CN103896773A - Novel acrylic monomer, polymer and resist composition comprising the polymer - Google Patents

Novel acrylic monomer, polymer and resist composition comprising the polymer Download PDF

Info

Publication number
CN103896773A
CN103896773A CN201310739412.2A CN201310739412A CN103896773A CN 103896773 A CN103896773 A CN 103896773A CN 201310739412 A CN201310739412 A CN 201310739412A CN 103896773 A CN103896773 A CN 103896773A
Authority
CN
China
Prior art keywords
chemical formula
group
carbon atoms
alkyl
resist
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201310739412.2A
Other languages
Chinese (zh)
Other versions
CN103896773B (en
Inventor
裵昌完
朱炫相
安浩益
申珍奉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aiskai New Material High Performance Co Ltd
Original Assignee
Korea Kumho Petrochemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Korea Kumho Petrochemical Co Ltd filed Critical Korea Kumho Petrochemical Co Ltd
Publication of CN103896773A publication Critical patent/CN103896773A/en
Application granted granted Critical
Publication of CN103896773B publication Critical patent/CN103896773B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/65—Halogen-containing esters of unsaturated acids
    • C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C07C57/04—Acrylic acid; Methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/78—Benzoic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/18—Esters containing halogen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/18—Esters containing halogen
    • C08F222/185—Esters containing halogen the ester chains containing seven or more carbon atoms

Abstract

The invention provides a chemical formula (1) acrylic monomer representation, containing repeat units derived from the acrylic monomer to resist additives and a polymer,and a resist composition comprising the polymer, . The acrylic monomer can be used as a resist monomer additive,when forming a resist pattern, before developing shows high hydrophobicity, water and resist to separate, and prevent as a resist composition materials of low molecular weight substances, hydrophilic additives was eluted into the water, and after developing into hydrophilic, in order to reduce the developing pattern defects: [chemical formula 1) (IMG file = 'DDA0000447576840000011.TIF' wi = '176' he = '256' /) in chemical formula (1), R represents a hydrogen atom or containing 1 to 8 carbon atoms in the alkyl; X represents a branched or cyclic alkyl, the branched or cyclic alkyl containing 3 to 30 carbon atoms, and contained by the chemical formula (2) indicates that the functional groups and at least one consists of the following The chemical formula (3) indicates that the functional groups: (2) the chemical formula (IMG file = 'DDA0000447576840000012.TIF' wi = '224' he = '96' /) (chemical formula (3) img file = 'DDA0000447576840000013.TIF' wi = '224' he = '96' /) in chemical formula (2) and (3), Y represents fluorine atom containing alkali labile group; Z represents fluorine free atoms of alkali labile groups so as to separate water, and prevent as a resist composition materials of lowmolecular weight substances, hydrophilic additives was eluted into the water, and after developing into hydrophilic,in order to reduce the developing pattern defects.

Description

Novel propylene acids monomer, polymkeric substance and the anti-corrosion agent composition that comprises this polymkeric substance
Technical field
The present invention relates to can be used as forming the novel propylene acids monomer of resist additive monomer, the polymkeric substance for resist additive that contains the repeating unit that is derived from described acrylic monomer, and the anti-corrosion agent composition that contains described polymkeric substance.
Background technology
Recently,, along with the height of large-scale integrated circuit (LSI) is integrated and accelerate, there is the miniaturization demand for photo-resist pattern.For the exposure light source using, mainly use g line (436nm) or the i line (365nm) etc. of mercury lamp in the time forming resist pattern.
But, along with substantially approach the increase of the resolving power that the limit causes because of exposure wavelength, propose to make the shorter method of exposure wavelength to be used as forming the means of even meticulousr photo-resist pattern.As its specific examples, use KrF excimer laser (248nm) or ArF excimer laser (both thering is shorter wavelength) etc. to replace i line (365nm).
Use ArF excimer laser to be characterised in that as ArF liquid immersion lithography (immersion lithography) method of light source, this technique is by carrying out water containing being immersed between projecting lens and wafer substrate.This method is utilized the specific refractory power of water at 193nm, even and if to use NA value be 1.0 or also can form pattern while being greater than 1.0 lens, the method is commonly referred to as liquid submersion exposure method (liquid immersion exposure method).But, due to resist film is directly contacted with pure water, the acid being produced by photo-acid agent (photoacid-generator), or add the amine compound in resist film to be very likely dissolved in water as quencher, the problem existing is thus can form because of the change of resist pattern form or the swelling pattern decomposition causing, and may there are various defect phenomenons, for example air blister defect or watermark defect.In addition, after scanning, remaining trace water droplet may infiltrate in resist film and cause defect.And in the case of not using the resist of top coat, owing to needing sweep velocity faster in the time exposing, therefore resist should have extremely strong hydrophobicity before development; But in order to reduce the generation of pattern defect, resist should have 50 DEG C or wetting ability lower than 50 DEG C after development.
Therefore,, in order to protect resist film to avoid the infringement of the medium of for example water, proposed to form the method for protective membrane or upper layer film between resist film and water.Such resist-protecting membrane requires to have following characteristic: this resist-protecting membrane can be formed on resist film in the situation that not mixing with resist film; thereby have sufficient light transmission for relevant wavelength is not hindered exposure simultaneously; in the time of liquid-immersed exposure, can form and keep stable film and can not be eluted in the medium of for example water, and protective membrane can easily be dissolved in the alkali lye as photographic developer in the time developing.
In addition, in other method, in the time preparing resist, mainly use so a kind of additive, this additive makes resist film before development, show higher hydrophobicity, but makes this resist film after development, demonstrate wetting ability by the alcohol radical being produced by release reaction.But, the alcohol radical generating rate of conventional resist additive is lower, and be difficult to make after developing the static contact angle on resist surface to there is enough wetting abilities (for example, referring to, the open No.2011-0084848 of Korean Patent No.0959841 (registration on May 18th, 2010) and korean patent application (on July 26th, 2011 is open)).
Summary of the invention
Technical problem
An object of the present invention is to provide a kind of novel propylene acids monomer, described acrylic monomer can be used as resist additive, this monomer is in the time forming resist pattern, before development, demonstrate high hydrophobicity, thus water and resist are separated, and prevent from being entered in water by wash-out as low molecular weight substance, the hydrophilic additive etc. of composition material in resist, and after development, be converted into wetting ability, thereby make this acrylic monomer can suppress pattern defect, and can form the meticulous resist pattern with excellent susceptibility and resolving power.
Another object of the present invention is to provide a kind of polymkeric substance for resist additive, and it contains the repeating unit that is derived from aforesaid propylene acids monomer.
A further object of the present invention is to provide a kind of anti-corrosion agent composition that contains above-mentioned polymkeric substance, and uses described anti-corrosion agent composition to form the method for resist pattern.
Technical scheme
To achieve these goals, according to an aspect of the present invention, provide a kind of acrylic monomer, it has the structure by chemical formula (1) represents below:
[Chemical formula 1]
Figure BDA0000447576820000031
Wherein, in chemical formula (1),
The alkyl that R represents hydrogen atom or contains 1 to 8 carbon atom;
X represents side chain or cyclic hydrocarbon group, and described alkyl contains 3 to 30 carbon atoms, and contains functional group and at least one functional group by chemical formula (3) expression below by chemical formula (2) represents below:
[Chemical formula 2]
Figure BDA0000447576820000032
[chemical formula 3]
Figure BDA0000447576820000033
Wherein, in chemical formula (2) and chemical formula (3),
Y represents the unstable group of the alkali that contains fluorine atom;
Z represents the not unstable group of alkali of contain fluorine atoms.
Preferably, the unstable group of alkali that contains fluorine atom described in can be selected from trifluoroacetyl group, pentafluoroethyl group carbonyl and seven fluoropropyl carbonyls; The unstable group of alkali of described not contain fluorine atoms can be selected from tribromo-acetyl base, phenylcarbonyl group, methoxycarbonyl and tertiary butyl carbonyl.
Preferably, the acrylic monomer of described chemical formula (1) can be to have by chemical formula (1a) or (1b) compound of the structure of expression below:
[Chemical formula 1 a]
Figure BDA0000447576820000034
[Chemical formula 1 b]
Figure BDA0000447576820000035
According to a further aspect in the invention, provide a kind of polymkeric substance for resist additive, it contains the repeating unit that is derived from aforesaid propylene acids monomer.
Described polymkeric substance can also contain the repeating unit by chemical formula (5) represents below:
[chemical formula 5]
Figure BDA0000447576820000041
Wherein, in chemical formula (5),
R 1represent hydrogen atom or the alkyl that contains 1 to 8 carbon atom;
R 2represent to be selected from hydrogen atom, any one in the alkyl that contains 1 to 10 carbon atom, the assorted alkyl that contains 1 to 10 carbon atom, the cycloalkyl that contains 3 to 30 carbon atoms, the Heterocyclylalkyl that contains 2 to 30 carbon atoms, the aryl that contains 6 to 30 carbon atoms, the heteroaryl that contains 5 to 30 carbon atoms and their combination.
Preferably, described polymkeric substance can be the polymkeric substance having by the structure that chemical formula (6) represents below:
[chemical formula 6]
Figure BDA0000447576820000042
Wherein, in chemical formula (6),
The alkyl that R represents hydrogen atom or contains 1 to 8 carbon atom;
X represents side chain or cyclic hydrocarbon group, and described alkyl contains 3 to 30 carbon atoms, and contains functional group and at least one functional group by chemical formula (3) expression below by chemical formula (2) represents below:
[Chemical formula 2]
Figure BDA0000447576820000043
[chemical formula 3]
Figure BDA0000447576820000044
(wherein,, in chemical formula (2) and chemical formula (3), Y represents the unstable group of the alkali that contains fluorine atom; Z represents the not unstable group of alkali of contain fluorine atoms);
R 11and R 12the alkyl that represents independently of one another hydrogen atom or contain 1 to 8 carbon atom;
R 21and R 22represent to be independently of one another selected from hydrogen atom, any one in the alkyl that contains 1 to 10 carbon atom, the assorted alkyl that contains 1 to 10 carbon atom, the cycloalkyl that contains 3 to 30 carbon atoms, the Heterocyclylalkyl that contains 2 to 30 carbon atoms, the aryl that contains 6 to 30 carbon atoms, the heteroaryl that contains 5 to 30 carbon atoms and their combination;
L, m and n represent respectively to show the number of the mol ratio of repeating unit in main chain, l+m+n=1 simultaneously, 0<l/ (l+m+n)≤0.99,0≤m/ (l+m+n)≤0.99,0<n/ (l+m+n)≤0.99.
Preferably, R 21for being selected from
Figure BDA0000447576820000051
in acid-unstable group, simultaneously Ra, Rb and Rc can be selected from the alkyl that contains 1 to 20 carbon atom, the cycloalkyl, (C that contains 3 to 30 carbon atoms independently of one another 1-C 10alkyl) cycloalkyl, hydroxyalkyl, the alkoxyl group, (C that contain 1 to 20 carbon atom 1-C 10alkoxyl group) alkyl, ethanoyl, ethanoyl alkyl, carboxyl, (C 1-C 10alkyl) carboxyl, (C 3-C 18cycloalkyl) carboxyl, the Heterocyclylalkyl that contains 3 to 30 carbon atoms and their combination, or adjacent group can be connected to each other and form saturated or undersaturated hydrocarbon ring or the heterocycle that contain 3 to 30 carbon atoms.Rd represents the alkyl that contains 1 to 10 carbon atom, and p represents 0 to 3 integer, and q represents 0 to 10 integer.
R 22represent
Figure BDA0000447576820000052
simultaneously Re and Rf can represent the alkyl that contains 1 to 10 carbon atom independently of one another, or can be connected to each other and form saturated hydrocarbon ring.R and s can represent 0 to 5 integer independently of one another.
More preferably, R 21be selected from the tertiary butyl, trimethyl silyl, hydroxyl-2-ethyl, 1-methoxy-propyl, 1-methoxyl group-1-methylethyl, 1-ethoxycarbonyl propyl, 1-oxyethyl group-1-methylethyl, 1-methoxyl group-1-ethyl, 1-oxyethyl group-1-ethyl, tert.-butoxy-2-ethyl, 1-isobutoxy-1-ethyl and chemical formula 7a to 7j below:
Figure BDA0000447576820000061
Wherein, in chemical formula 7a to 7j, R', R " and R " ' in the cycloalkyl silyl that is selected from independently of one another the alkyl that contains 1 to 10 carbon atom, the cycloalkyl that contains 3 to 10 carbon atoms, the alkyl silyl that contains 1 to 10 carbon atom and contains 3 to 18 carbon atoms; A and e are 0 to 15 integer independently of one another; B represents 0 to 11 integer; C and d represent 0 to 9 integer independently of one another; F represents 0 to 7 integer; G and i represent 0 to 6 integer independently of one another; 0≤c+d≤17; 0≤c+f≤15;
R 22can have by chemical formula (10a) or (10b) structure of expression below:
Figure BDA0000447576820000062
The weight-average molecular weight of described polymkeric substance is preferably 1,000g/mol to 20, and 000g/mol, described weight-average molecular weight is measured by gel permeation chromatography and is calculated with respect to polystyrene standards.
It is 1 to 3 that described polymkeric substance preferably makes its weight-average molecular weight and the ratio of number-average molecular weight.
Preferably, described polymkeric substance can be selected from and have by chemical formula (11a) below to the compound of (11p) represented structure:
Wherein, l, m and n make l+m+n=1,0<l/ (l+m+n)≤0.99,0<m/ (l+m+n)≤0.99,0<n/ (l+m+n)≤0.99.
According to a further aspect in the invention, provide a kind of anti-corrosion agent composition, it comprises above-mentioned for the polymkeric substance of resist additive, the matrix polymer for resist, raw sour agent and solvent.
With respect to the gross weight of described anti-corrosion agent composition, the ratio that comprises of the described polymkeric substance for resist additive can be 0.05 % by weight to 5 % by weight.
The sour agent of described life can be one or more compounds that are selected from by the compound that chemical formula (13) and (14) represent below:
[Chemical formula 1 3]
[Chemical formula 1 4]
Figure BDA0000447576820000092
Wherein, in chemical formula (13) and (14),
X 1, X 2, Y 1and Y 2represent to be independently of one another selected from hydrogen atom, any in the alkyl, allyl group, perfluoroalkyl, benzyl, the aryl that contains 6 to 30 carbon atoms and their combination that contain 1 to 10 carbon atom; X 1with X 2and Y 1with Y 2can be connected to each other respectively and form the saturated or unsaturated hydrocarbons ring that contains 3 to 30 carbon atoms;
X 3, X 4, X 5, Y 3, Y 4and Y 5represent to be independently of one another selected from hydrogen atom, any one in alkyl, the halogen radical that contains 1 to 30 carbon atom, the alkoxyl group that contains 1 to 30 carbon atom, the aryl that contains 6 to 30 carbon atoms, sulfo-phenoxy group, the thio alkoxy that contains 1 to 30 carbon atom, the alkoxy carbonyl methoxyl group that contains 1 to 20 carbon atom and their combination;
The Z of anionicsite represents OSO 2cF 3, OSO 2c 4f 9, OSO 2c 8f 17, N (CF 3) 2, N (C 2f 5) 2, N (C 4f 9) 2, C (CF 3) 3, C (C 2f 5) 3, C (C 4f 9) 3or the functional group being represented by chemical formula (15) below:
[Chemical formula 1 5]
Figure BDA0000447576820000093
Wherein, in chemical formula (15),
V 1and V 2represent independently of one another halogen atom;
W 1represent-(C=O)-or-(SO 2)-;
W 2represent the alkylidene group that contains 1 to 10 carbon atom;
W 3any one in the sub-Heterocyclylalkyl that represents to be selected from the cycloalkylidene that contains 3 to 30 carbon atoms, the arylidene that contains 6 to 30 carbon atoms and to contain 5 to 30 carbon atoms;
W 4represent to be selected from hydrogen atom, halogen radical, the alkyl that contains 1 to 10 carbon atom, the thiazolinyl that contains 2 to 20 carbon atoms, the alkoxyl group that contains 1 to 10 carbon atom, the haloalkyl, (C that contain 1 to 10 carbon atom 1-C 10alkyl) sulfenyl, the cycloalkyl that contains 3 to 30 carbon atoms, the aryl, (C that contain 6 to 30 carbon atoms 6-C 30aryl) oxygen base, (C 6-C 30aryl) any one in sulfenyl, the heterocyclic radical that contains 5 to 30 carbon atoms and their combination;
O represents 0 or 1 integer;
P represents 0 to 2 integer.
Described anti-corrosion agent composition can also comprise the additive being selected from alkali dissolution inhibitor, acid diffusion inhibitor, tensio-active agent and their mixture.
In accordance with a further aspect of the present invention, provide a kind of method that forms resist pattern, the method comprises: thus above-mentioned anti-corrosion agent composition is coated on to the step that forms resist film on substrate; Described resist film is heat-treated, then the step with predetermined pattern exposure by this resist film; And the step that the resist pattern after exposure is developed.
Described exposure process can carry out with the light source being selected from KrF excimer laser, ArF excimer laser, extreme ultraviolet laser, X ray and electron beam.
The details of other embodiment of the present invention comprise in the following detailed description.
Beneficial effect
The polymkeric substance for resist additive of being prepared by novel propylene acids monomer according to the present invention is in the time forming resist pattern, before development, demonstrate high hydrophobicity, thus water and resist are separated, and prevented from being entered in water by wash-out as low molecular weight substance, the hydrophilic additive etc. of composition material in resist; And after development, be converted into wetting ability, and the pattern defect reducing after developing occurs.In addition, the described polymkeric substance for resist additive can form the meticulous resist pattern with excellent susceptibility and resolving power.
Brief description of the drawings
Fig. 1 is the compound (1a) of preparation in displaying monomer synthetic example 1 13c-NMR (CDCl 3, 400MHz) and the schematic diagram of result;
Fig. 2 is the compound (1a) of preparation in displaying monomer synthetic example 1 1h-NMR (CDCl 3, 400MHz) and the schematic diagram of result.
Embodiment
Hereinafter, will describe embodiment of the present invention in detail.But these embodiment are only for illustrational object, and the present invention is not limited to these embodiment.The present invention will only be subject to the restriction of the scope in claim described below.
Unless otherwise specifically indicated, all compounds of mentioning in this manual or substituting group can be replacements or unsubstituted.Herein, term " replacement " refers to that hydrogen atom is selected from any one in halogen atom, hydroxyl, carboxyl, cyano group, nitro, amino, sulfenyl, methylthio group, alkoxyl group, itrile group, aldehyde radical, epoxy group(ing), ether, ester group, carbonyl, acetal radical, ketone group, alkyl, perfluoroalkyl, cycloalkyl, Heterocyclylalkyl, allyl group, benzyl, aryl, heteroaryl, their deriveding group and their combination and replaces.
In addition, unless otherwise stated, term as used herein " their combination " refers to that two or more substituting groups connect by singly-bound or linking group, or two or more substituting groups connect by condensation.
The invention is characterized in, comprise by use the additive that the monomer that contains fluorine atom and affect the unstable group of hydrophobic alkali (for example trifluoroacetyl group) and do not affect the unstable group of hydrophobic alkali is prepared convertible polarity, described additive is in the time forming resist pattern, before development, demonstrate high hydrophobicity, thus water and resist are separated, and prevented from being entered in water by wash-out as low molecular weight substance, the hydrophilic additive etc. of composition material in resist; And this additive is converted into wetting ability and reduces the pattern defect after developing after development.Particularly, the invention is characterized in, the alcohol radical producing after release reaction by generating two or more, the generation of defect in the time that development has strengthened afterwards wetting ability and develops further to reduce, thus can after development, form gratifying resist pattern.
Therefore, according to embodiment of the present invention, provide by the novel propylene acids monomer that chemical formula (1) represents below, it can be used as forming resist additive monomer:
[Chemical formula 1]
Figure BDA0000447576820000111
In chemical formula (1),
The alkyl that R represents hydrogen atom or contains 1 to 8 carbon atom, the alkyl that is preferably hydrogen atom or contains 1 to 4 carbon atom, more preferably hydrogen atom or methyl;
X represents side chain or cyclic hydrocarbon group, and described alkyl contains 3 to 30 carbon atoms, and contains functional group and at least one functional group by chemical formula (3) expression below by chemical formula (2) represents below; Be preferably and be selected from any one in following groups: the branched-chain alkyl that contains 3 to 20 carbon atoms, the monocyclic cycloalkyl that contains 3 to 14 carbon atoms, the bicyclic cycloalkyl that contains 8 to 18 carbon atoms, the tricyclic naphthenes base that contains 10 to 30 carbon atoms, the Fourth Ring cycloalkyl that contains 10 to 30 carbon atoms and their combination, described each group comprises by the functional group that chemical formula (2) represents below and at least one by chemical formula (3) represents below functional group; More preferably be selected from any one in following groups: sec.-propyl, cyclobutyl, cyclopentyl, cyclohexyl, ring octyl group, norborneol alkyl, adamantyl and their combination, described each group comprises by the functional group that chemical formula (2) represents below and at least one by chemical formula (3) represents below functional group:
[Chemical formula 2]
Figure BDA0000447576820000121
[chemical formula 3]
Figure BDA0000447576820000122
In chemical formula (2) and (3),
Y represents to affect the unstable group of the hydrophobic alkali that contains fluorine atom; particularly; Y can represent perfluoroalkyl carbonyl; for example trifluoroacetyl group, pentafluoroethyl group carbonyl or seven fluoropropyl carbonyls; while alkyl is in the case the alkyl that contains 1 to 10 carbon atom, is preferably the alkyl that contains 1 to 6 carbon atom.In these groups, trifluoroacetyl group is preferred.
Z represents the not unstable group of alkali of contain fluorine atoms, thereby makes this group not affect hydrophobicity and the only polarity conversion of impact development front and back.Particularly, Z can represent chloro alkyl-carbonyl, aryl carbonyl, alkoxy carbonyl or alkyl-carbonyl, for example tribromo-acetyl base, phenylcarbonyl group, methoxycarbonyl or tertiary butyl carbonyl, while alkyl is in the case the alkyl that contains 1 to 10 carbon atom, is preferably the alkyl that contains 1 to 6 carbon atom; Described aryl is the aryl that contains 6 to 30 carbon atoms, is preferably the aryl that contains 6 to 18 carbon atoms; Described alkoxyl group is the alkoxyl group that contains 1 to 10 carbon atom, is preferably the alkoxyl group that contains 1 to 6 carbon atom.In these groups, tribromo-acetyl base or phenylcarbonyl group are preferred.
In molecule, can comprise the one in the unstable group of the aforementioned alkali that contains fluorine atom according to the acrylic monomer of chemical formula of the present invention (1), one or more in the unstable group of alkali that this acrylic monomer contains fluorine atom described in can comprising simultaneously, the group number comprising is preferably the number that can replace hydrogen atom in 1 to the X of functional group, and more preferably 1 to 10.The unstable group of the described alkali that contains fluorine atom is in the time forming resist pattern, before development, demonstrate high hydrophobicity, thereby make the unstable group of this alkali play the effect that water and resist are separated, and prevent from being entered in water by wash-out as low molecular weight substance, the hydrophilic additive etc. of composition material in resist.In addition, described in contain fluorine atom the unstable group of alkali after development, be converted into wetting ability, and after development, play and reduce the effect of pattern defect.On the other hand, the unstable group of the alkali of described not contain fluorine atoms does not affect hydrophobicity, but is converted into wetting ability after the release reaction being caused by photographic developer.Thus, acrylic monomer according to the present invention demonstrates the hydrophobicity of raising by comprise the unstable group of a kind of alkali that contains fluorine atom in molecule, and can generate by comprise two or more release reactions that can cause by photographic developer after development the unstable group of alkali of alcohol radical, after development, make wetting ability obtain and strengthen.Therefore, can form the meticulous resist pattern with excellent susceptibility and resolving power.
Preferably, described acrylic monomer can be to have by chemical formula (1a) or (1b) compound of the structure of expression below:
[Chemical formula 1 a]
Figure BDA0000447576820000131
[Chemical formula 1 b]
Figure BDA0000447576820000132
The acrylic monomer with the chemical formula (1) of for example said structure can be prepared by the following method: make the compound that represented by chemical formula (4) below successively with the starting compound of the unstable group of alkali that contains fluorine atom is provided and provides the not starting compound of the unstable group of alkali of contain fluorine atoms to react.
[chemical formula 4]
Figure BDA0000447576820000133
Wherein, in chemical formula (4),
The implication of R is identical with above-mentioned definition;
Xa represents side chain or cyclic hydrocarbon group, and described alkyl contains 3 to 30 carbon atoms and contains two or more hydroxyls; Be preferably and be selected from any one in following groups: the branched-chain alkyl that contains 3 to 20 carbon atoms, the monocyclic cycloalkyl that contains 3 to 14 carbon atoms, the bicyclic cycloalkyl that contains 8 to 18 carbon atoms, the tricyclic naphthenes base that contains 10 to 30 carbon atoms, the Fourth Ring cycloalkyl that contains 10 to 30 carbon atoms and their combination, described each group comprises two or more hydroxyls; More preferably be selected from any one in following groups: sec.-propyl, cyclobutyl, cyclopentyl, cyclohexyl, ring octyl group, norborneol alkyl, adamantyl and their combination, described each group comprises two or more hydroxyls.
More specifically, the acrylic monomer of chemical formula (1) can be prepared by the following method: under the existence of basic cpd, the compound that makes chemical formula (4) in solvent successively with the starting compound of the unstable group of alkali that contains fluorine atom can be provided and can provide the not starting compound of the unstable group of alkali of contain fluorine atoms to react, now, be not particularly limited for the order of reaction.In addition,, according to the number that is included in the unstable group of alkali in chemical formula (1), react and can repeat with each of starting compound.
The example of operable chemical formula (4) compound comprises: 2-methacrylic acid-3,5-dihydroxyl diamantane-1-base ester, 3-hydroxyl-2-methylol-2-methyl-propionyl ester and 2-(diamantane-1-base oxygen ylmethyl)-2-methylpropane-1,3-glycol.
For the raw material that the unstable group of alkali that contains fluorine atom can be provided, can use the acid anhydrides that comprises the unstable group of alkali that contains fluorine atom, the implication of the unstable group of alkali that contains fluorine atom described in is now identical with above-mentioned definition.Can provide the specific examples of the starting compound of the unstable group of alkali that contains fluorine atom to comprise trifluoroacetic anhydride, PFPA and heptafluorobutyric anhydride.In these starting compounds, can use separately one, or can be used in combination two or more.
In addition, for the not starting compound of the unstable group of alkali of contain fluorine atoms can be provided, can use acid anhydrides, muriate, carboxylate salt of the unstable group of alkali of each self-contained not contain fluorine atoms etc., the implication of the unstable group of alkali of contain fluorine atoms is not identical with above-mentioned definition described in now.Operable specific examples comprises Trichloroacetic anhydride, Benzoyl chloride, methyl-chloroformate, the tertiary butyl two carbonic ethers and di-tert-butyl dicarbonic acid ester.In these starting compounds, can use separately one, or can be used in combination two or more.
In addition, the example of operable basic cpd comprises pyridine, Dimethylamino pyridine (DMAP), triethylamine and diethyl isopropylamine.In these basic cpds, can use separately one, or can be used in combination two or more.
For described solvent, can use any solvent being selected from ester class, ethers, lactone, ketone, amides, alcohols and their combination; Preferably, can be used in combination and be selected from any one in following solvent: methylene dichloride, chloroform, ethylene dichloride, acetonitrile, toluene, dimethyl formamide, tetrahydrofuran (THF), dimethyl formamide, methyl-sulphoxide, acetone and their mixture.
The consumption of reaction reagent can be determined with stoichiometry.
Following reaction scheme 1 schematically shows the reaction mechanism that generates alcohol radical in the time processing according to acrylic monomer of the present invention with photographic developer.Reaction scheme 1 is below only presented for purposes of illustration, and the present invention is not intended to be confined to this.
[reaction scheme 1]
Figure BDA0000447576820000151
As shown in reaction scheme 1, the polymer application that comprises the repeating unit that is derived from the monomer with for example said structure, in anti-corrosion agent composition, and forming when pattern, is discharged to trifluoroacetyl group and tribromo-acetyl base by photographic developer, thereby generate alcohol radical.In the case, because polarity is changed into wetting ability from hydrophobicity, therefore can improve the photographic developer that uses in said process and the accessibility of eluent solution, result is to reduce the defect occurring in patterned appearance.Particularly, in described acrylic monomer, owing to whether existing regardless of fluorine atom, can take off the unstable group of all alkali by photographic developer, therefore the alcohol amount of generation can be increased to the twice of the alcohol amount that can obtain with the convertible additive of conventional polarity or more times, result is higher to hydrophilic transforming degree by hydrophobicity.Therefore, described acrylic monomer can be used as the convertible toughener of polarity.
In addition; for example, for example, when monomer according to the present invention contains an impact unstable group of hydrophobic alkali (trifluoroacetyl group) and one or more while not affecting the unstable group of hydrophobic alkali (tribromo-acetyl base), the polarity difference before and after developing can be increased to twice or more times.But, because the unstable group of the alkali that contains fluorine atom of polarity after impact development only has one, therefore can meet the performance requriements of lower polarity relatively.Result is not exist resist surface hydrophobicity may become the strong risk that also may produce defect.
According to another embodiment of the invention, provide a kind of polymkeric substance for resist additive (hereinafter, being called " for the additive of resist "), the repeating unit that it comprises the acrylic monomer that is derived from chemical formula (1).
The described additive for resist can also comprise the repeating unit by chemical formula (5) represents below:
[chemical formula 5]
Figure BDA0000447576820000161
Wherein, in chemical formula (5),
R 1represent hydrogen atom or the alkyl that contains 1 to 8 carbon atom;
R 2represent to be selected from hydrogen atom, any one in the alkyl that contains 1 to 10 carbon atom, the assorted alkyl that contains 1 to 10 carbon atom, the cycloalkyl that contains 3 to 30 carbon atoms, the Heterocyclylalkyl that contains 2 to 30 carbon atoms, the aryl that contains 6 to 30 carbon atoms, the heteroaryl that contains 5 to 30 carbon atoms and their combination.
Preferably, the described additive for resist can be the polymkeric substance by chemical formula (6) represents below:
[chemical formula 6]
Figure BDA0000447576820000162
Wherein, in chemical formula (6),
The definition of R and X is identical with above-mentioned definition respectively;
R 11and R 12the alkyl that represents independently of one another hydrogen atom or contain 1 to 4 carbon atom, is more preferably selected from any one in hydrogen atom, methyl and ethyl;
R 21and R 22represent to be independently of one another selected from hydrogen atom, any one in the alkyl that contains 1 to 10 carbon atom, the assorted alkyl that contains 1 to 10 carbon atom, the cycloalkyl that contains 3 to 30 carbon atoms, the Heterocyclylalkyl that contains 2 to 30 carbon atoms, the aryl that contains 6 to 30 carbon atoms, the heteroaryl that contains 5 to 30 carbon atoms and their combination;
L, m and n represent respectively to show the number of the mol ratio of repeating unit in main chain, l+m+n=1 simultaneously, 0<l/ (l+m+n)≤0.99,0≤m/ (l+m+n)≤0.99,0<n/ (l+m+n)≤0.99.
Preferably, the R in chemical formula (6) 21it can be acid-unstable group.Thus; in the time that the described additive for resist contains acid-unstable group; exposure area is converted into wetting ability by the deprotection reaction being caused by acid in the time exposing from hydrophobicity; result is that the additive for resist in exposure area can be developed agent and easily rinse out in the time developing.
Particularly, R 21expression is selected from
Figure BDA0000447576820000171
in acid-unstable group, simultaneously R', R " and R " ' expression is independently of one another selected from the alkyl that contains 1 to 20 carbon atom, the cycloalkyl, (C that contains 3 to 30 carbon atoms 1-C 10alkyl) cycloalkyl, hydroxyalkyl, the alkoxyl group, (C that contain 1 to 20 carbon atom 1-C 10alkoxyl group) alkyl, ethanoyl, ethanoyl alkyl, carboxyl, (C 1-C 10alkyl) carboxyl, (C 3-C 18cycloalkyl) any one in carboxyl, the Heterocyclylalkyl that contains 3 to 30 carbon atoms and their combination, or adjacent group can be connected to each other and form saturated or undersaturated hydrocarbon ring or the heterocycle that contain 3 to 30 carbon atoms.R " " represents the alkyl that contains 1 to 10 carbon atom; Z represents 0 to 3 integer; W represents 0 to 10 integer.
More preferably, R 21represent to be selected from the tertiary butyl, trimethyl silyl, hydroxyl-2-ethyl, 1-methoxy-propyl, 1-methoxyl group-1-methylethyl, 1-ethoxycarbonyl propyl, 1-oxyethyl group-1-methylethyl, 1-methoxyl group-1-ethyl, 1-oxyethyl group-1-ethyl, tert.-butoxy-2-ethyl, 1-isobutoxy-1-ethyl and by any one in the compound that chemical formula (7a) to (7j) represents below:
Figure BDA0000447576820000181
Wherein, R', R " and R " ' be selected from independently of one another in the alkyl that contains 1 to 10 carbon atom, the cycloalkyl, the hydroxyl that contain 3 to 10 carbon atoms, the alkyl silyl that contains 1 to 10 carbon atom, the cycloalkyl silyl that contains 3 to 18 carbon atoms and their combination; O and s represent 0 to 15 integer independently of one another; P represents 0 to 11 integer; Q and r represent 0 to 9 integer independently of one another; T represents 0 to 7 integer; U and v represent 0 to 6 integer independently of one another; 0≤q+r≤17; 0≤q+t≤15.
More preferably, R 21can select in the group that freely chemical formula (8a) to (8h) represents below:
Figure BDA0000447576820000182
Particularly, the repeating unit m that is derived from acrylate derivative in chemical formula (6) preferably has by any one the represented structure in chemical formula (9a) to (9d) below:
Figure BDA0000447576820000191
In addition, in chemical formula (6), R 22can be preferably lactone groups.
Thus, in the time that described polymkeric substance contains lactone groups, can be increased in the bounding force on wafer.
Particularly, R 22can represent (wherein, R' and R " alkyl that expression contains 1 to 10 carbon atom independently of one another, or can be connected to each other and form stable hydrocarbon ring; X and y represent 0 to 5 integer independently of one another), more preferably, R 22can represent by chemical formula (10a) below or (10b) represented group:
Typically, in order to improve resist film in the sweep velocity in when exposure, should obtain 90 ° or static contact angle (SCA) higher than 90 °; But, due to after exposure in the time developing higher SCA can cause blob defect (blob defect), therefore by making resist film surface there is lower SCA can to reduce blob defect after exposure in the time developing.Thus; additive for resist according to the present invention is by comprising the unstable group of hydrophobic base (as the situation of trifluoroacetyl group) with the structure being replaced by electron-withdrawing group on α carbon potential; can improve the hydrophobicity of resist film, thereby in the time carrying out liquid-immersed exposure, can prevent by resist film component wash-out out.
More specifically, in the polymkeric substance of chemical formula (6), be derived from the hydrophobicity on resist film surface can strengthen exposure by comprising the unstable group of hydrophobic base by the repeating unit l of the represented monomer of chemical formula (1) time, thus the leaching that can suppress to be caused by water in photoetching process.While development after exposure, remove hydrophobic group and change into alcohol radical by for example trimethylammonium hydroxide of alkaline developer (TMAH), thereby make repeating unit become wetting ability in nature, and can improve thus the photographic developer that uses and the accessibility of eluent solution in technological process.Result is to reduce the defect occurring in patterned appearance.
In addition, except the unstable group of hydrophobic base, described repeating unit l also comprises does not affect the unstable group of hydrophobic alkali, can be developed thereby have two kinds the functional group that agent removes.Therefore, the approximately twice that is the alcohol amount that can obtain with the convertible additive of conventional polarity by the alcohol amount of generation is therefore higher to hydrophilic transforming degree by hydrophobicity.
Because described repeating unit l comprises the unstable group of hydrophobic base and do not affect the unstable group of hydrophobic alkali simultaneously, and the hydrophobic property on resist surface has been carried out to suitable adjusting, therefore can prevent the generation by too high the caused defect of resist surface hydrophobicity.
In addition; in the polymkeric substance of chemical formula (6), the repeating unit m that is derived from acrylate derivative comprises acid-unstable group, and result is in the time of exposure; in exposure area, this repeating unit is converted into wetting ability by the deprotection reaction being caused by acid by hydrophobicity.Therefore in the time developing, in exposure area, be easy to by photographic developer, polymkeric substance be rinsed out.
In addition,, in the polymkeric substance of chemical formula (6), the repeating unit n that is derived from acrylate derivative can strengthen the bounding force on wafer by comprising lactone group.
In the polymkeric substance being represented by chemical formula (6), reference symbol l, m and n represent repeating unit content separately, also mean the replacement ratio that this polymkeric substance dissolves in photographic developer simultaneously.The amount that polymkeric substance according to the present invention comprises repeating unit l, m and n is meeting under the condition of relational expression l+m+n=1, meet respectively following relational expression: 0<l/ (l+m+n)≤0.99,0<m/ (l+m+n)≤0.99 and 0<n/ (l+m+n)≤0.99.In the time that described polymkeric substance comprises described repeating unit with aforementioned proportion, this polymkeric substance can demonstrate the hydrophobic performance less with the affinity of water in the time of liquid-immersed exposure, the ratio that is particularly derived from the repeating unit l of the monomer of chemical formula (1) when this polymkeric substance is contained is 70mol% or while being less than 70mol%, in the time developing, can reduce CA value, defect can be reduced, and uniform pattern can be in whole wafer surface, formed.
What have for example said structure can be segmented copolymer, random copolymers or graft copolymer according to the additive for resist of the present invention.
Comprise the compound having by the structure that chemical formula (11a) to (11p) represents below according to the specific examples of the additive for resist of the present invention, and the order of various repeating units can change in structural formula.
Figure BDA0000447576820000211
Wherein, l, m and n meet relational expression: l+m+n=1,0<l (l+m+n)≤0.99,0<m/ (l+m+n)≤0.99,0<n/ (l+m+n)≤0.99.
According to the weight-average molecular weight of the additive for resist of the present invention (hereinafter, be called " Mw ") can be 1,000g/mol to 20,000g/mol, described weight-average molecular weight is measured and is calculated with respect to polystyrene standards by gel permeation chromatography (GPC).If the weight-average molecular weight of polymkeric substance is too small, this polymkeric substance may cause mixing, and the in the situation that of liquid-immersed exposure, polymkeric substance wash-out may occur and enter in pure water.If weight-average molecular weight is excessive, is difficult to form suitable film, or may reduces alkali dissolution.Preferable weight-average molecular weight is 2,000g/mol to 10, and 000g/mol, because be not eluted to the risk in pure water, and polymkeric substance can demonstrate excellent solvability in photographic developer.
In addition, for the described additive for resist, its weight-average molecular weight with the ratio (Mw/Mn) of number-average molecular weight for making molecular weight distribution be preferably 1 to 5, more preferably 1 to 3.And if the molecular weight distribution of polymkeric substance is greater than 3, the roughness of line edge may be bad.Therefore, when in photo-corrosion-resisting agent composition, use weight-average molecular weight and molecular weight distribution in above-mentioned scope the additive for resist time, this photo-corrosion-resisting agent composition can developability, demonstrate suitable character aspect coating performance and thermotolerance.
There is can preparing by the following method according to the additive for resist of the present invention of for example said structure: adopt conventional polymerization process, for example mass polymerization, solution polymerization process, suspension polymerization, body suspension polymerization or emulsion polymerization, make chemical formula (1) acrylic monomer and selectable have by chemical formula (12) below represent that the acrylic monomer of structure carries out polymerization.
[Chemical formula 1 2]
Figure BDA0000447576820000231
Wherein, in chemical formula (12), R 1and R 2implication identical with above-mentioned definition respectively.
Preferably, can adopt radical polymerization to carry out polymerization according to the additive for resist of the present invention, in the case, be not particularly limited for radical polymerization initiator, for example, as long as it is used as conventional radical polymerization initiator, Diisopropyl azodicarboxylate (AIBN), benzoyl peroxide (BPO), lauroyl peroxide, azo two isocapronitriles, 2,2'-Azobis(2,4-dimethylvaleronitrile) or tert-butyl hydroperoxide.
In addition,, for polymer solvent, select and use one or more in benzene,toluene,xylene, halogeno-benzene, ether, tetrahydrofuran (THF), ester class, ethers, lactone, ketone, amides and alcohols.
Polymerization temperature while carrying out polyreaction carrys out suitably choice and operation according to the kind of catalyzer.In addition, the molecular weight distribution of the polymkeric substance of preparation can suitably regulate by the consumption and the reaction times that change polymerization starter like this.After polymerization finishes, preferably use solvent to remove any unreacted monomer and by product remaining in reaction mixture by the precipitator method.
According to another embodiment of the invention, provide a kind of anti-corrosion agent composition comprising for the additive of resist.
More specifically, except the described additive for resist, described anti-corrosion agent composition also comprises for the matrix polymer of resist, raw sour agent and solvent.
The described additive for resist is same as described above, and with respect to the gross weight of anti-corrosion agent composition, its content can be 0.01 % by weight to 5 % by weight, is preferably 0.05 % by weight to 1 % by weight.If the content of the described additive for resist is less than 0.05 % by weight, use the effect of this additive to ignore, and if the content of the described additive for resist is greater than 5 % by weight, CA value exceedes suitable value, and may produce watermark defect, this is not preferred.
Can use without any particular limitation for the matrix polymer of resist, as long as it is forming when resist film as matrix resin.Particularly, can use the one being selected from following polymkeric substance: (methyl) acrylic ester polymer, (α-trifluoromethyl) Acrylic Ester-Maleic Anhydride, cyclenes-copolymer-maleic anhydride, polynorbornene, by the available polymer compound of open loop replacement(metathesis)reaction of cyclenes, by to carrying out the available polymer compound of hydrogenation by cyclenes open loop replacement(metathesis)reaction resulting polymers, by making hydroxy styrenes and being selected from (methyl) acrylate derivative, vinylbenzene, vinyl naphthalene, vinyl anthracene, vinylpyrene, hydroxyl vinyl naphthalene, hydroxyl vinyl anthracene, indenes, hydroxyl indenes, any one in acenaphthylene and norbornadiene carries out copolymerization and the polymer compound that makes, resol, and their mixture.
With respect to the gross weight of anti-corrosion agent composition, the content of described matrix polymer can be 3 % by weight to 20 % by weight.If the content of described polymkeric substance is less than 3 % by weight, the viscosity of composition becomes too low, can not form the film of desired thickness, and existence causes pattern loss to become serious problem because photo-acid agent content is relatively high.If the content of this polymkeric substance is greater than 20 % by weight, the problem of existence is, the thickness of film becomes blocked up, and the radiation transmissibility of film is poor, and is difficult to make rectilinear pattern.
For the sour agent of described life, can use salt as salt compounded of iodine, sulfonium salt, phosphonium salt, diazonium salt and pyridinium salt, or the raw sour agent of acid imide is as photo-acid agent, preferably, can use freely one or more in the sulfonium salt of chemical formula (13) and (14) expression below of choosing.More preferably, can use perfluoro butyl sulfonic acid triphenyl sulfonium salt.
[Chemical formula 1 3]
Figure BDA0000447576820000241
[Chemical formula 1 4]
Figure BDA0000447576820000251
Wherein, in chemical formula (13) and (14),
X 1, X 2, Y 1and Y 2represent to be independently of one another selected from hydrogen atom, any one in alkyl, the allyl group that contains 1 to 10 carbon atom, the perfluoroalkyl, the benzyl that contain 1 to 10 carbon atom, the aryl that contains 6 to 30 carbon atoms and their combination; X 1with X 2and Y 1with Y 2can be connected to each other and form the saturated or unsaturated hydrocarbons ring that contains 3 to 30 carbon atoms;
X 3, X 4, X 5, Y 3, Y 4and Y 5represent to be independently of one another selected from hydrogen atom, any one in alkyl, the halogen radical that contains 1 to 30 carbon atom, the alkoxyl group that contains 1 to 30 carbon atom, the aryl that contains 6 to 30 carbon atoms, sulfo-phenoxy group, the thio alkoxy that contains 1 to 30 carbon atom, the alkoxy carbonyl methoxyl group that contains 1 to 20 carbon atom and their combination;
The Z of anionicsite represents OSO 2cF 3, OSO 2c 4f 9, OSO 2c 8f 17, N (CF 3) 2, N (C 2f 5) 2, N (C 4f 9) 2, C (CF 3) 3, C (C 2f 5) 3, C (C 4f 9) 3or the functional group being represented by chemical formula (15) below:
[Chemical formula 1 5]
Wherein, in chemical formula (15),
V 1and V 2represent independently of one another halogen atom;
W 1represent-(C=O)-or-(SO 2)-;
W 2represent the alkylidene group that contains 1 to 10 carbon atom;
W 3any one in the heterocyclic radical that represents to be selected from the cycloalkyl that contains 3 to 30 carbon atoms, the aryl that contains 6 to 30 carbon atoms, the aralkyl that contains 7 to 30 carbon atoms, the aryloxy that contains 6 to 30 carbon atoms, the arylthio that contains 6 to 30 carbon atoms and to contain 5 to 30 carbon atoms;
W 4represent to be selected from hydrogen atom, halogen atom, any one in the alkyl that contains 1 to 10 carbon atom, the alkoxyl group that contains 1 to 10 carbon atom, the haloalkyl that contains 1 to 10 carbon atom, the alkylthio that contains 1 to 10 carbon atom, the aryl that contains 6 to 30 carbon atoms and their combination;
O represents 0 or 1 integer;
P represents 0 to 2 integer.
In the time that the sour agent of described life comprises cycloalkyl in negatively charged ion, make the diffusion length of acid in resist film keep suitably shorter, show higher transmissibility, therefore can make high-resolution resist.
Preferably, the anionicsite Z of chemical formula (15) can select in the functional group that freely chemical formula (16a) to (16l) and chemical formula (17a) to (17x) represent below:
Figure BDA0000447576820000261
Figure BDA0000447576820000271
Figure BDA0000447576820000281
In addition, in chemical formula (13) and (14), the preferred embodiment of cationic moiety comprises the structure by chemical formula (18a) to (18p) represents below:
Figure BDA0000447576820000291
The sour agent of all lifes described above can be used separately, or uses with the mixture of two or more.In addition, with respect to the solids content of 100 parts by weight polymer, the content of the sour agent of described life can be 0.3 weight part to 15 weight part, and can be 0.5 weight part to 10 weight part, more preferably 2 weight part to 10 weight parts.If the content of raw sour agent is greater than 15 weight parts, make the verticality of pattern occur significantly deteriorated, and if the content of raw sour agent is less than 0.3 weight part, there is the flexible risk reducing that may make pattern.
In order to make even and smooth resist film, preferably above-mentioned polymkeric substance is dissolved in the solvent with suitable vaporator rate and proper viscosity and is used with raw sour agent.The example that can be used for the solvent in the present invention comprises: ethers, for example ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol ether; Ester class, for example methylcellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetic ester; And ketone, for example methyl isopropyl Ketone, pimelinketone, 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2-heptanone, ethyl lactate and gamma-butyrolactone.In these solvents, can use separately a kind of solvent, or can be used as mixture and use two or more solvents.
For described solvent, can be that volatility and viscosity etc. suitably regulate its consumption according to the character of solvent, thereby can form uniform resist film.
In addition, can also comprise according to anti-corrosion agent composition of the present invention the additive using for the object that improves coating performance etc.
For described additive, can use routine to be applied to any additive of anti-corrosion agent composition and without any particular limitation, its specific examples comprises alkali dissolution inhibitor, acid diffusion inhibitor and tensio-active agent.In these additives, can only comprise a kind of additive, or can comprise the mixture of two or more additives.
For described alkali dissolution inhibitor, can use routine to be applied to any alkali dissolution inhibitor of anti-corrosion agent composition, its specific examples comprises phenol and carboxylic acid derivative.
The effect of described acid diffusion inhibitor is in the time that the acid being generated by raw sour agent by illumination diffuses in resist film, diffusion phenomena to be controlled, and suppresses the chemical reaction in unexposed area.In the time using this acid diffusion inhibitor, storage stability that can enhanced rad sensitive resin composition, the resolving power of resist can be further improved, and the line width variation of the resist pattern being caused by the time fluctuation that is exposed to development treatment (PED) can be suppressed.
For this acid diffusion inhibitor, can use basic cpd, its specific examples comprises: aminated compounds, for example ammonia, methylamine, Isopropylamine, normal hexyl Amine, cyclopentamine, methylene diamine, ethylene diamine, dimethylamine, Diisopropylamine, diethylenediamine, N, N-dimethylated methylene base diamines, N, N-dimethyl ethylene diamine, Trimethylamine 99, triethylamine, N, N, N', N'-tetramethyl-methylene diamine, N, N, N', N'-tetramethylethylened, N, N, N', N'-tetramethyl-tetren, dimethyl amine, methylethyl propylamine, benzylamine, phenylethylamine, benzyldimethylamine, tetramethylammonium hydroxide, aniline, N, N-dimethyl methyl aniline, triphenylamine, phenylenediamine, pyrroles, oxazole, isoxazole, thiazole, isothiazole, imidazoles, pyrazoles, pyrroline, tetramethyleneimine, imidazolidine derivatives, imidazolidine derivative, pyridine derivate, pyridazine derivatives, pyrimidine derivatives, pyrazines derivatives, pyrazoline derivative, pyrazolidine derivatives, piperidine derivative, bridged piperazine derivatives and morpholine, nitrogenous compound, for example benzaminic acid, indolecarboxylic acid, amino acid derivative (for example nicotinic acid, L-Ala, arginine and aspartic acid), 3-pyridine-sulfonic acid, tosic acid pyridine, 2 hydroxy pyrimidine, amino cresols, 2,4-quinoline diol, 2-(2-hydroxyethyl) pyridine and 1-(2-hydroxyethyl) piperazine, amide derivatives, for example methane amide, N-METHYLFORMAMIDE, DMF, ethanamide, N-methylacetamide, N,N-dimethylacetamide, propionic acid amide and benzamide, and imide derivative, for example phthalic imidine, succinimide and maleimide.
With respect to the polymer solids content of 100 weight parts, the content of described acid diffusion inhibitor can be 0.01 weight part to 20 weight part, is preferably 0.1 weight part to 15 weight part.As the content of tartaric acid diffusion inhibitor is less than 0.01 weight part, the effect of acid diffusion inhibitor increases with the retention time after exposing, and has the risk that may affect pattern form.As the content of tartaric acid diffusion inhibitor is greater than 5 weight parts, exists and may make resolving power and the deteriorated risk of susceptibility.
Described tensio-active agent is used for improving coating performance and can developability etc., and its specific examples includes but not limited to polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene and polyethylene glycol dilaurate.
When use have for example above-mentioned composition form resist pattern according to anti-corrosion agent composition of the present invention time, the line width roughness that the resist pattern displaying forming goes out to improve, and C/H pattern and L/S pattern both demonstrate excellent resolving power.In addition, obtain excellent process window, thereby no matter which kind of substrate can make excellent patterned appearance with, and demonstrated the contrast gradient of improvement.Therefore, described anti-corrosion agent composition to radiation (for example: far-ultraviolet radiation is as KrF excimer laser, ArF excimer laser or F can be used as 2excimer laser; X-radiation is as synchrotron light; Or charged particle beam is as EUV) responsive eurymeric chemical amplification photo-corrosion-resisting agent composition.
According to another embodiment of the present invention, provide a kind of method that uses above-mentioned anti-corrosion agent composition to form pattern.
Particularly, the method for described formation pattern comprises: above-mentioned anti-corrosion agent composition is coated on substrate and forms the step of resist film; Described resist film is heat-treated, then the step with the exposure of predetermined pattern form by this resist film; And the step that the resist pattern after exposure is developed.
For described substrate, can use wafer substrate; And for the coating process to substrate, can adopt for example method of spin-coating method, flow coat method and rolling method.
Particularly, described anti-corrosion agent composition is applied on the substrate of for example silicon wafer to the film thickness of 0.3 μ m to 2.0 μ m, and it is tentatively cured 1 to 10 minute at 60 DEG C to 150 DEG C, preferably at 80 DEG C to 130 DEG C, tentatively cure 1 to 5 minute.
Subsequently, in order to form meticulous pattern, gained resist film is carried out to part irradiation with radiation.Now, be not particularly limited for available radiation, but can use ultraviolet radiation as I line; Far-ultraviolet radiation is as KrF excimer laser, ArF excimer laser, F 2excimer laser or X-radiation; Charged particle beam is as electron beam etc.Described radiation can be according to the kind of raw sour agent and choice and operation suitably.
Particularly, to make exposure be about 1mJ/cm to illumination radiation 2to 200mJ/cm 2, be preferably about 10mJ/cm 2to 100mJ/cm 2, then at 60 DEG C to 150 DEG C, resist film is carried out to post-exposure bake (PEB) 1 to 5 minute, preferably at 80 DEG C to 130 DEG C, carry out post-exposure bake 1 to 3 minute.
After exposure process, adopt standard method as pickling process, paddling process or gunite, use the resist pattern of photographic developer development through exposing 0.1 to 3 minute, preferably 0.5 to 2 minute, thus on substrate, form required pattern.For the photographic developer that can use in this case, can use the aqueous solution that contains sodium hydroxide, potassium hydroxide, sodium carbonate, water glass, Starso, ammonia, ethamine, Tri N-Propyl Amine, triethylamine, tetramethylammonium hydroxide or tetraethylammonium hydroxide.Preferably, can use tetramethylammonium hydroxide.
In addition, described photographic developer can selectively comprise the additive of for example tensio-active agent and water-soluble alcohol.
As discussed above, by using the method that forms pattern according to anti-corrosion agent composition of the present invention, can form the meticulous resist pattern with excellent susceptibility and resolving power.
Embodiment
Hereinafter, will describe embodiments of the invention in detail, and make those skilled in the art can easily implement the present invention.But the present invention can realize with various embodiment, and these embodiments are not limited to described embodiment herein.
[Preparation Example: monomer and polymkeric substance synthetic]
Monomer synthetic example 1
step 1
By 2-methacrylic acid-3 of 30g, the Trichloroacetic anhydride of 5-dihydroxyl diamantane-1-base ester (1) and 36.71g adds in the acetone of 150g, then mixture is stirred at normal temperatures.After definite reaction reagent dissolves completely, the pyridine of 9.39g is dropwise slowly added in the solution obtaining thus.After dropping finishes, the DMAP of 0.8g (DMAP) is added in mixture, then gained mixture is stirred 2 hours at normal temperatures.After definite reaction, the reaction product that the methylene dichloride of use 150g and 1.7% aqueous hydrochloric acid wash gained, then uses twice of distilled water wash.Isolate organic layer from gained reaction product, remove subsequently solvent, and obtain compound (2) by column chromatography.
step 2
The compound (2) of the trifluoroacetic anhydride of 24.96g and 47g preparation described above is incorporated in 150g acetone, then mixture is stirred at normal temperatures.After in definite reaction reagent has been dissolved in acetone completely, the pyridine of 9.39g is dropwise slowly added in the solution obtaining thus.After pyridine dropping finishes, the DMAP of 0.8g is added wherein, then mixture is stirred 2 hours at normal temperatures.After definite reaction, the reaction product that the methylene dichloride of use 150g and 1.7% aqueous hydrochloric acid wash gained, then uses twice of distilled water wash.Isolate organic layer from gained reaction product, remove subsequently solvent, and obtain compound (1a) by column chromatography.
Utilize 13c-NMR and 1h-NMR identifies the compound making thus.Result is presented in Fig. 1 and Fig. 2.
Monomer synthetic example 2
Figure BDA0000447576820000332
In the step 1 of monomer synthetic example 1, use when preparing compound (1a) Benzoyl chloride of 16.7g to replace the Trichloroacetic anhydride of 36.71g, adopt with above-mentioned monomer synthetic example 1 in the same procedure of step 1 make compound (3).And except the compound (3) making like this with 42g replaces the compound (2) of 47g, in employing and monomer synthetic example 1, the same procedure of step 2 makes compound (1b).
Polymkeric substance synthetic example 1
By 2-methacrylic acid-5-(2 of 10g, 2,2-tribromo-acetyl oxygen base)-3-(2,2,2-trifluoroacetyl oxygen base) diamantane-1-base ester, 2-methacrylic acid-1-methylcyclohexyl ester of 1g and 2-methacrylic acid-2-oxo-tetrahydrofuran-3-base ester of 15g be dissolved in 1 of 255g, in 4-dioxane, prepare solution, this solution is added in jacketed reactor together with the dimethyl Diisopropyl azodicarboxylate (DMAB) of initiator with 1g, then stir the mixture.Now, be 75 DEG C by the Temperature Setting of circulator, the temperature of reactor is slowly raise, then mixture is stirred 8 hours at 75 DEG C.After definite reaction, the reaction liquid making is like this added drop-wise in the normal hexane of 2.4L and the methyl alcohol of 1L to produce precipitation, then filtering precipitate vacuum-drying.Thus, make polymkeric substance (I).The weight-average molecular weight that this polymer phase calculates for polystyrene standards is 14,000g/mol, and the mol ratio of various repeating units (l:m:n) is 1:1:1.
Figure BDA0000447576820000341
Polymkeric substance synthetic example 2
Except using 1-(2-sec.-propyl diamantane-2-yl)-3-methyl fourth-3-alkene-2-ketone to replace the 2-methacrylic acid-1-methylcyclohexyl ester using in polymkeric substance synthetic example 1, and use 2-methacrylic acid-5-oxo-4-oxatricyclo [4.2.1.03,7] ninth of the ten Heavenly Stems-2-base ester replaces beyond 2-methacrylic acid-2-oxo-tetrahydrofuran-3-base ester, adopts with the same procedure of polymkeric substance synthetic example 1 and makes polymkeric substance (II).The weight-average molecular weight that this polymer phase calculates for polystyrene standards is 13,000g/mol, and the mol ratio of various repeating units (l:m:n) is 1:1:1.
Polymkeric substance synthetic example 3
By phenylformic acid-3-of 10g (2-methacryloxy)-5-(2,2,2-trifluoroacetyl oxygen base) diamantane-1-base ester, 2-methacrylic acid-1-isopropylcyclohexyl-ester of 2g and 2-methacrylic acid-2-oxo-tetrahydrofuran-3-base ester of 17g be dissolved in 1 of 270g, in 4-dioxane, prepare solution, this solution is added in jacketed reactor together with the dimethyl Diisopropyl azodicarboxylate (DMAB) of initiator with 1.2g, then stir the mixture.Now, be 75 DEG C by the Temperature Setting of circulator, the temperature of reactor is slowly raise, then mixture is stirred 7 hours at 75 DEG C.After definite reaction, the reaction liquid making is like this added drop-wise in the normal hexane of 2.5L and the methyl alcohol of 1L to produce precipitation, then filtering precipitate vacuum-drying.Thus, make polymkeric substance (III).The weight-average molecular weight that this polymer phase calculates for polystyrene standards is 9,500g/mol, and the mol ratio of various repeating units (l:m:n) is 1:1:1.
Polymkeric substance synthetic example 4
Except using 1-(2-sec.-propyl diamantane-2-yl)-3-methyl fourth-3-alkene-2-ketone to replace the 2-methacrylic acid-1-isopropylcyclohexyl-ester using in polymkeric substance synthetic example 3, and use 2-methacrylic acid-5-oxo-4-oxatricyclo [4.2.1.03,7] ninth of the ten Heavenly Stems-2-base ester replaces beyond 2-methacrylic acid-2-oxo-tetrahydrofuran-3-base ester, adopts with the same procedure of polymkeric substance synthetic example 3 and makes polymkeric substance (IV).The weight-average molecular weight that this polymer phase calculates for polystyrene standards is 10,000g/mol, and the mol ratio of various repeating units (l:m:n) is 1:1:1.
Figure BDA0000447576820000352
[test example 1: the hydrophobicity evaluation of additive]
By polymkeric substance (I) synthetic in 1.0g polymkeric substance synthetic example 1 and 3 with (III) be dissolved in the 4-methyl amyl alcohol of 20g, the polypropylene filter that is then 0.2 μ m by aperture filters each solution, prepares resist respectively.The resist of preparation is like this coated on silicon substrate by spin-coating method, then this resist is cured 60 seconds at 100 DEG C.Thus, form the resist film that film thickness is 50nm.
For the resist film of such formation, use surface static contact angle measurement to measure the forward and backward surface static contact angle that develops.More specifically, make to be formed with on it silicon substrate maintenance level of resist film, then 50 μ l pure water are added drop-wise on this silicon substrate, form drop.Subsequently, this silicon substrate that slowly tilts, the slide angle of silicon substrate when measurement water droplet starts to slide.And, the TMAH photographic developer of the silicon substrate 2.38wt% that is formed with resist film on it is developed 60 seconds, then measure the static contact angle after developing by the method identical with aforesaid method.
In addition, in order to compare, the compound being represented by chemical formula (19) below and (20) that use is conventionally used as resist additive, carries out identical experiment by aforesaid method, then measures the forward and backward surface static contact angle that develops.
[Chemical formula 1 9]
Wherein, the mol ratio l:m:n of various repeating units is 1:1:1.
[Chemical formula 2 0]
Wherein, the mol ratio l:m:n of various repeating units is 1:1:1.
The results are shown in following table 1.
[table 1]
Figure BDA0000447576820000371
Result by table 1 can be found out, with the Compound Phase ratio of chemical formula (19) that only comprises a unstable group of alkali, the compound of the compound of the chemical formula that comprises two unstable groups of alkali (20) and preparation in polymkeric substance synthetic example 1 and 2 has demonstrated larger change in polarity.But; for example, because the compound of chemical formula (20) comprises two unstable groups of the alkali that contains fluorine atom (trifluoroacetyl group) as the unstable group of alkali; and the trifluoroacetyl group unstable group that is alkali and contain fluorine atom; increase hydrophobic effect thereby play; therefore before developing, the hydrophobicity on resist surface is excessively strong, and result is easily to produce defect.Therefore, pattern profile may be subject to suitable adverse influence.On the contrary, owing to comprising and contain fluorine atom and affect the unstable group of hydrophobic alkali and do not affect the unstable group of hydrophobic alkali with 1:1 according to the compound (Compound I and III) of preparation in polymkeric substance synthetic example 1 and 2 according to the present invention, therefore its resist surface shows the hydrophobicity in par with the hydrophobicity of the convertible additive of conventional polarity (being the compound of chemical formula (19)).But owing to there are two unstable groups of alkali, the forward and backward polarity difference that therefore develops is increased to and approaches twice.
[test example 2: the performance measurement of the formation of resist film and thus made resist film]
(embodiment 1 to 4)
Resist polymkeric substance (Mw:8 by 5g by chemical formula (21) expression below, 500g/mol, Mw/Mn:1.75, the mol ratio (x:y:z:w) of various repeating units is 1:1:1:1), 0.5g synthetic each additive polymer, 0.31g in polymkeric substance synthetic example 1 to 4 be dissolved in as the tri-isopropanolamine of inhibitor in the propylene glycol monoethyl ether acetate (PGMEA) of 80g by chemical formula (22) represents below photo-acid agent and 0.07g, the polypropylene filter that is then 0.2 μ m by aperture filters each solution.Thus, make the composition that is used to form photoresist film.
[Chemical formula 2 1]
Figure BDA0000447576820000381
[Chemical formula 2 2]
Figure BDA0000447576820000382
On silicon substrate, form the antireflective coating that film thickness is 90nm (BARC), the composition coating that is used to form photoresist film of preparation is as mentioned above formed with on this substrate of antireflective coating thereon, then molectron is cured 60 seconds at 110 DEG C.Thus, form the photoresist film that film thickness is 120nm.
Subsequently, in order to carry out liquid-immersed exposure, by pure water drip washing 5 minutes for the film after exposure.That is, use the ArF scanner 306C (NA=0.78,6% intermediate tone mask) that manufactured by Nikon Corp. to expose to film, and with pure water drip washing 5 minutes.This film is carried out at 110 DEG C to PEB60 second, then develop 60 seconds with 2.38% TMAH photographic developer.
Observe the pattern forming thus, result confirms, formed to have excellent pattern-forming and without any the fine pattern of surface imperfection.
More than describe the preferred embodiments of the present invention in detail, but interest field of the present invention is not intended to be limited, and utilized as the basic thought of the present invention defined in claim and various amendments and the improvement made are also included within interest field of the present invention below by those of ordinary skill in the art.

Claims (17)

1. an acrylic monomer, it has the structure by chemical formula (1) represents below:
[Chemical formula 1]
Figure FDA0000447576810000011
Wherein, in chemical formula (1),
The alkyl that R represents hydrogen atom or contains 1 to 8 carbon atom;
X represents side chain or cyclic hydrocarbon group, and this side chain or cyclic hydrocarbon group contain 3 to 30 carbon atoms, and contains functional group and at least one functional group by chemical formula (3) expression below by chemical formula (2) represents below:
[Chemical formula 2]
Figure FDA0000447576810000012
[chemical formula 3]
OZ
Wherein, in chemical formula (2) and chemical formula (3),
Y represents the unstable group of the alkali that contains fluorine atom;
Z represents the not unstable group of alkali of contain fluorine atoms.
2. acrylic monomer according to claim 1, wherein,
The unstable group of the described alkali that contains fluorine atom is selected from trifluoroacetyl group, pentafluoroethyl group carbonyl and seven fluoropropyl carbonyls,
The unstable group of alkali of described not contain fluorine atoms is selected from tribromo-acetyl base, phenylcarbonyl group, methoxycarbonyl and tertiary butyl carbonyl.
3. acrylic monomer according to claim 1, wherein, the acrylic monomer of described chemical formula (1) is for having the compound by the structure that chemical formula (1a) or chemical formula (1b) represent below:
[Chemical formula 1 a]
[Chemical formula 1 b]
Figure FDA0000447576810000022
4. for a polymkeric substance for resist additive, it comprises the repeating unit that is derived from acrylic monomer according to claim 1.
5. the polymkeric substance for resist additive according to claim 4, wherein, this polymkeric substance also comprises the repeating unit by chemical formula (5) represents below:
[chemical formula 5]
Figure FDA0000447576810000023
Wherein, R 1represent hydrogen atom or the alkyl that contains 1 to 8 carbon atom;
R 2represent to be selected from hydrogen atom, any one in the alkyl that contains 1 to 10 carbon atom, the assorted alkyl that contains 1 to 10 carbon atom, the cycloalkyl that contains 3 to 30 carbon atoms, the Heterocyclylalkyl that contains 2 to 30 carbon atoms, the aryl that contains 6 to 30 carbon atoms, the heteroaryl that contains 5 to 30 carbon atoms and their combination.
6. the polymkeric substance for resist additive according to claim 4, wherein, this polymkeric substance has the structure by chemical formula (6) represents below:
[chemical formula 6]
Figure FDA0000447576810000024
Wherein, in chemical formula (6),
The alkyl that R represents hydrogen atom or contains 1 to 8 carbon atom;
X represents side chain or cyclic hydrocarbon group, and this side chain or cyclic hydrocarbon group contain 3 to 30 carbon atoms, and contains functional group and at least one functional group by chemical formula (3) expression below by chemical formula (2) represents below:
[Chemical formula 2]
[chemical formula 3]
Figure FDA0000447576810000032
Wherein, in chemical formula (2) and chemical formula (3), Y represents the unstable group of the alkali that contains fluorine atom; Z represents the not unstable group of alkali of contain fluorine atoms;
R 11and R 12the alkyl that represents independently of one another hydrogen atom or contain 1 to 8 carbon atom;
R 21and R 22represent to be independently of one another selected from hydrogen atom, any one in the alkyl that contains 1 to 10 carbon atom, the assorted alkyl that contains 1 to 10 carbon atom, the cycloalkyl that contains 3 to 30 carbon atoms, the Heterocyclylalkyl that contains 2 to 30 carbon atoms, the aryl that contains 6 to 30 carbon atoms, the heteroaryl that contains 5 to 30 carbon atoms and their combination;
L, m and n represent respectively to show the number of the mol ratio of repeating unit in main chain, l+m+n=1 simultaneously, 0<l/ (l+m+n)≤0.99,0≤m/ (l+m+n)≤0.99, and 0<n/ (l+m+n)≤0.99.
7. the polymkeric substance for resist additive according to claim 6, wherein,
R 21expression is selected from
Figure FDA0000447576810000033
in acid-unstable group, wherein Ra, Rb and Rc represent to be selected from the alkyl that contains 1 to 20 carbon atom, the cycloalkyl, (C that contains 3 to 30 carbon atoms independently of one another 1-C 10alkyl) cycloalkyl, hydroxyalkyl, the alkoxyl group, (C that contain 1 to 20 carbon atom 1-C 10alkoxyl group) alkyl, ethanoyl, ethanoyl alkyl, carboxyl, (C 1-C 10alkyl) carboxyl, (C 3-C 18cycloalkyl) any one in carboxyl, the Heterocyclylalkyl that contains 3 to 30 carbon atoms and their combination, or adjacent group can be connected to each other and form saturated or undersaturated hydrocarbon ring or the heterocycle that contain 3 to 30 carbon atoms; Rd represents the alkyl that contains 1 to 10 carbon atom; P represents 0 to 3 integer; Q represents 0 to 10 integer;
R 22represent
Figure FDA0000447576810000041
re and Rf represent the alkyl that contains 1 to 10 carbon atom independently of one another simultaneously, or can be connected to each other and form saturated hydrocarbon ring; R and s represent 0 to 5 integer independently of one another.
8. the polymkeric substance for resist additive according to claim 6, wherein,
R 21be selected from the tertiary butyl, trimethyl silyl, hydroxyl-2-ethyl, 1-methoxy-propyl, 1-methoxyl group-1-methylethyl, 1-ethoxycarbonyl propyl, 1-oxyethyl group-1-methylethyl, 1-methoxyl group-1-ethyl, 1-oxyethyl group-1-ethyl, tert.-butoxy-2-ethyl, 1-isobutoxy-1-ethyl and the group by chemical formula (7a) to (7j) expression below:
Figure FDA0000447576810000042
At chemical formula (7a) in (7j), R', R " and R " ' represent independently of one another any one in the cycloalkyl silyl that is selected from the alkyl that contains 1 to 10 carbon atom, the cycloalkyl that contains 3 to 10 carbon atoms, the alkyl silyl that contains 1 to 10 carbon atom and contains 3 to 18 carbon atoms; A and e represent 0 to 15 integer independently of one another; B represents 0 to 11 integer; C and d represent 0 to 9 integer independently of one another; F represents 0 to 7 integer; G and i represent 0 to 6 integer independently of one another; 0≤c+d≤17; 0≤c+f≤15;
R 22have by chemical formula (10a) or (10b) structure of expression below:
9. the polymkeric substance for resist additive according to claim 4, wherein, the weight-average molecular weight that this polymkeric substance is measured by gel permeation chromatography and calculated with respect to polystyrene standards is 1,000g/mol to 20,000g/mol.
10. the polymkeric substance for resist additive according to claim 4, wherein, the weight-average molecular weight of this polymkeric substance is 1 to 3 with the ratio of number-average molecular weight.
11. polymkeric substance for resist additive according to claim 4, wherein, this polymkeric substance is selected from the compound having by any one represented structure in chemical formula (11a) to (11p) below:
Figure FDA0000447576810000052
Figure FDA0000447576810000061
Wherein, l, m and n meet relational expression below: l+m+n=1,0<l/ (l+m+n)≤0.99,0≤m/ (l+m+n)≤0.99,0<n/ (l+m+n)≤0.99.
12. 1 kinds of anti-corrosion agent compositions, its comprise according to described in any one in claim 4 to 11 for the polymkeric substance of resist additive, for the matrix polymer of resist, raw sour agent and solvent.
13. anti-corrosion agent compositions according to claim 12, wherein, with respect to the gross weight of described anti-corrosion agent composition, the described polymkeric substance for resist additive that this anti-corrosion agent composition comprises 0.05 % by weight to 5 % by weight.
14. anti-corrosion agent compositions according to claim 12, wherein, the sour agent of described life is one or more compounds in the choosing compound that freely chemical formula (13) and chemical formula (14) represent below:
[Chemical formula 1 3]
[Chemical formula 1 4]
In chemical formula (13) and chemical formula (14),
X 1, X 2, Y 1and Y 2any one in alkyl, allyl group, perfluoroalkyl, benzyl, the aryl that contains 6 to 30 carbon atoms and their combination that represents to be independently of one another selected from hydrogen atom, to contain 1 to 10 carbon atom, X simultaneously 1with X 2and Y 1with Y 2can be connected to each other and form the saturated or unsaturated hydrocarbons ring that contains 3 to 30 carbon atoms;
X 3, X 4, X 5, Y 3, Y 4and Y 5represent to be independently of one another selected from hydrogen atom, any one in alkyl, the halogen radical that contains 1 to 30 carbon atom, the alkoxyl group that contains 1 to 30 carbon atom, the aryl that contains 6 to 30 carbon atoms, sulfo-phenoxy group, the thio alkoxy that contains 1 to 30 carbon atom, the alkoxy carbonyl methoxyl group that contains 1 to 20 carbon atom and their combination;
Anionicsite Z represents OSO 2cF 3, OSO 2c 4f 9, OSO 2c 8f 17, N (CF 3) 2, N (C 2f 5) 2, N (C 4f 9) 2, C (CF 3) 3, C (C 2f 5) 3, C (C 4f 9) 3or the functional group being represented by chemical formula (15) below:
[Chemical formula 1 5]
Figure FDA0000447576810000073
In chemical formula (15),
V 1and V 2represent independently of one another halogen atom;
W 1represent-(C=O)-or-(SO 2)-;
W 2represent the alkylidene group that contains 1 to 10 carbon atom;
W 3any one in the sub-Heterocyclylalkyl that represents to be selected from the cycloalkylidene that contains 3 to 30 carbon atoms, the arylidene that contains 6 to 30 carbon atoms and to contain 5 to 30 carbon atoms;
W 4represent to be selected from hydrogen atom, halogen radical, the alkyl that contains 1 to 10 carbon atom, the thiazolinyl that contains 2 to 20 carbon atoms, the alkoxyl group that contains 1 to 10 carbon atom, the haloalkyl, (C that contain 1 to 10 carbon atom 1-C 10alkyl) sulfenyl, the cycloalkyl that contains 3 to 30 carbon atoms, the aryl, (C that contain 6 to 30 carbon atoms 6-C 30aryl) oxygen base, (C 6-C 30aryl) any one in sulfenyl, the heterocyclic radical that contains 5 to 30 carbon atoms and their combination;
O represents 0 or 1 integer;
P represents 0 to 2 integer.
15. anti-corrosion agent compositions according to claim 12, wherein, this anti-corrosion agent composition also comprises the additive being selected from alkali dissolution inhibitor, acid diffusion inhibitor, tensio-active agent and their mixture.
16. 1 kinds form the method for resist pattern, and the method comprises:
Anti-corrosion agent composition according to claim 12 is coated on substrate and forms resist film;
Described resist film is heat-treated to the then pattern form exposure to be scheduled to by this resist film; With
Resist pattern after exposure is developed.
The method of 17. formation resist patterns according to claim 16, wherein, described exposure process carries out with the light source being selected from KrF excimer laser, ArF excimer laser, extreme ultraviolet laser, X ray and electron beam.
CN201310739412.2A 2012-12-26 2013-12-26 Acrylic monomer, polymer and the anti-corrosion agent composition comprising this polymer Active CN103896773B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2012-0153142 2012-12-26
KR1020120153142A KR101447497B1 (en) 2012-12-26 2012-12-26 Novel acryl monomer, polymer and resist composition comprising the same

Publications (2)

Publication Number Publication Date
CN103896773A true CN103896773A (en) 2014-07-02
CN103896773B CN103896773B (en) 2017-03-01

Family

ID=50988402

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310739412.2A Active CN103896773B (en) 2012-12-26 2013-12-26 Acrylic monomer, polymer and the anti-corrosion agent composition comprising this polymer

Country Status (4)

Country Link
KR (1) KR101447497B1 (en)
CN (1) CN103896773B (en)
SG (1) SG2013095823A (en)
TW (1) TWI519518B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6631536B2 (en) * 2014-12-02 2020-01-15 Jsr株式会社 Photoresist composition, method for producing the same, and method for forming resist pattern
KR102285438B1 (en) * 2018-11-27 2021-08-02 주식회사 엘지화학 Preparation method of acrylic acid ester compound
CN109942741A (en) * 2019-02-22 2019-06-28 江苏南大光电材料股份有限公司 A kind of preparation method of photoresist resin
KR102371579B1 (en) * 2019-05-09 2022-03-07 주식회사 엘지화학 Method for preparing (meth)acrylic acid ester based compound

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101684086A (en) * 2008-09-23 2010-03-31 锦湖石油化学株式会社 Onium salt compound, polymer compound comprising the salt compound, chemically amplified resist composition comprising the polymer compound, and method for patterning using the composition
CN102030643A (en) * 2009-10-06 2011-04-27 韩国锦湖石油化学株式会社 Acrylic monomer, polymer and chemically amplication photoresist composition
WO2011125684A1 (en) * 2010-03-31 2011-10-13 Jsr株式会社 Radiation-sensitive resin composition, resist pattern formation method, polymer and compound

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5449909B2 (en) * 2008-08-04 2014-03-19 東京応化工業株式会社 Positive resist composition and resist pattern forming method
JP5375811B2 (en) * 2010-01-18 2013-12-25 信越化学工業株式会社 Polymer compound, resist material, and pattern forming method
JP5763463B2 (en) * 2010-08-03 2015-08-12 住友化学株式会社 Resist composition and method for producing resist pattern

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101684086A (en) * 2008-09-23 2010-03-31 锦湖石油化学株式会社 Onium salt compound, polymer compound comprising the salt compound, chemically amplified resist composition comprising the polymer compound, and method for patterning using the composition
CN102030643A (en) * 2009-10-06 2011-04-27 韩国锦湖石油化学株式会社 Acrylic monomer, polymer and chemically amplication photoresist composition
WO2011125684A1 (en) * 2010-03-31 2011-10-13 Jsr株式会社 Radiation-sensitive resin composition, resist pattern formation method, polymer and compound

Also Published As

Publication number Publication date
CN103896773B (en) 2017-03-01
SG2013095823A (en) 2014-07-30
KR101447497B1 (en) 2014-10-06
TWI519518B (en) 2016-02-01
TW201434813A (en) 2014-09-16
KR20140083421A (en) 2014-07-04

Similar Documents

Publication Publication Date Title
CN101684086B (en) Onium salt compound, polymer compound comprising the salt compound, chemically amplified resist composition comprising the polymer compound, and method for patterning using the composition
CN103186044B (en) Additive for resist and resist composition comprising same
JP2008133312A (en) Polymer, resist composition and method for producing substrate formed with pattern
EP2461213A1 (en) Polymers, photoresist compositions and methods of forming photolithographic patterns
JP2012073612A (en) Photoresists comprising multi-amide component
JP2006077228A (en) Copolymer of secondary hydroxy group-bearing alkyl cyclic olefin and acrylic compound, and chemical amplification-type resist composition containing the copolymer
TWI675255B (en) Active light sensitive or radiation sensitive resin composition, pattern forming method, and method for manufacturing electronic device
US20130164674A1 (en) Novel acryl monomer, polymer and resist composition comprising same
KR100931924B1 (en) Copolymer for chemically amplified photoresist comprising a 5-hydroxy-1-adamantyl (meth) acrylate derivative and a chemically amplified photoresist composition comprising the same
CN103896773A (en) Novel acrylic monomer, polymer and resist composition comprising the polymer
CN103186043B (en) Additive for resist, resist composition comprising same,and method for forming resist pattern
TWI286670B (en) Positive resist composition and resist pattern formation method
CN103186042B (en) Resist additive and resist composition containing same
JP2001022073A (en) Resin for resist and chemical amplification type resist composition
CN103186041B (en) Resist additive and resist composition containing same
CN114262404B (en) Photosensitive resin and photoresist composition using the same
JP5456365B2 (en) Polymer, resist composition, and method for producing substrate having fine pattern formed
JP4968026B2 (en) Pattern formation method
JP2001022075A (en) Resin for resist, chemical amplification type resist composition and resist pattern forming method
KR100669038B1 (en) Polymer containing norbornene derivatives having lactonyl and secondary hydroxyl group as repeating unit, and chemically amplified resist composition containing it
KR100252062B1 (en) Polymer mixture for use in photoresist, photoresist composition having thereof and preparation method thereof
JP5696868B2 (en) A method for producing a copolymer for resist.
JP2013065011A (en) Photoresists comprising multi-amide component
JP7180199B2 (en) Polymers, resist compositions, and methods of making patterned substrates
JP5793825B2 (en) Lithographic polymer manufacturing method, resist composition manufacturing method, and substrate manufacturing method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20200806

Address after: Han Guoshizongshi

Patentee after: Aiskai new material high performance Co., Ltd

Address before: Han Guoshouer

Patentee before: Korea Kumho Petrochemical Co.,Ltd.

TR01 Transfer of patent right