JP5552682B2 - Coating solution for forming titanium oxide film used for blocking layer for dye-sensitized solar cell, method for forming titanium oxide film used for blocking layer for dye-sensitized solar cell on substrate, and blocking layer for dye-sensitized solar cell Substrate with titanium oxide coating on the surface - Google Patents
Coating solution for forming titanium oxide film used for blocking layer for dye-sensitized solar cell, method for forming titanium oxide film used for blocking layer for dye-sensitized solar cell on substrate, and blocking layer for dye-sensitized solar cell Substrate with titanium oxide coating on the surface Download PDFInfo
- Publication number
- JP5552682B2 JP5552682B2 JP2010087301A JP2010087301A JP5552682B2 JP 5552682 B2 JP5552682 B2 JP 5552682B2 JP 2010087301 A JP2010087301 A JP 2010087301A JP 2010087301 A JP2010087301 A JP 2010087301A JP 5552682 B2 JP5552682 B2 JP 5552682B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- forming
- dye
- blocking layer
- oxide film
- 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.)
- Expired - Fee Related
Links
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Paints Or Removers (AREA)
Description
本発明は、ガラス、セラミックス等の基板あるいは被対象物上に酸化チタン被膜を形成するための酸化チタン被膜形成用塗布溶液及び酸化チタン被膜の製造方法に関し、光触媒や太陽電池などの製造に不可欠なチタン系被膜を形成するのに有用なものである。The present invention relates to a titanium oxide film-forming coating solution for forming a titanium oxide film on a substrate such as glass or ceramics or an object and a method for producing the titanium oxide film, and is indispensable for the production of photocatalysts, solar cells, and the like. It is useful for forming a titanium-based film.
従来、ゾルーゲル法を利用してチタン系被膜を形成するには、チタンの金属アルコキシドを原料として用い、これを加水分解及び重合させて金属酸化物前躯体ゾルを調製し、得られたゾルを基板表面に塗布し、基板表面に金属酸化物ゲルを形成した後、このゲル膜を適当な温度で加熱処理するようにする（非特許文献１等参照。Conventionally, in order to form a titanium-based film by using a sol-gel method, a metal oxide precursor sol is prepared by hydrolyzing and polymerizing a titanium metal alkoxide as a raw material, and the obtained sol is used as a substrate. After coating on the surface and forming a metal oxide gel on the surface of the substrate, the gel film is heat-treated at an appropriate temperature (see Non-Patent Document 1, etc.).
しかしながら、金属アルコキシドは、加水分解速度が非常に速いため、均質な成膜が可能であるような均質なゾルを調製するのが困難である。そこで、金属アルコキシドの加水分解速度を抑制するために濃度を極端に低くする方法があるが、この場合、均質なゾルを調製することはできるが、一回の制膜工程で得られる膜の厚みが非常に薄くなるため、実用的ではない。However, since the metal alkoxide has a very high hydrolysis rate, it is difficult to prepare a homogeneous sol that can form a uniform film. Therefore, there is a method of reducing the concentration extremely in order to suppress the hydrolysis rate of the metal alkoxide. In this case, a homogeneous sol can be prepared, but the thickness of the film obtained in one film-controlling step. Is very impractical because it becomes very thin.
また、一般に、金属アルコキシドを加水分解して得られるゾルは、長期保存により粘度変化が生じたり、沈殿物が生じたりして、長期保存性欠けるという問題もある。In general, a sol obtained by hydrolyzing a metal alkoxide also has a problem that a long-term storage causes a change in viscosity or a precipitate, resulting in a lack of long-term storage.
本発明はこのような事情に鑑み、有機溶媒を使用しないで比較的厚い酸化チタン被膜を一度塗りで容易に形成でき、溶液としても安定している酸化チタン被膜形成用塗布溶液及び酸化チタン被膜の製造方法を提供することを課題とする。In view of such circumstances, the present invention can easily form a relatively thick titanium oxide film by one coating without using an organic solvent, and is stable as a solution of a titanium oxide film forming coating solution and a titanium oxide film. It is an object to provide a manufacturing method.
前記課題を解決する本発明の第一の態様は、チタンのハロゲン化物を加水分解して得られるチタン水酸化物を有機強塩基の水溶液に溶解してなり且つ水溶性ポリマーを含有することを特徴とする酸化チタン被膜形成用塗布溶液にある。A first aspect of the present invention for solving the above-mentioned problems is characterized in that a titanium hydroxide obtained by hydrolyzing a titanium halide is dissolved in an aqueous solution of a strong organic base and contains a water-soluble polymer. And a coating solution for forming a titanium oxide film.
本発明の第２の態様は、第１の態様において、前記チタンのハロゲン化物が、四塩化チタン、四臭化チタン、四ヨウ化チタンからなる群から選択される少なくとも一種又はその水溶液であることを特徴とする酸化チタン被膜形成用塗布溶液にある。According to a second aspect of the present invention, in the first aspect, the titanium halide is at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, or an aqueous solution thereof. A coating solution for forming a titanium oxide film.
本発明の第３の態様は、第１又は２の態様において、前記有機強塩基がテトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）及びテトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）からなる群から選択される少なくとも一種であることを特徴とする酸化チタン被膜形成用塗布溶液にある。According to a third aspect of the present invention, in the first or second aspect, the organic strong base is at least one selected from the group consisting of tetramethylammonium hydroxide (TMAH) and tetraethylammonium hydroxide (TEAH). A coating solution for forming a titanium oxide film.
本発明の第四の態様は、第１又は２の態様において、前記塗布溶液がｐＨ１３以上を示すものであることを特徴とする酸化チタン被膜形成用塗布溶液にある。According to a fourth aspect of the present invention, there is provided a coating solution for forming a titanium oxide film according to the first or second aspect, wherein the coating solution exhibits a pH of 13 or more.
本発明の第５の態様は、第１−４の何れかの態様において、前記水溶性ポリマーが、ポリビニルアルコール（ＰＶＡ）、ポリビニルアセトアミド（ＰＮＶＡ）、ポリビニルホルムアミド（ＰＮＶＦ）、ポリジメチルアクリルアミド（ＰＤＭＡＡ）、ポリアクリルアミド（ＰＡＡＭ）、ポリアクリロイルモルホリン（ＰＡＭ）、ヒドロキシエチルセルロース（ＨＥＣ）、ヒドロキシプロピルセルロース（ＨＰＣ）、及びカルボキシメチルセルロース（ＣＭＣ）、からなる群から選択される少なくとも１種であることを特徴とする酸化チタン被膜形成用塗布溶液にある。According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the water-soluble polymer is polyvinyl alcohol (PVA), polyvinyl acetamide (PNVA), polyvinyl formamide (PNVF), polydimethylacrylamide (PDMAA). , Polyacrylamide (PAAM), polyacryloylmorpholine (PAM), hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), and carboxymethylcellulose (CMC). In the coating solution for forming a titanium oxide film.
本発明の第６の態様は、態様１から５いずれか記載のチタンのハロゲン化物を加水分解して得られるチタン水酸化物を有機強塩基の水溶液に溶解させ、次に水溶性ポリマーを含有させて、ｐＨ値が１３以上である酸化チタン被膜形成用塗布溶液を基板上に塗布して塗膜を形成する工程と、この塗膜を４００℃−８００℃で焼成して酸化チタン被膜とする工程とを具備することを特徴とする色素増感太陽電池用Ｂｌｏｃｋｉｎｇ層に用いる基板上に酸化チタン被膜の製造方法。 According to a sixth aspect of the present invention, a titanium hydroxide obtained by hydrolyzing the titanium halide according to any one of the first to fifth aspects is dissolved in an aqueous solution of a strong organic base, and then a water-soluble polymer is contained. A step of applying a coating solution for forming a titanium oxide film having a pH value of 13 or more on a substrate to form a coating film, and a step of baking the coating film at 400 ° C. to 800 ° C. to form a titanium oxide film The manufacturing method of a titanium oxide film on the board | substrate used for the blocking layer for dye-sensitized solar cells characterized by comprising these.
本発明の第７の態様は、第１の態様から第５の態様いずれか記載のチタンのハロゲン化物を加水分解して得られるチタン水酸化物を有機強塩基の水溶液に溶解させ、次に水溶性ポリマーを含有させて、ｐＨ値が１３以上である酸化チタン被膜形成用塗布溶液を１回塗布した塗膜を４００℃−８００℃で焼成して酸化チタン被膜を形成する工程を経て製造される酸化チタン被膜は１００ｎｍ−５００ｎｍである被膜を形成していることを特徴とする色素増感太陽電池用Ｂｌｏｃｋｉｎｇ層に用いる酸化チタンの被膜を基板上に形成する方法。 According to a seventh aspect of the present invention, a titanium hydroxide obtained by hydrolyzing the halide of titanium according to any one of the first to fifth aspects is dissolved in an aqueous solution of a strong organic base, and then water-soluble. contain a sexual polymers, prepared via more Engineering you forming a titanium oxide film by the applied coating film once titanium oxide film-forming coating solution pH value is 13 or more and baked at 400 ° C. -800 ° C. mETHOD titanium oxide coating to form a coating film of titanium oxide used in the dye-sensitized Blocking layer for a solar cell, characterized by forming a target layer which is a 100 nm-500 nm on the substrate to be.
本発明の第８の態様は、第１の態様から第５の態様いずれか記載のチタンのハロゲン化物を加水分解して得られるチタン水酸化物を有機強塩基の水溶液に溶解させ、次に水溶性ポリマーを含有させて、ｐＨ値が１３以上である酸化チタン被膜形成用塗布溶液を基板上に塗付し塗膜を形成する工程に引続いて、前記塗付した塗膜を４００℃−８００℃で焼成して酸化チタン被膜を形成する工程を経て製造することを特徴とする色素増感太陽電池用Ｂｌｏｃｋｉｎｇ層に用いる酸化チタンの被膜を基板上に形成する方法。 According to an eighth aspect of the present invention, a titanium hydroxide obtained by hydrolyzing the halide of titanium according to any one of the first to fifth aspects is dissolved in an aqueous solution of a strong organic base, and then dissolved in water. Subsequently to the step of coating the substrate with a coating solution for forming a titanium oxide film having a pH value of 13 or more containing a functional polymer, the coated film is coated at 400 ° C. to 800 ° C. how a coating of titanium oxide is formed on a substrate used in the dye-sensitized Blocking layer for a solar cell, characterized in that baked to manufactured through more Engineering you forming a titanium oxide film at ° C..
本発明の第９の態様は、第１の態様から第５の態様いずれか記載のチタンのハロゲン化物を加水分解して得られるチタン水酸化物を有機強塩基の水溶液に溶解させ、次に水溶性ポリマーを含有させて、ｐＨ値が１３以上である酸化チタン被膜形成用塗布溶液を基板に１回塗布した塗膜を４００℃−８００℃で焼成して酸化チタン被膜を形成する工程を経て製造される酸化チタン被膜は１００ｎｍ−５００ｎｍである被膜を形成していることを特徴とする請求項７記載の色素増感太陽電池用Ｂｌｏｃｋｉｎｇ層に用いる酸化チタンの被膜を基板上に形成する方法。 According to a ninth aspect of the present invention, a titanium hydroxide obtained by hydrolyzing the halide of titanium according to any one of the first to fifth aspects is dissolved in an aqueous solution of a strong organic base, and then water-soluble. contain a sex polymer, a titanium oxide film-forming coating solution pH value is 13 or more as engineering you form once coated coating film was calcined to titanium oxide film at 400 ° C. -800 ° C. to the substrate titanium oxide film manufactured through form a coating of titanium oxide used in the Blocking layer for dye-sensitized solar cell according to claim 7, wherein the forming a target layer which is a 100 nm-500 nm on a substrate Method.
かかる本発明は、チタンのハロゲン化物を加水分解して得られるチタン水酸化物が、所定の有機強塩基により脱プロトンされ、これで得られる陰イオン同士の相互反発により水溶液となり、均質で膜質の優れた被膜を得るための塗布溶液として有用であるという知見に基いて完成されたものである。In the present invention, a titanium hydroxide obtained by hydrolyzing a titanium halide is deprotonated by a predetermined organic strong base, and becomes an aqueous solution due to the mutual repulsion between the anions obtained thereby. It was completed based on the knowledge that it is useful as a coating solution for obtaining an excellent film.
本発明で提供される酸化チタンの被膜は非常に安価で、透明性、膜質も良好で高品質であり、且つ、通常の塗布法で簡便に製造できるので低製造コスト化を図ることができ、広範囲に適用され、使用されることができるものである。The titanium oxide coating provided in the present invention is very inexpensive, transparent, good in film quality and high quality, and can be easily manufactured by a normal coating method, so that the manufacturing cost can be reduced. It can be widely applied and used.
本発明の酸化チタン被膜形成用塗布溶液は、チタンのハロゲン化物を加水分解して得られるチタン水酸化物を有機強塩基の水溶液に溶解してなる。The coating solution for forming a titanium oxide film of the present invention is obtained by dissolving a titanium hydroxide obtained by hydrolyzing a titanium halide in an aqueous solution of a strong organic base.
本発明で用いるチタンのハロゲン化物は、好適には、四塩化チタン、四臭化チタン、及び四ヨウ化チタンからなる群から選択される少なくとも一種類のチタンハロゲン化物又はその水溶液を挙げることができる。 Halides of titanium used in the present invention are good applicable, titanium tetrachloride, titanium tetrabromide, and can include at least one compound of titanium halide or an aqueous solution thereof which is selected from the group consisting of titanium tetraiodide it can.
また、本発明で用いる有機強塩基は、上述したチタン水酸化物から脱プロトン作用を示すものであれば限定されない。具体的には、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）及びテトラエチルアンモニウムヒドロキシド（ＴＥＡＭ）からなる群から選択される少なくとも一種類の有機強塩基を挙げることができる。好適には、塗布溶液がｐＨ１３以上を示す有機強塩基を用いるのがよい。 The organic strong base used in the present invention is not limited as long as it exhibits the deprotonation action from titanium hydroxide as described above. Specifically, mention may be made of organic strong base of at least one compound selected from the group consisting of tetramethylammonium hydroxide (TMAH) and tetraethylammonium hydroxide (TEAM). Preferably, the coating solution is good to use a organic strong base shows the above pH 13.
本発明に係る酸化チタン被膜形成用塗布溶液は、上述したようにチタンのハロゲン化物を加水分解して得られる水酸化物を有機強塩基の水溶液に溶解させればよく、溶解する方法等は特に限定されない。例えば、チタンの塩化物を加水分解して得られるチタン水酸化物を、ろ別し、これをテトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）などの有機強塩基水溶液に添加して攪拌・放置することにより溶解させてもよいし、必要に応じて加熱溶解させてもよいし、水酸化物を炉別せずに有機強塩基を添加してもよい。 As described above, the coating solution for forming a titanium oxide film according to the present invention may be prepared by dissolving a hydroxide obtained by hydrolyzing a halide of titanium in an aqueous solution of a strong organic base. It is not limited. For example, titanium hydroxide obtained by hydrolyzing titanium chloride is separated by filtration , dissolved in an organic strong base aqueous solution such as tetramethylammonium hydroxide (TMAH), and stirred and allowed to stand. It may be allowed to dissolve, or may be heated and dissolved as necessary, or an organic strong base may be added without separating the hydroxide.
このように製造される溶液は、チタン濃度が、２−１５重量％程度とするのが好ましく、２−８重量％程度がより好ましい。これは、チタン濃度が１５重量％を超えると、長期間（１年以上）保存した場合に沈殿物が生じる可能性があるからである。しかしながら、この沈殿物は水を加えて攪拌すると溶解するので本質的な問題ではないので、１５重量％を超えた濃度としても構わない。
酸化チタン被膜形成用塗布溶液は、チタンのハロゲン化物を加水分解して得られるチタン水酸化物を用いる。チタンのアルコキシチタン化合物の溶液を用いると、アルコキシチタンの溶液は、ゲル化を引き起こすので使用しない。チタンのハロゲン化物を加水分解しても得られるチタン水酸化物であり、有機基を含むチタン化合物を生じないので、ゲル化を生じない。その結果、本発明の酸化チタン被膜形成用塗布溶液は、長期間に亘って極めて安定であり、少なくともチタン濃度が１０重量％以下の溶液は、空気中室温で一年以上保存しても沈殿等が生じることがない。
The solution thus produced preferably has a titanium concentration of about 2-15% by weight, more preferably about 2-8% by weight. This is because when the titanium concentration exceeds 15% by weight, a precipitate may be formed when stored for a long period (one year or more). However, since this precipitate dissolves when water is added and stirred, it is not an essential problem, so the concentration may exceed 15% by weight.
Acid titanium film-forming coating solution, a titanium hydroxide obtained by hydrolyzing a halide of titanium. If a solution of an alkoxytitanium compound of titanium is used, an alkoxytitanium solution is not used because it causes gelation. Titanium hydroxide Der also be obtained by hydrolysis of a halide of titanium is, since no titanium compound containing organic groups, no gelation. As a result , the coating solution for forming a titanium oxide film of the present invention is extremely stable over a long period of time. At least a solution having a titanium concentration of 10% by weight or less precipitates even when stored at room temperature in air for more than one year. Will not occur.
さらに、本発明の酸化チタン被膜形成塗布溶液には、粘性を大きくして、基板との密着性を向上させるために、水溶性ポリマーが含有させる。水溶性ポリマーは極性基を有する水溶性ポリマーであり、添加することにより、クラック発生の虞のない厚膜を形成することができる。水溶性ポリマーは塗布する前までに添加すればよいが、予め含有させておいてもよい。 Furthermore, the titanium oxide film-forming coating solution of the present invention contains a water-soluble polymer in order to increase the viscosity and improve the adhesion to the substrate . Water-soluble polymers are water soluble polymers having a polar group, by adding, it is possible to form a risk-free thick film cracking. The water-soluble polymer may be added before coating, but may be contained in advance.
本発明で用いる水溶性ポリマーとしては、ポリビニルアルコール（ＰＶＡ），ポリビニルアセトアミド（ＰＮＶＡ）、ポリビニルホルムアミド（ＰＮＶＦ）、ポリジメチルアクリルアミド（ＰＤＭＡＡ）、ポリアクリルアミド（ＰＡＡＭ）、ポリアクロイルモルホリン（ＰＡＭ），ヒドロキシエチルセルロース（ＨＥＣ）、ヒドキシプロピルセルロース（ＨＰＣ）、カルボキシメチルセルロース（ＣＭＣ），等をあげることができる。Examples of the water-soluble polymer used in the present invention include polyvinyl alcohol (PVA), polyvinyl acetamide (PNVA), polyvinyl formamide (PNVF), polydimethylacrylamide (PDMAA), polyacrylamide (PAAM), polyacryloylmorpholine (PAM), hydroxy Examples thereof include ethyl cellulose (HEC), hydroxypropyl cellulose (HPC), carboxymethyl cellulose (CMC), and the like.
水溶性ポリマーとしては、このようなものから最適なものを適宜選択することができるが、アルカリに対してできるだけ安定したものを選択するのが好ましい。すなわち、アルカリで分解したり、変質したりする水溶性ポリマーを用いるのは、塗布液の安定性の面で好ましくないからである。As the water-soluble polymer, an optimal one can be appropriately selected from these, but it is preferable to select a polymer that is as stable as possible with respect to alkali. In other words, the use of a water-soluble polymer that decomposes or deteriorates with an alkali is not preferable in terms of the stability of the coating solution.
このような極性基を有する水溶性ポリマーの添加量は、ポリマーの種類によっても異なるが、一般的には、０．１重量％−５重量％程度である。なお、水溶性ポリマーは塗布する前までに添加すればよい。The amount of the water-soluble polymer having such a polar group varies depending on the type of polymer, but is generally about 0.1% by weight to 5% by weight. The water-soluble polymer may be added before coating.
色素増感太陽電池用Ｂｌｏｃｋｉｎｇ層に用いる酸化チタン被膜形成用塗布溶液には、極性基を有する水溶性ポリマーを同時に用いることにより、これが成膜助剤として作用し、より実用的な膜厚を有する膜を形成することができる。また、水溶性ポリマーの添加量を変化させることにより、従来の塗布法では困難であった膜厚のコントロールを自由に行うことができる。一回の塗布で、１００ｎｍ以上の膜厚を有する酸化チタン被膜を形成することが可能となった。 The titanium oxide film-forming coating solution used in Blocking layer for dye-sensitized solar cell, by using a water-soluble polymer having a polar group at the same time, it acts as a film forming aid, it has a more practical thickness A film can be formed. Further, by changing the added amount of the water-soluble polymer, as possible out to perform freely the thickness control is difficult in the conventional coating method. In one application, it has become possible to form a titanium oxide film having a film thickness of at least 100 n m.
本発明の色素増感太陽電池用Ｂｌｏｃｋｉｎｇ層に用いる酸化チタンの被膜を基板上に形成する方法。
酸化チタン被膜形成用塗布溶液を用いて酸化チタンを形成するには、この塗布液をスピンナー法、スプレー法、スクリーン印刷法、ロールコーター法、剛毛塗り法等の慣用の塗布手段で基板上に塗布する。その後、４００−８００℃、好ましくは４５０℃−７００℃で焼成して、酸化チタンの被膜形成することができる。特に、大型基板に塗布する場合は、低速スピンナー法によって塗布することが好ましい。これにより、１５インチを超える大型基板上に均一な塗布膜が形成でき、これを焼成することで、１００−５００ｎｍの均一な透明酸チタン被膜を形成することができる。
The method of forming on the board | substrate the film of the titanium oxide used for the blocking layer for dye-sensitized solar cells of this invention.
To form the titanium oxide by using a titanium oxide film-forming coating solution, spinner method this coating solution, a spray method, a screen printing method, roll coater method, on a base plate by conventional coating means such as bristles coating method Apply. Thereafter, it is baked at 400 to 800 ° C., preferably 450 to 700 ° C., to form a titanium oxide film. In particular, when applying to a large substrate, it is preferable to apply by a low-speed spinner method. Thereby, a uniform coating film on a large substrate than 15 inches can be formed, by sintering this, it is possible to form a uniform transparent titanate coating 100-500 n m.
一方、本発明の酸化チタン被膜形成用塗布溶液を塗布する対象物は、特に限定されないが、例えば、半導体基板、ガラス基板、セラミックス基板、板ガラス表面をシリカコートしたものや珪酸ガラス、石英ガラス板等である。On the other hand, the object to which the coating solution for forming a titanium oxide film of the present invention is applied is not particularly limited. For example, a semiconductor substrate, a glass substrate, a ceramic substrate, a plate glass surface coated with silica, a silicate glass, a quartz glass plate, etc. It is.
本発明の酸化チタン被膜形成用塗布溶液を用いて形成された酸化チタン被膜は、透明で均質で、残留炭素によるクラックやボイドが無く、特に、極性基を有するポリマーが成膜助剤として作用する場合には、対象物との密着性も良好で、ピンホールやアッマイクロクラックのない良質なものである。The titanium oxide film formed using the titanium oxide film-forming coating solution of the present invention is transparent and homogeneous, free from cracks and voids due to residual carbon, and in particular, a polymer having a polar group acts as a film forming aid. In some cases, the adhesion to the object is good, and there is no pinhole or up-crack, and the quality is good.
かかる本発明は、比較的厚い酸化チタン被膜を一度塗りで容易に形成できる。In the present invention, a relatively thick titanium oxide film can be easily formed by coating once.
また、従来の酸化チタン系塗布溶液は、主にチタンの金属アルコキシドを加水分解して得られるプレポリマーを使用するので、ゾルの粘性が経時変化することが実用上、問題となっていた。しかしながら、本発明の酸化チタン被膜形成用塗布溶液は、上述したように、ゾルの粘性が経時変化することなく、また、その使用が限定されず、製造工程において安全に酸化チタン被膜を形成できるという利点もある。Moreover, since the conventional titanium oxide coating solution mainly uses a prepolymer obtained by hydrolyzing a metal alkoxide of titanium, it has been a practical problem that the viscosity of the sol changes with time. However, as described above, the coating solution for forming a titanium oxide film of the present invention does not change the viscosity of the sol with time, and its use is not limited, and it can be safely formed in a manufacturing process. There are also advantages.
次に、実施例及び比較例を挙げて本発明を詳細に説明するが、これにより本発明が限定されるものでないことはいうまでもない。Next, although an Example and a comparative example are given and this invention is demonstrated in detail, it cannot be overemphasized that this invention is not limited by this.
四塩化チタンの１６％水溶液（和光純薬社製）１０ｍｌをイオン交換水で１０倍に希釈したものを、水酸化アンモニウム溶液でｐＨ７．０に調整し、生成した沈殿物を濾別した。沈殿物をフラスコに採取し、イオン交換水を５０ｍｌ加え、攪拌しながら、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）をｐＨ１３．５になるまで加え、室温で放置した。チタンの水酸化物は徐々に溶解して透明な溶液が得られた。A 16% aqueous solution of titanium tetrachloride (manufactured by Wako Pure Chemical Industries, Ltd.) 10 ml diluted with ion-exchanged water 10 times was adjusted to pH 7.0 with an ammonium hydroxide solution, and the produced precipitate was separated by filtration. The precipitate was collected in a flask, 50 ml of ion exchanged water was added, tetramethylammonium hydroxide (TMAH) was added to pH 13.5 with stirring, and the mixture was allowed to stand at room temperature. The titanium hydroxide was gradually dissolved to obtain a transparent solution.
この透明な酸化チタン水溶液は極めて安定であり、６ヶ月以上貯蔵しても沈殿を生じることがなく、透明性を保ったままであった。This transparent titanium oxide aqueous solution was extremely stable, did not cause precipitation even when stored for more than 6 months, and remained transparent.
この水溶液５０ｍｌに攪拌しながらＰＶＡ（ＮＨ−１７ｑ：日本合成化学社製）１重量％を溶解し、ｐＨ１３．５の酸化チタン被膜形成用塗布溶液を得た。この溶液のチタン濃度は５．２５％である。While stirring in 50 ml of this aqueous solution, 1% by weight of PVA (NH-17q: manufactured by Nippon Synthetic Chemical Co., Ltd.) was dissolved to obtain a coating solution for forming a titanium oxide film having a pH of 13.5. The titanium concentration of this solution is 5.25%.
四ヨウ化チタン１６．６６ｇをイオン交換水１００ｍｌに溶解し、アンモニヤ水でｐＨ７．０に調整し、生成した沈殿物を、ろ別した。沈殿物を洗浄、乾燥した後、フラスコに採取し、イオン交換水２５ｍｌを加え、攪拌しながら、テトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）をｐＨが１３．７になるまで加えた。沈殿物は速やかに溶解し、無色、透明な溶液が得られた。 The titanium tetraiodide 16.66g was dissolved in ion-exchanged water 100 ml, was adjusted to pH7.0 with Anmoniya water, the precipitate formed was filtered off. The precipitate was washed and dried, then collected in a flask, 25 ml of ion-exchanged water was added, and tetraethylammonium hydroxide (TEAH) was added with stirring until the pH reached 13.7. The precipitate quickly dissolved, and a colorless and transparent solution was obtained.
この溶液は極めて安定で、６ヶ月以上常温で保存しても透明性等性状に変化は認められなかった。This solution was extremely stable, and no change was observed in the properties such as transparency even when stored at room temperature for 6 months or more.
この水溶液２０ｍｌに攪拌しながらＰＶＡ（ＮＨ−１７ｑ：日本合成化学社製）１重量％を溶解し、ｐＨ１３．７の酸化チタン被膜形成用塗布溶液を得た。この溶液のチタン濃度は５．３６％である。While stirring in 20 ml of this aqueous solution, 1% by weight of PVA (NH-17q: manufactured by Nippon Synthetic Chemical Co., Ltd.) was dissolved to obtain a coating solution for forming a titanium oxide film having a pH of 13.7. The titanium concentration of this solution is 5.36%.
実施例１で得られた酸化チタン被膜形成用塗布溶液を室温で、スピンコータを使用して耐熱性基板（コーニング７０５９：コーニング社製）に塗布した。５０ｒｐｍの回転数で５秒間、２０００ｒｐｍの回転数で２０秒間処理した後、３０℃で１時間乾燥させた。The titanium oxide film-forming coating solution obtained in Example 1 was coated at room temperature on a heat resistant substrate (Corning 7059, manufactured by Corning) using a spin coater. After treating at a rotation speed of 50 rpm for 5 seconds and at a rotation speed of 2000 rpm for 20 seconds, it was dried at 30 ° C. for 1 hour.
その後、５００℃で１時間加熱して、透明薄膜を得た。この透明薄膜は、クラック、ボイド等は観察されず、均質な膜であり、膜厚は１７０ｎｍであった。
Then, it heated at 500 degreeC for 1 hour, and obtained the transparent thin film. The transparent thin film, cracks, voids, etc. are not observed, a uniform film, the film thickness was 170 nm.
また、得られた薄膜のＸ線回折パターンから、アナターゼ相であることが確認された。Moreover, it was confirmed from the X-ray diffraction pattern of the obtained thin film that it is an anatase phase.
以上の結果より、本発明によるとチタンのハロゲン化物を加水分解して得られるチタン水酸化物を有機強塩基の水溶液に溶解してなる酸化チタン被膜形成用塗布溶液を用いることにより、有機溶媒を使用しないで比較的厚い酸化チタン被膜を一度塗りで容易に形成でき、溶液としても安定している酸化チタン被膜形成用塗布溶液及び酸化チタン被膜の製造方法を提供することができるという効果を奏する。From the above results, according to the present invention, by using a coating solution for forming a titanium oxide film obtained by dissolving a titanium hydroxide obtained by hydrolyzing a halide of titanium in an aqueous solution of a strong organic base, A relatively thick titanium oxide film can be easily formed by coating once without using it, and an effect of providing a coating solution for forming a titanium oxide film that is stable as a solution and a method for producing the titanium oxide film can be provided.
すなわち、本発明の酸化チタン被膜形成用塗布溶液は、常温で１年以上安定して保存でき、有機溶媒を含有せず、また、有機溶媒を使用する必要もなく、製膜後の薄膜中に残留する有機物も極めて少ないので、残留炭素によるクラックやボイドの生成もない、均質な被膜を作成することができる。That is, the coating solution for forming a titanium oxide film of the present invention can be stably stored for 1 year or more at room temperature, does not contain an organic solvent, and does not require the use of an organic solvent. Since the remaining organic matter is extremely small, a homogeneous coating without cracks and voids due to residual carbon can be produced.
また、安価なチタン塩化物を用いて容易に製造できるので、従来のチタンのアルコキシドを原料とする方法と比較して製造コストも大幅に低減することができる。Further, since it can be easily produced using inexpensive titanium chloride, the production cost can be greatly reduced as compared with the conventional method using titanium alkoxide as a raw material.
本発明の酸化チタン被膜形成用塗布溶液は、光触媒、色素増感太陽電池（酸化物複合型）等に用いても有用なものであり、大幅なコストダウンという効果を奏するものである。 さらに、本発明の酸化チタン被膜形成溶液は有機側鎖を含有しない水溶液であり、クラック、ボイド等が存在しない被膜が得られ、色素増感太陽電池の作成に不可欠である“Ｂｌｏｃｋｉｎｇ層”の形成に極めて有用であることが判明している。今後、さらに、広範囲に使用されることが期待される。The coating solution for forming a titanium oxide film of the present invention is useful even when used for a photocatalyst, a dye-sensitized solar cell (oxide composite type), and the like, and has an effect of significant cost reduction. Further, the titanium oxide film-forming solution of the present invention is an aqueous solution containing no organic side chain, and a film free from cracks, voids, etc. is obtained, and the “blocking layer” is indispensable for the production of a dye-sensitized solar cell. Has proved to be very useful. In the future, it is expected to be used in a wider range.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010087301A JP5552682B2 (en) | 2010-03-18 | 2010-03-18 | Coating solution for forming titanium oxide film used for blocking layer for dye-sensitized solar cell, method for forming titanium oxide film used for blocking layer for dye-sensitized solar cell on substrate, and blocking layer for dye-sensitized solar cell Substrate with titanium oxide coating on the surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010087301A JP5552682B2 (en) | 2010-03-18 | 2010-03-18 | Coating solution for forming titanium oxide film used for blocking layer for dye-sensitized solar cell, method for forming titanium oxide film used for blocking layer for dye-sensitized solar cell on substrate, and blocking layer for dye-sensitized solar cell Substrate with titanium oxide coating on the surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011195798A JP2011195798A (en) | 2011-10-06 |
| JP5552682B2 true JP5552682B2 (en) | 2014-07-16 |
Family
ID=44874410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010087301A Expired - Fee Related JP5552682B2 (en) | 2010-03-18 | 2010-03-18 | Coating solution for forming titanium oxide film used for blocking layer for dye-sensitized solar cell, method for forming titanium oxide film used for blocking layer for dye-sensitized solar cell on substrate, and blocking layer for dye-sensitized solar cell Substrate with titanium oxide coating on the surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5552682B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5991158B2 (en) | 2012-11-16 | 2016-09-14 | ウシオ電機株式会社 | Method for forming a titanium oxide film on the surface of a molded body comprising a cyclic olefin resin |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001210156A (en) * | 1999-11-17 | 2001-08-03 | Toyo Gosei Kogyo Kk | Method of manufacturing coating solution for forming film of transparent conductive tin oxide and transparent conductive tin oxide film, and transparent conductive tin oxide film |
| JP4349654B2 (en) * | 2002-12-09 | 2009-10-21 | 関西ペイント株式会社 | Inorganic film-forming coating agent, inorganic film-forming method, and inorganic film-coated substrate |
| JP5005467B2 (en) * | 2007-08-09 | 2012-08-22 | 株式会社リコー | Method for manufacturing photoelectric conversion element |
| JP2009267169A (en) * | 2008-04-25 | 2009-11-12 | Fujifilm Corp | Photoelectric converting element and solid-state imaging device |
-
2010
- 2010-03-18 JP JP2010087301A patent/JP5552682B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011195798A (en) | 2011-10-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6603916B2 (en) | Inorganic oxide coating | |
| Kotachi et al. | Morphological evaluation and film formation with iso-oriented calcite crystals using binary poly (acrylic acid) | |
| JP5279344B2 (en) | Optical element manufacturing method | |
| JP2011107359A5 (en) | Optical article and method of manufacturing optical article | |
| JP5118068B2 (en) | PHOTOCATALYST THIN FILM, PHOTOCATALYST THIN FILM FORMATION METHOD, AND PHOTOCATALYST THIN FILM COATED PRODUCT | |
| WO2021047206A1 (en) | Preparation method for zirconium oxide-titanium oxide composite ultrafiltration membrane | |
| US20030047111A1 (en) | Coating solution for forming transparent silica coating film and method for producing transparent silica coating film | |
| JP5552682B2 (en) | Coating solution for forming titanium oxide film used for blocking layer for dye-sensitized solar cell, method for forming titanium oxide film used for blocking layer for dye-sensitized solar cell on substrate, and blocking layer for dye-sensitized solar cell Substrate with titanium oxide coating on the surface | |
| WO2000046154A1 (en) | Process for producing anatase titania or composite oxide containing anatase titania | |
| JP3506481B2 (en) | Coating solution for coating and substrate with coating | |
| JP3020241B2 (en) | Manufacturing method of titanium ceramic film | |
| KR100952570B1 (en) | Fabrication Method of Titanium oxide or Titanium oxide-Silicon oxide aerogel thin film/thick film for electrode support of transparent solar cell | |
| KR20080093483A (en) | Synthesis method of coating agent for antipollution | |
| CN103198927B (en) | A kind of preparation method of DSSC titanium dioxide photo anode | |
| JP2004149327A (en) | Coating solution for forming titanium oxide coating film and process for producing titanium oxide coating film | |
| KR100625252B1 (en) | A neutral TiO2 colloid solution for preparing the mesoporous TiO2 thin film and A preparation method thereof | |
| CN102872726B (en) | Preparation method of Ti-Zr composite nanofiltration membrane | |
| JP2004143186A (en) | Coating solution for forming transparent silica film and method for producing transparent silica film | |
| JPH054839A (en) | Method for preparing thin film by sol-gel method | |
| JP5155597B2 (en) | Method for producing ceramic thin film | |
| JP2012144399A (en) | Method for producing silica-containing hydrous titanium oxide and silica-containing anatase type titanium oxide | |
| KR100568458B1 (en) | Humidity sensor using nanostructured-multilayered Al-doped ZnO:TiO2 thin films | |
| Long et al. | Photoinduced hydrophilic effect and its application on self-cleaning technology | |
| CN109647366A (en) | A kind of method that sol-gel method prepares photoelectrocatalysioxidization oxidization Ti electrode | |
| CN115074708B (en) | Thermally-induced phase-change multilayer film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20121010 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20121011 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130927 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131008 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20131208 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20131206 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140213 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140401 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140502 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20140502 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5552682 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |