JP2009013038A - Super-hydrophilic/hydrophobic patternized surface, anatase tio2 crystal pattern and their preparation methods - Google Patents
Super-hydrophilic/hydrophobic patternized surface, anatase tio2 crystal pattern and their preparation methods Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 107
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 63
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 138
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000002159 nanocrystal Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- -1 hexafluorotitanium (IV) salt Chemical class 0.000 claims description 2
- 229920000307 polymer substrate Polymers 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 abstract 1
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- 238000000034 method Methods 0.000 description 11
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- 239000000463 material Substances 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
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- 238000002003 electron diffraction Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002524 electron diffraction data Methods 0.000 description 3
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- 239000007789 gas Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ZGUIQJAPZVGYCM-UHFFFAOYSA-N O.O.[K] Chemical compound O.O.[K] ZGUIQJAPZVGYCM-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- UKUXETRNORBBBD-UHFFFAOYSA-L [O-]C(C([O-])=O)=O.N.[Ti+4] Chemical compound [O-]C(C([O-])=O)=O.N.[Ti+4] UKUXETRNORBBBD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
Abstract
Description
本発明は、超親水性／疎水性パターン化表面と、アナターゼＴｉＯ２結晶パターン及びそれらの作製方法に関するものであり、更に詳しくは、本発明は、フォトマスクを介した紫外線照射により形成されるＦＴＯ表面の超親水性／疎水性パターン化表面、及びこれを用いたアナターゼＴｉＯ２結晶パターンと、それらの作製方法に関するものである。
本発明品は、例えば、分子センサー、ガスセンサー、溶液センサー、色素増感型太陽電池、光触媒等の電子デバイスとして利用できるアナターゼＴｉＯ２結晶パターンを提供するものである。
The present invention relates to a superhydrophilic / hydrophobic patterned surface, anatase TiO 2 crystal pattern and methods for producing them, and more particularly, the present invention relates to FTO formed by ultraviolet irradiation through a photomask. The present invention relates to a superhydrophilic / hydrophobic patterned surface of a surface, an anatase TiO 2 crystal pattern using the same, and a production method thereof.
The product of the present invention provides an anatase TiO 2 crystal pattern that can be used as an electronic device such as a molecular sensor, a gas sensor, a solution sensor, a dye-sensitized solar cell, and a photocatalyst.
近年、分子センサー、ガスセンサー、溶液センサー、色素増感型太陽電池、光触媒等の様々な分野において、アナターゼ型ＴｉＯ２に注目が集まっている。特に、センサーや色素増感型太陽電池向け材料としては、高比表面積を有する多孔質アナターゼＴｉＯ２膜が必要とされている。また、これらのデバイスにおいては、透明導電性基板のフッ素ドープ酸化スズ膜（ＦＴＯ基板）や、ＩＴＯ基板、導電性ポリマー基板等上への多孔質アナターゼＴｉＯ２電極層の形成が求められている。 In recent years, attention has been focused on anatase TiO 2 in various fields such as molecular sensors, gas sensors, solution sensors, dye-sensitized solar cells, and photocatalysts. In particular, as a material for sensors and dye-sensitized solar cells, a porous anatase TiO 2 film having a high specific surface area is required. In these devices, formation of a porous anatase TiO 2 electrode layer on a fluorine-doped tin oxide film (FTO substrate) of a transparent conductive substrate, an ITO substrate, a conductive polymer substrate or the like is required.
先行技術文献では、例えば、ゾルゲル法による色素増感型太陽電池向けＴｉＯ２電極の形成技術が提案されている（非特許文献１）。また、他の先行技術文献では、例えば、アナターゼ型ＴｉＯ２膜の液相形成技術として、ナノ針状アナターゼＴｉＯ２結晶集積粒子と多孔質アナターゼＴｉＯ２結晶膜及びそれらの作製方法が提案されている（特許文献１）。 In the prior art document, for example, a technique for forming a TiO 2 electrode for a dye-sensitized solar cell by a sol-gel method has been proposed (Non-patent Document 1). Further, in other prior art documents, for example, as a liquid phase forming technique of an anatase TiO 2 film, nano acicular anatase TiO 2 crystal aggregated particles, a porous anatase TiO 2 crystal film, and methods for producing them are proposed. (Patent Document 1).
このように、センサーや色素増感型太陽電池への応用のためには、ＦＴＯ（フッ素ドープ酸化スズ）透明導電膜上へのＴｉＯ２膜形成技術が必要である。しかし、溶液中からのＴｉＯ２結晶の析出によりＴｉＯ２膜を形成させるためには、基板の表面状態により析出速度が異なり、特に、ＦＴＯ基板表面でのＴｉＯ２核形成密度が低いため、核形成密度を上げ、連続ＴｉＯ２膜を形成する必要があった。 Thus, for application to sensors and dye-sensitized solar cells, a technology for forming a TiO 2 film on an FTO (fluorine-doped tin oxide) transparent conductive film is necessary. However, in order to form a TiO 2 film by precipitation of TiO 2 crystals from the solution, the deposition rate varies depending on the surface state of the substrate, and in particular, the TiO 2 nucleation density on the surface of the FTO substrate is low. It was necessary to increase the density and form a continuous TiO 2 film.
また、デバイスとして用いる際に、基板上の特定部位にのみ、ＴｉＯ２電極を形成させる必要があった。更に、基材へのコーティングを行う際、反応溶液容器壁面へのＴｉＯ２が起こり、溶液中の原料イオンの低下による基材上へのＴｉＯ２析出速度の低下や、反応溶液容器の汚染が問題となっていた。 Further, when used as a device, it was necessary to form a TiO 2 electrode only at a specific portion on the substrate. Furthermore, when coating the base material, TiO 2 is generated on the reaction solution container wall surface, which causes problems such as a decrease in the deposition rate of TiO 2 on the base material due to a decrease in raw material ions in the solution and contamination of the reaction solution container. It was.
このような状況の中で、本発明者らは、上記従来技術に鑑みて、上記従来法の問題点を解決することが可能な新しいアナターゼＴｉＯ２結晶パターンの作製技術を開発することを目標として鋭意研究を積み重ねた結果、ＦＴＯ表面に形成した超親水性／疎水性パターン化表面を用いて、マイクロサイズのアナターゼＴｉＯ２結晶パターンを形成することに成功し、本発明を完成するに至った。本発明は、超親水性／疎水性パターン化表面、アナターゼＴｉＯ２結晶パターン及びそれらの作製方法を提供することを目的とするものである。 Under such circumstances, the present inventors have aimed at developing a new anatase TiO 2 crystal pattern production technique capable of solving the problems of the conventional method in view of the conventional technique. As a result of intensive research, the present inventors have succeeded in forming a micro-sized anatase TiO 2 crystal pattern using the superhydrophilic / hydrophobic patterned surface formed on the FTO surface, and completed the present invention. The present invention aims to provide superhydrophilic / hydrophobic patterned surfaces, anatase TiO 2 crystal patterns and methods for their preparation.
上記課題を解決するための本発明は、以下の技術的手段から構成される。
（１）基板に形成した超親水性／疎水性パターン化表面の超親水性領域に選択的に析出させたアナターゼＴｉＯ２結晶パターンからなることを特徴とするアナターゼＴｉＯ２結晶パターン。
（２）基板が、ＦＴＯ、シリコン、ガラス、金属、セラミックス又はポリマー基板である、前記（１）に記載のアナターゼＴｉＯ２結晶パターン。
（３）基板が、平板、粒子、繊維、又は複雑形状の形態を有する、前記（１）に記載のアナターゼＴｉＯ２結晶パターン。
（４）ＦＴＯ層の超親水性領域に析出させたナノＴｉＯ２結晶層を有する、前記（１）に記載のアナターゼＴｉＯ２結晶パターン。
（５）ナノＴｉＯ２結晶が、ｃ軸方向に該ｃ軸をＦＴＯ基板に垂直に立てるように異方成長している、前記（４）に記載のアナターゼＴｉＯ２結晶パターン。
（６）超親水性／疎水性パターン化表面が、フォトマスクを介した紫外線照射によりＦＴＯ表面に形成したものである、前記（１）に記載のアナターゼＴｉＯ２結晶パターン。
（７）アナターゼＴｉＯ２結晶パターンが、酸化チタン結晶が析出する反応系から液相反応により超親水性領域に選択的に析出させたものである、前記（１）に記載のアナターゼＴｉＯ２結晶パターン。
（８）ＦＴＯ層が、酸化スズの単相からなり、ＴｉＯ２層がアナターゼＴｉＯ２単相からなる、前記（４）に記載のアナターゼＴｉＯ２結晶パターン。
（９）ＴｉＯ２層が、ナノ結晶からなるナノサイズの凹凸と、ＦＴＯの表面形状由来の凹凸を合せ持ったハイブリッド階層凹凸構造を有している、前記（４）に記載のアナターゼＴｉＯ２結晶パターン。
（１０）前記（１）から（９）のいずれかに記載のアナターゼＴｉＯ２結晶パターンを作製する方法であって、フォトマスクを介した紫外線照射により基板表面に超親水性／疎水性パターン化表面を形成し、酸化チタン結晶が析出する反応系を用いて液相反応により、該超親水性領域にアナターゼＴｉＯ２結晶パターンを選択的に析出させることを特徴とするアナターゼＴｉＯ２結晶パターンの作製方法。
（１１）ＦＴＯ表面に超親水性／疎水性パターン化表面を形成する、前記（１０）に記載のアナターゼＴｉＯ２結晶パターンの作製方法。
（１２）酸化チタン結晶が析出する反応系として、フッ化チタン酸アンモニウム、ヘキサフルオロチタン（ＩＶ）酸塩、チタン酸塩、アセチルアセトンチタニル、しゅう酸チタン（ＩＶ）塩、又は硫酸チタンを含むチタン含有溶液を用いる、前記（１０）に記載のアナターゼＴｉＯ２結晶パターンの作製方法。
（１３）反応系が、水溶液反応、非水溶液反応、又は水熱反応による反応系である、前記（１０）に記載のアナターゼＴｉＯ２結晶パターンの作製方法。
（１４）反応系のホウ酸を添加して、あるいは反応系の温度、原料濃度又はｐＨを変化させてアナターゼＴｉＯ２結晶を析出させる、前記（１０）に記載のアナターゼＴｉＯ２結晶パターンの作製方法。
（１５）超親水領域に１０−３０ｎｍのナノ結晶の集積体により覆われたＴｉＯ２マイクロパターン領域を形成する、前記（１０）に記載のアナターゼＴｉＯ２結晶パターンの作製方法。
（１６）前記（１）から（９）のいずれかに記載のアナターゼＴｉＯ２結晶パターンを構成要素として含むことを特徴とする電子デバイス。
The present invention for solving the above-described problems comprises the following technical means.
(1) Anatase TiO 2 crystals pattern characterized in that it consists of anatase TiO 2 crystals pattern selectively precipitated superhydrophilic regions of superhydrophilic / hydrophobic patterned surface formed on the substrate.
(2) The anatase TiO 2 crystal pattern according to (1), wherein the substrate is an FTO, silicon, glass, metal, ceramic, or polymer substrate.
(3) The anatase TiO 2 crystal pattern according to (1), wherein the substrate has a form of a flat plate, particles, fibers, or a complicated shape.
(4) The anatase TiO 2 crystal pattern according to (1) above, which has a nano TiO 2 crystal layer precipitated in the superhydrophilic region of the FTO layer.
(5) The anatase TiO 2 crystal pattern according to (4), wherein the nano TiO 2 crystal is anisotropically grown in the c-axis direction so that the c-axis is perpendicular to the FTO substrate.
(6) The anatase TiO 2 crystal pattern according to (1) above, wherein the superhydrophilic / hydrophobic patterned surface is formed on the FTO surface by ultraviolet irradiation through a photomask.
(7) The anatase TiO 2 crystal pattern according to (1), wherein the anatase TiO 2 crystal pattern is selectively deposited in a superhydrophilic region by a liquid phase reaction from a reaction system in which a titanium oxide crystal is precipitated. .
(8) The anatase TiO 2 crystal pattern according to (4), wherein the FTO layer is composed of a single phase of tin oxide, and the TiO 2 layer is composed of an anatase TiO 2 single phase.
(9) TiO 2 layers, and the unevenness of the nano-sized consisting nanocrystals has a hybrid hierarchical uneven structure having combined the surface shape from the unevenness of the FTO, anatase TiO 2 crystals as described in (4) pattern.
(10) A method for producing the anatase TiO 2 crystal pattern according to any one of (1) to (9) above, wherein a superhydrophilic / hydrophobic patterned surface is formed on a substrate surface by ultraviolet irradiation through a photomask. forming a, by a liquid phase reaction using a reaction system of titanium oxide crystals precipitate, the method for manufacturing a anatase TiO 2 crystal pattern, characterized in that deposited selectively in the anatase TiO 2 crystal pattern on said ultra-hydrophilic region .
(11) The method for producing an anatase TiO 2 crystal pattern according to (10), wherein a superhydrophilic / hydrophobic patterned surface is formed on the FTO surface.
(12) Titanium containing ammonium fluoride crystal, hexafluorotitanium (IV) acid salt, titanate, acetylacetone titanyl, titanium oxalate (IV) salt, or titanium sulfate as a reaction system for depositing titanium oxide crystals The method for producing an anatase TiO 2 crystal pattern according to (10), wherein a solution is used.
(13) The method for producing an anatase TiO 2 crystal pattern according to (10), wherein the reaction system is a reaction system based on an aqueous solution reaction, a non-aqueous solution reaction, or a hydrothermal reaction.
(14) The method for producing an anatase TiO 2 crystal pattern according to (10) above, wherein anatase TiO 2 crystals are precipitated by adding boric acid in the reaction system or changing the temperature, raw material concentration or pH of the reaction system. .
(15) The method for producing an anatase TiO 2 crystal pattern according to (10), wherein a TiO 2 micropattern region covered with an aggregate of 10-30 nm nanocrystals is formed in the superhydrophilic region.
(16) An electronic device comprising the anatase TiO 2 crystal pattern according to any one of (1) to (9) as a constituent element.
次に、本発明について更に詳細に説明する。
本発明は、マイクロサイズのアナターゼＴｉＯ２結晶パターンであって、基板に形成した超親水性／疎水性パターン化表面の超親水性領域に選択的に析出させたアナターゼＴｉＯ２結晶パターンからなることを特徴とするものである。
Next, the present invention will be described in more detail.
The present invention relates to a anatase TiO 2 crystal pattern of micro-sized, in that it consists of selectively anatase TiO 2 crystal pattern were precipitated superhydrophilic regions of superhydrophilic / hydrophobic patterned surface formed on the substrate It is a feature.
また、本発明は、該アナターゼＴｉＯ２結晶パターンを作製する方法であって、フォトマスクを介した紫外線照射により基板表面に超親水性／疎水性パターン化表面を形成し、酸化チタン結晶が析出する反応系を用いて液相反応により、該超親水性領域にアナターゼＴｉＯ２結晶パターンを選択的に析出させることを特徴とするものである。 The present invention is also a method for producing the anatase TiO 2 crystal pattern, wherein a superhydrophilic / hydrophobic patterned surface is formed on the substrate surface by ultraviolet irradiation through a photomask, and titanium oxide crystals are precipitated. The anatase TiO 2 crystal pattern is selectively deposited in the superhydrophilic region by a liquid phase reaction using a reaction system.
更に、本発明は、上記アナターゼＴｉＯ２結晶パターンを構成要素として含む電子デバイスの点に特徴を有するものである。 Furthermore, the present invention has a characteristic feature of the electronic device including the anatase TiO 2 crystal pattern as components.
本発明では、フォトマスクを介した紫外線照射によりＦＴＯ表面に、超親水性／疎水性パターン化表面を形成させる。また、疎水性表面よりも、親水性表面において、ＴｉＯ２の核形成及び膜形成が促進されることを見いだし、疎水性／超親水性ＦＴＯパターン化表面を用いたアナターゼＴｉＯ２結晶のパターン化及び析出を実現した。 In the present invention, a superhydrophilic / hydrophobic patterned surface is formed on the FTO surface by ultraviolet irradiation through a photomask. We have also found that nucleation and film formation of TiO 2 is promoted on hydrophilic surfaces rather than hydrophobic surfaces, and patterning of anatase TiO 2 crystals using hydrophobic / superhydrophilic FTO patterned surfaces and Precipitation was achieved.
このプロセスでは、水溶液プロセスにおいて、アナターゼＴｉＯ２結晶を析出させることができるため、結晶化のための高温加熱処理を必要とせず、各種の低耐熱性基板などへの展開が可能である。本発明は、ＦＴＯ表面の超親水性／疎水性パターン化表面を用いて、アナターゼＴｉＯ２結晶パターンを形成することを最も主要な特徴とする。 In this process, since anatase TiO 2 crystals can be precipitated in an aqueous solution process, high temperature heat treatment for crystallization is not required, and development to various low heat resistant substrates is possible. The main feature of the present invention is that an anatase TiO 2 crystal pattern is formed using a superhydrophilic / hydrophobic patterned surface of the FTO surface.
ＦＴＯ成膜後、大気中で保管することによって、ＦＴＯ表面に大気中の浮遊有機分子の吸着等が起こり、疎水性を示す疎水性表面が形成される。疎水性表面として、有機分子等の付着したＦＴＯ表面が用いられるが、その他、疎水性表面修飾を行ったＦＴＯ表面を用いることもできる。 By storing in the air after the FTO film formation, adsorption of floating organic molecules in the air occurs on the FTO surface, and a hydrophobic surface showing hydrophobicity is formed. As the hydrophobic surface, an FTO surface to which organic molecules or the like are attached is used, but an FTO surface subjected to hydrophobic surface modification can also be used.
超親水性表面は、上記ＦＴＯ表面に、大気中にてＵＶ照射を行うことで形成されるが、その他、真空中や窒素ガス中などの異なる雰囲気でのＵＶ照射や、異なる波長の光照射、あるいは、有機溶媒での洗浄などによる親水化で形成することもできる。 The super-hydrophilic surface is formed by performing UV irradiation on the FTO surface in the atmosphere, but also UV irradiation in different atmospheres such as in vacuum and nitrogen gas, light irradiation with different wavelengths, Alternatively, it can be formed by hydrophilization by washing with an organic solvent.
チタン含有溶液には、後記する実施例に示すフッ化チタン酸アンモニウムの他、ヘキサフルオロチタン（ＩＶ）酸ナトリウム（Ｎａ２ＴｉＦ６）、ヘキサフルオロチタン（ＩＶ）酸カリウム（Ｋ２［ＴｉＦ６］）、チタン酸ナトリウム（Ｎａ２Ｔｉ３Ｏ７）、アセチルアセトンチタニル（ＴｉＯ（ＣＨ３ＣＯＣＨＣＯＣＨ３）２）、しゅう酸チタン（ＩＶ）アンモニウム（ｎ水和物）（（ＮＨ４）２［ＴｉＯ（Ｃ２Ｏ４）２］・ｎＨ２Ｏ）、しゅう酸チタン（ＩＶ）カリウム（２水和物）（Ｋ２［ＴｉＯ（Ｃ２Ｏ４）２］・２Ｈ２Ｏ）、硫酸チタン（ＩＩＩ）（ｎ水和物）〔第一〕（Ｔｉ２（ＳＯ４）３・ｎＨ２Ｏ）、硫酸チタン（ＩＶ）（ｎ水和物）〔第二〕（Ｔｉ（ＳＯ４）２・ｎＨ２Ｏ）等によるチタン含有水溶液を用いることができる。 Examples of the titanium-containing solution include ammonium hexafluorotitanate (Na 2 TiF 6 ) and potassium hexafluorotitanium (IV) (K 2 [TiF 6 ]) in addition to ammonium fluoride titanate shown in Examples described later. ), Sodium titanate (Na 2 Ti 3 O 7 ), acetylacetone titanyl (TiO (CH 3 COCHCOCH 3 ) 2 ), titanium (IV) ammonium oxalate (n hydrate) ((NH 4 ) 2 [TiO (C 2 O 4) 2] · nH 2 O), titanium oxalate (IV) potassium (dihydrate) (K 2 [TiO (C 2 O 4) 2] · 2H 2 O), titanium sulfate (III) ( n hydrate) [first] (Ti 2 (SO 4 ) 3 · nH 2 O), titanium sulfate (IV) (n hydrate) [second] (Ti (SO 4 ) 2 · nH 2 O) Etc. It can be a titanium-containing aqueous solution.
また、酸化チタン結晶が析出する反応系であれば、有機溶液等の、非水溶液反応系も用いることができる。更に、酸化チタン結晶が析出する反応系であれば、水熱反応等も用いることができる。ホウ酸を添加せず、温度や原料濃度、ｐＨを変化させて、アナターゼＴｉＯ２結晶を析出させることもできる。 In addition, a non-aqueous solution reaction system such as an organic solution can be used as long as it is a reaction system in which titanium oxide crystals are precipitated. Furthermore, a hydrothermal reaction or the like can be used as long as the reaction system allows titanium oxide crystals to precipitate. Anatase TiO 2 crystals can also be deposited by changing the temperature, raw material concentration, and pH without adding boric acid.
反応系の温度も、原料濃度、添加剤、ｐＨ等に合わせて、水溶液の凝固点以上かつ沸点以下（およそ０−９９℃）の範囲に調整することができる。ＴｉＯ２膜の作製の際、ＦＴＯ基板以外に、シリコン、ガラス、金属、セラミックス、ポリマー等の種々の基板を用いることができる。また、平板上基板以外に、粒子基材、繊維基材、複雑形状基材等も用いることができる。 The temperature of the reaction system can also be adjusted in the range from the freezing point of the aqueous solution to the boiling point (approximately 0-99 ° C.) according to the raw material concentration, additives, pH and the like. In producing the TiO 2 film, various substrates such as silicon, glass, metal, ceramics, and polymer can be used in addition to the FTO substrate. In addition to the flat substrate, a particle base material, a fiber base material, a complex shape base material, or the like can also be used.
従来、特に、センサーや色素増感型太陽電池向け材料として、ＦＴＯ基板等の透明導電性基板や、ＩＴＯ基板、導電性ポリマー基板等へ多孔質アナターゼＴｉＯ２電極層等を形成することが求められていたが、基板上の特定部位にのみ、マイクロサイズのＴｉＯ２結晶パターンを形成することは困難であった。 Conventionally, in particular, as a material for sensors and dye-sensitized solar cells, it is required to form a porous anatase TiO 2 electrode layer on a transparent conductive substrate such as an FTO substrate, an ITO substrate, a conductive polymer substrate, or the like. However, it was difficult to form a micro-sized TiO 2 crystal pattern only at a specific site on the substrate.
これに対し、本発明では、フォトマスクを介した紫外線照射によりＦＴＯ基板表面等に形成した超親水性／疎水性パターン化表面を用いて液相反応により、該超親水性領域にアナターゼＴｉＯ２結晶パターンを選択的に析出させることによりマイクロサイズのアナターゼＴｉＯ２結晶パターンを作製することを実現したものである。 In contrast, in the present invention, an anatase TiO 2 crystal is formed in the superhydrophilic region by a liquid phase reaction using a superhydrophilic / hydrophobic patterned surface formed on the surface of the FTO substrate or the like by ultraviolet irradiation through a photomask. It is possible to produce a micro-sized anatase TiO 2 crystal pattern by selectively depositing the pattern.
本発明により、次のような効果が奏される。
（１）基板に形成した超親水性／疎水性パターン化表面の超親水性領域に選択的に析出させたアナターゼＴｉＯ２結晶パターンを提供できる。
（２）ＦＴＯ基材表面等に、超親水性処理を施すことにより、アナターゼＴｉＯ２結晶膜を形成することができ、その膜密度を上げることができる。
（３）ＦＴＯ基材表面等に、超親水性領域及び疎水性領域にパターン化された表面を形成することができる。
（４）ＦＴＯ基材表面等に形成された超親水性／疎水性領パターン化表面を用いることにより、基材上にアナターゼＴｉＯ２結晶パターンを形成することができる。
（５）疎水性有機膜の形成などにより、反応容器に疎水処理を施すことで、容器壁面へのＴｉＯ２析出を抑制することができる。
（６）ＦＴＯ基材表面等に高いアスペクト比（２以上、実施例では７．５）を具備するナノＴｉＯ２結晶を析出させることができる。
（７）また、これらのナノＴｉＯ２結晶を基板に垂直方向にｃ軸配向させることができる。
The present invention has the following effects.
(1) It is possible to provide an anatase TiO 2 crystal pattern selectively deposited on the superhydrophilic region of the superhydrophilic / hydrophobic patterned surface formed on the substrate.
(2) An anatase TiO 2 crystal film can be formed by applying a superhydrophilic treatment to the surface of the FTO substrate and the like, and the film density can be increased.
(3) A surface patterned into a superhydrophilic region and a hydrophobic region can be formed on the surface of the FTO substrate or the like.
(4) An anatase TiO 2 crystal pattern can be formed on the substrate by using a superhydrophilic / hydrophobic patterned surface formed on the surface of the FTO substrate or the like.
(5) By performing a hydrophobic treatment on the reaction vessel by forming a hydrophobic organic film or the like, it is possible to suppress TiO 2 precipitation on the vessel wall surface.
(6) A nano TiO 2 crystal having a high aspect ratio (2 or more, 7.5 in the examples) can be deposited on the surface of the FTO substrate or the like.
(7) Moreover, these nano TiO 2 crystals can be c-axis oriented in the direction perpendicular to the substrate.
次に、実施例により本発明を具体的に説明するが、本発明は、以下の実施例によって何ら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited at all by the following examples.
本実施例では、ＦＴＯ基材表面等に、超親水性領域及び疎水性領域にパターン化された表面を形成した。また、ＦＴＯ基材表面等に形成された超親水性／疎水性領パターン化表面を用いることにより、基材上にアナターゼ結晶ＴｉＯ２パターンを形成した。 In this example, a surface patterned into a superhydrophilic region and a hydrophobic region was formed on the surface of the FTO base material or the like. In addition, an anatase crystal TiO 2 pattern was formed on the substrate by using a superhydrophilic / hydrophobic patterned surface formed on the surface of the FTO substrate or the like.
ＦＴＯ基板（ＦＴＯ，ＳｎＯ２：Ｆ，Ａｓａｈｉ Ｇｌａｓｓ Ｃｏ．，Ｌｔｄ．，９．３−９．７Ω／□，２６×５０×１．１ｍｍ）に、紫外線（ＵＶ）照射を１０分間行った。ＵＶ照射には、セン特殊光源製低圧水銀ランプ（ＰＬ１６−１１０）を用いた。この光源での主となる光の波長は、１８４．９ｎｍ及び２５３．７ｎｍである。照射ランプの波長スペクトルを図１に示す。 An FTO substrate (FTO, SnO 2 : F, Asahi Glass Co., Ltd., 9.3-9.7Ω / □, 26 × 50 × 1.1 mm) was irradiated with ultraviolet rays (UV) for 10 minutes. For UV irradiation, a low-pressure mercury lamp (PL16-110) manufactured by Sen Special Light Source was used. The main wavelengths of light in this light source are 184.9 nm and 253.7 nm. The wavelength spectrum of the irradiation lamp is shown in FIG.
初期のＦＴＯ表面は、水に対する接触角９６°を示す疎水性表面であるのに対し、ＵＶ照射時間の増加に伴い、接触角は７０°（０．５分）、５４°（１分）、３０°（２分）、１４°（３分）、５°（４分）、０°（５分）と減少し、５分以上では、接触角が計測限界以下のほぼ０°の超親水性を示した。ＵＶ照射によるＦＴＯ表面の接触角変化を図２に示す。 The initial FTO surface is a hydrophobic surface with a water contact angle of 96 °, whereas with increasing UV irradiation time, the contact angle is 70 ° (0.5 minutes), 54 ° (1 minute), It decreases to 30 ° (2 minutes), 14 ° (3 minutes), 5 ° (4 minutes), and 0 ° (5 minutes). After 5 minutes, the contact angle is almost 0 ° below the measurement limit. showed that. The change in the contact angle of the FTO surface due to UV irradiation is shown in FIG.
フォトマスク（凸版印刷製、テストチャートＮｏ．１−Ｎタイプ、（Ｔｅｓｔ−ｃｈａｒｔ−Ｎｏ．１−Ｎ ｔｙｐｅ，ｑｕａｒｔｚ ｓｕｂｓｔｒａｔｅ，１．５２４ｍｍ ｔｈｉｃｋｎｅｓｓ，ｇｕａｒａｎｔｅｅｄ ｌｉｎｅ ｗｉｄｔｈ ２μｍ±０．５μｍ，Ｔｏｐｐａｎ Ｐｒｉｎｔｉｎｇ Ｃｏ．，Ｌｔｄ．））を介したＵＶ照射により表面変性を行ったＦＴＯ基板を、以下に示す水溶液に浸漬することにより、ＦＴＯ基板上にＴｉＯ２パターンを形成した。ＴｉＯ２のパターン化プロセスを図３に示す。 Photomask (manufactured by Toppan Printing, test chart No. 1-N type, (Test-chart-No. 1-N type, quartz substrate, 1.524 mm thickness, guarded line width 2 μm ± 0.5 μm, Toppan Printing Co., Ltd.) The TiO 2 pattern was formed on the FTO substrate by immersing the FTO substrate subjected to surface modification by UV irradiation via Ltd.)) in the following aqueous solution. The TiO 2 patterning process is shown in FIG.
フッ化チタン酸アンモニウム（［ＮＨ４］２ＴｉＦ６）（２．００９６ｇ）及びホウ酸（１．８６４２２ｇ）を、それぞれ５０℃の蒸留水１００ｍＬに溶解した。両水溶液を混合し、シリコンラバースポンジで覆ったＦＴＯ基板（フォトマスクを介したＵＶ照射処理を施したＦＴＯ基板）を浸漬した後、ｗａｔｅｒ ｂａｔｈを用いて５０℃で２５時間保持した。 Ammonium fluoride titanate ([NH 4 ] 2 TiF 6 ) (2.0096 g) and boric acid (1.86422 g) were dissolved in 100 mL of distilled water at 50 ° C., respectively. Both aqueous solutions were mixed, and an FTO substrate covered with a silicon rubber sponge (an FTO substrate subjected to UV irradiation treatment through a photomask) was immersed, and then kept at 50 ° C. for 25 hours using a water bath.
フッ化チタン酸アンモニウム及びホウ酸の混合溶液中での濃度は、それぞれ０．１５Ｍ、０．０５Ｍであった。この溶液条件にて、ｐＨは約３．９となった。溶液は、反応開始１０分後程度から白濁しはじめた。その後、溶液中で生成した粒子は徐々に沈降し、数時間後には溶液上部は透明になった。 The concentrations in the mixed solution of ammonium fluorotitanate and boric acid were 0.15M and 0.05M, respectively. Under this solution condition, the pH was about 3.9. The solution began to become cloudy about 10 minutes after the start of the reaction. Thereafter, the particles generated in the solution gradually settled, and the upper part of the solution became transparent after several hours.
２５時間後、シリコンラバースポンジを外し、更に２時間浸漬した。浸漬後、蒸留水で基板を洗浄し、自然乾燥させた。浸漬前のＦＴＯは、青緑色を呈していたのに対し、浸漬後の超親水性領域は、黄緑色を呈していた。また、浸漬後の疎水性領域は、浸漬前と同様に、青緑色であった。 After 25 hours, the silicone rubber sponge was removed and immersed for another 2 hours. After immersion, the substrate was washed with distilled water and allowed to air dry. The FTO before immersion exhibited a bluish green color, whereas the superhydrophilic region after immersion exhibited a yellowish green color. Moreover, the hydrophobic area | region after immersion was blue-green similarly to before immersion.
これは、ＦＴＯ上に透明なＴｉＯ２膜が形成されたため、回折される光の波長が変化したためと考えられる。浸漬後のＦＴＯ基板表面のＳＥＭ像を図４に示す。超親水性領域は、黒色であり、疎水性領域は、白色であった。図４におけるパターンの平均線幅は、５５μｍであった。 This is presumably because the wavelength of the diffracted light changed because a transparent TiO 2 film was formed on the FTO. An SEM image of the surface of the FTO substrate after immersion is shown in FIG. The super hydrophilic region was black and the hydrophobic region was white. The average line width of the pattern in FIG. 4 was 55 μm.
ラインエッジラフネスの標準偏差を見積もったところ、約２．８μｍであり、これより、約５％のラフネスと見積もることができる（２．８／５５）。これは、現在の電子デバイス形成のための基準値５％と同程度であった。最小線幅は、フォトマスクの最小線幅及び照射光波長に依存するため、高解像度フォトマスクの使用などにより、少なくとも１μｍ以下にまで改良することが可能と考えられる。 The standard deviation of the line edge roughness is estimated to be about 2.8 μm, and from this, the roughness can be estimated to be about 5% (2.8 / 55). This was comparable to the current reference value of 5% for forming electronic devices. Since the minimum line width depends on the minimum line width of the photomask and the irradiation light wavelength, it is considered that the minimum line width can be improved to at least 1 μm or less by using a high-resolution photomask.
ＵＶ照射ＦＴＯ領域に析出したＴｉＯ２、及びＵＶ非照射領域のＦＴＯ表面のＳＥＭ像を図５に示す。基板となるＦＴＯ層は、図５ｂ１，ｂ２に見られるように、ラフネスの大きな粒子膜であり、直径約１００−５００ｎｍの角張った粒子から構成されていた。また、疎水性領域（図５ｂ１，ｂ２）からは、ＴｉＯ２は、ほとんど観察されなかった。 FIG. 5 shows SEM images of TiO 2 deposited in the UV irradiation FTO region and the FTO surface in the UV non-irradiation region. As seen in FIGS. 5 b 1 and b 2, the FTO layer serving as the substrate was a particle film having a large roughness, and was composed of angular particles having a diameter of about 100 to 500 nm. In addition, TiO 2 was hardly observed from the hydrophobic regions (FIGS. 5b1 and b2).
一方、超親水性領域に沿って形成されたＴｉＯ２マイクロパターン領域（図５ａ１，ａ２）は、１０−３０ｎｍのナノ結晶の集積体により覆われていた。このナノ結晶は、異方成長したアナターゼＴｉＯ２結晶であると考えられる。ナノ結晶から構成されるナノサイズの凹凸に加え、ＴｉＯ２膜は、直径約１００−５００ｎｍからなる大きな凹凸も有していた。 On the other hand, the TiO 2 micropattern region (FIGS. 5a1 and a2) formed along the superhydrophilic region was covered with an aggregate of 10-30 nm nanocrystals. This nanocrystal is considered to be an anatase TiO 2 crystal grown anisotropically. In addition to the nano-sized irregularities composed of nanocrystals, the TiO 2 film also had large irregularities with a diameter of about 100-500 nm.
これは、角張った粒子から構成されるＦＴＯ層の上に、薄くナノＴｉＯ２層が形成されたため、ＴｉＯ２層表面がＦＴＯ基板の大きな凹凸形状を有しているためと考えられる。これらの効果により、ＴｉＯ２膜は、小さなナノ結晶からなるナノサイズの凹凸と、ＦＴＯの表面形状由来の大きな凹凸を合わせ持った、特異なハイブリッド階層凹凸構造を有していた。 This is presumably because the nano-TiO 2 layer was thinly formed on the FTO layer composed of angular particles, and thus the surface of the TiO 2 layer had a large uneven shape of the FTO substrate. Due to these effects, the TiO 2 film had a unique hybrid hierarchical concavo-convex structure having nano-sized concavo-convex composed of small nanocrystals and large concavo-convex derived from the surface shape of FTO.
ＦＴＯ上に形成したＴｉＯ２膜の断面ＳＥＭ写真を図６に示す。ガラス基板上に、表面凹凸の大きい多結晶ＦＴＯ層が約９００ｎｍ形成されていた。ＦＴＯ層のラフネスは、約１００−２００ｎｍであった。超親水性ＦＴＯ表面からは、ナノＴｉＯ２結晶が観察された。 FIG. 6 shows a cross-sectional SEM photograph of the TiO 2 film formed on the FTO. On the glass substrate, a polycrystalline FTO layer with large surface irregularities was formed with a thickness of about 900 nm. The roughness of the FTO layer was about 100-200 nm. Nano TiO 2 crystals were observed from the superhydrophilic FTO surface.
一方、疎水性ＦＴＯ表面からは、ＴｉＯ２は観察されなかった。超親水性ＦＴＯ表面は、ナノＴｉＯ２結晶のアレイで覆われており、それらは、直径約２０ｎｍ、長さ約１５０ｎｍの長い形状をしていた。これらの観察結果は、ＸＲＤやＴＥＭにおける評価と矛盾しない。 On the other hand, TiO 2 was not observed from the hydrophobic FTO surface. The superhydrophilic FTO surfaces were covered with an array of nano TiO 2 crystals, which had a long shape with a diameter of about 20 nm and a length of about 150 nm. These observation results are consistent with the evaluation in XRD and TEM.
ナノＴｉＯ２結晶は、ｃ軸方向に優先的に異方成長し、その結果、ＸＲＤやＴＥＭ観察時の電子線回折において、１０１回折線の強度に対し、００４回折強度が強くなったものと考えられる。 The nano TiO 2 crystal preferentially grows anisotropically in the c-axis direction, and as a result, it is considered that the 004 diffraction intensity is stronger than the 101 diffraction line intensity in electron diffraction during XRD or TEM observation. It is done.
このｃ軸方向への異方成長の結果、ナノＴｉＯ２結晶は、高いアスペクト比（長さ１５０ｎｍ／直径２０ｎｍ）を有する形状へと成長したものと考えられる。また、図６の断面ＳＥＭ像に見られるように、ｃ軸方向に異方成長した結晶が、ｃ軸をＦＴＯ基板に垂直に立てるように結晶成長していることも、ＸＲＤや電子線回折における強い００４の回折強度（ｃ軸配向）をもたらしたものと考えられる。 As a result of anisotropic growth in the c-axis direction, the nanoTiO 2 crystal is considered to have grown into a shape having a high aspect ratio (length 150 nm / diameter 20 nm). In addition, as seen in the cross-sectional SEM image of FIG. 6, the crystal grown anisotropically in the c-axis direction is also grown in such a manner that the c-axis is perpendicular to the FTO substrate. It is thought that the strong 004 diffraction intensity (c-axis orientation) was brought about.
ＦＴＯ基板上に形成したＴｉＯ２膜のＸＲＤ観察を行った際には、酸化スズ由来の強いＸＲＤピークによりＴｉＯ２からの回折線の評価が困難であったため、ＦＴＯコーティングなしのガラス基板上に形成したＴｉＯ２膜のＸＲＤパターンを示す（図７）。シリコンラバースポンジを用いず、混合溶液調整直後から基板を浸漬した。 When XRD observation of the TiO 2 film formed on the FTO substrate was performed, it was difficult to evaluate the diffraction line from TiO 2 due to the strong XRD peak derived from tin oxide, so it was formed on the glass substrate without FTO coating. FIG. 7 shows an XRD pattern of the obtained TiO 2 film. Without using a silicon rubber sponge, the substrate was immersed immediately after adjusting the mixed solution.
２θ＝２５．３，３７．７，４８．０，５３．９，５５．１及び６２．７°の位置に弱い回折線が観察され、アナターゼＴｉＯ２（ＩＣＳＤ Ｎｏ．９８５２）の１０１，００４，２００，１０５，２１１及び２０４回折線に帰属された。００４回折線の強度は非常に強く、高いｃ軸配向を示している。００４回折線と１０１回折線の積分強度比（積分面積比）は２．６倍、強度高さ比は２．２倍であった。 Weak diffraction lines are observed at 2θ = 25.3, 37.7, 48.0, 53.9, 55.1 and 62.7 °, and 101,004 of anatase TiO 2 (ICSD No. 9852). Assigned to the 200, 105, 211 and 204 diffraction lines. The intensity of the 004 diffraction line is very strong, indicating a high c-axis orientation. The integrated intensity ratio (integrated area ratio) of the 004 diffraction line and the 101 diffraction line was 2.6 times, and the intensity height ratio was 2.2 times.
（００４）面に垂直方向の結晶子サイズは、回折線半値幅よりシェラーの式を用いて１７ｎｍと見積もられた。また、ガラス基板由来のブロードなピークも２θ＝２５°に観察された。シリコンラバースポンジを用いず、混合溶液調整直後から、２５時間浸漬して、ＦＴＯ基板上に形成したＴｉＯ２膜のＴＥＭ写真及び電子線回折パターンを図８に示す。 The crystallite size in the direction perpendicular to the (004) plane was estimated to be 17 nm using the Scherrer equation from the half-width of the diffraction line. A broad peak derived from the glass substrate was also observed at 2θ = 25 °. FIG. 8 shows a TEM photograph and an electron beam diffraction pattern of a TiO 2 film formed on an FTO substrate by using a silicon rubber sponge without immersion for 25 hours immediately after adjusting the mixed solution.
ＦＴＯ基板上に形成したアナターゼＴｉＯ２結晶膜のＴＥＭ像及び電子線回折パターンである。（ｄ）は、（ａ）の拡大像であり、（ｅ）は（ｄ）の拡大像であり、（ｂ）は、（ａ）のＴｉＯ２領域の電子線回折像であり、（ｃ）は、（ａ）のＦＴＯ領域の電子線回折像である。 FTO is a TEM image and an electron diffraction pattern of the formed anatase TiO 2 crystal film on the substrate. (D) is an enlarged image of (a), (e) is an enlarged image of (d), (b) is an electron diffraction image of the TiO 2 region of (a), (c) These are the electron diffraction patterns of the FTO area | region of (a).
図８ａからは、ＦＴＯ層が大きなラフネスを有していること、及びその表面に、ＴｉＯ２結晶が析出していることが示されている。図８ｂからは、ＴｉＯ２層が、アナターゼＴｉＯ２単相から成ること、１０１回折線よりも００４回折線強度が強く高いｃ軸配向を有していること、及びＦＴＯ面に垂直方向に、ｃ軸が向いていることが示されている。 FIG. 8a shows that the FTO layer has a large roughness and that TiO 2 crystals are deposited on its surface. From FIG. 8b, the TiO 2 layer is composed of a single phase of anatase TiO 2 , has a c-axis orientation with a stronger 004 diffraction line intensity than the 101 diffraction line, and perpendicular to the FTO plane, c It is shown that the axis is facing.
図８ｃからは、ＦＴＯ層が、酸化スズ単相から成っていること、及び結晶方位が揃っていることが示されている。図８ｄからは、ＴｉＯ２層は、ＦＴＯ面に垂直方向に長手方向を向けた、長い結晶の集積から成っていることが示されている。 FIG. 8 c shows that the FTO layer is composed of a single phase of tin oxide and that the crystal orientation is aligned. FIG. 8d shows that the TiO 2 layer consists of an accumulation of long crystals with the longitudinal direction oriented perpendicular to the FTO plane.
また、その拡大像の図８ｅにおいては、長い結晶領域からアナターゼＴｉＯ２に帰属される格子像が観察されており、結晶がアナターゼＴｉＯ２単相であること、及びそのｃ軸がＦＴＯ面と垂直方向を向いていることが示されている。これらのＴＥＭ観察結果は、上述のＳＥＭ観察及びＸＲＤ評価結果と矛盾しない。 Also, in FIG. 8e of the enlarged image, a lattice image attributed to anatase TiO 2 is observed from a long crystal region, the crystal is anatase TiO 2 single phase, and its c-axis is perpendicular to the FTO plane. It is shown facing the direction. These TEM observation results are consistent with the above-described SEM observation and XRD evaluation results.
以上詳述したように、本発明は、超親水性／疎水性パターン化表面、アナターゼＴｉＯ２結晶パターン及びそれらの作製方法に係るものであり、本発明により、基板に形成した超親水性／疎水性パターン化表面の超親水性領域に選択的に析出させたアナターゼＴｉＯ２結晶パターンを提供できる。ＦＴＯ基材表面等に形成された超親水性／疎水性領パターン化表面を用いることにより、基材上にアナターゼＴｉＯ２結晶パターンを形成することができる。本発明は、例えば、分子センサー、ガスセンサー、溶液センサー、色素増感型太陽電池、光触媒等として好適に利用できるマイクロサイズのアナターゼＴｉＯ２結晶パターンを提供するものとして有用である。 As described above in detail, the present invention relates to a superhydrophilic / hydrophobic patterned surface, anatase TiO 2 crystal pattern, and methods for producing them, and the superhydrophilic / hydrophobic formed on a substrate according to the present invention. Anatase TiO 2 crystal pattern can be provided that is selectively deposited in the superhydrophilic region of the sex patterned surface. An anatase TiO 2 crystal pattern can be formed on a substrate by using a superhydrophilic / hydrophobic patterned surface formed on an FTO substrate surface or the like. The present invention is useful, for example, as providing a micro-sized anatase TiO 2 crystal pattern that can be suitably used as a molecular sensor, gas sensor, solution sensor, dye-sensitized solar cell, photocatalyst, and the like.
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