WO2009133699A1 - 加熱装置、膜形成装置、膜形成方法およびデバイス - Google Patents
加熱装置、膜形成装置、膜形成方法およびデバイス Download PDFInfo
- Publication number
- WO2009133699A1 WO2009133699A1 PCT/JP2009/001937 JP2009001937W WO2009133699A1 WO 2009133699 A1 WO2009133699 A1 WO 2009133699A1 JP 2009001937 W JP2009001937 W JP 2009001937W WO 2009133699 A1 WO2009133699 A1 WO 2009133699A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas
- substrate
- film
- temperature
- film forming
- Prior art date
Links
- 238000010438 heat treatment Methods 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims description 45
- 239000000758 substrate Substances 0.000 claims abstract description 314
- 239000011521 glass Substances 0.000 claims abstract description 123
- 238000007664 blowing Methods 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims description 479
- 239000010408 film Substances 0.000 claims description 242
- 229910052710 silicon Inorganic materials 0.000 claims description 80
- 239000010703 silicon Substances 0.000 claims description 80
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 79
- 229910052799 carbon Inorganic materials 0.000 claims description 68
- 238000005507 spraying Methods 0.000 claims description 59
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 55
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 51
- 230000008021 deposition Effects 0.000 claims description 51
- 229910000077 silane Inorganic materials 0.000 claims description 36
- 238000000197 pyrolysis Methods 0.000 claims description 32
- 239000010409 thin film Substances 0.000 claims description 31
- 229910052732 germanium Inorganic materials 0.000 claims description 25
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 25
- 239000004033 plastic Substances 0.000 claims description 25
- 229920003023 plastic Polymers 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 238000005121 nitriding Methods 0.000 claims description 17
- 230000001590 oxidative effect Effects 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 150000004756 silanes Chemical class 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910007264 Si2H6 Inorganic materials 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 229910052734 helium Inorganic materials 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 10
- 239000001307 helium Substances 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 238000000151 deposition Methods 0.000 abstract description 44
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 23
- 229920005591 polysilicon Polymers 0.000 description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 19
- 229910001873 dinitrogen Inorganic materials 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 9
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 9
- 235000012431 wafers Nutrition 0.000 description 9
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 230000007246 mechanism Effects 0.000 description 8
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 description 7
- 229910052986 germanium hydride Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005224 laser annealing Methods 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910020323 ClF3 Inorganic materials 0.000 description 2
- 101100441092 Danio rerio crlf3 gene Proteins 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910004014 SiF4 Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910000078 germane Inorganic materials 0.000 description 2
- -1 graphite Chemical compound 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004433 infrared transmission spectrum Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000000624 total reflection X-ray fluorescence spectroscopy Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67098—Apparatus for thermal treatment
- H01L21/67109—Apparatus for thermal treatment mainly by convection
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/24—Deposition of silicon only
-
- 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
- C23C16/45563—Gas nozzles
- C23C16/4557—Heated nozzles
-
- 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
- C23C16/45595—Atmospheric CVD gas inlets with no enclosed reaction chamber
-
- 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
-
- 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
- C23C16/46—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 heating the substrate
-
- 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
- C23C16/46—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 heating the substrate
- C23C16/463—Cooling of the substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02524—Group 14 semiconducting materials
- H01L21/02532—Silicon, silicon germanium, germanium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02587—Structure
- H01L21/0259—Microstructure
- H01L21/02595—Microstructure polycrystalline
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
Definitions
- the present invention relates to a heating apparatus for forming, for example, a silicon thin film on a glass substrate, a film forming apparatus provided with the heating apparatus, and a film forming method.
- the present invention relates to an improvement in film formation suitable for manufacturing a large area electronic device, for example, a support that supports this substrate on a substrate that cannot be heated to a high temperature, for example, a glass substrate or a substrate that has already completed a wiring process.
- Method for forming a film that grows or heats at a high temperature that requires a temperature higher than the temperature of the table such as a silicon film, a silicon oxide film, a silicon nitride film, or a ternary or more compound film, and a film forming apparatus therefor About.
- devices having a silicon thin film grown on a glass substrate include liquid crystal display devices, organic EL display devices, solar cells, and the like.
- the silicon thin film is used in any device by generating electrons or holes or accelerating it by an electric field.
- the characteristics of the silicon thin film grown on the glass substrate are inferior to those of the silicon crystal, and the mobility is 1/100 to 1/1000 or less.
- the temperature of the process is limited to a glass softening point (for example, 300 ° C.) or lower.
- a plasma amorphous silicon film that can be grown at 300 ° C. or lower or a recrystallized silicon film that is rapidly melted and solidified with a laser is used as the silicon thin film.
- the technical development for processing the substrate temperature at a low temperature below the glass substrate softening point is necessary for a device using the glass substrate.
- a technique for producing a silicon thin film that governs the efficiency of a solar cell device that converts light into electricity and the performance of a thin film transistor of a display device is important.
- thin film transistors are manufactured using an amorphous silicon film on a glass substrate.
- the film growth is performed by decomposing silane gas with plasma, it contains several percent or more of hydrogen, and bonding does not occur regularly. Therefore, the mobility is small, and the characteristics deteriorate with the aging of temperature and light irradiation. In particular, deterioration due to light is fatal in the application of solar cells.
- laser annealing is used because only the surface is annealed.
- This plasma melting seems to be more reproducible than laser melting, but it is necessary to arrange a large number of these in order to apply to a large area substrate.
- some devices in which a film is formed on a substrate must hold the substrate at a low temperature.
- a glass substrate as a substrate and a silicon substrate after a required film is already formed.
- large-area electronic devices such as a liquid crystal display device (LCD), an organic EL (electrominescence) display device, and a solar cell.
- Thin films are often used as amorphous films, crystal films, insulating films, and protective films in any device.
- the film to be grown on the substrate is, for example, non-equilibrium growth (growth without reversible reaction) in the case of a plasma-excited amorphous thin film. Therefore, it is more unstable in composition and structure than a high temperature thermal CVD (chemical vapor deposition) film. For this reason, the film contains impurities such as hydrogen, its structure is not stable, it is easy to absorb moisture, and its density is poor.
- the temperature of the processing step is lower than the softening point of the glass (for example, 300 ° C. to 400 ° C.) Limited to Because of this limitation, a plasma growth film that can be grown at 300 ° C. or lower or a film that has been surface-annealed with a laser is used as the thin film.
- the technique of processing the substrate at a low temperature is necessary for a device manufacturing process using a glass substrate.
- an electrode (through electrode) that penetrates the silicon substrate is formed after the wiring process is completed.
- Cu is embedded in deep through holes, but in order to prevent Cu from diffusing into the substrate silicon, a thick oxide film or nitride film is grown inside the holes.
- a dense film cannot be obtained, and even when grown on the surface, it does not grow sufficiently to the inner surface or the bottom surface.
- Non-Patent Document 1 there is a conventional technique for growing a film at a low temperature (for example, see Non-Patent Document 1).
- the substrate temperature is generally required to be 500 ° C. or higher at the lowest.
- plasma enhanced chemical vapor deposition is effective for growing a film flat on a substrate surface held at a low temperature.
- ECR Electro Cyclotron Resonance
- plasma CVD is capable of film growth even at a substrate temperature of 300 ° C. or lower, but it is used for bottom-up growth because it has poor coverage.
- ECR plasma has a limitation on the wavelength of microwaves and cannot be freely expanded, and therefore cannot be applied to large substrates such as glass.
- thermal CVD using a high temperature of 500 ° C. or higher is ideal, and since the film has a proven record in the semiconductor industry in terms of characteristics, a thermal CVD film can be formed without increasing the temperature of the substrate. If it can be grown, it is the most reliable and reliable method for forming a film.
- Japanese Patent Laid-Open No. 2000-60130 "Development of low-temperature growth technology for polycrystalline SiGe thin film by reactive thermal CVD" Tokyo Institute of Technology graduate School of Science and Engineering, Image Information Engineering Laboratory Hanna Laboratory [Search June 12, 2008] Internet (URL: http: //www.isl.titech.ac.jp-hanna/cvd.html)
- a glass substrate is inexpensive and a large substrate can be used.
- the substrate must be normally held at 300 degrees or less because of a low melting point.
- a film grown from silane gas by plasma CVD (chemical vapor deposition) at 300 ° C. is amorphous and contains dangling bonds and hydrogen, and the initial performance of mobility is 1000 times that of single crystal or polysilicon. Low. Since there is aging, there is no choice but to design the product within the range of low performance that can be obtained.
- the substrate temperature must be maintained at 400 ° C. or lower.
- a film grown from silane gas by plasma CVD (chemical vapor deposition) at 300 ° C. is amorphous and contains dangling bonds and hydrogen, and the initial performance of mobility is 1000 times that of single crystal or polysilicon. Low. Since there is aging, there is no choice but to design the product within the range of low performance that can be obtained.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide an inexpensive heating apparatus capable of efficiently forming a film on a glass substrate and an inexpensive film forming apparatus including the same. There is to do.
- the present invention has been made in consideration of such circumstances.
- the purpose of the present invention is to heat a surface film over the entire substrate or to form a thermal CVD film on the substrate surface while maintaining the substrate at a low temperature.
- Another object of the present invention is to provide an inexpensive film forming method and film forming apparatus that can be used.
- the temperature of the gas can be transmitted to the substrate.
- the gas flows parallel to the substrate surface unless a structure is made. Then, a stagnant layer is formed, and this layer becomes a thermal resistance, and the temperature of the gas cannot be transmitted to the substrate.
- FIG. 1 shows the principle of this heating device.
- This heating apparatus has a gas heating mechanism 21 that heats the introduced gas 12 by a heat source 20 to produce a high-temperature gas 22.
- the hot gas 22 travels through the gas guide 23 in parallel with its wall. Since the stagnant layer is formed, the efficiency of heat exchange with the vessel wall is low, and the beam exits in a beam shape while maintaining a high temperature, and hits the surface 25 of the glass substrate 24 perpendicularly.
- symbol C is a columnar part formed into a cylinder or a prism by carbon or the like, for example, and a gas passage R into which the introduction gas 12 is introduced is formed inside the columnar part.
- One end of the gas passage R communicates with the gas introduction pipe, and the other end communicates with the gas guide 23.
- the heat conduction of the glass substrate 24 is lower than that of silicon or metal. For this reason, the substrate surface 25 is heated, but the substrate back surface 27 in contact with the substrate support 26 is maintained at the temperature of the support 26. When the support base 26 is cooled, the glass substrate back surface 27 is kept at a low temperature depending on the cooling temperature. For this reason, even if the glass substrate surface 25 has a high temperature, the glass substrate 24 can be maintained at a temperature below the softening point of the glass. In order to improve thermal contact, vacuum suction or electrostatic chuck may be used. When the glass substrate 24 is moved, the high temperature surface 29 of the glass substrate surface 25 can be moved. Maintaining the substrate surface 25 at a higher temperature while maintaining the temperature of the substrate back surface 27 at 300 ° C. can be achieved by adjusting the capacity of the gas flow rate.
- polysilicon grows.
- Polysilicon can be grown at a surface temperature of 600 ° C. or higher from silane SiH 4 and at 570 ° C. or higher from disilane Si 2 H 6.
- phosphine PH3 is added as an example of a doping gas
- n-type polysilicon can be grown.
- diborane B2H6 is simultaneously added, p-type polysilicon grows.
- Polysilicon grows from silane, but when germane gas GeH4 is added at the same time, a mixed crystal of germanium and silicon grows.
- Silicon and germanium are crystal systems that can be mixed indefinitely. Since germanium strains silicon and changes its electronic structure, it is effective in efficiently absorbing sunlight at an appropriate ratio. Since an arbitrary composition is possible, a thin film having an inclined structure can be formed by changing the mixing amount of germanium in the thickness direction of the film.
- the surface 25 of the glass substrate 24 can be heated to a high temperature by spraying the high temperature gas 22 so as to collide with the glass substrate 24 substantially perpendicularly, and the glass substrate 24 is kept at a melting point or lower at 570 ° C. or higher. It is possible to grow a growing silicon film, a mixed crystal film of silicon and germanium, and a doping film thereof. If an oxidizing gas or a nitriding gas is introduced at the same time, a silicon oxide film or a silicon nitride film can be grown on the principle of chemical vapor deposition (CVD).
- CVD chemical vapor deposition
- the temperature of the gas can be transmitted to the substrate. Further, the gas flows parallel to the flat substrate surface. Then, a stagnant layer is formed in parallel with the substrate, and this stagnant layer becomes a thermal resistance layer, and the temperature of the gas cannot be transmitted to the substrate in a short time. In other words, it can be said that the transmission efficiency is lowered.
- the stagnant layer becomes thin. Or it can be made relatively thin so that it is virtually impossible. If the stagnant layer is thin, the temperature of the hot gas can be efficiently transmitted to the substrate. That is, the substrate surface efficiently receives heat from the hot gas incident vertically.
- the substrate has thermal conductivity depending on the material, and if the back surface of the substrate is cooled, it has a heat sink with a certain heat capacity, so the temperature rises and reaches the gas temperature. It is limited to. When this principle is used, only the substrate surface is heated, and the back surface and the inside of the substrate are maintained below a certain temperature.
- FIG. 6 schematically illustrates this principle. That is, when the hot gas 102 is squeezed into the beam shape 102a from the blowing hole 103a of the gas spraying device 103 and sprayed almost vertically onto the surface of the substrate 101, the substrate 101 is held by the support base 104, and thus the substrate 101
- the back surface temperature T ⁇ b> 1 is kept constant at a predetermined temperature by the coolant 104 a of the support base 104.
- the hot gas beam 102 a forms a stagnant layer 105 on the surface of the substrate 101.
- the thickness S of the stagnant layer 105 depends on the incident velocity V of the high temperature gas beam 102a and the incident angle incident on the surface of the substrate 101.
- the thickness S of the stagnant layer 105 decreases.
- the surface temperature of the substrate 101 is lower than the temperature T2 of the high temperature gas beam 102a. Since the heat transfer from the high temperature gas beam 102 a can be controlled by the thickness S of the stagnant layer 105, the surface temperature of the substrate 101 can be controlled by the temperature T 2 of the high temperature gas beam 102 a and the velocity V incident on the substrate 101. Therefore, only the substrate surface or the film thereon can be heated by the high temperature gas beam.
- FIG. 9 is a schematic diagram showing the principle of the film forming method of the present invention based on such a new technical idea. That is, according to the present invention, as shown in FIG. 9, for example, pyrolysis for forming a film having a deposition property is performed in a high temperature room 106 which is a high temperature space surrounded by two high temperature gas beams 102 b and 102 c and the surface of the substrate 101.
- a high temperature room 106 which is a high temperature space surrounded by two high temperature gas beams 102 b and 102 c and the surface of the substrate 101.
- the silane gas 107 when the silane gas 107 is supplied from the blowout hole 108, the thermal decomposition of the silane gas 107 proceeds in the high temperature room 106 to generate active species and diffuse the stagnant layer to grow a silicon film on the surface of the substrate 101. .
- heat transfer is performed with the stagnant layer 105 interposed therebetween, and the surface of the substrate 101 is lower than the temperatures T2 of the hot gases 102b and 102c, but is lower than the back surface temperature T1 of the substrate 101 and the inside.
- the temperature is high.
- the temperature T1 on the back surface of the substrate 101 and the temperature T2 of the high temperature gas 102b, 102c are measured by a temperature sensor such as a thermocouple, for example, but it is not easy to measure the actual temperature on the surface of the substrate 101.
- a temperature sensor such as a thermocouple
- the desired film is grown by adjusting the spray speed, spray angle (incidence), temperature, gas exhaust, etc. of the high temperature gas 102b, 102c accordingly. It is possible to make it. Since the thermal decomposition active species moves near the surface of the substrate 101 maintained at a high surface temperature, it can move to deep holes and form a film. In FIG.
- reference numeral 104b denotes a plurality of vacuum chuck grooves formed on the upper surface of the support base 104 for supporting the substrate 101, and the inside of these vacuum chuck grooves 104b, 104b,.
- the back surface 101b of the substrate 101 is attracted to the surface of the support base 104 and fixed and supported by evacuating to a vacuum. Further, the substrate 101 can be detached from the support base 104 by filling the vacuum chuck grooves 104b, 104b,... With air or the like.
- the invention according to claim 1 is a heating device characterized in that a high-temperature gas higher than the softening point temperature of the glass substrate is blown vertically onto the surface of the glass substrate placed on the support base.
- the invention according to claim 2 is the heating apparatus according to claim 1, wherein the gas is any one of nitrogen, hydrogen, Ar, He, oxygen, or a mixed gas of two or more thereof.
- the invention according to claim 3 has a heating device that vertically blows a high-temperature gas higher than the softening point temperature of the glass substrate onto the surface of the glass substrate placed on the support base, and the gas of the heating device
- the film forming apparatus is configured to thermally decompose with any one or a mixed gas and simultaneously spray a deposition gas for film deposition onto the surface of the glass substrate.
- a high-temperature gas higher than the softening point temperature of the glass substrate is blown vertically onto the surface of the glass substrate placed on the support table, and the gas is nitrogen, hydrogen, Ar, He, oxygen Or a mixed gas of two or more of them, and thermally decomposes together with any of the gases of the heating device or a mixed gas, and converts the deposition gas for film deposition into the glass substrate.
- the film forming apparatus is configured to be sprayed simultaneously on a surface.
- the invention according to claim 5 is the film forming apparatus according to claim 3 or 4, wherein the deposition gas contains silicon.
- a doping gas may be introduced simultaneously with the gas and the deposition gas.
- the deposition gas may contain silicon, and a doping gas may be introduced simultaneously with the gas and the deposition gas.
- an oxidizing gas and a nitriding gas may be introduced simultaneously with the gas and the deposition gas.
- the deposition gas contains silicon, and an oxidizing gas and a nitriding gas may be simultaneously introduced together with the gas and the deposition gas.
- the deposition gas may contain silicon, and a doping gas, an oxidizing gas, and a nitriding gas may be introduced simultaneously with the gas and the deposition gas.
- the invention according to claim 6 has a heating device that blows a high-temperature gas higher than the softening point temperature of the glass substrate perpendicularly to the surface of the glass substrate, and thermally decomposes together with the high-temperature gas to deposit a deposition gas for film deposition and doping
- the film forming apparatus is characterized in that a film having a tilted structure or a heterojunction structure is formed on a substrate by changing the kind and concentration of gas with respect to the thickness direction of the deposited film.
- the surface of the glass substrate may be a rough surface.
- the deposition gas may contain silicon, and the glass substrate may have a rough surface.
- the deposition gas may contain silicon, and a doping gas may be introduced simultaneously with the gas and the deposition gas so that the surface of the glass substrate is formed into a rough surface.
- the heating device that blows a high temperature gas higher than the softening point temperature of the glass substrate perpendicularly to the surface of the glass substrate, and it is thermally decomposed together with the high temperature gas, and the kind and concentration of deposition gas and doping gas for film deposition Is changed with respect to the thickness direction of the deposited film to form a film having a tilted structure or a heterojunction structure on the substrate, and the deposition gas contains silicon, and the gas, the deposition gas, a doping gas, an oxidation gas A gas and a nitriding gas may be introduced simultaneously, and the surface of the glass substrate may be formed into a rough surface.
- the invention according to claim 7 is a device including a thin film formed by the film forming apparatus according to any one of claims 3 to 6.
- the invention according to claim 8 anneals the film by spraying a plurality of high temperature gas beams on the film on the surface of the substrate supported on the support table that can be cooled substantially perpendicularly to each other at a predetermined interval.
- a film forming method characterized by the above.
- a plurality of high temperature gas beams are sprayed substantially perpendicularly to each other on the surface of the substrate supported on a support table that can be cooled, and the surfaces of the substrate and the high temperature gas beams are sprayed.
- the film forming method is characterized in that a pyrolytic gas for forming a film having a deposition property is supplied to a high-temperature space defined by and sprayed on the surface of the substrate.
- the invention according to claim 10 is characterized in that the substrate is made of glass or plastics, and the high-temperature gas has a temperature higher than the softening temperature of the glass or plastics. Is the method.
- the invention according to claim 11 is the film forming method according to claim 9, wherein the substrate is a silicon substrate on which a device is formed, and the high-temperature gas is at a temperature higher than a temperature at the time of film formation of the device. It is.
- the invention according to claim 12 is a substrate, a coolable and movable support that supports the substrate, a gas passage for passing a required gas, a heating device for heating the gas in the gas passage to a required high temperature gas, and the high temperature
- a film forming apparatus comprising: a gas spraying device provided with a plurality of blowout holes that squeeze gas into a beam shape and spray the gas substantially vertically onto a plurality of locations on the substrate surface.
- the invention according to claim 13 is characterized in that the required gas includes any one of nitrogen, hydrogen, argon, helium, oxygen, or a mixed gas of two or more of these. Forming device.
- the invention according to claim 14 includes a substrate, a coolable and movable support that supports the substrate, a gas passage for passing a required gas, a heating device for heating the gas in the gas passage to a required high temperature gas, and the high temperature
- a plurality of blowing holes that squeeze the gas into a beam shape and spray the gas substantially perpendicularly to a plurality of locations on the substrate surface, and a high-temperature space that is defined between the plurality of high-temperature gas beams and the substrate surface.
- a gas spraying device provided with a gas blowing hole for spraying a pyrolytic gas for film formation having a deposition property to the substrate surface through the film forming device.
- the invention according to claim 15 is the film forming apparatus according to claim 14, wherein the pyrolysis gas for forming the film contains silicon, carbon, or germanium.
- the pyrolysis gas for forming the film contains silane (SiH4, Si2H6) or halogenated silane, and the required gas is an oxidizing gas containing N2O, NO2 which reacts with these, or NH3
- the film forming apparatus includes one or both of nitriding gases including
- the pyrolysis gas for film formation includes silicon, carbon, or germanium, and the pyrolysis gas for film formation includes silane (SiH4, Si2H6) or halogenated silane, 15.
- the gas includes an oxidizing gas containing N2O and NO2 that reacts with these gases, a nitriding gas containing NH3, or both.
- a plurality of the gas spraying devices may be arranged side by side, and the support table may be configured to be movable in the direction in which the gas spraying devices are arranged.
- the required gas includes any one of nitrogen, hydrogen, argon, helium, oxygen, or a mixed gas of two or more of these, and a plurality of the gas spraying devices are arranged side by side. You may comprise the said support stand so that a movement is possible in the parallel arrangement direction.
- the pyrolysis gas for film formation includes silicon, carbon, or germanium, and a plurality of the gas spraying devices are arranged side by side, and the support base is configured to be movable in the juxtaposition direction of these gas spraying devices. Also good.
- the pyrolysis gas for forming the film contains silane (SiH4, Si2H6) or halogenated silane, and the required gas is an oxidizing gas containing N2O or NO2 that reacts with these or a nitriding gas containing NH3.
- silane SiH4, Si2H6
- halogenated silane an oxidizing gas containing N2O or NO2 that reacts with these or a nitriding gas containing NH3.
- One or both of them may be included, and a plurality of the gas spraying devices may be provided side by side, and the support base may be configured to be movable in the direction in which the gas spraying devices are provided side by side.
- the film-forming pyrolysis gas contains silicon, carbon, or germanium, the film-forming pyrolysis gas contains silane (SiH 4, Si 2 H 6) or halogenated silane, and the required gases are these
- the gas spraying apparatus includes a plurality of gas spraying devices arranged in parallel, and includes the support base in the juxtaposition direction of the gas spraying devices. It may be configured to be movable.
- the substrate may be made of glass or plastics, and the high temperature gas may have a temperature higher than the softening temperature of the glass or plastics.
- the required gas includes any one of nitrogen, hydrogen, argon, helium, oxygen, or a mixed gas of two or more thereof, the substrate is made of glass or plastics, and the high-temperature gas is this The temperature may be higher than the softening temperature of glass or plastics.
- the pyrolysis gas for forming the film may include silicon, carbon, or germanium, the substrate may be made of glass or plastics, and the high-temperature gas may have a temperature higher than the softening temperature of the glass or plastics. .
- the pyrolysis gas for forming the film contains silane (SiH4, Si2H6) or halogenated silane, and the required gas is an oxidizing gas containing N2O or NO2 that reacts with these or a nitriding gas containing NH3.
- the substrate may be made of glass or plastics, and the high-temperature gas may have a temperature higher than the softening temperature of the glass or plastics.
- the film-forming pyrolysis gas contains silicon, carbon, or germanium, the film-forming pyrolysis gas contains silane (SiH 4, Si 2 H 6) or halogenated silane, and the required gases are these
- the substrate is made of glass or plastics, and the high-temperature gas is higher than the softening temperature of the glass or plastics. High temperature may be used.
- a plurality of the gas spraying devices are arranged side by side, the support base is configured to be movable in the juxtaposition direction of the gas spraying devices, the substrate is made of glass or plastics, and the high-temperature gas is glass or plastic.
- the temperature may be higher than the softening temperature.
- the required gas includes any one of nitrogen, hydrogen, argon, helium, oxygen, or a mixed gas of two or more of these, and a plurality of the gas spraying devices are arranged side by side.
- the support base may be configured to be movable in the juxtaposed direction, the substrate is made of glass or plastics, and the high-temperature gas may be at a temperature higher than the softening temperature of the glass or plastics.
- the film-forming pyrolysis gas contains silicon, carbon, or germanium, and a plurality of the gas spraying devices are arranged side by side, and the support base is configured to be movable in the juxtaposition direction of these gas spraying devices,
- the substrate may be made of glass or plastics, and the hot gas may be at a temperature higher than the softening temperature of the glass or plastics.
- the pyrolysis gas for forming the film contains silane (SiH4, Si2H6) or halogenated silane, and the required gas is an oxidizing gas containing N2O or NO2 that reacts with these or a nitriding gas containing NH3.
- the gas spraying devices are arranged side by side, the support base is configured to be movable in the juxtaposition direction of the gas spraying devices, the substrate is made of glass or plastics, and the high temperature The gas may be at a temperature higher than the softening temperature of the glass or plastics.
- the film-forming pyrolysis gas contains silicon, carbon, or germanium, the film-forming pyrolysis gas contains silane (SiH 4, Si 2 H 6) or halogenated silane, and the required gases are these
- the gas spraying apparatus includes a plurality of gas spraying devices arranged in parallel, and includes the support base in the juxtaposition direction of the gas spraying devices. It may be configured to be movable, and the substrate may be made of glass or plastics, and the high temperature gas may have a temperature higher than the softening temperature of the glass or plastics.
- the substrate may be a silicon substrate on which a device is formed, and the high temperature gas may be set to a temperature higher than the temperature at the time of the film formation process of the device.
- the required gas includes any one of nitrogen, hydrogen, argon, helium, oxygen, or a mixed gas of two or more thereof, and the substrate is a silicon substrate on which a device is formed, and the high-temperature gas However, the temperature may be higher than the temperature during the film formation process of the device.
- the film-forming pyrolysis gas contains silicon, carbon, or germanium, and the substrate is a silicon substrate on which a device is formed.
- the high-temperature gas is set to a temperature higher than the temperature at the time of film formation of the device. Also good.
- the pyrolysis gas for forming the film contains silane (SiH4, Si2H6) or halogenated silane, and the required gas is an oxidizing gas containing N2O or NO2 that reacts with these or a nitriding gas containing NH3.
- silane SiH4, Si2H6
- halogenated silane an oxidizing gas containing N2O or NO2 that reacts with these or a nitriding gas containing NH3.
- the substrate may be a silicon substrate on which a device is formed, and the high-temperature gas may be at a temperature higher than the temperature at the time of film formation of the device.
- the film-forming pyrolysis gas contains silicon, carbon, or germanium, the film-forming pyrolysis gas contains silane (SiH 4, Si 2 H 6) or halogenated silane, and the required gases are these
- the substrate is a silicon substrate on which a device is formed, and includes either or both of an oxidizing gas containing N2O and NO2 that reacts with NO2, or a nitriding gas containing NH3, and the high-temperature gas is used during the film formation process of the device.
- the temperature may be higher than the temperature.
- a plurality of the gas spraying devices are arranged side by side, the support base is configured to be movable in the juxtaposition direction of the gas spraying devices, the substrate is a silicon substrate on which a device is formed, and the high-temperature gas is the device You may make it high temperature more than the temperature at the time of this film formation process.
- the required gas includes any one of nitrogen, hydrogen, argon, helium, oxygen, or a mixed gas of two or more of these, and a plurality of the gas spraying devices are arranged side by side.
- the support base may be configured to be movable in the juxtaposed direction, the substrate may be a silicon substrate on which a device is formed, and the high-temperature gas may have a temperature higher than the temperature at the time of the film formation process of the device.
- the film-forming pyrolysis gas contains silicon, carbon, or germanium, and a plurality of the gas spraying devices are arranged side by side, and the support base is configured to be movable in the juxtaposition direction of these gas spraying devices,
- the substrate may be a silicon substrate on which a device is formed, and the high temperature gas may have a temperature higher than a temperature at the time of the device film formation process.
- the pyrolysis gas for forming the film contains silane (SiH4, Si2H6) or halogenated silane, and the required gas is an oxidizing gas containing N2O or NO2 that reacts with these or a nitriding gas containing NH3.
- a plurality of the gas spraying devices are arranged side by side, the support base is configured to be movable in the juxtaposition direction of these gas spraying devices, and the substrate is a silicon substrate on which a device is formed,
- the high temperature gas may have a temperature higher than the temperature during the film forming process of the device.
- the film-forming pyrolysis gas contains silicon, carbon, or germanium, the film-forming pyrolysis gas contains silane (SiH 4, Si 2 H 6) or halogenated silane, and the required gases are these
- the gas spraying apparatus includes a plurality of gas spraying devices arranged in parallel, and includes the support base in the juxtaposition direction of the gas spraying devices. It may be configured to be movable, and the substrate may be a silicon substrate on which a device is formed, and the high-temperature gas may be set to a temperature higher than a temperature at the time of film formation of the device.
- a film is formed on the glass substrate by creating a high temperature gas and spraying it with the deposition gas so as to vertically collide with the glass substrate, so that laser annealing or microplasma is created and brought together.
- a polysilicon film can be formed and grown at a lower cost than the conventional apparatus for irradiation.
- only the substrate surface can be annealed (heated) by blowing a high-temperature gas beam almost vertically onto the substrate surface while maintaining the substrate placed on a support table that can be cooled and moved at a low temperature.
- a film can be formed by annealing only the film on the substrate surface.
- a thermally decomposable gas for forming a film having deposition properties is supplied to a high temperature space defined by a plurality of high temperature gas beams and a substrate surface, and the thermally decomposable gas is thermally decomposed in the high temperature space. Then, since it is sprayed on the substrate surface, a film is formed on the substrate surface.
- the stagnant layer of the thermal resistance layer is formed on the substrate surface, and the heat conduction to the substrate can be suppressed.
- the support base that supports the substrate can be cooled, the substrate temperature can be kept low, and inconveniences caused by the high temperature such as softening of the substrate can be prevented or suppressed.
- the support base can be moved, it enables annealing and film deposition over the entire area of the substrate, and by placing multiple types of gas beam spraying devices in the direction of substrate movement, multiple types of film formation can be performed. Makes it possible to do continuously on top.
- FIG. 2 is a schematic cross-sectional view of a film forming apparatus provided with a heating device configured according to substantially the same principle as the heating device shown in FIG.
- the glass substrate 24 has a thickness of 0.7 mm, for example, and is placed in close contact with the glass substrate support 26.
- the support base 26 has a vacuum suction groove 31 that effectively adsorbs the glass substrate 24 to make thermal contact, and the temperature of the back surface 32 of the glass substrate 34 is controlled by the temperature of the support base 26.
- the heating mechanism of the heating introduction gas 12 will be described.
- the heating mechanism is a solid flat carbon center plate 33 made of carbon (including graphite, isotropic carbon, etc.) and carbon solid flat plate left and right attached to the left and right sides, respectively.
- a pair of carbon side plates 39L and 39R is provided, and a groove 34 is provided in the depth direction of the carbon center plate 33 (the front and back direction in FIG. 2).
- nitrogen was used as the heating introduction gas 12. Nitrogen is introduced from above through the introduction pipe 35, passes through the groove 34, passes through the gap between the first slit 37 and the second slit 36, and collides with the glass substrate 24 almost vertically.
- the carbon center plate 33 is provided with a lamp 38 that penetrates in the depth direction as a heat source, and the carbon center plate 33 can be heated to, for example, 1000 ° C. according to the input power of the lamp 38.
- FIG. 3A is a longitudinal sectional view of the carbon center plate 33 and a pair of left and right carbon side plates 39L and 39R
- FIG. 3B is a sectional view taken along the line AA in FIG. 3A
- (D) is a YY sectional view of the same (B).
- These carbon center plate 33 and a pair of left and right carbon side plates 39L and 39R are used to form a pair of left and right first and second pairs shown in FIG.
- a pair of left and right grooves 34, 34 communicating with the second slits 36, 37, respectively, are formed.
- the pair of left and right grooves 34, 34 are formed so as to individually pass the introduced gas 12 in the vertical direction in FIG. 2, and the pair of left and right grooves 34, 34 are not connected in the left-right (lateral) direction.
- the carbon center plate 33 is fixed to the inlet 33a by inserting one end portion of the gas introduction pipe 35 in an airtight manner, and a gas inflow space 33b is formed in the inlet 33a.
- Reference numeral 33c in FIG. 3B is a plurality of vertical holes
- reference numeral 38a is an insertion hole into which the heating lamp 38 is inserted. It is.
- channel 34 is made as a channel
- a vertical groove 40 (corresponding to 33C) through which nitrogen escapes in the lower groove.
- the vertical groove 40 is located apart from the lower vertical groove in FIG. 2, and the nitrogen fed from the vertical groove 40 hits the ribs 41 serving as the upper and lower walls of the groove vertically, and the efficiency of the ribs 41 and It is often heat exchanged.
- Nitrogen that passes through the rib 41 of the carbon central plate 33 is efficiently heated and goes down.
- heated nitrogen passes through the first slit 37 and the second slit 36 formed by the carbon central plate 33 and the left and right side plates 39L and 39R, the flow is parallel to both walls of the slits 36 and 37.
- a stagnant layer is formed, which becomes thermal resistance and lowers the efficiency of heat exchange. For this reason, the introduced gas 12 heated by the upper lamp 38 collides with the glass substrate 24 while maintaining a high temperature.
- a slit-like cavity 42 into which a deposition gas 43 and a doping gas 44 are introduced and sprayed onto the substrate surface.
- the deposition gas 43 is supplied to the cavity 42 through the deposition gas pipe 43a, and the doping gas 44 is supplied into the cavity 42 through the doping gas pipe 44a.
- thermocouple 45 the temperature of the heating gas ejected from the ejection ports of the first and second slits 37 and 36 at the lower end is monitored by a thermocouple 45. Although the temperature of the surface of the glass substrate 24 cannot be measured accurately, the monitor temperature Tm of the monitoring thermocouple 45 can be measured.
- the monitor temperature Tm is set to 650 ° C.
- silane SiH 4 is introduced as the deposition gas 43
- a film can be grown on the glass substrate 24 by, for example, about 200 nm. It was.
- Exhaust is performed in an exhaust box 46 and exhausted through a duct of an exhaust mechanism 47. Since the atmospheric gas 48 is also exhausted from the exhaust box 46 at the same time, if necessary, it is necessary to create a nitrogen atmosphere according to the flow rate and the mixing ratio so that the mixed gas does not explode or burn.
- the deposited film 49 was examined. First, it was confirmed by total reflection fluorescent X-ray analysis that the deposited film 49 was a silicon film. In order to evaluate the crystallinity of the silicon film, the spectrum was examined by the backscattering Raman method. From the spectral peak shift, it was confirmed to be polysilicon. When a cross-sectional TEM was observed, a lattice image indicating polysilicon was observed. Therefore, it was confirmed that the deposited film 49 is polysilicon.
- B2H6 gas diluted to 1% with nitrogen as a doping gas was introduced at the same time to deposit a deposited film 49 on the glass substrate 24. It was confirmed that the film was p-type with a commercially available pn detector.
- Silicon can make mixed crystals with germanium. Mixed crystals are also used when making strained silicon and as a method of making heterogeneous junctions with silicon. Therefore, germane GeH4 gas diluted to 1% with nitrogen was introduced simultaneously with silane SiH4. Total reflection X-ray fluorescence analysis confirmed that the film had a composition of Si1-XGex containing silicon and germanium. When composition analysis was performed by SIMS analysis, the composition X of germanium increased with an increase in the flow rate of GeH4. From this, it was confirmed that X of Si1-XGex can be controlled depending on the amount of GeH4 introduced.
- a silicon oxide film can be deposited even with a single gas.
- a silicon nitride film can be formed by introducing ammonia gas NH3, which is a nitriding gas.
- Monosilane SiH4 was used here to deposit a silicon film, but disilane Si2H6 was used to lower the temperature, and a gas such as SiF4 was used freely to reduce the temperature further by utilizing reactivity. it can. In addition, it is free to introduce a cleaning gas such as ClF3 or NF3 that reacts with silicon from the inlet of a deposition gas, a doping gas, or a heating gas for cleaning the film-deposited device parts for stable operation of the device. Can design.
- the surface 25 of the glass substrate 24 is formed flat has been described.
- the present invention is not limited to this.
- the glass substrate surface 25 is roughened by a method such as sandblasting. You may form in. According to this, an initial nucleus for the growth of the deposited film 49 is easily formed, so that the film growth is uniform over the entire substrate surface 25.
- a thin film transistor device can be directly manufactured on the glass substrate. Further, when a thin film having a gradient composition is grown, a solar cell device using a gradient composition thin film or a heterojunction that can effectively use the spectrum of sunlight can be manufactured at low cost.
- FIG. 7 is a block diagram showing the configuration of the film forming apparatus 111 according to the second embodiment of the present invention
- FIG. 8 is an enlarged view of a main part thereof.
- the film forming apparatus 111 includes a substrate 112 for forming a desired film, a coolable and movable support base 113 that supports the substrate 112, and a gas spraying device 114. .
- the substrate 112 is made of a required large flat glass substrate, plastic substrate, or the like, and has a silicon oxide film or the same nitride on the surface 112a at a temperature higher than the softening temperature (for example, 300 ° C. to 400 ° C.) of the substrate 112. It is intended to form and grow a film of a high temperature thermal CVD material such as a film or polysilicon.
- a high temperature thermal CVD material such as a film or polysilicon.
- the support 113 is formed with a plurality of grooves 113b, 113b,...
- suction having an upper surface opened in the figure on the surface 113a that is in close contact with the back surface 112b of the substrate 112, and the inside of these grooves 113b, 113b,. Is exhausted by an exhaust device (not shown) to adsorb and fix the back surface 112b of the substrate 112.
- the substrate 112 can be detached from the support base 113 by filling the grooves 113b, 113b,.
- the support table 113 incorporates a coolant 113c that can be circulated therein so that the support table 113 can be appropriately controlled to a required temperature.
- the temperature of the back surface 112b of the substrate 112 can be controlled.
- the substrate support 113 can be configured to be movable in at least one of the horizontal direction (X) and the vertical direction (Y).
- a stainless cylindrical inner casing 116 is disposed in a stainless covered cylindrical outer casing 115, and the bottom surface of the outer casing 115 is opened.
- the outer casing 115 is provided with a pair of left and right exhaust pipes 121 and 122 on a pair of left and right side surfaces, respectively, and inner opening ends 121a and 122a of the exhaust pipes 121 and 122 are defined by the outer casing 115 and the inner casing 116.
- An opening is formed in the formed annular exhaust space 123, and exhaust such as nitrogen gas that has entered the exhaust space 123 from the bottom opening of the outer casing 115 is exhausted to the outside through the exhaust pipes 121 and 122.
- the heating device 117 is composed of a solid flat carbon center plate 124 made of carbon (for example, including graphite, isotropic carbon, etc.), and a solid carbon made of carbon that is attached and fixed to both the left and right sides.
- the carbon center plate 24 has a pair of left and right carbon side plates 125 and 126 in the shape of a flat plate, and the carbon center plate 24 opens toward the outer surface at both left and right end portions in FIG.
- a pair of left and right U-shaped grooves 127 and 128 extending in a vertical direction) are formed in a plurality of stages at a predetermined interval in the longitudinal direction of the carbon central plate 124 (vertical direction in FIG. 7).
- the outer ends of the pair of left and right grooves 127, 127,..., 128, 128... Are hermetically sealed by facing surfaces of the pair of left and right carbon side plates 125, 126 as shown in FIG.
- the carbon center plate 124 has the first and second lower gas blowing vertical holes 131 and 132 communicate with the grooves 127b and 128b at the lower ends in the column direction of the pair of left and right grooves 127 and 128, respectively.
- These first and second lower gas blowout vertical holes 131 and 132 are formed at the left and right side ends of the lower portion in the longitudinal direction of the carbon central plate 124, and are formed by recesses whose one side ends open to the outside. Is hermetically sealed by a pair of left and right carbon side plates 125 and 126.
- the first to third blowing holes 135 to 137 are illustrated as lines for convenience of illustration, but the planar (bottom) shape is a thin rectangular slit.
- the first to third blowing holes 135 to 137 may be a single elongated slit, but a plurality of small rectangular slits, a plurality of small circular holes, or a plurality of rectangular holes are arranged at predetermined intervals. You may comprise by arrange
- the third blowout hole 137 is connected to the blowout end of the third inner gas introduction pipe 120 so that the third gas is blown out from the third gas blowout hole 137 to the substrate surface 113a. .
- FIG. 9A is a front view of one side surface (for example, the left side surface) of the carbon central plate 124
- FIG. 9B is a sectional view taken along the line BB in FIG. 9A
- (D) is a DD cross-sectional view of the same (A)
- first and second lower gas blowout vertical holes 131, 132 are formed, respectively.
- These pair of left and right grooves 127, 127,..., 128, 128,... Are formed so as to individually pass the first and second introduced gases in the vertical direction in FIGS. 127 and 128 are not connected in the left-right (lateral) direction.
- Reference numeral 138 in FIG. 9A denotes a plurality of vertical communication grooves that communicate with each of the pair of left and right grooves 127 and 128 in the vertical direction in the figure, and 139 denotes an insertion hole into which the heating lamp 140 is inserted.
- the heating lamp 140 is, for example, a 100 V, 1 kW lamp, and is a clean heat source that is connected to the power line 119 and is supplied with required power to generate heat at a high temperature.
- reference numeral 141 denotes a temperature sensor such as a thermocouple, which detects the temperature of the first and second gases blown from the first and second gas blowing holes 135 and 136 to the surface 112a of the substrate 112, The temperature detection signal is supplied to a temperature control device (not shown).
- a temperature sensor such as a thermocouple
- the temperature control device receives the temperature detection signal and controls the power supplied from the power line 119 to the heating lamp 140, thereby setting the blowing temperature of the first and second gases to a predetermined temperature (for example, 650 ° C.). It can be controlled.
- energization of required power supplied from the power line 119 to the heating lamp 140 of the heating device 117 is started by a temperature control device (not shown).
- the carbon center plate 124 and the pair of left and right carbon side plates 125, 126 are heated to a high temperature by the heat generated by the heating lamp 140, and the first and second upper gas introduction vertical lines formed by these 124, 125, 126 are provided.
- nitrogen gas is introduced from the first and second gas introduction pipes 118 a and 118 b into the pair of left and right first and second upper gas introduction vertical holes 129 and 130 of the heating device 117.
- the nitrogen gas further passes through a pair of left and right grooves 127, 127,..., 128, 128, and first and second lower gas blowing vertical holes in order, and enters the first and second blowing holes 135 and 136.
- a required high temperature for example, 650 ° C.
- the first and second blow holes 135 and 136 are respectively squeezed into a beam and sprayed almost vertically onto the surface 112a of the substrate 112. It is done.
- a high-temperature room (space) 6 shown in FIG. 5 is provided between the two adjacent high-temperature nitrogen gas beams.
- the same high temperature room 42 is formed.
- the outlet temperature of the nitrogen gas is detected by the temperature sensor 141, and the electric power to the heating lamp 140 is controlled by the control device, and feedback control is performed to a required temperature.
- silane gas which is an example of a pyrolysis gas for forming a film having deposition properties.
- This silane gas is diluted to 1% with, for example, nitrogen gas, and is introduced into the third blow-out hole 137 in a state of being insulated by the quartz inner gas introduction pipe 20, that is, in a state of being insulated so as not to be heated by the heating device 117. Then, it is blown to the substrate surface 112 a side through the high temperature room 142 by the third blowing hole 37.
- the silane gas which is the third gas, is heated to a high temperature by the high temperature room 142 and thermally decomposed and sprayed onto the substrate surface 113a.
- a 10 ⁇ cm silicon wafer substrate was placed on the support table 113 at 300 ° C. as the substrate 112.
- Silane is introduced from the third gas inlet 118c and nitrogen gas containing an oxidizing gas N2O gas is introduced from the first and second gas inlets 118a and 118b, and the detection temperature of the temperature sensor 141 is set to 700 ° C.
- N2O gas is introduced from the first and second gas inlets 118a and 118b
- the detection temperature of the temperature sensor 141 is set to 700 ° C.
- a film grew on the surface 112a of the silicon wafer substrate.
- An attempt was made to measure the sheet resistance, but this film was an insulating film. From the infrared transmission spectrum using an infrared spectrophotometer using the same lot wafer on which this film was not deposited as a reference wafer, a Si—O peak was observed, and this film was an oxide of silicon. It could be confirmed.
- the first and second high-temperature gases are used during the plasma nitride film and silicon oxide film forming process used in manufacturing the device.
- a thermal CVD film can be formed on this silicon wafer substrate by heating to a temperature higher than or equal to (400 ° C.).
- the gas introduced into the first and second gas inlets 118a and 118b is replaced with nitrogen gas containing ammonia NH3 and the temperature detected by the temperature sensor 141 is set to 700 ° C.
- growth occurs on the substrate surface 112a.
- the resulting film was an insulating film.
- an Si—N vibration peak was observed from an infrared transmission spectrum of the film using an infrared spectrophotometer, and it was confirmed that the film was a nitride of silicon.
- monosilane SiH4 is used for depositing a silicon film on the substrate surface 112a.
- this monosilane may be replaced with disilane Si2H6, or reactive.
- a gas such as SiF4 in order to further lower the temperature by using.
- a gas containing silicon a gas containing carbon can be introduced.
- acetylene C2H2 can be used because it is easily pyrolyzed.
- a silicon carbide film is formed.
- GeH4 and SiH4 containing germanium are simultaneously introduced, a mixed crystal of silicon and germanium can be grown.
- the doped polysilicon by introducing the doping gas PH3 or B2H6 simultaneously with the silane gas. Further, it is possible to introduce a cleaning gas such as ClF3 or NF3 that reacts with silicon from the first to third inlets 118a to 118c of the heating gas for cleaning the components of the film forming apparatus 11 on which the film is deposited. It can be designed freely for stable operation.
- a cleaning gas such as ClF3 or NF3 that reacts with silicon from the first to third inlets 118a to 118c of the heating gas for cleaning the components of the film forming apparatus 11 on which the film is deposited. It can be designed freely for stable operation.
- films of different materials can be formed and grown by selecting a gas, it is possible to form a stacked film and select and design a stacked structure by moving the substrate 112.
- FIG. 10 is a schematic diagram showing the configuration of a film forming apparatus 111A according to a modification of the second embodiment of the present invention.
- the film forming apparatus 111A in the film forming apparatus 111 shown in FIG. 7, fixes and arranges a plurality of gas spraying apparatuses 114 side by side, for example, in a line at a required pitch.
- a support moving device 150 is provided that supports the gas spray devices 114, 114, 114 so as to be reciprocally movable in the juxtaposed direction.
- the rest of the configuration is almost the same as the configuration of the film forming apparatus 111 shown in FIG.
- an elevating table 152 is arranged on a base 151 so as to be adjustable in the vertical direction by a plurality of screws 153, 153,.
- This adjustment can be mechanically designed to be driven by a motor.
- a pair of bearings 155 and 155 that rotatably support both ends in the axial direction of the moving screw 154 and a motor 156 that rotates the moving screw 154 about its axis are disposed on the lifting platform 152. .
- a pair of left and right support legs 113c and 113d are projected on the lower surface of the support base 113 in FIG. 6, and screw holes that engage with the moving screw 154 are formed in the support legs 113c and 113d.
- the support base 113 moves to the left and right.
- a slide mechanism (not shown) that restricts the rotation so that the support base 113 does not rotate is provided.
- the support pedestal 113 is sequentially moved in the parallel arrangement direction of the plurality of gas spraying devices 114, 114, 114 by the support pedestal moving device 150, or the gas spraying devices 114, 114, 114 are reciprocated appropriately.
- the thickness of the film formed on the substrate surface 112a every time it passes through 114 can be increased.
- a plurality of types of films may be formed on the substrate surface 112a or a plurality of films may be stacked by appropriately changing the type and combination of high-temperature gas or film forming gas introduced into each gas spraying device 114. Can do.
- FIG. 11A and 11B are schematic plan views showing arrangement rows of a plurality of gas spraying devices 114, 114, 114 in the film forming apparatus 111A shown in FIG.
- FIG. 11A is characterized in that a plurality of gas spraying devices 114, 114, 114 are arranged in a line at a required interval in the moving direction of the substrate 112 indicated by an arrow in the drawing of the substrate 12.
- the configuration is the same as that of the film forming apparatus 111A shown in FIG.
- the length in the width direction (the length in the vertical direction in FIG. 11A) of the facing surface facing the substrate surface 112a is the length in the short direction of the substrate 112 ( This is suitable when the length is longer than the length in the vertical direction in FIG.
- FIG. 11 (B) is characterized in that a plurality of gas spraying devices 114, 114, 114 are disposed in the longitudinal direction of the substrate 112, that is, in an oblique direction with respect to the moving direction indicated by an arrow in the drawing.
- each gas spraying device 114 when the length in the width direction of each gas spraying device 114 (the length in the vertical direction in FIG. 11B) is shorter than the length in the vertical direction in the drawing of the substrate 112, these are the spraying devices 114. , 114, 114 can form a film over almost the entire length of the substrate 112 in the short direction.
- the substrate 112 is warped, so it is desirable to arrange the gas spraying device 114 in a position-divided manner. Further, when cutting out from the large substrate 112 on which the film is formed into a plurality of panel substrates 112, by placing a division of the arrangement of the plurality of gas spraying devices 114 at the boundary, the substrate surface is small by the small gas spraying device 114 for one panel. It can be designed as an apparatus capable of forming a film almost all over 112a.
- the set temperature of the temperature sensor 141 was selected and set in the range of 700 to 800 ° C., and a high-temperature nitrogen gas beam was blown almost vertically onto the film on the surface 112 a of the substrate 112. Thereafter, the Raman scattering spectrum of this film was examined, and it was confirmed that the peak shift component in the vicinity of 520 cm ⁇ 1 could be converted into polysilicon. That is, it was confirmed that the film can be fixedly formed on the annealed substrate surface 112a by heating the film placed on the substrate surface 112a by the film forming apparatus 111 or 111A.
- a thin film transistor device can be directly manufactured on the glass substrate. become.
- a thin film having a gradient composition is grown, it becomes possible to produce a solar cell device using a gradient composition thin film or a heterojunction that can effectively use the spectrum of sunlight at low cost.
- the carbon center plate 124 and the carbon side plates 125 and 126 are made of carbon.
- oxygen can be introduced into the center plate and the side plates by using a material that does not burn by oxygen. .
- silane gas was blown vertically along with the nitrogen gas at 650 ° C. to grow polysilicon on the glass substrate. Since it is possible to form a film whose composition is changed in a gradient manner by doping, devices such as a thin film transistor, an organic EL, and a solar cell can be manufactured on a large glass substrate at low cost.
- the present invention maintains a substrate made of glass or the like at a temperature lower than its softening point, and allows a high-temperature gas having a temperature higher than its softening point to be substantially perpendicular to the substrate in the form of a beam from two or more different outlets. It was shown that only the film on the surface of the substrate can be annealed while maintaining the substrate at a low temperature below the softening point. Further, a high-temperature gas stagnation room is created at a position sandwiched between two beam-like high-temperature gas beams on the substrate, and the pyrolysis gas for forming a film having deposition properties can be pyrolyzed with high efficiency in this high-temperature room.
- polysilicon can be grown on the substrate, and a high-temperature thermal CVD film used in a semiconductor can be stacked and grown. Furthermore, since it is also possible to generate a film or a laminated film structure in which the composition is changed in an inclined manner, for example, a device such as a thin film transistor, an organic EL (electroluminescence), or a solar cell on a large glass substrate is inexpensive. Can be made.
- the cross-sectional schematic diagram which is a principle figure of a heating apparatus.
- 1 is a schematic cross-sectional view of a film forming apparatus according to a first embodiment of the present invention.
- 2A is a longitudinal sectional view of the carbon center plate and the pair of left and right side plates shown in FIG. 2
- FIG. 2B is a sectional view taken along the line AA in FIG. 2A
- FIG. 2C is a sectional view taken along the line BB in FIG.
- (D) is a YY sectional view of (B).
- Schematic shows the method of the conventional film quality improvement.
- the schematic diagram which shows the principle of the film formation method which concerns on the 2nd Embodiment of this invention.
- FIG. 4 is a side sectional view showing a carbon center plate and a pair of left and right carbon side plates shown in FIG. 3.
- A is a front view of one side surface of the carbon central plate shown in FIG. 3
- B is a cross-sectional view taken along line BB of (A)
- C is a cross-sectional view taken along line CC of (A)
- D is the DD sectional view taken on the line (A).
- FIG. 6A is a schematic plan view of an arrangement example in which a plurality of gas spraying apparatuses shown in FIG. 6 are arranged in parallel in the moving direction of the substrate, and FIG. The schematic diagram which shows the example of arrangement
Landscapes
- 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)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
また、本発明は例えば大面積電子デバイスの作製に好適な膜形成の改良に係り、例えば高温にできない基板、例えばガラス基板上や既に配線工程を終了させた基板上に、この基板を支持する支持台の温度よりも高い温度を必要とする高温で成長または加熱する膜、例えばシリコン膜やシリコン酸化膜、シリコン窒化膜、または3元以上の化合物膜等の膜を形成する方法およびその膜形成装置に関する。
例えば、シリコン基板を貫通させる電極(貫通電極)形成を配線工程完了後に行う。一般には深い貫通孔の中にCuを埋め込むが、Cuが基板シリコンの中に拡散をするのを防ぐために、厚い酸化膜や窒化膜を孔の内側に成長させる。しかし、400℃以下の低温で成長させても緻密な膜が得られないのと、表面には成長しても内面や底面にまで十分に成長しない。成長を全表面に起こさせる必要がある。また、低温ガス雰囲気で成長させても活性種の表面移動が不十分であるために均一な厚みで孔の内面を被覆できない。これがウエハ張り合わせ製造の妨げになる。このような背景があるので低温で膜を成長させるための技術が従来からある(例えば、非特許文献1参照)。
この停滞層105の厚みSは高温ガスビーム102aの入射速度Vや基板101の表面に入射する入射角度に依存する。入射速度Vが速いほど停滞層105の厚みSは薄くなる。基板101表面の温度は高温ガスビーム102aの温度T2よりも低い。高温ガスビーム102aからの熱の伝達は停滞層105の厚みSで制御できるので、基板101の表面温度は高温ガスビーム102aの温度T2と基板101に衝突入射する速度Vにより制御できることになる。したがって、高温ガスビームにより基板表面またはその上の膜のみを加熱できる。
この高温ルームを作るためには、高温ガスビーム102aを所定間隔置いた2箇所から基板101の表面上に吹き付けることが有効である。すなわち、加熱した高温ガス102を離間配置された2箇所の吹出口103a,103aから吹出し、対向する基板101の表面にほぼ垂直に衝突入射させる。このために、これら2つの高温ガスビーム102b,102cにより挟まれた空間に高温空間が形成される。
図2は上記図1で示す加熱装置とほぼ同一の原理により構成された加熱装置を具備した膜形成装置の断面模式図を示す。図2に示すようにガラス基板24は例えば厚さが0.7mmで、ガラス基板支持台26の上に密着させて置かれる。この支持台26には真空吸着の溝31があり、ガラス基板24を吸着して熱接触を効果的に行い、支持台26の温度でガラス基板34の裏面32の温度が制御される。
堆積ガスとしてテトラエトキシシランTEOSを導入すると単独ガスでもシリコン酸化膜の堆積が可能である。窒化性のガスであるアンモニアガスNH3を導入するとシリコン窒化膜の生成も可能である。
図7は本発明の第2実施形態に係る膜形成装置111の構成を示す構成図であり、図8はその要部拡大図である。
また、支持台113の温度を制御することにより、基板112の裏面112bの温度を制御できる。必要なときは基板支持台113は水平方向(X)と垂直方向(Y)の少なくとも一方向に移動可能に構成できる。
この膜を堆積させていない同一ロットウエハを参照ウエハとして用いて赤外分光光度計を用いた赤外透過スペクトルからはSi-Oのピークが観察されて、この膜はシリコンの酸化物であることが確認できた。
また、ドーピングガスPH3やB2H6をシランガスと同時に導入してドーピングされたポリシリコンを成長させることも自由にできる。さらに、膜堆積した膜形成装置11の部品のクリーニングのためにシリコンと反応するClF3やNF3などのクリーニングガスを加熱用ガスの第1~第3の導入口118a~118cから導入することは装置の安定稼動のために自由に設計できる。
図10は本発明の第2の実施形態の変形例に係る膜形成装置111Aの構成を示す模式図である。この膜形成装置111Aは、上記図7で示す膜形成装置111において、そのガス吹付装置114の複数台を所要のピッチを置いて、例えば1列状に並設し固定する一方、上記支持台113を複数台のガス吹付装置114,114,114の並設方向に往復動可能に支持する支持台移動装置150を設けた点に特徴がある。これ以外の構成は、図7で示す膜形成装置111の構成とほぼ同一である。
12 導入ガス
13 コイル
14 高周波電力源
15 マッチング回路
16 マイクロプラズマ
17 基板
18 非結晶質膜
19 溶融膜
20 熱源
21 ガス加熱機構
22 高温ガス
23 ガスガイド
24 ガラス基板
25 基板表面
26 基板の支持台
27,32 基板裏面
28,31 真空吸着の溝
29 高温の表面
33 カーボン中央板
34 溝
35 ガス導入パイプ
36 第2スリット
37 第1スリット
38 熱源としてのランプ
39L,39R カーボン側板
40 縦溝
41 リブ
42 空洞
43 堆積用ガス
44 ドーピング用ガス
45 熱電対
46 排気箱
47 排気機構
48 雰囲気ガス
49 堆積した膜
101 基板
102a 高温ガスビーム
103 ガス吹付装置
103a 吹出孔
104 支持台
111,111A 膜形成装置
112 基板
112a 基板表面
112b 基板裏面
113 支持台
113a 支持台表面
113b 真空チャック吸着用の複数の溝
113c 冷却材
114 ガス吹付装置
115 外ケーシング
116 内ケーシング
117 加熱装置
118a 第1のガス導入口
118b 第2のガス導入口
118c 第3のガス導入口
119 電力線
120 第3の内側ガス導入管
121,122 一対の排気管
123 排気空間
124 カーボン中央板
125,126 左右一対のカーボン側板
127,128 左右一対の溝
127a,128a 左右一対の上部溝
129 第1の上部ガス導入縦孔
130 第2の上部ガス導入縦孔
131 第1の下部ガス吹出縦孔
132 第2の下部ガス吹出縦孔
135 第1のガス吹出孔
136 第2のガス吹出孔
137 第3のガス吹出孔
139 加熱用ランプ挿入孔
140 加熱用ランプ
141 温度センサ
142 高温ルーム
150 移動装置
151 基台
152 昇降台
153 ネジ
154 移動ネジ
155 軸受
156 モータ
Claims (17)
- 支持台上に載置されたガラス基板の表面に、このガラス基板の軟化点温度よりも高い高温ガスを垂直に吹き付けることを特徴とする加熱装置。
- 前記ガスが窒素、水素,Ar,He,酸素のいずれか、またはそれらの2種以上の混合ガスであることを特徴とする請求項1に記載の加熱装置。
- 支持台上に載置されたガラス基板の表面に、このガラス基板の軟化点温度よりも高い高温ガスを垂直に吹き付ける加熱装置を有し、
この加熱装置の前記ガスのいずれか、または混合ガスとともに加熱分解して膜堆積用の堆積ガスを前記ガラス基板の表面に同時に吹き付けるように構成されたことを特徴とする膜形成装置。 - 支持台上に載置されたガラス基板の表面に、このガラス基板の軟化点温度よりも高い高温ガスを垂直に吹き付け、前記ガスが窒素、水素,Ar,He,酸素のいずれか、またはそれらの2種以上の混合ガスである加熱装置を有し、
この加熱装置の前記ガスのいずれか、または混合ガスとともに加熱分解して膜堆積用の堆積ガスを前記ガラス基板の表面に同時に吹き付けるように構成されたことを特徴とする膜形成装置。 - 前記堆積ガスがシリコンを含むことを特徴とする請求項3または4に記載の膜形成装置。
- ガラス基板の軟化点温度よりも高い高温ガスをこのガラス基板の表面に垂直に吹き付ける加熱装置を有し、前記高温ガスと共に加熱分解して膜堆積用の堆積ガスとドーピングガスの種類と濃度を堆積膜の厚み方向に対して変化させることにより、傾斜構造または異種接合の構造の膜を基板の上に作ることを特徴とする膜形成装置。
- 請求項3ないし6のいずれか1項に記載の膜形成装置により形成された薄膜を搭載したことを特徴とするデバイス。
- 冷却可能の支持台上に支持された基板の表面にある膜上に、複数の高温ガスビームを相互に所要の間隔を置いてほぼ垂直に吹き付けて前記膜をアニールすることを特徴とする膜形成方法。
- 冷却可能の支持台上に支持された基板の表面上に、複数の高温ガスビームを相互に所要の間隔を置いてほぼ垂直に吹き付けると共に、これら高温ガスビームと前記基板の表面とにより画成された高温空間に、堆積性を有する膜形成用の熱分解ガスを供給し、前記基板の表面に吹き付けることを特徴とする膜形成方法。
- 前記基板がガラスまたはプラスチックスよりなり、前記高温ガスがこのガラスまたはプラスチックスの軟化温度よりも高い温度であることを特徴とする請求項8または9に記載の膜形成方法。
- 前記基板がデバイスを形成したシリコン基板であり、前記高温ガスが前記デバイスの膜形成工程時の温度以上の高温であることを特徴とする請求項9記載の膜形成方法。
- 基板およびこの基板を支持する冷却可能で移動可能な支持台と、
所要のガスを通すガス通路およびこのガス通路のガスを所要の高温ガスに加熱する加熱装置およびこの高温ガスをビーム状に絞って前記基板表面の複数箇所にほぼ垂直にそれぞれ吹き付ける複数の吹出孔を備えたガス吹付装置と、
を具備していることを特徴とする膜形成装置。 - 前記所要のガスは、窒素,水素,アルゴン,ヘリウム,酸素のいずれか1つ、またはこれらの2種以上の混合ガスを含むことを特徴とする請求項12記載の膜形成装置。
- 基板およびこの基板を支持する冷却可能で移動可能な支持台と、
所要のガスを通すガス通路およびこのガス通路のガスを所要の高温ガスに加熱する加熱装置およびこの高温ガスをビーム状に絞って前記基板表面の複数箇所にほぼ垂直にそれぞれ吹き付ける複数の吹出孔およびこれら吹出孔の間に配設されて、複数の高温ガスビームと基板表面とにより画成された高温空間を通して堆積性を有する膜形成用の熱分解ガスを前記基板表面に吹き付けるガス吹出孔を備えたガス吹付装置と、
を具備していることを特徴とする膜形成装置。 - 前記膜形成用の熱分解ガスは、シリコンまたはカーボンまたはゲルマニュームを含むことを特徴とする請求項14記載の膜形成装置。
- 前記膜形成用の熱分解ガスは、シラン(SiH4、Si2H6)またはハロゲン化シランを含み、前記所要のガスは、これらと反応するN2O,NO2を含む酸化ガス、あるいはNH3を含む窒化ガスのいずれか、または両者を含むことを特徴とする請求項14記載の膜形成装置。
- 前記膜形成用の熱分解ガスは、シリコンまたはカーボンまたはゲルマニュームを含み、前記膜形成用の熱分解ガスは、シラン(SiH4、Si2H6)またはハロゲン化シランを含み、前記所要のガスは、これらと反応するN2O,NO2を含む酸化ガス、あるいはNH3を含む窒化ガスのいずれか、または両者を含むことを特徴とする請求項14記載の膜形成装置。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2009801157553A CN102017084B (zh) | 2008-04-30 | 2009-04-28 | 加热装置、膜形成装置及膜形成方法和元件 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008119211A JP2009272343A (ja) | 2008-04-30 | 2008-04-30 | 加熱装置およびこれを具備した膜形成装置 |
JP2008-119211 | 2008-04-30 | ||
JP2008-162332 | 2008-06-20 | ||
JP2008162332A JP2010001541A (ja) | 2008-06-20 | 2008-06-20 | 膜形成方法および膜形成装置 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009133699A1 true WO2009133699A1 (ja) | 2009-11-05 |
Family
ID=41254923
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/001937 WO2009133699A1 (ja) | 2008-04-30 | 2009-04-28 | 加熱装置、膜形成装置、膜形成方法およびデバイス |
Country Status (3)
Country | Link |
---|---|
KR (1) | KR101598239B1 (ja) |
CN (1) | CN102017084B (ja) |
WO (1) | WO2009133699A1 (ja) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103137444A (zh) * | 2011-11-29 | 2013-06-05 | 上海华虹Nec电子有限公司 | 改善锗硅膜层厚度均一性的方法 |
JP5955089B2 (ja) * | 2012-05-08 | 2016-07-20 | 株式会社フィルテック | 流体加熱冷却シリンダー装置 |
KR101680291B1 (ko) * | 2015-10-02 | 2016-11-30 | 참엔지니어링(주) | 증착 장치 및 증착 방법 |
KR101862085B1 (ko) * | 2016-03-03 | 2018-05-30 | 에이피시스템 주식회사 | Ela 공정용 탈산소 장치 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0888186A (ja) * | 1994-09-19 | 1996-04-02 | Sanyo Electric Co Ltd | 薄膜形成方法 |
JP2005109081A (ja) * | 2003-09-30 | 2005-04-21 | Hitachi Displays Ltd | 表示装置の製造方法 |
JP2006339520A (ja) * | 2005-06-03 | 2006-12-14 | Sharp Corp | 酸化膜形成装置及び酸化膜形成方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000060130A (ja) | 1998-08-18 | 2000-02-25 | Toshiba Corp | 直流高電圧発生装置 |
KR100693396B1 (ko) * | 2003-12-26 | 2007-03-12 | 가부시키가이샤 유테크 | Cvd용 기화기, 용액 기화식 cvd 장치 및 cvd용 기화 방법 |
KR100584812B1 (ko) * | 2004-07-19 | 2006-05-30 | 뉴영엠테크 주식회사 | 유리기판의 열처리 장치 |
-
2009
- 2009-04-28 WO PCT/JP2009/001937 patent/WO2009133699A1/ja active Application Filing
- 2009-04-28 CN CN2009801157553A patent/CN102017084B/zh not_active Expired - Fee Related
- 2009-04-28 KR KR1020107024916A patent/KR101598239B1/ko active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0888186A (ja) * | 1994-09-19 | 1996-04-02 | Sanyo Electric Co Ltd | 薄膜形成方法 |
JP2005109081A (ja) * | 2003-09-30 | 2005-04-21 | Hitachi Displays Ltd | 表示装置の製造方法 |
JP2006339520A (ja) * | 2005-06-03 | 2006-12-14 | Sharp Corp | 酸化膜形成装置及び酸化膜形成方法 |
Also Published As
Publication number | Publication date |
---|---|
CN102017084B (zh) | 2012-09-05 |
CN102017084A (zh) | 2011-04-13 |
KR101598239B1 (ko) | 2016-02-26 |
KR20110011612A (ko) | 2011-02-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6427622B2 (en) | Hot wire chemical vapor deposition method and apparatus using graphite hot rods | |
US6214706B1 (en) | Hot wire chemical vapor deposition method and apparatus using graphite hot rods | |
JP3991315B2 (ja) | 薄膜形成装置及び方法 | |
CN100490077C (zh) | 碳化硅半导体元件及其制造方法 | |
US20110033638A1 (en) | Method and apparatus for deposition on large area substrates having reduced gas usage | |
JP2014505363A (ja) | マイクロ波プラズマを用いた薄膜堆積 | |
US20120068161A1 (en) | Method for forming graphene using laser beam, graphene semiconductor manufactured by the same, and graphene transistor having graphene semiconductor | |
DE112009004253T5 (de) | Trockenreinigung einer Siliziumoberfläche für Solarzellenanwendungen | |
JP5678883B2 (ja) | プラズマcvd装置、および、シリコン薄膜の製造方法 | |
US20100275981A1 (en) | Apparatus and method for manufacturing photoelectric conversion elements, and photoelectric conversion element | |
JP2566914B2 (ja) | 薄膜半導体素子及びその形成法 | |
US11511316B2 (en) | Plasma annealing method and device for the same | |
WO2009133699A1 (ja) | 加熱装置、膜形成装置、膜形成方法およびデバイス | |
US20060124971A1 (en) | Semiconductor structure, semiconductor device, and method and apparatus for manufacturing the same | |
CN101156247A (zh) | 使用透明基板制造多晶硅膜的方法和装置 | |
US9673062B1 (en) | Plasma processing method | |
JPWO2007049402A1 (ja) | 大気圧水素プラズマを用いた膜製造方法、精製膜製造方法及び装置 | |
JP2011001591A (ja) | ガス加熱装置 | |
Kakiuchi et al. | Characterization of Si and SiOx films deposited in very high‐frequency excited atmospheric‐pressure plasma and their application to bottom‐gate thin film transistors | |
JP5105620B2 (ja) | 膜形成方法および膜形成装置 | |
US20140291290A1 (en) | Plasma processing apparatus and method thereof | |
JP2010001541A (ja) | 膜形成方法および膜形成装置 | |
US10510876B2 (en) | Quantum doping method and use in fabrication of nanoscale electronic devices | |
US7833579B2 (en) | Method for in-situ polycrystalline thin film growth | |
JP2010001560A (ja) | 膜形成方法および膜形成装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980115755.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09738636 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20107024916 Country of ref document: KR Kind code of ref document: A |
|
32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 29/03/2011) |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 09738636 Country of ref document: EP Kind code of ref document: A1 |