CN110234719A - 用于从表面去除氧化铈粒子的组合物和方法 - Google Patents
用于从表面去除氧化铈粒子的组合物和方法 Download PDFInfo
- Publication number
- CN110234719A CN110234719A CN201880007539.6A CN201880007539A CN110234719A CN 110234719 A CN110234719 A CN 110234719A CN 201880007539 A CN201880007539 A CN 201880007539A CN 110234719 A CN110234719 A CN 110234719A
- Authority
- CN
- China
- Prior art keywords
- removal composition
- aqueous removal
- acid
- composition according
- cerium oxide
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 125
- 239000002245 particle Substances 0.000 title claims abstract description 69
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 46
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000004377 microelectronic Methods 0.000 claims abstract description 52
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 41
- 231100000719 pollutant Toxicity 0.000 claims abstract description 41
- 238000005498 polishing Methods 0.000 claims abstract description 17
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 glycol ethers Chemical class 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000003002 pH adjusting agent Substances 0.000 claims description 36
- 229910001868 water Inorganic materials 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 239000003638 chemical reducing agent Substances 0.000 claims description 27
- 239000006259 organic additive Substances 0.000 claims description 27
- 239000008139 complexing agent Substances 0.000 claims description 26
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 claims description 4
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 4
- 235000019252 potassium sulphite Nutrition 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical group NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical group 0.000 claims 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 22
- 239000000356 contaminant Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 26
- 239000000758 substrate Substances 0.000 description 23
- 239000002002 slurry Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000001446 dark-field microscopy Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OIRDTQYFTABQOQ-KQYNXXCUSA-N adenosine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O OIRDTQYFTABQOQ-KQYNXXCUSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 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 description 5
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000006577 C1-C6 hydroxyalkyl group Chemical group 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 4
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000000059 patterning Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229930024421 Adenine Natural products 0.000 description 3
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002126 C01EB10 - Adenosine Substances 0.000 description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 3
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- 241000894007 species Species 0.000 description 3
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- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
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- CSNFMBGHUOSBFU-UHFFFAOYSA-N pyrimidine-2,4,5-triamine Chemical compound NC1=NC=C(N)C(N)=N1 CSNFMBGHUOSBFU-UHFFFAOYSA-N 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
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- 239000003870 refractory metal Substances 0.000 description 1
- 150000003290 ribose derivatives Chemical class 0.000 description 1
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- 150000004760 silicates Chemical class 0.000 description 1
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- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000010352 sodium erythorbate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229940054269 sodium pyruvate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical class [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-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
- 239000010936 titanium Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
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- SGKOGTXWLOGBID-UHFFFAOYSA-M triphenyl(propyl)phosphanium;hydroxide Chemical class [OH-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCC)C1=CC=CC=C1 SGKOGTXWLOGBID-UHFFFAOYSA-M 0.000 description 1
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- 229940116269 uric acid Drugs 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
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Abstract
本发明涉及一种去除组合物和工艺,其用于从上面具有化学机械抛光CMP后污染物和氧化铈粒子的微电子装置清洁所述粒子和污染物。所述组合物实现所述氧化铈粒子和CMP污染物材料从所述微电子装置的表面的高度有效去除而不会损坏低k介电材料、氮化硅或含钨材料。
Description
相关申请案
本申请案主张于2017年1月18日提出申请的美国临时申请案第62/447,729号的权益,所述申请案的整个揭示内容的全文都以引用方式并入本文中。
技术领域
本发明大概来说涉及用于从上面具有氧化铈粒子和其它化学机械抛光浆液污染物的微电子装置去除所述粒子和污染物的组合物。
背景技术
微电子装置晶片用于形成集成电路。微电子装置晶片包含衬底,例如硅,多个区域图案化到所述衬底中以沉积具有绝缘、导电或半导电性质的不同材料。
为获得正确的图案化,必须去除用于在衬底上形成各层的过量材料。此外,为制造有功能且可靠的电路,在后续处理之前制备平滑或平坦的微电子晶片表面至关重要。因此,必需去除和/或抛光微电子装置晶片的某些表面。
化学机械抛光或平坦化(“CMP”)是从微电子装置晶片的表面去除材料,并通过偶合物理工艺(例如磨蚀)与化学工艺(例如氧化或螯合)抛光(例如平坦化)表面的工艺。在其最基本形式中,CMP涉及将具有活性化学的磨蚀浆液施加到抛光垫,所述抛光垫在去除、平坦化和抛光工艺期间擦亮微电子装置晶片的表面。利用纯物理或纯化学作用的去除或抛光工艺在实现快速、均匀的去除方面不如二者的协同组合有效。另外,在集成电路的制造中,CMP浆液还应能够优先去除包括金属和其它材料的复合层的膜,以使得可产生高度平坦的表面用于后续光微影或图案化、蚀刻和薄膜处理。
在使用浅沟槽隔离(STI)工艺在硅衬底中形成隔离区的前段工艺(FEOL)方法中,将垫氧化物膜和垫氮化物膜沉积在半导体衬底上且图案化以暴露衬底的对应于隔离区的部分。然后,蚀刻衬底的所暴露区域以形成沟槽。此后,使衬底经受牺牲氧化工艺以去除由衬底蚀刻引起的损害,随后在沟槽的表面上形成壁氧化物膜。然后,将沟槽埋藏的氧化物膜(例如通过高密度等离子体化学气相沉积形成的氧化物膜,称为HDP-氧化物膜)以使其埋藏于沟槽中的方式沉积在衬底的表面上。然后,使HDP-氧化物膜的表面经受化学机械抛光直到垫氮化物膜暴露。随后清洁所得衬底且去除在沟槽蚀刻期间用作蚀刻屏障的垫氮化物膜,从而完成隔离区的形成。
相对于含二氧化硅的浆液,使用氧化铈粒子的CMP浆液实现绝缘体的较快抛光速度。此外,基于氧化铈的浆液因实现STI图案平坦化和最少氧化物腐蚀的能力而最常使用。不利地,相对于氧化硅和氮化硅表面,基于氧化铈的浆液因氧化铈粒子电性相反的ζ电位而难以从STI结构去除。如果装置经制造且这些残余物仍留在晶片上,那么所述残余物将引起短路和电阻升高。氧化铈粒子还具有在使用氧化铈浆液进行CMP处理后具有FinFET结构的问题。
目前用于去除氧化铈粒子的最有效的湿式清洁调配物是稀氢氟酸(DHF)。然而,DHF不利地蚀刻氧化硅和其它低k介电材料。
因此,业内仍需要可有效地从微电子装置的表面去除氧化铈粒子、同时不会损害下伏材料(例如氮化硅、低k电介质(例如氧化硅)和含钨层)的氧化铈粒子去除组合物和工艺。氧化铈粒子去除组合物还应有效地从微电子装置的表面去除CMP浆液污染物。
发明内容
本发明大概来说涉及去除组合物和工艺,具体来说可用于从上面具有氧化铈粒子和CMP污染物的微电子装置清洁所述粒子和CMP污染物。
在一方面中,描述水性去除组合物,所述组合物包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂、水、任选地至少一种络合剂和任选地至少一种氧清除剂。
在另一方面中,描述从上面具有氧化铈粒子和CMP污染物的微电子装置去除所述粒子和污染物的方法,所述方法包括使微电子装置与去除组合物接触足够时间以从微电子装置至少部分地清洁所述粒子和污染物,其中所述去除组合物包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂、水、任选地至少一种络合剂和任选地至少一种氧清除剂。
在另一方面中,描述制品,所述制品包括水性去除组合物、微电子装置晶片和选自由氧化铈粒子、CMP污染物和其组合组成的群组的材料,其中清洁组合物包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂、水、任选地至少一种络合剂和任选地至少一种氧清除剂。
从随后揭示内容和所附权利要求书将更全面地明了其它方面、特征和优点。
具体实施方式
本发明大概来说涉及可用于从上面具有氧化铈粒子和CMP污染物的微电子装置去除所述材料的组合物。有利地,氧化铈粒子和CMP污染物使用组合物有效地去除,并且另外组合物与氮化硅和低k介电(例如氧化硅)层相容。
为便于提到,“微电子装置”对应于半导体衬底、平板显示器、相变化存储器装置、太阳电池板和其它产品,包含太阳能衬底、光伏打装置和微机电***(MEMS),其经制造用于微电子、集成电路或计算机芯片应用。太阳能衬底包含(但不限于)硅、非晶形硅、多晶硅、单晶硅、CdTe、铜铟硒化物、铜铟硫化物和镓载砷化镓。太阳能衬底可经掺杂或未经掺杂。应理解,术语“微电子装置”不旨在以任何方式进行限制且包含最终将变成微电子装置或微电子组合件的任何衬底。
如本文所用的“氧化铈粒子”对应于可用于化学机械抛光浆液中的基于铈的磨蚀粒子,包含例如具有式Ce2O3和CeO2的氧化铈。应了解,“氧化铈粒子”可包括氧化铈、由其组成或基本上由其组成。
如本文所用的“污染物”对应于存在于CMP浆液中的化学品、抛光浆液的反应副产物、CMP后残余物、存在于湿式蚀刻组合物中的化学品、湿式蚀刻组合物的反应副产物和为CMP工艺、湿式蚀刻、等离子体蚀刻或等离子体灰化工艺的副产物的任何其它材料。
如本文所用的“CMP后残余物”对应于来自抛光浆液的粒子,例如存在于浆液中的化学品、抛光浆液的反应副产物、富含碳的粒子、抛光垫粒子、刷涂减载粒子、构筑粒子的设备材料、金属、有机残余物和为CMP工艺的副产物的任何其它材料。另外,如果钨是在CMP工艺期间去除,那么CMP后残余物可另外包括含钨粒子。
如本文所定义的“低k介电材料”对应于在分层微电子装置中用作介电材料的任何材料,其中所述材料具有小于约3.5的介电常数。优选地,低k介电材料包含低极性材料,例如含硅有机聚合物、含硅杂合有机/无机材料、有机硅酸盐玻璃(OSG)、TEOS、氟化硅酸盐玻璃(FSG)、二氧化硅和碳掺杂氧化物(CDO)玻璃。应了解,低k介电材料可具有不同密度和不同孔隙度。
如本文所定义的“络合剂”包含所属领域技术人员理解为络合剂、螯合剂和/或钳合剂的那些化合物。络合剂将在化学上与待使用本文所述的组合物去除的金属原子和/或金属离子组合或在物理上抓住所述金属原子和/或金属离子。
“大体上不含”在本文中定义为小于2wt.%,优选小于1wt.%,更优选小于0.5wt.%,并且最优选小于0.1wt.%。“不含”旨在对应于小于0.001wt%以将环境污染考虑在内。
如本文所用的“约”旨在对应于所述值±5%。
如本文所用的“氧化剂”对应于氧化所暴露金属以腐蚀金属或在金属上形成氧化物的化合物。氧化剂包含(但不限于):过氧化氢;其它过化合物,例如含有过氧单硫酸根、过硼酸根、过氯酸根、过碘酸根、过硫酸根、高锰酸根和过乙酸根阴离子的盐和酸;和胺-N-氧化物。
如本文所用的“含氟化合物”对应于包括离子键结到另一原子的氟离子(F-)的盐或酸化合物。
如本文所定义的术语“屏障材料”对应于业内用于密封金属线条(例如铜互连件)以最小化所述金属(例如铜)扩散到介电材料中的任何材料。优选屏障层材料包含钽、钛、钌、铪、钨和其它耐火金属和其氮化物和硅化物。
出于本发明的目的,“腺苷和腺苷衍生物的降解产物”包含(但不限于)腺嘌呤(C5H5N5)、甲基化腺嘌呤(例如N-甲基-7H-嘌呤-6-胺,C6H7N5)、二甲基化腺嘌呤(例如N,N-二甲基-7H-嘌呤-6-胺,C7H9N5)、N4,N4-二甲基嘧啶-4,5,6-三胺(C6H11N5)、4,5,6-三氨基嘧啶、尿囊素(C4H6N4O3)、羟基化C-O-O-C二聚体((C5H4N5O2)2)、C-C桥接二聚体((C5H4N5)2或(C5H4N5O)2)、核糖(C5H10O5)、甲基化核糖(例如5-(甲氧基甲基)四氢呋喃-2,3,4-三醇,C6H12O5)、四甲基化核糖(例如2,3,4-三甲氧基-5-(甲氧基甲基)四氢呋喃,C9H18O5),和其它核糖衍生物(例如甲基化水解二核糖化合物)。
如本文所用的“表面活性剂”对应于具有疏水基团和亲水基团的两亲性物种,如所属领域技术人员所易于理解,但不包含聚合物。如本文所定义的“聚合物”对应于具有重复单体基团且可为自然或合成的物种。应了解,“聚合物”可为仅具有一种类型的重复单体的均聚物或具有多于一种类型的重复单体的共聚物。
如本文所用的用于从上面具有氧化铈粒子和CMP污染物的微电子装置去除所述粒子和污染物的“适用性”对应于从微电子装置至少部分地去除所述粒子/污染物。清洁效能是通过微电子装置上的物体的减少来评级。举例来说,清洁前和清洁后分析可使用原子力显微镜来实施。样品上的粒子可记录为一系列像素。可施加直方图(例如Sigma Scan Pro)以过滤某一强度(例如231-235)的像素且对粒子数进行计数。粒子减少可使用下式来计算:
应注意,提供测定清洁效能的方法以仅用于举例而不旨在限于此方法。或者,清洁效能可视为经颗粒物覆盖的总表面的百分比。举例来说,AFM可经编程以执行z平面扫描来鉴别高于某一高度阈值的所关注地形区域且然后计算经所述关注区域覆盖的总表面的面积。所属领域技术人员将容易理解,清洁后经所述关注区域覆盖的区域越小,去除组合物越有效。优选地,使用本文所述的组合物从微电子装置去除至少75%的粒子/污染物,更优选去除至少90%、甚至更优选至少95%、且最优选至少99%的粒子/污染物。
本文所述的组合物可以广泛多种具体调配物体现,如下文更全面描述。
在所有所述组合物中,其中组合物的具体组分参考包含零下限的重量百分比范围论述,应理解,所述组分可存在或不存在于组合物的多个具体实施例中且在所述组分存在的情况下,其可基于采用所述组分的组合物的总重量以低到0.00001重量%的浓度存在。
在第一方面中,描述去除组合物,其在一些实施例中优选是水性去除组合物,包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂、任选地至少一种络合剂、任选地至少一种聚合物和任选地至少一种氧清除剂,由其组成或基本上由其组成。在第一方面的一实施例中,去除组合物包括至少一种pH调节剂、至少一种还原剂和至少一种有机添加剂,由其组成或基本上由其组成。在第一方面的另一实施例中,去除组合物包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂和至少一种络合剂,由其组成或基本上由其组成。在第一方面的另一实施例中,去除组合物包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂和至少一种聚合物,由其组成或基本上由其组成。在第一方面的另一实施例中,去除组合物包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂和至少一种氧清除剂,由其组成或基本上由其组成。在第一方面的另一实施例中,去除组合物包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂、至少一种络合剂和至少一种氧清除剂,由其组成或基本上由其组成。在第一方面的另一实施例中,去除组合物包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂、至少一种络合剂和至少一种聚合物,由其组成或基本上由其组成。在第一方面的另一实施例中,去除组合物包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂、至少一种聚合物和至少一种氧清除剂,由其组成或基本上由其组成。在第一方面的另一实施例中,去除组合物包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂、至少一种络合剂、至少一种聚合物和至少一种氧清除剂,由其组成或基本上由其组成。所属领域技术人员应理解,本文所述的水性清洁组合物进一步包括水,优选去离子水。
在每一实施例中,在从微电子装置去除残余材料之前,去除组合物大体上可不含以下各项中的至少一者:氧化剂;含氟来源;表面活性剂;四甲基氢氧化铵;化学机械抛光磨蚀材料(例如二氧化硅、氧化铝等);和选自由以下组成的群组的腐蚀抑制剂:氰尿酸、巴比妥酸和其衍生物、葡糖醛酸、方酸、α-酮酸、腺苷和其衍生物、核糖基嘌呤和其衍生物、嘌呤化合物和其衍生物、腺苷和腺苷衍生物的降解产物、三氨基嘧啶和其它经取代嘧啶、嘌呤-糖复合物、膦酸和其衍生物、菲咯啉、甘氨酸、烟碱酰胺和其衍生物、类黄酮(例如黄酮醇和花青素和其衍生物)、槲黄素和其衍生物和其组合。另外,去除组合物不应固化形成聚合固体,包含例如光致抗蚀剂。
络合剂(如果存在)包含具有通式NR1R2R3的物种,其中R1、R2和R3可彼此相同或不同且选自由以下组成的群组:氢、直链或具支链C1-C6烷基(例如甲基、乙基、丙基、丁基、戊基和己基)、直链或具支链C1-C6羟基烷基(例如羟基甲基、羟基乙基、羟基丙基、羟基丁基、羟基戊基和羟基己基)和如上文所定义直链或具支链C1-C6羟基烷基的C1-C6烷基醚。最优选地,R1、R2和R3中的至少一者是直链或具支链C1-C6羟基烷基。实例包含(但不限于)烷醇胺,例如氨基乙基乙醇胺、N-甲基氨基乙醇、氨基乙氧基乙醇、二甲基氨基乙氧基乙醇、二乙醇胺、N-甲基二乙醇胺、单乙醇胺(MEA)、三乙醇胺(TEA)、1-氨基-2-丙醇、2-氨基-1-丁醇、异丁醇胺、三乙二胺、其它C1-C8烷醇胺和其组合。当胺包含烷基醚组分时,所述胺可视为烷氧基胺,例如1-甲氧基-2-氨基乙烷。或者或除NR1R2R3胺外,络合剂可为多官能胺,包含(但不限于)4-(2-羟基乙基)吗啉(HEM)、1,2-环己烷二胺-N,N,N′,N′-四乙酸(CDTA)、乙二胺四乙酸(EDTA)、间-二甲苯二胺(MXDA)、亚氨基二乙酸(IDA)、2-(羟基乙基)亚氨基二乙酸(HIDA)、氮基三乙酸、硫脲、1,1,3,3-四甲脲、尿素、尿素衍生物、尿酸、丙氨酸、精氨酸、天冬酰胺、天冬氨酸、半胱氨酸、谷氨酸、谷氨酰胺、组氨酸、异亮氨酸、亮氨酸、赖氨酸、甲硫氨酸、苯丙氨酸、脯氨酸、丝氨酸、苏氨酸、色氨酸、酪氨酸、缬氨酸和其组合。或者或除上文所提到的络合剂外,其它络合剂可包含膦酸类(例如1-羟基亚乙基-1,1-二膦酸(HEDP)、1,5,9-三氮杂环十二烷-N,N',N"-三(亚甲基膦酸)(DOTRP)、1,4,7,10-四氮杂环十二烷-N,N',N",N'"-四(亚甲基膦酸)(DOTP)、氮基三(亚甲基)三膦酸、二亚乙基三胺五(亚甲基膦酸)(DETAP)、氨基三(亚甲基膦酸)、双(六亚甲基)三胺五亚甲基膦酸、1,4,7-三氮杂环壬烷-N,N',N"-三(亚甲基膦酸)(NOTP)、二膦酸羟基乙基酯、氮基三(亚甲基)膦酸、2-膦酰基-丁烷-1,2,3,4-四甲酸、羧基乙基膦酸、氨基乙基膦酸、草甘膦、亚乙基二胺四(亚甲基膦酸)苯基膦酸、其盐和其衍生物)和/或羧酸(例如草酸、琥珀酸、马来酸、苹果酸、丙二酸、己二酸、苯二甲酸、柠檬酸、柠檬酸钠、柠檬酸钾、柠檬酸铵、丙三甲酸、三甲基醇丙酸、酒石酸、葡糖醛酸、2-羧基吡啶)和/或磺酸(例如试钛灵(4,5-二羟基-1,3-苯二磺酸二钠盐))。优选地,至少一种络合剂包括选自由单乙醇胺、三乙醇胺、硫酸、柠檬酸和其组合组成的群组的物种。如果存在,基于去除组合物的总重量,去除组合物中络合剂的量介于约0.01wt%到约10wt%范围内。
pH调节剂包含酸和/或碱。碱包含(但不限于)碱金属氢氧化物(例如LiOH、KOH、RbOH、CsOH)、碱土金属氢氧化物(例如Be(OH)2、Mg(OH)2、Ca(OH)2、Sr(OH)2、Ba(OH)2)、氢氧化铵(即氨)和具有式NR1R2R3R4OH的四烷基氢氧化铵化合物,其中R1、R2、R3和R4可彼此相同或不同且选自由以下组成的群组:氢、直链或具支链C1-C6烷基(例如甲基、乙基、丙基、丁基、戊基和己基)、C1-C6羟基烷基(例如羟基甲基、羟基乙基、羟基丙基、羟基丁基、羟基戊基和羟基己基)和经取代或未经取代的C6-C10芳基(例如苄基)。可使用市售四烷基氢氧化铵,包含四甲基氢氧化铵(TMAH)、四乙基氢氧化铵(TEAH)、四丙基氢氧化铵(TPAH)、四丁基氢氧化铵(TBAH)、三丁基甲基氢氧化铵(TBMAH)、苄基三甲基氢氧化铵(BTMAH)、氢氧化胆碱、乙基三甲基氢氧化铵、三(2-羟基乙基)甲基氢氧化铵、二乙基二甲基氢氧化铵和其组合。或者或另外,pH调节剂可为具有式(PR1R2R3R4)OH的季碱,其中R1、R2、R3和R4可彼此相同或不同且选自由以下组成的群组:氢、直链C1-C6烷基(例如甲基、乙基、丙基、丁基、戊基和己基)、具支链C1-C6烷基、C1-C6羟基烷基(例如羟基甲基、羟基乙基、羟基丙基、羟基丁基、羟基戊基和羟基己基)、经取代的C6-C10芳基、未经取代的C6-C10芳基(例如苄基)和其任何组合,例如四丁基氢氧化鏻(TBPH)、四甲基氢氧化鏻、四乙基氢氧化鏻、四丙基氢氧化鏻、苄基三苯基氢氧化鏻、甲基三苯基氢氧化鏻、乙基三苯基氢氧化鏻、正丙基三苯基氢氧化鏻。酸包含(但不限于)硝酸、硫酸、磷酸、盐酸、氢溴酸、甲磺酸、苯磺酸、对甲苯磺酸、三氟甲磺酸、乙酸、乳酸、乙醇酸和其任何组合。在一个实施例中,pH调节剂包括KOH。在另一实施例中,pH调节剂包括氢氧化胆碱。在另一实施例中,pH调节剂包括氢氧化铵。在另一实施例中,pH调节剂包括至少一种碱金属氢氧化物和至少一种本文所列举的其它氢氧化物。在另一实施例中,pH调节剂包括KOH和至少一种本文所列举的其它氢氧化物。在另一实施例中,pH调节剂包括KOH以及氢氧化胆碱和氢氧化铵中的至少一者。关于所述所列举实施例中的任一者,pH调节剂可进一步包含至少一种酸,例如硫酸、柠檬酸或柠檬酸和硫酸的组合。
所涵盖有机添加剂包含(但不限于)2-吡咯烷酮、1-(2-羟基乙基)-2-吡咯烷酮(HEP)、甘油、1,4-丁二醇、四氢噻吩砜(环丁砜)、二甲砜、乙二醇、丙二醇、二丙二醇、四甘二甲醚、二甘二甲醚、甲基异丁基酮、甲基乙基酮、丙酮、异丙醇、辛醇、乙醇、丁醇、甲醇、异佛尔酮、二醇醚(例如二乙二醇单甲醚、三乙二醇单甲醚、二乙二醇单***、三乙二醇单***、乙二醇单丙醚、乙二醇单丁醚、二乙二醇单丁醚(DEGBE)、三乙二醇单丁醚(TEGBE)、乙二醇单己醚(EGHE)、二乙二醇单己醚(DEGHE)、乙二醇苯基醚、二乙二醇苯基醚、丙二醇甲醚、二丙二醇甲醚(DPGME)、三丙二醇甲醚(TPGME)、二丙二醇二甲醚、二丙二醇***、丙二醇正丙醚、二丙二醇正丙醚(DPGPE)、三丙二醇正丙醚、丙二醇正丁醚(例如DOWANOL PnB)、二丙二醇正丁醚、三丙二醇正丁醚、二丙二醇苯基醚、丙二醇苯基醚(PPh,例如DOWANOL PPh)、4-甲基-2-戊酮、2,4-二甲基-3-戊酮、环己酮、5-甲基-3-庚酮、3-戊酮、5-羟基-2-戊酮、2,5-己烷二酮、4-羟基-4-甲基-2-戊酮、丙酮、丁酮、2-甲基-2-丁酮、3,3-二甲基-2-丁酮、4-羟基-2-丁酮、环戊酮、2-戊酮、3-戊酮、1-苯基乙酮、苯乙酮、二苯甲酮、2-己酮、3-己酮、2-庚酮、3-庚酮、4-庚酮、2,6-二甲基-4-庚酮、2-辛酮、3-辛酮、4-辛酮、二环己基酮、2,6-二甲基环己酮、2-乙酰基环己酮、2,4-戊二酮、薄荷酮、单乙醇胺(MEA)和其组合。在优选实施例中,去除组合物中的至少一种有机添加剂包括至少一种二醇醚,包括丙二醇苯基醚。
聚合物(如果存在)包含(但不限于)甲基丙烯酸与例如丙烯酰胺基甲基丙磺酸和马来酸的均聚物和共聚物;马来酸/乙烯醚共聚物;聚(乙烯基吡咯烷酮)/乙酸乙烯酯;均聚物,例如膦酸酯化聚乙二醇寡聚物、聚(丙烯酸酸)(PAA)、聚(丙烯酰胺)、聚(乙酸乙烯酯)、聚(乙二醇)(PEG)、聚(丙二醇)(PPG)、聚(苯乙烯磺酸)、聚(乙烯基磺酸)、聚(乙烯基膦酸)、聚(乙烯基磷酸)、聚(乙烯亚胺)、聚(丙烯亚胺)、聚烯丙基胺、聚氧化乙烯(PEO)、聚乙烯吡咯烷酮(PVP);PPG-PEG-PPG嵌段共聚物;PEG-PPG-PEG嵌段共聚物;和其组合。如果存在,基于去除组合物的总重量,去除组合物中聚合物的量介于约0.0001wt%到约1wt%范围内。
氧清除剂(如果存在)包含(但不限于)二烷基羟基胺、羟基烷基羟基胺、碳酰肼、2-氨基乙基哌嗪(AEP)、甲基乙基酮肟、氢醌、肼、单独或与3-甲氧基丙胺组合的1,3-环己二酮、1,4-环己二酮和2,5-环己二酮、氨基酚、直链水溶性聚乙烯胺(例如三亚乙基四胺、四亚乙基五胺、五亚乙基六胺)、亚硫酸钠、亚硫酸铵、亚硫酸钾和其组合。优选地,氧清除剂包含碳酰肼、2-氨基乙基哌嗪(AEP)、甲基乙基酮肟、氢醌、肼、单独或与3-甲氧基丙胺组合的1,3-环己二酮、1,4-环己二酮和2,5-环己二酮、氨基酚、直链水溶性聚乙烯胺(例如三亚乙基四胺、四亚乙基五胺、五亚乙基六胺)和其组合。不受限于理论,认为氧清除剂有助于稳定还原剂。如果存在,基于去除组合物的总重量,去除组合物中氧清除剂的量介于约0.0001wt%到约1wt%范围内。
还原剂包含(但不限于)抗坏血酸、L(+)-抗坏血酸、异抗坏血酸、抗坏血酸衍生物、亚硫酸、亚硫酸铵、亚硫酸钾、亚硫酸钠、多巴胺HCl、磷酸、次膦酸、焦亚硫酸钾、焦亚硫酸钠、焦亚硫酸铵、羟基胺、还原糖(例如半乳糖、核糖、***糖、木糖、岩藻糖、鼠李糖、甘露糖、果糖、山梨糖、半乳糖醛酸、葡糖胺、麦芽糖、乳糖)、丙酮酸钾、丙酮酸钠、丙酮酸铵、甲酸、甲酸钠、甲酸钾、甲酸铵、多巴胺、二氧化硫溶液,和其任何组合。优选地,至少一种还原剂包括至少一个亚硫酸根离子和至少一种其它所列举还原剂,例如亚硫酸、亚硫酸钾、亚硫酸铵、次膦酸和其任何组合。应了解,当亚硫酸铵存在时,亚硫酸铵可原位产生,其中具体组分的组合形成亚硫酸铵以帮助去除残余物,例如氧化铈粒子和其它CMP后残余物。
包含上文所述组分的水性去除组合物特别可用于从微电子装置结构去除氧化铈粒子和污染物(例如CMP后残余物和污染物)。本文所述的水性去除组合物的pH可介于约1到约13.9范围内。在一个实施例中,pH介于约3到约13.9、优选约3.5到约13.9范围内。在另一实施例中,pH介于约3.5到约5.5范围内。在另一实施例中,pH介于约4.5到约8.5、优选约7.5到8.5范围内。在另一实施例中,pH介于约9到约13.7范围内。
在特别优选实施例中,水性去除组合物包括还原剂、至少一种pH调节剂、至少一种有机添加剂和水,由其组成或基本上由其组成。在另一实施例中,水性去除组合物包括包括亚硫酸根离子的化合物、至少一种pH调节剂、至少一种有机添加剂和水,由其组成或基本上由其组成。在另一实施例中,水性去除组合物包括还原剂、至少一种pH调节剂、丙二醇苯基醚和水,由其组成或基本上由其组成。在另一实施例中,水性去除组合物包括包括亚硫酸根离子的化合物、至少一种pH调节剂、丙二醇苯基醚和水,由其组成或基本上由其组成。在另一实施例中,水性去除组合物包括还原剂、至少一种络合剂、至少一种pH调节剂、至少一种有机添加剂和水,由其组成或基本上由其组成。在另一实施例中,水性去除组合物包括包括亚硫酸根离子的化合物、至少一种络合剂、至少一种pH调节剂、至少一种有机添加剂和水,由其组成或基本上由其组成。在另一实施例中,水性去除组合物包括包括亚硫酸根离子的化合物、柠檬酸、至少一种pH调节剂、至少一种有机添加剂和水,由其组成或基本上由其组成。在另一实施例中,水性去除组合物包括包括亚硫酸根离子的化合物、柠檬酸、至少一种pH调节剂、丙二醇苯基醚和水,由其组成或基本上由其组成。在另一实施例中,水性去除组合物包括还原剂(例如包括亚硫酸根离子的化合物)、至少一种pH调节剂、至少一种有机添加剂、至少一种氧清除剂和水,由其组成或基本上由其组成。在另一实施例中,水性去除组合物包括还原剂(例如包括亚硫酸根离子的化合物)、至少一种pH调节剂、至少一种有机添加剂、至少一种络合剂(例如柠檬酸)、至少一种氧清除剂和水,由其组成或基本上由其组成。
关于组成量,有机添加剂与还原剂的重量%比率介于约0.001:1到约10:1、优选约0.1:1到约5:1范围内。基于本文所揭示的pH值和所属领域技术人员的知识,pH调节剂的量根据在制备去除组合物以供使用时寻求的最终pH而定。
各组分的重量%比率的范围将覆盖组合物的所有可能的浓或稀实施例。为此,在一个实施例中,提供浓去除组合物,其可经稀释以用作清洁溶液。浓组合物或“浓缩物”有利地允许用户(例如CMP工艺工程师)在使用时将所述浓缩物稀释到所需强度和pH。浓水性去除组合物的稀释度可介于约1:1到约2500:1、优选约5:1到约200:1、且最优选约20:1到约120:1范围内,其中水性去除组合物是在工具处或工具稍前处用溶剂(例如去离子水)稀释。所属领域技术人员应了解,在稀释后,本文所揭示组分的重量%比率的范围应保持不变。
本文所述的组合物可用于多个应用中,包含(但不限于)蚀刻后残余物去除、灰分后残余物去除表面制备、电镀后清洁和CMP后残余物去除。另外,涵盖本文所述的水性清洁组合物可用于清洁和保护其它金属(例如含铜和含钨)产品,包含(但不限于)装饰金属、金属打线、印刷电路板和使用金属或金属合金的其它电子封装。
在另一优选实施例中,本文所述的水性去除组合物进一步包含氧化铈粒子和/或CMP污染物。氧化铈粒子和污染物在清洁开始后变成去除组合物的组分且将溶解和/或悬浮于组合物中。
水性去除组合物容易地通过简单地添加相应成分并混合到均质状态来调配。此外,组合物可容易地调配为单包装调配物或在使用时或使用前混合的多部分调配物,例如可在工具处或在工具上游的储存罐中混合多部分调配物的个别部分。相应成分的浓度在多种具体组合物中可广泛变化,即更稀或更浓,并且应了解,本文所述的组合物可变化地且替代性地包括与本文揭示内容一致的成分的任一组合、由其组成或基本上由其组成。
因此,另一方面涉及试剂盒,其包含一或多个容器中的一或多种适于形成本文所述组合物的组分。所述试剂盒可包含一或多个容器中的至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂、水、任选地至少一种络合剂、任选地至少一种聚合物和任选地至少一种氧清除剂,用于在晶片制造厂(fab)处或在使用时与其它溶剂(例如水)组合。或者,所述试剂盒可包含一或多个容器中的至少一种还原剂、至少一种有机添加剂、水、任选地至少一种络合剂、任选地至少一种聚合物和任选地至少一种氧清除剂,用于在晶片制造厂处或在使用时与至少一种pH调节剂和其它溶剂(例如水)组合。所述试剂盒的容器必须适于储存和运送组合物且可为例如容器(英特格公司(Entegris,Inc.),美国马萨诸塞州比尔里卡(Billerica,Mass.,USA))。
一或多个含有水性去除组合物的组分的容器优选包含使所述一或多个容器中的组分流体连通以供掺和和分配的构件。举例来说,在提到容器时,可将气压施加到所述一或多个容器中的衬里的外部以排放衬里的至少一部分内容物且因此实现流体连通用于掺和和分配。或者,可将气压施加到常规可加压容器的顶隙或可使用泵来实现流体连通。另外,所述***优选包含用于将经掺和去除组合物分配到工艺工具的分配端口。
在施加到微电子制造操作时,本文所述的水性去除组合物可用于从微电子装置的表面清洁氧化铈粒子和/或CMP污染物(例如CMP后残余物和污染物)。水性去除组合物不会损害装置表面上的低k介电材料(例如氧化硅)、氮化硅层或含钨层。优选地,水性去除组合物去除在去除粒子之前存在于装置上的至少85%的氧化铈粒子,更优选至少90%,甚至更优选至少95%,并且最优选至少99%。
在CMP后粒子和污染物去除应用中,本文所述的水性去除组合物可与诸如兆声波和刷洗等众多种常规清洁工具一起使用,包含(但不限于)Verteq单晶片兆声波金指、OnTrak***DDS(双面刷洗器)、SEZ或其它单晶片喷雾清洗、应用材料Mirra-MesaTM/ReflexionTM/Reflexion LKTM和兆声波批式湿洗台式***。
在使用本文所述的组合物从上面具有氧化铈粒子和CMP污染物的微电子装置去除所述粒子和污染物时,通常使水性去除组合物与装置在介于约20℃到约90℃、优选约20℃到约50℃范围内的温度下接触约5秒到约10分钟、优选约1秒到20分钟、优选约15秒到约5分钟的时间。所述接触时间和温度具有说明性,并且可采用在所述方法的广泛实践内有效地从装置至少部分地去除氧化铈粒子和CMP污染物的任何其它适宜时间和温度条件。“至少部分地清洁”和“实质去除”仅对应于去除在粒子去除之前存在于装置上的至少85%的氧化铈粒子,更优选至少90%,甚至更优选至少95%,并且最优选至少99%。
在实现所需粒子去除作用后,水性去除组合物可容易地从先前已施加其的装置去除,如可能在本文所述组合物的给定最终用途应用中所需且有效。优选地,清洗溶液包含去离子水。此后,可使用氮或旋转-干燥循环干燥装置。
另一方面涉及根据本文所述的方法制造的经改良微电子装置和含有所述微电子装置的产品。
另一方面涉及再循环水性去除组合物,其中去除组合物可再循环直到粒子和/或污染物负载达到水性去除组合物可适应的最大量,如所属领域技术人员容易地确定。
另一方面涉及制造包括微电子装置的制品的方法,所述方法包括使微电子装置与水性去除组合物接触足够时间,以使用本文所述的去除组合物从上面具有氧化铈粒子和CMP污染物的微电子装置去除所述粒子和污染物并将所述微电子装置纳入所述制品中。
在另一方面中,描述从上面具有氧化铈粒子和CMP污染物的微电子装置去除所述粒子和污染物的方法。所述方法包括用CMP浆液抛光微电子装置,其中CMP浆液包括氧化铈粒子;使微电子装置与水性去除组合物接触足够时间以从微电子装置去除氧化铈粒子和CMP污染物以形成含CMP后粒子的组合物,所述水性去除组合物包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂、水、任选地至少一种络合剂、任选地至少一种聚合物和任选地至少一种氧清除剂;和使微电子装置与含CMP后粒子的组合物连续接触足够时间量以实现微电子装置的实质清洁。可将上文所述的任一组分用于去除氧化铈粒子和CMP污染物的本方法中。
另一方面涉及制品,其包括水性去除组合物、微电子装置晶片和选自由氧化铈粒子、CMP污染物和其组合组成的群组的材料,其中去除组合物包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂、水、任选地至少一种络合剂、任选地至少一种聚合物和任选地至少一种氧清除剂。
通过以下非限制性实例更全面地说明本发明的特征和优点,其中除非另有明确说明,否则所有份数和百分比都是以重量计。
实例1
制备下文所显示的去除组合物(每一调配物中的余量是DI水)且用水以100:1稀释。所述工艺涉及将TEOS衬底于含氧化铈的浆液中浸没5分钟,将衬底在DI水中清洗30秒,将衬底于去除组合物中浸没60秒,并且然后再用DI水清洗30秒。浸没期间的温度是室温。利用扫描电子显微法(SEM)、电感耦合等离子体质谱(ICP-MS)和暗视野显微法(DFM)测定清洁的程度,并且与比较调配物1比较。
调配物A:2wt%柠檬酸、2wt%丙二醇苯基醚、余量水。调节和1:100稀释后的pH=2.5
调配物B:2wt%柠檬酸、2wt%亚硫酸钠、余量水。调节和1:100稀释后的pH=2.6
调配物C:2wt%柠檬酸、2wt%丙二醇苯基醚、2wt%亚硫酸钠、余量水。调节和1:100稀释后的pH=2.6
比较调配物1:NH4OH:H2O2:H2O=1:1:5
DFM数据指示清洁后氧化铈污染的总面积。发现调配物A-C在清洁方面都比比较调配物1有效。具体来说,发现调配物C比比较调配物有效3.5×且比调配物A有效2×。
基于调配物C的有效性,制备其它组合物且测定DFM数据,如表1中所显示。每一调配物中的余量是DI水。添加KOH以将pH调节到目标pH。用水以100:1稀释调配物且在室温下将包括含氧化铈浆液的TEOS衬底于其中浸没5分钟。
表1:调配物和DFM数据
发现调配物J相对于比较调配物1具有150×改良的性能。调配物D、F、H、I和N-R在清洁方面也比比较调配物有效。应注意,这些调配物具有介于4-6范围内的较高pH。
实例2
制备下文所显示的去除组合物(每一调配物中的余量是DI水)且用水以100:1稀释。所述工艺涉及将TEOS衬底于含氧化铈的浆液中浸没5分钟,将衬底在DI水中清洗30秒,将衬底于去除组合物中浸没60秒,并且然后再用DI水清洗30秒。浸没期间的温度是室温。利用扫描电子显微法(SEM)、电感耦合等离子体质谱(ICP-MS)和暗视野显微法(DFM)测定清洁的程度。具体来说,表2显示每一去除组合物的DMF数据。
表2:调配物和DFM数据
尽管本发明的说明性实施例和特征已多番揭示于本文中,但应了解,上文所述的实施例和特征不旨在限制本发明,并且所属领域技术人员基于本文的揭示内容将明了其它变化形式、修改和其它实施例。因此,本发明应在广义上理解为涵盖在所附权利要求书的精神和范围内的所有所述变化形式、修改和替代性实施例。
Claims (20)
1.一种水性去除组合物,其包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂和水,其中所述水性去除组合物适于从上面具有氧化铈粒子和化学机械抛光CMP污染物的微电子装置去除所述粒子和CMP污染物。
2.根据权利要求1所述的水性去除组合物,其中所述氧化铈粒子是具有式Ce2O3和CeO2的氧化铈。
3.根据权利要求1所述的水性去除组合物,其中所述至少一种pH调节剂是碱金属氢氧化物、氢氧化铵、氢氧化胆碱或四烷基氢氧化铵。
4.根据权利要求1所述的水性去除组合物,其中所述至少一种pH调节剂是硫酸、柠檬酸或其组合。
5.根据权利要求1所述的水性去除组合物,其中所述至少一种有机添加剂包括二醇醚。
6.根据权利要求1所述的水性去除组合物,其中所述至少一种有机添加剂是丙二醇苯基醚。
7.根据权利要求1所述的水性去除组合物,其中所述至少一种还原剂包括至少一个亚硫酸根离子。
8.根据权利要求7所述的水性去除组合物,其进一步包括亚硫酸、亚硫酸钾、亚硫酸铵、次膦酸或其任何组合。
9.根据权利要求1所述的水性去除组合物,其进一步包括至少一种氧清除剂。
10.根据权利要求9所述的水性去除组合物,其中所述至少一种氧清除剂是碳酰肼、2-氨基乙基哌嗪AEP、甲基乙基酮肟、氢醌、肼或1,3-环己二酮、1,4-环己二酮或2,5-环己二酮。
11.根据权利要求1所述的水性去除组合物,其进一步包括至少一种络合剂。
12.根据权利要求11所述的水性去除组合物,其中所述至少一种络合剂是烷醇胺。
13.根据权利要求1所述的水性去除组合物,其进一步包括至少一种聚合物。
14.根据权利要求13所述的水性去除组合物,其中所述至少一种聚合物是聚(甲基丙烯酸)或聚(丙烯酸)。
15.根据权利要求1所述的水性去除组合物,其中所述微电子装置包括氮化硅和低k介电层。
16.一种从上面具有氧化铈粒子和CMP污染物的微电子装置去除所述粒子和污染物的方法,所述方法包括
使所述微电子装置与包括至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂和水的水性去除组合物接触;和
从所述微电子装置至少部分地清洁所述粒子和污染物,其中所述微电子装置包括氮化硅和低k介电层。
17.根据权利要求16所述的方法,其中所述水性去除组合物进一步包括至少一种氧清除剂、至少一种络合剂或至少一种聚合物。
18.根据权利要求16所述的方法,其中所述水性去除组合物基本上不会损害所述氮化硅或所述低k介电层。
19.根据权利要求16中任一权利要求所述的方法,其进一步包括在使用时或使用前用溶剂稀释所述水性去除组合物,其中所述溶剂包括水。
20.一种试剂盒,其包括一或多个容器,所述容器中具有适于从上面具有氧化铈粒子和化学机械抛光CMP污染物的微电子装置去除所述粒子和CMP污染物的组分,其中所述试剂盒的一或多个容器含有至少一种pH调节剂、至少一种还原剂、至少一种有机添加剂和水。
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JP2021192429A (ja) | 2021-12-16 |
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KR20190094426A (ko) | 2019-08-13 |
KR20240074891A (ko) | 2024-05-28 |
JP2020504460A (ja) | 2020-02-06 |
TW201831666A (zh) | 2018-09-01 |
KR20210090294A (ko) | 2021-07-19 |
JP7443300B2 (ja) | 2024-03-05 |
US11164738B2 (en) | 2021-11-02 |
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