JP4590579B2 - Highly efficient photocatalytic thin film and method for producing the same - Google Patents
Highly efficient photocatalytic thin film and method for producing the same Download PDFInfo
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- JP4590579B2 JP4590579B2 JP2000339096A JP2000339096A JP4590579B2 JP 4590579 B2 JP4590579 B2 JP 4590579B2 JP 2000339096 A JP2000339096 A JP 2000339096A JP 2000339096 A JP2000339096 A JP 2000339096A JP 4590579 B2 JP4590579 B2 JP 4590579B2
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- 239000010409 thin film Substances 0.000 title claims description 26
- 230000001699 photocatalysis Effects 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 16
- 239000010408 film Substances 0.000 claims description 12
- 230000001133 acceleration Effects 0.000 claims description 11
- 238000005468 ion implantation Methods 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 238000002513 implantation Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000011941 photocatalyst Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 230000005284 excitation Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、可視光応答性及び高活性を有する光触媒薄膜、ならびに、該光触媒薄膜の製造方法に関するものである。
【０００２】
【従来の技術】
近年酸化チタン（ＴｉＯ2）を代表とする金属酸化物が光触媒を有する機能性コーティング材料として、空気及び水の浄化、脱臭、殺菌、抗菌などに広く利用されている。この主なメカニズムは現在以下のように考えられている。１．金属酸化物表面にバンドギャップ以上のエネルギーを有する光を照射することによって、内部に電子−正孔対が生じる。２．金属酸化物の表面の酸素欠損に起因する電位勾配により正孔が薄膜表面に励起される。３．この正孔が表面に吸着している水を酸化することで、非常に酸化力の強い水のラジカルが生じ、この中間生成物が機能性コーティング材料としての役割を果たす。
【０００３】
このように光触媒効果を利用するためには励起光として、そのバンドギャップ以上の光が必要となる。代表的な光触媒体であるＴｉＯ2のバンドギャップは約３．０〜３．２ｅＶであり、これは励起光として４００ｎｍ以下の紫外光が必要であることを意味している。しかし自然光の大部分は可視光（波長約４２０ｎｍ以上）であるため、紫外光を必要とするＴｉＯ2光触媒は十分な分解効率が得られないという欠点があり、自然光下もしくは屋内照明下においても高効率な光触媒を形成する方法が望まれている。
【０００４】
イオン注入による光触媒体の可視光化の試みは、粉体及び多結晶薄膜に対して行われているが（例えば特開平１１−１９７５１２）、イオン注入における深さ方向の濃度プロファイルを利用した傾斜効果（バンドの傾きやバンドギャップの変化）に関しては言及していない。
【０００５】
【発明が解決しようとする課題】
本発明の目的は、自然光下、特に６００〜２５０ｎｍの波長域の光照射下において高効率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。
【０００６】
【課題を解決しようとするための手段】
基板上に製膜した光触媒薄膜にＮｂ、Ｖ及びＣｒのうちいずれからの金属イオンを注入する。その際、厚さ方向に金属イオンの濃度勾配を加速電圧及び注入量を制御することにより意図的にもうけて、バンドギャップもしくは電位勾配を厚さ方向に変化させた構造を有する薄膜を提供するものである。このような構造を持つ薄膜は、薄膜の深部に向かって徐々にバンドギャップが減少もしくは増大していることで可視光領域まで利用することができ、あるいは電子−正孔対生成後の両者の再結合確率が低下するような電位勾配が内部に形成されることにより、結果的に効率良く表面まで正孔を導くことが可能となる。
【０００７】
【発明の実施の形態】
本発明の光触媒薄膜は、酸化チタンにＮｂ、ＶおよびＣｒなどの金属イオンのうち少なくとも一種の金属イオン注入を行い、その際膜厚方向に意図的に濃度分布をもうけた傾斜機能薄膜である。
【０００８】
酸化チタンの合成法は、例えば、パルスレーザー製膜（ＰＬＤ）法、ＣＶＤ法、スパッタ法、ゾルゲル用、ＭＢＥ法〜真空蒸着法などから少なくとも１種類を用いて製膜した膜を使用する。
【０００９】
イオン注入の際、加速電圧及び注入量を制御させることにより膜厚方向に金属イオンの濃度分布を形成させる。具体的には高い加速電圧で、比較的長時間注入を行った後、加速電圧を減少させ短時間注入を行えば、表面から徐々に金属イオン濃度が増加するような傾斜膜が得られ、加速電圧と注入時間との関係を逆に実行すれば、膜表面から徐々に減少するような傾斜膜が得られる。
【００１０】
イオン注入後、熱処理を大気中、温度２００℃〜７００℃で１〜１０時間程度熱処理を行うことにより、イオン注入の際に結晶内に生じた欠陥が消失し、定常的に高い触媒性能を持つ膜を得ることができる。以下、本発明を実施例に基づいて説明する。
【００１１】
【実施例１】
まず、注入量と光応答性との関係を明らかにするために、単結晶のバルクの試料に注入を行った。これは、後に濃度プロファイルを持った傾斜薄膜を実際に作製する際の知見を得るためである。
【００１２】
１ｃｍ角、厚さ５００μｍの単結晶ＴｉＯ2（ルチル型）基板にＣｒイオンを１５０ｋｅＶの加速電圧で、５．５×１０14ｉｏｎｓ／ｃｍ2、３．２×１０15ｉｏｎｓ／ｃｍ2、２．６×１０16ｉｏｎｓ／ｃｍ2の注入量でイオン注入をそれぞれ行った後、６００℃で５時間大気中で熱処理を行った。この試料の濃度プロファイルを２次イオン質量分析法（ＳＩＭＳ）により分析を行うと表面から約３０００Å付近まで徐々に濃度が減少しているような分布を有していることが確認された。
【００１３】
これら３つの注入量の異なる試料の光伝導度の波長依存性を図１に示す。注入量が増加するにつれ光応答が低エネルギー側へシフトしていることがわかる。
２．６×１０16ｉｏｎｓ／ｃｍ2注入した試料について、深さ１５００Åまでの平均のバンドギャップを算出すると約２．０ｅＶであった。つまり、Ｃｒイオン注入を行うことによりＴｉＯ2のバンドギャップを低エネルギー側へ制御することが可能であることが明らかとなった。
【００１４】
【実施例２】
ＰＬＤ法を用いて１ｃｍ角のＡｌ2Ｏ3 基板に単結晶ルチル膜を約５０００Å製膜した。次にＣｒイオンを１５０ｋｅＶで１×１０16ｉｏｎｓ／ｃｍ2注入後６００℃で５時間熱処理を行った。また、比較のため光触媒性能が高いとされる単結晶アナターゼ膜を１ｃｍ角のＬａＡｌＯ3膜上に厚さ約５０００Å堆積させた。
【００１５】
これらの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（特願２０００−２１３７７２号）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。
【００１６】
図２より、注入前のルチル単結晶薄膜は３４０ｎｍ付近まで、アナターゼ単結晶薄膜はそのバンドギャップに相当する３９０ｎｍ付近（約３．２ｅＶ）までしか表面への正孔が励起していないのに対し、Ｃｒイオン注入試料は５００ｎｍ付近まで正孔の励起が観測された。このＣｒ注入試料の結晶構造をＸ線回折法で評価したところルチル単結晶であった。ルチルのバンドギャップは約３．０ｅＶ（４１０ｎｍ程度）であるので、明らかにＣｒイオン注入の影響によるものである。
【００１７】
【発明の効果】
本発明の光触媒薄膜は可視光から紫外光までの広い範囲のエネルギーを有する光の照射下においても効率的に正孔を表面に導くことができ、結果的に光触媒性能が向上することが期待される。
【図面の簡単な説明】
【図１】図１は、Ｃｒ注入された単結晶ルチル型ＴｉＯ2の光伝導特性を測定したものを示す図である（注入量を増加するにつれＴｉＯ2の光応答が低エネルギー側へシフトしている）。
【図２】図２は、アナターゼ単結晶薄膜、ルチル単結晶薄膜及びＣｒ注入ルチル薄膜の表面励起正孔量測定結果を示す図である（Ｃｒ注入ルチル薄膜のみ５００ｎｍ付近まで正孔が表面まで励起されているのが確認できる）。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photocatalytic thin film having visible light responsiveness and high activity, and a method for producing the photocatalytic thin film.
[0002]
[Prior art]
In recent years, a metal oxide typified by titanium oxide (TiO 2 ) has been widely used as a functional coating material having a photocatalyst for purification, deodorization, sterilization, antibacterial and the like of air and water. This main mechanism is currently considered as follows. 1. By irradiating the metal oxide surface with light having energy greater than or equal to the band gap, electron-hole pairs are generated inside. 2. Holes are excited on the surface of the thin film by a potential gradient caused by oxygen vacancies on the surface of the metal oxide. 3. By oxidizing the water adsorbed on the surface by the holes, water radicals with very strong oxidizing power are generated, and this intermediate product plays a role as a functional coating material.
[0003]
Thus, in order to utilize the photocatalytic effect, light exceeding the band gap is required as excitation light. The band gap of TiO 2 , which is a typical photocatalyst, is about 3.0 to 3.2 eV, which means that ultraviolet light of 400 nm or less is necessary as excitation light. However, since most of the natural light is visible light (wavelength of about 420 nm or more), a TiO 2 photocatalyst that requires ultraviolet light has a drawback that sufficient decomposition efficiency cannot be obtained, and it is high even under natural light or indoor lighting. A method for forming an efficient photocatalyst is desired.
[0004]
Attempts to make photocatalysts visible by ion implantation have been performed on powders and polycrystalline thin films (for example, JP-A-11-197512), but a gradient effect using a concentration profile in the depth direction in ion implantation is used. No mention is made of (band tilt or band gap change).
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a highly efficient photocatalytic thin film under natural light, particularly under light irradiation in the wavelength range of 600 to 250 nm, and to provide a method for producing the photocatalytic thin film.
[0006]
[Means for solving problems]
Metal ions from any of Nb, V and Cr are implanted into the photocatalytic thin film formed on the substrate . At that time, a thin film having a structure in which a band gap or a potential gradient is changed in the thickness direction by intentionally generating a concentration gradient of metal ions in the thickness direction by controlling the acceleration voltage and the implantation amount is provided. It is. A thin film having such a structure can be used up to the visible light region because the band gap gradually decreases or increases toward the deep part of the thin film, or both of them after the generation of electron-hole pairs are regenerated. As a result, a potential gradient that reduces the coupling probability is formed inside, and as a result, holes can be efficiently guided to the surface.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The photocatalytic thin film of the present invention is a functionally graded thin film in which at least one kind of metal ions such as Nb, V and Cr is implanted into titanium oxide and a concentration distribution is intentionally distributed in the film thickness direction.
[0008]
As the titanium oxide synthesis method, for example, a film formed using at least one of a pulse laser film formation (PLD) method, a CVD method, a sputtering method, a sol-gel method, an MBE method to a vacuum deposition method, and the like is used.
[0009]
At the time of ion implantation, the concentration distribution of metal ions is formed in the film thickness direction by controlling the acceleration voltage and the implantation amount. Specifically, after implanting for a relatively long time at a high acceleration voltage, if the acceleration voltage is decreased and implantation is performed for a short time, a gradient film in which the metal ion concentration gradually increases from the surface can be obtained. If the relationship between the voltage and the injection time is reversed, a gradient film that gradually decreases from the film surface can be obtained.
[0010]
After ion implantation, heat treatment is performed in the atmosphere at a temperature of 200 ° C. to 700 ° C. for about 1 to 10 hours, so that defects generated in the crystal at the time of ion implantation disappear, and the catalyst performance is constantly high. A membrane can be obtained. Hereinafter, the present invention will be described based on examples.
[0011]
[Example 1]
First, in order to clarify the relationship between the injection amount and the photoresponsiveness, a single crystal bulk sample was injected. This is to obtain knowledge when actually manufacturing a gradient thin film having a concentration profile later.
[0012]
A 1 cm square, 500 μm thick single crystal TiO 2 (rutile type) substrate with Cr ions at an acceleration voltage of 150 keV, 5.5 × 10 14 ions / cm 2 , 3.2 × 10 15 ions / cm 2 , 2. After performing ion implantation at an implantation amount of 6 × 10 16 ions / cm 2 , heat treatment was performed in the air at 600 ° C. for 5 hours. When the concentration profile of this sample was analyzed by secondary ion mass spectrometry (SIMS), it was confirmed that the sample had a distribution in which the concentration gradually decreased from the surface to around 3000 mm.
[0013]
FIG. 1 shows the wavelength dependence of the photoconductivity of these three different injection amounts. It can be seen that the optical response shifts to the low energy side as the injection amount increases.
With respect to the sample injected with 2.6 × 10 16 ions / cm 2 , the average band gap up to a depth of 1500 mm was calculated to be about 2.0 eV. That is, it has become clear that the band gap of TiO 2 can be controlled to the low energy side by performing Cr ion implantation.
[0014]
[Example 2]
A single crystal rutile film was formed on a 1 cm square Al 2 O 3 substrate by using the PLD method. Next, after Cr ions were implanted at 150 keV at 1 × 10 16 ions / cm 2, heat treatment was performed at 600 ° C. for 5 hours. For comparison, a single crystal anatase film, which has high photocatalytic performance, was deposited on a 1 cm square LaAlO 3 film to a thickness of about 5000 mm.
[0015]
In order to estimate the photocatalytic performance of these films, evaluation was performed by a pulsed photoexcitation surface hole content measurement method (Japanese Patent Application No. 2000-213772). 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).
[0016]
From FIG. 2, the rutile single crystal thin film before injection is excited up to about 340 nm, while the anatase single crystal thin film is excited only up to about 390 nm (about 3.2 eV) corresponding to the band gap. In the Cr ion-implanted sample, hole excitation was observed up to around 500 nm. When the crystal structure of this Cr-implanted sample was evaluated by X-ray diffraction, it was a rutile single crystal. Since the rutile band gap is about 3.0 eV (about 410 nm), it is clearly due to the influence of Cr ion implantation.
[0017]
【The invention's effect】
The photocatalytic thin film of the present invention can efficiently lead holes to the surface even under irradiation with light having a wide range of energy from visible light to ultraviolet light, and as a result, it is expected to improve the photocatalytic performance. The
[Brief description of the drawings]
FIG. 1 is a diagram showing the measurement of photoconductive properties of Cr-implanted single crystal rutile TiO 2 (the optical response of TiO 2 shifts to a lower energy side as the injection amount is increased). ing).
FIG. 2 is a diagram showing the results of surface excitation hole measurement of anatase single crystal thin film, rutile single crystal thin film and Cr-implanted rutile thin film (only Cr-implanted rutile thin film is excited to the surface up to about 500 nm). Can be confirmed).
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| JP4295231B2 (en) | 2005-03-01 | 2009-07-15 | 富士通株式会社 | Broadband light-absorbing photocatalyst and method for producing the same, and broadband light-absorbing photocatalyst-containing composition and molded article |
| US8236146B2 (en) | 2008-10-30 | 2012-08-07 | Panasonic Corporation | Photoelectrochemical cell and energy system using the same |
| US8758578B2 (en) | 2009-08-05 | 2014-06-24 | Panasonic Corporation | Photoelectrochemical cell and energy system using the same |
| EP2500449B1 (en) | 2009-11-10 | 2017-09-27 | Panasonic Intellectual Property Management Co., Ltd. | Photoelectrochemical cell and energy system using same |
| EP2555314B1 (en) | 2010-03-31 | 2016-09-21 | Panasonic Intellectual Property Management Co., Ltd. | Photoelectrochemical cell and energy system using same |
| JP6009254B2 (en) * | 2012-07-17 | 2016-10-19 | シャープ株式会社 | Photocatalyst, method for producing the same, and purification device |
| WO2014068944A1 (en) | 2012-10-31 | 2014-05-08 | パナソニック株式会社 | Photosemiconductor electrode, photoelectrochemical cell, and energy system |
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| JPH1192176A (en) * | 1997-07-22 | 1999-04-06 | Bridgestone Corp | Photocatalytic film and its production |
| JPH11197512A (en) * | 1998-01-08 | 1999-07-27 | Sumitomo Chem Co Ltd | Thin photocatalyst film, photocatalytic reaction method and production of thin photocatalyst film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1192176A (en) * | 1997-07-22 | 1999-04-06 | Bridgestone Corp | Photocatalytic film and its production |
| JPH11197512A (en) * | 1998-01-08 | 1999-07-27 | Sumitomo Chem Co Ltd | Thin photocatalyst film, photocatalytic reaction method and production of thin photocatalyst film |
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