JP2020133002A - 反応チャンバーにおいて循環堆積プロセスにより基材上に酸化ハフニウムランタン膜を堆積させるための方法 - Google Patents
反応チャンバーにおいて循環堆積プロセスにより基材上に酸化ハフニウムランタン膜を堆積させるための方法 Download PDFInfo
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- JP2020133002A JP2020133002A JP2020023278A JP2020023278A JP2020133002A JP 2020133002 A JP2020133002 A JP 2020133002A JP 2020023278 A JP2020023278 A JP 2020023278A JP 2020023278 A JP2020023278 A JP 2020023278A JP 2020133002 A JP2020133002 A JP 2020133002A
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- hafnium
- film
- lanthanum
- precursor
- hafnium oxide
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- 239000000758 substrate Substances 0.000 title claims abstract description 151
- 238000000151 deposition Methods 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 105
- DBOSVWZVMLOAEU-UHFFFAOYSA-N [O-2].[Hf+4].[La+3] Chemical compound [O-2].[Hf+4].[La+3] DBOSVWZVMLOAEU-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 83
- 238000005137 deposition process Methods 0.000 title claims abstract description 62
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 98
- 230000008021 deposition Effects 0.000 claims abstract description 93
- 229910000449 hafnium oxide Inorganic materials 0.000 claims abstract description 73
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000002243 precursor Substances 0.000 claims description 206
- 125000004122 cyclic group Chemical group 0.000 claims description 67
- 239000007800 oxidant agent Substances 0.000 claims description 65
- 230000001590 oxidative effect Effects 0.000 claims description 59
- 230000008569 process Effects 0.000 claims description 49
- 229910052735 hafnium Inorganic materials 0.000 claims description 46
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 35
- 229910052746 lanthanum Inorganic materials 0.000 claims description 34
- 238000000231 atomic layer deposition Methods 0.000 claims description 32
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 23
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012808 vapor phase Substances 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001882 dioxygen Inorganic materials 0.000 claims description 10
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- -1 lanthanum cyclopentadienyl compound Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical group Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 150000002362 hafnium Chemical class 0.000 claims description 4
- FEEFWFYISQGDKK-UHFFFAOYSA-J hafnium(4+);tetrabromide Chemical compound Br[Hf](Br)(Br)Br FEEFWFYISQGDKK-UHFFFAOYSA-J 0.000 claims description 4
- JIGXARPLYFNBCG-UHFFFAOYSA-N C1(C=CC=C1)[Hf](N(C)C)(N(C)C)N(C)C Chemical compound C1(C=CC=C1)[Hf](N(C)C)(N(C)C)N(C)C JIGXARPLYFNBCG-UHFFFAOYSA-N 0.000 claims description 2
- DJXOAIAWZXGNDH-UHFFFAOYSA-N CC1(C=CC=C1)[Hf](COC)C1(C=CC=C1)C Chemical compound CC1(C=CC=C1)[Hf](COC)C1(C=CC=C1)C DJXOAIAWZXGNDH-UHFFFAOYSA-N 0.000 claims description 2
- VBCSQFQVDXIOJL-UHFFFAOYSA-N diethylazanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]CC.CC[N-]CC.CC[N-]CC.CC[N-]CC VBCSQFQVDXIOJL-UHFFFAOYSA-N 0.000 claims description 2
- ZYLGGWPMIDHSEZ-UHFFFAOYSA-N dimethylazanide;hafnium(4+) Chemical compound [Hf+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C ZYLGGWPMIDHSEZ-UHFFFAOYSA-N 0.000 claims description 2
- NPEOKFBCHNGLJD-UHFFFAOYSA-N ethyl(methyl)azanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C NPEOKFBCHNGLJD-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 170
- 239000012528 membrane Substances 0.000 description 29
- 238000010926 purge Methods 0.000 description 29
- 239000000376 reactant Substances 0.000 description 21
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 20
- 238000005229 chemical vapour deposition Methods 0.000 description 16
- 239000010410 layer Substances 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 14
- 239000002356 single layer Substances 0.000 description 14
- 239000003446 ligand Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000003989 dielectric material Substances 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 230000007423 decrease Effects 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 4
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000001451 molecular beam epitaxy Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 241001465382 Physalis alkekengi Species 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- YCJQNNVSZNFWAH-UHFFFAOYSA-J hafnium(4+);tetraiodide Chemical compound I[Hf](I)(I)I YCJQNNVSZNFWAH-UHFFFAOYSA-J 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910003855 HfAlO Inorganic materials 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000003877 atomic layer epitaxy Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000002188 cycloheptatrienyl group Chemical group C1(=CC=CC=CC1)* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- IWTIUUVUEKAHRM-UHFFFAOYSA-N germanium tin Chemical compound [Ge].[Sn] IWTIUUVUEKAHRM-UHFFFAOYSA-N 0.000 description 2
- IEUGECIXKSSZDX-UHFFFAOYSA-N hafnium(4+) lanthanum(3+) oxygen(2-) Chemical compound [O-2].[La+3].[O-2].[Hf+4] IEUGECIXKSSZDX-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BHWFVSOAOOHARF-UHFFFAOYSA-N C(C)(C)C1(C=CC=C1)[La](C1(C=CC=C1)C(C)C)C1(C=CC=C1)C(C)C Chemical compound C(C)(C)C1(C=CC=C1)[La](C1(C=CC=C1)C(C)C)C1(C=CC=C1)C(C)C BHWFVSOAOOHARF-UHFFFAOYSA-N 0.000 description 1
- MXVFWIHIMKGTFU-UHFFFAOYSA-N C1=CC=CC1[Hf] Chemical compound C1=CC=CC1[Hf] MXVFWIHIMKGTFU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910004129 HfSiO Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VZVQQBDFMNEUHK-UHFFFAOYSA-N [La].[Hf] Chemical compound [La].[Hf] VZVQQBDFMNEUHK-UHFFFAOYSA-N 0.000 description 1
- KAJBHOLJPAFYGK-UHFFFAOYSA-N [Sn].[Ge].[Si] Chemical compound [Sn].[Ge].[Si] KAJBHOLJPAFYGK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009739 binding Methods 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- ZDYNTRMQDURVDM-UHFFFAOYSA-N bis(trimethylsilyl)azanide;lanthanum(3+) Chemical compound [La+3].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C ZDYNTRMQDURVDM-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000004871 chemical beam epitaxy Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007740 vapor deposition Methods 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02194—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing more than one metal element
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
-
- C—CHEMISTRY; METALLURGY
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Abstract
Description
HfL1L2L3L4
式中、L1〜L4までのL配位子の各々は、
a)ハロゲン化物、例えば塩化物、臭化物、またはヨウ化物、
b)アルキルアミド、例えばジメチルアミド(‐NMe2)、ジエチルアミド(‐NEt2)、エチルメチルアミド(‐NEtMe)、
c)アミジネート、例えばN,N’‐ジメチルホルムアミジネート、
d)グアニジネート、例えばN,N’‐ジイソプロピル‐2‐エチルメチルアミドグアニジネート、
e)シクロペンタジエニルまたはそれらの誘導体、例えばシクロペンタジエニルもしくはメチルシクロペンタジエニルまたは他のアルキル置換シクロペンタジエニル配位子、
f)シクロヘプタジエニルまたはシクロヘプタトリエニル系、例えばシクロヘプタトリエニルまたはシクロヘプタジエニル
g)アルキル、例えばC1〜C5アルキル、例えばヘテロレプティック前駆体の場合はほとんどがメチル、
h)アルコキシド、例えばメトキシド(‐OMe)、エトキシド(‐OEt)、イソプロポキシド(‐OiPr)、n‐ブトキシド(‐OBu)またはtert‐ブトキシド(‐OtBu)
i)ベータジケトネート、例えば(2,2,6,6‐テトラメチル‐3,5‐ヘプタンジオナト)(thd)、および/または
j)ドナー官能化アルコキシド、例えばジメチルエタノールアミン、であるように独立して選択され得る。
Claims (29)
- 反応チャンバー内で循環堆積プロセスにより基材上に酸化ハフニウムランタン膜を堆積させるための方法であって、
前記循環堆積プロセスの第1のサブサイクルの少なくとも1回の堆積サイクルを利用して、前記基材上に酸化ハフニウム膜を堆積させることであって、前記第1のサブサイクルの1回の堆積サイクルが、
前記基材を、ハフニウム気相前駆体と接触させることと、
前記基材を水(H2O)を含む第1の酸化剤前駆体と接触させることと、を含む、堆積させることと、
前記循環堆積プロセスの第2のサブサイクルの少なくとも1回の堆積サイクルを利用して、前記基材上に酸化ランタン膜を堆積させることであって、前記第2のサブサイクルの1回の堆積サイクルが、
前記基材をランタン気相前駆体と接触させることと、
前記基材を、分子状酸素(O2)を含む第2の酸化剤前駆体と接触させることとを、含む、堆積させることと、を含む、方法。 - 前記ハフニウム気相前駆体が、ハロゲン化ハフニウム前駆体またはハフニウム有機金属前駆体のうちの少なくとも1つを含む、請求項1に記載の方法。
- 前記ハロゲン化ハフニウム前駆体が、四塩化ハフニウム(HfCl4)、四ヨウ化ハフニウム(HfI4)、または四臭化ハフニウム(HfBr4)のうちの少なくとも1つを含む、請求項2に記載の方法。
- 前記ハフニウム有機金属前駆体が、テトラキス(エチルメチルアミド)ハフニウム(Hf(NEtMe)4)、テトラキス(ジメチルアミド)ハフニウム(Hf(NMe2)4)、テトラキス(ジエチルアミド)ハフニウム(Hf(NEt2)4)、(トリス(ジメチルアミド)シクロペンタジエニルハフニウムHfCp(NMe2)3、またはビス(メチルシクロペンタジエニル)メトキシメチルハフニウム(MeCp)2Hf(CH)3(OCH3)のうちの少なくとも1つを含む、請求項2に記載の方法。
- 前記ランタン気相前駆体が、ランタンアミジネートまたはランタンシクロペンタジエニル化合物のうちの少なくとも1つを含む、請求項1に記載の方法。
- 前記基材上に前記酸化ハフニウム膜を堆積する前に、前記基材を100℃〜400℃の温度に加熱する、請求項1に記載の方法。
- 前記酸化ハフニウムランタン膜におけるランタン組成の均一性が、2原子%(1シグマ)未満である、請求項1に記載の方法。
- 前記酸化ハフニウムランタン膜が、10原子%未満のランタン組成を有する、請求項1に記載の方法。
- 前記酸化ハフニウムランタン膜が、1原子%以下のランタン組成を有する、請求項8に記載の方法。
- 前記酸化ハフニウムランタン膜が、20ナノメートル未満の厚さを有する、請求項1に記載の方法。
- 前記酸化ハフニウムランタン膜が、3ナノメートル〜10ナノメートルの厚さを有する、請求項10に記載の方法。
- 前記第2の酸化剤前駆体が、99.999%を超える純度を有する分子状酸素(O2)を含む、請求項1に記載の方法。
- 前記第1の酸化剤前駆体が、5MΩ・cmを超える電気抵抗率を有する水を含む、請求項1に記載の方法。
- 前記酸化ハフニウム膜が、3ナノメートル未満の厚さに堆積される、請求項1に記載の方法。
- 前記酸化ランタン膜が、3ナノメートル未満の厚さに堆積される、請求項1に記載の方法。
- 前記酸化ハフニウムランタン膜が、三級酸化ハフニウムランタン膜を含む、請求項1に記載の方法。
- 前記酸化ハフニウムランタン膜が、ナノラミネートを含む、請求項1に記載の方法。
- 前記循環堆積プロセスが、実行される第2のサブサイクルの数に対する実行される第1のサブサイクルの数の比を変えることを含み、スーパーサイクル当たりの、実行される第1のサブサイクルに対する実行される第2のサブサイクルの比率が、0.2未満である、請求項1に記載の方法。
- 前記循環堆積プロセスが、第1のサブサイクルに対する実行される第2のサブサイクルの比が0.1未満であることを含む、請求項18に記載の方法。
- 前記酸化ハフニウムランタン膜が、2原子%未満の炭素含有量を含む、請求項1に記載の方法。
- 前記酸化ハフニウムランタン膜の堆積に続いて、前記酸化ハフニウムランタン膜を熱アニールすることをさらに含む、請求項1に記載の方法。
- 前記酸化ハフニウムランタン膜が、800℃未満の温度で熱アニールされる、請求項21に記載の方法。
- 前記酸化ハフニウムランタン膜を熱アニールすることが、前記酸化ハフニウムランタン膜を少なくとも部分的に結晶化させることをさらに含む、請求項21に記載の方法。
- 前記酸化ハフニウムランタン膜が、約600℃未満の結晶化温度を有する1原子%以下のランタンの組成を含む、請求項23に記載の方法。
- 前記酸化ハフニウムランタン膜が、約450℃未満の結晶化温度を有する1原子%以下のランタンの組成を含む、請求項23に記載の方法。
- 前記少なくとも部分的に結晶化された酸化ハフニウムランタン膜が、主に斜方晶結晶構造を含む、請求項23に記載の方法。
- 前記第1のサブサイクルおよび前記第2のサブサイクルが、原子層堆積プロセスを含む、請求項1に記載の方法。
- 前記循環堆積プロセスが、1つ以上の繰り返されるスーパーサイクルを含み、各スーパーサイクルが、前記基材上に前記酸化ハフニウム膜を堆積することと、前記基材上に前記酸化ランタン膜を堆積することと、を含む、請求項1に記載の方法。
- 前記第2のサブサイクルが、単位スーパーサイクル内で、前記第1のサブサイクルの前に実行される、請求項28に記載の方法。
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TW202044345A (zh) | 2020-12-01 |
US20200266055A1 (en) | 2020-08-20 |
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