JP7411021B2 - レニウム含有薄膜の原子層堆積 - Google Patents
レニウム含有薄膜の原子層堆積 Download PDFInfo
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- JP7411021B2 JP7411021B2 JP2022099676A JP2022099676A JP7411021B2 JP 7411021 B2 JP7411021 B2 JP 7411021B2 JP 2022099676 A JP2022099676 A JP 2022099676A JP 2022099676 A JP2022099676 A JP 2022099676A JP 7411021 B2 JP7411021 B2 JP 7411021B2
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- rhenium
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- 229910052702 rhenium Inorganic materials 0.000 title claims description 302
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical group [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 title claims description 265
- 239000010409 thin film Substances 0.000 title claims description 93
- 238000000231 atomic layer deposition Methods 0.000 title claims description 56
- 239000000376 reactant Substances 0.000 claims description 174
- 239000010408 film Substances 0.000 claims description 170
- 238000000151 deposition Methods 0.000 claims description 154
- 239000002243 precursor Substances 0.000 claims description 145
- 239000000758 substrate Substances 0.000 claims description 138
- 230000008021 deposition Effects 0.000 claims description 137
- 238000000034 method Methods 0.000 claims description 104
- USBWXQYIYZPMMN-UHFFFAOYSA-N rhenium;heptasulfide Chemical compound [S-2].[S-2].[S-2].[S-2].[S-2].[S-2].[S-2].[Re].[Re] USBWXQYIYZPMMN-UHFFFAOYSA-N 0.000 claims description 69
- 239000000463 material Substances 0.000 claims description 60
- 239000007789 gas Substances 0.000 claims description 44
- -1 rhenium halide compound Chemical class 0.000 claims description 44
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 39
- 229910052717 sulfur Inorganic materials 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- 239000011593 sulfur Substances 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 32
- 229910052760 oxygen Inorganic materials 0.000 claims description 31
- 239000012071 phase Substances 0.000 claims description 31
- 239000012808 vapor phase Substances 0.000 claims description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 28
- 239000001301 oxygen Substances 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 150000002431 hydrogen Chemical class 0.000 claims description 18
- XZQYTGKSBZGQMO-UHFFFAOYSA-I rhenium pentachloride Chemical compound Cl[Re](Cl)(Cl)(Cl)Cl XZQYTGKSBZGQMO-UHFFFAOYSA-I 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229910019593 ReF6 Inorganic materials 0.000 claims description 4
- YUCDNKHFHNORTO-UHFFFAOYSA-H rhenium hexafluoride Chemical compound F[Re](F)(F)(F)(F)F YUCDNKHFHNORTO-UHFFFAOYSA-H 0.000 claims description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 76
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 37
- 238000010926 purge Methods 0.000 description 37
- 229910052751 metal Inorganic materials 0.000 description 29
- 239000002184 metal Substances 0.000 description 27
- 238000005229 chemical vapour deposition Methods 0.000 description 25
- 238000005137 deposition process Methods 0.000 description 24
- 239000012528 membrane Substances 0.000 description 23
- 239000000460 chlorine Substances 0.000 description 22
- 239000010410 layer Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- 239000002356 single layer Substances 0.000 description 21
- 229910052752 metalloid Inorganic materials 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 150000002738 metalloids Chemical class 0.000 description 18
- 241000894007 species Species 0.000 description 18
- 239000012535 impurity Substances 0.000 description 17
- 210000002381 plasma Anatomy 0.000 description 17
- 239000006227 byproduct Substances 0.000 description 14
- USWJSZNKYVUTIE-UHFFFAOYSA-N bis(sulfanylidene)rhenium Chemical compound S=[Re]=S USWJSZNKYVUTIE-UHFFFAOYSA-N 0.000 description 10
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 10
- 238000001341 grazing-angle X-ray diffraction Methods 0.000 description 10
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 8
- 229910052756 noble gas Inorganic materials 0.000 description 8
- 238000005019 vapor deposition process Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 5
- 150000003282 rhenium compounds Chemical class 0.000 description 5
- 229910003449 rhenium oxide Inorganic materials 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910052798 chalcogen Inorganic materials 0.000 description 4
- 150000001787 chalcogens Chemical class 0.000 description 4
- 238000001678 elastic recoil detection analysis Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000002052 molecular layer Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010574 gas phase reaction Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002835 noble gases Chemical class 0.000 description 3
- IZVAOCKUNBYXSU-UHFFFAOYSA-J rhenium;tetrafluoride Chemical group [F-].[F-].[F-].[F-].[Re] IZVAOCKUNBYXSU-UHFFFAOYSA-J 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006557 surface reaction Methods 0.000 description 3
- KXLQKNLVPVYVKX-UHFFFAOYSA-J tetrabromorhenium Chemical group Br[Re](Br)(Br)Br KXLQKNLVPVYVKX-UHFFFAOYSA-J 0.000 description 3
- KGKLLWHEYDUTBF-UHFFFAOYSA-J tetraiodorhenium Chemical group I[Re](I)(I)I KGKLLWHEYDUTBF-UHFFFAOYSA-J 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910019595 ReF 6 Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000003281 rhenium Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000000427 thin-film deposition Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 241000976924 Inca Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
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- 229910052594 sapphire Inorganic materials 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- 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
- C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
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- 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
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- 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
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- 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
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- 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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- 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
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- C23C16/305—Sulfides, selenides, or tellurides
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- 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
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- 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
- 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]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- 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
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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 System
- 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 System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
Description
本出願は、2016年12月2日に出願された米国特許出願第62/429,527号、2017年1月19日に出願された第62/448,211号、及び2017年6月7日に出願された第62/516,282号の優先権を主張し、これらの各々は参照により本明細書に組み込まれる。
上述のように、レニウム含有材料から形成される薄膜を、基材をレニウム反応物質及び第2の反応物質と接触させる蒸着プロセスにより堆積させることができる。いくつかの実施形態では、基材を、例えばALDプロセス又はパルスCVDプロセス等で、反応物質と逐次接触させる。反応物質及び反応条件は、金属性レニウム、酸化レニウム、窒化レニウム、硫化レニウム、及びそれらの混合物を堆積するように選択され得る。以下により詳細に説明するように、いくつかの実施形態では、金属性レニウム、窒化レニウム及びそれらの混合物を、レニウム前駆体及び窒素反応物質を用いて堆積させることができる。いくつかの実施形態では、硫化レニウム薄膜を、レニウム前駆体及び硫黄反応物質を用いて堆積させることができる。
工程20において、基材の表面を気化したレニウム前駆体と接触させて、基材上にレニウム含有種の最大で1単分子層を形成することと、
工程30において、過剰なレニウム前駆体及び反応副生成物がある場合には、これらを表面から除去することと、
第2の反応物質が基材の表面上のレニウム含有種と反応してレニウム含有物質を形成するように、工程40において、基材の表面を気化した第2の反応物質と接触させることと、
工程50において、レニウム種と第2の反応物質との間の反応において形成される過剰な第2の反応物質及び任意の気体副生成物を表面から除去することと、を含む。
本明細書に記載の蒸着プロセスは、レニウム、例えばReS2 2D材料等、を含む2D材料を堆積させるのに使用され得る。単層材料とも称される2D材料は、単一の連結された単分子層からなる材料である。2D材料は、単一の連結された単分子層を形成するが、本明細書に開示の堆積プロセスにより複数の単層を堆積し得る。例えば、2D ReS2の場合、2D材料は、Re原子の1つの層がS原子の2つの層の間に挟まれるように配置された、共有結合したReS2分子の単一層を含む。しかし、ReS2は、より厚い層を有する2D層としても機能することができる。したがって、上記のように、複数の単層を堆積させて2D材料を形成することができる。
いくつかの実施形態によれば、金属性レニウム薄膜は、基材を気相レニウム前駆体及び気相第2の反応物質と逐次的に接触させる1つ又は複数の堆積サイクルを含む蒸着プロセスにより基材の表面上に堆積される。いくつかの実施形態では、蒸着プロセスは、基材を2つ以上の気相反応物質と繰り返し接触させる周期的堆積プロセス、例えば、原子層堆積(ALD)プロセス、逐次化学蒸着(CVD)プロセス又はパルスCVDプロセス、である。いくつかの実施形態では、堆積サイクルを2回以上繰り返して、所望の厚さの金属性レニウム膜を形成する。
いくつかの実施形態では、二硫化レニウム薄膜等の硫化レニウム薄膜を、蒸着プロセスにより基材上に堆積させる。硫化レニウムは、二次元材料であってもよい。いくつかの実施形態では、蒸着プロセスは、基材を2つ以上の気相反応物質と繰り返し接触させる周期的堆積プロセス、例えば、原子層堆積(ALD)プロセス、又はCVDプロセス、例えば逐次化学蒸着(CVD)プロセス若しくはパルスCVDプロセス、である。
前駆体としてReCl5及びNH3を用いて金属性レニウムの堆積を実施した。ReCl5(99.9%Re、Strem)を、110℃で反応器内に保持されたオープンボートから昇華させ、不活性ガスバルブを用いて反応チャンバー内にパルス注入した。質量流量計及びニードルバルブを介して連続フローの間、H2S(99.5%、Linde)及びNH3(99.9999%、Linde)の流量を10sccmに設定した。全ての前駆体のパルス長はそれぞれ2秒であったが、パージはそれぞれ1~2秒であった。
前駆体としてReCl5及びH2Sを用いてALDにより硫化レニウムを堆積させた。図24は、150~500℃の堆積温度でSi基材上に成長させた膜から得られたGIXRDパターンを示す。200~500℃で成長させた膜は、三斜晶系のReS2(00-024-0922、未知の鉱物、syn [NR])として同定されることができたが、パターンには多数のピークが存在した。パターンの最高強度は14~15°近傍に現れ、ReS2(001)であるのに対して、その隣の300℃で現れる低強度ピークは、ReS2(100)である。200℃及び300℃で成長させた膜の32°近傍に現れる主ピークは、ReS2の(200)[32.113°]、(0-21)[32.364]、(-220)[32.766]、又は(-201)[32.915]のいずれかに属するであろう。150℃で成長させた膜は、パターンが測定される前にプラスチック袋の表面と反応したが、ほぼX線的非晶質であった。図25に見られるように、目に見える反応は膜の亀裂に関連している可能性がある。
Claims (20)
- 基材上に硫化レニウムを含む薄膜を堆積する方法であって、前記方法は、2つ以上の逐次堆積サイクルを含み、各堆積サイクルは、前記基材を、ハロゲン化レニウム化合物を含む気相レニウム前駆体及び気相硫黄反応物質と交互に逐次接触させることを含み、
前記方法は、原子層堆積(ALD)プロセスである、方法。 - 前記気相レニウム前駆体は、ReCl5又はReF6を含む、請求項1に記載の方法。
- 前記気相硫黄反応物質は、水素及び硫黄を含む、請求項1に記載の方法。
- 前記気相硫黄反応物質は、アルキル硫黄化合物を含む、請求項1に記載の方法。
- 前記気相硫黄反応物質は、硫黄元素を含む、請求項1に記載の方法。
- 前記気相硫黄反応物質は、式R-S-H(式中、Rは、置換又は非置換の炭化水素である)を有する、請求項1に記載の方法。
- Rは、C1~C8アルキル又は置換アルキルである、請求項6に記載の方法。
- 前記気相硫黄反応物質は、H2Sn(式中、nは4~10である)を含む、請求項1に記載の方法。
- 前記気相硫黄反応物質は、H2S、(CH3)2S、(NH4)2S、(CH3)2SO及びH2S2のうち1種以上を含む、請求項1に記載の方法。
- 前記気相硫黄反応物質は、(NH4)2Sを含む、請求項1に記載の方法。
- 前記堆積サイクルは、200~350℃の堆積温度で実施する、請求項1に記載の方法。
- 前記硫化レニウム薄膜は、ReS2を含む、請求項1に記載の方法。
- 前記硫化レニウム薄膜は、ReS2を含み、前記気相レニウム前駆体は、ReCl5を含み、前記気相硫黄反応物質は、H2Sを含む、請求項1に記載の方法。
- 前記硫化レニウム薄膜は、二次元材料を含む、請求項1に記載の方法。
- 前記硫化レニウム薄膜は、論理デバイス内の高移動度チャネル材料として機能する、請求項1に記載の方法。
- 前記堆積サイクルは、ReS2の20分子層以下を形成するために逐次繰り返される、請求項1に記載の方法。
- 前記硫化レニウム薄膜は、S:Reの元素比が0.5~3である、請求項1に記載の方法。
- 前記硫化レニウム薄膜は、90%を超えるステップカバレッジで三次元構造上に堆積される、請求項1に記載の方法。
- 前記硫化レニウム薄膜は、20at%未満の水素、2at%未満の炭素、及び20at%未満の酸素を含む、請求項1に記載の方法。
- 前記硫化レニウム薄膜は、10at%未満のClを含む、請求項1に記載の方法。
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JP2017231579A JP6953295B2 (ja) | 2016-12-02 | 2017-12-01 | レニウム含有薄膜の原子層堆積 |
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US11155917B2 (en) | 2021-10-26 |
US20200340114A1 (en) | 2020-10-29 |
KR102269681B1 (ko) | 2021-06-28 |
KR20210081315A (ko) | 2021-07-01 |
US20220002868A1 (en) | 2022-01-06 |
KR20230133251A (ko) | 2023-09-19 |
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