JP2001233615A - MESO-POROUS TiO2 THIN MEMBRANE HAVING THREE-DIMENSIONAL STRUCTURE AND METHOD FOR PRODUCING THE SAME - Google Patents
MESO-POROUS TiO2 THIN MEMBRANE HAVING THREE-DIMENSIONAL STRUCTURE AND METHOD FOR PRODUCING THE SAMEInfo
- Publication number
- JP2001233615A JP2001233615A JP2000043325A JP2000043325A JP2001233615A JP 2001233615 A JP2001233615 A JP 2001233615A JP 2000043325 A JP2000043325 A JP 2000043325A JP 2000043325 A JP2000043325 A JP 2000043325A JP 2001233615 A JP2001233615 A JP 2001233615A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- tio
- substrate
- dimensional structure
- mesoporous tio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000012528 membrane Substances 0.000 title abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 229920001400 block copolymer Polymers 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- DMKKMGYBLFUGTO-UHFFFAOYSA-N 2-methyloxirane;oxirane Chemical compound C1CO1.C1CO1.CC1CO1 DMKKMGYBLFUGTO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 63
- 239000010409 thin film Substances 0.000 claims description 60
- 239000000463 material Substances 0.000 claims description 19
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 9
- 239000011941 photocatalyst Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 230000008016 vaporization Effects 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000010936 titanium Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- PXDRFTPXHTVDFR-UHFFFAOYSA-N propane;titanium(4+) Chemical compound [Ti+4].C[CH-]C.C[CH-]C.C[CH-]C.C[CH-]C PXDRFTPXHTVDFR-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 239000013081 microcrystal Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は規則正しく整列した三次
元構造を有するメソポーラスTiO2薄膜、及びその製造
方、さらにはそれを用いたエネルギー変換素子、光触媒
材料、有害ガスを吸着し、光で分解する浄化材料に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mesoporous TiO 2 thin film having a regularly arranged three-dimensional structure, a method of manufacturing the same, and an energy conversion element, a photocatalytic material, and a harmful gas using the thin film, which are adsorbed and decomposed by light. Purifying material.
【０００２】[0002]
【従来の方法】酸化チタンTiO2においては、バンドギャ
ップ以上のエネルギーを有する光を照射すると、励起さ
れて電子と正孔を発生し、表面に吸着している物質が電
子授受により酸化分離される。これを利用した光触媒技
術或は浄化技術の研究が盛んに行われている。環境の改
善を目的として、自動車による排気ガス、工場からの汚
水や有毒ガス、家庭内においてタバコの煙りや壁に付着
する臭いなどの浄化要求は日増し大きくなっている。こ
の目的のためにTiO2薄膜を形成させる方法が沢山提案さ
れているが、実用的な材料となりうるTiO2薄膜は比表面
積が大きく、且つ微結晶が含んでいるメソポーラスTiO2
薄膜が要求されている。TiO2微粒子を利用した多孔質の
場合には、ポーラス細孔のサイズと構造の整列が制御さ
れていない。表面活性剤を鋳型としてMCM41（ヘキサゴ
ナル）とMCM48（キュービック）のメソポーラスシリカ
（SiO2）薄膜の合成が成功されているから、同じの方法
を用いて三次元構造を有するメソポーラスTiO2薄膜の合
成が注目されているが、成功されている例がほとんどな
い。その代わりに、メソポーラスシリカ（SiO2）材料の
細孔の内側表面にチタンで修飾したチタンシリケート材
料が研究されているが、微結晶のTiO2ができないので、
光触媒の活性が低いので、実用段階に入れない。最近、
表面活性剤の代わりにブロックコポリマーが鋳型として
ヘキサゴナルとキュービック構造を持つメソポーラスシ
リカ（SiO2）粉末と薄膜の合成を成功された。また、ブ
ロックコポリマーが鋳型として、塩化チタンからヘキサ
ゴナル構造を持つTiO2粉末の合成も成功したが、三次元
構造を有するメソポーラスTiO2薄膜はまだ成功していな
い。 2. Description of the Related Art Titanium oxide TiO 2 is excited by irradiation with light having energy greater than the band gap to generate electrons and holes, and the substance adsorbed on the surface is oxidized and separated by electron transfer. . Research on photocatalytic technology or purification technology utilizing this is being actively conducted. With the aim of improving the environment, the demand for purification of exhaust gas from automobiles, sewage and toxic gas from factories, smoke from cigarettes in homes and odor adhering to walls is increasing day by day. A method of forming a TiO 2 thin film for this purpose have been many proposals, practical and TiO 2 thin film which may be have a large specific surface area material, mesoporous TiO 2 containing the and microcrystalline
Thin films are required. In the case of a porous material using TiO 2 fine particles, the alignment of the size and structure of the porous pores is not controlled. MCM41 (hexagonal) and MCM48 (cubic) mesoporous silica (SiO 2 ) thin films have been successfully synthesized using a surfactant as a template, so the same method can be used to synthesize mesoporous TiO 2 thin films having a three-dimensional structure. Attention has been paid, but few have been successful. Instead, a titanium silicate material modified with titanium on the inner surface of the pores of mesoporous silica (SiO 2 ) material has been studied, but since microcrystalline TiO 2 cannot be formed,
Since the activity of the photocatalyst is low, it cannot be put into practical use. Recently,
Instead of surfactants, block copolymers were used as templates to successfully synthesize mesoporous silica (SiO 2 ) powders and thin films with hexagonal and cubic structures. In addition, although TiO 2 powder having a hexagonal structure has been successfully synthesized from titanium chloride using a block copolymer as a template, a mesoporous TiO 2 thin film having a three-dimensional structure has not been successful yet.
【０００３】[0003]
【発明が解決しようとする課題】本発明で解決しようと
する課題は、（１）高い比表面積を有する三次元構造を
持つメソポーラスTiO2薄膜を製造すること、（２）ポー
ラス構造のフレームワークの中にアナタゼ及び又はルチ
ルのTiO2微結晶を有すること（３）その製造プロセスを
簡単化すること、（４）その材料を用いてエネルギー変
換素子、光触媒、浄化材料の作製を図ることである。材
料の形態は薄膜であることが望ましい。また、その膜を
担持する基板の素材についても、多種多様な素材に適用
できることが望ましい。The problem to be solved by the present invention is to (1) manufacture a mesoporous TiO 2 thin film having a three-dimensional structure having a high specific surface area, and (2) to form a framework having a porous structure. Anataze and or have a TiO 2 crystallites rutile (3) to simplify the manufacturing process while, at (4) to achieve the energy conversion device using the material, a photocatalyst, a fabrication of the purification material. The form of the material is desirably a thin film. Further, it is desirable that the material of the substrate supporting the film can be applied to various kinds of materials.
【０００４】[0004]
【課題を解決するための手段】テトラアルコキシチタン
とエチレンオキサイドープロピレンオキサイドーエチレ
ンオキサイドブロックコポリマーと安定化剤と溶剤から
なるゾル溶液を基板の上に滴下し、基板を高速回転さ
せ、溶剤を蒸発させ、ゲル化させることにより基板上に
形成した規則正しく整列した三次元構造を有する有機無
機複合TiO2薄膜を作成し、次いで高温で燒結することに
より、ブロックコポリマーが除去されることにより形成
される規則正しく整列した三次元構造を有するメソポー
ラスTiO2薄膜を得た。得られた薄膜はエネルギー変換素
子、光触媒、浄化材料の作製に用いることができる。A sol solution comprising tetraalkoxytitanium, ethylene oxide-propylene oxide-ethylene oxide block copolymer, a stabilizer and a solvent is dropped on a substrate, and the substrate is rotated at a high speed to evaporate the solvent. Then, an organic-inorganic composite TiO 2 thin film having an ordered three-dimensional structure formed on the substrate by gelation is formed, and then sintered at a high temperature to form an ordered TiO 2 thin film formed by removing the block copolymer. A mesoporous TiO 2 thin film having an ordered three-dimensional structure was obtained. The obtained thin film can be used for producing an energy conversion element, a photocatalyst, and a purification material.
【０００５】本発明において用いられるエチレンオキサ
イドープロピレンオキサイドーエチレンオキサイドブロ
ックコポリマーは、一般式The ethylene oxide-propylene oxide-ethylene oxide block copolymer used in the present invention has a general formula
【化１】 で示される「エチレンオキサイド(20)ープロピレンオキ
サイド(70)ーエチレンオキサイド(20)」ブロックコポリ
マーのP123{(EO)20(PO)70(EO)20}であるが、エチレンオ
キサイドとプロピレンオキサイドの長さ（重合度）を変
えることができるのは云うに及ばない。本発明で用いら
れる溶剤は2-プロパノール(CH3)2CHOHがあるが、エタノ
ール、ｎ−プロパノール、ブタノール等のアルコール類
でも有効である。本発明で用いられるテトラアルコキシ
チタンとしてはテトライソプロピルチタンTi(OC3H7)4、
テトラエトキシチタンTi(OC２H５)4、テトラn-ブチルオ
キシチタンTi(O n-C４H９)4、テトライソブチルオキシ
チタンTi(O i-C４H９)4、等がある。本発明で用いられ
る安定剤としては、アセチルアセトンCH3COCH2COCH3、
酢酸CH3CH2COOH等がある。Embedded image `` Ethylene oxide (20)-propylene oxide (70)-ethylene oxide (20) '' is a block copolymer P123 {(EO) 20 (PO) 70 (EO) 20 }, ethylene oxide and propylene oxide It goes without saying that the length (degree of polymerization) can be changed. The solvent used in the present invention is 2-propanol (CH 3 ) 2 CHOH, but alcohols such as ethanol, n-propanol and butanol are also effective. As the tetraalkoxy titanium used in the present invention, tetraisopropyl titanium Ti (OC 3 H 7 ) 4 ,
Tetraethoxytitanium Ti (OC 2 H 5 ) 4 , tetra-n-butyloxytitanium Ti (O nC 4 H 9 ) 4 , tetraisobutyloxytitanium Ti (O iC 4 H 9 ) 4 , and the like. As the stabilizer used in the present invention, acetylacetone CH 3 COCH 2 COCH 3 ,
There are acetic acid CH 3 CH 2 COOH and the like.
【０００６】以下に具体的な作製方法を示す。はじめ
に、ブロックコポリマーのP123{(EO)2 0(PO)70(EO)20}を
2-プロパノールに溶解させ、安定化剤としてアセチルア
セトンを加えたテトライソプロピルチタンと混合して得
られた前駆体溶液を2時間攪拌した後、HClでｐHを行
い、０〜７、望ましくは１〜２の範囲を1.21まで調整し
ながら加水分解を行った。さらに各時間で攪拌した後、
スピンキャストコーティングで膜を作製してから60℃で
数日間熱処理をし、高温（400℃〜600℃の範囲）で燒結
することにより、TiO2薄膜中に複合な構造をしているブ
ロックコポリマーのP123{(EO)20(PO)70(EO)20}が除去さ
れ、目的の三次元構造を有するメソポーラスTiO2薄膜を
得た。基板の素材は、石英、ガラス、シリコン、金等の
金属等であり、また、酸化スズ、酸化インジューム等の
透明金属酸化物も基板として使用できる。また、焼結後
に三次元構造を有するメソポーラスTiO2薄膜が、どのよ
うな因子で、六方（ヘキサゴナル）或は立方（キュービ
ック）型構造となるかについては十分に解明されていな
いが、結晶を分析すると六方（ヘキサゴナル）或は立方
（キュービック）型構造となっていることが確認されて
いる。さらに、いずれの三次元構造であっても、ポーラ
ス構造のフレームワークの中にあるTiO2はアナタゼ型及
び又はルチル型TiO2微結晶であることが確認されてい
る。A specific manufacturing method will be described below. First, the block copolymer of P123 {(EO) 2 0 ( PO) 70 (EO) 20}
A precursor solution obtained by dissolving in 2-propanol and mixing with tetraisopropyltitanium to which acetylacetone was added as a stabilizer was stirred for 2 hours, and then subjected to pH with HCl to give 0 to 7, preferably 1 to 2 Was adjusted while adjusting the range to 1.21. After further stirring each hour,
After forming the film by spin-cast coating, heat-treat it at 60 ° C for several days, and then sinter it at a high temperature (range of 400 ° C to 600 ° C) to form a block copolymer P123 that has a complex structure in the TiO2 thin film. {(EO) 20 (PO) 70 (EO) 20 } was removed to obtain a mesoporous TiO 2 thin film having a desired three-dimensional structure. The material of the substrate is a metal such as quartz, glass, silicon, and gold, and a transparent metal oxide such as tin oxide and indium oxide can also be used as the substrate. In addition, it has not been fully elucidated by what factors a mesoporous TiO 2 thin film having a three-dimensional structure becomes a hexagonal (cubic) or cubic (cubic) type structure after sintering. It has been confirmed that the structure has a hexagonal or cubic structure. Further, even in any of the three dimensional structure, TiO 2 that are in the framework of the porous structure it has been confirmed that Anataze type and or rutile TiO 2 crystallites.
【０００７】[0007]
【実施の形態】本発明の実施の形態は以下の通りであ
る。 （１） テトラアルコキシチタンとエチレンオキサイド
ープロピレンオキサイドーエチレンオキサイドブロック
コポリマーと安定化剤と溶剤からなるゾル溶液を基板の
上に滴下し、基板を高速回転させ、溶剤を蒸発させ、ゲ
ル化させることにより基板上に形成した規則正しく整列
した三次元構造を有する有機無機複合TiO2薄膜を作成
し、次いで高温で燒結することにより、ブロックコポリ
マーが除去されることにより形成される規則正しく整列
した三次元構造を有するメソポーラスTiO2薄膜。 （２） 三次元の六方（ヘキサゴナル）或は立方（キュ
ービック）型構造を有する上記１記載のメソポーラスTi
O2薄膜。 （３） ポーラス構造のフレームワークの中にアナタゼ
のTiO2微結晶を有する上記１記載のメソポーラスTiO2薄
膜。 （４） テトラアルコキシチタンとエチレンオキサイド
ープロピレンオキサイドーエチレンオキサイドブロック
コポリマーと安定化剤と溶剤とからなるゾル溶液を基板
の上に滴下し、基板を高速回転させ、溶剤を蒸発させ、
ゲル化させることにより基板上に形成した規則正しく整
列した三次元構造を有する有機無機複合TiO2薄膜を作成
し、次いで高温で燒結することにより、規則正しく整列
した三次元構造を有するメソポーラスTiO2薄膜の製造方
法。 （５） ゾル溶液にHClでpHを調整しながら加水分解を
行い、ゾル溶液を調整する上記４記載の規則正しく整列
した三次元構造を有する上記４記載のいメソポーラスTi
O2薄膜の製造方法。 （６） エチレンオキサイドープロピレンオキサイドー
エチレンオキサイドブロックコポリマーとして{(EO)n(P
O)m(EO)n ここでｎは１５〜２００、ｍは２０〜２００
の整数である}を用いる上記４記載のメソポーラスTiO2
薄膜の製造方法。 （７） 安定化剤としてアセチルアセトンを用いる三次
元構造を有する上記４記載のメソポーラスTiO2薄膜の製
造方法。 （８） 基板上に上記１〜３のいずれかひとつに記載の
メソポーラスTiO2薄膜を用いたエネルギー変換素子。 （９） 基板上に上記１〜３のいずれかひとつに記載の
メソポーラスTiO2薄膜を用いた光触媒。 （１０） 基板上に上記１〜３のいずれかひとつに記載
のメソポーラスTiO2薄膜を用いた浄化材料。 （１１） 基板が石英、ガラス、シリコン、金属、透明
な金属酸化物の何れかである上記８〜上記１０記載のい
ずれか一つに記載されたエネルギー変換素子、光触媒又
は浄化材料。Embodiments of the present invention are as follows. (1) Dropping a sol solution composed of tetraalkoxytitanium, ethylene oxide-propylene oxide-ethylene oxide block copolymer, a stabilizer and a solvent onto a substrate, rotating the substrate at a high speed, evaporating the solvent, and gelling. To form an organic-inorganic composite TiO 2 thin film with an ordered three-dimensional structure formed on a substrate, followed by sintering at a high temperature to remove the orderly three-dimensional structure formed by removing the block copolymer. Mesoporous TiO 2 thin film. (2) The mesoporous Ti as described in 1 above, having a three-dimensional hexagonal or cubic structure.
O 2 thin film. (3) The mesoporous TiO 2 thin film according to the above item 1, wherein the TiO 2 microcrystal of anatase is contained in a framework having a porous structure. (4) A sol solution comprising tetraalkoxytitanium, ethylene oxide-propylene oxide-ethylene oxide block copolymer, a stabilizer and a solvent is dropped on the substrate, and the substrate is rotated at a high speed to evaporate the solvent.
Preparation of an organic-inorganic composite TiO 2 thin film with an ordered three-dimensional structure formed on a substrate by gelling, followed by sintering at high temperature to produce a mesoporous TiO 2 thin film with an ordered three-dimensional structure Method. (5) The sol solution is hydrolyzed while adjusting the pH with HCl, and the sol solution is adjusted. The mesoporous Ti according to the above item 4 having a regularly arranged three-dimensional structure according to the above item 4.
Method for producing O 2 thin film. (6) As an ethylene oxide-propylene oxide-ethylene oxide block copolymer, {(EO) n (P
O) m (EO) n where n is 15 to 200 and m is 20 to 200
The mesoporous TiO 2 according to the above item 4, wherein the integer is
Manufacturing method of thin film. (7) The method for producing a mesoporous TiO 2 thin film according to the above (4), which has a three-dimensional structure using acetylacetone as a stabilizer. (8) An energy conversion element using the mesoporous TiO 2 thin film according to any one of the above 1 to 3 on a substrate. (9) a photocatalyst using the mesoporous TiO 2 thin film according to any one on the substrate of the 1-3. (10) A purification material using the mesoporous TiO 2 thin film according to any one of the above items 1 to 3 on a substrate. (11) The energy conversion element, photocatalyst or purification material according to any one of the above items 8 to 10, wherein the substrate is any one of quartz, glass, silicon, metal, and a transparent metal oxide.
【０００８】[0008]
【実施例】三次元構造を有するメソポーラスTiO2薄膜の
作製 アセチルアセトンを加えたテトライソプロピルチタンと
ブロックコポリマーのP123{(EO)20(PO)70(EO)20}とから
なり、ブロックコポリマーのP123{(EO)20(PO)7 0(EO)20}
がナノレベルでTiO2薄膜中に構造を複合化している三次
元構造を有するTiO2薄膜の作製手順は図１に示す手順で
行った。はじめに、ブロックコポリマーのP123{(EO)
20(PO)70(EO)20}を2-プロパノールに溶解させ、安定化
剤としてアセチルアセトンを加えたテトライソプロピル
チタンと混合して得られた前駆体溶液を2時間攪拌した
後、HClでｐHを1.21まで調整しながら加水分解を行っ
て、ゾル溶液になった、ゾル溶液の各化学物質の成分ｍ
ｏｌ比はテトライソプロピルチタン：P123ブロックコポ
リマー{(EO)20(PO)70(EO)20}：アセチルアセトン：水：
2-プロパノール＝１：０.０１７：０.５：１：３５.４
７である。さらに数十時間で攪拌した後、スピンキャス
ティング法により基板上に膜を作製し、ゾル溶液を基板
上に適量滴下し、その基板を高速回転した。このとき、
石英基板上にＨ会合体膜が形成された。60℃で数日間熱
処理をし、450℃で燒結することにより、TiO2薄膜中に
複合な構造をしているブロックコポリマーのP123{(EO)
20(PO)70(EO)20}が除去され、目的の規則正しく整列し
た三次元構造を有するメソポーラスTiO2薄膜を得た。膜
のキャラクタリゼーションはX線回折と透過電子顕微鏡
により行った。EXAMPLE Preparation of a Mesoporous TiO 2 Thin Film Having a Three-Dimensional Structure A block copolymer P123 {(EO) 20 (PO) 70 (EO) 20 } comprising tetraisopropyl titanium to which acetylacetone was added and a block copolymer P123 { (EO) 20 (PO) 7 0 (EO) 20 }
The procedure for producing a TiO 2 thin film having a three-dimensional structure in which the structure is complexed in the TiO 2 thin film at the nano level was performed by the procedure shown in FIG. First, the block copolymer P123 {(EO)
20 (PO) 70 (EO) 20 } was dissolved in 2-propanol, and a precursor solution obtained by mixing with tetraisopropyltitanium to which acetylacetone was added as a stabilizer was stirred for 2 hours, and then the pH was adjusted with HCl. Hydrolysis was carried out while adjusting to 1.21, and a sol solution was obtained. Component m of each chemical substance in the sol solution
The ol ratio is tetraisopropyl titanium: P123 block copolymer {(EO) 20 (PO) 70 (EO) 20 }: acetylacetone: water:
2-propanol = 1: 0.017: 0.5: 1: 35.4
7 After further stirring for several tens of hours, a film was formed on the substrate by spin casting, an appropriate amount of a sol solution was dropped on the substrate, and the substrate was rotated at high speed. At this time,
An H-associated body film was formed on the quartz substrate. Heat treatment at 60 ° C for several days and sintering at 450 ° C give P123 {(EO), a block copolymer with a complex structure in the TiO 2 thin film.
20 (PO) 70 (EO) 20 } was removed to obtain a desired mesoporous TiO 2 thin film having a regularly ordered three-dimensional structure. The characterization of the membrane was performed by X-ray diffraction and transmission electron microscopy.
【０００９】[0009]
【膜の構造の制御因子と性質】スピンキャスティング法
による膜作製におけるゾル溶液からメソポーラスTiO2薄
膜形成に至る過程には、主に（１）有機溶媒2-プロバナ
ールの蒸発、（２）ブロックコポリマーのP123{(EO)
20(PO)70(EO)20}分子の凝集、（３）テトライソプロピ
ルチタンの縮重合反応の３反応が競合すると考えられ
る。これらの優劣はゾル溶液の濃度、温度、pHに依存
し、最終的に生じる三次元構造を有するメソポーラスTi
O2薄膜の中の細孔の構造と膜の質が異なると考えられ
る。燒結するする前（図２）と後（図３）のX線回折は
メソポーラスTiO2薄膜の三次元構造は立方（キュービッ
ク）であることを示唆している。また、透過電子顕微鏡
の写真（図４）は三次元の構造を示している。その部分
の電子線のX線回折（図５）はアナタゼのTiO2微結晶の
（101）、（200）、（211）と（301）とルチルの（20
0）と（311）からの回折パタンが出ている。ポーラス構
造のフレームワークの中にアナタゼのTiO2微結晶を有す
ることを確認した。[Control factors and properties of film structure] In the process of forming a mesoporous TiO 2 thin film from a sol solution in film formation by spin casting, the process mainly consists of (1) evaporation of organic solvent 2-provanal, (2) block copolymer P123 {(EO)
20 (PO) 70 (EO) 20 } It is considered that three reactions of molecular aggregation and (3) polycondensation reaction of tetraisopropyl titanium compete. Their superiority depends on the concentration, temperature, and pH of the sol solution, and the resulting mesoporous Ti has a three-dimensional structure.
It is considered that the structure of the pores in the O 2 thin film and the quality of the film are different. X-ray diffraction before (FIG. 2) and after (FIG. 3) sintering suggests that the three-dimensional structure of the mesoporous TiO 2 thin film is cubic. A photograph of a transmission electron microscope (FIG. 4) shows a three-dimensional structure. X-ray diffraction (Fig. 5) of the electron beam at that part shows that (101), (200), (211) and (301) of anatase TiO 2 microcrystal and
Diffraction patterns from (0) and (311) appear. It was confirmed that TiO 2 microcrystals of anatase were contained in the framework of the porous structure.
【００１０】[0010]
【発明の効果】これまで、TiO2薄膜を形成させる方法が
沢山提案されているが、実用的な材料となりうるTiO2薄
膜は比表面積が大きいメソポーラスTiO2薄膜が要求され
ているが、実際には三次元構造を有するメソポーラスTi
O2薄膜はまだ成功していない、またTiO2微粒子を利用し
た多孔質の場合には、ポーラス細孔のサイズと構造が制
御されていない。我々の発明した三次元構造を有するメ
ソポーラスTiO2薄膜の製造方法は極めて簡便な方法であ
るばかりでなく、ポーラス細孔のサイズと構造が制御す
ることが可能である。この特性に基づき、従来のTiO2薄
膜の知られた用途であるエネルギー変換素子、光触媒材
料、有害ガスを吸着し、光で分解する浄化材料などのエ
ネルギー変換技術及び環境技術の開発が可能となる。EFFECTS OF THE INVENTION Heretofore, a method for forming a TiO 2 thin film is much proposed, although TiO 2 thin film which can be a practical material has a large mesoporous TiO 2 thin film specific surface area is required, actually Is a mesoporous Ti with a three-dimensional structure
O 2 thin films have not been successful yet, and in the case of porous materials using TiO 2 fine particles, the size and structure of the porous pores are not controlled. The method of manufacturing a mesoporous TiO 2 thin film having a three-dimensional structure we have invented is not only an extremely simple method, but also allows control of the size and structure of porous pores. Based on this characteristic, it is possible to develop energy conversion technology and environmental technology such as energy conversion devices, photocatalytic materials, and purification materials that adsorb harmful gases and decompose by light, which are known applications of conventional TiO 2 thin films. .
【００１１】[0011]
【図１】は、TiO2薄膜を製作する手順を示すプロセス図FIG. 1 is a process diagram showing a procedure for manufacturing a TiO 2 thin film.
【図２】は、TiO2薄膜を焼結する前のＸ線回折図FIG. 2 is an X-ray diffraction diagram before sintering a TiO 2 thin film.
【図３】は、TiO2薄膜を焼結した後のＸ線回折図FIG. 3 is an X-ray diffraction diagram after sintering a TiO 2 thin film.
【図４】は、TiO2薄膜を焼結した後の透過電子顕微鏡の
写真FIG. 4 is a photograph of a transmission electron microscope after sintering a TiO 2 thin film.
【図５】は、TiO2微結晶のＸ線回折図FIG. 5 is an X-ray diffraction diagram of TiO 2 microcrystals.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 周 豪慎 茨城県つくば市梅園１丁目１番４ 工業技 術院電子技術総合研究所内 (72)発明者 本間 格 茨城県つくば市梅園１丁目１番４ 工業技 術院電子技術総合研究所内 (72)発明者 桑原 誠 東京都中野区上高田４丁目８号１−706 (72)発明者 ユン ヒスク 東京都新宿区上落合２−25−８ ファミー ユメゾン301室 Ｆターム(参考） 4G047 CA02 CB06 CC03 CD02 CD07 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Zhou Goshin 1-4-1 Umezono, Tsukuba City, Ibaraki Prefecture Within the Institute of Electronics and Technology (72) Inventor Tadashi Honma 1-1-1 Umezono, Tsukuba City, Ibaraki Prefecture 4. Inside the Electronic Technology Research Laboratory, National Institute of Industrial Science (72) Inventor Makoto Kuwahara 4-7-1, Kamikata, Nakano-ku, Tokyo (72) Inventor Yun Hisk 2-25-8 Kamiochiai, Shinjuku-ku, Tokyo Family Yumaison 301 Room F term (reference) 4G047 CA02 CB06 CC03 CD02 CD07
Claims (11)
イドープロピレンオキサイドーエチレンオキサイドブロ
ックコポリマーと安定化剤と溶剤からなるゾル溶液を基
板の上に滴下し、基板を高速回転させ、溶剤を蒸発さ
せ、ゲル化させることにより基板上に形成した規則正し
く整列した三次元構造を有する有機無機複合TiO2薄膜を
作成し、次いで高温で燒結することにより、ブロックコ
ポリマーが除去されることにより形成される規則正しく
整列した三次元構造を有するメソポーラスTiO2薄膜。1. A sol solution comprising a tetraalkoxytitanium, an ethylene oxide-propylene oxide-ethylene oxide block copolymer, a stabilizer and a solvent is dropped on a substrate, and the substrate is rotated at a high speed to evaporate the solvent to form a gel. To form an organic-inorganic composite TiO 2 thin film having a regularly ordered three-dimensional structure formed on the substrate, and then sintering at high temperature to remove the block copolymer to form a regularly ordered three-dimensional structure Mesoporous TiO 2 thin film with structure.
（キュービック）型構造を有する請求項１記載のメソポ
ーラスTiO2薄膜。2. The mesoporous TiO 2 thin film according to claim 1, having a three-dimensional hexagonal or cubic structure.
ナタゼ及び又はルチルのTiO2微結晶を有する請求項１記
載のメソポーラスTiO2薄膜。3. The mesoporous TiO 2 thin film according to claim 1, wherein an anatase and / or rutile TiO 2 crystallite is contained in a framework having a porous structure.
サイドープロピレンオキサイドーエチレンオキサイドブ
ロックコポリマーと安定化剤と溶剤とからなるゾル溶液
を基板の上に滴下し、基板を高速回転させ、溶剤を蒸発
させ、ゲル化させることにより基板上に形成した規則正
しく整列した三次元構造を有する有機無機複合TiO2薄膜
を作成し、次いで高温で燒結することにより、規則正し
く整列した三次元構造を有するメソポーラスTiO2薄膜の
製造方法。4. A sol solution comprising tetraalkoxytitanium, ethylene oxide-propylene oxide-ethylene oxide block copolymer, a stabilizer and a solvent is dropped on a substrate, the substrate is rotated at a high speed, the solvent is evaporated, and Of an organic-inorganic composite TiO 2 thin film having a regularly ordered three-dimensional structure formed on a substrate by crystallization and then sintering at a high temperature to produce a mesoporous TiO 2 thin film having a regularly ordered three-dimensional structure .
分解を行い、ゾル溶液を調整する請求項４記載の規則正
しく整列した三次元構造を有するメソポーラスTiO2薄膜
の製造方法。5. The method for producing a mesoporous TiO 2 thin film having an ordered three-dimensional structure according to claim 4, wherein the sol solution is hydrolyzed while adjusting the pH with HCl.
イドーエチレンオキサイドブロックコポリマーとして
{(EO)n(PO)m(EO)n ここでｎは１５〜２００、ｍは２０
〜２００の整数である}を用いる請求項４記載のメソポ
ーラスTiO2薄膜の製造方法。6. An ethylene oxide-propylene oxide-ethylene oxide block copolymer
{(EO) n (PO) m (EO) n where n is 15 to 200 and m is 20
5. The method for producing a mesoporous TiO 2 thin film according to claim 4, wherein the integer is from 200 to 200}.
る三次元構造を有する請求項４記載のメソポーラスTiO2
薄膜の製造方法。7. The mesoporous TiO 2 according to claim 4, which has a three-dimensional structure using acetylacetone as a stabilizer.
Manufacturing method of thin film.
に記載のメソポーラスTiO2薄膜を用いたエネルギー変換
素子。8. An energy conversion device using the mesoporous TiO 2 thin film according to claim 1 on a substrate.
に記載のメソポーラスTiO2薄膜を用いた光触媒。9. A photocatalyst using the mesoporous TiO 2 thin film according to claim 1 on a substrate.
つに記載のメソポーラスTiO2薄膜を用いた浄化材料。10. A purification material using the mesoporous TiO 2 thin film according to claim 1 on a substrate.
属、透明な金属酸化物の何れかである請求項８〜請求項
１０記載のいずれか一つに記載されたエネルギー変換素
子、光触媒又は浄化材料。11. The energy conversion element, photocatalyst or purification material according to claim 8, wherein the substrate is any one of quartz, glass, silicon, metal, and a transparent metal oxide. .
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002041043A2 (en) * | 2000-11-14 | 2002-05-23 | The Regents Of The University Of California | Inorganic/block copolymer-dye composites and dye doped mesoporous materials for optical and sensing applications |
| WO2003087002A1 (en) * | 2002-04-17 | 2003-10-23 | Saint-Gobain Glass France | Substrate with a self-cleaning coating |
| JP2003335506A (en) * | 2002-05-16 | 2003-11-25 | Japan Science & Technology Corp | Method for synthesizing mesoporous oxide having high three-dimensional regularity |
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| JP2005225705A (en) * | 2004-02-12 | 2005-08-25 | Toyota Central Res & Dev Lab Inc | Mesoporous body, air purifying material, and method of manufacturing mesoporous body |
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| JP2007070136A (en) * | 2005-09-05 | 2007-03-22 | Kyoto Univ | Titania nano-rod, its manufacture method, and dye sensitizing solar battery using this titania nano-rod |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58167428A (en) * | 1982-03-26 | 1983-10-03 | Matsushita Electric Ind Co Ltd | Preparation of titanium oxide film |
| JPH01108161A (en) * | 1987-10-19 | 1989-04-25 | Toray Ind Inc | Method for forming titania thin film |
| JPH0899041A (en) * | 1993-12-09 | 1996-04-16 | Agency Of Ind Science & Technol | Photocatalyst of titanium oxide porous thin film and preparation of the same |
| JPH08103631A (en) * | 1993-12-09 | 1996-04-23 | Agency Of Ind Science & Technol | Photocatalytic filter and its production |
| JPH10226598A (en) * | 1997-02-13 | 1998-08-25 | Sanyo Electric Co Ltd | Transparent conductive titanium oxide film and its production |
-
2000
- 2000-02-21 JP JP2000043325A patent/JP3530896B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58167428A (en) * | 1982-03-26 | 1983-10-03 | Matsushita Electric Ind Co Ltd | Preparation of titanium oxide film |
| JPH01108161A (en) * | 1987-10-19 | 1989-04-25 | Toray Ind Inc | Method for forming titania thin film |
| JPH0899041A (en) * | 1993-12-09 | 1996-04-16 | Agency Of Ind Science & Technol | Photocatalyst of titanium oxide porous thin film and preparation of the same |
| JPH08103631A (en) * | 1993-12-09 | 1996-04-23 | Agency Of Ind Science & Technol | Photocatalytic filter and its production |
| JPH10226598A (en) * | 1997-02-13 | 1998-08-25 | Sanyo Electric Co Ltd | Transparent conductive titanium oxide film and its production |
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| WO2002041043A3 (en) * | 2000-11-14 | 2003-03-27 | Univ California | Inorganic/block copolymer-dye composites and dye doped mesoporous materials for optical and sensing applications |
| FR2838734A1 (en) * | 2002-04-17 | 2003-10-24 | Saint Gobain | Substrates with self-cleaning coatings, e.g. for filter, windows, electronic components, have mesoporous structure with photocatalytic properties and comprises titanium oxide at least partially crystallized |
| KR100973747B1 (en) * | 2002-04-17 | 2010-08-04 | 쌩-고벵 글래스 프랑스 | Substrate with a self-cleaning coating |
| WO2003087002A1 (en) * | 2002-04-17 | 2003-10-23 | Saint-Gobain Glass France | Substrate with a self-cleaning coating |
| CN100439271C (en) * | 2002-04-17 | 2008-12-03 | 法国圣戈班玻璃厂 | Substrate with a self-cleaning coating |
| US7510763B2 (en) | 2002-04-17 | 2009-03-31 | Saint-Gobain Glass France | Substrate with a self-cleaning coating |
| JP2003335506A (en) * | 2002-05-16 | 2003-11-25 | Japan Science & Technology Corp | Method for synthesizing mesoporous oxide having high three-dimensional regularity |
| JP4520088B2 (en) * | 2002-05-16 | 2010-08-04 | 独立行政法人科学技術振興機構 | Method for synthesizing mesoporous oxides with high three-dimensional regularity |
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| JP4528975B2 (en) * | 2003-11-17 | 2010-08-25 | 独立行政法人産業技術総合研究所 | Nano-sized microcrystalline oxide-glass composite mesoporous powder or thin film, production method thereof, lithium battery or lithium intercalation electric device, photocatalytic device, solar cell, energy storage device and secondary battery |
| US7771871B2 (en) | 2003-11-17 | 2010-08-10 | National Institute Of Advanced Industrial Science And Technology | Nanocrystal oxide/glass composite mesoporous powder or thin film, process for producing the same, and utilizing the powder or thin film, various devices, secondary battery and lithium storing device |
| JPWO2005047199A1 (en) * | 2003-11-17 | 2007-08-23 | 独立行政法人産業技術総合研究所 | Nano-sized microcrystalline oxide-glass composite mesoporous powder or thin film, method for producing the same, various devices using the same powder or thin film, secondary battery and lithium storage device |
| JP2005219959A (en) * | 2004-02-05 | 2005-08-18 | Asahi Kasei Chemicals Corp | Modified mesoporous oxide |
| JP4578116B2 (en) * | 2004-02-05 | 2010-11-10 | 旭化成ケミカルズ株式会社 | Modified mesoporous oxide |
| JP2005225705A (en) * | 2004-02-12 | 2005-08-25 | Toyota Central Res & Dev Lab Inc | Mesoporous body, air purifying material, and method of manufacturing mesoporous body |
| JP4596233B2 (en) * | 2004-02-12 | 2010-12-08 | 株式会社豊田中央研究所 | Mesoporous material, air purification material, and method for producing mesoporous material |
| JP2006104047A (en) * | 2004-09-08 | 2006-04-20 | Mitsubishi Materials Corp | Porous body and manufacturing method thereof |
| JP4577159B2 (en) * | 2004-09-08 | 2010-11-10 | 三菱マテリアル株式会社 | Porous material and method for producing the same |
| JP2007070136A (en) * | 2005-09-05 | 2007-03-22 | Kyoto Univ | Titania nano-rod, its manufacture method, and dye sensitizing solar battery using this titania nano-rod |
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| WO2010107088A1 (en) | 2009-03-18 | 2010-09-23 | Toto株式会社 | Measurement device used for specifically detecting substance to be examined using photocurrent, sensor unit used for same, and method for specifically detecting substance to be examined using photocurrent |
| CN101792178A (en) * | 2010-03-08 | 2010-08-04 | 厦门大学 | Ordered mesoporous titanium dioxide film with three-dimensionally communicated vertical open pores and preparation method thereof |
| CN102933744A (en) * | 2010-06-09 | 2013-02-13 | 埃西勒国际通用光学公司 | Method for the low-temperature preparation of electrically conductive mesostructured coatings |
| WO2013047624A1 (en) | 2011-09-26 | 2013-04-04 | Toto株式会社 | Method for specifically detecting test substance |
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