CN113296360A - Acid inhibitor for photoresist composition, preparation method and photoresist composition - Google Patents
Acid inhibitor for photoresist composition, preparation method and photoresist composition Download PDFInfo
- Publication number
- CN113296360A CN113296360A CN202110559802.6A CN202110559802A CN113296360A CN 113296360 A CN113296360 A CN 113296360A CN 202110559802 A CN202110559802 A CN 202110559802A CN 113296360 A CN113296360 A CN 113296360A
- Authority
- CN
- China
- Prior art keywords
- acid inhibitor
- formula
- carbon atoms
- structural unit
- photoresist composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002253 acid Substances 0.000 title claims abstract description 73
- 239000003112 inhibitor Substances 0.000 title claims abstract description 66
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 49
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 26
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 36
- 229910052731 fluorine Inorganic materials 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000004334 fluoridation Methods 0.000 claims 1
- 239000003999 initiator Substances 0.000 description 32
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 15
- 239000011737 fluorine Substances 0.000 description 15
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 238000009792 diffusion process Methods 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- -1 hydrogen ions Chemical class 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229940116333 ethyl lactate Drugs 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 6
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 5
- QLNYTCSELYEEPV-UHFFFAOYSA-N 2,2-dimethylpropyl acetate Chemical compound CC(=O)OCC(C)(C)C QLNYTCSELYEEPV-UHFFFAOYSA-N 0.000 description 5
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012025 fluorinating agent Substances 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 2
- 229920003050 poly-cycloolefin Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 1
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- UWQPDVZUOZVCBH-UHFFFAOYSA-N 2-diazonio-4-oxo-3h-naphthalen-1-olate Chemical class C1=CC=C2C(=O)C(=[N+]=[N-])CC(=O)C2=C1 UWQPDVZUOZVCBH-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940126142 compound 16 Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 229940073584 methylene chloride Drugs 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an acid inhibitor for a photoresist composition, which has an acidity coefficient pKa value of 8-12, wherein the structure of the acid inhibitor contains fluorine atoms, and the content of the fluorine atoms in each mole of the acid inhibitor is less than or equal to 6 moles. In addition, the invention also discloses a preparation method for preparing the acid inhibitor, which comprises the following steps: step A: carrying out polymerization reaction on monomers containing hydroxyl to obtain corresponding polymers; and step B, carrying out fluorination reaction on the polymer obtained in the step A to obtain the acid inhibitor. In addition, the invention also discloses a photoresist composition.
Description
Technical Field
The invention belongs to the technical field of semiconductor preparation, and particularly relates to preparation of a fluorine-containing acid inhibitor and application of the fluorine-containing acid inhibitor in photoresist.
Background
In the current semiconductor technology, the conversion of the patterns of the integrated circuit is realized by the photolithography technology. The light source wavelengths of the currently used lithography technologies have been developed from 436nm (g-line), 365nm (i-line), 248nm (KrF-line), 193nm (ArF-line) to extreme ultraviolet light source 13nm (euv). While the lithography wavelength is continuously decreased, in order to further improve the sensitivity of the photoresist, a chemically amplified photoresist is the type of photoresist mainly used at present.
Resolution, sensitivity and line width roughness are among the three most important criteria for photoresists, which determine the size of the patterns of integrated circuits and the fabrication process during chip fabrication. In order to reduce the size of the pattern and optimize the manufacturing process, these three most important criteria must be improved.
In the case of a chemical amplification type photoresist, the sensitivity of the photoresist is improved by generating photoacid, but the resolution is reduced and the line width roughness is increased by diffusion after the generation of photoacid, and thus, it is very important to control the influence of the diffusion of photoacid. At present, the method for controlling the diffusion of the photoacid is to add a basic compound, and reduce the diffusion range and concentration of the photoacid by a method of acid-base neutralization, and the compound is generally called an acid inhibitor. However, current research shows that controlling photoacid diffusion after exposure of chemically amplified photoresist is an important means to improve resolution and reduce line width roughness. One of the ways to improve the ability to control photoacid diffusion is to use basic compounds, known as acid inhibitors, to reduce the photoacid diffusion range by using the principle of acid-base neutralization.
The alkalinity of the acid inhibitor also influences the range of photoacid diffusion, and the alkalinity of the alkaline compound is generally characterized by a pKa value, so that the resolution can be improved and the line width roughness can be reduced by controlling the pKa value of the acid inhibitor or preparing the acid inhibitor with a certain pKa value.
The uniformity of dispersion of the acid inhibitor in the matrix resin is also very important, and chinese patent publication No. CN106154747, published 2016, 11, 23, entitled "photobase generator and photoresist composition containing the same" discloses a photobase generator. In the solution disclosed in this patent document, a photoacid inhibitor (photobase generator) is used, but it is difficult to uniformly disperse the photoacid inhibitor into the resist film unlike the matrix resin structure, and the effects of improving the resolution and reducing the line width roughness due to the photobase generator are greatly reduced.
Therefore, obtaining an acid inhibitor with an appropriate pKa value and improving the compatibility of the acid inhibitor with the matrix resin while not degrading the performance of the photoresist are currently major issues.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an acid inhibitor for a photoresist composition, a preparation method and the photoresist composition.
In order to achieve the above object, the present invention is achieved by the following aspects:
in a first aspect, the present invention provides a photoresist composition comprising an acid inhibitor which is a polymer and has an acidity coefficient pKa value of 8 to 12, wherein the acid inhibitor has a fluorine atom content of 6 mol or less per mol of the acid inhibitor.
The acidity coefficient pKa value is an index for indicating the ability of a compound to bind hydrogen ions, and a smaller value indicates a poorer ability to react with an acid, while a larger value indicates a stronger ability to react with an acid. The principle of the photoresist is that an acid is generated after exposure, but a matrix resin reacts with the acid to generate an alkali soluble resin, and when the acid inhibitor has too strong capacity, i.e., a pKa value is too high, the solubility of the matrix resin at the exposed part is reduced, thereby reducing the sensitivity. When the acid inhibitor is too weak, i.e., the pKa value is too low, it cannot control the diffusion of the photoacid, and the line width roughness of the finally formed pattern becomes large. Therefore, it is important to select an acid inhibitor having an appropriate acidity coefficient.
The present invention provides an acid inhibitor having a suitable acidity coefficient pKa of 8 to 12, preferably 9 to 11.5 from the viewpoint of achieving higher sensitivity and lower line width roughness.
In the invention, the acid inhibitor structure contains fluorine atoms, and the content of the fluorine atoms in each mole of acid inhibitor structural unit is less than or equal to 6 moles. Fluorine atoms have strong electron-withdrawing effect, and can change the acidity coefficient of the acid inhibitor, so that the acidity coefficient can be adjusted by adjusting the molar content of the fluorine atoms in the acid inhibitor, so that the photoresist composition can obtain higher sensitivity and lower line width roughness. In addition, the fluorine-containing compound can reduce the surface tension of the photoresist paste, and a film pattern with more excellent performance is obtained. The fluorine atom content per mole of the acid inhibitor structural unit is less than or equal to 2 in terms of synthetic convenience.
The acid inhibitor of the present invention has a structure described by formula 1, wherein formula 1 is represented by: X-Y-Z;
wherein Z is a group having a pKa value greater than 8, and Z is selected from amine-containing groups, such as: primary amine with alkyl, aryl or cycloalkyl, or secondary amine with alkyl, aryl or cycloalkyl, or tertiary amine with alkyl, aryl or cycloalkyl;
at least one of Y and Z is a group containing fluorine atom for adjusting the pKa value of Z to control the diffusion of photoacid.
Preferably, X has the structure of formula 2 and is a position bonded to Y, and X does not contain a fluorine atom.
The structure of formula 2 is as follows:
wherein R1, R2 and R3 are selected from one or more of hydrogen, alkyl with 1-12 carbon atoms, alicyclic alkyl with 5-12 carbon atoms and aryl with 6-30 carbon atoms;
the R1-R3 group may contain a substituent selected from one or more of an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an aromatic group or heteroaromatic group having 6 to 30 carbon atoms.
In the formula 2, n is an integer of 2-100;
when there are a plurality of Y and Z in formula 1, Y and Z may be the same or different, respectively.
The acid inhibitor widely used at present is generally a micromolecular alkaline compound, but because matrix resins are all polymers, micromolecules are difficult to be uniformly dispersed in a photoresist film, and the effects of improving the resolution and reducing the line width roughness by the acid inhibitor are greatly reduced. In addition, the small molecule compound has difficult adjustment of the acidity coefficient, and the addition of electron-withdrawing groups or electron-donating groups can change the acidity coefficient to a large extent. For the polymer shown in the formula 1, the acidity coefficient can be accurately regulated by controlling the molar weight of fluorine atoms of the polymer, so that the diffusion of the photoacid can be accurately controlled.
The acid inhibitor in the invention is preferably selected from structural units shown in formula 3, and the structure of formula 3 is shown as follows:
wherein R4, R5 and R6 are selected from one or more of hydrogen atoms, alkyl with 1-12 carbon atoms, alicyclic alkyl with 5-12 carbon atoms and aryl with 6-30 carbon atoms; the R4-R6 group may contain a substituent selected from one or more of halogen, hydroxyl, an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an aromatic group having 6 to 30 carbon atoms or a heteroaromatic group.
In the structure shown in the formula 3, Fo, Fp and Fq respectively represent different fluorine atoms, and o, p and q represent the number of corresponding fluorine atoms;
wherein o, p and q are integers of 0-6, and o + p + q is less than or equal to 6, and when a plurality of o, p and q exist, the o, p and q can be the same or different;
all structural units shown in formula 3 in the acid inhibitor contain at least one structural unit, and the sum of o + p + q is more than or equal to 1 and less than or equal to 6.
The acid inhibitor of the present invention is further preferably selected from the group consisting of structural units represented by formula 4, wherein the structure of formula 4 is as follows:
r7, R8 and R9 are selected from one or more of hydrogen atoms, alkyl with 1-12 carbon atoms, alicyclic alkyl with 5-12 carbon atoms and aryl with 6-30 carbon atoms; the R7-R9 group may contain a substituent selected from one or more of an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an aromatic group or heteroaromatic group having 6 to 30 carbon atoms.
Wherein (OH) a, (OH) b and (OH) c represent different hydroxyl groups, respectively, and a, b and c represent the number of the corresponding hydroxyl groups; fo, Fp and Fq represent different fluorine atoms, respectively, o, p and q represent the number of corresponding fluorine atoms;
in the formula 4, a, b, c, o, p and q are integers of 0-6, and o + p + q is less than or equal to 6, and when a plurality of a, b, c, o, p and q exist, the a, b, c, o, p and q can be the same or different;
the acid inhibitor contains at least one structural unit in all structural units shown in formula 4, and the structural unit is more than or equal to 1 and less than or equal to 6.
The fluorine substitution of hydroxyl on an alkyl chain is a common method for preparing fluorine-containing alkane at present, and amine compounds with different fluorine contents and hydroxyl contents can be obtained by controlling reaction conditions such as the feeding amount during the fluorine substitution reaction, so that the acidity coefficient of the acid inhibitor can be effectively controlled.
The invention also discloses a preparation method of the acid inhibitor, which is characterized by comprising the following steps:
step A: the monomer shown in the formula 5 is subjected to polymerization reaction to obtain the corresponding polymer.
The structure of formula 5 is as follows:
r10, R11 and R12 are selected from one or more of hydrogen atoms, alkyl with 1-12 carbon atoms, alicyclic alkyl with 5-12 carbon atoms and aryl with 6-30 carbon atoms; the R10-R12 group may contain a substituent selected from one or more of an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, an aromatic group or heteroaromatic group having 6 to 30 carbon atoms.
Wherein d, e, f are integers from 0 to 6, and 0< d + e + f ≦ 6.
The structures of formulae 3 and 4 are derived from the monomer represented by formula 5, the polymerized structural unit and the structural unit obtained by subjecting the structural unit to a fluorination reaction, and therefore the preferred structures of formulae 3 and 4 are determined according to the preferred structure of formula 5. The compound of formula 5 is preferably of the following structure in terms of convenience of starting materials,
the process for obtaining the corresponding polymer by the polymerization reaction of the monomers comprises the following steps:
1) dissolving the monomer of the formula 5 in a first organic solvent to obtain a mixed solution, wherein the molar concentration of the monomer of the mixed solution is 0.05M to 0.2M; then dissolving an initiator in a second organic solvent to obtain an initiator solution, wherein the molar concentration of the initiator in the solution is 0.2M-0.5M; and the molar ratio of the initiator to the monomer of the formula 5 is 0.1-5%.
2) Adding the initiator solution into the monomer mixed solution, refluxing at a constant temperature of 25-120 ℃, reacting for 0.5-24 hours, cooling to room temperature, precipitating the resin with a non-polar solvent, filtering, and drying to obtain the polymer X.
The initiator used in the polymerization process is selected from: one or at least two of azodiisobutyronitrile, azodiisoheptonitrile, tert-butyl peroxypivalate, tert-butoxy hydroperoxide, benzoic acid hydroperoxide or benzoyl peroxide;
the first organic solvent in the polymerization process is: one or at least two of ethyl acetate, butyl acetate, neopentyl acetate, ethyl lactate, propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methyl tetrahydrofuran, chloroform, dichloromethane, 1, 2-dichloroethane, n-hexane, n-pentane, n-heptane, acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, p-xylene or biphenyl;
the second organic solvent is: : one or at least two of ethyl acetate, butyl acetate, neopentyl acetate, ethyl lactate, propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methyl tetrahydrofuran, chloroform, dichloromethane, 1, 2-dichloroethane, n-hexane, n-pentane, n-heptane, acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, p-xylene or biphenyl;
the polymer obtained in the step B is subjected to fluorination reaction to obtain the target acid inhibitor with the pKa value of 8-12, and the specific process comprises the following steps:
dissolving the polymer X obtained in the first step in an organic solvent to obtain a mixed solution, wherein the molar concentration of the mixed solution is 0.01M-0.2M; and then adding a fluoro reagent into the mixed solution, stirring at a constant temperature of 0-200 ℃, reacting for 0.5-24 hours, cooling to room temperature, precipitating the resin with a non-polar solvent, filtering, and drying to obtain the acid inhibitor polymer.
The fluorinating agent in the above-mentioned fluorination process is an agent capable of introducing a fluorine atom to an organic compound, and is preferably selected from the following fluorinating agents,
the solvent in the fluorination process is as follows: one or at least two of ethyl acetate, butyl acetate, neopentyl acetate, ethyl lactate, propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methyl tetrahydrofuran, chloroform, dichloromethane, 1, 2-dichloroethane, n-hexane, n-pentane, n-heptane, acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, p-xylene or biphenyl;
the ratio of the molar amount of the fluorinating agent to the structural unit contained in the polymer X in the fluorination reaction is in the range of 0.01 to 6, preferably 0.1 to 3, more preferably 0.5 to 2.
The photoresist composition disclosed by the invention also comprises resin with acid activity, a photoacid generator and an organic solvent.
The resin having acid activity is preferably a polyacrylate polymer or a polycycloolefin polymer, and the monomer of such a radical polymerizable compound is preferably one or more of the following structures,
the preparation of the acrylate polymer or the polycycloolefin polymer from the above monomers is obtained by radical polymerization, and the monomers used in the polymerization process can be one or more, and the polymerization method is as follows:
1) dissolving one or more monomers in a first organic solvent to obtain a mixed solution, wherein the molar concentration of the monomers in the mixed solution is 0.05M to 0.2M; then dissolving an initiator in a second organic solvent to obtain an initiator solution, wherein the molar concentration of the initiator in the solution is 0.2M-0.5M; and the molar ratio of the initiator to the monomer of the formula 5 is 5-10%.
2) Adding the initiator solution into the monomer mixed solution, refluxing at a constant temperature of 60-120 ℃, reacting for 12-24 hours, cooling to room temperature, precipitating resin by using a non-polar solvent, filtering, and drying to obtain the polymer.
The initiator used in the polymerization process is selected from: one or at least two of azodiisobutyronitrile, azodiisoheptonitrile, tert-butyl peroxypivalate, tert-butoxy hydroperoxide, benzoic acid hydroperoxide or benzoyl peroxide;
the first organic solvent in the polymerization process is: one or at least two of ethyl acetate, butyl acetate, neopentyl acetate, ethyl lactate, propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methyl tetrahydrofuran, chloroform, dichloromethane, 1, 2-dichloroethane, n-hexane, n-pentane, n-heptane, acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, p-xylene or biphenyl;
the second organic solvent is: : one or at least two of ethyl acetate, butyl acetate, neopentyl acetate, ethyl lactate, propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methyl tetrahydrofuran, chloroform, dichloromethane, 1, 2-dichloroethane, n-hexane, n-pentane, n-heptane, acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, p-xylene or biphenyl;
for photoacid generators, the photoacid generator includes one or more of sulfonium salts, iodonium salts, sulfonyldiazamethane, N-sulfonyloxybenzoimide, arylsulfonyl and alkylsulfonyl oximes, diazonaphthoquinone derivatives.
The organic solvent is not particularly limited as long as it can dissolve the above components, and is preferably diethylene glycol monomethyl ether, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, methylene chloride, ethyl acetate, methyl lactate, ethyl lactate, 3-methoxymethyl propionate, 3-ethoxy and propionate, propylene glycol monomethyl ether, methanol, ethanol, propanol, butanol, tetrahydrofuran, diethylene glycol dimethyl ether, methoxybutyl acetate, methyl cellosolve, and ethyl cellosolve. The organic solvent may be used alone or in combination of two or more.
Detailed Description
In order that the objects and advantages of the invention will become more apparent, the invention is further described in detail below with reference to examples, which will assist those skilled in the art in further understanding the invention, but are not to be construed as limiting the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The monomer having the structure of formula 5 used in the examples can be obtained by general synthetic methods including, but not limited to, acid-alcohol esterification, condensation of acid chloride with alcohol, transesterification, reduction of acid or aldehyde, halogen hydroxyl activation.
In the specific implementation process, the methods for measuring the molecular weight of the polymer, the pKa value of the acid inhibitor and the content of fluorine element in the acid inhibitor are listed as the following methods: 1. molecular weight determination method, the molecular weight of the polymer is measured by GPC from Shimadzu corporation, using polystyrene as a control; method for determining pKa value: the determination was carried out using a pKa/logP/logD/solubility multi-functional tester PulseTM from Pion, USA; 3. the content of F element in the polymer was measured by 19F-NMR using nuclear magnetism of JNM-ECZ400S model manufactured by Japan electronic Co., Ltd, and the content of fluorine element was calculated using trifluoroacetic acid as an internal standard in the measurement.
Synthesis example 1
Dissolving the compound 1 in tetrahydrofuran to obtain a solution A1 with the monomer molar concentration of 0.1M; then, dissolving an initiator azobisisobutyronitrile into tetrahydrofuran to obtain an initiator solution B1, wherein the molar concentration of the initiator in the solution is 0.5M; and the molar ratio of the initiator to the monomer of formula 5 is 3%.
Then, the initiator solution B1 was added dropwise to the monomer solution A1 (3 hours), reacted at 40 ℃ for 2 hours, cooled to room temperature, precipitated with n-hexane, filtered, and dried to obtain polymer C1, the weight average molecular weight (Mw) of the obtained polymer was 5000, and the acidity coefficient was 12.1.
Synthesis example 2
Dissolving compound 16 in propylene glycol monoethyl ether to obtain solution A2 with a molar concentration of 0.2M of monomer; then, dissolving an initiator tert-butoxy hydroperoxide in tetrahydrofuran to obtain an initiator solution B2, wherein the molar concentration of the initiator in the solution is 0.2M; and the molar ratio of the initiator to the monomer of formula 5 is 0.1%.
Then, the initiator solution B2 was added dropwise to the monomer solution A2 (2 hours), reacted at 40 ℃ for 4 hours, cooled to room temperature, and precipitated with n-hexane, filtered, and dried to obtain polymer C2, wherein the weight average molecular weight (Mw) of the obtained polymer was 3000, and the acidity coefficient was 12.5.
Synthesis example 3
Dissolving the compound 30 in ethyl lactate to obtain a solution A3 with the monomer molar concentration of 0.05M; then dissolving an initiator benzoyl peroxide in ethyl acetate to obtain an initiator solution B3, wherein the molar concentration of the initiator in the solution is 0.3M; and the molar ratio of the initiator to the monomer of formula 5 is 5%.
Then, the initiator solution B3 was added dropwise to the monomer solution A3 (1h), reacted at 80 ℃ for 2 hours, cooled to room temperature, precipitated with n-hexane, filtered, and dried to obtain polymer C3, the weight average molecular weight (Mw) of the obtained polymer was 4000, and the acidity coefficient was 12.8.
Synthesis example 4
The polymer C1 was dissolved in tetrahydrofuran to give a mixture having a molar concentration of structural units of 0.01M, and then a reagent 8 for fluorination (0.5 equivalent relative to the structural units of the polymer) was added to the mixture, stirred at a constant temperature of 80 ℃ and reacted for 6 hours, followed by precipitation of the resin with n-hexane, filtration and drying to give an acid inhibitor polymer D1 having a molar fluorine content of 0.2 and an acidity coefficient of 11.4 by test.
Synthesis example 5
The polymer C1 was dissolved in propylene glycol monoethyl ether to give a mixture having a molar concentration of structural units of 0.1M, and then the fluorination reagent 18(2 equivalents relative to the structural units of the polymer) was added to the mixture, stirred at a constant temperature of 100 ℃ and reacted for 12 hours, followed by precipitation of the resin with n-hexane, filtration and drying to give an acid inhibitor polymer D2 having a molar fluorine content of 1.6 and an acidity coefficient of 10.0 as measured.
Synthesis example 6
Polymer C2 was dissolved in methylene chloride to give a mixture having a molar concentration of structural units of 0.2M, and then a reagent for fluorination 18(6 equivalents relative to the structural units of the polymer) was added to the mixture, stirred at a constant temperature of 60 ℃ for 24 hours, followed by precipitation of the resin with n-hexane, filtration and drying to give an acid inhibitor polymer D3 having a fluorine-containing molar number of 5.6 and an acidity coefficient of 8.3 by test.
Synthesis example 7
Polymer C2 was dissolved in methylene chloride to give a mixture having a molar concentration of structural units of 0.1M, and then a fluorination reagent 18(3 equivalents relative to the structural units of the polymer) was added to the mixture, stirred at a constant temperature of 60 ℃ for 12 hours, followed by precipitation of the resin with n-hexane, filtration and drying to give acid inhibitor polymer D4 having a fluorine-containing molar number of 2.0 and an acidity coefficient of 10.8 by test.
Synthesis example 8
Polymer C3 was dissolved in dichloroethane to give a mixture having a molar concentration of structural units of 0.12M, and then a reagent 8 for fluorination (2 equivalents relative to the structural units of the polymer) was added to the mixture, stirred at a constant temperature of 70 ℃ for 24 hours, followed by precipitation of the resin with n-hexane, filtration and drying to give an acid inhibitor polymer D5 having a molar fluorine content of 0.95 and an acidity coefficient of 10.9 as measured.
Synthesis example 9
Polymer C3 was dissolved in dichloroethane to give a mixture having a molar concentration of structural units of 0.05M, and then reagent 8 for fluorination (0.8 equivalent relative to the structural units of the polymer) was added to the mixture, stirred at a constant temperature of 70 ℃ and reacted for 12 hours, followed by precipitation of the resin with n-hexane, filtration and drying to give acid inhibitor polymer D6 having a molar fluorine content of 0.45 and an acidity coefficient of 11.5 as measured.
Synthesis example 10
Dissolving the monomer 21, the monomer 42 and the monomer 43 in tetrahydrofuran to obtain a solution A4, wherein the molar concentration of the monomer is 0.2M; then, dissolving an initiator azobisisobutyronitrile into tetrahydrofuran to obtain an initiator solution B4, wherein the molar concentration of the initiator in the solution is 0.5M; and the molar ratio of the initiator to the monomer of formula 5 is 6%.
Then, the initiator solution B4 was added dropwise to the monomer solution A4 (1h), reacted at 70 ℃ for 12 hours, cooled to room temperature, and then precipitated with n-hexane, filtered, and dried to obtain polymer C4, wherein the weight average molecular weight (Mw) of the obtained polymer was 35000.
A method for preparing a photoresist composition, which comprises adding a resin with acid activity, a photoacid generator and an acid inhibitor into an organic solvent to obtain a photoresist resin composition G. Then, using the obtained resin G, evaluation of film forming property and pattern property after lithography was performed as described above. The procedure for evaluating the photoresist resin composition G was as follows: photoresist composition G was coated on an 8-inch silicon wafer using a spin coater, followed by baking at 120 ℃ for 180 seconds, and tested to give a film thickness of 800 nm. Then, exposure was carried out, and baking was continued at 120 ℃ for 180 seconds after exposure. The wafer was then developed by immersing it in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH). The developed silicon wafer was observed under SEM to evaluate exposure performance, in which line width roughness was measured by a high resolution electron microscope (SEM), and the calculation method was as follows,
wherein sigmaLERFor line width roughness, wi is the measured value of each line width, wn is the average of all line width measured values, and N is the number of line width tests. Line width roughness less than 5nm is ^ X, line width roughness between 5nm and 10nm is ^ X, 10nm to 20nm is Δ, and more than 20nm is X.
Specific photoresist compositions are shown in table 1, and the properties of patterns formed after exposure using the photoresist are shown in table 2. The photoacid generator used in the photoresist composition was a structure shown in E1,
table one: photoresist G composition List
| Photoresist composition | Acid reactive resins | Photoacid generators | Acid inhibitors | Organic solvent | |
| Preparation example 1 | G1 | C4(20g) | E1(0.5g) | D1(0.2g) | Propylene glycol methyl ether acetate (140 ml)/Cyclohexanone (60ml) |
| Preparation example 2 | G2 | C4(20g) | E1(0.5g) | D2(0.2g) | Propylene glycol methyl ether acetate (140 ml)/Cyclohexanone (60ml) |
| Preparation example 3 | G3 | C4(20g) | E1(0.5g) | D3(0.2g) | Propylene glycol methyl ether acetate (140 ml)/Cyclohexanone (60ml) |
| Preparation example 4 | G4 | C4(20g) | E1(0.5g) | D4(0.2g) | Propylene glycol methyl ether acetate (140 ml)/Cyclohexanone (60ml) |
| Preparation example 5 | G5 | C4(20g) | E1(0.5g) | D5(0.2g) | Propylene glycol methyl ether acetate (140 ml)/Cyclohexanone (60ml) |
| Preparation example 6 | G6 | C4(20g) | E1(0.5g) | D6(0.2g) | Propylene glycol methyl ether acetate (140 ml)/Cyclohexanone (60ml) |
| Comparative example 1 | G7 | C4(20g) | E1(0.5g) | C1(0.2g) | Propylene glycol methyl ether acetate (140 ml)/Cyclohexanone (60ml) |
| Comparative example 2 | G8 | C4(20g) | E1(0.5g) | C2(0.2g) | Propylene glycol methyl ether acetate (140 ml)/Cyclohexanone (60ml) |
| Comparative example 3 | G9 | C4(20g) | E1(0.5g) | C3(0.2g) | Propylene glycol methyl ether acetate (140 ml)/Cyclohexanone (60ml) |
Table two: exposure Performance evaluation Table for respective samples
| Photoresist composition | Maximum resolution | LWR (line width roughness) | Pattern(s) |
| G1 | 200nm | ◎ | Rectangle |
| G2 | 200nm | ○ | Rectangle |
| G3 | 200nm | ○ | Rectangle |
| G4 | 200nm | ◎ | Rectangle |
| G5 | 200nm | ◎ | Rectangle |
| G6 | 200nm | ○ | Rectangle |
| G7 | 200nm | △ | Rectangle |
| G8 | 200nm | X | Rectangle |
| G9 | 200nm | X | Rectangle |
As can be seen from the above table, the acid inhibitors with various pKa values are obtained by the fluorination reaction according to the scheme of the present invention, and for the photoresist composition having the same acid-reactive resin, photoacid generator and organic solvent, the acid inhibitor with the pKa value regulated by the fluorination reaction is used, the line width roughness of the obtained pattern is more excellent, and the obtained pattern is clearer.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. A resist composition comprising an acid inhibitor which is a polymer and has an acidity coefficient pKa value of 8 to 12, wherein the acid inhibitor has a fluorine atom-containing structural unit in an amount of 6 mol or less per mol of the acid inhibitor structural unit.
2. The photoresist composition of claim 1, wherein the acid inhibitor is represented by formula 1,
X-Y-Z is formula 1;
in formula 1, Z represents a group with a pKa value larger than 8, at least one of Y and Z is a group containing a fluorine atom, X has a structure shown in formula 2, and is a position bonded with Y, and X does not contain a fluorine atom;
wherein R1, R2, and R3 are selected from: one or more of hydrogen, an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 5 to 12 carbon atoms, and an aromatic group having 6 to 30 carbon atoms;
n is an integer of 2 to 100.
3. The photoresist composition of claim 1 or 2, wherein the acid inhibitor comprises a structural unit represented by formula 3,
r4, R5 and R6 are selected from one or more of hydrogen atoms, alkyl with 1-12 carbon atoms, alicyclic alkyl with 5-12 carbon atoms and aryl with 6-30 carbon atoms; fo, Fp and Fq represent different fluorine atoms, respectively, o, p and q represent the number of corresponding fluorine atoms;
wherein o, p and q are integers of 0-6, and o + p + q is less than or equal to 6, and when a plurality of o, p and q exist, the o, p and q can be the same or different;
all structural units shown in formula 3 in the acid inhibitor contain at least one structural unit, and the sum of o + p + q is more than or equal to 1 and less than or equal to 6.
4. The photoresist composition of claim 1 or 2, wherein the acid inhibitor specifically comprises a structural unit represented by formula 4,
r7, R8 and R9 are selected from one or more of hydrogen atoms, alkyl with 1-12 carbon atoms, alicyclic alkyl with 5-12 carbon atoms and aryl with 6-30 carbon atoms; wherein (OH) a, (OH) b and (OH) c represent different hydroxyl groups, respectively, and a, b and c represent the number of the corresponding hydroxyl groups; fo, Fp and Fq represent different fluorine atoms, respectively, o, p and q represent the number of corresponding fluorine atoms;
in the formula 4, a, b, c, o, p and q are integers of 0-6, and o + p + q is less than or equal to 6, and when a plurality of a, b, c, o, p and q exist, the a, b, c, o, p and q can be the same or different;
the acid inhibitor contains at least one structural unit in all structural units shown in formula 4, and the structural unit is more than or equal to 1 and less than or equal to 6.
5. A method for preparing an acid inhibitor in a photoresist according to any one of claims 1 to 4, comprising the steps of:
step A: carrying out polymerization reaction on monomers containing hydroxyl to obtain corresponding polymers;
and step B, carrying out fluorination reaction on the polymer obtained in the step A to obtain the acid inhibitor.
6. The method of claim 5, wherein in step A, the monomer has a formula shown in formula 5:
r10, R11 and R12 are selected from one or more of hydrogen atoms, alkyl with 1-12 carbon atoms, alicyclic alkyl with 5-12 carbon atoms and aryl with 6-30 carbon atoms; wherein (OH) d, (OH) e and (OH) f are respectively different hydroxyl groups, d, e and f represent the number of corresponding hydroxyl groups, d, e and f are integers from 0 to 6, and 0< d + e + f ≦ 6.
7. The method according to claim 6, wherein in the step B, the ratio of the molar amount of the fluoridation reagent to the structural unit represented by the formula 5 contained in the acid inhibitor is 0.01 to 6.
8. The photoresist composition of claims 1-4, further comprising an acid-reactive resin, a photoacid generator, and an organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110559802.6A CN113296360B (en) | 2021-05-21 | 2021-05-21 | Acid inhibitor for photoresist composition, preparation method and photoresist composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110559802.6A CN113296360B (en) | 2021-05-21 | 2021-05-21 | Acid inhibitor for photoresist composition, preparation method and photoresist composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113296360A true CN113296360A (en) | 2021-08-24 |
| CN113296360B CN113296360B (en) | 2024-06-14 |
Family
ID=77323811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110559802.6A Active CN113296360B (en) | 2021-05-21 | 2021-05-21 | Acid inhibitor for photoresist composition, preparation method and photoresist composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113296360B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424626A (en) * | 2001-12-03 | 2003-06-18 | 东京应化工业株式会社 | Forming method for photoresist design and its laminating products |
| CN1505773A (en) * | 2001-03-22 | 2004-06-16 | 希普雷公司 | Solvents and photoresist compositions for short wavelength imaging |
| CN1930523A (en) * | 2004-03-05 | 2007-03-14 | 东京应化工业株式会社 | Positive resist composition for immersion exposure and method for forming resist pattern |
| CN101080674A (en) * | 2004-12-03 | 2007-11-28 | 捷时雅株式会社 | Composition for forming antireflection film, layered product, and method of forming resist pattern |
| CN105363042A (en) * | 2015-10-21 | 2016-03-02 | 苏州圣诺生物医药技术有限公司 | Medicine composition and application thereof |
| WO2018070327A1 (en) * | 2016-10-13 | 2018-04-19 | Jsr株式会社 | Radiation-sensitive resin composition and resist-pattern forming method |
| US20180195030A1 (en) * | 2017-01-11 | 2018-07-12 | Daicel Corporation | Composition for removing resist |
| CN109991811A (en) * | 2019-02-27 | 2019-07-09 | 江苏南大光电材料股份有限公司 | A kind of acid dispersion inhibitor and preparation method thereof and photoetching compositions |
| CN111302959A (en) * | 2020-02-28 | 2020-06-19 | 宁波南大光电材料有限公司 | Acid diffusion inhibitor with ester bond, preparation method thereof and photoresist composition |
-
2021
- 2021-05-21 CN CN202110559802.6A patent/CN113296360B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1505773A (en) * | 2001-03-22 | 2004-06-16 | 希普雷公司 | Solvents and photoresist compositions for short wavelength imaging |
| CN1424626A (en) * | 2001-12-03 | 2003-06-18 | 东京应化工业株式会社 | Forming method for photoresist design and its laminating products |
| CN1930523A (en) * | 2004-03-05 | 2007-03-14 | 东京应化工业株式会社 | Positive resist composition for immersion exposure and method for forming resist pattern |
| CN101080674A (en) * | 2004-12-03 | 2007-11-28 | 捷时雅株式会社 | Composition for forming antireflection film, layered product, and method of forming resist pattern |
| CN105363042A (en) * | 2015-10-21 | 2016-03-02 | 苏州圣诺生物医药技术有限公司 | Medicine composition and application thereof |
| WO2018070327A1 (en) * | 2016-10-13 | 2018-04-19 | Jsr株式会社 | Radiation-sensitive resin composition and resist-pattern forming method |
| US20180195030A1 (en) * | 2017-01-11 | 2018-07-12 | Daicel Corporation | Composition for removing resist |
| CN109991811A (en) * | 2019-02-27 | 2019-07-09 | 江苏南大光电材料股份有限公司 | A kind of acid dispersion inhibitor and preparation method thereof and photoetching compositions |
| CN111302959A (en) * | 2020-02-28 | 2020-06-19 | 宁波南大光电材料有限公司 | Acid diffusion inhibitor with ester bond, preparation method thereof and photoresist composition |
Non-Patent Citations (3)
| Title |
|---|
| WILLSON, CG ET AL: "The design of resist materials for 157nm lithography", JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY, vol. 15, no. 4, pages 583 - 590 * |
| 李桃等: "基于多苯烯丙基醚无氟抗粘的巯基-烯纳米压印光刻胶", 微纳电子技术, vol. 55, no. 6, pages 401 - 407 * |
| 汪称意;李光;江建明;杨胜林;金俊弘;: "聚酰亚胺研究新进展", 化学进展, no. 01, 24 January 2009 (2009-01-24) * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113296360B (en) | 2024-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101423977B1 (en) | Positive resist composition and pattern forming method using the same | |
| US6916594B2 (en) | Overcoating composition for photoresist and method for forming photoresist pattern using the same | |
| KR100231242B1 (en) | Chemically amplified positive resist composition | |
| TWI481627B (en) | Novel copolymer and photoresist composition comprising the same | |
| JP5407941B2 (en) | Positive resist material and pattern forming method using the same | |
| JP5463963B2 (en) | Positive resist material and pattern forming method using the same | |
| TWI386759B (en) | Positive resist composition and pattern forming method utilizing the same | |
| KR101841452B1 (en) | Lactone Photoacid Generators and Resins and Photoresists comprising same | |
| KR100220885B1 (en) | Chemically amplified positive resist composition | |
| KR101464215B1 (en) | Positive resist composition and pattern forming method using the same | |
| TW548522B (en) | Positive-working photoresist composition and resist patterning method using same | |
| CN108983549B (en) | Acid generator and photoresist containing the same | |
| TWI302638B (en) | Positive resist composition and method for forming resist pattern | |
| TW201616224A (en) | Negative-tone resist compositions and multifunctional polymers therein | |
| TW200948830A (en) | Actinic ray-sensitive or radiation-sensitive resin composition and method of forming pattern therewith | |
| TWI304153B (en) | Positive resist composition and manufacturing method of resist pattern | |
| JP5819810B2 (en) | Negative resist material and pattern forming method using the same | |
| TW201805317A (en) | Polymer, positive resist composition, and pattern forming process wherein the polymer can be used as a base resin of positive resist composition having a higher resolution and smaller edge roughness | |
| KR100931924B1 (en) | Copolymer for chemically amplified photoresist comprising a 5-hydroxy-1-adamantyl (meth) acrylate derivative and a chemically amplified photoresist composition comprising the same | |
| US6951705B2 (en) | Polymers for photoresist compositions for microlithography | |
| TW201715299A (en) | Resist composition and patterning process using the same | |
| TW200527137A (en) | Resist composition and resist pattern formation method | |
| JPWO2006070694A1 (en) | Acrylic copolymer | |
| WO2004108780A1 (en) | Resin for photoresist composition, photoresist composition and method for forming resist pattern | |
| WO1997027515A1 (en) | Resist composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |