JP4590580B2 - Titanium oxide mixed type highly active photocatalytic thin film and method for producing the same - Google Patents
Titanium oxide mixed type highly active photocatalytic thin film and method for producing the same Download PDFInfo
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- JP4590580B2 JP4590580B2 JP2000372691A JP2000372691A JP4590580B2 JP 4590580 B2 JP4590580 B2 JP 4590580B2 JP 2000372691 A JP2000372691 A JP 2000372691A JP 2000372691 A JP2000372691 A JP 2000372691A JP 4590580 B2 JP4590580 B2 JP 4590580B2
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- thin film
- anatase
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 35
- 239000010409 thin film Substances 0.000 title claims description 21
- 230000001699 photocatalysis Effects 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 description 12
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、アナターゼ型結晶構造のＴｉＯ2とＴｉ2Ｏ3の混在した配向性膜を作製することにより、従来のアナターゼ型及びルチル型ＴｉＯ2薄膜に比べ光触媒反応効率などの特性を向上させようとするものである。即ち、本発明は、ＴｉＯ2とＴｉ2Ｏ3の混在した膜を光触媒として用いることにより窒素酸化物等の有害ガスの分解、除去を行う反応効率の向上を目的としている。
【０００２】
【従来の技術】
近年の環境問題への関心の高まりから、酸化チタン（ＴｉＯ2）の光触媒効果を利用した機能性コーティング材料が注目を集めている。ＴｉＯ2の持つ３つの結晶構造（ルチル、アナターゼ、ブロッカイト）の中で光触媒薄膜として適しているのはアナターゼであると言われている。その理由としては、アナターゼのバンドギャップが他２種の結晶構造のそれより大きい（約３．２ｅＶ）ため、バンドギャップ以上のエネルギーが入射した際に生じる電子−正孔対の再結合確率が低くなり、結果的に表面において正孔が寄与する触媒作用が高くなるからであると言われている。
【０００３】
しかし、実際に光触媒性能の優劣を決定する要因は非常に複雑であり、結晶性の良いアナターゼ膜の堆積に成功したとしても十分な光触媒活性を得ることができないため、白金（Ｐｔ）などの別の金属を担持させたりして触媒活性を向上させる必要があった。
【０００４】
【発明が解決しようとする課題】
本発明は、アナターゼ型ＴｉＯ2にＴｉ2Ｏ3を混在させることで、異種金属を添加することなく高活性な光触媒薄膜を提供すること、ならびに、該光触媒薄膜の製造方法を提供することにある。
【０００５】
【課題を解決するための手段】
本発明は、アナターゼ型ＴｉＯ2にＴｉ2Ｏ3を混在させることにより、高活性な光触媒効果を実現させるものである。また、実際にそのような薄膜を作製する手段として、レーザー蒸着法を使用し、基板温度、酸素分圧、蒸着速度を制御して薄膜を作製するものである。このように、アナターゼ型ＴｉＯ2とＴｉ2Ｏ3を混在させることで、新たに金属担持等を行うことなく、高い光触媒活性を実現することができる。
【０００６】
【発明の実施の形態】
本発明においては、金属チタンを低圧酸素ガス雰囲気で、レーザ照射によって蒸発させ、無機あるいは金属の平滑表面あるいは単結晶表面の基板にＴｉＯ2およびＴｉ2Ｏ3の形態で蒸着させて、薄膜状の結晶を成長させるものである。
【０００７】
この作製条件としては、レーザの出力と照射方法、酸素雰囲気の圧力、基板の種類と温度が重要な項目である。
即ち、本発明は、低圧酸素雰囲気（３０ｍＴｏｒｒ〜４０ｍＴｏｒｒ）でレーザ蒸着法によりα−Ａｌ2Ｏ3平滑な単結晶基板上に厚さが１０ｎｍ（ナノメータ）から１μｍの範囲に制御されたアナターゼ型のＴｉＯ2とＴｉ2Ｏ3の混在した薄膜を作製させるものである。アナターゼ型のＴｉＯ2とＴｉ2Ｏ3の混在した薄膜を形成させる基板温度は、４５０℃〜５５０℃（最も好ましくは５００℃）に制御される条件、酸素ガス圧は３０ｍＴｏｒｒ〜４０ｍＴｏｒｒ（最も好ましくは３５ｍＴｏｒｒ）に制御される条件とする。以下、本発明を実施例に基づいて説明する。
【０００８】
【実施例１】
１パルス当たり４０ｍＪ、繰り返し周波数１０ＨｚのＹＡＧ（イットリウムアルミニウムガーネット）レーザ（波長５３２ｎｍ）を低圧酸素雰囲気中（３５ｍＴｏｒｒ）に置いた金属チタンターゲットに直径１ｍｍに集光させて入射した。金属チタンターゲットより５ｃｍの距離に基板温度５００℃に保持したα−Ａｌ2Ｏ3単結晶基板を設置し、２時間のレーザー照射で酸化チタン膜を作製した。得られた酸化チタン薄膜は厚さ０．２μｍであった。ここで用いた単結晶基板（０００１）面はα−Ａｌ2Ｏ3であり、各基板は鏡面研磨処理をしているものを使用した。
【０００９】
この薄膜の結晶構造をＸ線回析法により評価したところ、アナターゼ型ＴｉＯ2（００４）配向とＴｉ2Ｏ3（００６）配向のピークが観測され、両者の混在膜が形成されていることを確認した。このＸＲＤ測定（Ｘ回折測定）結果を図１に示す。図１から、（０００１）面のα−Ａｌ2Ｏ3基板上にアナターゼＴｉＯ2（００４）とＴｉ2Ｏ3（００６）が配向していることが示されている。
【００１０】
【実施例２】
実施例１で製膜した試料の実際の光触媒性能評価を行った。石英容器に試料、及び有機色素（メチレンブルー）溶液を入れ封入し、ブラックライトを光源として室温で照射しながら、色素の分解を吸光度変化として一定時間おきに観測した。
【００１１】
また比較のため、同じレーザ蒸着法を用いて、製膜条件及び基盤を調節して、ルチル単結晶薄膜、及びアナターゼ単結晶薄膜を製膜し、これらに対しても同評価を行った。測定結果を図２に示す。なお、いずれも膜厚はおよそ０．２μｍであり、実施例１で製膜したアナターゼ型ＴｉＯ2とＴｉ2Ｏ3混在膜と同程度とした。
【００１２】
図２の縦軸は色素の除去率、横軸は光照射時間である。これより、アナターゼＴｉＯ2とＴｉ2Ｏ3混在薄膜は、ルチル単結晶薄膜及びアナターゼ単結晶薄膜より多くの色素を分解しており、高い光触媒活性を有することを確認した。即ち、図２から、アナターゼ型ＴｉＯ2とＴｉ2Ｏ3の混在膜がより多くの有機色素を分解したことがわかる。
【００１３】
【発明の効果】
アナターゼ型ＴｉＯ2にＴｉ2Ｏ3を混在させることで、新たに金属担持等を行うことなく、高い光触媒活性を実現することができる。
【図面の簡単な説明】
【図１】実施例１で製膜されたアナターゼ型ＴｉＯ2とＴｉ2Ｏ3混在膜のＸ線回析測定結果である。（０００１）面のα−Ａｌ2Ｏ3基板上にアナターゼＴｉＯ2（００４）とＴｉ2Ｏ3（００６）が配向している。
【図２】アナターゼ型ＴｉＯ2とＴｉ2Ｏ3の混在膜、ルチル型ＴｉＯ2単結晶薄膜及びアナターゼＴｉＯ2単結晶薄膜の光触媒性能評価を有機色素の分解量により評価したものである。アナターゼ型ＴｉＯ2とＴｉ2Ｏ3の混在膜がより多くの有機色素を分解したことがわかる。[0001]
BACKGROUND OF THE INVENTION
The present invention improves the characteristics such as photocatalytic reaction efficiency as compared with the conventional anatase type and rutile type TiO 2 thin films by preparing an orientation film in which TiO 2 and Ti 2 O 3 having anatase type crystal structure are mixed. It is what. That is, an object of the present invention is to improve the reaction efficiency of decomposing and removing harmful gases such as nitrogen oxides by using a film containing TiO 2 and Ti 2 O 3 as a photocatalyst.
[0002]
[Prior art]
Due to the increasing interest in environmental issues in recent years, functional coating materials that utilize the photocatalytic effect of titanium oxide (TiO 2 ) have attracted attention. It is said that anatase is suitable as a photocatalytic thin film among the three crystal structures (rutile, anatase, broccite) of TiO 2 . The reason is that since the band gap of anatase is larger than that of the other two crystal structures (about 3.2 eV), the probability of recombination of electron-hole pairs generated when energy exceeding the band gap is incident is low. As a result, it is said that the catalytic action contributed by holes on the surface is increased.
[0003]
However, the factors that actually determine the superiority or inferiority of the photocatalytic performance are very complicated, and even if the anatase film having good crystallinity is successfully deposited, sufficient photocatalytic activity cannot be obtained. It was necessary to improve the catalytic activity by supporting a metal.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a highly active photocatalytic thin film without adding different metals by mixing Ti 2 O 3 with anatase TiO 2 and to provide a method for producing the photocatalytic thin film. .
[0005]
[Means for Solving the Problems]
The present invention realizes a highly active photocatalytic effect by mixing Ti 2 O 3 with anatase TiO 2 . In addition, as a means for actually producing such a thin film, a laser vapor deposition method is used, and the thin film is produced by controlling the substrate temperature, oxygen partial pressure, and vapor deposition rate. Thus, by mixing anatase TiO 2 and Ti 2 O 3 , high photocatalytic activity can be realized without newly carrying metal or the like.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, titanium metal is evaporated by laser irradiation in a low-pressure oxygen gas atmosphere, and vapor-deposited in the form of TiO 2 and Ti 2 O 3 on a substrate having an inorganic or metal smooth surface or single crystal surface, thereby forming a thin film It is for growing crystals.
[0007]
As production conditions, laser output and irradiation method, pressure in an oxygen atmosphere, substrate type and temperature are important items.
That is, the present invention is an anatase type in which the thickness is controlled in the range of 10 nm (nanometer) to 1 μm on a α-Al 2 O 3 smooth single crystal substrate by laser vapor deposition in a low pressure oxygen atmosphere (30 mTorr to 40 mTorr). A thin film in which TiO 2 and Ti 2 O 3 are mixed is produced. The substrate temperature for forming a thin film containing anatase type TiO 2 and Ti 2 O 3 is controlled at 450 ° C. to 550 ° C. (most preferably 500 ° C.), and the oxygen gas pressure is 30 mTorr to 40 mTorr (most preferably). 35 mTorr). Hereinafter, the present invention will be described based on examples.
[0008]
[Example 1]
A YAG (yttrium aluminum garnet) laser (wavelength: 532 nm) having a frequency of 40 mJ per pulse and a repetition frequency of 10 Hz was focused on a metal titanium target placed in a low-pressure oxygen atmosphere (35 mTorr) and incident on a 1 mm diameter. An α-Al 2 O 3 single crystal substrate maintained at a substrate temperature of 500 ° C. was placed at a distance of 5 cm from the metal titanium target, and a titanium oxide film was produced by laser irradiation for 2 hours. The obtained titanium oxide thin film had a thickness of 0.2 μm. The single crystal substrate (0001) plane used here was α-Al 2 O 3 and each substrate was subjected to mirror polishing.
[0009]
When the crystal structure of this thin film was evaluated by X-ray diffraction, peaks of anatase TiO 2 (004) orientation and Ti 2 O 3 (006) orientation were observed, indicating that a mixed film of both was formed. confirmed. The results of this XRD measurement (X diffraction measurement) are shown in FIG. FIG. 1 shows that anatase TiO 2 (004) and Ti 2 O 3 (006) are oriented on the (0001) plane α-Al 2 O 3 substrate.
[0010]
[Example 2]
The actual photocatalytic performance evaluation of the sample formed in Example 1 was performed. A sample and an organic dye (methylene blue) solution were placed in a quartz container, sealed, and the decomposition of the dye was observed as a change in absorbance at regular intervals while irradiating with black light as a light source at room temperature.
[0011]
For comparison, the same laser deposition method was used to adjust the film forming conditions and the base, and a rutile single crystal thin film and an anatase single crystal thin film were formed, and the same evaluation was performed on these. The measurement results are shown in FIG. In all cases, the film thickness was about 0.2 μm, which was the same as the mixed film of anatase TiO 2 and Ti 2 O 3 formed in Example 1.
[0012]
The vertical axis in FIG. 2 represents the dye removal rate, and the horizontal axis represents the light irradiation time. From this, it was confirmed that the anatase TiO 2 and Ti 2 O 3 mixed thin film decomposes more dye than the rutile single crystal thin film and the anatase single crystal thin film and has high photocatalytic activity. That is, FIG. 2 shows that the mixed film of anatase TiO 2 and Ti 2 O 3 decomposes more organic dyes.
[0013]
【The invention's effect】
By mixing Ti 2 O 3 with anatase TiO 2 , high photocatalytic activity can be realized without newly carrying metal or the like.
[Brief description of the drawings]
1 is a result of X-ray diffraction measurement of an anatase TiO 2 and Ti 2 O 3 mixed film formed in Example 1. FIG. Anatase TiO 2 (004) and Ti 2 O 3 (006) are oriented on the (0001) plane α-Al 2 O 3 substrate.
FIG. 2 is an evaluation of the photocatalytic performance of a mixed film of anatase TiO 2 and Ti 2 O 3 , a rutile TiO 2 single crystal thin film, and an anatase TiO 2 single crystal thin film based on the amount of decomposition of an organic dye. It can be seen that the mixed film of anatase TiO 2 and Ti 2 O 3 decomposes more organic dyes.
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