TWI510667B - A composite substrate, a manufacturing method thereof, a functional element and a seed crystal substrate - Google Patents
A composite substrate, a manufacturing method thereof, a functional element and a seed crystal substrate Download PDFInfo
- Publication number
- TWI510667B TWI510667B TW103124879A TW103124879A TWI510667B TW I510667 B TWI510667 B TW I510667B TW 103124879 A TW103124879 A TW 103124879A TW 103124879 A TW103124879 A TW 103124879A TW I510667 B TWI510667 B TW I510667B
- Authority
- TW
- Taiwan
- Prior art keywords
- substrate
- nitride
- seed crystal
- tantalum
- producing
- Prior art date
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- 239000000758 substrate Substances 0.000 title claims description 191
- 239000013078 crystal Substances 0.000 title claims description 85
- 239000002131 composite material Substances 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 67
- 229910002601 GaN Inorganic materials 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 62
- 229910052715 tantalum Inorganic materials 0.000 claims description 38
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 38
- 239000010410 layer Substances 0.000 claims description 32
- 239000000919 ceramic Substances 0.000 claims description 31
- 229910052795 boron group element Inorganic materials 0.000 claims description 22
- 150000004767 nitrides Chemical class 0.000 claims description 22
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002346 layers by function Substances 0.000 claims description 8
- 239000012808 vapor phase Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 35
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 25
- 229910052707 ruthenium Inorganic materials 0.000 description 25
- 229910052732 germanium Inorganic materials 0.000 description 11
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 230000004907 flux Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 8
- 229910052733 gallium Inorganic materials 0.000 description 8
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052594 sapphire Inorganic materials 0.000 description 6
- 239000010980 sapphire Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910002704 AlGaN Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000006061 abrasive grain Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 229910003460 diamond Inorganic materials 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000007716 flux method Methods 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 235000005811 Viola adunca Nutrition 0.000 description 2
- 240000009038 Viola odorata Species 0.000 description 2
- 235000013487 Viola odorata Nutrition 0.000 description 2
- 235000002254 Viola papilionacea Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000000407 epitaxy Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910017083 AlN Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ALYHFNJJTGKTOG-UHFFFAOYSA-L [O-]OOO[O-].[Mg+2] Chemical compound [O-]OOO[O-].[Mg+2] ALYHFNJJTGKTOG-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 150000002259 gallium compounds Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 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
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B19/00—Liquid-phase epitaxial-layer growth
- C30B19/02—Liquid-phase epitaxial-layer growth using molten solvents, e.g. flux
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B19/00—Liquid-phase epitaxial-layer growth
- C30B19/12—Liquid-phase epitaxial-layer growth characterised by the substrate
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/403—AIII-nitrides
- C30B29/406—Gallium nitride
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/12—Salt solvents, e.g. flux growth
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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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02373—Group 14 semiconducting materials
- H01L21/02381—Silicon, silicon germanium, germanium
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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- H01L21/0237—Materials
- H01L21/02387—Group 13/15 materials
- H01L21/02389—Nitrides
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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- H01L21/02439—Materials
- H01L21/02441—Group 14 semiconducting materials
- H01L21/0245—Silicon, silicon germanium, germanium
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- 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
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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- H01L21/02439—Materials
- H01L21/02455—Group 13/15 materials
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- 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
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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- H01L21/02494—Structure
- H01L21/02496—Layer structure
- H01L21/02502—Layer structure consisting of two layers
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- 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
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02516—Crystal orientation
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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- H01L21/02623—Liquid deposition
- H01L21/02625—Liquid deposition using melted materials
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- H—ELECTRICITY
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- 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
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
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Description
本發明係關於13族元素氮化物複合基板的製作方法、以此方法製作的磊晶圓(Epi-Wafer)以及電子元件。
(助熔法)
根據液相法的一種之助熔法,可以得到位錯密度低的氮化鎵單結晶基板。助熔法產生的GaN(氮化鎵)單結晶生長,一般使用種結晶,以種結晶為起點生長GaN(氮化鎵)。生長用的基板在藍寶石基板上,使用晶圓(種結晶基板),以MOCVD(有機金屬化學氣相沉積)法或HVPE(混合氣相磊晶)法等的氣相法生長1~20微米左右的種結晶層(專利文件1)。
(MOCVD法)
取代習知的藍寶石基板,在矽基板上以有機金屬化學氣相沉積(MOCVD)法形成氮化物半導體膜,並形成功率元件構造或LED元件構造也盛行起來。矽基板具有可以取得大尺寸晶圓的優點。
(複合基板)
藍色LED(發光二極體)、藍紫色半導體雷射及功率半導體等的半導體元件的製作中,可以使用氮化鎵等的Ⅲ族氮化物構成的基板與底層基板貼合的複合基板(專利文件2)。
使用氮化鎵薄膜的功率元件或LED元件的話,在元件形成步驟後,根據提高散熱性的觀點,一般是研磨薄化矽基板或藍寶石基板,貼合更高熱傳導性的藍寶石或AlN(氮化鋁)多結晶基板等。
[先行技術文件]
[非專利文件]
[非專利文件1](根據MOCVD法的矽基板氮化鎵(GaN-on-Si)): “High power AlGaN/GaN HFET with a high breakdown voltage of over 1.8kV on 4 inch Si substrates and the suppression of current collapse(4吋矽基板上具有超過1.8kV (1800伏特)高貫穿電壓以及抑制崩潰電流之高功率AlGaN/GaN HFET)", Nariaki Ikeda, Syuusuke Kaya, Jiang Li, Yoshihiro Sato, Sadahiro Kato, Seikoh Yoshida, Proceedings of the 20th International Symposium on Power Semiconductor Devices & IC's(功率半導體元件和積體電路的第20次國際討論會會議記鎵)5月18-22,2008 Oralando, FL",第287-290頁。
[專利文件]
[專利文件1]WO2010/084675(國際專利2010/084675)
[專利文件2]日本專利第2012-124473號公開公報
使用矽基板時,尤其是功率元件用途,為了成為高耐壓元件,形成複雜疊層GaN、AlGaN、AlN等的多層膜構造,其上必須加厚形成GaN層(非專利文件1)。又,矽基板上以MOCVD法形成的GaN薄膜,難以降低位錯密度。
要以助熔(Flux)法得到大尺寸的晶圓的話,與其晶圓尺寸相同程度或以上尺寸的種結晶基板是必需的。與藍寶石基板相較,因為矽基板可以容易且廉價取得大尺寸晶圓,矽基板上可以以MOCVD法形成GaN薄膜作為種結晶基板的話,在工業上是有用的。不過,一般使用具有矽基板的種結晶基板的話,以助熔(Flux)法難以得到GaN單結晶。理由是,矽在用作助熔的鈉中容易溶解,又助熔中的矽濃度上升時,GaN結晶的生長速度極度下降,GaN結晶幾乎不生長。實際上,使用矽基板的種結晶基板應用於根據助熔(Flux)法產生的單結晶GaN培育時,矽基板完全熔化於助焊劑中,而且也看不到GaN單結晶的培育。又即使可以極力抑制矽的熔化,助焊劑中即使熔化少許矽,因為作為無意圖的不純物混入GaN結晶中,難以控制GaN單結晶的載子濃度是容易想像的。
本發明如下。
(1)複合基板的製造方法,特徵在於包括:薄層化步驟,將直接接合多結晶陶瓷基板與矽基板而成的複合基板之上述矽基板薄層化;成膜步驟,在上述矽基板上,以氣相法形成13族元素氮化物構成的種結晶膜;以及
培育步驟,在上述種結晶膜上以助熔法培育氮化鎵結晶層。
(2)以上述13族元素氮化物係氮化鎵為特徵之(1)的方法。
(3)上述多結晶陶瓷基板係以氧化鋁或氮化鋁構成之(1)或(2)的方法。
(4)以在上述薄層化步驟薄層化上述矽基板至0.2微米以上、8微米以下的厚度為特徵之(1)~(3)其中任一記載的方法。
(5)機能元件的製造方法,特徵在於包括:薄層化步驟,將直接接合多結晶陶瓷基板與矽基板而成的的複合基板之上述矽基板薄層化;成膜步驟,在上述矽基板上,以氣相法形成13族元素氮化物構成的種結晶膜;培育步驟,在上述結晶膜上以助熔法培育氮化鎵結晶層;以及在上述氮化鎵結晶層上以氣相法形成13族元素氮化物構成的機能層之步驟。
(6)以上述機能層具有發光機能為特徵之(5)的方法。
(7)以上述13族元素氮化物係氮化鎵為特徵之(5)或(6)的方法。
(8)上述多結晶陶瓷基板係以氧化鋁或氮化鋁構成(5)~(7)其中任一記載的方法。
(9)以在上述薄層化步驟薄層化上述矽基板至0.2微米以上、8微米以下的厚度為特徵之(5)~(8)其中任一記載的方法。
(10)種結晶基板的製造方法,特徵在於包括:薄層化步驟,將直接接合多結晶陶瓷基板與矽基板而成的
矽基板薄層化;以及成膜步驟,在上述矽基板上,以氣相法形成13族元素氮化物構成的種結晶膜。
(11)以上述13族元素氮化物係氮化鎵為特徵之(10)的方法。
(12)上述多結晶陶瓷基板係以氧化鋁或氮化鋁構成之(10)或(11)記載的方法。
(13)以上述矽基板是被薄層化至0.2微米以上、8微米以下的厚度的步驟為特徵之(10)~(12)其中任一記載的方法。
使用底層基板,對於矽基板,以直接接合氧化鋁或AlN的多結晶陶瓷基板貼合複合化的底層基板,最好是薄化加工此矽基板後,矽面上以氣相法(尤其是MOCVD)形成13族元素氮化物構成的種結晶膜。此基板作為種結晶基板,應用助熔法。因此,應用助熔法時,引起生長阻礙的矽不接觸助溶劑,GaN薄膜上可以製成結晶性良好的液相法加厚形成GaN之GaN模板基板(複合基板)。
又,由於矽基板與多結晶陶瓷基板的複合化,13族元素氮化物厚膜生長之際,具有可以抑制發生的應力引起彎曲或裂痕之優點。因此,為了以MOCVD法在矽基板上製作高耐壓功率元件,即使必須形成厚的GaN層的情況下,可以大幅簡化或不要複雜的多層應力緩和層,可以提高生產性。
根據上述,廉價且尺寸大的矽基板與多結晶陶瓷基板複合化的底層基板上,使用生長氮化鎵的種結晶基板,可以得到結晶性良好的GaN模板基板。結果,不使用通常使用
的高價單結晶SiC,提高LED或功率元件的性能,可以更提高散熱性。
又,矽基板與多結晶陶瓷基板複合化的底層基板的矽上,藉由設置種結晶膜,因為矽基板的兩方的主面以多結晶陶瓷與種結晶膜覆蓋,根據助熔法結晶培育時,可以抑制溶解液產生的矽基板的溶解。矽基板薄層化加工時,更提高防止溶解效果。
尤其是薄層化矽基板的情況下,不必覆蓋矽基板的側面,因為可以最小化矽基板對溶解液的接觸,可以降低製造成本。
1‧‧‧矽基板
1A‧‧‧薄層化的矽基板
1a‧‧‧主面
1b‧‧‧接合面
1c‧‧‧加工面
2‧‧‧多結晶陶瓷基板
3‧‧‧種結晶膜
4‧‧‧氮化鎵結晶層
5‧‧‧發光元件構造
7‧‧‧底層基板
7A‧‧‧側面
8‧‧‧種結晶基板
9‧‧‧複合基板
10‧‧‧機能元件
11‧‧‧側面
[第1圖]第1(a)圖係顯示多結晶陶瓷基板上形成矽基板1的狀態之模式圖,第1(b)圖係顯示底層基板7之模式圖,第1(c)圖係顯示種結晶基板8之模式圖。
[第2圖]第2(a)圖係顯示複合基板9之模式圖,第2(b)圖係顯示發光元件10之模式圖。
如第1(a)圖所示,對多結晶陶瓷基板2直接接合矽基板1。1b係矽基板對多結晶陶瓷基板的接合面,1a係露出的主面,11係露出的側面。其次,如第1(b)圖所示,薄層化加工矽基板1,形成薄層化的矽基板1A。1c係薄層化矽基板的加工面,7A係露出的側面。以此矽基板1A與多結晶陶瓷基板2形成底層基板7。
其次,如第1(c)圖所示,矽基板1A的加工面1c上形成種結晶膜3,得到種結晶板8。
其次,如第2(a)圖所示,在種結晶膜3上,以助熔法形成氮化鎵結晶層4,得到GaN(氮化鎵)模板基板(複合基板)9。其次,根據需要,在GaN模板基板9上,形成發光元件構造5,得到機能元件10(第2(b)圖)。
可以舉例說明氧化鋁、氮化鋁等,作為多結晶陶瓷基板2。
多結晶陶瓷基板與矽基板的接合方法,例如研磨兩方的基板,照射氬氣束,在真空中使研磨面之間接觸,施加負載,可以直接接合。
藉由薄層化加工矽基板,最好降低厚度至例如8微米以下。薄層化加工,最好是研磨加工。薄層化加工後的矽基板厚度,最好是8微米以下,但3微米以下更佳。藉由如此薄化矽基板,顯著抑制矽基板的側面溶解至溶解液。
又,根據薄層化加工的觀點,薄層化矽基板的厚度通常是0.2微米以上,最好是0.5微米以上。
即使不薄層化加工矽基板的情況下,當初與多結晶陶瓷基板接合的階梯矽基板也儘可能薄化,藉此可以抑制矽基板的側面對溶解液的接觸。在此情況下,矽基板的厚度也最好在30微米以下。
又,在矽基板上形成種結晶膜之際,也以種結晶膜覆蓋矽基板的側面,可以防止矽基板露出。
矽基板上,以氣相法設置13族元素氮化物構成的
種結晶膜。
種結晶膜,可以一層,或是在底層基板側包含緩衝層也可以。種結晶膜的形成方法可以以氣相生長法為一理想的範例,可以舉例說明有機金屬化學氣相沉積(MOCVD)法、混合氣相磊晶(HVPE)、脈衝激發堆積(PXD)法、MBE法、昇華法。尤其是MOCVD法最想理。
所謂13族元素,係根據IUPAC擬定的周期表之第13族元素,13族元素具體為鎵、鋁、銦、鉈等。又,添加劑,例如是碳元素、低融點金屬(錫、鉍、銀、金)、高融點金屬(鐵、錳、鈦、鉻等的遷移金屬)。有時添加低融點金屬作為防止鈉氧化為目的,而有時從放入坩鍋的容器或培育爐的加熱器等混入高融點金屬。又,13族元素氮化物最好是GaN、AlN、GaAlN、GaInN、AlInN、GaAlInN。
其次,種結晶膜上,以助熔法形成氮化鎵結晶層。此時,助熔劑的種類,只要可以產生氮化鎵結晶,不特別限定。適當的實施例中,使用包含鹼金屬與鹼土金屬中至少一方的助熔劑,尤其最好包含鈉的助熔劑。
助熔劑中,混合使用鎵原料物質。鎵原料物質,可以應用鎵單體、鎵合金、鎵化合物,但鎵單體在處理上也適合。
助熔法中的氮化鎵結晶的培育溫度或培育時的保持時間不特別限定,根據助熔劑的組成適當變更。一範例中,使用含有鈉或鋰的助熔劑培育氮化鎵結晶時,培育溫度最好為800~950℃,而溫度為850~900℃更佳。
助熔法中,在包含氮原子氣體的空氣下,培育單結晶。此氣體最好是氮氣,但也可以是氨。空氣的壓力不特別限定,但根據防止助熔劑蒸發的觀點來看,最好是10個大氣壓力以上,而30個大氣壓力以上更佳。但是,高壓的話,因為變成大型裝置,空氣的全壓最好是2000大氣壓力以下,而500大氣壓力以下更佳。不限定包含空氣中的氮原子氣體以外的氣體,但最好是非活性氣體,尤其氬氣、氦氣、氖氣更佳。
如此得到的複合基板上以氣相法形成機能層。複合基板上以氣相法,最好以MOCVD法製作半導體發光二極體(LED),因為LED內部的位錯密度變成與GaN模板基板的GaN單結晶幾乎相同密度,變得可以抑制高亮度化或衰減(DROOP)現象。
機能層的形成溫度,根據結晶品質的觀點來看,最好1000℃以上,而1050℃以上更佳。又,根據不使氮化鎵結晶層的結晶品質下降的觀點來看,機能層的形成溫度,最好1200℃以下,而1150℃以下更佳。
機能層的材質,最好是13族元素氮化物。所謂13族元素,係根據IUPAC擬定的周期表之第13族元素,13族元素具體為鎵、鋁、銦、鉈等。又,添加劑,例如是碳元素、遷移金屬(鐵、錳、鈦、鉻等的遷移金屬)。
發光元件的構造,例如包括,n型半導體層、在此n型半導體層上設置的發光區域、以及在此發光區域設置的p型半導體層。例如,在氮化鎵結晶層上,形成n型接觸層、n型包層、活性層、p型包層、p型接觸層,構成發光元件構造。
本發明係要求高品質的技術領域,可以用於例如高顯色性的高亮度白色LED或高速高密度光碟用藍紫雷射、混合動力車用的轉換器中使用的功率元件等。
[實施例]
(基板的複合化)
準備直徑4吋500微米厚的氮化鋁構成的多結晶陶瓷基板2,使用鑽石磨粒研磨以平坦化。研磨的表面以原子力顯微鏡(AFM)在10微米□的區域中觀察,測量表面粗細後,結果均方粗細為0.8奈米。
此研磨的氮化鋁構成的多結晶陶瓷基板2、以及研磨兩面的直徑4吋300微米厚的(111)面矽基板1放入真空室內,真空中,對於分別研磨的面,照射氬氣束3分鐘。之後,在真空室內接觸照射的面,在常溫下施加1噸的負載接合,成為複合晶圓。
複合晶圓7的矽面以鑽石磨粒研磨。矽的厚度研磨薄膜化至5微米厚,其次以切斜角步驟進行外周切面加工。以切斜角加工矽面從多結晶陶瓷基板的外周開始到0.5毫米內側為止施加漸細加工。矽面的研磨表面以AFM在10微米□的區域中觀察,測量表面粗細後,結果均方粗細為0.1奈米以下。
(種結晶基板製作)
對於底層基板7,以氫氟酸/純水=1/10(體積比)構成的組成之稀氟酸產生的稀氟酸洗淨,成為除去表面氧化膜的狀態,設定此為MOCVD裝置的反應器內基座。此時,為了在矽面上成膜,多結晶陶瓷基板2側接觸基座。其次,反應器內為氫.
氮混合空氣,基板溫度加熱至初期層形成溫度的1050℃為止。
反應器內壓力為10kPa(千帕斯卡),以既定流量比導入TMA(偏苯三酸酐)起泡氣體至反應器內,使NH3
與TMA反應,形成AlN膜100奈米的厚度。之後,使NH3
與TMA與TMG(三甲基鎵)反應,形成AlGaN膜40奈米的厚度。
其次,保持基板溫度,以TMG(三甲基鎵)與氨作為原料,使GaN膜3生長至3微米厚。之後,下降基板溫度至室溫,取出複合晶圓。
(助溶法)
此複合晶圓作為種結晶基板8以助溶法培育GaN(氮化鎵)結晶層4。生長使用的原料為鎵、鈉及鋰。為了接觸以MOCVD法形成的GaN膜,配置種結晶基板於氧化鋁坩鍋內。此坩鍋內分別裝填鎵30公克、鈉44公克、鋰30毫克,以爐內溫度900℃,壓力5MPa(百萬帕斯卡)約10小時培育GaN單結晶。從坩鍋取出種結晶基板8,結果基板表面上堆積GaN單結晶約100微米的厚度。
如此得到的複合基板的GaN單結晶之生長面,使用鑽石磨粒研磨平坦化,結果得到無裂痕透明直徑4吋的氮化鎵單結晶膜生長之複合基板9。
以CL(陰極發光)法計算暗斑(由於發光微弱比周圍看起來暗的點)作為在基板表面上出現的位錯,算出氮化鎵單結晶膜的位錯密度。根據CL法的測量,使用安裝陰極發光檢測器的日立高科技製「S-3400N Type Ⅱ(S-3400N第2型)」。結果,位錯密度為7×106
cm-2
(公分-2
)左右。
(發光元件的製作)
上述得到的直徑4吋氮化鎵單結晶的複合基板9上方形成發光元件構造5。
複合基板9再度放入MOCVD爐內,氫.氮混合空氣中上升基板溫度至1100℃為止,TMG(三甲基鎵)與氨為原料,矽甲烷為摻雜物,生長n型GaN膜至1微米厚。
其次下降溫度至750℃為止,形成3對InGaN/GaN量子井構造。其次,上升基板溫度至1050℃為止,TMG(三甲基鎵)與氨為原料,Cp2Mg(二茂鎂)為摻雜物,生長p型GaN膜至1微米厚。
(比較例1、2)
矽基板1,使用直徑4吋300微米厚的(111)面,但不執行薄層化研磨加工,矽基板1上維持原狀形成種結晶膜3(比較例1)。又,矽基板1,使用直徑4吋500微米厚的(111)面矽基板,但不使用多結晶陶瓷基板2,不實施基板的複合化(比較例2)。其他與上述的實施例相同,嘗試複合基板的製作。
結果,比較例1、2其中任一的情況下,以助溶法產生的GaN結晶培育步驟,矽基板1與種結晶膜3也消失。此原因被認為是矽基板1與種結晶膜3在助溶劑中溶解。因此,得到複合基板9。
1A‧‧‧薄層化的矽基板
1b‧‧‧接合面
1c‧‧‧加工面
2‧‧‧多結晶陶瓷基板
3‧‧‧種結晶膜
4‧‧‧氮化鎵結晶層
7A‧‧‧側面
9‧‧‧複合基板
Claims (13)
- 一種複合基板的製造方法,包括:薄層化步驟,將直接接合多結晶陶瓷基板與矽基板而成的複合基板之上述矽基板薄層化;成膜步驟,在上述矽基板上,以氣相法形成13族元素氮化物構成的種結晶膜;以及培育步驟,在上述種結晶膜上以助熔法培育氮化鎵結晶層。
- 如申請專利範圍第1項所述的複合基板的製造方法,其中上述13族元素氮化物係氮化鎵。
- 如申請專利範圍第1或2項所述的複合基板的製造方法,其中上述多結晶陶瓷基板係以氧化鋁或氮化鋁構成。
- 如申請專利範圍第1或2項所述的複合基板的製造方法,其中在上述薄層化步驟中,薄層化上述矽基板至0.2微米以上、8微米以下的厚度。
- 一種機能元件的製造方法,包括:薄層化步驟,將直接接合多結晶陶瓷基板與矽基板而成的複合基板之上述矽基板薄層化;成膜步驟,在上述矽基板上,以氣相法形成13族元素氮化物構成的種結晶膜;培育步驟,在上述種結晶膜上以助熔法培育氮化鎵結晶層;以及在上述氮化鎵結晶層上以氣相法形成13族元素氮化物構成的機能層之步驟。
- 如申請專利範圍第5項所述的機能元件的製造方法,其中 上述機能層具有發光機能。
- 如申請專利範圍第5或6項所述的機能元件的製造方法,其中上述13族元素氮化物係氮化鎵。
- 如申請專利範圍第5或6項所述的機能元件的製造方法,其中上述多結晶陶瓷基板係以氧化鋁或氮化鋁構成。
- 如申請專利範圍第5或6項所述的機能元件的製造方法,其中在上述薄層化步驟中,薄層化上述矽基板至0.2微米以上、8微米以下的厚度。
- 一種種結晶基板的製造方法,包括:薄層化步驟,將直接接合多結晶陶瓷基板與矽基板而成的複合基板之上述矽基板薄層化;以及成膜步驟,在上述矽基板上以氣相法形成13族元素氮化物構成的種結晶膜。
- 如申請專利範圍第10項所述的種結晶基板的製造方法,其中上述13族元素氮化物係氮化鎵。
- 如申請專利範圍第10或11項所述的種結晶基板的製造方法,其中上述多結晶陶瓷基板係以氧化鋁或氮化鋁構成。
- 如申請專利範圍第10或11項所述的種結晶基板的製造方法,其中上述矽基板是被薄層化至0.2微米以上、8微米以下的厚度。
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