JP2002253974A - Photocatalytic thin film material and application article thereof - Google Patents
Photocatalytic thin film material and application article thereofInfo
- Publication number
- JP2002253974A JP2002253974A JP2001057058A JP2001057058A JP2002253974A JP 2002253974 A JP2002253974 A JP 2002253974A JP 2001057058 A JP2001057058 A JP 2001057058A JP 2001057058 A JP2001057058 A JP 2001057058A JP 2002253974 A JP2002253974 A JP 2002253974A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- crystal
- photocatalytic
- photocatalytic thin
- film material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 117
- 239000010409 thin film Substances 0.000 title claims abstract description 86
- 239000000463 material Substances 0.000 title claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims description 17
- 230000000844 anti-bacterial effect Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000003373 anti-fouling effect Effects 0.000 claims description 3
- 230000001877 deodorizing effect Effects 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 abstract description 8
- 238000005240 physical vapour deposition Methods 0.000 abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- 239000011941 photocatalyst Substances 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 230000001443 photoexcitation Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 241000554155 Andes Species 0.000 description 1
- 102100024522 Bladder cancer-associated protein Human genes 0.000 description 1
- 101150110835 Blcap gene Proteins 0.000 description 1
- 101100493740 Oryza sativa subsp. japonica BC10 gene Proteins 0.000 description 1
- 101710162453 Replication factor A Proteins 0.000 description 1
- 102100035729 Replication protein A 70 kDa DNA-binding subunit Human genes 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/77—Coatings having a rough surface
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は化学的または物理的
蒸着技術により作製した薄膜において、高活性な光触媒
機能を示す光触媒薄膜材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalytic thin film material exhibiting a highly active photocatalytic function in a thin film produced by a chemical or physical vapor deposition technique.
【０００２】[0002]
【従来の技術】酸化チタンなどの酸化物半導体薄膜は、
そのバンドギャップ以上のエネルギーを持つ波長の光を
照射すると、光励起により光触媒機能を発現することが
従来から知られている。その発現機構は、光励起により
伝導帯に電子を生じ、価電子帯に正孔を生じることに起
因し、電子の強い還元作用、正孔の強い酸化作用によ
り、光触媒に接触してくる有機物や窒素酸化物を水や炭
酸ガスなどに分解するものであり、防臭機能、抗菌機能
等を有している。2. Description of the Related Art An oxide semiconductor thin film such as titanium oxide is
It has been conventionally known that when light having a wavelength having energy equal to or greater than the band gap is applied, a photocatalytic function is exhibited by photoexcitation. The mechanism of its development is that photoexcitation produces electrons in the conduction band and holes in the valence band, resulting in strong reduction of electrons and strong oxidation of holes. It decomposes oxides into water, carbon dioxide, and the like, and has a deodorant function, an antibacterial function, and the like.
【０００３】光触媒機能は、光が照射される光触媒体表
面で起こるものである。このため有害物質の分解効果向
上を目的に、光触媒体の表面状態を制御する技術、ある
いは光触媒体表層部の結晶を制御する技術が従来から知
られている。例えば、光触媒体の表面状態を制御する技
術として特開平9-57912号公報、特開平10-36144号公
報、特開平10-57817号公報および特開平10-231146号公
報が開示されている。これら先行技術に開示される基本
構成は、ガラス基板の表面に、直接あるいはアルカリ遮
断用の下地膜を介して光触媒としての酸化チタン層が形
成され、この酸化チタン層の表面に酸化ケイ素を形成し
たものである。[0003] The photocatalytic function occurs on the surface of a photocatalyst to which light is applied. For this reason, a technique for controlling the surface state of the photocatalyst or a technique for controlling crystals in the surface layer of the photocatalyst has been conventionally known in order to improve the effect of decomposing harmful substances. For example, JP-A-9-57912, JP-A-10-36144, JP-A-10-57817 and JP-A-10-231146 disclose techniques for controlling the surface state of the photocatalyst. In the basic structure disclosed in these prior arts, a titanium oxide layer as a photocatalyst is formed directly or via an underlayer for blocking alkali, on the surface of a glass substrate, and silicon oxide is formed on the surface of this titanium oxide layer. Things.
【０００４】上記の先行技術は酸化ケイ素膜を多孔質に
形成したり、酸化チタン膜やガラス基板に微細加工を施
すことにより表面上に凹凸を設けることで、光触媒機能
を高める工夫をしている。すなわち、表面に微細な凹凸
を形成することで光触媒体が露出する表面の面積が増大
するので、光触媒機能が向上するというものであるが、
必ずしも顕著な向上は見られない。また基板の加工、膜
の加工、下地層の挿入などコスト面でも問題がある。In the above prior art, a photocatalytic function is devised by forming a silicon oxide film in a porous form, or performing fine processing on a titanium oxide film or a glass substrate to provide irregularities on the surface. . That is, the formation of fine irregularities on the surface increases the area of the surface where the photocatalyst is exposed, so that the photocatalytic function is improved.
There is not always a noticeable improvement. There is also a problem in terms of cost such as processing of the substrate, processing of the film, and insertion of the underlayer.
【０００５】また、光触媒体表層部を構成する結晶を制
御する技術として特開平2000-288403号公報が開示され
ている。この先行技術に開示される基本構成は、酸化チ
タンがアナターゼ型の結晶であり、その表層部に存在す
る酸化チタンの結晶粒のうち、30％以上の結晶粒の形状
が、楕円形又は半楕円形であることを特徴したものであ
る。そして楕円形又は半楕円形の酸化チタンの結晶を形
成することで高活性な光触媒機能が得られるというもの
である。この先行技術は、結晶粒を楕円形又は半楕円形
にすることで、光触媒体の露出する表面の面積が増加
し、光触媒機能が向上するというものであるが、必ずし
も顕著な向上は見られない。Japanese Patent Application Laid-Open No. 2000-288403 discloses a technique for controlling crystals constituting the surface layer of the photocatalyst body. The basic structure disclosed in this prior art is that titanium oxide is an anatase type crystal, and among titanium oxide crystal grains present in the surface layer portion, 30% or more of the crystal grains have an elliptical or semi-elliptical shape. It is characterized by being a shape. By forming an elliptical or semi-elliptical titanium oxide crystal, a highly active photocatalytic function can be obtained. In this prior art, by making the crystal grains into an elliptical or semi-elliptical shape, the area of the exposed surface of the photocatalyst increases, and the photocatalytic function is improved. .
【０００６】一方、薄膜の作製技術として、化学的蒸着
法(Chemical Vapar Deposition：以下「CVD」と称す)及
び物理的蒸着法(Pysical Vapar Deposition：以下「PV
D」と称す)が知られている。これらの方法は、薄膜を各
種基板に直接成膜でき、膜厚や薄膜の結晶構造を制御で
きることから、光触媒機能を示す光触媒薄膜を作製する
ために適した方法である。特にスパッタリング法は薄膜
を比較的低温で成膜でき、膜厚や薄膜の結晶構造を制御
できる薄膜作製技術として知られている。このスパッタ
リング法により光触媒薄膜の結晶を制御する先行技術と
して特開平11-130434号公報が開示されている。この先
行技術に開示される基本構成は、対向ターゲット式スパ
ッタリング法でアナターゼ型柱状結晶を持つ酸化チタン
膜を形成する方法であり、アナターゼ型リッチの柱状結
晶の集合体を形成することにより高活性な光触媒機能が
得られるというものである。しかし、この先行技術はア
ナターゼ型柱状結晶を形成することである程度の光触媒
機能が発現されてはいるものの、顕著な向上は見られて
いない。On the other hand, as a thin film manufacturing technique, a chemical vapor deposition method (hereinafter referred to as “CVD”) and a physical vapor deposition method (hereinafter referred to as “PV”) are used.
D ") is known. These methods are suitable for producing a photocatalytic thin film having a photocatalytic function because a thin film can be directly formed on various substrates and the crystal structure of the thin film and the thin film can be controlled. In particular, the sputtering method is known as a thin film manufacturing technique capable of forming a thin film at a relatively low temperature and controlling the film thickness and the crystal structure of the thin film. Japanese Patent Application Laid-Open No. H11-130434 discloses a prior art for controlling crystals of a photocatalytic thin film by this sputtering method. The basic structure disclosed in this prior art is a method of forming a titanium oxide film having an anatase-type columnar crystal by a facing target type sputtering method. That is, a photocatalytic function can be obtained. However, in this prior art, although a certain degree of photocatalytic function has been exhibited by forming an anatase type columnar crystal, no remarkable improvement has been observed.
【０００７】[0007]
【発明が解決しようとする課題】上述した従来技術にお
いては、光触媒体表面状態の制御および光触媒体の表面
層部を構成する結晶を制御することで形成した光触媒薄
膜は良好な光触媒機能を示しているが、更に高活性な光
触媒機能を有する光触媒薄膜が求められている。本願発
明者等はこのような従来事情に鑑み、更に高活性な光触
媒機能を有する光触媒薄膜を作製するため、薄膜を各種
基板に直接成膜でき、膜厚や薄膜の結晶構造を制御でき
るCVD、PVDにより光触媒薄膜作製について鋭意検討し
た。その結果、作製した光触媒薄膜の表面における結晶
の形状を角錐型又は円錐型とすることにより、極めて高
活性な光触媒機能が得られることを見出し、本発明を完
成するに至った。In the above-mentioned prior art, the photocatalytic thin film formed by controlling the surface state of the photocatalyst and controlling the crystals constituting the surface layer of the photocatalyst exhibits a good photocatalytic function. However, there is a demand for a photocatalytic thin film having a more active photocatalytic function. In view of such conventional circumstances, the present inventors have developed a CVD method capable of directly forming a thin film on various substrates and controlling the film thickness and the crystal structure of the thin film in order to produce a photocatalytic thin film having a more active photocatalytic function. We studied the preparation of photocatalytic thin film by PVD. As a result, they have found that an extremely high activity photocatalytic function can be obtained by making the shape of the crystal on the surface of the produced photocatalytic thin film into a pyramidal or conical shape, and completed the present invention.
【０００８】[0008]
【課題を解決するための手段】すなわち本願の請求項１
に係る発明は、基板上に光触媒薄膜を形成してなる光触
媒薄膜材料であって、前記光触媒薄膜の表面における少
なくとも一部の結晶の形状が角錐型又は円錐型であり、
且つその頂部が上方に向いていることにより高活性な光
触媒機能を発揮することを特徴とする。That is, claim 1 of the present application.
The invention according to the present invention is a photocatalytic thin film material formed by forming a photocatalytic thin film on a substrate, wherein the shape of at least a part of the crystal on the surface of the photocatalytic thin film is pyramidal or conical,
In addition, since the top is directed upward, a highly active photocatalytic function is exhibited.
【０００９】このような構成によれば、角錐型又は円錐
型の結晶がその頂点を上にして光触媒薄膜表面の一部又
は全部を形成するので、光触媒薄膜表面において光を受
ける面積が大きくなり、光触媒反応が効率良く行われる
ようになる。According to such a configuration, the pyramidal or conical crystal forms a part or all of the surface of the photocatalytic thin film with its apex facing upward, so that the light receiving area on the surface of the photocatalytic thin film increases, The photocatalytic reaction can be performed efficiently.
【００１０】また本願の請求項２に係る発明は、請求項
１における上記結晶の形状が四角錐型であり、且つ該四
角錐型結晶の底面部における二つの対角線のうち、一方
の対角線の距離が１０ｎｍ〜２００ｎｍ、他方の対角線
の距離が１０ｎｍ〜２００ｎｍであることを特徴とす
る。According to the invention of claim 2 of the present application, the crystal in claim 1 has a quadrangular pyramid shape, and the distance between one diagonal line of the two diagonal lines on the bottom surface of the quadrangular pyramidal crystal. Is 10 nm to 200 nm, and the distance of the other diagonal is 10 nm to 200 nm.
【００１１】上記対角線の距離がそれぞれ１0ｎｍ未満
の場合、結晶が微細化し形状そのものが光触媒機能に有
効である四角錐型に形成されない。また上記対角線の距
離がそれぞれ２００ｎｍを越えた場合、結晶の形状とし
ては四角錐型を形成するものの、結晶サイズが増大し、
光触媒機能に有効である四角錐型結晶の数が減少してし
まう。故に、四角錐型結晶の結晶サイズを請求項2のよ
うに限定することが、高活性な光触媒機能を示すのに有
効である。When the distance between the diagonal lines is less than 10 nm, the crystal becomes finer and the shape itself is not formed into a quadrangular pyramid which is effective for the photocatalytic function. Further, when the distance between the diagonal lines exceeds 200 nm, although the crystal shape is a quadrangular pyramid, the crystal size increases,
The number of pyramidal crystals effective for the photocatalytic function is reduced. Therefore, limiting the crystal size of the quadrangular pyramidal crystal as in claim 2 is effective for exhibiting a highly active photocatalytic function.
【００１２】請求項３に係る発明は、請求項１又は２に
おける上記結晶の形状が四角錐型であり、且つ該四角錐
型結晶が、シェラーの式により算出された粒径５ｎｍ〜
５０ｎｍの結晶子から形成されていることを特徴とす
る。According to a third aspect of the present invention, in the first or second aspect, the crystal has a quadrangular pyramid shape, and the quadrangular pyramid type crystal has a particle size of 5 nm or more calculated by Scherrer's formula.
It is characterized by being formed from a crystallite of 50 nm.
【００１３】四角錐型結晶を構成する結晶子の粒径が５
ｎｍ未満の場合、結晶の微細化により結晶形状そのもの
が光触媒機能に有効である四角錐型に形成されない。ま
た、四角錐型結晶を構成する結晶子の粒径が１０ｎｍを
越えると、結晶の形状としては四角錐型を形成するもの
の、結晶サイズが増大し、光触媒機能に有効である四角
錐型結晶の数が減少してしまう。故に、四角錐型結晶の
結晶子のサイズを請求項３のように限定することが、高
活性な光触媒機能を示すのに有効である。The crystallites constituting the quadrangular pyramidal crystal have a grain size of 5
If it is less than nm, the crystal shape itself is not formed in a quadrangular pyramid shape that is effective for the photocatalytic function due to the miniaturization of the crystal. Further, when the particle size of the crystallites constituting the quadrangular pyramidal crystal exceeds 10 nm, although the crystal shape forms a quadrangular pyramid, the crystal size increases and the quadrangular pyramidal crystal which is effective for the photocatalytic function is formed. The number decreases. Therefore, it is effective to limit the size of the crystallite of the quadrangular pyramid type crystal as described in claim 3 in order to exhibit a highly active photocatalytic function.
【００１４】請求項４に係る発明は、請求項１〜３の何
れかにおける上記結晶の形状が四角錐型であり、且つ該
四角錐型結晶の数が、０．５μｍ×０．５μｍ四方内の
観察において５〜２０個であることを特徴とする。According to a fourth aspect of the present invention, the shape of the crystal in any one of the first to third aspects is a quadrangular pyramid, and the number of the quadrangular pyramidal crystals is 0.5 μm × 0.5 μm square. Is characterized by the observation of 5 to 20 pieces.
【００１５】０．５μｍ×０．５μｍ四方内の観察にお
いて、四角錐型結晶の数が5個未満の場合、光触媒機能
に有効な四角錐型結晶の数が少なく、高活性な光触媒機
能を得ることが出来ない。また、四角錐型結晶の数が２
０個を越えた場合、形成される結晶のサイズが小さくな
り、光触媒機能に有効である四角錐型結晶形状が得られ
ず、高活性な光触媒機能を示さないと考えられる。故
に、四角錐型結晶の数を請求項４のように限定すること
が、高活性な光触媒機能を示すのに有効である。In the observation within 0.5 μm × 0.5 μm square, when the number of the pyramidal crystals is less than 5, the number of the pyramidal crystals effective for the photocatalytic function is small, and a highly active photocatalytic function is obtained. I can't do that. In addition, the number of quadrangular pyramidal crystals is 2
When the number exceeds 0, the size of the formed crystal becomes small, a quadrangular pyramidal crystal shape effective for the photocatalytic function cannot be obtained, and it is considered that the photocatalytic function does not exhibit high activity. Therefore, limiting the number of quadrangular pyramidal crystals as in claim 4 is effective for exhibiting a highly active photocatalytic function.
【００１６】請求項５に係る発明は、請求項１〜４の何
れかにおける上記結晶の形状が四角錐型であり、且つ該
四角錐型結晶の四つの側面部のうちの少なくとも一つの
側面部に階段状の凹凸が形成されていることを特徴とす
る。According to a fifth aspect of the present invention, the shape of the crystal according to any one of the first to fourth aspects is a quadrangular pyramid, and at least one of the four lateral sides of the quadrangular pyramid-shaped crystal. Is formed with step-like irregularities.
【００１７】この場合、四角錐型結晶自体が光触媒機能
に有効であるが、さらにその結晶の側面部に階段状の凹
凸が形成されることで、光触媒機能に有効な面積が増加
し、活性がさらに高まると推測される。In this case, the quadrangular pyramid-shaped crystal itself is effective for the photocatalytic function, but the stepwise unevenness is formed on the side surface of the crystal, so that the area effective for the photocatalytic function is increased and the activity is increased. It is estimated that it will increase further.
【００１８】請求項６に係る発明は、請求項１〜５の何
れかにおける上記結晶の形状が四角錐型であり、且つ該
四角錐型結晶が光触媒薄膜中において、(１０１)面、
(１１２)面、（２００）面、（２１１）面、（２２０）
面のいずれかに配向していることを特徴とする。According to a sixth aspect of the present invention, the crystal according to any one of the first to fifth aspects has a quadrangular pyramid shape, and the quadrangular pyramid type crystal has a (101) plane,
(112) plane, (200) plane, (211) plane, (220) plane
It is characterized in that it is oriented on one of the planes.
【００１９】光触媒機能と結晶配向の関連性については
明らかではないが、光触媒機能が結晶自体に大きく影響
されることから、本発明で得られた(１０１)、(１１
２)、(２００)、(２１１)、(２２０)面の配向が光触媒
機能に関与していることは十分考えられる。Although the relationship between the photocatalytic function and the crystal orientation is not clear, since the photocatalytic function is greatly affected by the crystal itself, (101) and (11) obtained by the present invention are obtained.
It is fully conceivable that the orientation of the (2), (200), (211) and (220) planes is involved in the photocatalytic function.
【００２０】請求項７に係る発明は、請求項１〜６の光
触媒薄膜材料を使用して清浄機能、抗菌機能、脱臭機
能、防汚機能等を発揮することを特徴とする光触媒薄膜
材料応用品である。光触媒薄膜材料用用品の具体例とし
ては、例えば空気清浄機，脱臭機，冷暖房機等の各種空
調機器あるいは清水器や水質浄化機器などの環境浄化装
置をあげることができる。According to a seventh aspect of the present invention, there is provided a photocatalytic thin film material-applied product which exhibits a cleaning function, an antibacterial function, a deodorizing function, an antifouling function, etc. by using the photocatalytic thin film material of the first to sixth aspects. It is. Specific examples of the photocatalyst thin film material article include various air conditioning equipment such as an air purifier, a deodorizer, and a cooling / heating machine, and an environmental purification device such as a water purifier or a water purification equipment.
【００２１】[0021]
【発明の実施の形態】以下、図面を参照しながら本発明
を具体的に説明する。図１は（ａ）は本発明に係る光触
媒薄膜材料の実施形態の一例を示す要部の断面図で、１
は基板、２は光触媒薄膜、３は光触媒薄膜２の表面にお
ける一部又は全部を構成する四角錐型結晶を示す。図１
（ｂ）は四角錐型結晶３の模式図を示し、該四角錐型結
晶３は、鉛直方向の頂点１１と、底面部１２の四つの角
部の点１２ａ，１２ｂ，１２ｃ，１２ｄと、四つの側面
部１３，１４，１５，１６から構成される。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to the drawings. FIG. 1A is a sectional view of a main part showing an example of an embodiment of a photocatalytic thin film material according to the present invention.
Denotes a substrate, 2 denotes a photocatalytic thin film, and 3 denotes a quadrangular pyramid crystal constituting part or all of the surface of the photocatalytic thin film 2. Figure 1
(B) is a schematic view of the quadrangular pyramid-shaped crystal 3. The quadrangular pyramid-shaped crystal 3 has a vertical vertex 11, four corner points 12 a, 12 b, 12 c, and 12 d of the bottom surface 12, It is composed of three side portions 13, 14, 15 and 16.
【００２２】本例の光触媒薄膜材料Ａは、光触媒薄膜２
をガラス、金属または網目状構造を有する繊維等の各種
の基板１に直接成膜できると共にその膜厚や薄膜２の結
晶構造を制御できるCVD、PVDにより作製したものであ
る。そして、光触媒薄膜2の表面の一部または全ての結
晶が四角錐型形状の結晶３であり、且つその結晶３が頂
点を上にすることにより、光触媒薄膜２表面において光
を受ける面積が大きくなり、光触媒反応が効率良く行わ
れるようになって高活性の光触媒機能を発現する。The photocatalytic thin film material A of this embodiment is composed of the photocatalytic thin film 2
Is formed by CVD or PVD in which a film can be formed directly on various substrates 1 such as glass, metal or fibers having a network structure, and the thickness and the crystal structure of the thin film 2 can be controlled. A part or all of the crystals on the surface of the photocatalytic thin film 2 are quadrangular pyramid-shaped crystals 3, and the crystal 3 has its apex facing upward, so that the light receiving area on the photocatalytic thin film 2 surface increases. In addition, a photocatalytic reaction is efficiently performed, and a highly active photocatalytic function is exhibited.
【００２３】四角錐型結晶３は上記したように、その形
状的特徴により高活性の光触媒機能を発現するが、その
大きさ、二次的微細構造を以下のような構成とすること
でさらに顕著な高活性の光触媒機能を発現する。As described above, the quadrangular pyramid-shaped crystal 3 exhibits a highly active photocatalytic function due to its shape characteristics, but is more remarkable when its size and secondary microstructure are as follows. It exhibits a highly active photocatalytic function.
【００２４】図１（ｂ）の模式図において、四角錐の底
面部１２の対角線である点１２ａと１２ｃ間の距離が１
０ｎｍ〜２００ｎｍ、点１２ｂと１２ｄの距離が１０ｎ
ｍ〜２００ｎｍである。また、四角錐型結晶３における
四つの側面部１３〜１６のいずれか１つ以上には、図示
しないが、階段状の凹凸が形成されている。また四角錐
型結晶３は、シェラーの式により算出された粒径５〜５
０ｎｍの結晶子から構成されている。さらに、光触媒薄
膜２の表面において、０．５μｍ×０．５μｍ四方内で
観察される四角錐型結晶３の数は５〜２０個の範囲であ
る。また四角錐型結晶３は、(１０１)、(１１２)、(２
００)、(２１１)、(２２０)のいずれかの面に配向して
いる。In the schematic diagram of FIG. 1B, the distance between points 12a and 12c, which are diagonals of the bottom 12 of the pyramid, is 1
0 nm to 200 nm, the distance between points 12b and 12d is 10n
m to 200 nm. Although not shown, step-like irregularities are formed on one or more of the four side surfaces 13 to 16 of the quadrangular pyramidal crystal 3. The quadrangular pyramidal crystal 3 has a particle size of 5 to 5 calculated by Scherrer's formula.
It is composed of 0 nm crystallites. Further, on the surface of the photocatalytic thin film 2, the number of the pyramidal crystals 3 observed within 0.5 μm × 0.5 μm square is in the range of 5 to 20. Further, the quadrangular pyramid-shaped crystal 3 has (101), (112), (2)
(00), (211), and (220).
【００２５】[0025]
【実施例】以下、実施例について説明する。中性洗剤、
イソプロピルアルコール、純水で洗浄処理を施した無ア
ルカリガラスを基板１とし、その基板１の表面に、ＲＦ
マグネトロンスパッタリング法にて光触媒薄膜(酸化チ
タン薄膜)２を作製した。Embodiments will be described below. Neutral detergent,
An alkali-free glass that has been subjected to a cleaning treatment with isopropyl alcohol and pure water is used as a substrate 1, and the surface of the substrate 1 is provided with an RF
A photocatalytic thin film (titanium oxide thin film) 2 was produced by magnetron sputtering.
【００２６】酸化チタン薄膜の成膜方法および条件は次
の通りである。成膜装置はＲＦマグネトロンスパッタリ
ング装置を用い、基板の無アルカリガラス板の寸法は７
５ｍｍ×７５ｍｍ、ターゲットは純度９９．９９％以上
のＴｉＯ２、導入ガスは純度９９．９９９％のアルゴン
ガスである。The method and conditions for forming the titanium oxide thin film are as follows. An RF magnetron sputtering apparatus was used as a film forming apparatus.
5 mm × 75 mm, the target is TiO 2 having a purity of 99.99% or more, and the introduced gas is an argon gas having a purity of 99.999%.
【００２７】成膜手順は以下の通りである。まず、成膜
室内に基板をターゲットに対向させて設置し、油回転ポ
ンプにより室内を１０Ｐａまで排気する。その後、ター
ボ分子ポンプで排気して成膜室内を所定の真空度にす
る。次いで、基板を所定温度にまで加熱し、アルゴンガ
スを導入して成膜室内をアルゴン雰囲気とする。このと
き、所定のアルゴンガス圧力(スパッタ圧力)になるよう
に導入ガス流量とメインバルブの開閉度を調節する。そ
うして、高周波電源によりターゲットに高周波電力を印
加して、基板の表面に酸化チタンを成膜する。このと
き、基板を回転速度３ｒｐｍで回転させる。The film forming procedure is as follows. First, a substrate is placed in a film formation chamber so as to face a target, and the inside of the chamber is evacuated to 10 Pa by an oil rotary pump. Thereafter, the film is evacuated by a turbo-molecular pump to make the inside of the film formation chamber a predetermined vacuum degree. Next, the substrate is heated to a predetermined temperature, and an argon gas is introduced to make the deposition chamber an argon atmosphere. At this time, the flow rate of the introduced gas and the degree of opening / closing of the main valve are adjusted so that a predetermined argon gas pressure (sputtering pressure) is obtained. Then, high-frequency power is applied to the target by a high-frequency power supply, and a titanium oxide film is formed on the surface of the substrate. At this time, the substrate is rotated at a rotation speed of 3 rpm.
【００２８】このようにして得られる光触媒薄膜材料を
試料とし、光触媒機能の評価として、有害物質であるア
セトアルデヒドの分解性能試験を実施した。試験方法
は、まず光触媒薄膜材料を２０リットルのガラス製の容
器に入れ、容器内を人工空気で置換したのち、アセトア
ルデヒドガスを２０ｐｐｍとなるように容器内に注入す
る。次に、ブラックライトで光触媒薄膜を照射し、アセ
トアルデヒドが１時間に減少する濃度をガスモニターに
て測定した。Using the photocatalytic thin film material thus obtained as a sample, a decomposition performance test of acetaldehyde, a harmful substance, was carried out as an evaluation of the photocatalytic function. In the test method, first, the photocatalytic thin film material is placed in a 20-liter glass container, the inside of the container is replaced with artificial air, and then acetaldehyde gas is injected into the container so as to have a concentration of 20 ppm. Next, the photocatalytic thin film was irradiated with black light, and the concentration at which acetaldehyde was reduced in one hour was measured with a gas monitor.
【００２９】また、上記光触媒薄膜材料における光触媒
薄膜の結晶構造解析をＸ線回折により行った。また、光
触媒薄膜の表面観察を走査型電子顕微鏡（ＳＥＭ）にて
行った。The crystal structure of the photocatalytic thin film in the photocatalytic thin film material was analyzed by X-ray diffraction. The surface of the photocatalytic thin film was observed with a scanning electron microscope (SEM).
【００３０】光薄膜の成膜条件を表１記載のようにする
ことで得られた実施例と比較例について、上記測定及び
試験を行った。結果を表２に示す。The above measurements and tests were performed on the examples and comparative examples obtained by setting the conditions for forming the optical thin film as shown in Table 1. Table 2 shows the results.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】各例において、成膜条件の印加電力は４０
０Ｗ、基板温度は２００〜３００℃の範囲、スパッタ圧
力は表中記載の通りである。In each example, the applied power under the film forming conditions is 40
0 W, the substrate temperature is in the range of 200 to 300 ° C., and the sputtering pressure is as described in the table.
【００３４】比較例１は１６００ｎｍの膜厚の光触媒薄
膜を作製した。この条件で作製した光触媒薄膜は、光触
媒機能に有効であるアナターゼ型の結晶構造を示してい
るものの、結晶形状が四角錐型に形成されておらず、分
解効果もほとんど認められないことがわかる。In Comparative Example 1, a photocatalytic thin film having a thickness of 1600 nm was prepared. Although the photocatalytic thin film prepared under these conditions shows an anatase-type crystal structure that is effective for the photocatalytic function, the crystal shape is not formed in a quadrangular pyramid shape, and it can be seen that the decomposition effect is hardly recognized.
【００３５】比較例２は３００ｎｍの膜厚の光触媒薄膜
を作製したものである。この条件で作製した光触媒薄膜
は、光触媒機能に有効であるアナターゼ型の結晶構造を
示しているものの、結晶形状が四角錐型に形成されてお
らず、分解性能も３ｐｐｍ／ｈｒであり、分解効果は非
常に小さい。In Comparative Example 2, a photocatalytic thin film having a thickness of 300 nm was prepared. Although the photocatalytic thin film produced under these conditions shows an anatase-type crystal structure that is effective for the photocatalytic function, the crystal shape is not formed in a square pyramid shape, and the decomposition performance is 3 ppm / hr. Is very small.
【００３６】比較例3は３００ｎｍの膜厚の光触媒薄膜
を作製したものである。この条件で作製した光触媒薄膜
は、光触媒機能に有効であるアナターゼ型の結晶構造を
示しているものの、結晶形状が四角錐型に形成されてお
らず、分解性能も４ｐｐｍ／ｈｒであり分解効果は非常
に小さい。In Comparative Example 3, a photocatalytic thin film having a thickness of 300 nm was prepared. Although the photocatalytic thin film produced under these conditions shows an anatase-type crystal structure that is effective for the photocatalytic function, the crystal shape is not formed in a quadrangular pyramid shape, and the decomposition performance is 4 ppm / hr. Very small.
【００３７】これら比較例に対して、実施例１は１７０
０ｎｍの膜厚の光触媒薄膜を作製したものである。この
条件で作製した光触媒薄膜は、光触媒機能に有効である
アナターゼ型の結晶構造を示しており、その分解性能も
１７ｐｐｍ／ｈｒと非常に優れた分解性能を示してい
る。そして、この高活性な光触媒機能を示した実施例１
の光触媒薄膜では、比較例１〜３で見られなかった四角
錐型の結晶形状を有している。In contrast to these comparative examples, the example 1
This is a photocatalytic thin film having a thickness of 0 nm. The photocatalytic thin film produced under these conditions has an anatase-type crystal structure that is effective for the photocatalytic function, and its decomposition performance is as excellent as 17 ppm / hr. Example 1 showing this highly active photocatalytic function
The photocatalytic thin film has a quadrangular pyramid-shaped crystal shape not seen in Comparative Examples 1 to 3.
【００３８】また、実施例２は１７００ｎｍの膜厚の光
触媒薄膜を作製したものである。この条件で作製した光
触媒薄膜は、光触媒機能に有効であるアナターゼ型の結
晶構造を示しており、その分解性能も１８ｐｐｍ／ｈｒ
となり、非常に優れた分解性能を示している。そして、
この高活性な光触媒機能を示した実施例２の光触媒薄膜
は実施例１と同様に、比較例１〜３で見られなかった四
角錐型の結晶形状を有している。In Example 2, a photocatalytic thin film having a thickness of 1700 nm was produced. The photocatalytic thin film prepared under these conditions has an anatase-type crystal structure effective for the photocatalytic function, and its decomposition performance is also 18 ppm / hr.
, Indicating very excellent decomposition performance. And
The photocatalytic thin film of Example 2 exhibiting this highly active photocatalytic function has a quadrangular pyramid-shaped crystal shape not seen in Comparative Examples 1 to 3, as in Example 1.
【００３９】図２（ａ），（ｂ）に本発明に係る四角錐
型結晶の電子顕微鏡写真を示す。これら四角錐型結晶
は、高活性な光触媒機能を示す光触媒薄膜表面において
観察されたものである。ここで見られる四角錐型結晶
は、図１（ｂ）の模式図で示すように、その頂点１が上
方に向いており、また上述したように点１２ａと１２ｃ
の距離が１０〜２００ｎｍ、点１２ｂと１２ｄの距離が
１０〜２００ｎｍであることが観察された。さらに、四
角錐型結晶における四つの側面部１３〜１６のうちのい
ずれか１つ以上において、階段状の凹凸が形成されてい
るのが観察された。FIGS. 2A and 2B show electron micrographs of the pyramidal crystal according to the present invention. These quadrangular pyramidal crystals are observed on the surface of a photocatalytic thin film exhibiting a highly active photocatalytic function. As shown in the schematic diagram of FIG. 1 (b), the quadrangular pyramidal crystal seen here has its apex 1 facing upward, and points 12a and 12c as described above.
Was observed to be 10 to 200 nm, and the distance between points 12b and 12d was found to be 10 to 200 nm. Further, it was observed that step-like irregularities were formed on any one or more of the four side surfaces 13 to 16 of the quadrangular pyramidal crystal.
【００４０】以上の実施例より、光触媒薄膜において表
面の一部または全ての結晶が四角錐型形状を形成するこ
とにより高活性な光触媒機能を発現することが確認でき
た。また、上記実施例ではCVD、PVDの代表としてスパッ
タリング法のみを記したが、例えば通常の気相化学的蒸
着法、すなわち狭義のCVDを用いた場合、PVDとして蒸着
法，イオンプレーティング法などの方式を用いた場合で
あっても、上記実施例と同様の結果が得られることは確
認済みである。すなわち、いかなる方法で薄膜を形成し
ても、その表面の一部または全てが四角錐型結晶であれ
ば、そうではないものに比べ分解能は高いことが明らか
である。また、その結晶の大きさや二次的微細構造を前
述のように限定したものは、さらに顕著な分解性能が得
られることも確認済みである。また、本発明の光触媒薄
膜は紫外線光源と共に筺体に組み込み空気を循環するこ
とにより臭い成分や有害成分を分解し、空気の清浄を効
率的に行い得ることは確認済みである。From the above examples, it was confirmed that a part or all of the surface of the photocatalytic thin film had a quadrangular pyramid shape to exhibit a highly active photocatalytic function. Further, in the above embodiment, only the sputtering method is described as a representative of the CVD and PVD. However, for example, when a general vapor-phase chemical vapor deposition method, that is, when CVD in a narrow sense is used, as the PVD, a vapor deposition method, an ion plating method, or the like is used. It has been confirmed that the same result as in the above embodiment can be obtained even when the method is used. That is, no matter how the thin film is formed, if part or all of the surface is a quadrangular pyramid-shaped crystal, it is clear that the resolution is higher than that of the other case. It has also been confirmed that those having the crystal size and secondary microstructure limited as described above can obtain more remarkable decomposition performance. In addition, it has been confirmed that the photocatalytic thin film of the present invention can be decomposed into odor components and harmful components by circulating the air together with the ultraviolet light source in the housing to efficiently clean the air.
【００４１】[0041]
【発明の効果】以上説明したように本発明は、化学的ま
たは物理的蒸着技術で作製した光触媒薄膜において、そ
の表面の一部または全ての結晶が角錐型又は円錐型を成
していることを特徴とし、このような形状の結晶を形成
することにより、高活性な光触媒機能を発現する光触媒
薄膜材料を得ることができる。また本発明の光触媒薄膜
材料は、清浄機能、抗菌機能、脱臭機能、防汚機能等に
おいて顕著な効果を有し、空気清浄機，脱臭機，冷暖房
機等の各種空調機器あるいは清水器や水質浄化機器など
の環境浄化装置に応用することが可能である。As described above, according to the present invention, in a photocatalytic thin film produced by a chemical or physical vapor deposition technique, a part or all of the crystal of the surface has a pyramidal or conical shape. By forming a crystal having such a shape, a photocatalytic thin film material exhibiting a highly active photocatalytic function can be obtained. In addition, the photocatalytic thin film material of the present invention has remarkable effects in a cleaning function, an antibacterial function, a deodorizing function, an antifouling function, etc. It can be applied to environmental purification devices such as equipment.
【図１】本発明に係る光触媒薄膜材料の実施形態の一例
を示し、（ａ）は要部の拡大断面図、（ｂ）は四角錐型
結晶の模式図である。FIG. 1 shows an example of an embodiment of a photocatalytic thin film material according to the present invention, in which (a) is an enlarged sectional view of a main part, and (b) is a schematic view of a quadrangular pyramid crystal.
【図２】本発明に係る光触媒薄膜材料における光触媒薄
膜表面の四角錐型結晶の電子顕微鏡写真である。FIG. 2 is an electron micrograph of a pyramidal crystal on the surface of the photocatalytic thin film in the photocatalytic thin film material according to the present invention.
Ａ：光触媒薄膜材料 １：基板 ２：光触媒薄膜 ３：四角錐型結晶 １１：頂点 １２：底面部 １２ａ〜１２ｄ：底面部の角部の点 １３〜１６：側面部 A: Photocatalytic thin film material 1: Substrate 2: Photocatalytic thin film 3: Square pyramid crystal 11: Apex 12: Bottom part 12a to 12d: Corner point of bottom part 13 to 16: Side part
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 21/06 Ｆ２４Ｆ 7/00 Ａ 37/02 ３０１ Ｃ０３Ｃ 17/245 Ａ Ｆ２４Ｆ 1/00 Ｚ 7/00 Ｂ０１Ｄ 53/36 Ｈ // Ｃ０３Ｃ 17/245 Ｇ ＺＡＢＪ Ｆ２４Ｆ 1/00 ３７１Ｚ (71)出願人 501085533 佐々木 正司 青森県八戸市大字市川町字田ノ沢頭３番22 号 青森県機械金属技術研究所内 (71)出願人 501085544 天間 毅 青森県青森市大字八ツ役字芦谷202番４号 青森県産業技術開発センター内 (71)出願人 501084732 千葉 昌彦 青森県青森市大字八ツ役字芦谷202番４号 青森県産業技術開発センター内 (71)出願人 501085566 八戸工業高等専門学校長 青森県八戸市大字田面木字上野平16番地１ 号 (72)発明者 工藤 武志 青森県八戸市大字市川町字長七谷地２番 672号 アンデス電気株式会社内 (72)発明者 工藤 一人 青森県八戸市大字市川町字長七谷地２番 672号 アンデス電気株式会社内 (72)発明者 類家 東 青森県八戸市大字市川町字長七谷地２番 672号 アンデス電気株式会社内 (72)発明者 富沢 知成 青森県八戸市大字市川町字田ノ沢頭３番22 号 株式会社八戸インテリジェントプラザ 内 (72)発明者 佐々木 正司 青森県八戸市大字市川町字田ノ沢頭３番22 号 青森県機械金属技術研究所内 (72)発明者 天間 毅 青森県青森市大字八ツ役字芦谷202番４号 青森県産業技術開発センター内 (72)発明者 千葉 昌彦 青森県青森市大字八ツ役字芦谷202番４号 青森県産業技術開発センター内 (72)発明者 長谷川 章 青森県八戸市田面木字上野平16番１号 八 戸工業高等専門学校内 Ｆターム(参考） 3L051 BC03 BC10 4C080 AA07 AA10 BB02 BB05 CC01 HH05 JJ03 JJ09 KK08 LL10 MM02 NN02 QQ03 4D048 AA19 AA22 BA07X BA41X BB03 EA01 4G059 AA01 AC22 AC30 EA04 EB03 4G069 AA03 AA08 BA04B BA48A CA01 CA17 CD10 DA05 EA08 EB01 EB18X EC22Y EC27 EC30 ED04 FA03 FB02 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B01J 21/06 F24F 7/00 A 37/02 301 C03C 17/245 A F24F 1/00 Z 7/00 B01D 53/36 H // C03C 17/245 G ZABJ F24F 1/00 371Z (71) Applicant 501085533 Masashi Sasaki 3-22, Tanozawa, Ichikawa-cho, Hachinohe-shi, Aomori Pref. Applicant 501085544 Takeshi Amama 202-4, Ashiya, Azamori, Aomori, Aomori Prefecture Inside the Industrial Technology Development Center, Aomori Prefecture (71) Prefectural Industrial Technology Development Center (71) Applicant 501085566 Director of Hachinohe National College of Technology 16-1 Uenodaira, Tajiki, Hamabe-shi, Aomori Prefecture (72) Invention Takeshi Kudo No. 672, Nagachichichi, Ichikawa-cho, Hachinohe-shi, Aomori Prefecture, Japan No.672 Inventor Electric Co., Ltd. 72) Inventor's ancestor No. 672 Nagachiyachi, Ichikawa-cho, Hachinohe-shi, Aomori, Higashi-Aomori Prefecture Inside the Andes Electric Co., Ltd. Hachinohe Intelligent Plaza Co., Ltd. (72) Inventor Masaji Sasaki 3-22 Tanozawa, Ichikawa-cho, Hachinohe-shi, Aomori Prefecture Inside Machinery Research Laboratory, Aomori Prefecture 202-4 Ashiya Aomori Prefectural Industrial Technology Development Center (72) Inventor Masahiko Chiba Aomori City Aomori Pref. 16-1 Uenodaira, Tamenoki, Hachinohe City Hachinohe National College of Technology F Term (Reference) 3L051 BC03 BC10 4C080 AA07 AA10 BB02 BB05 CC01 HH05 JJ03 JJ09 KK08 LL10 MM02 NN02 QQ03 4D048 AA19 AA22 BA07X BA41X BB03 EA01 4G059 AA01 AC22 AC30 EA04 CA04 EC03 BA04A04 EC04 FA03 FB02
Claims (7)
媒薄膜材料であって、前記光触媒薄膜の表面における少
なくとも一部の結晶の形状が角錐型又は円錐型であり、
且つその頂部が上方に向いていることにより高活性な光
触媒機能を発揮する光触媒薄膜材料。1. A photocatalytic thin film material formed by forming a photocatalytic thin film on a substrate, wherein at least a part of the crystal on the surface of the photocatalytic thin film has a pyramidal or conical shape,
A photocatalytic thin film material that exhibits a highly active photocatalytic function when its top is directed upward.
該四角錐型結晶の底面部における二つの対角線のうち、
一方の対角線の距離が１０ｎｍ〜２００ｎｍ、他方の対
角線の距離が１０ｎｍ〜２００ｎｍであることを特徴と
する請求項１記載の光触媒薄膜材料。2. The shape of the crystal is a quadrangular pyramid, and among two diagonals on a bottom surface of the quadrangular pyramid,
2. The photocatalytic thin film material according to claim 1, wherein one diagonal distance is 10 nm to 200 nm, and the other diagonal distance is 10 nm to 200 nm.
該四角錐型結晶が、シェラーの式により算出された粒径
５ｎｍ〜５０ｎｍの結晶子から形成されていることを特
徴とする請求項１又は２記載の光触媒薄膜材料。3. The method according to claim 1, wherein the crystal has a quadrangular pyramid shape, and the quadrangular pyramidal crystal is formed from crystallites having a particle size of 5 nm to 50 nm calculated by Scherrer's formula. Item 3. The photocatalytic thin film material according to item 1 or 2.
該四角錐型結晶の数が、０．５μｍ×０．５μｍ四方内
の観察において５〜２０個であることを特徴とする請求
項１〜３の何れか１項記載の光触媒薄膜材料。4. The method according to claim 1, wherein the shape of the crystal is a quadrangular pyramid, and the number of the quadrangular pyramid is 5 to 20 when observed in a square of 0.5 μm × 0.5 μm. Item 4. The photocatalytic thin film material according to any one of Items 1 to 3.
該四角錐型結晶の四つの側面部のうちの少なくとも一つ
の側面部に階段状の凹凸が形成されていることを特徴と
する請求項１〜４の何れか１項記載の光触媒薄膜材料。5. The method according to claim 1, wherein the crystal has a quadrangular pyramid shape, and stepwise irregularities are formed on at least one of the four side surfaces of the quadrangular pyramid crystal. The photocatalytic thin film material according to claim 1.
該四角錐型結晶が光触媒薄膜中において、(１０１)面、
(１１２)面、（２００）面、（２１１）面、（２２０）
面のいずれかに配向していることを特徴とする請求項１
〜５の何れか１項記載の光触媒薄膜材料。6. The shape of the crystal is a quadrangular pyramid type, and the quadrangular pyramid type crystal has a (101) plane,
(112) plane, (200) plane, (211) plane, (220) plane
2. The semiconductor device according to claim 1, wherein the crystal is oriented in one of the planes.
6. The photocatalytic thin film material according to any one of claims 1 to 5.
て清浄機能、抗菌機能、脱臭機能、防汚機能等を発揮す
ることを特徴とする光触媒薄膜材料応用品。7. A photocatalytic thin film material-applied product which exhibits a cleaning function, an antibacterial function, a deodorizing function, an antifouling function and the like by using the photocatalytic thin film material according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001057058A JP2002253974A (en) | 2001-03-01 | 2001-03-01 | Photocatalytic thin film material and application article thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001057058A JP2002253974A (en) | 2001-03-01 | 2001-03-01 | Photocatalytic thin film material and application article thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002253974A true JP2002253974A (en) | 2002-09-10 |
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ID=18916995
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| Country | Link |
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| JP (1) | JP2002253974A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006242390A (en) * | 2005-02-28 | 2006-09-14 | Central Res Inst Of Electric Power Ind | Heat exchanger |
| JP2006241717A (en) * | 2005-02-28 | 2006-09-14 | Central Res Inst Of Electric Power Ind | Building material |
| JP2006239486A (en) * | 2005-02-28 | 2006-09-14 | Central Res Inst Of Electric Power Ind | Playing implement |
| JP2006263711A (en) * | 2005-02-28 | 2006-10-05 | Central Res Inst Of Electric Power Ind | Component for vehicle |
-
2001
- 2001-03-01 JP JP2001057058A patent/JP2002253974A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006242390A (en) * | 2005-02-28 | 2006-09-14 | Central Res Inst Of Electric Power Ind | Heat exchanger |
| JP2006241717A (en) * | 2005-02-28 | 2006-09-14 | Central Res Inst Of Electric Power Ind | Building material |
| JP2006239486A (en) * | 2005-02-28 | 2006-09-14 | Central Res Inst Of Electric Power Ind | Playing implement |
| JP2006263711A (en) * | 2005-02-28 | 2006-10-05 | Central Res Inst Of Electric Power Ind | Component for vehicle |
| JP4716309B2 (en) * | 2005-02-28 | 2011-07-06 | 財団法人電力中央研究所 | Heat exchanger |
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