WO2012031453A1 - 一种含氟清洗液 - Google Patents
一种含氟清洗液 Download PDFInfo
- Publication number
- WO2012031453A1 WO2012031453A1 PCT/CN2011/001451 CN2011001451W WO2012031453A1 WO 2012031453 A1 WO2012031453 A1 WO 2012031453A1 CN 2011001451 W CN2011001451 W CN 2011001451W WO 2012031453 A1 WO2012031453 A1 WO 2012031453A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fluorine
- cleaning liquid
- acid
- containing cleaning
- fluoride
- Prior art date
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 56
- 239000007788 liquid Substances 0.000 title claims abstract description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 10
- 150000003077 polyols Chemical class 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 22
- 229910052731 fluorine Inorganic materials 0.000 claims description 22
- 239000011737 fluorine Substances 0.000 claims description 22
- 230000007797 corrosion Effects 0.000 claims description 20
- 238000005260 corrosion Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 12
- -1 alcohol amine Chemical class 0.000 claims description 12
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 12
- 239000008103 glucose Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 7
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 7
- 150000003462 sulfoxides Chemical class 0.000 claims description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 6
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 229930195725 Mannitol Natural products 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000594 mannitol Substances 0.000 claims description 6
- 235000010355 mannitol Nutrition 0.000 claims description 6
- 239000000600 sorbitol Substances 0.000 claims description 6
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims description 5
- ZAQJHHRNXZUBTE-NQXXGFSBSA-N D-ribulose Chemical compound OC[C@@H](O)[C@@H](O)C(=O)CO ZAQJHHRNXZUBTE-NQXXGFSBSA-N 0.000 claims description 5
- ZAQJHHRNXZUBTE-UHFFFAOYSA-N D-threo-2-Pentulose Natural products OCC(O)C(O)C(=O)CO ZAQJHHRNXZUBTE-UHFFFAOYSA-N 0.000 claims description 5
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 5
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 5
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical compound OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 claims description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 4
- 229960004889 salicylic acid Drugs 0.000 claims description 4
- 150000003457 sulfones Chemical class 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- MNZHBXZOPHQGMD-UHFFFAOYSA-N acetic acid;azane Chemical compound N.CC(O)=O.CC(O)=O.CC(O)=O MNZHBXZOPHQGMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229940074391 gallic acid Drugs 0.000 claims description 2
- 235000004515 gallic acid Nutrition 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 2
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002894 organic compounds Chemical group 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims 2
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical group CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 claims 1
- 235000014459 Sorbus Nutrition 0.000 claims 1
- 241001092391 Sorbus Species 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 claims 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims 1
- 229960004063 propylene glycol Drugs 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052710 silicon Inorganic materials 0.000 abstract description 12
- 239000010703 silicon Substances 0.000 abstract description 12
- 238000005530 etching Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 235000012431 wafers Nutrition 0.000 description 15
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 14
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000009972 noncorrosive effect Effects 0.000 description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000000992 sputter etching Methods 0.000 description 3
- OWQPOVKKUWUEKE-UHFFFAOYSA-N 1,2,3-benzotriazine Chemical compound N1=NN=CC2=CC=CC=C21 OWQPOVKKUWUEKE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002843 nonmetals Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- ZCFWXOXFBWWDMN-UHFFFAOYSA-N 4,5-dimethyl-1,2,3-benzotriazine Chemical compound N1=NC(C)=C2C(C)=CC=CC2=N1 ZCFWXOXFBWWDMN-UHFFFAOYSA-N 0.000 description 1
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- OUCXYSRPMBQONT-UHFFFAOYSA-N acetamide;phenol Chemical compound CC(N)=O.OC1=CC=CC=C1 OUCXYSRPMBQONT-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
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- 150000005846 sugar alcohols Polymers 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2065—Polyhydric alcohols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/261—Alcohols; Phenols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Definitions
- the present invention relates to a fluorine-containing cleaning liquid for semiconductor industry.
- the application, exposure and imaging of the photoresist layer is a necessary process step for the pattern fabrication of the components.
- the residue of the photoresist layer material needs to be completely removed before the next process step (i.e., after coating, imaging, ion implantation, and etching of the photoresist layer). Ion bombardment in the doping step hardens the photoresist layer polymer, thus making the photoresist layer less soluble and more difficult to remove.
- this layer of photoresist film has been removed using a two-step process (dry ashing and wet etching).
- the first step utilizes dry ashing to remove most of the photoresist layer (PR); the second step utilizes the corrosion inhibitor composition wet etch/clean process to remove and clean the remaining photoresist layer, typically in the form of a cleaning solution. / rinse / deionized water rinse. Only residual polymer photoresist layers and inorganic materials can be removed in this process, and damage to metal layers (such as aluminum layers) and non-metal layers (such as silicon oxynitride layers) cannot be attacked.
- Typical cleaning solutions in the prior art are as follows: amine cleaning solutions (hydroxylamines), semi-aqueous amine based (non-hydroxylamine) cleaning solutions, and fluoride cleaning solutions.
- the first two types of cleaning liquids need to be cleaned at high temperature, generally between 60 ° C and 80 ° C, there is a problem of large corrosion rate of metal; while the existing fluoride cleaning liquid can be at a lower temperature Cleaning (at room temperature to 50 ⁇ ), but there are still various shortcomings, such as the inability to simultaneously control the corrosion of metal and non-metal substrates, and the change in the size of the channel features after cleaning, thereby changing the semiconductor structure; In terms of its large etching rate, the cleaning operation window is relatively small.
- US 5,320,709 discloses a cleaning combination
- the materials include: Polyhydric alcohol, ammonium fluoride for removing organometallic residues on the semiconductor substrate, silicone residues and silicon oxide, but specifically indicating that the water content does not exceed 4%, and its ability to remove organic polymers Weak.
- the cleaning liquid composition disclosed in US 6,828,289 comprises: an acidic buffer, an organic polar solvent, a fluorine-containing substance and water, and a pH of between 3 and 7, wherein the acidic buffer is corresponding to an organic carboxylic acid or a polybasic acid.
- the ammonium salt composition has a composition ratio of between 10:1 and 1:10, and it is specifically indicated that it does not contain a polyol.
- Fluorine-containing cleaning solutions are disclosed, for example, in U.S. Patent No. 5,698, 503, the disclosure of which is incorporated herein by reference.
- a cleaning composition for a fluorine-containing substance which comprises a fluorine-containing substance, an inorganic or organic acid, a quaternary ammonium salt and an organic polar solvent, having a pH of from 7 to 11, is disclosed, for example, in US Pat. No. 5,972,862. There are various problems.
- cleaning fluid compositions have been disclosed, there is a need and a need to prepare a more suitable cleaning composition or system to accommodate new cleaning requirements, such as a more environmentally friendly, low defect level, low etch. Rate as well as large operating window and long service life.
- the object of the present invention is to solve the problem of safe, healthy and efficient cleaning of intermediate ion etching residues in the semiconductor industry and to provide a safe and effective long-life cleaning composition.
- SUMMARY OF THE INVENTION The present invention is a cleaning fluid composition for intermediate ion etching residues in the semiconductor industry, including fluorides, polyols, water, solvents, and other conventional additives in the art. Other conventional additives described therein include, but are not limited to, one or more of corrosion inhibitors and chelating agents.
- the weight percentage of the cleaning liquid composition is:
- the fluoride according to the present invention is preferably hydrogen fluoride or a salt of hydrogen fluoride and a base.
- the base may be ammonia water, quaternary ammonium hydroxide and alcohol amine.
- the fluoride is preferably hydrogen fluoride (HF) or ammonium fluoride (NH)
- ammonium hydrogen fluoride NH4HF 2
- tetramethylammonium fluoride N (CH 3 ) 4 F
- trishydroxyethyl ammonium fluoride N (CH20H) 3 HF
- the polyol according to the present invention means a glycol, a triol, a tetrahydric alcohol, a pentaol, and a hexahydric alcohol.
- Preferred are ethylene glycol, 1,2-propanediol, glycerol, tetramethylene alcohol, pentaerythritol, ribose, ribulose, glucose, glucose alcohol, hexitol, mannitol and sorbitol; more preferably
- the pentahydric alcohol and the hexahydric alcohol, tetrabutyl alcohol, pentaerythritol, ribose, ribulose, glucose, glucose alcohol, hexitol, mannitol and sorbitol are preferred.
- the invention may further comprise water.
- the solvent may be selected from one or more of a sulfoxide, a sulfone, an imidazolidinone, a pyrrolidone, an imidazolidinone, an ether, and an amide.
- the sulfoxide is preferably dimethyl sulfoxide; the sulfone is preferably sulfolane; and the imidazolidinone is preferably 1,3-dimethyl-2-imidazolium
- the pyrrolidone is N-methylpyrrolidone or hydroxyethylpyrrolidone; and the imidazolidinone is preferably 1,3-dimethyl-2-imidazolidinone ( DMI)
- the ether is preferably propylene glycol monomethyl ether or dipropylene glycol monomethyl ether; and the amide is preferably dimethylformamide or dimethylacetamide.
- the cleaning solution of the present invention may also contain other conventional additives in the art, such as corrosion inhibitors and chelating agents. Its content generally does not exceed 20%.
- the corrosion inhibitor may be a corrosion inhibitor commonly used in the art, preferably from a benzotriazole, a carboxylic acid, a polycarboxylic acid. Classes and phosphonic acid ester inhibitors, etc.
- the chelating agent means an organic compound containing a plurality of functional groups.
- the positive progress of the present invention is that the cleaning liquid composition of the present invention can function in a relatively large temperature range, generally in the range of room temperature to 55 Torr, and can be used in a wide range of fields, such as batch immersion/batch. Rotary / single-piece rotary. At the same time, the cleaning fluid composition has a smaller metal and dielectric etch rate.
- the cleaning fluid composition of the present invention can also effectively clean medium ion etching residues in metal and semiconductor manufacturing processes without eroding SiO 2 , ion enhanced tetraethoxysilane silicon dioxide (PETEOS), silicon, silicon oxynitride and Some metal substances (such as Ti, Al, Cu).
- PETEOS ion enhanced tetraethoxysilane silicon dioxide
- the cleaning fluid compositions of the present invention can be used in batch soaking, batch spinning, and monolithic rotary processors.
- Base-2-mi 1 70.9 glycerol 20 8 benzoic acid 0.1 0 0 oxazolidinone
- Glucose o-phenyl sulfolane 35 45 4 ammonium fluoride 1 0 0 15
- Wafer cleaning method is a Wafer cleaning method
- the cleaning liquid composition of the present invention is used for the metal used in the manufacture of semiconductors.
- the cleaning liquid of the present invention has strong cleaning ability and can simultaneously clean metal/via/Pad wafers, and can simultaneously control the corrosion rate of metals and non-metals, especially nitrogen.
- the lower etching rate of the silicon oxide facilitates the expansion of the cleaning operation window of the fluorine-containing cleaning liquid, prolongs the service life of the cleaning liquid, and reduces the operating cost of the semiconductor factory. With a large operating window, it can be applied to both batch batch/batch-spray/single wafer tool.
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- Manufacturing & Machinery (AREA)
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Description
一种含氟清洗液 技术领域
本发明涉及一种半导体工业用含氟清洗液。 技术背景
在半导体元器件制造过程中, 光阻层的涂敷、 曝光和成像对元器件的图 案制造来说是必要的工艺步骤。在图案化的最后(即在光阻层的涂敷、成像、 离子植入和蚀刻之后)进行下一工艺步骤之前, 光阻层材料的残留物需彻底 除去。在掺杂步骤中离子轰击会硬化光阻层聚合物, 因此使得光阻层变得不 易溶解从而更难于除去。 至今在半导体制造工业中一般使用两步法(干法灰 化和湿蚀刻)除去这层光阻层膜。第一步利用干法灰化除去光阻层(PR)的 大部分;第二步利用缓蚀剂组合物湿蚀刻 /清洗工艺除去且清洗掉剩余的光阻 层, 其步骤一般为清洗液清洗 /漂洗 /去离子水漂洗。 在这个过程中只能除去 残留的聚合物光阻层和无机物, 而不能攻击损害金属层(如铝层)和非金属 层 (如氮氧化硅层)。
现有技术中典型的清洗液有以下几种: 胺类清洗液 (羟胺类), 半水性 胺基(非羟胺类)清洗液以及氟化物类清洗液。其中前两类清洗液需要在高 温下清洗, 一般在 60°C到 80°C之间, 存在对金属的腐蚀速率较大的问题; 而 现存的氟化物类清洗液虽然能在较低的温度(室温到 50Ό )下进行清洗, 但 仍然存在着各种各样的缺点, 例如不能同时控制金属和非金属基材的腐蚀, 清洗后容易造成通道特征尺寸的改变, 从而改变半导体结构; 另一方面由于 其较大蚀刻速率, 清洗操作窗口比较小等。 US5320709公开了一种清洗组合
物包括: 多元醇、 氟化铵用于去除半导体基板上的有机金属残留物、 有机硅 的残留物和氧化硅, 但特别指明其水含量不超过 4%, 而且其对有机聚合物 的去除能力较弱。 US 6,828,289公开的清洗液组合物包括: 酸性缓冲液、 有 机极性溶剂、含氟物质和水, 且 pH值在 3〜7之间, 其中的酸性缓冲液由有机 羧酸或多元酸与所对应的铵盐组成, 组成比例为 10: 1至 1 : 10之间, 并特别 指出其不含有多元醇。如 US 5, 698, 503公开了含氟清洗液, 但大量使用多元 醇, 其含量为 55-85%; 因此造成清洗液的粘度与表面张力都很大, 从而影响 清洗效果。如 US 5, 972, 862公开了含氟物质的清洗组合物,其包括含氟物质、 无机或有机酸、 季铵盐和有机极性溶剂, pH为 7〜11, 由于其清洗效果不是 很稳定, 存在多样的问题。
因此尽管己经揭示了一些清洗液组合物,但还是需要而且近来更加需要 制备一类更合适的清洗组合物或体系, 适应新的清洗要求, 比如环境更为友 善、 低缺陷水平、 低刻蚀率以及较大操作窗口和较长的使用寿命。
发明概要
本发明的目的是为了解决如何安全、健康和有效的清洗半导体工业中等 离子刻蚀残留物, 并提供了一种安全有效的使用寿命长的清洗液组合物。 本发明是一种用于半导体工业中等离子刻蚀残留物的清洗液组合物,其 包括氟化物、 多元醇、 水、 溶剂、 其他本领域的常规添加剂。 其中所述的其 他本领域的常规添加剂包括但不限于腐蚀抑制剂及螯合剂等中的一种和多 种。 所述的清洗液组合物重量百分比含量为:
a)氟化物 0.1%〜20%
b)多元醇 0.01%〜20%
c)水 5%〜75%
d)溶剂 1%〜75%
e)其他本领域的常规添加剂 0〜20%
本发明所述的氟化物较佳地为氟化氢、或氟化氢与碱形成的盐。 该碱可 以是氨水、季胺氢氧化物和醇胺。氟化物较佳地为氟化氢(HF)、氟化铵(NH
4F) 、 氟化氢铵 (NH4HF2) 、 四甲基氟化铵 (N (CH3 ) 4F) 或三羟乙基 氟化铵 (N (CH20H) 3HF) 中的一种或多种。
本发明所述的多元醇是指二元醇、 三元醇、 四元醇、 五元醇和六元醇。 较佳地为乙二醇、 1 , 2-丙二醇、 丙三醇、 丁四醇、 戊五醇、 核糖、 核酮糖、 葡萄糖、 葡萄糖醇、 己六醇、 甘露醇和山梨醇; 更较佳地为四元醇、 五元醇 和六元醇, 优选丁四醇、 戊五醇、 核糖、 核酮糖、 葡萄糖、 葡萄糖醇、 己六 醇、 甘露醇和山梨醇。 本发明还可进一步含有水。
本发明中, 所述的溶剂可选自亚砜、 砜、 咪唑烷酮、 吡咯烷酮、 咪唑啉 酮、 醚、 酰胺中的一种或多种。 其中, 所述的亚砜较佳的为二甲基亚砜; 所 述的砜较佳的为环丁砜; 所述的咪唑烷酮较佳的为 1,3-二甲基 -2-咪唑垸酮; 所述的吡咯垸酮较佳的为 N-甲基吡咯垸酮、 羟乙基吡咯垸酮; 所述的咪唑 啉酮较佳的为 1,3-二甲基 -2-咪唑啉酮 (DMI); 所述的醚较佳的为丙二醇单 甲醚、二丙二醇单甲醚;所述的酰胺较佳的为二甲基甲酰胺、二甲基乙酰胺。
本发明的清洗液还可含有其他本领域的常规添加剂,如腐蚀抑制剂及螯 合剂等。 其含量一般不超过 20%。 在本发明中, 所述的腐蚀抑制剂可以为本 领域常用的腐蚀抑制剂,优选来自苯并三氮唑类、羧酸(酯)类、聚羧酸(酯)
类和膦酸 (酯)类缓蚀剂等。 如苯并三氮唑、 苯甲酸、 聚丙烯酸、 1,3- (羟 乙基) -2,4,6-三膦酸等。 在本发明中, 所述的螯合剂是指含有多个官能团的 有机化合物。 优选乙醇酸、 丙二酸、 柠檬酸、 亚氨基二乙酸、 氨三乙酸、 三 乙醇胺、 乙二胺四乙酸、邻苯二酚、没食子酸、水杨酸、五甲基二乙烯三胺、 氨基磺酸和磺基水杨酸等。
本发明的积极进步效果在于:本发明清洗液组合物能在一个温度比较大 的范围内发挥作用, 一般在室温到 55Ό范围内, 并且能用于很广的领域中, 比如批量浸泡式 /批量旋转式 /单片旋转式。 同时, 清洗液组合物有较小的金 属和电介物质刻蚀率。 本发明的清洗液组合物还可有效地清洗金属和半导体制造过程中等离 子刻蚀残留物, 而且不会侵蚀 Si02、 离子增强四乙氧基硅烷二氧化硅 (PETEOS)、 硅、 氮氧化硅和一些金属物质 (如 Ti, Al, Cu) 。 对于半导体制 造工业来说, 本发明的清洗液组合物能在批量浸泡、批量旋转和单片旋转处 理器中使用。
发明内容
基 -2-咪 1 70.9 丙三醇 20 8 苯甲酸 0.1 0 0 唑烷酮
N-甲基
四甲 * 聚内烯酸
吡咯垸 15.9 65 丁四醇 15 2 0.1 丙二酸 2
氟化铵 (Mn=3000)
酮
羟乙基 三羟乙 1,3- (羟乙
吡咯垸 5 60 戊五醇 10 基氟化 20 基) -2,4,6- 0.1 柠檬酸 4.9 酮 铰 三膦酸
1,3-二甲 三羟乙
基 -2-咪 10 60 核糖 5 基氟化 15 0 0 乙醇酸 10 唑啉酮 铵
三羟乙
氨三乙
26.9 55 核酮糖 8 基氟化 】0 0 0 0.1 甲酰胺 n 酸
铵
三羟乙
三乙醇
20 50 葡萄糖 2 基氟化 8 0 0 20 乙酰胺 胺
铵
葡萄糖 邻苯二 环丁砜 35 45 4 氟化铵 1 0 0 15
醇 酚 二丙二
乙二胺 醇单甲 56 40 己六醇 0.5 氟化铵 3 0 0 0.5
四乙酸 醚
二甲基 苯并三氮
60 35 甘露醇 0.1 氟化铵 1 2.5 没食子 1.4 亚砜 ¾
酸 苯并三氮
65 30 山梨醇 0.05 氟化铵 1 3.45 水杨酸 0.5 亚砜 唑
苯并三氮 氨基磺
45 25 葡萄糖 15 氟化铵 5 5 5 乙酰胺 酸
葡萄糖 苯并三氮 三乙醇
40 20 20 氟化铵 0.5 4.5 15 乙酰胺 醇 唑 胺 二甲基 邻苯二
50 15 己六醇 19 氟化铰 3 苯甲酸 3 10 乙酰胺 酚
三乙醇
70 ] 0 i m 10 氟化铵 3 0 0 7 乙酰胺 胺
N-甲基
聚 W烯酸 三乙醇 吡咯垸 30 40 山梨醇 10 氟化铵 1.9 0.1 18
( n=3000) 胺
1M
50 45 葡萄糖 3 籠按 2 0 0 0 0 乙酰胺
五甲基 二甲基
30 二乙烯 5 亚砜
三胺
32 山梨醇 5 氟化钹 3 0 0
二 W二
磺基水 醇单甲 24 1
杨酸 醚 二甲基 三乙醇
30 5 亚砜 胺 聚丙烯酸 五甲基
23 甘露醇 5 氟化铵 2 0.1
二丙二 (Mn=3000) 二乙烯 5 醇单甲 27.4 三胺 醚 亚氨基
2.5 二乙酸
我们选用了上表中部分实施例进行了性能测试, 以说明本发明的效果, 其结果见下表 2。 表 2 部分实施例性能测试结果一览
实施 腐烛速率, A/min 不同类型晶圆清洗结果
例 金属铝 氮氧化硅 金属线 通道 金 垫
干净,通道
1 1 1.64 1.93 干净, 无腐蚀 尺寸未改 干净, 无腐蚀
变
干净,通道
12 1.53 1.87 干净, 无腐蚀 尺寸未改 干净, 无腐蚀
变
干净,通道
16 1.05 0.62 干净, 无腐蚀 尺寸未改 干净, 无腐蚀
变
干净,通道
18 1.89 0.73 干净, 基本无腐蚀 尺寸未明 干净, 基本无腐蚀
显改变
干净,通道
19 1 .71 0.51 干净, 无腐蚀 尺寸未改 干净, 无腐蚀
变
干净,通道
20 1.32 1.02 干净, 无腐蚀 尺寸未改 干净, 无腐蚀
变
溶液的金属腐蚀速率测试方法:
1 ) 利用 Napson四点探针仪测试 4*4cm铝空白硅片的电阻初值 (Rsl );
2) 将该 4*4cm铝空白硅片浸泡在预先已经恒温到 40°C的溶液中 60分钟;
3 )取出该 4*4cm铝空白硅片, 用去离子水清洗, 高纯氮气吹干, 再利用 Napson 四点探针仪测试 4*4cm铝空白硅片的电阻值 (Rs2);
4 ) 把上述电阻值和浸泡时间输入到合适的程序可计算出其腐蚀速率。
溶液的非金属腐蚀速率测试方法:
1 ) 利用 Nanospec6100测厚仪测试 4*4cm氮氧化硅硅片的厚度 (T1 );
2 ) 将该 4*4cmPETEOS硅片浸泡在预先已经恒温到 40'C的溶液中 60分钟;
3 ) 取出该 4*4cm 氮氧化硅硅片, 用去离子水清洗, 高纯氮气吹干, 再利用
Nanospec6100测厚仪测试 4*4cm氮氧化硅硅片的厚度 (T2 );
4 ) 把上述厚度值和浸泡时间输入到合适的程序可计算出其腐蚀速率。
晶圆清洗的方法:
1 ) 将待清洗的晶圆放入预先己经恒温到 40Ό的溶液中;
2 ) 按照金属线浸泡 20分钟、 通道和金属垫浸泡 30分钟的原则浸泡晶圆;
3 )浸泡时间到后, 取出该晶圆, 用去离子水清洗, 高纯氮气吹干后; 送 SEM测 试。 从表 2中可以看出:本发明的清洗液组合物对半导体制成中所用的金属
(如金属铝)和非金属 (如氮氧化硅)基本不会侵蚀, 其腐蚀速率均接近或 小于半导体业界通常所要求的 2埃每分钟。用该溶液对等离子刻蚀残留物进 行清洗发现, 其等离子刻蚀残留物均被去除, 而且没有腐蚀金属和非金属。
综上,本发明的清洗液清洗能力强,能同时对金属线(Metal ) /通道(Via) /金属垫 (Pad) 晶圆清洗, 能同时控制金属和非金属的腐蚀速率, 特别是氮
氧化硅刻蚀速率较低, 从而有利于扩大含氟清洗液的清洗操作窗口, 延长清 洗液的使用寿命, 降低半导体厂的运营成本。 具有较大的操作窗口, 能同时 适用于批量浸泡式 (wet Batch) /批量旋转喷雾式 (Batch-spray) /单片旋转 式 ( single wafer tool )。
Claims
1、 一种含氟清洗液, 其包括: 氟化物、 多元醇、 水、 溶剂; 其中: 所 述多元醇的重量百分比含量为 0.01%〜20%, 所述水的重量百分比含量为 5%〜75%。
2、 如权利要求 1 所述含氟清洗液, 其特征在于, 所述氟化物的重量百 分比含量为 0.1%〜20%, 所述溶剂的重量百分比含量为 1。/。〜75%。
3、 如权利要求 1所述含氟清洗液, 其特征在于, 所述氟化物为氟化氢、 或氟化氢与碱形成的盐, 该碱是氨水、 季胺氢氧化物或醇胺。
4、 如权利要求 3所述含氟清洗液, 其特征在于, 所述氟化物为氟化氢 (HF) 、 氟化铰、 氟化氢铵、 四甲基氟化铵和 /或三羟乙基氟化铵。
5、 如权利要求 1所述含氟清洗液, 其特征在于, 所述多元醇为二元醇、 三元醇、 四元醇、 五元醇和 /或六元醇。
6、 如权利要求 5所述含氟清洗液, 其特征在于, 所述多元醇为乙二醇、 1, 2-丙二醇、 丙三醇、 丁四醇、 戊五醇、 核糖、 核酮糖、 葡萄糖、 葡萄糖 醇、 己六醇、 甘露醇和 /或山梨醇。
7、 如权利要求 6所述含氟清洗液, 其特征在于, 所述多元醇为丁四醇、 戊五醇、 核糖、 核酮糖、 葡萄糖、 葡萄糖醇、 己六醇、 甘露醇和 /或山梨醇。
8、 如权利要求 1 所述含氟清洗液, 其特征在于, 所述溶剂选自亚砜、 砜、 咪唑垸酮、 吡咯垸酮、 咪唑啉酮、 醚和酰胺中的一种或多种。
9、 如权利要求 1 所述含氟清洗液, 其特征在于, 所述亚砜为二甲基亚 砜; 所述砜为环丁砜; 所述咪唑垸酮为 1 ,3-二甲基 -2-咪唑垸酮; 所述吡咯垸 酮为 N-甲基吡咯烷酮和 /或羟乙基吡咯垸酮; 所述咪唑啉酮为 1 ,3-二甲基 -2- 咪唑啉酮;所述醚为丙二醇单甲醚和 /或二丙二醇单甲醚;所述酰胺为二甲基 甲酰胺和 /或二甲基乙酰胺。
10、 如权利要求 1所述含氟清洗液, 其特征在于, 所述含氟清洗液还含 有其他添加剂。
11、 如权利要求 10所述含氟清洗液, 其特征在于, 所述其他添加剂的重 量百分比含量为不超过 20%。
12、 如权利要求 10所述含氟清洗液, 其特征在于, 所述其他添加剂为腐 蚀抑制剂和 /或螯合剂
13、 如权利要求 12所述含氟清洗液, 其特征在于, 所述腐蚀抑制剂选自 苯并三氮唑、苯甲酸、聚丙烯酸和 1 ,3- (羟乙基) -2,4,6-三膦酸中的一种或多 种; 所述的螯合剂是含有多个官能团的有机化合物。
14、 如权利要求 12所述含氟清洗液, 其特征在于, 所述螯合剂选自乙醇 酸、丙二酸、柠檬酸、亚氨基二乙酸、氨三乙酸、三乙醇胺、 乙二胺四乙酸、 邻苯二酚、 没食子酸、 水杨酸、 五甲基二乙烯三胺、 氨基磺酸和磺基水杨酸 中的一种或多种。
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CN104419563A (zh) * | 2013-08-23 | 2015-03-18 | 南通恒鼎重型机床有限公司 | 一种专用于擦拭传送带的清洁剂 |
CN104678719A (zh) * | 2013-11-28 | 2015-06-03 | 安集微电子科技(上海)有限公司 | 一种对金属极低腐蚀的光刻胶清洗液 |
CN103695190B (zh) * | 2013-12-31 | 2016-06-08 | 江苏美科硅能源有限公司 | 硅片清洗液 |
CN104060291B (zh) * | 2014-06-09 | 2017-07-28 | 安徽华东光电技术研究所 | 化学清洗剂组合物及其配制方法和应用 |
CN105527803B (zh) * | 2014-09-29 | 2020-08-18 | 安集微电子(上海)有限公司 | 一种光刻胶清洗液 |
CN106479696A (zh) * | 2016-08-31 | 2017-03-08 | 惠晶显示科技(苏州)有限公司 | 用于液晶显示面板玻璃酸刻所生结垢物的清洗液及其制备方法 |
CN107229192B (zh) * | 2017-07-25 | 2019-05-10 | 上海新阳半导体材料股份有限公司 | 一种含氟等离子刻蚀残留物清洗液、其制备方法和应用 |
CN107229194B (zh) * | 2017-07-25 | 2019-05-10 | 上海新阳半导体材料股份有限公司 | 一种含氟等离子刻蚀残留物清洗液、其制备方法和应用 |
CN107300839B (zh) * | 2017-07-25 | 2019-06-07 | 上海新阳半导体材料股份有限公司 | 一种含氟等离子刻蚀残留物清洗液、其制备方法和应用 |
CN107589637A (zh) * | 2017-08-29 | 2018-01-16 | 昆山艾森半导体材料有限公司 | 一种含氟铝线清洗液 |
CN109976110A (zh) * | 2017-12-27 | 2019-07-05 | 安集微电子(上海)有限公司 | 一种清洗液 |
TWI800025B (zh) * | 2021-10-07 | 2023-04-21 | 德揚科技股份有限公司 | 清洗水溶液 |
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