JP2007187785A - Dual structured self-cleaning film having anti-reflection function, structure formed with this dual structure self-cleaning film, and its manufacturing method - Google Patents
Dual structured self-cleaning film having anti-reflection function, structure formed with this dual structure self-cleaning film, and its manufacturing method Download PDFInfo
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- 238000004140 cleaning Methods 0.000 title claims abstract description 39
- 230000009977 dual effect Effects 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000002135 nanosheet Substances 0.000 claims abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 103
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 72
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 57
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 36
- 239000002356 single layer Substances 0.000 claims description 10
- 229920006317 cationic polymer Polymers 0.000 claims description 8
- 238000000151 deposition Methods 0.000 abstract description 7
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract 2
- 229920000642 polymer Polymers 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000010453 quartz Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000000411 transmission spectrum Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- UKGZHELIUYCPTO-UHFFFAOYSA-N dicesium;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Cs+].[Cs+] UKGZHELIUYCPTO-UHFFFAOYSA-N 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000004924 electrostatic deposition Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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- Surface Treatment Of Optical Elements (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
Description
本発明は、セルフクリーニング機能と反射防止機能の両方を併せ持つ二重構造セルフクリーニング膜とこの二重構造セルフクリーニング膜が形成された構造体ならびに製造方法に関する。 The present invention relates to a dual structure self-cleaning film having both a self-cleaning function and an antireflection function, a structure on which the dual structure self-cleaning film is formed, and a manufacturing method.
ＴｉＯ２の酸化分解機能と超親水性が利用され、ＴｉＯ２がコーティングされた各種製品が市販されている。この製品では、ＴｉＯ２の酸化分解機能により、紫外線（ＵＶ）照射条件下で有機汚染物を分解し、また、表面に付着した微生物を殺すことができる。さらに、ＴｉＯ２の超親水性により、表面上の水滴を急速かつ完全に拡散させることができる（たとえば、特許文献１、２）。このような機能は、一般に、セルフクリーニング機能と呼ばれている。
ＴｉＯ２のコーティングはガラスやプラスチックなどの透明基材にも簡単に適用してセルフクリーニング機能を付与することが可能であると考えられる。 It is thought that the coating of TiO 2 can be easily applied to a transparent substrate such as glass or plastic to give a self-cleaning function.
しかしながら、実際には、ＴｉＯ２の屈折率ｎは大きく（アナターゼで約２．５２、ルチルでは２．７６）、これまでに開発されたコーティング技術では透明基材の表面反射を増強させてしまう。可視光での空気−ガラス界面における反射は約４％であるが、空気−ＴｉＯ２界面における反射は２０％にも上る。太陽電池、照明器具、温室などへの応用を考慮すると、セルフクリーニング機能を持ちながらも、表面反射を低減させ、光透過率を大きくすることが望まれる。 However, in practice, the refractive index n of TiO 2 is large (about 2.52 for anatase and 2.76 for rutile), and the coating techniques developed so far enhance the surface reflection of the transparent substrate. The reflection at the air-glass interface with visible light is about 4%, but the reflection at the air-TiO 2 interface is as high as 20%. Considering application to solar cells, lighting fixtures, greenhouses, etc., it is desirable to reduce surface reflection and increase light transmittance while having a self-cleaning function.
本発明は、以上の通りの事情に鑑みてなされたものであり、セルフクリーニング機能と反射防止機能の両方を併せ持つ二重構造セルフクリーニング膜とこの二重構造セルフクリーニング膜が形成された構造体ならびに製造方法を提供することを課題としている。 The present invention has been made in view of the circumstances as described above, and has a double structure self-cleaning film having both a self-cleaning function and an antireflection function, a structure on which the double structure self-cleaning film is formed, and It is an object to provide a manufacturing method.
本発明は、上記の課題を解決するものとして、第１に、多孔性のＳｉＯ２層の上にＴｉＯ２層が形成されていることを特徴としている。 In order to solve the above problems, the present invention is characterized in that a TiO 2 layer is first formed on a porous SiO 2 layer.
本発明は、第２に、ＳｉＯ２層は二次元的に広がるＳｉＯ２粒子の単層または該単層が積層した複層から形成されていることを特徴としている。 Secondly, the present invention is characterized in that the SiO 2 layer is formed from a single layer of SiO 2 particles that spreads two-dimensionally or a multilayer in which the single layers are laminated.
本発明は、第３に、ＴｉＯ２はチタン酸ナノシートから変換されたものであることを特徴としている。 Third, the present invention is characterized in that TiO 2 is converted from titanate nanosheets.
本発明は、第４に、ＴｉＯ２層はチタン酸ナノシートの単層または複層から変換されて形成されていることを特徴としている。 Fourthly, the present invention is characterized in that the TiO 2 layer is formed by converting from a single layer or multiple layers of titanate nanosheets.
本発明は、第５に、透明基板の表面に第１ないし第４の特徴を有する反射防止機能を持つ二重構造セルフクリーニング膜が形成されていることを特徴としている。 Fifth, the present invention is characterized in that a double structure self-cleaning film having an antireflection function having the first to fourth characteristics is formed on the surface of the transparent substrate.
本発明は、第６に、カチオンポリマーを介在させ、透明基板上にＳｉＯ２粒子、チタン酸ナノシートを静電気力により順次沈着させ、ＴｉＯ２が生成する温度で焼成し、カチオンポリマーを除去するとともにチタン酸ナノシートをＴｉＯ２に変換し、透明基板の表面にＳｉＯ２層を形成させ、かつＳｉＯ２層の上にＴｉＯ２層を形成させることを特徴としている。 Sixth, the present invention includes a cationic polymer interposed, SiO 2 particles and titanic acid nanosheets are sequentially deposited on a transparent substrate by electrostatic force, and baked at a temperature at which TiO 2 is generated to remove the cationic polymer and titanium. It is characterized in that the acid nanosheet is converted to TiO 2 , a SiO 2 layer is formed on the surface of the transparent substrate, and a TiO 2 layer is formed on the SiO 2 layer.
本発明は、第７に、カチオンポリマーを介在させ、透明基板上にＳｉＯ２粒子、チタン酸ナノシートを静電気力により順次沈着させ、ＴｉＯ２が生成する温度で焼成し、カチオンポリマーを除去するとともにチタン酸ナノシートをＴｉＯ２に変換し、透明基板の表面にＳｉＯ２層を形成させ、かつＳｉＯ２層の上にＴｉＯ２層を形成させた後、透明基板を除去することを特徴としている。 Seventh, the present invention includes a cationic polymer, SiO 2 particles and titanate nanosheets are sequentially deposited on a transparent substrate by electrostatic force, and baked at a temperature at which TiO 2 is generated to remove the cationic polymer and titanium. The acid nanosheet is converted to TiO 2 , a SiO 2 layer is formed on the surface of the transparent substrate, and after forming the TiO 2 layer on the SiO 2 layer, the transparent substrate is removed.
本発明によれば、上層のＴｉＯ２層によりセルフクリーニング機能を保持しつつ、下層の多孔性ＳｉＯ２層によって反射防止機能を発現させ、表面反射を低減させることができる。反射防止機能を持つ二重構造セルフクリーニング膜が実現され、この二重構造セルフクリーニング膜は、ガラス、プラスチックなどの透明基材の表面にコーティングすることができ、このようにして反射防止機能を持つ二重構造セルフクリーニング膜が形成された構造体は、太陽電池、照明器具、温室などに応用可能となる。反射防止機能を持つ二重構造セルフクリーニング膜および構造体は、二重構造セルフクリーニング膜を構成する各層を静電気引力によって沈着させることにより容易に製造することができる。また、各層の厚みを精度よく制御することができる。 According to the present invention, while maintaining the self-cleaning function by the upper TiO 2 layer, the antireflection function can be exhibited by the lower porous SiO 2 layer and the surface reflection can be reduced. A double-structure self-cleaning film with anti-reflection function is realized, and this double-structure self-cleaning film can be coated on the surface of transparent substrates such as glass and plastic, thus having anti-reflection function The structure in which the double structure self-cleaning film is formed can be applied to solar cells, lighting fixtures, greenhouses, and the like. The double structure self-cleaning film and structure having an antireflection function can be easily manufactured by depositing each layer constituting the double structure self-cleaning film by electrostatic attraction. Moreover, the thickness of each layer can be controlled with high accuracy.
以下、実施例を示し、本発明の反射防止機能を持つ二重構造セルフコーティング膜とこの二重構造セルフコーティング膜が形成された構造体ならびに製造方法を詳しく説明する。 Hereinafter, the double structure self-coating film having an antireflection function according to the present invention, the structure on which the double structure self-coating film is formed, and the manufacturing method will be described in detail.
（材料の調製）
直鎖状四級アンモニウムポリカチオンであるPoly(diallyldimethyl ammonium)（ＰＤＤＡ）には市販品（Aldrich、409022、中程度ＭＷ）を使用し、２ｍｇ ｍＬ−１の濃度でそれ以上精製せず、０．１ｍｏｌ Ｌ−１のアンモニウム水を用いてｐＨを９．０に調整した。ＳｉＯ２コロイド水溶液（平均直径：１７ｎｍ；Cataloid SI-40；Catalyst Chemical Co., Japan）を脱イオン水で希釈し、１ｍｇ ｍＬ−１（ｐＨ約９）の濃度にした。脱イオン水には比抵抗が約１８ＭΩｃｍのものを用いた。
(Preparation of materials)
A commercially available product (Aldrich, 409022, medium MW) is used for poly (diallyldimethyl ammonium) (PDDA), which is a linear quaternary ammonium polycation, and it is not further purified at a concentration of 2 mg mL −1 . The pH was adjusted to 9.0 using 1 mol L −1 ammonium water. An aqueous SiO 2 colloid solution (average diameter: 17 nm; Cataloid SI-40; Catalyst Chemical Co., Japan) was diluted with deionized water to a concentration of 1 mg mL −1 (pH about 9). Deionized water having a specific resistance of about 18 MΩcm was used.
チタン酸ナノシートコロイド水溶液はSasakiの方法により０．０８ｇ Ｌ−１（ｐＨ約９）の濃度に調整した。Ｃｓ２ＣＯ３とＴｉＯ２の化学両論組成の混合物を８００℃で２０時間焼成し、セシウム・チタネート前駆体を作製する。得られたセシウム・チタネート前駆体の７０ｇを１ｍｏｌ ｄｍ−３のＨＣｌ溶液２ｄｍ３により室温で処理する。この酸処理を２４時間毎に新しい酸溶液で３度行う。得られた酸置換物を濾過、水洗浄、そして大気中で乾燥させる。得られたプロトン・チタネートを、０．００１７ｍｏｌ ｄｍ−３のテトラブチルアンモニウム水酸化物溶液を用いて室温で１０日間勢いよく振る。乳白色のコロイド状のサスペンションを得る。サスペンションは単一層の結晶を含む。
（二重構造膜および構造体の作製）
ＳｉＯ２粒子とチタン酸ナノシートはいずれも負に帯電している。一方、ＰＤＤＡ分子は正に帯電している。したがって、図１の模式図に示したように、交互に静電沈着を行うことによって、ガラスや石英などの透明基板上にＳｉＯ２粒子層およびチタン酸ナノシートを形成することができる。チタン酸ナノシートは５００℃で焼成すると、アナターゼ型のＴｉＯ２に変換し、多孔性のＳｉＯ２層上に高密度なＴｉＯ２層が形成する。
The aqueous colloidal titanate sheet was adjusted to a concentration of 0.08 g L −1 (pH about 9) by the method of Sasaki. A mixture of the stoichiometric composition of Cs 2 CO 3 and TiO 2 is calcined at 800 ° C. for 20 hours to prepare a cesium titanate precursor. The 70g of the resulting cesium titanate precursor at room temperature with HCl solution 2 dm 3 of 1 mol dm -3. This acid treatment is performed three times with a fresh acid solution every 24 hours. The resulting acid substitute is filtered, washed with water, and dried in air. The obtained proton titanate is vigorously shaken at room temperature for 10 days using a 0.0017 mol dm −3 tetrabutylammonium hydroxide solution. A milky white colloidal suspension is obtained. The suspension includes a single layer of crystals.
(Production of double structure film and structure)
Both the SiO 2 particles and the titanate nanosheet are negatively charged. On the other hand, PDDA molecules are positively charged. Therefore, as shown in the schematic diagram of FIG. 1, by alternately performing electrostatic deposition, a SiO 2 particle layer and a titanate nanosheet can be formed on a transparent substrate such as glass or quartz. When the titanate nanosheet is fired at 500 ° C., it is converted into anatase TiO 2 , and a high-density TiO 2 layer is formed on the porous SiO 2 layer.
ガラスならびに石英基板を濃縮Ｈ２ＳＯ４/Ｈ２Ｏ２（７：３ｖ/ｖ）溶液で洗浄した後、脱イオン水で洗った。洗浄した基板をＰＤＤＡ溶液、ＳｉＯ２コロイド溶液中に交互に５分間ずつ浸漬した。各溶液に浸漬する前には基板を水で洗浄した。 The glass and quartz substrate were washed with a concentrated H 2 SO 4 / H 2 O 2 (7: 3 v / v) solution and then with deionized water. The cleaned substrate was alternately immersed for 5 minutes in PDDA solution and SiO 2 colloid solution. Prior to immersion in each solution, the substrate was washed with water.
複層（ＰＤＤＡ/ＳｉＯ２）６（６回にわたり交互に浸漬したもの）を基板上に作製した。次いで、基板をＰＤＤＡ溶液ならびにチタン酸ナノシートコロイド溶液中に交互に浸漬した。この後、５００℃で１時間焼成してＰＤＤＡを除去し、チタン酸ナノシートをアナターゼ型のＴｉＯ２に変換した。
（セルフクリーニング機能）
焼成して得たＴｉＯ２−ＳｉＯ２二重構造膜の表面を、オクタドデシルリン酸（ＯＤＰ）を用いて修飾した。オクタドデシルリン酸は和光純薬工業（株）より購入し、ヘプタンとイソプロパノール（１０００：５ｖ/ｖ）（いずれも和光純薬工業（株）より購入、精製なし）の混合溶媒に溶解して１ｍＭのＯＤＰ溶液とした。このＯＤＰ溶液にＴｉＯ２−ＳｉＯ２二重構造膜が形成したガラス基板を７２分以上浸漬した。次いで、ＯＤＰ溶液からガラス基板を取り出し、イソプロパノールで洗浄した。ＯＤＰ分子はＴｉＯ２層の表面に緻密な単層を形成する。ＯＤＰ分子の吸着後、ＴｉＯ２層の表面の水接触角は１００°以上に増加した。表面は疎水性となった。
A multi-layer (PDDA / SiO 2 ) 6 (6 times alternately immersed) was produced on the substrate. Then, the substrate was alternately immersed in the PDDA solution and the titanate nanosheet colloid solution. Thereafter, the PDDA was removed by baking at 500 ° C. for 1 hour, and the titanate nanosheet was converted to anatase-type TiO 2 .
(Self-cleaning function)
The surface of the TiO 2 —SiO 2 double structure film obtained by firing was modified with octadodecyl phosphate (ODP). Octadodecyl phosphate is purchased from Wako Pure Chemical Industries, Ltd. and dissolved in a mixed solvent of heptane and isopropanol (1000: 5 v / v) (both purchased from Wako Pure Chemical Industries, Ltd., no purification) to give 1 mM. ODP solution. The glass substrate on which the TiO 2 —SiO 2 double structure film was formed was immersed in this ODP solution for 72 minutes or more. Subsequently, the glass substrate was taken out from the ODP solution and washed with isopropanol. ODP molecules form a dense monolayer on the surface of the TiO 2 layer. After adsorption of ODP molecules, the water contact angle on the surface of the TiO 2 layer increased to 100 ° or more. The surface became hydrophobic.
ガラス基板をＵＶ−Ａ帯の紫外光を放出するＵＶ光照射条件下（林時計工業（株）製 UV-310）に配置した。ＵＶ照射中に１０カ所の異なる位置で水の接触角を測定し、ＴｉＯ２−ＳｉＯ２二重構造膜のセルフクリーニング機能を評価した。ガラス基板表面に照射した光の強度は２．６ｍＷ ｃｍ−２とした（浜松ホトニクス（株）製の電力計を用いて測定）。日光のＵＶ成分の範囲内である。接触角の測定は、固着モード、室温で接触角測定計（協和界面科学（株）製CA-X）を用いて行い、市販のＦＭＡＳソフトウェアで分析した。従来の静的な接触角測定に加えて、液滴が表面に広がる途中の一時的な接触角を測定することもできる。また、ＯＤＰ単層の分解について、日本分光（株）製のFTIR分光計により赤外線（ＩＲ）スペクトルを用いて調べた。
（その他の測定）
ＴｉＯ２−ＳｉＯ２二重構造膜の透過スペクトルを、（株）島津製作所製の分光計を用いて垂直入射で測定した。ＴｉＯ２−ＳｉＯ２二重構造膜の表面形態と断面を、（株）日立製作所製のS4500走査型電子顕微鏡（ＳＥＭ）を用いて調べた。ＳＥＭ測定は、試料に市販のスパッタリング装置を用いてプラチナをコーティングしてから行った。ＴｉＯ２−ＳｉＯ２二重構造膜の屈折率および各層の厚みを偏光解析装置（J.A.Woollam Co., Inc. M-2000U）を用いて測定した。
（結果）
アルカリ性媒体の中ではガラスや石英などの基材は負に帯電している。したがって、静電沈着によりＳｉＯ２およびチタン酸ナノシートの複層を基板上に沈着させることが可能であった。ＳｉＯ２ナノ粒子が沈着している証拠は表面反射の減少により得られる。６サイクルの沈着により基材の表面反射が非常に弱くなり、淡黄色を示した。
The glass substrate was placed under UV light irradiation conditions (UV-310 manufactured by Hayashi Watch Industry Co., Ltd.) that emits UV light in the UV-A band. The contact angle of water was measured at 10 different positions during UV irradiation, and the self-cleaning function of the TiO 2 —SiO 2 double structure film was evaluated. The intensity of light applied to the glass substrate surface was 2.6 mW cm −2 (measured using a wattmeter manufactured by Hamamatsu Photonics Co., Ltd.). Within the UV component of sunlight. The contact angle was measured using a contact angle meter (CA-X, manufactured by Kyowa Interface Science Co., Ltd.) in the fixing mode and at room temperature, and analyzed with commercially available FMAS software. In addition to the conventional static contact angle measurement, it is also possible to measure a temporary contact angle while the droplet is spreading on the surface. Further, the decomposition of the ODP monolayer was examined using an infrared (IR) spectrum with an FTIR spectrometer manufactured by JASCO Corporation.
(Other measurements)
The transmission spectrum of the TiO 2 —SiO 2 double structure film was measured at normal incidence using a spectrometer manufactured by Shimadzu Corporation. The surface morphology and cross section of the TiO 2 —SiO 2 double structure film were examined using an S4500 scanning electron microscope (SEM) manufactured by Hitachi, Ltd. The SEM measurement was performed after coating the sample with platinum using a commercially available sputtering apparatus. The refractive index and the thickness of each layer of the TiO 2 —SiO 2 double structure film were measured using an ellipsometer (JAWoollam Co., Inc. M-2000U).
(result)
In alkaline media, substrates such as glass and quartz are negatively charged. Therefore, it was possible to deposit a multilayer of SiO 2 and titanate nanosheet on the substrate by electrostatic deposition. Evidence that SiO 2 nanoparticles are deposited is obtained by a decrease in surface reflection. After 6 cycles of deposition, the surface reflection of the substrate was very weak and light yellow.
一方、チタン酸ナノシートには２６０ｎｍを中心とする特徴的な吸収帯が存在する。図２に示したように、チタン酸ナノシートを一層ずつ沈着させる過程で２６０ｎｍの吸収はほぼ線形に増加した。このことは、チタン酸ナノシートが均一に積層していることを示している。チタン酸ナノシートの沈着時間が増えるにつれて基板の表面反射が徐々に増加し、表面反射の色は、淡黄色から暗い黄色（３層ナノシート）、ピンク（６層ナノシート）、青（９層ナノシート）に変化した。１２層ナノシートでは反射防止機能は実現されなかった。 On the other hand, the titanate nanosheet has a characteristic absorption band centered at 260 nm. As shown in FIG. 2, the absorption at 260 nm increased almost linearly in the process of depositing the titanate nanosheets one by one. This indicates that the titanate nanosheets are uniformly laminated. As the deposition time of titanate nanosheets increases, the surface reflection of the substrate gradually increases, and the color of the surface reflection changes from light yellow to dark yellow (3-layer nanosheet), pink (6-layer nanosheet), and blue (9-layer nanosheet) changed. The antireflection function was not realized with the 12-layer nanosheet.
図３に、６層ＳｉＯ２コーティング石英、３層チタン酸ナノシート/６層ＳｉＯ２コーティング石英、６層チタン酸ナノシート/６層ＳｉＯ２コーティング石英および９層チタン酸ナノシート/６層ＳｉＯ２コーティング石英の５００℃焼成後の透過スペクトルを示した。リファレンスとして、２５０ｎｍ−８００ｎｍ範囲の石英の透過スペクトルも示した。 FIG. 3 shows six layers of SiO 2 coated quartz, three layers of titanate nanosheets / 6 layers of SiO 2 coated quartz, six layers of titanate nanosheets / 6 layers of SiO 2 coated quartz, and nine layers of titanate nanosheets / 6 layers of SiO 2 coated quartz. The transmission spectrum after baking at 500 ° C. is shown. As a reference, the transmission spectrum of quartz in the range of 250 nm to 800 nm is also shown.
２８０ｎｍでは、６層ＳｉＯ２コーティング石英が９９．９％を超える最大の透過性を示した。３９０ｎｍでは、３層ナノシート/６層ＳｉＯ２二重構造が９９．４％を超える最大の透過性を示した。４８５ｎｍでは、６層ナノシート/６層ＳｉＯ２二重構造が９８．５％を超える最大の透過性を示した。５８５ｎｍでは、９層ナノシート/６層ＳｉＯ２二重構造が９７．６％を超える最大の透過性を示した。全ての試料は４００−８００ｎｍの範囲で石英基板を超える透過性を示しており、反射防止機能を裏付けている。 At 280 nm, the 6-layer SiO 2 coated quartz showed the maximum permeability exceeding 99.9%. At 390 nm, the three-layer nanosheet / 6-layer SiO 2 double structure showed the maximum permeability exceeding 99.4%. At 485 nm, the 6-layer nanosheet / 6-layer SiO 2 double structure showed the maximum permeability exceeding 98.5%. At 585 nm, the 9-layer nanosheet / 6-layer SiO 2 double structure showed the maximum permeability exceeding 97.6%. All the samples show a transmissivity exceeding the quartz substrate in the range of 400 to 800 nm, which supports the antireflection function.
図４に、上記の内の３種類のＴｉＯ２−ＳｉＯ２二重構造膜の吸収スペクトルを示した。リファレンスとしてチタン酸ナノシートコロイド水溶液の吸収スペクトルを併せて示した。 FIG. 4 shows absorption spectra of three types of the above-described TiO 2 —SiO 2 double structure films. The absorption spectrum of the aqueous solution of titanate nanosheet colloid is also shown as a reference.
全ての二重構造膜が示す吸収特性はチタン酸ナノシートと異なっているが、ＴｉＯ２の特性に類似しており、５００℃での焼成途中でチタン酸からＴｉＯ２へと相変化が生じたことが確認される。３種類の二重構造膜のバンドギャップを計算すると、３層ナノシート試料では３．５９ｅＶ、６層ナノシート試料では３．４３ｅＶ、９層ナノシート試料では３．３２ｅＶとなった。これらのバンドギャップ値はチタン酸ナノシートの値３．９ｅＶよりかなり小さいが、それでもバルク状態のアナターゼのバンドギャップ値３．２ｅＶよりは大きくなっており、ＴｉＯ２超薄層による２次元量子閉じ込め効果がその原因ではないかと考えられた。 Although the absorption characteristics shown all the dual structure film is different from the titanate nanosheet, that are similar to the properties of TiO 2, firing middle phase change from titanate to TiO 2 at 500 ° C. resulted Is confirmed. When the band gaps of the three types of double structure films were calculated, it was 3.59 eV for the 3-layer nanosheet sample, 3.43 eV for the 6-layer nanosheet sample, and 3.32 eV for the 9-layer nanosheet sample. Although these band gap values are considerably smaller than the value of 3.9 eV for titanate nanosheets, they are still larger than the band gap value of 3.2 eV for bulk anatase, and the two-dimensional quantum confinement effect by the TiO 2 ultrathin layer is It was thought to be the cause.
偏光解析装置を用いた５００℃焼成後の複層ナノシートの厚み測定の結果、３層、６層、９層のナノシートの厚みは、それぞれ、２．２ｎｍ、４．３ｎｍ、６．５ｎｍであり、ナノシート１層の厚みの平均は０．７２ｎｍであった。このデータは２００２年のSasaki et al.による報告と一致している。６３３ｎｍでの屈折率は、３層ナノシートで１．８０、６層ナノシートで２．０４、９層ナノシートで２．０７であった。屈折率がアナターゼ（屈折率：２．５２）と比較して小さい理由は、おそらく超薄層に起因していると考えられる。 As a result of measuring the thickness of the multilayer nanosheet after baking at 500 ° C. using an ellipsometer, the thicknesses of the nanosheets of 3 layers, 6 layers, and 9 layers are 2.2 nm, 4.3 nm, and 6.5 nm, respectively. The average thickness of one nanosheet layer was 0.72 nm. This data is consistent with a 2002 report by Sasaki et al. The refractive index at 633 nm was 1.80 for the 3-layer nanosheet, 2.04 for the 6-layer nanosheet, and 2.07 for the 9-layer nanosheet. The reason why the refractive index is small compared to anatase (refractive index: 2.52) is probably due to the ultrathin layer.
同様に、偏光解析装置による６層ＳｉＯ２の厚みの測定値は５５ｎｍであった。６層ＳｉＯ２の６３３ｎｍにおける屈折率測定値は１．２６であったが、この値は、純粋なＳｉＯ２（屈折率：１．４６）に比べ大幅に減少しており、ＳｉＯ２層が多孔性であることを裏付けている。 Similarly, the measured value of the thickness of the 6-layer SiO 2 by the ellipsometer was 55 nm. The refractive index measured at 633 nm of the 6-layer SiO 2 was 1.26, but this value was significantly reduced compared to pure SiO 2 (refractive index: 1.46), and the SiO 2 layer was porous. It confirms that it is sex.
図５に、いくつかの試料の電子顕微鏡写真を示した。上の２枚は厚さ５５ｎｍのＳｉＯ２層、中央の２枚は厚さ４．３ｎｍのＴｉＯ２層/厚さ５５ｎｍのＳｉＯ２層、下の２枚の内左側は、厚さ２．２ｎｍのＴｉＯ２層/厚さ５５ｎｍのＳｉＯ２層、右側は厚さ６．５ｎｍのＴｉＯ２層/厚さ５５ｎｍのＳｉＯ２層をそれぞれ示している。 FIG. 5 shows electron micrographs of some samples. The upper two sheets are 55 nm thick SiO 2 layers, the middle two sheets are 4.3 nm thick TiO 2 layers / 55 nm thick SiO 2 layers, and the lower two sheets are 2.2 nm thick TiO 2 layer / 55 nm thick SiO 2 layer, and the right side shows a 6.5 nm thick TiO 2 layer / 55 nm thick SiO 2 layer.
ＳｉＯ２層は多孔性が大きく、屈折率が低いことに対応している。チタン酸ナノシートを沈着させることにより、多孔性ＳｉＯ２層を覆う表面薄層が生じる。チタン酸ナノシート層の多孔性ＳｉＯ２層上におけるコーティング度は沈着回数が増えるに伴い増大し、９層ナノシートはほぼ完全に多孔性ＳｉＯ２層をコーティングした。断面の顕微鏡写真よりＴｉＯ２の高密度層が多孔性ＳｉＯ２層の上に形成しているのが明確に確認される。 The SiO 2 layer corresponds to the large porosity and low refractive index. By depositing the titanate nanosheet, a thin surface layer covering the porous SiO 2 layer is generated. The degree of coating of the titanate nanosheet layer on the porous SiO 2 layer increased as the number of depositions increased, and the 9-layer nanosheet almost completely coated the porous SiO 2 layer. It is clearly confirmed from the micrograph of the cross section that a high-density layer of TiO 2 is formed on the porous SiO 2 layer.
セルフクリーニング機能の結果については図６に示した通りである。全てのＴｉＯ２−ＳｉＯ２二重構造膜において、ＵＶ照射により水接触角が著しく減少している。また、接触角の減少速度はＴｉＯ２層の厚みに依存することが確認された。３種類の試料の内で最も速い水接触角の減少が観察されたのは、６．５ｎｍＴｉＯ２/５５ｎｍＳｉＯ２二重構造膜（△）であった。水接触角が３．５時間で１０７°から約０°に減少した。２．１ｎｍＴｉＯ２/５５ｎｍＳｉＯ２二重構造膜（■）は、水接触角の減少が最も遅く、接触角が１１５°から約０°に減少するまでに６時間を要した。４．３ｎｍＴｉＯ２/５５ｎｍＳｉＯ２二重構造膜（●）は両者の中間である。 The result of the self-cleaning function is as shown in FIG. In all TiO 2 —SiO 2 double structure films, the water contact angle is significantly reduced by UV irradiation. Moreover, it was confirmed that the decreasing rate of the contact angle depends on the thickness of the TiO 2 layer. Three of reduction of the fastest water contact angle of the sample was observed, was 6.5nmTiO 2 / 55nmSiO 2 double structure layer (△). The water contact angle decreased from 107 ° to about 0 ° in 3.5 hours. 2.1nmTiO 2 / 55nmSiO 2 double structure film (■), the reduction in water contact angle slowest, the contact angle is over 6 hours to decrease from 115 ° to approximately 0 °. 4.3nmTiO 2 / 55nmSiO 2 double structure film (●) is an intermediate between them.
ＵＶ照射中のＩＲスペクトルは図７に示した通りである。図７は、６．５ｎｍＴｉＯ２/５５ｎｍＳｉＯ２二重構造膜についてのＩＲスペクトルである。２９１９ｃｍ−１ならびに２８５０ｃｍ−１に現れるメチレン基のＩＲ吸収は、ＵＶの照射にともなって次第に減少した。３時間後、シグナルはほぼ消失した。接触角測定の結果が追認された。ＴｉＯ２−ＳｉＯ２二重構造膜はセルフクリーニング機能を持つ。ＯＤＰ単層の分解後、二重構造膜の接触角は０°近くになったが、これはＴｉＯ２層の超親水性によるものである。 The IR spectrum during UV irradiation is as shown in FIG. Figure 7 is an IR spectrum for 6.5nmTiO 2 / 55nmSiO 2 double structure film. The IR absorption of the methylene group appearing at 2919 cm −1 and 2850 cm −1 gradually decreased with UV irradiation. After 3 hours, the signal almost disappeared. The result of contact angle measurement was confirmed. The TiO 2 —SiO 2 double structure film has a self-cleaning function. After the decomposition of the ODP single layer, the contact angle of the double structure film became close to 0 °, which is due to the superhydrophilicity of the TiO 2 layer.
以上の通り、静電引力法により作製したＴｉＯ２−ＳｉＯ２二重構造膜は、反射防止機能とともにセルフクリーニング機能を併せ持つ。反射防止機能は多孔性のＳｉＯ２層により実現され、セルフクリーニング機能は、多孔性ＳｉＯ２層の上に形成されたＴｉＯ２層により発現する。ＴｉＯ２層の屈折率は比較的大きいが、ＴｉＯ２−ＳｉＯ２二重構造のコーティングによってガラスまたは石英基板の最大透過率が９７％を超える程度まで改善する。反射防止機能とセルフクリーニング機能は、形成するＴｉＯ２層とＳｉＯ２層の相対的な厚みを調節することによって最適化することが可能である。ＴｉＯ２層とＳｉＯ２層の相対的な厚みの調節は、静電気力法により容易に可能である。 As described above, the TiO 2 —SiO 2 double structure film produced by the electrostatic attraction method has a self-cleaning function as well as an antireflection function. Antireflection function is realized by a porous SiO 2 layer, a self-cleaning function is expressed by the TiO 2 layer formed on the porous SiO 2 layer. Although the refractive index of the TiO 2 layer is relatively large, the maximum transmittance of the glass or quartz substrate is improved to over 97% by the coating of the TiO 2 —SiO 2 double structure. The antireflection function and the self-cleaning function can be optimized by adjusting the relative thicknesses of the TiO 2 layer and the SiO 2 layer to be formed. The relative thickness of the TiO 2 layer and the SiO 2 layer can be easily adjusted by an electrostatic force method.
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| WO2011004992A1 (en) * | 2009-07-10 | 2011-01-13 | Korea University Research And Business Foundation | Self-cleaning surfaces |
| JP2013218651A (en) * | 2012-04-06 | 2013-10-24 | Hotoku Technology Co Ltd | Optical dustproof mouse |
| US10732325B2 (en) | 2015-09-29 | 2020-08-04 | Fujifilm Corporation | Hydrophilic multilayer film and method for producing same, and imaging system |
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| JP2002265223A (en) * | 2001-03-12 | 2002-09-18 | National Institute For Materials Science | Titania ultrathin film and producing method therefor |
| JP2002361767A (en) * | 2001-04-06 | 2002-12-18 | Dainippon Printing Co Ltd | Fine particle layer laminated film and optically functional material using the same |
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| JP2001009295A (en) * | 1999-04-28 | 2001-01-16 | Toshiba Lighting & Technology Corp | Photocatalyst body, lamp and lighting fixture |
| JP2002265223A (en) * | 2001-03-12 | 2002-09-18 | National Institute For Materials Science | Titania ultrathin film and producing method therefor |
| JP2002361767A (en) * | 2001-04-06 | 2002-12-18 | Dainippon Printing Co Ltd | Fine particle layer laminated film and optically functional material using the same |
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| WO2011004992A1 (en) * | 2009-07-10 | 2011-01-13 | Korea University Research And Business Foundation | Self-cleaning surfaces |
| JP2012530028A (en) * | 2009-07-10 | 2012-11-29 | コリア・ユニバーシティ・リサーチ・アンド・ビジネス・ファウンデーション | Self-cleaning surface |
| JP2013218651A (en) * | 2012-04-06 | 2013-10-24 | Hotoku Technology Co Ltd | Optical dustproof mouse |
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