrane of lower membrane)

The present invention relates to be used to form the composition of lower membrane, wherein, this composition that is used to form lower membrane contains any one among the above-mentioned radiation-ray sensitive composition C.

In addition, the present invention relates to be used to form the composition of lower membrane, wherein, this composition that is used to form lower membrane contains the ring compound shown in the following formula (45).

[chemical formula 86]

(in the formula, R ¹Represent that independently carbonatoms is straight chain shape, chain or the alkyl of ring-type or aryl, allyl group, hydroxyalkyl, cyano group alkyl, haloalkyl, hydroxyaryl, cyano-aryl or the halogenated aryl that carbonatoms is 6-24 of 1-20.）

Above-mentioned ring compound is owing to have second-order transition temperature, thermotolerance height more than 200 ℃, have amorphism, thereby film-forming properties well and not has sublimability.Further, it is shocking when having the benzene structure, lower to the optical extinction coefficient of the light of 193nm, and to have the high advantage of specific refractory power.

As the R in the formula of the present invention (45) ¹Object lesson, can enumerate: carbonatoms is the alkyl of straight chain shape, chain or the ring-type of 1-20, as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, cyclohexyl ethyl, cyclohexyl propyl group etc.; Carbonatoms is the hydroxyalkyl of straight chain shape, a chain or the ring-type of 1-20, as methylol, hydroxyethyl, hydroxypropyl, hydroxyl butyl, hydroxyl amyl group, hydroxyl hexyl, hydroxyl heptyl, hydroxyl octyl group, hydroxyl nonyl, hydroxy decyl, hydroxy-cyclohexyl ethyl, hydroxy-cyclohexyl propyl group etc.; Carbonatoms is the cyano group alkyl of straight chain shape, a chain or the ring-type of 1-20, as cyano methyl, cyano ethyl, cyano group propyl group, cyano group butyl, cyano group amyl group, cyano group hexyl, cyano group heptyl, cyano group octyl group, cyano group nonyl, cyano group decyl, cyanocyclohexanoic base ethyl, cyanocyclohexanoic base propyl group etc.; Carbonatoms is the haloalkyl of straight chain shape, a chain or the ring-type of 1-20, as halogenated methyl, halogenated ethyl, halopropyl, halogenated butyl, halo amyl group, halo hexyl, halo heptyl, halo octyl group, halo nonyl, halo decyl, halo cyclohexyl ethyl, halo cyclohexyl propyl group etc.; Carbonatoms is the aryl of 6-20, as phenyl, naphthyl, indanyl, indenyl, fluorenyl, anthryl, phenanthryl, pyrenyl, xenyl, terphenylyl, tolyl, ethylphenyl, isopropyl phenyl, the n-propyl phenyl, isobutyl phenenyl, tert-butyl-phenyl, xenyl, the 4-cyclohexyl phenyl, 4-propyl group-4-cyclohexyl phenyl, 4-butyl-4-cyclohexyl phenyl, 4-amyl group-4-cyclohexyl phenyl, 4-salicyl phenyl (4-サリチ Le Off エニ Le base), 4-norcamphyl phenyl, 4-adamantyl phenyl, 4-dicyclopentadienyl phenyl, 4-three cyclopentyl phenyl etc.; Cyano-aryl, as 4-cyano-phenyl, 4-cyanobiphenyl base etc.; Halogenated aryl is as 4-halogenophenyl, 4-halogenated biphenyl base etc.; Hydroxyaryl is as 4-hydroxy phenyl etc.

Wherein, be preferably aryl, hydroxyaryl, cyano-aryl, the halogenated aryl that carbonatoms is 6-24 especially.

Ring compound among the present invention can obtain cis body and trans body, can be any structure or mixture.Only had any one the method for ring compound of structure in cis body and the trans body, for example can use: utilizing column chromatography or the preparation separation carried out of liquid-liquid chromatography or in the preparation, known method such as optimization such as reaction solvent and temperature of reaction are carried out.

Further, the ring compound that contains in the composition of lower membrane that is used to form of the present invention is preferably the ring compound shown in following (46) formula.

[chemical formula 87]

(in the formula, R ²Be hydrogen atom independently, carbonatoms is the alkyl of straight chain shape, a chain or the ring-type of 1-12, halogen atom, cyano group, hydroxyl, alkoxyl group, ester group.）

By having the structure shown in (46) formula, can be undertaken resolization by aldehydes (as formaldehyde or acetaldehyde etc.) and acid catalyst, can give further elching resistant, and can not use relatively expensive linking agent and light acid producing agent and suppress to mix.

R in the formula of the present invention (46) ²Can enumerate: carbonatoms is the alkyl of straight chain shape, a chain or the ring-type of 1-12, as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, cyclohexyl, 4-methylcyclohexyl, 4-ethyl cyclohexyl, 4-n-propyl cyclohexyl, 4-normal-butyl cyclohexyl, 4-n-pentyl cyclohexyl, 4-n-hexyl cyclohexyl, dicyclohexyl, norcamphyl, norbornene, cyclopentenyl, three cyclopentenyls, adamantyl etc.; Halogeno-group, fluorine-based, chloro, bromo, iodo etc.; Cyano group; Hydroxyl; Alkoxyl group is as methoxyl group, oxyethyl group, propoxy-, isopropoxy etc.; Ester group is as methoxycarbonyl, ethoxycarbonyl, propyl ester base, isopropyl ester group, butyl ester base, isobutyl ester group etc.

Wherein, especially carbonatoms is that the alkyl (cyclohexyl, 4-methylcyclohexyl, 4-ethyl cyclohexyl, 4-n-propyl cyclohexyl, 4-normal-butyl cyclohexyl, 4-n-pentyl cyclohexyl, 4-n-hexyl cyclohexyl, norcamphyl etc.) of straight chain shape, chain or the ring-type of 1-12 is given high refractive index and suitable optical extinction coefficient to the light of 193nm, thereby preferred.

Further, as the ring compound that contains in the composition of lower membrane that is used to form of the present invention, be preferably the material shown in described formula (2) or the formula (3).

Ring compound shown in described (45) formula can be that more than one and the condensation reaction that contains the compound of Resorcinol in the group formed of the aliphatics of 1-20 or aromatic aldehyde that carbonatoms is 6-24 obtains by being selected from by carbonatoms.

Be that fatty aldehyde or the carbonatoms of 1-20 is the aromatic aldehyde of 6-24 as carbonatoms, can enumerate: straight chain shape or a chain fatty aldehyde, as formaldehyde, acetaldehyde, propionic aldehyde, isopropyl aldehyde, 1-butyraldehyde, isobutyric aldehyde, 1-valeral, isovaleric aldehyde, pivalyl aldehyde, 1-hexanal, isocaproaldehyde, 1-capraldehyde, 1-dodecanal etc.; Aromatic aldehyde is as phenyl aldehyde, toluic aldehyde, ethylbenzene formaldehyde, cumylene, n-propylbenzene formaldehyde, isobutyric aldehyde, uncle's butyraldehyde, phenyl phenyl aldehyde, 4-cyclohexyl benzaldehyde, 4-propyl group-4-cyclohexyl benzaldehyde, 4-butyl-4-cyclohexyl benzaldehyde, 4-amyl group-4-cyclohexyl benzaldehyde, 4-cyanobenzaldehyde, 4-halogeno-benzene formaldehyde, 4-hydroxy benzaldehyde, 4-salicyl phenyl aldehyde, 4-norcamphyl phenyl aldehyde, 4-adamantyl phenyl aldehyde, 4-Dicyclopentadiene (DCPD) benzaldehyde, 4-three cyclopentyl phenyl aldehydes, naphthaldehyde, formaldehyde, anthraldehyde, pyrene formaldehyde etc.

Contain in the compound of the aromatic aldehyde that fatty aldehyde that these carbonatomss are 1-20 or carbonatoms be 6-24, be preferably 4-propyl group-4-cyclohexyl benzaldehyde, 4-amyl group-4-cyclohexyl benzaldehyde, further, be preferably 4-(trans-4-n-propyl cyclohexyl) phenyl aldehyde, 4-(trans-4-n-pentyl cyclohexyl) phenyl aldehyde especially.

Ring compound shown in the formula (45) can prepare by known method.For example, can obtain by following method: at organic solvent (toluene, methyl alcohol, ethanol etc.) in, at thioacetic acid or β-Qiu Jibingsuan, and acid catalyst (hydrochloric acid, sulfuric acid or tosic acid) existence under, use molar ratio as 1:(1 to excessive) carbonyl compound (as aromatic aldehyde etc.) and phenols (as phenol, ortho-cresol, Resorcinol etc.), 60-150 ℃ of degree of reacting 0.5-20 hour down, after reaction finishes, in reaction solution, add toluene and be heated to 60-80 ℃, stir after 0.5-2 hour, cool to room temperature, filter then and separate, make its drying at last.

The molecular weight of above-mentioned ring compound is preferably more than 400 below 2000, more preferably more than 600 below 2000, more preferably more than 800 below 1500.In the time of in above-mentioned scope, can obtain that film-forming properties is good, elching resistant is good and the few lower membrane material of distillation composition.

Described ring compound can obtain cis body and trans body, can be any one structure or mixture.

In lower membrane composition of the present invention, also can use by the ring compound shown in above-mentioned and the dehydration condensation resin that obtain, that have the such repeating unit of following formula of aldehydes.

[chemical formula 88]

As aldehydes as used herein, for example can enumerate: formaldehyde, trioxane, Paraformaldehyde 96, acetaldehyde etc.Wherein, be preferably formaldehyde especially.

At this, repeating unit is unqualified.Because polyphenol self does not have sublimability, therefore also unreacted polyphenolic substance can residually be arranged, but surpass at 50000 o'clock at Mw, because the excessive situation that can not be rotated coating that has of viscosity.

The present invention can contain linking agent G and the acidogenic agent C that is useful on the inhibition mixing.

If enumerate the object lesson of operable linking agent among the present invention, can enumerate: be selected from the melamine compound that at least a group replaced, guanamines compound, glycoluril compounds or carbamide compound, epoxy compounds, sulfo-epoxy compounds, isocyanate compound, triazo-compound in methylol, alkoxy methyl, the acyloxy methyl, contain the compound of two keys of alkenyl ether etc.They also can be used as additive, also these crosslinkable groups can be incorporated in the polymer lateral chain as side group.In addition, the compound that contains hydroxyl also can be used as linking agent.

In above-mentioned all compounds, if the illustration epoxy compounds can example illustrate: three (2,3-epoxypropyl) isocyanuric acid ester, Pehanorm triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, trimethylolethane trimethacrylate glycidyl ether etc.If illustration melamine compound particularly can be enumerated: the 1-6 of hexamethylolmelamine, HMMM, a hexamethylolmelamine methylol by 1-6 methylol of the compound of methoxymethylization or its mixture, hexa methoxy ethyl trimeric cyanamide, six acyloxy methyl melamines, hexamethylolmelamine by the methylated compound of acyloxy or its mixture.As the guanamines compound, can enumerate: 1-4 methylol of tetra methylol guanamines, tetramethoxy methyl guanamines, tetra methylol guanamines by 1-4 methylol of the compound of methoxymethylization or its mixture, tetramethoxy ethyl guanamines, four acyloxy guanamines, tetra methylol guanamines by the methylated compound of acyloxy or its mixture.As glycoluril compounds, can enumerate: 1-4 methylol of tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethylglycoluril, tetramethylol glycoluril by 1-4 methylol of the compound of methoxymethylization or its mixture, tetramethylol glycoluril by the methylated compound of acyloxy or its mixture.As carbamide compound, can enumerate 1-4 methylol of tatramethylol urea, tetramethoxy methyl urea, tatramethylol urea by the compound of methoxymethylization or its mixture, tetramethoxy ethyl carbamide etc.

As the compound that contains the alkenyl ether, can enumerate: ethylene glycol bisthioglycolate vinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, 1,4-butyleneglycol divinyl ether, tetramethyl glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane tris vinyl ether, hexylene glycol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetramethylolmethane trivinyl ether, tetramethylolmethane tetrem alkene ether, Sorbitol Powder tetrem alkene ether, Sorbitol Powder five vinyl ether, trimethylolpropane tris vinyl ether etc.

With respect to the ring compound of 100 parts (mass parts, below identical), the blended amount of linking agent G is preferably 5-50 part, is preferably 10-40 part especially.During 5 parts of less thaies, there is the situation of mixing with resist; When surpassing 50 parts, exist to prevent that reflecting effect from reducing and the situation of crackle appears in the film after crosslinked.

Can add the acidogenic agent C for the crosslinking reaction that further promotes to be caused by heat.Acidogenic agent C has by thermolysis acidic acidogenic agent and by rayed and acidic acidogenic agent can add any one acidogenic agent.

As employed acidogenic agent C among the present invention, can enumerate:

1) following general formula (P1a-1), (P1a-2), (P1a-3) or salt (P1b),

2) diazomethane derivative of following general formula (P2),

3) the glyoxime derivative of following general formula (P3),

4) two sulfone derivativess of following general formula (P4),

5) sulphonate of the N-hydroxyimide compound of following general formula (P5),

6) β-ketosulfonic acid derivative,

7) two sulfone derivativess,

8) nitrobenzyl sulfonate esters derivative,

9) sulfonate derivatives etc.

[chemical formula 89]

(in the formula, R ^101a, R ^101b, R ^101cRepresent that separately carbonatoms is aralkyl or the aryl oxide substituted alkyl that alkyl, alkenyl, oxoalkyl group or the oxo alkenyl of straight chain shape, chain or the ring-type of 1-12, aryl that carbonatoms is 6-20 or carbonatoms are 7-12, part or all of the hydrogen atom of these groups also can alkoxy etc. replacement.In addition, R ^101bAnd R ^101cAlso can form ring, when forming ring, R ^101b, R ^101cRepresent that separately carbonatoms is the alkylidene group of 1-6.K ^-Represent non-nucleophilicity gegenion.Show at R ^101d, R ^101e, R ^101f, R ^101gExpression R ^101a, R ^101b, R ^101cThe middle hydrogen atom that adds.R ^101dAnd R ^101e, R ^101dAnd R ^101eAnd R ^101fAlso can form ring, when forming ring, R ^101dAnd R ^101eAnd R ^101dAnd R ^101eAnd R ^101fThe expression carbonatoms is the alkylidene group of 3-10.The aromatic heterocycle that also has the nitrogen-atoms in the formula in the representative ring.）

Above-mentioned R ^101a, R ^101b, R ^101c, R ^101d, R ^101e, R ^101f, R ^101gCan be the same or different each other, particularly, as alkyl, can enumerate: methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, cyclopentyl, cyclohexyl, suberyl, cyclopropyl methyl, 4-methylcyclohexyl, cyclohexyl methyl, norcamphyl, adamantyl etc.As alkenyl, can enumerate: vinyl, allyl group, propenyl, butenyl, hexenyl, cyclohexenyl etc.As oxoalkyl group, can enumerate: 2-oxocyclopentyl, 2-oxo cyclohexyl etc., also can enumerate: 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, 2-(4-methylcyclohexyl)-2-oxoethyl etc.As aryl, can enumerate: phenyl; Naphthyl etc.; Or alkoxyl phenyl, as p-methoxyphenyl, key p-methoxy-phenyl, o-methoxyphenyl, ethoxyl phenenyl, to tert.-butoxy phenyl, a tert.-butoxy phenyl etc.; Alkyl phenyl is as 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, ethylphenyl, 4-tert-butyl-phenyl, 4-butyl phenyl, 3,5-dimethylphenyl etc.; The alkyl naphthyl is as methyl naphthyl, ethyl naphthyl etc.; The alkoxyl group naphthyl is as methoxyl group naphthyl, oxyethyl group naphthyl etc.; The dialkyl group naphthyl is as dimethyl naphthyl, diethyl naphthyl etc.; The dialkoxy naphthyl is as dimethoxy naphthyl, diethoxy naphthyl etc.As aralkyl, can enumerate: benzyl, styroyl, styroyl etc.As the aryl oxide substituted alkyl, can enumerate: 2-aryl 2-oxoethyl, as 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, 2-(2-naphthyl)-2-oxoethyl etc.As K ^-Non-nucleophilicity gegenion, can enumerate: halide ions, as chloride ion, bromide ion etc.; The fluoro-alkyl sulphonate, as trifluoromethane sulfonic acid ester, 1,1,1-trifluoroethyl sulphonate, nine fluoro butyl sulfonic acid esters etc.; Aromatic yl sulphonate is as tosylate, benzene sulfonate, 4-fluorobenzene sulphonate, 1,2,3,4,5-penta fluoro benzene sulphonate etc.; Alkyl sulfonic ester is as methanesulfonates (メシレ one ト), butyl sulfonic acid ester etc.

In addition, R ^101d, R ^101e, R ^101f, R ^101gFor having the aromatic heterocycle of the nitrogen-atoms in the formula in the ring, can example illustrate: imdazole derivatives (imidazoles for example, 4-methylimidazole, 4-methyl-2-phenylimidazole etc.), pyrazole derivatives, Furazan Derivatives, pyrroline derivative (pyrroline for example, 2-methyl isophthalic acid-pyrroline etc.), pyrrolidin derivatives (tetramethyleneimine for example, the N-crassitude, pyrrolidone, N-Methyl pyrrolidone etc.), imidazolidine derivatives, imidazolidine derivative, pyridine derivate (pyridine for example, picoline, ethylpyridine, the propyl group pyridine, butyl-pyridinium, 4-(1-butyl amyl group) pyridine), lutidine, trimethylpyridine, the triethyl pyridine, phenylpyridine, 3-methyl-2-phenylpyridine, the 4-tert .-butylpyridine, the xenyl pyridine, benzyl-pyridine, methoxypyridine, the butoxy pyridine, dimethoxy-pyridine, 1-methyl-2-pyridine, 4-pyrrolidyl pyridine, 1-methyl-4-phenylpyridinium, 2-(1-ethyl propyl) pyridine, aminopyridine, Dimethylamino pyridine etc.), pyridazine derivatives, pyrimidine derivatives, pyrazines derivatives, pyrazoline derivative, pyrazolidine derivatives, piperidine derivative, bridged piperazine derivatives, morpholine derivative, indole derivatives, isoindole derivatives, the 1H-indazole derivatives, the indoline derivative thing, quinoline (quinoline for example, 3-cyano quinolines etc.), isoquinilone derivatives, cinnoline derivatives, quinazoline derivant, quinoxaline derivatives, phthalazine derivatives, purine derivative, pteridine derivatives, carbazole derivative, phenanthroline derivative, acridine derivatives, the azophenlyene derivative, 1,10-phenanthrolene derivative, adenine derivative, adenosine derivative, guanine derivatives, the guanosine derivative, uracil derivative, uridine derivatives etc.

Above-mentioned general formula (P1a-1) and general formula (P1a-2) have the two effect of light acid producing agent, hot acidogenic agent, but above-mentioned general formula (P1a-3) plays a role as hot acidogenic agent.

[chemical formula 90]

(in the formula, R ^102a, R ^102bRepresent that separately carbonatoms is the alkyl of straight chain shape, a chain or the ring-type of 1-8.R ¹⁰³The expression carbonatoms is the alkylidene group of straight chain shape, a chain or the ring-type of 1-10.R ^104a, R ^104bRepresent that separately carbonatoms is the 2-oxoalkyl group of 3-7.K ^-Represent non-nucleophilicity gegenion.）

As R ^102a, R ^102b, can enumerate particularly: methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, cyclopentyl, cyclohexyl, cyclopropyl methyl, 4-methylcyclohexyl, cyclohexyl methyl etc.As R ¹⁰³, can enumerate methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, octylene, nonamethylene, 1,4-cyclohexylidene, 1,2-cyclohexylidene, 1,3-cyclopentylidene, 1, the inferior ring of 4-octyl group, 1,4-cyclohexanedimethyleterephthalate etc.As R ^104a, R ^104b, can enumerate: 2-propionyl, 2-ring pentanoyl, 2-hexamethylene acyl group, 2-ring oenanthyl etc.K ^-Can enumerate: with in formula (P1a-1), (P1a-2) and the identical group of the group that illustrated (P1a-3).

[chemical formula 91]

(in the formula, R ¹⁰⁵, R ¹⁰⁶The expression carbonatoms is alkyl or the haloalkyl of straight chain shape, a chain or the ring-type of 1-12; Carbonatoms is aryl or the halogenated aryl of 6-20; Perhaps carbonatoms is the aralkyl of 7-12.）

As R ¹⁰⁵, R ¹⁰⁶, can enumerate: methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, amyl group, cyclopentyl, cyclohexyl, suberyl, norcamphyl, adamantyl etc.As haloalkyl, can enumerate: trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-three chloroethyls, nine fluorine butyl etc.As aryl, can enumerate: phenyl; Alkoxyl phenyl is as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyl phenenyl, to tert.-butoxy phenyl, a tert.-butoxy phenyl etc.; Alkyl phenyl is as 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, ethylphenyl, 4-tert-butyl-phenyl, 4-butyl phenyl, 3,5-dimethylphenyl etc.As halogenated aryl, can enumerate: fluorophenyl, chloro-phenyl-, 1,2,3,4,5-pentafluorophenyl group etc.As aralkyl, can enumerate: benzyl, styroyl etc.

[chemical formula 92]

(in the formula, R ¹⁰⁷, R ¹⁰⁸, R ¹⁰⁹The expression carbonatoms is alkyl or the haloalkyl of straight chain shape, a chain or the ring-type of 1-12; Carbonatoms is aryl or the halogenated aryl of 6-20; Perhaps carbonatoms is the aralkyl of 7-12.R ¹⁰⁸, R ¹⁰⁹The formation ring texture that also can mutually combine, when forming ring texture, R ¹⁰⁸, R ¹⁰⁹Represent that separately carbon atom is the straight chain shape of 1-6 or the alkylidene group of a chain.）

As R ¹⁰⁷, R ¹⁰⁸, R ¹⁰⁹Alkyl, haloalkyl, aryl, halogenated aryl, aralkyl, can enumerate with at R ¹⁰⁵, R ¹⁰⁶The middle identical group of group that illustrated.Moreover, as R ¹⁰⁸, R ¹⁰⁹, can enumerate: methylene radical, ethylidene, propylidene, butylidene, hexylidene etc.

[chemical formula 93]

(in the formula, R ^101a, R ^101bSame as described above.）

[chemical formula 94]

(in the formula, R ¹¹⁰The expression carbonatoms is that the arylidene of 6-10, alkylidene group or the carbonatoms that carbonatoms is 1-6 are the alkylene group of 2-6, and part or all of the hydrogen atom of these groups also can further be replaced by alkyl or alkoxyl group, nitro, ethanoyl or the phenyl of carbonatoms by the straight chain shape of 1-4 or a chain.R ¹¹¹The expression carbonatoms is alkyl, alkenyl or alkoxyalkyl, phenyl or the naphthyl of straight chain shape, a chain or the replacement of 1-8, and part or all of the hydrogen atom of these groups also can further be replaced by following radicals: carbonatoms is alkyl or the alkoxyl group of 1-4; Can be the phenyl that alkyl, alkoxyl group, nitro or ethanoyl replaced of 1-4 by carbonatoms also; Carbonatoms is the heteroaromatic group of 3-5; Or chlorine atom, fluorine atom.）

At this, as R ¹¹⁰Arylidene, can enumerate 1,2-phenylene, 1,8-naphthylidene etc.; As alkylidene group, can enumerate methylene radical, ethylidene, propylidene, butylidene, styrene, norbornane-2,3-two bases etc.; As alkylene group, can enumerate vinylene, 1-phenyl-vinylene, 5-norbornylene-2,3-two bases etc.As R ¹¹¹Alkyl, for R ^101a～R ^101cIdentical group; As alkenyl, can enumerate vinyl, 1-propenyl, allyl group, 1-butylene base, 3-butenyl, isobutenyl, 1-pentenyl, 3-pentenyl, 4-pentenyl, dimethyl-allyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, 1-heptenyl, 3-heptenyl, 6-heptenyl, 7-octenyl etc.; As alkoxyalkyl, can enumerate methoxymethyl, ethoxyl methyl, propoxy-methyl, butoxymethyl, pentyloxy methyl, hexyloxy methyl, heptan oxygen ylmethyl, methoxy ethyl, ethoxyethyl group, propoxy-ethyl, butoxyethyl group, pentyloxy ethyl, hexyloxy ethyl, methoxy-propyl, ethoxycarbonyl propyl, propoxy-propyl group, butoxy propyl group, methoxyl group butyl, oxyethyl group butyl, propoxy-butyl, methoxyl group amyl group, oxyethyl group amyl group, methoxyl group hexyl, methoxyl group heptyl etc.

Moreover, as also can further substituted carbonatoms the alkyl that is 1-4, can enumerate methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl etc.; Be the alkoxyl group of 1-4 as carbonatoms, can enumerate methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy etc.; As being the alkyl, alkoxyl group, nitro of 1-4 or the phenyl that ethanoyl replaces by carbonatoms also, can enumerate phenyl, tolyl, to the tert.-butoxy phenyl, to acetylphenyl, p-nitrophenyl etc.; Be the heteroaromatic group of 3-5 as carbonatoms, can enumerate pyridyl, furyl etc.

Can enumerate particularly: salt, as the trifluoromethane sulfonic acid tetramethyl-ammonium, nine fluorine butyl sulfonic acid tetramethyl-ammoniums, nine fluorine butyl sulfonic acid triethyl ammoniums, nine fluorine butyl sulfonic acid pyridinium salts, Camphanyl sulfonic acid triethyl ammonium, Camphanyl sulfonic acid pyridinium salt, nine fluorine butyl sulfonic acid tetra-n-butyl ammoniums, nine fluorine butyl sulfonic acid tetraphenyl ammoniums, the tosic acid tetramethyl-ammonium, trifluoromethane sulfonic acid phenylbenzene iodine, trifluoromethane sulfonic acid (to the tert.-butoxy phenyl) phenyl-iodide, tosic acid phenylbenzene iodine, tosic acid (to the tert.-butoxy phenyl) phenyl-iodide, the trifluoromethane sulfonic acid triphenylsulfonium, trifluoromethane sulfonic acid (to tert-butyl-phenyl) phenylbenzene sulfonium, two (to the tert.-butoxy phenyl) the phenyl sulfoniums of trifluoromethane sulfonic acid, trifluoromethane sulfonic acid three (to the tert.-butoxy phenyl) sulfonium, the tosic acid triphenylsulfonium, tosic acid (to the tert.-butoxy phenyl) phenylbenzene sulfonium, two (to the tert.-butoxy phenyl) the phenyl sulfoniums of tosic acid, tosic acid three (to the tert.-butoxy phenyl) sulfonium, nine fluorine butyl sulfonic acid triphenylsulfonium, the butyl sulfonic acid triphenylsulfonium, the trifluoromethane sulfonic acid trimethylsulfonium, the tosic acid trimethylsulfonium, trifluoromethane sulfonic acid cyclohexyl methyl (2-oxo cyclohexyl) sulfonium, tosic acid cyclohexyl methyl (2-oxo cyclohexyl) sulfonium, trifluoromethane sulfonic acid 3,5-dimethylphenyl sulfonium, tosic acid 3,5-dimethylphenyl sulfonium, trifluoromethane sulfonic acid dicyclohexyl phenyl sulfonium, tosic acid dicyclohexyl phenyl sulfonium, trifluoromethane sulfonic acid three naphthyl sulfoniums, trifluoromethane sulfonic acid cyclohexyl methyl (2-oxo cyclohexyl) sulfonium, trifluoromethane sulfonic acid (2-norcamphyl) methyl (2-oxo cyclohexyl) sulfonium, ethylene two [trifluoromethane sulfonic acid methyl (2-oxocyclopentyl) sulfonium salt], trifluoromethanesulfonic acid 1,2 '-naphthyl carbonyl methyl tetramethylene sulfide salt etc.;

Diazomethane derivative is as two (phenyl sulfonyl) diazomethane; two (p-methylphenyl alkylsulfonyl) diazomethane; two (xylyl alkylsulfonyl) diazomethane; two (cyclohexyl alkylsulfonyl) diazomethane; two (cyclopentyl alkylsulfonyl) diazomethane; two (normal-butyl alkylsulfonyl) diazomethane; two (isobutyl-alkylsulfonyl) diazomethane; two (sec-butyl alkylsulfonyl) diazomethane; two (n-propyl alkylsulfonyl) diazomethane; two (sec.-propyl alkylsulfonyl) diazomethane; two (tertiary butyl alkylsulfonyl) diazomethane; two (n-pentyl alkylsulfonyl) diazomethane; two (isopentyl alkylsulfonyl) diazomethane; two (sec.-amyl sec-pentyl secondary amyl alkylsulfonyl) diazomethane; two (tert-pentyl alkylsulfonyl) diazomethane; 1-cyclohexyl alkylsulfonyl-1-(tertiary butyl alkylsulfonyl) diazomethane; 1-cyclohexyl alkylsulfonyl-1-(tert-pentyl alkylsulfonyl) diazomethane; 1-tert-pentyl alkylsulfonyl-1-(tertiary butyl alkylsulfonyl) diazomethane etc.

The glyoxime derivative, as two-(p-methylphenyl alkylsulfonyl)-alpha-alpha-dimethyl glyoxime, two-(p-methylphenyl alkylsulfonyl)-α-phenylbenzene glyoxime, two-(p-methylphenyl alkylsulfonyl)-α-dicyclohexyl glyoxime, two-(p-methylphenyl alkylsulfonyl)-2,3-diacetylmethane glyoxime, two-(p-methylphenyl alkylsulfonyl)-2-methyl-3,4-diacetylmethane glyoxime, two-(normal-butyl alkylsulfonyl)-alpha-alpha-dimethyl glyoxime, two-(normal-butyl alkylsulfonyl)-α-phenylbenzene glyoxime, two-(normal-butyl alkylsulfonyl)-α-dicyclohexyl glyoxime, two-(normal-butyl alkylsulfonyl)-2,3-diacetylmethane glyoxime, two-(normal-butyl alkylsulfonyl)-2-methyl-3,4-diacetylmethane glyoxime, two-(methyl sulphonyl)-alpha-alpha-dimethyl glyoxime, two-(trifluoromethyl sulfonyl)-alpha-alpha-dimethyl glyoxime, two-(1,1,1-trifluoroethyl alkylsulfonyl)-the alpha-alpha-dimethyl glyoxime, two-(tertiary butyl alkylsulfonyl)-alpha-alpha-dimethyl glyoxime, two-(perfluorooctyl sulfonyl)-alpha-alpha-dimethyl glyoxime, two-(cyclohexyl alkylsulfonyl)-alpha-alpha-dimethyl glyoxime, two-(phenyl sulfonyl)-alpha-alpha-dimethyl glyoxime, two-(to the fluorophenyl alkylsulfonyl)-alpha-alpha-dimethyl glyoxime, two-(to the tert-butyl-phenyl alkylsulfonyl)-alpha-alpha-dimethyl glyoxime, two-(xylyl alkylsulfonyl)-alpha-alpha-dimethyl glyoxime, two-(Camphanyl alkylsulfonyl)-alpha-alpha-dimethyl glyoxime etc.;

Two sulfone derivativess are as two naphthyl alkylsulfonyl methane, bis trifluoromethyl alkylsulfonyl methane, two methyl sulfonyl methane, two ethylsulfonyl methane, two sulfonyl propyl methylmethane, two sec.-propyl alkylsulfonyl methane, biconjugate tolylsulfonyl methylmethane, two benzenesulfonyl methane etc.

β-ketone sulfone derivatives is as 2-cyclohexyl-carbonyl-2-(p-methylphenyl alkylsulfonyl) propane, 2-sec.-propyl carbonyl-2-(p-methylphenyl alkylsulfonyl) propane etc.;

Two sulfone derivativess are as phenylbenzene two sulfone derivativess, dicyclohexyl two sulfone derivativess etc.;

Sulfonic acid nitrobenzyl ester derivative, as p-methylphenyl sulfonic acid 2,6-dinitrobenzene benzyl ester, p-methylphenyl sulfonic acid 2,4-dinitrobenzene benzyl ester etc.

Sulfonate derivatives is as 1,2,3-three (sulfonyloxy methyl oxygen base) benzene, 1,2,3-three (trifluoromethyl sulfonyloxy) benzene, 1,2,3-three (p-methylphenyl sulfonyloxy) benzene etc.;

The sulfonate derivatives of N-hydroxyimide compound, as N-maloyl formimino sulphonate, N-maloyl imines trifluoromethane sulfonic acid ester, N-maloyl imines ethylsulfonic acid ester, N-maloyl imines 1-propyl sulfonic acid ester, N-maloyl imines 2-propyl sulfonic acid ester, N-maloyl imines 1-amyl group sulphonate, N-maloyl imines 1-octyl group sulphonate, N-maloyl imines p-methylphenyl sulphonate, N-maloyl imines p-methoxyphenyl sulphonate, N-maloyl imines 2-chloroethyl sulphonate, N-maloyl imines phenylbenzimidazole sulfonic acid ester, N-maloyl imines-2,4,6-trimethylphenyl sulphonate, N-maloyl imines 1-naphthyl sulphonate, N-maloyl imines 2-naphthyl sulphonate, N-hydroxyl-2-phenyl succimide methanesulfonate ester, N-hydroxyl maleimide methanesulfonate ester, N-hydroxyl maleimide ethylsulfonic acid ester, N-hydroxyl-2-phenyl maleimide methanesulfonate ester, N-hydroxyl glutarimide methanesulfonate ester, N-hydroxyl glutarimide phenylbenzimidazole sulfonic acid ester, N-hydroxyl phthalimide methanesulfonate ester, N-hydroxyl phthalimide phenylbenzimidazole sulfonic acid ester, N-hydroxyl phthalimide trifluoromethane sulfonic acid ester, N-hydroxyl phthalimide p-methylphenyl sulphonate, N-hydroxyl naphthalimide methanesulfonate ester, N-hydroxyl benzene-naphthalene diimide phenylbenzimidazole sulfonic acid ester, N-hydroxyl-5-norcamphyl-2,3-dicarboxyl formimino sulphonate, N-hydroxyl-5-norcamphyl-2,3-dicarboxyl imines trifluoromethane sulfonic acid ester, N-hydroxyl-5-norcamphyl-2,3-dicarboxyl imines p-methylphenyl sulphonate etc.;

Especially preferably use: salt, as the trifluoromethane sulfonic acid triphenylsulfonium, trifluoromethane sulfonic acid (to the tert.-butoxy phenyl) phenylbenzene sulfonium, trifluoromethane sulfonic acid three (to the tert.-butoxy phenyl) sulfonium, p-methylphenyl sulfonic acid triphenylsulfonium, tosic acid (to the tert.-butoxy phenyl) phenylbenzene sulfonium, tosic acid three (to the tert.-butoxy phenyl) sulfonium, trifluoromethane sulfonic acid three naphthyl sulfoniums, trifluoromethane sulfonic acid cyclohexyl methyl (2-oxo cyclohexyl) sulfonium, trifluoromethane sulfonic acid (2-norcamphyl) methyl (2-oxo cyclohexyl) sulfonium, trifluoromethanesulfonic acid 1,2 '-naphthyl carbonyl methyl tetramethylene sulfide salt etc.; Diazomethane derivative is as two (phenyl sulfonyl) diazomethane, two (p-methylphenyl alkylsulfonyl) diazomethane, two (cyclohexyl alkylsulfonyl) diazomethane, two (normal-butyl alkylsulfonyl) diazomethane, two (isobutyl-alkylsulfonyl) diazomethane, two (sec-butyl alkylsulfonyl) diazomethane, two (n-propyl alkylsulfonyl) diazomethane, two (sec.-propyl alkylsulfonyl) diazomethane, two (tertiary butyl alkylsulfonyl) diazomethane etc.; The glyoxime derivative is as two-(p-methylphenyl alkylsulfonyl)-alpha-alpha-dimethyl glyoxime, two-(normal-butyl alkylsulfonyl)-alpha-alpha-dimethyl glyoxime etc.; Two sulfone derivativess are as two naphthyl alkylsulfonyl methane etc.; The sulfonate derivatives of N-hydroxyl imide compound is as N-maloyl formimino sulphonate, N-maloyl imines trifluoromethane sulfonic acid ester, N-maloyl imines 1-propyl sulfonic acid ester, N-maloyl imines 2-propyl sulfonic acid ester, N-maloyl imines 1-amyl group sulphonate, N-maloyl imines p-methylphenyl sulphonate, N-hydroxyl benzene-naphthalene diimide methanesulfonate ester, N-hydroxyl benzene-naphthalene diimide phenylbenzimidazole sulfonic acid ester etc.

In addition, above-mentioned acidogenic agent C can be used alone or be used in combination.With respect to 100 parts polyphenolic substance, the addition of acidogenic agent C is preferably 0.1-50 part, more preferably 0.5-40 part.When being less than 0.1 part, the acid of existence product is measured less, the inadequate situation of crosslinking reaction; When surpassing 50 parts, exist by acid and move and the situation of the mixing phenomena that causes to the upper strata resist.

Further, in the material that is used to form lower membrane of the present invention, can fusion be used for improving the basic cpd of stability in storage.

As basic cpd, be used for preventing that the acid of the trace that produced by acidogenic agent C from carry out crosslinking reaction, thereby play the effect to the quenching of acid.As such basic cpd, can enumerate primary, secondary, uncle's aliphatics amine; Mix amine; Aromatic amine; Heterocyclic amine; Nitrogenous compound with carboxyl; Nitrogenous compound with alkylsulfonyl; Nitrogenous compound with hydroxyl; Nitrogenous compound with hydroxyphenyl; Alcohol formula nitrogenous compound; Amide derivatives; Imide derivative etc.

Particularly, as the Armeen class, can ammonia be shown example, methylamine, ethamine, Tri N-Propyl Amine, Isopropylamine, n-Butyl Amine 99, isobutylamine, sec-butylamine, TERTIARY BUTYL AMINE, amylamine, uncle's amylamine, cyclopentamine, hexylamine, hexanaphthene, heptyl amice, octylame, nonyl amine, decyl amine, n-Laurylamine, cetylamine, the methylene diamines, quadrol, tetren etc., as the aliphatic secondary amine, can dimethylamine be shown example, diethylamine, di-n-propylamine, Diisopropylamine, Di-n-Butyl Amine, diisobutylamine, di-sec-butylamine, diamylamine, two cyclopentamine, dihexylamine, dicyclohexyl amine, two heptyl amices, Di-Octyl amine, nonyl amine, didecylamine, two n-Laurylamines, two cetylamines, N, N-dimethyl methylene diamines, N, N-ethylene dimethyl diamines, N, N-dimethyl tetraethylenepentamine etc., as the aliphatic tertiary amine class, can Trimethylamine 99 be shown example, triethylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, tri-isobutylamine, tri sec-butylamine, triamylamine, three cyclopentamine, trihexylamine, tricyclohexyltin amine, three heptyl amices, trioctylamine, TNA trinonylamine, tridecylamine, tridodecylamine, three (hexadecyl) amine, N, N, N ', N '-tetramethyl-methylene diamines, N, N, N ', N '-tetramethyl-Edamine, N, N, N ', N '-tetramethyl-tetraethylenepentamine etc.

As mixing amine, can example for example illustrate: dimethyl amine, methylethyl propylamine, benzylamine, phenylethylamine, benzyldimethylamine etc.Object lesson as aromatic amine and heterocyclic amine, can example illustrate: anils (aniline for example, methylphenylamine, N-ethylaniline, N propyl aniline, N, accelerine, 2-aminotoluene, the 3-monomethylaniline, the 4-monomethylaniline, ethylaniline, propyl group aniline, trimethylaniline, the 2-N-methyl-p-nitroaniline, the 3-N-methyl-p-nitroaniline, the 4-N-methyl-p-nitroaniline, 2, the 4-dinitraniline, 2, the 6-dinitraniline, 3, the 5-dinitraniline, N, N-dimethyl methyl aniline etc.), (p-methylphenyl) pentanoic, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamines, naphthylene diamine, pyrrole derivative (pyrroles for example, 2H-pyrroles, the 1-methylpyrrole, 2, the 4-dimethyl pyrrole, 2, the 5-dimethyl pyrrole, N-methylpyrrole etc.) oxazole derivative (Li such as oxazole, isoxzzole etc.), thiazole derivative (thiazole for example, isothiazole etc.), imdazole derivatives (imidazoles for example, 4-methylimidazole, 4-methyl-2-phenylimidazole etc.), pyrazole derivatives, Furazan Derivatives, pyrroline derivative (pyrroline for example, 2-methyl isophthalic acid-pyrroline etc.), pyrrolidin derivatives (tetramethyleneimine for example, the N-crassitude, pyrrolidone, N-Methyl pyrrolidone etc.), imidazolidine derivatives, imidazolidine derivative, pyridine derivate (pyridine for example, picoline, ethylpyridine, the propyl group pyridine, butyl-pyridinium, 4-(1-butyl amyl group) pyridine, lutidine, trimethylpyridine, the triethyl pyridine, phenylpyridine, 3-methyl-2-phenylpyridine, the 4-tert .-butylpyridine, the xenyl pyridine, benzyl-pyridine, methoxypyridine, the butoxy pyridine, dimethoxy-pyridine, 1-methyl-2-pyridine, 4-pyrrolidyl pyridine, 1-methyl-4-phenylpyridinium, 2-(1-ethyl propyl) pyridine, aminopyridine, Dimethylamino pyridine etc.), pyridazine derivatives, pyrimidine derivatives, pyrazines derivatives, pyrazoline derivative, pyrazolidine derivatives, piperidine derivative, bridged piperazine derivatives, morpholine derivative, indole derivatives, isoindole derivatives, the 1H-indazole derivatives, the indoline derivative thing, quinoline (quinoline for example, 3-Cyanoisoquinoline etc.), isoquinilone derivatives, cinnoline derivatives, quinazoline derivant, quinoxaline derivatives, phthalazine derivatives, purine derivative, pteridine derivatives, carbazole derivative, luxuriant and rich with fragrance Lip river quinoline derivant, acridine derivatives, the azophenlyene derivative, 1,10-phenanthrolene derivative, adenine derivative, adenosine derivative, guanine derivatives, the guanosine derivative, uracil derivative, uridine derivatives etc.

Further, as the nitrogenous compound with carboxyl, can example illustrate: benzaminic acid, indole-carboxylic acid, amino acid derivative (for example nicotinic acid, L-Ala, arginine, asparagus fern amino acid, L-glutamic acid, glycine, Histidine, Isoleucine, glutamy L-LEU, leucine, methionine(Met), phenylalanine, Threonine, Methionin, the amino pyrazine of 3--2-carboxylic acid, methoxy propyl propylhomoserin) etc.; As the nitrogenous compound with alkylsulfonyl, can example illustrate: 3-pyridine-sulfonic acid, tosic acid pyridinium salt etc.; As the nitrogenous compound with hydroxyl, nitrogenous compound with hydroxyphenyl, alcohol formula nitrogenous compound, can example illustrate: 2 hydroxy pyrimidine, amino cresols, 2, the 4-quinoline diol, 3-indole-alcohol hydrosol (3-イ Application De one Le メタノ one Le ヒ De レ one ト), monoethanolamine, diethanolamine, trolamine, the N-ethyldiethanolamine, N, the N-diethylethanolamine, tri-isopropanolamine, 2,2 '-imino-diacetic ethanol, the 2-monoethanolamine, 3-amino-1-propyl alcohol, 4-amino-1-butanols, 4-(2-hydroxyethyl) morpholine, 2-(2-hydroxyethyl) pyridine, 1-(2-hydroxyethyl) piperazine, 1-[2-(2-hydroxyl-oxethyl) ethyl] piperazine, piperidines ethanol, 1-(2-hydroxyethyl) tetramethyleneimine, 1-(2-hydroxyethyl)-2-Pyrrolidone, 3-piperidyl-1, the 2-propylene glycol, 8-hydroxyl julolidine, the 3-quinuclidone, the 3-tropanol, 1-methyl-2-tetramethyleneimine ethanol, 1-acridine ethanol, N-(2-hydroxyethyl) phthalimide, N-(2-hydroxyethyl) Yi Yansuan acid amides etc.As amide derivatives, can example illustrate: methane amide, N-methylformamide, N, dinethylformamide, ethanamide, N-methylacetamide, N,N-dimethylacetamide, propionic acid amide, benzamide etc.As inferior amide derivatives, can example illustrate: phthalimide, succinimide, maleimide etc.

With respect to 100 parts ring compound, the blended amount of basic cpd is 0.001-2 part, especially is preferably 0.01-1 part.Blended amount is during less than 0.001 part, no fusion effect; When surpassing 2 parts, exist by thermogenetic acid all to be trapped and to become and to carry out crosslinked situation.

In addition, in the composition that is used to form lower membrane of the present invention, also can add to control absorbancy and be other polymkeric substance of purpose.Also can add: at the transparent high naphthol resin of 193nm; The naphthol-modified resin of xylene resin; The phenol-modified resin of naphthalene resin; The Dicyclopentadiene (DCPD) resin; (methyl) acrylate; Contain naphthalene nucleus (vinyl naphthalene, polyace naphthylene etc.), cyclohexyl biphenyl (phenanthrenequione, fluorenes etc.), have the resin of heteroatomic heterocycle (thiophene, indenes etc.) or do not contain the resin of aromatic nucleus.

In addition, by importing condensation aromatic series or alicyclic substituting group, compare with common resol, can reduce glass transition point.At this moment, though also depend on substituent kind or its ratio of introducing, can make glass transition point reduce 10-50 ℃.

As another method for reducing glass transition point, can enumerate with carbonatoms is the method for the hydrogen atom of acid-unstable group, ethanoyl, the pivaloyl of the alkyl, the tertiary butyl, tert-pentyl, acetal etc. of straight chain shape, chain or the ring-type of the 1-20 hydroxyl that waits substituted hydroxy vinylbenzene.

The replacement rate of this moment is the 10-80 mole % of hydroxyl, is preferably the scope of 15-70 mole %.

As operable organic solvent in the lower floor of the present invention film formation material, so long as the solvent that described ring compound, acidogenic agent C, linking agent G, other additive F etc. can dissolve just has no particular limits.

For example can enumerate: ketones solvent, as acetone, butanone, mibk, pimelinketone etc.; Cellosolve is as propylene glycol monomethyl ether, propylene glycol methyl ether acetate etc.; Esters solvent is as ethyl lactate, methyl acetate, ethyl acetate, butylacetate, Isoamyl Acetate FCC, vinyl acetic monomer, methoxypropionic acid methyl esters, hydroxy-methyl isobutyl acid etc.; Alcoholic solvent is as methyl alcohol, ethanol, Virahol, 1-oxyethyl group-2-propyl alcohol etc.; Aromatic hydrocarbon is as toluene, dimethylbenzene etc.

In the above-mentioned solvent, be preferably pimelinketone, propylene glycol monomethyl ether, ethyl lactate, hydroxy-methyl isobutyl acid especially.

With respect to 100 parts ring compound, the blended amount of solvent is preferably 200-10000 part, is preferably 300-5000 part especially.

The formation method of lower membrane of the present invention after spin coating, makes solvent evaporates, in order to prevent mixing with the upper strata resist, and in order to promote crosslinking reaction, preferably toasts.The temperature of baking is preferably carried out in the 10-300 scope in second in 80-300 ℃ scope.In addition, the thickness of this lower membrane can suitably be selected, and is preferably 30-20000nm, is preferably 50-15000nm especially.After making lower membrane, under the two-layer process situation, make siliceous resist layer thereon or contain the individual layer resist layer of common hydrocarbon; Under the situation of three layer process, make siliceous middle layer thereon, and then make not siliceous individual layer resist layer thereon again.

At this moment, as the photoetching compositions that is used to form this resist layer, can use known material.

As being used for siliceous resist composition with two-layer process, consider from the viewpoint of oxygen elching resistant, use the eurymeric photoetching compositions, wherein in said composition, use the polymkeric substance (polysilsesquioxane derivative or vinyl silanes derivative etc.) of silicon atoms as stock polymer, and contain organic solvent, acidogenic agent in the said composition and the basic cpd that contains as required etc.In addition, as the polymkeric substance of silicon atoms, can use the known polymkeric substance that can be used in this kind resist composition.As the siliceous middle layer that is used for three layer process, preferably use with the middle layer of polysilsesquioxane as raw material.By the middle layer is had as the effect that prevents reflectance coating, can inhibitory reflex.

As the exposure that is used for 193nm, to use when containing the high material of a large amount of aromatic groups and substrate elching resistant as lower membrane, it is big that k value becomes, and the substrate reflection raises, but passes through at the middle layer inhibitory reflex, and substrate is reflected into below 0.5%.As having the middle layer that prevents reflecting effect, preferably use polysilsesquioxane, this polysilsesquioxane has been introduced the extinction group with phenyl or silicon-silicon bond of the exposure that is used for 193nm and has been undertaken crosslinked by acid or heat.In addition, also can use the middle layer that utilizes the chemical vapor deposition (CVD) method to form.As the effective middle layer that the conduct that utilizes the CVD method to make prevents reflectance coating, known have a SiON film.Compare with the CVD method, it is simple and have a advantage on the cost to utilize spin-coating method to form the method in middle layer.Upper strata resist in three layer process can be eurymeric, also can be minus, can use the resist identical with normally used individual layer resist.

Lower membrane of the present invention also can be used as the common reflectance coating that prevents for the individual layer resist.Because lower membrane of the present invention has the good elching resistant that is used for substrate processing, thereby also can expect the function as the dura mater that is used for substrate processing.

The present invention relates to the formation method of multilayer resist pattern, wherein, this method comprises: form above-mentioned lower membrane at substrate, after this lower membrane forms at least one deck photoresist layer, at the scope internal radiation radioactive rays of using of this photoresist layer, alkaline development and form resist pattern after, with this resist pattern as mask, utilize the plasma body that contains oxygen at least to come the described lower membrane of etching, resist pattern is copied on the described lower membrane.

When forming resist layer by above-mentioned photoetching compositions, can similarly preferably use spin-coating method when forming above-mentioned lower membrane.Behind the spin-coating erosion resistant agent composition, carry out prebake conditions, preferably in the scope in 80-180 ℃ of following 10-300 second, carry out.Afterwards, expose according to ordinary method, postexposure bake (PEB), carry out alkaline development, obtain resist pattern.In addition, there is no particular limitation for the thickness of resist film, is preferably 30-500nm, is preferably 50-400nm especially.

In addition, as the light that is used for exposure, for wavelength is high-energy rays below the 300nm, can enumerate the excimer laser of 248nm, 193nm, 157nm particularly; The soft X-ray of 3-20nm, electron beam, X ray etc.

Then, the resist pattern that obtains is sheltered and carried out etching.Lower membrane etching in the two-layer process has utilized the etching of oxygen.Except oxygen, can also add rare gas element (He, Ar etc.) or CO, CO ₂, NH ₃, SO ₂, N ₂, NO ₂, H ₂Gas; Or also can not utilize oxygen, only at CO, CO ₂, NH ₃, N ₂, NO ₂, H ₂Carry out etching under the gas.Especially the latter's gas can be used for the sidewall protection that purpose is to prevent the undercut of pattern side wall.The etching in the middle layer in three layer process utilizes fluorocarbon (Off ロ Application is ガス) to shelter resist pattern and carry out the processing in middle layer.Then, carry out above-mentioned oxygen etch, shelter the middle layer figure and carry out the processing of lower membrane.

The etching of following processed substrate also can utilize ordinary method to carry out, and for example substrate is SiO ₂, during SiN, carry out the etching based on fluorocarbon; When substrate was p-Si or Al, W, carrying out based on chlorine was that gas, bromine are the etching of gas.During with the processed substrate of fluorocarbon etching, the siliceous resist in the two-layer resist technology and the siliceous middle layer in three layer process, be stripped from simultaneously with processed substrate.Utilizing chlorine is gas, bromine when being the gas etch substrate, and peeling off of siliceous resist layer or siliceous middle layer need utilize the dry etching of fluorocarbon to peel off after substrate processing in addition.

Lower membrane of the present invention is characterised in that the elching resistant of these processed substrates is good.

In addition, as processed substrate, be formed on the substrate.As substrate, be not the substrate of special restriction, can use because of Si, α-Si, p-Si, SiO ₂, SiN, SiON, W, TiN, Al etc. and the substrate of the material character different with machined membrane (processed substrate).As machined membrane, can use various low-k films (Si, SiO ₂, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si etc.) and stopper film (stopper film), can form 50-10000nm usually, especially the thickness of 100-5000nm.

(preparation method of ring compound B0 (1))

The present invention relates to the preparation method of ring compound B0.As the reaction of fs, to make acid dissociation functional group introduce reagent be 2-59 with carbonatoms and have reactive functional groups and the aldehyde compound A1b of 1-4 formyl radical reaction, to synthesize the aldehyde compound A1c that introducing has acid dissociation functional group; As the reaction of subordinate phase, carry out the condensation reaction of aldehyde compound A1c and phenolic compound A2.

Ring compound B0 for by the condensation reaction of aldehyde compound A1c and phenolic compound A2 synthetic, molecular weight is the ring compound B0 of 800-5000.

Ring compound B0 can obtain by following method: as the reaction of fs, be to introduce acid dissociation functional group among 2-59 and the aldehyde compound A1b with 1-4 formyl radical at carbonatoms, with synthesizing aldehyde compound A1c; As the reaction of subordinate phase, carry out the condensation reaction of aldehyde compound A1c and phenolic compound A2.

The general ring-type low molecular compound with acid dissociation functional group by the low molecule polyphenolic substance of synthesis of cyclic, and makes this ring-type low molecular compound and the compound for introducing acid dissociation functional group described later react to prepare.

But there is following situation in such method: the ring-type low molecular compound is insoluble in employed organic solvent in the reaction (as tetrahydrofuran (THF) etc.), is difficult to carry out the reaction with the compound that is used for introducing acid dissociation functional group.In addition, even the ring-type low molecular compound dissolves in organic solvent, can not optionally carry out the reaction of ring-type low molecular compound and compound that be used for to introduce described acid dissociation functional group, and become by multiple substituent and the substituent mixture that makes up not.Generally being difficult to optionally emanate from this mixture has the ring-type low molecular compound of acid dissociation functional group, moreover yield is low, does not have practicality.

Relative with it, preparation method of the present invention by the reaction of fs, is that 2-59 and the aldehyde compound A1b with 1-4 formyl radical introduce acid dissociation functional group at carbonatoms, with synthesizing aldehyde compound A1c.At this moment; the carbonatoms that becomes the raw material of aldehyde compound A1c is 2-59 and the compd A 1b with 1-4 formyl radical and the compound that is used for introducing acid dissociation functional group; dissolve in the reaction of THF etc. in the employed organic solvent, reaction is successfully carried out.

Afterwards, reaction as subordinate phase, imported the condensation reaction of aldehyde compound A1c and the phenolic compound A2 of acid dissociation functional group, obtained importing the ring compound B0 of acid dissociation functional group, thereby to the favorable solubility of the organic solvent that uses in the reaction, and reaction there is not bad influence, in addition, the position that comes from aldehyde compound A1c has acid dissociation functional group, the position that comes from phenolic compound A2 does not have acid dissociation functional group, can optionally be introduced the ring compound B0 of acid dissociation functional group with high yield, and the productivity height.

Aldehyde compound A1c is that the carbonatoms with acid dissociation functional group is 3-60 and the aldehyde with 1-4 formyl radical.

Aldehyde compound A1c can be by being to introduce acid dissociation functional group among 2-59 and the compd A 1b with 1-4 formyl radical to prepare at carbonatoms.

Carbonatoms is 2-59 and the aldehyde cpd with 1-4 formyl radical, and there is no particular limitation, for example can enumerate: fatty aldehyde compound, alicyclic aldehyde cpd, aromatic aldehyde compound etc.

As the fatty aldehyde compound, that can enumerate acetaldehyde, Ra-CHO(Ra and be carbonatoms and be 2-20 also can have substituent alkyl), OHC-Rb-CHO(Rb be carbonatoms be 1-20 also can have substituent alkylidene group), Rc-(CHO) ₃(Rc is that carbonatoms is the organic group that also can have substituent trivalent of 2-20), Rd-(CHO) ₄(Rd is that carbonatoms is the organic group that also can have substituent tetravalence of 2-20) etc.In the literary composition, so-called substituting group is the functional group that is selected from the group of being made up of alkyl, cycloalkyl, aryl, alkoxyl group, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, carboxyl, alkyl silane, their derivative.

As alicyclic aldehyde cpd, can enumerate: hexahydrobenzaldehyde (シ Network ロヘキサ Application カ Le ボア Le デヒ De); also can have carbonatoms is the substituent hexahydrobenzaldehyde of 2-20; ring octyl group formaldehyde; norcamphyl formaldehyde; adamantyl formaldehyde; furfural; the diformyl hexanaphthene; the diformyl cyclooctane; the diformyl norbornane; the diformyl diamantane; three formyl radical hexanaphthenes; three formyl radical cyclooctane; three formyl radical norbornanes; three formyl radical diamantane; three formyl radical hexanaphthenes; tetramethyl acyl group cyclooctane; tetramethyl acyl group norbornane; tetramethyl acyl group diamantane etc.In the literary composition, so-called substituting group is the functional group that is selected from the group of being made up of alkyl, cycloalkyl, aryl, alkoxyl group, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, carbonyl, alkyl silane, their derivative.

As the aromatic aldehyde compound, can enumerate: phenyl aldehyde; tolyl aldehyde; also can have carbonatoms is the substituent phenyl aldehyde of 2-20; aubepine; naphthaldehyde; anthracene aldehyde; biphenyl aldehyde; the formyl radical fluorenes; formyl biphenyl; the formyl radical anthracene; the formyl radical phenanthrene; the formyl radical thiodiphenylamine; the formyl radical pyrene; the formyl radical benzopyrene; formyl radical benzo two indenes; formyl radical benzo naphthalene; the formyl radical acenaphthylene; the formyl radical naphthacene; the formyl radical pentacene; formyl radical three adjacent inferior benzene; the formyl radical pyridine; the formyl radical ovalene; diformyl-benzenes; diformyl toluene; diformyl dimethylbenzene; the diformyl naphthalene; diformyl biphenyl; the diformyl terphenyl; the diformyl anthracene; the diformyl phenanthrene; the diformyl pyrene; diformyl benzo two indenes; non-that alkene of diformyl; the diformyl acenaphthylene; non-that alkene of diformyl; the diformyl naphthacene; the diformyl pentacene; diformyl three adjacent inferior benzene; the diformyl pyridine; the diformyl imidazoles; the diformyl furans; the diformyl thiazole; the diformyl flavones; the diformyl isoflavones; three formyl radical benzene; three formyl radical toluene; three formyl radical dimethylbenzene; the front three acyl-naphthaline; three formyl radical biphenyl; three formyl radical terphenyls; three formyl radical anthracenes; three formyl radical phenanthrene; three formyl radical pyrenes; three formyl radical benzos, two indenes; non-that alkene of three formyl radicals; three formyl radical acenaphthylenes; non-that alkene of three formyl radicals; front three acyl group naphthacene; three formyl radical pentacenes; three formyl radicals, three adjacent inferior benzene; front three acyl pyridine ketone quinoline; three formyl imidazoles; three formyl radical furans; three formyl radical thiazoles; three formyl radical flavones; three formyl radical isoflavones; tetramethyl acyl group benzene; the tetramethyl acyl-naphthaline; tetramethyl acyl group biphenyl; tetramethyl acyl group terphenyl; tetramethyl acyl group anthracene; tetramethyl acyl group phenanthrene; tetramethyl acyl group pyrene; tetramethyl acyl group benzo two indenes; non-that alkene of tetramethyl acyl group; tetramethyl acyl group acenaphthylene; non-that alkene of tetramethyl acyl group; tetramethyl acyl group naphthacene; tetramethyl acyl group pentacene; the inferior benzene of tetramethyl acyl group neighbours; tetramethyl acyl pyridine ketone alkane; the tetramethyl acylimidazole; tetramethyl acyl group furans; tetramethyl acyl group thiazole; tetramethyl acyl group flavones; tetramethyl acyl group isoflavones etc.In the literary composition, so-called substituting group is the functional group that is selected from the group of being made up of alkyl, cycloalkyl, aryl, alkoxyl group, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, carboxyl, alkyl silane, their derivative.

Further, as the aldehyde cpd that contains heterocycle, can enumerate: furfural, cigarette aldehyde, 2-tetrahydrofuran (THF) formaldehyde, 2 thiophene carboxaldehyde etc.

These compounds are introduced acid dissociation functional group easily by replacement such as hydroxyl, borate, halogen atom and carboxyl, thereby preferred.

Wherein, consider from the viewpoint of elching resistant, be preferably the aromatic aldehyde with 1-4 formyl radical; From being conducive to form the viewpoint consideration of Micropicture, more preferably has the aromatic aldehyde of 1-2 formyl radical; From can high yield, the viewpoint of high purity ground preparation aromatic aldehyde self and ring compound B0 considers further preferably have the aromatic aldehyde of 1 formyl radical.

It is can be with known method synthetic or can easily obtain be used for to introduce the compound of acid dissociation functional group, can enumerate for example active carboxylic acid derivative's compound, as acyl chlorides, acid anhydrides, two carbonic ethers etc.; Haloalkane; Vinyl alkyl ethers, dihydropyrane, halogenated carboxylic acid alkane ester etc., but not special restriction.Carbonatoms be the purity of 2-59 and the compound with 1-4 formyl radical and the being used for compound of introducing acid dissociation functional group there is no particular limitation, but be generally more than the 95 quality %, be preferably more than the 99 quality %.Carbonatoms is that the compound that 2-59 and the compound with 1-4 formyl radical and being used for introduced acid dissociation functional group can be used alone or in combination of two or more, but the homogeneity height of the solids component of resist film when using separately, thereby preferred.

Aldehyde compound A1c can for example prepare according to as described below.For example, can be dissolved or suspended in the organic solvent (as acetone, tetrahydrofuran (THF) etc.) by making the phenyl aldehyde (as 4-hydroxy benzaldehyde etc.) that contains phenolic hydroxyl group.Then, add haloalkane (as the cyclohexyl chloride methyl ether etc.) or halogenated carboxylic acid alkane ester (as bromoacetic acid methyl adamantane ester etc.), in the presence of alkaline catalysts (as salt of wormwood etc.), under normal pressure, 20-110 ℃, reacted 0.1-72 hour; Use sour neutralization reaction liquid then, add to separate out white solid in the distilled water after, with the white solid that distilled water wash separates, final drying.

Can obtain aldehyde compound A1c by the following method: the phenyl aldehyde (as 4-hydroxy benzaldehyde etc.) with phenolic hydroxyl group is dissolved or suspended in the non-protonic solvent (as acetone, tetrahydrofuran (THF), propylene glycol methyl ether acetate etc.); Then, add vinyl alkyl ethers (as cyclohexyl vinyl ether etc.), in the presence of acid catalyst (as the tosic acid pyridinium salt etc.), under normal pressure, 20-60 ℃, reacted 0.1-72 hour; Use alkali cpd neutralization reaction liquid then, add to separate out white solid in the distilled water after, with the white solid that distilled water wash separates, final drying.

Can obtain aldehyde compound A1 by following method: in organic solvent (as tetrahydrofuran (THF) etc.), use esterifying catalyst (as acid, alkali etc.), the alcohol (as methyl adamantane base methyl alcohol etc.) that makes carboxyl benzaldehyde (as the 3-carboxyl benzaldehyde etc.) and have an acid dissociation functional group reacts.

Can obtain aldehyde compound A1c by following method: make halogeno-benzene formaldehyde (as 4-chlorobenzaldehyde, 4-bromobenzaldehyde etc.) or 4-chloromethylbenzene formaldehyde or 4-brooethyl phenyl aldehyde and Grignard reagent, react by the grignard reaction that has used copper catalyst.

Can obtain aldehyde compound A1c by following method: in organic solvent (as tetrahydrofuran (THF) etc.), make halogeno-benzene formaldehyde (as 4-chlorobenzaldehyde, 4-bromobenzaldehyde etc.) or 4-chloromethylbenzene formaldehyde or 4-brooethyl phenyl aldehyde and Grignard reagent, react by the grignard reaction that has used copper catalyst.

Can obtain aldehyde compound A1c by following method: in organic solvent (as tetrahydrofuran (THF) etc.); make formylation phenyl-boron dihydroxide (as 4-formyl radical phenyl-boron dihydroxide etc.) and haloalkane (as the cyclohexyl chloride methyl ether etc.) or halogenated carboxylic acid alkane ester (as bromoacetic acid methyl adamantane ester etc.), react by the Suzuki linked reaction of having used palladium and alkaline catalysts.

Described aldehyde compound A1c limits especially, for example can enumerate: described as carbonatoms be 2-59 and the compound with 1-4 formyl radical and in the illustrative compound, introduced the compound of acid dissociation functional group etc.

As aldehyde compound A1c, consider from the viewpoint of elching resistant, be preferably the aromatic aldehyde compound; From being conducive to form the viewpoint consideration of Micropicture, more preferably has the aromatic aldehyde compound of 1-2 formyl radical; The aromatic aldehyde compound that more preferably has 1 formyl radical.

Described aldehyde compound A1c is preferably the compound shown in the following formula (47).

[chemical formula 95]

(in the formula, L be selected from by singly-bound, carbonatoms are the alkylidene group of 1-20, cycloalkylidene that carbonatoms is 3-20, carbonatoms is 6-20 arylidene ,-O-,-OC (=O)-,-OC (=O) O-,-N (R ₅)-C (=O)-,-N (R ₅)-C (=O) O-,-S-,-SO-,-SO ₂-and their group of forming arbitrarily in the organic group of divalence; R ¹Be the substituent methyl of 2-20 for being selected from by carbonatoms, carbonatoms is that the 1-of 3-20 replaces ethyl, carbonatoms is that the 1-of 4-20 replaces n-propyl, carbonatoms is the 1-branched-chain alkyl of 3-20, carbonatoms is the silyl of 1-20, carbonatoms is the acyl group of 2-20, carbonatoms is the 1-substituted alkoxy alkyl of 2-20, carbonatoms is the cyclic ethers base of 2-20, carbonatoms is acid dissociation functional group or the hydrogen atom in the carbalkoxy of 2-20 and the group that alkoxycarbonyl alkyl is formed; R ²Be functional group in the alkyl silane of 1-20 and the group that their derivative is formed for being selected from by hydrogen atom, carbonatoms are the alkyl of 1-20, cycloalkyl that carbonatoms is 3-20, carbonatoms is 6-20 aryl, alkoxyl group, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, carboxyl, carbonatoms that carbonatoms is 1-20; R ⁵For hydrogen atom or carbonatoms are the alkyl of 1-10; m ₁Integer for 1-5; m ₂Integer for 0-4; m ₁+ m ₂=5.）

Compound shown in the above-mentioned formula (47) can prepare by the method for above-mentioned record.

Described aldehyde compound A1c is the compound shown in the following formula (48) more preferably.

[chemical formula 96]

(in the formula, L, R ¹, m ₁Same as described above.）

Compound shown in the above-mentioned formula (48) can prepare by the method for above-mentioned record.

Described aldehyde compound A1c is the compound shown in the following formula (49) more preferably.

[chemical formula 97]

(in the formula, L, R ¹Same as described above.）

Compound shown in the above-mentioned formula (1-3) can prepare by the method for above-mentioned record.

Described aldehyde compound A1c is preferably the compound shown in the following formula (50) especially.

[chemical formula 98]

(in the formula, R ¹Same as described above.）

Compound shown in the above-mentioned formula (50) can prepare by the method for above-mentioned record.

In formula (47)-(50), R ¹Be the substituent methyl of 2-20 for being selected from by carbonatoms; carbonatoms is that the 1-of 3-20 replaces ethyl; carbonatoms is that the 1-of 4-20 replaces n-propyl; carbonatoms is the 1-branched-chain alkyl of 3-20; carbonatoms is the silyl of 1-20; the acyl group of C2-20; carbonatoms is the 1-substituted alkoxy alkyl of 2-20; carbonatoms is the cyclic ethers base of 2-20; carbonatoms is the acid dissociation functional group in the group formed of the carbalkoxy of 2-20 and alkoxycarbonyl alkyl that carbonatoms is 2-20.These can use the group identical with the group of describing about above-mentioned ring compound.R ¹Can be the same or different, the homogeneity height of the solids component of resist film when identical, thereby preferred.

R ¹More preferably have and be selected from the acid dissociation functional group of structure that cycloalkanes, lactone and carbonatoms that carbonatoms is 3-20 are the aromatic nucleus of 6-12.Being the cycloalkanes of 3-12 as carbonatoms, can be that monocycle also can be many rings, more preferably many rings.Concrete example can be enumerated mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane etc.; More specifically, can enumerate the mononaphthene of cyclopropane, tetramethylene, pentamethylene, hexanaphthene etc., the polynaphthene of diamantane, norbornane, iso-borneol alkane, tristane, Fourth Ring decane etc.Wherein, be preferably diamantane, three cycloalkanes, tetracycloalkane, be preferably diamantane, three cycloalkanes especially.Carbonatoms is that the cycloalkanes of 3-12 also can have substituting group.As lactone, the carbonatoms that can enumerate butyrolactone or have a lactone group is the cycloalkyl of 3-12.Be the aromatic nucleus of 6-12 as carbonatoms, can enumerate phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, pyrene ring etc., be preferably phenyl ring, naphthalene nucleus, be preferably naphthalene nucleus especially.

Especially more preferably the acid dissociation functional group shown in the following formula (50-1).By having this acid dissociation functional group, resolving power and the LER of the resist pattern that obtains are improved.

[chemical formula 99]

(in the formula, R ⁵, R ⁶, n ₀, n ₁, n ₂Same as described above.）

As the example of phenolic compound A2, can enumerate phenol, pyrocatechol, Resorcinol, Resorcinol, pyrogallol etc., be preferably Resorcinol, pyrogallol, more preferably Resorcinol.In the scope of not damaging effect of the present invention, phenolic compound A2 also can have to be selected from and replaces ethyl, 1-by halogen atom, alkyl, cycloalkyl, aryl, aralkyl, alkoxyl group, alkenyl, carboxyl, acyl group, carbalkoxy, alkanoyloxy, aryl acyloxy, cyano group, nitro, heterocyclic radical, alkyl silane, substituent methyl, 1-and replace substituting group in the group that n-propyl, 1-branched-chain alkyl, silyl, 1-substituted alkoxy alkyl, cyclic ethers base and alkoxycarbonyl alkyl form etc.There is no particular limitation for the purity of phenolic compound A2, is generally more than the 95 weight %, is preferably more than the 99 weight %.Phenolic compound A2 can be used alone or in combination of two or more, the homogeneity height of the solids component of resist film when using separately, thereby preferred.

In a kind of mode of the present invention, ring compound B0 is preferably the compound shown in the following formula (51).

[Chemical formula 1 00]

In the formula, R ³Independently for being selected from by hydrogen atom, carbonatoms is the alkyl of 1-20, carbonatoms is the cycloalkyl of 3-20, carbonatoms is the aryl of 6-20, carbonatoms is the alkoxyl group of 1-20, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, carboxyl, carbonatoms is the alkyl silane of 1-20, and the functional group in the group formed of their derivative, be the substituent methyl of 2-20 for being selected from by carbonatoms perhaps, carbonatoms is that the 1-of 3-20 replaces ethyl, carbonatoms is that the 1-of 4-20 replaces n-propyl, carbonatoms is the 1-branched-chain alkyl of 3-20, carbonatoms is the silyl of 1-20, carbonatoms is the acyl group of 2-20, carbonatoms is the 1-substituted alkoxy alkyl of 2-20, carbonatoms is the cyclic ethers base of 2-20, carbonatoms is the acid dissociation functional group in the carbalkoxy of 2-20 and the group that alkoxycarbonyl alkyl is formed; L, R ¹, R ², m ₁And m ₂With identical in the above-mentioned formula (47).

In the formula, R ³Can be the same or different, the homogeneity of radiation-ray sensitive composition increases when identical, and the roughness of the resist pattern that obtains reduces, thereby more preferably.

The described ring compound B0 of above-mentioned formula (51) can for example prepare according to as described below.

For example, can prepare by following method: in organic solvent (as methyl alcohol, ethanol etc.), in the presence of acid catalyst (hydrochloric acid, sulfuric acid or tosic acid etc.), use molar ratio to be 1:(0.1-10) aldehyde compound A1c and phenolic compound A2,0-100 ℃ of down reaction about 0.5-72 hour, after the filtration, with alcohols (as methyl alcohol etc.) washing after washing, filter then and separate, make its drying at last.Also can use basic catalyst (sodium hydroxide, hydrated barta or 1,8-diazabicyclo [5.4.0], 11 carbon-7-alkene etc.) by replacing acid catalyst, similarly obtain by reaction.Further, ring compound B0 also can become dihalide by make above-mentioned aldehyde compound A1c with hydrogen halide or halogen gas, makes dihalide and phenolic compound A2 behind the segregation react to prepare.

Above-mentioned ring compound B0 is the compound shown in the following formula (52) more preferably.

[Chemical formula 1 01]

(in the formula, L, R ¹, R ², m ₁And m ₂With identical in the above-mentioned formula (51).）

Ring compound B0 shown in the above-mentioned formula (52) can prepare by the method for above-mentioned record.

Above-mentioned ring compound B0 is the compound shown in the following formula (53) more preferably.

[Chemical formula 1 02]

(in the formula, L, R ¹, m ₁With identical in the above-mentioned formula (51).）

Ring compound B0 shown in the above-mentioned formula (53) can prepare by the method for above-mentioned record.

Above-mentioned ring compound B0 is preferably the compound shown in the following formula (54) especially.

[Chemical formula 1 03]

(in the formula, R ¹With identical in the above-mentioned formula (51).）

Ring compound B0 shown in the above-mentioned formula (54) can prepare by the method for above-mentioned record.

In the formula (51), R ³For being selected from the functional group in the group of being formed by hydrogen atom, alkyl, cycloalkyl, aryl, alkoxyl group, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, carboxyl, alkyl silane, their derivative, the perhaps acid dissociation functional group in the group of forming for the carbalkoxy of the cyclic ethers base of the 1-substituted alkoxy alkyl of the acyl group of the silyl that is selected from 1-branched-chain alkyl that 1-that 1-by the substituent methyl of C2-20, C3-20 replaces ethyl, C4-20 replaces n-propyl, C3-20, C1-20, C2-20, C2-20, C2-20 and C2-20.

Acid dissociation functional group in the group of forming as the carbalkoxy of the cyclic ethers base of the 1-substituted alkoxy alkyl of the acyl group of the silyl that is selected from 1-branched-chain alkyl that 1-that 1-by the substituent methyl of C2-20, C3-20 replaces ethyl, C4-20 replaces n-propyl, C3-20, C1-20, C2-20, C2-20, C2-20 and C2-20 can enumerate and described R ¹Identical acid dissociation functional group etc.

In the scope of not damaging effect of the present invention, also can introduce acid dissociation functional group at least one phenolic hydroxyl group of ring compound B0.The method of introducing acid dissociation functional group at least one phenolic hydroxyl group of ring compound B0 is known.For example, can with above-mentioned be that the method for introducing acid dissociation functional group in 2-59 and the compound with 1-4 formyl radical is similarly carried out at carbonatoms.

For example, can obtain target compound by the following method: ring compound B0 is dissolved or suspended in the non-protonic solvent (as acetone, tetrahydrofuran (THF) (THF), propylene glycol methyl ether acetate etc.); Then, add vinyl alkyl ethers (as ethyl vinyl ether etc.) or dihydropyrane, in the presence of acid catalyst (as the tosic acid pyridinium salt etc.), under normal pressure, 20-60 ℃, reacted 1-72 hour; Use alkali cpd neutralization reaction liquid then, add to separate out white solid in the distilled water after, with the white solid that distilled water wash separates, final drying.

Can obtain target compound by the following method: ring compound B0 is dissolved or suspended in the non-protonic solvent (as acetone, THF, propylene glycol methyl ether acetate etc.); Then, add haloalkane (as the ethyl chloride methyl ether etc.) or halogenated carboxylic acid alkane ester (as bromoacetic acid methyl adamantane ester etc.), in the presence of alkaline catalysts (as salt of wormwood etc.), under normal pressure, 20-110 ℃, reacted 1-72 hour; Then with the sour neutralization reaction liquid of hydrochloric acid etc., add to separate out white solid in the distilled water after, with the white solid that distilled water wash separates, final drying.

In the scope of not damaging effect of the present invention, also can at least one phenolic hydroxyl group of ring compound B0, introduce non-acid dissociation functional group.So-called non-acid dissociation functional group refers to not divide, do not produce the characteristic group of alkali-soluble group in the presence of acid.For example can enumerate: the decomposition that causes of effect of the acid of having no way of, be selected from functional group in the group of being formed by the alkyl silane of the alkoxyl group of the aryl of the cycloalkyl of the alkyl of C1-20, C3-20, C6-20, C1-20, cyano group, nitro, hydroxyl, heterocyclic radical, halogen, carboxyl, C1-20, their derivative etc.

Ring compound B0 is owing to be low-molecular weight compound, has film-forming properties, thermotolerance, anti-dry etching, low ease gas simultaneously, and be the pure substance compound, so the homogeneity height of composition in the resist film, thereby preferably as the resist composition of radiation-ray sensitive composition.The radiation-ray sensitive composition that contains ring compound B0 has good resolving power, susceptibility, low line edge roughness.

(preparation method of ring compound B0 (2))

The present invention relates to the preparation method of ring compound B0, wherein, reaction as the fs, to carry out carbonatoms be 2-59 and have 1-2 carboxyl or the aldehyde compound A1d of ester group and 1-4 formyl radical and the condensation reaction of phenolic compound A2, is the ring compound A0 of 700-5000 with the molecular weight that has 1-8 carboxyl in the synthetic molecules; As the reaction of subordinate phase, have the ring compound A0 and the reaction with compound A-13 of halo methyl ether base of carboxyl.

Also can replace halo methyl ether based compound A3, use halogenated carboxylic acid alkane ester A4 to obtain ring compound B0.

There is no particular limitation for halogenated carboxylic acid alkane ester A4, for example can enumerate: have 1-2 haloalkyl carboxyl fatty compounds, have 1-2 haloalkyl carboxyl alicyclic compound, have the aromatics of 1-2 haloalkyl carboxyl etc., be preferably the compound shown in the following formula (55).

[Chemical formula 1 04]

(in the formula, R ⁷For carbonatoms is that straight chain shape alkyl, the carbonatoms of 1-20 is that the alkyl of the chain of 3-20, cycloalkyl or the carbonatoms that carbonatoms is 3-20 are the aryl of 6-20; X is halogen atom; L ₁Be the organic group of the divalence in the alkyl of the straight chain shape of 1-4 or chain for being selected from by singly-bound, carbonatoms.）

Be the alkyl of the chain of 3-20 as carbonatoms, preferred carbonatoms is 3-10, can enumerate sec.-propyl, the tertiary butyl, isopentyl, neo-pentyl etc. particularly.

Be the cycloalkyl of 3-20 as carbonatoms, preferred carbonatoms is 6-14.In addition, the cycloaliphatic ring that contains in the cycloalkyl can be that monocycle also can be many rings, more preferably many rings.Concrete example can be enumerated mononaphthene, dicyclo alkane, three cycloalkanes, tetracycloalkane etc.; More specifically can enumerate the mononaphthene of cyclopropane, tetramethylene, pentamethylene, hexanaphthene etc., the polynaphthene of diamantane, norbornane, iso-borneol alkane, tristane, Fourth Ring decane etc.Wherein, be preferably diamantane, three cycloalkanes, tetracycloalkane, be preferably diamantane, three cycloalkanes especially.

Halogenated carboxylic acid alkane ester A4 can obtain by following method: for example alcohols (as 2-methyl-2-adamantanol etc.) is dissolved in the organic solvent (as tetrahydrofuran (THF) etc.), adding is the alkali of pyridine of 0.8-2.4 equivalent etc. with respect to alcohols, adding is the halogen carboxylic acid halides (halocarboxylic acid halide) (as bromoacetyl bromide etc.) of 0.8-2.4 equivalent with respect to alcohols, reacts under 0-100 ℃; After reaction finishes, with segregation resultants such as column chromatographies, thereby obtain target product halogenated carboxylic acid alkane ester A4.

Ring compound B0 can be by having carboxyl ring compound A0 and the reaction of halogenated carboxylic acid alkane ester A4 obtain.For example, can obtain ring compound B0 by following method: for example, make the ring compound A0 with carboxyl be dissolved or suspended in non-protonic solvent (as acetone, THF, propylene glycol methyl ether acetate etc.) in, then, add halogenated carboxylic acid alkane ester A4, be the 0.5-4 equivalent at the carboxyl with respect to the ring compound A0 with carboxyl, be preferably the 0.9-1.1 equivalent, more preferably the alkaline catalysts of 1.0 equivalents is (as pyridine, triethylamine, the diazabicyclo undecylene, salt of wormwood etc.) under the existence, at normal pressure, 0-110 ℃ was reacted 1-168 hour down, thereafter, wash after washing with alcohols (as methyl alcohol etc.), filter then and separate, make its drying at last.This compound also can carry out the refining of column chromatography etc. as required.

About identical with about the above-mentioned described mistake of radiation-ray sensitive composition B of other each prerequisite except above-mentioned.

(the formation method of resist pattern)

The present invention relates to form the method for resist pattern, this method comprises: any one among the radiation-ray sensitive composition A-C of use the invention described above forms operation of resist film at substrate; Operation with described resist film exposure; And the operation of described resist film being developed to form resist pattern.

In order to form resist pattern, at first, the coating process by rotary coating, curtain coating coating, roller coat etc. substrate (wafer that coats as silicon chip, by aluminium etc.) be coated with as described in radiation-ray sensitive composition of the present invention, form resist film.Also can be as required coating surface treatment agent (as hexa-methylene disilazane etc.) on substrate in advance.

Then, as required the substrate that has been coated with is heated.Heating temperature is according to the fusion composition of radiation-ray sensitive composition etc. and different, but is preferably 20-250 ℃, more preferably 20-150 ℃.By heating, exist to make resist to the situation of the tackiness raising of substrate, thereby preferred.Then, by being selected from any one the radioactive rays in the group of being formed by visible light, ultraviolet ray, excimer laser, electron rays, extreme ultraviolet (EUV), X ray and ionic fluid, resist film is exposed into the figure of expectation.Conditions of exposures etc. suit selected according to the fusion composition of radiation-sensitive resist composition etc.In the present invention, in order stably to form the Micropicture of the high fidelity in the exposure, preferably behind radiation exposure, heat.Heating condition is according to the fusion composition of radiation-sensitive resist composition etc. and different, but is preferably 20-250 ℃, more preferably 20-150 ℃.

Then, by with alkaline developer the resist film after exposing being developed, form the resist pattern of regulation.As described alkaline developer, for example can use to be preferably 1-10 weight %, more preferably the concentration of 1-5 weight % is dissolved with more than one the alkaline aqueous solution in the following basic cpd, described basic cpd is monoalkyl amine, dialkyl amine or trialkyl amines, monoalkanolamine class, dialkanol amine or three alkanol amines, the hetero ring type amine, Tetramethylammonium hydroxide (TMAH), choline etc.The concentration of above-mentioned alkaline aqueous solution is 10 quality % when following, can suppress the dissolving of exposed portion in developing solution, thereby preferred.

In addition, also can in described alkaline developer, add an amount of alcohols or above-mentioned tensio-active agent (as methyl alcohol, ethanol, Virahol etc.).Wherein especially preferably add the Virahol of 10-30 weight %.Can improve developing solution thus to the wettability of resist, thus preferred.In addition, when using such developing solution that is formed by alkaline aqueous solution, the general water in the back of developing washs.

After forming resist pattern, obtain the graph wiring substrate by etching.Etching method can be undertaken by known method, as the dry-etching that uses plasma gas and the Wet-type etching that uses alkaline solution, Cupric Chloride Solution, ferric chloride Solution etc. etc.

After forming resist pattern, can also carry out plating.As above-mentioned solution and coating method, for example copper facing, zinc-plated, nickel plating, gold-plated etc. are arranged.

Residual resist pattern after the etching can be peeled off with organic solvent or than the alkaline strong alkaline aqueous solution of employed alkali aqueous solution in development.As above-mentioned organic solvent, can enumerate the PGMEA(propylene glycol methyl ether acetate), the PGME(propylene glycol monomethyl ether), the EL(ethyl lactate) etc.; As strong alkali aqueous solution, for example can enumerate: the potassium hydroxide aqueous solution of the aqueous sodium hydroxide solution of 1-20 weight % and 1-20 weight %.As above-mentioned stripping means, for example can enumerate: dipping method, spray regime etc.In addition, being formed with the circuit board of resist pattern, can be multi-layer wire substrate, also can have the through hole of minor diameter.

The circuit board that obtains among the present invention can be by after forming resist pattern, evaporation metal in a vacuum, and with the method for solution dissolving resist pattern, the method for namely lifting from forms subsequently.

Embodiment

Below be described more specifically embodiments of the present invention by enumerating embodiment.But the present invention is not limited only to these embodiment.In following synthesis example, embodiment, the structure of compound is passed through ¹H-NMR measures to confirm.

＜synthesis example 1〉ring compound A's is synthetic

CR-1's is synthetic

Under stream of nitrogen gas, Resorcinol (22g with Northeast chemistry society system, 0.2mol), 4-isopropyl benzene formaldehyde (29.6g, 0.2mol) and dehydrated alcohol (200ml) put into abundant drying and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, be mixed with ethanolic soln.Be heated to 85 ℃ with mantle heater when stirring this solution.Then, behind dropping funnel cost dropping in 30 minutes 75ml concentrated hydrochloric acid (35%), continue to stir 3 hours down at 85 ℃.After reaction finishes, put be chilled to room temperature after, cool off with ice bath.After leaving standstill 1 hour, generate flaxen target coarse crystallization, with its filtering separation.With 500ml methanol wash coarse crystallization 2 times, filtering separation obtains target resultant (following table is shown CR-1) (45.6g, yield are 95%) by vacuum-drying.Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 960 as a result.In addition, in deuterated dimethyl sulfoxide (the heavy ジメチ Le ス Le ホキシ De) solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.1-1.2(m, 24H), 2.6-2.7(m, and 4H), 5.5(s, 24H), 6.0-6.8(m, 24H), 8.4,8.5(d, 8H).

[Chemical formula 1 05]

CR-2's is synthetic

Except the 4-isopropyl benzene formaldehyde in the synthesis example of CR-1 being replaced by 4-n-propylbenzene formaldehyde, similarly synthesize with CR-1.Its result obtains CR-2(45.6g, and yield is 95%).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 960 as a result.In addition, the resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.0(m, 12H), 1.4-1.6(m, and 8H), 2.3-2.5(m, 8H), 5.5(s, 4H), 6.0-6.8(m, 24H), 8.4,8.5(d, 8H).

[Chemical formula 1 06]

CR-3's is synthetic

Except half molar weight in the 4-isopropyl benzene formaldehyde in the synthesis example of CR-1 being replaced by 4-n-propylbenzene formaldehyde, similarly synthesize with CR-1.Its result obtains CR-3(45.6g).Analyze this compound with LC-MS, the molecular weight of display-object material is 960 as a result.In addition, the resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.2(m, 36H), 1.4-1.6(m, and 8H), 2.3-2.7(m, 12H), 5.5(d, 8H), 6.0-6.8(m, 48H), 8.4,8.5(m, 16H).

[Chemical formula 1 07]

R ^1A=sec.-propyl/n-propyl (1/1)

CR-4's is synthetic

Except 1/4 molar weight in the 4-isopropyl benzene formaldehyde in the synthesis example of CR-1 being replaced by bromobenzaldehyde, similarly synthesize with CR-1.Its result obtains the CR-4 of 45.5g.In addition, the resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.1-1.2(m, 18H), 2.6-2.7(m, and 3H), 5.5(m, 4H), 6.0-6.8(m, 24H), 8.4-8.5(m, 8H).

By ¹The chemical displacement value of H-NMR hints out that the bromine atoms number is 0.8% with respect to the ratio of total constituting atom number of CR-4.

[Chemical formula 1 08]

CR-5's is synthetic

Be replaced by the dimethylaminobenzaldehyde except 1/4 molar weight in the 4-isopropyl benzene formaldehyde in the synthesis example of CR-1 being replaced by bromobenzaldehyde, 1/8 molar weight, similarly synthesize with CR-1.Its result obtains the CR-5 of 45.5g.

In addition, the resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.1-1.2(m, 30H), 2.6-2.7(m, and 5H), 2.9(m, 6H), 5.5(m, 8H), 6.0-6.8(m, 48H), 8.4,8.5(m, 16H).

By ¹The chemical displacement value of H-NMR as can be seen, with respect to total constituting atom number of CR-5, the ratio of bromine atoms number is 0.8%, the ratio of nitrogen-atoms number is 0.4%.

[Chemical formula 1 09]

R ^1C=sec.-propyl/bromine/N (CH ₃) ₂(5/2/1)

CR-6's is synthetic

Except the 4-isopropyl benzene formaldehyde in the synthesis example of CR-1 is replaced by beyond 2, the 4-dimethylbenzaldehyde, similarly synthesize with CR-1.Its result obtains CR-6(44.3g, and yield is 98%).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 904 as a result.In addition, the resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.0(d, 12H), 1.4-1.6(d, and 12H), 5.6(t, 4H), 6.1-6.5(m, 20H), 8.3-8.5(m, 8H).

[Chemical formula 1 10]

CR-7's is synthetic

Except the 4-isopropyl benzene formaldehyde in the synthesis example of CR-1 being replaced by isobutyl-benzene formaldehyde, similarly synthesize with CR-1.Its result obtains CR-7(49.0g, and yield is 96%).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1017 as a result.In addition, the resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.7(m, 4H), 2.3-2.4(m, and 8H), 5.5(d, 4H), 5.8-6.8(m, 24H), 8.4-8.6(t, 8H).

[Chemical formula 1 11]

CR-8's is synthetic

Except the 4-isopropyl benzene formaldehyde in the synthesis example of CR-1 being replaced by biphenylcarboxaldehyde (PVC Off エニ Le ア Le デヒ De), similarly synthesize with CR-1.Its result obtains CR-8(53.5g, and yield is 98%).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1096 as a result.In addition, the resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 6.0-7.4(d, 4H), 6.1-6.5(m, and 24H), 8.6-8.7(t, 8H).

[Chemical formula 1 12]

CR-9's is synthetic

Except the 4-isopropyl benzene formaldehyde in the synthesis example of CR-1 being replaced by 3-bromo-4-tolyl aldehyde, similarly synthesize with CR-1.Its result obtains CR-9(56.3g, and yield is 97%).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1160 as a result.In addition, the resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.0-1.2(d, 12H), 6.0-7.4(d, and 4H), 6.1-6.5(m, 20H), 8.6-8.7(t, 8H).

[Chemical formula 1 13]

CR-10's is synthetic

Except the 4-isopropyl benzene formaldehyde in the synthesis example of CR-1 is replaced by 5-bromo-2, beyond the 4-dimethylbenzaldehyde, similarly synthesize with CR-1.Its result obtains CR-10(57.8g, and yield is 95%).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1216 as a result.In addition, the resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.0(d, 12H), 1.4-1.6(d, and 12H), 6.0-7.4(d, 4H), 6.1-6.5(m, 16H), 8.6-8.7(t, 8H).

[Chemical formula 1 14]

CP-1's is synthetic

Except the Resorcinol in the synthesis example of CR-1 being replaced by pyrogallol, similarly synthesize with CR-1.Its result obtains CP-1(49.9g, and yield is 97%).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1024 as a result.In addition, the resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.0(m, 12H), 1.4-1.6(m, and 8H), 2.3-2.5(m, 8H), 5.5(s, 4H), 6.0-6.8(m, 20H), 8.4-8.5(m, 12H).

[Chemical formula 1 15]

CP-2's is synthetic

Except the 4-isopropyl benzene formaldehyde in the synthesis example of CR-1 being replaced by the 4-biphenylcarboxaldehyde, Resorcinol being replaced by the pyrogallol, similarly synthesize with CR-1.Its result obtains CP-2(55.8g, and yield is 96%).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1160 as a result.In addition, the resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 6.0-7.4(d, 4H), and 6.1-6.5(m, 20H), 8.6-8.7(m, 12H).

[Chemical formula 1 16]

＜synthesis example 2〉ring compound B's is synthetic

BOC50CR-1's is synthetic

Fully dry and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, to by 9.6g(10mmol) synthesis example 1 in synthetic CR-1,0.1g(1mmol) 4, drip 8.7g(40mmol in the solution that 4 '-Dimethylamino pyridine and 500ml acetone are formed) tert-Butyl dicarbonate.At room temperature stirring reaction liquid is 1 hour.After reaction finished, desolventizing was made with extra care with the mixed solvent of hexane/ethyl acetate=1/3 solid that obtains by column chromatography.The BOC50CR-1 that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by tert-butoxycarbonyl is 13.0g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.1-1.3(m, 60H), 2.6-2.7(m, and 4H), 5.5(s, 4H), 6.0-6.8(m, 24H), 8.4,8.5(d, 4H).

TBu50CR-1's is synthetic

Fully dry and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, to by 9.6g(10mmol) synthesis example 1 in drip 7.7g(40mmol in the solution formed of the THF of salt of wormwood, 400ml of synthetic CR-1,13.8g) the 100ml THF solution of bromo-acetic acid tert-butyl.At room temperature stirring reaction liquid is 1 hour.After reaction finished, desolventizing was made with extra care with the mixed solvent of hexane/ethyl acetate=1/3 solid that obtains by column chromatography.The phenolic hydroxyl group that obtains 50 moles of % by the tert-butoxycarbonyl methyl substituted tBu50CR-1 12.9g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.1-1.2(m, 24H), 1.5(d, and 36H), 2.6-2.7(m, 4H), 4.4-4.5(d, 4H), 5.5(s, 4H), 6.0-6.8(m, 24H), 8.4,8.5(d, 4H).

MAD50CR-1's is synthetic

Fully dry and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, to by 9.6g(10mmol) synthesis example 1 in drip 11.4g(40mmol in the solution formed of the THF of salt of wormwood, 400ml of synthetic CR-1,13.8g) the 100ml THF solution of bromoacetic acid methyl adamantane ester.At room temperature stirring reaction liquid is 1 hour.After reaction finished, desolventizing was made with extra care with the mixed solvent of hexane/ethyl acetate=1/3 solid that obtains by column chromatography.The phenolic hydroxyl group that obtains 50 moles of % by methyl adamantane oxygen carbonyl methyl substituted MAD50CR-1 14.0g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.1-1.2(m, 24H), 1.4-2.2(m, and 68H), 2.6-2.7(m, 4H), 4.4-4.5(d, 4H), 5.5(s, 4H), 6.0-6.8(m, 24H), 8.4,8.5(d, 4H).

EE50CR-1's is synthetic

Fully dry and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, to by 9.6g(10mmol) synthesis example 1 in drip 2.9g(40mmol in the solution formed of the acetone of synthetic CR-1,2.5g tosic acid pyridinium salt, 400ml) ethyl vinyl ether.At room temperature stirring reaction liquid is 24 hours.After reaction finished, desolventizing was made with extra care with the mixed solvent of hexane/ethyl acetate=1/3 solid that obtains by column chromatography.The EE50CR-1 that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by ethoxyethyl group is 11.2g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, the TMS benchmark) be 0.9-1.0(m, 12H), 1.1-1.2(m, 24H), 1.3-1.4(m, 12H), 2.6-2.7(m, 4H), 3.3-3.4(m, 8H), 5.1(m, 4H), 5.5(s, 4H), 6.0-6.8(m, 24H), 8.4,8.5(d, 4H).

CE50CR-1's is synthetic

Fully dry and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, to by 9.6g(10mmol) synthesis example 1 in synthetic CR-1,2.5g tosic acid pyridinium salt, 400ml 1, Dropwise 5 .0g(40mmol in the solution that 3-two oxa-s penta ring is formed) cyclohexyl vinyl ether.At room temperature stirring reaction liquid is 24 hours.After reaction finished, desolventizing was made with extra care with the mixed solvent of hexane/ethyl acetate=1/3 solid that obtains by column chromatography.The CE50CR-1 that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by the cyclohexyloxy ethyl is 12.2g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.1-1.2(m, 24H), 1.3-1.4(m, and 12H), 2.6-2.7(m, 4H), 5.1(m, 4H), 5.5(s, 4H), 6.0-6.8(m, 24H), 8.4,8.5(d, 4H).

BOC50CR-2's is synthetic

Except the CR-1 in the synthesis example of BOC50CR-1 being replaced by CR-2, similarly synthesize with BOC50CR-1.Its result, the BOC50CR-2 that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by tert-butoxycarbonyl is 30.0g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.0(m, 12H), 1.4-1.6(m, and 8H), 2.3-2.5(m, 8H), 5.5(s, 4H), 6.0-6.8(m, 24H), 8.4,8.5(d, 4H).

TBu50CR-2's is synthetic

Except the CR-1 in the synthesis example of tBu50CR-1 being replaced by CR-2, similarly synthesize with tBu50CR-1.Its result, the phenolic hydroxyl group that obtains 50 moles of % by the tert-butoxycarbonyl methyl substituted tBu50CR-2 30.0g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.0(m, 12H), 1.4-1.6(m, and 44H), 2.3-2.5(m, 8H), 4.4-4.5(d, 4H), 5.5(s, 4H), 6.0-6.8(m, 24H), 8.4,8.5(d, 4H).

MAD50CR-2's is synthetic

Except the CR-1 in the synthesis example of MAD50CR-1 being replaced by CR-2, similarly synthesize with MAD50CR-1.Its result, the phenolic hydroxyl group that obtains 50 moles of % by methyl adamantane oxygen carbonyl methyl substituted MAD50CR-2 30.0g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.0(m, 12H), 1.4-2.2(m, and 76H), 2.3-2.5(m, 8H), 4.4-4.5(d, 4H), 5.5(s, 4H), 6.0-6.8(m, 24H), 8.4,8.5(d, 4H).

EE50CR-2's is synthetic

Except the CR-1 in the synthesis example of EE50CR-1 being replaced by CR-2, similarly synthesize with EE50CR-1.Its result, the EE50CR-2 that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by ethoxyethyl group is 30.0g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.0(m, 12H), 1.3-1.4(m, and 12H), 3.3-3.4(m, 8H), 5.1(m, 4H), 5.5(s, 4H), 6.0-6.8(m, 24H), 8.4,8.5(d, 4H).

CE50CR-2's is synthetic

Except the CR-1 in the synthesis example of CE50CR-1 being replaced by CR-2, similarly synthesize with CE50CR-1.Its result, the CE50CR-2 that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by the cyclohexyloxy ethyl is 30.0g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.0(m, 12H), 1.3-1.4(m, and 12H), 1.4-1.6(m, 8H), 2.3-2.5(m, 8H), 5.1(m, 4H), 5.5(s, 4H), 6.0-6.8(m, 24H), 8.4,8.5(d, 4H).

BOC50CR-3's is synthetic

CR-1 in the synthesis example of BOC50CR-1 is replaced by the CR-3, similarly synthesizes with BOC50CR-1.Its result, the BOC50CR-3 that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by tert-butoxycarbonyl is 30.0g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.2(m, 36H), 1.2-1.3(m, and 72H), 1.4-1.6(m, 8H), 2.3-2.7(m, 12H), 5.5(d, 8H), 6.0-6.8(m, 48H), 8.4,8.5(m, 8H).

BOC50CR-4's is synthetic

CR-1 in the synthesis example of BOC50CR-1 is replaced by the CR-4, similarly synthesizes with BOC50CR-1.Its result, the BOC50CR-4 that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by tert-butoxycarbonyl is 30.0g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.1-1.2(m, 18H), 1.2-1.3(m, and 36H), 2.6-2.7(m, 3H), 5.5(m, 4H), 6.0-6.8(m, 24H), 8.4-8.5(m, 4H).

BOC50CR-5's is synthetic

Except the CR-1 in the synthesis example of BOC50CR-1 being replaced by CR-5, similarly synthesize with BOC50CR-1.Its result, the BOC50CR-5 that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by tert-butoxycarbonyl is 30.0g altogether.

¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.1-1.2(m, 30H), 1.2-1.3(m, and 72H), 2.6-2.7(m, 5H), 2.9(m, 6H), 5.5(m, 8H), 6.0-6.8(m, 48H), 8.4,8.5(m, 8H).

BOC50CR-6's is synthetic

Except the CR-1 in the synthesis example of BOC50CR-1 being replaced by CR-6, similarly synthesize with BOC50CR-1.Its result, the BOC50CR-6 that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by tert-butoxycarbonyl is 31.0g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.0(d, 12H), 1.4-1.6(d, and 12H), 5.6(t, 4H), 6.1-6.5(m, 20H), 8.3-8.5(m, 4H).

BOC50CR-7's is synthetic

Except the CR-1 in the synthesis example of BOC50CR-1 being replaced by CR-7, similarly synthesize with BOC50CR-1.Its result, the BOC50CR-7 that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by tert-butoxycarbonyl is 30.8g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.8-0.9(d, 24H), 1.1-1.3(s, and 36H), 1.7(m, 4H), 2.3-2.4(m, 8H), 5.5(d, 4H), 5.8-6.8(m, 24H), 8.4-8.6(t, 4H).

BOC50CR-8's is synthetic

Except the CR-1 in the synthesis example of BOC50CR-1 being replaced by CR-8, similarly synthesize with BOC50CR-1.Its result, the BOC50CR-8 that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by tert-butoxycarbonyl is 30.5g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.1-1.3(s, 36H), 6.0-7.4(d, and 4H), 6.1-6.5(m, 24H), 8.6-8.7(t, 4H).

BOC50CR-9's is synthetic

Except the CR-1 in the synthesis example of BOC50CR-1 being replaced by CR-9, similarly synthesize with BOC50CR-1.Its result, the BOC50CR-9 that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by tert-butoxycarbonyl is 29.5g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.0-1.2(d, 12H), 1.1-1.3(s, and 36H), 6.0-7.4(d, 4H), 6.1-6.5(m, 20H), 8.6-8.7(t, 4H).

BOC50CR-10's is synthetic

Except the CR-1 in the synthesis example of BOC50CR-1 being replaced by CR-10, similarly synthesize with BOC50CR-1.Its result, the BOC50CR-10 that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by tert-butoxycarbonyl is 29.4g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.0(d, 12H), 1.1-1.3(s, and 36H), 1.4-1.6(d, 12H), 6.0-7.4(d, 4H), 6.1-6.5(m, 16H), 8.6-8.7(t, 4H).

BOC67CP-1's is synthetic

Except the CR-1 in the synthesis example of BOC50CR-1 being replaced by CP-1, similarly synthesize with BOC50CR-1.Its result, the BOC67CP-1 that the phenolic hydroxyl group that obtains 67 moles of % has been replaced by tert-butoxycarbonyl is 37.2g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.0(m, 12H), 1.1-1.3(s, and 72H), 1.4-1.6(m, 8H), 2.3-2.5(m, 8H), 5.5(s, 4H), 6.0-6.8(m, 20H), 8.4-8.5(m, 4H).

BOC67CP-2's is synthetic

Except the CR-1 in the synthesis example of BOC50CR-1 being replaced by CP-2, similarly synthesize with BOC50CR-1.Its result, the BOC67CP-2 that the phenolic hydroxyl group that obtains 67 moles of % has been replaced by tert-butoxycarbonyl is 38.6g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.1-1.3(s, 72H), 6.0-7.4(d, and 4H), 6.1-6.5(m, 20H), 8.6-8.7(m, 4H).

Embodiment 1-57 and comparative example 1-3

Modulate the composition that the 1st souvenir carries, form homogeneous solution after, be that the teflon made membrane filter of 0.2 μ m filters with the aperture, be mixed with the resist composition, carry out following evaluation separately.The result is shown in the 2nd table.

(1) the film-forming properties evaluation of resist film

Visual observation utilizes spin coater that the resist composition is spun onto on the silicon chip and the foursquare resist overlay film of 10 * 10mm that forms, confirms that all surface propertys are all good.

(2) figure forms test

(2-1) evaluation of resolving power

After being spun onto resist on the clean silicon chip, the preceding baking (PB) that in baking oven, exposes, forming thickness is the resist film of 0.1 μ m.This resist film irradiation is set at line and the electron rays at interval of the 1:1 that is spaced apart 50nm with electron rays drawing apparatus (ELS-7500, (strain) エリオニ Network ス society system).After the irradiation, under the temperature of stipulating separately, heated for 90 seconds, in the TMAH aqueous solution of 2.38 weight %, developed for 60 seconds.Then, wash 30 seconds and dry with water, form the resist pattern of eurymeric.By sweep electron microscope (the Ha イテ of (strain) Hitachi Network ノロジ one S-4800 processed) observable line and interval.In addition, with dosage (μ C/cm at this moment ²) as susceptibility.

(2-2) evaluation of graphics shape

By observable line and the cross-section photograph at interval that is spaced apart the 1:1 of 50nm of sweep electron microscope (the Ha イテ of (strain) Hitachi Network ノロジ one S-4800 processed), and estimate.

A: rectangular graph (good figure)

B: be roughly rectangular graph (roughly good figure)

C: non-rectangle figure (bad figure)

(2-3) evaluation of line edge roughness (LER)

At the line of the 1:1 that is spaced apart 50nm and any 300 points of length direction (0.75 μ m) at interval, the distance of use Hitachi semi-conductor between SEM タ one ミ Na Le PC V5 off line survey Great Wall Software's part (the サイエ of (strain) Hitachi Application スシステ system ズ system) mensuration edge and the reference line.Calculate standard deviation (3 σ) by measurement result.

The LER that A:LER(3 σ) ≦ 3.0nm(is good)

B:3.0nm ﹤ LER(3 σ) ≦ 3.5nm(is good LER roughly)

C:3.5nm ﹤ LER(3 σ) (bad LER)

(2-4) mensuration of ease tolerance

Dosage (the μ C/cm that calculates in the resist film irradiation (2-1) to coating on the area of 1.2 * 1.2mm ²) the electron rays of 2 times of amounts.Then, shone the part of electron rays and do not shone the film thickness difference of the part of electron rays with Scanning Probe Microscopy mensuration, with the index of this film thickness difference as ease tolerance.Film reduction during poly(4-hydroxystyrene) (PHS) that its result and the hydroxyl that has used 50 moles of % as compound have been replaced by tert-butoxycarbonyl compares.

A: the film reduction when the film reduction is less than or equal to the PHS that the hydroxyl that used 50 moles of % replaced by tert-butoxycarbonyl

C: the film reduction when the film reduction has been replaced the PHS of hydroxyl greater than the hydroxyl that has used 50 moles of % by tert-butoxycarbonyl

(3) the safety solvent solubility test of compound

The solubility test of the compound that obtains in the synthesis example 2 in safety solvent carried out under 23 ℃.Evaluation in being selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, methyl-phenoxide, N-BUTYL ACETATE, ethyl propionate, ethyl lactate and pimelinketone and the most diffluent solvent in meltage.

A:10.0 weight % ≦ meltage

B:1.0 weight % ≦ meltage ﹤ 10.0 weight %

C: meltage ﹤ 1.0 weight %

[table 1]

The 1st table-1

[table 2]

The 1st table-2

[table 3]

The 1st table-3

Comparative compound

BOC75CR-11

Replace the 4-isopropyl benzene formaldehyde of synthesis example 1 to use the 4-hydroxy benzaldehyde, similarly be synthesized into following CR-11, replace the CR-1 of synthesis example 2 to use CR-11 to obtain the replacement rate that target substance BOC75CR-11(phenolic hydroxyl group is substituted by tert-butoxycarbonyl and be 75mol%).

BOC50CR-12

Replace the 4-isopropyl benzene formaldehyde of synthesis example 1 to use acetaldehyde, similarly be synthesized into following CR-12, replace the CR-1 of synthesis example 2 to use CR-12 to obtain the replacement rate that target substance BOC50CR-12(phenolic hydroxyl group is substituted by tert-butoxycarbonyl and be 50mol%).

BOC50CR-13

Replace the 4-isopropyl benzene formaldehyde of synthesis example 1 to use 4-tert.-butylbenzene formaldehyde, similarly be synthesized into following CR-13, replace the CR-1 of synthesis example 2 to use CR-13 to obtain the replacement rate that target substance BOC50CR-13(phenolic hydroxyl group is substituted by tert-butoxycarbonyl and be 50mol%).

[Chemical formula 1 17]

[Chemical formula 1 18]

[Chemical formula 1 19]

Acidogenic agent C

P-1: nine fluorine fourth sulfonic acid triphenyl phenyl sulfonium salts

(body どり chemistry (strain))

P-2: trifluoromethanesulfonic acid triphenyl phenyl sulfonium salt

(body どり chemistry (strain))

P-3: tosic acid phenylbenzene (trimethylammonium) phenyl sulfonium salt

(with the pure pharmaceutical worker's industry of light (strain))

Acid diffusion control agent E

Q-1: trioctylamine (Tokyo changes into industry (strain))

Q-2: lophine (Tokyo changes into industry (strain))

Other composition F(tensio-active agent)

D-1: メガ Off ア Star Network R08(Japanese ink chemical industry (strain) system)

D-2:BYK-302(PVC Star Network ケミ one ジヤパ Application (strain) system)

Solvent

S-1 propylene glycol monomethyl ether (Tokyo changes into industry (strain))

[table 4]

The 2nd table-1

[table 5]

The 2nd table-2

[table 6]

The 2nd table-3

PEB: the temperature during electron rays irradiation post-heating

＜synthesis example 1A〉has phenyl aldehyde synthetic that the substituent carbonatoms that contains alicyclic ring or aromatic nucleus is 10-24

Add 74.3g(3.71mol) anhydrous HF, 50.5g(0.744mol) BF ₃Be in the autoclave that has electromagnetic mixing apparatus (SUS316L system) of 500ml to the internal volume that can control temperature, stir content, keeping fluid temperature to utilize carbon monoxide to boost to 2MPa under for-30 ℃.Then, keep-up pressure for 2MPa, fluid temperature for-30 ℃ supply with down mixed 57.0g(0.248mol) the 4-phenylcyclohexane and the raw material of the normal heptane of 50.0g, keep after 1 hour, in ice, extract content, after the benzene dilution, the oil reservoir that neutralizing treatment obtains is analyzed with vapor-phase chromatography, obtain reaction result, the transformation efficiency of 4-phenylcyclohexane is 100%, and the selection rate of 4-cyclohexyl benzaldehyde is 97.3%.By the simple distillation target component of emanating out, by the result that GC-MS analyzes, the molecular weight of target substance 4-cyclohexyl benzaldehyde (following table is shown CHBAL) is 188.In addition, in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.0-1.6(m, 10H), 2.55(m, and 1H), 7.36(d, 2H), 7.8(d, 2H), 10.0(s, 1H).

[Chemical formula 1 20]

＜synthesis example 2A〉ring-type polyphenolic substance A's is synthetic

Under stream of nitrogen gas, Resorcinol (22g with Northeast chemistry society system, 0.2mol), the synthetic 4-cyclohexyl benzaldehyde (46.0g of synthesis example 1A, 0.2mol) and dehydrated alcohol (200ml) put into abundant drying and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, be mixed with ethanolic soln.Be heated to 85 ℃ with mantle heater when stirring this solution.Then, behind dropping funnel cost dropping in 30 minutes 75ml concentrated hydrochloric acid (35%), continue to stir 3 hours down at 85 ℃.After reaction finishes, put be chilled to room temperature after, cool off by ice bath.After leaving standstill 1 hour, generate flaxen target coarse crystallization, with its filtering separation.With 500ml methanol wash coarse crystallization 2 times, filtering separation obtains target resultant (following table is shown CR-1A) (50g, yield are 91%) by vacuum-drying.Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1121 as a result.In addition, in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.8-1.9(m, 56H), 5.5, and 5.6(d, 4H), 6-6.8(m, 24H), 8.4,8.5(m, 8H).

[Chemical formula 1 21]

＜synthesis example 3A〉ring compound B's is synthetic

BOC50CR-1A's is synthetic

Fully dry and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, to by 11.2g(10mmol) synthesis example 2A in synthetic CR-1A, 0.1g(1mmol) 4, drip 8.7g(40mmol in the solution that 4 '-Dimethylamino pyridine and 500ml acetone are formed) tert-Butyl dicarbonate.At room temperature stirring reaction liquid is 1 hour.After reaction finished, desolventizing was made with extra care with the mixed solvent of hexane/ethyl acetate=1/3 solid that obtains by column chromatography.The BOC50CR-1A that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by tert-butoxycarbonyl is 13.0g altogether.

The resultant that obtains is in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.8-1.9(m, 92H), 5.5, and 5.6(d, 4H), 6-6.8(m, 24H), 8.4,8.5(m, 4H).

TBu50CR-1A's is synthetic

Fully dry and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, to by 11.2g(10mmol) synthesis example 2A in drip 7.7g(40mmol in the solution formed of the THF of salt of wormwood, 400ml of synthetic CR-1A, 13.8g) the 100ml THF solution of bromo-acetic acid tert-butyl.At room temperature stirring reaction liquid is 1 hour.After reaction finished, desolventizing was made with extra care with the mixed solvent of hexane/ethyl acetate=1/3 solid that obtains by column chromatography.The phenolic hydroxyl group that obtains 50 moles of % by the tert-butoxycarbonyl methyl substituted tBu50CR-1A 12.9g altogether.

The resultant that obtains is in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.8-1.9(m, 92H), 4.7(s, 8H), 5.5,5.6(d, 4H), 6-6.8(m, and 24H), 8.4,8.5(m, 4H).

MAD50CR-1A's is synthetic

Fully dry and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, to by 11.2g(10mmol) synthesis example 2A in drip 11.4g(40mmol in the solution formed of the THF of salt of wormwood, 400ml of synthetic CR-1A, 13.8g) the 100ml THF solution of bromoacetic acid methyl adamantane ester.At room temperature stirring reaction liquid is 1 hour.After reaction finished, desolventizing was made with extra care with the mixed solvent of hexane/ethyl acetate=1/3 solid that obtains by column chromatography.The phenolic hydroxyl group that obtains 50 moles of % by methyl adamantane oxygen carbonyl methyl substituted MAD50CR-1A 14.0g altogether.

The resultant that obtains is in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.8-2.1(m, 124H), 4.7(s, 8H), 5.5,5.6(d, 4H), 6-6.8(m, and 24H), 8.4,8.5(m, 4H).

EE50CR-1A's is synthetic

Fully dry and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, to by 11.2g(10mmol) synthesis example 2A in drip 2.9g(40mmol in the solution formed of the acetone of tosic acid pyridinium salt, 400ml of synthetic CR-1A, 2.5g) ethyl vinyl ether.At room temperature stirring reaction liquid is 24 hours.After reaction finished, desolventizing was made with extra care with the mixed solvent of hexane/ethyl acetate=1/3 solid that obtains by column chromatography.The EE50CR-1A that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by ethoxyethyl group is 11.2g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.8-1.9(m, 80H), 3.5(m, 8H), 5.5,5.6(d, 8H), 6-6.8(m, and 24H), 8.4,8.5(m, 4H).

CE50CR-1A's is synthetic

Fully dry and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, to by 11.2g(10mmol) synthesis example 2 in synthetic CR-1A, 2.5g tosic acid pyridinium salt, 400ml 1, Dropwise 5 .0g(40mmol in the solution that 3-two oxa-s penta ring is formed) cyclohexyl vinyl ether.At room temperature stirring reaction liquid is 24 hours.After reaction finished, desolventizing was made with extra care with the mixed solvent of hexane/ethyl acetate=1/3 solid that obtains by column chromatography.The CE50CR-1A that the phenolic hydroxyl group that obtains 50 moles of % has been replaced by the cyclohexyloxy ethyl is 12.2g altogether.

The resultant that obtains is in the deuterated dimethyl sulfoxide solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.8-1.9(m, 108H), 3.5(m, 4H), 5.5,5.6(d, 8H), 6-6.8(m, and 24H), 8.4,8.5(m, 4H).

Embodiment 1A-20A

Modulate the composition that the 1A souvenir carries, form homogeneous solution after, be that the teflon made membrane filter of 0.2 μ m filters with the aperture, be mixed with the resist composition.About acidogenic agent C, sour diffusion control agent E, other additive F and solvent, use the material identical with above-described embodiment 1-43, except in figure formation test, carrying out following evaluation, similarly estimate with above-mentioned.

(2-3) evaluation of line edge roughness (LER)

The LER that A:LER(3 σ) ≦ 3.5nm(is good)

B:3.5nm ﹤ LER(3 σ) ≦ 4.5nm(is good LER roughly)

C:4.5nm ﹤ LER(3 σ) (bad LER)

In addition, in the safety solvent solubility test of (3) compound, confirm that the meltage of all compounds is all more than 2.5wt%.

[table 7]

The 1A table

[table 8]

The 2A table

PEB: the temperature during electron rays irradiation post-heating

＜synthesis example 1B〉is synthetic for the compound of introducing acid dissociation functional group

Synthesizing of bromoacetic acid methyl adamantane ester

Fully dry and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, drip the THF solution 20ml of bromo acetyl bromide (12.65g/62.7mmol) in the solution of under 0 ℃, forming to the THF by 2-methyl-2-adamantanol (8.31g/50mmol) (Golden Elephant chemical industry system), pyridine (5.0g/62.7mmol), 100ml.At room temperature stirring reaction liquid is 72 hours.

Reaction removes by filter insoluble substance after finishing, and by the filtrate desolventizing, the solid that obtains is made with extra care by column chromatography with the mixed solvent of hexane/ethyl acetate=50/1.Obtaining the 9.0g(yield is 62%) following bromoacetic acid methyl adamantane ester.

The resultant that obtains is in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.0-2.5(m, 17H), 4.5(m, and 2H).

Synthesizing of bromoacetic acid ethyl diamantane ester

Except the methyl of the 2-in the synthesis example of bromoacetic acid methyl adamantane ester-2-adamantanol being replaced by 2-ethyl-2-adamantanol (Mitsubishi's gas chemistry (strain) system), similarly synthesize following bromoacetic acid ethyl diamantane ester with bromoacetic acid methyl adamantane ester.

Synthesizing of bromo-propionic acid ethyl diamantane ester

Except the methyl of the 2-in the synthesis example of bromoacetic acid methyl adamantane ester-2-adamantanol is replaced by 2-ethyl-2-adamantanol (Golden Elephant chemical industry system), bromo acetyl bromide is replaced by beyond the bromo acid bromine, similarly synthesizes following bromo acid ethyl diamantane ester with monobromo-acetic acid methyl adamantane ester.

The resultant that obtains is in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.0-2.5(m, 19H), 4.5(m, and 2H).

[Chemical formula 1 22]

Shown in following, at first synthesizing aldehyde compound A1 follows the synthesis of cyclic compound.

＜synthesis example 2B〉aldehyde compound A1's is synthetic

AD1-HBA's is synthetic

Fully dry and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, drip 28.6g(100mmol in the solution of forming to the THF by p-Hydroxybenzaldehyde (12.2g/100mmol), salt of wormwood (13.8g/100mmol), 200ml) the 100ml THF solution of monobromo-acetic acid methyl adamantane ester.Stirring reaction liquid is 24 hours under refluxing.

After reaction finished, desolventizing was made with extra care with the mixed solvent of hexane/ethyl acetate=1/3 solid that obtains by column chromatography.Obtain the 29.0g phenolic hydroxyl group by methyl adamantane oxygen carbonyl methyl substituted following A D1-HBA.

The resultant that obtains is in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.5-2.2(m, 17H), 4.9(s, and 2H), 7.8-8.4(m, 4H), 10.0(m, 1H).

AD2-HBA's is synthetic

Except the bromoacetic acid methyl adamantane ester in the synthesis example of AD1-HBA being replaced by bromoacetic acid ethyl diamantane ester, similarly synthesize with AD1-HBA.Its result, obtain the 30.1g phenolic hydroxyl group by ethyl Buddha's warrior attendant carbalkoxy methyl substituted following A D2-HBA.The resultant that obtains is in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.5-2.2(m, 19H), 4.9(s, and 2H), 7.8-8.4(m, 4H), 10.0(m, 1H).

AD3-HBA's is synthetic

Except the bromoacetic acid methyl adamantane ester in the synthesis example of AD1-HBA being replaced by bromo-propionic acid ethyl diamantane ester, similarly synthesize with AD1-HBA.Its result obtains the following A D3-HBA that the 31.1g phenolic hydroxyl group has been replaced by ethyl Buddha's warrior attendant carbalkoxy ethyl.The resultant that obtains is in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.5-2.2(m, 19H), 2.7(m, and 2H), 4.9(s, 2H), 7.8-8.4(m, 4H), 10.0(m, 1H).

[Chemical formula 1 23]

Synthesizing of＜synthesis example 3B〉ring compound

AD1-CR-1's is synthetic

Under stream of nitrogen gas, Resorcinol (5.5g with Northeast chemistry society system, 50mmol), the AD1-HBA(16.4g that synthesizes among the synthesis example 2B, 50mol) and ethanol (330ml) put into abundant drying and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, be mixed with ethanolic soln.Then, at room temperature by behind dropping funnel cost dropping in the 60 minutes 75ml concentrated hydrochloric acid (35%), continue at room temperature to stir 6 hours.Reaction is cooled off the flaxen target coarse crystallization of filtering separation after finishing by ice bath.With 300ml distilled water, use 300ml methanol wash coarse crystallization 2 times again, filtering separation obtains target resultant (following table is shown AD1-CR-1) (20.2g) by vacuum-drying.Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1681 as a result.In addition, in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.5-2.2(m, 68H), 4.9(s, and 8H), 5.4-5.7(m, 4H), 6.1-6.5(m, 24H), 7.8-8.4(m, 8H).

AD2-CR-1's is synthetic

Except the AD1-HBA in the synthesis example of AD1-CR-1 being replaced by AD2-HBA, similarly synthesize with AD1-CR-1.Its result obtains the AD2-CR-1 of 30.0g.Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1733 as a result.The resultant that obtains is in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.5-2.2(m, 25H), 4.9(s, and 2H), 7.8-8.4(m, 4H), 10.0(m, 1H).

AD3-CR-1's is synthetic

Except the AD1-HBA in the synthesis example of AD1-CR-1 being replaced by AD3-HBA, similarly synthesize with AD1-CR-1.Its result obtains the AD3-CR-1 of 32.0g.Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1793 as a result.In addition, the resultant that obtains is in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.5-2.2(m, 25H), 2.7(m, and 8H), 4.9(s, 2H), 7.8-8.4(m, 4H), 10.0(m, 1H).

[Chemical formula 1 24]

[Chemical formula 1 25]

[Chemical formula 1 26]

Comparative compound AD4-CR-2's is synthetic

After in comparative example 1, obtaining CR-11, fully dry and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, to by 11.2g(10mmol) the solution formed of the THF of salt of wormwood, 400ml of CR-2,13.8g in drip 11.4g(40mmol) the 100ml THF solution of bromoacetic acid methyl adamantane ester.At room temperature stirring reaction liquid is 1 hour.After reaction finished, desolventizing was made with extra care with the mixed solvent of hexane/ethyl acetate=1/3 solid that obtains by column chromatography.The phenolic hydroxyl group that obtains 50 moles of % by methyl adamantane oxygen carbonyl methyl substituted AD4-CR-2 14.0g altogether.

The resultant that obtains is in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.5-2.2(m, 102H), 4.9(s, and 12H), 5.4-5.7(m, 4H), 6.1-6.5(m, 24H), 7.8-8.4(m, 6H).

＜synthesis example 4B〉aldehyde compound A1d's is synthetic

MADM-4HBA's is synthetic

Fully dry and with nitrogen replacement the four-hole boiling flask (1000mL) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, drip 28.6g(100mmol in the solution of forming to the THF by p-Hydroxybenzaldehyde (12.2g/100mmol), salt of wormwood (13.8g/100mmol), 200ml) the 100ml THF solution of bromoacetic acid methyl adamantane ester.Stirring reaction liquid is 24 hours under refluxing.

After reaction finished, desolventizing was made with extra care with the mixed solvent of hexane/ethyl acetate=1/3 solid that obtains by column chromatography.Obtain the 29.0g phenolic hydroxyl group by methyl adamantane oxygen carbonyl methyl substituted MADM-4HBA.

The resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.5-2.2(m, 17H), 4.9(s, and 2H), 7.8-8.4(m, 4H), 10.0(s, 1H).

TBuM-4HBA's is synthetic

Except the bromoacetic acid methyl adamantane ester in the synthesis example of MADM-4HBA being replaced by bromo-acetic acid tert-butyl, similarly synthesize with MADM-4HBA.Its result, obtain the 20.0g phenolic hydroxyl group by the tert-butoxycarbonyl methyl substituted tBuM-4HBA.The resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.4(s, 9H), 5.0(s, and 2H), 7.1-7.9(m, 4H), 9.9(s, 1H).

TBuM-3HBA's is synthetic

Be replaced by the m-hydroxybenzaldehyde except the bromoacetic acid methyl adamantane ester in the synthesis example of MADM-4HBA being replaced by bromo-acetic acid tert-butyl, p-Hydroxybenzaldehyde, similarly synthesize with MADM-4HBA.Its result, obtain the 20.0g phenolic hydroxyl group by the tert-butoxycarbonyl methyl substituted tBuM-3HBA.The resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.4(s, 9H), 4.9(s, and 2H), 7.3-7.6(m, 4H), 10.0(s, 1H).

TBuM-2HBA's is synthetic

Be replaced by the salicylaldhyde except the bromoacetic acid methyl adamantane ester in the synthesis example of MADM-4HBA being replaced by bromo-acetic acid tert-butyl, p-Hydroxybenzaldehyde, similarly synthesize with MADM-4HBA.Its result, obtain the 20.0g phenolic hydroxyl group by the tert-butoxycarbonyl methyl substituted tBuM-2HBA.The resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.4(s, 9H), 4.9(s, and 2H), 7.1-7.8(m, 4H), 10.5(s, 1H).

TBuM-3Br4HBA's is synthetic

Be replaced by the 3-bromo-4-hydroxy benzaldehyde except the bromoacetic acid methyl adamantane ester in the synthesis example of MADM-4HBA being replaced by bromo-acetic acid tert-butyl, p-Hydroxybenzaldehyde, similarly synthesize with MADM-4HBA.Its result, obtain the 19.5g phenolic hydroxyl group by the tert-butoxycarbonyl methyl substituted tBuM-3Br4HBA.The resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.4(s, 9H), 5.0(s, and 2H), 7.2-8.2(m, 3H), 9.9(s, 1H).

MeM-4HBA's is synthetic

Except the bromoacetic acid methyl adamantane ester in the synthesis example of MADM-4HBA being replaced by methyl bromoacetate, similarly synthesize with MADM-4HBA.Its result, obtain the 15.2g phenolic hydroxyl group by the methoxycarbonyl methyl substituted MeM-4HBA.The resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 3.7(s, 3H), 5.0(s, and 2H), 7.1-7.9(m, 4H), 9.9(s, 1H).

EtM-4HBA's is synthetic

Except the bromoacetic acid methyl adamantane ester in the synthesis example of MADM-4HBA being replaced by ethyl bromoacetate, similarly synthesize with MADM-4HBA.Its result, obtain the 15.8g phenolic hydroxyl group by the ethoxy carbonyl methyl substituted EtM-4HBA.The resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.3(t, 9H), 4.3(m, and 2H), 4.8(s, 2H), 7.1-7.9(m, 4H), 9.9(s, 1H).

＜synthesis example 5B〉has compound A-13 synthetic of halo methyl ether base

ADCME's is synthetic

Fully dry and with nitrogen replacement the four-hole boiling flask (100mL) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, in the solution of being formed by the chloroform of 1-adamantyl methyl alcohol (3.32g/10mmol), 63ml, add 92% Paraformaldehyde 96 (1.20g/20mmol).Then, under ice-cold, when being blown into hydrogen halide, stirred 2.5 hours.

Reaction stops to be blown into hydrogen halide after finishing, and gets back to room temperature, separates not tolerant layer with separating funnel, adds anhydrous sodium sulphate in the normal hexane layer, after at room temperature stirring, carries out filtration treatment.Desolventizing from the filtrate that obtains obtains 4.1g target substance ADCME.

The resultant that obtains is in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.0-1.6(m, 15H), 3.3-3.6(m, and 2H), 5.5(s, 2H).

CHCME's is synthetic

Except the 1-adamantyl methyl alcohol in the synthesis example of ADCME being replaced by hexalin, similarly synthesize with ADCME.Its result obtains target resultant (following table is shown CHCME) (6.0g).The resultant that obtains is in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.4-1.6(m, 10H), 2.8(m, and 1H), 5.5(s, 2H).

＜synthesis example 6B〉ring compound B0's is synthetic

As follows, at first the synthesis of cyclic compound A-40 is followed synthesis of cyclic compd B 0.

CM-CR-1's is synthetic

Under stream of nitrogen gas, Resorcinol (5.5g with Northeast chemistry society system, 50mmol), the MADM-4HBA(16.4g that synthesizes among the synthesis example 1B, 50mmol) and ethanol (330ml) put into abundant drying and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, be mixed with ethanolic soln.Then, at room temperature by behind dropping funnel cost dropping in the 60 minutes 75ml concentrated hydrochloric acid (35%), stirred 48 hours down at 80 ℃.Reaction is got back to room temperature after finishing, and the interpolation aqueous sodium hydroxide solution also stirred 24 hours.Then, this solution is transferred in the separating funnel, added the diethyl ether separatory, isolate its water layer and neutralize with hydrochloric acid, filter to isolate the solid matter of separating out, obtain target resultant (following table is shown CM-CR-1) (10.2g) by vacuum-drying.Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1088 as a result.In addition, at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 4.5-4.6(t, 8H), 5.3-5.5(t, and 4H), 6.1-6.5(m, 24H), 8.4-8.5(t, 8H), 12.7(brs, 4H).

[Chemical formula 1 27]

Synthetic-2 of CM-CR-1

Except the MADM-4HBA in the synthetic synthesis example of CM-CR-1 being replaced by tBuM-4HBA, similarly synthesize with CM-CR-1.Its result obtains target resultant (following table is shown CM-CR-1) (10.2g).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1088 as a result.In addition, the resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 4.5-4.6(t, 8H), 5.3-5.5(t, and 4H), 6.1-6.5(m, 24H), 8.4-8.5(t, 8H), 12.7(brs, 4H).

CM-CR-2's is synthetic

Except the MADM-4HBA in the synthetic synthesis example of CM-CR-1 being replaced by tBuM-3HBA, similarly synthesize with CM-CR-1.

Its result obtains target resultant (following table is shown CM-CR-2) (10.0g).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1088 as a result.In addition, the resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) be 4.3-4.4 (d, 8H), 5.5-5.6 (s, 4H), 6.1-6.9 (m, 24H), 8.5 (brs, 8H), 12.9(brs, 4H).

[Chemical formula 1 28]

CM-CR-3's is synthetic

Except the MADM-4HBA in the synthetic synthesis example of CM-CR-1 being replaced by BuM-2HBA, similarly synthesize with CM-CR-1.

Its result obtains target resultant (following table is shown CM-CR-3) (10.0g).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1088 as a result.In addition, the resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 4.1(t, 8H), 5.8-5.9(t, and 4H), 6.0-7.0(m, 24H), 8.0(brs, 8H), 12.5(brs, 4H).

[Chemical formula 1 29]

CM-CR-4's is synthetic

Except the MADM-4HBA in the synthetic synthesis example of CM-CR-1 being replaced by tBuM-3Br4HBA, similarly synthesize with CM-CR-1.Its result obtains target resultant (following table is shown CM-CR-1) (11.0g).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1400 as a result.In addition, the resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 4.7(s, 8H), 5.2-5.5(t, and 4H), 6.0-6.8(m, 20H), 8.6(brs, 8H), 12.9(brs, 4H).

[Chemical formula 1 30]

CM-CR-5's is synthetic

Except the MADM-4HBA in the synthetic synthesis example of CM-CR-1 being replaced by 4-formyl radical phenylformic acid (ア Le De リ Star チ reagent processed), similarly synthesize with CM-CR-1.

Its result obtains target resultant (following table is shown CM-CR-5) (5.0g).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 968 as a result.In addition, the resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 5.5-5.7(t, 4H), 6.1-7.7(m, and 24H), 8.6-8.8(t, 8H), 12.3(brs, 4H).

[Chemical formula 1 31]

ADM-CR-1's is synthetic

Fully dry and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, under stream of nitrogen gas, to by synthetic CM-CR-1(10.9g, 10mmol), the salt of wormwood of 13.8g, THF(330ml) drop into ADCME(8.6g synthetic among the synthesis example 5B in the solution formed, 100ml THF 40mmol), the preparation tetrahydrofuran solution.Then, at room temperature stir 6 hours.After reaction finished, concentration of reaction solution was made with extra care by column chromatography, and distillation is removed post and launched solvent, and the solid matter that filtering separation obtains obtains target resultant (following table is shown ADM-CR-1) (15.2g) by vacuum-drying.Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1801 as a result.In addition, at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.0-1.6(m, 60H), 3.3-3.6(m, and 8H), 4.5-4.6(t, 8H), 5.3-5.5(m, 12H), 6.1-6.5(m, 24H), 8.4-8.5(t, 8H).

[Chemical formula 1 32]

ADM-CR-2's is synthetic

Except the CM-CR-1 in the synthetic synthesis example of ADM-CR-1 being replaced by CM-CR-2, similarly synthesize with ADM-CR-1.

Its result obtains target resultant (following table is shown ADM-CR-2) (9.2g).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1801 as a result.In addition, the resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.0-1.6(m, 60H), 3.3-3.6(m, and 8H), 4.3-4.4(t, 8H), 5.3-5.6(m, 12H), 6.1-6.9(m, 24H), 8.4-8.5(t, 8H).

[Chemical formula 1 33]

ADM-CR-3's is synthetic

Except the CM-CR-1 in the synthetic synthesis example of ADM-CR-1 being replaced by CM-CR-3, similarly synthesize with ADM-CR-1.

Its result obtains target resultant (following table is shown ADM-CR-3) (9.8g).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1801 as a result.In addition, the resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.0-1.6(m, 60H), 3.3-3.6(m, and 8H), 4.1-4.2(t, 8H), 5.8-5.9(m, 12H), 6.0-7.0(m, 24H), 8.1(t, 8H).

[Chemical formula 1 34]

ADM-CR-4's is synthetic

Except the CM-CR-1 in the synthetic synthesis example of ADM-CR-1 being replaced by CM-CR-4, similarly synthesize with ADM-CR-1.

Its result obtains target resultant (following table is shown ADM-CR-4) (11.2g).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 2112 as a result.In addition, the resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.0-1.6(m, 60H), 3.3-3.6(m, and 8H), 4.7(t, 8H), 5.2-5.5(m, 12H), 6.0-6.8(m, 20H), 8.6(brs, 8H).

[Chemical formula 1 35]

ADM-CR-5's is synthetic

Except the CM-CR-1 in the synthetic synthesis example of ADM-CR-1 being replaced by CM-CR-5, similarly synthesize with ADM-CR-1.

Its result obtains target resultant (following table is shown ADM-CR-5) (6.2g).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1680 as a result.In addition, the resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.0-1.6(m, 60H), 3.3-3.6(m, and 8H), 5.3-5.5(m, 12H), 6.1-7.7(m, 24H), 8.6-8.8(t, 8H).

[Chemical formula 1 36]

CHM-CR-1's is synthetic

Except the ADCME in the synthetic synthesis example of ADM-CR-1 being replaced by CHCME, similarly synthesize with ADM-CR-1.

Its result obtains target resultant (following table is shown CHM-CR-1) (10.1g).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1537 as a result.In addition, the resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.4-1.6(m, 40H), 2.8(m, and 4H), 4.5-4.6(t, 8H), 5.3-5.5(m, 12H), 6.1-6.5(m, 24H), 8.4-8.5(t, 8H).

[Chemical formula 1 37]

CHM-CR-4's is synthetic

Except the ADCME in the synthetic synthesis example of ADM-CR-4 being replaced by CHCME, similarly synthesize with ADM-CR-4.

Its result obtains target resultant (following table is shown CHM-CR-4) (10.2g).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1848 as a result.In addition, the resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.4-1.6(m, 40H), 2.8(m, and 4H), 4.7(t, 8H), 5.2-5.5(m, 12H), 6.0-6.8(m, 20H), 8.6(brs, 8H).

[Chemical formula 1 38]

NOM-CR-1's is synthetic

Except the ADCME in the synthetic synthesis example of ADM-CR-1 being replaced by the n-octyl chloride methyl ether, similarly synthesize with ADM-CR-1.

Its result obtains target resultant (following table is shown NOM-CR-1) (8.2g).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1657 as a result.In addition, the resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.0-1.5(60m, 8H), 3.4(m, and 8H), 4.5-4.6(t, 8H), 5.3-5.5(m, 12H), 6.1-6.5(m, 24H), 8.4-8.5(t, 8H).

[Chemical formula 1 39]

＜MADM-CR-1's is synthetic 〉

Except the ADCME in the synthetic synthesis example of ADM-CR-1 being replaced by bromoacetic acid 2-methyl-2-diamantane ester, similarly synthesize with ADM-CR-1.

Its result obtains target resultant (following table is shown MADM-CR-1) (9.8g).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1913 as a result.In addition, the resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.5-2.2(m, 68H), 4.5-4.6(t, and 8H), 4.9(s, 8H), 5.3-5.5(t, 4H), 6.1-6.5(m, 24H), 8.4-8.5(t, 8H).

[Chemical formula 1 40]

MADM-CR-5's is synthetic

Except the ADCME in the synthetic synthesis example of ADM-CR-1 being replaced by bromoacetic acid 2-methyl-2-diamantane ester, similarly synthesize with ADM-CR-5.

Its result obtains target resultant (following table is shown MADM-CR-1) (10.2g).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 2224 as a result.In addition, the resultant that obtains at deuterium in the DMSO solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 1.5-2.2(m, 68H), 4.5-4.6(t, and 8H), 4.9(s, 8H), 5.3-5.5(t, 4H), 6.1-7.7(m, 20H), 8.4-8.5(t, 8H).

[Chemical formula 1 41]

Embodiment 1B-44B and comparative example 1B

Modulating the composition that the 1B souvenir carries, behind the formation homogeneous solution, is that 0.2 μ m teflon made membrane filter filters with the aperture, is mixed with radiation-ray sensitive composition.About acidogenic agent C, sour diffusion control agent E, other additive F and solvent, use the material identical with described embodiment 1A-20A, similarly estimate.The result is shown in the 2B table.

[table 9]

The 1B-1 table

[table 10]

The 1B-2 table

[table 11]

The 1B-3 table

[table 12]

The 2B-1 table

[table 13]

The 2B-2 table

[table 14]

The 2B-3 table

PEB: the temperature during electron rays irradiation post-heating

＜synthesis example 1D〉ring compound A's is synthetic

With the CR-1 ~ CR-10 and the CR-11,12 that similarly prepare among the described embodiment 1-57 as ring compound A.

Embodiment 1D-43D and comparative example 1D, 2D

Modulating the composition that the 1D souvenir carries, behind the formation homogeneous solution, is that 0.2 μ m teflon made membrane filter filters with the aperture, is mixed with the resist composition.About comparative compound, acidogenic agent C, sour diffusion control agent E and solvent, use the material identical with above-described embodiment 1-57, similarly estimate.The result is shown in the 2D table.

[table 15]

The 1D-1 table

[table 16]

The 1D-2 table

[table 17]

The 1D-3 table

Acid crosslinking agent C

C-1 ニカラ Star Network MW-100LM(three and ケミカ Le (strain))

C-2 ニカラ Star Network MX-270(three and ケミカ Le (strain))

C-3 ニカラ Star Network MX-290(three and ケミカ Le (strain))

C-42, two (the methylol)-p-cresol (Tokyo changes into industry (strain)) of 6-

[table 18]

The 2D-1 table

[table 19]

The 2D-2 table

PEB: the temperature during electron rays irradiation post-heating

Embodiment 1E-10E and comparative example 1E-2E

Have phenyl aldehyde and a ring compound A that the substituent carbonatoms that contains alicyclic ring or aromatic nucleus is 10-24 with embodiment 1A-20A is similarly synthetic.

Modulate the composition that the 1E souvenir carries, form homogeneous solution after, be that the teflon made membrane filter of 0.2 μ m filters with the aperture, be mixed with the resist composition.About comparative compound, acidogenic agent C, acid crosslinking agent G, sour diffusion control agent E and solvent, use the material identical with above-described embodiment 1D-43D, except in figure formation test, carrying out following evaluation, similarly estimate.

(2-3) evaluation of line edge roughness (LER)

The LER that A:LER(3 σ) ≦ 3.5nm(is good)

C:3.5nm ﹤ LER(3 σ) (bad LER)

[table 20]

The 1E table

[table 21]

The 2E table

PEB: the temperature during electron rays irradiation post-heating

The synthesis example of＜synthesis example 1F〉aldehydes

(1) synthesis example of 4-(4-n-propyl cyclohexyl) phenyl aldehyde

Add 74.3g(3.71mol) anhydrous HF, 50.5g(0.744mol) BF ₃Be in the autoclave that has electromagnetic mixing apparatus (SUS316L system) of 500ml to the internal volume that can control temperature, stir content, keeping fluid temperature to utilize carbon monoxide to boost to 2MPa under for-30 ℃.Then, keep-up pressure for 2MPa, fluid temperature for-30 ℃ supply with down mixed 50.0g(0.248mol) (trans-4-n-propyl cyclohexyl) benzene (Northeast chemistry system, purity are more than 98%) and the raw material of the normal heptane of 50.0g, keep after 1 hour, in ice, extract content, after the benzene dilution, the oil reservoir that neutralizing treatment obtains is analyzed with vapor-phase chromatography, obtain reaction result, the transformation efficiency of (trans-4-n-propyl cyclohexyl) benzene is that the selection rate of 100%, 4-(trans-4-n-propyl cyclohexyl) phenyl aldehyde is 95.2%.By the simple distillation target component of emanating out, by the result that GC-MS analyzes, the molecular weight of target substance 4-(trans-4-n-propyl cyclohexyl) phenyl aldehyde is 230.In addition, in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9(t, 3H), 1.0-1.6(m, and 9H), 1.9(m, 4H), 2.55(m, 1H), 7.36(d, 2H), 7.8(d, 2H), 10(s, 1H).The purity of 4-(4-n-propyl cyclohexyl) phenyl aldehyde is 98.3%, and the purity of trans-isomer(ide) is 99.0%.

(2) synthesis example of 4-(trans-4-n-pentyl cyclohexyl) phenyl aldehyde

Except adding 57.0g(0.248mol) (trans-4-n-pentyl cyclohexyl) benzene and the mixture of the normal heptane of 57.0g as the raw material, similarly carry out the processing of formylation reaction and reaction solution with (1).Obtain reaction result with the resulting oil reservoir of gc analysis, the transformation efficiency of (trans-4-n-pentyl cyclohexyl) benzene is 100%, and 4-(trans-4-n-pentyl cyclohexyl) phenyl aldehyde selection rate is 96.2%.

(3) synthesis example of 4-cyclohexyl benzaldehyde

Except adding 57.0g(0.248mol) the 4-phenylcyclohexane and the mixture of the normal heptane of 57.0g as the raw material, similarly carry out the processing of formylation reaction and reaction solution with (1).Obtain reaction result with the resulting oil reservoir of gc analysis, the transformation efficiency of 4-phenylcyclohexane is 100%, and the selection rate of 4-cyclohexyl benzaldehyde is 97.3%.

Be used to form composition synthetic of lower membrane

The synthesis example of＜synthesis example 2F〉ring compound (hereinafter referred to as " CR ")

(1) synthesis example of CR-1F

Under stream of nitrogen gas, Resorcinol (22g with Northeast chemistry society system, 0.2mol), synthetic 4-(4-n-propyl cyclohexyl) phenyl aldehyde (46.0g among the synthesis example 1F, 0.2mol) and dehydrated alcohol (200ml) put into abundant drying and with nitrogen replacement the four-hole boiling flask (1000L) that is provided with dropping funnel, Dai Shi prolong, thermometer, agitating wing in, be mixed with ethanolic soln.Be heated to 85 ℃ with mantle heater when stirring this solution.Then, behind dropping funnel cost dropping in 30 minutes 75ml concentrated hydrochloric acid (35%), continue to stir 3 hours down at 85 ℃.After reaction finishes, put be chilled to room temperature after, cool off by ice bath.After leaving standstill 1 hour, generate flaxen target coarse crystallization, with its filtering separation.With 500ml methanol wash coarse crystallization 2 times, filtering separation obtains all R in (4) formula by vacuum-drying ⁴All be the CR-1F(58g of n-propyl, yield is 91%).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1289 as a result.In addition, in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.9-1.9(m, 68H), 5.5, and 5.6(d, 4H), 6-6.8(m, 24H), 8.4,8.5(m, 8H).

Thermogravimetric quantitative changeization when being warming up to 200 ℃ by CR-1F confirms thus that below 1% sublimability is little.

(2) synthesis example of CR-2F

Except the 4-in the synthesis example of CR-1F (4-n-propyl cyclohexyl) phenyl aldehyde being replaced by 4-(trans-4-n-pentyl cyclohexyl) phenyl aldehyde synthetic among the synthesis example 2F, similarly synthesize with the synthesis example of CR-1F.Its result obtains all R in (4) formula ⁴All be the CR-2F(63.0g of n-pentyl, yield is 90%).Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1401 as a result.In addition, in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.8-1.9(m, 84H), 5.5, and 5.6(d, 4H), 6-6.8(m, 24H), 8.4,8.5(m, 8H).

Thermogravimetric quantitative changeization when being warming up to 200 ℃ by CR-2F confirms thus that below 1% sublimability is little.

(3) synthesis example of CR-3F

Except the 4-in the synthesis example of CR-1F (4-n-propyl cyclohexyl) phenyl aldehyde being replaced by 4-cyclohexyl benzaldehyde synthetic among the synthesis example 2F, similarly synthesize with CR-1F.Its result obtains all R in (3) formula ³The CR-3F(yield that all is hydrogen atom is 87%).Carry out NMR mensuration, IR mensuration, ultimate analysis etc. and the structure of definite this compound.Analyze the structure of this compound with LC-MS, the molecular weight of display-object material is 1117 as a result.In addition, in the deuterochloroform solvent ¹The chemical displacement value of H-NMR (δ ppm, TMS benchmark) is 0.8-1.9(m, 56H), 5.5, and 5.6(d, 4H), 6-6.8(m, 24H), 8.4,8.5(m, 8H).

Thermogravimetric quantitative changeization when being warming up to 200 ℃ by CR-3F confirms thus that below 1% sublimability is little.

(4) synthesis example of CR-4F

Except the cumylene that the 4-in the synthesis example of CR-1F (4-n-propyl cyclohexyl) phenyl aldehyde is replaced by Mitsubishi's gas chemistry system, similarly synthesize with the synthesis example of CR-1F.Its result obtains all R in (2) formula ²The CR-4F(yield that all is sec.-propyl is 47%).Carry out NMR mensuration, IR mensuration, ultimate analysis etc. and the structure of definite this compound.

Thermogravimetric quantitative changeization when being warming up to 200 ℃ by CR-4F confirms thus that below 1% sublimability is little.

(4) synthesis example of CR-5F

Except the n-propylbenzene formaldehyde that the 4-in the synthesis example of CR-1F (4-n-propyl cyclohexyl) phenyl aldehyde is replaced by Mitsubishi's gas chemistry system, similarly synthesize with the synthesis example of CR-1F.Its result obtains all R in (2) formula ²All be the CR-5F(63.0 of n-propyl, yield is 90%).Carry out NMR mensuration, IR mensuration, ultimate analysis etc. and the structure of definite this compound.

Thermogravimetric quantitative changeization when being warming up to 200 ℃ by CR-5F confirms thus that below 1% sublimability is little.

(6) synthesis example of CR-6F

Except the 4-in the synthesis example of CR-1F (4-n-propyl cyclohexyl) phenyl aldehyde being replaced by the tert.-butylbenzene formaldehyde of ア Le De リ Star チ system, similarly synthesize with the synthesis example of CR-1F.Its result obtains all R in (2) formula ²The CR-6F(yield that all is the tertiary butyl is 30%).Carry out NMR mensuration, IR mensuration, ultimate analysis etc. and the structure of definite this compound.

Thermogravimetric quantitative changeization when being warming up to 200 ℃ by CR-6F confirms thus that below 1% sublimability is little.

(7) synthesis example of CR-7F

Except the 1-decanol that the 4-in the synthesis example of CR-1F (4-n-propyl cyclohexyl) phenyl aldehyde is replaced by Northeast chemistry system, similarly synthesize with the synthesis example of CR-1F.Its result obtains all R in (1) formula ¹The CR-7F(yield that all is n-nonyl is 67%).Carry out NMR mensuration, IR mensuration, ultimate analysis etc. and the structure of definite this compound.

Thermogravimetric quantitative changeization when being warming up to 200 ℃ by CR-7F confirms thus that below 1% sublimability is little.

(8) synthesis example of CR-8F

By known method, CR-1F obtains having the resin CR-8F of the phenolic aldehydeization of repeating unit via methylene radical.The result that GPC measures, Mw=9100, Mw/Mn=5.8.

Thermogravimetric quantitative changeization when being warming up to 200 ℃ by CR-8F confirms thus that below 1% sublimability is little.

(9) comparative compound 1 is synthetic

Except with the 4-in the synthesis example of CR-1F (4-n-propyl cyclohexyl) phenyl aldehyde be replaced by 1,3,5-benzene trioxin, Resorcinol is replaced by 2,3, the 6-pseudocuminol, and the concentrated hydrochloric acid in the toluene solvant is replaced by beyond the 1ml vitriol oil, similarly synthesize with the synthesis example of CR-1F.Its result obtains the compound (yield is 85%) of following formula.Carry out NMR mensuration, IR mensuration, ultimate analysis etc. and the structure of definite this compound.

[Chemical formula 1 42]

(10) comparative compound 2 is synthetic

Except 1,3 in 1 of synthesizing with comparative compound, 5-benzene trioxin is replaced by beyond the 2-diamantane ketone, similarly synthesizes.Its result obtains the compound (yield is 81%) of following formula.Carry out NMR mensuration, IR mensuration, ultimate analysis etc. and the structure of definite this compound.

[Chemical formula 1 43]

The preparation of＜preparation example 1F〉lower membrane

Make poly(4-hydroxystyrene) (hereinafter referred to as the PHS) Mw:8000 of above-mentioned CF-1F ~ 8F, comparative compound 1 ~ 2, ア Le De リ Star チ society system or meta-cresol resol (Mw:8800) (hereinafter referred to as phenolic aldehyde) be dissolved into solvent PGME(propylene glycol monomethyl ether with the ratio of 5 quality %) in, filter by the strainer with the fluoro-resin system of 0.1 μ m, be mixed with the solution that is used to form lower membrane respectively.

Then, the solution rotating that is used to form down film forming in the container is applied on the silicon substrate, toasted for 90 seconds down at 110 ℃, obtaining as the thickness of lower membrane is the lower membrane (hereinafter referred to as lower membrane 1-9, comparison lower membrane 1-4) of 200nm.Incidence angle variable spectroscopic ellipsometers (VASE) with J.A. ウ one ラ system society is under the 193nm each lower membrane to be measured at wavelength.With broad sense oscillator model (General Oscillator Model) and utilize Gaussian oscillation device approximation (Gaussian oscillator approximation) to come the absorption value that records is proofreaied and correct, obtain lower membrane 1-9, the refractive index n of comparative example lower membrane 1-4, optical extinction coefficient k thus, the result is shown in table 1F.

[table 22]

Table 1F

Acidogenic agent: nine fluorine methylsulfonic acid triphenyl sulfonium salts (TPS109)

Linking agent: three and the ニカラ Star Network MX270 of ケミカ Le society system

Then, be the SiO of 300nm to thickness with the solution coat that is used to form the material of lower membrane ₂On the substrate, toasted for 60 seconds down at 250 ℃, forming thickness is the lower membrane of 200nm.And coating ArF resist solution toasted for 60 seconds down at 130 ℃, and forming thickness is the photoresist layer of 200nm.In addition, ArF resist solution blending has the compound of following formula (110): 5 parts, TPS109:1 part, Tributylamine: 2 parts, PGMEA:92 part are regulated.

Then, by electron rays drawing apparatus (エリオニ Network ス society system; ELS-7500,50keV) exposure 115 ℃ of following baking (PEB) 90 seconds, was developed for 60 seconds with Tetramethylammonium hydroxide (TMAH) aqueous solution of 2.38 quality %, obtained the figure of eurymeric.The 60nmL/S(1:1 of observable figure) graphics shape, the result is shown in table 2F.

[table 23]

Table 2F

	Lower membrane	Resolving power	Susceptibility
				Embodiment	1	60nmL&S	12μC/cm ²
Embodiment	2	60nmL&S	12μC/cm ²
				Embodiment	3	60nmL&S	12μC/cm ²
Embodiment	8	60nmL&S	12μC/cm ²
				Embodiment	9	60nmL&S	12μC/cm ²
Comparative example	Do not have	80nmL&S	26μC/cm ²

[Chemical formula 1 44]

Then, will copy on the lower membrane under the following conditions by the resist pattern that obtains after above-mentioned electron rays exposure and the development.Etching condition is as shown in following.

Etching system: エリオニ Network ス society system

Voltage: 400V

Current density: 0.9mA/cm ²

Time: 2min

Argon flow amount: carbon tetrafluoride gas flow: oxygen flow=10:1:1 volume ratio

Observe the figure tee section by (strain) Hitachi electron microscope processed (S-4800), and compare shape.

Can confirm: the shape after developing in the processing of multilayer resist, the shape of the lower membrane after oxygen candle is carved, after the substrate processing etching is good; During as individual layer resist dura mater, the shape after the back of developing, substrate processing and the etching is also good.

Industrial applicibility

The present invention is applicable to: be used for sour proliferous type on-macromolecular class anticorrosive additive material, with the resist compound shown in the specific chemical structure formula, contain the radiation-ray sensitive composition of this ring compound and use the lower membrane of this radiation-ray sensitive composition and form the method for resist pattern.

Claims

1. ring compound, wherein, this ring compound is for being selected from following formula (2-1) or the represented compound of formula (2-2),

In formula (2-1) and the formula (2-2), R ^7ABe straight chain shape alkyl, halogen atom, cyano group or the hydroxyl of 1-12 for hydrogen atom, carbonatoms independently.

2. radiation-ray sensitive composition, wherein, this radiation-ray sensitive composition contains the described ring compound of claim 1 and solvent.

3. radiation-ray sensitive composition according to claim 2; wherein; described ring compound is for being the ring compound A of 700-5000 by the synthetic molecular weight of the condensation reaction of aldehyde compound A1 and phenolic compound A2; wherein said aldehyde compound A1 is that carbonatoms is 2-59 and the compound with 1-4 formyl radical, and described phenolic compound A2 is that carbonatoms is 6-15 and the compound with 1-3 phenolic hydroxyl group.

4. radiation-ray sensitive composition according to claim 3, this radiation-ray sensitive composition contains the solids component of 1-80 weight % and the solvent of 20-99 weight %, wherein, described radiation-ray sensitive composition contains ring compound A, and ring compound A is more than the 50 weight % of gross weight of described solids component; Be the phenyl aldehyde of 7-24 for the synthesis of the described aldehyde compound A1 of ring compound A for any one the carbonatoms in not hydroxyl and the tertiary butyl wherein.

5. radiation-ray sensitive composition according to claim 3, this radiation-ray sensitive composition contains the solids component of 1-80 weight % and the solvent of 20-99 weight %, wherein, described radiation-ray sensitive composition contains ring compound B, and ring compound B is the 50-99.999 weight % of the gross weight of described solids component; Wherein ring compound B has to introduce by being selected from substituent methyl, 1-at least one phenolic hydroxyl group of ring compound A and replaces ethyl, 1-and replace the structure that silyl that n-propyl, carbonatoms are 1-20, acyl group, 1-substituted alkoxy alkyl, carbonatoms that carbonatoms is 2-20 are the acid dissociation functional group in the group formed of the cyclic ethers base of 2-20 and carbalkoxy that carbonatoms is 2-20, and aldehyde compound A1 is the phenyl aldehyde of 7-24 for any one the carbonatoms in not hydroxyl and the tertiary butyl; Wherein,

Described substituent methyl is selected from the substituting group shown in methoxymethyl, methylthiomethyl, ethoxyl methyl, n-propoxymethyl, isopropoxy methyl, n-butoxy methyl, tert.-butoxy methyl, 2-methyl-prop oxygen ylmethyl, ethylmercapto group methyl, methoxy ethoxy methyl, phenoxymethyl, 1-cyclopentyloxy methyl, 1-cyclohexyloxy methyl, benzyl sulphomethyl, phenacyl, 4-bromobenzene formyl methyl, 4-methoxybenzoyl methyl, piperonyl and the following formula (7)

In the formula (7), R ²Be the alkyl of 1-4 for carbonatoms;

Described 1-replaces ethyl and is selected from the 1-methoxy ethyl, the 1-methylmercaptoethyl, 1, the 1-dimethoxy-ethyl, the 1-ethoxyethyl group, 1-ethylmercapto group ethyl, 1,1-diethoxy ethyl, the positive propoxy ethyl, the isopropoxy ethyl, the n-butoxy ethyl, the tert.-butoxy ethyl, 2-methyl propoxy-ethyl, 1-phenoxy group ethyl, 1-phenyl thio-ethyl, 1,1-two phenoxy group ethyls, 1-cyclopentyloxy ethyl, 1-cyclohexyloxy ethyl, the 1-phenylethyl, 1, substituting group shown in 1-diphenyl-ethyl and the following formula (8)

In the formula (8), R ²Be the alkyl of 1-4 for carbonatoms;

Described 1-replaces n-propyl and is selected from 1-methoxyl group n-propyl and 1-oxyethyl group n-propyl;

Described 1-substituted alkoxy alkyl is selected from 1-cyclopentyl methoxymethyl, 1-cyclopentyl ethoxyl methyl, 1-cyclohexyl methoxymethyl, 1-cyclohexyl ethoxyl methyl, 1-ring octyl group methoxymethyl and 1-adamantyl methoxymethyl.

6. radiation-ray sensitive composition according to claim 3, wherein, this radiation-ray sensitive composition contains ring compound B0, this ring compound B0 has the aldehyde compound A1c of acid dissociation functional group and condensation reaction that carbonatoms is 6-15 and the phenolic compound A2 with 1-3 phenolic hydroxyl group and synthetic by introducing, and the molecular weight of described ring compound B0 is 700-5000, wherein carbonatoms is that 2-59 and the aldehyde compound A1 with 1-4 formyl radical are the aldehyde compound A1c with acid dissociation functional group, and described acid dissociation functional group is for being selected from substituent methyl, 1-replaces ethyl, 1-replaces n-propyl, carbonatoms is the silyl of 1-20, carbonatoms is the acyl group of 2-20,1-substituted alkoxy alkyl, carbonatoms is the acid dissociation functional group in the group formed of the cyclic ethers base of 2-20 and carbalkoxy that carbonatoms is 2-20; Wherein

In the formula (7), R ²Be the alkyl of 1-4 for carbonatoms;

In the formula (8), R ²Be the alkyl of 1-4 for carbonatoms;

7. composition that is used to form lower membrane, wherein, this composition that is used to form lower membrane contains the described radiation-ray sensitive composition of claim 2.

8. the composition that is used to form lower membrane according to claim 7, wherein, this composition that is used to form lower membrane contains resin, and this resin has by making ring compound A and be selected from the repeating unit that the aldehydes dehydrating condensation in formaldehyde, trioxane, Paraformaldehyde 96 and the acetaldehyde obtains in the presence of acid catalyst; Described ring compound A is for being the ring compound of 700-5000 by the synthetic molecular weight of the condensation reaction of aldehyde compound A1 and phenolic compound A2; wherein said aldehyde compound A1 is that carbonatoms is 2-59 and the compound with 1-4 formyl radical, and described phenolic compound A2 is that carbonatoms is 6-15 and the compound with 1-3 phenolic hydroxyl group.

9. lower membrane, wherein, this lower membrane is formed by the described composition that is used to form lower membrane of claim 7.

10. the formation method of a resist pattern, wherein, this method comprises: right to use requires 2 described radiation-ray sensitive compositions to form the operation of resist film at substrate; Operation with described resist film exposure; And the operation of described resist film being developed to form resist pattern.