CN113960879B - Hard mask composition, preparation method thereof and method for forming patterns - Google Patents
Hard mask composition, preparation method thereof and method for forming patterns Download PDFInfo
- Publication number
- CN113960879B CN113960879B CN202111287631.2A CN202111287631A CN113960879B CN 113960879 B CN113960879 B CN 113960879B CN 202111287631 A CN202111287631 A CN 202111287631A CN 113960879 B CN113960879 B CN 113960879B
- Authority
- CN
- China
- Prior art keywords
- hard mask
- mass ratio
- polymer
- mask composition
- solvent
- 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.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004305 biphenyl Substances 0.000 claims abstract description 8
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 21
- 239000003431 cross linking reagent Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- 229920002120 photoresistant polymer Polymers 0.000 claims description 19
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 239000004014 plasticizer Substances 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- 229940116333 ethyl lactate Drugs 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims 2
- 238000005530 etching Methods 0.000 abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- 238000011049 filling Methods 0.000 abstract description 9
- 150000003220 pyrenes Chemical class 0.000 abstract description 7
- 125000001033 ether group Chemical group 0.000 abstract description 6
- 238000000059 patterning Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000178 monomer Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000006267 biphenyl group Chemical group 0.000 description 12
- -1 hydroxy, methoxy, ethoxy Chemical group 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000001312 dry etching Methods 0.000 description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- KDBGLWGYIXORDW-UHFFFAOYSA-N 1,3-bis(methoxymethyl)-5-phenylbenzene Chemical group COCC=1C=C(C=C(C=1)COC)C1=CC=CC=C1 KDBGLWGYIXORDW-UHFFFAOYSA-N 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 150000001278 adipic acid derivatives Chemical class 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 150000002688 maleic acid derivatives Chemical class 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 150000002888 oleic acid derivatives Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- JRCJYPMNBNNCFE-UHFFFAOYSA-N 1,6-dibromopyrene Chemical compound C1=C2C(Br)=CC=C(C=C3)C2=C2C3=C(Br)C=CC2=C1 JRCJYPMNBNNCFE-UHFFFAOYSA-N 0.000 description 1
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- VIUUKFKERNSOOZ-UHFFFAOYSA-N 2-(5-ethyltetradecan-5-yloxycarbonyl)benzoic acid Chemical compound CCCCCCCCCC(CC)(CCCC)OC(=O)C1=CC=CC=C1C(=O)O VIUUKFKERNSOOZ-UHFFFAOYSA-N 0.000 description 1
- VLJYUDGCEKORNG-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-(2-nitrophenyl)-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CC=C1[N+]([O-])=O VLJYUDGCEKORNG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CJFLBOQMPJCWLR-UHFFFAOYSA-N bis(6-methylheptyl) hexanedioate Chemical compound CC(C)CCCCCOC(=O)CCCCC(=O)OCCCCCC(C)C CJFLBOQMPJCWLR-UHFFFAOYSA-N 0.000 description 1
- ULBTUVJTXULMLP-UHFFFAOYSA-N butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCC ULBTUVJTXULMLP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- 229940031769 diisobutyl adipate Drugs 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940075529 glyceryl stearate Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- MXQOYLRVSVOCQT-UHFFFAOYSA-N palladium;tritert-butylphosphane Chemical compound [Pd].CC(C)(C)P(C(C)(C)C)C(C)(C)C.CC(C)(C)P(C(C)(C)C)C(C)(C)C MXQOYLRVSVOCQT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a hard mask composition, a preparation method thereof and a patterning method, wherein the hard mask composition comprises a polymer, and the polymer comprises a pyrene derivative condensed with a compound with biphenyl or ether groups. The flexibility of the above polymers is increased due to the rotational characteristics of biphenyl and ether groups, thereby enabling to improve the solubility and coatability of the hard mask composition, which can be applied to filling open topographical features, such as vias, trenches, in patterned material layers. In addition, the polymer contains pyrene derivative with high carbon content, so that the hard mask has better etching resistance.
Description
Technical Field
The invention relates to the technical field of photoetching, in particular to a hard mask composition, a preparation method thereof and a method for forming patterns.
Background
In recent years, the semiconductor industry has developed ultra-fine technology with patterns of several nanometers to tens of nanometers in size. In order to realize such a finer pattern, the wavelength of the lithography light source has been shortened, for example, from g-line (436 nm) and i-line (365 nm) of mercury lamps widely used in the past to KrF excimer laser (248 nm) and ArF excimer laser (193 nm); on the other hand, in order to prevent collapse of the finer photoresist pattern, the thickness of the photoresist film is gradually reduced. Accordingly, there are two problems that, firstly, the depth of focus is reduced with the reduction of the wavelength of the exposure light, and secondly, it is difficult for the thinned photoresist pattern to provide sufficient etching resistance to etch the material layer. In order to solve the problems of the first aspect, it is important to improve the planarization of a film formed on a substrate, i.e., to form a resist underlayer film that is a flat coating film without level differences on the substrate, in order to form a desired resist pattern with high accuracy; for the second aspect, it is necessary to introduce an inorganic or organic film with strong etching resistance, i.e., a resist underlayer film or a hard mask, between the photoresist and the material layer. The inorganic material used as the hard mask is usually made of silicon nitride, silicon oxynitride, polysilicon, silicon nitride, amorphous carbon, etc., and is usually prepared by a Chemical Vapor Deposition (CVD) method, and has a characteristic of excellent etching resistance, but also has problems of particle problems, high equipment cost, etc. To solve these problems, a method of using a spin-coated organic hard mask instead of the above-mentioned chemical vapor deposition inorganic hard mask has been proposed.
The typical application process of the organic hard mask comprises the following steps: spin-coating an organic hard mask layer with high carbon content on the material layer; thereafter forming a silicon layer thereon, which may be formed by spin coating or chemical vapor deposition; finally, a photoresist layer is spin-coated on the silicon layer. Silicon has a high degree of etch resistance when etched using oxygen and by providing a high carbon content organic mask layer under the silicon layer, a very large aspect ratio can be achieved. Thus, the high carbon organic hard mask layer is much thicker than the silicon layer and photoresist layer above it.
The high carbon content organic hard mask composition is typically composed of a high carbon content resin, a crosslinking agent, a catalyst, additives, and a solvent. Wherein, the high carbon content resin generally contains a large amount of aromatic groups, on the one hand, excellent etching resistance can be brought about; on the other hand, a large amount of aromatic groups causes the rigidity of the resin structure to be too strong, and the solubility in the conventional organic hard mask composition is deteriorated; meanwhile, fluidity of the resin is deteriorated, and it is not uniformly coated on the surface of the substrate, especially the surface of the substrate which has been patterned.
Disclosure of Invention
In view of the above, the present invention provides a hard mask composition, a method for preparing the same, and a method for forming a pattern. The hard mask composition provided by the invention can ensure the solubility of a solvent, gap filling characteristics and planarization characteristics and has excellent etching resistance.
In order to solve the technical problems, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a hard mask composition, wherein the hard mask composition comprises a polymer and a solvent, and the polymer is a compound shown in chemical formula 1:
Wherein R 1 is selected from any one of hydrogen atom, alkyl with 1-6 carbon atoms and substituted or unsubstituted aryl with 6-30 carbon atoms; ar 1 is selected from any one of a substituted or unsubstituted biphenyl group having 6 to 18 carbon atoms and a substituted or unsubstituted biphenyl group having 6 to 18 carbon atoms separated by at least one oxygen atom; n is any integer between 1 and 100.
Further, when the R 1 is selected from any one of substituted aryl groups having 6 to 30 carbon atoms, the substituted groups in the substituted aryl groups include: phenyl, substituted phenyl, naphthyl, substituted naphthyl;
When Ar 1 is selected from any one of substituted or unsubstituted biphenyl groups having 6 to 18 carbon atoms, the substituted groups in the substituted biphenyl groups include: methyl, ethyl, propyl, butyl, t-butyl;
When Ar 1 is selected from any one of substituted or unsubstituted biphenyl groups having 6 to 18 carbon atoms separated by at least one oxygen atom, the substituted groups in the substituted biphenyl groups include: methyl, ethyl, propyl, butyl, tert-butyl.
Further, ar 1 is selected from any one of the divalent groups shown in group 1, wherein group 1 includes compounds shown in chemical formula a and chemical formula B:
Wherein R 2、R3 is independently selected from any one of hydrogen, hydroxy, methoxy, ethoxy, halogen, substituted or unsubstituted alkyl with 1-6 carbon atoms and substituted or unsubstituted aryl with 6-12 carbon atoms, X is oxygen atom or single bond, and X represents a connecting point.
Further, the solvent comprises any one of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone and ethyl lactate.
Further, the hard mask composition further comprises at least one of a cross-linking agent, a catalyst, a surfactant and a plasticizer.
Further, the mass ratio of the polymer is 4-25%, the mass ratio of the cross-linking agent is 0.4-3%, the mass ratio of the catalyst is 0.001-0.05%, the mass ratio of the surfactant is 0.01-0.1%, the mass ratio of the plasticizer is 0-2.5%, and the mass ratio of the solvent is 75-95.6% based on the total amount of the hard mask composition.
In a second aspect, the present invention provides a method for preparing the hard mask composition as described above, the method comprising: mixing the polymer with a solvent, wherein the mass ratio of the polymer is 4% -25%, and the mass ratio of the solvent is 75% -95.6%.
Further, the preparation method comprises the following steps: taking and mixing the polymer, the solvent, the cross-linking agent, the catalyst, the surfactant and the plasticizer, wherein the mass ratio of the polymer is 4-25%, the mass ratio of the cross-linking agent is 0.4-3%, the mass ratio of the catalyst is 0.001-0.05%, the mass ratio of the surfactant is 0.01-0.1%, the mass ratio of the plasticizer is 0-2.5%, and the mass ratio of the solvent is 75-95.6% based on the total weight of the hard mask composition.
In a third aspect, the present invention provides a method of forming a pattern, the method comprising the steps of:
providing a material layer on a substrate;
applying a hard mask composition as described above on the material layer;
thermally treating the hard mask composition to form a hard mask;
Forming a thin layer containing silicon on the hard mask;
Forming a photoresist resist layer on the silicon-containing thin layer;
exposing and developing the photoresist resist layer to form a photoresist pattern;
Selectively removing the thin silicon-containing layer and the hard mask using the photoresist pattern to expose a portion of the material layer;
the exposed portions of the material layer are etched.
Further, the method for forming the hard mask comprises the following steps: the hard mask composition is spin-coated on the material layer in the form of a solution, and the hard mask composition is heat-treated at 200 to 500 ℃ for about 10 seconds to 10 minutes to form a hard mask.
The technical scheme of the invention has the following beneficial effects:
The invention provides a hard mask composition, a preparation method thereof and a patterning method, wherein the hard mask composition comprises a polymer, and the polymer comprises a pyrene derivative condensed with a compound with biphenyl or ether groups. The flexibility of the above polymers is increased due to the rotational characteristics of biphenyl and ether groups, thereby enabling to improve the solubility and coatability of the hard mask composition, which can be applied to filling open topographical features, such as vias, trenches, in patterned material layers. In addition, the polymer contains pyrene derivative with high carbon content, so that the hard mask has better etching resistance.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it is to be understood that these descriptions are merely intended to illustrate further the features and advantages of the invention and are not limiting of the invention.
In a first aspect, the present invention provides a hard mask composition, wherein the hard mask composition comprises a polymer and a solvent, and the polymer is a compound shown in chemical formula 1:
Wherein R 1 is selected from any one of hydrogen atom, alkyl with 1-6 carbon atoms and substituted or unsubstituted aryl with 6-30 carbon atoms; ar 1 is selected from any one of a substituted or unsubstituted biphenyl group having 6 to 18 carbon atoms and a substituted or unsubstituted biphenyl group having 6 to 18 carbon atoms separated by at least one oxygen atom; n is any integer between 1 and 100.
The hard mask composition of the present invention contains a polymer comprising a pyrene derivative condensed with a compound having a biphenyl or ether group. The flexibility of the above polymers is increased due to the rotational characteristics of biphenyl and ether groups, thereby enabling to improve the solubility and coatability of the hard mask composition, which can be applied to filling open topographical features, such as vias, trenches, in patterned material layers. In addition, the polymer contains pyrene derivative with high carbon content, so that the hard mask has better etching resistance.
According to some embodiments of the invention, when R 1 is selected from any one of substituted aryl groups having 6 to 30 carbon atoms, the substituted groups in the substituted aryl groups include: phenyl, substituted phenyl, naphthyl, substituted naphthyl;
When Ar 1 is selected from any one of substituted or unsubstituted biphenyl groups having 6 to 18 carbon atoms, the substituted groups in the substituted biphenyl groups include: methyl, ethyl, propyl, butyl, t-butyl;
When Ar 1 is selected from any one of substituted or unsubstituted biphenyl groups having 6 to 18 carbon atoms separated by at least one oxygen atom, the substituted groups in the substituted biphenyl groups include: methyl, ethyl, propyl, butyl, tert-butyl.
According to some embodiments of the invention, ar 1 is selected from any one of the divalent groups set forth in group 1, the group 1 including compounds of formula a and formula B:
Wherein R 2、R3 is independently selected from any one of hydrogen, hydroxy, methoxy, ethoxy, halogen, substituted or unsubstituted alkyl with 1-6 carbon atoms and substituted or unsubstituted aryl with 6-12 carbon atoms, X is oxygen atom or single bond, and X represents a connecting point.
Specifically, a polymer contained in the hard mask composition provided in the present invention can be synthesized by performing a polymerization reaction in a solvent in the presence of an acidic catalyst such as sulfonic acid from a pyrene derivative represented by chemical formula 2 and a glycol derivative represented by group 2, wherein the glycol derivative represented by group 2 includes compounds represented by chemical formula C and chemical formula D:
wherein R 1 is selected from any one of hydrogen atom, alkyl with 1-6 carbon atoms and substituted or unsubstituted aryl with 6-30 carbon atoms; r 2、R3 is independently selected from any one of hydrogen, hydroxyl, methoxy, ethoxy, halogen, substituted or unsubstituted alkyl with 1-6 carbon atoms and substituted or unsubstituted aryl with 6-12 carbon atoms, and X is oxygen atom or single bond.
The acid catalyst used in the polycondensation reaction may be an inorganic acid such as sulfuric acid, phosphoric acid, or perchloric acid, or an organic acid such as p-toluenesulfonic acid, formic acid, or oxalic acid. The acid catalyst is used in an amount of 0.1 to 100 parts by mass based on 100 parts by mass of the aromatic ring-containing polymer.
The polycondensation reaction is usually carried out in a solvent. The solvent may be any solvent as long as it does not inhibit the reaction, and examples thereof include tetrahydrofuran, propylene glycol monomethyl ether, and propylene glycol dimethyl ether. The acid catalyst used may also be used as a solvent if it is a liquid such as formic acid.
Further, the temperature of the polycondensation reaction is usually 40 to 200℃and the reaction time is selected according to the reaction temperature and molecular weight requirements, and is usually about 30 minutes to 50 hours.
According to some embodiments of the invention, the solvent comprises any one of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, and ethyl lactate.
According to some embodiments of the invention, the hard mask composition further comprises at least one of a cross-linking agent, a catalyst, a surfactant, and a plasticizer.
According to some embodiments of the invention, the polymer is present in an amount of 4% to 25% by weight, the cross-linking agent is present in an amount of 0.4% to 3% by weight, the catalyst is present in an amount of 0.001% to 0.05% by weight, the surfactant is present in an amount of 0.01% to 0.1% by weight, the plasticizer is present in an amount of 0% to 2.5% by weight, and the solvent is present in an amount of 75% to 95.6% by weight, based on the total amount of the hard mask composition.
According to some embodiments of the invention, the crosslinking agent includes any one or two or more of a glycoluril compound, an epoxy compound, melamine, and a melamine derivative. Wherein the glycoluril compound may be a compound shown in chemical formula 3, the epoxy compound may be a compound shown in chemical formula 4, and the melamine and melamine derivatives may be a compound shown in chemical formula 5:
further, a crosslinking agent having high heat resistance can be used as the crosslinking agent. As the crosslinking agent having high heat resistance, a compound having an aromatic ring such as a benzene ring or a naphthalene ring in the molecule may be preferably used, and a polymer or oligomer having a compound represented by chemical formula 6 and a structural unit represented by chemical formula 7 may be exemplified.
Wherein R 7 is selected from any one of hydrogen atom, alkyl with 1-6 carbon atoms or substituted or unsubstituted aryl with 6-30 carbon atoms; r 8、R9 is independently selected from any one of hydrogen atom and alkyl with 1-6 carbon atoms; n 1 is an integer between 1 and 5; n 2 is an integer between 1 and 3; the polymer or oligomer having the structural unit of formula 7 preferably has a repeating unit of 2 to 50.
According to some embodiments of the present invention, the catalyst is generally an acidic compound, and plays a role in promoting a crosslinking reaction, and the catalyst includes any one or more of chemical formulas 1-a to 1-F, and the chemical formulas 1-a to 1-F are as follows:
According to some embodiments of the invention, the surfactant includes any one or two or more of polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters.
According to some embodiments of the invention, the plasticizer is mainly used for improving fluidity of the hard mask composition, and the plasticizer includes any one or more of phthalic acid derivative, adipic acid derivative, oleic acid derivative, maleic acid derivative and stearic acid derivative. Among them, phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, butylethyldecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate; oleic acid derivatives such as butyl oleate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate; stearic acid derivatives such as n-butyl stearate, glyceryl stearate.
In a second aspect, the present invention provides a method of preparing the hard mask composition described above, the method comprising: mixing the polymer with the solvent, wherein the mass ratio of the polymer is 4-25%, and the mass ratio of the solvent is 75-95.6%.
According to some embodiments of the invention, the method of preparing is: taking and mixing the polymer, the solvent, the cross-linking agent, the catalyst, the surfactant and the plasticizer, wherein the mass ratio of the polymer is 4-25%, the mass ratio of the cross-linking agent is 0.4-3%, the mass ratio of the catalyst is 0.001-0.05%, the mass ratio of the surfactant is 0.01-0.1%, the mass ratio of the plasticizer is 0-2.5%, and the mass ratio of the solvent is 75-95.6% based on the total weight of the hard mask composition.
In a third aspect, the present invention provides a method of forming a pattern, the method comprising the steps of: providing a material layer on a substrate; applying a hard mask composition as described above on the material layer; thermally treating the hard mask composition to form a hard mask; forming a thin layer containing silicon on the hard mask; forming a photoresist resist layer on the silicon-containing thin layer; exposing and developing the photoresist resist layer to form a photoresist pattern; selectively removing the thin silicon-containing layer and the hard mask using the photoresist pattern to expose a portion of the material layer; the exposed portions of the material layer are etched.
According to some embodiments of the invention, the substrate comprises any one of a silicon wafer, a glass substrate, or a polymer substrate.
According to some embodiments of the invention, the material layer is a material to be finally patterned, including a metal layer such as an aluminum layer or a copper layer, a semiconductor layer such as a silicon layer, and an insulating layer such as silicon dioxide or silicon nitride.
According to some embodiments of the invention, the method of forming the hard mask comprises: the hard mask composition is spin-coated on the material layer in the form of a solution, and the hard mask composition is heat-treated at 200 to 500 ℃ for about 10 seconds to 10 minutes to form a hard mask. Further, the thickness of the hard mask composition is not particularly limited and may be 100 to 10000 a.
According to some embodiments of the invention, the thin silicon-containing layer comprises any one of silicon nitride, silicon oxide, or silicon oxynitride.
According to some embodiments of the invention, the photoresist resist exposure may be performed using, for example, arF, krF, or EUV.
The invention is further illustrated by the following examples.
Example 1
Synthesis of monomer 1:
To a 1000ml reaction flask, 18.0g (50 mmol) of 1, 6-dibromopyrene, 26.2g (105 mmol) of 2-nitrobenzeneboronic acid pinacol ester, 27.6g (200 mmol) of potassium carbonate, 2.3g (2 mmol) of tetraphenylphosphino-palladium and 500ml of toluene were added under the protection of argon gas, and after stirring uniformly, the temperature was raised to 120℃for reaction for 6 hours, the reaction solution was cooled, and water was added to quench the reaction. The organic phase was separated, the aqueous phase was extracted three times with toluene, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, the solvent was spin-dried, and purified by silica gel thin layer chromatography to give the intermediate product.
17.8G (40 mmol) of the intermediate, 50.4g (192 mmol) of triphenylphosphine, 0.69g (2 mmol) of molybdenum-based catalyst and 250ml of 1, 2-dichlorobenzene are added into a 500ml reaction bottle under the protection of argon, stirred uniformly and then subjected to reflux reaction for 12h, the reaction solution is cooled to room temperature, toluene is used for extraction, then water washing, anhydrous magnesium sulfate drying, filtration and spin-drying of the solvent are carried out, and the monomer 1 is obtained by purifying the solvent by silica gel thin layer chromatography, wherein the carbon content of the monomer 1 is 88.4%. The synthesis of the monomer 1 is shown in the following equation 1.
Synthesis of monomer 2
Under the protection of argon, 11.4g (30 mmol) of monomer 1, 13.3g (65 mmol) of iodobenzene, 9.0g (65 mmol) of potassium carbonate, 0.3g (0.6 mmol) of bis (tri-tert-butylphosphine) palladium, 200ml of toluene and reflux reaction were put into a 500ml reaction flask, after which the reaction solution was cooled to room temperature, filtered, washed with water, dried over anhydrous magnesium sulfate, and the spin-dried solvent was purified by column chromatography to give monomer 2, the carbon content of monomer 2 was 90.2%.
The synthesis of monomer 2 is shown in equation 2.
Synthetic polymer:
synthesis of Polymer 1-1
Into a 100ml three-necked flask, 3.80g (0.01 mol) of 1,2.42g (0.01 mol) of 3, 5-dimethoxymethyl biphenyl and 50ml of propylene glycol monomethyl ether acetate were added, and after mixing uniformly, 0.19g (0.001 mol) of p-toluenesulfonic acid was added, and reacted at 100℃for 10 hours under nitrogen protection. After the completion of the reaction, the reaction solution was cooled, and then the reaction solution was poured into methanol to remove unreacted monomer 1 and low molecular weight polymer, the mixed solution was filtered, and after further washing the cake with methanol 2 times, it was dried using a vacuum oven at 50 ℃ for 12 hours to obtain polymer 1 (mw=4900, polydispersity=2.1) as a repeating unit represented by chemical formula 1-1.
Example 2
The synthesis procedure of example 1 was repeated except that 2.42g (0.01 mol) of 4,4' -dimethoxymethylbiphenyl was used instead of 2.42g (0.01 mol) of 3, 5-dimethoxymethylbiphenyl to obtain polymer 2 (mw=5500, polydispersity=1.8) having the repeating unit represented by chemical formula 1-2.
Example 3
The synthesis procedure of example 1 was repeated except that 2.58g (0.01 mol) of 4,4' -dimethoxymethyl-diphenyl ether was used instead of 2.42g (0.01 mol) of 3, 5-dimethoxymethyl-biphenyl to obtain polymer 3 (mw=4400, polydispersity=1.9) having repeating units represented by chemical formula 1-3.
Example 4
The synthesis procedure of example 3 was repeated except that 5.32g (0.01 mol) of monomer 2 was used instead of 3.80g (0.01 mol) of monomer 1, to obtain polymer 3 (mw=5900, polydispersity=2.2) having the repeating unit represented by chemical formula 1-4.
Comparative example 4
The procedure of example 1 was repeated except that 2.02g (0.01 mol) of pyrene was used instead of monomer 1 and 1.66g (0.01 mol) of 1,4' -dimethoxymethylbenzene was used instead of 2.42g (0.01 mol) of 3, 5-dimethoxymethylbiphenyl to give polymer 5 (mw=6700, polydispersity=1.6) having the repeating unit represented by chemical formula 1-5.
Example 5
The polymers 1 to 5 prepared in examples 1 to 4 and comparative example 1, respectively, were uniformly mixed with a solvent, a crosslinking agent, a catalyst and a surfactant in the proportions shown in Table 1 to obtain resist underlayer film compositions 1 to 5. Wherein, the solvent is a mixed solvent prepared by Propylene Glycol Monomethyl Ether Acetate (PGMEA) and cyclohexanone according to a volume ratio of 7:3, the catalyst is p-toluenesulfonic acid, the surfactant is polyoxyethylene lauryl ether, and the cross-linking agent is a triazine compound with the structure shown as follows:
TABLE 1 (wt%)
And (3) testing:
the solubility, void filling characteristics, planarization characteristics, and etching resistance of the resist underlayer film compositions 1 to 5 of examples and comparative examples were evaluated by the following evaluation methods.
(1) Solubility evaluation
The synthesized polymer 1, polymer 2, polymer 3, polymer 4 and polymer 5 were added to PGMEA at a mass ratio of 15%, and after stirring at 50 ℃ for 1 hour, the dissolved state was confirmed; cooling to 25 ℃, and immediately confirming the dissolution state; finally, the mixture was allowed to stand at 25℃for 6 hours to confirm the dissolved state, and the results are shown in Table 2.
Solubility criterion:
And (3) the following materials: after standing at 25 ℃ for 6 hours, undissolved substances are not confirmed by naked eyes;
O: insoluble matter was not visually confirmed in the heated state and the as-cooled state, but a small amount of insoluble matter was visually confirmed after leaving at 25℃for 6 hours;
Delta: insoluble matter was not visually confirmed in the heated state, but was visually confirmed in the just cooled state and after standing at 25℃for 6 hours;
TABLE 2
| Project | Solubility of |
| Polymer 1 | ○ |
| Polymer 1 | ○ |
| Polymer 1 | ◎ |
| Polymer 1 | ○ |
| Polymer 5 | △ |
From the results of Table 2, it can be seen that polymers 1 to 5 exhibit good solubility properties due to inclusion of flexible structural units, whereas polymer 5 has poor solubility properties due to relatively high molecular rigidity.
(2) Void filling and planarization characteristics
The hard mask compositions 1 to 5 prepared in Table 1 were spin-coated on a silicon substrate coated with silicon oxide having a line/space width of 160nm/200nm and a height of 300nm, respectively, and baked at 350℃for 180 seconds to form a resist underlayer film. Observing the profile of the formed resist underlayer film by using a field emission scanning electron microscope, and determining whether a gap exists or not to evaluate gap filling characteristics;
the planarization characteristics were determined by the difference between the high-thickness portion (line portion) and the low-thickness portion (space portion) of the spin-coated resist underlayer film, wherein the difference between the two portions was determined to be "very good" when the difference was less than 20nm, was determined to be "good" when the difference was between 20nm and 50nm, and was determined to be "poor" when the difference was greater than 50nm, and the obtained results are shown in table 3.
(3) Evaluation of etching resistance
The hard mask compositions 1 to 5 of examples and comparative examples in Table 1 were applied to a silicon wafer by a spin coater, and baked at 350℃for 180 seconds to form a resist underlayer film having a thickness of 250 nm. Then using CF 4 gas as etching gas to carry out dry etching and measuring the dry etching rate; further, a solution of 0.5g of a commercially available cresol novolac resin (weight average molecular weight: 5000, polydispersity: 1.7), 0.05g of the same crosslinking agent as in comparative example, and 0.005g of p-toluenesulfonic acid dissolved in 4.5g of PGMEA was spin-coated on a silicon substrate to form a hard mask, and also dry etching was performed using CF 4 gas as an etching gas and the dry etching rate was measured, and the dry etching rate ratio was obtained by comparing the dry etching rates of the hard masks 1 to 5 formed in examples and comparative examples, and the results are shown in table 3. The dry etch rate ratio in table 3 is calculated from equation 1.
Equation 1:
Dry etch rate ratio = dry etch rate of hard masks 1-5/dry etch rate of cresol novolac
TABLE 3 Table 3
| Project | Planarization characteristics | Gap filling characteristics | Dry etching rate ratio |
| Example 1 | Excellent quality | Without gaps | 0.71 |
| Example 2 | Excellent quality | Without gaps | 0.70 |
| Example 3 | Very good | Without gaps | 0.70 |
| Example 4 | Excellent quality | Without gaps | 0.69 |
| Comparative example 1 | Failure of | With gaps | 0.79 |
As can be seen from the test results of table 3, in one aspect, the hard mask composition provided by the present invention exhibits excellent gap filling characteristics and planarization characteristics because of its excellent dissolution properties; on the other hand, the hard mask composition provided by the present invention also exhibits improved etching resistance compared to the comparative example.
Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The terms "first," "second," and the like, as used herein, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms "connected" or "connected," and the like, are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "upper", "lower", "left", "right", etc. are used merely to indicate a relative positional relationship, which changes accordingly when the absolute position of the object to be described changes.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A hard mask composition, comprising a polymer and a solvent, wherein the polymer is a compound represented by chemical formula 1:
Wherein R 1 is selected from any one of hydrogen atom, alkyl with 1-6 carbon atoms and substituted or unsubstituted aryl with 6-30 carbon atoms; ar 1 is selected from biphenyl without substituent and biphenyl without substituent separated by oxygen atom, and the carbon atoms are 12; n is any integer between 1 and 100.
2. The hardmask composition according to claim 1, wherein when the R 1 is selected from any one of substituted aryl groups having 6 to 30 carbon atoms, the substituted group in the substituted aryl group includes: phenyl, substituted phenyl, naphthyl, substituted naphthyl.
3. The hard mask composition according to claim 1, wherein the solvent comprises any one of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, and ethyl lactate.
4. The hardmask composition according to claim 3, further comprising at least one of a cross-linking agent, a catalyst, a surfactant, and a plasticizer.
5. The hard mask composition according to claim 4, wherein the mass ratio of the polymer is 4% to 25%, the mass ratio of the crosslinking agent is 0.4% to 3%, the mass ratio of the catalyst is 0.001% to 0.05%, the mass ratio of the surfactant is 0.01% to 0.1%, the mass ratio of the plasticizer is 0% to 2.5%, and the mass ratio of the solvent is 75% to 95.6%, based on the total amount of the hard mask composition.
6. A method of preparing a hardmask composition according to claim 1, wherein the method comprises:
mixing the polymer with a solvent, wherein the mass ratio of the polymer is 4% -25%, and the mass ratio of the solvent is 75% -95.6%.
7. The preparation method according to claim 6, wherein the preparation method comprises:
taking and mixing the polymer, the solvent, the cross-linking agent, the catalyst, the surfactant and the plasticizer, wherein the mass ratio of the polymer is 4-25%, the mass ratio of the cross-linking agent is 0.4-3%, the mass ratio of the catalyst is 0.001-0.05%, the mass ratio of the surfactant is 0.01-0.1%, the mass ratio of the plasticizer is 0-2.5%, and the mass ratio of the solvent is 75-95.6% based on the total weight of the hard mask composition.
8. A method of forming a pattern, the method comprising the steps of:
providing a material layer on a substrate;
applying the hard mask composition of any one of claims 1-5 to the material layer;
thermally treating the hard mask composition to form a hard mask;
Forming a thin layer containing silicon on the hard mask;
Forming a photoresist resist layer on the silicon-containing thin layer;
exposing and developing the photoresist resist layer to form a photoresist pattern;
Selectively removing the thin silicon-containing layer and the hard mask using the photoresist pattern to expose a portion of the material layer;
the exposed portions of the material layer are etched.
9. The method of claim 8, wherein the method of forming the hard mask is:
spin-coating the hard mask composition on the material layer in the form of a solution, and heat-treating the hard mask composition at 200 to 500 ℃ for 10 seconds to 10 minutes to form a hard mask.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111287631.2A CN113960879B (en) | 2021-11-02 | 2021-11-02 | Hard mask composition, preparation method thereof and method for forming patterns |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111287631.2A CN113960879B (en) | 2021-11-02 | 2021-11-02 | Hard mask composition, preparation method thereof and method for forming patterns |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113960879A CN113960879A (en) | 2022-01-21 |
| CN113960879B true CN113960879B (en) | 2024-05-24 |
Family
ID=79468929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111287631.2A Active CN113960879B (en) | 2021-11-02 | 2021-11-02 | Hard mask composition, preparation method thereof and method for forming patterns |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113960879B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100874655B1 (en) * | 2007-07-20 | 2008-12-17 | 금호석유화학 주식회사 | Polymer for spin on carbon hardmask and preparation method thereof, spin on carbon hardmask composition containing the polymer and patterning method of semiconductor device using the composition |
| CN107797385A (en) * | 2016-09-07 | 2018-03-13 | 东友精细化工有限公司 | Hard mask composition |
| CN111240153A (en) * | 2020-02-12 | 2020-06-05 | 厦门恒坤新材料科技股份有限公司 | Hardmask composition, hardmask and method of forming pattern |
| CN111290216A (en) * | 2020-02-12 | 2020-06-16 | 厦门恒坤新材料科技股份有限公司 | Hardmask composition, hardmask and method of forming pattern |
| CN112194780A (en) * | 2019-07-08 | 2021-01-08 | 厦门恒坤新材料科技股份有限公司 | Polymer, hard mask composition and method for forming pattern |
-
2021
- 2021-11-02 CN CN202111287631.2A patent/CN113960879B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100874655B1 (en) * | 2007-07-20 | 2008-12-17 | 금호석유화학 주식회사 | Polymer for spin on carbon hardmask and preparation method thereof, spin on carbon hardmask composition containing the polymer and patterning method of semiconductor device using the composition |
| CN107797385A (en) * | 2016-09-07 | 2018-03-13 | 东友精细化工有限公司 | Hard mask composition |
| CN112194780A (en) * | 2019-07-08 | 2021-01-08 | 厦门恒坤新材料科技股份有限公司 | Polymer, hard mask composition and method for forming pattern |
| CN111240153A (en) * | 2020-02-12 | 2020-06-05 | 厦门恒坤新材料科技股份有限公司 | Hardmask composition, hardmask and method of forming pattern |
| CN111290216A (en) * | 2020-02-12 | 2020-06-16 | 厦门恒坤新材料科技股份有限公司 | Hardmask composition, hardmask and method of forming pattern |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113960879A (en) | 2022-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101413069B1 (en) | Monomer for hardmask composition and hardmask composition including the monomer and method of forming patterns using the hardmask composition | |
| KR101556277B1 (en) | Hardmask composition and method of forming patterns and semiconductor integrated circuit device including the patterns | |
| KR101566533B1 (en) | Hardmask composition and method of forming patterns using the hardmask composition | |
| KR20120077466A (en) | Hardmask composition and method of forming patterns and semiconductor integrated circuit device including the patterns | |
| JP2016524171A (en) | Resist underlayer film composition and pattern forming method using the same | |
| CN111240153B (en) | Hard mask composition, hard mask and method for forming pattern | |
| EP3336126A1 (en) | Polyarylene resins | |
| KR20130078432A (en) | Monomer for hardmask composition and hardmask composition including the monomer and method of forming patterns using the hardmask composition | |
| CN111290216B (en) | Hard mask composition, hard mask and method for forming pattern | |
| KR20170037441A (en) | Polymer, organic layer composition, and method of forming patterns | |
| CN113960879B (en) | Hard mask composition, preparation method thereof and method for forming patterns | |
| KR101696197B1 (en) | Hardmask composition, method of forming patterns using the hardmask composition and semiconductor integrated circuit device including the patterns including the patterns | |
| KR101976016B1 (en) | Polymer, organic layer composition, organic layer, and method of forming patterns | |
| KR101994365B1 (en) | Polymer, organic layer composition, organic layer, and method of forming patterns | |
| KR101700150B1 (en) | New compounds and underlayer film composition used in semiconductor production process using the same | |
| CN111542558B (en) | Polymer, organic layer composition and method for forming pattern | |
| CN113960882B (en) | Hard mask composition, preparation method thereof and method for forming patterns | |
| CN113960880B (en) | Hard mask composition, preparation method thereof and method for forming patterns | |
| JP7353445B2 (en) | Hardmask composition, hardmask layer and pattern formation method | |
| KR20140083844A (en) | Monomer for hardmask composition and hardmask composition including the monomer and method of forming patterns using the hardmask composition | |
| KR20190052478A (en) | Monomer, polymer, organic layer composition, and method of forming patterns | |
| JP7428766B2 (en) | Hardmask composition, hardmask layer and pattern forming method | |
| KR20180138405A (en) | Organic layer composition, polymer, and method of forming patterns | |
| KR20180065652A (en) | Compound, organic layer composition, and method of forming patterns | |
| KR101856567B1 (en) | New compounds and underlayer film composition used in semiconductor production process using the same |
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 |