JP2004275964A - Device and method for producing visible-light-responsive titanium dioxide-based photocatalyst - Google Patents
Device and method for producing visible-light-responsive titanium dioxide-based photocatalyst Download PDFInfo
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- JP2004275964A JP2004275964A JP2003073972A JP2003073972A JP2004275964A JP 2004275964 A JP2004275964 A JP 2004275964A JP 2003073972 A JP2003073972 A JP 2003073972A JP 2003073972 A JP2003073972 A JP 2003073972A JP 2004275964 A JP2004275964 A JP 2004275964A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 66
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000012159 carrier gas Substances 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000004544 sputter deposition Methods 0.000 claims abstract description 5
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 239000012876 carrier material Substances 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- -1 titanium alkoxide Chemical class 0.000 claims description 3
- 230000005284 excitation Effects 0.000 claims description 2
- 239000003039 volatile agent Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910021393 carbon nanotube Inorganic materials 0.000 claims 1
- 239000002041 carbon nanotube Substances 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 238000009489 vacuum treatment Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- Catalysts (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は可視光領域において高い光触媒機能を有する可視光応答型の二酸化チタン系光触媒の製造装置及び製造方法に関する。
【０００２】
【従来の技術】
光触媒活性が高く安全性や安定性などの面から、最も優れた光触媒材料として二酸化チタンが広く使用されている。しかし、従来使用されている二酸化チタン光触媒は紫外光領域の光のみを吸収するものであって、可視光領域の光は吸収できないため利用できなく、屋外で使用する場合には、太陽光の全エネルギーに占める３〜５％の紫外光しか利用されない。したがって、室内もしくは装置内で使用する際には、水銀ランプ等の特殊な紫外光を放射する光源の設置を必要とし、有害な紫外光を使うことから実用化の面で用途が大きく制約される。
【０００３】
このため、太陽光の大分を占める可視光を吸収し、高効率に有害物質を分解無害化できる新規な可視光応答型の光触媒が現在強く求められている。
近年、二酸化チタン光触媒にＣｒ、Ｖ、Ｎｉ、Ｆｅ等を微量イオン注入すると、二酸化チタンの吸収スペクトルが紫外から可視光領域へシフトすることが見出されており、二酸化チタン光触媒へＣｒ、Ｖ等の遷移金属をイオン注入する可視光応答型の二酸化チタン光触媒の製造方法が提案されている（特許文献１参照）。
【０００４】
Ｃｒ、Ｖ等の遷移金属イオンをイオン注入した二酸化チタン光触媒では、注入された遷移金属イオンは二酸化チタン表面の構造を変えることなく内部の適切な深さに均一に注入され格子の位置に置換型で存在しているため、注入前に備えていた二酸化チタン光触媒の高い紫外光領域における固有の光触媒活性を維持しながら、可視光領域においても高い光触媒活性が発現する。
【０００５】
【特許文献１】
特開平９−２６２４８２号公報
【０００６】
【発明が解決しようとする課題】
しかしながら、イオン注入する製造方法では、イオン注入を真空下で行うため、大規模な製造装置が必要で装置が高価となり、処理が複雑で厳密な製造工程管理を必要とし、大量処理が不可能で生産効率が高くないという問題がある。
本発明は、可視光応答型の二酸化チタン系光触媒の製造における上記問題を解決するものであって、真空処理の必要がなく、可視光応答型の二酸化チタン系光触媒を効率よく製造できる、簡単で安価な可視光応答型の二酸化チタン系光触媒の製造装置及び製造方法を提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明の可視光応答型の二酸化チタン系光触媒の製造装置は、二酸化チタン光触媒前駆物質とナノカーボン材などの光触媒担体物質とキャリアガスの入口及び調製された光触媒の出口を有するハウジングと、ハウジング内にプラズマを発生させる電極とを備え、キャリアガスをプラズマ励起して光触媒前駆物質を活性種として活用し、二酸化チタン光触媒をナノカーボン材などの光触媒担体に担持させる光触媒の製造装置において、少なくとも一方の電極の前段部分の表面と後段部分の表面とを異なる物質で構成している。
【０００８】
この製造装置において、少なくとも一方の電極の前段部分の表面は、二酸化チタン光触媒にドープされ可視光領域における光触媒活性を発現させる注入物質で構成し、また、電極の前段部分の表面の注入物質がクラスタ飛散するように、プラズマがスパッタ条件に設定されることが好ましい。
本発明の可視光応答型の二酸化チタン系光触媒の製造方法では、上記製造装置のハウジングに、光触媒前駆物質としてＴｉＣｌ４ やチタニウムアルコキサイドないし有機チタニウム化合物など揮発性化合物、光触媒担体物質としてフラーレンやナノチューブ状のナノカーボン材、キャリアガスとしてＯ２ を導入し、キャリアガスをプラズマ励起して活性種として活用し、ＴｉＯ２ 創製中にドープ物質が二酸化チタンの格子の位置に置換型でドープされた二酸化チタン光触媒を光触媒担体に担持させる。
ドープ物質としては、二酸化チタンに可視光領域において光触媒活性を発現させるＣｒ、Ｖ、ＮｉまたはＦｅ等の遷移金属を用いることが好ましい。
【０００９】
【発明の実施の形態】
図１は本発明の可視光応答型の二酸化チタン系光触媒の製造装置の構成図である。
この可視光応答型の二酸化チタン系光触媒の製造装置は、二酸化チタン光触媒前駆物質の入口１、光触媒担体物質とキャリアガスの入口２、及び調製された光触媒の出口３を有するハウジング４と、ハウジング４内にプラズマを発生させるための電極である中心電極５と外部電極６とを備えている。
【００１０】
中心電極５はハウジング４の中心にその内壁と所定の間隔を開けて設けられ、外部電極６は中心電極５を包囲するようにハウジング４の外壁上に設けられている。そして、ハウジング４の内壁と中心電極５との間には、外気から遮断されたプラズマ生成空間７が形成されている。
ハウジング４は石英ガラス等の誘電体で製作してもよく、金属または合金等の導電体で製作してもよい。
【００１１】
なお、ハウジング４が導電体である場合には、ハウジング４の中心電極５と対向する部分を外部電極６として使用することもできる。
中心電極５は、Ｃｕ、Ａｕ、Ｐｔ、Ｐｄ、Ｆｅ、Ｎｉ等で製作される。
この中心電極５は、前段部分５Ａの表面と後段部分５Ｂの表面とが異なる物質で構成されるようになっており、ここでは、二酸化チタンにドープされて可視光領域における光触媒活性を発現させるＣｒが、ドープ物質として前段部分５Ａの表面にコートされている。
【００１２】
中心電極５と外部電極６は電源８に接続されている。中心電極５の前段部分５Ａと外部電極６の前段部分６Ａは前段部分電源８Ａ、中心電極５の後段部分５Ｂと外部電極６の後段部分６Ｂは後段部分電源８Ｂからそれぞれ高圧の交流電圧が印加される。
可視光応答型の二酸化チタン系光触媒を製造するときには、入口１から二酸化チタン光触媒前駆物質としてＴｉＣｌ４ やチタニウムアルコキサイドないし有機チタニウム化合物からなる少なくとも一種の揮発性チタニウム化合物、入口２から光触媒担体物質としてフラーレンやナノチューブ状のナノカーボン材、キャリアガスとしてＯ２ が導入される。導入されたこれらの原料は、プラズマ生成空間７を通って出口３へ誘導される。このとき、プラズマ生成空間７で反応が進行する。
【００１３】
中心電極５と外部電極６には電源８から高圧の交流電圧（例えば１０ｋＶ、１ｋＨｚ）が印加されて、プラズマ生成空間７でキャリアガスをプラズマ励起する。
中心電極５は前段部分５Ａの表面物質がＣｒであり、図２に示すグロー領域で電圧を印加しプラズマをスパッタ条件に設定することにより、プラズマ生成空間７中にＣｒのクラスタがプラズマ飛散する。また、光触媒前駆物質として、例えばＴｉＣｌ４ を使用した場合は、ＴｉＣｌ４ はＴｉとＣｌの結合が解離する。
【００１４】
後段部分５Ｂでは、アーク領域で電圧を印加しプラズマを非スパッタ条件に設定することにより、周辺のプラズマ生成空間７において、次式に示すようにＣｒイオンが注入された酸化チタンが生成され、この酸化チタンがナノカーボン上に担持される。
【００１５】
【化１】
上記の可視光応答酸化チタン系光触媒生成の化学反応は式（２）〜（５）に示される。
ＴｉＣｌ４ →Ｔｉ＋２Ｃｌ２ ・・・・・（２）
Ｔｉ＋Ｏ２ →ＴｉＯ２ ・・・・・・・・（３）
ＴｉＯ２ ＋Ｃｒ・・・・・・・・・・・（４）
ＴｉＯ２ ＋Ｃｒ ｏｎ ＮＣＴｓ・・・（５）
プラズマ生成空間７を通過した物質は、反応生成物、キャリアガス、未反応ガスの混合物として出口３から装置外へ排出される。この混合物から、目的とするＣｒイオンがドープされた二酸化チタンがナノカーボンに担持されている可視光応答型の二酸化チタン系光触媒を分離回収する。残余の生成物はキャリアガス、未反応ガスと共に入口１、２へ再投入される。
【００１７】
このように、キャリアガスをプラズマ励起して活性種として活用し、ＴｉＯ２ にＣｒなどがドープされた二酸化チタン光触媒をナノカーボンに担持させた、可視光応答型の二酸化チタン系光触媒は、紫外光から可視光領域において高い光触媒活性を発現する。
【００１８】
【発明の効果】
以上説明したように、本発明の可視光応答型の二酸化チタン系光触媒の製造装置は、真空処理の必要がなく、構成が簡単で装置コストを低減でき、可視光応答型の二酸化チタン系光触媒を効率よく製造することができる。
また、本発明の可視光応答型の二酸化チタン系光触媒の製造方法により、可視光領域において極めて高い光触媒活性を発現する可視光応答型の二酸化チタン系光触媒が得られる。
【図面の簡単な説明】
【図１】図１は本発明の可視光応答型の二酸化チタン系光触媒の製造装置の構成図である。
【図２】電極に印加される電圧の説明図である。
【符号の説明】
１ 入口
２ 入口
３ 出口
４ ハウジング
５ 中心電極
５Ａ 前段部分
５Ｂ 後段部分
６ 外部電極
６Ａ 前段部分
６Ｂ 後段部分
７ プラズマ生成空間
８ 電源
８Ａ 前段部分電源
８Ｂ 後段部分電源[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an apparatus and method for producing a visible light responsive titanium dioxide photocatalyst having a high photocatalytic function in the visible light region.
[0002]
[Prior art]
Titanium dioxide is widely used as the most excellent photocatalytic material from the viewpoint of high photocatalytic activity, safety and stability. However, the titanium dioxide photocatalyst conventionally used absorbs only light in the ultraviolet light range, and cannot be used because it cannot absorb light in the visible light range. Only 3-5% of the energy in the ultraviolet light is used. Therefore, when used indoors or in equipment, it is necessary to install a light source that emits special ultraviolet light such as a mercury lamp, and the use of harmful ultraviolet light is greatly restricted in terms of practical use. .
[0003]
For this reason, a novel visible light responsive photocatalyst that absorbs visible light, which accounts for a large portion of sunlight, and can decompose and detoxify harmful substances with high efficiency is currently strongly demanded.
In recent years, it has been discovered that when a small amount of Cr, V, Ni, Fe, or the like is implanted into a titanium dioxide photocatalyst, the absorption spectrum of titanium dioxide shifts from ultraviolet to visible light. A method for producing a visible light responsive titanium dioxide photocatalyst in which a transition metal is ion-implanted has been proposed (see Patent Document 1).
[0004]
In a titanium dioxide photocatalyst in which transition metal ions such as Cr and V are ion-implanted, the implanted transition metal ions are uniformly implanted at an appropriate depth inside without changing the structure of the titanium dioxide surface, and are substituted at lattice positions. Therefore, while maintaining the inherent photocatalytic activity in the high ultraviolet light region of the titanium dioxide photocatalyst provided before injection, a high photocatalytic activity is also exhibited in the visible light region.
[0005]
[Patent Document 1]
JP-A-9-262482
[Problems to be solved by the invention]
However, in the manufacturing method in which the ion implantation is performed, since the ion implantation is performed in a vacuum, a large-scale manufacturing apparatus is required and the apparatus is expensive, the processing is complicated, and strict control of the manufacturing process is required. There is a problem that the production efficiency is not high.
The present invention solves the above-mentioned problem in the production of a visible light responsive titanium dioxide photocatalyst, which eliminates the need for vacuum treatment and can efficiently produce a visible light responsive titanium dioxide photocatalyst. An object of the present invention is to provide an inexpensive apparatus and method for producing a visible light responsive titanium dioxide photocatalyst.
[0007]
[Means for Solving the Problems]
An apparatus for manufacturing a visible light responsive titanium dioxide photocatalyst according to the present invention includes a housing having an inlet for a titanium dioxide photocatalyst precursor, a photocatalyst carrier material such as a nanocarbon material, an inlet for a carrier gas, and an outlet for a prepared photocatalyst; In the photocatalyst manufacturing apparatus that includes an electrode that generates plasma, excites a carrier gas by plasma and utilizes a photocatalyst precursor as an active species, and supports a titanium dioxide photocatalyst on a photocatalyst carrier such as a nanocarbon material. The surface of the former part and the surface of the latter part of the electrode are made of different materials.
[0008]
In this manufacturing apparatus, at least one of the front surfaces of the electrodes is formed of an injection material doped with titanium dioxide photocatalyst to exhibit photocatalytic activity in the visible light region, and the injection material on the front surface of the electrodes is clustered. Preferably, the plasma is set to sputtering conditions so that it is scattered.
In the method for producing a visible light responsive titanium dioxide photocatalyst of the present invention, a volatile compound such as TiCl 4 or titanium alkoxide or an organic titanium compound is used as a photocatalyst precursor, and a fullerene or nanotube nano carbon material, introducing O 2 as a carrier gas, utilizing the carrier gas as the active species by plasma excitation, dopant into TiO 2 created is doped with substituted to the position of the lattice of titanium dioxide A titanium dioxide photocatalyst is supported on a photocatalyst carrier.
As the doping substance, it is preferable to use a transition metal such as Cr, V, Ni, or Fe that causes titanium dioxide to exhibit photocatalytic activity in the visible light region.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
FIG. 1 is a configuration diagram of an apparatus for producing a visible light responsive titanium dioxide photocatalyst according to the present invention.
This visible light responsive titanium dioxide photocatalyst manufacturing apparatus comprises a housing 4 having an inlet 1 for a titanium dioxide photocatalyst precursor, an inlet 2 for a photocatalyst carrier material and a carrier gas, and an outlet 3 for a prepared photocatalyst; A central electrode 5 which is an electrode for generating plasma therein and an external electrode 6 are provided.
[0010]
The center electrode 5 is provided at a predetermined distance from the inner wall of the housing 4 at the center thereof, and the outer electrode 6 is provided on the outer wall of the housing 4 so as to surround the center electrode 5. A plasma generation space 7 is formed between the inner wall of the housing 4 and the center electrode 5 and is shielded from the outside air.
The housing 4 may be made of a dielectric such as quartz glass or a conductor such as a metal or an alloy.
[0011]
When the housing 4 is a conductor, a portion of the housing 4 facing the center electrode 5 can be used as the external electrode 6.
The center electrode 5 is made of Cu, Au, Pt, Pd, Fe, Ni, or the like.
The center electrode 5 has a structure in which the surface of the front part 5A and the surface of the rear part 5B are made of different materials. In this case, the center electrode 5 is doped with titanium dioxide to exhibit photocatalytic activity in the visible light region. Is coated on the surface of the former part 5A as a doping substance.
[0012]
The center electrode 5 and the external electrode 6 are connected to a power supply 8. A high AC voltage is applied to the front part 5A of the center electrode 5 and the front part 6A of the external electrode 6 from the front part power supply 8A, and to the rear part 5B of the center electrode 5 and the back part 6B of the external electrode 6 from the rear
When producing a visible light responsive titanium dioxide photocatalyst, at least one volatile titanium compound made of TiCl 4 , titanium alkoxide or an organic titanium compound as a titanium dioxide photocatalyst precursor from the inlet 1, and a photocatalyst carrier material from the inlet 2. Fullerene or nanotube-like nanocarbon material, and O 2 as a carrier gas. These introduced raw materials are guided to the outlet 3 through the plasma generation space 7. At this time, the reaction proceeds in the plasma generation space 7.
[0013]
A high AC voltage (for example, 10 kV, 1 kHz) is applied from a power supply 8 to the center electrode 5 and the external electrode 6, and the carrier gas is plasma-excited in the plasma generation space 7.
The surface material of the center electrode 5 in the front part 5A is Cr. By applying a voltage in the glow region shown in FIG. 2 and setting the plasma to the sputtering condition, the clusters of Cr are scattered in the plasma generation space 7 by plasma. When TiCl 4 is used as the photocatalyst precursor, for example, the bond between Ti and Cl is dissociated in TiCl 4 .
[0014]
In the latter part 5B, by applying a voltage in the arc region and setting the plasma to a non-sputtering condition, titanium oxide into which Cr ions are implanted as shown in the following equation is generated in the peripheral plasma generation space 7, and this is generated. Titanium oxide is supported on the nanocarbon.
[0015]
Embedded image
The chemical reactions for producing the visible light-responsive titanium oxide-based photocatalyst are shown in equations (2) to (5).
TiCl 4 → Ti + 2Cl 2 (2)
Ti + O 2 → TiO 2 (3)
TiO 2 + Cr ・ ・ ・ (4)
TiO 2 + Cr on NCTs (5)
The substance that has passed through the plasma generation space 7 is discharged out of the apparatus from the outlet 3 as a mixture of a reaction product, a carrier gas, and an unreacted gas. From this mixture, a visible light responsive titanium dioxide-based photocatalyst in which titanium dioxide doped with a desired Cr ion is supported on nanocarbons is separated and recovered. The remaining products are recharged to the inlets 1 and 2 together with the carrier gas and the unreacted gas.
[0017]
As described above, the visible light responsive titanium dioxide photocatalyst in which the carrier gas is plasma-excited and used as an active species, and the titanium dioxide photocatalyst in which TiO 2 is doped with Cr or the like is supported on nanocarbon, is an ultraviolet light. To exhibit high photocatalytic activity in the visible light region.
[0018]
【The invention's effect】
As described above, the visible light responsive titanium dioxide photocatalyst manufacturing apparatus of the present invention does not require a vacuum treatment, is simple in configuration, can reduce the apparatus cost, and can provide a visible light responsive titanium dioxide photocatalyst. It can be manufactured efficiently.
Further, according to the method for producing a visible light responsive titanium dioxide photocatalyst of the present invention, a visible light responsive titanium dioxide photocatalyst exhibiting extremely high photocatalytic activity in the visible light region can be obtained.
[Brief description of the drawings]
FIG. 1 is a configuration diagram of an apparatus for producing a visible light responsive titanium dioxide photocatalyst according to the present invention.
FIG. 2 is an explanatory diagram of a voltage applied to an electrode.
[Explanation of symbols]
Reference Signs List 1 inlet 2 inlet 3 outlet 4 housing 5 center electrode 5A front part 5B rear part 6 external electrode 6A front part 6B rear part 7 plasma generation space 8 power supply 8A front
Claims (5)
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| JP2003073972A JP2004275964A (en) | 2003-03-18 | 2003-03-18 | Device and method for producing visible-light-responsive titanium dioxide-based photocatalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009107681A1 (en) * | 2008-02-25 | 2009-09-03 | 国立大学法人京都大学 | Method for producing impurity-doped metal oxide by using microwave |
| JP2015008196A (en) * | 2013-06-25 | 2015-01-15 | 東京エレクトロン株式会社 | Processing device |
-
2003
- 2003-03-18 JP JP2003073972A patent/JP2004275964A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009107681A1 (en) * | 2008-02-25 | 2009-09-03 | 国立大学法人京都大学 | Method for producing impurity-doped metal oxide by using microwave |
| JPWO2009107681A1 (en) * | 2008-02-25 | 2011-08-04 | 国立大学法人京都大学 | Method for producing impurity-doped metal oxide using microwave |
| JP2015008196A (en) * | 2013-06-25 | 2015-01-15 | 東京エレクトロン株式会社 | Processing device |
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