CN102269931A - Photoproduced acid agent, preparation method thereof and resist composition containing photoproduced acid agent - Google Patents
Photoproduced acid agent, preparation method thereof and resist composition containing photoproduced acid agent Download PDFInfo
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- CN102269931A CN102269931A CN2011101399621A CN201110139962A CN102269931A CN 102269931 A CN102269931 A CN 102269931A CN 2011101399621 A CN2011101399621 A CN 2011101399621A CN 201110139962 A CN201110139962 A CN 201110139962A CN 102269931 A CN102269931 A CN 102269931A
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Abstract
The invention provides a photoproduced acid agent and a preparation method thereof, and a resist composition containing the photoproduced acid agent. The photoproduced acid agent is a compound represented by the following formula 1. [ formula 1 ] wherein, y represents any one of a alkyl group and a cycloalkyl group containing 3 to 30 carbon atoms, Q1 and Q2 independently represents a halogen atom; X represents any one of alkano nimoto and gadoleic dydrocarbon diyl group, NR', S, O, CO and combinations thereof; r'is selected from the group consisting of hydrogen atoms and alkyl groups; n represents an integer of 0 to 5; and A+ represents an organic counterion; The photoproduced acid agent is capable of generating an acid upon exposure. The acid has a low diffusion rate of an acid and a short diffusion distance, which display an appropriate degree of acidity, thereby making it possible to improve line width roughness (LWR) characteristics, and is also capable of controlling the sprocessing in a solvent such as purified water.
Description
Technical field
The resist composition that the present invention relates to photo-acid agent (photoacid generator), its preparation method and contain this photo-acid agent.More specifically, the present invention relates to can acidic photo-acid agent in when exposure, described acid has low rate of diffusion, the diffusion length of weak point and moderate acidity, thereby can improve line width roughness (LWR) characteristic, can also control that it is used such as the wash-out in the solvent of pure water in processing.The resist composition that the invention still further relates to the preparation method of this photo-acid agent and contain this photo-acid agent.
Background technology
Along with a generation generation is used the variation of photolithographic little disposal route, need more high-resolution photoresist, need at this, developed the chemical reinforcing type resist.This chemical reinforced slushing compound composition contains photo-acid agent.
Photo-acid agent in the chemical reinforced slushing compound composition is important composition, and it gives the character of chemical reinforced slushing compound with excellence with the resist composition at aspects such as resolution, LWR, sensitivity.Therefore, various types of photo-acid agents are studied, had the chemical reinforced slushing compound composition of suitable character with preparation.
Particularly, to having carried out modifying significantly and testing as the cationic moiety of photo-acid agent with those compounds of the rate of diffusion, transparency etc. of improving acid (this is some character that shows such as the characteristic of resolution, LWR and the sensitivity of excellence).Yet in present level, the research of character that is used for improving by the anionicsite of modifying photo-acid agent chemical reinforced slushing compound is still not enough.
Experimental data has been reported, for remarkable physics and the chemical property of improving the character of sour flowability and resist composition, anionicsite can apply bigger influence than cationic moiety, based on these experimental datas, finished the new invention relevant recently with the anionicsite of photo-acid agent.In addition, the photo-acid agent of rate of diffusion that reduces acid simultaneously for the penetrating power that can regulate acid has the demand that continues to increase.
In addition, the light source that is used for chemical reinforced slushing compound recently need be than the shorter wavelength of normally used g-line or i-line district, therefore, the photoetching process of using extreme ultraviolet irradiation, KrF excimer laser, ArF excimer laser, extreme ultraviolet (EUV) irradiation, X-ray and electron beam is studied.Particularly, owing to use pure water to carry out exposure process in immersion ArF method, so require that used photoresist composition has following feature in such immersion ArF method: contained photo-acid agent or the acid that is produced by this photo-acid agent are not eluted in the pure water in the photoresist composition.
Summary of the invention
The purpose of this invention is to provide can acidic photo-acid agent in when exposure, described acid has low rate of diffusion, the diffusion length of weak point and moderate acidity, thereby can improve line width roughness (LWR) characteristic, can also control that it is used such as the wash-out in the solvent of pure water in processing.
To achieve these goals, according to an embodiment of the invention, provide photo-acid agent by following formula 1 expression:
[formula 1]
In formula 1, Y represents to be selected from any in naphthenic base with 3 to 30 carbon atoms and the cycloalkenyl group with 3 to 30 carbon atoms; Q
1And Q
2Represent halogen atom independently of one another; X represents to be selected from any in alkane two bases, alkene two bases, NR ', S, O, CO and the combination thereof; R ' expression is selected from any in hydrogen atom and the alkyl; N represents 0 to 5 integer; And A+ represents organic gegenion.
According to another embodiment of the present invention, the preparation method of photo-acid agent is provided, it comprises first step, will be in solvent by the compound dissolution of following formula 8 expression, and make this solution and the compound of reductive agent reaction to obtain to represent by following formula 6; Second step makes the compound by following formula 7 expressions react in the presence of base catalyst to obtain the compound by following formula 4 expressions with the compound of being represented by following formula 6; And third step, make compound carry out substitution reaction, thereby obtain compound by following formula 1 expression with the compound of representing by following formula 5 by following formula 4 expressions.
[formula 8]
[formula 6]
[formula 7]
[formula 4]
[formula 5]
A+Z-
[formula 1]
In formula 1, formula 4, formula 5, formula 6, formula 7 and formula 8, R
6The expression alkyl, Q
1, Q
2And Q
5Represent halogen atom independently of one another; Y represents to be selected from any in naphthenic base with 3 to 30 carbon atoms and the cycloalkenyl group with 3 to 30 carbon atoms; X represents to be selected from any in alkane two bases, alkene two bases, NR ', S, O, CO and the combination thereof; In R ' expression hydrogen atom and the alkyl any; N represents 0 to 5 integer; And A+ represents organic gegenion.M+ represents to be selected from any among Li+, Na+ and the K+; And Z-represents to be selected from (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)
3)-, F-, Cl-, Br-, I-, BF
4-, AsF
6-and PF
6-in any.
According to another embodiment of the present invention, provide the chemical reinforced slushing compound composition that contains above-mentioned photo-acid agent (chemically amplified resist composition).
Below with more detailed description the present invention.
Term used in this instructions is defined as follows.
Unless specialize in addition in this article, halogen atom means and is selected from fluorine, chlorine, bromine and the iodine any.
Unless specialize in addition in this article, alkyl comprises primary alkyl, secondary alkyl and tertiary alkyl.
Unless specialize in addition in this article, alkane two bases are by two bivalent atom groups that hydrogen atom obtains of removal from alkane, and can be by general formula-C
nH
2n-expression.In addition, alkene two bases are by two bivalent atom groups that hydrogen atom obtains of removal from alkene, and can be by general formula-C
nH
n-expression.
Unless specialize in addition in this article, perfluoroalkyl means part hydrogen atom wherein or whole alkyl of being replaced by fluorine of hydrogen atom, and perfluoro alkoxy means part hydrogen atom wherein or whole alkoxys of being replaced by fluorine of hydrogen atom.
Unless specialize in addition in this article, all compounds and substituting group can be that replace or unsubstituted.Herein, be substituted and mean hydrogen atom and be selected from any replacement in halogen atom, hydroxyl, carboxyl, cyano group, nitro, amino, sulfydryl (thio group), methyl mercapto, alkoxy, itrile group, aldehyde radical, epoxy radicals, ether, ester group, carbonyl, acetyl group (acetal group), ketone group, alkyl, perfluoroalkyl, naphthenic base, Heterocyclylalkyl, allyl, benzyl, aryl, heteroaryl, its derivant and the combination thereof.
Unless specialize in addition in this article, prefix " is mixed " and is meant carbon atom and replaced by one to three heteroatoms that is selected from N, O, S and P.
Unless specialize in addition in this article, alkyl means the straight or branched alkyl with 1 to 10 carbon atom; Alkane two bases mean alkane two bases with 1 to 10 carbon atom; Alkene two bases mean alkene two bases with 2 to 10 carbon atoms; Thiazolinyl means the thiazolinyl with 2 to 10 carbon atoms; Alkoxy means the alkoxy with 1 to 10 carbon atom; Perfluoroalkyl means the perfluoroalkyl with 1 to 10 carbon atom; Perfluoro alkoxy means the perfluoro alkoxy with 1 to 10 carbon atom; Hydroxy alkyl means the hydroxy alkyl with 1 to 10 carbon atom; Naphthenic base means the naphthenic base with 3 to 32 carbon atoms; Heterocyclylalkyl means the Heterocyclylalkyl with 2 to 32 carbon atoms; Aryl means the aryl with 6 to 30 carbon atoms; And heteroaryl means the heteroaryl with 2 to 30 carbon atoms.
Me used herein is the abbreviation of methyl.
Photo-acid agent is according to the embodiment of the present invention represented by following formula 1:
[formula 1]
In following formula 1, Q
1And Q
2Represent halogen atom independently of one another, be preferably fluorine atom.
N is 0 to 5 integer, and is preferably 0 to 2 integer.
X represents to be selected from any of alkane two bases, alkene two bases, NR ', S, O, CO and combination thereof, and R ' expression is selected from hydrogen atom and the alkyl any.
X can represent to be selected from following any :-O-,-OCH
2-,-OCH (Cl)-,-CO-,-COCH
2-,-COCH
2CH
2-,-CH
2-,-CH
2CH
2-,-CH
2-O-,-CH
2-O-CH
2-,-CH
2CH
2-O-,-CH
2-O-CH
2CH
2-,-CH
2CH
2-O-CH
2-,-CH
2CH
2CH
2-O-,-CH
2-O-CH
2CH
2CH
2-,-CH
2CH
2-O-CH
2CH
2-,-CH
2CH
2CH
2-O-CH
2-,-CH (CH
3)-,-C (CH
3)
2CH
2-,-CH (CH
3) CH
2-,-CH (CH
2CH
3)-,-CH (OCH
3)-,-C (CF
3) (OCH
3)-,-CH
2-S-,-CH
2-S-CH
2-,-CH
2CH
2-S-,-CH
2-S-CH
2CH
2-,-CH
2CH
2-S-CH
2-,-CH
2CH
2CH
2-S-,-CH
2-S-CH
2CH
2CH
2-,-CH
2CH
2-S-CH
2CH
2-,-CH
2CH
2CH
2-S-CH
2-,-CH (CH
2) CH-,-C (CH
2CH
2)-,-CH
2CO-,-CH
2CH
2CO-,-CH (CH
3) CH
2CO-,-CH (OH)-,-C (OH) (CH
3)-,-CH (F)-,-CH (Br)-,-CH (Br) CH (Br)-,-CH=CH-,-CH
2CH=CH-,-CH=CHCH
2-,-CH=CH-O-,-CH=CH-S-and-CH=CHCO-.
In following formula 1, Y represents to be selected from any in naphthenic base with 3 to 30 carbon atoms and the cycloalkenyl group with 3 to 30 carbon atoms.
Y can represent to be selected from following any: adamantyl, norborny, contain the norborny with 10 to 30 carbon atoms the polycyclic naphthene base, have 3 to 14 carbon atoms monocyclic cycloalkyl, have 8 to 20 carbon atoms bicyclic cycloalkyl, have the tricyclic naphthenes base of 10 to 30 carbon atoms and have the Fourth Ring naphthenic base of 10 to 30 carbon atoms.
Any replacement among hydroxy alkyl, halogen atom, hydroxyl, cyano group, nitro, amino, sulfydryl, methyl mercapto, methoxyl, OR ', COR ' and the COOR ' that in the hydrogen atom of Y one to five can be selected from alkyl, the alkoxy with 1 to 6 carbon atom, the perfluoroalkyl with 1 to 4 carbon atom, the perfluoro alkoxy with 1 to 4 carbon atom with 1 to 6 carbon atom, have 1 to 6 carbon atom.R ' expression is selected from any in alkyl and the aryl.
Preferably, Y can represent to be selected from any among the following formula 1-a to 1-i.
[formula 1-a]
[formula 1-b]
[formula 1-c]
[formula 1-d]
[formula 1-e]
[formula 1-f]
[formula 1-g]
[formula 1-h]
[formula 1-i]
In formula 1-a to 1-i, R
11And R
12Can represent hydrogen atom, alkyl, alkoxy, perfluoroalkyl, perfluoro alkoxy, halogen atom, hydroxyl, carboxyl, cyano group, nitro, amino, sulfydryl, methyl mercapto, methoxyl, OR ', COR ' and COOR ' independently of one another.R ' expression is selected from any in alkyl and the aryl.
In the subscript that illustrates in the above, a, c and d represent 0 to 9 integer independently of one another; B represents 0 to 11 integer; E represents 0 to 15 integer; F represents 0 to 7 integer; And 0≤c+d≤17 and 0≤c+f≤15.
Preferably, in formula 1-a, 1-b, 1-d and 1-g, R
11Can represent to be selected from following any: hydrogen atom, have 1 to 6 carbon atom alkyl, have 1 to 6 carbon atom alkoxy, have 1 to 4 carbon atom perfluoroalkyl, have 1 to 4 carbon atom perfluoro alkoxy, have hydroxy alkyl, halogen atom, hydroxyl, cyano group, nitro, amino, sulfydryl, methyl mercapto and the methoxyl of 1 to 6 carbon atom.
In addition, in formula 1-c, 1-e, 1-f, 1-h and 1-i, R
11And R
12Can represent to be selected from following any independently of one another: hydrogen atom, have 1 to 6 carbon atom alkyl, have 1 to 6 carbon atom alkoxy, have 1 to 4 carbon atom perfluoroalkyl, have 1 to 4 carbon atom perfluoro alkoxy, have hydroxy alkyl, halogen atom, hydroxyl, cyano group, nitro, amino, sulfydryl, methyl mercapto, methoxyl and the combination thereof of 1 to 6 carbon atom.
Preferably, by the part of following formula 3 expression, i.e. the anionicsite of the compound of formula 1 expression shown in above can represent to be selected among the following formula 1-i to 1-xx any.
[formula 3]
[formula 1-i to 1-xx]
Compound (being the anionicsite of the compound of formula 1 expression) the introducing alicyclic ring of representing by upper quadrant 3 obtains above-mentioned photo-acid agent, and it can be provided at the rate of diffusion that can regulate acid when using ArF as light source and the photo-acid agent that has such as the characteristic of high osmosis.
In formula 1, A+ represents organic gegenion.
Especially, by the part of following formula 2 expression,, can be selected among following formula 2a and the 2b any promptly by the cationic moiety of the compound of formula 1 expression.
[formula 2]
A+
[formula 2a]
[formula 2b]
In following formula 2a and 2b, R
1And R
2Expression independently of one another is selected from any in hydrogen atom, alkyl, allyl, perfluoroalkyl, aryl and the combination thereof, and R
1And R
2Can be combined together to form saturated or undersaturated hydrocarbon ring with 3 to 30 carbon atoms.
R4 represents to be selected from any in halogen atom, alkyl, alkoxy, aryl, thio alkoxy (thioalkoxy group), alkoxy carbonyl methoxyl, sulfo-phenoxy group and the combination thereof.
R
3And R
5Expression independently of one another is selected from any in hydrogen atom, alkyl, allyl, perfluoroalkyl, aryl and the combination thereof.
In formula 2a and 2b, the example of alkyl comprises methyl, ethyl, propyl group, isopropyl, normal-butyl, amyl group, hexyl and octyl group, and the example of alkoxy comprises methoxyl, ethoxy, propoxyl group, butoxy, own oxygen base and octyloxy.
In addition, by the part of formula 2 expression,, can represent to be selected among the following formula 2-i to 2-xx any promptly by the cationic moiety of the compound of formula 1 expression.
[formula 2-i to 2-xx]
By the part of formula 2 expression,, can represent to be selected among following formula 3a and the 3b any promptly by the cationic moiety of the compound of formula 1 expression.
[formula 3a]
[formula 3b]
In formula 3a and 3b, R
1Expression is selected from any in hydrogen atom, alkyl, allyl, perfluoroalkyl, aryl and the combination thereof.
R
2And R
3Expression independently of one another is selected from any in hydrogen atom, alkyl, allyl, perfluoroalkyl, aryl and the combination thereof.
R
4Expression is selected from any in halogen atom, alkyl, alkoxy, aryl, thio alkoxy, alkoxy carbonyl methoxyl, sulfo-phenoxy group and the combination thereof.
In formula 3a and 3b, the example of alkyl comprises methyl, ethyl, propyl group, isopropyl, normal-butyl, amyl group, hexyl and octyl group, and the example of alkoxy comprises methoxyl, ethoxy, propoxyl group, butoxy, own oxygen base and octyloxy.
In addition, by the part of formula 2 expression,, can represent to be selected among the following formula 3-i to 3-ix any promptly by the cationic moiety of the compound of formula 1 expression.
[formula 3-i to 3-ix]
According to another embodiment of the present invention, comprise first step by the preparation method of the photo-acid agent of formula 1 expression, will be in solvent by the compound dissolution of following formula 8 expressions, and make this solution and the compound of reductive agent reaction to obtain to represent by following formula 6; Second step makes the compound by following formula 7 expressions react in the presence of base catalyst to obtain the compound by following formula 4 expressions with the compound of being represented by following formula 6; And third step, make compound carry out substitution reaction, thereby obtain compound by following formula 1 expression with the compound of representing by following formula 5 by following formula 4 expressions.
First step comprises following operation: will add reductive agent, thereby obtain the compound by following formula 6 expressions by the compound dissolution of following formula 8 expression in solvent.
[formula 8]
[formula 6]
In formula 6 and formula 8, R
6Represent alkyl, can represent to be selected from methyl, trifluoromethyl, trichloromethyl, trisbromomethyl, three iodomethyls, ethyl, propyl group and the butyl any especially.Q
1And Q
2Represent halogen atom independently of one another, and preferably represent fluorine atom.M+ represents to be selected from any among Li+, Na+ and the K+.
Solvent for being used in the first step reaction dissolve by the compound of formula 8 expressions can use any solvent, as long as this solvent can dissolve the ester compounds of being represented by formula 8 and cause reduction reaction.
For solvent, can use and be selected from ester, ether, lactone, ketone, acid amides, alcohol and the combination thereof any, and any alcohols solvent that uses that preferably can be in being selected from methylene chloride, chloroform, ethylene dichloride, acetonitrile, toluene, dimethyl formamide, tetrahydrofuran, dimethyl sulfoxide (DMSO) and combination thereof, but the present invention is not intended to be limited to these.
Described alcohols solvent can be for being selected from following any: methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, the tert-butyl alcohol, oxobutanol, hendecanol, hydroxyl decyl alcohol, enanthol, 2-methyl-1-pentene alcohol, allyl alcohol, ethoxy carbonyl methyl alcohol, methyl cellosolve, 1-methoxyl-2-propyl alcohol, benzylalcohol, phenylethyl alcohol, cyclohexanol, menthol (menthyl alcohol), tetrahydrofurfuryl alcohol, oxinane alcohol, cyano group butanols, 4-hydroxyl-2-butanone and combination thereof, but the present invention is not intended to be limited to these.
As reductive agent, can use to be selected from NaBH
4, LiAlH
4, BH
3-THF, NaBH
4-AlCl
3, NaBH
4-LiCl, LiAl (OMe)
3And the combination in any.
Compound and reductive agent by formula 8 expressions can use with 1: 1 to 1: 5 mol ratio, and preferably use with 1: 2 to 1: 3.5 mol ratio.When being used with above-mentioned mol ratio by the compound of formula 8 expression and reductive agent, product can increase with respect to the yield of the amount of used reductive agent.
Especially, first reaction can comprise the steps: in ice bath will be by the compound dissolution of formula 8 expressions in above-mentioned solvent, in solution, drip reductive agent with the preparation feedback mixture liquid, remove reaction mixture liquid from ice bath, and heating and stirred reaction mixture liquid.
Preferably, whipping process can carry out 2 to 6 hours at 20 ℃ to 120 ℃, more preferably carried out 3 to 5 hours at 45 ℃ to 80 ℃.When whipping process is finished in said temperature and time range, can increase the yield of product, and the formation of accessory substance is minimized.
Reaction by cancellation cessation reaction mixture liquid removes solvent, then collecting reaction product.
For the method for collecting reaction product, can use anyly can from reaction mixture liquid, remove the solvent and the conventional method of collecting reaction product therefrom.For example, the potpourri that can use recrystallization method, the solvent by utilizing easy dissolving gained compound and dissolve the solvent of described compound hardly come the method for curing reaction product, with the method for the concentrate of solvent extraction reaction product or the method for concentration response product.
The preferred embodiment of the method for operable collecting reaction product can be following method: remove solvent from reaction mixture liquid, residue is dissolved in the distilled water, subsequently solution is acidified to pH 5-6, with the reaction mixture liquid concentration, in concentrate, add alcohol once more to remove the inorganic salts of slurries form, residue is filtered, and use diethyl ether etc. to make the filtrate crystallization.
Can prepare the compound of representing by formula 8 by following steps: the intermediate preparation step, wherein make alkoxide (alkoxide) and halide reaction have the dialkoxy halogenide of two alkoxys, make the oxidation of one of halid two alkoxys of dialkoxy subsequently to produce compound by following formula 9 expressions with generation; And sulfonation procedure, wherein make the compound of representing by formula 8 with generation by the compound and the inorganic sulfite reaction of formula 9 expressions.
[formula 9]
In formula 9, R
6Represent alkyl, and can represent to be selected from methyl, trifluoromethyl, trichloromethyl, trisbromomethyl, three iodomethyls, ethyl, propyl group and the butyl any especially; And Q
1To Q
3Represent halogen atom independently of one another, and be preferably fluorine atom.
Particularly, used alkoxide can be the alkoxy alkene with 3 to 10 carbon atoms that contains carbon-to-carbon double bond in the intermediate preparation step, and alkoxide especially can be methoxy-ethylene, ethoxy ethylene etc.Halogenide can be alkyl halide, and especially can be perfluoromethane, dibromodifluoromethane, perbromo-methane or perchloromethane.
In the intermediate preparation step, alkoxide and halogenide are reacted in alcohols solvent, and these compounds can also with sodium hydrosulfite (Na
28
2O
4) and sodium bicarbonate (NaHCO
3) reaction.In addition, make as the reaction of one of halid two alkoxys of the dialkoxy of above-mentioned generation oxidation and can in the presence of oxygenant, carry out, and the instantiation of the oxygenant that can use is KHSO
5
As inorganic sulfite used in the sulfonation procedure, especially can use sodium hydrosulfite, and should reaction also can add sodium bicarbonate (NaHCO
3) carry out afterwards.When using sodium hydrosulfite to carry out sulfonating reaction, can prepare compound by the organic sulfonate oxidation that will so produce by formula 8 expressions.In this case, can use hydrogen peroxide (H
2O
2), sodium tungstate (Na
2WO
4) wait as oxygenant.
Second step comprises that the compound that makes by following formula 7 expressions reacts in the presence of base catalyst with the compound of being represented by formula 6, thereby obtains the process by the compound of following formula 4 expressions.
[formula 7]
[formula 4]
In formula 4 and formula 7, Q
1, Q
2And Q
5Represent halogen atom independently of one another; And n represents 0 to 5 integer, preferably represents 0 to 2 integer.
M+ represents to be selected from any among Li+, Na+ and the K+.
X and Y have with above for the described identical definition of compound by formula 1 expression, and no longer repeat this definition.
As base catalyst, can use to be selected from triethylamine, diethylamine, pyridine, diethyl isopropylamine and the combination thereof any.When in second step reaction, using base catalyst, can in the shortest reaction time, obtain the product of expectation.
The reaction of second step can be carried out in the presence of solvent, and can use and be selected from ester, ether, lactone, ketone, acid amides, alcohol and the combination thereof any as solvent.Preferably, solvent can be to be selected from methylene chloride, chloroform, ethylene dichloride, acetonitrile, toluene and the combination thereof any.
Can be used for reaction with 1: 1 to 1: 3 mol ratio by the compound of formula 6 expressions and the compound of representing by formula 7, and preferably use with 1: 1.1 to 1: 1.5 mol ratio.When making by the compound of formula 6 expression with by the compound of formula 7 expressions during with above-mentioned molar ratio reaction, these two kinds of compounds can fall in full consumption, thereby can increase the efficient of reaction.
In addition, compound and the base catalyst represented by formula 6 can be used for reaction with 1: 1 to 1: 4 mol ratio, and preferably use with 1: 1.1 to 1: 1.8 mol ratio.When being used to react with above-mentioned mol ratio by the compound of formula 6 expression and base catalyst, can the accelerated reaction time, and can remove the base catalyst of any remnants easilier.
Second step reaction especially can comprise following operation: will by the compound of formula 6 expression and by the compound dissolution of formula 7 expressions in solvent mentioned above with the preparation feedback potpourri, stir this reaction mixture, in reaction mixture, drip above-mentioned base catalyst, stir the gained potpourri then.
Agitating procedure can preferably carry out under 20 ℃ to 120 ℃ temperature 1 to 4 hour, and more preferably carried out under 45 ℃ to 80 ℃ temperature 1.5 to 3 hours.When agitating procedure carries out in said temperature and time range, can increase the yield of product, and the formation of accessory substance is minimized.
Make the reaction terminating of reaction mixture liquid by cancellation, remove solvent, make the reaction product crystallization then.Can obtain compound like this by formula 4 expressions.
For method for crystallising, can unrestrictedly use any method, as long as this method is the usual method that removes solvent and make the reaction product crystallization from reaction mixture liquid, but preferably, can use following method: from reaction mixture liquid, remove solvent, in residue, add alcohol once more, filter the slurries that so obtain, by filtering the solid that obtains, and dry and make solid crystal with washing such as distilled water, diethyl ether.
Third step comprises makes compound of being represented by formula 4 above and the compound of being represented by following formula 5 carry out substitution reaction, thereby obtains the operation by the compound of following formula 1 expression.
[formula 5]
A+Z-
In formula 5, Z-represents to be selected from (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)
3)-, F-, Cl-, Br-, I-, BF
4-, AsF
6-and PF
6-in any; A+ represents organic gegenion.Because the concrete definition of this organic gegenion is with identical for the definition of being represented by formula 1 that compound provided, so no longer repeat this description.
Can use with 1: 1 to 5: 1 mol ratio by the compound of formula 4 expressions with by the compound that formula 5 is represented, preferably use, and more preferably use with 1: 1 to 2: 1 mol ratio with 1: 1 to 3: 1 mol ratio.When these compounds use with above-mentioned mol ratio, reacting treatment time is minimized, and can suppress any subsidiary reaction because of using excessive reaction product to cause.
Can be by using recrystallization method, or use the solvent (good solvent) of the salt of gained in the solubilizing reaction satisfactorily and the potpourri that poorly dissolves the solvent (poor solvent) of this salt that this salt is solidified and the method that reclaims is carried out substitution reaction, and also can use by solvent-extracted method the method that perhaps makes the salt of gained concentrate and reclaim.
Preferably, these compound dissolutions are two-layer to form in methylene chloride and water, can stir this then and two-layer substitution reaction be taken place.Under the situation of using this two-layer reaction method, advantageously, do not need other method to come separated product.Stirring can be carried out 2 to 6 hours, can also carry out 2 to 4 hours.When in being reflected at above-mentioned time range, carrying out, can increase the yield of product the biglyyest.
When preparing the compound of representing by formula 1 by above-mentioned operation, can be by the compound of effective and simple method preparation by formula 1 expression.
Comprise photo-acid agent according to the resist composition of another embodiment of the present invention by formula 1 expression shown in above.Therefore the resist composition no longer is repeated in this description the resist composition in this article with the basis that is configured to of the resist composition of routine.
Photo-acid agent according to the present invention can produce acid when exposure, described acid has low rate of diffusion, has short diffusion length, and the acidity that shows suitable degree, thereby can improve line width roughness (LWR) characteristic, and can control that it is used such as the wash-out in the solvent of pure water in processing.In addition, the method for preparing photo-acid agent according to the present invention can produce above-mentioned photo-acid agent by effective and simple method.
Embodiment
Hereinafter, will describe the present invention in detail, and make those skilled in the art can implement this invention at an easy rate by the mode of embodiment.Yet the present invention can implement with variations and modifications, and its scope is not limited to embodiment as herein described.
Synthesizing of photo-acid agent
[the synthetic embodiment 1 of photo-acid agent]
Diamantane-1-formic acid-3,3-two fluoro-3-sulfo groups-propyl diester diphenyl methyl phenyl sulfonium salt synthetic
(step 1) shown in following reaction equation 1, with 83g (0.376mol) 1,1-two fluoro-3-methoxyls-3-oxo propane-1-sodium sulfonate is dissolved in the 160ml methyl alcohol (MeOH) and 1.2L tetrahydrofuran (THF) as solvent in ice bath.In solution, slowly drip 44g (1.16mol) sodium borohydride (NaBH
4), thereby the preparation feedback mixture liquid.After dropwising, reaction mixture liquid is shifted out from ice bath, and be heated to 60 ℃.When remaining on this temperature, with about 4 hours of reaction mixture liquid agitation.
, remove then and desolvate the cancellation of reaction mixture liquid with distilled water.Crude product mixture is dissolved in the distilled water, solution is acidified to pH 5 to 6 with concentrated hydrochloric acid.
The reaction mixture of acidifying is concentrated, and then to wherein adding methyl alcohol.With the dope filtration that so obtains to remove inorganic salts.To methanol layer be concentrated once more by removing the filtrate usefulness hexane wash twice that slurries obtain, use the diethyl ether crystallization then.
Will be by the white solid vacuum drying that crystallization obtained, and compound structure passes through
1H-NMR is confirmed.Obtained 68.5g (0.346mol) 1 like this, 1-two fluoro-3-hydroxy propane-1-sodium sulfonates (yield 95%).
1H-NMR(D
2O)：(ppm)2.38(t，2H)，4.18(t，2H)
[reaction equation 1]
As a reference, 1 shown in above, 1-two fluoro-3-methoxyls-3-oxo propane-1-sodium sulfonate can prepare by the reaction of for example following reaction equation 2.
[reaction equation 2]
(step 2) is shown in following reaction equation 3, with 1 of preparation in 20g (0.101mol) step 1,1-two fluoro-3-hydroxy propane-1-sodium sulfonates and 29g (0.146mol) diamantane formyl chloride (it is represented by formula A in reaction equation 3 below) are dissolved in the 400ml ethylene dichloride with the preparation feedback potpourri, then reaction mixture are at room temperature stirred.In 20 ℃ to 25 ℃ downhill reaction potpourris, slowly drip 23ml (0.165mol) triethylamine (Et
3N).Then, make the temperature of reaction of reaction mixture be increased to 60 ℃, under this temperature, potpourri is stirred and heated 2 hours.
After the reaction of reaction mixture is finished, from reaction mixture, remove reaction dissolvent, and residue is made slurries, then with its filtration with ether.Wash by filtering the solid that slurries obtained, then with its vacuum drying with distilled water and ether.
Vacuum drying solid is carried out
1H-NMR analyzes, and has confirmed structure.Obtain 30g (0.0832mol, yield 80%) diamantane-1-formic acid-3 like this, 3-two fluoro-3-sulfo group-propyl diester sodium salts, it is represented by formula B in reaction equation 3 below.
1H-NMR (dimethyl sulfoxide (DMSO)-d
6, tetramethylsilane): (ppm) 1.67-1.98 (m, 15H), 2.45 (t, 2H), 4.52 (t, 2H)
[reaction equation 3]
(step 3) is shown in following reaction equation 4, diamantane-1-formic acid-3 with preparation in 8.5g (0.0236mol) step 2,3-two fluoro-3-sulfo group-propyl diester sodium salts and 10g (0.0234mol) diphenyl methyl phenyl sulfonium trifluoro-methanyl sulfonate (it is represented by formula C in reaction equation 4 below) be dissolved in the 100ml methylene chloride (or carrene, MC) and in the 100ml water to form two-layer reaction mixture.With reaction mixture vigorous stirring 3 hours, so that reaction (two-layer reaction) is taken place.
When the stirring of reaction mixture is finished, get the organic layer of equal portions, by
19F-NMR checks reaction process.When reaction is finished, collected organic layer, and remove and desolvate.Use methylene chloride as good solvent and the hexane slurries that washing obtains like this as poor solvent, thereby obtain solid.With the solid drying under reduced pressure, thus the compound that acquisition is represented by the formula B in the following reaction equation 4.Obtained 13.3g (0.0216mol, yield 94.3%) diamantane-1-formic acid-3 like this, 3-two fluoro-3-sulfo groups-propyl diester diphenyl methyl phenyl sulfonium salt, it is represented by formula D in reaction equation 4 below, and its structure is passed through
1H-NMR is confirmed.
1H-NMR (chloroform-d
3, tetramethylsilane): (ppm) 1.69-1.97 (m, 15H), 2.47 (t, 2H), 2.64 (s, 3H), 4.36 (t, 2H), 7.50 (d, 2H), 7.62-7.77 (m, 12H)
[reaction equation 4]
[the synthetic embodiment 2 of photo-acid agent]
Dicyclo [2.2.1] heptane-2-formic acid-3,3-two fluoro-3-sulfo groups-propyl diester diphenyl methyl phenyl sulfonium salt synthetic
(this operation of step 1) with the step 1 of synthetic embodiment 1 in identical mode carry out, thereby obtain 1,1-two fluoro-3-hydroxy propane-1-sodium sulfonates.
(step 2) with the step 2 of synthetic embodiment 1 in identical mode carry out this operation, different dicyclo [2.2.1] heptane-2-formyl chlorides (it is represented by formula E in reaction equation 5 below) that are to use replace the diamantane formyl chloride.Thereby obtained dicyclo [2.2.1] heptane-2-formic acid-3 of representing by formula F in the following reaction equation 5,3-two fluoro-3-sulfo group-propyl diester sodium salts.
[reaction equation 5]
(step 3) makes dicyclo [2.2.1] heptane-2-formic acid-3 of preparation in the step 2, the diphenyl methyl phenyl sulfonium trifluoro-methanyl sulfonate reaction that formula C in 3-two fluoro-3-sulfo group-propyl diester sodium salts and the following reaction equation 6 represents, thereby obtain dicyclo [2.2.1] heptane-2-formic acid-3 that the formula G in the following reaction equation 6 represents, 3-two fluoro-3-sulfo groups-propyl diester diphenyl methyl phenyl sulfonium salt.
1H-NMR (chloroform-d
3, tetramethylsilane): (ppm) 1.09-1.38 (m, 8H), 1.43 (d, 1H), 1.50 (m, 1H), 2.27 (m, 1H), 2.48 (s, 3H), 2.67 (m, 2H), 4.38 (m, 2H), 7.50 (d, 2H), 7.63-7.77 (m, 12H)
[reaction equation 6]
Synthesizing of resin
[the synthetic embodiment 1 of resin]
Add 3-dicyclo [2.2.1] heptan-5-alkene-2-base-3-hydracrylic acid tert-butyl ester, 1-methyl adamantane acrylate (2-methyl-2-adamantyl acrylate) and gamma-butyrolacton methacrylate (the basic acrylate of 2-oxo-tetrahydrofuran-3-) with 1: 1: 1 mol ratio, and use 1, the 4-diox is as polymer solvent, and its amount is equal to 3 times of reaction monomers gross mass.As initiating agent, use azoisobutyronitrile, its ratio is 4mol% based on the integral molar quantity of monomer, and makes system 65 ℃ of reactions 16 hours.
After the reaction, use normal hexane to make the reaction solution precipitation, and will precipitate vacuum drying.Obtained resin like this by following formula 10 expressions.As the weight-average molecular weight that precipitates the multipolymer that obtains is 8,500.
[formula 10]
The preparation of resist
[Comparative Examples 1]
The resin by formula 10 expressions that obtains in the synthetic embodiment 1 of resin of 100 weight portions, 4 weight portions are dissolved in 1 as the triphenyl sulphur trifluoro-methanyl sulfonate of photo-acid agent (PAG) and the Tetramethylammonium hydroxide as alkalinity additive (BASE) of 0.5 weight portion, in the methyl proxitol acetate of 000 weight portion, then solution is filtered by 0.2-μ m film filter.Prepared resist solution like this.
Use spinner that resist solution is coated on the matrix, and with resist solution 110 ℃ of dryings 90 seconds, be the film of 0.20 μ m to form thickness.Use ArF excimer laser stepper (stepper) (lens aperture number: the film exposure that 0.78) will so form, and 110 ℃ of heat treated 90 seconds.The film development that the aqueous solution of use 2.38wt% Tetramethylammonium hydroxide will so form 40 seconds is then with film washing and dry.Formed the resist pattern like this.
[embodiment 1]
Prepare resist solution in the mode identical with Comparative Examples 1, diamantane-1-formic acid-3 that the formula D by in the reaction equation 4 of preparation represents among the different synthetic embodiment 1 that is to use 3 weight portions, 3-two fluoro-3-sulfo groups-propyl diester diphenyl methyl phenyl sulfonium salt is as photo-acid agent.Estimate the character of resist solution.
[embodiment 2]
Prepare resist solution in the mode identical with Comparative Examples 1, diamantane-1-formic acid-3 that the formula D by in the reaction equation 4 of preparation represents among the different synthetic embodiment 1 that is to use 5 weight portions, 3-two fluoro-3-sulfo groups-propyl diester diphenyl methyl phenyl sulfonium salt is as photo-acid agent.Estimate the character of resist solution.
[embodiment 3]
Prepare resist solution in the mode identical with Comparative Examples 1, diamantane-1-formic acid-3 that the formula D by in the reaction equation 4 of preparation represents among the different synthetic embodiment 1 that is to use 7 weight portions, 3-two fluoro-3-sulfo groups-propyl diester diphenyl methyl phenyl sulfonium salt is as photo-acid agent.Estimate the character of resist solution.
Estimate the character of Comparative Examples 1 and embodiment 1 to 3, for example sensitivity, resolution and LWR, and with in result's row and the following table 1.
Under the situation of LWR, (pattern of acquisition is classified as 1 in the Comparative Examples 1 for line-and-space, L/S) the pattern roughness of pattern, and with the grading that improves of LWR be 1 to 5 to have observed 0.10-μ m line that the back of developing forms and spacing.Bigger numeric representation is the LWR characteristic preferably.
Under the situation of sensitivity, the exposure that forms 0.10-μ m line and spacing (L/S) pattern with 1: 1 line width is designated as optimum exposure, and when sensitivity was set equal to optimum exposure, the minimum pattern size that obtains by imaging was designated as resolution.
[table 1]
(1) photo-acid agent (PAG)
Embodiment 1 to 3: diamantane-1-formic acid-3 that the formula D by in the reaction equation 4 of preparation represents among the synthetic embodiment 1,3-two fluoro-3-sulfo groups-propyl diester diphenyl methyl phenyl sulfonium salt
Comparative Examples 1: triphenyl sulphur trifluoro-methanyl sulfonate
(2) alkalinity additive (BASE): Tetramethylammonium hydroxide
Prepared photo-acid agent (PAG) used among the embodiment 1 to 3 by introducing alicyclic ring to the negative ion of photo-acid agent.Compare with existing fluoroform sulphonate or perfluor fourth sulfonate photo-acid agent, this photo-acid agent keeps and the similar acidity of fluoroform sulphonate, and has low sour rate of diffusion and short diffusion length.Like this, this photo-acid agent has the characteristic that is suitable for realizing meticulousr L/S pattern.
When the property analysis in the look-up table 1 as a result the time, to compare with existing fluoroform sulphonate type photo-acid agent, photo-acid agent shows excellent performance aspect LWR and resolution.With rayed the time, also shown excellent result aspect its transparency even introduce aromatic rings to the negative ion of photo-acid agent.In case acid produces from photo-acid agent and moves with anionic form, aromatic rings does not influence transparency, and has obtained favourable effect: can be according to the sour rate of diffusion and the diffusion length of size control of aromatic rings.Therefore, photo-acid agent shows the feature that is different from existing photo-acid agent.
Like this, described preferred implementation of the present invention in detail, but be not intended to scope of the present invention is limited to this, and various modifications and improvement that those of ordinary skill can use the key concept of the present invention that defines in the appending claims to carry out are also included within the scope of the present invention.
Claims (8)
1. photo-acid agent, it is by following formula 1 expression:
[formula 1]
Wherein, in formula 1,
Y represents to be selected from any in naphthenic base with 3 to 30 carbon atoms and the cycloalkenyl group with 3 to 30 carbon atoms;
Q
1And Q
2Represent halogen atom independently of one another;
X represents to be selected from any in alkane two bases, alkene two bases, NR ', S, O, CO and the combination thereof, and wherein R ' expression is selected from any in hydrogen atom and the alkyl;
N represents 0 to 5 integer; And
A+ represents organic gegenion.
2. photo-acid agent according to claim 1, wherein Y represents to be selected from following any: adamantyl, norborny, contain the norborny with 10 to 30 carbon atoms the polycyclic naphthene base, have 3 to 14 carbon atoms monocyclic cycloalkyl, have 8 to 20 carbon atoms bicyclic cycloalkyl, have the tricyclic naphthenes base of 10 to 30 carbon atoms and have the Fourth Ring naphthenic base of 10 to 30 carbon atoms.
3. photo-acid agent according to claim 1, wherein Y represents to be selected from any among the following formula 1-a to 1-i:
[formula 1-a]
[formula 1-b]
[formula 1-c]
[formula 1-d]
[formula 1-e]
[formula 1-f]
[formula 1-g]
[formula 1-h]
[formula 1-i]
Wherein, in formula 1-a to 1-i,
R
11And R
12Be selected from any replacement among alkyl, alkoxy, perfluoroalkyl, perfluoro alkoxy, halogen atom, hydroxyl, carboxyl, cyano group, nitro, amino, sulfydryl, methyl mercapto, methoxyl, OR ', COR ' and the COOR ' independently of one another, wherein R ' expression is selected from any in alkyl and the aryl;
A, c and d represent 0 to 9 integer independently of one another; B represents 0 to 11 integer; E represents 0 to 15 integer; F represents 0 to 7 integer; And 0≤c+d≤17 and 0≤c+f≤15.
4. photo-acid agent according to claim 1, the X in its Chinese style 1 represent to be selected from-O-,-OCH
2-,-OCH (C1)-,-CO-,-COCH
2-,-COCH
2CH
2-,-CH
2-,-CH
2CH
2-,-CH
2-O-,-CH
2-O-CH
2-,-CH
2CH
2-O-,-CH
2-O-CH
2CH
2-,-CH
2CH
2-O-CH
2-,-CH
2CH
2CH
2-O-,-CH
2-O-CH
2CH
2CH
2-,-CH
2CH
2-O-CH
2CH
2-,-CH
2CH
2CH
2-O-CH
2-,-CH (CH
3)-,-C (CH
3)
2CH
2-,-CH (CH
3) CH
2-,-CH (CH
2CH
3)-,-CH (OCH
3)-,-C (CF
3) (OCH
3)-,-CH
2-S-,-CH
2-S-CH
2-,-CH
2CH
2-S-,-CH
2-S-CH
2CH
2-,-CH
2CH
2-S-CH
2-,-CH
2CH
2CH
2-S-,-CH
2-S-CH
2CH
2CH
2-,-CH
2CH
2-S-CH
2CH
2-,-CH
2CH
2CH
2-S-CH
2-,-CH (CH
2) CH-,-C (CH
2CH
2)-,-CH
2CO-,-CH
2CH
2CO-,-CH (CH
3) CH
2CO-,-CH (OH)-,-C (OH) (CH
3)-,-CH (F)-,-CH (Br)-,-CH (Br) CH (Br)-,-CH=CH-,-CH
2CH=CH-,-CH=CHCH
2-,-CH=CH-O-,-CH=CH-S-and-among the CH=CHCO-any.
5. photo-acid agent according to claim 1, wherein by the part of following formula 3 expression, promptly by the anionicsite of the compound of formula 1 expression, expression is selected from any among the following formula 1-i to 1-xx:
[formula 3]
[formula 1-i to 1-xx]
6. preparation is by the method for the photo-acid agent of following formula 1 expression, and described method comprises:
First step will be by the compound dissolution of following formula 8 expression in solvent, and makes this solution and the compound of reductive agent reaction to obtain to be represented by following formula 6;
Second step makes the compound by following formula 7 expressions react in the presence of base catalyst with the compound of being represented by following formula 6, thereby obtains the compound by following formula 4 expressions; And
Third step makes the compound by following formula 4 expressions carry out substitution reaction with the compound of being represented by following formula 5, thereby obtains the compound by following formula 1 expression:
[formula 8]
[formula 6]
[formula 7]
[formula 4]
[formula 5]
A+Z-
[formula 1]
Wherein, in formula 1, formula 4, formula 5, formula 6, formula 7 and formula 8,
R
6The expression alkyl;
Q
1, Q
2And Q
5Represent halogen atom independently of one another;
Y represents to be selected from any in naphthenic base with 3 to 30 carbon atoms and the cycloalkenyl group with 3 to 30 carbon atoms;
X represents to be selected from any in alkane two bases, alkene two bases, NR ', S, O, CO and the combination thereof, and wherein R ' expression is selected from any in hydrogen atom and the alkyl;
N represents 0 to 5 integer;
A+ represents organic gegenion;
M+ represents to be selected from any among Li+, Na+ and the K+; And
Z-represents to be selected from (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)
3)-, F-, Cl-, Br-, I-, BF
4-, AsF
6-and PF
6-in any.
7. compound, it is by following formula 4 expressions:
[formula 4]
Wherein, in formula 4,
Y represents to be selected from any in naphthenic base with 3 to 30 carbon atoms and the cycloalkenyl group with 3 to 30 carbon atoms;
Q
1And Q
2Represent halogen atom independently of one another;
X represents to be selected from any in alkane two bases, alkene two bases, NR ', S, O, CO and the combination thereof, and wherein R ' expression is selected from any in hydrogen atom and the alkyl;
N represents 0 to 5 integer; And
M+ represents to be selected from any among Li+, Na+ and the K+.
8. chemical reinforced slushing compound composition, it comprises each described photo-acid agent in the claim 1 to 5.
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| KR20100051592 | 2010-06-01 | ||
| KR1020110006934A KR20110132207A (en) | 2010-06-01 | 2011-01-24 | Photoacid generator, method for manufacturing the same and resist composition comprising the same |
| KR10-2011-0006934 | 2011-01-24 |
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| JP6079217B2 (en) * | 2011-12-28 | 2017-02-15 | Jsr株式会社 | Photoresist composition, resist pattern forming method, and acid generator |
| KR20130076364A (en) * | 2011-12-28 | 2013-07-08 | 금호석유화학 주식회사 | Additive for resist and resist composition comprising same |
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| JP2008039815A (en) * | 2006-08-01 | 2008-02-21 | Shin Etsu Chem Co Ltd | Resist undercoat film material, and resist undercoat film substrate and pattern forming method using the same |
| CN101208298A (en) * | 2005-06-07 | 2008-06-25 | 纳幕尔杜邦公司 | Hydrofluoroalkanesulfonic acids and salts from fluorovinyl ethers |
| US20100086873A1 (en) * | 2008-10-07 | 2010-04-08 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition and method of forming resist pattern |
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| US8283106B2 (en) * | 2007-11-01 | 2012-10-09 | Central Glass Company, Limited | Sulfonic acid salt and derivative thereof, photoacid generator agent, and resist material and pattern formation method using the photoacid generator agent |
| JP5347433B2 (en) * | 2007-11-01 | 2013-11-20 | セントラル硝子株式会社 | Novel sulfonate and derivative thereof, photoacid generator, resist material and pattern forming method using the same |
| KR100940915B1 (en) * | 2008-03-13 | 2010-02-08 | 금호석유화학 주식회사 | Acid generator for chemically amplified resist compositions |
| JP5173642B2 (en) * | 2008-07-18 | 2013-04-03 | 東京応化工業株式会社 | Positive resist composition and resist pattern forming method |
| KR20100121427A (en) * | 2009-05-07 | 2010-11-17 | 제이에스알 가부시끼가이샤 | Radiation-sensitive resin composition |
| JP5474867B2 (en) * | 2010-06-01 | 2014-04-16 | コリア クンホ ペトロケミカル カンパニー リミテッド | Photoacid generator, production method thereof, and resist composition containing the same |
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| CN101208298A (en) * | 2005-06-07 | 2008-06-25 | 纳幕尔杜邦公司 | Hydrofluoroalkanesulfonic acids and salts from fluorovinyl ethers |
| JP2008039815A (en) * | 2006-08-01 | 2008-02-21 | Shin Etsu Chem Co Ltd | Resist undercoat film material, and resist undercoat film substrate and pattern forming method using the same |
| US20100086873A1 (en) * | 2008-10-07 | 2010-04-08 | Tokyo Ohka Kogyo Co., Ltd. | Positive resist composition and method of forming resist pattern |
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