JP6478103B2 - Film forming apparatus and film forming method - Google Patents
Film forming apparatus and film forming method Download PDFInfo
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- JP6478103B2 JP6478103B2 JP2015023488A JP2015023488A JP6478103B2 JP 6478103 B2 JP6478103 B2 JP 6478103B2 JP 2015023488 A JP2015023488 A JP 2015023488A JP 2015023488 A JP2015023488 A JP 2015023488A JP 6478103 B2 JP6478103 B2 JP 6478103B2
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- film forming
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- 238000000034 method Methods 0.000 title claims description 24
- 239000003595 mist Substances 0.000 claims description 103
- 239000000758 substrate Substances 0.000 claims description 63
- 239000012159 carrier gas Substances 0.000 claims description 57
- 239000002994 raw material Substances 0.000 claims description 33
- 238000000889 atomisation Methods 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 description 160
- 230000015572 biosynthetic process Effects 0.000 description 32
- 239000000243 solution Substances 0.000 description 32
- 239000012895 dilution Substances 0.000 description 15
- 238000010790 dilution Methods 0.000 description 15
- 239000010409 thin film Substances 0.000 description 14
- 238000005229 chemical vapour deposition Methods 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002019 doping agent Substances 0.000 description 8
- 230000001771 impaired effect Effects 0.000 description 8
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000010431 corundum Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 229910052594 sapphire Inorganic materials 0.000 description 4
- 239000010980 sapphire Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 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
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229940071870 hydroiodic acid Drugs 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000000644 propagated effect Effects 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- ZVYYAYJIGYODSD-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]gallanyloxypent-3-en-2-one Chemical compound [Ga+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZVYYAYJIGYODSD-LNTINUHCSA-K 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- -1 ammine complexes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical class [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- SRVXDMYFQIODQI-UHFFFAOYSA-K gallium(iii) bromide Chemical compound Br[Ga](Br)Br SRVXDMYFQIODQI-UHFFFAOYSA-K 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—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
- C23C16/448—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4486—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by producing an aerosol and subsequent evaporation of the droplets or particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B17/00—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups
- B05B17/04—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods
- B05B17/06—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods using ultrasonic or other kinds of vibrations
- B05B17/0607—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods using ultrasonic or other kinds of vibrations generated by electrical means, e.g. piezoelectric transducers
- B05B17/0615—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods using ultrasonic or other kinds of vibrations generated by electrical means, e.g. piezoelectric transducers spray being produced at the free surface of the liquid or other fluent material in a container and subjected to the vibrations
-
- 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
- C23C16/4412—Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps
-
- 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
- C23C16/45502—Flow conditions in reaction chamber
- C23C16/45506—Turbulent flow
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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
- C23C16/45502—Flow conditions in reaction chamber
- C23C16/45508—Radial flow
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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
- C23C16/458—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 supporting substrates in the reaction chamber
- C23C16/4582—Rigid and flat substrates, e.g. plates or discs
- C23C16/4583—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally
- C23C16/4586—Elements in the interior of the support, e.g. electrodes, heating or cooling devices
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Dispersion Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Description
本発明は、ミスト化学気相成長法の適用に有用な新規な成膜装置および成膜方法に関する。 The present invention relates to a novel film formation apparatus and film formation method useful for application of mist chemical vapor deposition.
従来から、パルスレーザー堆積法(Pulsed laser deposition: PLD)、分子線エピタキシー法(Molecular beam epitaxy: MBE)、スパッタリング法等の非平衡状態を実現できる高真空製膜装置が検討されており、これまでの融液法等では作製不可能であった酸化物半導体の作製が可能となってきている。中でも、霧化された原料（ミスト）を用いて、基板上に結晶成長させるミスト化学気相成長法（Mist Chemical Vapor Deposition: Mist CVD。以下、ミストＣＶＤ法ともいう。）が検討されており、コランダム構造を有する酸化ガリウム（α−Ｇａ２Ｏ３）の作製が可能となってきている。α−Ｇａ２Ｏ３は、バンドギャップの大きな半導体として、高耐圧、低損失および高耐熱を実現できる次世代のスイッチング素子への応用が期待されている。 Conventionally, high-vacuum film forming apparatuses that can realize non-equilibrium states such as pulsed laser deposition (PLD), molecular beam epitaxy (MBE), and sputtering have been studied. It has become possible to produce oxide semiconductors that could not be produced by the melt method. Among them, a mist chemical vapor deposition method (Mist Chemical Vapor Deposition: Mist CVD, hereinafter also referred to as a mist CVD method) in which crystals are grown on a substrate using an atomized raw material (mist) has been studied. Fabrication of gallium oxide (α-Ga 2 O 3 ) having a corundum structure has become possible. As a semiconductor having a large band gap, α-Ga 2 O 3 is expected to be applied to a next-generation switching element that can realize high breakdown voltage, low loss, and high heat resistance.
ミストＣＶＤ法については、特許文献１には、管状炉型のミストＣＶＤ装置が記載されている。特許文献２には、ファインチャネル型のミストＣＶＤ装置が記載されている。特許文献３には、リニアソース型のミストＣＶＤ装置が記載されている。特許文献４には、管状炉のミストＣＶＤ装置が記載されており、特許文献１記載のミストＣＶＤ装置とは、ミスト発生器内にキャリアガスを導入する点で異なっている。また、特許文献５には、ミスト発生器の上方に基板を設置し、さらにサセプタがホットプレート上に備え付けられた回転ステージであるミストＣＶＤ装置が記載されている。 Regarding the mist CVD method, Patent Document 1 describes a tubular furnace type mist CVD apparatus. Patent Document 2 describes a fine channel type mist CVD apparatus. Patent Document 3 describes a linear source type mist CVD apparatus. Patent Document 4 describes a mist CVD apparatus for a tubular furnace, and differs from the mist CVD apparatus described in Patent Document 1 in that a carrier gas is introduced into a mist generator. Patent Document 5 describes a mist CVD apparatus which is a rotary stage in which a substrate is installed above a mist generator and a susceptor is provided on a hot plate.
しかしながら、ミストＣＶＤ法は、他の方法とは異なり、高温にする必要もなく、α−酸化ガリウムのコランダム構造のような準安定相の結晶構造も作製可能である一方、非特許文献１記載のライデンフロスト効果により、ミスト揮発層で基板表面を覆うことで、ミストの液滴が直接膜に接触することなく結晶成長させる必要があるため、その制御が容易ではなく、均質な結晶膜を得ることが困難であった。また、ミストＣＶＤ法では、ミストの粒子にバラつきがあったり、基板に至るまでに、供給管内でミストが沈んでしまったりする問題もあり、成膜レートが低い等の問題があった。 However, unlike other methods, the mist CVD method does not require a high temperature and can produce a metastable phase crystal structure such as a corundum structure of α-gallium oxide. By covering the substrate surface with a mist volatile layer due to the Leidenfrost effect, it is necessary to grow crystals without causing the mist droplets to directly contact the film, so that the control is not easy, and a homogeneous crystal film is obtained. It was difficult. In addition, the mist CVD method has a problem in that the mist particles vary or the mist sinks in the supply pipe before reaching the substrate, and the film formation rate is low.
本発明は、成膜レートに優れ、ミストＣＶＤ法が適用可能な成膜装置および成膜方法を提供することを目的とする。 An object of the present invention is to provide a film forming apparatus and a film forming method that are excellent in film forming rate and to which a mist CVD method can be applied.
本発明者らは、上記目的を達成すべく鋭意検討した結果、成膜部に、前記ミストまたは前記液滴を旋回させて旋回流を発生させる手段を設けたミストＣＶＤ装置の創製に成功し、このようなミストＣＶＤ装置を用いて、ミストＣＶＤ法により成膜すると、驚くべきことに、成膜レートに優れていること、均一な膜厚分布であること、大面積成膜が可能であること等を知見した。そして、このような装置が、上記した従来の問題を一挙に解決できることを見出した。 As a result of intensive studies to achieve the above object, the present inventors have succeeded in creating a mist CVD apparatus provided with means for generating a swirling flow by swirling the mist or the droplet in the film forming unit, Surprisingly, when such a mist CVD apparatus is used to form a film by the mist CVD method, the film formation rate is excellent, the film thickness is uniform, and large-area film formation is possible. I found out. And it discovered that such an apparatus can solve the above-mentioned conventional problem at a stretch.
また、本発明者らは、上記知見を得た後、さらに検討を重ねて本発明を完成させるに至った。 In addition, after obtaining the above knowledge, the present inventors have further studied and completed the present invention.
すなわち、本発明は、以下の発明に関する。
［１］原料溶液を霧化または液滴化する霧化・液滴化部、前記霧化・液滴化部で発生したミストまたは液滴をキャリアガスでもって基体まで搬送する搬送部、および該ミストまたは該液滴を熱処理して該基体上に成膜する成膜部を備える成膜装置において、
成膜部が、前記ミストまたは前記液滴を旋回させて旋回流を発生させる手段を具備することを特徴とする成膜装置。
［２］旋回流が、内向きに流れる前記［１］記載の成膜装置。
［３］成膜部が、円筒状または略円筒状であり、成膜部の側面に、前記ミストまたは前記液滴の搬入口が設けられている前記［１］または［２］に記載の成膜装置。
［４］成膜部の前記搬入口よりも前記基体から離れているところに、前記ミストまたは前記液滴の排気口が設けられている前記［３］記載の成膜装置。
［５］さらに、排気ファンが備え付けられている前記［１］〜［４］のいずれかに記載の成膜装置。
［６］ホットプレートを成膜部に備えている前記［１］〜［５］のいずれかに記載の成膜装置。
［７］超音波振動子を霧化・液滴化部に備えている前記［１］〜［６］のいずれかに記載の成膜装置。
［８］原料溶液を霧化または液滴化して生成されるミストまたは液滴を、キャリアガスでもって成膜室内に設置されている基体まで搬送し、ついで該基体上で該ミストまたは該液滴を熱反応させて成膜する成膜方法において、
前記成膜室内において、前記ミストまたは前記液滴を旋回させて旋回流を発生させることを特徴とする成膜方法。
［９］旋回流が、内向きに流れる前記［８］記載の成膜方法。
［１０］成膜室が円筒状または略円筒状であり、成膜室の側面に前記ミストまたは前記液滴の搬入口が設けられている前記［８］または［９］に記載の成膜方法。
［１１］成膜室の前記搬入口よりも前記基体から離れているところに、前記ミストまたは前記液滴の排気口が設けられている前記［１０］記載の成膜方法。
［１２］排気ファンを用いて排気する前記［１１］記載の成膜方法。
［１３］霧化または液滴化を、超音波振動により行う前記［８］〜［１２］のいずれかに記載の成膜方法。
That is, the present invention relates to the following inventions.
[1] An atomization / droplet forming unit for atomizing or dropletizing a raw material solution, a transfer unit for transferring mist or droplets generated in the atomization / droplet forming unit to a substrate with a carrier gas, and In a film forming apparatus including a film forming unit that heat-treats the mist or the droplet to form a film on the substrate,
A film forming apparatus, wherein the film forming unit includes means for rotating the mist or the droplet to generate a swirling flow.
[2] The film forming apparatus according to [1], wherein the swirling flow flows inward.
[3] The film forming unit according to [1] or [2], wherein the film forming unit has a cylindrical shape or a substantially cylindrical shape, and the mist or the droplet inlet is provided on a side surface of the film forming unit. Membrane device.
[4] The film forming apparatus according to [3], wherein an exhaust port for the mist or the droplet is provided at a position farther from the substrate than the carry-in port of the film forming unit.
[5] The film forming apparatus according to any one of [1] to [4], further including an exhaust fan.
[6] The film forming apparatus according to any one of [1] to [5], wherein the film forming unit includes a hot plate.
[7] The film forming apparatus according to any one of [1] to [6], wherein an ultrasonic vibrator is provided in the atomizing / droplet forming unit.
[8] A mist or droplet generated by atomizing or dropletizing the raw material solution is conveyed to a substrate installed in a film forming chamber with a carrier gas, and then the mist or droplet on the substrate. In a film forming method for forming a film by reacting with heat,
A film forming method, wherein a swirl flow is generated by swirling the mist or the droplet in the film forming chamber.
[9] The film forming method according to [8], wherein the swirling flow flows inward.
[10] The film forming method according to [8] or [9], wherein the film forming chamber is cylindrical or substantially cylindrical, and the mist or the droplet inlet is provided on a side surface of the film forming chamber. .
[11] The film forming method according to [10], wherein an exhaust port for the mist or the droplet is provided at a position farther from the substrate than the carry-in port of the film forming chamber.
[12] The film forming method according to [11], wherein exhaust is performed using an exhaust fan.
[13] The film forming method according to any one of [8] to [12], wherein atomization or droplet formation is performed by ultrasonic vibration.
本発明の成膜装置および成膜方法は、ミストＣＶＤ法が適用可能であり、成膜レートに優れている。 The mist CVD method can be applied to the film forming apparatus and the film forming method of the present invention, and the film forming rate is excellent.
本発明の成膜装置は、原料溶液を霧化または液滴化する霧化・液滴化部、前記霧化・液滴化部で発生したミストまたは液滴をキャリアガスでもって基体まで搬送する搬送部、および該ミストまたは該液滴を熱処理して該基体上に成膜する成膜部を備える成膜装置において、成膜部が、前記ミストまたは前記液滴を旋回させて旋回流を発生させる手段を具備することを特徴とする。 The film-forming apparatus of the present invention transports the mist or droplet generated in the atomizing / droplet forming unit for atomizing or dropping the raw material solution to the substrate with the carrier gas. In a film forming apparatus including a transport unit and a film forming unit that heat-treats the mist or the droplet to form a film on the substrate, the film forming unit rotates the mist or the droplet to generate a swirling flow. It has the means to make it comprise, It is characterized by the above-mentioned.
以下、本発明の成膜装置について、図面を用いて説明するが、本発明は、これら図面に限定されるものではない。 Hereinafter, although the film-forming apparatus of this invention is demonstrated using drawing, this invention is not limited to these drawings.
図１は、本発明の成膜装置の一例を示している。成膜装置１は、キャリアガスを供給するキャリアガス源２ａと、キャリアガス源２ａから送り出されるキャリアガスの流量を調節するための流量調節弁３ａと、希釈用キャリアガスを供給する希釈用キャリアガス源２ｂと、希釈用キャリアガス源２ｂから送り出される希釈用キャリアガスの流量を調節するための流量調節弁３ｂと、原料溶液４ａが収容されるミスト発生源４と、水５ａが入れられる容器５と、容器５の底面に取り付けられた超音波振動子６と、成膜室７と、ミスト発生源４から成膜室７までをつなぐ供給管９と、成膜室７内に設置されたホットプレート８と、排気管１７と排気ファン１１とを備えている。ホットプレート８上には、基板１０が設置されている。 FIG. 1 shows an example of a film forming apparatus of the present invention. The film forming apparatus 1 includes a carrier gas source 2a for supplying a carrier gas, a flow rate adjusting valve 3a for adjusting the flow rate of the carrier gas sent from the carrier gas source 2a, and a dilution carrier gas for supplying a dilution carrier gas. A source 2b, a flow rate adjusting valve 3b for adjusting the flow rate of the dilution carrier gas sent out from the dilution carrier gas source 2b, a mist generating source 4 in which the raw material solution 4a is stored, and a container 5 in which water 5a is placed. An ultrasonic transducer 6 attached to the bottom of the container 5, a film forming chamber 7, a supply pipe 9 connecting the mist generation source 4 to the film forming chamber 7, and a hot installed in the film forming chamber 7. A plate 8, an exhaust pipe 17 and an exhaust fan 11 are provided. A substrate 10 is installed on the hot plate 8.
本発明の成膜装置１は、原料溶液を霧化または液滴化する霧化・液滴化部を備えている。図２は、霧化・液滴化部の一態様を示している。原料溶液４ａが収容されている容器からなるミスト発生源４が、水５ａが収容されている容器５に、支持体（図示せず）を用いて収納されている。容器５の底部には、超音波振動子６が備え付けられており、超音波振動子６と発振器１６とが接続されている。そして、発振器１６を作動させると、超音波振動子６が振動し、水５ａを介して、ミスト発生源４内に超音波が伝播し、原料溶液４ａが霧化または液滴化するように構成されている。 The film forming apparatus 1 of the present invention includes an atomization / droplet forming unit that atomizes or drops the raw material solution. FIG. 2 shows one mode of the atomization / droplet forming unit. A mist generating source 4 composed of a container in which the raw material solution 4a is accommodated is accommodated in a container 5 in which water 5a is accommodated using a support (not shown). An ultrasonic transducer 6 is provided at the bottom of the container 5, and the ultrasonic transducer 6 and the oscillator 16 are connected to each other. Then, when the oscillator 16 is operated, the ultrasonic vibrator 6 vibrates, the ultrasonic wave propagates into the mist generation source 4 through the water 5a, and the raw material solution 4a is atomized or dropletized. Has been.
図３は、図２に示されている超音波振動子６の一態様を示している。図２の超音波振動子は、支持体６ｅ上の円筒状の弾性体６ｄ内に、円板状の圧電体素子６ｂが備え付けられており、圧電体素子６ｂの両面に電極６ａ、６ｃが設けられている。そして、電極に発振器を接続して発振周波数を変更すると、圧電振動子の厚さ方向の共振周波数及び径方向の共振周波数を持つ超音波が発生されるように構成されている。 FIG. 3 shows one mode of the ultrasonic transducer 6 shown in FIG. The ultrasonic transducer of FIG. 2 includes a disk-like piezoelectric element 6b in a cylindrical elastic body 6d on a support 6e, and electrodes 6a and 6c are provided on both sides of the piezoelectric element 6b. It has been. When the oscillator is connected to the electrode and the oscillation frequency is changed, an ultrasonic wave having a resonance frequency in the thickness direction and a resonance frequency in the radial direction of the piezoelectric vibrator is generated.
上記したとおり、霧化・液滴化部では、原料溶液を調整し、前記原料溶液を霧化または液滴化してミストまたは液滴を発生させる。霧化または液滴化手段は、前記原料溶液を霧化または液滴化できさえすれば特に限定されず、公知の霧化手段または液滴化手段であってよいが、本発明においては、超音波振動により行う霧化手段または液滴化手段であるのが好ましい。 As described above, the atomization / droplet forming unit adjusts the raw material solution and atomizes or drops the raw material solution to generate mist or droplets. The atomization or droplet formation means is not particularly limited as long as the raw material solution can be atomized or dropletized, and may be a known atomization means or droplet formation means. An atomizing means or a droplet forming means performed by sonic vibration is preferable.
搬送部では、キャリアガスおよび所望により供給管等を用いて前記ミストまたは前記液滴を基体まで搬送する。キャリアガスの種類としては、本発明の目的を阻害しない限り特に限定されず、例えば、酸素、オゾン、窒素やアルゴン等の不活性ガス、または水素ガスやフォーミングガス等の還元ガスなどが好適な例として挙げられる。また、キャリアガスの種類は１種類であってよいが、２種類以上であってもよい。例えば、第１のキャリアガスと同じガスをそれ以外のガスで希釈した（例えば１０倍に希釈した）希釈ガスなどを、第２のキャリアガスとしてさらに用いてもよい。また、キャリアガスの供給箇所も１箇所だけでなく、２箇所以上あってもよい。キャリアガスの流量は、特に限定されないが、例えば３０ｍｍ角基板上に成膜する場合には、０．０１〜２０Ｌ／分であるのが好ましく、１〜１０Ｌ／分であるのがより好ましい。 In the transfer unit, the mist or the droplet is transferred to the substrate using a carrier gas and, if desired, a supply pipe. The type of the carrier gas is not particularly limited as long as the object of the present invention is not impaired. For example, an inert gas such as oxygen, ozone, nitrogen or argon, or a reducing gas such as hydrogen gas or forming gas is preferable. As mentioned. Further, the type of carrier gas may be one, but may be two or more. For example, a diluted gas obtained by diluting the same gas as the first carrier gas with another gas (for example, diluted 10 times) may be further used as the second carrier gas. Further, the supply location of the carrier gas is not limited to one location but may be two or more locations. The flow rate of the carrier gas is not particularly limited. For example, in the case of forming a film on a 30 mm square substrate, it is preferably 0.01 to 20 L / min, and more preferably 1 to 10 L / min.
成膜部では、前記ミストまたは前記液滴を熱処理して、熱反応を生じさせて、前記基体表面の一部または全部に成膜する。前記熱反応は、加熱でもって前記ミストまたは前記液滴が反応すればそれでよく、反応条件等も本発明の目的を阻害しない限り特に限定されない。本工程において、熱反応を行う際の条件等については特に制限はないが、通常、加熱温度は１２０〜６００℃の範囲であり、好ましくは１２０℃〜３５０℃の範囲であり、より好ましくは１３０℃〜３００℃の範囲である。また、熱反応は、本発明の目的を阻害しない限り、真空下、非酸素雰囲気下、還元ガス雰囲気下および酸素雰囲気下のいずれの雰囲気下で行われてもよく、また、大気圧下、加圧下および減圧下のいずれの条件下で行われてもよいが、本発明においては、大気圧下で行われるのが好ましい。 In the film forming section, the mist or the droplet is heat-treated to cause a thermal reaction, and the film is formed on a part or all of the substrate surface. The thermal reaction is not particularly limited as long as the mist or the droplet reacts by heating, and the reaction conditions and the like are not particularly limited as long as the object of the present invention is not impaired. In this step, there are no particular restrictions on the conditions for carrying out the thermal reaction, but the heating temperature is usually in the range of 120 to 600 ° C, preferably in the range of 120 ° C to 350 ° C, more preferably 130. It is the range of ° C to 300 ° C. Further, the thermal reaction may be performed in any atmosphere of a vacuum, a non-oxygen atmosphere, a reducing gas atmosphere, and an oxygen atmosphere as long as the object of the present invention is not impaired. Although it may be carried out under any conditions of reduced pressure and reduced pressure, it is preferably carried out under atmospheric pressure in the present invention.
図４は、成膜部の一態様を示している。図４の成膜室７は、円筒状であり、ホットプレート８上に設けられている。そして、成膜室７は、ミスト発生源４と供給管９を介して接続されており、ミスト発生源４で発生したミストまたは液滴４ｂが、キャリアガスによって供給管９を通って成膜室７内に流れ込み、ホットプレート上に載置された基板１０上で、熱反応するように構成されている。また、成膜室７は、天井面（上面）の中心に排気口を有しており、前記搬入口よりも前記基体から離れているところに、前記ミストまたは前記液滴の排気口が設けられている。そして、成膜室７は、排気口から排気管１９ａと接続されており、熱反応後のミスト、液滴もしくは排気ガスが、排気管１９ａへと運ばれるように構成されている。本発明においては、熱反応後のミスト、液滴もしくは排気ガスがトラップ処理に付されるように、トラップ手段をさらに備えていてもよい。成膜室７に、ミストまたは液滴４ｂが搬送されると、図４において矢印で表されるように、基板に向かってミストまたは液滴４ｂが流れ出す。このとき、内向きの旋回流が発生する。そして、ミストまたは液滴４ｂが旋回しながら、基板上で熱反応する。ついで、熱反応後のミスト、液滴もしくは排気ガスは、図４において矢印で表されるように、排気口へと流れていき、そして、排気管１９ａへと運ばれていく。 FIG. 4 shows one mode of the film forming unit. The film formation chamber 7 in FIG. 4 is cylindrical and is provided on a hot plate 8. The film formation chamber 7 is connected to the mist generation source 4 via the supply pipe 9, and the mist or droplet 4b generated by the mist generation source 4 passes through the supply pipe 9 by the carrier gas and forms the film formation chamber. 7 and is configured to react with heat on the substrate 10 placed on the hot plate. The film formation chamber 7 has an exhaust port at the center of the ceiling surface (upper surface), and the exhaust port for the mist or the droplet is provided at a position farther from the base than the carry-in port. ing. The film forming chamber 7 is connected to the exhaust pipe 19a from the exhaust port, and is configured such that the mist, liquid droplets or exhaust gas after the thermal reaction is carried to the exhaust pipe 19a. In the present invention, a trap means may be further provided so that the mist, droplet or exhaust gas after the thermal reaction is subjected to the trap process. When the mist or droplet 4b is transferred to the film forming chamber 7, the mist or droplet 4b flows toward the substrate as indicated by an arrow in FIG. At this time, an inward swirl flow is generated. Then, the mist or the liquid droplet 4b performs a thermal reaction on the substrate while turning. Next, the mist, droplets or exhaust gas after the thermal reaction flows to the exhaust port and is carried to the exhaust pipe 19a as represented by the arrow in FIG.
前記旋回流は、内向きでも外向きでもいずれの向きに流れてもよいが、本発明においては、内向きに流れるのが好ましい。図８は、図４の成膜室における基板上のミストまたは液滴の流れを説明する模式図である。図８（ａ）は、円筒状の成膜室７の断面を上面から見た図であり、成膜室７内には、基板１０が設置されており、ミストまたは液滴の流れが矢印で表されている。図４の成膜室においては、図８（ａ）の矢印方向に旋回流が生じ、ミストまたは液滴が内向きに旋回して基板中心へと流れる。図８（ｂ）は、円筒状の成膜室７の断面を側面から見た模式図であり、成膜室７内に基板１０が設置されている。図８（ｂ）において矢印で表されるように、外側から内側に向かってミストまたは液滴が流れる。そして、基板中心付近上に到達したミストまたは液滴は、上方の排気口に向かって流れる。なお、本発明においては、基体を成膜室上面に設置するなどして、フェイスダウンとしてもよいし、図４のように、基体を底面に設置して、フェイスアップとしてもよい。なお、前記旋回流の発生手段は、本発明の目的を阻害しない限り特に限定されず、公知の手段を用いてもよい。例えば、成膜室を円筒状にして、底面または上面に基体を配置し、側面からミストまたは液滴を導入し、基体が配置されている面の対称となる面（好ましくは箇所）に排出口を設けて、旋回流を発生させる手段等が挙げられる。ミストまたは液滴は、ミストまたは液滴が成膜室の内壁面に沿って移動するように、成膜室内に導入することが好ましい。このため、ミストまたは液滴の導入口が、実質的に、成膜室の内壁面の接線方向に向いていることが好ましい。但し、ミストまたは液滴を成膜室の径方向中央に向かって成膜室内に導入した場合でも、例えばキャリアガスの流速を適宜調整すること等の公知の手段を用いることによって、旋回流を発生させることが可能であるので、ミストまたは液滴の導入方向は、特に限定されない。なお、旋回流の流速は、本発明の目的を阻害しない限り特に限定されないが、好ましくは１０〜１００ｃｍ／秒であり、より好ましくは２０〜７０ｃｍ／秒である。 The swirling flow may flow in either an inward direction or an outward direction, but in the present invention, it preferably flows inward. FIG. 8 is a schematic diagram for explaining the flow of mist or droplets on the substrate in the film forming chamber of FIG. FIG. 8A is a view of a cross section of the cylindrical film forming chamber 7 as viewed from above. A substrate 10 is installed in the film forming chamber 7, and the flow of mist or droplets is indicated by arrows. It is represented. In the film forming chamber of FIG. 4, a swirling flow is generated in the direction of the arrow in FIG. 8A, and the mist or droplet swirls inward and flows to the center of the substrate. FIG. 8B is a schematic view of a cross section of the cylindrical film forming chamber 7 as viewed from the side, and the substrate 10 is installed in the film forming chamber 7. As shown by arrows in FIG. 8B, mist or droplets flow from the outside toward the inside. Then, the mist or droplet that reaches near the center of the substrate flows toward the upper exhaust port. In the present invention, the substrate may be placed on the upper surface of the film forming chamber to be face-down, or the substrate may be installed on the bottom surface as shown in FIG. The means for generating the swirling flow is not particularly limited as long as the object of the present invention is not impaired, and a known means may be used. For example, the film forming chamber is cylindrical, a substrate is disposed on the bottom or top surface, mist or droplets are introduced from the side surface, and a discharge port is formed on a surface (preferably a location) that is symmetrical to the surface on which the substrate is disposed. And a means for generating a swirling flow. The mist or droplet is preferably introduced into the deposition chamber so that the mist or droplet moves along the inner wall surface of the deposition chamber. For this reason, it is preferable that the mist or droplet inlet is substantially directed in the tangential direction of the inner wall surface of the film forming chamber. However, even when mist or droplets are introduced into the film formation chamber toward the radial center of the film formation chamber, a swirl flow is generated by using a known means such as appropriately adjusting the flow rate of the carrier gas. Therefore, the direction of introducing the mist or droplet is not particularly limited. The flow rate of the swirl flow is not particularly limited as long as the object of the present invention is not impaired, but is preferably 10 to 100 cm / second, more preferably 20 to 70 cm / second.
以下、図１を用いて、本発明の製造装置の使用態様を説明する。
まず、原料溶液４ａをミスト発生源４内に収容し、基板１０をホットプレート８上に設置させ、ホットプレート８を作動させる。次に、流量調節弁３（３ａ、３ｂ）を開いてキャリアガス源２（２ａ、２ｂ）からキャリアガスを成膜室７内に供給し、成膜室７の雰囲気をキャリアガスで十分に置換した後、キャリアガスの流量と希釈用キャリアガスの流量をそれぞれ調節する。次に、超音波振動子６を振動させ、その振動を、水５ａを通じて原料溶液４ａに伝播させることによって、原料溶液４ａを霧化または液滴化させてミストまたは液滴４ｂを生成する。ついで、ミストまたは液滴４ｂが、キャリアガスによって成膜室７内に導入される。成膜室７の上面真ん中には、排気口が設けられており、排気管１７と接続されている。また、排気管１７は排気ファン１１に接続されており、排気ファン１７によって、成膜室７内の排気ガス等が排気口から吸気されるように構成されている。また、円筒状の成膜室７の側面には、ミストまたは液滴の搬入口が設けられており、成膜室７内に導入されたミストまたは液滴が旋回して、内向きに流れる旋回流が生じるように構成されている。そして、旋回しながら、ミストまたは液滴が、成膜室７内でホットプレート８の加熱により熱反応して、基板１０上に成膜することができる。
Hereinafter, the usage mode of the manufacturing apparatus of the present invention will be described with reference to FIG.
First, the raw material solution 4a is accommodated in the mist generating source 4, the substrate 10 is placed on the hot plate 8, and the hot plate 8 is operated. Next, the flow rate adjusting valve 3 (3a, 3b) is opened to supply the carrier gas from the carrier gas source 2 (2a, 2b) into the film forming chamber 7, and the atmosphere in the film forming chamber 7 is sufficiently replaced with the carrier gas. After that, the flow rate of the carrier gas and the flow rate of the carrier gas for dilution are adjusted. Next, the ultrasonic vibrator 6 is vibrated, and the vibration is propagated to the raw material solution 4a through the water 5a, whereby the raw material solution 4a is atomized or formed into droplets to generate mist or droplets 4b. Subsequently, the mist or the droplet 4b is introduced into the film forming chamber 7 by the carrier gas. An exhaust port is provided in the middle of the upper surface of the film forming chamber 7 and is connected to the exhaust pipe 17. Further, the exhaust pipe 17 is connected to the exhaust fan 11, and the exhaust fan 17 is configured such that exhaust gas or the like in the film forming chamber 7 is sucked from the exhaust port. Further, a mist or droplet inlet is provided on the side surface of the cylindrical film formation chamber 7, and the mist or droplet introduced into the film formation chamber 7 swirls and swirls to flow inwardly. It is comprised so that a flow may arise. Then, while turning, the mist or droplets can be thermally reacted by heating the hot plate 8 in the film forming chamber 7 to form a film on the substrate 10.
なお、前記成膜室の形状は、本発明の目的を阻害しない限り特に限定されず、筒状であることが好ましい。成膜室は、円筒状または略円筒状であってもよいし、角柱状（例えば立方体、直方体、五角柱、六角柱もしくは八角柱等）または略角柱状であってもよいが、本発明においては、円筒状または略円筒状が好ましい。
また、前記基体は成膜時に回転されてもよく、回転方向は、前記旋回流の向きと逆向きにするのが好ましい。
Note that the shape of the film forming chamber is not particularly limited as long as the object of the present invention is not impaired, and a cylindrical shape is preferable. The film formation chamber may have a cylindrical shape or a substantially cylindrical shape, and may have a prismatic shape (for example, a cube, a rectangular parallelepiped, a pentagonal column, a hexagonal column, or an octagonal column) or a substantially prismatic shape. Is preferably cylindrical or substantially cylindrical.
The substrate may be rotated during film formation, and the rotation direction is preferably opposite to the direction of the swirl flow.
（原料溶液）
原料溶液は、霧化または液滴化が可能な材料を含んでいれば特に限定されず、無機材料であっても、有機材料であってもよいが、本発明においては、金属または金属化合物であるのが好ましく、ガリウム、鉄、インジウム、アルミニウム、バナジウム、チタン、クロム、ロジウム、ニッケルおよびコバルトから選ばれる１種または２種以上の金属を含むのがより好ましい。
(Raw material solution)
The raw material solution is not particularly limited as long as it contains a material that can be atomized or formed into droplets, and may be an inorganic material or an organic material. It is preferable that it contains one or more metals selected from gallium, iron, indium, aluminum, vanadium, titanium, chromium, rhodium, nickel and cobalt.
前記原料溶液は、上記金属を霧化または液滴化できるものであれば特に限定されないが、前記原料溶液として、前記金属を錯体または塩の形態で有機溶媒または水に溶解または分散させたものを好適に用いることができる。錯体の形態としては、例えば、アセチルアセトナート錯体、カルボニル錯体、アンミン錯体、ヒドリド錯体などが挙げられる。塩の形態としては、例えば、塩化金属塩、臭化金属塩、ヨウ化金属塩などが挙げられる。 The raw material solution is not particularly limited as long as the metal can be atomized or formed into droplets, but the raw material solution is a solution in which the metal is dissolved or dispersed in an organic solvent or water in the form of a complex or salt. It can be used suitably. Examples of complex forms include acetylacetonate complexes, carbonyl complexes, ammine complexes, hydride complexes, and the like. Examples of the salt form include metal chloride salts, metal bromide salts, metal iodide salts, and the like.
また、前記原料溶液には、ハロゲン化水素酸や酸化剤等の添加剤を混合してもよい。前記ハロゲン化水素酸としては、例えば、臭化水素酸、塩酸、ヨウ化水素酸などが挙げられるが、中でも、臭化水素酸またはヨウ化水素酸が好ましい。前記酸化剤としては、例えば、過酸化水素（Ｈ２Ｏ２）、過酸化ナトリウム（Ｎａ２Ｏ２）、過酸化バリウム（ＢａＯ２）、過酸化ベンゾイル（Ｃ６Ｈ５ＣＯ）２Ｏ２等の過酸化物、次亜塩素酸（ＨＣｌＯ）、過塩素酸、硝酸、オゾン水、過酢酸やニトロベンゼン等の有機過酸化物などが挙げられる。 Moreover, you may mix additives, such as a hydrohalic acid and an oxidizing agent, with the said raw material solution. Examples of the hydrohalic acid include hydrobromic acid, hydrochloric acid, hydroiodic acid, etc. Among them, hydrobromic acid or hydroiodic acid is preferable. Examples of the oxidizing agent include hydrogen peroxide (H 2 O 2 ), sodium peroxide (Na 2 O 2 ), barium peroxide (BaO 2 ), and benzoyl peroxide (C 6 H 5 CO) 2 O 2. Peroxides, hypochlorous acid (HClO), perchloric acid, nitric acid, ozone water, organic peroxides such as peracetic acid and nitrobenzene.
前記原料溶液には、ドーパントが含まれていてもよい。前記ドーパントは、本発明の目的を阻害しない限り、特に限定されない。前記ドーパントとしては、例えば、スズ、ゲルマニウム、ケイ素、チタン、ジルコニウム、バナジウムまたはニオブ等のｎ型ドーパント、またはｐ型ドーパントなどが挙げられる。ドーパントの濃度は、通常、約１×１０１６／ｃｍ３〜１×１０２２／ｃｍ３であってもよいし、また、ドーパントの濃度を例えば約１×１０１７／ｃｍ３以下の低濃度にしてもよい。また、さらに、本発明によれば、ドーパントを約１×１０２０／ｃｍ３以上の高濃度で含有させてもよい。 The raw material solution may contain a dopant. The dopant is not particularly limited as long as the object of the present invention is not impaired. Examples of the dopant include n-type dopants such as tin, germanium, silicon, titanium, zirconium, vanadium or niobium, or p-type dopants. The concentration of the dopant may usually be about 1 × 10 16 / cm 3 to 1 × 10 22 / cm 3 , and the concentration of the dopant is set to a low concentration of about 1 × 10 17 / cm 3 or less, for example. May be. Furthermore, according to the present invention, the dopant may be contained at a high concentration of about 1 × 10 20 / cm 3 or more.
（基体）
前記基体は、前記膜を支持できるものであれば特に限定されない。前記基体の材料も、本発明の目的を阻害しない限り特に限定されず、公知の基体であってよく、有機化合物であってもよいし、無機化合物であってもよい。前記基体の形状としては、どのような形状のものであってもよく、あらゆる形状に対して有効であり、例えば、平板や円板等の板状、繊維状、棒状、円柱状、角柱状、筒状、螺旋状、球状、リング状などが挙げられるが、本発明においては、基板が好ましい。基板の厚さは、本発明においては特に限定されないが、好ましくは、１０〜２０００μｍであり、より好ましくは５０〜８００μｍである。
(Substrate)
The substrate is not particularly limited as long as it can support the film. The material of the substrate is not particularly limited as long as the object of the present invention is not impaired, and may be a known substrate, an organic compound, or an inorganic compound. The shape of the substrate may be any shape and is effective for all shapes, for example, a plate shape such as a flat plate or a disk, a fiber shape, a rod shape, a columnar shape, a prismatic shape, A cylindrical shape, a spiral shape, a spherical shape, a ring shape and the like can be mentioned. In the present invention, a substrate is preferable. Although the thickness of a board | substrate is not specifically limited in this invention, Preferably, it is 10-2000 micrometers, More preferably, it is 50-800 micrometers.
上記のようにして本発明の成膜装置および成膜方法を用いることにより、ミストＣＶＤ法でも成膜レートに優れたものになり、均一な膜厚分布でかつ大面積成膜が可能となる。 By using the film forming apparatus and the film forming method of the present invention as described above, the film forming rate is excellent even by the mist CVD method, and a film can be formed with a uniform film thickness distribution and a large area.
以下、本発明の実施例を説明するが、本発明はこれらに限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited thereto.
（実施例１）
１．製造装置
まず、図１を用いて、本実施例で用いた成膜装置１を説明する。成膜装置１は、キャリアガスを供給するキャリアガス源２ａと、キャリアガス源２ａから送り出されるキャリアガスの流量を調節するための流量調節弁３ａと、希釈用キャリアガスを供給する希釈用キャリアガス源２ｂと、希釈用キャリアガス源２ｂから送り出される希釈用キャリアガスの流量を調節するための流量調節弁３ｂと、原料溶液４ａが収容されるミスト発生源４と、水５ａが入れられる容器５と、容器５の底面に取り付けられた超音波振動子６と、成膜室７と、ミスト発生源４から成膜室７までをつなぐ石英製の供給管９と、成膜室７内に設置されたホットプレート８と、排気管１７および排気ファン１１とを備えている。ホットプレート８上には、基板１０が設置されている。
Example 1
1. Manufacturing Apparatus First, the film forming apparatus 1 used in this example will be described with reference to FIG. The film forming apparatus 1 includes a carrier gas source 2a for supplying a carrier gas, a flow rate adjusting valve 3a for adjusting the flow rate of the carrier gas sent from the carrier gas source 2a, and a dilution carrier gas for supplying a dilution carrier gas. A source 2b, a flow rate adjusting valve 3b for adjusting the flow rate of the dilution carrier gas sent out from the dilution carrier gas source 2b, a mist generating source 4 in which the raw material solution 4a is stored, and a container 5 in which water 5a is placed. And an ultrasonic transducer 6 attached to the bottom surface of the container 5, a film forming chamber 7, a quartz supply pipe 9 connecting the mist generating source 4 to the film forming chamber 7, and the film forming chamber 7. The hot plate 8, the exhaust pipe 17 and the exhaust fan 11 are provided. A substrate 10 is installed on the hot plate 8.
２．原料溶液の作製
臭化ガリウム０．１ｍｏｌ／Ｌの水溶液を調整し、この際、さらに４８％臭化水素酸溶液を体積比で１０％となるように含有させ、これを原料溶液とした。
2. Preparation of Raw Material Solution An aqueous solution of gallium bromide 0.1 mol / L was prepared. At this time, a 48% hydrobromic acid solution was further added so as to be 10% by volume, and this was used as a raw material solution.
３．成膜準備
上記２．で得られた原料溶液４ａをミスト発生源４内に収容した。次に、基板１０として４インチのｃ面サファイア基板を用いて、ｃ面サファイア基板をホットプレート８上に設置し、ホットプレート８を作動させて成膜室７内の温度を５００℃にまで昇温させた。次に、流量調節弁３（３ａ、３ｂ）を開いてキャリアガス源２（２ａ、２ｂ）からキャリアガスを成膜室７内に供給し、成膜室７の雰囲気をキャリアガスで十分に置換した後、キャリアガスの流量を５Ｌ／ｍｉｎに、希釈用キャリアガスの流量を０．５Ｌ／ｍｉｎにそれぞれ調節した。なお、キャリアガスとして酸素を用いた。
3. Preparation of film formation The raw material solution 4a obtained in the above was accommodated in the mist generating source 4. Next, using a 4-inch c-plane sapphire substrate as the substrate 10, the c-plane sapphire substrate is placed on the hot plate 8, and the hot plate 8 is operated to raise the temperature in the film forming chamber 7 to 500 ° C. Allowed to warm. Next, the flow rate adjusting valve 3 (3a, 3b) is opened to supply the carrier gas from the carrier gas source 2 (2a, 2b) into the film forming chamber 7, and the atmosphere in the film forming chamber 7 is sufficiently replaced with the carrier gas. Then, the flow rate of the carrier gas was adjusted to 5 L / min, and the flow rate of the carrier gas for dilution was adjusted to 0.5 L / min. Note that oxygen was used as a carrier gas.
４．単層膜形成
次に、超音波振動子６を２．４ＭＨｚで振動させ、その振動を、水５ａを通じて原料溶液４ａに伝播させることによって、原料溶液４ａを霧化してミスト４ｂを生成した。このミスト４ｂが、キャリアガスによって成膜室７内に導入され、成膜室７内でミストが旋回して、図８に示されるような内向きに流れる旋回流が発生した。そして、大気圧下、５６０℃にて、成膜室７内で旋回流のミストが反応して、基板１０上に薄膜が形成された。なお、ミストの流速は４５．６ｃｍ／秒であり、成膜時間は３０分であった。
4). Next, the ultrasonic vibrator 6 was vibrated at 2.4 MHz, and the vibration was propagated to the raw material solution 4a through the water 5a, whereby the raw material solution 4a was atomized to generate a mist 4b. The mist 4b was introduced into the film forming chamber 7 by the carrier gas, and the mist swirled in the film forming chamber 7 to generate a swirling flow flowing inward as shown in FIG. Then, at atmospheric pressure and 560 ° C., the swirl mist reacted in the film forming chamber 7 to form a thin film on the substrate 10. The flow rate of mist was 45.6 cm / second, and the film formation time was 30 minutes.
５．評価
上記４．にて得られたα−Ｇａ２Ｏ３薄膜の相の同定をした。同定は、薄膜用ＸＲＤ回折装置を用いて、１５度から９５度の角度で２θ／ωスキャンを行うことによって行った。測定は、ＣｕＫα線を用いて行った。その結果、得られた薄膜はα−Ｇａ２Ｏ３であった。
5. Evaluation 4. The phase of the α-Ga 2 O 3 thin film obtained in (1) was identified. Identification was performed by performing 2θ / ω scanning at an angle of 15 to 95 degrees using an XRD diffractometer for thin films. The measurement was performed using CuKα rays. As a result, the obtained thin film was α-Ga 2 O 3 .
また、図５に示される基板１０上の薄膜の各測定箇所（Ａ１、Ａ２、Ａ３、Ａ４、Ａ５）につき、段差計を用いて膜厚を測定し、それぞれの膜厚の値から平均値を算出したところ、平均膜厚は、３，９６０ｎｍであった。そして、平均膜厚を成膜時間で割った成膜レートは、１３２ｎｍ／分であった。 Further, for each measurement point (A1, A2, A3, A4, A5) of the thin film on the substrate 10 shown in FIG. 5, the film thickness is measured using a step gauge, and the average value is calculated from the respective film thickness values. When calculated, the average film thickness was 3,960 nm. The film formation rate obtained by dividing the average film thickness by the film formation time was 132 nm / min.
（比較例）
図６を用いて、比較例で用いた成膜装置１９を説明する。ミストＣＶＤ装置１９は、基板２０を載置するサセプタ２１と、キャリアガスを供給するキャリアガス供給手段２２ａと、キャリアガス供給手段２２ａから送り出されるキャリアガスの流量を調節するための流量調節弁２３ａと、希釈用キャリアガスを供給する希釈用キャリアガス供給手段２２ｂと、希釈用キャリアガス供給手段２２ｂから送り出されるキャリアガスの流量を調節するための流量調節弁２３ｂと、原料溶液２４ａが収容されるミスト発生源２４と、水２５ａが入れられる容器２５と、容器２５の底面に取り付けられた超音波振動子２６と、内径４０ｍｍの石英管からなる供給管２７と、供給管２７の周辺部に設置されたヒーター２８と、排気口２９とを備えている。サセプタ２１は、石英からなり、基板２０を載置する面が水平面から４５度傾斜している。成膜室となる供給管２７とサセプタ２１をどちらも石英で作製することにより、基板２０上に形成される膜内に装置由来の不純物が混入することを抑制している。
(Comparative example)
The film forming apparatus 19 used in the comparative example will be described with reference to FIG. The mist CVD apparatus 19 includes a susceptor 21 on which the substrate 20 is placed, a carrier gas supply means 22a for supplying a carrier gas, and a flow rate adjusting valve 23a for adjusting the flow rate of the carrier gas sent from the carrier gas supply means 22a. A dilution carrier gas supply means 22b for supplying a dilution carrier gas, a flow rate adjusting valve 23b for adjusting the flow rate of the carrier gas sent from the dilution carrier gas supply means 22b, and a mist in which the raw material solution 24a is accommodated Installed in the periphery of the supply tube 27, a source 25, a container 25 in which water 25 a is placed, an ultrasonic transducer 26 attached to the bottom surface of the container 25, a supply tube 27 made of a quartz tube having an inner diameter of 40 mm, and the supply tube 27. The heater 28 and the exhaust port 29 are provided. The susceptor 21 is made of quartz, and the surface on which the substrate 20 is placed is inclined 45 degrees from the horizontal plane. Both the supply pipe 27 and the susceptor 21 serving as a film formation chamber are made of quartz, so that impurities derived from the apparatus are prevented from being mixed into the film formed on the substrate 20.
図６に示す成膜装置を用いたこと、および基板２０として１０ｍｍ角のｃ面サファイア基板を用いたこと以外は、実施例１と同様にして成膜した。得られた薄膜につき、上記実施例と同様にして、薄膜用ＸＲＤ回折装置を用いて、相を同定した。その結果、得られた薄膜はα−Ｇａ２Ｏ３であった。また、上記実施例と同様にして膜厚を測定した。なお、膜厚測定箇所は、図６に示される基板２０上の薄膜の各測定箇所（Ｂ１、Ｂ２、Ｂ３、Ｂ４およびＢ５）とした。結果を比較例として表１に示す。 A film was formed in the same manner as in Example 1 except that the film forming apparatus shown in FIG. 6 was used and a 10 mm square c-plane sapphire substrate was used as the substrate 20. About the obtained thin film, it carried out similarly to the said Example, and identified the phase using the XRD diffraction apparatus for thin films. As a result, the obtained thin film was α-Ga 2 O 3 . The film thickness was measured in the same manner as in the above example. In addition, the film thickness measurement location was made into each measurement location (B1, B2, B3, B4, and B5) of the thin film on the board | substrate 20 shown by FIG. The results are shown in Table 1 as comparative examples.
（実施例２）
基板１０として、１０ｍｍ角のｃ面サファイア基板を用いたこと以外は、実施例１と同様にして成膜した。得られた薄膜につき、上記比較例と同様にして、薄膜用ＸＲＤ回折装置を用いて、相を同定した。その結果、得られた薄膜はα−Ｇａ２Ｏ３であった。また、上記比較例と同様にして膜厚を測定した。なお、膜厚測定箇所は、基板２０を基板１０としたこと以外は、比較例と同様に、薄膜の各測定箇所（Ｂ１、Ｂ２、Ｂ３、Ｂ４およびＢ５）とした。結果を実施例２として表１に示す。
(Example 2)
A film was formed in the same manner as in Example 1 except that a 10 mm square c-plane sapphire substrate was used as the substrate 10. About the obtained thin film, the phase was identified using the XRD diffraction apparatus for thin films similarly to the said comparative example. As a result, the obtained thin film was α-Ga 2 O 3 . Further, the film thickness was measured in the same manner as in the comparative example. The film thickness measurement locations were the thin film measurement locations (B1, B2, B3, B4, and B5), as in the comparative example, except that the substrate 20 was the substrate 10. The results are shown in Table 1 as Example 2.
表１の結果から、平均膜厚、成膜レート、変動係数および面内均一性を求めた。結果を表２に示す。なお、平均膜厚は、各測定箇所の膜厚の平均値であり、成膜レートは、各測定箇所の膜厚の平均値を成膜時間（分）で割った値であり、変動係数は、膜厚の標準偏差を膜厚の平均値で割ったものであり、面内均一性は、平均値と、最大値または最小値との差を百分率で表して、バラツキの範囲を表したものである。 From the results in Table 1, the average film thickness, film formation rate, coefficient of variation, and in-plane uniformity were determined. The results are shown in Table 2. The average film thickness is the average value of the film thickness at each measurement location, the film formation rate is the value obtained by dividing the average value of the film thickness at each measurement location by the film formation time (minutes), and the coefficient of variation is The standard deviation of the film thickness is divided by the average value of the film thickness, and the in-plane uniformity is the difference between the average value and the maximum or minimum value, expressed as a percentage, indicating the range of variation. It is.
表１および表２から明らかなとおり、実施例では、成膜レートにおいて、桁違いに優れており、成膜レートや面内均一性等の成膜品質の差も歴然としていることがわかる。そのため、本発明の成膜装置および成膜方法は、従来のミストＣＶＤ装置よりも成膜レートや膜厚の均一性に優れている。 As is apparent from Tables 1 and 2, in the examples, the film formation rate is excellent by an order of magnitude, and it can be seen that the difference in film formation quality such as film formation rate and in-plane uniformity is obvious. Therefore, the film forming apparatus and film forming method of the present invention are superior in film forming rate and film thickness uniformity as compared with the conventional mist CVD apparatus.
（実施例３）
ガリウムアセチルアセトナートとアルミニウムアセチルアセトナートとがモル比で１：６となり、かつ塩酸が体積比で２％となるように水溶液を調整し、これを原料溶液とした。
得られた原料溶液を用いたこと、成膜温度を６００℃としたこと、キャリアガスの流量を８ＬＰＭとしたこと、成膜時間を３時間としたこと以外は、実施例１と同様にして成膜した。なお、ミストの流速は７３．０ｃｍ／秒であった。得られた膜につき、アルミニウムの含有率をＸ線にて測定した。ＸＲＤ測定結果を図９に示す。ＸＲＤ測定結果から、得られた膜は、今まで成膜が困難とされてきたコランダム構造のアルミニウム６２．８％含有ＡｌＧａＯ系半導体膜であった。また、得られたコランダム構造のＡｌＧａＯ系半導体膜につき、膜厚を測定したところ、７２０ｎｍであった。
今まではコランダム構造のＡｌＧａＯ系半導体膜が得られたとしても、５０ｎｍ以上の厚い膜を得ることは困難であったが、本発明によれば、７００ｎｍ以上もの厚いコランダム構造のＡｌＧａＯ系半導体膜を得ることができた。このことからも、本発明の成膜装置は、ミストＣＶＤ法の適性に優れ、さらに、成膜レートが格別に優れていることがわかる。
(Example 3)
An aqueous solution was prepared so that gallium acetylacetonate and aluminum acetylacetonate were in a molar ratio of 1: 6, and hydrochloric acid was in a volume ratio of 2%, and this was used as a raw material solution.
The process was performed in the same manner as in Example 1 except that the obtained raw material solution was used, the film formation temperature was 600 ° C., the carrier gas flow rate was 8 LPM, and the film formation time was 3 hours. Filmed. The mist flow rate was 73.0 cm / second. About the obtained film | membrane, the content rate of aluminum was measured by the X ray. The XRD measurement results are shown in FIG. From the XRD measurement results, the obtained film was an AlGaO-based semiconductor film containing 62.8% aluminum having a corundum structure, which has been difficult to form. Moreover, when the film thickness was measured about the obtained AlGaO type semiconductor film of the corundum structure, it was 720 nm.
Up to now, even if an AlGaO-based semiconductor film having a corundum structure has been obtained, it has been difficult to obtain a film having a thickness of 50 nm or more. However, according to the present invention, an AlGaO-based semiconductor film having a thickness of 700 nm or more can be obtained. I was able to get it. This also shows that the film forming apparatus of the present invention is excellent in the suitability of the mist CVD method and has a particularly excellent film forming rate.
本発明の成膜装置および成膜方法は、あらゆる成膜分野に用いることができ、工業的に有用である。特に、ミストＣＶＤ法にて得られる薄膜を成膜する場合には、本発明の成膜装置および成膜方法を好適に利用することができる。 The film forming apparatus and film forming method of the present invention can be used in any film forming field and are industrially useful. In particular, when a thin film obtained by the mist CVD method is formed, the film forming apparatus and the film forming method of the present invention can be suitably used.
１ 成膜装置
２ａ キャリアガス源
２ｂ 希釈用キャリアガス源
３ａ 流量調節弁
３ｂ 流量調節弁
４ ミスト発生源
４ａ 原料溶液
４ｂ ミスト
４ｃ 排気ガス
５ 容器
５ａ 水
６ 超音波振動子
６ａ 電極
６ｂ 圧電体素子
６ｃ 電極
６ｄ 弾性体
６ｅ 支持体
７ 成膜室
８ ホットプレート
９ 供給管
１０ 基板
１１ 排気ファン
１６ 発振器
１７ 排気管
１９ ミストＣＶＤ装置
２０ 基板
２１ サセプタ
２２ａ キャリアガス供給手段
２２ｂ 希釈用キャリアガス供給手段
２３ａ 流量調節弁
２３ｂ 流量調節弁
２４ ミスト発生源
２４ａ 原料溶液
２５ 容器
２５ａ 水
２６ 超音波振動子
２７ 供給管
２８ ヒーター
２９ 排気口
DESCRIPTION OF SYMBOLS 1 Film-forming apparatus 2a Carrier gas source 2b Dilution carrier gas source 3a Flow control valve 3b Flow control valve 4 Mist generation source 4a Raw material solution 4b Mist 4c Exhaust gas 5 Container 5a Water 6 Ultrasonic transducer 6a Electrode 6b Piezoelectric element 6c Electrode 6d Elastic body 6e Support body 7 Deposition chamber 8 Hot plate 9 Supply pipe 10 Substrate 11 Exhaust fan 16 Oscillator 17 Exhaust pipe 19 Mist CVD apparatus 20 Substrate 21 Susceptor 22a Carrier gas supply means 22b Dilution carrier gas supply means 23a Flow rate adjustment Valve 23b Flow control valve 24 Mist generation source 24a Raw material solution 25 Container 25a Water 26 Ultrasonic vibrator 27 Supply pipe 28 Heater 29 Exhaust port
Claims (11)
成膜部が、前記ミストまたは前記液滴を旋回させて内向きに流れる旋回流を発生させる手段を具備することを特徴とする成膜装置。 An atomization / droplet forming unit for atomizing or dropletizing a raw material solution, a transport unit for transporting a mist or droplet generated in the atomization / droplet forming unit to a substrate with a carrier gas, and the mist or the In a film forming apparatus including a film forming unit that heat-treats droplets to form a film on the substrate,
A film forming apparatus, wherein the film forming unit includes means for generating a swirling flow that swirls the mist or the droplets to flow inward .
前記成膜室内において、前記ミストまたは前記液滴を旋回させて内向きに流れる旋回流を発生させることを特徴とする成膜方法。 Mist or droplets generated by atomizing or dropletizing the raw material solution are transported to a substrate installed in a film forming chamber with a carrier gas, and then the mist or droplets are thermally reacted on the substrate. In a film forming method for forming a film,
In the film forming chamber, the mist or the droplet is swirled to generate a swirling flow that flows inward .
The atomization or liquid droplets, film deposition method according to any one of claims 7-10 carried out by ultrasonic vibration.
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| KR101708283B1 (en) | 2017-02-20 |
| TW201627521A (en) | 2016-08-01 |
| KR20160093510A (en) | 2016-08-08 |
| JP2016146442A (en) | 2016-08-12 |
| TWI535883B (en) | 2016-06-01 |
| CN105986246A (en) | 2016-10-05 |
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