JP2005029866A - 金属酸化物被膜の成膜方法および蒸着装置 - Google Patents
金属酸化物被膜の成膜方法および蒸着装置 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000007740 vapor deposition Methods 0.000 title claims description 61
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 27
- 239000000758 substrate Substances 0.000 claims abstract description 118
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000011941 photocatalyst Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 40
- 150000004706 metal oxides Chemical class 0.000 claims description 26
- 150000002736 metal compounds Chemical class 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000005019 vapor deposition process Methods 0.000 claims description 5
- 229910001510 metal chloride Inorganic materials 0.000 claims description 4
- 239000012702 metal oxide precursor Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 61
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 58
- 230000001699 photocatalysis Effects 0.000 abstract description 25
- 239000002131 composite material Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 4
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- 230000008021 deposition Effects 0.000 description 19
- 238000002347 injection Methods 0.000 description 18
- 239000007924 injection Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 15
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- 238000012360 testing method Methods 0.000 description 14
- 238000005229 chemical vapour deposition Methods 0.000 description 13
- 230000007423 decrease Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000010793 Steam injection (oil industry) Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
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- 238000009776 industrial production Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- -1 titanium alkoxide Chemical class 0.000 description 2
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/45502—Flow conditions in reaction chamber
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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Abstract
【解決手段】 TiCl4 蒸気と水蒸気を、それらの噴射流が基材に到着する前に交差することにより混合した後、混合蒸気を基材と接触させ、前記混合から基材との接触までの時間を3秒以内とする。TiCl4 蒸気は基材進行方向に対して逆向きに配置された多孔式ノズルから、水蒸気は、基材との交差角がより小さいスリット式ノズルから噴射することが好ましい。
【選択図】 図1
Description
40 mm 角の正方形の基材を石英製の反応セルに入れて、閉鎖循環ラインに接続し(合計内体積約3.0 L)、酸素を20 vol% 含む窒素ガスでアセトアルデヒドを希釈したガス(アセトアルデヒド濃度:250 ppm)を系内に導入した。このガスを循環させながら、水銀ランプからの紫外線を照射した。紫外線照射量は4mW/cm2であった。反応の追跡は、アセトアルデヒドが分解して生成する二酸化炭素の濃度を、循環ラインに接続した自動ガスクロマトグラフで経時的に測定することにより行った。光触媒活性は二酸化炭素の生成速度から評価した。
◎:均一性に優れる (干渉色が一様) 、
○:ほぼ均一、
△:やや不均一、
×:非常に不均一。
Claims (12)
- 加水分解性金属化合物の蒸気と水蒸気を基材に接触させて基材表面に金属酸化物前駆体の被膜を形成する蒸着工程と、この基材を次に酸化性雰囲気中で加熱して前記前駆体を金属酸化物に転化させる焼成工程とを含む、金属酸化物被膜の成膜方法であって、
蒸着工程において、使用する加水分解性金属化合物の蒸気と水蒸気を予め混合し、混合蒸気を混合から3秒以内に基材と接触させることを特徴とする金属酸化物被膜の成膜方法。 - 蒸着工程が、連続的に移動する基材に対して加水分解性金属化合物の蒸気と水蒸気を噴射することによって行われ、加水分解性金属化合物の蒸気の噴射流と水蒸気の噴射流とが基材に到着する前に交差させることにより前記混合を行う、請求項1に記載の金属酸化物被膜の成膜方法。
- 加水分解性金属化合物の蒸気を基材進行方向に対して逆向きに配置された多孔式ノズルから噴射し、水蒸気をスリット式ノズルから噴射する、請求項2記載の金属酸化物被膜の成膜方法。
- 基材面に対する加水分解性金属化合物の蒸気と水蒸気の噴射流中心線の角度 (それぞれ、θMとθH2O とする)が、30°≦θM≦80°かつ、θM>θH2O を満たし、加水分解性金属化合物の蒸気流速>水蒸気流速である、請求項2または3に記載の金属酸化物被膜の成膜方法。
- 加水分解性金属化合物の蒸気が金属塩化物である、請求項1〜4のいずれかに記載の金属酸化物被膜の成膜方法。
- 金属塩化物がTiCl4 蒸気であり、蒸着工程における基材温度が 150〜250 ℃であり、焼成工程における加熱温度が 300〜600 ℃である、請求項5に記載の金属酸化物被膜の成膜方法。
- 蒸着工程に供給するTiCl4 蒸気と水蒸気の比率がH2O/TiCl4 モル比=0.05〜4 となる割合である、請求項6に記載の金属酸化物被膜の成膜方法。
- 金属酸化物被膜が光触媒として機能するものである、請求項1〜7のいずれかに記載の金属酸化物被膜の成膜方法。
- 連続的に移動する基材の表面に2種類の蒸気の反応により生ずる被膜を形成するための蒸着装置であって、多孔式ノズルとスリット式ノズルとを備え、これらのノズルが、それらからの噴射流が互いに交差する向きに配置されていることを特徴とする蒸着装置。
- 多孔式ノズルが基材の進行方向に対して逆向きに配置されている、請求項9に記載の蒸着装置。
- 2種類の蒸気が加水分解性金属化合物の蒸気と水蒸気であり、加水分解性金属化合物の蒸気が多孔式ノズルから、水蒸気がスリット式ノズルから噴射される、請求項9または10に記載の蒸着装置。
- 多孔式ノズルの中心軸と基材面との角度θ1 が30〜80°であり、スリット式ノズルの中心軸と基材面との角度θ2 はθ1 より小さい、請求項11に記載の蒸着装置。
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JP2003272936A JP4124046B2 (ja) | 2003-07-10 | 2003-07-10 | 金属酸化物被膜の成膜方法および蒸着装置 |
CNA2004800194228A CN1820091A (zh) | 2003-07-10 | 2004-07-06 | 金属氧化物被膜的成膜方法及蒸镀装置 |
PCT/JP2004/009903 WO2005005686A1 (ja) | 2003-07-10 | 2004-07-06 | 金属酸化物被膜の成膜方法および蒸着装置 |
EP04747371A EP1650325A4 (en) | 2003-07-10 | 2004-07-06 | METHOD FOR FORMING METAL OXIDE COATING FILM AND STEAM SEPARATION DEVICE |
US10/564,015 US20070054044A1 (en) | 2003-07-10 | 2004-07-06 | Method for forming metal oxide coating film and vapor deposition apparatus |
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US20070054044A1 (en) | 2007-03-08 |
CN1820091A (zh) | 2006-08-16 |
EP1650325A4 (en) | 2009-06-03 |
WO2005005686A1 (ja) | 2005-01-20 |
EP1650325A1 (en) | 2006-04-26 |
JP4124046B2 (ja) | 2008-07-23 |
WO2005005686A8 (ja) | 2005-03-17 |
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