JP2003512527A - 遷移金属炭化物の堆積 - Google Patents
遷移金属炭化物の堆積Info
- Publication number
- JP2003512527A JP2003512527A JP2001532259A JP2001532259A JP2003512527A JP 2003512527 A JP2003512527 A JP 2003512527A JP 2001532259 A JP2001532259 A JP 2001532259A JP 2001532259 A JP2001532259 A JP 2001532259A JP 2003512527 A JP2003512527 A JP 2003512527A
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- source gas
- substrate
- compound
- reaction space
- 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
Links
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 68
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 63
- 230000008021 deposition Effects 0.000 title description 24
- 239000000758 substrate Substances 0.000 claims abstract description 102
- 150000001875 compounds Chemical class 0.000 claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- 239000007789 gas Substances 0.000 claims abstract description 49
- 239000010409 thin film Substances 0.000 claims abstract description 36
- 238000000151 deposition Methods 0.000 claims abstract description 32
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 29
- 230000004888 barrier function Effects 0.000 claims abstract description 10
- 238000009792 diffusion process Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 97
- 230000008569 process Effects 0.000 claims description 33
- 239000006227 byproduct Substances 0.000 claims description 27
- -1 alkyl boron compound Chemical class 0.000 claims description 19
- 239000010410 layer Substances 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 229910052796 boron Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 claims description 6
- 239000012808 vapor phase Substances 0.000 claims description 6
- 150000001639 boron compounds Chemical class 0.000 claims description 5
- 150000004696 coordination complex Chemical class 0.000 claims description 5
- 229910001507 metal halide Inorganic materials 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001721 carbon Chemical group 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- 230000009977 dual effect Effects 0.000 claims description 3
- 150000005309 metal halides Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 239000011800 void material Substances 0.000 claims 2
- 150000001722 carbon compounds Chemical class 0.000 claims 1
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 239000004020 conductor Substances 0.000 claims 1
- 125000004437 phosphorous atom Chemical group 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000010926 purge Methods 0.000 description 26
- 239000000126 substance Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- 238000005137 deposition process Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000010408 film Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 238000006557 surface reaction Methods 0.000 description 7
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 239000002052 molecular layer Substances 0.000 description 6
- 239000010955 niobium Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 150000001247 metal acetylides Chemical class 0.000 description 5
- 150000003018 phosphorus compounds Chemical class 0.000 description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000009738 saturating Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 150000003623 transition metal compounds Chemical class 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000010923 batch production Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910003460 diamond Inorganic materials 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 229910003468 tantalcarbide Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 101100219325 Phaseolus vulgaris BA13 gene Proteins 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- PPWPWBNSKBDSPK-UHFFFAOYSA-N [B].[C] Chemical compound [B].[C] PPWPWBNSKBDSPK-UHFFFAOYSA-N 0.000 description 1
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001678 elastic recoil detection analysis Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
-
- 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
- C23C16/04—Coating on selected surface areas, e.g. using masks
- C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
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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
- C23C16/08—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 metal halides
-
- 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
- C23C16/08—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 metal halides
- C23C16/14—Deposition of only one other metal element
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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
- C23C16/22—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
- C23C16/32—Carbides
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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
- C23C16/22—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
- C23C16/34—Nitrides
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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
- C23C16/44—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
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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
- C23C16/44—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
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
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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
- C23C16/44—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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- 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
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Abstract
Description
々の基体上に遷移金属炭化物を形成するための連続自己飽和表面反応(sequenti
al self-saturating surface reactions)の使用に関する。
r、Mo、W)における遷移金属元素の炭化物は、いくつかの魅力的な特性を有
する。それらは、比較的不活性であり、非常に高い融点を有し、非常に硬くそし
て耐摩耗性(wear resistant)であり、そして高い熱伝導率および金属様電気伝
導率を有する。これらの理由のため、遷移金属炭化物は、半導体製造における低
抵抗拡散バリア(low resistance diffusion barriers)としての使用に提案さ
れている(例えば、国際特許出願WO 00/01006; 米国特許No.5,916,365を参照の
こと)。
Industrial Chemistry, 5th Edition, Vol. A5, VCH Verlagsgesellschaft, 198
6, pp.61-77、およびthe Kirk-Othmer Encyclopedia of Chemical Technology,
4th Edition , Vol. 4, John Wiley & Sons, Inc., 1992, pp. 841-878に見られ
得る。遷移金属炭化物は、広範な組成を有し得る。秩序化および無秩序化炭素不
足形態(ordered and disordered carbon deficient forms)が存在し、この例
は、炭化タングステンW3C、W2C、WCおよびWC1-xである。これらの形態
において、炭素は、金属原子間の格子間キャビティ(interstitial cavities)
に存在する。
長(MOCVD)および物理蒸着(PVD)が挙げられる。
イププロセスによって堆積されている。タングステンヘキサフルオリド、水素お
よび炭素含有ガスから炭化タングステンを堆積するCVD法は、例えば、国際特
許出願WO 00/47796に記載されている。炭素含有ガスは、最初に、熱的に活性化
される。ガス状ソース化学物質の全てが、同時に反応空間に存在し、基体におけ
る不揮発性炭化タングステンの堆積を生じさせる。トリメチルアミンおよびH2
とのWF6のCVD反応が、700℃〜800℃でWC膜をそして400℃〜6
00℃でベータ−WC1-x膜を生じることについて、開示されている(Nakajima
ら, J. Electrochem. Soc. 144:2096-2100 (1997))。H2流速は、炭化タングス
テンの堆積速度に影響を与える。開示されるプロセスに伴う1つの課題は、基体
温度が、特にメタリゼーション(metallization)段階における、当該技術水準
半導体製造のための熱経費に対してかなり高いことである。
れるか、または気相の他の有機化合物と結合されて、次いで基体と接触され、従
ってソース化学分子を分解しそして最終生成物を形成する。炭化タングステンは
また、低圧力でのW(CO)6の有機タングステン誘導体の熱分解によって基体
上に堆積された(Laiら, Chem. Mater. 7:2284-2292 (1995))。同様に、TiC
が、有機金属チタン化合物の熱分解によってCVDプロセスにおいて堆積された
(Girolamiら, Mater. Res. Soc. Symp. Proc. 121: 429-438 (1988))。米国特
許No. 5,916,365はまた、ペンタジメチル−アミノタンタルの熱分解を開示する
。これらのプロセスにおいて、ソース化学分子は、金属および炭素の両方を含む
。しかし、複雑で不規則な表面におけるその有用性は公知でない。
PVDによって拡散バリア層のための炭化タンタルを堆積させる1つの方法が、
米国特許No. 5,973,400に記載されている。炭化タンタル層が、N2/CH4/A
r雰囲気下でタンタルまたは炭化タンタルをスパッタリングすることによって形
成された。しかし、照準線堆積(line of sight deposition)は、複雑な基体輪郭
が、陰になった領域における不十分な薄膜カバレージ(coverage)を有すること
を意味する。さらに、照準線堆積は、ソースから基体へ直接到達する低揮発性ソ
ース材料は、それが出くわす最初の固体表面へ付着する傾向にあり、従って低コ
ンフォーマリティ(low-conformality)カバレージを生じることを意味する。
当該分野において存在する。
化物薄膜を堆積させるための方法が開示される。例示される実施形態において、
少なくとも1つの遷移金属ソース化合物および少なくとも1つの炭素ソース化合
物の気相パルス(vapor-phase pulses)が、基体を含む反応空間へ交互に供給さ
れる。
Cr、MoおよびWからなる群から選択される金属ソースガスを含む。例示的な
遷移金属ソースガスは、タングステンヘキサフルオリドのような金属ハロゲン化
物である。例示的な炭素ソース化合物は、ホウ素化合物、ケイ素化合物およびリ
ン化合物を含む。望ましくは、これらの例示的ソースガス化合物において、ホウ
素、ケイ素またはリンのいずれかが、炭素へ直接結合している。
品質層を堆積する場合に、特に有用である。例えば、金属炭化物薄膜は、有利に
は、集積回路トポグラフィー(topography)(例えば、デュアルダマシントレン
チおよびビア(dual damascene trenches and vias))にわたって伝導性かつコ
ンフォーマル(conformal)である薄い拡散バリア(diffusion barrier)を形成
し得る。
D”タイププロセスは、薄膜の基体上への堆積が、連続および交互自己飽和表面
反応(sequential and alternating self-saturating surface reactions)に基
づくプロセスを意味する。ALDの原理は、例えば、米国特許No. 4,058,430お
よび5,711,811において開示され、これらの開示は本明細書において参考として
援用される。
しいサブセットは、元素周期表の5族(チタン、ジルコニウムおよびハフニウム
)、6族(バナジウム、ニオブおよびタンタル)ならびに7族(クロム、モリブ
デンおよびタングステン)のものである。これらの元素の金属炭化物は、格子間
(interstitial)炭素を含み、そして純金属の特性のいくつかを有する。
リアクターまたは反応チャンバを意味するために使用される。
プロセス(chemical gaseous deposition process)によって調製される。好ま
しい化学ガス状堆積プロセスは、原子層堆積(ALD)タイププロセスである。
ALDの原理は、当業者に周知である。
空間に配置された基体上に成長される。従って、基体は、好ましくは、反応空間
中に配置され、そして少なくとも2つの気相反応物の連続交互反復表面反応(se
quential, alternately repeated surface reactions)へ供され、その結果、遷
移金属炭化物薄膜が基体上で成長する。好ましくは、反応空間における条件は、
気相反応、すなわちガス状反応物間の反応が起こらないように、調節される。好
ましいALDタイププロセスにおいて、金属ソース化合物および炭素ソース化合
物は、それらが反応空間において気相で同時に存在しないように、ガス状形態で
反応空間へ交互に供給される。従って、基体の表面上における化学吸着によって
吸着された化学種またはコンプレックスとガス状反応物との間の表面反応のみが
、許容される。反応は、好ましくは、自己飽和(self-saturating)および自己
制御式(self-limiting)である。
ース化合物の気相パルスは、交互にそして連続して、反応空間へ供給され、そし
て基体の表面と接触される。ソース化合物は、好ましくは、不活性または希キャ
リアガス(例えば、窒素またはアルゴン)の助けを借りて、反応空間へ供給され
る。基体の“表面”は、最初は、基体材料を含む。1つの実施形態において、基
体は、例えば、その表面特性を修飾するためにそれを化学物質と接触させること
によって、予め前処理されている。一旦遷移金属炭化物層が堆積されると、それ
は、任意の連続遷移金属炭化物層のための表面を形成する。
図2に記載される。堆積における各サイクルは、好ましくは、以下を含む: 遷移金属ソース化合物の気相パルスを、不活性キャリアガス中で反応空間へ供
給すること; 余分の遷移金属ソース化合物およびどのようなガス状副生成物も、反応空間か
ら除去すること(例えば、不活性ガスでパージすることによる); 炭素ソース化合物の気相パルスを、不活性キャリアガス中で反応空間へ供給す
ること;ならびに、 余分の炭素ソース化合物およびどのようなガス状副生成物も、反応空間から除
去すること(例えば、不活性ガスでパージすることによる)。
け反復され得る。パージング時間は、好ましくは、気相反応を防止し、そして1
サイクル当たり遷移金属炭化物の1格子定数より高い遷移金属炭化物薄膜成長速
度を防止するに十分な長さとなるように、選択される。
で行うことが好ましい。リアクター中の圧力は、好ましくは、約0.01mba
r〜50mbar、そしてより好ましくは約0.1mbar〜10mbarであ
る。基体温度は、好ましくは、ガス状反応物の熱分解を防止するに十分に低い。
他方、基体温度は、好ましくは、ソース材料の凝縮(condensation)、または物
理吸着(physisorption)を回避するに十分に高い。さらに、基体温度は、好ま
しくは、表面反応のための活性化エネルギーを提供するに十分に高い。基体の温
度は、好ましくは、約200℃〜600℃、そしてより好ましくは約250℃〜
400℃である。しかし、当業者は、最も好ましい基体温度および反応空間圧力
は、反応物および基体のアイデンティティー(identity)に依存することを認識
する。
える場合、遷移金属炭化物膜の制御された層ごと(layer-by-layer)の成長が失
われる。従って、好ましい実施形態において、ソース容器の温度は、好ましくは
、基体温度未満に設定される。
(chemisorbed)されて、表面結合遷移金属コンプレックス(surface bound tra
nsition metal complex)を形成する。化学吸着によって基体の表面へ結合され
る反応物の量は、表面自体によって決定される。反応物分子は、利用可能な結合
部位が表面上に残らなくなるまで、表面へ結合し、そして単層(monolayer)の
末端リガンド(terminating ligands)は、依然として気相中にある過剰なソー
ス化合物と非反応性となる。この現象は、“自己飽和(self-saturation)”と
して公知である。使用される反応物に依存して、反応物分子の物理的サイズは、
全ての結合部位が占められると、表面の完全なカバレージ(coverage)を防止し
得る。しかし、基体上の好ましいカバレージは、遷移金属ソースコンプレックス
の1以下の単層が1パルシングシークエンス当たり吸着される場合に、得られる
。従って、いくつかのサイクルが、遷移金属炭化物の完全な単層を生成するため
に必要であり得る。
ために利用可能な時間量は、主に経済的因子によって制限される。例えば、経済
的効率のために必要とされる基体スループット時間(throughtput time)は、自
己飽和反応に利用可能な時間に制限を課する。
ン、シリカ、被覆シリコン(coated silicon)、金属、金属窒化物、金属酸化物
、多孔性材料、炭化ケイ素および窒化ケイ素が挙げられる。上述のように、好ま
しい実施形態において、一旦遷移金属炭化物薄膜層が本発明によって堆積される
と、その層は、任意の連続層のための基体表面を形成する。
分な蒸気圧、熱安定性、および基体表面における化合物の十分な反応性について
の要求を満たすように、選択される。十分な蒸気圧は、表面での自己飽和反応を
可能にするに十分な気相のソース化合物分子が、基体表面付近に存在することを
意味する。十分な熱安定性は、ソース化学物質自体が基体上に成長妨害凝縮可能
相(growth-disturbing condensable phases)を形成しないか、または熱分解を
介して基体表面上に有害なレベルの不純物を残さないことを意味する。従って、
反応物は、好ましくは、基体上における原子または分子の制御されない凝縮を回
避するように選択される。
料が必要とされる。炭素ソース材料は、好ましくは、ホウ素ソース化合物、ケイ
素ソース化合物またはリンソース化合物である。しかし、1つの実施形態におい
て、プラズマが使用され、そして好ましい炭素ソース材料は炭化水素である。
化合物である。これらの遷移金属化合物は、好ましくは、W、Ti、Zr、Hf
、V、Nb、Ta、CrおよびMoからなる群から選択される遷移金属を含む。
より好ましくは、金属ソース化合物は、金属フッ化物および金属塩化物を含む金
属ハロゲン化物である。例示される好ましい実施形態において、金属ソース材料
は、タングステンヘキサフルオリドである。
温度未満の温度で揮発性であるホウ素化合物である。より好ましくは、ホウ素ソ
ース材料は、ホウ素ソース化合物分子中に少なくとも1つのホウ素−炭素結合を
有するホウ素化合物である。
数、好ましくは2、4または6である。
ニド(nido)−カルボラン(C2BnHn+4)、およびアラクノ(arachno)−カルボラ
ン(C2BnHn+6)を含む。
ルまたはHであり、そしてXは直鎖または分枝鎖のC1〜C10、好ましくはC
1〜C4アルキル、Hまたはハロゲンである。
キルまたは置換もしくは非置換のアリール基である。
2〜C4アルキルである、アルキルボロンまたはアルキルボラン。
ソース材料は、トリエチルボロン(CH3CH2)3Bである。
イ素化合物である。より好ましくは、ケイ素ソース材料は、ケイ素ソース化学分
子において少なくとも1つのケイ素−炭素結合を有する、ケイ素化合物である。
なおより好ましくは、ケイ素ソース材料は、アルキルケイ素化合物である。
化合物である。より好ましくは、リンソース材料は、リンソース化学分子におい
て少なくとも1つのリン−炭素結合を有する、リン化合物である。なおより好ま
しくは、リンソース材料は、アルキルリン化合物である。
て使用される。より好ましくは、直鎖または分枝鎖アルカンが、炭素ソース化学
物質として使用される。
、反応空間において、気相で存在しない。好ましくは、ソース化学物質は、交互
に、反応空間へ供給され、そして基体表面と接触され、従って基体上における金
属炭化物のALDタイプ成長を提供する。
しくはガス状であり、従って反応空間圧力を変化させることによっておよび/ま
たは不活性ガス流を用いて、容易に反応空間から除去され得る。好ましくは、炭
素ソース化合物は、金属炭化物膜中にいくらかの炭素を残し、そして基体表面か
らハロゲンを除く。
ていないが、炭素原子間の結合が、トリエチルボロン分子において、該分子がフ
ッ化タンングステン分子付近にあるときに破壊されると、いくらかのCH3Fが
副生成物として生成されると仮に想定される。また、トリエチルボロン分子にお
けるホウ素と炭素との間の結合が、該分子がフッ化タングステン分子付近にある
ときに破壊されると、いくらかのCH3CH2FおよびBF3が気相副生成物とし
て生成されると仮に想定される。しかし、本発明は、これらの仮の想定に限定さ
れない。
ることもまた可能である。本発明の薄膜の分析によって、炭化物薄膜における高
い金属−対−炭素比W3Cが明らかになった。これは、表面におけるタングステ
ンの部分的還元を示す。
おいて重要でなくなる(insignificant)まで、炭素ソース化合物と表面結合遷
移金属化合物との間の反応の副生成物を希釈する。
す。遷移金属ハロゲン化物が金属ソース化合物として使用される場合、ハロゲン
化物副生成物が、炭素ソース化合物との反応において形成され得る。例えば、ホ
ウ素炭素ソースが使用される場合、ハロゲン化ホウ素が、副生成物として形成さ
れ得る。表1における例は、得られるハロゲン化ホウ素は、好ましい基体温度(
例えば、350℃)で揮発性であり、そしてそれらは基体表面において凝縮しな
いことを示す。揮発性は、それらが上記のように反応空間から除去されることを
可能にする。
orr)であることを示す。しかし、約0.01〜0.1mbarまでの非常に
より低い蒸気圧が、ALDプロセスについて十分である。
い揮発性(表2)を有する。
い蒸気圧を有し、反応性有機ケイ素およびリン化合物を、金属炭化物堆積のため
の炭素ソースとして使用することを可能にすることを示す。
そしてトリエチルボロン(CH3CH2)3Bを、炭素ソースとして使用し、基体
上に遷移金属炭化物薄膜を生成した。
stry OYから市販される)の反応空間へ積み込んだ(loaded)。反応空間
を、メカニカル真空ポンプで排気した(evacuated)。排気後、反応空間の圧力
を、99.9999%の純度を有する流動窒素ガスを用いて、約5mbar〜1
0mbar(絶対(absolute))へ調節した。次いで、反応空間を、約350℃
で安定化させた。電気グレード(electronic grade)WF6および(CH3CH2
)3Bの交互パルスを、外部ソースから気化させて、反応空間へ導入し、そして
基体表面と接触させた。ソース化合物パルスを、流動窒素ガスでパージすること
によって互いに隔離させた。パルシングサイクルは、2つのソース化合物パルス
および2つの窒素パージから構成された。パルシングサイクルを、167回反復
した。
間は、以下の通りであった: WF6パルス 0.25s N2パージ 3.0s (CH3CH2)3Bパルス 0.5s N2パージ 3.0s。
。
き取った(unloaded)。薄膜は基体の全上部表面をカバーし、そしてそれは、金
属的光沢および灰色を有した。それは、ウエハーへの良好な付着を有し、そして
電気伝導性であった。薄膜サンプルを、元素についてTOF−ERDA(飛行時
間型弾性反跳粒子検出法(Time-Of-Flight Elastic Recoil Detection Analysis
))を用いて、薄膜厚みについてEDS(電子回折分光法(Electron Diffracti
on Spectroscopy))を用いて、そしてシート抵抗(sheet resistance)につい
て4点プローブ(four-point probe)を用いて分析した。抵抗率を、厚みおよび
シート抵抗値から計算した。
グステンおよび炭素から構成された。サンプルの厚みは約23nmであり、炭化
タングステン膜の成長速度は約1.4Å/サイクルであったことを示す。この値
は、炭化タングステンの格子定数未満であり、おそらくタングステンおよび炭素
原子が占めるよりも広い基体表面を占める前駆体の分子サイズに起因する。膜の
抵抗率は、200マイクロ−オーム−cmの範囲であった。膜は、不純物として
約1.0原子%〜1.5原子%のみのフッ素を有した。
応空間のガス雰囲気を好ましい圧力へ調節する。次いで、4つの基本工程からな
る反復可能なプロセスシークエンスを開始する。遷移金属ソース化合物の気相パ
ルスを、反応空間へ導入し、そして基体表面と接触させる。第1接触時間後、余
分の遷移金属ソース化合物およびどのような反応副生成物も、反応空間圧力を変
化させることによっておよび/または不活性ガス流によって、反応空間から除去
する。第1パージング時間後、炭素ソース化合物の気相パルスを、反応チャンバ
へ導入し、そして基体表面と接触させる。第2接触時間後、余分の炭素ソース化
合物およびどのような反応副生成物も、反応空間圧力を変化させることによって
および/または不活性ガス流によって、反応空間から除去する。第2パージング
時間後、プロセスシークエンスは、特定の厚みの金属炭化物薄膜が得られるまで
反復され得る。最後に、薄膜を有する基体を、反応チャンバから移す。
。
エッチ停止層(etch stop layers)3、ビア絶縁体4およびトレンチ絶縁体5を
有する基体を、ALDリアクターの反応空間に配置する。反応空間を、真空へ排
気し、そして反応空間の圧力を、不活性ガス(好ましくは、窒素)で好ましい圧
力へ調節する。好ましい圧力は、約1mbar〜50mbar、より好ましくは
約3mbar〜10mbarの範囲内である。次いで、反応空間の温度を、好ま
しいプロセス温度で安定させる。温度は、好ましくは、300℃〜425℃の範
囲内、より好ましくは約325℃〜375℃の範囲内であり、そして最も好まし
くは、約350℃に設定される。次いで、遷移金属炭化物層6を、以下のサイク
ルによって基体上に生成させる。
体と接触させる; 余分の遷移金属ソース化合物分子およびどのような副生成物分子も、第1パー
ジ時間の間、反応空間から除去する; 炭素ソース化合物を、反応空間へ導入し、そして第2パルス時間の間、基体と
接触させる; 余分の炭素ソース化合物分子およびどのような副生成物分子も、第2パージ時
間の間、反応空間から除去する。
Cr、MoおよびW化合物からなる群から選択される。金属ハロゲン化物化合物
が、より好ましい。炭素ソース化合物は、炭素を含む、ホウ素、ケイ素およびリ
ン化合物からなる群から選択される。アルキルホウ素、アルキルケイ素およびア
ルキルリン化合物が、より好ましい。
をポンピングラインへ入れることによって、余分の化合物および副生成物濃度を
微々たる(insignificant)レベルまで希釈する。
せる。パルシングサイクルの正確な数は、膜の所望の厚みおよび用途に依存する
。
金属シード(seed)層の堆積によって、さらに操作され得る。
提供することは、有益である。これは、それらを金属炭化物でコーティングする
ことによって達成され得る。本発明のALDタイププロセスは、サンプル形状に
感受性でないので、バッチプロセスが使用され得る。従って、コーティングされ
るパーツは、比較的小さくてもよい。バッチプロセスを使用する能力はまた、1
パーツ当たりのコーティングコストを顕著に減少させる。
応空間へ積み込む。反応空間を真空まで排気(evacuate)する。反応空間の圧力を
、不活性ガス(好ましくは、窒素)で好ましい圧力へ調節する。好ましい圧力は
、約1mbar〜50mbar、より好ましくは3mbar〜10mbarの範
囲内である。次いで、反応空間の温度を、好ましいプロセス温度で安定化させる
。温度は、好ましくは、約300℃〜425℃の範囲内、より好ましくは約32
5℃〜375℃の範囲内であり、そして例示される実施形態において、約350
℃に設定される。
能なプロセス工程から構成される: 遷移金属ソース化合物を、反応空間へ導入し、そして第1パルス時間の間、基
体と接触させる; 余分の遷移金属ソース化合物分子およびどのような副生成物分子も、第1パー
ジ時間の間、反応空間から除去する; 炭素ソース化合物を、反応空間へ導入し、そして第2パルス時間の間、基体と
接触させる; 余分の炭素ソース化合物分子およびどのような副生成物分子も、第2パージ時
間の間、反応空間から除去する。
Cr、MoおよびW化合物からなる群から選択される。金属ハロゲン化物化合物
が、より好ましい。炭素ソース化学物質は、炭素を含む、揮発性のホウ素、ケイ
素およびリン化合物からなる群から選択される。アルキルホウ素、アルキルケイ
素およびアルキルリン化合物が、より好ましい。
および副生成物分子をポンピングラインへ入れることによって、余分の化合物お
よび副生成物濃度を微々たるレベルまで希釈する。
せる。パルシングサイクルの正確な数は、膜の所望の厚みおよび用途に依存する
。
得る。金属炭化物薄膜は、本発明のALDタイププロセスによって基体上へ堆積
される。次いで、金属炭化物薄膜は、基体上でのダイアモンド薄膜のその後の堆
積のための開始層として使用され得る。
物薄膜からなる中間層を、本発明のALDタイププロセスによって生成する。炭
化ケイ素基体が提供される。基体表面は、第1のほとんどない(few)金属炭化
物分子層の核形成のために十分な反応性部位を有する。該プロセスの最も重要な
部分は、炭化ケイ素表面上におけるALDソース化学物質の第1分子層の吸着で
ある。堆積プロセスは、金属ソース化学物質または炭素ソース化学物質のいずれ
かで開始され得る。
の材料層の接着を改善し得る。金属炭化物薄膜は、上述の堆積プロセスに従って
生成される。
よって、より低い堆積温度の使用が可能となる。それはまた、ALDタイププロ
セスによる金属炭化物薄膜の堆積のためにラジカルの形態の有機化合物のフラグ
メントを使用することを可能にする。
力を、真空ポンプおよび流動不活性ガスを用いて、好ましい圧力へ設定する。反
応空間の温度を、好ましい温度へ設定し、そして堆積プロセスを開始する。
パージ工程を含む: 金属ソース化合物を、反応チャンバへ導入し、そして第1パルス時間の間、基
体と接触させる; 余分の金属ソース化合物分子およびどのような副生成物分子も、第1パージ時
間の間、反応空間から除去する; 炭素ソース化合物を、プラズマラジカルの形態で反応チャンバへ導入し、そし
て第2パルス時間の間、基体と接触させる; 余分の炭素ソース化合物分子およびどのような副生成物分子も、第2パージ時
間の間、反応空間から除去する。
クル当たり1分子層である。炭素ソース化合物は、好ましくは、炭素および水素
のみを含む有機化合物である。炭素ソース化合物は、好ましくは、UV放射、電
気アーク、RFジェネレーター、またはガス原子もしくは分子からプラズマを形
成し得る当該分野に公知の任意の他の方法を用いて、プラズマへ変換される。得
られるラジカルは、好ましくは、高い水素/炭素比を有し、従って、これらの化
学種の揮発性を改善し、そして基体上に低揮発性炭素富化コーティング(low-vo
latility carbon-rich coating)を得る可能性を減少させる。この実施形態はパ
ルスプラズマを使用するので、基体上の金属の制御されない堆積を回避するため
に、金属ソース化合物パルスの間、プラズマソースをスイッチオフするかまたは
リダイレクトする(redirect)ことが好ましい。
堆積プロセス後、基体は、反応空間から抜き取られる。
、基体ホルダーは、両端に焼結部(sinter)を含むある長さの容器からなる。基
体ホルダーは、反応空間中に水平に配置され得る。この配向において、基体ホル
ダーは、基体粉末で充填され、その結果、基体ホルダー内部にフリーのガス空間
がなくなる。この配向において、ソース化合物ガスおよびパージングガスは、好
ましくは、粉末を通過する。あるいは、基体ホルダーは、反応空間中に垂直に配
置され得る。この配向において、基体ホルダー内部に残されるいくらかのフリー
のガス空間が存在し得、その結果、基体粉末は、好ましくは下部焼結部から入り
そして上部焼結部へと出るガス流中に浮遊し得る。
る。しかし、この実施形態において、ソース化合物ガスは、好ましくは、粉末を
保持する容器へ向けられ、従って、ガスが粉末の粒子と接触することを確実にす
る。コーティングされる大きな表面積のために、パルスおよびパージ時間は、好
ましくは、非粉末基体について与えられる値と比較して延長される。
外部層によって利益を得ることができるパーツの例である。ベアリングのセット
を、穴あき(perforated)基体ホルダーへ積み込む。基体ホルダーにおけるホー
ルは、ホルダーの上部表面に円錐形開口部を有する。ベアリグは、これらの浅い
円錐体の下部にある。基体ホルダーを反応空間へ移し、それをソースガスおよび
不活性ガスラインへ接続する。反応空間を真空へ排気した。反応チャンバの圧力
を、流動不活性ガスで、好ましいプロセッシング圧力へ調節する。不活性ガスは
、基体ホルダーのホールを通って反応チャンバへ入り、そして円錐体の下部から
ベアリングを上げる。ベアリングは、好ましくは、流動窒素流中で自由に回転し
(ベルヌーイの法則)、そしてそれらは、堆積プロセスの間、いずれの固体表面
とも接触しない。反応空間の温度を、好ましい堆積温度へ調節する。
む: 金属ソース化合物を、反応空間へ導入し、そして第1パルス時間の間、基体と
接触させる; 余分の金属ソース化合物分子およびどのような副生成物分子も、第1パージ時
間の間、反応空間から除去する; 炭素ソース化合物を、反応空間へ導入し、そして第2パルス時間の間、基体と
接触させる; 余分の炭素ソース化合物分子およびどのような副生成物分子も、第2パージ時
間の間、反応空間から除去する。
直ガス流に保持されるベアリングと接触する。プロセスは、1パルシングサイク
ル当たり金属炭化物の1までの分子層を形成する。堆積プロセス後、ベアリング
が円錐体の下部へと戻るまで、窒素流を徐々に減少させる。基体ホルダーは、ロ
ードロック(load lock)を通してアンロードされてもよく、または反応チャン
バの圧力は、不活性ガスを用いて外部室内圧力へ増加されてもよく、そして基体
ホルダーは、ロードロックチャンバを使用することなくアンロードされる。
示す。
Claims (29)
- 【請求項1】 原子層堆積(ALD)プロセスによって遷移金属炭化物薄膜
を堆積する方法。 - 【請求項2】 気相パルスが、以下: 遷移金属ソースガスを、基体を含む反応空間へ導入すること; 過剰の遷移金属ソースガスおよびガス状反応副生成物を、該反応空間から除去
すること; 炭素ソースガスを該反応空間へ導入すること;ならびに、 過剰の炭素ソースガスおよびガス状反応副生成物を、該反応空間から除去する
こと、 を含むサイクルにおいて交互に導入される、請求項1に記載の方法。 - 【請求項3】 前記金属ソースガスが前記基体の表面と反応し、それによっ
て表面結合遷移金属コンプレックスを生成する、請求項2に記載の方法。 - 【請求項4】 前記表面結合遷移金属コンプレックスが、約1以下の単層を
形成する、請求項3に記載の方法。 - 【請求項5】 前記炭素ソースガスが前記表面結合遷移金属コンプレックス
と反応し、遷移金属炭化物を残す、請求項3に記載の方法。 - 【請求項6】 ガス状反応副生成物が、前記表面結合遷移金属コンプレック
スと前記炭素ソースガスとの反応によって形成される、請求項5に記載の方法。 - 【請求項7】 前記遷移金属ソースガスおよび炭素ソースガスが、各々、不
活性キャリアガスの助けを借りて前記反応空間へ供給される、請求項2に記載の
方法。 - 【請求項8】 遷移金属ソースガスおよび炭素ソースガスの各パルス後、前
記反応空間へ不活性ガスパルスを供給することをさらに含む、請求項2に記載の
方法。 - 【請求項9】 前記遷移金属ソースガスが、Ti、Zr、Hf、V、Nb、
Ta、Cr、MoおよびWからなる群から選択される金属を含む、請求項2に記
載の方法。 - 【請求項10】 前記遷移金属ソースガスが金属ハロゲン化物である、請求
項9に記載の方法。 - 【請求項11】 前記遷移金属ソースガスがタングステンヘキサフルオリド
である、請求項10に記載の方法。 - 【請求項12】 前記炭素ソースガスが、少なくとも1つのホウ素原子およ
び少なくとも1つの炭素原子を含むホウ素化合物を含む、請求項2に記載の方法
。 - 【請求項13】 前記ホウ素ソース化合物が、アルキルホウ素化合物である
、請求項12に記載の方法。 - 【請求項14】 前記ホウ素化合物がトリエチルボロンである、請求項13
の方法。 - 【請求項15】 前記炭素ソースガスが、少なくとも1つのケイ素原子およ
び少なくとも1つの炭素原子を含むケイ素化合物を含む、請求項2に記載の方法
。 - 【請求項16】 前記ケイ素ソース化合物がアルキルケイ素化合物である、
請求項15に記載の方法。 - 【請求項17】 前記炭素ソースガスが、少なくとも1つのリン原子および
少なくとも1つの炭素原子を含むリン化合物を含む、請求項2に記載の方法。 - 【請求項18】 前記リンソース化合物がアルキルリン化合物である、請求
項17に記載の方法。 - 【請求項19】 前記炭素ソースガスが炭化水素を含む、請求項2に記載の
方法。 - 【請求項20】 前記炭化水素が直鎖または分枝鎖アルカンである、請求項
19に記載の方法。 - 【請求項21】 前記炭素ソースガスが、炭化水素から形成されるプラズマ
において発生されるラジカルを含む、請求項19に記載の方法。 - 【請求項22】 遷移金属炭化物薄膜が、集積回路における伝導拡散バリア
(conductive diffusion barrier)を形成する、請求項1に記載の方法。 - 【請求項23】 前記伝導拡散バリアが、デュアルダマシンボイド(dual d
amascene void)におけるライナー(liner)を含む、請求項22に記載の方法。 - 【請求項24】 前記遷移金属炭化物薄膜が、基体上にハードコーティング
を形成して、機械的摩耗(mechanical wear)から保護する、請求項1に記載の
方法。 - 【請求項25】 前記遷移金属炭化物薄膜が腐食保護層を形成する、請求項
1に記載の方法。 - 【請求項26】 前記遷移金属炭化物薄膜が化学反応触媒を形成する、請求
項1に記載の方法。 - 【請求項27】 原子層堆積(ALD)プロセスによって集積回路における
エレクトロンコンダクタ(electron conductor)を製造する方法であって、ここ
で、複数のサイクルの各々が、基体上に吸着された金属コンプレックスを炭素化
合物へ曝すことを含み、該炭素化合物が、該吸着された金属コンプレックスと反
応して、金属炭化物の約1以下の単層を形成する、方法。 - 【請求項28】 前記金属ソースガスの少なくとも一部が、前記基体上で吸
着され、それによって前記吸着された金属コンプレックスを生成する、請求項2
7に記載の方法。 - 【請求項29】 前記金属コンプレックスが、Ti、Zr、Hf、V、Nb
、Ta、Cr、MoおよびWからなる群から選択される金属を含む、請求項27
に記載の方法。
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US15979999P | 1999-10-15 | 1999-10-15 | |
FI992234A FI117944B (fi) | 1999-10-15 | 1999-10-15 | Menetelmä siirtymämetallinitridiohutkalvojen kasvattamiseksi |
FI19992235 | 1999-10-15 | ||
FI992235A FI117943B (fi) | 1999-10-15 | 1999-10-15 | Menetelmä alkuaineohutkalvojen kasvattamiseksi |
FI19992234 | 1999-10-15 | ||
FI992233A FI118158B (sv) | 1999-10-15 | 1999-10-15 | Förfarande för modifiering av utgångsämneskemikalierna i en ALD-prosess |
FI19992233 | 1999-10-15 | ||
US60/159,799 | 1999-10-15 | ||
US17694800P | 2000-01-18 | 2000-01-18 | |
US60/176,948 | 2000-01-18 | ||
FI20000564 | 2000-03-10 | ||
FI20000564A FI119941B (fi) | 1999-10-15 | 2000-03-10 | Menetelmä nanolaminaattien valmistamiseksi |
PCT/US2000/028537 WO2001029280A1 (en) | 1999-10-15 | 2000-10-16 | Deposition of transition metal carbides |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Also Published As
Publication number | Publication date |
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US7485340B2 (en) | 2009-02-03 |
US20070190248A1 (en) | 2007-08-16 |
US20030031807A1 (en) | 2003-02-13 |
JP4965782B2 (ja) | 2012-07-04 |
US6482262B1 (en) | 2002-11-19 |
US6800552B2 (en) | 2004-10-05 |
US20020187256A1 (en) | 2002-12-12 |
US7144809B2 (en) | 2006-12-05 |
US6821889B2 (en) | 2004-11-23 |
US6475276B1 (en) | 2002-11-05 |
US20050064098A1 (en) | 2005-03-24 |
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