JP3864214B2 - Surface treatment method of zinc oxide photocatalyst thin film - Google Patents
Surface treatment method of zinc oxide photocatalyst thin film Download PDFInfo
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- JP3864214B2 JP3864214B2 JP2002044216A JP2002044216A JP3864214B2 JP 3864214 B2 JP3864214 B2 JP 3864214B2 JP 2002044216 A JP2002044216 A JP 2002044216A JP 2002044216 A JP2002044216 A JP 2002044216A JP 3864214 B2 JP3864214 B2 JP 3864214B2
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- zinc oxide
- thin film
- nitrogen
- oxide thin
- substrate
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 135
- 239000011787 zinc oxide Substances 0.000 title claims description 68
- 239000010409 thin film Substances 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 12
- 239000011941 photocatalyst Substances 0.000 title claims description 10
- 238000004381 surface treatment Methods 0.000 title claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims description 10
- 150000003254 radicals Chemical class 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 3
- -1 nitrogen radicals zinc oxide Chemical class 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 12
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 150000002831 nitrogen free-radicals Chemical class 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-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、酸化亜鉛薄膜の処理方法、特にその光触媒活性を向上させるための処理方法に関する。
【０００２】
【従来の技術】
酸化亜鉛はガラスをはじめとした基板表面には容易に薄膜化可能である。ＭＯＣＶＤ法でＣ−軸配向した酸化亜鉛薄膜を合成することができる。酸化亜鉛は光触媒として用いられるが、従来の酸化亜鉛光触媒は、材料形態が粉末であるものが多い。また、薄膜の形態の酸化亜鉛光触媒も知られており（例；特開平９−２９９７９１号公報）、酸化亜鉛光触媒に窒素を添加する試みもある（例；特開２００１−２０５０９４号公報）。
【０００３】
【発明が解決しようとする課題】
酸化亜鉛薄膜の配向の容易さは多くの文献で見られる。安価なガラスをはじめとした多くの基板で報告されている。薄膜に窒素を添加する試みも行われているが、酸化亜鉛薄膜中に窒素だけを成膜時に添加すると配向性や結晶性の低下を引き起こし、酸化亜鉛の透明性を維持しながら１at％以上の窒素を添加することは困難である。本発明は、環境浄化等のために使用する酸化亜鉛光触媒薄膜の光触媒活性を向上させる方法の提供を目的とする。
【０００４】
【課題を解決するための手段】
本発明者らは、窒素添加ではなく酸化亜鉛表面のラジカル処理で、酸化亜鉛の透明性を維持しながら触媒活性を向上させることができることを見出した。
【０００５】
すなわち、本発明は、基板表面にＭＯＣＶＤ法によってＣ−軸が基板表面に対して垂直に成長している酸化亜鉛薄膜を成膜した後、さらに、ＭＯＣＶＤ装置に搭載されているラジカル源で窒素ラジカルを酸化亜鉛 表面に基板の温度５０℃から４００℃の範囲で、照射すること で表面窒素濃度を高めることを特徴とする酸化亜鉛光触媒薄膜の表面処理方法である。
【０００６】
酸化亜鉛を光触媒として応用する場合、その光触媒活性が低いことが問題になる。薄膜化し窒素ラジカル処理することで光触媒活性が向上する。酸化亜鉛は薄膜化かつ大面積化が容易であり、同様に窒素ラジカル処理も大面積化が容易である。また、窒素ラジカル処理は５０℃から４００℃、例えば１５０℃の低温で行うプロセスであるため、酸化亜鉛薄膜の基板の多様化にも使用可能なプロセスである。
【０００７】
【作用】
本発明は、基板表面に成膜したＣ−軸が基板表面に対して垂直な高配向の酸化亜鉛薄膜に窒素ラジカル処理を施すことを特徴とする。この処理で酸化亜鉛表面を構成する酸素占有サイトの一部が窒素で置換される。この処理した酸化亜鉛の光触媒活性は処理無しに比較して３倍程度の向上が見られる。光触媒反応が表面反応であることを考えると、表面修飾により表面の酸素占有サイトを窒素で置換することにより、酸化亜鉛中に正孔が供給され、もともと酸化亜鉛に存在する電子との作用で、光触媒活性が向上する。
【０００８】
【発明の実施の形態】
このような高配向の酸化亜鉛光触媒薄膜は基板表面にＭＯＣＶＤ法によって形成可能である。さらに、ＭＯＣＶＤ装置に搭載されているラジカル源で窒素ラジカルを酸化亜鉛薄膜に照射できる。このような酸化亜鉛薄膜の表面に１０×１０−２から１×１０−５Ｔｏｒｒの範囲で窒素ラジカルを照射する。
窒素ラジカル照射を、酸化亜鉛基板の温度５０℃から４００℃の範囲でおこなうことにより 表面上の窒素が確認される。基板の温度がこの温度範囲外では窒素ラジカル処理による表面上での窒素が検出されない。また、照射時間に関しては、１０分以上では表面で検出される窒素量に変化がない。
【０００９】
【実施例】
比較例１
酸化亜鉛薄膜の合成はＭＯＣＶＤ法で行った。亜鉛ソースに安価な亜鉛アセチルアセトナートを用い８５℃、アルゴン気流中で気化させ、真空チャンバー内のリングインジェクターから基板に噴射した。表１に示す酸化亜鉛合成条件で、酸素は基板上１５ｃｍに搭載されたラジカル源から基板にラジカルとして照射し、基板上で反応させ厚さ約５００ｎｍの酸化亜鉛薄膜を合成した。
【００１０】
【表１】
その後、Ｘ−線回折法で酸化亜鉛薄膜の配向性を調べた。図５に示した通り、酸化亜鉛の強い（００２）ピーク強度と弱い（００４）ピークが検出され、酸化亜鉛が基板表面に対してＣ−軸が垂直に成長していることを確認した。また、ＭＯＣＶＤ法で合成した酸化亜鉛薄膜表面をオージェ分光法で調べた。図６にオージェ分光法で得られたスペクトルを示す。この表面では酸化亜鉛表面に窒素のピークは検出されなかった。
【００１２】
実施例１
比較例１と同じ条件で酸化亜鉛薄膜を合成した。その後、そのままＭＯＣＶＤ装置を用いて、窒素ラジカルを真空度４×１０-4Ｔｏｒｒ、基板温度１５０℃で１５分間照射した。その後、酸化亜鉛薄膜をオージェ分光法で調べ、窒素が酸化亜鉛薄膜上に存在することを確認した。図１にオージェ分光法で得られたスペクトルを示す。窒素の存在は窒素ラジカル処理の効果である。
【００１３】
実施例１で得られた酸化亜鉛薄膜の表面をＸＰＳ法で酸化亜鉛表面における窒素の状態を調べた。図２にＸＰＳで得られた窒素のスペクトルを示す。これによると、酸化亜鉛上の表面の窒素の状態はほとんど窒素分子であり、一部酸化亜鉛の酸素サイトを置換していることが分かった。この酸化亜鉛格子中の酸素サイトを置換した窒素が酸化亜鉛に正孔を供給している。
【００１４】
実施例１で窒素ラジカル照射した酸化亜鉛薄膜の吸収スペクトルを波長３４０ｎｍから９００ｎｍの範囲で測定した。可視光領域から紫外領域のバンド端まで８５％以上の透過率があり、窒素照射が光吸収に与える影響は見られないことを確認した。
【００１５】
実施例１および比較例１で得られた酸化亜鉛薄膜の光触媒の評価を行った。光触媒活性の評価は、酸化亜鉛薄膜を石英製の容器に入れ、１０００ｐｐｍのアセトアルデヒドを含むガスを充填する。そこに紫外光を照射して、酸化亜鉛の光触媒反応で分解された二酸化炭素を各反応時間で測定した。図３に測定結果を示す。その結果、実施例１の窒素ラジカル照射処理をした酸化亜鉛薄膜から得られる、二酸化炭素の量は、処理なしの酸化亜鉛薄膜を用いた場合の生成量よりも３倍程度に達することが分かった。これは、窒素ラジカル照射により酸化亜鉛表面に窒素が吸着することの効果である。
【００１６】
実施例２
窒素ラジカルの照射時間を３０分とした以外は実施例１と同じ条件で窒素ラジカル処理をした。図４にオージェ分光法で得られたスペクトルを示す。窒素ラジカルを３０分照射しても強度に変化がないことを確認した。
【００１７】
比較例２
基板温度を５００℃とした以外は実施例１と同じ条件で窒素ラジカル処理をした。図７にオージェ分光法で得られたスペクトルを示す。窒素の存在は確認できなかった。
【００１８】
【発明の効果】
酸化亜鉛薄膜は基板によらずＣ−軸配向し易い物質である。本発明は、Ｃ−軸配向した酸化亜鉛薄膜へ基板温度が低い条件で、窒素ラジカルを短時間照射することを特徴としている。この処理条件のため、ラジカル処理が酸化亜鉛薄膜やその基板に与える影響が殆どないことが特徴である。このため、２００℃程度の基板温度条件で合成された酸化亜鉛に対しても同様のラジカル処理を施せ、酸化亜鉛の応用の広がりが期待できる。
【図面の簡単な説明】
【図１】実施例１で窒素ラジカル処理した酸化亜鉛薄膜のオージェ分光法で得られたスペクトル図である。
【図２】実施例１で窒素ラジカル処理した酸化亜鉛薄膜表面のＸＰＳで得られた窒素のスペクトル図である。
【図３】実施例１および比較例１で得られた酸化亜鉛薄膜の光触媒の評価結果を示すグラフである。
【図４】実施例２で合成した酸化亜鉛薄膜のオージェ分光法で得られたスペクトル図である。
【図５】比較例１で合成した酸化亜鉛薄膜のＸ−線回折パターン図である。
【図６】比較例１で合成した酸化亜鉛薄膜のオージェ分光法で得られたスペクトル図である。
【図７】比較例２で合成した酸化亜鉛薄膜のオージェ分光法で得られたスペクトル図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for treating a zinc oxide thin film, and more particularly to a treatment method for improving the photocatalytic activity thereof.
[0002]
[Prior art]
Zinc oxide can be easily thinned on the surface of a substrate such as glass. A C-axis oriented zinc oxide thin film can be synthesized by MOCVD. Zinc oxide is used as a photocatalyst, but many conventional zinc oxide photocatalysts are in powder form. In addition, a zinc oxide photocatalyst in the form of a thin film is also known (for example, JP-A-9-299791), and there is an attempt to add nitrogen to the zinc oxide photocatalyst (for example, JP-A-2001-205094).
[0003]
[Problems to be solved by the invention]
The ease of orientation of zinc oxide thin films can be found in many literatures. It has been reported on many substrates including inexpensive glass. Attempts have been made to add nitrogen to the thin film, but if only nitrogen is added to the zinc oxide thin film at the time of film formation, the orientation and crystallinity will be lowered, and the transparency of zinc oxide will be maintained while maintaining at least 1 at%. It is difficult to add nitrogen. An object of this invention is to provide the method of improving the photocatalytic activity of the zinc oxide photocatalyst thin film used for environmental purification etc.
[0004]
[Means for Solving the Problems]
The present inventors have found that catalytic activity can be improved while maintaining the transparency of zinc oxide by radical treatment on the surface of zinc oxide rather than addition of nitrogen.
[0005]
That is, according to the present invention, after a zinc oxide thin film having a C-axis growing perpendicularly to the substrate surface is formed on the substrate surface by the MOCVD method, a nitrogen radical is further formed by a radical source mounted on the MOCVD apparatus. Is a surface treatment method for a zinc oxide photocatalytic thin film characterized in that the surface nitrogen concentration is increased by irradiating the surface of the zinc oxide at a substrate temperature of 50 ° C. to 400 ° C.
[0006]
When zinc oxide is applied as a photocatalyst, its photocatalytic activity is low. The photocatalytic activity is improved by thinning and nitrogen radical treatment. Zinc oxide can be easily reduced in thickness and area, and similarly, nitrogen radical treatment can be easily increased in area. Further, since the nitrogen radical treatment is a process performed at a low temperature of 50 to 400 ° C., for example, 150 ° C., it can be used for diversification of the substrate of the zinc oxide thin film.
[0007]
[Action]
The present invention, C-axis was formed on the substrate surface is characterized by applying nitrogen radical treatment to the zinc oxide thin film of the height perpendicular orientation with respect to the substrate surface. This treatment replaces part of the oxygen-occupying sites constituting the zinc oxide surface with nitrogen. The photocatalytic activity of the treated zinc oxide is improved by about 3 times compared to the case without the treatment. Considering that the photocatalytic reaction is a surface reaction, by replacing the oxygen-occupied sites on the surface with nitrogen by surface modification, holes are supplied into the zinc oxide, and with the action of electrons originally present in the zinc oxide, The photocatalytic activity is improved.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Such a highly oriented zinc oxide photocatalytic thin film can be formed on the substrate surface by MOCVD. Furthermore, the zinc oxide thin film can be irradiated with nitrogen radicals by a radical source mounted on the MOCVD apparatus. The surface of such a zinc oxide thin film is irradiated with nitrogen radicals in the range of 10 × 10 −2 to 1 × 10 −5 Torr.
Nitrogen radical irradiation is performed at a temperature of the zinc oxide substrate in the range of 50 ° C. to 400 ° C. to confirm nitrogen on the surface. When the temperature of the substrate is outside this temperature range, nitrogen on the surface by nitrogen radical treatment is not detected. Regarding the irradiation time, the amount of nitrogen detected on the surface does not change after 10 minutes or longer.
[0009]
【Example】
Comparative Example 1
The synthesis of the zinc oxide thin film was performed by the MOCVD method. Inexpensive zinc acetylacetonate was used as a zinc source, vaporized in an argon stream at 85 ° C., and sprayed from a ring injector in a vacuum chamber onto a substrate . Zinc oxide synthesis conditions shown in Table 1, the oxygen is irradiated as a radical from the radical source mounted on the substrate 15cm substrate was synthesized zinc oxide thin film having a thickness of about 500nm is reacted on the substrate.
[0010]
[Table 1]
Thereafter, the orientation of the zinc oxide thin film was examined by X-ray diffraction. As shown in FIG. 5, a strong (002) peak intensity and a weak (004) peak of zinc oxide were detected, confirming that the C-axis of zinc oxide grew perpendicular to the substrate surface . Further, the surface of the zinc oxide thin film synthesized by MOCVD method was examined by Auger spectroscopy. FIG. 6 shows a spectrum obtained by Auger spectroscopy. On this surface, no nitrogen peak was detected on the zinc oxide surface.
[0012]
Example 1
A zinc oxide thin film was synthesized under the same conditions as in Comparative Example 1. Thereafter, using a MOCVD apparatus as it is, nitrogen radicals were irradiated for 15 minutes at a vacuum degree of 4 × 10 −4 Torr and a substrate temperature of 150 ° C. Thereafter, the zinc oxide thin film was examined by Auger spectroscopy, and it was confirmed that nitrogen was present on the zinc oxide thin film. FIG. 1 shows a spectrum obtained by Auger spectroscopy. The presence of nitrogen is an effect of nitrogen radical treatment.
[0013]
The surface of the zinc oxide thin film obtained in Example 1 was examined for the state of nitrogen on the zinc oxide surface by the XPS method. FIG. 2 shows the spectrum of nitrogen obtained by XPS. According to this, it was found that the state of nitrogen on the surface of zinc oxide was almost nitrogen molecules, and partially substituted the oxygen sites of zinc oxide. Nitrogen replacing oxygen sites in the zinc oxide lattice supplies holes to the zinc oxide.
[0014]
The absorption spectrum of the zinc oxide thin film irradiated with nitrogen radicals in Example 1 was measured in the wavelength range of 340 nm to 900 nm. It was confirmed that there was a transmittance of 85% or more from the visible light region to the band edge in the ultraviolet region, and no effect of nitrogen irradiation on light absorption was observed.
[0015]
The photocatalyst of the zinc oxide thin film obtained in Example 1 and Comparative Example 1 was evaluated. For the evaluation of the photocatalytic activity, a zinc oxide thin film is placed in a quartz container and filled with a gas containing 1000 ppm of acetaldehyde. This was irradiated with ultraviolet light, and carbon dioxide decomposed by the photocatalytic reaction of zinc oxide was measured at each reaction time. FIG. 3 shows the measurement results. As a result, it was found that the amount of carbon dioxide obtained from the zinc oxide thin film subjected to the nitrogen radical irradiation treatment in Example 1 reached about three times the amount produced when the untreated zinc oxide thin film was used. . This is an effect of adsorption of nitrogen on the surface of zinc oxide by nitrogen radical irradiation.
[0016]
Example 2
The nitrogen radical treatment was performed under the same conditions as in Example 1 except that the irradiation time of nitrogen radicals was 30 minutes. FIG. 4 shows a spectrum obtained by Auger spectroscopy. It was confirmed that there was no change in intensity even after irradiation with nitrogen radicals for 30 minutes.
[0017]
Comparative Example 2
The nitrogen radical treatment was performed under the same conditions as in Example 1 except that the substrate temperature was 500 ° C. FIG. 7 shows a spectrum obtained by Auger spectroscopy. The presence of nitrogen could not be confirmed.
[0018]
【The invention's effect】
The zinc oxide thin film is a substance that is easily C-axis oriented regardless of the substrate . The present invention is characterized by irradiating a C-axis oriented zinc oxide thin film with nitrogen radicals for a short time under a low substrate temperature. Due to these treatment conditions, the radical treatment is characterized by almost no influence on the zinc oxide thin film and its substrate . For this reason, the same radical treatment can be applied to zinc oxide synthesized under a substrate temperature condition of about 200 ° C., and the application of zinc oxide can be expected to expand.
[Brief description of the drawings]
1 is a spectrum diagram obtained by Auger spectroscopy of a zinc oxide thin film treated with nitrogen radicals in Example 1. FIG.
2 is a spectrum diagram of nitrogen obtained by XPS on the surface of a zinc oxide thin film treated with nitrogen radicals in Example 1. FIG.
FIG. 3 is a graph showing the evaluation results of the photocatalyst of the zinc oxide thin film obtained in Example 1 and Comparative Example 1.
4 is a spectrum diagram obtained by Auger spectroscopy of the zinc oxide thin film synthesized in Example 2. FIG.
5 is an X-ray diffraction pattern diagram of the zinc oxide thin film synthesized in Comparative Example 1. FIG.
6 is a spectrum diagram obtained by Auger spectroscopy of the zinc oxide thin film synthesized in Comparative Example 1. FIG.
7 is a spectrum diagram obtained by Auger spectroscopy of the zinc oxide thin film synthesized in Comparative Example 2. FIG.
Claims (1)
Priority Applications (1)
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| JP4565897B2 (en) | 2004-06-14 | 2010-10-20 | 株式会社Ａｄｅｋａ | Thin film forming raw material and thin film manufacturing method |
| JP5063074B2 (en) * | 2006-10-03 | 2012-10-31 | 株式会社Ａｄｅｋａ | Thin film forming raw material, thin film manufacturing method, and zinc compound |
| CN102580716B (en) * | 2012-01-18 | 2014-02-26 | 黑龙江大学 | Method for synthesizing zinc oxide/graphene composite by solvothermal method |
| US20230142848A1 (en) | 2020-04-01 | 2023-05-11 | Adeka Corporation | Zinc compound, thin-film forming raw material, thin-film, and method of producing thin-film |
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