JP3785614B2 - Titanium oxide film showing photocatalytic property under visible light and method for producing the same - Google Patents
Titanium oxide film showing photocatalytic property under visible light and method for producing the same Download PDFInfo
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- JP3785614B2 JP3785614B2 JP2001323194A JP2001323194A JP3785614B2 JP 3785614 B2 JP3785614 B2 JP 3785614B2 JP 2001323194 A JP2001323194 A JP 2001323194A JP 2001323194 A JP2001323194 A JP 2001323194A JP 3785614 B2 JP3785614 B2 JP 3785614B2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 62
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 38
- 230000001699 photocatalysis Effects 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 229910052594 sapphire Inorganic materials 0.000 claims description 14
- 239000010980 sapphire Substances 0.000 claims description 14
- 238000000608 laser ablation Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 230000001747 exhibiting effect Effects 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims 1
- 239000010408 film Substances 0.000 description 41
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000007740 vapor deposition Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical group [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 4
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000001443 photoexcitation Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- Physical Vapour Deposition (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【０００１】
【発明の属する技術分野】
この発明は、可視光下で光触媒性を示す酸化チタン膜の作製に関するものであり、レーザアブレーション成膜法による蒸着とその後の熱処理により可視光下で光触媒性を有した酸化チタン膜が得られることを見出した。即ち、本発明に従うことにより、太陽光及び自然光等の可視光下で光触媒性を示す酸化チタン膜が得られるので、従来、光触媒として使用されている二酸化チタンに比べて、窒素酸化物等の有害ガスの分解、除去への利用に拡大が図れる。
【０００２】
【従来の技術】
従来、真空蒸着法やゾル・ゲル法により光触媒として使用される二酸化チタン膜の作製が行われているが、これまでの二酸化チタン膜はその結晶構造がルチルおよびアナターゼの多結晶構造のものしか作製できなかった。
【０００３】
また、可視光領域での光触媒性を有した酸化チタンは、水素プラズマ処理により酸素欠損型酸化チタンを形成することにより粉体状のものを作製することができるが、数十ｎｍ（ナノメートル）の膜厚で均一な膜厚の酸化チタン膜を作製することは困難であった。
【０００４】
【発明が解決しようとする課題】
本件の課題は、数十ｎｍ程度の非常に薄い厚さで平滑な膜の作製が可能なレーザアブレーション成膜法による蒸着とその後の熱処理により、酸素欠損を含まない、即ち、熱的に安定で、可視光下で光触媒性を示す酸化チタン膜を作製することにある。
【０００５】
【課題を解決するための手段】
本発明では、レーザアブレーション成膜法により、（０００１）面方位のサファイア単結晶基板上に室温付近（例えば、２０℃）で酸化チタンを蒸着し、その後、空気中で熱処理させることが重要である。このためにサファイア基板上に酸化チタンを形成する蒸着条件およびその後の熱処理条件を見出した。作製した膜の結晶構造はＸ線回折法により評価し、さらに光触媒性をパルス光励起表面正孔量測定法により評価した。
【０００６】
【発明の実施の形態】
本発明は、レーザアブレーション成膜法によりサファイア基板上に酸化チタンを蒸着し、空気中で熱処理をすることにより可視光下で光触媒性を示す酸化チタン膜を作製するものである。
【０００７】
この作製条件として、レーザアブレーション成膜法による蒸着時の基板温度、酸素ガス圧、蒸発物質、そして蒸着後の熱処理温度が重要な項目である。即ち、レーザアブレーション成膜法により、（０００１）面方位のサファイア単結晶基板上に酸化チタンを蒸着する条件は、サファイア単結晶基板の温度を室温付近（２０℃〜８０℃）とし、酸素雰囲気中（１．３Ｐａ（１０ｍＴｏｒｒ）〜８．０Ｐａ（６０ｍＴｏｒｒ））で、蒸発物質としてＴｉＯ２焼結体を用いることである。レーザアブレーション成膜法において用いるレーザーは、蒸発物質を蒸発することができるものであればいずれでもよいが、好ましくはＹＡＧ（イットリウムアルミニウムガーネット）レーザー（波長５３２ｎｍ）である。次に、空気中の熱処理条件としては、加熱温度は、７００℃〜９００℃（好ましくは７５０℃〜８５０℃、最も好ましくは８００℃）であり、加熱保持時間は１〜２時間である。
【０００８】
以下、本発明を実施例に基づいて説明する。
【０００９】
【実施例】
（実施例１）
本発明では、まず、レーザアブレーション成膜法により酸化チタンの蒸着を行った。１パルス当たり１００ｍＪ、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）レーザー（波長５３２ｎｍ）を酸素雰囲気中（４．７Ｐａ（３５ｍＴｏｒｒ））に置いたＴｉＯ２焼結体ターゲット（ＴｉＯ２：φ５０ｍｍ、厚さ５ｍｍ）に直径１ｍｍに集光させて入射した。ＴｉＯ２焼結体ターゲットより５ｃｍの距離に室温約２０℃で（０００１）面方位のサファイア単結晶基板を設置し、４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膜は厚さ０．２μｍであった。次に、電気炉を用いて、蒸着した酸化チタン膜を空気中で８００℃、１時間の熱処理を行った。熱処理後の酸化チタン膜の結晶構造をＸ線回折法により評価した。その結果を図１に示す。低角度側のピークからそれぞれルチル構造のＴｉＯ２（１０１）、アナターゼ構造のＴｉＯ２（００４）、Ｔｉ２Ｏ３（０００６）、およびルチル構造のＴｉＯ２（２００）からのピークに対応している。従って、このＸ線回折測定の結果から、本発明による酸化チタン膜は、アナターゼ及びルチル構造のＴｉＯ２からなる従来の膜とは異なり、（０００１）面のサファイア基板上にアナターゼ及びルチル構造のＴｉＯ２とさらにＴｉ２Ｏ３とが混在した酸化チタン膜であることがわかる。
【００１０】
上記の条件で作製した二酸化チタン膜の光触媒性能を見積もるため、パルス光励起表面正孔量測定法により評価を行った。その結果を図２に示す。横軸は励起光の波長、縦軸は量子効率（表面励起正孔数／入射光強度）でプロットしている。この量子効率が高いほど、光の入射に対して多くの正孔が表面に励起することを意味しているので、高い光触媒性能が期待される。熱処理温度を８００℃として作製した酸化チタン膜の光触媒性能を評価したところ、図２に示すように可視光領域（４６０ｎｍ）まで光触媒反応を示すことがわかった。
【００１１】
従来の酸素欠損を含む酸化チタンでは、一般に、空気中で５００℃程度に加熱をすると酸化チタンに空気中の酸素が供給されて（酸化されて）単なるルチル及びアナターゼの二酸化チタンに変化し、可視光に対する光触媒性が失われてしまうが、本発明による酸化チタン膜は例えば８００℃で熱処理を施すことにより作製されるものであることから、熱的に安定、即ち空気中で５００℃程度まで加熱しても可視光に対する光触媒性の変化が見られない。
【００１２】
（比較例１）
実施例１と同様の条件で（０００１）面方位のサファイア基板上に蒸着した酸化チタン膜について、熱処理における加熱温度を６００℃として作製した酸化チタン膜の光触媒性を評価したところ、図２に示すように加熱温度が８００℃の酸化チタン膜（実施例１）に比べて低い量子効率を示し、入射光波長が３７０ｎｍ以上で量子効率は測定限界以下であった。さらに、（１１−２０）、（１０−１０）、（０１−１２）面方位のサファイア基板上に実施例１と同様の条件で蒸着し、８００℃で熱処理した酸化チタン膜の光触媒性を評価したところ、本発明による酸化チタン膜に比べて低い光触媒性を示した。
【００１３】
（比較例２）
（０００１）面方位のサファイア基板上に蒸着した金属チタン膜を実施例１と同様の条件で熱処理して酸化チタン膜を作製し、光触媒性能を評価したところ、本発明による酸化チタン膜に比べて低い光触媒性を示した。
【００１４】
【発明の効果】
レーザアブレーション成膜法による蒸着とその後の熱処理により、可視光下で光触媒性を有した酸化チタン膜が得られることを見出した。即ち、太陽光及び自然光等の可視光下で光触媒性を示すことにより、従来の二酸化チタンに比べて、窒素酸化物等の有害ガスの分解、除去への利用への拡大が図れる。
【図面の簡単な説明】
【図１】 図１は、レーザアブレーション成膜法により（０００１）面方位のサファイア基板上に蒸着及び８００℃、１時間の熱処理後に得られた酸化チタン膜のＸ線回折（θ−２θ）図である。
【図２】 図２は、レーザアブレーション成膜法により（０００１）面方位のサファイア基板上に蒸着した酸化チタン膜について６００℃と８００℃で熱処理して作製した膜の表面励起正孔量測定結果を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to the production of a titanium oxide film exhibiting photocatalytic properties under visible light, and a titanium oxide film having photocatalytic properties under visible light can be obtained by vapor deposition using a laser ablation film forming method and subsequent heat treatment. I found. That is, according to the present invention, a titanium oxide film exhibiting photocatalytic properties under visible light such as sunlight and natural light can be obtained. Therefore, compared with titanium dioxide that has been conventionally used as a photocatalyst, nitrogen oxides and the like are harmful. It can be used for gas decomposition and removal.
[0002]
[Prior art]
Conventionally, titanium dioxide films used as photocatalysts by vacuum evaporation or sol-gel methods have been produced. Conventionally, titanium dioxide films are only produced with a polycrystalline structure of rutile and anatase. could not.
[0003]
In addition, titanium oxide having photocatalytic properties in the visible light region can be produced in the form of powder by forming oxygen-deficient titanium oxide by hydrogen plasma treatment, but several tens of nanometers It was difficult to produce a titanium oxide film having a uniform thickness.
[0004]
[Problems to be solved by the invention]
The problem of this case is that it does not contain oxygen vacancies, that is, it is thermally stable by vapor deposition by the laser ablation film forming method that can produce a very thin film with a very thin thickness of about several tens of nanometers, and subsequent heat treatment. It is to produce a titanium oxide film exhibiting photocatalytic properties under visible light.
[0005]
[Means for Solving the Problems]
In the present invention, it is important to deposit titanium oxide near a room temperature (for example, 20 ° C.) on a (0001) plane sapphire single crystal substrate by a laser ablation film forming method, and then heat-treat in air. . For this purpose, the vapor deposition conditions for forming titanium oxide on the sapphire substrate and the subsequent heat treatment conditions were found. The crystal structure of the produced film was evaluated by an X-ray diffraction method, and the photocatalytic property was evaluated by a pulsed photoexcitation surface hole content measurement method.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, titanium oxide is deposited on a sapphire substrate by a laser ablation film-forming method, and heat-treated in air to produce a titanium oxide film exhibiting photocatalytic properties under visible light.
[0007]
As production conditions, the substrate temperature, the oxygen gas pressure, the evaporated substance, and the heat treatment temperature after the vapor deposition by the laser ablation film forming method are important items. That is, the conditions for depositing titanium oxide on a sapphire single crystal substrate having a (0001) plane orientation by laser ablation film formation are that the temperature of the sapphire single crystal substrate is around room temperature (20 ° C. to 80 ° C.) and in an oxygen atmosphere. (1.3 Pa (10 mTorr) to 8.0 Pa (60 mTorr)) and using a TiO 2 sintered body as an evaporating substance. The laser used in the laser ablation film forming method may be any laser capable of evaporating the evaporated substance, but is preferably a YAG (yttrium aluminum garnet) laser (wavelength: 532 nm). Next, as heat treatment conditions in air, the heating temperature is 700 ° C. to 900 ° C. (preferably 750 ° C. to 850 ° C., most preferably 800 ° C.), and the heating and holding time is 1 to 2 hours.
[0008]
Hereinafter, the present invention will be described based on examples.
[0009]
【Example】
Example 1
In the present invention, first, titanium oxide was deposited by a laser ablation film forming method. A TiO 2 sintered body target (TiO 2 : φ50 mm, thickness 5 mm) in which a YAG (yttrium aluminum garnet) laser (wavelength: 532 nm) with a repetition rate of 10 Hz per pulse is placed in an oxygen atmosphere (4.7 Pa (35 mTorr)). ) Was focused to a diameter of 1 mm and entered. A sapphire single crystal substrate with a (0001) plane orientation was placed at a room temperature of about 20 ° C. at a distance of 5 cm from the TiO 2 sintered compact target, and a titanium oxide film was produced by laser irradiation for 4 hours. The obtained titanium oxide film had a thickness of 0.2 μm. Next, using an electric furnace, the deposited titanium oxide film was heat-treated in air at 800 ° C. for 1 hour. The crystal structure of the titanium oxide film after the heat treatment was evaluated by an X-ray diffraction method. The result is shown in FIG. Corresponding to the peaks from the rutile structure TiO 2 (101), the anatase structure TiO 2 (004), Ti 2 O 3 (0006), and the rutile structure TiO 2 (200) from the low angle side peak, respectively. . Therefore, from the result of the X-ray diffraction measurement, the titanium oxide film according to the present invention is different from the conventional film made of TiO 2 having anatase and rutile structure, and the TiO 2 having anatase and rutile structure on a (0001) sapphire substrate. It can be seen that this is a titanium oxide film in which 2 and Ti 2 O 3 are mixed.
[0010]
In order to estimate the photocatalytic performance of the titanium dioxide film produced under the above conditions, evaluation was performed by a pulsed photoexcitation surface hole content measurement method. The result is shown in FIG. The horizontal axis plots the wavelength of the excitation light, and the vertical axis plots the quantum efficiency (number of surface excited holes / incident light intensity). Higher quantum efficiency means that more holes are excited on the surface with respect to the incidence of light, so higher photocatalytic performance is expected. When the photocatalytic performance of the titanium oxide film produced at a heat treatment temperature of 800 ° C. was evaluated, it was found that the photocatalytic reaction was exhibited up to the visible light region (460 nm) as shown in FIG.
[0011]
In the conventional titanium oxide containing oxygen deficiency, generally, when heated to about 500 ° C. in the air, oxygen in the air is supplied to the titanium oxide (oxidized) and converted into mere rutile and anatase titanium dioxide. Although the photocatalytic property to light is lost, the titanium oxide film according to the present invention is prepared by performing a heat treatment at 800 ° C., for example, so that it is thermally stable, that is, heated to about 500 ° C. in the air. However, no change in photocatalytic property to visible light is observed.
[0012]
(Comparative Example 1)
The titanium oxide film deposited on the (0001) plane sapphire substrate under the same conditions as in Example 1 was evaluated for the photocatalytic property of the titanium oxide film produced at a heating temperature of 600 ° C., as shown in FIG. Thus, the quantum efficiency was lower than that of the titanium oxide film having a heating temperature of 800 ° C. (Example 1), the incident light wavelength was 370 nm or more, and the quantum efficiency was below the measurement limit. Furthermore, the photocatalytic property of the titanium oxide film deposited on the sapphire substrate with (11-20), (10-10), (01-12) orientation under the same conditions as in Example 1 and heat-treated at 800 ° C. was evaluated. As a result, the photocatalytic property was lower than that of the titanium oxide film according to the present invention.
[0013]
(Comparative Example 2)
A titanium metal film deposited on a (0001) -oriented sapphire substrate was heat-treated under the same conditions as in Example 1 to produce a titanium oxide film, and the photocatalytic performance was evaluated. Compared with the titanium oxide film according to the present invention. The photocatalytic property was low.
[0014]
【The invention's effect】
It has been found that a titanium oxide film having photocatalytic properties under visible light can be obtained by vapor deposition by laser ablation film formation and subsequent heat treatment. That is, by exhibiting photocatalytic properties under visible light such as sunlight and natural light, it can be expanded to use for decomposition and removal of harmful gases such as nitrogen oxides as compared with conventional titanium dioxide.
[Brief description of the drawings]
FIG. 1 is an X-ray diffraction (θ-2θ) diagram of a titanium oxide film obtained by vapor deposition on a (0001) plane sapphire substrate and heat treatment at 800 ° C. for 1 hour by a laser ablation film forming method. It is.
FIG. 2 is a result of surface excitation hole measurement of a film prepared by heat treatment at 600 ° C. and 800 ° C. of a titanium oxide film deposited on a (0001) plane sapphire substrate by a laser ablation film forming method. FIG.
Claims (2)
レーザーアブレーション成膜法により、（０００１）面方位のサファイア単結晶基板上に酸化チタンを蒸着し、その後、空気中で熱処理することを含み、
酸化チタンの蒸着が、蒸発物質としてＴｉＯ２焼結体を用いて、２０℃〜８０℃の基板温度で、１．３Ｐａ（１０ｍＴｏｒｒ）〜８．０Ｐａ（６０ｍＴｏｒｒ）の酸素雰囲気中で行われ、
熱処理が７００℃〜９００℃で１〜２時間行われることを特徴とする、前記製造方法。A method for producing a titanium oxide film exhibiting photocatalytic activity under visible light,
Including vapor-depositing titanium oxide on a (0001) -oriented sapphire single crystal substrate by a laser ablation film-forming method, followed by heat treatment in air;
The deposition of titanium oxide is performed in an oxygen atmosphere of 1.3 Pa (10 mTorr) to 8.0 Pa (60 mTorr) at a substrate temperature of 20 ° C. to 80 ° C. using a TiO 2 sintered body as an evaporating substance,
The said manufacturing method characterized by heat-processing being performed at 700 to 900 degreeC for 1 to 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001323194A JP3785614B2 (en) | 2001-10-22 | 2001-10-22 | Titanium oxide film showing photocatalytic property under visible light and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001323194A JP3785614B2 (en) | 2001-10-22 | 2001-10-22 | Titanium oxide film showing photocatalytic property under visible light and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003126700A JP2003126700A (en) | 2003-05-07 |
| JP3785614B2 true JP3785614B2 (en) | 2006-06-14 |
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| JP5035060B2 (en) * | 2008-03-24 | 2012-09-26 | 三菱マテリアル株式会社 | Method for manufacturing titanium oxide target having high density and low specific resistance |
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