CN105676592A - Shrink material and pattern forming process - Google Patents

Abstract

A shrink material is provided comprising a specific polymer and a solvent containing an anti-vanishing solvent. A pattern is formed by applying a resist composition comprising a base resin and an acid generator onto a substrate to form a resist film, exposing, developing in an organic solvent developer to form a negative resist pattern, applying the shrink material onto the pattern, and removing the excessive shrink material with an organic solvent for thereby shrinking the size of holes and/or slits in the pattern.

Description

Shrink material and pattern forming method

The cross reference of related application

This non-provisional application requires the right of priority of patent application No.2014-248080 and 2015-077690 submitted to respectively on December 8th, 2014 and on April 6th, 2015 in Japan under 35U.S.C. § 119 (a), thus their whole contents is incorporated to by reference herein.

Technical field

The present invention relates to the contraction material of the dimensional contraction for making the feature in resist pattern and use the pattern forming method of this contraction material.

Background technology

Along with the effort reducing pattern dimensions develops rapidly to meet recently to the higher integrated horizontal of LSI and the needs of running speed, photolithography widely uses. Photolithography has the substantial limit of the resolving power determined by the wavelength of light source. A kind of micro-pattern method of limit surmounting this resolving power is combined ArF excimer laser immersion lithography process and double patterning. A typical version of double patterning is photoetching-etching-photoetching-etching (LELE) method, it comprises via exposure light forming pattern, by etching by this pattern transfer to the hard mask on base material, implement the 2nd exposure in the position of half spacing displacement, and this hard mask is etched. The method has the problem of misalignment or overlapping error between two exposures. Another version of double patterning is autoregistration double patterning (SADP) method, it comprises the steps: resist pattern transfer in hard mask, in the both sides of hard mask features, film is grown, and the sidewall making film remains thus to make pattern dimension double. SADP method needs only exposure once and alleviates the problem of overlapping error. In order to simplify the method, it is also proposed the modified version of following SADP method: on the sidewall of the resist pattern characteristics through development instead of the sidewall of hard mask features, form silicon oxide film thus to make pattern dimension double. Owing to SADP method successfully makes the spacing of line pattern be reduced to half, therefore by SADP method is repeated twice, it is possible to make spacing be reduced to 1/4.

Not only need the contraction of line pattern, and need the contraction of sectional hole patterns. If not making sectional hole patterns shrink, then the contraction on whole chip is incomplete. A kind of known method that sectional hole patterns is shunk is described in patent documentation 1Method. The method is intended to by and curing this coating to form crosslinked layer on the surface so that resist pattern becomes thick at resist through the resist pattern of development with the water-soluble material coating containing linking agent, thus the size of reduction holes pattern. Patent documentation 2 describes the contraction material of the polymkeric substance comprised containing amino or polyamine, its via the neutralization reaction with the carboxyl on resist surface with resist surface bond, thus make resist film become thick.Non-patent literature 1 it is also proposed by utilizing the direct self-assembly (DSA) of segmented copolymer to make sectional hole patterns shrink.

AdoptThe contraction of method has following problem: owing under the existence of acid catalyst in resist, linking agent becomes to have activity, and therefore as uneven in tartaric acid diffusion, then the size shrinking metapore is uneven. Based on amino polymer bonding and in sum shrinkage method in, as the direct reflection that resist is concavo-convex on the surface, make pattern become thick so that through development resist pattern dimensional variations and contraction after dimensional variations identical. Utilizing the shrinkage method of the DSA function of segmented copolymer to have advantage, it comprises the shrinkage of increase and shrinks rear minimum dimensional variations, but there are some problems. That is, if the hole that DSA is applied to different size, those are caused to the hole of size that the opposition of segmented copolymer assembles, contraction can not be brought out. If DSA is applied to channel patterns, shape distortion becomes problem, such as, forms multiple sectional hole patterns.

Needing following contraction material, it can make sectional hole patterns shrink under the shape not changing resist pattern, and improves dimensional variations and the edge roughness (LWR) of the resist pattern after development.

Quote list

Patent documentation 1:JP-AH10-073927 (USP6579657)

Patent documentation 2:JP-A2008-275995 (US20100119717)

Patent documentation 3:JP-A2007-293294

Non-patent literature 1:Proc.SPIE the 8323rd volume 83230W-1 page (2012)

Summary of the invention

As above discuss like that, by cross-linking type or neutralization reaction mediation bonding typeThe method that material is applied on resist pattern does not cause pattern deformation, but the dimensional variations not making resist pattern reduces. Patent documentation 3 proposes the contraction material of the alkali aqueous solution processing-type of the eurymeric resist pattern that paint is produced by alkali development. About the contraction of the sectional hole patterns with narrow spacing, this contraction material there is no enough shrinkage and do not make dimensional variations reduce.

It is an object of the invention to provide the pattern forming method shunk material and use it, hole dimension can be made to shrink when described contraction material is applied on the hole resist pattern of development, improve dimensional variations simultaneously.

Seek effectively to make the contraction material of the resist pattern shrinkage through development, the present inventor has found by being formed based on having the base resin of carboxyl and the resist film of acidogenic agent that acid-unstable group replaces, negative resist pattern is formed by it via exposure and organic solvent development, it is coated with this resist pattern with the contraction material comprising particular polymers and the solvent containing anti-disappearance solvent, cure, with with organic solvent, excessive contraction material is removed, it is possible to make the dimensional contraction of the hole in resist pattern and/or slit in a controlled manner.

On the one hand, providing package of the present invention is containing the contraction material of polymkeric substance and solvent, this solvent contains anti-disappearance solvent, this anti-disappearance solvent does not cause the resist pattern loss after development, and this polymkeric substance comprises the repeating unit of at least one being selected from the unit with formula (1a) and (1b).

Wherein A is singly-bound or the C that can contain ether oxygen atom in the midway of chain₁-C₁₀Alkylidene group; R¹For hydrogen, fluorine, methyl or trifluoromethyl; R²Be hydrogen independently of one another, halogen, optional halogen substiuted, the C of straight chain, branching or ring-type₂-C₈Acyloxy, optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkyl, or optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkoxyl group;L is hydrogen, straight chain, branching or ring-type, C that ether oxygen atom, carbonyl moieties or carbonyl oxygen based structures part can be contained in the midway of chain₁-C₁₀Monovalent aliphatic alkyl, or optional group that replace, that monovalence contains aromatic ring; Z and carbon atom bonding are to form C₅-C₁₅Alicyclic group; R^xAnd R^yC that be hydrogen or straight chain, branching or ring-type independently of one another, that can be replaced by hydroxyl or alkoxy moieties₁-C₁₅Alkyl, R^xAnd R^yAt least one be the C of ring-type₅-C₁₅Alkyl; F is the integer of 1-3, and s is the integer of 0-2, and a equals (5+2s-f), and m is 0 or 1.

Preferably, this polymkeric substance also comprises the repeating unit with formula (2).

Wherein B is singly-bound or the C that can contain ether oxygen atom in the midway of chain₁-C₁₀Alkylidene group; R¹As defined above; R³Be hydrogen independently of one another, halogen, optional halogen substiuted, the C of straight chain, branching or ring-type₂-C₈Acyloxy, optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkyl, or optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkoxyl group; G is the integer of 0-3, and t is the integer of 0-2, and b equals (5+2t-g), and n is 0 or 1.

Preferably, this polymkeric substance also comprises the repeating unit with formula (3).

Wherein C is singly-bound or the C that can contain ether oxygen atom in the midway of chain₁-C₁₀Alkylidene group; R¹As defined above; R⁴It is hydrogen independently of one another, halogen, optional halogen substiuted, the C of straight chain, branching or ring-type₂-C₈Acyloxy, optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkyl, or optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkoxyl group; C that D is singly-bound or straight chain, branching or ring-type, ether oxygen atom, carbonyl group or carbonyl oxygen base group can be contained in the midway of chain₁-C₁₀(v+1) valency alkyl, wherein some or all hydrogen atoms of bond with carbon can replaced by fluorine; Rf¹And Rf²It is the C containing at least one fluorine atom independently of one another₁-C₆Alkyl, Rf¹The carbon atom to combine with them can be bonded with D and form ring; R be 0 or 1, h be the integer of 1-3, u is the integer of 0-2, and c equals (5+2u-h), and v is 1 or 2.

Preferably, this polymkeric substance also comprises the repeating unit of at least one being selected from the unit with formula (4) and (5).

Wherein R⁵And R⁶It is hydrogen independently of one another, halogen, optional halogen substiuted, straight chain, branching or ring-type, C₂-C₈Acyloxy, optional halogen substiuted, straight chain, branching or ring-type, C₁-C₆Alkyl, or optional halogen substiuted, straight chain, branching or ring-type, C₁-C₆Alkoxyl group; I and j is the integer of 0-2 independently of one another, and d equals (6-i), and e equals (4-j).

Preferably, this polymkeric substance also comprises the repeating unit of at least one being selected from the unit with formula (A)-(E).

Wherein R¹As defined above; X^AFor acid-unstable group; X^BAnd X^CIt is the C of singly-bound or straight chain or branching independently of one another₁-C₄Bivalent hydrocarbon radical; X^DFor straight chain, branching or ring-type, C₁-C₁₆Divalence to the aliphatic hydrocarbyl of pentavalent, wherein any composition-CH₂-can by-O-or-C (=O)-replacement; X^EFor acid-unstable group; Y^AFor having the substituting group of lactone, sultone or structural carbonate; Z^AFor hydrogen, C₁-C₃₀Fluothane base or C₁-C₁₅Containing the substituting group of fluorinated alcohols; k^1AFor the integer of 1-3, and k^1BFor the integer of 1-4.

Preferably, this polymkeric substance also comprises the repeating unit with formula (F).

Wherein R¹⁰¹For hydrogen or methyl; X is singly-bound ,-C (=O)-,-C (=O)-O-or-C (=O)-NH-; R¹⁰²For the C of Han You the ether structure part of singly-bound or straight chain, branching or ring-type, ester structure part, carbonyl moieties ,-N=or-S-₁-C₁₀Alkylidene group, or phenylene or naphthylidene;R¹⁰³And R¹⁰⁴It is the C of hydrogen, straight chain or branching independently of one another₁-C₄Alkyl, or acid-unstable group, or R¹⁰³And R¹⁰⁴Can being bonded the nitrogen-atoms to combine with them each other and form ring, this ring is optionally containing ehter bond, or R¹⁰³And R¹⁰⁴Any one can with R¹⁰²It is bonded the formation ring of the nitrogen-atoms to combine with them; And k^1CIt is 1 or 2.

This contraction material can also comprise the salt with formula (9):

R¹¹-CO₂ ^-M⁺(9)

Wherein R¹¹For the C of straight chain, branching or ring-type₁-C₂₀Alkyl, the C of straight chain, branching or ring-type₂-C₂₀Alkene base or C₆-C₂₀Monovalence is containing aromatic ring group, and wherein some or all hydrogen atoms of bond with carbon can be replaced by fluorine, the structure part containing lactonic ring, the structure part containing lactam nucleus or hydroxyl moiety, and wherein ether, ester or carbonyl group can between C-Cs, and M⁺For sulfonium, iodine or ammonium cation.

This contraction material can also comprise the salt with formula (10):

R¹²-SO₃ ^-M⁺(10)

Wherein R¹²For the C of Han You the Sauerstoffatom of straight chain, branching or ring-type₁-C₃₅Monovalent hydrocarbon, the hydrogen atom of some of them or all bond with carbon can replaced by fluorine, and condition does not replaced by fluorine relative to the hydrogen atom of sulfonic acid and the carbon atom bonding of alpha-position, and M⁺For sulfonium, iodine or ammonium cation.

In preferred embodiment, this contraction material can also comprise and is selected from by least one basic cpd in the following group formed: the primary, secondary and tertiary amine of aliphatic series, mixed amine; aromatic amine; heterocyclic amine, has the nitrogenous compound of carboxyl, has the nitrogenous compound of alkylsulfonyl; there is the nitrogenous compound of hydroxyl; the nitrogenous compound with hydroxy phenyl, alcohol type nitrogenous compound, amide derivatives; imide derivative, and carbamate (salt).

Preferably, this anti-disappearance solvent is the alcoholic solvent of the ester solvent of 7-16 carbon atom, the ketone solvent of 8-16 carbon atom or 4-10 carbon atom.

Specifically, this anti-disappearance solvent is be selected from least one solvent by the following group formed:

The ester solvent of 7-16 carbon atom, comprise amyl acetate-n, isoamyl acetate, acetic acid 2-methyl fourth ester, capryl acetate, acetic acid 2-ethylhexyl, cyclohexyl acetate, methyl cyclohexanol acetate, hexyl formate, Valeric acid ethylester, propyl valerate, valeric acid isopropyl ester, butyl valerate, isobutyl isovalerate, pentanoate, oil of apple, valeric acid isopentyl ester, Ethylisovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, the isovaleric acid tert-butyl ester, isoamyl isovalerate, 2 methyl valeric acid second ester, 2 methyl valeric acid fourth ester, PIVALIC ACID CRUDE (25) second ester, PIVALIC ACID CRUDE (25) propyl ester, PIVALIC ACID CRUDE (25) isopropyl ester, PIVALIC ACID CRUDE (25) fourth ester, the PIVALIC ACID CRUDE (25) tert-butyl ester, pentenoic acid ethyl ester, pentenoic acid propyl ester, pentenoic acid isopropyl ester, amylene acid butyl ester, the pentenoic acid tert-butyl ester, β-crotonic acid propyl ester, β-crotonic acid isopropyl ester, butyl crotonate, the β-crotonic acid tert-butyl ester, butyl propionate, isobutyl propionate, the propionic acid tert-butyl ester, benzyl propionate, ethyl hexanoate, pineapple aldehyde, propyl butyrate, butyl butyrate, isobutyl butyrate, butyric acid 3-methyl fourth ester, tert-butyl acetate, ethyl 2-methylbutyrate, 2-Methyl Butyric Acid isopropyl ester, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, Benzyl Acetate, phenyl ritalin, benzyl formate, formic acid phenyl chlorocarbonate, 3-phenylpropionic acid methyl esters, phenyl vinyl acetic monomer, with acetic acid 2-phenyl chlorocarbonate,

The ketone solvent of 8-16 carbon atom, comprises methyln-hexyl ketone, 3-octanone, 4-octanone, methyl n-heptyl ketone, 3-nonanone, 4-nonanone, butyl ketone, diisobutyl ketone, ethyl cyclohexanone, ethyl methyl phenyl ketone, ethyl normal-butyl ketone, di-n-butyl ketone, and diisobutyl ketone, and

The alcoholic solvent of 4-10 carbon atom, comprise n-butyl alcohol, 2-butanols, isopropylcarbinol, the trimethyl carbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, tertiary amyl alcohol, neopentyl alcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 3-methyl-3-amylalcohol, cyclopentanol, the own alcohol of 1-, the own alcohol of 2-, the own alcohol of 3-, 2, 3-dimethyl-2-butanols, 3, 3-dimethyl-n-butyl alcohol, 3, 3-dimethyl-2-butanols, 2, 2-diethyl-n-butyl alcohol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 3-methyl-3-amylalcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 4-methyl-3-amylalcohol, hexalin, with 1-octanol.

Preferably, this solvent contains anti-disappearance solvent and other solvent, and this other solvent is selected from by the following group formed: methyln-hexyl ketone, methyl n-heptyl ketone, 2-heptanone, 3-heptanone, dipropyl ketone, methyl-n-butyl ketone, the own ketone of 3-, diisobutyl ketone, methylcyclohexanone, methyl phenyl ketone, methyl acetophenone, propyl acetate, N-BUTYL ACETATE, isobutyl acetate, amyl acetate-n, isoamyl acetate, acetic acid butene esters, propyl formate, butyl formate, tetryl formate, pentyl formate, isoamyl formate, methyl valerate, amylene-4 acid methyl ester, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, 3-ethoxyl ethyl propionate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, 2-hydroxy-methyl isobutyl acid, 2-ethyl butyrate of hydroxyl iso, methyl benzoate, ethyl benzoate, phenyl acetate, Benzyl Acetate, phenyl ritalin, benzyl formate, formic acid phenyl chlorocarbonate, 3-phenylpropionic acid methyl esters, benzyl propionate, phenyl vinyl acetic monomer, with acetic acid 2-phenyl chlorocarbonate.

On the other hand, the present invention provides pattern forming method, comprise the steps: to be applied on base material by resist composition, this resist composition comprises the base resin, acidogenic agent and the organic solvent that comprise the repeating unit with the carboxyl that acid-unstable group replaces, and prebake is to form resist film; This resist film is exposed to high-energy irradiation, this film is cured; Organic solvent system photographic developer make the resist film of exposure develop to form negative resist pattern; The contraction material limited herein is applied on this negative resist pattern, cures; With with organic solvent, excessive contraction material is removed.

Typically, the base resin in resist composition comprises the repeating unit (a) of carboxyl that represent, that have acid-unstable group and replace by formula (11).

Wherein R²¹For hydrogen or methyl, R²²For acid-unstable group, Z is singly-bound or-C (=O)-O-R²³-, and R²³For the C of straight chain, branching or ring-type₁-C₁₀Alkylidene group, wherein ether or ester bond can between C-Cs, or naphthylidene.

In pattern forming method, photographic developer comprises at least one organic solvent being selected from by the following group formed: methyln-hexyl ketone, methyl n-heptyl ketone, 2-heptanone, 3-heptanone, dipropyl ketone, methyl-n-butyl ketone, the own ketone of 3-, diisobutyl ketone, methylcyclohexanone, methyl phenyl ketone, methyl acetophenone, propyl acetate, N-BUTYL ACETATE, isobutyl acetate, amyl acetate-n, isoamyl acetate, acetic acid butene esters, propyl formate, butyl formate, tetryl formate, pentyl formate, isoamyl formate, methyl valerate, amylene-4 acid methyl ester, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, 3-ethoxyl ethyl propionate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, 2-hydroxy-methyl isobutyl acid, 2-ethyl butyrate of hydroxyl iso, methyl benzoate, ethyl benzoate, phenyl acetate, Benzyl Acetate, phenyl ritalin, benzyl formate, formic acid phenyl chlorocarbonate, 3-phenylpropionic acid methyl esters, benzyl propionate, phenyl vinyl acetic monomer, with acetic acid 2-phenyl chlorocarbonate.

Preferably, the step removed by excessive contraction material uses and is selected from by least one organic solvent in the following group formed: propyl acetate, N-BUTYL ACETATE, isobutyl acetate, acetic acid butene esters, amyl acetate-n, isoamyl acetate, acetic acid 2-methyl fourth ester, capryl acetate, acetic acid 2-ethylhexyl, cyclohexyl acetate, methyl cyclohexanol acetate, propyl formate, butyl formate, tetryl formate, pentyl formate, isoamyl formate, hexyl formate, methyl valerate, Valeric acid ethylester, propyl valerate, valeric acid isopropyl ester, butyl valerate, isobutyl isovalerate, pentanoate, oil of apple, valeric acid isopentyl ester, Ethylisovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, the isovaleric acid tert-butyl ester, isoamyl isovalerate, 2 methyl valeric acid second ester, 2 methyl valeric acid fourth ester, methyl crotonate, ethyl crotonate, β-crotonic acid propyl ester, β-crotonic acid isopropyl ester, butyl crotonate, the β-crotonic acid tert-butyl ester, methyl propionate, ethyl propionate, pentenoic acid ethyl ester, pentenoic acid propyl ester, pentenoic acid isopropyl ester, amylene acid butyl ester, the pentenoic acid tert-butyl ester, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, 2-hydroxy-methyl isobutyl acid, 2-ethyl butyrate of hydroxyl iso, PIVALIC ACID CRUDE (25) second ester, PIVALIC ACID CRUDE (25) propyl ester, PIVALIC ACID CRUDE (25) isopropyl ester, PIVALIC ACID CRUDE (25) fourth ester, the PIVALIC ACID CRUDE (25) tert-butyl ester, butyl propionate, isobutyl propionate, the propionic acid tert-butyl ester, benzyl propionate, 3-ethoxyl ethyl propionate, ethyl hexanoate, pineapple aldehyde, propyl butyrate, butyl butyrate, isobutyl butyrate, butyric acid 3-methyl fourth ester, tert-butyl acetate, ethyl 2-methylbutyrate, 2-Methyl Butyric Acid isopropyl ester, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, Benzyl Acetate, phenyl ritalin, benzyl formate, formic acid phenyl chlorocarbonate, 3-phenylpropionic acid methyl esters, phenyl vinyl acetic monomer, acetic acid 2-phenyl chlorocarbonate, 2-heptanone, 3-heptanone, dipropyl ketone, methyl-n-butyl ketone, the own ketone of 3-, methyln-hexyl ketone, 3-octanone, 4-octanone, methyl n-heptyl ketone, 3-nonanone, 4-nonanone, butyl ketone, methylcyclohexanone, ethyl cyclohexanone, methyl phenyl ketone, methyl acetophenone, ethyl methyl phenyl ketone, ethyl normal-butyl ketone, di-n-butyl ketone, diisobutyl ketone, n-butyl alcohol, 2-butanols, isopropylcarbinol, the trimethyl carbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, tertiary amyl alcohol, neopentyl alcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 3-methyl-3-amylalcohol, cyclopentanol, the own alcohol of 1-, the own alcohol of 2-, the own alcohol of 3-, 2, 3-dimethyl-2-butanols, 3, 3-dimethyl-n-butyl alcohol, 3, 3-dimethyl-2-butanols, 2, 2-diethyl-n-butyl alcohol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 3-methyl-3-amylalcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 4-methyl-3-amylalcohol, hexalin, with 1-octanol.

Typically, high-energy irradiation is the i line of wavelength 364nm, the KrF excimer laser of wavelength 248nm, the ArF excimer laser of wavelength 193nm, EUV or EB of wavelength 13.5nm.

The advantageous effects of invention

Comprise and formed based on the resist film with the base resin of carboxyl that acid-unstable group replaces and acidogenic agent, it exposed and organic solvent development successfully makes the dimensional contraction of the hole in resist pattern and/or slit in a controlled manner with the method forming negative resist pattern and the contraction material of the present invention coating resist pattern.

Accompanying drawing explanation

Fig. 1 (A)-Fig. 1 (F) represents the step of the formation of the pattern according to the present invention or contraction method with cross-sectional view; Fig. 1 (A) represents the resist film formed on base material; Fig. 1 (B) represents the resist film in exposure process; Fig. 1 (C) represent resist film PEB and development after pattern formed; Fig. 1 (D) represents the contraction material of coating on resist pattern; Fig. 1 (E) represents by curing and remove excessive contraction material from the resist pattern making its gap constrictions; The dry etching of the base material by the pattern through shrinking as mask is represented with Fig. 1 (F).

Embodiment

Term " one " and " one " herein do not represent number quantitative limitation, but represent the project existed described at least one. " optional " or " optionally " means that event described subsequently or situation may occur or may not occur, and this record comprises situation and its situation not occurred of this event or situation generation. Mark (C used herein_n-C_m) mean that each group contains the group of n to m carbon atom. Term used herein " film " can use interchangeably with " coating " or " layer ".

Abbreviation and acronym have following implication.

EB: electron beam

Mw: weight-average molecular weight

Mn: number-average molecular weight

Mw/Mn: molecular weight distribution or dispersity

GPC: gel permeation chromatography

PEB: post exposure bake

PAG: photo-acid generator

In chemical formula, Me represents methyl, and Ac represents ethanoyl; Dotted line represents valency key.

Shrink material

The present invention provides contraction material, and it comprises polymkeric substance and solvent, and this solvent contains the anti-disappearance solvent of the resist pattern loss after not making development. This polymkeric substance is defined as the repeating unit comprising at least one being selected from the unit with formula (1a) and (1b). Should be that this polymkeric substance is sometimes referred to as " contraction material polymers " with pointing out.

In formula (1a) and (1b), " A " is singly-bound or the C that can contain ether oxygen atom in the half-way of chain₁-C₁₀Alkylidene group. The alkylidene group being applicable to comprises methylene radical, ethylidene, propylidene, trimethylene, tetramethylene, five methylene radical, hexa-methylene, cyclopentylidene, cyclohexylidene, and has its constitutional isomer of branching or ring texture. Wherein, A is preferably singly-bound, methylene radical, ethylidene, propylidene or trimethylene. When A is the group containing ether oxygen atom, in formula (1) when m=1, ether oxygen atom can be included on any position of getting rid of between alpha-position and the carbon of β-position relative to ester oxygen. When m=0, ether oxygen atom becomes the atom being bonded with main chain, and the 2nd ether oxygens atom can be included on any position of getting rid of between alpha-position and the carbon of β-position relative to ether oxygen atom.

In formula (1a) and (1b), R¹For hydrogen, fluorine, methyl or trifluoromethyl. R²It is hydrogen independently of one another, halogen, the C of the straight chain of optional halogen substiuted, branching or ring-type₂-C₈Acyloxy, the C of the straight chain of optional halogen substiuted, branching or ring-type₁-C₆Alkyl, or the C of the straight chain of optional halogen substiuted, branching or ring-type₁-C₆Alkoxyl group.

The example of halogen is fluorine, chlorine, bromine and iodine. The acyloxy being applicable to comprises acetoxyl group, propionyloxy, butyryl acyloxy, new pentane acyloxy, and cyclohexyl carbonyl oxygen base. Be applicable to alkyl comprise methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, amyl group, cyclopentyl, own base, cyclohexyl, heptyl, octyl group, nonyl, the last of the ten Heavenly stems base, undecyl, dodecyl, norcamphyl and adamantyl. The alkoxyl group being applicable to comprises methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, pentyloxy, hexyloxy, cyclopentyloxy, cyclohexyloxy, 1-methyl isophthalic acid-cyclopentyloxy, 1-ethyl-1-cyclopentyloxy, 1-methyl isophthalic acid-cyclohexyloxy, and 1-ethyl-1-cyclohexyloxy.

In formula (1a) and (1b), L is hydrogen, the C that can contain ether oxygen atom, carbonyl moieties or carbonyl oxygen based structures part in the half-way of chain of straight chain, branching or ring-type₁-C₁₀Monovalent aliphatic alkyl, or the optional monovalence replaced is containing the group of aromatic ring. The monovalent aliphatic alkyl being applicable to is the alkyl of straight chain, branching or ring-type, alkene base and alkynes base. The alkyl being applicable to comprises the group of above-mentioned illustration, but has 1-10 carbon atom. The alkene base being applicable to comprises vinyl, allyl group, propenyl, cyclopropenyl radical, butenyl, cyclobutene base, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, tetrahydrotoluene base, octenyl, dimethyl cyclohexenyl, and cyclooctene base. The alkynes base being applicable to comprises ethynyl, proyl, butynyl, pentynyl, own alkynes base, heptyne base, and octynyl. The monovalence being applicable to comprises phenyl, naphthyl, phenanthryl, anthryl, pyrenyl, xenyl, acenaphthenyl containing the group of aromatic ring, and fluorenes base. Preferably, L is hydrogen, methyl, ethyl, propyl group, sec.-propyl, cyclopentyl, cyclohexyl, adamantyl, methyl carbonyl, or phenyl.

In formula (1a), Z and carbon atom bonding are to form C₅-C₁₅Alicyclic group. The alicyclic group being applicable to comprises following radicals, but is not limited to this.

In formula (1b), R^xAnd R^yIt is hydrogen or straight chain, branching or ring-type independently of one another, the C that can be replaced by hydroxyl or alkoxy moieties₁-C₁₅Alkyl, R^xAnd R^yAt least one be ring-type C₅-C₁₅Alkyl. Preferably, R^xAnd R^yIt is selected from methyl, ethyl, propyl group, butyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, adamantyl, norcamphyl, and with the above-mentioned group that hydroxyl or alkoxy moieties replace.

In formula (1a) and (1b), f is the integer of 1-3, and s is the integer of 0-2, and a equals (5+2s-f), and m is 0 or 1.

In the repeating unit of formula (1a) and (1b), it is preferable that the repeating unit of following formula (1a') and (1b').

Wherein R¹、R^x、R^y, L and f as defined above.

The preferred embodiment of the repeating unit of formula (1a) and (1b) is below shown, but is not limited to this.

Preferably, in order to provide fully with the adhesivity of resist pattern and with the binding property of base material, contraction material polymers is also contained (2) and/or the repeating unit of (3). The repeating unit of formula (2) or (3) allows the suitable thermal vibration of this polymkeric substance, and it advantageously promotes the result eliminated as the acid-unstable group in the repeating unit of formula (1a) or (1b) and makes this polymkeric substance become to be not dissolved in the not dissolving shunk in material stripper and react. Especially, it is more preferable to the repeating unit of formula (2).

In formula (2), B is singly-bound or the C that can contain ether oxygen atom in the half-way of chain₁-C₁₀Alkylidene group. The alkylidene group being applicable to and above identical to illustrated in " A ".

In formula (2), R¹As defined above.R³It is hydrogen independently of one another, halogen, the C of the straight chain of optional halogen substiuted, branching or ring-type₂-C₈Acyloxy, the C of the straight chain of optional halogen substiuted, branching or ring-type₁-C₆Alkyl; Or optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkoxyl group. The example of acyloxy, alkyl and alkoxyl group and above to R²Illustrated is identical.

In formula (2), g is the integer of 0-3, and t is the integer of 0-2, and b equals (5+2t-g), and n is 0 or 1. At this, g represents the number of the hydroxyl being bonded with aromatic ring. Preferably, the not dissolving reaction making this polymkeric substance become to be not dissolved in stripper in order to the result by being eliminated by the acid-unstable group in the repeating unit as formula (1a) or (1b) provides high reactivity, thus obtaining enough shrinkage, g is at least 1. More preferably, wherein g is at least 50 moles of % that those unit of the formula (2) of at least 1 account for the unit of formula (2). Although the adjustment for the adjustment of dissolution rate and the admissibility of the thermal vibration of polymkeric substance is effective, but depends on concrete design, can comprise the unit of the formula (2) of wherein g=0.

In the repeating unit of formula (2), not containing the repeating unit connecting base, that is, wherein g be at least 1, n=0 and B be singly-bound, namely, make aromatic ring be directly the unit typically hydroxystyrene unit from the monomer with the substituted or unsubstituted vinyl of 1-that the aromatic ring with hydroxyl replacement is connected with those repeating units of the formula (2) of main polymer chain bonding. The unit being applicable to comprises from those of 3-hydroxybenzene ethene, 4-Vinyl phenol, 5-hydroxyl-2-vinyl-naphthalene and 6-hydroxyl-2-vinyl naphthalene. It is preferably from those unit of 3-hydroxybenzene ethene or 4-Vinyl phenol, as shown in the formula (2') like that shown.

Wherein R¹As defined above and k is the integer of 1-3.

In the repeating unit of formula (2), with the repeating unit connecting base, that is, wherein n=1, that is, those repeating units with the formula (2) of ester structure connection base are the unit of the vinyl monomer from carbonyl substituted, typically (methyl) acrylate.

Have in the repeating unit of formula (2) of connection base (-CO-O-B-) coming from (methyl) acrylate, below illustrate that wherein g is the preferred embodiment of those unit of at least 1, but be not limited to this.

In the repeating unit of formula (2), wherein those unit of g=0 are from unit by halogen, acyloxy, alkyl, alkoxyl group or the partially substituted above-claimed cpd of similar structure of vinylbenzene, vinyl naphthalene, vinyl anthracene and its aromatic ring. Wherein g=0 and have those unit from connection base (-CO-O-B-) of (methyl) acrylate comprise wherein hydroxyl is therefrom eliminated, g that wherein hydrogen of hydroxyl is replaced by acyl group or alkyl be at least 1 the preferred embodiment of unit.

In formula (3), C is singly-bound or the C that can contain ether oxygen atom in the half-way of chain₁-C₁₀Alkylidene group. The alkylidene group being applicable to is as above to as illustrated in " A ".

In formula (3), R¹As defined above. R⁴Be hydrogen independently of one another, halogen, optional halogen substiuted, the C of straight chain, branching or ring-type₂-C₈Acyloxy, optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkyl, or optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkoxyl group. The example of acyloxy, alkyl and alkoxyl group as above to R²Illustrate like that.

In formula (3), C that D is singly-bound or straight chain, branching or ring-type, ether oxygen atom, carbonyl moieties or carbonyl oxygen based structures part can be contained in the half-way of chain₁-C₁₀(v+1) valency alkyl, wherein some or all hydrogen atoms of bond with carbon can replaced by fluorine.Preferred alkyl is aliphatic hydrocarbyl, the example be with above for L monovalent aliphatic alkyl illustrated in the identical group of group, wherein the number " v " of hydrogen atom is eliminated.

In formula (3), Rf¹And Rf²It is the C containing at least one fluorine atom independently of one another₁-C₆Alkyl. Rf¹Ring can be formed with the carbon atom being connected with them with D bonding. The alkyl containing at least one fluorine atom being applicable to comprises a methyl fluoride, difluoromethyl,

Trifluoromethyl, 2,2,2-trifluoroethyl,

1,1,2,2,2-pentafluoroethyl group,

2,2,2-tri-fluoro-1-(trifluoromethyl) ethyl, perfluoroisopropyl,

Seven fluorine propyl group, 2,2,3,3-tetra-fluorine propyl group,

2,2,3,3,3-five fluorine propyl group,

3,3,3-tri-fluoro-2-(trifluoromethyl) propyl group, nine fluorine butyl,

1H, 1H, 5H-eight fluorine amyl group, 1H, 1H-nine fluorine amyl group,

Perfluoropentyl, 1H, 1H-4-trifluoromethyl perfluoropentyl,

Perfluoro hexyl, 4-pentafluoroethyl group perfluorocyclohexyl,

1H, 1H, 2H, 2H-perfluoro hexyl, and perfluorocyclohexyl.

In formula (3), h is the integer of 1-3, and u is the integer of 0-2, and c equals (5+2u-h).

In formula (3), r is 0 or 1. When r=1, aromatic ring between main polymer chain and hydroxyl, this hydroxyl and the bond with carbon contiguous with the carbon that replaces with fluoro-containing group. In this case, represent that the v of the number of the substituting group on D is 1 or 2. If D is not singly-bound, D has one or two hydroxyl, and each hydroxyl and the bond with carbon contiguous with the carbon replaced with fluoro-containing group, that is, v is 1 or 2.

When r=0, h is 1, and C is singly-bound, but D is not singly-bound. In this case, D is bonded with main polymer chain via carbonyl oxygen base. In this case, also it is that D has one or two hydroxyl, each hydroxyl and the bond with carbon contiguous with the carbon replaced with fluoro-containing group.

The preferred embodiment of the repeating unit with formula (3) is below shown, but is not limited to this.

The unit of formula (2) or (3) uses with separately or can mixing (that is, a kind of or two or more).

Contraction material polymers can also comprise the repeating unit of at least one being selected from the unit with following formula (4) and (5) as main composition unit. In the present embodiment, except the advantage of the intrinsic elching resistant of aromatic ring, this polymkeric substance can have another following advantage: the resist pattern shunk is given dry etching resistance by the combination of ring texture and main chain.

Wherein R⁵And R⁶Be hydrogen independently of one another, halogen, optional halogen substiuted, the C of straight chain, branching or ring-type₂-C₈Acyloxy, optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkyl, or optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkoxyl group. The example of acyloxy, alkyl and alkoxyl group and above for R²What illustrate is identical.

In formula (4) and (5), i and j is the integer of 0-2 independently of one another, and d equals (6-i), and e equals (4-j).

The unit of formula (4) or (5) uses with separately or can mixing (that is, a kind of or two or more).

In order to improve the elching resistant of polymkeric substance, relative to other repeating units of polymkeric substance, when selecting formula (4) or the unit of (5) that wherein i or j is at least 1, can easily obtain and obtain following unit compound (4') or (5') by it and effective for the effect needed for realizing.

Shrink the repeating unit that material polymers can also comprise at least one being selected from the unit with following formula (A)-(E). These unit can be used as making polymkeric substance to be more bonded in resist pattern or the auxiliary unit for telomerized polymer solubleness in a solvent.

Wherein R¹As defined above. X^AFor acid-unstable group. X^BAnd X^CIt is the C of singly-bound or straight chain or branching independently of one another₁-C₄Bivalent hydrocarbon radical. X^DFor straight chain, branching or ring-type, wherein any composition-CH₂-can by the C of-O-or-C (=O)-replacement₁-C₁₆Divalence is to the aliphatic hydrocarbyl of pentavalent. X^EFor acid-unstable group. Y^AFor having the substituting group of lactone, sultone or structural carbonate. Z^AFor hydrogen, C₁-C₃₀Fluoro-alkyl or C₁-C₁₅Containing the substituting group of fluorinated alcohols, k^1AFor the integer of 1-3, and k^1BFor the integer of 1-4.

The repeating unit of formula (A) is made to decompose to produce carboxylic acid under the action of an acid. By introducing this unit, adjustable contraction material polymers solubleness in organic solvent. By X^AThe acid-unstable group represented can be selected from various such group. The example of acid-unstable group comprises the group of following general formula (L1)-(L4), the tertiary alkyl of 4-20 carbon atom, preferably 4-15 carbon atom, wherein each Alliyl moieties has the trialkylsilkl of 1-6 carbon atom, and the oxoalkyl group of 4-20 carbon atom.

Wherein R^L01And R^L02It is the straight chain of hydrogen or 1-18 carbon atom, preferably 1-10 carbon atom, branching or cyclic alkyl independently of one another. R^L03For the monovalent hydrocarbon of 1-18 carbon atom, preferably 1-10 the carbon atom of heteroatoms such as oxygen can be contained, the example comprises the alkyl of straight chain, branching or ring-type, some of them hydrogen atom is by hydroxyl, alkoxyl group, oxo, amino, the replacement form of such alkyl that alkylamino etc. replace, with the identical group separated by ether oxygen atom. R^L04For the tertiary alkyl of 4-20 carbon atom, preferably 4-15 carbon atom, wherein each Alliyl moieties has the trialkylsilkl of 1-6 carbon atom, the oxoalkyl group of 4-20 carbon atom, or the group of formula (L1). R^L05For what optionally replace, the C of straight chain, branching or ring-type₁-C₁₀Alkyl or the optional C replaced₆-C₂₀Aryl. R^L06For what optionally replace, the C of straight chain, branching or ring-type₁-C₁₀Alkyl or the optional C replaced₆-C₂₀Aryl. R^L07-R^L16Independently represent hydrogen or the monovalent hydrocarbon of optional 1-15 the carbon atom replaced. Letter x is the integer of 0-6, y equal 0 or 1, z equal 0,1,2 or 3, and 2y+z equals 2 or 3.

In formula (L1), R^L01And R^L02Illustration group comprise methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, n-octyl, and adamantyl.

By R^L03The example of monovalent hydrocarbon that represents and above to by R^L01And R^L02It is identical that the alkyl represented illustrates, but is not limited to this. By R^L03The example of the alkyl of the replacement represented is as follows.

R^L01And R^L02A couple, R^L01And R^L03A couple or R^L02And R^L03A couple can be bonded the carbon atom to combine with them each other and Sauerstoffatom forms ring. When they form ring, each forms the R of ring^L01、R^L02And R^L03For 1-18 carbon atom, the preferably straight chain of 1-10 carbon atom or the alkylidene group of branching.

In formula (L2), R^L04The example of tertiary alkyl be the tertiary butyl, tert-pentyl, 1,1-diethyl propyl group, 2-cyclopentyl propane-2-base, 2-cyclohexyl propane-2-base,

2-(two ring [2.2.1] heptane-2-base) propane-2-base,

2-(diamantane-1-base) propane-2-base, 1-ethylcyclopentyl,

1-butyl cyclopentyl, 1-ethylcyclohexyl, 1-butyl cyclohexyl,

1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, 2-methyl-2-adamantyl, and 2-ethyl-2-adamantyl. The example of trialkylsilkl is trimethyl silyl, triethylsilyl, and dimethyl-tert. butylsilyl-group.The example of oxoalkyl group is 3-oxocyclohexyl, 4-methyl-2-oxo alkane-4-base, and 5-methyl-2-oxo tetrahydrofuran-5-base.

In formula (L3), R^L05The example of alkyl comprise the alkyl such as methyl of straight chain, branching or ring-type, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, tert-pentyl, just own base, cyclopentyl, cyclohexyl, and two ring [2.2.1] heptyl, and some of them hydrogen atom is replaced by hydroxyl, alkoxyl group, carboxyl, carbalkoxy, oxo, amino, alkylamino, cyano group, sulfydryl, alkylthio, sulfo group etc. or the replacement form of wherein these groups that methylene moiety is substituted by oxygen or sulphur atom. R^L05The example of aryl comprise phenyl, aminomethyl phenyl, naphthyl, anthryl, phenanthryl, and pyrenyl.

In formula (L4), R^L06Alkyl and aryl example with for R^L05Illustrated is identical. R^L07-R^L16C₁-C₁₅The example of monovalent hydrocarbon comprises the alkyl such as methyl of straight chain, branching or ring-type, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, tert-pentyl, just own base, n-octyl, positive nonyl, positive last of the ten Heavenly stems base, cyclopentyl, cyclohexyl, cyclopentyl-methyl, cyclopentyl ethyl, cyclopentyl butyl, cyclohexyl methyl, cyclohexyl ethyl and cyclohexyl butyl, and some of them hydrogen atom is by hydroxyl, alkoxyl group, carboxyl, alkoxy carbonyl, oxo, amino, alkylamino, cyano group, sulfydryl, alkylthio, the replacement form of these groups that sulfo group etc. replace. Or, R^L07-R^L16In two such as, can be bonded the carbon atom (one or more) to combine with them each other and form ring (R^L07And R^L08A couple, R^L07And R^L09A couple, R^L08And R^L10A couple, R^L09And R^L10A couple, R^L11And R^L12A couple, or R^L13And R^L14A couple formed ring). R^L07-R^L16Each represent C₁-C₁₅Bivalent hydrocarbon radical, typically alkylidene group, when their form ring, the example is above for those illustrated in monovalent hydrocarbon, and one of them hydrogen atom is eliminated. With the R that ortho position carbon atom is combined^L07-R^L16In two can each other Direct Bonding such as, to form double bond (R^L07And R^L09A couple, R^L09And R^L15A couple, or R^L13And R^L15A couple).

In the acid-unstable group of formula (L1), the group of straight chain and branching is illustrated by following radicals, but is not limited to this.

In the acid-unstable group of formula (L1), cyclic group is such as tetrahydrofuran (THF)-2-base,

2-methyltetrahydrofuran-2-base, tetrahydropyrans-2-base, and

2-methyl tetrahydropyrans-2-base.

The example of the acid-unstable group of formula (L2) comprises tert-butoxycarbonyl, tert-Butoxycarbonyl-methyl,

Tert-pentyloxy carbonyl, tert-pentyloxy carbonyl methyl,

1,1-diethyl propoxycarbonyl,

1,1-diethyl propoxycarbonyl methyl,

1-ethyl cyclopentyloxy carbonyl,

1-ethyl cyclopentyloxy carbonvlmethyl,

1-ethyl-2-cyclopentenes oxygen base carbonyl,

1-ethyl-2-cyclopentenes oxygen base carbonvlmethyl,

1-ethoxy ethoxy carbonvlmethyl,

2-THP trtrahydropyranyl oxygen base carbonvlmethyl, and

2-tetrahydrofuran base oxygen base carbonvlmethyl.

The example of the acid-unstable group of formula (L3) comprises 1-methylcyclopentyl, 1-ethylcyclopentyl,

1-n-propyl cyclopentyl, 1-sec.-propyl cyclopentyl,

1-normal-butyl cyclopentyl, 1-sec-butyl cyclopentyl,

1-cyclohexyl ring amyl group, 1-(4-methoxyl group-normal-butyl) cyclopentyl,

1-(two ring [2.2.1] heptane-2-base) cyclopentyl,

1-(7-oxabicyclo [2.2.1] heptane-2-base) cyclopentyl,

1-methyl cyclohexane base, 1-ethylcyclohexyl,

3-methyl isophthalic acid-cyclopentenes-3-base, 3-ethyl-1-cyclopentenes-3-base,

3-methyl isophthalic acid-tetrahydrobenzene-3-base, and 3-ethyl-1-tetrahydrobenzene-3-base.

In the acid-unstable group of formula (L4), it is preferable that those groups of following formula (L4-1) to (L4-4).

Formula (L4-1) is to, in (L4-4), dotted line represents bonding position and direction. R^L41It is monovalent hydrocarbon, the typically C of straight chain, branching or ring-type independently of one another₁-C₁₀Alkyl, such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, tert-pentyl, just own base, cyclopentyl and cyclohexyl.

For formula (L4-1) to (L4-4), it is possible to there is enantiomer and diastereomer. Each of formula (L4-1) to (L4-4) represents all such steric isomers allly. X^ADuring for the acid-unstable group of formula (L4), multiple steric isomer can be comprised.

Such as, formula (L4-3) represents one or two the mixture being selected from the group with following formula (L4-3-1) and (L4-3-2).

Should be with pointing out, R^L41As defined above.

Equally, formula (L4-4) represents one or two the above mixtures being selected from the group with following formula (L4-4-1)-(L4-4-4).

Should be with pointing out, R^L41As defined above.

Each unified mixture representing its enantiomer and enantiomer of formula (L4-1) to (L4-4), (L4-3-1) and (L4-3-2) and (L4-4-1) to (L4-4-4).

Should be with pointing out, in above-mentioned formula (L4-1) to (L4-4), (L4-3-1) and (L4-3-2) and (L4-4-1)-(L4-4-4), bonding direction is in the outside relative to two ring [2.2.1] heptane ring, and this guarantees the hyperergy for acid catalysis eliminative reaction (see JP-A2000-336121). In preparation these have two ring [2.2.1] heptane structure outer-monomer of tertiary alkyl alternatively base in, can containing have with represent by following formula (in L4-1-)-(in L4-4-) interior-monomer of alkyl replacement. In order to good reactivity, it is preferable that the outer ratio of at least 50 moles of %, it is more preferable to the outer ratio of at least 80 moles of %.

Should be with pointing out, R^L41As defined above.

Hereinafter provide the illustrated example of the acid-unstable group of formula (L4).

By X^AThe tertiary C represented₄-C₂₀Alkyl, wherein each Alliyl moieties has the trialkylsilkl of 1-6 carbon atom, and C₄-C₂₀The example of oxoalkyl group is with for R^L04Illustrated is identical.

Hereinafter provide the illustrated example of the repeating unit with formula (A), but it is not limited to this. Wherein R¹As defined above.

Hereinafter provide the illustrated example of the repeating unit with formula (B), but it is not limited to this. Wherein R¹As defined above.

Hereinafter provide the illustrated example of the repeating unit with formula (C), but it is not limited to this. Wherein R¹As defined above.

Hereinafter provide the illustrated example of the repeating unit with formula (D), but it is not limited to this. Wherein R¹As defined above.

Make the polymer unwinds of repeating unit of contained (E) to produce hydroxyl so that its solubleness alterable in all kinds of SOLVENTS under the action of an acid. In formula (E), acid-unstable group X^EVarious such group can be selected from. Acid-unstable group X^EExample be the group of formula (L1)-(L4), the tertiary alkyl of 4-20 carbon atom, wherein each alkyl group has the trialkylsilkl of 1-6 carbon atom, and the oxoalkyl group of 4-20 carbon atom, acid-unstable group X described above^ALike that.

Hereinafter provide the illustrated example of the repeating unit with formula (E), but it is not limited to this. Wherein R¹As defined above.

In the repeating unit of formula (A)-(E), it is preferable that those unit of formula (A)-(C), being thus can easily the solvent solubility of telomerized polymer and binding property.

Shrink the repeating unit that material polymers can comprise following formula (F) further.The unit of formula (F) can bring out the neutralization reaction of the carboxyl with existence on the surface of the resist pattern film of coated shrink material. As a result, this contraction material polymers adheres to resist film surface, the adhesivity that display increases.

Wherein R¹⁰¹For hydrogen or methyl. X is singly-bound ,-C (=O)-,-C (=O)-O-or-C (=O)-NH-. R¹⁰²For the C of Han You the ether structure part of singly-bound or straight chain, branching or ring-type, ester structure part, carbonyl moieties ,-N=or-S-₁-C₁₀Alkylidene group, or phenylene or naphthylidene. R¹⁰³And R¹⁰⁴It is the C of hydrogen, straight chain or branching independently of one another₁-C₄Alkyl, or acid-unstable group, or R¹⁰³And R¹⁰⁴Can being bonded the nitrogen-atoms to combine with them each other and form ring, this ring is optionally containing ehter bond, or R¹⁰³And R¹⁰⁴In any one can with R¹⁰²It is bonded the formation ring of the nitrogen-atoms to combine with them, and k^1CIt is 1 or 2.

The repeating unit of formula (F) can from the monomer with following formula (Fa).

Wherein R¹⁰¹-R¹⁰⁴, X and k^1CAs defined above.

The example of the monomer with formula (Fa) is below shown, but is not limited to this.

Wherein R¹⁰¹-R¹⁰⁴As defined above.

Shrink material polymers can be used alone or as a mixture. When being used alone this polymkeric substance, by selecting the repeating unit with required function, it is determined that the composition of this repeating unit carries out designing to provide suitable contraction and size uniformity to the contraction material prepared by it.

By in a standardized manner by applicable combination of monomers and by they copolymerization, if needing prepared by protection reaction and deprotection reaction combination contraction material polymers. Copolyreaction is preferably radical polymerization, although being not limited to this.

Shrink in material polymers, based on whole repeating unit, it is preferable that with the repeating unit of the amount drawing-in system (1a) of at least 5 moles of %, more preferably at least 10 moles of % and/or (1b).

Based on whole repeating unit, it is preferable that with the repeating unit of the amount drawing-in system (2) of 0-90 mole of %. In order to more adhesivityes with resist pattern and substrate adherence, the amount of the unit of formula (2) is more preferably 5-85 mole of %, further preferred 10-80 mole of %.

Based on whole repeating unit, it is preferable that with the repeating unit of the amount drawing-in system (3) of 0-90 mole of %. In order to more adhesivity with resist pattern and substrate adherence, the amount of the unit of formula (3) is more preferably 5-85 mole of %, further preferred 10-80 mole of %.

Based on whole repeating unit, it is preferable that with the repeating unit of the amount drawing-in system (4) of 0-30 mole of % or (5). In order to more elching resistant, the amount of the unit of formula (4) or (5) is more preferably 5-30 mole of %, more preferably 5-20 mole of %.

Based on whole repeating unit, it is preferable that with the repeating unit of amount drawing-in system (A)-(E) of 0-30 mole of %. In order to more substrate adherence and solubleness regulate, the amount of the unit of formula (A)-(E) is more preferably 1-30 mole of %, more preferably 5-20 mole of %.

Based on whole repeating unit, it is preferable that with the repeating unit of the amount drawing-in system (F) of 0-30 mole of %. In order to more adhesivity, the amount of the unit of formula (F) is more preferably 1-30 mole of %, more preferably 1-20 mole of %.

Shrink in material polymers, the repeating unit of formula (1a) and/or (1b) and the repeating unit being selected from the unit of formula (2), (4) and (5) preferably account at least 60 moles of % based on whole repeating unit, and reason is that this guarantees to prepare the contraction material with desired properties. More preferably, based on whole repeating unit, the repeating unit of the repeating unit of formula (1a) and/or (1b) and formula (2), (4) and (5) accounts at least 70 moles of %, it is more preferable at least 85 moles of %.

The whole Component units shrinking material polymers are the repeating unit of formula (1a) and/or (1b) and when being selected from the repeating unit of formula (2), (4) and (5), can obtain high elching resistant and high resolving power in the way of compatible. Shrink in material polymers, can drawing-in system (1a), (1b), (2), (4) and (5) repeating unit beyond repeating unit. Such as, (methyl) acrylic ester unit with the protection of conventional acid-unstable group can be used and/or there is (methyl) acrylic ester unit of binding property group such as lactone structure. Although other repeating unit is optional, but by introducing such other repeating unit, can regulate the characteristic shrinking material film meticulously.

Shrinking the weight-average molecular weight (Mw) that material polymers preferably has 1,000-500,000, more preferably 2,000-100,000, further preferably 2,000-20,000, it measures relative to vinylbenzene standard specimen with the use of the GPC of tetrahydrofuran solvent. If Mw is too low, it is possible to make acid diffusion length prolongation and contraction may be made to increase and become uncontrollable. If Mw is too high, the solubleness in stripper solvent may be reduced to the degree remaining in space by scum silica frost at the end of strip step, causes undercutting (footing) phenomenon.

If polymkeric substance has wide molecular weight distribution or dispersity (Mw/Mn), it represents existence that is lower and higher molecular weight polymer fraction, then likely foreign matter remains on pattern or pattern contour is deteriorated. Along with pattern dimensions becomes meticulousr, the impact of molecular weight and dispersity becomes stronger. Therefore, in order to provide applicable micro-patternization to the contraction material of small-feature-size, multicomponent copolymer, that is, shrink the narrow dispersity (Mw/Mn) that material polymers should preferably have 1.0-2.0, especially 1.0-1.5.

The blend of the two or more polymkeric substance that ratio of components, molecular weight or dispersity can be used different.

Except above-mentioned polymkeric substance, shrinking material and comprise solvent, this solvent contains the anti-disappearance solvent of the resist pattern loss after not making development. The solvent that anti-disappearance solvent comprises is the ether solvents of 6-12 carbon atom, the hydrocarbon solvent of 6-12 carbon atom, the ester solvent of 7-16 carbon atom, the ketone solvent of 8-16 carbon atom, the alcoholic solvent of 4-10 carbon atom, He Shui. As long as anti-disappearance solvent accounts at least 50 weight % of whole solvent, then can containing other solvents making the resist pattern loss after development.

Although having proposed many water systems to shrink material, but the surface tension due to high water, they are difficult to be applied to rapidly major diameter wafer. Particularly when the meticulous sectional hole patterns formed via the development of negative type, have problems. When being coated with this contraction material filling orifice by revolving, the water solvent with high surface tension prevents this contraction material to be embedded to bottom in hole. Under contrast, be applied in the organic solvent with the surface tension lower than water dissolve contraction material time, fill or be embedded to the ability bottom hole and improve. And the organic solvent shrinking use in material must dissolve contraction material polymers.

As shrinking in material the solvent used, owing to they are for the high solvency power shrinking material polymers, it is preferred to the alcoholic solvent of the ketone solvent of the ester solvent of 7-16 carbon atom, 8-16 carbon atom and 4-10 carbon atom.

The example of the ester solvent of 7-16 carbon atom comprises amyl acetate-n, isoamyl acetate, acetic acid 2-methyl fourth ester, capryl acetate, acetic acid 2-ethylhexyl, cyclohexyl acetate, methyl cyclohexanol acetate, hexyl formate, Valeric acid ethylester, propyl valerate, valeric acid isopropyl ester, butyl valerate, isobutyl isovalerate, pentanoate, oil of apple, valeric acid isopentyl ester, Ethylisovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, the isovaleric acid tert-butyl ester, isoamyl isovalerate, 2 methyl valeric acid second ester, 2 methyl valeric acid fourth ester, PIVALIC ACID CRUDE (25) second ester, PIVALIC ACID CRUDE (25) propyl ester, PIVALIC ACID CRUDE (25) isopropyl ester, PIVALIC ACID CRUDE (25) fourth ester, the PIVALIC ACID CRUDE (25) tert-butyl ester, pentenoic acid ethyl ester, pentenoic acid propyl ester, pentenoic acid isopropyl ester, amylene acid butyl ester, the pentenoic acid tert-butyl ester, β-crotonic acid propyl ester, β-crotonic acid isopropyl ester, butyl crotonate, the β-crotonic acid tert-butyl ester, butyl propionate, isobutyl propionate, the propionic acid tert-butyl ester, benzyl propionate, ethyl hexanoate, pineapple aldehyde, propyl butyrate, butyl butyrate, isobutyl butyrate, butyric acid 3-methyl fourth ester, tert-butyl acetate, ethyl 2-methylbutyrate, 2-Methyl Butyric Acid isopropyl ester, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, Benzyl Acetate, phenyl ritalin, benzyl formate, formic acid phenyl chlorocarbonate, 3-phenylpropionic acid methyl esters, phenyl vinyl acetic monomer, with acetic acid 2-phenyl chlorocarbonate.

The example of the ketone solvent of 8-16 carbon atom comprises methyln-hexyl ketone, 3-octanone, 4-octanone, methyl n-heptyl ketone, 3-nonanone, 4-nonanone, butyl ketone, diisobutyl ketone, ethyl cyclohexanone, ethyl methyl phenyl ketone, ethyl normal-butyl ketone, di-n-butyl ketone, and diisobutyl ketone.

The example of the alcoholic solvent of 4-10 carbon atom comprises n-butyl alcohol, 2-butanols, isopropylcarbinol, the trimethyl carbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, tertiary amyl alcohol, neopentyl alcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 3-methyl-3-amylalcohol, cyclopentanol, the own alcohol of 1-, the own alcohol of 2-, the own alcohol of 3-, 2, 3-dimethyl-2-butanols, 3, 3-dimethyl-n-butyl alcohol, 3, 3-dimethyl-2-butanols, 2, 2-diethyl-n-butyl alcohol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 3-methyl-3-amylalcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 4-methyl-3-amylalcohol, hexalin, with 1-octanol. these solvents can be used alone or used in combination.

Mix with the mutual of resist pattern to prevent shrinking material, can by C₈-C₁₂Ether, C₆-C₁₂Any solvent in alkane, alkene, alkynes and aromatic solvent mixes with anti-disappearance solvent.

The ether compound of 8-12 the carbon atom being applicable to comprises di-n-butyl ether, diisobutyl ether, two sec-butyl ether, two n-pentyl ethers, diisoamyl ether, di-secondary amyl ether, two tert-amyl ethers, and two positive hexyl ether. The alkane of 6-12 the carbon atom being applicable to comprises hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, hexanaphthene, methylcyclohexane, dimethyl cyclohexane, suberane, cyclooctane, and cyclononane. The alkene of 6-12 the carbon atom being applicable to comprises own alkene, heptene, octene, tetrahydrobenzene, tetrahydrotoluene, dimethyl tetrahydrobenzene, suberene, and cyclooctene. The alkynes of 6-12 the carbon atom being applicable to comprises own alkynes, heptyne, and octyne. The aromatic solvent being applicable to comprises toluene, dimethylbenzene, ethylbenzene, isopropyl benzene, tert.-butylbenzene, 1,3,5-Three methyl Benzene and phenylmethylether. These solvents can be used alone or as a mixture.

Except anti-disappearance solvent, shrinking material can containing other solvent. this other solvent is selected from methyln-hexyl ketone, methyl n-heptyl ketone, 2-heptanone, 3-heptanone, dipropyl ketone, methyl-n-butyl ketone, the own ketone of 3-, diisobutyl ketone, methylcyclohexanone, methyl phenyl ketone, methyl acetophenone, propyl acetate, N-BUTYL ACETATE, isobutyl acetate, amyl acetate-n, isoamyl acetate, acetic acid butene esters, propyl formate, butyl formate, tetryl formate, pentyl formate, isoamyl formate, methyl valerate, amylene-4 acid methyl ester, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, 3-ethoxyl ethyl propionate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, 2-hydroxy-methyl isobutyl acid, 2-ethyl butyrate of hydroxyl iso, methyl benzoate, ethyl benzoate, phenyl acetate, Benzyl Acetate, phenyl ritalin, benzyl formate, formic acid phenyl chlorocarbonate, 3-phenylpropionic acid methyl esters, benzyl propionate, phenyl vinyl acetic monomer, with acetic acid 2-phenyl chlorocarbonate. if used, it is preferable that mix this other solvent to be less than the amount of 50 weight % of whole solvent.

Shrink in material, relative to the polymkeric substance of 100 weight parts, it is preferable that use solvent with the amount of 100-100,000 weight part, more preferably 200-50,000 weight part.

If needing to add salt, basic cpd and tensio-active agent to shrinking in material. The salt that can add typically is selected from the sulfonium salt and salt compounded of iodine and ammonium salt that typically add in resist composition.The basic cpd that can add can be selected from those basic cpds typically added in resist composition, such as, and primary, secondary and tertiary aliphatic amine; mixed amine; aromatic amine, heterocyclic amine, has the nitrogenous compound of carboxyl; there is the nitrogenous compound of alkylsulfonyl; the nitrogenous compound with hydroxyl, has the nitrogenous compound of hydroxy phenyl, alcohol type nitrogenous compound; amide derivatives, imide derivative and carbamate (salt). Adding for suppression acid from the excess diffusion in resist film and effective for control shrinkage of salt or basic cpd. The tensio-active agent that can add can be selected from those tensio-active agents typically added in resist composition.

As salt, it is preferable that have the carboxylate salt of formula (9).

R¹¹-CO₂ ^-M⁺(9)

Wherein R¹¹For straight chain, branching or ring-type C₁-C₂₀Alkyl, straight chain, branching or ring-type C₂-C₂₀Alkene base or C₆-C₂₀Monovalence is containing aromatic ring group, and wherein some or all hydrogen atoms of bond with carbon can be replaced by fluorine, the group containing lactonic ring, the group containing lactam nucleus or oh group, and wherein ether, ester or carbonyl group can between carbon-carbon alkali. M⁺For sulfonium, iodine or ammonium cation.

Alkyl, alkene base and monovalence containing aromatic ring group example as previously mentioned.

Preferred sulfonium, iodine and ammonium cation have following formula (P1)-(P3). By adding, there is such cationic carboxylate salt, it is possible to control acid diffusion effectively.

Wherein R¹⁰¹-R¹⁰⁹It is the C of straight chain, branching or ring-type independently of one another₁-C₁₂Alkyl or oxoalkyl group, the C of straight chain, branching or ring-type₂-C₁₂Alkene base or oxo alkene base, C₆-C₂₀Monovalence is containing aromatic ring group, or C₇-C₁₂Aralkyl or aryl oxoalkyl group, some of them or all hydrogen atom can be replaced by halogen, alkyl, alkoxyl group etc. R¹⁰¹And R¹⁰²A couple or R¹⁰⁶And R¹⁰⁷A couple can be bonded the sulphur to combine with them each other or nitrogen-atoms forms ring. When they form ring, they form C together₁-C₁₀Alkylidene group or arylidene and this ring can contain ether, ester, sultone or amino group wherein.

Alkyl, alkene base and monovalence are containing aromatic ring group as previously mentioned. The oxoalkyl group being applicable to and oxo alkene base comprise above-mentioned alkyl and the alkene base of wherein oxo group and carbon atom bonding. The aralkyl being applicable to comprises benzyl, 1-phenylethyl and 2-phenylethyl. The aryl oxoalkyl group being applicable to is 2-aryl-2-oxoethyl, comprises 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl and 2-(2-naphthyl)-2-oxoethyl.

The preferred example of the negatively charged ion of above-mentioned carboxylate salt comprises the carboxylate anion described in JP3991462 and shown below those, but is not limited to this.

The cationic preferred example of above-mentioned carboxylate salt comprises shown below those, but is not limited to this.

There is the sulfonate of formula (10) it is also preferred that as this salt.

R¹²-SO₃ ^-M⁺(10)

Wherein M⁺As defined above. R¹²For the C of Han You the Sauerstoffatom of straight chain, branching or ring-type₁-C₃₅Monovalent hydrocarbon, wherein some or all hydrogen atoms of bond with carbon can replaced by fluorine, and condition does not replaced by fluorine relative to the hydrogen atom of sulfonic acid and the carbon atom bonding of alpha-position.

Have in the sulfonate of formula (10), it is preferable that there are formula (10') those.

Wherein M⁺As defined above, R¹¹⁰And R¹¹¹It is hydrogen or trifluoromethyl independently of one another, and l is the integer of 1-3.

Shrink in material, relative to the polymkeric substance of 100 weight parts, it is preferable that use this salt with 0-50 weight part, the more preferably amount of 0.1-20 weight part.

The basic cpd illustrated comprises primary, secondary and tertiary amine compound, particularly there is the amine compound of hydroxyl, ether base, ester group, lactone group, cyano group or sulfonate group, such as JP-A2008-111103, paragraph [0146]-[0164] (USP7,537,880) described in, and there is the compound of carboxylamine ester group, as described in JP3790649.Wherein, it is preferable that tertiary amine compound, particularly there is the amine compound of hydroxyl, ether base, ester group or lactonic ring, and there is the compound of carboxylamine ester group.

Shrink in material, relative to the polymkeric substance of 100 weight parts, it is preferable that use this basic cpd with 0-30 weight part, the more preferably amount of 0.1-20 weight part.

The tensio-active agent being applicable to comprises JP-A2008-111103, paragraph [0165]-[0166] is recorded those. Relative to the contraction material polymers of 100 weight parts, it is preferable that use tensio-active agent with the amount of 0-10 weight part, more preferably 0.1-5 weight part.

Resist composition

The resist composition used in the pattern forming method of the present invention is defined as and comprises base resin, acidogenic agent (or can produce the compound of acid in response to high-energy irradiation) and organic solvent. Optionally, resist composition also comprises basic cpd, dissolution regulator, tensio-active agent, acetylene alcohol and other additives.

Base resin used herein is defined as to comprise has the carboxyl that acid-unstable group replaces, the repeating unit (a) preferably represented by formula (11).

Wherein R²¹For hydrogen or methyl. R²²For acid-unstable group. Z is singly-bound or-C (=O)-O-R²³-, wherein R²³For the C of straight chain, branching or ring-type₁-C₁₀Alkylidene group, wherein ehter bond or ester bond can between carbon-carbon, or naphthylidene.

The alkylidene group being applicable to is as illustrated on. The acid-unstable group being applicable to is JP-A2014-088557, paragraph [0039]-[0044] (USP9,017,918) records those.

In order to improve substrate adherence to prevent pattern collapse, base resin can also comprise the repeating unit (b) with the binding property group being selected from hydroxyl, lactonic ring group, ether base, ester group, carbonyl and cyano group. Base resin can also comprise the repeating unit (c) (such as JP-A2012-037867, described in paragraph [0085]) coming from indenes, acenaphthylene, chromone, tonka bean camphor and Norbornadiene derivatives; Come from the repeating unit (d) (as described in paragraph [0088]) of vinylbenzene, vinyl naphthalene, vinyl anthracene, vinylpyrene and methylene radical indan derivative; And/or derive from the repeating unit (e) (as described in paragraph [0089]-[0091]) of the salt that there is polymerizability alkene and play function as acidogenic agent.

In base resin, based on whole repeating unit, introduce repeating unit (a) with the amount being greater than 0 mole of % and 100 moles of below %, preferably 1 mole of more than % and being less than 100 moles of %, more preferably 20-90 mole of %. Based on whole repeating unit, with 0 mole of more than % and amount introducing repeating unit (b) being less than 100 moles of %, preferably 10-80 mole of %. The total of repeating unit (a) and (b) is preferably 30-100 mole of %. When introducing repeating unit (c)-(e), preferably, repeating unit (c) is introduced with the amount of 0-40 mole of %, repeating unit (d) is introduced with the amount of 0-20 mole of %, repeating unit (e) is introduced, and the total of repeating unit (c)-(e) is 0-70 mole of % with the amount of 0-30 mole of %.

Base resin should preferably have the Mw in the scope of 1,000-500,000, more preferably 2,000-100,000, and it is measured by GPC relative to polystyrene standards. If Mw is too low, it is possible to make the diffusion length of the acid produced by acidogenic agent extend the reduction to cause resolving power. If Mw is too high, it is possible to make polymkeric substance solubleness in a developer reduce the reduction to cause resolving power.

If polymkeric substance has wide molecular weight distribution or dispersity (Mw/Mn), it represents existence that is lower and higher molecular weight polymer fraction, then likely foreign matter remains on pattern or pattern contour is deteriorated. Along with pattern dimensions becomes meticulousr, the impact of molecular weight and dispersity becomes stronger. Therefore, in order to provide applicable micro-patternization to the resist composition of small-feature-size, base resin should preferably have the narrow dispersity (Mw/Mn) of 1.0-2.0, special 1.0-1.5.

The blend of the two or more polymkeric substance that ratio of components, molecular weight or dispersity are different can be used as base resin.

Resist composition contains acidogenic agent so that it can be used as chemical amplification positive resist composition performance function. Acidogenic agent typically is the compound that can produce acid in response to photochemical light or irradiation being called photo-acid generator (PAG). Relative to the base resin of 100 weight parts, it may also be useful to the suitable amount of PAG be 0.5-30 weight part, it is more preferable to ground 1-20 weight part. PAG is any compound that can produce acid when being exposed to high-energy irradiation. The PAG being applicable to comprises sulfonium salt, salt compounded of iodine, alkylsulfonyl diazomethane, N-sulfonyloxy imide, and oxime-O-sulphonate acidogenic agent. Acidogenic agent can be used alone or two or more used in combination. The example of the acid produced by PAG is sulfonic acid, imido acid and methyl acid (methideacids). In these, it is generally used in alpha-position most by the sulfonic acid of fluoro. When acid-unstable group is the acetal radical being easy to deprotection, the fluoride at alpha-position is not always necessary. When base resin has the repeating unit of the acidogenic agent of wherein copolymerization, acidogenic agent need not add individually.

The example of organic solvent comprises ketone such as pimelinketone and the n-amyl ketone of methyl-2-as used herein; Alcohol is 3-methoxybutanol such as, 3-methyl-3-methoxybutanol, 1-methoxyl group-2-propyl alcohol, and 1-oxyethyl group-2-propyl alcohol; Ether is propylene glycol monomethyl ether such as, ethylene glycol monomethyl ether, propylene glycol list ethyl ether, ethylene glycol monomethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; Ester is propylene glycol monomethyl ether (PGMEA) such as, propylene glycol list monoethyl ether acetate, ethyl lactate, Pyruvic Acid Ethyl ester, N-BUTYL ACETATE, 3-methoxypropionic acid methyl esters, 3-ethoxyl ethyl propionate, tert-butyl acetate, the propionic acid tert-butyl ester, and propylene glycol list tertbutyl ether acetic ester; With lactone such as gamma-butyrolactone, and their mixture. When using the acid-unstable group of acetal form, can adding high-boiling point alcohol solvent such as glycol ether, propylene glycol, glycerine, 1,4-butyleneglycol or 1,3 butylene glycol are to accelerate the deprotection reaction of acetal.

Relative to the base resin of 100 weight parts, the suitable amount of organic solvent is 100-10,000 weight part, it is preferable that 300-8,000 weight part.

The basic cpd illustrated comprises primary, secondary and tertiary amine compound, particularly there is the amine compound of hydroxyl, ether base, ester group, lactone group, cyano group or sulfonate group, such as JP-A2008-111103, described in paragraph [0146]-[0164], with the compound with carboxylamine ester group, as described in JP3790649. And, salt such as sulfonium salt, salt compounded of iodine and do not can be used as quencher by the salt (being recorded in JP3991462 and JP4226803) of the ammonium salt (being recorded in US2008153030 (JP-A2008-158339)) of the sulfonic acid of fluoro and similar carboxylic acid at alpha-position. They also can add in contraction material.

When acid-unstable group is for the acetal radical that acid is very responsive, may not be sour for sulfonic acid, imido acid or the methylization being fluorinated at alpha-position for eliminating the acid of protecting group.Namely being used in the sulfonic acid that alpha-position is not fluorinated, in some situations, deprotection reaction also can occur. Owing to the salt of sulfonic acid in this case can not be used as quencher, it is preferred to be used alone the salt of imido acid.

Relative to the base resin of 100 weight parts, the suitable amount of basic cpd is 0.0001-30 weight part, it is preferable to 0.001-20 weight part.

The tensio-active agent illustrated is recorded in JP-A2008-111103, in paragraph [0165]-[0166]. The dissolution regulator illustrated is recorded in JP-A2008-122932 (US2008090172), and in paragraph [0155]-[0178], the acetylene alcohol of illustration is recorded in paragraph [0179]-[0182]. Depend on their adding purpose, it is possible to use tensio-active agent, dissolution regulator and acetylene alcohol with arbitrary suitable amount.

In order to the water repellency on the surface improving the resist film of rotary coating, it is possible to add polymeric additive. Water repellency improving agent can be used in without finishing coat immersion lithography process. Water repellency improving agent has the ad hoc structure with the fluoro-2-propyl alcohol residue of 1,1,1,3,3,3-six and is recorded in JP-A2007-297590 and JP-A2008-111103. Adding the water repellency improving agent in resist composition to should be solvable in as the organic solvent of photographic developer. Photographic developer can be dissolved in well with the water repellency improving agent of the ad hoc structure of the fluoro-2-propyl alcohol residue of 1,1,1,3,3,3-six. The polymkeric substance with the amine salt as repeating unit copolymerization or amino can be used as water repellency additive and bad for any sectional hole patterns opening after preventing the evaporation of acid in PEB process and avoiding development be effective. Relative to the base resin of 100 weight parts, the suitable amount of water repellency improving agent is 0.1-20 weight part, it is preferable to 0.5-10 weight part.

Pattern forming method

Another embodiment is pattern forming method, and it comprises the steps:, on resist composition paint base material, prebake is to form resist film; This resist film is exposed to high-energy irradiation, this film is cured; By this through exposure resist film develop to form negative resist pattern in organic solvent system photographic developer; To shrink on this negative resist pattern of material paint, cure; With with organic solvent, excessive contraction material is removed.

With reference to Fig. 1 (A)-Fig. 1 (F), the pattern shrinkage method of the present invention is described. First, as shown in Fig. 1 (A), by the processibility base material 20 on chemical amplification positive resist composition paint base material 10 to form resist film 30 thereon. If needed, hard mask layer (not shown) can between resist film 30 and processibility base material 20. By the technology of standard, resist film 30 is exposed (Fig. 1 (B)), PEB and organic solvent and develops to form negative resist pattern 30a (Fig. 1 (C)). To shrink with by pattern covers on material 40 paint negative resist pattern 30a, as shown in Fig. 1 (D). Being cured by contraction material coating, heat plays a role to remove solvent evaporation and acid is diffused into from resist pattern 30a and shrinks material coating 40 in this process. Under the action of an acid, the experience deprotection reaction of the polymkeric substance in material coating is shunk. Then, apply solvent to be removed by excessive contraction material 40, contraction material film is remained on resist pattern 30a. This means to make resist pattern 30a become thick, that is, make the shrinkage in width in the gap in resist pattern, as shown in Fig. 1 (E).Use the pattern shunk as mask, processibility base material 20 is carried out dry etching, as shown in Fig. 1 (F).

Base material 10 used herein is generally silicon substrate. Processibility base material (or target film) 20 used herein comprises SiO₂, SiN, SiON, SiOC, p-Si, α-Si, TiN, WSi, BPSG, SOG, Cr, CrO, CrON, MoSi, low dielectric film, and etching stop film. Hard mask can be SiO₂, SiN, SiON or p-Si. Sometimes, hard mask can be replaced and carbon film or the undercoat of the form containing film in the middle of silicon are set, and organic antireflection coatings can be inserted between hard mask and resist film.

As mentioned above directly or via the processibility base material (20) of interposer on base material (10) upper form chemical amplification positive resist composition resist film (30) time, resist film preferably has the thickness of 10-1,000nm and more preferably 20-500nm. Before exposure, it is preferable that by resist film heating or prebake 10-300 second at the temperature of 50-180 DEG C, particularly by resist film heating or prebake 15-200 second at the temperature of 60-150 DEG C.

Next, resist film is exposed to high-energy irradiation or the EB of below wavelength 400nm. High-energy irradiation typically is the EUV of the i line of wavelength 364nm, the KrF excimer laser of wavelength 248nm, the ArF excimer laser of wavelength 193nm or wavelength 13.5nm. Most preferably ArF193-nm photolithography. Can carry out exposing in dry atmosphere such as air or nitrogen gas stream or by water in immersion lithography process expose. ArF immersion lithography process use deionized water or have at least 1 specific refractory power and to the liquid such as alkane of exposure wavelength highly transparent as submergence solvent. In immersion lithography process, by projecting lens, the resist film of prebake is exposed, between resist film and projecting lens, introduce pure water or other liquid. Owing to this can make lens be designed to the NA of 1.0 or higher, relatively fine-feature size pattern therefore can be formed. Immersion lithography process is important in reach meticulousr node for ArF photolithography. When immersion lithography process; deionized water rinsing (or afterwards soak) can be carried out after exposure to remove the water droplet remaining on resist film, or can protective membrane be applied on resist film after prebake to prevent from any leaching of resist film and the water sliding improving film surface. The resist-protecting membrane used in immersion lithography process is preferably by soluble in water but solvable in alkaline developer have 1; 1; 1; 3; the solution of the polymkeric substance of the fluoro-2-propyl alcohol residue of 3,3-six in the solvent being selected from the alcohol of 4-10 carbon atom, the ether of 8-12 carbon atom and their mixture is formed. After forming resist film, deionized water rinsing (or soaking afterwards) can be carried out to be extracted or eccysis particle from film surface by acidogenic agent etc., or after exposure, can carry out rinsing (or soaking afterwards) and remove with the water droplet that will remain on resist film.

Preferably with about 1-200mJ/cm², more preferably about 10-100mJ/cm²Exposure dose expose. Then at 50-150 DEG C, on hot plate, (PEB) is cured 30 seconds-5 minutes, it is preferable that at 60-120 DEG C, cure 30 seconds-3 minutes.

Then adopt any routine techniques such as to flood, revolve and cover submergence (puddle) and the spraying technique photographic developer being made up of organic solvent the resist film through exposure is carried out development 0.1-3 minute, preferably 0.5-2 minute. by this way, base material forms negative resist pattern. organic solvent as photographic developer is preferably selected from methyln-hexyl ketone, methyl n-heptyl ketone, 2-heptanone, 3-heptanone, dipropyl ketone, methyl-n-butyl ketone, the own ketone of 3-, diisobutyl ketone, methylcyclohexanone, methyl phenyl ketone, methyl acetophenone, propyl acetate, N-BUTYL ACETATE, isobutyl acetate, amyl acetate-n, acetic acid butene esters, isoamyl acetate, propyl formate, butyl formate, tetryl formate, pentyl formate, isoamyl formate, methyl valerate, amylene-4 acid methyl ester, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, 3-ethoxyl ethyl propionate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, 2-hydroxy-methyl isobutyl acid, 2-ethyl butyrate of hydroxyl iso, methyl benzoate, ethyl benzoate, phenyl acetate, Benzyl Acetate, phenyl ritalin, benzyl formate, formic acid phenyl chlorocarbonate, 3-phenylpropionic acid methyl esters, benzyl propionate, phenyl vinyl acetic monomer, with acetic acid 2-phenyl chlorocarbonate, and their mixture.

At the end of development, resist film can be rinsed. as washing fluid, it is preferable that miscible and do not dissolve the solvent of resist film with photographic developer. the solvent being applicable to comprises the alcohol of 3-10 carbon atom, the ether compound of 8-12 carbon atom, the alkane of 6-12 carbon atom, alkene and alkynes, and aromatic solvent. especially, the alcohol of 3-10 the carbon atom being applicable to comprises n-propyl alcohol, Virahol, n-butyl alcohol, 2-butanols, isopropylcarbinol, the trimethyl carbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, tertiary amyl alcohol, neopentyl alcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 3-methyl-3-amylalcohol, cyclopentanol, the own alcohol of 1-, the own alcohol of 2-, the own alcohol of 3-, 2, 3-dimethyl-2-butanols, 3, 3-dimethyl-n-butyl alcohol, 3, 3-dimethyl-2-butanols, 2-ethyl-n-butyl alcohol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 3-methyl-3-amylalcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 4-methyl-3-amylalcohol, hexalin, with 1-octanol. the alkane of 6-12 the carbon atom being applicable to comprises hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, hexanaphthene, methylcyclohexane, dimethyl cyclohexane, suberane, cyclooctane, and cyclononane. the alkene of 6-12 the carbon atom being applicable to comprises own alkene, heptene, octene, tetrahydrobenzene, tetrahydrotoluene, dimethyl tetrahydrobenzene, suberene, and cyclooctene. the alkynes of 6-12 the carbon atom being applicable to comprises own alkynes, heptyne, and octyne. the ether compound of 8-12 the carbon atom being applicable to comprises di-n-butyl ether, diisobutyl ether, two sec-butyl ether, two n-pentyl ethers, diisoamyl ether, di-secondary amyl ether, two tert-amyl ethers, and two positive hexyl ether. the aromatic solvent being applicable to comprises toluene, dimethylbenzene, ethylbenzene, isopropyl benzene, tert.-butylbenzene, and 1,3,5-Three methyl Benzene. these solvents can be used alone or as a mixture. apply after washing fluid, by Rotary drying with cure base material dry. but, it is not essential to rinse. apply it after photographic developer the step of base material Rotary drying then can be omitted rinse step as long as comprising.

After development, by the contraction material paint resist pattern of the present invention to form contraction material coating, it is preferable that there is the thickness of 1-150nm, more preferably 30-80nm. At the temperature of 40-180 DEG C, this contraction material coating is cured the 5-300 second. Cure for solvent evaporation is removed and induce acid to be diffused into from resist film and shrink the auxiliary eliminative reaction of material and acid material coating to produce alkene or crosslinked structure to bring out change in polarity shrinking, thus make this contraction material coating soluble in organic solvent.

Finally, excessive contraction material is removed, it is preferred to use organic solvent. the organic solvent that can be applicable to as used herein comprises propyl acetate, N-BUTYL ACETATE, isobutyl acetate, acetic acid butene esters, amyl acetate-n, isoamyl acetate, acetic acid 2-methyl fourth ester, capryl acetate, acetic acid 2-ethylhexyl, cyclohexyl acetate, methyl cyclohexanol acetate, propyl formate, butyl formate, tetryl formate, pentyl formate, isoamyl formate, hexyl formate, methyl valerate, Valeric acid ethylester, propyl valerate, valeric acid isopropyl ester, butyl valerate, isobutyl isovalerate, pentanoate, oil of apple, valeric acid isopentyl ester, Ethylisovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, the isovaleric acid tert-butyl ester, isoamyl isovalerate, 2 methyl valeric acid second ester, 2 methyl valeric acid fourth ester, methyl crotonate, ethyl crotonate, β-crotonic acid propyl ester, β-crotonic acid isopropyl ester, butyl crotonate, the β-crotonic acid tert-butyl ester, methyl propionate, ethyl propionate, amylene-4 acid methyl ester, pentenoic acid ethyl ester, pentenoic acid propyl ester, pentenoic acid isopropyl ester, amylene acid butyl ester, the pentenoic acid tert-butyl ester, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, 2-hydroxy-methyl isobutyl acid, 2-ethyl butyrate of hydroxyl iso, PIVALIC ACID CRUDE (25) second ester, PIVALIC ACID CRUDE (25) propyl ester, PIVALIC ACID CRUDE (25) isopropyl ester, PIVALIC ACID CRUDE (25) fourth ester, the PIVALIC ACID CRUDE (25) tert-butyl ester, butyl propionate, isobutyl propionate, the propionic acid tert-butyl ester, benzyl propionate, 3-ethoxyl ethyl propionate, ethyl hexanoate, pineapple aldehyde, propyl butyrate, butyl butyrate, isobutyl butyrate, butyric acid 3-methyl fourth ester, tert-butyl acetate, ethyl 2-methylbutyrate, 2-Methyl Butyric Acid isopropyl ester, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, Benzyl Acetate, phenyl ritalin, benzyl formate, formic acid phenyl chlorocarbonate, 3-phenylpropionic acid methyl esters, phenyl vinyl acetic monomer, acetic acid 2-phenyl chlorocarbonate, 2-heptanone, 3-heptanone, dipropyl ketone, methyl-n-butyl ketone, the own ketone of 3-, methyln-hexyl ketone, 3-octanone, 4-octanone, methyl n-heptyl ketone, 3-nonanone, 4-nonanone, butyl ketone, methylcyclohexanone, ethyl methyl phenyl ketone, methyl phenyl ketone, methyl acetophenone, ethyl methyl phenyl ketone, ethyl normal-butyl ketone, di-n-butyl ketone, diisobutyl ketone, n-butyl alcohol, 2-butanols, isopropylcarbinol, the trimethyl carbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, tertiary amyl alcohol, neopentyl alcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 3-methyl-3-amylalcohol, cyclopentanol, the own alcohol of 1-, the own alcohol of 2-, the own alcohol of 3-, 2, 3-dimethyl-2-butanols, 3, 3-dimethyl-n-butyl alcohol, 3, 3-dimethyl-2-butanols, 2, 2-diethyl-n-butyl alcohol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 3-methyl-3-amylalcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 4-methyl-3-amylalcohol, hexalin, with 1-octanol.

Can be identical with the organic solvent being used as photographic developer for shrinking the organic solvent of the stripping of material. This means to use identical organic solvent carry out the development of resist film and shrink the removing of material. Advantageously, it is necessary to nozzle be one.

When being applied over negative type style (negativetone) the resist pattern via organic solvent development formation, it may also be useful to the pattern forming method shrinking material successfully makes the hole of negative type style resist pattern and/or the size of slit reduce in a controlled manner.

Embodiment

Below by way of illustration but not by restriction provide embodiments of the invention. Abbreviation " pbw " is weight part. For whole polymkeric substance, determine Mw and Mn by GPC relative to polystyrene standards.

[1] synthesis of polymkeric substance

Synthesis example 1

The synthesis of polymkeric substance 1

In nitrogen atmosphere, by the dimethyl 2 of 4-(1-hydroxyl-1-cyclopropyl) vinylbenzene of the acenaphthylene of the 4-acetoxy-styrene of 37.43g, 5.85g, 21.72g, 7.08g, 2'-azo two (2 Methylpropionic acid ester) (V-601, WakoPureChemicalIndustries, Ltd.) and the methyl ethyl ketone as solvent of 60g load in 200-mL dropping liquid graduated cylinder to form monomer solution. 500-mL flask in nitrogen atmosphere loads the methyl ethyl ketone of 48g, it is heated at 80 DEG C. Under agitation, last 4 hours to be added drop-wise in this flask by this monomer solution. After being added dropwise to complete, this polymeric solution is stirred 18 hours continuously, at its temperature being remained on 80 DEG C simultaneously. By this polymeric solution cool to room temperature, now it is added dropwise in the hexane of 1,000g. By filtering the multipolymer of collecting precipitation and clean twice with the hexane of 200g. This multipolymer is dissolved in the mixture of the tetrahydrofuran (THF) of 126g and the methyl alcohol of 42g by the 1-L flask of nitrogen atmosphere, and the thanomin of 16.9g is added in this solution, it is stirred 3 hours at 60 DEG C. Under reduced pressure this reaction soln is concentrated. Enriched material is dissolved in the mixture of the vinyl acetic monomer of 300g and the water of 80g. This solution is transferred in separatory funnel, and the acetic acid of 8.5g is added to wherein, then carry out lock out operation. Lower floor is removed. In organic layer, add the water of 80g and the pyridine of 11.3g, then carry out lock out operation. Lower floor is removed. In organic layer, add the water of 80g, then carry out washing and lock out operation. Washing and lock out operation are repeated 5 times. Organic layer after separation is concentrated and is dissolved in the acetone of 140g, now this acetone soln is added drop-wise in the water of 2,500g. The throw out of crystallization is filtered, cleans with water, and inhale filter 2 hours. Filter cake is dissolved in the acetone of 150g again, now this acetone soln is added drop-wise in the water of 2,800g. The throw out of crystallization is filtered, washes with water and drying, obtain the white polymer of 45.0g. Pass through¹³C-NMR、¹This polymkeric substance is analyzed by H-NMR spectral method and GPC, and result is as follows.

Hydroxybenzene ethene: acenaphthylene: 4-(1-hydroxyl-1-cyclopropyl) vinylbenzene=60.0:10.0:30.0

Mw=4,000

Mw/Mn=1.66

Synthesis example 2-22 and compare synthesis example 1-3

The synthesis of polymkeric substance 2-22 and comparative polymers 1-3

Except the kind that changes monomer and amount, adopt and the polymkeric substance in identical program preparation table 1 in synthesis example 1. Table 1 illustrates the ratio (mol ratio) of the unit introduced in polymkeric substance. Table 2-5 illustrates the structure of repeating unit.

Table 1

Table 2

Table 3

Table 4

Table 5

Synthesis example 23,24

The synthesis of resist polymkeric substance 1 and water repellency polymkeric substance 1

By in tetrahydrofuran solvent by applicable combination of monomers, implement copolyreaction, crystallization from methyl alcohol, repeat with hexane clean, separation and dry, thus synthetic polymer.Obtain random copolymers, it is labeled as resist polymkeric substance 1 and water repellency polymkeric substance 1. Pass through¹Polymkeric substance is analyzed by H-NMR spectral method and GPC. With their analytical data, polymkeric substance is differentiated below.

Resist polymkeric substance 1

Mw=7,500

Mw/Mn=1.61

Water repellency polymkeric substance 1

Mw=7,800

Mw/Mn=1.55

[2] preparation of material is shunk

Embodiment 1-42 and comparative example 1-6

By polymkeric substance (polymkeric substance 1-22 or comparative polymers 1-3), salt, basic cpd and the solvent mixing that will synthesize above according to the formula of table 6 and 7, by having the aperture of 0.2 μmStrainer filters, thus prepares contraction material. Component shown in table 6 and 7 is below shown.

Table 6

Table 7

[3] preparation of resist composition

By the formula according to table 8, polymkeric substance (resist polymkeric substance 1), acidogenic agent, quencher and water repellency polymkeric substance are dissolved in solvent, add the tensio-active agent FC-4430 (3M) of 100ppm wherein, and filtered by the strainer in the aperture with 0.2 μm, thus prepare the resist composition of solution form. In table 8, PGMEA is propylene glycol monomethyl ether, and PAG1 is as follows.

Table 8

[4] ArF photolithography patterning experiment

On silicon chip, deposit to the thickness of 180nm by revolving painting type (spin-on) carbon film ODL-101 (Shin-EtsuChemicalCo., Ltd.) and revolve, by containing silicon, the thickness that the hard mask SHB-A940 of painting type deposits to 40nm thereon. At this base material for three layer process, by the resist composition rotary coating in table 8, at 100 DEG C, on hot plate, then cure 60 seconds to form the thick resist film of 90nm. Use ArF excimer laser immersion lithography process scanner NSR-610C (NikonCorp., NA1.30, σ 0.90/0.70, ring illumination), by 6% shadow tone phase shifting mask, resist film is exposed while changing exposure dose. After exposure, at 90 DEG C, resist film is cured (PEB) 60 seconds and revolve in n-butyl acetate and cover immersion and develop 30 seconds to form the sectional hole patterns with the hole dimension of 50nm and the spacing of 150nm.

Contraction material shown in table 6 and 7 is applied on the resist pattern after development with by this pattern covers. At temperature shown in table 9 and 10, contraction material coating is cured 60 seconds. Then revolve in 4-methyl-2-amylalcohol and cover immersion and develop 10 seconds to be removed by excessive contraction material. After development and after shrink process, all under CD-SEM (CG-4000 is manufactured by Hitachi, Ltd.), observe pattern to measure the size of spacing as the hole of 150nm. Show the result in table 9 and 10.

Table 9

Table 10

Although illustrating invention has been and illustrate in a typical implementation, but being not intended to limit in shown details, reason is to carry out various distortion and replacement when definitely not departing from the purport of the present invention. Like this, to those skilled in the art, only using conventional experimental technique just can obtain the further distortion of the present invention disclosed herein and equivalent formation, all such distortion and equivalent formation are all considered in the purport and scope defined by the following claims of the present invention.

By reference Japanese patent application No.2014-248080 and 2015-077690 is incorporated herein.

Although some preferred embodiments being illustrated, but it can be carried out many distortion and change according to above-mentioned instruction.Therefore it will be appreciated that the present invention can be implemented beyond concrete explanation when not departing from the scope of claims.

Claims (17)

1. shrinking material, comprise polymkeric substance and solvent, this solvent contains the anti-disappearance solvent of the resist pattern loss after not making development,

Described polymkeric substance comprises the repeating unit of at least one being selected from the unit with formula (1a) and (1b):

Wherein A is singly-bound or the C that can contain ether oxygen atom in the midway of chain₁-C₁₀Alkylidene group,

R¹For hydrogen, fluorine, methyl or trifluoromethyl,

R²Be hydrogen independently of one another, halogen, optional halogen substiuted, the C of straight chain, branching or ring-type₂-C₈Acyloxy, optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkyl, or optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkoxyl group,

L is hydrogen, straight chain, branching or ring-type, C that ether oxygen atom, carbonyl moieties or carbonyl oxygen based structures part can be contained in the midway of chain₁-C₁₀Monovalent aliphatic alkyl, or optional group that replace, that monovalence contains aromatic ring,

Z and carbon atom bonding are to form C₅-C₁₅Alicyclic group,

R^xAnd R^yIt is the C that can be replaced by hydroxyl or alkoxy moieties of hydrogen or straight chain, branching or ring-type independently of one another₁-C₁₅Alkyl, R^xAnd R^yAt least one be ring-type C₅-C₁₅Alkyl,

F is the integer of 1-3, and s is the integer of 0-2, and a equals (5+2s-f), and m is 0 or 1.

2. the contraction material of claim 1, wherein said polymkeric substance also comprises the repeating unit with formula (2):

Wherein B is singly-bound or the C that can contain ether oxygen atom in the midway of chain₁-C₁₀Alkylidene group,

R¹It is as defined above,

R³Be hydrogen independently of one another, halogen, optional halogen substiuted, straight chain, branching or ring-type, C₂-C₈Acyloxy, optional halogen substiuted, straight chain, branching or ring-type, C₁-C₆Alkyl, or optional halogen substiuted, straight chain, branching or ring-type, C₁-C₆Alkoxyl group,

G is the integer of 0-3, and t is the integer of 0-2, and b equals (5+2t-g), and n is 0 or 1.

3. the contraction material of claim 1, wherein said polymkeric substance also comprises the repeating unit with formula (3):

Wherein C is singly-bound or the C that can contain ether oxygen atom in the midway of chain₁-C₁₀Alkylidene group,

R¹It is as defined above,

R⁴Be hydrogen independently of one another, halogen, optional halogen substiuted, straight chain, branching or ring-type, C₂-C₈Acyloxy, optional halogen substiuted, straight chain, branching or ring-type, C₁-C₆Alkyl, or optional halogen substiuted, straight chain, branching or ring-type, C₁-C₆Alkoxyl group,

C that D is singly-bound or straight chain, branching or ring-type, ether oxygen atom, carbonyl moieties or carbonyl oxygen based structures part can be contained in the midway of chain₁-C₁₀(v+1) valency alkyl, wherein some or all hydrogen atoms of bond with carbon can replaced by fluorine,

Rf¹And Rf²It is the C containing at least one fluorine atom independently of one another₁-C₆Alkyl, Rf¹The carbon atom to combine with them can be bonded with D and form ring,

R be 0 or 1, h be the integer of 1-3, u is the integer of 0-2, and c equals (5+2u-h), and v is 1 or 2.

4. the contraction material of claim 1, wherein said polymkeric substance also comprises the repeating unit of at least one being selected from the unit with formula (4) and (5):

Wherein R⁵And R⁶Be hydrogen independently of one another, halogen, optional halogen substiuted, the C of straight chain, branching or ring-type₂-C₈Acyloxy, optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkyl, or optional halogen substiuted, the C of straight chain, branching or ring-type₁-C₆Alkoxyl group, i and j is the integer of 0-2 independently of one another, and d equals (6-i), and e equals (4-j).

5. the contraction material of claim 1, wherein said polymkeric substance also comprises the repeating unit of at least one being selected from the unit with formula (A)-(E):

Wherein R¹As defined above, X^AFor acid-unstable group, X^BAnd X^CIt is the C of singly-bound or straight chain or branching independently of one another₁-C₄Bivalent hydrocarbon radical, X^DFor straight chain, branching or ring-type, C₁-C₁₆Divalence to the aliphatic hydrocarbyl of pentavalent, wherein any composition-CH₂-can by-O-or-C (=O)-replacement, X^EFor acid-unstable group, Y^AFor there is the substituting group of lactone, sultone or structural carbonate, Z^AFor hydrogen, C₁-C₃₀Fluothane base or C₁-C₁₅Containing the substituting group of fluorinated alcohols, k^1AFor the integer of 1-3, and k^1BFor the integer of 1-4.

6. the contraction material of claim 1, wherein said polymkeric substance also comprises the repeating unit with formula (F):

Wherein R¹⁰¹For hydrogen or methyl, X is singly-bound ,-C (=O)-,-C (=O)-O-or-C (=O)-NH-, R¹⁰²For the C of Han You the ether of singly-bound or straight chain, branching or ring-type, ester, carbonyl moieties ,-N=or-S-₁-C₁₀Alkylidene group, or phenylene or naphthylidene, R¹⁰³And R¹⁰⁴It is the C of hydrogen, straight chain or branching independently of one another₁-C₄Alkyl, or acid-unstable group, or R¹⁰³And R¹⁰⁴Can being bonded the nitrogen-atoms to combine with them each other and form ring, this ring is optionally containing ehter bond, or R¹⁰³And R¹⁰⁴Any one can with R¹⁰²It is bonded the formation ring of the nitrogen-atoms to combine with them, and k^1CIt is 1 or 2.

7. the contraction material of claim 1, also comprises the salt with formula (9):

R¹¹-CO₂ ^-M⁺(9)

Wherein R¹¹For the C of straight chain, branching or ring-type₁-C₂₀Alkyl, the C of straight chain, branching or ring-type₂-C₂₀Alkene base or C₆-C₂₀Monovalence is containing the group of aromatic ring, wherein some or all hydrogen atoms of bond with carbon can be replaced by fluorine, the structure part containing lactonic ring, the structure part containing lactam nucleus or hydroxyl moiety, wherein ether structure part, ester structure part or carbonyl moieties can between C-Cs, and M⁺For sulfonium, iodine or ammonium cation.

8. the contraction material of claim 1, also comprises the salt with formula (10):

R¹²-SO₃ ^-M⁺(10)

Wherein R¹²For the C of Han You the Sauerstoffatom of straight chain, branching or ring-type₁-C₃₅Monovalent hydrocarbon, wherein some or all hydrogen atoms of bond with carbon can replaced by fluorine, and condition does not replaced by fluorine relative to the hydrogen atom of sulfonic acid and the carbon atom bonding of alpha-position, and M⁺For sulfonium, iodine or ammonium cation.

9. the contraction material of claim 1, also comprises at least one basic cpd being selected from by the following group formed: primary, secondary and tertiary aliphatic amine, mixed amine; aromatic amine; heterocyclic amine, has the nitrogenous compound of carboxyl, has the nitrogenous compound of alkylsulfonyl; there is the nitrogenous compound of hydroxyl; the nitrogenous compound with hydroxy phenyl, alcohol type nitrogenous compound, amide derivatives; imide derivative, and carbamate.

10. the contraction material of claim 1, wherein this anti-disappearance solvent is the alcoholic solvent of the ester solvent of 7-16 carbon atom, the ketone solvent of 8-16 carbon atom or 4-10 carbon atom.

The contraction material of 11. claims 10, wherein this this anti-disappearance solvent is be selected from least one solvent by the following group formed:

The ester solvent of 7-16 carbon atom, comprise amyl acetate-n, isoamyl acetate, acetic acid 2-methyl fourth ester, capryl acetate, acetic acid 2-ethylhexyl, cyclohexyl acetate, methyl cyclohexanol acetate, hexyl formate, Valeric acid ethylester, propyl valerate, valeric acid isopropyl ester, butyl valerate, isobutyl isovalerate, pentanoate, oil of apple, valeric acid isopentyl ester, Ethylisovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, the isovaleric acid tert-butyl ester, isoamyl isovalerate, 2 methyl valeric acid second ester, 2 methyl valeric acid fourth ester, PIVALIC ACID CRUDE (25) second ester, PIVALIC ACID CRUDE (25) propyl ester, PIVALIC ACID CRUDE (25) isopropyl ester, PIVALIC ACID CRUDE (25) fourth ester, the PIVALIC ACID CRUDE (25) tert-butyl ester, pentenoic acid ethyl ester, pentenoic acid propyl ester, pentenoic acid isopropyl ester, amylene acid butyl ester, the pentenoic acid tert-butyl ester, β-crotonic acid propyl ester, β-crotonic acid isopropyl ester, butyl crotonate, the β-crotonic acid tert-butyl ester, butyl propionate, isobutyl propionate, the propionic acid tert-butyl ester, benzyl propionate, ethyl hexanoate, pineapple aldehyde, propyl butyrate, butyl butyrate, isobutyl butyrate, butyric acid 3-methyl fourth ester, tert-butyl acetate, ethyl 2-methylbutyrate, 2-Methyl Butyric Acid isopropyl ester, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, Benzyl Acetate, phenyl ritalin, benzyl formate, formic acid phenyl chlorocarbonate, 3-phenylpropionic acid methyl esters, phenyl vinyl acetic monomer, with acetic acid 2-phenyl chlorocarbonate,

The ketone solvent of 8-16 carbon atom, comprises methyln-hexyl ketone, 3-octanone, 4-octanone, methyl n-heptyl ketone, 3-nonanone, 4-nonanone, butyl ketone, diisobutyl ketone, ethyl cyclohexanone, ethyl methyl phenyl ketone, ethyl normal-butyl ketone, di-n-butyl ketone, and diisobutyl ketone, and

The alcoholic solvent of 4-10 carbon atom, comprise n-butyl alcohol, 2-butanols, isopropylcarbinol, the trimethyl carbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, tertiary amyl alcohol, neopentyl alcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 3-methyl-3-amylalcohol, cyclopentanol, the own alcohol of 1-, the own alcohol of 2-, the own alcohol of 3-, 2, 3-dimethyl-2-butanols, 3, 3-dimethyl-n-butyl alcohol, 3, 3-dimethyl-2-butanols, 2, 2-diethyl-n-butyl alcohol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 3-methyl-3-amylalcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 4-methyl-3-amylalcohol, hexalin, with 1-octanol.

The contraction material of 12. claims 1, wherein said solvent contains this anti-disappearance solvent and other solvent,

This other solvent is selected from by the following group formed: methyln-hexyl ketone, methyl n-heptyl ketone, 2-heptanone, 3-heptanone, dipropyl ketone, methyl-n-butyl ketone, the own ketone of 3-, diisobutyl ketone, methylcyclohexanone, methyl phenyl ketone, methyl acetophenone, propyl acetate, N-BUTYL ACETATE, isobutyl acetate, amyl acetate-n, isoamyl acetate, acetic acid butene esters, propyl formate, butyl formate, tetryl formate, pentyl formate, isoamyl formate, methyl valerate, amylene-4 acid methyl ester, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, 3-ethoxyl ethyl propionate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, 2-hydroxy-methyl isobutyl acid, 2-ethyl butyrate of hydroxyl iso, methyl benzoate, ethyl benzoate, phenyl acetate, Benzyl Acetate, phenyl ritalin, benzyl formate, formic acid phenyl chlorocarbonate, 3-phenylpropionic acid methyl esters, benzyl propionate, phenyl vinyl acetic monomer, with acetic acid 2-phenyl chlorocarbonate.

13. pattern forming methods, comprise the steps:

Being applied on base material by resist composition, described resist composition comprises: comprise the base resin of repeating unit, acidogenic agent and the organic solvent with the carboxyl that acid-unstable group replaces,

Prebake to form resist film,

This resist film is exposed to high-energy irradiation,

This film is cured,

Develop to form negative resist pattern in organic solvent system photographic developer by the resist film of this exposure,

The contraction material of claim 1 is applied on this negative resist pattern,

Cure, and

With organic solvent, excessive contraction material is removed.

The pattern forming method of 14. claims 13, wherein the base resin in this resist composition comprises the repeating unit (a) with the carboxyl that acid-unstable group replaces represented by formula (11):

Wherein R²¹For hydrogen or methyl, R²²For acid-unstable group, Z is singly-bound or-C (=O)-O-R²³-, and R²³For the C of straight chain, branching or ring-type₁-C₁₀Alkylidene group, wherein ether or ester bond can between C-Cs, or naphthylidene.

The pattern forming method of 15. claims 13, wherein this photographic developer comprises at least one organic solvent being selected from by the following group formed: methyln-hexyl ketone, methyl n-heptyl ketone, 2-heptanone, 3-heptanone, dipropyl ketone, methyl-n-butyl ketone, the own ketone of 3-, diisobutyl ketone, methylcyclohexanone, methyl phenyl ketone, methyl acetophenone, propyl acetate, N-BUTYL ACETATE, isobutyl acetate, amyl acetate-n, isoamyl acetate, acetic acid butene esters, propyl formate, butyl formate, tetryl formate, pentyl formate, isoamyl formate, methyl valerate, amylene-4 acid methyl ester, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, 3-ethoxyl ethyl propionate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, 2-hydroxy-methyl isobutyl acid, 2-ethyl butyrate of hydroxyl iso, methyl benzoate, ethyl benzoate, phenyl acetate, Benzyl Acetate, phenyl ritalin, benzyl formate, formic acid phenyl chlorocarbonate, 3-phenylpropionic acid methyl esters, benzyl propionate, phenyl vinyl acetic monomer, with acetic acid 2-phenyl chlorocarbonate.

The pattern forming method of 16. claims 13, the step use wherein removing excessive contraction material is selected from by least one organic solvent in the following group formed: propyl acetate, N-BUTYL ACETATE, isobutyl acetate, acetic acid butene esters, amyl acetate-n, isoamyl acetate, acetic acid 2-methyl fourth ester, capryl acetate, acetic acid 2-ethylhexyl, cyclohexyl acetate, methyl cyclohexanol acetate, propyl formate, butyl formate, tetryl formate, pentyl formate, isoamyl formate, hexyl formate, methyl valerate, Valeric acid ethylester, propyl valerate, valeric acid isopropyl ester, butyl valerate, isobutyl isovalerate, pentanoate, oil of apple, valeric acid isopentyl ester, Ethylisovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, the isovaleric acid tert-butyl ester, isoamyl isovalerate, 2 methyl valeric acid second ester, 2 methyl valeric acid fourth ester, methyl crotonate, ethyl crotonate, β-crotonic acid propyl ester, β-crotonic acid isopropyl ester, butyl crotonate, the β-crotonic acid tert-butyl ester, methyl propionate, ethyl propionate, pentenoic acid ethyl ester, pentenoic acid propyl ester, pentenoic acid isopropyl ester, amylene acid butyl ester, the pentenoic acid tert-butyl ester, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, 2-hydroxy-methyl isobutyl acid, 2-ethyl butyrate of hydroxyl iso, PIVALIC ACID CRUDE (25) second ester, PIVALIC ACID CRUDE (25) propyl ester, PIVALIC ACID CRUDE (25) isopropyl ester, PIVALIC ACID CRUDE (25) fourth ester, the PIVALIC ACID CRUDE (25) tert-butyl ester, butyl propionate, isobutyl propionate, the propionic acid tert-butyl ester, benzyl propionate, 3-ethoxyl ethyl propionate, ethyl hexanoate, pineapple aldehyde, propyl butyrate, butyl butyrate, isobutyl butyrate, butyric acid 3-methyl fourth ester, tert-butyl acetate, ethyl 2-methylbutyrate, 2-Methyl Butyric Acid isopropyl ester, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl acetate, Benzyl Acetate, phenyl ritalin, benzyl formate, formic acid phenyl chlorocarbonate, 3-phenylpropionic acid methyl esters, phenyl vinyl acetic monomer, acetic acid 2-phenyl chlorocarbonate, 2-heptanone, 3-heptanone, dipropyl ketone, methyl-n-butyl ketone, the own ketone of 3-, methyln-hexyl ketone, 3-octanone, 4-octanone, methyl n-heptyl ketone, 3-nonanone, 4-nonanone, butyl ketone, methylcyclohexanone, ethyl cyclohexanone, methyl phenyl ketone, methyl acetophenone, ethyl methyl phenyl ketone, ethyl normal-butyl ketone, di-n-butyl ketone, diisobutyl ketone, n-butyl alcohol, 2-butanols, isopropylcarbinol, the trimethyl carbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, tertiary amyl alcohol, neopentyl alcohol, 2-methyl-1-butene alcohol, 3-methyl isophthalic acid-butanols, 3-methyl-3-amylalcohol, cyclopentanol, the own alcohol of 1-, the own alcohol of 2-, the own alcohol of 3-, 2, 3-dimethyl-2-butanols, 3, 3-dimethyl-n-butyl alcohol, 3, 3-dimethyl-2-butanols, 2, 2-diethyl-n-butyl alcohol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 3-methyl-3-amylalcohol, 4-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 4-methyl-3-amylalcohol, hexalin, with 1-octanol.

The pattern forming method of 17. claims 13, wherein this high-energy irradiation is the i line of wavelength 364nm, the KrF excimer laser of wavelength 248nm, the ArF excimer laser of wavelength 193nm, EUV or EB of wavelength 13.5nm.