JP5057355B2 - 集積回路内での金属層の選択的形成 - Google Patents
集積回路内での金属層の選択的形成 Download PDFInfo
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- JP5057355B2 JP5057355B2 JP2005309116A JP2005309116A JP5057355B2 JP 5057355 B2 JP5057355 B2 JP 5057355B2 JP 2005309116 A JP2005309116 A JP 2005309116A JP 2005309116 A JP2005309116 A JP 2005309116A JP 5057355 B2 JP5057355 B2 JP 5057355B2
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- layer
- copper
- noble metal
- metal
- cvd
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- 229910052751 metal Inorganic materials 0.000 title description 69
- 239000002184 metal Substances 0.000 title description 69
- 230000015572 biosynthetic process Effects 0.000 title description 11
- 239000010949 copper Substances 0.000 claims description 186
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 116
- 229910052802 copper Inorganic materials 0.000 claims description 114
- 229910000510 noble metal Inorganic materials 0.000 claims description 112
- 238000005229 chemical vapour deposition Methods 0.000 claims description 52
- 238000000231 atomic layer deposition Methods 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 49
- 238000006467 substitution reaction Methods 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 28
- 238000000151 deposition Methods 0.000 claims description 28
- 239000012808 vapor phase Substances 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910052741 iridium Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000011810 insulating material Substances 0.000 claims description 5
- 239000010970 precious metal Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 224
- 239000007789 gas Substances 0.000 description 53
- 239000002243 precursor Substances 0.000 description 51
- 238000006243 chemical reaction Methods 0.000 description 48
- 230000004888 barrier function Effects 0.000 description 39
- 238000009792 diffusion process Methods 0.000 description 34
- 230000008569 process Effects 0.000 description 23
- 238000012545 processing Methods 0.000 description 23
- 239000000376 reactant Substances 0.000 description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 230000009977 dual effect Effects 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 239000012071 phase Substances 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 235000012431 wafers Nutrition 0.000 description 18
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 17
- 239000006227 byproduct Substances 0.000 description 17
- 239000012212 insulator Substances 0.000 description 17
- 239000000758 substrate Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 125000004429 atom Chemical group 0.000 description 15
- 239000011261 inert gas Substances 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 238000001465 metallisation Methods 0.000 description 14
- 230000008021 deposition Effects 0.000 description 13
- 239000010408 film Substances 0.000 description 12
- 239000010948 rhodium Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- 239000005751 Copper oxide Substances 0.000 description 9
- 229910000431 copper oxide Inorganic materials 0.000 description 9
- 239000003446 ligand Substances 0.000 description 9
- 238000010926 purge Methods 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- -1 ethylcyclopentadienyl Chemical group 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 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 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 238000011534 incubation Methods 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000003870 refractory metal Substances 0.000 description 3
- BPEVHDGLPIIAGH-UHFFFAOYSA-N ruthenium(3+) Chemical compound [Ru+3] BPEVHDGLPIIAGH-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000006557 surface reaction Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 2
- OXJUCLBTTSNHOF-UHFFFAOYSA-N 5-ethylcyclopenta-1,3-diene;ruthenium(2+) Chemical compound [Ru+2].CC[C-]1C=CC=C1.CC[C-]1C=CC=C1 OXJUCLBTTSNHOF-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- JAZCEXBNIYKZDI-UHFFFAOYSA-N [Ir+] Chemical compound [Ir+] JAZCEXBNIYKZDI-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- HUXQFHGMLXCFNA-UHFFFAOYSA-N cycloocta-1,5-diene;ruthenium(2+) Chemical compound [Ru+2].C1CC=CCCC=C1 HUXQFHGMLXCFNA-UHFFFAOYSA-N 0.000 description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- BUYVJWVYKPKZEX-DWVXZKBMSA-N (1z,5z)-cycloocta-1,5-diene;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\1C\C=C/CC\C=C/1 BUYVJWVYKPKZEX-DWVXZKBMSA-N 0.000 description 1
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- AZFHXIBNMPIGOD-UHFFFAOYSA-N 4-hydroxypent-3-en-2-one iridium Chemical compound [Ir].CC(O)=CC(C)=O.CC(O)=CC(C)=O.CC(O)=CC(C)=O AZFHXIBNMPIGOD-UHFFFAOYSA-N 0.000 description 1
- 241000579895 Chlorostilbon Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- VRPNNGZSPZMMKZ-UHFFFAOYSA-N [Rh+].C=C.C=C Chemical compound [Rh+].C=C.C=C VRPNNGZSPZMMKZ-UHFFFAOYSA-N 0.000 description 1
- 150000003869 acetamides Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- YHGGQZOFJGJAMR-UHFFFAOYSA-N cyclopenta-1,3-diene ruthenium Chemical compound C1=CC=CC1.C1=CC=CC1.[Ru] YHGGQZOFJGJAMR-UHFFFAOYSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 125000004989 dicarbonyl group Chemical group 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
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- 230000005593 dissociations Effects 0.000 description 1
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- 229910052876 emerald Inorganic materials 0.000 description 1
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
- 239000005383 fluoride glass Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
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- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000009666 routine test Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
Images
Classifications
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- 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
- C23C16/06—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 metallic material
- C23C16/18—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 metallic material from metallo-organic compounds
-
- 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]
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- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
- H01L21/28562—Selective deposition
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- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/32051—Deposition of metallic or metal-silicide layers
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- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
- H01L21/76814—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
- H01L21/76834—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers formation of thin insulating films on the sidewalls or on top of conductors
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
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Description
他の実施例において、信頼性強化層307及び328のような信頼性強化層がALDを使って選択的に形成される。ALDにより形成された信頼性強化層は、高融点金属、好ましくは貴金属、より好ましくはPt、Au、Ru、Rh、Ir及びPdの群から選択される貴金属から成る。ALD処理を使った貴金属層の形成は、ここに参考文献として組み込む2005年3月15日出願のHuotariらによる米国仮特許出願第60/662,144号に記載されている。ALD処理において、材料組成及び性質が異なる第1表面及び第2表面から成る基板が貴金属(貴金属前駆体)の気相化合物と接触する。第1面は所望の貴金属層を形成するためのALD処理に敏感であるが、第2面は同じALD処理に対して実質的に鈍感である。結果として、貴金属は第2面に比較して第1面上に選択的に蒸着される。図示された実施例において、第1面は特に銅のメタライゼーションであるが、第2表面は金属が陥凹または埋め込まれるところの絶縁体である。
基板の第1表面上に貴金属前駆体の層を形成するよう、貴金属化合物(貴金属前駆体)の気相化合物を反応チャンバ内にパルス供給する工程と、
余分な貴金属前駆体及び反応副産物を除去するべく反応チャンバをパージする工程と、
酸素、オゾン、アンモニアまたはアンモニアプラズマ含有ガスのような第2反応物質のパルスを第1及び第2表面上に与える工程と、
余分な第2反応物質及び、基板の第1表面上の貴金属前駆体層と第2反応物質との間の反応で形成されたあらゆる気体副産物を除去するべく、反応チャンバをパージする工程と、
所望の厚さの貴金属層が形成されるまで、パルス供給工程及びパージ工程を繰り返す工程と、
から成る。
本発明の好適実施例において、信頼性強化層307(図3)及び328(図8)のような信頼性強化層が化学気相成長(CVD)を使って選択的に形成される。CVDにより形成される信頼性強化層は、好ましくは高融点金属、より好ましくは貴金属、さらに好ましくはPt、Au、Ru、Rh、Ir及びPdの群から選択される貴金属から成る。CVDを使った信頼性強化層の選択的形成は、第1表面及び第2表面から成る基板を、貴金属の気相化合物(貴金属前駆体ガス)及び反応物質ガスと同時に接触させる工程を含む。第1表面は所望の貴金属層を形成するためのCVD型処理に敏感であるが、第2面は同じCVD処理に対して実質的に鈍感である。気相化合物の核生成速度が第2面と比べ第1面の方が実質的に大きいため、貴金属層は第1表面上には蒸着されるが第2表面には蒸着されない。例えば、第1表面が銅の上面であり、第2表面がSiO2ベースの絶縁層により形成されていれば、該表面を貴金属前駆体ガス及び反応物質ガスと同時に接触させることで、銅の露出した上面には貴金属が蒸着するが、絶縁層上へは蒸着されない。上記したように、貴金属のCVDにおいて、金属表面への蒸着の潜伏時間は絶縁体表面への蒸着の潜伏時間に比べ非常に短い。したがって、第2表面(典型的に絶縁体)上への貴金属蒸着の潜伏時間より短い時間中にCVDが実行されれば、貴金属は第1表面上に選択的に蒸着される。銅の導電性に影響を及ぼさず及び/または絶縁層の絶縁性を劣化させない程度の微小量の貴金属が絶縁層の表面上に蒸着しても問題はない。
(1,3-シクロヘキサジエン)Ru(CO)3+NH3→Ru+副産物
Ru(Cp)2+O2→Ru+副産物
Ru(EtCp)2+O2→Ru+副産物
Ru(McCp)(EtCp)+O2→Ru+副産物
本発明の好適実施例において、信頼性強化層310(図4及び5)及び325(図6及び7)のような信頼性強化層が金属置換反応を使って形成される。信頼性強化層は、好ましくは高融点金属、より好ましくは貴金属、さらに好ましくはPt、Au、Ru、Ir、及びPdから成る群から選択される貴金属から形成される。金属置換反応において、好適に銅などの金属により画成される第1表面及び絶縁体により画成される第2表面が貴金属の気相化合物と接触する。第1表面からの金属原子は貴金属原子により置換され、それにより第2表面と比較して第1表面上に貴金属層が蒸着される。この処理は第1表面を画成する金属(例えば、Cu)の気相化合物の生成と同時に起こる。
ここで、Mは金属化合物または複数の金属の化合物を表し、Lは配位子または複数の配位子を表し、銅の露出面上でのみ反応が起こる。CuLはCu置換反応で生成された配位子(L)から成る気相化合物である。置換反応は、Cu表面を貴金属の気相化合物と接触させることにより進行する。結果として、Cuの露出面はMで置換される。この置換反応は、Mがより高い標準電極ポテンシャルを有するか、Cuよりよりノーブルである場合に起こる。よって、MはCuほど簡単に拡散せず、Cu配線間またはCu配線表面に沿ったCuのマイグレーションが抑制される。M層は絶縁層と組み合わせてCuバリア層として作用する。
Cu/Cu+:E°=+0.52V
Pt/Pt2+:E°=+1.18V
Au/Au+:E°=+1.69V
MがCuより低い標準電極ポテンシャルを有すれば、反応は反対方向に生じやすくなる。
1)ビス(2,2,6,6-テトラメチル-3,5-ヘプタンジオネート)(1,5-シクロオクタジエン)ルテニウム(II)[(tmhd)2Ru(COD)]:
Cu+(tmhd)2Ru(COD)→Cu(tmhd)2↑+Ru+COD
2)ルテニウム(III)アセチルアセトネート[Ru(acac)3]:
3Cu+2Ru(acac)3→3Cu(acac)2↑+2Ru
3)トリス(2,2,6,6-テトラメチル-3,5-ヘプタンジオネート)ルテニウム(III)[Ru(tmhd)3]:
3Cu+2Ru(tmhd)3→3Cu(tmhd)2↑+2Ru
4)トリス(N,N’-ジイソプロピルアセトアミジネート)ルテニウム(III)[Ru(iPr-amd)3]:
3Cu+2Ru(iPr-amd)3→3Cu(iPr-amd)2↑+2Ru
5)ビス(N,N’-ジイソプロピルアセトアミジネート)ルテニウム(II)ジカルボニル[Ru(iPr-amd)2(CO)2]:
Cu+Ru(iPr-amd)2(CO)2→Cu(iPr-amd)2(CO)2↑+Ru
6)1,5-シクロオクタジエン(アセチルアセトネート)イリジウム(I)[(acac)Ir(COD)]:
Cu+2(acac)Ir(COD)→Cu(acac)2↑+2Ir+2COD
7)ジカルボニル(アセチルアセトネート)イリジウム(I)[(acac)Ir(CO)2]:
Cu+2(acac)Ir(CO2)→Cu(acac)2↑+2Ir+2CO
8)イリジウム(III)アセチルアセトネート[Ir(acac)3]:
3Cu+2Ir(acac)3→3Cu(acac)2↑+2Ir
9)白金(II)ヘキサフルオロアセチルアセトネート[Pt(hfac)2]:
Cu+Pt(hfac)2→Cu(hfac)2↑+Pt
10)パラジウム(II)ヘキサフルオロアセチルアセトネート[Pd(hfac)2]:
Cu+Pd(hfac)2→Cu(hfac)2↑+Pd
11)(アセチルアセトネート)ビス(シクロオクテン)ロジウム(I)[(acac)Rh(cyclooctene)]:
Cu+2(acac)Rh(cyclooctene)2→Cu(acac)2↑+2Rh+4cyclooctene
12)(アセチルアセトネート)ビス(エチレン)ロジウム(I)[(acac)Rh(CH2=CH2)2]:
Cu+2(acac)Rh(CH2=CH2)2→Cu(acac)2↑+2Rh+4CH2=CH2
13)アセチルアセトネート(1,5-シクロオクタジエン)ロジウム(I)[(acac)Rh(COD)]:
Cu+2(acac)Rh(COD)→Cu(acac)2↑+2Rh+2COD
14)ロジウム(III)アセチルアセトネート[Rh(acac)3]:
3Cu+2Rh(acac)3→3Cu(acac)2↑+2Rh
Claims (2)
- 集積回路中に導電層を選択的に形成するための方法であって、
銅から成る第1表面、及び絶縁材料から成る第2表面を与える工程と、
前記第1表面及び前記第2表面を貴金属の気相化合物と接触させ、それによって前記貴金属から成る導電層を前記第2表面と比較して前記第1表面上に選択的に形成するところの工程と、から成り、
前記導電層を選択的に形成する工程は、前記第1表面の原子を前記貴金属で置換する工程から成り、さらに、原子層蒸着(ALD)または化学気相成長(CVD)により、付加的貴金属を、置換により形成された前記貴金属上に選択的に蒸着する工程を含む、ところの方法。 - 請求項1に記載の方法であって、前記貴金属は、Pt、Au、Ru、Ir及びPdの群から選択される、ところの方法。
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US62214104P | 2004-10-26 | 2004-10-26 | |
US60/622,141 | 2004-10-26 | ||
US66214405P | 2005-03-15 | 2005-03-15 | |
US60/662,144 | 2005-03-15 |
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