JP2005240139A - Production method for anatase type titanium oxide film by anodic electrolytic oxidation treatment - Google Patents
Production method for anatase type titanium oxide film by anodic electrolytic oxidation treatment Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 103
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 230000003647 oxidation Effects 0.000 title claims description 20
- 238000007254 oxidation reaction Methods 0.000 title claims description 20
- 239000010936 titanium Substances 0.000 claims abstract description 60
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 55
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 37
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 9
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- 238000005530 etching Methods 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 239000008151 electrolyte solution Substances 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000007743 anodising Methods 0.000 claims description 9
- 238000007751 thermal spraying Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 238000005240 physical vapour deposition Methods 0.000 description 8
- 238000002048 anodisation reaction Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000001182 laser chemical vapour deposition Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
本発明は、光触媒や光電変換素子等として有用であるアナターゼ型酸化チタン皮膜を製造する方法に関する。 The present invention relates to a method for producing an anatase-type titanium oxide film that is useful as a photocatalyst, a photoelectric conversion element, or the like.
酸化チタンは、光エネルギーを化学エネルギーや電気エネルギーに変換させることが可能であり、様々な分野への応用が期待されている材料である。酸化チタンの結晶構造は、ルチル型、ブルッカイト型、アナターゼ型の３種類が存在しており、中でもアナターゼ型の酸化チタンが光触媒特性や光電変換特性において優れていることが知られている。 Titanium oxide is a material that can convert light energy into chemical energy and electrical energy, and is expected to be applied in various fields. There are three types of crystal structures of titanium oxide: rutile type, brookite type, and anatase type. Among them, it is known that anatase type titanium oxide is excellent in photocatalytic characteristics and photoelectric conversion characteristics.
従来、チタン又はチタン合金の表面に酸化チタン皮膜を製造する方法として、一般的には、リン酸等の通常の電解液中でチタン又はチタン合金を陽極酸化処理する方法等が知られている。しかしながら、このような従来の酸化チタン皮膜の製造方法では、アモルファス型の酸化チタンが生成し、アナターゼ型の酸化チタンは生成しないことが分かっている。 Conventionally, as a method for producing a titanium oxide film on the surface of titanium or a titanium alloy, generally, a method of anodizing titanium or a titanium alloy in a normal electrolyte such as phosphoric acid is known. However, it has been found that such a conventional method for producing a titanium oxide film produces amorphous titanium oxide and does not produce anatase titanium oxide.
近年、アナターゼ型の酸化チタン皮膜を製造する方法が精力的に検討されており、種々の方法が提案されている。例えば、特許文献１には、希薄酸性溶液中でチタンを陽極酸化処理を行った後に、酸化性雰囲気で加熱処理する方法が提案されている。また、特許文献２には、酸及び光触媒活性を有する微粒子が添加されている電解浴中で、火花放電発生電圧以上の電圧を印加してチタンを陽極電解酸化する方法が開示されている。また、特許文献３には、硫酸、リン酸及び過酸化水素を含有する電解液でチタンを陽極電解酸化する方法が開示されている。しかしながら、これらの方法では、工程が煩雑で実用的ではない、或いは、得られるアナターゼ型の酸化チタンが不均一になるため光触媒としての特性に劣る、得られるアナターゼ型の酸化チタンの量が少ない等といった問題点があった。 In recent years, methods for producing anatase-type titanium oxide films have been energetically studied, and various methods have been proposed. For example, Patent Document 1 proposes a method in which titanium is anodized in a dilute acidic solution and then heat-treated in an oxidizing atmosphere. Patent Document 2 discloses a method of subjecting titanium to anodic electrolytic oxidation by applying a voltage higher than a spark discharge generation voltage in an electrolytic bath to which fine particles having acid and photocatalytic activity are added. Patent Document 3 discloses a method for anodic electrolytic oxidation of titanium with an electrolytic solution containing sulfuric acid, phosphoric acid and hydrogen peroxide. However, in these methods, the process is complicated and impractical, or the obtained anatase-type titanium oxide is not uniform, resulting in poor photocatalytic properties, and the amount of the obtained anatase-type titanium oxide is small. There was a problem.
このような従来技術を背景として、工業的生産に適しており、しかもアナターゼ型酸化チタンの形成量が多く、光触媒活性等の特性に優れているアナターゼ型酸化チタン皮膜を製造する方法の確立が望まれている。
そこで本発明の目的は、上記従来技術の課題を解決することである。具体的には、本発明は、工業的生産に適しており、アナターゼ型酸化チタンの形成量が多く、光触媒や光電変換素子等として有用であるアナターゼ型酸化チタン皮膜を製造する方法を提供することを目的とするものである。 Accordingly, an object of the present invention is to solve the above-described problems of the prior art. Specifically, the present invention provides a method for producing an anatase-type titanium oxide film that is suitable for industrial production, has a large amount of anatase-type titanium oxide, and is useful as a photocatalyst or a photoelectric conversion element. It is intended.
本発明者らは、上記課題を解決すべく鋭意検討したところ、チタン又はチタン合金の表面にチタン窒化物を形成した後に、該チタン又はチタン合金を特定条件下で陽極酸化することにより、アナターゼ型酸化チタンの形成量が多くて、光触媒や光電変換素子等に適したアナターゼ型酸化チタン皮膜を調製できることを見出した。本発明は、かかる知見に基づき、更に改良を重ねることによって完成したものである。 The present inventors have intensively studied to solve the above-mentioned problems. After forming titanium nitride on the surface of titanium or titanium alloy, the anatase type is formed by anodizing the titanium or titanium alloy under specific conditions. It has been found that an anatase-type titanium oxide film suitable for photocatalysts, photoelectric conversion elements and the like can be prepared because of the large amount of titanium oxide formed. The present invention has been completed by making further improvements based on this finding.
即ち、本発明は下記に掲げるアナターゼ型酸化チタン皮膜の製造方法である：
項１． 以下の工程を含む、アナターゼ型酸化チタン皮膜の製造方法：
(i)チタン又はチタン合金の表面にチタン窒化物を形成する工程、及び
(ii)チタンに対してエッチング作用を有する無機酸及び該作用を有する有機酸よりなる群から選択される少なくとも１種の酸を含有する電解液中に、上記工程(i)で得られたチタン又はチタン合金を浸漬し、火花放電発生電圧以上の電圧を印加することにより陽極酸化を行う工程。
項２． 工程(i)におけるチタン窒化物の形成が、ＰＶＤ、ＣＶＤ、溶射、及び窒素ガス雰囲気下での加熱よりなる群から選択される少なくとも１種の処理により行われる、項１に記載のアナターゼ型酸化チタン皮膜の製造方法。
項３． 窒素ガス雰囲気下での加熱処理が、窒素ガス雰囲気下でチタン又はチタン合金を７５０℃以上の温度に加熱することにより行われる、項２に記載のアナターゼ型酸化チタン皮膜の製造方法。
項４． 工程(ii)の陽極酸化において、電解液が硫酸を含有するものである、項１乃至３のいずれかに記載のアナターゼ型酸化チタン皮膜の製造方法。
項５． 工程(ii)の陽極酸化において、電解液が更に過酸化水素を含有するものである、項１乃至４のいずれかに記載のアナターゼ型酸化チタン皮膜の製造方法。
項６． 工程(ii)の陽極酸化において、火花放電発生電圧まで一定の割合にて電圧を上昇させ、火花放電発生電圧以上の電圧にて、一定時間定電圧を印加する、項１乃至５のいずれかに記載のアナターゼ型酸化チタン皮膜の製造方法。
項７． アナターゼ型酸化チタン皮膜が光触媒用又は光電変換素子用材料である、項１乃至６のいずれかに記載のアナターゼ型酸化チタン皮膜の製造方法。
That is, this invention is the manufacturing method of the anatase type titanium oxide film hung up below:
Item 1. A method for producing anatase-type titanium oxide film comprising the following steps:
(i) forming titanium nitride on the surface of titanium or titanium alloy; and
(ii) Titanium obtained in the above step (i) in an electrolytic solution containing at least one acid selected from the group consisting of an inorganic acid having an etching action on titanium and an organic acid having the action Or the process of anodizing by immersing a titanium alloy and applying a voltage higher than the spark discharge generation voltage.
Item 2. Item 4. The anatase oxidation according to Item 1, wherein the formation of titanium nitride in step (i) is performed by at least one treatment selected from the group consisting of PVD, CVD, thermal spraying, and heating in a nitrogen gas atmosphere. A method for producing a titanium film.
Item 3. Item 3. The method for producing an anatase-type titanium oxide film according to Item 2, wherein the heat treatment in a nitrogen gas atmosphere is performed by heating titanium or a titanium alloy to a temperature of 750 ° C or higher in the nitrogen gas atmosphere.
Item 4. Item 4. The method for producing an anatase-type titanium oxide film according to any one of Items 1 to 3, wherein in the anodic oxidation in the step (ii), the electrolytic solution contains sulfuric acid.
Item 5. Item 5. The method for producing an anatase-type titanium oxide film according to any one of Items 1 to 4, wherein in the anodic oxidation in step (ii), the electrolytic solution further contains hydrogen peroxide.
Item 6. In the anodic oxidation in step (ii), the voltage is increased at a constant rate up to the spark discharge generation voltage, and a constant voltage is applied for a predetermined time at a voltage equal to or higher than the spark discharge generation voltage. The manufacturing method of the anatase type titanium oxide film as described.
Item 7. Item 7. The method for producing an anatase-type titanium oxide film according to any one of Items 1 to 6, wherein the anatase-type titanium oxide film is a material for a photocatalyst or a photoelectric conversion element.
以下、本発明を詳細に説明する。本発明のアナターゼ型酸化チタン皮膜の製造方法は、以下の工程(i)及び工程(ii)を含むことを特徴とするものである。以下、本発明を工程毎に説明する。なお、以下本明細書において、チタン及びチタン合金を、単にチタン材料と記すこともある。 Hereinafter, the present invention will be described in detail. The method for producing an anatase-type titanium oxide film of the present invention includes the following steps (i) and (ii). Hereinafter, this invention is demonstrated for every process. Hereinafter, in the present specification, titanium and a titanium alloy may be simply referred to as a titanium material.
工程(i)
工程(i)では、チタン又はチタン合金の表面にチタン窒化物の形成を行う。
Process (i)
In step (i), titanium nitride is formed on the surface of titanium or a titanium alloy.
本発明においてチタン合金を使用する場合、その種類については、特に限定されない。当該チタン合金として、例えばTi-6Al-4V、Ti-0.5Pd等が挙げられる。 When a titanium alloy is used in the present invention, the type is not particularly limited. Examples of the titanium alloy include Ti-6Al-4V and Ti-0.5Pd.
当該工程(i)において、チタン材料の表面にチタン窒化物の層を、通常０．１〜１００μｍ、好ましくは０．５〜５０μｍ、更に好ましくは１〜３０μｍ程度形成する。 In the step (i), a titanium nitride layer is usually formed on the surface of the titanium material in the range of 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably about 1 to 30 μm.
チタン材料の表面にチタン窒化物を形成する手段については、特に制限されず、例えば、チタン材料の表面にチタン窒化物を物理的又は化学的に付着させる方法や、チタン材料の表面上でチタンと窒素とを反応させてチタン窒化物を形成させる方法が挙げられる。かかる方法として、具体的には、ＰＶＤ（物理気相蒸着）処理、ＣＶＤ（化学気相蒸着）処理、溶射処理（吹きつけによる被膜形成）、及び窒素ガス雰囲気下でのチタン材料の加熱処理等を例示できる。 The means for forming titanium nitride on the surface of the titanium material is not particularly limited. For example, a method of physically or chemically attaching titanium nitride to the surface of the titanium material, or titanium on the surface of the titanium material. There is a method of forming titanium nitride by reacting with nitrogen. Specific examples of such methods include PVD (physical vapor deposition) processing, CVD (chemical vapor deposition) processing, thermal spray processing (film formation by spraying), and heat treatment of a titanium material in a nitrogen gas atmosphere. Can be illustrated.
ＰＶＤ処理としては、例えば、イオンプレーティング、スパッタリング等が挙げられる。 Examples of the PVD process include ion plating and sputtering.
ＣＶＤ処理としては、例えば、熱ＣＶＤ、プラズマＣＶＤ、レーザーＣＶＤ等が挙げられる。 Examples of the CVD process include thermal CVD, plasma CVD, and laser CVD.
溶射処理としては、例えば、フレーム溶射、アーク溶射、プラズマ溶射、レーザー溶射等の溶射処理が挙げられる。 Examples of the thermal spraying process include thermal spraying processes such as flame spraying, arc spraying, plasma spraying, and laser spraying.
窒素ガス雰囲気下でのチタン材料の加熱処理としては、具体的には、窒素ガス雰囲気下で、通常５００℃以上（好ましくは７５０〜１５０℃、更に好ましくは８５０〜９５０℃）にチタン材料を加熱する方法を例示できる。当該加熱処理時の窒素ガス雰囲気としては、特に制限されるものではないが、窒素ガスの気圧が、通常０．０１〜１００ＭＰａ、好ましくは０．１〜１０ＭＰａ、更に好ましくは０．１〜１ＭＰａとなる程度であればよい。当該加熱処理におけるチタン材料の加熱時間は、通常１〜１２時間、好ましくは２〜８時間、更に好ましくは３〜６時間に設定することができる。 As the heat treatment of the titanium material in a nitrogen gas atmosphere, specifically, the titanium material is usually heated to 500 ° C. or higher (preferably 750 to 150 ° C., more preferably 850 to 950 ° C.) in a nitrogen gas atmosphere. The method of doing can be illustrated. The nitrogen gas atmosphere during the heat treatment is not particularly limited, but the pressure of the nitrogen gas is usually 0.01 to 100 MPa, preferably 0.1 to 10 MPa, more preferably 0.1 to 1 MPa. As long as it is about. The heating time of the titanium material in the heat treatment can be generally set to 1 to 12 hours, preferably 2 to 8 hours, and more preferably 3 to 6 hours.
工程(i)の方法において、チタン材料の表面に形成されるチタン窒化物の種類につい
ては、特に制限されない。当該チタン窒化物の一例として、TiN、Ti2N、α-TiN0.3、η-Ti3N2-X、ζ-Ti4N3-X（但し、ｘは０以上３未満の数値を示す）、これらの混在物、及びアモルファス状チタン窒化物等が挙げられる。これらの中で好ましくは、TiN、Ti2N、及びこれらの混在物、更に好ましくはTiN、及びTiNとTi2Nの混在物、特に好ましくはTiNが例示される。
In the method of step (i), the type of titanium nitride formed on the surface of the titanium material is not particularly limited. As an example of the titanium nitride, TiN, Ti 2 N, α-TiN 0.3 , η-Ti 3 N 2-X , ζ-Ti 4 N 3-X (however, x represents a numerical value of 0 or more and less than 3) , Mixtures thereof, amorphous titanium nitride, and the like. Among these, TiN, Ti 2 N, and a mixture thereof, more preferably TiN, and a mixture of TiN and Ti 2 N, particularly preferably TiN are exemplified.
本発明では、上記チタン窒化物を形成する手段として、上記方法の内、１つの方法を単独で行ってもよく、また２種以上の方法を任意に組み合わせて行ってもよい。上記チタン窒化物を形成する方法の中で、簡便性、量産性、或いは製造コスト等の観点から、好ましくは、窒素ガス雰囲気下でのチタン材料の加熱処理である。 In the present invention, as a means for forming the titanium nitride, one of the above methods may be performed alone, or two or more methods may be arbitrarily combined. Among the methods for forming titanium nitride, from the viewpoints of simplicity, mass productivity, production cost, etc., heat treatment of the titanium material in a nitrogen gas atmosphere is preferable.
工程(ii)
工程(ii)では、チタンに対してエッチング作用を有する無機酸及び該作用を有する有機酸よりなる群から選択される少なくとも１種の酸を含有する電解液中に、上記工程(i)で得られたチタン又はチタン合金を浸漬し、火花放電発生電圧以上の電圧を印加することにより陽極酸化を行う。
Step (ii)
In the step (ii), an electrolyte containing at least one acid selected from the group consisting of an inorganic acid having an etching action on titanium and an organic acid having the action is obtained in the step (i). Anodization is performed by immersing the obtained titanium or titanium alloy and applying a voltage higher than the spark discharge generation voltage.
工程(ii)の陽極酸化において、電解液として、チタンに対してエッチング作用を有する無機酸及び／又は該作用を有する有機酸が含有されている水溶液を用いる。チタンに対してエッチング作用を有する無機酸としては、例えば、硫酸、リン酸、フッ化水素酸、塩酸、硝酸、王水等が挙げられる。また、チタンに対してエッチング作用を有する有機酸としては、例えば、シュウ酸、ギ酸、クエン酸、トリクロル酢酸等が挙げられる。これらの酸の中で、好ましくは、硫酸、リン酸、塩酸、シュウ酸、及びトリクロル酢酸、更に好ましくは硫酸を挙げることができる。これらの酸は、１種単独で使用してもよく、また有機酸、無機酸の別を問わず、これらの酸を２種以上任意に組み合わせて使用してもよい。２種以上の酸を含有する電解液の好ましい態様の一例として、硫酸及びリン酸を含有する水溶液が挙げられる。 In the anodic oxidation in the step (ii), an aqueous solution containing an inorganic acid having an etching action on titanium and / or an organic acid having the action is used as an electrolytic solution. Examples of inorganic acids having an etching action on titanium include sulfuric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, nitric acid, aqua regia and the like. Moreover, as an organic acid which has an etching effect | action with respect to titanium, an oxalic acid, a formic acid, a citric acid, a trichloroacetic acid etc. are mentioned, for example. Among these acids, sulfuric acid, phosphoric acid, hydrochloric acid, oxalic acid, and trichloroacetic acid are preferable, and sulfuric acid is more preferable. These acids may be used alone, or two or more of these acids may be used in any combination regardless of whether they are organic acids or inorganic acids. As an example of the preferable aspect of the electrolyte solution containing 2 or more types of acids, the aqueous solution containing a sulfuric acid and phosphoric acid is mentioned.
当該電解液における上記酸の配合割合については、使用する酸の種類、陽極酸化条件等によって異なるが、通常、上記酸の総量で０．０１〜１０Ｍ、好ましくは０．１〜１０Ｍ、更に好ましくは１〜１０Ｍとなる割合を挙げることができる。例えば、硫酸及びリン酸を含有する電解液の場合であれば、硫酸１〜８Ｍ及びリン酸０．１〜２Ｍの割合で含有する電解液を例示できる。 The mixing ratio of the acid in the electrolytic solution varies depending on the type of acid used, anodizing conditions, and the like, but is usually 0.01 to 10 M, preferably 0.1 to 10 M, more preferably the total amount of the acid. The ratio which becomes 1-10M can be mentioned. For example, in the case of an electrolytic solution containing sulfuric acid and phosphoric acid, an electrolytic solution containing sulfuric acid 1 to 8M and phosphoric acid 0.1 to 2M can be exemplified.
当該電解液は、上記有機酸及び／又は無機酸に加えて、過酸化水素を含有しているものが望ましい。電解液中に過酸化水素が含まれていることによって、一層効率的にアナターゼ型酸化チタン皮膜を調製することが可能になる。電解液に過酸化水素を配合する場合、その配合割合については、特に制限されないが、例えば０．０１〜５Ｍ、好ましくは０．０１〜１Ｍ、更に好ましくは０．１〜１Ｍとなる割合が例示される。 The electrolyte solution preferably contains hydrogen peroxide in addition to the organic acid and / or inorganic acid. By containing hydrogen peroxide in the electrolytic solution, an anatase-type titanium oxide film can be prepared more efficiently. When hydrogen peroxide is blended in the electrolytic solution, the blending ratio is not particularly limited. For example, the ratio is 0.01 to 5M, preferably 0.01 to 1M, and more preferably 0.1 to 1M. Is done.
工程(ii)の陽極酸化で使用される電解液の好ましい態様の一例として、硫酸１〜８Ｍ、リン酸０．１〜２Ｍ及び過酸化水素０．１〜１Ｍの割合で含有する水溶液が挙げられる。 As an example of the preferable aspect of the electrolyte solution used by the anodic oxidation of process (ii), the aqueous solution contained in the ratio of 1-8M sulfuric acid, 0.1-2M phosphoric acid, and 0.1-1M hydrogen peroxide is mentioned. .
上記電解液中に上記工程(i)で得られたチタン又はチタン合金を浸漬し、火花放電発生電圧以上の電圧を印加して陽極酸化を行うことにより、アナターゼ型の酸化チタンの皮膜が得られる。 An anatase-type titanium oxide film can be obtained by immersing the titanium or titanium alloy obtained in the step (i) in the electrolyte and applying a voltage higher than the spark discharge generation voltage to perform anodization. .
当該陽極酸化では、火花放電発生電圧以上の電圧を印加して行う。火花放電発生電圧以上の電圧としては、通常１００Ｖ以上、好ましくは１５０Ｖ以上が例示される。 In the anodic oxidation, a voltage higher than the spark discharge generation voltage is applied. The voltage higher than the spark discharge generation voltage is typically 100 V or higher, preferably 150 V or higher.
当該陽極酸化は、例えば、上記の火花放電発生電圧まで一定の割合にて電圧を上昇させ、火花放電発生電圧以上の電圧にて、一定時間定電圧を印加することにより行うことができる。火花放電発生電圧まで電圧を上昇させる速度としては、通常０．０１〜１Ｖ／秒、好ましくは０．０５〜０．５Ｖ／秒、更に好ましくは０．１〜０．５Ｖ／秒に設定される。また、火花放電発生電圧以上の電圧を印加する時間としては、通常１分以上、好ましくは１〜６０分間、更に好ましくは１０〜３０分間に設定される。 The anodization can be performed, for example, by increasing the voltage at a constant rate up to the spark discharge generation voltage and applying a constant voltage for a predetermined time at a voltage equal to or higher than the spark discharge generation voltage. The speed at which the voltage is increased to the spark discharge generation voltage is usually set to 0.01 to 1 V / second, preferably 0.05 to 0.5 V / second, more preferably 0.1 to 0.5 V / second. . Moreover, as time to apply the voltage more than a spark discharge generation voltage, it is 1 minute or more normally, Preferably it is set to 1 to 60 minutes, More preferably, it is set to 10 to 30 minutes.
上記製造方法によれば、膜厚が１〜１００μｍ程度のアナターゼ型酸化チタン皮膜を得ることができる。また、本発明の方法によれば、アナターゼ型酸化チタンの量が多い皮膜を形成することができる。本発明の方法により得られるアナターゼ型酸化チタン皮膜は、光触媒や光電変換素子等の特性において優れているので、光触媒用材料や光電変換素子用材料等として有用である。 According to the manufacturing method, an anatase-type titanium oxide film having a thickness of about 1 to 100 μm can be obtained. Moreover, according to the method of the present invention, a film having a large amount of anatase-type titanium oxide can be formed. Since the anatase-type titanium oxide film obtained by the method of the present invention is excellent in the characteristics of a photocatalyst, a photoelectric conversion element, etc., it is useful as a photocatalyst material, a photoelectric conversion element material, or the like.
本発明によれば、膜厚が大きく、しかもアナターゼ型酸化チタンの形成量が多い皮膜を、簡便な方法で製造することができる。また、本発明により得られるアナターゼ型酸化チタン皮膜は光触媒特性や光電変換特性を効果的に発揮できるので、本発明の方法は、光触媒用材料又は光電変換素子用材料の製造方法としても有用である。 According to the present invention, a film having a large film thickness and a large amount of anatase-type titanium oxide can be produced by a simple method. Further, since the anatase-type titanium oxide film obtained by the present invention can effectively exhibit photocatalytic properties and photoelectric conversion properties, the method of the present invention is also useful as a method for producing a photocatalyst material or a photoelectric conversion element material. .
以下、実施例を挙げて本発明を説明するが、本発明はこれらの実施例に限定されるものではない。
実施例１
５０ｍｍ角の金属チタンを窒素ガス雰囲気下（窒素ガス気圧約０．１ＭＰａ）で、７５０℃、８５０℃、及び９５０℃のそれぞれの温度で６時間加熱した。この加熱処理後、金属チタン上の窒化チタン（TiN）の生成量を確認するために、TiN結晶相の２００面、１１１面及び２２０面のＸ線回折強度を測定した。得られた結果を図１に示す。この結果から、窒素ガス雰囲気下でチタンを７５０℃以上に加熱することによって、チタン表面に窒化チタンが形成されることが確認された。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to these Examples.
Example 1
50 mm square titanium metal was heated at 750 ° C., 850 ° C., and 950 ° C. for 6 hours in a nitrogen gas atmosphere (nitrogen gas pressure of about 0.1 MPa). After this heat treatment, the X-ray diffraction intensities of the 200, 111, and 220 planes of the TiN crystal phase were measured in order to confirm the amount of titanium nitride (TiN) produced on the titanium metal. The obtained results are shown in FIG. From this result, it was confirmed that titanium nitride was formed on the titanium surface by heating titanium to 750 ° C. or higher in a nitrogen gas atmosphere.
次いで、窒化チタンが形成された各々の金属チタンに対して下記条件で陽極酸化を行い、得られたアナターゼ型酸化チタン皮膜の量を、アナターゼ型酸化チタン結晶相の１０１面及び２００面のＸ線回折強度を測定することにより評価した。また、比較として、チタン窒化物を形成していない金属チタンを用いて同様に陽極酸化したものについてもアナターゼ型酸化チタン皮膜の量を評価した。また、併せて、８５０℃の温度条件下で窒化チタンの形成を行った後に、１５０Ｖ、１８０Ｖ又は２００Ｖで陽極酸化処理を行うことにより得られたアナターゼ型酸化チタン皮膜についてＸ線回折を行った。当該Ｘ線回折については、比較として、８５０℃の温度条件下でチタン窒化物の形成のみを行い、陽極酸化処理をしなかったものについても評価した。なお、下記陽極酸化条件では、何れの電圧においても火花放電の発生が確認された。
＜陽極酸化条件＞
電解液：１．５Ｍ硫酸、０．３Ｍリン酸及び０．３Ｍ過酸化水素を含有する水溶液
電圧上昇速度：０．１Ｖ／秒
ピーク電圧：１５０、１６０、１７０、１８０、１９０及び２００Ｖ
ピーク電圧保持時間：１０分
アナターゼ型酸化チタン皮膜の量に関して、得られた結果を図２（１０１面）及び３（２００面）に示す。この結果から、窒化チタン形成量が多い程、アナターゼ型酸化チタンの生成量が増大することが確認された。
Subsequently, each metal titanium on which titanium nitride was formed was anodized under the following conditions, and the amount of the obtained anatase-type titanium oxide film was determined by the X-rays on the 101- and 200-planes of the anatase-type titanium oxide crystal phase. The diffraction intensity was evaluated by measuring. For comparison, the amount of the anatase-type titanium oxide film was also evaluated for those that were similarly anodized using metal titanium that did not form titanium nitride. In addition, after the formation of titanium nitride under a temperature condition of 850 ° C., X-ray diffraction was performed on the anatase-type titanium oxide film obtained by anodizing at 150V, 180V or 200V. For the X-ray diffraction, as a comparison, a case where only titanium nitride was formed under a temperature condition of 850 ° C. and anodization treatment was not performed was also evaluated. Note that generation of spark discharge was confirmed at any voltage under the following anodic oxidation conditions.
<Anodic oxidation conditions>
Electrolyte solution: aqueous solution containing 1.5 M sulfuric acid, 0.3 M phosphoric acid and 0.3 M hydrogen peroxide Voltage rise rate: 0.1 V / sec Peak voltage: 150, 160, 170, 180, 190 and 200 V
Peak voltage holding time: 10 minutes The results obtained with respect to the amount of the anatase-type titanium oxide film are shown in FIGS. 2 (101 plane) and 3 (200 plane). From this result, it was confirmed that the production amount of anatase-type titanium oxide increases as the titanium nitride formation amount increases.
また、併せて、８５０℃の温度条件下でチタン窒化物の形成を行った後に、１５０Ｖ、１８０Ｖ又は２００Ｖで陽極酸化処理を行うことにより得られたアナターゼ型酸化チタン皮膜のＸ線回折パターンを図４に示す。また、図４には、比較として、８５０℃の温度条件下でチタン窒化物の形成のみを行い、陽極酸化処理をしなかったもののＸ線回折パターンについても併せて示す。なお、図４中のＡ１０１及びＡ２００は、アナターゼ酸化チタンの１０１面及び２００面を夫々示す。当該図４からも、本発明の方法によって、アナターゼ型酸化チタンが生成していることが確認された。 In addition, an X-ray diffraction pattern of the anatase-type titanium oxide film obtained by performing anodization at 150 V, 180 V or 200 V after forming titanium nitride at 850 ° C. is also shown. 4 shows. For comparison, FIG. 4 also shows the X-ray diffraction pattern of titanium nitride formed only at 850 ° C. and not anodized. In addition, A101 and A200 in FIG. 4 show the 101 surface and 200 surface of anatase titanium oxide, respectively. FIG. 4 also confirmed that anatase-type titanium oxide was produced by the method of the present invention.
実施例２
５０ｍｍ角の金属チタンにイオンプレーティング法によるＰＶＤ処理を行い、表面に窒化チタンを形成させた。金属チタン上の窒化チタン（TiN）の生成量を、TiN結晶相の２００面、１１１面のＸ線回折強度を測定することにより確認した。得られた結果を図５に示す。なお、図５には、実施例１において窒素ガス雰囲気下でチタンを９５０℃で加熱することにより形成された窒化チタンのＸ線回折強度の測定結果についても併せて示す。この結果から、ＰＶＤ処理により、チタン金属表面に窒化チタンが形成されていることが確認された。
Example 2
A 50 mm square metal titanium was subjected to PVD treatment by an ion plating method to form titanium nitride on the surface. The amount of titanium nitride (TiN) produced on titanium metal was confirmed by measuring the X-ray diffraction intensity on the 200th and 111th surfaces of the TiN crystal phase. The obtained results are shown in FIG. FIG. 5 also shows the measurement result of the X-ray diffraction intensity of titanium nitride formed by heating titanium at 950 ° C. in a nitrogen gas atmosphere in Example 1. From this result, it was confirmed that titanium nitride was formed on the titanium metal surface by the PVD treatment.
次いで、ＰＶＤ処理により窒化チタンが形成された金属チタンを実施例１と同条件の陽極酸化（但し、ピーク電圧は２００Ｖ）を行い、得られたアナターゼ型酸化チタン皮膜の量を、アナターゼ型酸化チタン結晶相の１０１面及び２００面のＸ線回折強度を測定することにより評価した。また、得られたアナターゼ型酸化チタン皮膜を走査型電子顕微鏡により確認した。 Subsequently, the metal titanium on which titanium nitride was formed by PVD treatment was anodized under the same conditions as in Example 1 (however, the peak voltage was 200 V), and the amount of the obtained anatase-type titanium oxide film was determined by the amount of the anatase-type titanium oxide film. Evaluation was made by measuring X-ray diffraction intensities on the 101 and 200 planes of the crystal phase. Moreover, the obtained anatase type titanium oxide film was confirmed with a scanning electron microscope.
得られた結果を図６及び７に示す。なお、図６には、９５０℃の加熱処理によって窒化チタンを形成した後に陽極酸化することにより得られたアナターゼ型酸化チタン皮膜（実施例１）のＸ線回折強度の測定結果についても併せて示す。この結果から、ＰＶＤ処理してチタン窒化物を形成させた後に、陽極酸化を行うことによって、アナターゼ型酸化チタンを生成できることが確認された。また、この結果からは、陽極酸化に先だって行われるチタン窒化物の形成が、アナターゼ型酸化チタンの効率的な生成に重要であることが確認された。 The obtained results are shown in FIGS. FIG. 6 also shows the measurement results of the X-ray diffraction intensity of the anatase-type titanium oxide film (Example 1) obtained by anodizing after forming titanium nitride by heat treatment at 950 ° C. . From this result, it was confirmed that anatase-type titanium oxide can be generated by performing anodic oxidation after PVD treatment to form titanium nitride. Also, from this result, it was confirmed that the formation of titanium nitride performed prior to anodic oxidation is important for the efficient production of anatase-type titanium oxide.
また、本実施例２において得られたアナターゼ型酸化チタン皮膜を走査型電子顕微鏡により観察したところ、当該アナターゼ型酸化チタン皮膜は膜厚が５μｍ以上あることが確認された（図７参照）。 Further, when the anatase-type titanium oxide film obtained in Example 2 was observed with a scanning electron microscope, it was confirmed that the anatase-type titanium oxide film had a thickness of 5 μm or more (see FIG. 7).
実施例３
実施例１において得られたアナターゼ型酸化チタン皮膜の光触媒活性を以下の方法で評価した。
Example 3
The photocatalytic activity of the anatase-type titanium oxide film obtained in Example 1 was evaluated by the following method.
実施例１で得られた３種のアナターゼ型酸化チタン皮膜形成金属チタン（窒化チタン形成時の温度が各７５０、８５０及び９５０℃で、陽極酸化時の印加電圧のピークが１５０Ｖのもの）を１０ｐｐｍのメチレンブルー水溶液に２４時間浸漬した。次いで、このアナターゼ型酸化チタン皮膜形成金属チタンを取り出し、再度１０ｐｐｍメチレンブルー水溶液１０ｍｌに浸漬して、これに中心波長３６０ｎｍ近辺の近紫外領域の光線を照射し、該メチレンブルー水溶液の６６３ｎｍの吸光度（光路長１ｃｍ、石英セル）の経時的変化を測定した。また、比較として、窒化チタンの形成を行わずに実施例１と同条件の陽極酸化（但し、陽極酸化時の印加電圧のピークは１５０Ｖ）のみを行った金属チタン、及びチタン窒化物の形成及び陽極酸化を行っていない金属チタンについても、同様に試験を行った。 10 ppm of the three types of anatase-type titanium oxide film-formed metal titanium obtained in Example 1 (temperatures when forming titanium nitride are 750, 850 and 950 ° C., respectively, and the peak of the applied voltage during anodization is 150 V) For 24 hours. Next, this anatase-type titanium oxide film-forming metal titanium is taken out and immersed again in 10 ml of a 10 ppm methylene blue aqueous solution. 1 cm, quartz cell) was measured over time. Further, as a comparison, the formation of titanium metal and titanium nitride that were subjected only to anodic oxidation under the same conditions as in Example 1 without forming titanium nitride (however, the applied voltage peak during anodic oxidation was 150 V) The same test was performed on metal titanium that had not been anodized.
得られた結果を図８に示す。この結果から、予めチタン窒化物を形成した後に、火花発生電圧以上の電圧で陽極酸化を行って得られたアナターゼ型酸化チタン皮膜では、メチレンブルーの退色が認められ、優れた光触媒活性を有していることが確認された。特に、陽極酸化処理に先立って行われるチタン窒化物の形成において、そのチタン窒化物の形成量が多い程、優れた光触媒活性を有するアナターゼ型酸化チタンが得られることが分かった。 The obtained result is shown in FIG. From this result, in the anatase-type titanium oxide film obtained by performing anodization at a voltage higher than the spark generation voltage after forming titanium nitride in advance, fading of methylene blue was observed and it had excellent photocatalytic activity. It was confirmed that In particular, in the formation of titanium nitride performed prior to the anodic oxidation treatment, it was found that the more the amount of titanium nitride formed, the more anatase-type titanium oxide having excellent photocatalytic activity can be obtained.
実施例４
実施例２で得られたアナターゼ型酸化チタン皮膜の光電変換特性を以下の方法で評価した。具体的には、下記色素溶液にアナターゼ型酸化チタン皮膜を浸漬して酸化チタン皮膜に色素を被覆させた。得られた色素被覆酸化チタン皮膜について、下記電解液及び対極として白金をスパッタリングしたITO（Indium Tin Oxide）を使用して下記試験装置により、光電変換特性を評価した。
＜色素溶液＞
0.0003Ｍルテニウム系色素（商品名「535-bisTBA」、SOLAONIX社製）含有アセトニトリル・ｔ−ブタノール混合液（混合比は体積比で５０：５０）
＜電解液＞
0.1Ｍヨウ化リチウム、0.05Ｍヨウ素、0.5Ｍ ＴＢＰ（tetrabutylammonium）、及び0.6Ｍ有機系ヨウ化物塩（1-propyl-2,3-dimethylmidazolium iodize）を含有する水溶液
＜試験装置＞
光電気特性評価装置（分光計器、光源：キセノンランプ）（CLR―25、分光計器社製）。
Example 4
The photoelectric conversion characteristics of the anatase-type titanium oxide film obtained in Example 2 were evaluated by the following methods. Specifically, the anatase-type titanium oxide film was immersed in the following dye solution to coat the titanium oxide film with the dye. The obtained dye-coated titanium oxide film was evaluated for photoelectric conversion characteristics by the following test apparatus using the following electrolyte and ITO (Indium Tin Oxide) obtained by sputtering platinum as a counter electrode.
<Dye solution>
A mixture of acetonitrile and t-butanol containing 0.0003M ruthenium dye (trade name “535-bisTBA”, manufactured by SOLAONIX) (mixing ratio is 50:50 by volume)
<Electrolyte>
Aqueous solution containing 0.1M lithium iodide, 0.05M iodine, 0.5M TBP (tetrabutylammonium), and 0.6M organic iodide salt (1-propyl-2,3-dimethylmidazolium iodize)
Photoelectric characteristic evaluation device (spectrometer, light source: xenon lamp) (CLR-25, manufactured by Spectrometer Co., Ltd.).
得られた結果を図９に示す。この結果から、本発明により得られたアナターゼ型酸化チタン皮膜は、光電変換素子として使用し得ることが確認された。 The results obtained are shown in FIG. From this result, it was confirmed that the anatase-type titanium oxide film obtained by the present invention can be used as a photoelectric conversion element.
Claims (7)
(i)チタン又はチタン合金の表面にチタン窒化物を形成する工程、及び
(ii)チタンに対してエッチング作用を有する無機酸及び該作用を有する有機酸よりなる群から選択される少なくとも１種の酸を含有する電解液中に、上記工程(i)で得られたチタン又はチタン合金を浸漬し、火花放電発生電圧以上の電圧を印加することにより陽極酸化を行う工程。 A method for producing anatase-type titanium oxide film comprising the following steps:
(i) forming titanium nitride on the surface of titanium or titanium alloy; and
(ii) Titanium obtained in the above step (i) in an electrolytic solution containing at least one acid selected from the group consisting of an inorganic acid having an etching action on titanium and an organic acid having the action Or the process of anodizing by immersing a titanium alloy and applying a voltage higher than the spark discharge generation voltage.
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