JPH1192146A - Photocatalytic multilayer film - Google Patents
Photocatalytic multilayer filmInfo
- Publication number
- JPH1192146A JPH1192146A JP9252885A JP25288597A JPH1192146A JP H1192146 A JPH1192146 A JP H1192146A JP 9252885 A JP9252885 A JP 9252885A JP 25288597 A JP25288597 A JP 25288597A JP H1192146 A JPH1192146 A JP H1192146A
- Authority
- JP
- Japan
- Prior art keywords
- film
- photocatalytic
- metal
- photocatalyst
- sputtering
- 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.)
- Granted
Links
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 37
- 239000010408 film Substances 0.000 claims abstract description 86
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 238000004544 sputter deposition Methods 0.000 claims abstract description 29
- 239000010409 thin film Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 239000002344 surface layer Substances 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000011941 photocatalyst Substances 0.000 claims description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 239000011135 tin Substances 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000005546 reactive sputtering Methods 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000001771 vacuum deposition Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000004332 deodorization Methods 0.000 description 4
- 239000005001 laminate film Substances 0.000 description 4
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 3
- 240000001592 Amaranthus caudatus Species 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 238000004887 air purification Methods 0.000 description 3
- 239000004178 amaranth Substances 0.000 description 3
- 235000012735 amaranth Nutrition 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- BGPVFRJUHWVFKM-UHFFFAOYSA-N N1=C2C=CC=CC2=[N+]([O-])C1(CC1)CCC21N=C1C=CC=CC1=[N+]2[O-] Chemical compound N1=C2C=CC=CC2=[N+]([O-])C1(CC1)CCC21N=C1C=CC=CC1=[N+]2[O-] BGPVFRJUHWVFKM-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Laminated Bodies (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水浄化、空気浄
化、消臭、油分の分解等に有効に用いられる光触媒積層
膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalytic laminated film which is effectively used for water purification, air purification, deodorization, oil decomposition, and the like.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来よ
り、ＴｉＯ2，ＺｎＯ，ＷＯ3，Ｆｅ2Ｏ3，ＳｒＴｉＯ3
等の金属酸化物は光触媒として水浄化、空気浄化、消
臭、油分の分解等に広く使用されている。このような光
触媒は、通常粉末状で用いられ、例えば浄化、脱臭すべ
き水などの液体中に撹拌分散させて使用されているが、
かかる粉末状の光触媒では使用後に回収することに手間
を要し、回収が困難な場合もある。粉末状の光触媒を固
定化するために、粉末にバインダーとして樹脂やゴムな
どを混ぜて練り、それを基材に塗って数百℃で焼結させ
る方法もある。しかし、このバインダー固定法の場合、
金属酸化物を基材に密着よく担持することが難しく、密
着性を上げるためにバインダー量を多くすると触媒効果
が弱まり、少ないと密着できない。また、光触媒を基材
に膜状に密着させる方法として金属アルコキシド溶液を
用いてゲルコーティング膜を形成し、それを数百℃で加
熱するゾル−ゲル法で得た金属酸化膜を光触媒に用いる
ことも知られている。しかし、これらバインダー固定法
も、ゾル−ゲル法も、金属酸化物膜の形成時には高温で
加熱する必要があるため、高温耐熱性を有する基材しか
用いることができず、使用できる基材が著しく制限され
る。 2. Description of the Related Art Conventionally, TiO 2 , ZnO, WO 3 , Fe 2 O 3 , SrTiO 3
Metal oxides such as are widely used as photocatalysts for water purification, air purification, deodorization, oil decomposition, and the like. Such a photocatalyst is usually used in the form of a powder, for example, purified, and used by being stirred and dispersed in a liquid such as water to be deodorized.
With such a powdery photocatalyst, it takes time and effort to recover it after use, and in some cases, recovery is difficult. In order to immobilize the powdered photocatalyst, there is a method in which a resin or rubber is mixed and kneaded with the powder as a binder, and the mixture is applied to a base material and sintered at several hundred degrees Celsius. However, in the case of this binder fixing method,
It is difficult to carry the metal oxide on the substrate with good adhesion. If the amount of the binder is increased to increase the adhesion, the catalytic effect is weakened, and if the amount is small, the adhesion cannot be achieved. In addition, as a method for adhering the photocatalyst to the substrate in a film form, a gel coating film is formed using a metal alkoxide solution, and a metal oxide film obtained by a sol-gel method of heating it at several hundred degrees Celsius is used for the photocatalyst. Is also known. However, both the binder fixing method and the sol-gel method require heating at a high temperature when forming a metal oxide film, so that only a substrate having high-temperature heat resistance can be used. Limited.
【０００３】従って、担持する基材の種類を選ばず、取
り扱い性に優れ、触媒効率が良好な光触媒に対する要求
が高まっている。[0003] Accordingly, there is an increasing demand for photocatalysts that are not limited to the type of substrate to be supported, are easy to handle, and have good catalytic efficiency.
【０００４】そこで、本出願人は、各種基材に密着性よ
く担持され、バインダーを使用しなくても光触媒効果が
得られ、膜状で取り扱い性がよく回収等を容易に行うこ
とができ、低温で成膜できる光触媒を先に提案している
（特開平８−３０９２０４号公報）。そして、この光触
媒を低温で成膜する方法として、酸素分子を有するガス
と不活性ガスとの存在下において金属ターゲットを用い
るマグネトロンスパッタリングを採用することを開示し
ている。[0004] The applicant of the present invention has proposed that a photocatalytic effect can be obtained without using a binder, that the film is in the form of a film, that it can be easily handled, and that it can be easily collected. A photocatalyst capable of forming a film at a low temperature has already been proposed (JP-A-8-309204). As a method for forming a film of the photocatalyst at a low temperature, it discloses that magnetron sputtering using a metal target in the presence of a gas having oxygen molecules and an inert gas is employed.
【０００５】しかし、上記方法で得られる光触媒膜は良
好な触媒効率を有しているが、更に高活性の光触媒膜が
要望されている。[0005] However, the photocatalytic film obtained by the above method has good catalytic efficiency, but a photocatalytic film having higher activity is demanded.
【０００６】[0006]
【課題を解決するための手段及び発明の実施の形態】本
発明者は、上記要望を達成し、より高活性の光触媒膜に
つき鋭意検討を行った結果、酸化チタン等の金属酸化物
光触媒膜と白金、ニッケル、クロム、コバルト、錫、ニ
オブ、タンタルなどの金属又はその酸化物薄膜とを最表
面層が光触媒膜となるように交互に積層すると共に、得
られた積層膜にその最表面層から最下層に達する孔又は
溝を多数形成することにより、酸化チタン等の光触媒膜
は上記金属又はその酸化物と接すると電荷分離が促進さ
れるので、高活性化すると共に、上記孔又は溝の形成で
積層膜の比表面積が大きくなり、被分解物は高活性な光
触媒膜に最表面層のみならず、上記孔又は溝の形成によ
り露呈された中間光触媒膜にも接するので、分解性が顕
著に向上することを知見した。Means for Solving the Problems and Embodiments of the Invention The inventor of the present invention has achieved the above-mentioned demands and has conducted intensive studies on a photocatalytic film having higher activity. Platinum, nickel, chromium, cobalt, tin, niobium, tantalum and other metals or oxide thin films thereof are alternately laminated such that the outermost layer becomes a photocatalytic film, and from the outermost layer to the obtained laminated film. By forming a large number of holes or grooves reaching the lowermost layer, the photocatalytic film of titanium oxide or the like promotes charge separation when it comes into contact with the metal or its oxide, so that it is highly activated and forms the holes or grooves. The specific surface area of the laminated film increases, and the decomposed substance contacts not only the outermost surface layer of the highly active photocatalyst film but also the intermediate photocatalyst film exposed by the formation of the holes or grooves. To improve And knowledge.
【０００７】またこの場合、上記光触媒膜は、スパッリ
ング法、特に対向ターゲット式スパッタリング法により
作製すること、この際、好ましくは不活性ガスと酸素分
子を有するガスからの酸素ガスとの容量比を２：１〜
１：３としてスパッタリングを行うこと、更に好ましく
はターゲットに対する投入パワーを高くして成膜するこ
とが高活性化の点で有効であることを知見した。In this case, the photocatalyst film is formed by a sputtering method, in particular, a facing target type sputtering method. In this case, preferably, the volume ratio of the inert gas to the oxygen gas from the gas containing oxygen molecules is adjusted. 2: 1 ~
It has been found that performing sputtering at a ratio of 1: 3, and more preferably increasing the input power to the target to form a film is effective in terms of high activation.
【０００８】即ち、対向ターゲット式スパッタリング法
は、特公昭６２−５６５７５号、同６３−２０３０４
号、特公平３−１８１０号公報等で公知の手法であり、
対向ターゲット式スパッタリング法で垂直磁気記録薄膜
などを成膜している。そして、この方法によれば、結晶
性の良好な膜を形成し得ることが記載されている。That is, the facing target sputtering method is disclosed in JP-B-62-56575 and JP-B-63-20304.
No. 3-1810, etc.
A perpendicular magnetic recording thin film or the like is formed by a facing target type sputtering method. It is described that this method can form a film having good crystallinity.
【０００９】ところで、触媒活性が高い酸化チタン膜を
得るためにはアナターゼ型の結晶系がリッチである必要
があるが、酸化チタンの成膜に当り、種々の方法で結晶
性の高い薄膜を形成することはできるものの、得られた
結晶系はルチル型のものが多いため、光触媒効果が低い
ものである。ところが、対向ターゲット式スパッタリン
グ法により酸化チタンを成膜した場合、低温でアナター
ゼリッチの光触媒膜を作製することができ、特にアルゴ
ンガスと酸素ガスとの比率を上記の比率とすることによ
り、アナターゼ型結晶がよりリッチな光触媒膜を形成し
得ること、また、投入パワーを高くすることで膜質を粗
くし、表面積を大きくすることができるので、触媒活性
をより高くし得ることを知見し、また光触媒膜をこのよ
うにスパッタリング法で作製する場合は、上記金属又は
その酸化物薄膜を気相コーティング法にて行うことで効
率的に光触媒積層膜を形成することができることを見出
し、本発明をなすに至ったものである。By the way, in order to obtain a titanium oxide film having high catalytic activity, it is necessary that the anatase type crystal system is rich. However, in forming the titanium oxide film, a thin film having high crystallinity is formed by various methods. However, since the obtained crystal systems are often rutile type, the photocatalytic effect is low. However, when titanium oxide is formed by a facing target sputtering method, an anatase-rich photocatalytic film can be produced at a low temperature. In particular, by setting the ratio of argon gas to oxygen gas to the above ratio, anatase type He discovered that a photocatalytic film with more rich crystals could be formed, and that the higher the input power, the coarser the film quality and the larger the surface area. When the film is formed by the sputtering method in this way, it has been found that the photocatalyst laminated film can be efficiently formed by performing the metal or the oxide thin film by the gas phase coating method, and the present invention is achieved. It has been reached.
【００１０】従って、本発明は下記光触媒積層膜を提供
する。 請求項１：金属酸化物からなる光触媒膜と金属又はその
酸化物薄膜とが交互に積層されていると共に、最表面層
が光触媒膜であり、かつ最表面層から最下層に至る深さ
の孔又は溝を多数形成してなることを特徴とする光触媒
積層膜。 請求項２：金属が、白金、ニッケル、クロム、コバル
ト、錫、ニオブ、タンタル、銅、セリウム、鉛、鉄、バ
ナジウム、金、銀、ジルコニウム、ナトリウム、アルミ
ニウム、マグネシウム、カリウム、カルシウム、マンガ
ン、亜鉛、ガリウム、セレン、モリブデン、インジウ
ム、ストロンチウム、テルル、バリウム、タングステ
ン、ビスマス、及びイットリウムから選ばれる１種又は
２種以上である請求項１記載の光触媒積層膜。 請求項３：光触媒膜が酸化チタンである請求項１又は２
記載の光触媒積層膜。 請求項４：光触媒膜が、酸素分子を有するガスを含有す
る不活性ガス中で金属ターゲットを用いたリアクティブ
スパッタリングを行うことによって得られたものである
請求項１、２又は３記載の光触媒積層膜。 請求項５：スパッタリングが、互いに対向するターゲッ
ト間のスパッタ空間の側方に基板を配置し、該基板上に
スパッタ膜を形成する対向ターゲット式スパッタリング
である請求項４記載の光触媒積層膜。 請求項６：金属又はその酸化物薄膜が気相コーティング
法により形成されたものである請求項１乃至５のいずか
１項記載の光触媒積層膜。 請求項７：気相コーティング法が真空蒸着又はスパッタ
リング法である請求項６記載の光触媒積層膜。Accordingly, the present invention provides the following photocatalyst laminated film. Claim 1: A photocatalyst film composed of a metal oxide and a metal or an oxide thin film thereof are alternately laminated, the outermost surface layer is a photocatalytic film, and a hole having a depth from the outermost surface layer to the lowermost layer. Or a photocatalyst laminated film characterized by forming a large number of grooves. Claim 2: The metal is platinum, nickel, chromium, cobalt, tin, niobium, tantalum, copper, cerium, lead, iron, vanadium, gold, silver, zirconium, sodium, aluminum, magnesium, potassium, calcium, manganese, zinc 2. The photocatalyst laminate film according to claim 1, wherein the photocatalyst laminate film is at least one member selected from the group consisting of gallium, selenium, molybdenum, indium, strontium, tellurium, barium, tungsten, bismuth, and yttrium. Claim 3: The photocatalytic film is titanium oxide.
The photocatalyst laminated film according to the above. In a preferred embodiment, the photocatalyst film is obtained by performing reactive sputtering using a metal target in an inert gas containing a gas having oxygen molecules. film. In a preferred embodiment, the photocatalyst layered film is a sputtering method in which a substrate is disposed on a side of a sputtering space between targets facing each other and a sputtered film is formed on the substrate. [6] The photocatalyst laminate film according to any one of [1] to [5], wherein the metal or the oxide thin film thereof is formed by a vapor phase coating method. In a preferred embodiment, the photocatalytic laminate film is a vacuum deposition or sputtering method.
【００１１】以下、本発明につき更に詳しく説明する。
本発明の光触媒膜は、図１に示すように、光触媒膜１１
と金属又はその酸化物薄膜１２を最表面層が光触媒膜１
１となるように交互に積層すると共に、最表面層から最
下層に達する深さの孔又は溝１３を多数形成してなるも
のである。なお、図中１４は基板を示す。Hereinafter, the present invention will be described in more detail.
As shown in FIG. 1, the photocatalyst film of the present invention
And a metal or oxide thin film 12 of the photocatalyst film 1
1, and a number of holes or grooves 13 having a depth from the outermost surface layer to the lowermost layer are formed. In the figure, reference numeral 14 denotes a substrate.
【００１２】この場合、光触媒膜の形成方法は特に制限
されるものではないが、酸素分子を有するガスを含有す
る不活性ガス中で金属ターゲットを用いてリアクティブ
スパッタリングリングによって形成することが好まし
い。In this case, the method of forming the photocatalytic film is not particularly limited, but it is preferable to form the photocatalytic film by a reactive sputtering ring using a metal target in an inert gas containing a gas having oxygen molecules.
【００１３】ここで、スパッタリングは公知の方法にて
行うことができ、通常のマグネトロンスパッタリング法
等にて形成することができるが、特に対向ターゲット式
スパッタリング法を採用することが好ましい。Here, the sputtering can be performed by a known method, and can be formed by a usual magnetron sputtering method or the like, but it is particularly preferable to adopt a facing target type sputtering method.
【００１４】この対向ターゲット式スパッタリング装置
としては、公知の装置を用いることができ、例えば図２
に示す装置を使用し得る。即ち、図２において、１は内
部を脱気真空可能な装置本体で、この装置本体１内に一
対の金属ターゲット２，２が互いに所定間隔離間対向し
て配置されたものである。これらターゲット２，２は、
それぞれ支持部３ａ，３ａを有するホールド３，３に保
持され、これらホールド３，３を介して直流電源（スパ
ッタ電源）４の陰極に接続されていると共に、上記ター
ゲット２，２の背後に磁石５，５が互いに異なる磁極が
対向するように配置され、上記ターゲット２，２間のス
パッタ空間６にターゲット２，２に対して垂直方向の磁
界が発生するようになっている。そして、上記スパッタ
空間の側方には、スパッタ膜を形成すべき基板７が配置
されたものである。なお、８は基板７を所定方向に移動
可能に支持する支持部材である。As the facing target type sputtering apparatus, a known apparatus can be used.
The following apparatus can be used. That is, in FIG. 2, reference numeral 1 denotes an apparatus main body whose inside can be degassed and evacuated, in which a pair of metal targets 2 and 2 are arranged so as to face each other for a predetermined distance. These targets 2 and 2
Holders 3, 3 having supporting portions 3 a, 3 a, respectively, are connected to a cathode of a DC power source (sputter power source) 4 via the holders 3, 3, and a magnet 5 is provided behind the targets 2, 2. , 5 are arranged such that different magnetic poles are opposed to each other, and a magnetic field perpendicular to the targets 2 is generated in the sputtering space 6 between the targets 2. A substrate 7 on which a sputtered film is to be formed is arranged on the side of the sputter space. Reference numeral 8 denotes a support member that supports the substrate 7 so as to be movable in a predetermined direction.
【００１５】上記のような装置を用いてスパッタリング
を行い、基板上に光触媒膜を形成するに際し、使用する
金属ターゲットとしては、光触媒作用を有する金属酸化
物ＭｅＯx（ＭｅはＡｌ，Ｃｏ，Ｃｕ，Ｆｅ，Ｉｎ，Ｍ
ｇ，Ｓｎ，Ｔｉ，Ｚｎ等の金属を示し、ｘは金属の種類
によって異なるが、０〜１０、好ましくは０〜５の範囲
の正数であり、ｘは必ずしも金属の価数に相当していな
くてもよい）を得るための金属酸化物に対応した金属が
選定されるが、特には酸化チタン膜を形成するチタンが
好ましい。When a photocatalyst film is formed on a substrate by performing sputtering using the above-mentioned apparatus, a metal oxide having photocatalytic action MeO x (Me is Al, Co, Cu, Fe, In, M
represents a metal such as g, Sn, Ti, Zn, etc., and x is a positive number in the range of 0 to 10, preferably 0 to 5, and x necessarily corresponds to the valence of the metal, although it varies depending on the type of the metal. The metal corresponding to the metal oxide for obtaining the metal oxide may be selected, but titanium that forms a titanium oxide film is particularly preferable.
【００１６】また、上記スパッタリングを行う上で真空
度は０．１〜１００ｍＴｏｒｒ、特に１〜３０ｍＴｏｒ
ｒとした後、不活性ガスと酸素分子を有するガスが導入
される。ここで、上記スパッタ空間に供給される酸素分
子を有するガス（酸化性ガス）としては、公知のガスを
使用することができ、具体的には、酸素、オゾン、空
気、水等が挙げられ、通常は酸素が用いられる。また、
不活性ガスとしては、ヘリウム、アルゴンなどを用いる
ことができ、特に工業的に安価なアルゴンが好適に使用
し得る。In performing the above sputtering, the degree of vacuum is 0.1 to 100 mTorr, particularly 1 to 30 mTorr.
After r, a gas containing an inert gas and oxygen molecules is introduced. Here, as the gas containing oxygen molecules (oxidizing gas) supplied to the sputtering space, a known gas can be used, and specific examples thereof include oxygen, ozone, air, and water. Usually, oxygen is used. Also,
Helium, argon, or the like can be used as the inert gas, and industrially inexpensive argon can be suitably used.
【００１７】この場合、不活性ガスと酸素分子を有する
ガスとは、不活性ガスと酸素ガスとの比率が２：１〜
１：３、特に１．５：１〜１：２（容量比）となるよう
に導入することが好ましい。これにより酸化チタンを成
膜する場合は高活性のアナターゼ型リッチの酸化チタン
結晶を形成し得る。上記比率を逸脱すると、ルチル型結
晶が多くなるおそれがある。なお、上記ガスの流量は、
チャンバーの大きさ、カソードの数などにより適宜選定
されるが、不活性ガスと酸素分子を有するガスとの合計
量で、通常２〜１０００ｃｃ／ｍｉｎ程度である。In this case, the inert gas and the gas containing oxygen molecules are such that the ratio of the inert gas to the oxygen gas is 2: 1 to 1
It is preferable to introduce them in a ratio of 1: 3, particularly 1.5: 1 to 1: 2 (volume ratio). Thereby, when forming a titanium oxide film, a highly active anatase-type rich titanium oxide crystal can be formed. If the ratio is out of the above range, rutile type crystals may increase. The flow rate of the above gas is
Although it is appropriately selected depending on the size of the chamber, the number of cathodes, and the like, the total amount of the inert gas and the gas containing oxygen molecules is usually about 2 to 1000 cc / min.
【００１８】投入電力も適宜選定されるが、高い投入電
力とすることが好ましく、例えば２枚の直径１００ｍｍ
のターゲットを用いた場合、４００ワット以上、特に８
００ワット以上とすることが推奨され、この場合、ター
ゲット面積当りのエネルギー量を１．３Ｗ／ｃｍ2以
上、好ましくは２．６Ｗ／ｃｍ2以上、特に５．１Ｗ／
ｃｍ2以上とすることが推奨され、これにより得られる
光触媒膜の膜質を粗くすると共に、表面積を大きくでき
るので、光触媒膜の性能を更に向上させることができ
る。この場合、供給電力が４００ワット未満、ターゲッ
ト面積当りのエネルギー量が１．３Ｗ／ｃｍ2未満であ
ると、活性の高い光触媒膜を得ることができなくなる場
合がある。The input power is also appropriately selected, but is preferably set to a high input power. For example, two sheets having a diameter of 100 mm
400 watts or more, especially 8
00 It is recommended to watts, in this case, the amount of energy per target area 1.3 W / cm 2 or more, preferably 2.6 W / cm 2 or more, in particular 5.1 W /
cm 2 or more is recommended, and the resulting photocatalyst film can be made coarser and the surface area can be increased, so that the performance of the photocatalyst film can be further improved. In this case, if the supplied power is less than 400 watts and the amount of energy per target area is less than 1.3 W / cm 2 , a photocatalytic film having high activity may not be able to be obtained.
【００１９】なお、電源は、図示の例では直流電流であ
るが、これに限られず、例えば高周波電源等を使用する
ことができ、また装置の構成も図示の例に限定されるも
のではない。The power supply is a direct current in the illustrated example, but is not limited to this. For example, a high frequency power supply or the like can be used, and the configuration of the apparatus is not limited to the illustrated example.
【００２０】更に、スパッタリングのその他の条件は公
知の条件でよく、例えばスパッタリング時の圧力は１ｍ
Ｔｏｒｒ〜１Ｔｏｒｒとし得、金属酸化物膜（光触媒
膜）が形成される基板の種類なども適宜選定される。Further, other conditions for sputtering may be known conditions, for example, the pressure during sputtering is 1 m
The pressure may be Torr to 1 Torr, and the type of the substrate on which the metal oxide film (photocatalytic film) is formed is appropriately selected.
【００２１】一方、金属又はその酸化物薄膜としては、
真空蒸着、スパッタリング等の気相コーティング法にて
形成でき、この場合弁で仕切られた一つのチャンバー内
に光触媒膜形成用スパッタリング装置と、金属又はその
酸化物薄膜形成用スパッタリング装置を配設し、弁の切
り換えにより交互に光触媒膜と金属又はその酸化物薄膜
とを形成することが好適である。On the other hand, as a metal or its oxide thin film,
Vapor deposition, it can be formed by a vapor phase coating method such as sputtering, in this case, a sputtering apparatus for forming a photocatalytic film and a sputtering apparatus for forming a metal or its oxide thin film are arranged in one chamber separated by a valve, It is preferable to alternately form a photocatalyst film and a metal or its oxide thin film by switching the valve.
【００２２】この場合、金属としては、白金、ニッケ
ル、クロム、コバルト、錫、ニオブ、タンタル、銅、セ
リウム、鉛、鉄、バナジウム、金、銀、ジルコニウム、
ナトリウム、アルミニウム、マグネシウム、カリウム、
カルシウム、マンガン、亜鉛、ガリウム、セレン、モリ
ブデン、インジウム、ストロンチウム、テルル、バリウ
ム、タングステン、ビスマス、及びイットリウムから選
ばれる１種又は２種以上とすることができ、中でも白
金、ニッケル、クロム、コバルト、錫、ニオブ、タンタ
ルが好ましい。In this case, as the metal, platinum, nickel, chromium, cobalt, tin, niobium, tantalum, copper, cerium, lead, iron, vanadium, gold, silver, zirconium,
Sodium, aluminum, magnesium, potassium,
Calcium, manganese, zinc, gallium, selenium, molybdenum, indium, strontium, tellurium, barium, tungsten, bismuth, and one or more selected from yttrium, among which platinum, nickel, chromium, cobalt, Tin, niobium and tantalum are preferred.
【００２３】光触媒膜の厚さは適宜選定し得るが、１０
Å〜１μｍ、特に２０〜２０００Åとすることが好まし
く、また金属又はその酸化物薄膜の厚さは５〜２０００
Å、特に１０〜５００Åとすることが好ましい。更に、
光触媒膜と金属又はその酸化物薄膜との合計積層数も適
宜なものとし得るが、数層乃至数十層である。The thickness of the photocatalyst film can be appropriately selected.
Å-1 μm, particularly preferably 20-2000Å, and the thickness of the metal or its oxide thin film is 5-2000
Å, particularly preferably 10 to 500Å. Furthermore,
The total number of layers of the photocatalyst film and the metal or oxide thin film thereof may be an appropriate number, but is several to several tens.
【００２４】上記孔又は溝は、レーザー等によって形成
し得るが、その形状は図示のＶ字状に限られず、種々選
定し得る。孔又は溝の形成個数も限定されないが、通常
０．００１〜５ｍｍ間隔で形成することができる。The hole or groove can be formed by a laser or the like, but the shape is not limited to the V-shape shown in the figure, and various shapes can be selected. Although the number of holes or grooves to be formed is not limited, it can be usually formed at an interval of 0.001 to 5 mm.
【００２５】以上のようにして得られる光触媒積層膜
は、公知の光触媒膜と同様にして使用することができ、
例えばこの光触媒膜に光を照射することによって光触媒
が励起し、殺菌、脱臭等の作用を発揮するもので、水浄
化、空気浄化、消臭、油分の分解などに用いることがで
きる。The photocatalyst layered film obtained as described above can be used in the same manner as a known photocatalyst film.
For example, by irradiating the photocatalyst film with light, the photocatalyst is excited, and exhibits effects such as sterilization and deodorization, and can be used for water purification, air purification, deodorization, decomposition of oil, and the like.
【００２６】[0026]
【発明の効果】本発明によれば、高い触媒活性を有する
光触媒膜を作製することができる。According to the present invention, a photocatalytic film having high catalytic activity can be produced.
【００２７】[0027]
【実施例】以下、実施例と比較例を示し、本発明を具体
的に説明するが、本発明は下記の実施例に制限されるも
のではない。EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.
【００２８】〔実施例１、比較例１〜３〕図２に示すよ
うな対向ターゲット式スパッタリング装置とマグネトロ
ンスパッタリング装置が、弁で仕切られた一つのチャン
バー内にある装置を用いて、表１に示す条件でステンレ
ス板（５×５ｃｍ2）上にＴｉＯ2薄膜とＰｔ薄膜を交互
に積層した。Example 1, Comparative Examples 1 to 3 Table 1 shows an apparatus using a facing target type sputtering apparatus and a magnetron sputtering apparatus as shown in FIG. 2 in a single chamber separated by a valve. Under the conditions shown, a TiO 2 thin film and a Pt thin film were alternately laminated on a stainless steel plate (5 × 5 cm 2 ).
【００２９】[0029]
【表１】 [Table 1]
【００３０】実施例１：この積層膜にレーザーで約０．
１ｍｍ間隔のＶ字状の溝を切った。 比較例１：ＴｉＯ2膜のみ 比較例２：Ｐｔ／ＴｉＯ2積層膜のみ（表面加工なし） 比較例３：ＴｉＯ2膜にレーザーで約０．１ｍｍ間隔の
Ｖ字状の溝を切った。Example 1: A laser was applied to this laminated film to a thickness of about 0.1 mm.
V-shaped grooves were cut at 1 mm intervals. Comparative Example 1: Only TiO 2 film Comparative Example 2: Pt / TiO 2 laminated film only (no surface processing) Comparative Example 3: V-shaped grooves were cut in the TiO 2 film at intervals of about 0.1 mm by laser.
【００３１】これらの光触媒積層膜を２２ｍｌアマラン
ス（赤色顔料）溶液（３ｍｇ／ｌ）中に浸し、２５０Ｗ
超高圧水銀灯（３００ｍｎ以下カット）を照射して、そ
の濃度変化をＵＶ−可視光度計で測定し、アマランスの
分解率を求めた。結果を表２に示す。These photocatalyst laminated films were immersed in a 22 ml amaranth (red pigment) solution (3 mg / l),
Irradiation with an ultra-high pressure mercury lamp (cut at 300 nm or less) was performed, and the change in concentration was measured with a UV-visible photometer to determine the decomposition rate of amaranth. Table 2 shows the results.
【００３２】[0032]
【表２】 [Table 2]
【００３３】〔実施例２、比較例４〕実施例１におい
て、金属薄膜の形成にＮｉターゲットを用いてＮｉ薄膜
を形成した以外は実施例１と同様にして光触媒積層膜を
得た。また、比較例としてはＮｉ積層膜のみを形成し、
上記と同様にしてアマランスの分解率を調べた。結果を
表３に示す。Example 2, Comparative Example 4 A photocatalytic laminated film was obtained in the same manner as in Example 1, except that a Ni thin film was formed using a Ni target for forming a metal thin film. Also, as a comparative example, only a Ni laminated film was formed,
The degradation rate of amaranth was examined in the same manner as above. Table 3 shows the results.
【００３４】[0034]
【表３】 [Table 3]
【００３５】以上の結果より、本発明法によれば、光触
媒活性の非常に高い薄膜を形成し得ることが認められ
た。From the above results, it was confirmed that according to the method of the present invention, a thin film having extremely high photocatalytic activity can be formed.
【図１】本発明の光触媒積層膜の一例を示す概略断面図
である。FIG. 1 is a schematic cross-sectional view showing one example of a photocatalytic laminated film of the present invention.
【図２】本発明の実施に用いる対向ターゲット式スパッ
タリング装置の一例を示す概略図である。FIG. 2 is a schematic view showing an example of a facing target type sputtering apparatus used for carrying out the present invention.
１ 装置本体 ２ 金属ターゲット ３ ホールド ３ａ 支持部 ４ 直流電源 ５ 磁石 ６ スパッタ空間 ７ 基板 ８ 支持部材 １１ 光触媒膜 １２ 金属又はその酸化物薄膜 １３ 孔又は溝 １４ 基板 DESCRIPTION OF SYMBOLS 1 Apparatus main body 2 Metal target 3 Hold 3a Support part 4 DC power supply 5 Magnet 6 Sputter space 7 Substrate 8 Support member 11 Photocatalytic film 12 Metal or its oxide thin film 13 Hole or groove 14 Substrate
Claims (7)
その酸化物薄膜とが交互に積層されていると共に、最表
面層が光触媒膜であり、かつ最表面層から最下層に至る
深さの孔又は溝を多数形成してなることを特徴とする光
触媒積層膜。1. A photocatalyst film composed of a metal oxide and a metal or an oxide thin film thereof are alternately stacked, the outermost surface layer is a photocatalytic film, and the depth from the outermost surface layer to the lowermost layer is reduced. A photocatalytic laminated film comprising a large number of holes or grooves.
ルト、錫、ニオブ、タンタル、銅、セリウム、鉛、鉄、
バナジウム、金、銀、ジルコニウム、ナトリウム、アル
ミニウム、マグネシウム、カリウム、カルシウム、マン
ガン、亜鉛、ガリウム、セレン、モリブデン、インジウ
ム、ストロンチウム、テルル、バリウム、タングステ
ン、ビスマス、及びイットリウムから選ばれる１種又は
２種以上である請求項１記載の光触媒積層膜。2. The method according to claim 1, wherein the metal is platinum, nickel, chromium, cobalt, tin, niobium, tantalum, copper, cerium, lead, iron,
One or two selected from vanadium, gold, silver, zirconium, sodium, aluminum, magnesium, potassium, calcium, manganese, zinc, gallium, selenium, molybdenum, indium, strontium, tellurium, barium, tungsten, bismuth, and yttrium The photocatalyst laminated film according to claim 1, which is the above.
は２記載の光触媒積層膜。3. The photocatalytic laminated film according to claim 1, wherein the photocatalytic film is titanium oxide.
有する不活性ガス中で金属ターゲットを用いたリアクテ
ィブスパッタリングを行うことによって得られたもので
ある請求項１、２又は３記載の光触媒積層膜。4. The photocatalyst according to claim 1, wherein the photocatalyst film is obtained by performing reactive sputtering using a metal target in an inert gas containing a gas having oxygen molecules. Laminated film.
ゲット間のスパッタ空間の側方に基板を配置し、該基板
上にスパッタ膜を形成する対向ターゲット式スパッタリ
ングである請求項４記載の光触媒積層膜。5. The photocatalytic laminated film according to claim 4, wherein the sputtering is a facing target type sputtering in which a substrate is arranged on a side of a sputtering space between opposing targets and a sputtered film is formed on the substrate.
ング法により形成されたものである請求項１乃至５のい
ずか１項記載の光触媒積層膜。6. The photocatalyst laminated film according to claim 1, wherein the metal or the oxide thin film is formed by a vapor phase coating method.
ッタリング法である請求項６記載の光触媒積層膜。7. The photocatalytic laminated film according to claim 6, wherein the vapor phase coating method is a vacuum deposition or sputtering method.
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|---|---|---|---|
| JP25288597A JP3838297B2 (en) | 1997-07-22 | 1997-09-02 | Photocatalyst laminated film |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-211270 | 1997-07-22 | ||
| JP21127097 | 1997-07-22 | ||
| JP25288597A JP3838297B2 (en) | 1997-07-22 | 1997-09-02 | Photocatalyst laminated film |
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| Publication Number | Publication Date |
|---|---|
| JPH1192146A true JPH1192146A (en) | 1999-04-06 |
| JP3838297B2 JP3838297B2 (en) | 2006-10-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25288597A Expired - Fee Related JP3838297B2 (en) | 1997-07-22 | 1997-09-02 | Photocatalyst laminated film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1147609A (en) * | 1997-08-01 | 1999-02-23 | Sharp Corp | Photocatalyst body and its preparation |
| WO2001087593A1 (en) * | 2000-05-17 | 2001-11-22 | Murakami Corporation | Composite material |
| JP2016043304A (en) * | 2014-08-21 | 2016-04-04 | 日本電信電話株式会社 | Photocatalyst device |
| JP2016527078A (en) * | 2013-07-05 | 2016-09-08 | 日東電工株式会社 | Transparent photocatalytic coating and method for producing the same |
| JP2018134602A (en) * | 2017-02-22 | 2018-08-30 | 多摩火薬機工株式会社 | Photocatalyst body, photocatalyst body group and production method thereof |
-
1997
- 1997-09-02 JP JP25288597A patent/JP3838297B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1147609A (en) * | 1997-08-01 | 1999-02-23 | Sharp Corp | Photocatalyst body and its preparation |
| WO2001087593A1 (en) * | 2000-05-17 | 2001-11-22 | Murakami Corporation | Composite material |
| US6742902B2 (en) | 2000-05-17 | 2004-06-01 | Murakami Corporation | Composite material |
| CN100363173C (en) * | 2000-05-17 | 2008-01-23 | 株式会社村上开明堂 | Composite material |
| JP2016527078A (en) * | 2013-07-05 | 2016-09-08 | 日東電工株式会社 | Transparent photocatalytic coating and method for producing the same |
| US10391482B2 (en) | 2013-07-05 | 2019-08-27 | Nitto Denko Corporation | Transparent photocatalyst coating and methods of manufacturing the same |
| US10710063B2 (en) | 2013-07-05 | 2020-07-14 | Nitto Denko Corporation | Transparent photocatalyst coating and methods of manufacturing the same |
| JP2016043304A (en) * | 2014-08-21 | 2016-04-04 | 日本電信電話株式会社 | Photocatalyst device |
| JP2018134602A (en) * | 2017-02-22 | 2018-08-30 | 多摩火薬機工株式会社 | Photocatalyst body, photocatalyst body group and production method thereof |
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| Publication number | Publication date |
|---|---|
| JP3838297B2 (en) | 2006-10-25 |
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