JP2004260168A - ナノラミネート膜の原子層堆積 - Google Patents
ナノラミネート膜の原子層堆積 Download PDFInfo
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- JP2004260168A JP2004260168A JP2004042166A JP2004042166A JP2004260168A JP 2004260168 A JP2004260168 A JP 2004260168A JP 2004042166 A JP2004042166 A JP 2004042166A JP 2004042166 A JP2004042166 A JP 2004042166A JP 2004260168 A JP2004260168 A JP 2004260168A
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- Prior art keywords
- metal
- precursor
- containing precursor
- oxide
- chamber
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Links
- 238000000231 atomic layer deposition Methods 0.000 title claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 250
- 238000000034 method Methods 0.000 claims abstract description 136
- 230000008569 process Effects 0.000 claims abstract description 83
- 238000000151 deposition Methods 0.000 claims abstract description 67
- -1 hafnium nitride Chemical class 0.000 claims abstract description 63
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 62
- 239000007800 oxidant agent Substances 0.000 claims abstract description 42
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 40
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 34
- 239000010703 silicon Substances 0.000 claims abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 32
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 20
- 239000003446 ligand Substances 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims description 138
- 239000002184 metal Substances 0.000 claims description 138
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 60
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 60
- 238000010926 purge Methods 0.000 claims description 59
- 239000000758 substrate Substances 0.000 claims description 43
- 229910044991 metal oxide Inorganic materials 0.000 claims description 33
- 150000004706 metal oxides Chemical class 0.000 claims description 33
- 150000004767 nitrides Chemical class 0.000 claims description 27
- 239000004065 semiconductor Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Chemical group 0.000 claims description 19
- 238000000137 annealing Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 150000004703 alkoxides Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims 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 claims description 5
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000005594 diketone group Chemical group 0.000 claims description 5
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229910001507 metal halide Inorganic materials 0.000 claims description 5
- 150000005309 metal halides Chemical class 0.000 claims description 5
- 229910052987 metal hydride Inorganic materials 0.000 claims description 5
- 150000004681 metal hydrides Chemical class 0.000 claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 239000010408 film Substances 0.000 abstract description 71
- 239000010409 thin film Substances 0.000 abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003990 capacitor Substances 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 33
- 230000008021 deposition Effects 0.000 description 29
- 239000010410 layer Substances 0.000 description 27
- 238000005229 chemical vapour deposition Methods 0.000 description 16
- 235000012239 silicon dioxide Nutrition 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 14
- 239000000376 reactant Substances 0.000 description 11
- 230000001590 oxidative effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003989 dielectric material Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000012384 transportation and delivery Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000006870 function Effects 0.000 description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000012705 liquid precursor Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 238000010574 gas phase reaction Methods 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- USPBSVTXIGCMKY-UHFFFAOYSA-N hafnium Chemical compound [Hf].[Hf] USPBSVTXIGCMKY-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Chemical group 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- TZNXTUDMYCRCAP-UHFFFAOYSA-N hafnium(4+);tetranitrate Chemical compound [Hf+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O TZNXTUDMYCRCAP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000000391 spectroscopic ellipsometry Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- H01L21/02104—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
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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
- C23C16/40—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]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
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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]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
-
- 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
- C23C16/56—After-treatment
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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
- H01L21/02104—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
- H01L21/02178—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 aluminium, e.g. Al2O3
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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
- H01L21/02104—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
- H01L21/02181—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 hafnium, e.g. HfO2
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- H—ELECTRICITY
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Abstract
【解決手段】 酸化物ナノラミネート薄膜を堆積する原子層堆積法が提供される。この方法は、第1のプリカーサのニトレート配位子を、第2のプリカーサのための酸化剤として用いて、酸化物ナノラミネートを形成する。窒化ハフニウムプリカーサおよびアルミニウムプリカーサを用いることによって、この方法は、水素終端処理されたシリコン表面上に、ゲート誘電体またはキャパシタ誘電体に用いるHigh−k酸化ハフニウム/酸化アルミニウムナノラミネート誘電体を堆積することによく適している。
【選択図】 図2
Description
金属酸化物ナノラミネート膜を形成する間、第1の窒化金属含有プリカーサを第2の金属含有プリカーサのための酸化剤として用いる方法が提供される。
酸化物ナノラミネート薄膜を堆積する原子層堆積法が提供される。この方法は、第1のプリカーサのニトレート配位子を、第2のプリカーサのための酸化剤として用いて、酸化物ナノラミネートを形成する。窒化ハフニウムプリカーサおよびアルミニウムプリカーサを用いることによって、この方法は、水素終端処理されたシリコン表面上に、ゲート誘電体またはキャパシタ誘電体に用いるHigh−k酸化ハフニウム/酸化アルミニウムナノラミネート誘電体を堆積することによく適している。
141 シリコン基板
142 フィールド酸化物
143 酸化ハフニウム層
143’ 他の酸化ハフニウム層
144 酸化アルミニウム層
144’ 他の酸化アルミニウム層
Claims (20)
- 酸化物ナノラミネート膜を形成する原子層堆積プロセスにおいて、第1の窒化金属含有プリカーサを第2の金属含有プリカーサのための酸化剤として用いる方法であって、
a.第1の窒化金属含有プリカーサを導入する工程と、
b.該第1の窒化金属含有プリカーサをパージする工程と、
c.第2の金属含有プリカーサを導入する工程と、
d.該第2の金属含有プリカーサをパージする工程と
を包含する、方法。 - 前記金属は、Cu、Zn、Y、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Co、Ni、Al、Ga、In、Ge、Sn、La、Ce、Nd、Sm、およびGdからなる群から選択される、請求項1に記載の方法。
- 前記第1の窒化金属含有プリカーサのニトレート配位子のうちの一部であって、全てではないニトレート配位子が、置換基Rと置換され、該置換基Rは、水素、酸素、オキシニトレート、ヒドロキシル、芳香族、アミン、アルキル、シリル、アルコキシド、ジケトンおよびこれらの混合物からなる群から選択される、請求項1に記載の方法。
- 前記第2の金属含有プリカーサは、酸素非含有プリカーサである、請求項1に記載の方法。
- 前記第2の金属含有プリカーサは、金属アルキル、ハロゲン化金属、金属ジケトネート、金属アルコキシド、金属水素化物、金属シリル、金属アミド、金属アセチルアセトネート、金属t−ブトキシド、金属エトキシド、ならびにこれらの混合物および組合せからなる群から選択される、請求項1に記載の方法。
- 酸化ハフニウム/金属酸化物ナノラミネート膜を形成する原子層堆積プロセスにおいて、窒化ハフニウム含有プリカーサを金属含有プリカーサのための酸化剤として用いる方法であって、
a.窒化ハフニウム含有プリカーサを導入する工程と、
b.該窒化ハフニウム含有プリカーサをパージする工程と、
c.金属含有プリカーサを導入する工程と、
d.該金属含有プリカーサをパージする工程と
を包含する、方法。 - 前記第1の窒化金属含有プリカーサのニトレート配位子のうちの一部であって、全てではないニトレート配位子が、置換基Rと置換され、該置換基Rは、水素、酸素、オキシニトレート、ヒドロキシル、芳香族、アミン、アルキル、シリル、アルコキシド、ジケトンおよびこれらの混合物からなる群から選択される、請求項6に記載の方法。
- 前記金属含有プリカーサは、酸素非含有プリカーサである、請求項6に記載の方法。
- 前記金属含有プリカーサは、金属アルキル、ハロゲン化金属、金属ジケトネート、金属アルコキシド、金属水素化物、金属シリル、金属アミド、金属アセチルアセトネート、金属t−ブトキシド、金属エトキシド、ならびにこれらの混合物および組合せからなる群から選択される、請求項6に記載の方法。
- 半導体基板上に酸化ハフニウム/酸化アルミニウムナノラミネート膜を形成する原子層堆積プロセスにおいて、窒化ハフニウムプリカーサをアルミニウム含有プリカーサのための酸化剤として用いる方法であって、
a.水素終端処理されたシリコン表面を原子層堆積チャンバ内の半導体基板上に提供する工程と、
b.窒化ハフニウムプリカーサを該チャンバに導入する工程と、
c.該チャンバをパージする工程と、
d.アルミニウム含有プリカーサを該チャンバに導入する工程と、
e.該チャンバをパージする工程と
を包含する、方法。 - 前記窒化ハフニウムプリカーサは、無水窒化ハフニウムプリカーサである、請求項10に記載の方法。
- 前記アルミニウム含有プリカーサは、ハロゲン化アルミニウムプリカーサである、請求項10に記載の方法。
- 前記アルミニウム含有プリカーサは、トリメチルアルミニウムおよびトリエチルアルミニウムからなる群から選択される有機金属プリカーサである、請求項10に記載の方法。
- 工程aの後、工程bの前に、200℃未満の温度まで前記基板を加熱する工程をさらに包含する、請求項10に記載の方法。
- 前記チャンバをパージする工程は、窒素または不活性ガスを該チャンバに流すことによって達成される、請求項10に記載の方法。
- 前記チャンバをパージする工程は、該チャンバから全てのガスを排出することによって達成される、請求項10に記載の方法。
- 所望の厚さが得られるまで前記工程b〜前記工程eが繰り返され、最後の工程は、工程bまたは工程cである、請求項10に記載の方法。
- 所望の厚さが得られるまで前記工程b〜前記工程eが繰り返され、最後の工程は、工程dまたは工程eである、請求項10に記載の方法。
- 前記所望の厚さが得られた後に、堆積後アニーリング工程をさらに包含する、請求項18に記載の方法。
- 前記堆積後アニーリングの時間は、10秒から5分の間の時間であり、該堆積後アニーリングの温度は、400〜1000℃の間の温度である、請求項19に記載の方法。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/376,794 US6930059B2 (en) | 2003-02-27 | 2003-02-27 | Method for depositing a nanolaminate film by atomic layer deposition |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2004260168A true JP2004260168A (ja) | 2004-09-16 |
JP4158975B2 JP4158975B2 (ja) | 2008-10-01 |
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KR100696765B1 (ko) * | 2005-11-17 | 2007-03-19 | 주식회사 하이닉스반도체 | 반도체소자의 유전체막 및 그 형성방법 |
JP2010538498A (ja) * | 2007-09-05 | 2010-12-09 | インターモレキュラー,インク. | 蒸気に基づく組合せ処理 |
JP2011520035A (ja) * | 2008-05-02 | 2011-07-14 | インターモレキュラー,インク. | 組合わせプラズマ励起堆積技術 |
JP2014116626A (ja) * | 2009-09-30 | 2014-06-26 | Hitachi Kokusai Electric Inc | 半導体装置の製造方法、基板処理方法および基板処理装置 |
JP2022091739A (ja) * | 2018-04-13 | 2022-06-21 | アプライド マテリアルズ インコーポレイテッド | 選択的原子層堆積方法 |
JP7290760B2 (ja) | 2018-04-13 | 2023-06-13 | アプライド マテリアルズ インコーポレイテッド | 選択的原子層堆積方法 |
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US7053009B2 (en) | 2006-05-30 |
TWI276700B (en) | 2007-03-21 |
KR20040077565A (ko) | 2004-09-04 |
US20050170667A1 (en) | 2005-08-04 |
US20040171280A1 (en) | 2004-09-02 |
US6930059B2 (en) | 2005-08-16 |
TW200424348A (en) | 2004-11-16 |
KR100591507B1 (ko) | 2006-06-19 |
JP4158975B2 (ja) | 2008-10-01 |
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