CN102473638B - 用于高级半导体应用的离子植入后剥离剂 - Google Patents
用于高级半导体应用的离子植入后剥离剂 Download PDFInfo
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- CN102473638B CN102473638B CN201080033645.5A CN201080033645A CN102473638B CN 102473638 B CN102473638 B CN 102473638B CN 201080033645 A CN201080033645 A CN 201080033645A CN 102473638 B CN102473638 B CN 102473638B
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- 239000007943 implant Substances 0.000 title abstract description 3
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- 239000006184 cosolvent Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 16
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 13
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 12
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- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 8
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 7
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 7
- -1 ethyl diglycol Chemical compound 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 4
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940113088 dimethylacetamide Drugs 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002513 implantation Methods 0.000 claims description 4
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- 229940011051 isopropyl acetate Drugs 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 claims description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 4
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 3
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 3
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 3
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 claims description 2
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 2
- 229940035429 isobutyl alcohol Drugs 0.000 claims description 2
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- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 claims 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims 1
- 238000005468 ion implantation Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
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- 239000002904 solvent Substances 0.000 description 6
- 206010040844 Skin exfoliation Diseases 0.000 description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
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- 239000002671 adjuvant Substances 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229920005591 polysilicon Polymers 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000252506 Characiformes Species 0.000 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 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000005360 alkyl sulfoxide group Chemical group 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000035618 desquamation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 150000003138 primary alcohols Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
-
- 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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- 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
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
-
- 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
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Abstract
本发明涉及一种基本无水的光致抗蚀剂剥离组合物。特别地，本发明涉及一种用于在离子植入工艺之后去除光致抗蚀剂的基本无水的光致抗蚀剂剥离组合物，其包含：(a)胺，(b)有机溶剂A，和(c)共溶剂，其中所述组合物基本无水(＜3重量％H2O)。本发明还提供一种通过使用本发明组合物的离子植入后剥离的方法。
Description
技术领域
本发明涉及一种用于剥离光致抗蚀剂的组合物。特别地，本发明涉及一种用于离子植入后剥离光致抗蚀剂的组合物。
背景技术
离子植入是一种半导体器件制造中的关键工艺。掺杂离子如硼、磷或砷由高纯度气体源产生并植入半导体衬底中。各掺杂原子形成空穴或电子型载流子且因此改善其周围半导体器件的导电性。离子植入通常用于源/漏结和沟道以获得待制造器件所需的电特性。
在典型的离子植入工艺中，首先对衬底(例如硅晶片)进行有机化学预处理，随后将正型光致抗蚀剂涂覆于该衬底上。在热烘烤、边缘球状物去除、曝光、显影和旋转干燥步骤之后，形成有机光致抗蚀剂掩模。在离子植入工艺期间，掺杂剂渗入衬底的曝光(未掩盖)表面以及光致抗蚀剂掩模中。掺杂剂可与光致抗蚀剂掩模反应以形成相对无孔层，通常称为“外壳”。在离子植入工艺结束后，然后通过剥离工艺去除光致抗蚀剂掩模。典型的离子植入后剥离通过干等离子体灰化，随后湿piranha清洁(其使用硫酸与过氧化氢的混合物作为清洁剂)以及marangoni干燥而进行。尽管上述工艺广泛用于半导体工业中，但已注意到一些缺点，如长处理时间以及对硅衬的破坏。当临界尺寸缩小至45nm及更小时，诸如硅损失的硅衬底破坏已成为关键问题。大于的硅损失可能导致不希望的掺杂剂外扩散并导致器件故障。出于这些原因，用于离子植入后剥离处理的典型方法不再被接受且需要一种新颖方法。
用于在离子植入工艺后去除光致抗蚀剂的各种方法描述于现有技术中。例如，Hallock等的美国专利6,524,936公开了一种将晶片曝露于200-400nm以及至少100mJ/cm2的UV辐射下，然后进行常规湿法或干法剥离工艺。Tseng等的美国专利5,811,358公开了一种三步程序。首先用氧气以及氮气/氢气等离子体在低温(＜220℃)下剥离衬底以使光致抗蚀剂溶剂间歇振荡问题最少化。随后，采用较高温度(＞220℃)去除剩余的光致抗蚀剂。最后，用氢氧化铵和过氧化氢的混合物清洁衬底。然而，上述方法仍存在无法接受的硅损失。
光致抗蚀剂剥离组合物公开于许多现有技术中。例如，Moore的美国专利6,551,973公开了一种剥离组合物，其包含苄基三甲基氢氧化铵(BTMAH)、包含烷基亚砜和任选的二醇共溶剂的溶剂体系、腐蚀抑制剂和用于从金属化无机衬底上去除聚合有机物质的非离子型表面活性剂。Phenis等的美国公开专利2007/0099805公开了一种包含二甲亚砜和氢氧化季铵以及链烷醇胺的剥离溶液。然而，在离子植入，尤其是大剂量离子植入后采用常规剥离组合物去除光致抗蚀剂的尝试总是失败，这是因为光致抗蚀剂在离子植入后变得无孔隙且形成外壳。所述无孔外壳阻止湿化学物质渗入光致抗蚀剂的内部并因此显著降低湿化学物质与光致抗蚀剂之间的接触面积。此外，外壳部分高度不均匀并因此使湿法清洁的处理难度增加。因此，使用常规湿化学物质进行离子植入后剥离是不切实际的。
发明简述
本发明的一个目的是提供一种可用于在离子植入工艺之后去除光致抗蚀剂的基本无水的光致抗蚀剂剥离组合物。本发明组合物包含：
(a)胺
(b)有机溶剂A，和
(c)共溶剂，
其中所述组合物基本无水。
在本发明的优选实施方案中，所述胺为氢氧化季铵。
在本发明的更优选实施方案中，所述胺为苄基三甲基氢氧化铵(BTMAH)。
在本发明的另一更优选实施方案中，所述胺为四甲基氢氧化铵(TMAH)。
本发明的另一目的是提供一种离子植入后的剥离方法。该方法包括如下步骤：
(a)提供其上具有植入的光致抗蚀剂的衬底，和
(b)使所述衬底与本发明组合物接触达足以将所述光致抗蚀剂从衬底上去除的时间。
附图简介
图1为典型离子植入后剥离与本发明方法比较的流程示意图。
图2为剥离方法中可能机理的示意图。
发明详述
本发明的第一个目的是提供一种能在离子植入后将光致抗蚀剂从衬底上去除的光致抗蚀剂剥离组合物。本发明剥离组合物包含：
(a)胺
(b)有机溶剂A，和
(c)共溶剂，
其中所述组合物基本无水。
本发明组合物中的胺可分解固化的光致抗蚀剂的聚合物骨架并剥离固化光致抗蚀剂的碎片。
在本发明组合物中可使用任何合适的伯、仲、叔或季胺。合适的伯胺包括但不限于乙醇胺(MEA)、N-甲基乙醇胺(NMEA)、环己胺和羟胺(HA)。合适的仲胺包括但不限于二乙基羟胺、二乙胺和喹啉。合适的叔胺包括但不限于二甲基乙醇胺和三甲胺。合适的季铵包括但不限于四甲基氢氧化铵(TMAH)、苄基三甲基氢氧化铵(BTMAH)、四乙基氢氧化铵(TEAH)和四丁基氢氧化铵(TBAH)。
优选的胺为氢氧化季铵。在氢氧化季铵中，BTMAH和TMAH出乎意料地有效且因此是最优选的。
发明组合物中的胺含量可为1-10重量％，优选1-4重量％。
本发明的有机溶剂A和共溶剂具有不同的功能。本发明的有机溶剂A可通过图2中(X)所示的剥离和切割机理从衬底上去除光致抗蚀剂。单独使用溶剂A而不使用共溶剂可将光致抗蚀剂从衬底上剥离，然而此时剥离剂溶液会因光致抗蚀剂碎片悬浮于溶液中而变浑浊。光致抗蚀剂碎片将降低剥离组合物的负载能力并污染衬底和设备。
另一方面，本发明的共溶剂在将光致抗蚀剂从衬底剥离方面不那么有效，但可溶解光致抗蚀剂碎片以提高剥离组合物的负载能力。共溶剂无法单独从衬底完全去除光致抗蚀剂且一些光致抗蚀剂残余物，尤其是“外壳”会留在衬底上。共溶剂的机理如图2中的(Y)所示。
因此，本发明组合物适当地组合了溶剂A和共溶剂，从而获得优异的剥离性能。其机理如图2中的(Z)所示。
必须仔细选择溶剂A和共溶剂。就安全性而言，合适的溶剂A和共溶剂应具有比处理温度高至少10℃，优选30℃的闪点，以及比处理温度高至少40℃的沸点。其熔点应低于室温，优选低于0℃以避免在储存或运输过程中结晶。然而，如果单一溶剂不具有所有上述物理性质，例如DMSO具有18.5℃的熔点，但对剥离或溶解植入的光致抗蚀剂特别有效，则其可与其他合适溶剂混合以符合要求。
合适的有机溶剂A选自烷基亚砜，如二甲亚砜(DMSO)、二甲基砜(DMSO2)和环丁砜；酮，如1-甲基-2-吡咯烷酮(NMP)、γ-丁内酯(BLO)(GBL)、乙基甲基酮、2-戊酮、3-戊酮、2-己酮和异丁基甲基酮；醇，如CnH2n+1OH，其中n＝3-10，例如1-丙醇、2-丙醇、丁醇、戊醇、1-己醇、1-庚醇和1-辛醇、乙基二甘醇(EDG)、丁基二甘醇(BDG)和苄醇；醛，如苯甲醛；烷烃，如十三烷、十二烷、十一烷和癸烷；胺，如N，N-二甲基乙醇胺、二正丙胺、三正丙胺、异丁胺、仲丁胺、环己胺、甲基苯胺、邻甲苯胺、间甲苯胺、邻氯苯胺、间氯苯胺、辛基胺、N，N-二乙基羟胺、喹啉、N，N-二甲基乙醇胺或N，N-二甲基甲酰胺，或其组合。
合适的共溶剂选自醇，包括伯、仲和叔醇，如异丙醇、异丁醇、仲丁醇、异戊醇、叔戊醇、乙二醇(EG)、丙二醇、1，2-丙二醇、1，3-丙二醇、1，2，3-丙三醇和1-氨基-2-丙醇；酯，如乙酸异丙酯和乙酰乙酸乙酯；含有羟基的胺，如三乙醇胺、乙醇胺(MEA)；甲酰胺、二甲基乙酰胺(DMAC)、2-甲基氨基乙醇(NMEA)和N-乙基二异丙胺；或其组合。
在上述有机溶剂中，本发明优选将DMSO、NMP、苄醇、丙醇、丁基二甘醇、戊醇、N，N-二甲基乙醇胺、苯甲醛或其混合物用作溶剂A。更优选DMSO、NMP、苄醇、丁基二甘醇及其混合物。
在本发明中优选使用乙二醇、1，2-丙二醇、1-氨基-2-丙醇、三乙醇胺、MEA、乙酸异丙酯或其混合物作为共溶剂，更优选为乙二醇、三乙醇胺、MEA或其混合物。
如果不添加其他添加剂，则溶剂A和共溶剂的含量基本占所述组合物的90-99重量％。溶剂A与共溶剂之比并不重要。
本发明剥离组合物可任选含有诸如螯合剂和表面活性剂的添加剂。合适的螯合剂包括但不限于乙二胺四乙酸(EDTA)、二亚乙基三胺五乙酸(DTPA)和2，4-戊二酮。合适的表面活性剂包括但不限于非离子型烷氧基化醇、壬基酚和壬基乙氧基化物。各添加剂的量可视需要改变且可由本领域技术人员根据现有技术确定。优选各添加剂的总量占所述组合物的少于约1重量％。
与大多数常规剥离组合物不同，本发明剥离组合物基本无水，即水含量必须少于3重量％，优选少于1重量％，更优选少于0.5重量％，以避免破坏硅衬底。硅损失很大程度上与组合物的含水量有关。
本发明的另一目的是提供一种离子植入后的湿法工艺。所述方法包括如下步骤：
(a)提供其上具有植入的光致抗蚀剂的衬底，和
(b)使所述衬底与本发明组合物接触达足以将所述光致抗蚀剂从衬底去除的时间。
应当注意的是，本发明剥离方法无需干法等离子体灰化，因而有利于减少循环时间和所消耗的能量。
本发明方法可在任何合适的设备如常规湿台或清洁器中实施。衬底与组合物的接触可通过任何合适的常规方式如浸渍、漂洗、喷雾和喷射而实施。
在本发明的优选实施方案中，所述方法在湿台中实施。该方法可在25-90℃，优选40-80℃，更优选60-80℃的温度下进行。所述温度远低于piranha清洁的处理温度(通常为120-140℃)。据信升高的温度会增加衬底的硅损失，因此较低温度是有利的。
一般而言，植入的光致抗蚀剂可在20分钟至2小时内从衬底上完全去除。实际时间取决于光致抗蚀剂的类型、所用设备和处理条件。
实施例
下文通过实施例对本发明进行阐述，所述实施例并非意欲限制本发明的范围。应当理解的是，对本领域技术人员而言为显而易见的任何改变或变化均落入本说明书的公开范围之内。
实施例1-H2O对多晶硅蚀刻速率
进行以下实施例以评价水含量对多晶硅蚀刻速率的影响。将不同量的TMAH或其甲醇溶液(实施例1-6)以及BTMAH的甲醇溶液(实施例7-9)加入DMSO中。将不同量的水加入一些溶液中(实施例1-5、8和9)。在不同处理条件下将多晶硅晶片浸入溶液中并测定各晶片的厚度差异。结果示于表1中。
表1
结果显示H2O的增加显著提高了多晶硅的蚀刻速率。此外，实施例1-3表明温度越高，则多晶硅的蚀刻速率就越大。
实施例2-5
测试不同组合物在不同条件下的剥离能力，结果示于下表2-5中。
表2
表2表明在所用的胺中，TMAH在给定的处理条件下显示出出乎意料有效的光致抗蚀剂剥离性能。应当注意的是，其他胺也能去除光致抗蚀剂，但其性能不及TMAH和BTMAH。
表3
A：澄清；B：在晶片上具有少量光致抗蚀剂残余物；C：在晶片上具有一些光致抗蚀剂残余物
表3表明TMAH的加工窗口比BTMAH宽。就BTMAH而言，在70℃下需60分钟完成剥离。就TMAH而言，在60℃下需60分钟。如上所述，升高的温度是不利的，因为其增加了对硅衬底的破坏。
表4
A：清洁；C：在晶片上具有一些光致抗蚀剂残余物
已对各种溶剂进行了测试。表4表明所测试的溶液具有可接受的光致抗蚀剂去除能力，但在剥离后导致溶液变浑浊(其归类为溶剂A)，或具有差的光致抗蚀剂去除能力但可溶解光致抗蚀剂(其归类为共溶剂)。未发现对光致抗蚀剂去除和溶解均有效的溶剂。
表5
表5所示的是本发明实施方案的性能。应当注意的是，溶剂A与共溶剂之比并不重要。
Claims (12)
1.一种用于离子植入后剥离的组合物，其包含：
(a)胺
(b)有机溶剂A，和
(c)共溶剂，
所述胺为氢氧化季铵；
所述有机溶剂A选自二甲亚砜(DMSO)、二甲基砜(DMSO2)、1-甲基-2-吡咯烷酮(NMP)、γ-丁内酯(BLO)(GBL)、乙基甲基酮、2-戊酮、3-戊酮、2-己酮和异丁基甲基酮、1-丙醇、2-丙醇、丁醇、戊醇、1-己醇、1-庚醇、1-辛醇、乙基二甘醇(EDG)、丁基二甘醇(BDG)、苄醇、苯甲醛、十三烷、十二烷、十一烷、癸烷、N,N-二甲基乙醇胺、二正丙胺、三正丙胺、异丁胺、仲丁胺、环己胺、甲基苯胺、邻甲苯胺、间甲苯胺、邻氯苯胺、间氯苯胺、辛胺、N,N-二乙基羟胺、喹啉、N,N-二甲基乙醇胺、N,N-二甲基甲酰胺；及其组合；
所述共溶剂选自异丙醇、异丁醇、仲丁醇、异戊醇、叔戊醇、乙二醇(EG)、丙二醇、1,2-丙二醇、1,3-丙二醇、1,2,3-丙三醇、1-氨基-2-丙醇、乙酸异丙酯、乙酰乙酸乙酯、三乙醇胺、乙醇胺(MEA)、甲酰胺、二甲基乙酰胺(DMAC)、2-甲基氨基乙醇(NMEA)、N-乙基二异丙胺及其组合；
其中所述胺的含量占该组合物的1-4重量％；
其中所述组合物的水含量占该组合物的小于1重量％。
2.如权利要求1的组合物，其中所述胺为四甲基氢氧化铵(TMAH)、苄基三甲基氢氧化铵(BTMAH)或其组合。
3.如权利要求1的组合物，其中所述有机溶剂A为二甲亚砜(DMSO)、1-甲基-2-吡咯烷酮(NMP)、苄醇、丙醇、丁基二甘醇、戊醇、N,N-二甲基乙醇胺、苯甲醛或其混合物。
4.如权利要求3的组合物，其中所述有机溶剂A为二甲亚砜(DMSO)、1-甲基-2-吡咯烷酮(NMP)、苄醇、丁基二甘醇或其混合物。
5.如权利要求1的组合物，其中所述共溶剂选自乙二醇、1,2-丙二醇、1-氨基-2-丙醇、三乙醇胺、乙醇胺(MEA)、乙酸异丙酯及其组合。
6.如权利要求5的组合物，其中所述共溶剂为乙二醇、三乙醇胺、乙醇胺(MEA)或其组合。
7.如权利要求1的组合物，其中所述组合物的水含量占该组合物的小于0.5重量％。
8.一种用于离子植入后剥离的方法，其包括如下步骤：
(a)提供其上具有植入的光致抗蚀剂的衬底，和
(b)使所述衬底与权利要求1的组合物在处理温度下接触达足以将所述光
致抗蚀剂从所述衬底去除的时间。
9.如权利要求8的方法，其中所述处理温度为25-90℃。
10.如权利要求9的方法，其中所述处理温度为40-80℃。
11.如权利要求10的方法，其中所述处理温度为60-80℃。
12.如权利要求8的方法，其中所述接触时间为20分钟至1小时。
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| US22976009P | 2009-07-30 | 2009-07-30 | |
| US61/229,760 | 2009-07-30 | ||
| PCT/EP2010/060762 WO2011012559A2 (en) | 2009-07-30 | 2010-07-26 | Post ion implant stripper for advanced semiconductor application |
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| CN102473638A CN102473638A (zh) | 2012-05-23 |
| CN102473638B true CN102473638B (zh) | 2015-02-18 |
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| EP (1) | EP2460177B1 (zh) |
| JP (1) | JP6165442B2 (zh) |
| KR (1) | KR101746879B1 (zh) |
| CN (1) | CN102473638B (zh) |
| IL (1) | IL217708A (zh) |
| MY (1) | MY185453A (zh) |
| SG (2) | SG177755A1 (zh) |
| TW (1) | TWI594088B (zh) |
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Also Published As
| Publication number | Publication date |
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| EP2460177B1 (en) | 2016-03-23 |
| WO2011012559A2 (en) | 2011-02-03 |
| SG10201404328QA (en) | 2014-10-30 |
| JP2013500503A (ja) | 2013-01-07 |
| EP2460177A2 (en) | 2012-06-06 |
| CN102473638A (zh) | 2012-05-23 |
| IL217708A (en) | 2017-07-31 |
| RU2012107135A (ru) | 2013-09-10 |
| TWI594088B (zh) | 2017-08-01 |
| JP6165442B2 (ja) | 2017-07-19 |
| KR20120041777A (ko) | 2012-05-02 |
| IL217708A0 (en) | 2012-03-29 |
| KR101746879B1 (ko) | 2017-06-14 |
| SG177755A1 (en) | 2012-03-29 |
| WO2011012559A3 (en) | 2011-03-24 |
| MY185453A (en) | 2021-05-19 |
| US9484218B2 (en) | 2016-11-01 |
| TW201128327A (en) | 2011-08-16 |
| US20120129747A1 (en) | 2012-05-24 |
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