JP2016510090A - 金イオン及びフッ素イオンを含有する溶液を用いた金属ケイ化物の形成方法 - Google Patents
金イオン及びフッ素イオンを含有する溶液を用いた金属ケイ化物の形成方法 Download PDFInfo
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- JP2016510090A JP2016510090A JP2015558531A JP2015558531A JP2016510090A JP 2016510090 A JP2016510090 A JP 2016510090A JP 2015558531 A JP2015558531 A JP 2015558531A JP 2015558531 A JP2015558531 A JP 2015558531A JP 2016510090 A JP2016510090 A JP 2016510090A
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- Prior art keywords
- nickel
- cobalt
- less
- silicon
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000000034 method Methods 0.000 title claims abstract description 63
- -1 gold ion Chemical class 0.000 title claims abstract description 37
- 239000010931 gold Substances 0.000 title claims abstract description 35
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 26
- 229910021332 silicide Inorganic materials 0.000 title claims abstract description 16
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 title claims abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 139
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 65
- 239000000758 substrate Substances 0.000 claims abstract description 59
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 56
- 239000010703 silicon Substances 0.000 claims abstract description 56
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 47
- 239000010941 cobalt Substances 0.000 claims abstract description 47
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- RUFLMLWJRZAWLJ-UHFFFAOYSA-N nickel silicide Chemical compound [Ni]=[Si]=[Ni] RUFLMLWJRZAWLJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910021334 nickel silicide Inorganic materials 0.000 claims abstract description 24
- 239000004094 surface-active agent Substances 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 230000015654 memory Effects 0.000 claims abstract description 9
- 125000000129 anionic group Chemical group 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000010030 laminating Methods 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 55
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 23
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 4
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 27
- 238000004151 rapid thermal annealing Methods 0.000 abstract description 16
- 230000004913 activation Effects 0.000 description 22
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 19
- 230000008569 process Effects 0.000 description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910000990 Ni alloy Inorganic materials 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229920002873 Polyethylenimine Polymers 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 235000015165 citric acid Nutrition 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 3
- 150000001638 boron Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000003827 glycol group Chemical group 0.000 description 3
- CBMIPXHVOVTTTL-UHFFFAOYSA-N gold(3+) Chemical class [Au+3] CBMIPXHVOVTTTL-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013500 data storage Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- PEUPIGGLJVUNEU-UHFFFAOYSA-N nickel silicon Chemical compound [Si].[Ni] PEUPIGGLJVUNEU-UHFFFAOYSA-N 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 150000003017 phosphorus Chemical class 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
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- 229920001661 Chitosan Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910003767 Gold(III) bromide Inorganic materials 0.000 description 1
- 235000019766 L-Lysine Nutrition 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 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 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- WVMHLYQJPRXKLC-UHFFFAOYSA-N borane;n,n-dimethylmethanamine Chemical compound B.CN(C)C WVMHLYQJPRXKLC-UHFFFAOYSA-N 0.000 description 1
- PVYPHUYXKVVURH-UHFFFAOYSA-N boron;2-methylpropan-2-amine Chemical compound [B].CC(C)(C)N PVYPHUYXKVVURH-UHFFFAOYSA-N 0.000 description 1
- YJROYUJAFGZMJA-UHFFFAOYSA-N boron;morpholine Chemical compound [B].C1COCCN1 YJROYUJAFGZMJA-UHFFFAOYSA-N 0.000 description 1
- VEWFZHAHZPVQES-UHFFFAOYSA-N boron;n,n-diethylethanamine Chemical compound [B].CCN(CC)CC VEWFZHAHZPVQES-UHFFFAOYSA-N 0.000 description 1
- NNTOJPXOCKCMKR-UHFFFAOYSA-N boron;pyridine Chemical compound [B].C1=CC=NC=C1 NNTOJPXOCKCMKR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical class O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 125000003438 dodecyl group Chemical group [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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- OVWPJGBVJCTEBJ-UHFFFAOYSA-K gold tribromide Chemical compound Br[Au](Br)Br OVWPJGBVJCTEBJ-UHFFFAOYSA-K 0.000 description 1
- ZBKIUFWVEIBQRT-UHFFFAOYSA-N gold(1+) Chemical class [Au+] ZBKIUFWVEIBQRT-UHFFFAOYSA-N 0.000 description 1
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- 238000004377 microelectronic Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
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- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical class Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
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- 229920005591 polysilicon Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical class 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
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 description 1
- 229910021342 tungsten silicide Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Abstract
Description
・金イオン及びフッ素イオンを含有する水溶液にケイ素含有基板の表面を接触させて、金属金(Au(0))粒子を形成する工程、
・上記金属金粒子で被覆された基板上に、ニッケル又はコバルトで本質的に構成された層を無電解法によって積層する工程、及び、
・300℃超750℃未満の温度でラピッドサーマルアニール(RTA)を施して、ケイ化ニッケル又はケイ化コバルトを形成する工程
を含む方法である。
・ケイ素基板に付着する。
・類型学的特徴(平面であるか、エッチング面であるか)に関わらず、基板の表面全体にわたって厚さが不変である。これは、厚さが小さい、典型的には50nm未満の場合にも当てはまる。
・低温、典型的には350℃程度であってもラピッドサーマルアニールの間にケイ素中に拡散する。
・金イオンを0.1mM〜10mM、好ましくは0.5mM〜1.0mM、
・フッ素イオンを0.6M〜3.0M、好ましくは1.0M〜2.0M含有する。
・少なくとも1つのニッケル又はコバルトイオンの金属塩を、好ましくは10−3M超1M未満の濃度で;
・少なくとも1つのニッケル又はコバルトイオン用還元剤を、好ましくは10−4M超1M未満の量で;
・必要に応じて、少なくとも1つのニッケル又はコバルトイオン用安定化剤を、好ましくは10−3M超1M未満の量で
含有する水溶液に活性化した基板を曝露することによって得られることが好ましい。
・金イオンと、フッ素イオンと、アニオン性又はノニオン性極性基及び炭素数10〜14のアルキル鎖を有する重合体及び化合物から選択される界面活性剤とを含有する水溶液にケイ素含有基板の表面を曝露して、金属金粒子を形成する工程、及び、
・上記金粒子で被覆された基板上に、ニッケル又はコバルトで本質的に構成された厚さ10nm超150nm未満、好ましくは10nm〜40nm、より好ましくは10nm〜25nmの層を無電解法によって積層する工程
を含む方法である。
当業者であれば、基板の由来及びその要件に従って、表面洗浄のプロトコルをどのように適合させればよいか分かるであろう。ここでは、活性化溶液が低速エッチング溶液でもあるため、洗浄の必要は無かった。本実施例で使用した基板は、辺の長さが1cm×2cm、厚さが750μmのケイ素片を、厚さが約90nmの二酸化ケイ素(SiO2)層で被覆し、該層自体を厚さが約190nmの多結晶シリコン層で被覆したものである。
(b1)活性化溶液の調製
フッ化水素酸2.5重量%(1.5M)と、選択した貴金属塩15mgとの混合液50mLを清浄なPTFEビーカー中、周囲温度で調製する。使用した貴金属塩の種類及び量について表1に示す。
工程(b1)で調製した混合液に工程(a)に記載した基板を所定時間(表1参照)浸漬する。このように処理した基板を脱イオン水で充分に洗滌し、窒素気流下で乾燥させる。
(c1)無電解溶液の事前調製
硫酸ニッケル六水和物31.11g(0.118mol)、クエン酸44.67g(0.232mol)、N−メチルエタノールアミン52.26g(0.700mol)及びMn=600g/molのポリエチレンイミン(PEI)2.5ppmをこの順番で1L容器及び必要最低限の脱イオン水に投入する。塩基によって最終pHを9に調整し、全体積を脱イオン水で1Lに調整した。
事前に調製し、65℃とした無電解溶液に工程(b)で処理した基板表面を所望の最終厚さに従って30秒間〜5分間浸漬して、該表面上にNiBニッケル合金層を積層した。
工程(c)で得られたニッケル合金で被覆されたサンプルに対して350℃で1分間ラピッドサーマルアニール(RTA)を施す。該操作はチューブオーブン又はホットプレートで実施できる。
これら第一の試験群により、ケイ素中へニッケルを移動させるのに使用する貴金属の種類がいかに重要であるかが明らかである。パラジウム(II)溶液は表面を活性化できるものの、得られたコンフォーマルなニッケルの厚さが目的としたものより非常に大きい。さらに、銀及び銅塩の場合、サーマルアニール温度が350℃ではケイ素中にニッケルが移動できないことが分かる。最後に、金(III)塩では、薄いニッケル/ホウ素合金層が得られるだけでなく、そのケイ素中への移動も均一である。
本工程は実施例1の工程(a)と同様である。
(b1)本発明における活性化溶液の調製
フッ化水素酸2.5重量%、塩酸金(III)240ppm及び界面活性剤(表2参照)の混合液50mLを清浄なPTFEビーカー中、周囲温度で調製した。
工程(b1)で調製した混合液に工程(a)に記載した基板を所定時間(表2参照)、本例では30秒間、浸漬する。このように処理した基板を脱イオン水で充分に洗滌し、窒素気流下で乾燥させる。
(c1)無電解溶液の事前調製
使用した無電解溶液及び操作条件は、実施例1の工程(c1)と同様である。
事前に調製し、65℃とした無電解溶液に工程(b)で処理した基板表面を所望の最終厚さに従って30秒間〜5分間浸漬して、該表面上にNiB金属合金層を作製した。無電解溶液への浸漬時間は、良好な均一性及び伝導性を有する必要最低限のニッケル厚さが得られるように決定する。
実施例1の工程(d)と同様に、工程(c)で得られたニッケル合金で被覆されたサンプルに対して350℃で1分間ラピッドサーマルアニールを施す。続いて、上記サンプルを化学溶液で処理して未反応のニッケルを除去する。
Claims (18)
- ケイ化ニッケル又はケイ化コバルトを形成する方法であって、
金イオン及びフッ素イオンを含有する水溶液にケイ素含有基板の表面を接触させて、金属金粒子を形成する工程、
前記金属金粒子で被覆された基板上に、ニッケル又はコバルトで本質的に構成された層を無電解法によって積層する工程、及び、
300℃超750℃未満の温度でラピッドサーマルアニールを施して、ケイ化ニッケル又はケイ化コバルトを形成する工程を含み、
前記水溶液は、少なくとも1つのアニオン性又はノニオン性極性基及び炭素数10〜16のアルキル鎖を有する化合物から選択される界面活性剤を含有することを特徴とする方法。 - 前記水溶液に前記ケイ素含有基板の表面を5秒間超5分間未満接触させることを特徴とする、請求項1に記載の方法。
- 前記フッ素イオンは、フッ化水素酸(HF)、NH4F又はそれらの混合物のうちの1つから得られることを特徴とする、請求項1又は2に記載の方法。
- 前記金イオンは、塩化金酸(HAuCl4)から得られることを特徴とする、請求項1〜3のいずれか1項に記載の方法。
- 前記水溶液は、金イオンを0.1mM〜10mM、好ましくは0.5mM〜1.0mM、フッ素イオンを0.6M〜3.0M、好ましくは1.0M〜2.0M含有することを特徴とする、請求項1〜4のいずれか1項に記載の方法。
- 前記アルキル鎖は、炭素数が10〜14であることを特徴とする、請求項1〜5のいずれか1項に記載の方法。
- 前記ニッケル又はコバルトで本質的に構成された層は、10nm超150nm未満、好ましくは10nm超60nm未満の均一な又はコンフォーマルな厚さを有することを特徴とする、請求項1〜6のいずれか1項に記載の方法。
- 前記ニッケル又はコバルトで本質的に構成された層は、ニッケル塩、ホウ素系還元剤、ニッケル用安定化剤及びポリアミンを含有する水溶液に活性化した前記基板表面を曝露することによって積層されたニッケル/ホウ素層であり、前記水溶液のpHは9超12未満であり、前記水溶液の温度は50℃超90℃未満であることを特徴とする、請求項1〜7のいずれか1項に記載の方法。
- 被覆対象である前記ケイ素基板は垂直中空構造を有しており、その開口径が20nm超100nm未満、その深さが500nm超3μm未満の大きさであることを特徴とする、請求項1〜8のいずれか1項に記載の方法。
- 前記ケイ素含有基板の表面において、ケイ素領域と、SiO2、Si3N4、SiC及びSiOCから選択される誘電体領域とが垂直方向に交互に配置されていることを特徴とする、請求項1〜9のいずれか1項に記載の方法。
- 前記サーマルアニール工程終了時までにケイ素中に移動しなかったニッケル又はコバルトを化学洗浄により除去できることを特徴とする、請求項1〜10のいずれか1項に記載の方法。
- 前記サーマルアニールの温度は350℃〜450℃であることを特徴とする、請求項1〜11のいずれか1項に記載の方法。
- 前記界面活性剤は、分子量が100g/mol超1500g/mol未満であることを特徴とする、請求項1〜12のいずれか1項に記載の方法。
- 前記界面活性剤はアニオン性極性基を有することを特徴とする、請求項1〜13のいずれか1項に記載の方法。
- 前記界面活性剤はドデシル硫酸ナトリウムであることを特徴とする、請求項13又は14に記載の方法。
- ケイ素基板上にニッケル又はコバルト層を形成する方法であって、
金イオンと、フッ素イオンと、少なくとも1つのアニオン性又はノニオン性極性基及び炭素数10〜16のアルキル鎖を有する化合物から選択される界面活性剤とを含有する水溶液にケイ素含有基板の表面を曝露する工程;及び、
活性化した前記基板上に、ニッケル又はコバルトで本質的に構成された厚さ10nm超150nm未満の層を無電解法によって積層する工程を含む方法。 - 請求項1〜15のいずれか1項に記載のケイ化ニッケル又はケイ化コバルトを形成する方法を含む、NANDメモリの製造方法。
- 請求項1〜15のいずれか1項に記載のケイ化ニッケル又はケイ化コバルトを形成する方法を含む、太陽電池の製造方法。
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