TWI435375B - Iii-v族氮化物半導體基板之製造方法 - Google Patents
Iii-v族氮化物半導體基板之製造方法 Download PDFInfo
- Publication number
- TWI435375B TWI435375B TW096107986A TW96107986A TWI435375B TW I435375 B TWI435375 B TW I435375B TW 096107986 A TW096107986 A TW 096107986A TW 96107986 A TW96107986 A TW 96107986A TW I435375 B TWI435375 B TW I435375B
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- Prior art keywords
- base substrate
- nitride semiconductor
- iii
- substrate
- inorganic particles
- Prior art date
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- 239000000758 substrate Substances 0.000 title claims description 183
- 150000004767 nitrides Chemical class 0.000 title claims description 84
- 239000004065 semiconductor Substances 0.000 title claims description 84
- 238000000034 method Methods 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000010954 inorganic particle Substances 0.000 claims description 49
- 239000002245 particle Substances 0.000 claims description 43
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 23
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 230000035882 stress Effects 0.000 claims description 10
- -1 borides Chemical class 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- 230000006355 external stress Effects 0.000 claims description 5
- 150000003346 selenoethers Chemical class 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001247 metal acetylides Chemical class 0.000 claims description 3
- 239000011800 void material Substances 0.000 claims description 3
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims 1
- 229910052594 sapphire Inorganic materials 0.000 description 55
- 239000010980 sapphire Substances 0.000 description 55
- 239000007789 gas Substances 0.000 description 22
- 239000002994 raw material Substances 0.000 description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 238000001312 dry etching Methods 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052738 indium Inorganic materials 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000012159 carrier gas Substances 0.000 description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 6
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 238000001947 vapour-phase growth Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 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
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 1
- OTRPZROOJRIMKW-UHFFFAOYSA-N triethylindigane Chemical compound CC[In](CC)CC OTRPZROOJRIMKW-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 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
- 239000012808 vapor phase Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/12—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a stress relaxation structure, e.g. buffer layer
-
- 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
- C30B29/38—Nitrides
-
- 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
-
- 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
-
- 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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Description
本發明係有關III-V族氮化物半導體基板之製造方法。
可以Inx
Gay
Alz
N(但是,0≦x≦1、0≦y≦1、0≦z≦1、x+y+z=1)表示的III-V族氮化物半導體,已應用於紫外、藍色或綠色發光二極體元件、或紫外、藍色或綠色雷射二極體元件等的半導體發光元件上。半導體發光元件可應用在顯示裝置上。
由於III-V族氮化物半導體不易塊狀(bulk)結晶成長,故尚未有商業化的III-V族氮化物半導體自立基板之製造方法。所以,利用以在藍寶石基板上的有機金屬氣相成長法(MOVPE)等,使III-V族氮化物半導體磊晶成長的方法,而製成III-V族氮化物半導體基板。
然而,因藍寶石基板與III-V族氮化物半導體的格子常數或熱膨脹係數不同,在使用藍寶石基板的方法時,所得之III-V族氮化物半導體基板中或是導入高密度的轉位、或是產生翹曲、而發生割裂現象。
另外,有提案將成長在如藍寶石基板的底基板上之III-V族氮化物半導體,從該底基板分離而製造III-V族氮化物半導體基板的方法。例如,有提案以混生(hybrid)氣相成長法(HVPE)使GaN層在藍寶石基板上成長,之後研磨藍寶石基板以機械性的去除方法、或在藍寶石基板上以HVPE使GaN層成長,之後經雷射胍衝(laser pulse)照射後,使GaN層剝離的方法。又,在日本特開2000-12900號公報中,揭示利用GaAs基板作為容易去除的基板,以HVPE使GaN在GaAs基板上成長,之後以王水將GaAs基板溶解去除的方法。同時,在日本特開2004-55799號公報中,係揭示將藍寶石基板凹凸加工後,在凸部的側面及上面形成SiO2
膜之後,使GaN成長,然後使其冷卻而剝離,即得III-V族氮化物半導體基板的方法。
然而,這些方法均未曾商業化,因而殷切要求製造III-V族氮化物半導體基板的方法。
本發明的目的是提供III-V族氮化物半導體基板的製造方法。本發明人等針對III-V族氮化物半導體基板的製造方法進行探討的結果,而完成本發明。
即本發明係提供包括步驟(I-1)至(I-6)的III-V族氮化物半導體基板之製造方法。
(I-1)在底基板上配置無機粒子、(I-2)以無機粒子作為蝕刻遮罩使底基板乾式蝕刻後,在底基板上形成凸部、(I-3)在底基板上形成磊晶成長遮罩用的被膜(用遮罩阻止磊晶成長)、(I-4)去除無機粒子以形成底基板的露出面、(I-5)使III-V族氮化物半導體在底基板的露出面上成長、(I-6)使III-V族氮化物半導體從底基板分離。
又本發明係提供包括步驟(II-1)至(II-7)的III-V族氮化物半導體基板之製造方法。
(II-1)在底基板上配置無機粒子、(II-2)以無機粒子作為蝕刻遮罩使底基板乾式蝕刻後,在底基板上形成凸部、(II-3)去除無機粒子、(II-4)在底基板上形成磊晶成長遮罩用的被膜、(II-5)去除凸部的頂部之被膜,以形成底基板的露出面、(II-6)使III-V族氮化物半導體在底基板的露出面上成長、(II-7)使III-V族氮化物半導體從底基板分離。
本發明的III-V族氮化物半導體基板之製造方法1,包括步驟(I-1)至(I-6)。
在步驟(I-1)中,係在底基板上配置無機粒子。例如,第1圖(a)中所示,準備底基板1後,將無機粒子2配置在底基板1之表面1A上。
底基板,例如,係由藍寶石、SiC、Si、MgAl2
O4
、LiTaO3
、ZrB2
、CrB2
形成,自與III-V族氮化物半導體的反應性、熱膨脹係數差、高溫安定性之觀點而言,係以藍寶石、SiC、Si為佳,更好是藍寶石。
無機粒子,例如,係由氧化物、氮化物、碳化物、硼化物、硫化物、硒化物、金屬形成。相對於無機粒子,這些的含量通常是在50重量%以上,以90重量%以上為佳,而以在95重量%以上更佳。至於氧化物,可舉例如:氧化矽、氧化鋁、氧化鋯、氧化鈦、氧化鈰、氧化鋅、氧化錫、釔鋁柘榴石(YAG)。至於氮化物,可舉例如氮化矽、氮化硼。至於碳化物,可舉例如碳化矽(SiC)、碳化硼、鑽石、石英、富烯倫(fullerene,碳60)類。至於硼化物,可舉例如硼化鋯(ZrB2
)、硼化鉻(CrB2
)。至於硫化物,可舉例如硫化鋅、硫化鎘、硫化鈣、硫化鍶。至於硒化物,可舉例如硒化鋅、硒化鎘。氧化物、氮化物、碳化物、硼化物、硫化物、硒化物,也可由其他的元素部份取代含在其中的元素,這些例可列舉如含有鈰或銪作為賦活劑的矽酸鹽或鋁酸鹽之螢光體。至於金屬,可舉例如矽(Si)、鎳(Ni)、鎢(W)、鉭(Ta)、鉻(Cr)、鈦(Ti)、鎂(Mg)、鈣(Ca)、鋁(Al)、金(Au)、銀(Ag)、鋅(Zn)。
要進行加熱處理時,無機粒子也可以是由前述之氧化物、氮化物、碳化物、硼化物、硫化物、硒化物、金屬所組成的材料,例如也可以為聚矽氧(silicone)。聚矽氧係具有以Si-O-Si的無機性結合為主架構,並在Si上具有機取代基結構的高分子,在約500℃中加熱處理後,即成為氧化矽。
無機粒子可以單獨使用,也可以使用這些的混合。並且,無機粒子也可以是例如以氧化物被覆由氮化物所形成的無機粒子之被覆粒子。其中,理想的無機粒子是氧化物,而以氧化矽更佳。
無機粒子的形狀可以是球狀(例如,剖面為圓形、楕圓形者)、板狀(長度L與厚度T的外觀比L/T為1.5至100者)、針狀(例如,寬度W與長度L之比L/W為1.5至100者)、或不定形(含各種形狀的粒子,整體而言是形狀不齊者),以球狀者為佳。所以,無機粒子是以球狀氧化矽為較佳。
無機粒子的平均粒徑通常為5nm至50 μm,以10nm至10 μm為佳。平均粒徑只要在5nm以上時,即有可能使後述的乾式蝕刻步驟長時間的進行,而容易使底基板深入蝕刻。平均粒徑只要在50 μm以下時,將因使後述的III-V族氮化物半導體之成長步驟中的凸部間隔變近,而容易使個別成為合體而成長。在上述平均粒徑的範圍內,也可混合使用粒徑不同的無機粒子。平均粒徑係由離心沉澱法而測定的體積平均粒徑。平均粒徑雖然可用離心沉澱法以外的測定法,例如,雖可以藉由動態光散亂法、柯爾塔計數器(Coulter counter)、雷射繞射法、電子顯微鏡測定,但此時的校正是只要換算成以離心沉澱法測定的體積平均粒徑即可。例如,以離心沉澱法及其他的粒度測定法求得作為標準粒子的平均粒徑,並計算出這些的相關係數。對於複種粒徑相異的標準粒子,相關係數是以相對於離心沉澱法所測得的體積平均粒徑之計算出相關係數,作成校正曲線而求得者為佳。只要使用校正曲線,即以離心沉澱法之外的測定法所得之平均粒徑求得體積平均粒徑。
配置是以例如將底基板浸漬在含有無機粒子與媒體的漿液中的方法,或將漿液塗布或噴鍍在底基板上後再乾燥的方法進行即可。
媒體,例如為水、甲醇、乙醇、異丙醇、正丁醇、乙二醇、二甲基乙醯胺、甲基乙基酮、甲基異丁酮,並以水較佳。
塗布是利用旋轉塗布來進行為佳。藉由此方法,可使無機粒子均勻的密度配置在底基板上。乾燥只要使用旋轉離心塗布器(spinner)進行即可。
相對於無機粒子之底基板的被覆率,通常為1%至95%,以30%至95%為佳,以50%至95%更佳。只要在1%以上,即可以在後步驟中,輕易地將III-V族氮化物半導體層從底基板剝離。配置在底基板上的無機粒子,雖亦可為幾層的結構,但是以單粒子結構者的一層結構為佳。被覆率只要利用掃描型電子顯微鏡(SEM)即可求得,例如在第1圖(a)中,在從上方觀察配置有無機粒子2的底基板1之表面1A時,即可由測定視野內(面積S)中的粒子數P與粒子的平均粒徑d,依下式而求得。
被覆率(%)=((d/2)2
×π.P.100)/S
在步驟(I-2)中,係以無機粒子作為蝕刻遮罩而使底基板乾式蝕刻後,即在底基板上形成凸部。例如,如第1圖(b)中所示,以無機粒子2作為遮罩藉由底基板1之乾式蝕刻後,即在底基板1上形成對應於無機粒子2的凸部1B。
乾式蝕刻也可使用例如ECR乾式蝕刻裝置、ICP乾式蝕刻裝置來進行。乾式蝕刻通常是以使凸部的高度成為10nm至5 μm,較好的在30nm至3 μm之條件下進行。
在步驟(I-3)中,是於底基板上形成磊晶成長遮罩用的被膜。例如,如第1圖(c)所示,在底基板1上形成磊晶成長遮罩用的被膜3後,使凸部1B之間的谷部之表面、無機粒子2的露出面以被膜3所覆蓋。
被膜只要是由可抑制III-V族氮化物半導體的磊晶成長之材料所形成者即可,例如由二氧化矽(SiO2
)、氮化矽(SiNx
)形成。
形成,只要是由例如CVD、蒸鍍法,覆蓋底基板的條件下來進行即可。
(I-4)係去除無機粒子以形成底基板的露出面。例如,如第1圖(d)中所示,在去除無機粒子2後,使底基板1的凸部1B之各頂部露出,或由在凸部1B之間形成的各谷部1C之表面上有被膜3的殘留,而形成成長遮罩4。
去除,只要是利用如刷滾(brush roll)洗淨機、研磨機以物理方法進行即可。又,在可選擇無機粒子與被膜的蝕刻時,也可以由濕式蝕刻進行去除。
(I-5)係使III-V族氮化物半導體在底基板的露出面上形成磊晶成長。例如,如第1圖(d)及(e)所示,在未被成長遮罩4覆蓋之凸部1B之各頂部1Ba,將成長的各III-V族氮化物半導體合體後而形成III-V族氮化物半導體層5。
III-V族氮化物半導體層通常是以Inx
Gay
Alz
N(但是,0≦x≦1、0≦y≦1、0≦z≦1、x+y+z=1)表示。
磊晶成長,例如藉由應用有機金屬氣相成長法(MOVPE)、混生氣相成長法(HVPE)、分子線磊晶法(MBE)來進行即可。
在MOVPE中,只要使用以下的原料即可。至於III族原料,可舉例如三甲基鎵[(CH3
)3
Ga,以下稱“TMG”]、三乙基鎵[(C2
H5
)3
Ga,以下稱“TEG”]等可以式R1
R2
R3
Ga(R1
、R2
、R3
表示低級烷基)表示的三烷基鎵;如三甲基鋁[(CH3
)3
Al,以下稱“TMA”]、三乙基鋁[(C2
H5
)3
Al,以下稱“TEA”]、三異丁基鋁[(i-C4
H9
)3
Al]等以式R1
R2
R3
Ga(R1
、R2
、R3
表示低級烷基)表示的三烷基鋁;三甲基胺明礬(trimethylaminealum)[(CH3
)3
N:AlH3
];三甲基銦[(CH3
)3
In,以下稱“TMI”]、三乙基銦[(C2
H5
)3
In,以下稱”TMI”]等以式R1
R2
R3
In(R1
、R2
、R3
表示低級烷基)表示的三烷基銦、如二乙基氯化銦[(C2
H5
)3
InCl]等使三烷基銦中的一或二個烷基為鹵原子所取代者、如氯化銦[InCl]等以式InX(X為鹵原子)表示的鹵化銦。這些化合物可以單獨或也可以混合使用。在這些III族原料中,鎵源是以TMG為佳、鋁源是以TMA、銦源是以TMI為佳。至於V族原料,可舉例如氨、肼聯胺、甲基肼聯胺、1,1-二甲基肼聯胺、1,2-二甲基肼聯胺、第三-丁基胺、乙二胺等。這些化合物可以單獨或亦可以任意的組合混合使用。在這些原料之中,因氨與肼聯胺的分子中不含碳原子,故在半導體中的碳污染少而較適用,自容易取得高純度物品的觀點,以氨為理想。在MOVPE中,只要使用氮、氫、氬、氦為成長時的環境氣體及有機金屬原料的載體氣體即可,以氫、氦為佳。這些氣體可以單獨或可以混合使用。在MOVPE中,通常是將原料氣體導入反應爐後,使III-V族氮化物半導體層成長在形成成長遮罩的底基板上。反應爐備有可從原料供應裝置將原料氣體供應至反應爐中的原料供應管道,在反應爐內為了能使基板加熱而設有感受器(susceptor)。感受器通常是形成以旋轉器使其旋轉的結構,可使氮化物半導體層均勻的成長。在感受器的內部,備有為了加熱感受器的紅外線燈等的加熱裝置。藉由此加熱,可使通過原料供應管道而供應到反應爐中的原料氣體在成長基板上熱分解後,即可使所求的化合物在基板上氣相成長。供應到反應爐內的原料氣體之中有未反應的原料氣體,可經由排氣管道而排放到反應爐外部,並送至廢氣處理設備中。
在HVPE中,可使用以下的原料就可以。至於III族原料,可舉例如使鎵金屬與氯化氫氣體於高溫中反應而生成的氯化鎵,或使銦金屬與氯化氫氣體於高溫中反應而生成的氯化鎵氣體或銦金屬與氯化氫氣體在高溫中反應而生成氯化銦氣體。至於V族原料,可舉例如氨。至於載體氣體,可舉例如氮、氫、氬、氦,並以氫、氦為佳。這些氣體可以單獨或混合使用。在HVPE中,只要將這些原料氣體導入反應爐後,使III-V族氮化物半導體層在底基板上形成到預定的厚度即可。
另外,在MBE中,使用以下的原料就可以。至於III族原料,可舉例如鎵、鋁、銦的金屬。至於V族原料,可舉例如氮、氨。MBE也是只要將這些原料氣體導入反應爐後,使III-V族氮化物半導體層在底基板上成長即可。
在磊晶成長中,是在底基板與III-V族氮化物半導體層之間以形成空隙者為佳。例如,如第1圖(b)及(e)所示,以在底基板1的各谷部1C中形成空隙的方式,使III-V族氮化物半導體層5成長者為佳。在形成空隙後,即可使III-V族氮化物半導體層與底基板容易分離。
在步驟(I-6)中,係要使III-V族氮化物半導體層從底基板分離。例如,如第1圖(f)中所示,III-V族氮化物半導體層5從底基板1分離後,即可得由III-V族氮化物半導體層5所形成的自立基板。
只要施加應力以機械性的將底基板從III-V族氮化物半導體層剝離的方法,即可進行分離,應力可為內部應力、外部應力的任一種。
分離,例如,可以在底基板與III-V族氮化物半導體層的界面上施加內部應力及/或外部應力的方法進行。藉由在界面上施加內部應力及/或外部應力,使底基板與III-V族氮化物半導體層輕易的分離(剝離)。
至於利用內部應力的方法,可舉例如在III-V族氮化物半導體層成長後,藉由III-V族氮化物半導體層與底基板之間的熱膨脹係數差而產生的應力,使底基板自然剝離的方法。典型的方法可進行:使III-V族氮化物半導體層的由成長溫度冷卻到室溫者,藉由低溫媒體(液態氮等)從室溫冷卻到低溫者,或從室溫加熱後,再以低溫媒體(液態氮等)冷卻到低溫者。
至於利用外部應力的方法,可舉例如使III-V族氮化物半導體層、底基板的任一方固定後,再給予另一方衝擊的方法。
本發明的III-V族氮化物半導體基板之製造方法2,包括步驟(II-1)至(II-7)。
在步驟(II-1)中,係在底基板上配置無機粒子。例如,如第2圖(a)所示,準備底基板1後,將無機粒子2配置在底基板1之表面1A上。至於底基板、無機粒子,只要使用與前述步驟(I-1)同樣者即可,並且也是與前述步驟(I-1)同樣的方法進行配置。
在步驟(II-2)中,係以無機粒子作為蝕刻遮罩而使底基板乾式蝕刻後,即在底基板上形成凸部。例如,如第2圖(b)所示,藉由以無機粒子2作為遮罩而使底基板1進行乾式蝕刻後,而在底基板1上形成對應於無機粒子2的凸部1B。乾式蝕刻是以與前述步驟(I-2)同樣的方法進行。
在步驟(II-3)中,係去除無機粒子。例如,如第2圖(b)及(c)所示,將無機粒子2去除,形成凸部1B後,即在凸部1B之間的谷部1C得基板1。可利用刷滾洗淨機、研磨機的物理方法進行去除。
在步驟(II-4)中,係於底基板上形成磊晶成長遮罩用的被膜。例如,如第2圖(d)所示,在底基板1上形成磊晶成長遮罩用的被膜13。在第2圖(d)中,被膜13覆蓋在整個凹凸狀態的底基板1之表面,即,覆蓋凸部1B間的谷部1C之表面及凸部1B的各頂部。被膜只要用與前述步驟(I-3)所用之被膜相同者即可,同時以與前述步驟(I-3)同樣的方法進行形成之步驟。
在步驟(II-5)中,係去除凸部頂端的被膜以形成底基板的露出面。例如,如第2圖(e)所示,使殘留在凸部1B間之谷部1C表面上的被膜13形成磊晶成長遮罩4,另一方面,去除其餘的被膜。可利用研磨機進行去除。
在步驟(II-6)中,係使III-V族氮化物半導體在底基板的露出面上成長。例如,如第2圖(e)及(f)所示,而使III-V族氮化物半導體在未被成長遮罩4覆蓋的凸部1B的各頂部1Ba上成長,並將成長的各III-V族氮化物半導體合體後而形成III-V族氮化物半導體層5。
在步驟(II-7)中,係使III-V族氮化物半導體層從底基板分離。例如,如第2圖(g)所示,III-V族氮化物半導體層5從底基板1分離後,即可得由III-V族氮化物半導體層5所形成的自立基板。可與前述步驟(I-6)同樣的方法進行分離。
藉由實施例說明本發明,但本發明的範圍並不限定於這些實施例。
利用藍寶石的C面經鏡面研磨過的藍寶石基板作為底基板。至於無機粒子,係使用球狀的二氧化矽粒子(宇部日東化成(股)社製,HIPRESICA(商品名),平均粒徑3 μm),使用將其分散在乙醇中而成的8重量%漿液。以停止中的旋轉離心塗布器(spinner)上將漿液塗布在藍寶石基板上之後,以500rpm使其旋轉10秒,接著再以2,500rpm旋轉40秒使藍寶石基板乾燥。藍寶石基板上的二氧化矽粒子之被覆率為87%。
將藍寶石基板乾式蝕刻至深度達0.35 μm後,可在藍寶石基板表面上形成對應於二氧化矽粒子形狀的凸部。乾式蝕刻是利用ICP乾式蝕刻裝置,在基板偏電力300W、ICP電力800W、壓力2Pa、氯氣32sccm、三氯化硼氣體48 sccm、氬氣190 sccm、處理時間5分鐘的條件下進行。
在藍寶石基板上附著二氧化矽粒子的狀態下,蒸鍍後在藍寶石基板上形成2,000的二氧化矽(SiO2
)膜。
將藍寶石基板的凸部上之SiO2
與二氧化矽粒子一起以棉棒去除。
使III-V族氮化物半導體層在藍寶石基板上磊晶成長。磊晶成長是藉由MOVPE,於1大氣壓下,感受器溫度485℃,以氫氣為載體氣體,供應載體氣體、氨及TMG後,可成長出厚度約500的GaN緩衝層。在感受器溫度達到900℃後,供應載體氣體、氨、TMG,形成無摻雜(undoped)GaN層。感受器溫度達到1040℃爐壓力下降到1/4氣壓,供應載體氣體、氨及TMG就形成無摻雜GaN層。在使無摻雜之GaN層成長到20 μm後,由1040℃的成長溫度緩慢的冷卻到室溫。經由冷卻,即可在藍寶石基板界面產生剝離。在使藍寶石基板分離後,可得III-V族氮化物半導體自立基板(GaN單晶,厚度約20 μm)。
利用藍寶石的C面經鏡面研磨過的藍寶石基板作為底基板。至於無機粒子,係使用球狀的二氧化矽粒子(宇部日東化成(股)社製,HIPRESICA(商品名),平均粒徑1 μm),使用將其分散在乙醇中而成的8重量%漿液。以停止中的旋轉離心塗布器(spinner)上將漿液塗布在藍寶石基板上之後,以500rpm使其旋轉10秒,接著再以2,500rpm旋轉40秒使藍寶石基板乾燥。藍寶石基板上的二氧化矽粒子之被覆率為83%。
將藍寶石基板乾式蝕刻至深度達0.21 μm後,在藍寶石基板表面上形成對應於二氧化矽粒子形狀的凸部。乾式蝕刻是利用ICP乾式蝕刻裝置,在基板偏電力300W、ICP電力800W、壓力2Pa、氯氣32sccm、三氯化硼氣體48 sccm、氬氣190 sccm、處理時間3分鐘的條件下進行。
以藍寶石基板上附著二氧化矽粒子的狀態下,蒸鍍後在藍寶石基板上形成2,000的二氧化矽(SiO2
)膜。
將藍寶石基板的凸部上之SiO2
與氧化矽粒子一起以棉棒去除。
接著,與實施例1同樣的使III-V族氮化物半導體層在藍寶石基板上磊晶成長。
在使無摻雜的GaN層成長到20 μm後,由1040℃的成長溫度緩慢的冷卻到室溫。經由冷卻,即可在藍寶石基板界面產生剝離。在使藍寶石基板分離後,可得III-V族氮化物半導體自立基板(GaN單晶,厚度約20 μm)。
利用藍寶石的C面經鏡面研磨過的藍寶石基板作為底基板。至於無機粒子,是使用含有膠體氧化矽(日本觸媒(股)製,SEAHOSTAR KE-W50(商品名),平均粒徑550um,水溶劑)之球狀二氧化矽粒子。將藍寶石基板安裝在旋轉離心塗布器(spinner)上之後,一邊以800rpm旋轉,一邊使稀釋成16重量%的漿液滴下,再以8,000rpm旋轉40秒使藍寶石基板乾燥。藍寶石基板上的二氧化矽粒子之被覆率為92%。
將藍寶石基板乾式蝕刻至深度達0.1 μm後,可在藍寶石基板表面上形成對應於二氧化矽粒子形狀的凸部。乾式蝕刻是利用ICP乾式蝕刻裝置,在基板偏電力300W、ICP電力800W、壓力2Pa、氯氣32sccm、三氯化硼氣體48 sccm、氬氣190 sccm、處理時間1.5分鐘的條件下進行。
在藍寶石基板上附著二氧化矽粒子的狀態下,蒸鍍後在藍寶石基板上形成2,000的二氧化矽(SiO2
)膜。
將藍寶石基板的凸部上之SiO2
與二氧化矽粒子一起以棉棒去除。
接著,與實施例1同樣的使III-V族氮化物半導體層在藍寶石基板上磊晶成長。
在使無摻雜之GaN層成長到20 μm後,由1040℃的成長溫度緩慢的冷卻到室溫。經由冷卻,即可在藍寶石基板界面產生剝離。在使藍寶石基板分離後,可得III-V族氮化物半導體自立基板(GaN單晶,厚度約20 μm)。
以未進行藍寶石基板加工之底基板,與實施例1同樣的,在未加工的藍寶石基板上,進行III-V族氮化物半導體層的磊晶成長。
在使無摻雜之GaN層成長到20 μm後,由1040℃的成長溫度緩慢的冷卻到室溫。並無發生GaN層與藍寶石基板界面的剝離。
再繼續使其成長直至無摻雜之GaN層到45 μm後,由1040℃的成長溫度緩慢的冷卻到室溫。在此冷卻中,並無發生GaN層與藍寶石基板界面的剝離,而是GaN層與藍寶石基板一起碎裂。
依照本發明的製造方法,即可容易的得到III-V族氮化物半導體自立基板。
1...底基板
1A...底基板的表面
1B...凸部
1Ba...頂部
1C...谷部
2...無機粒子
3、13...被膜
4...成長遮罩
5...III-V族氮化物半導體層
第1圖(a)至(f)係表示本發明的III-V族氮化物半導體基板之製造方法1之步驟。
第2圖(a)至(g)係表示本發明的III-V族氮化物半導體基板之製造方法2之步驟。
1...底基板
1A...底基板的表面
1B...凸部
1Ba...頂部
1C...谷部
2...無機粒子
3...被膜
4...成長遮罩
5...III-V族氮化物半導體層
Claims (7)
- 一種III-V族氮化物半導體基板之製造方法,包括下列(I-1)至(I-6)之步驟:(I-1)在底基板上配置平均粒徑為5nm至50μm之球狀的無機粒子;(I-2)以球狀的無機粒子作為蝕刻遮罩(etching mask)將底基板乾式蝕刻而在底基板上形成凸部;(I-3)在底基板上形成磊晶(epitaxial)成長遮罩用的被膜;(I-4)去除球狀的無機粒子以形成底基板的露出面;(I-5)使III-V族氮化物半導體在底基板的露出面上成長,並在底基板與III-V族氮化物半導體層之間形成用於使接下來的步驟中底基板與III-V族氮化物半導體層易於分離的空隙;(I-6)使III-V族氮化物半導體從底基板分離。
- 一種III-V族氮化物半導體基板之製造方法,包括下列(II-1)至(II-7)之步驟:(II-1)在底基板上配置平均粒徑為5nm至50μm之球狀的無機粒子;(II-2)以球狀的無機粒子作為蝕刻遮罩將底基板乾式蝕刻後而在底基板上形成凸部;(II-3)去除球狀的無機粒子;(II-4)在底基板上形成磊晶成長遮罩用的被膜;(II-5)去除凸部的頂部上之被膜,以形成底基板的露出 面,並在底基板與III-V族氮化物半導體層之間形成用於使接下來的步驟中底基板與III-V族氮化物半導體層易於分離的空隙;(II-6)使III-V族氮化物半導體在底基板的露出面上成長;(II-7)使III-V族氮化物半導體從底基板分離。
- 如申請專利範圍第1項或第2項的方法,其中球狀的無機粒子係選自由氧化物、氮化物、碳化物、硼化物、硫化物、硒化物及金屬所形成群族中的至少一種而組成。
- 如申請專利範圍第3項的方法,其中氧化物是選自由二氧化矽、氧化鋁、氧化鋯、氧化鈦、氧化鈰、氧化鋅、氧化錫及釔鋁柘榴石所形成群族中的至少一種。
- 如申請專利範圍第1項或第2項的方法,其在步驟(I-6)或步驟(II-7)中,係施加應力以機械性的將底基板從III-V族氮化物半導體層剝離的方法進行分離。
- 如申請專利範圍第5項的方法,係利用內部應力或外部應力以進行分離。
- 如申請專利範圍第6項的方法,其係藉由III-V族氮化物半導體層與底基板之間的熱膨脹係數差而產生的應力,使底基板自然剝離的方法進行分離。
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US20090093122A1 (en) | 2009-04-09 |
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TW200739692A (en) | 2007-10-16 |
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