Photoresist composition, pattern forming method and application thereof
阅读说明：本技术 光致抗蚀剂组合物、其图案形成方法及应用 (Photoresist composition, pattern forming method and application thereof ) 是由 钱晓春 胡春青 金晓蓓 于 2018-08-06 设计创作，主要内容包括：本发明提供了一种光致抗蚀剂组合物、其图案形成方法及应用。该光致抗蚀剂组合物包括a组分和b组分,该a组分为光产酸剂,该b组分为光阻聚合物,其中该光产酸剂为式(Ⅰ)、式(Ⅱ)、式(Ⅲ)、式(Ⅳ)、式(Ⅴ)以及式(Ⅵ)所示的化合物中的一种或多种。本发明的该光致抗蚀剂组合物对365-435nm的LED光源具有高敏感度,光谱范围广,并且该光致抗蚀剂组合物保存稳定性优良、灵敏度高,透明性佳。<Image he="901" wi="700" file="DDA0001755604390000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention provides a photoresist composition, a pattern forming method and application thereof. The photoresist composition comprises a component a and a component b, wherein the component a is a photoacid generator, the component b is a photoresist polymer, and the photoacid generator is one or more of compounds shown in a formula (I), a formula (II), a formula (III), a formula (IV), a formula (V) and a formula (VI). The photoresist composition has high sensitivity and wide spectral range to 365-.)
1. The photoresist composition is characterized by comprising a component a and a component b, wherein the component a is a photoacid generator, the component b is a photoresist polymer, the photoacid generator is one or more of compounds shown in a formula (I), a formula (II), a formula (III), a formula (IV), a formula (V) and a formula (VI),
wherein, in the formula (I),
R1is a sulfonyl group, wherein the sulfonyl group is an alkylsulfonyl, phenylsulfonyl or camphorylsulfonyl group, wherein the H atoms in the sulfonyl group may each independently be replaced by-NO2、-CN、C1～C18Alkyl radical, C3～C8Cycloalkyl radical, C1～C4Alkyl radicals and C3～C8Cycloalkylalkyl consisting of cycloalkyl, or a heterocyclic group containing O, S, N atoms,
n is an integer of 1 to 1000,
when n is 1, X-R0And Q-R2Independently of one another are hydrogen,Wherein R is4、R5、R6、R7、R8Independently of one another, hydrogen, halogen, -Ra、-ORa、-SRa、-NRaRa’、-CH2OH、-CH2ORaor-CH2NRaRa', wherein RaOr Ra' independently of one another are hydrogen, C1～C24Straight or branched alkyl of, or C6～C12Aryl of (A), RaOr Ra' optionally containing 1-6 non-consecutive O, N or S, RaAnd Ra' when present together, optionally form a three-, four-, five-or six-membered ring therebetween, Y is-CH ═ CH-or a single bond; r9、R10、R11Are all RaSaid R is9、R10、R11Any two of which may optionally form a three-, four-, five-or six-membered ring,
when n is an integer of 2-1000, R0And R2Each independently selected from straight chain or branched chain alkylene, substituted straight chain or branched chain alkylene, wherein the substituent is one or more of hydroxyl, amino, sulfhydryl, ester group, nitrile group, carbonyl and alkoxy, and the R is0And R2Any two of them are adjacent to-CH2May be interrupted by-O-, -C (O) O-or-OC (O); x and Q are each independently selected from n-valent groups comprising-NHC (O) O-units;
R3is an olefin group, Ra、-C(O)-Ra，RaHave the same definition as in formula (I);
wherein, in the formula (II),
R12and R13All have the same structure as R in the formula (I)1The same definition;
wherein, in the formula (III) and the formula (IV),
R14and R15Each independently selected from C1～C20Straight or branched alkyl of (2), C3～C12A cycloalkyl, cycloalkyl derivative or heterocycloalkyl derivative of (A),
wherein the cycloalkyl derivative has the following structure:
the heterocycloalkyl derivative has the following structure:
R16and R17Independently of one another are hydrogen,
Wherein, in said formula (V) and said formula (VI),
R18is composed of
R19is composed of
R20is composed of
R21is composed of
m is an integer of 1 to 1000,
wherein, when M is 1, M-R22Is hydrogen, halogen, -Ra、-ORa、-SRa、-NRaRa’、-CH2OH、-CH2ORaor-CH2NRaRa', wherein RaAnd Ra' has the same definition as in formula (I);
when m is an integer of 2-1000, R22is-CH2-、-CH2CH2-、-CH2CH(OH)CH2-、-CH2CH(ORa)CH2-、-CH2CH(OC(O)Ra)CH2-、-CH2CH2C(O)OCH2CH2-、-CH2CH(Me)C(O)OCH2CH2-、-CH2CH2C(O)OCH2CH2OCH2CH2-、-CH2CH2C(O)OCH2CH2CH2-or-CH2CH2C(O)OCH2CH2CH2CH2-, M is C substituted by 2 to 6C ═ C double bonds2～C36M-valent alkyl groups of (a).
2. The photoresist composition according to claim 1, characterized in that, in the formula (I) of the photoacid generator,
R4、R6、R8are all made of-CH3And R is5、R7Are all H; or
R4、R5、R7、R8Are all H, and R6is-CH3(ii) a Or
R5、R6Are all-OCH3And R is4、R7、R8Are all H; or
R4、R6、R8Are all-CH3And R is5、R7Are all-CH2OH; or
R4、R6、R7、R8Are all H, and R5is-SCH3(ii) a Or
R4、R5、R7、R8Are all H, and R6is-SCH3(ii) a Or
R4、R6、R8Are all CH3And R is5、R7Are all CH2OC(O)Ra(ii) a Or
R4、R6、R8Are all CH3And R is5Is CH2OH, and R7Is H; or
R4、R6、R8Are all CH3And R is5、R7Are all CH2ORa(ii) a Or
R4、R6、R8Are all CH3And R is5、R7Are all CH2NRaRa'; or
R4、R6、R8Are all CH3And R is5Is CH2OH, and R7Is CH2NRaRa’。
3. The photoresist composition of claim 1, wherein in said formula (i) of said photoacid generator, R is9、R10Are all CH3，R11Is H; or, R9、R10、R11Are all CH2CH3(ii) a Or, R9Is CH3，R10、R11And substituted carbon atoms form a cycloalkyl group.
4. The photoresist composition of claim 1, wherein in said formula (i) of said photoacid generator, R is3is-CH3、-CH2CH3、-CH(CH3)2、-C6H5、-p-CH3OC6H4、-CH2CH＝CH2、-CH2Ph、-C(O)CEt3、-C(O)CMe3Or a biphenyl group.
5. The photoresist composition according to any one of claims 1 to 4, wherein in the formula (I) of the photoacid generator, n is an integer of 1 to 100; preferably, n is an integer of 1 to 10.
6. The photoresist composition of claim 1, wherein in said formula (I) of said photoacid generator, when n is 1, X-R0And Q-R2Independently of one another, hydrogen, C containing 0 to 4 substituents6～C24Aryl group, -CH3、-CH2CH3、-CH(CH3)2、-ORa、-CH2OH、-CH2ORa、-CH2OC(O)Ra、-CH2NRaRa’、-CHRa(OH)、-CRaRa’(OH)、-CCH3(CH2OH)OH、-C(CH2OH)2OH、-CH2CH2OH、-CH2CHMeOH、-CHMeCH2OH、-CH2CHPhOH、-CH2C(O)Ra、-CH2CO2H or a metal or amine salt thereof, -CH2CH2CO2H or a metal or amine salt thereof, -CH2CH2C(O)OCH2CH2OH、-CH2CHMeC(O)OCH2CH2OH、-CH2CH2C(O)OCH2CH2OCH2CH2OH、-CH2CH2C(O)OZ’、-CH2OC (O) -NHZ' or-CH2CH2OC (O) NHZ', wherein the C having 0 to 4 substituents is preferable6～C24Aryl of (a) is phenyl, biphenyl or naphthyl, and Z' is C containing 2-6C ═ C double bond substituents2-C36An alkylene group; preferably, Z' is C containing 2 to 6 substituents of acrylate units2-C36An alkylene group; more preferably, Z' is one of the groups shown below:
wherein Z is-CH2-or-CH2OCH2CH2-, m is 0, 1,2 or 3.
7. The photoresist composition of claim 1, wherein in the formula (I) of the photoacid generator, when n is an integer of 2 to 1000,
R0and R2Are respectively-CH2-、-CH2CH2-、-CH2CH(OH)CH2-、-CH2CH(ORa)CH2-、-CH2CH(OC(O)Ra)CH2-、-CH2CH2C(O)OCH2CH2-、-CH2CH(Me)C(O)OCH2CH2-、-CH2CH2C(O)OCH2CH2OCH2CH2-、-CH2CH2C(O)OCH2CH2CH2-or-CH2CH2C(O)OCH2CH2CH2CH2-；
X and Q are each independently-NHC (O) O-, or-C (O) O-, or-CH with at least 2-NHC (O) —, or-C (O) —, or-CH with at least 22CH2C (O) O-, or at least 2-CH2CH (Me) C (O) O-, or at least 2-CH2CH2C (O) O-, or at least 2-CH2CH (Me) C (O) O-, or at least 2-CH2CH2C (O) -, or at least 2-CH2CH (Me) C (O) -, or at least 2-CH2CH2C (O) NH-, or at least 2-CH2CH (Me) C (O) NH-, or at least 2-CH2CH2C (O) -, or at least 2-CH2CH (Me) C (O) -, or at least 2-CH2CH2C (O) NH-, or at least 2-CH2CH (Me) C (O) NH-, or at least 2-CH2CH2C(O)NRa-, or at least 2-CH2CH(Me)C(O)NRa-, or at least 2-CH2CH2SO2-, or at least 2-CH2CH(Me)SO2-, or at least 2-CH2CH2S(O)Ra-, or at least 2-CH2CH(Me)S(O)Ra-, or at least 2-CH2CH (OH) -or-CH2CH(ORa) -an n-valent group;
preferably, X and Q are each one of the groups shown below:
wherein R is11Is hydrogen or RaP is an integer of 0 to 20;
wherein Z is-CH2-or-CH2OCH2CH2P is an integer of 0 to 20;
wherein m is 0, 1,2 or 3, R is Ra，RaHave the same definitions as in formula (I).
8. The photoresist composition of claim 1, wherein in said formula (i) of said photoacid generator, R is1Is composed of C1～C3A sulfonyl group which is a linear or branched alkyl group, or a sulfonyl group which contains a phenyl group, preferably the sulfonyl group is trifluoromethanesulfonyl, p-trifluoromethanesulfonyl, methanesulfonyl or p-toluenesulfonyl.
9. The photoresist composition of claim 1, wherein in said formula (III) and said formula (IV) of said photoacid generator, R is16is-CH3、-CH2CH3、-CH2CH(CH3)2、-CH2Ph, a cycloalkyl derivative or a heterocycloalkyl derivative; preferably, U is-CH2-or a single bond, R'5、R′6、R′8、R′9Are all H and R'7Is CH3。
10. The photoresist composition of claim 1, wherein R in the formula (V) and the formula (VI) of the photoacid generator18In, R23、R25Are all-CH3And R is24Is H; or R23is-CH3And R is24、R25Are all H; or R23、R24Are all-CH3And R is25is-OH; or R23、R24Are all H and R25is-CH2CH2CH3(ii) a Or R23、R24、R25Are all Br; or R24、R25Are all-CH3And R is23Is Cl; or R23Is H and R24-R25Are all cyclohexane; or R23、R24Are all-CH3And R is25is-N (CH)3)2(ii) a Or R23、R25Are all-CH3And R is24is-N (CH)2CH2)2O; or R23、R24、R25Are all-CH3(ii) a Or R23、R25Are all-CH3And R is24is-CH2NRaRa'; or R23、R25Are all-CH3And R is24is-CH2OH。
11. The photoresist composition of claim 1, wherein R in the formula (V) and the formula (VI) of the photoacid generator19And R20In, R26、R27、R28、R29、R30、R31、R32、R33Are all H; or R30、R31Are all-CH3And R is26、R27、R28、R29、R32、R33Are all H; or R30、R33Are all-OCH3And R is26、R27、R28、R29、R31、R32Are all H; or R30、R33Are all tert-butyl and R26、R27、R28、R29、R31、R32Are all H; or R26is-CH3And R is27、R28、R29、R30、R31、R32、R33Are all H; or R26、R29Are all-CH3And R is27、R28、R30、R31、R32、R33Are all H; orR26、R30、R33Are all-CH3And R is27、R28、R29、R31、R32Are all H.
12. The photoresist composition of claim 1, wherein R in the formula (V) and the formula (VI) of the photoacid generator21In, R34is-CH3And R is35、R36Are all H; or R34、R35Are all-CH3And R is36Is H; or R34Is H and R35-R36Is cyclohexane; or R34is-CF3And R is35、R36Are all H.
13. The photoresist composition of claim 1, wherein R in the formula (V) and the formula (VI) of the photoacid generator21In, R39is-CH3And R is37、R38、R40、R41Are all H; or R39is-CF3And R is37、R38、R40、R41Are all H; or R37Is Cl and R38、R39、R40、R41Are all H; or R37、R39Are all Cl and R38、R40、R41Are all H; or R39is-OCH3And R is37、R38、R40、R41Are all H; or R39Is F and R37、R38、R40、R41Are all H; or R37、R38、R39、R40、R41Are all F.
14. The photoresist composition of claim 1, wherein in said formula (V) and said formula (VI) of said photoacid generator, when M is 1, M-R22Is hydrogen, -CH3、-Cl、-CH3O、-CH3CH2O、-N(CH3)2、-N(C6H5)2、-SCH3T-butyl, -CH2OH、-CH2ORa、-CH2OC(O)Ra、-CH2NRaRa’、-CHRa(OH)、-CRaRa’(OH)、-CCH3(CH2OH)OH、-C(CH2OH)2OH、-CH2CH2OH、-CH2CHMeOH、-CHMeCH2OH、-CH2CHPhOH、-CH2C(O)Ra、-CH2CO2H or a metal or amine salt thereof, -CH2CH2CO2H or a metal or amine salt thereof, -CH2CH2C(O)OCH2CH2OH、-CH2CHMeC(O)OCH2CH2OH、-CH2CH2C(O)OCH2CH2OCH2CH2OH、-CH2CH2C(O)OT、-CH2OC (O) -NHT or-CH2CH2OC (O) NHT, wherein T has the same definition as Z' defined in claim 1.
15. The photoresist composition of claim 1, wherein the photoresist polymer is a negative chemically amplified resin or a positive chemically amplified resin.
16. The photoresist composition of claim 15, wherein the negative-type chemically amplified resin comprises a phenolic hydroxyl group-containing resin and a cross-linking agent, wherein the phenolic hydroxyl group-containing resin is one or more of a novolac resin, a polyhydroxystyrene, a copolymer of hydroxystyrene and styrene, a copolymer of hydroxystyrene, styrene and a (meth) acrylic acid derivative, a phenol-xylene glycol condensation resin, a cresol-xylene glycol condensation resin, a phenolic hydroxyl group-containing polyimide, a phenolic hydroxyl group-containing polyamic acid and a phenol-dicyclopentadiene condensation resin, wherein the phenolic hydroxyl group-containing resin is one or more of a novolac resin, a polyhydroxystyrene, a copolymer of hydroxystyrene and styrene, a hydroxystyrene, a copolymer of styrene and a (meth) acrylic acid derivative, a phenol-xylene glycol condensation resin, wherein the phenolic hydroxyl group-containing resin is one or more of a novolac resin, a polyhydroxystyrene, a copolymer of polyhydroxystyrene and styrene, a copolymer of hydroxystyrene, a styrene and a (meth) acrylic acid derivative, a phenol-xylene glycol condensation resin, wherein the novolac resin is one or more of a novolac resin, a novolac resin is one or a novolac resin obtained by condensing phenol formaldehyde, a novolac resin, wherein the novolac resin is one or the phenol formaldehyde, wherein the novolac resin is one or the novolac resin is preferably, wherein the novolac resin is one or the novolac resin is the phenol formaldehyde condensation phenol formaldehyde, wherein the phenol formaldehyde condensation of the phenol formaldehyde, the.
17. The photoresist composition of claim 16, wherein the phenolic hydroxyl group-containing resin further comprises a phenolic compound; preferably, the phenolic compound is 4,4 '-dihydroxydiphenylmethane, 4' -dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) -1-phenylethane, tris (4-hydroxyphenyl) ethane, 1, 3-bis [1- (4-hydroxyphenyl) -1-methylethyl ] benzene, 1, 4-bis [1- (4-hydroxyphenyl) -1-methylethyl ] benzene, 4, 6-bis [1- (4-hydroxyphenyl) -1-methylethyl ] -1, 3-dihydroxybenzene, 1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethane, methyl-ethyl-1, 4-dihydroxyphenyl-1- [4- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethane, methyl-ethyl-1, 4-methyl-ethyl-1, 4-bis (4-hydroxyphenyl) -1, 1-methyl-ethyl ] phenyl ], 1,1,2, 2-tetrakis (4-hydroxyphenyl) ethane and one or more of 4, 4' - {1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethylidene } bisphenol; preferably, the phenolic hydroxyl group-containing resin contains less than 40% by weight of the phenolic compound, more preferably 1 to 30% by weight of the phenolic compound; preferably, the weight average molecular weight of the phenolic hydroxyl group-containing resin is 2000 or more, more preferably 2000 to 20000; preferably, the photoresist composition after the solvent is removed contains 30 to 90% by weight of the phenolic hydroxyl group-containing resin, more preferably 40 to 80% by weight of the phenolic hydroxyl group-containing resin.
18. The photoresist composition according to claim 16, wherein the crosslinking agent is bisphenol a-based epoxy compound, bisphenol F-based epoxy compound, bisphenol S-based epoxy compound, novolac-based epoxy compound, resol-based epoxy compound, poly (hydroxystyrene) -based epoxy compound, oxetane compound, methylol-containing melamine compound, methylol-containing benzoguanamine compound, methylol-containing urea compound, methylol-containing phenol compound, alkoxyalkyl-containing melamine compound, alkoxyalkyl-containing benzoguanamine compound, alkoxyalkyl-containing urea compound, alkoxyalkyl-containing phenol compound, carboxymethyl-containing melamine resin, carboxymethyl-containing benzoguanamine resin, carboxymethyl-containing urea resin, carboxymethyl-containing phenol resin, carboxymethyl-containing melamine compound, bisphenol F-based epoxy compound, epoxy compound, One or more of a carboxymethyl group-containing benzoguanamine compound, a carboxymethyl group-containing urea compound, and a carboxymethyl group-containing phenol compound; preferably, the crosslinking agent is one or more of a methylol-containing phenol compound, a methoxymethyl-containing melamine compound, a methoxymethyl-containing phenol compound, a methoxymethyl-containing glycoluril compound, a methoxymethyl-containing urea compound, and an acetoxymethyl-containing phenol compound; more preferably, the crosslinking agent is one or more of a methoxymethyl group-containing melamine compound such as hexamethoxymethylmelamine, a methoxymethyl group-containing glycoluril compound, and a methoxymethyl group-containing urea compound.
19. The photoresist composition of claim 16, wherein the molar ratio of the cross-linking agent is 5 to 60%, preferably 10 to 50%, more preferably 15 to 40% by mole percentage based on the number of moles of acidic functional groups in the phenolic hydroxyl group containing resin.
20. The photoresist composition of claim 15, wherein the positive-type chemical amplification resin is a resin having introduced therein a protective group in which at least a part of hydrogen atoms of an acidic functional group in an alkali-soluble resin is substituted by an acid-dissociable group, wherein the acid-dissociable group is a group dissociated in the presence of a strong acid generated from the photo-agent, wherein the alkali-soluble resin is one or more of a phenolic hydroxyl group-containing resin, a carboxyl group-containing resin, and a sulfonic acid group-containing resin, wherein the phenolic hydroxyl group-containing resin is preferably the same as the phenolic hydroxyl group-containing resin, wherein the carboxyl group-containing resin is obtained by vinyl polymerization of a carboxyl group-containing vinyl monomer and a hydrophobic group-containing vinyl monomer, wherein the carboxyl group-containing vinyl monomer is an unsaturated monocarboxylic acid such as (meth) acrylic acid, crotonic acid, and cinnamic acid, wherein the unsaturated polybasic carboxylic acid such as 2-membered carboxylic acid, e.g. (anhydrous) maleic acid, itaconic acid, and an alkaline earth-containing vinyl sulfonic acid, such as ethylene sulfonic acid, a salt of 2-vinyl-containing alkyl methacrylate, wherein the carboxyl group-containing vinyl methacrylate, such as ethylene sulfonic acid, a salt of ethylene-vinyl-ethyl methacrylate, wherein the carboxyl group-containing vinyl-acrylate, the carboxyl group-containing vinyl-acrylate, such as ethylene-styrene-acrylate, and the acrylic acid alkyl methacrylate, wherein the carboxyl group-vinyl-acrylate, the carboxyl group-containing vinyl-acrylate, such as ethylene-vinyl-acrylate, such as ethylene-vinyl-acrylate, the acrylic acid, and acrylic acid-vinyl-acrylate, and acrylic acid alkyl methacrylate, wherein the acrylic acid-acrylate, wherein the acrylic acid-vinyl-acrylate, the acrylic acid-acrylate, such as the acrylic acid-vinyl-acrylate, wherein the acrylic acid-acrylate, such as the acrylic acid-vinyl-acrylate, such as the acrylic acid, the acrylic acid-vinyl-acrylate, and acrylic acid, such as the acrylic acid-vinyl-acrylate, and acrylic acid-vinyl-acrylate, wherein the acrylic acid-vinyl-acrylate, such as the acrylic acid-acrylate, and acrylic acid, wherein the acrylic acid-vinyl.
21. The photoresist composition according to claim 20, wherein the acid dissociative group is one or more of a 1-substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group and a cyclic acid dissociative group, preferably the 1-substituted methyl group is a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, a benzyloxymethyl group, a benzylthiomethyl group, a phenacyl group, a bromoformylmethyl group, a methoxybenzoylmethyl group, a methylthiophenacyl group, an α -methylbenzoylmethyl group, a cyclopropylmethyl group, a benzyl group, a diphenylmethyl group, a triphenylmethyl group, a bromobenzyl group, a nitrobenzyl group, a methoxybenzyl group, a methylthiobenzyl group, an ethoxybenzyl group, an ethylthiobenzyl group, a piperonyl group, a methoxycarbonylmethyl group, an n-propoxycarbonylmethyl group, an n-butoxycarbonylmethyl group or a tert-butoxycarbonylmethyl group, preferably the 1-substituted ethyl group is a 1-methoxyethyl group, a 1-methylthioethyl group, a 1-dimethoxyethyl group, a 1-ethoxyethyl group, a 1-ethylthioethyl group, a 1-butylbenzoyl group, a 1-butylpropoxymethylpropionyl group, a 1-butylmethacryloyl group, a tert-butylthiopropionyl group, a 1-butylmethacryloyl group, a tetrahydrobutylthiopropionyl group, a tetrahydrobutylmethoxy-butylbenzoyl group, a tert-butylmethoxy propionyl group, a tetrahydrobutylbenzoyl group, a tert-butylbenzoyl group, a tetrahydrobutylbenzoyl group, a tetrahydrobutylpropionyl group, a tert-butylpropionyl group, a 1-butylbenzoyl group, a tert-butylpropionyl group, a tetrahydrobutylbenzoyl group, a tert-butylpropionyl group, a tetrahydrobutylpropionyl group, a tert-butylpropionyl group, a tert-butylbenzoyl group, a tert-butylpropionyl group, a tetrahydrobutylbenzoyl group, a butylbenzoyl group, a tert-butylpropionyl group, a 1-butylbenzoyl group, a tetrahydrobenzoyl group, a tert-butylbenzoyl group, a butylpropionyl group, a tert-butylpropionyl group, a butylbenzoyl group, a butylpropionyl group, a tert-butylbenzoyl group, a butylpropionyl group, a tert-butylpropionyl group, a butylbenzoyl group, a tert-butylbenzoyl group, a tetrahydrobenzoyl group, a butylbenzoyl group, a tert-butylbenzoyl group, a butylbenzoyl group.
22. The photoresist composition of claim 1, wherein the photoresist composition further comprises (c) an organic solvent; preferably, the organic solvent is a ketone such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, 2-heptanone, or the like; polyhydric alcohols and derivatives thereof such as monomethyl, monoethyl, monopropyl, monobutyl or monophenyl ethers of ethylene glycol, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol, or dipropylene glycol monoacetate; cyclic ethers such as dioxane; and esters such as one or more of methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; preferably, the organic solvent is one or more of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, gamma-lactone, cyclohexanone and ethyl lactate; preferably, the photoresist composition comprises 1 to 20% by weight, preferably 2 to 15% by weight of an organic solvent.
23. The photoresist composition of claim 1, wherein the photoresist composition further comprises (d) an additive; preferably, the additive is one or more of a flow regulator, a wetting agent, an adhesive, a thixotropic agent, a colorant, a pigment, a filler, and a solvent promoter.
24. A pattern forming method of the photoresist composition according to any one of claims 1 to 23, characterized by comprising the steps of:
(1) coating the photoresist composition of any one of claims 1 to 27 on a substrate;
(2) baking the photoresist composition at a temperature of 60-160 ℃ after coating;
(3) irradiating the photoresist composition in an image mode by using light with the wavelength of 180-450 nm;
(4) baking the photoresist composition after irradiation, optionally at a temperature of 60 to 160 ℃; and
(5) developing the photoresist composition with a developer.
25. Use of the photoresist composition of any one of claims 1 to 23 in the manufacture of photosensitive materials for electronic devices, integrated circuits, thin film transistors, and printing plates.
26. Use of a photoresist composition of any one of claims 1 to 23 in the manufacture of intermetal dielectric layers for semiconductor devices, buffer layers, passivation coatings, waveguides for optoelectronic devices, and microelectromechanical systems.
Technical Field
The invention relates to the technical field of photocuring, in particular to a photoresist composition, a pattern forming method and application thereof. More particularly, the present invention relates to a chemically amplified photoresist composition containing an oxime sulfonate photoinitiator, a pattern forming method of the photosensitive resin composition, and an application of the photosensitive resin composition.
Background
The chemically amplified photoresist is characterized in that after the composition is irradiated by radiation, a photosensitive compound, namely a photo-acid generator (PAG), in the composition can be subjected to photochemical decomposition during exposure to generate a small amount of acid, and under the heating condition, the acid can catalyze polymers in an exposed area to be decomposed (positive photoresist) or crosslinked (negative photoresist), so that the solubility difference of the exposed area and an unexposed area in a developing solution is large, the exposed area and the unexposed area are not consumed by reaction, and the chemically amplified photoresist can be recycled, and the quantum efficiency and the sensitivity of exposure are greatly improved. It is widely used in the fine processing of integrated circuits and semiconductor discrete devices in the electronics industry.
As such a photoresist composition, for example, a chemically amplified resist based on an oxime sulfonate as an acid generator and poly-p-t-butoxycarbonyloxystyrene as an acid component, after exposure to radiation, the acid generated from the acid generator catalyzes the decomposition of the poly-p-butoxycarbonyloxystyrene component into poly-p-hydroxystyrene, with the result that, after exposure, the exposed portion becomes soluble in an alkaline developer, and a positive image can be obtained with such a developer. Wherein the oxime sulfonate has a maximum absorption wavelength of 250nm in the UV/VIS spectrum and has a low absorption intensity at a wavelength of 313nm or more; for example, the photoresist compositions containing oxime sulfonate ester connected with perfluoroalkyl or perfluoroaryl all have certain defects, are only sensitive to specific radiation wavelength, and are mostly subjected to radiation curing by i-line obtained by interference of a filter by using a high-pressure mercury lamp as a light source, so that the spectrum range is narrow, and the defects are more obvious particularly for long-wavelength.
It is known that mercury lamps as radiation sources generate ozone, which causes environmental pollution, and that their use is increasingly limited due to low energy conversion efficiency and short life. The LED light source has the advantages of small volume, high efficiency, long service life, low temperature, no ozone generation and the like, is a preferential substitute for radiation curing instead of mercury lamps, but has no related report of the photoresist composition containing the oxime sulfonate photoinitiator applicable to the LED lamp.
Disclosure of Invention
The invention mainly aims to provide a photoresist composition, a pattern forming method and application thereof, so as to solve the problems that the photoresist composition in the prior art has low sensitivity and narrow spectral range to 365-435nm LED light sources, and the photoresist composition has poor storage stability, low sensitivity and poor transparency.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a photoresist composition comprising a component a which is a photoacid generator and a component b which is a photoresist polymer, wherein the photoacid generator is one or more of compounds represented by formula (i), formula (ii), formula (iii), formula (iv), formula (v) and formula (vi),
wherein, in the formula (I),
R1is a sulfonyl group, wherein the sulfonyl group is an alkylsulfonyl, phenylsulfonyl or camphorylsulfonyl group, wherein the H atoms in the sulfonyl group may each independently be replaced by NO2-、CN-、C1～C18Alkyl radical, C3～C8Cycloalkyl radical, C1～C4Alkyl radicals and C3～C8Cycloalkylalkyl consisting of cycloalkyl radicals, or containing O, S, N atomsA heterocyclic group is substituted with a heterocyclic group,
n is an integer of 1 to 1000,
when n is 1, X-R0And Q-R2Independently of one another are hydrogen,
when n is an integer of 2-1000, R0And R2Each independently selected from straight chain or branched chain alkylene, substituted straight chain or branched chain alkylene, wherein the substituent is one or more of hydroxyl, amino, sulfhydryl, ester group, nitrile group, carbonyl and alkoxy, and R is0And R2Any two of them are adjacent to-CH2May be interrupted by-O-, -C (O) O-or-OC (O); x and Q are each independently selected from n-valent groups comprising-NHC (O) O-units;
R3is an olefin group, Raor-C (O) -Ra，RaHave the same definition as in formula (I);
wherein, in the formula (II),
R12and R13All have the same structure as R in the formula (I)1The same definition;
wherein, in the formula (III) and the formula (IV),
R14and R15Each independently selected from C1～C20Straight or branched alkyl of (2), C3～C12A cycloalkyl, cycloalkyl derivative or heterocycloalkyl derivative of (A),
wherein the cycloalkyl derivative has the following structure:
the heterocycloalkyl derivative has the following structure:
R16and R17Independently of one another are hydrogen,
Wherein, in the formula (V) and the formula (VI),
R18is composed of
R19is composed of
R20is composed of
R21is composed ofWherein R is37、R38、R39、R40、R41Independently of one another, hydrogen, halogen, -Ra、-ORa、-SRa、-NRaRa′、-CH2OH、-CH2ORaor-CH2NRaRa', wherein RaAnd Ra' has the same definition as in formula (I); wherein R is34、R35、R36Are all Ra，RaHas the same definition as in formula (I), R9、R10、R11Any two of which may optionally form a three-, four-, five-or six-membered ring; d
m is an integer of 1 to 1000,
wherein, when M is 1, M-R22Is hydrogen, halogen, -Ra、-ORa、-SRa、-NRaRa′、-CH2OH、-CH2ORaor-CH2NRaRa', wherein RaAnd Ra' has the same definition as in formula (I);
when m is an integer of 2-1000, R22is-CH2-、-CH2CH2-、-CH2CH(OH)CH2-、-CH2CH(ORa)CH2-、-CH2CH(OC(O)Ra)CH2-、-CH2CH2C(O)OCH2CH2-、-CH2CH(Me)C(O)OCH2CH2-、-CH2CH2C(O)OCH2CH2OCH2CH2-、-CH2CH2C(O)OCH2CH2CH2-or-CH2CH2C(O)OCH2CH2CH2CH2-, M is C substituted by 2 to 6C ═ C double bonds2～C36M-valent alkyl groups of (a).
According to another aspect of the present invention, there is provided a pattern forming method of the above photoresist composition, the pattern forming method comprising the steps of: (1) coating the photoresist composition on a substrate; (2) baking the photoresist composition at a temperature of 60-160 ℃ after coating; (3) irradiating the photoresist composition in an image mode by using light with the wavelength of 180-450 nm; (4) baking the photoresist composition after irradiation, optionally at a temperature of 60 to 160 ℃; (5) the photoresist composition is developed with a developer.
According to another aspect of the present invention, there is provided a use of the above photoresist composition for manufacturing a photosensitive material for electronic devices, an integrated circuit, a thin film transistor, and a printing plate.
According to another aspect of the present invention, there is provided a use of the above photoresist composition in the manufacture of inter-metal dielectric layers for semiconductor devices, buffer layers, passivation coatings, waveguides for optoelectronic devices, and microelectromechanical systems.
According to the technical scheme, the photoresist composition comprises a component a and a component b, wherein the component a is a photoacid generator, and the component b is a photoresist polymer, wherein the photoacid generator is one or more of compounds shown in a formula (I), a formula (II), a formula (III), a formula (IV), a formula (V) and a formula (VI). The photoresist composition has high sensitivity and wide spectral range to 365-435nm LED light sources, and has excellent storage stability, high sensitivity and good transparency.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background section, the existing photoresist composition can not effectively solve the problems of low sensitivity, narrow spectral range, poor storage stability, low sensitivity and poor transparency of the photoresist composition to 365-435nm LED light source in the prior art. In order to solve the above problems, the present invention provides a photoresist composition comprising a component a which is a photoacid generator and a component b which is a photoresist polymer which is a compound capable of being imparted with a change in solubility in a solution in the presence of an acid, wherein the photoacid generator is one or more of compounds represented by formula (i), formula (ii), formula (iii), formula (iv), formula (v) and formula (vi),
wherein, in the formula (I),
R1is a sulfonyl group, wherein the sulfonyl group is an alkylsulfonyl, phenylsulfonyl or camphorylsulfonyl group, wherein the H atoms in the sulfonyl group may each independently be replaced by NO2-、CN-、C1～C18Alkyl radical, C3～C8Cycloalkyl radical, C1～C4Alkyl radicals and C3～C8Cycloalkylalkyl consisting of cycloalkyl, or a heterocyclic group containing O, S, N atoms,
n is an integer of 1 to 1000,
when n is 1, X-R0And Q-R2Independently of one another are hydrogen,
when n is an integer of 2-1000, R0And R2Each independently selected from straight chain or branched chain alkylene, substituted straight chain or branched chain alkylene, wherein the substituent is one or more of hydroxyl, amino, sulfhydryl, ester group, nitrile group, carbonyl and alkoxy, and R is0And R2Any two of them are adjacent to-CH2May be interrupted by-O-, -C (O) O-or-OC (O); x and Q are each independently selected from n-valent groups comprising-NHC (O) O-units;
R3is an olefin group, Raor-C (O) -Ra，RaHave the same definition as in formula (I);
wherein, in the formula (II),
R12and R13All have the same structure as R in the formula (I)1The same definition;
wherein, in the formula (III) and the formula (IV),
R14and R15Each independently selected from C1～C20Straight or branched alkyl of (2), C3～C12A cycloalkyl, cycloalkyl derivative or heterocycloalkyl derivative of (A),
wherein the cycloalkyl derivative has the following structure:
the heterocycloalkyl derivative has the following structure:
R16and R17Independently of one another are hydrogen,
Wherein, in the formula (V) and the formula (VI),
R18is composed of
R19is composed of
R20is composed of
R21is composed of
m is an integer of 1 to 1000,
wherein, when M is 1, M-R22Is hydrogen, halogen, -Ra、-ORa、-SRa、-NRaRa′、-CH2OH、-CH2ORaor-CH2NRaRa', wherein RaAnd Ra' has the same definition as in formula (I);
when m is an integer of 2-1000, R22is-CH2-、-CH2CH2-、-CH2CH(OH)CH2-、-CH2CH(ORa)CH2-、-CH2CH(OC(O)Ra)CH2-、-CH2CH2C(O)OCH2CH2-、-CH2CH(Me)C(O)OCH2CH2-、-CH2CH2C(O)OCH2CH2OCH2CH2-、-CH2CH2C(O)OCH2CH2CH2-or-CH2CH2C(O)OCH2CH2CH2CH2-, M is C substituted by 2 to 6C ═ C double bonds2～C36M-valent alkyl groups of (a).
The photoresist composition has high sensitivity and wide spectral range to 365-435nm LED light sources, and has excellent storage stability, high sensitivity and good transparency.
To further enhance the above-described advantages and benefits of the photoresist composition of the present invention, in a preferred embodiment, in the formula (i) of the photoacid generator,
R4、R6、R8are all-CH3And R is5、R7Are all H; or
R4、R5、R7、R8Are all H, and R6is-CH3(ii) a Or
R5、R6Are all-OCH3And R is4、R7、R8Are all H; or
R4、R6、R8Are all-CH3And R is5、R7Are all-CH2OH; or
R4、R6、R7、R8Are all H, and R5is-SCH3(ii) a Or
R4、R5、R7、R8Are all H, and R6is-SCH3(ii) a Or
R4、R6、R8Are all CH3And R is5、R7Are all CH2OC(O)Ra(ii) a Or
R4、R6、R8Are all CH3And R is5Is CH2OH, and R7Is H; or
R4、R6、R8Are all CH3And R is5、R7Are all CH2ORa(ii) a Or
R4、R6、R8Are all CH3And R is5、R7Are all CH2NRaRa'; or
R4、R6、R8Are all CH3And R is5Is CH2OH, and R7Is CH2NRaRa′。
To further enhance the above-described advantages and benefits of the photoresist compositions of the present invention, in a preferred embodiment, the photoacid generator is of formula (I)In, R9、R10Are all CH3，R11Is H; or, R9、R10、R11Are all CH2CH3(ii) a Or, R9Is CH3，R10、R11And substituted carbon atoms form a cycloalkyl group. More preferably, in the formula (I) of the photoacid generator, R3is-CH3、-CH2CH3、-CH(CH3)2、-C6H5、-p-CH3OC6H4、-CH2CH＝CH2、-CH2Ph、-C(O)CEt3、-C(O)CMe3Or a biphenyl group. More preferably, in the formula (I) of the photoacid generator, n is an integer of 1 to 100; preferably, n is an integer of 1 to 10.
To further enhance the above-described advantages and benefits of the photoresist composition of the present invention, in a preferred embodiment, in the formula (I) of the photoacid generator, when n is 1, X-R0And Q-R2Independently of one another, hydrogen, C containing 0 to 4 substituents6～C24Aryl group, -CH3、-CH2CH3、-CH(CH3)2、-ORa、-CH2OH、-CH2ORa、-CH2OC(O)Ra、-CH2NRaRa′、-CHRa(OH)、-CRaRa′(OH)、-CCH3(CH2OH)OH、-C(CH2OH)2OH、-CH2CH2OH、-CH2CHMeOH、-CHMeCH2OH、-CH2CHPhOH、-CH2C(O)Ra、-CH2CO2H or a metal or amine salt thereof, -CH2CH2CO2H or a metal or amine salt thereof, -CH2CH2C(O)OCH2CH2OH、-CH2CHMeC(O)OCH2CH2OH、-CH2CH2C(O)OCH2CH2OCH2CH2OH、-CH2CH2C(O)OZ′、-CH2OC (O) -NHZ' or-CH2CH2OC (O) NHZ', wherein C having 0 to 4 substituents is preferable6～C24Aryl of (a) is phenyl, biphenyl or naphthyl, and Z' is C containing 2-6C ═ C double bond substituents2-C36Alkylene group, preferably Z' is C containing 2 to 6 substituents of acrylate unit2-C36An alkylene group; more preferably, Z' is one of the groups shown below:
wherein Z is-CH2-or-CH2OCH2CH2-, m is 0, 1,2 or 3.
To further enhance the above advantages and benefits of the photoresist composition of the present invention, in a preferred embodiment, in the formula (I) of the photoacid generator, when n is an integer of 2 to 1000, R0And R2Are respectively-CH2-、-CH2CH2-、-CH2CH(OH)CH2-、-CH2CH(ORa)CH2-、-CH2CH(OC(O)Ra)CH2-、-CH2CH2C(O)OCH2CH2-、-CH2CH(Me)C(O)OCH2CH2-、-CH2CH2C(O)OCH2CH2OCH2CH2-、-CH2CH2C(O)OCH2CH2CH2-or-CH2CH2C(O)OCH2CH2CH2CH2-；
X and Q are each independently-NHC (O) O-, or-C (O) O-, or-CH with at least 2-NHC (O) —, or-C (O) —, or-CH with at least 22CH2C (O) O-, or at least 2-CH2CH (Me) C (O) O-, or at least 2-CH2CH2C (O) O-, or at least 2-CH2CH (Me) C (O) O-, or at least 2-CH2CH2C(O)C(O) -, or at least 2-CH2CH (Me) C (O) -, or at least 2-CH2CH2C (O) NH-, or at least 2-CH2CH (Me) C (O) NH-, or at least 2-CH2CH2C (O) -, or at least 2-CH2CH (Me) C (O) -, or at least 2-CH2CH2C (O) NH-, or at least 2-CH2CH (Me) C (O) NH-, or at least 2-CH2CH2C(O)NRa-, or at least 2-CH2CH(Me)C(O)NRa-, or at least 2-CH2CH2SO2-, or at least 2-CH2CH(Me)SO2-, or at least 2-CH2CH2S(O)Ra-, or at least 2-CH2CH(Me)S(O)Ra-, or at least 2-CH2CH (OH) -or-CH2CH(ORa) -an n-valent group;
preferably, X and Q are each one of the groups shown below:
wherein R is11Is hydrogen or RaP is an integer of 0 to 20;
as is apparent to those skilled in the art, it is readily apparent that the polyisocyanate [ -NHC (O) O-]Unit or polyester [ -C (O) O-]The units are all derived from R0Or R2The hydroxyl groups in the structure are obtained by esterification reaction with corresponding polyurethane polyol NCO groups or polybasic acid anhydride or polybasic acid halide, therefore, the preferable X or Q structure is only an exemplary and non-limiting structure, and all the X or Q structures meeting the essence of the chemical reaction belong to the scope of the disclosure of the invention;
wherein Z is-CH2-or-CH2OCH2CH2P is an integer of 0 to 20;
it will be apparent to those of ordinary skill in the art that-CH in the above X or Q structure is readily apparent2CH2C(O)O-，-CH2CH(Me)C(O)O-，-CH2CH2C(O)C(O)O-，-CH2CH(Me)C(O)C(O)O-，-CH2CH2C(O)C(O)-，-CH2CH(Me)C(O)C(O)-，-CH2CH2C(O)C(O)NH-，-CH2CH2C(O)-，-CH2CH(Me)C(O)C(O)NH-，-CH2CH(Me)C(O)-，-CH2CH2C(O)NH-，-CH2CH(Me)C(O)NH-，-CH2CH2C(O)NR-，-CH2CH(Me)C(O)NR-，-CH2CH2SO2-，-CH2CH(Me)SO2-，-CH2CH2S (O) R-, or-CH2The CH (Me) S (O) R-units are derived from the Michael addition reaction of an intermediate having nucleophilic properties to the corresponding unsaturated ester, unsaturated amide, unsaturated sulfone or sulfoxide, or the like. Thus, the preferred X or Q structures are exemplary only and not limiting structures, and all small molecule or polymeric X or Q structures that meet the spirit of the chemical reaction are within the scope of the present disclosure;
wherein m is 0, 1,2 or 3, R is Ra，RaHas the definition as above;
it will be apparent to those of ordinary skill in the art that-CH in the above X or Q structure is readily apparent2CH (OH) -or-CH2The CH (OR) -units are all derived from intermediates having nucleophilic properties towards the corresponding epoxyAnd (3) ring-opening reaction preparation of the compound. Thus, the preferred X or Q structures are exemplary only and not limiting structures, and all small molecule or polymeric X or Q structures that meet the spirit of the chemical reaction are within the scope of the present disclosure.
To further enhance the above-described advantages and benefits of the photoresist compositions of the present invention, in a preferred embodiment, in the formula (I) of the photoacid generator, R1Is composed of C1～C3A sulfonyl group which is a linear or branched alkyl group, or a sulfonyl group which contains a phenyl group, preferably the sulfonyl group is trifluoromethanesulfonyl, p-trifluoromethanesulfonyl, methanesulfonyl or p-toluenesulfonyl.
To further enhance the above-described advantages and benefits of the photoresist composition of the present invention, in a preferred embodiment, in the formula (III) and the formula (IV) of the photoacid generator, R16is-CH3、-CH2CH3、-CH2CH(CH3)2、-CH2Ph, a cycloalkyl derivative or a heterocycloalkyl derivative; preferably, U is-CH2-or a single bond, R'5、R′6、R′8、R′9Are all H and R'7Is CH3。
To further enhance the above-described advantages and benefits of the photoresist composition of the present invention, in a preferred embodiment, R of the formula (V) and the formula (VI) in the photoacid generator18In, R23、R25Are all-CH3And R is24Is H; or R23is-CH3And R is24、R25Are all H; or R23、R24Are all-CH3And R is25is-OH; or R23、R24Are all H and R25is-CH2CH2CH3(ii) a Or R23、R24、R25Are all Br; or R24、R25Are all-CH3And R is23Is Cl; or R23Is H and R24-R25Are all cyclohexane; or R23、R24Are all-CH3And R is25is-N (CH)3)2(ii) a Or R23、R25Are all-CH3And R is24is-N (CH)2CH2)2O; or R23、R24、R25Are all-CH3(ii) a Or R23、R25Are all-CH3And R is24is-CH2NRaRa'; or R23、R25Are all-CH3And R is24is-CH2OH。
To further enhance the above-described advantages and benefits of the photoresist composition of the present invention, in a preferred embodiment, R in the formula (VI) of the photoacid generator22To R in the formula (V)22One less-CH2-。
To further enhance the above-mentioned advantages and benefits of the photoresist composition of the present invention, in a preferred embodiment, in the formula (v) and the formula (vi) of the photoacid generator,
To further enhance the above-described advantages and benefits of the photoresist composition of the present invention, in a preferred embodiment, R of the formula (V) and the formula (VI) in the photoacid generator19And R20In, R26、R27、R28、R29、R30、R31、R32、R33Are all H; or R30、R31Are all-CH3And R is26、R27、R28、R29、R32、R33Are all H; or R30、R33Are all-OCH3And R is26、R27、R28、R29、R31、R32Are all H; or R30、R33Are all tert-butyl and R26、R27、R28、R29、R31、R32Are all H; or R26is-CH3And R is27、R28、R29、R30、R31、R32、R33Are all H; or R26、R29Are all-CH3And R is27、R28、R30、R31、R32、R33Are all H; or R26、R30、R33Are all-CH3And R is27、R28、R29、R31、R32Are all H. More preferably, R in the formula (V) and the formula (VI) of the photoacid generator21In, R34is-CH3And R is35、R36Are all H; or R34、R35Are all-CH3And R is36Is H; or R34Is H and R35-R36Is cyclohexane; or R34is-CF3And R is35、R36Are all H.
To further enhance the above-described advantages and benefits of the photoresist composition of the present invention, in a preferred embodiment, R of the formula (V) and the formula (VI) in the photoacid generator21In, R39is-CH3And R is37、R38、R40、R41Are all H; or R39is-CF3And R is37、R38、R40、R41Are all H; or R37Is Cl and R38、R39、R40、R41Are all H; or R37、R39Are all Cl and R38、R40、R41Are all H; or R39is-OCH3And R is37、R38、R40、R41Are all H; or R39Is F and R37、R38、R40、R41Are all H; or R37、R38、R39、R40、R41Are all F.
To further enhance the inventionThe above advantages and advantageous effects of the photoresist composition of (1), in a preferred embodiment, in the formula (V) and the formula (VI) of the photoacid generator, when M is 1, M-R22Is hydrogen, -CH3、-Cl、-CH3O、-CH3CH2O、-N(CH3)2、-N(C6H5)2、-SCH3T-butyl, -CH2OH、-CH2ORa、-CH2OC(O)Ra、-CH2NRaRa′、-CHRa(OH)、-CRaRa′(OH)、-CCH3(CH2OH)OH、-C(CH2OH)2OH、-CH2CH2OH、-CH2CHMeOH、-CHMeCH2OH、-CH2CHPhOH、-CH2C(O)Ra、-CH2CO2H or a metal or amine salt thereof, -CH2CH2CO2H or a metal or amine salt thereof, -CH2CH2C(O)OCH2CH2OH、-CH2CHMeC(O)OCH2CH2OH、-CH2CH2C(O)OCH2CH2OCH2CH2OH、-CH2CH2C(O)OT、-CH2OC (O) -NHT or-CH2CH2OC (O) NHT, where T has the same definition as Z' defined above.
In order to further enhance the above advantages and benefits of the photoresist composition of the present invention, in a preferred embodiment, the photoresist polymer (b component) is a negative chemically amplified resin (QN) or a positive chemically amplified resin (QP). The difference in resist solubility between the irradiated and non-irradiated portions resulting from the acid-catalyzed reaction of component b during or after irradiation may be of two types, a negative-type chemically amplified resin (QN) in which a crosslinking reaction occurs such that the exposed areas of the resist coating are less soluble in the developer than the non-exposed areas, a negative-type photoresist corresponding to the composition, and a positive-type chemically amplified resin (QP) in which the acid-labile groups in the polymer or copolymer are deprotected such that the exposed areas are more soluble in the developer than the non-exposed areas, and a positive-type photoresist corresponding to the composition.
In order to further enhance the above advantages and benefits of the photoresist composition of the present invention, in a preferred embodiment, the negative chemical amplification resin (QN) comprises a phenolic hydroxyl group-containing resin (QN1) and a crosslinking agent (QN2), preferably, the phenolic hydroxyl group-containing resin (QN1) is one or more of a novolac resin, a polyhydroxystyrene copolymer, a hydroxystyrene and styrene copolymer, a hydroxystyrene and (meth) acrylic acid derivative copolymer, a phenol-xylylene glycol condensation resin, a cresol-xylylene glycol condensation resin, a phenolic hydroxyl group-containing polyimide, a phenolic hydroxyl group-containing polyamic acid and a phenol-dicyclopentadiene condensation resin, preferably, the phenolic hydroxyl group-containing resin (QN1) is one or more of a novolac resin, a polyhydroxystyrene copolymer, a hydroxystyrene and styrene copolymer, a phenol-cresol-formaldehyde condensation resin, a phenol formaldehyde condensation catalyst, a phenol formaldehyde condensation catalyst, a phenol formaldehyde condensation catalyst, a phenol formaldehyde condensation catalyst, a phenol.
To further enhance the above-mentioned advantages and benefits of the photoresist composition of the present invention, in a preferred embodiment, the phenolic hydroxyl group containing resin (QN1) further comprises a phenolic compound; preferably, the phenolic compound is 4,4 '-dihydroxydiphenylmethane, 4' -dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) -1-phenylethane, tris (4-hydroxyphenyl) ethane, 1, 3-bis [1- (4-hydroxyphenyl) -1-methylethyl ] benzene, 1, 4-bis [1- (4-hydroxyphenyl) -1-methylethyl ] benzene, 4, 6-bis [1- (4-hydroxyphenyl) -1-methylethyl ] -1, 3-dihydroxybenzene, 1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethane, 1,1,2, 2-tetrakis (4-hydroxyphenyl) ethane and one or more of 4, 4' - {1- [4- [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl ] ethylidene } bisphenol; preferably, the phenolic hydroxyl group-containing resin (QN1) contains less than 40% by weight of the phenolic compound, more preferably 1 to 30% by weight of the phenolic compound; preferably, the weight average molecular weight of the phenolic hydroxyl group-containing resin (QN1) is 2000 or more, more preferably 2000 to 20000; preferably, the photoresist composition after the solvent removal comprises 30 to 90% by weight of the phenolic hydroxyl group-containing resin (QN1), more preferably 40 to 80% by weight of the phenolic hydroxyl group-containing resin (QN 1).
In order to further enhance the above advantages and advantageous effects of the photoresist composition of the present invention, in a preferred embodiment, the crosslinking agent (QN2) is a bisphenol a-based epoxy compound, a bisphenol F-based epoxy compound, a bisphenol S-based epoxy compound, a novolac-based epoxy compound, a resol-based epoxy compound, a poly (hydroxystyrene) -based epoxy compound, an oxetane compound, a methylol-containing melamine compound, a methylol-containing benzoguanamine compound, a methylol-containing urea compound, a methylol-containing phenol compound, an alkoxyalkyl-containing melamine compound, an alkoxyalkyl-containing benzoguanamine compound, an alkoxyalkyl-containing urea compound, an alkoxyalkyl-containing phenol compound, a carboxymethyl-containing melamine resin, a carboxymethyl-containing benzoguanamine resin, a carboxymethyl-containing urea resin, a, One or more of a carboxymethyl group-containing phenol resin, a carboxymethyl group-containing melamine compound, a carboxymethyl group-containing benzoguanamine compound, a carboxymethyl group-containing urea compound, and a carboxymethyl group-containing phenol compound; preferably, the crosslinking agent (QN2) is one or more of a methylol-containing phenol compound, a methoxymethyl-containing melamine compound, a methoxymethyl-containing phenol compound, a methoxymethyl-containing glycoluril compound, a methoxymethyl-containing urea compound, and an acetoxymethyl-containing phenol compound; more preferably, the crosslinking agent (QN2) is one or more of a methoxymethyl group-containing melamine compound such as hexamethoxymethylmelamine, a methoxymethyl group-containing glycoluril compound, and a methoxymethyl group-containing urea compound.
In order to further balance the effects between the components, in a preferred embodiment, the molar proportion of the crosslinking agent (QN2) is 5 to 60%, preferably 10 to 50%, more preferably 15 to 40% in terms of mole percent, based on the number of moles of acidic functional groups in the phenolic hydroxyl group-containing resin (QN 1).
In order to further enhance the above advantages and advantageous effects of the photoresist composition of the present invention, in a preferred embodiment, the positive chemically amplified resin (QP) is a resin (QP2) in which at least a part of hydrogen atoms of an acidic functional group, such as one or more of a phenolic hydroxyl group, a carboxyl group and a sulfonyl group, in an alkali-soluble resin (QP1), is substituted with an acid-dissociable group, such as a group dissociated in the presence of a strong acid generated by the above photoacid generator, preferably, the alkali-soluble resin (QP1) is one or more of a phenolic hydroxyl group-containing resin (QP11), a carboxyl group-containing resin (QP12) and a sulfonic acid group-containing resin (QP13), preferably, the phenolic hydroxyl group-containing resin (QP11) is the same as the phenolic hydroxyl group-containing resin (QN1), preferably, the carboxyl group-containing resin (QP 365) is obtained by polymerizing a carboxyl group-containing vinyl sulfonic acid-containing vinyl alkyl methacrylate monomer, such as ethylene alkyl methacrylate, preferably, a carboxyl group-containing vinyl methacrylate, a vinyl methacrylate-containing acrylate, a vinyl methacrylate.
In order to further enhance the above advantages and advantageous effects of the photoresist composition of the present invention, in a preferred embodiment, the acid dissociative group is one or more of a 1-substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group and a cyclic acid dissociative group, preferably, the 1-substituted methyl group is a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, a benzyloxymethyl group, a benzylthiomethyl group, a benzoylmethyl group, a bromoformylmethyl group, a methoxybenzoylmethyl group, a methylthiophenacyl group, an α -methylbenzoylmethyl group, a cyclopropylmethyl group, a benzyl group, a diphenylmethyl group, a triphenylmethyl group, a bromobenzyl group, a nitrobenzyl group, a methoxybenzyl group, a methylthiobenzyl group, an ethoxybenzyl group, an ethylthiobenzyl group, a piperonylmethyl group, a methoxycarbonylmethyl group, an n-propoxycarbonylmethyl group, an isopropoxycarbonylmethyl group, a n-butoxycarbonylmethyl group or a tert-butoxycarbonylmethyl group, preferably, the 1-substituted ethyl group is a 1-methoxyethyl group, a 1-methylthioethyl group, a 1-butylmethacryloyl group, a 1-butylthiopropionyl group, a tert-butylmethacryloyl group, a tetrahydrobutyrylmethoxy group, a tert-butylbenzoyl group, a benzoyloxy group, a butylbenzoyl group, a benzoyloxy group, a butylbenzoyl group.
In order to further balance the effect between the components, in a preferred embodiment, the acid-dissociable group accounts for 10 to 100%, preferably 15 to 100%, of the total amount of the acid-functional group and the acid-dissociable group that are unprotected in the resin (QP2) into which the protecting group is introduced.
In order to further enhance the above advantages and advantageous effects of the photoresist composition of the present invention, in a preferred embodiment, the weight average molecular weight of the protective group-introduced resin (QP2) as measured by gel permeation chromatography in terms of polystyrene is 1000 to 150000, preferably 3000 to 100000.
For ease of coating, in a preferred embodiment, the photoresist composition further comprises (c) an organic solvent; preferably, the organic solvent is a ketone such as acetone, methyl ethyl ketone, cyclohexanone, methyl n-amyl ketone, methyl isoamyl ketone, 2-heptanone, or the like; polyhydric alcohols and derivatives thereof such as monomethyl, monoethyl, monopropyl, monobutyl or monophenyl ethers of ethylene glycol, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol, or dipropylene glycol monoacetate; cyclic ethers such as dioxane; and esters such as one or more of methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; preferably, the organic solvent is one or more of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, gamma-lactam ester, cyclohexanone and ethyl lactate; preferably, the photoresist composition comprises 1 to 20% by weight, preferably 2 to 15% by weight of an organic solvent.
To further enhance the above-mentioned advantages and benefits of the photoresist composition of the present invention, in a preferred embodiment, the photoresist composition further comprises (d) an additive; preferably, the additive is one or more of a flow modifier, a wetting agent, an adhesive, a thixotropic agent, a colorant, a pigment, a filler, and a solvent promoter.
In addition, according to another aspect of the present invention, there is provided a pattern forming method of the above photoresist composition, the pattern forming method comprising the steps of: (1) coating the photoresist composition on a substrate; (2) baking the photoresist composition at a temperature of 60-160 ℃ after coating; (3) irradiating the photoresist composition in an image mode by using light with the wavelength of 180-450 nm; (4) baking the photoresist composition after irradiation, optionally at a temperature of 60 to 160 ℃; (5) the photoresist composition is developed with a developer.
For the purpose of reducing production costs while improving product properties, in a preferred embodiment, the coating in step (1) is a uniform application of the photoresist composition to the substrate by spin coating, dipping, blade coating, curtain pouring, brushing, spraying or roller coating; preferably, the coating has a thickness of 0.01 to 150 μm; preferably, the substrate is a substrate for electronic parts, on which a predetermined wiring pattern is formed, wherein the material of the wiring pattern is copper, aluminum, nickel or gold; preferably, the substrate is a silicon wafer, a metal such as copper, chromium, iron, an aluminum substrate or a glass substrate.
For the purpose of reducing production costs while improving product properties, in a preferred embodiment, the temperature in step (2) is 50 to 160 ℃, preferably 60 to 140 ℃.
For the purpose of reducing the production cost while improving the product properties, in a preferred embodiment, the light in step (3) is derived from a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an LED light source, a chemical lamp or a laser generating device; preferably, when the low-pressure mercury lamp, the high-pressure mercury lamp, or the ultra-high-pressure mercury lamp is used, light having a wavelength of g-line (436nm), i-line (365nm), or h-line (405nm) may be preferable; when the laser generating apparatus is used, the solid-state laser (YAG) uses a light of 343nm or 355nm, and the excimer laser uses a light of 248nm (KrF) or 193nm (ArF); when the LED light source is used, light having a wavelength of 365nm, 385nm, 395nm or 405nm is preferably used.
For the purpose of reducing production costs while improving product properties, in a preferred embodiment, the baking time in step (4) is 1 to 30 min.
For the purpose of reducing the production cost while improving the product properties, in a preferred embodiment, the development in step (5) is dip development or jet development; preferably, the developer is a metal base, such as sodium hydroxide, potassium hydroxide, the corresponding carbonate, bicarbonate, silicate or metasilicate; metal-free bases such as ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide or tetraethylammonium hydroxide; preferably, the developer is a solution having an equivalent concentration of about 0.1 to 0.3.
In addition, according to another aspect of the present invention, there is provided a use of the above photoresist composition in the manufacture of a photosensitive material for electronic devices, an integrated circuit, a Thin Film Transistor (TFT), and a printing plate.
Further, according to another aspect of the present invention, there is provided a use of the above photoresist composition for manufacturing an inter-metal dielectric layer, a buffer layer, a passivation coating layer, a waveguide of an optoelectronic device, and a micro-electromechanical system of a semiconductor device.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
1. Preparation of negative photoresist
A resist solution was prepared by mixing 65 parts of polyvinylphenol (Mw 22000), 30 parts of hexa (methoxy) melamine (Cymel 303, Cyanamide) and 5 parts of an oxime sulfonate compound, dissolving 25g of this mixture in 75g of Propylene Glycol Methyl Ether Acetate (PGMEA) containing 1000ppm of a flow aid (FC430), and uniformly mixing with high speed stirring.
The resist compositions were subjected to the following evaluations, and the evaluation results are shown in table 1.
< evaluation of solution stability with time >
The viscosity (initial viscosity) of the resist composition immediately after the preparation and the viscosities (viscosity with time) after leaving at 30 ℃ for 1 week and 2 weeks were measured with a NDJ-79A rotational viscometer and evaluated by O, a viscosity increase ratio of 5% or less, ◎, a viscosity increase ratio of more than 5% and less than 10%, and ●, a viscosity increase ratio of more than 10%.
< evaluation of sensitivity >
The above solution was applied to a silicon wafer polished and treated with hexamethyldisilazane by a spin coater at a rate of 5000rev/min for 1min, dried in an oven at 110 ℃ for 60s, and the solvent was removed to give a resin composition layer having a thickness of 3 μm.
Subsequently, the obtained resist composition layer was exposed through a prescribed mask using LED lamps of different wavelengths, then baked at 90 ℃ for 1min, developed with 0.4% tetramethylammonium hydroxide aqueous solution at 23 ℃ for 60s, and rinsed with ultrapure water for 20 s.
The lowest exposure required for obtaining an image in which lines and gaps of 10 μm are analyzed at a ratio of 1:1 was used as a basis for sensitivity evaluation, and the lower the exposure required, the higher the sensitivity. The specific evaluation criteria are as follows: level 1: less than 50mj/cm2(ii) a And 2, stage: greater than 50mj/cm2Less than 100mj/cm2(ii) a And 3, level: greater than 100mj/cm2。
< evaluation of transparency >
On a glass substrate (CORNING1737, 0.7mm thick), after slit coating of the resist composition, heating at 90 ℃ for 2min to remove the solvent to obtain a resin composition layer having a thickness of 3 μm, the obtained composition layer was exposed to light with a 405nm LED lamp, and the cumulative exposure amount was 100mj/cm2Then, the substrate was heated at 230 ℃ for 1 hour in an oven to obtain a cured film.
The light transmittance of the cured film-coated glass substrate was measured at a wavelength in the range of 400-800nm using a spectrophotometer "150-20 type DOUBLE BEAM (Hitachi Co., Ltd)", and the lowest transmittance was used as the evaluation criterion of the transparency. The specific evaluation criteria are as follows: level 1: more than 95 percent; and 2, stage: more than 90% and less than 95%; and 3, level: more than 85% and less than 90%; 4, level: less than 85%.
TABLE 1
The structural formulas of compounds 1-21 and comparative compounds 1-2 in the above tables are shown below, respectively:
2. preparation of positive photoresist
50 parts of resin adhesive A (obtained by copolymerizing 4-hydroxystyrene and 4- (1-ethoxyethoxy) styrene according to the molar ratio of 62:38, M)W12000), 45 parts of resin binder B (M-cresol novolac resin, M)W6500) and 5 parts of an oxime sulfonate compound, and 25g of this mixture was dissolved in 75g of Propylene Glycol Methyl Ether Acetate (PGMEA) containing 1000ppm of a flow aid (FC430), and uniformly mixed with stirring at a high speed to prepare a resist solution.
The resist compositions were subjected to the following evaluations, and the evaluation results are shown in table 2.
< evaluation of solution stability with time >
The viscosity of the resist composition immediately after the start of the preparation (initial viscosity) and the viscosity after the standing at 30 ℃ for 1 week and 2 weeks (viscosity with time) were measured using an NDJ-79A rotational viscometer and evaluated on a scale of ○: the viscosity increase ratio is 5% or less, ◎: the viscosity increase ratio is more than 5% and less than 10%, and ●: the viscosity increase ratio is more than 10%.
< evaluation of sensitivity >
Coating the solution on a polished silicon wafer treated with hexamethyldisilazane by a spin coater at 5000rev/min for 1min, drying the coated gel in an oven at 90 ℃ for 3min, and removing the solvent to give a film having a thickness of 3 μmA resin composition layer. Next, the obtained resist composition layer was exposed through a prescribed mask using a different wavelength LED lamp, then baked at 90 ℃ for 1min, and then developed. Evaluation of resist sensitivity by determining the dose E of the scavenger0(units mj/cm)2) The measurement, the removal dose, means the dose of the exposed portion just enough to completely remove the resist film by immersion development in a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds, and the smaller the required dose, the higher the sensitivity of the resist composition, and the specific evaluation criteria are as follows: level 1: less than 50mj/cm2(ii) a And 2, stage: greater than 50mj/cm2Less than 100mj/cm2(ii) a And 3, level: greater than 100mj/cm2。
< evaluation of transparency >
On a glass substrate (CORNING1737, 0.7mm thick), after slit coating of the resist composition, heating at 90 ℃ for 2min to remove the solvent to obtain a resin composition layer having a thickness of 3 μm, the obtained composition layer was exposed to light with a 405nm LED lamp, and the cumulative exposure amount was 100mj/cm2Then, the substrate was heated at 230 ℃ for 1 hour in an oven to obtain a cured film.
The light transmittance of the cured film-coated glass substrate was measured at a wavelength in the range of 400-800nm using a spectrophotometer "150-20 type DOUBLE BEAM (Hitachi Co., Ltd)", and the lowest transmittance was used as the evaluation criterion of the transparency. The specific evaluation criteria are as follows: level 1: more than 95 percent; and 2, stage: more than 90% and less than 95%; and 3, level: more than 85% and less than 90%; 4, level: less than 85%.
TABLE 2
In summary, from the test results in tables 1 and 2, the resist composition of the present invention, which contains at least one or more oxime sulfonate compounds of formula (i), formula (ii), formula (iii), formula (iv), formula (v) or formula (vi), has good stability, is sensitive to LED lamps of different wavelength bands, has a light spectrum range, high sensitivity, and good transparency.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
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