JP2019067850A - Compact layer for perovskite solar cell and method of manufacturing the same, and perovskite solar cell - Google Patents
Compact layer for perovskite solar cell and method of manufacturing the same, and perovskite solar cell Download PDFInfo
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- JP2019067850A JP2019067850A JP2017189764A JP2017189764A JP2019067850A JP 2019067850 A JP2019067850 A JP 2019067850A JP 2017189764 A JP2017189764 A JP 2017189764A JP 2017189764 A JP2017189764 A JP 2017189764A JP 2019067850 A JP2019067850 A JP 2019067850A
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- solar cell
- compact layer
- perovskite solar
- layer
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
本発明は、ペロブスカイト太陽電池用コンパクト層とその製造方法、及びペロブスカイト太陽電池に関する。 The present invention relates to a compact layer for a perovskite solar cell, a method for producing the same, and a perovskite solar cell.
太陽電池は、シリコン型太陽電池、色素増感型太陽電池、有機薄膜太陽電池等の様々な方式が知られている。近年、有機無機ハイブリッド構造のペロブスカイト結晶を光吸収に用いる、ペロブスカイト太陽電池が報告され（例えば、非特許文献１参照）、改良により急速に変換効率を向上させている。ペロブスカイト太陽電池は、ペロブスカイト層をはじめとする素子を溶液塗布によって高速かつ低コストで製造できるというメリットがあり、有力な発電方式として注目されている。 Various types of solar cells are known, such as silicon-type solar cells, dye-sensitized solar cells, and organic thin-film solar cells. In recent years, a perovskite solar cell using an organic-inorganic hybrid structure of perovskite crystal for light absorption has been reported (see, for example, Non-Patent Document 1), and the conversion efficiency is rapidly improved by improvement. Perovskite solar cells have the merit of being able to manufacture elements including a perovskite layer at high speed and at low cost by solution coating, and are attracting attention as a powerful power generation system.
ぺロブスカイト太陽電池素子の典型的な構造は、正極／正孔輸送層／ペロブスカイト結晶層／多孔性ＴｉＯ２層／コンパクト層／透明電極／ガラス基板を順次積層したものである。このうちコンパクト層は、透明電極上への正孔の到達を防ぐために設けられており、一般にＴｉＯ２薄膜が用いられる。ＴｉＯ２薄膜の形成方法としては、チタンテトライソプロポキシドやチタンジイソプロポキシドビス（アセチルアセトナート）等の前駆体を、スプレーコーティング法やスピンコート等の方法で塗布し熱分解を行う方法がある（例えば、特許文献１、非特許文献２参照）。 A typical structure of a perovskite solar cell element is one in which a positive electrode / hole transport layer / perovskite crystal layer / porous TiO 2 layer / compact layer / transparent electrode / glass substrate are sequentially laminated. Among these, the compact layer is provided to prevent the arrival of holes on the transparent electrode, and a TiO 2 thin film is generally used. As a method of forming a TiO 2 thin film, a method of applying a precursor such as titanium tetraisopropoxide or titanium diisopropoxide bis (acetylacetonate) by a spray coating method or a spin coat method and performing thermal decomposition is known. (See, for example, Patent Document 1 and Non-Patent Document 2).
コンパクト層はペロブスカイト太陽電池の効率向上やヒステリシス（測定条件によって素子特性が変わる現象）の抑制に重要であることが知られている。一般にピンホールやトラップ準位が少ないコンパクト層程効果が大きいとされているが、コンパクト層の物理的状態とその効果の関係は必ずしも明らかになっていない。例えば非特許文献３では、四塩化チタン溶液を前駆体に用いたコンパクト層を有するペロブスカイト太陽電池が開示されている。この太陽電池はヒステリシスや耐久性が向上しているが、効率は向上していない。このように、太陽電池の効率を向上させるためにどのような前駆体が有用であるかについて、一般的な知見は得られていないのが現状である。 The compact layer is known to be important for the improvement of the efficiency of the perovskite solar cell and the suppression of the hysteresis (the phenomenon in which the device characteristics change depending on the measurement conditions). In general, it is considered that the effect is larger as the compact layer has less pinholes and trap levels, but the relationship between the physical state of the compact layer and the effect is not necessarily clear. For example, Non-Patent Document 3 discloses a perovskite solar cell having a compact layer using a titanium tetrachloride solution as a precursor. Although this solar cell has improved hysteresis and durability, its efficiency has not. Thus, at present, no general knowledge has been obtained as to what precursors are useful for improving the efficiency of solar cells.
本発明の目的は、ペロブスカイト太陽電池の変換効率を向上させるために有用なコンパクト層、及びその前駆体を提供することにある。 An object of the present invention is to provide a compact layer useful for improving the conversion efficiency of a perovskite solar cell, and a precursor thereof.
本発明者らは上記の課題を解決すべく鋭意検討した結果、特定のチタン酸化物クラスター化合物及び有機溶媒を含んでなる成膜溶液を塗布して加熱した酸化物膜を含んでなるコンパクト層がペロブスカイト太陽電池素子の効率を向上させることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors found that a compact layer comprising an oxide film obtained by applying and heating a film forming solution comprising a specific titanium oxide cluster compound and an organic solvent It has been found that the efficiency of the perovskite solar cell element is improved, and the present invention has been completed.
すなわち本発明は、一般式（１）
ＴｉｘＯｙ（ＯＲ）ｚ （１）
（式中、ｘは３以上１００以下の整数、ｙは、１以上の整数、ｚは２以上の整数を表す。ただし、ｘ、ｙ及びｚは４ｘ＝２ｙ＋ｚを満たすものとする。Ｒは同一又は相異なって、水素原子、アルキル基、アリール基を表す。ただし、Ｒはヘテロ原子を含む官能基を含有していてもよい。）で示されるチタン酸化物クラスター化合物及び有機溶媒を含んでなる成膜溶液を塗布して加熱した酸化物膜を含んでなるコンパクト層に関する。
That is, the present invention relates to the general formula (1)
Ti x O y (OR) z (1)
(Wherein x is an integer of 3 to 100, y is an integer of 1 or more, and z is an integer of 2 or more, provided that x, y and z satisfy 4x = 2y + z, and R is the same. Or different from each other, each representing a hydrogen atom, an alkyl group, or an aryl group, provided that R represents a titanium oxide cluster compound represented by the following formula) and an organic solvent: The present invention relates to a compact layer comprising an oxide film coated and heated with a deposition solution.
さらに本発明は、前記コンパクト層を含むことを特徴とする、ペロブスカイト太陽電池に関する。 Furthermore, the present invention relates to a perovskite solar cell characterized by comprising the compact layer.
以下に本発明を詳細に説明する。 The present invention will be described in detail below.
まず、本発明の請求項１において、酸化物膜はチタン酸化物クラスター化合物及び有機溶媒から成る製膜溶液を基板上に塗布して加熱した酸化物膜と記載せざるを得ない理由を説明する。 First, in claim 1 of the present invention, the reason why the oxide film must be described as an oxide film which is formed by applying a film forming solution comprising a titanium oxide cluster compound and an organic solvent on a substrate and heating it .
製膜溶液の成分として、チタン酸化物クラスター化合物を用いた場合、及びチタン酸化物クラスター化合物ではない化合物を用いた場合のいずれにおいても、酸化物膜の組成について大差はない。例えば、実施例に記載の金属酸化物クラスターであるＴｉ１１Ｏ１３（ＯｉＰｒ）１８を用いた場合、及び比較例に記載の金属酸化物クラスターではないチタンジイソプロポキシドビス（アセチルアセトナート）を用いた場合のいずれにおいても焼成した後の酸化物膜の組成はＴｉＯ２である。しかしながら、実施例比較例より金属酸化物クラスター化合物を用いた場合と金属酸化物クラスター化合物ではないチタンジイソプロポキシドビス（アセチルアセトナート）を用いた場合とでは、得られる酸化物膜（ＴｉＯ２膜）をコンパクト層に用いると、ペロブスカイト太陽電池の特性に差が生じる。 There is no significant difference in the composition of the oxide film in any of the case of using a titanium oxide cluster compound and the case of using a compound that is not a titanium oxide cluster compound as a component of the film forming solution. For example, titanium diisopropoxide bis (acetylacetonate) which is not the metal oxide cluster described in the comparative example when Ti 11 O 13 (O i Pr) 18 which is the metal oxide cluster described in the example is used. The composition of the oxide film after firing is TiO 2 in any of the cases of using. However, according to the comparative example of the embodiment, the obtained oxide film (TiO 2 ) is obtained when the metal oxide cluster compound is used and when titanium diisopropoxide bis (acetylacetonate) which is not the metal oxide cluster compound is used. When the film is used in the compact layer, the characteristics of the perovskite solar cell differ.
この特性の違いは出発原料のチタン酸化物クラスター化合物とチタン酸化物クラスター化合物でないチタンジイソプロポキシドビス（アセチルアセトナート）との違いであり、出発原料の違いにより得られる酸化物膜（ＴｉＯ２膜）を用いたコンパクト層の特性に差が出る。 The difference in this property is the difference between the starting titanium oxide cluster compound and the titanium diisopropoxide bis (acetylacetonate) which is not a titanium oxide cluster compound, and the oxide film obtained by the difference in starting material (TiO 2 Differences in the characteristics of the compact layer using the membrane).
このようにコンパクト層に用いる酸化物膜の特性に差が出ることから、組成に大差はないものの酸化物膜自体が異なることが予想される。ただし、酸化物膜自体を規定するとなると、本願発明のチタン酸化物クラスター化合物を用いた酸化物膜以外の多様な酸化物膜を包含することになるため、酸化物膜自体による規定は本願発明の対象物である酸化物膜を的確に表すことが困難であり、酸化物膜自体による規定は実際的でない。 Since there is a difference in the characteristics of the oxide film used for the compact layer as described above, it is expected that the oxide film itself is different although there is no significant difference in the composition. However, when the oxide film itself is defined, various oxide films other than the oxide film using the titanium oxide cluster compound of the present invention will be included. It is difficult to accurately represent the target oxide film, and the definition by the oxide film itself is not practical.
本発明において、チタン酸化物クラスター化合物とは、一般式（１）で表される化合物である。
ＴｉｘＯｙ（ＯＲ）ｚ （１）
（式中、ｘは３以上１００以下の整数、ｙは１以上の整数、ｚは２以上の整数である。ただし、ｘ、ｙ及びｚは、４ｘ＝２ｙ＋ｚを満たすものとする。Ｒは同一又は相異なって、水素原子、アルキル基、アリール基を表す。ただし、Ｒはヘテロ原子を含む官能基を含有していてもよい。）
一般式（１）のｘは３以上１００以下の整数であり、好ましくは５以上１５以下の整数であり、特に好ましくは１１又は１２である。ｙは１以上の整数であり、好ましくは４以上２８以下の整数、特に好ましくは１３又は１６である。ｚは２以上の整数であり、好ましくは１６以上２２以下の整数特に好ましくは１６又は１８である。ｙ及びｚは、４ｘ＝２ｙ＋ｚを満たす値が選択される。
In the present invention, the titanium oxide cluster compound is a compound represented by the general formula (1).
Ti x O y (OR) z (1)
(Wherein x is an integer of 3 to 100, y is an integer of 1 or more, z is an integer of 2 or more, provided that x, y and z satisfy 4x = 2y + z, and R is the same. And each independently represents a hydrogen atom, an alkyl group, or an aryl group, provided that R may contain a functional group containing a hetero atom.)
In general formula (1), x is an integer of 3 or more and 100 or less, preferably 5 or more and 15 or less, and particularly preferably 11 or 12. y is an integer of 1 or more, preferably an integer of 4 or more and 28 or less, particularly preferably 13 or 16. z is an integer of 2 or more, preferably an integer of 16 or more and 22 or less, particularly preferably 16 or 18. As y and z, values satisfying 4x = 2y + z are selected.
Ｒは同一又は相異なって、水素原子、アルキル基、アリール基を表す。アルキル基としては、例えばメチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、シクロブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、１−メチルブチル基、２−メチルブチル基、ヘキシル基、１−メチルヘキシル基、１−エチルヘキシル基、１−ブチルヘキシル基、２−メチルヘキシル基、２−エチルヘキシル基、４−メチルヘキシル基、６−メチルヘキシル基、１，３，５−トリメチルヘキシル基、ヘプチル基、１−メチルヘプチル基、１−エチルヘプチル基、２−エチルヘプチル基、１−ブチルヘプチル基、１，３，５−トリメチルヘプチル基、オクチル基、１−メチルオクチル基、１−エチルオクチル基、４−メチルオクチル基、１，３，５−トリメチルオクチル基、ノニル基、１−メチルノニル基、１−エチルノニル基、４−メチルノニル基、１，３，５−トリメチルノニル基、デシル基、１−メチルデシル基、１−エチルデシル基、４−メチルデシル基、１，３，５−トリメチルデシル基、ドデシル基、１−メチルドデシル基、１−エチルドデシル基、４−メチルドデシル基、１，３，５−トリメチルドデシル基、アダマンチル基、トリデシル基、１−メチルトリデシル基、１−エチルトリデシル基、４−メチルトリデシル基、１，３，５−トリメチルトリデシル基、ブタデシル基、１−メチルブタデシル基、１−エチルブタデシル基、４−メチルブタデシル基、１，３，５−トリメチルブタデシル基、ヘキサデシル基、１−メチルヘキサデシル基、１−エチルヘキサデシル基、４−メチルヘキサデシル基、１，３，５−トリメチルヘキサデシル基、ペンタデシル基、１−メチルペンタデシル基、１−エチルペンタデシル基、４−メチルペンタデシル基、１，３，５−トリメチルペンタデシル基、ヘプタデシル基、１−メチルヘプタデシル基、１−エチルヘプタデシル基、４−メチルヘプタデシル基、１，３，５−トリメチルヘプタデシル基、ステアリル基、１−メチルステアリル基、１−エチルステアリル基、４−メチルステアリル基、１，３，５−トリメチルステアリル基、ウンステアリル基、１−メチルウンステアリル基、１−エチルウンステアリル基、４−メチルウンステアリル基、１，３，５−トリメチルウンステアリル基、ドステアリル基、１−メチルドステアリル基、１−エチルドステアリル基、４−メチルドステアリル基、１，３，５−トリメチルドステアリル基等が挙げられ、アリール基としては、例えばフェニル基、２−メチルフェニル基、４−メチルフェニル基、４−エチルフェニル基、２，６−ジメチルフェニル基、２，３，４，５，６−ペンタメチルフェニル基、２−プロピルフェニル基、４−プロピルフェニル基、２，６−ジメチル−４−プロピルフェニル基、２−ブチルフェニル基、４−ブチルフェニル基、４−ｓｅｃ−ブチルフェニル基、４−ｔｅｒｔ−ブチルフェニル基、２−ペンチルフェニル基、４−ペンチルフェニル基、２−ヘキシルフェニル基、４−ヘキシルフェニル基、２，６−ジメチル−４−ヘキシルフェニル基、４−シクロヘキシルフェニル基、４−（４−メチルシクロヘキシル）フェニル基、２−オクチルフェニル基、４−オクチルフェニル基、４−（１，１−ジエチル−２−メチルプロピル）フェニル基、４−（１，１，３，３−テトラメチルブチル）フェニル基、４−（１，１，２，３，３−ペンタメチルブチル）フェニル基、２−デシルフェニル基、２−デシル，４−エチルフェニル基、４−デシルフェニル基、２−エチル−５−デシルフェニル基、４−（１，１−ジメチルオクチル）フェニル基、４−（１，１−ジメチルデシル）フェニル基、２−ドデシルフェニル基、４−ドデシルフェニル基、２−ヘキシル，４−ドデシルフェニル基、３，４，５−トリドデシルフェニル基、４−アダマンチルフェニル基、２−トリデシルフェニル基、４−トリデシルフェニル基、３，４，５−トリデシルフェニル基、２−ブタデシルフェニル基、４−ブタデシルフェニル基、３，４，５−トリブタデシルフェニル基、２−ペンタデシルフェニル基、４−ペンタデシルフェニル基、３，４，５−トリス（ペンタデシル）フェニル基、２−ヘキサデシルフェニル基、４−ヘキサデシルフェニル基、３，４，５−トリス（ヘキサデシル）フェニル基、２−ヘプタデシルフェニル基、４−ヘプタデシルフェニル基、３，４，５−トリス（ヘプタデシル）フェニル基、２−（４−ドデシルシクロヘキシル）フェニル基、４−（４−ドデシルシクロヘキシル）フェニル基、３，４，５−トリス（４−ドデシルシクロヘキシル）フェニル基、２−ステアリルフェニル基、４−ステアリルフェニル基、３，４，５−トリステアリルフェニル基、２−ウンステアリルフェニル基、４−ウンステアリルフェニル基、３，４，５−トリス（ウンステアリル）フェニル基、２−ドステアリルフェニル基、４−ドステアリルフェニル基、３，４，５−トリドステアリルフェニル基等が挙げられる。 R is the same or different and represents a hydrogen atom, an alkyl group or an aryl group. As the alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, isopentyl group, neopentyl group, tert-Pentyl group, 1-methylbutyl group, 2-methylbutyl group, hexyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-butylhexyl group, 2-methylhexyl group, 2-ethylhexyl group, 4-methylhexyl group Group, 6-methylhexyl group, 1,3,5-trimethylhexyl group, heptyl group, 1-methylheptyl group, 1-ethylheptyl group, 2-ethylheptyl group, 1-butylheptyl group, 1,3,5 -Trimethylheptyl group, octyl group, 1-methyloctyl group, 1-ethyloctyl group, -Methyloctyl group, 1,3,5-trimethyloctyl group, nonyl group, 1-methyl nonyl group, 1-ethyl nonyl group, 4-methyl nonyl group, 1,3,5-trimethyl nonyl group, decyl group, 1-methyl decyl group 1-ethyldecyl group, 4-methyldecyl group, 1,3,5-trimethyldecyl group, dodecyl group, 1-methyldodecyl group, 1-ethyldodecyl group, 4-methyldodecyl group, 1,3,5-trimethyldodecyl group Group, adamantyl group, tridecyl group, 1-methyltridecyl group, 1-ethyltridecyl group, 4-methyltridecyl group, 1,3,5-trimethyltridecyl group, butadecyl group, 1-methylbutadecyl group, 1-ethylbutadecyl group, 4-methylbutadecyl group, 1,3,5-trimethylbutadecyl group, hexadecyl group, 1-methylhexade Group, 1-ethylhexadecyl group, 4-methylhexadecyl group, 1,3,5-trimethylhexadecyl group, pentadecyl group, 1-methylpentadecyl group, 1-ethylpentadecyl group, 4-methylpentadecyl group Group, 1,3,5-trimethylpentadecyl group, heptadecyl group, 1-methyl heptadecyl group, 1-ethyl heptadecyl group, 4-methyl heptadecyl group, 1,3,5-trimethylheptadecyl group, stearyl group 1-methyl stearyl group, 1-ethyl stearyl group, 4-methyl stearyl group, 1,3,5-trimethyl stearyl group, unstearyl group, 1-methyl unstearyl group, 1-ethyl unstearyl group, 4-methyl Unstearyl group, 1,3,5-trimethylunstearyl group, dostearyl group, 1-methyldostearyl group, 1-ethyl dostearyl group, 4-methyl dostearyl group, 1,3,5-trimethyl dostearyl group etc. are mentioned, As an aryl group, a phenyl group, 2-methylphenyl group, 4-methylphenyl group, etc. are mentioned, for example. 4-ethylphenyl, 2,6-dimethylphenyl, 2,3,4,5,6-pentamethylphenyl, 2-propylphenyl, 4-propylphenyl, 2,6-dimethyl-4-propyl Phenyl group, 2-butylphenyl group, 4-butylphenyl group, 4-sec-butylphenyl group, 4-tert-butylphenyl group, 2-pentylphenyl group, 4-pentylphenyl group, 2-hexylphenyl group, 4 -Hexylphenyl group, 2,6-dimethyl-4-hexylphenyl group, 4-cyclohexylphenyl group, 4- (4-methylcyclohexyl) group Syl) phenyl group, 2-octylphenyl group, 4-octylphenyl group, 4- (1,1-diethyl-2-methylpropyl) phenyl group, 4- (1,1,3,3-tetramethylbutyl) phenyl Group, 4- (1,1,2,3,3-pentamethylbutyl) phenyl group, 2-decylphenyl group, 2-decyl, 4-ethylphenyl group, 4-decylphenyl group, 2-ethyl-5-yl group Decylphenyl, 4- (1,1-dimethyloctyl) phenyl, 4- (1,1-dimethyldecyl) phenyl, 2-dodecylphenyl, 4-dodecylphenyl, 2-hexyl, 4-dodecylphenyl Group, 3,4,5-tridodecylphenyl group, 4-adamantylphenyl group, 2-tridecylphenyl group, 4-tridecylphenyl group, 3,4,5-tridecylphenyl group , 2-butadecylphenyl group, 4-butadecylphenyl group, 3,4,5-tributadecylphenyl group, 2-pentadecylphenyl group, 4-pentadecylphenyl group, 3,4,5-tris (pentadecyl) ) Phenyl group, 2-hexadecylphenyl group, 4-hexadecylphenyl group, 3,4,5-tris (hexadecyl) phenyl group, 2-heptadecylphenyl group, 4-heptadecylphenyl group, 3,4,5 -Tris (heptadecyl) phenyl group, 2- (4-dodecylcyclohexyl) phenyl group, 4- (4-dodecylcyclohexyl) phenyl group, 3,4,5-tris (4-dodecylcyclohexyl) phenyl group, 2-stearylphenyl Group, 4-stearylphenyl group, 3,4,5-tristearylphenyl group, 2-unstearylphenyl group Group, 4-unstearylphenyl group, 3,4,5-tris (unstearyl) phenyl group, 2-dostearylphenyl group, 4-dostearylphenyl group, 3,4,5-tridostearylphenyl group etc. It can be mentioned.
また、Ｒはヘテロ原子を含む官能基を含有していてもよく、該ヘテロ原子を含む官能基としては、例えばメトキシエチル基、エトキシエチル基、ブトキシエチル基、ペンチルオキシエチル基、ヘキシルオキシエチル基、オクチルオキシエチル基、デシルオキシエチル基、ブタデシルオキシエチル基、ドデシルオキシエチル基、ペンタデシルオキシエチル基、ヘキサデシルオキシエチル基、ステアリルオキシエチル基、ウンステアリルオキシエチル基、ドステアリルオキシエチル基、１−ヘキシルオキシ−２−プロピル基、１−オクチルオキシ−２−プロピル基、１−デシルオキシ−２−プロピル基、１−ブタデシルオキシ−２−プロピル基、１−ドデシルオキシ−２−プロピル基、１−ペンタデシルオキシ−２−プロピル基、１−ヘキサデシルオキシ−２−プロピル基、１−ステアリル−２−プロピル基、１−ウンステアリル−２−プロピル基、１−ドステアリル−２−プロピル基、モノメチルエーテルジエチレングリコキシ基、モノエチルエーテルジエチレングリコキシ基、モノプロピルエーテルジエチレングリコキシ基、モノブチルエーテルジエチレングリコキシ基、モノペンチルエーテルジエチレングリコキシ基、モノヘキシルエーテルジエチレングリコキシ基、モノオクチルジエチレングリコキシ基、モノデシルエーテルジエチレングリコキシ基、モノブタデシルエーテルジエチレングリコキシ基、モノドデシルエーテルジエチレングリコキシ基、モノペンタデシルエーテルジエチレングリコキシ基、モノヘキサデシルエーテルジエチレングリコキシ基、モノステアリルエーテルジエチレングリコキシ基、モノヘキサデシルエーテルジエチレングリコキシ基、モノウンステアリルエーテルジエチレングリコキシ基、モノドステアリルエーテルジエチレングリコキシ基等が挙げられる。 Further, R may contain a functional group containing a hetero atom, and as the functional group containing the hetero atom, for example, methoxyethyl group, ethoxyethyl group, butoxyethyl group, pentyloxyethyl group, hexyloxyethyl group , Octyloxyethyl group, decyloxyethyl group, butadecyloxyethyl group, dodecyloxyethyl group, pentadecyloxyethyl group, hexadecyloxyethyl group, stearyloxyethyl group, unsteallyloxyethyl group, dostearyloxyethyl group 1-hexyloxy-2-propyl group, 1-octyloxy-2-propyl group, 1-decyloxy-2-propyl group, 1-butadecyloxy-2-propyl group, 1-dodecyloxy-2-propyl group , 1-pentadecyloxy-2-propyl group, 1-hexadecy Oxy-2-propyl group, 1-stearyl-2-propyl group, 1-unstearyl-2-propyl group, 1-dostearyl-2-propyl group, monomethylether diethyleneglycoxy group, monoethylether diethyleneglycoxy group, mono Propylether diethyleneglycoxy group, monobutylether diethyleneglycoxy group, monopentylether diethyleneglycoxy group, monohexylether diethyleneglycoxy group, monooctyldiethyleneglycoxy group, monodecylether diethyleneglycoxy group, monobutadecylether diethyleneglycoxy group, monododecyl ether Diethyleneglycoxy group, monopentadecylether diethyleneglycoxy group, monohexadecylether diethyleneglycoxy group, monostearic acid Ether diethylene glycoxy group, mono hexadecyl ether diethylene glycoxy group, mono down stearyl ether diethylene glycoxy group, mono de stearyl ether diethylene glycoxy group.
これらの中でもＲとしては、アルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、シクロブチル基等が好ましく、特に好ましくはエチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基であり、アリール基としては、フェニル基、２−メチルフェニル基、４−メチルフェニル基、４−エチルフェニル基、２，６−ジメチルフェニル基、２，３，４，５，６−ペンタメチルフェニル基、２−プロピルフェニル基、４−プロピルフェニル基、２，６−ジメチル−４−プロピルフェニル基、２−ブチルフェニル基、４−ブチルフェニル基、４−ｓｅｃ−ブチルフェニル基、４−ｔｅｒｔ−ブチルフェニル基、２−ペンチルフェニル基、４−ペンチルフェニル基、２−ヘキシルフェニル基、４−ヘキシルフェニル基又は２，６−ジメチル−４−ヘキシルフェニル基が好ましく、特に好ましくはフェニル基、２−メチルフェニル基又は４−メチルフェニル基、４−エチルフェニル基であり、ヘテロ原子を含む官能基としては、メトキシエチル基、エトキシエチル基、ブトキシエチル基、ペンチルオキシエチル基、ヘキシルオキシエチル基、オクチルオキシエチル基、デシルオキシエチル基、ブタデシルオキシエチル基、ドデシルオキシエチル基、ペンタデシルオキシエチル基、ヘキサデシルオキシエチル基、ステアリルオキシエチル基、ウンステアリルオキシエチル基又はドステアリルオキシエチル基が好ましく、特に好ましくはメトキシエチル基、エトキシエチル基又はブトキシエチル基である。 Among these, as R, as the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group and the like are preferable, Particularly preferred is an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group, and an aryl group is a phenyl group, a 2-methylphenyl group or a 4-methylphenyl group, 4-ethylphenyl, 2,6-dimethylphenyl, 2,3,4,5,6-pentamethylphenyl, 2-propylphenyl, 4-propylphenyl, 2,6-dimethyl-4-propyl Phenyl group, 2-butylphenyl group, 4-butylphenyl group, 4-sec-butylphenyl group, 4-ter -Butylphenyl group, 2-pentylphenyl group, 4-pentylphenyl group, 2-hexylphenyl group, 4-hexylphenyl group or 2,6-dimethyl-4-hexylphenyl group is preferable, and a phenyl group, 2 -Methylphenyl group or 4-methylphenyl group, 4-ethylphenyl group, and as a functional group containing a hetero atom, a methoxyethyl group, an ethoxyethyl group, a butoxyethyl group, a pentyloxyethyl group, a hexyloxyethyl group, Octyl oxyethyl group, decyloxy ethyl group, butadecyl oxyethyl group, dodecyl oxyethyl group, pentadecyl oxyethyl group, hexadecyl oxyethyl group, stearyloxy ethyl group, unsteallyloxy ethyl group or dosteallyloxy ethyl group Preferred, particularly preferred Methoxyethyl group, ethoxyethyl group or butoxyethyl group.
一般式（１）で表されるチタン酸化物クラスター化合物としては、例えば、Ｔｉ３Ｏ（ＯｉＰｒ）１０、Ｔｉ３Ｏ（ＯＭｅ）（ＯｉＰｒ）９、Ｔｉ３Ｏ（ＯＨ）（ＯｉＰｒ）９、Ｔｉ３Ｏ（ＯｉＰｒ）７（ｄｍｈｅｔｏ）、Ｔｉ６Ｏ４（ＯＥｔ）８（ＯＣＯＣＨ３）８、Ｔｉ６Ｏ４（ＯｉＰｒ）８（ＯＣＯＣＨ３）８、Ｔｉ６Ｏ４（ＯｎＢｕ）８（ＯＣＯＣＨ３）８、Ｔｉ６Ｏ４（ＯｉＰｒ）１２（ＯＣＯＣＨ３）４、Ｔｉ７Ｏ４（ＯＥｔ）２０、Ｔｉ８Ｏ６（ＯＣＨ２Ｃ６Ｈ５）２０、Ｔｉ９Ｏ８（ＯｎＰｒ）４（ＯＭｃ）４、Ｔｉ１０Ｏ８（ＯＥｔ）２４、Ｔｉ１１Ｏ１３（ＯｉＰｒ）１８、Ｔｉ１１Ｏ１３（ＯｉＰｒ）１３（ＯＥｔ）５、Ｔｉ１２Ｏ１６（ＯｉＰｒ）１６、Ｔｉ１２Ｏ１６（ＯＥｔ）６（ＯｉＰｒ）１０、Ｔｉ１２Ｏ１６（ＯＥｔ）４（ＯｔＢｕ）１２（ｔＢｕＯＨ）２、Ｔｉ１２Ｏ１６（ＯＣＨ２ ｔＢｕ）１６、Ｔｉ１４Ｏ１９（ＯＨ）（ＯｔＢｕ）１３（ＯＣＯＣＨ３）４、Ｔｉ１５Ｏ１４（ＯＥｔ）３２、Ｔｉ１６Ｏ１６（ＯＥｔ）３２、Ｔｉ１６Ｏ１６（ＯＥｔ）２８（ＯｎＰｒ）４、Ｔｉ１６Ｏ１６（ＯＥｔ）２４（ＯｎＰｒ）８、Ｔｉ１７Ｏ２４（ＯｉＰｒ）２０、Ｔｉ１８Ｏ２８（Ｈ）（ＯｔＢｕ）１７、Ｔｉ１８Ｏ２８（ＯｔＢｕ）１６（ｔＢｕＯＨ）、Ｔｉ１８Ｏ２５（ＯｔＢｕ）１２（ＯＣＯＣＨ３）１０、Ｔｉ１８Ｏ２２（ＯｎＢｕ）２６（ａｃａｃ）２、Ｔｉ２８Ｏ４０（ＯｔＢｕ）２０（ＯＣＯＣＨ３）１２、Ｔｉ２８Ｏ３４（ＯＥｔ）４４、Ｔｉ３４Ｏ５０（ＯｉＰｒ）３６、Ｔｉ４２Ｏ６０（ＯＨ）１２（ＯｉＰｒ）４２（Ｈ）６、Ｔｉ４２Ｏ６０（ＯＨ）１２（ＯｉＰｒ）３６（ｉＰｒＯＨ）６などの化合物が挙げられ、その中でも入手が容易である点で、Ｔｉ６Ｏ４（ＯＥｔ）８（ＯＣＯＣＨ３）８、Ｔｉ６Ｏ４（ＯｉＰｒ）８（ＯＣＯＣＨ３）８、Ｔｉ６Ｏ４（ＯｎＢｕ）８（ＯＣＯＣＨ３）８、Ｔｉ６Ｏ４（ＯｉＰｒ）１２（ＯＣＯＣＨ３）４、Ｔｉ７Ｏ４（ＯＥｔ）２０、Ｔｉ１０Ｏ８（ＯＥｔ）２４、Ｔｉ１１Ｏ１３（ＯｉＰｒ）１８、Ｔｉ１１Ｏ１３（ＯｉＰｒ）１３（ＯＥｔ）５、Ｔｉ１２Ｏ１６（ＯｉＰｒ）１６、Ｔｉ１２Ｏ１６（ＯＣＨ２ ｔＢｕ）１６、Ｔｉ１４Ｏ１９（ＯＨ）（ＯｔＢｕ）１３（ＯＣＯＣＨ３）４、Ｔｉ１６Ｏ１６（ＯＥｔ）３２、Ｔｉ１７Ｏ２４（ＯｉＰｒ）２０、Ｔｉ１８Ｏ２８（Ｈ）（ＯｔＢｕ）１７、Ｔｉ１８Ｏ２８（ＯｔＢｕ）１６（ｔＢｕＯＨ）、Ｔｉ１８Ｏ２５（ＯｔＢｕ）１２（ＯＣＯＣＨ３）１０が好ましく、特に好ましくはＴｉ１１Ｏ１３（ＯｉＰｒ）１８、Ｔｉ１１Ｏ１３（ＯｉＰｒ）１３（ＯＥｔ）５、Ｔｉ１２Ｏ１６（ＯｉＰｒ）１６、Ｔｉ１２Ｏ１６（ＯＣＨ２ ｔＢｕ）１６である。ここで、Ｍｅはメチル基、Ｅｔはエチル基、ｎＰｒはプロピル基、ｉＰｒはイソプロピル基、ｔＢｕはｔｅｒｔ−ブチル基、（ＯＭｃ）はメタクリラト配位子、（ａｃａｃ）はアセチルアセトナト配位子、（ｄｍｈｅｔｏ）は２，６−ジメチルヘプタ−３−エン−２，４，６−トリス（オラト）配位子の略である。 As a titanium oxide cluster compound represented by General formula (1), for example, Ti 3 O (O i Pr) 10 , Ti 3 O (OMe) (O i Pr) 9 , Ti 3 O (OH) (O) i Pr) 9, Ti 3 O (O i Pr) 7 (dmheto), Ti 6 O 4 (OEt) 8 (OCOCH 3) 8, Ti 6 O 4 (O i Pr) 8 (OCOCH 3) 8, Ti 6 O 4 (O n Bu) 8 (OCOCH 3 ) 8 , Ti 6 O 4 (O i Pr) 12 (OCOCH 3 ) 4 , Ti 7 O 4 (OEt) 20 , Ti 8 O 6 (OCH 2 C 6 H 5) ) 20, Ti 9 O 8 ( O n Pr) 4 (OMc) 4, Ti 10 O 8 (OEt) 24, Ti 11 O 13 (O i Pr) 18, Ti 11 O 13 (O i Pr) 13 (OEt ) 5, Ti 2 O 16 (O i Pr) 16, Ti 12 O 16 (OEt) 6 (O i Pr) 10, Ti 12 O 16 (OEt) 4 (O t Bu) 12 (t BuOH) 2, Ti 12 O 16 ( OCH 2 t Bu) 16 , Ti 14 O 19 (OH) (O t Bu) 13 (OCOCH 3 ) 4 , Ti 15 O 14 (OEt) 32 , Ti 16 O 16 (OEt) 32 , Ti 16 O 16 (OEt) ) 28 (O n Pr) 4 , Ti 16 O 16 (OEt) 24 (O n Pr) 8 , Ti 17 O 24 (O i Pr) 20 , Ti 18 O 28 (H) (O t Bu) 17 , Ti 18 O 28 (O t Bu) 16 (t BuOH), Ti 18 O 25 (O t Bu) 12 (OCOCH 3) 10, Ti 18 O 22 (O n Bu) 26 (ac c) 2, Ti 28 O 40 (O t Bu) 20 (OCOCH 3) 12, Ti 28 O 34 (OEt) 44, Ti 34 O 50 (O i Pr) 36, Ti 42 O 60 (OH) 12 (O Compounds such as i Pr) 42 (H) 6 and Ti 42 O 60 (OH) 12 (O i Pr) 36 ( i PrOH) 6 may be mentioned, among which Ti 6 O 4 OEt) 8 (OCOCH 3 ) 8 , Ti 6 O 4 (O i Pr) 8 (OCOCH 3 ) 8 , Ti 6 O 4 (O n Bu) 8 (OCOCH 3 ) 8 , Ti 6 O 4 (O i Pr) 12 (OCOCH 3) 4, Ti 7 O 4 (OEt) 20, Ti 10 O 8 (OEt) 24, Ti 11 O 13 (O i Pr) 18, Ti 11 O 13 (O i Pr) 13 OEt) 5, Ti 12 O 16 (O i Pr) 16, Ti 12 O 16 (OCH 2 t Bu) 16, Ti 14 O 19 (OH) (O t Bu) 13 (OCOCH 3) 4, Ti 16 O 16 (OEt) 32 , Ti 17 O 24 (O i Pr) 20 , Ti 18 O 28 (H) (O t Bu) 17 , Ti 18 O 28 (O t Bu) 16 ( t BuOH), Ti 18 O 25 ( O t Bu) 12 (OCOCH 3 ) 10 is preferred, and particularly preferably Ti 11 O 13 (O i Pr) 18 , Ti 11 O 13 (O i Pr) 13 (OEt) 5 , Ti 12 O 16 (O i Pr) 16 ) Ti 12 O 16 (OCH 2 t Bu) 16 Here, Me is a methyl group, Et is an ethyl group, n Pr is a propyl group, i Pr is an isopropyl group, t Bu is a tert-butyl group, (OMc) is a methacrylato ligand, and (acac) is an acetylacetonate arrangement The directive (dmheto) is an abbreviation of 2,6-dimethylhept-3-ene-2,4,6-tris (orato) ligand.
本発明に用いるチタン酸化物クラスター化合物は、例えば、特開２０１５−０９３８２１号公報、国際特許公開２０１３／０３５６７２Ａ１号、Ｒｕｓｓｉａｎ Ｃｈｅｍｉｃａｌ Ｒｅｖｉｅｗｓ、第７３巻、第１１号、１０４１頁（２００４年）、Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ Ｒｅｖｉｅｗｓ、第４０巻、１００６頁（２０１１年）、Ｃｈｅｍｉｃａｌ Ｒｅｖｉｅｗｓ、第１１４巻、第１９号、９６４５頁（２０１４年）、Ｎｅｗ Ｊｏｕｒｎａｌ ｏｆ Ｃｈｅｍｉｓｔｒｙ、第２３巻、１０７９頁（１９９９年）、又はＤ．Ｃ．Ｂｒａｄｌｅｙら著、「Ａｌｋｏｘｏ ａｎｄ Ａｒｙｌｏｘｏ Ｄｅｒｉｖａｔｉｖｅｓ ｏｆ Ｍｅｔａｌｓ」、第１版、ＡＣＡＤＥＭＩＣ ＰＲＥＳＳ、４−５１ページ（２００１年）などの公知文献に開示されている方法に従い製造することができる。 The titanium oxide cluster compounds used in the present invention are described, for example, in JP-A-2015-093821, International Patent Publication 2013/035672 A1, Russian Chemical Reviews, Vol. 73, No. 11, page 1041 (2004), Chemical Society Reviews, Vol. 40, p. 1006 (2011), Chemical Reviews, Vol. 114, p. 19, p. 9645 (2014), New Journal of Chemistry, Vol. 23, p. 1079 (1999), or D.A. C. Bradley et al., "Alkoxo and Aryloxo Derivatives of Metals", 1st edition, ACADEMIC PRESS, pages 4-51 (2001), etc. can be used according to the method disclosed in the known literature.
チタン酸化物クラスターの溶解に用いる有機溶媒は、不要性の固体を生ずるものでなければよく、具体的にはペンタン、ヘキサン、シクロヘキサン、ヘプタン、メチルシクロヘキサン、エチルシクロヘキサン、オクタンなどの脂肪族炭化水素、ベンゼン、トルエン、エチルベンゼン、キシレン、ベンゾトリフルオリドなどの芳香族炭化水素、ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、シクロペンチルメチルエーテル、シクロペンチルエチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、１，３−プロパンジオールジメチルエーテル、１，２−ブタンジオールジメチルエーテル、１，３−ブタンジオールジメチルエーテル、１，４−ブタンジオールジメチルエーテル、２，３−ブタンジオールジメチルエーテル、１，４−ジオキサン、１，３−ジオキサン、テトラヒドロフランなどのエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、２−ジメチルアミノエタノール、２−ジエチルアミノエタノールなどのセルソルブ類、ジクロロメタン、クロロホルム、１，１−ジクロロエタン、１，２−ジクロロエタン、１，１，１−トリクロロエタン、１，１，２−トリクロロエタンなどのハロアルカン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミドなどのカルボン酸アミド、ジメチルスルホキシド、ジエチルスルホキシドなどのスルホキシドなどを例示することができ、これらのうち一種類を単独で用いても良く、二種類以上の有機溶媒を任意の比率で混合して用いても良い。原料又は生成物の溶解性が良い点で、芳香族炭化水素又はセルソルブ類が好ましく、トルエン又はエチレングリコールモノメチルエーテルがさらに好ましく、エチレングリコールモノメチルエーテルが殊更好ましい。 The organic solvent used to dissolve the titanium oxide cluster should be one which does not produce an unwanted solid, specifically, aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, methylcyclohexane, ethylcyclohexane, octane, etc. Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, benzotrifluoride, diethyl ether, diisopropyl ether, dibutyl ether, dibutyl ether, cyclopentyl methyl ether, cyclopentyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, 1,3 -Propanediol dimethyl ether, 1,2-butanediol dimethyl ether, 1,3-butanediol dimethyl ether, 1,4- Tandiol dimethyl ether, 2,3-butanediol dimethyl ether, ethers such as 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 2-dimethylaminoethanol, 2-diethyl Cellosolves such as minoethanol, dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, haloalkanes such as 1,1,2-trichloroethane, N, N-dimethylformamide, N And carboxylic acid amides such as N-dimethylacetamide, sulfoxides such as dimethylsulfoxide and diethylsulfoxide, and the like, and one kind of them may be used alone, and two or more kinds of organic solvents may be used in any ratio. You may mix and use. Aromatic hydrocarbons or cellosolves are preferable, toluene or ethylene glycol monomethyl ether is more preferable, and ethylene glycol monomethyl ether is particularly preferable in that the raw materials or the product have good solubility.
チタン酸化物クラスターを有機溶媒に溶解させて成膜溶液とする際のチタン酸化物クラスターの濃度には特に限定はなく、０．０１〜１５重量％が好ましく、０．１〜５重量％が殊更好ましい。 There is no particular limitation on the concentration of the titanium oxide cluster when the titanium oxide cluster is dissolved in an organic solvent to form a film forming solution, and 0.01 to 15% by weight is preferable, and 0.1 to 5% by weight is particularly preferable. preferable.
成膜溶液の塗布方法には特に制限はなく、湿式法による薄膜作製プロセスにおいて一般的な方法を用いることができる。具体的には、スピンコーティング法、ディップコーティング法、スプレーコーティング法、フローコーティング法、ロールコーティング法、カーテンコーティング法、バーコーティング法、超音波コーティング法、スクリーン印刷法、刷毛塗り、スポンジ塗りなどを例示することができる。コンパクト層として良好な膜厚と性能を発揮できる点で、スピンコーティング法、ディップコーティング法、スプレーコーティング法が好ましく、スピンコーティング法又はスプレーコーティング法が殊更好ましい。 There is no restriction | limiting in particular in the coating method of the film-forming solution, A general method can be used in the thin film preparation process by a wet method. Specifically, spin coating, dip coating, spray coating, flow coating, roll coating, curtain coating, bar coating, ultrasonic coating, screen printing, brush coating, sponge coating, etc. are illustrated. can do. The spin coating method, the dip coating method and the spray coating method are preferable, and the spin coating method and the spray coating method are particularly preferable in that they can exhibit a good film thickness and performance as a compact layer.
成膜溶液を塗布する基板には特に制限はなく、金属基板、半導体基板、有機半導体基板、絶縁体基板、樹脂基板、透明導電性酸化物基板などを任意に用いることができる。ペロブスカイト太陽電池素子から効率よく電流を取り出せる点で、金属基板、半導体基板、透明導電性酸化物基板が好ましく、透明導電性酸化物基板が殊更好ましい。 There is no restriction | limiting in particular in the board | substrate which apply | coats the film-forming solution, A metal substrate, a semiconductor substrate, an organic semiconductor substrate, an insulator board | substrate, a resin substrate, a transparent conductive oxide substrate etc. can be used arbitrarily. A metal substrate, a semiconductor substrate, and a transparent conductive oxide substrate are preferable, and a transparent conductive oxide substrate is particularly preferable, from the viewpoint of efficiently extracting current from the perovskite solar cell element.
成膜溶液を塗布した基板の加熱温度に特に制限はなく、基板や素子の耐熱性に応じて任意の温度で加熱することができる。チタン酸化物クラスター化合物が十分熱分解し良好なコンパクト層を形成できる点で、８０℃〜１０００℃が好ましく、１００℃〜８００℃がさらに好ましく、２００℃〜５００℃が殊更好ましい。 There is no restriction | limiting in particular in the heating temperature of the board | substrate which apply | coated the film-forming solution, According to the heat resistance of a board | substrate or an element, it can heat at arbitrary temperature. C. to 1000.degree. C. is preferable, 100.degree. C. to 800.degree. C. is more preferable, and 200.degree. C. to 500.degree. C. is particularly preferable because a titanium oxide cluster compound can be sufficiently pyrolyzed to form a good compact layer.
成膜溶液を塗布した基板の加熱時間に特に制限はなく、基板や素子の耐熱性に応じて任意の時間で加熱することができる。チタン酸化物クラスター化合物が十分熱分解し良好なコンパクト層を形成できる点で、１分〜２４時間が好ましく、１０分〜１２時間がさらに好ましく、３０分〜５時間が殊更好ましい。 There is no restriction | limiting in particular in the heating time of the board | substrate which apply | coated the film-forming solution, According to the heat resistance of a board | substrate or an element, it can heat for arbitrary time. 1 minute to 24 hours are preferable, 10 minutes to 12 hours are more preferable, and 30 minutes to 5 hours is particularly preferable in that titanium oxide cluster compounds can be sufficiently pyrolyzed to form a good compact layer.
成膜溶液を塗布する回数には特に制限はなく、１回で塗布してもよいし、数回に分けて塗布を行ってもよい。数回に分けて塗布を行う場合は、各塗布工程の間に熱処理を行うことで、膜を効率よく堆積させることができる。 There is no restriction | limiting in particular in the frequency | count which apply | coats the film-forming solution, You may apply | coat by 1 time, and you may divide into several times and may apply. In the case where coating is performed several times, the film can be deposited efficiently by performing heat treatment between each coating process.
本発明のコンパクト層を用いて、これを含むことを特徴とするペロブスカイト太陽電池を製造することができる。ペロブスカイト太陽電池の製造方法に特に制限はなく、透明導電性酸化物基板上に製造したコンパクト層に対し、ペロブスカイト層、正孔輸送層及び対抗電極を順次積層して製造することが好ましく、コンパクト層とペロブスカイト層の間に多孔性ＴｉＯ２層を含むことが殊更好ましい。ペロブスカイト太陽電池の製造方法としては、例えばＥｎｅｒｇｙ ＆ Ｅｎｖｉｒｏｎｍｅｎｔａｌ Ｓｃｉｅｎｃｅ 第９号、１８５３頁（２０１６年）に記載の方法等を例示することができる。 The compact layer of the present invention can be used to produce a perovskite solar cell characterized by including this. There is no particular limitation on the method of producing the perovskite solar cell, and it is preferable to produce by sequentially laminating the perovskite layer, the hole transport layer and the counter electrode to the compact layer produced on the transparent conductive oxide substrate, compact layer It is particularly preferred to include a porous TiO 2 layer between the and the perovskite layer. As a method for producing a perovskite solar cell, for example, the method described in Energy & Environmental Science No. 9, page 1853 (2016) can be exemplified.
本発明のコンパクト層は、ペロブスカイト太陽電池素子の効率を向上させることができる、有用な材料である。 The compact layer of the present invention is a useful material that can improve the efficiency of the perovskite solar cell element.
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
参考例１
アルゴン雰囲気下で、チタンテトライソプロポキシド（Ｔｉ（ＯｉＰｒ）４）４．２２ｇ（１４．８ｍｍｏｌ）、トルエン２０ｍｌ及び磁気撹拌子を５０ｍｌシュレンク管に入れ、チタンテトライソプロポキシドのトルエン溶液を調製した。該トルエン溶液に、ジアセトンアルコール１．７２ｇ（１４．８ｍｍｏｌ）を室温で撹拌中に添加した。２４時間後、反応溶液をろ過し、不溶解物の白色沈殿を分取した。該白色沈殿にアセトニトリル６ｍｌを加え、不溶解物の白色沈殿を分取した。該不溶解物を減圧乾燥することにより、Ｔｉ１１Ｏ１３（ＯｉＰｒ）１８を主成分とする白色固体０．７６ｇを得た。
Reference Example 1
In an argon atmosphere, 4.22 g (14.8 mmol) of titanium tetraisopropoxide (Ti (O i Pr) 4 ), 20 ml of toluene and a magnetic stirrer are placed in a 50 ml Schlenk tube, and a solution of titanium tetraisopropoxide in toluene is added. Prepared. To the toluene solution was added 1.72 g (14.8 mmol) of diacetone alcohol while stirring at room temperature. After 24 hours, the reaction solution was filtered and a white precipitate of insoluble matter was separated. 6 ml of acetonitrile was added to the white precipitate, and the white precipitate of insoluble matter was separated. The insoluble matter was dried under reduced pressure to obtain 0.76 g of a white solid mainly containing Ti 11 O 13 (O i Pr) 18 .
実施例１
ペロブスカイト太陽電池素子は、Ｅｎｅｒｇｙ ＆ Ｅｎｖｉｒｏｎｍｅｎｔａｌ Ｓｃｉｅｎｃｅ 第９号、１８５３頁（２０１６年）に開示されている方法に従って、以下の通り作成した。洗浄したフッ素ドープ酸化スズ（ＦＴＯ）基板上に、Ｔｉ１１Ｏ１３（ＯｉＰｒ）１８を主成分とする白色固体のエチレングリコールモノメチルエーテル溶液（３．０ｗｔ％）を４０００ｒｐｍ／１０秒スピンコートし、１２５℃で熱処理した。その後再度同じ条件でスピンコートを行い、３５０℃で５時間熱処理し、成膜を行った。得られた膜をコンパクト層とし、これにペロブスカイト試薬（ヨウ化ホルムアミジン（１Ｍ）、ヨウ化メチルアンモニウム（０．２Ｍ）、臭化メチルアンモニウム（０．２Ｍ）、臭化鉛（０．２Ｍ）、ヨウ化鉛（１．１Ｍ）のジメチルホルムアミド：ジメチルスルホキシド（１：１）溶液にヨウ化セシウム（１．５Ｍ）のジメチルスルホキシド溶液を加えたもの）を最高回転速度６０００ｒｐｍ／３０秒でスピンコートし、１００℃で６０分熱処理を行いペロブスカイト層を形成した。さらに、正孔輸送材料（Ｓｐｉｒｏ−ＯＭｅＴＡＤ）溶液として７０ｍＭのクロロベンゼン溶液に リチウムビス（トリフルオロメタンスルホニル）イミド（０．５Ｍ）、ｔｅｒｔ−ブチルピリジン（３．３Ｍ）を溶解して溶液とし、これを２０００ｒｐｍ／３０秒でスピンコートし、７０℃で１０分熱処理を行い正孔輸送層を形成した。これに金を蒸着して対抗電極を形成し、ペロブスカイト太陽電池素子を作製した。作成した素子の電流−電圧曲線を図１に、光電変換特性の測定結果を表１に示す。図１及び表１から明らかなように、実施例１の素子は比較例１の素子よりも高い変換効率を示した。
Example 1
Perovskite solar cell elements were prepared as follows according to the method disclosed in Energy & Environmental Science No. 9, page 1853 (2016). A spin-coated solution of Ti 11 O 13 (O i Pr) 18 in white solid ethylene glycol monomethyl ether (3.0 wt%) was spin-coated on a cleaned fluorine-doped tin oxide (FTO) substrate at 4000 rpm / 10 seconds. Heat-treated at 125 ° C. Thereafter, spin coating was performed again under the same conditions, and heat treatment was performed at 350 ° C. for 5 hours to form a film. The obtained membrane is used as a compact layer, and a perovskite reagent (formamidine iodide (1 M), methyl ammonium iodide (0.2 M), methyl ammonium bromide (0.2 M), lead bromide (0.2 M) is used. Spin coating of lead iodide (1.1 M) in dimethylformamide: dimethyl sulfoxide (1: 1) solution of cesium iodide (1.5 M) in dimethyl sulfoxide) at a maximum rotation speed of 6000 rpm / 30 seconds Then, heat treatment was performed at 100 ° C. for 60 minutes to form a perovskite layer. Furthermore, lithium bis (trifluoromethanesulfonyl) imide (0.5 M) and tert-butylpyridine (3.3 M) are dissolved in 70 mM chlorobenzene solution as a hole transport material (Spiro-OMeTAD) solution to form a solution, which is Spin coating was performed at 2000 rpm / 30 seconds, and heat treatment was performed at 70 ° C. for 10 minutes to form a hole transport layer. Gold was vapor-deposited thereon to form a counter electrode, thereby producing a perovskite solar cell element. The current-voltage curve of the prepared element is shown in FIG. 1, and the measurement results of the photoelectric conversion characteristics are shown in Table 1. As apparent from FIG. 1 and Table 1, the device of Example 1 exhibited higher conversion efficiency than the device of Comparative Example 1.
比較例１
コンパクト層原料としてチタンジイソプロポキシドビス（アセチルアセトナート）を用い、５００℃でＦＴＯ基板上にスプレー後、５００℃で４５分加熱処理したコンパクト層を用いた以外は、実施例１と同様にしてペロブスカイト太陽電池素子を作製した。作成した素子の電流−電圧曲線を図１に、光電変換特性の測定結果を表１に示す。
Comparative Example 1
The same procedure as in Example 1 was repeated except that titanium diisopropoxide bis (acetylacetonate) was used as a compact layer material, and a compact layer was used which was sprayed on an FTO substrate at 500 ° C. and heat treated at 500 ° C. for 45 minutes. Perovskite solar cell elements were fabricated. The current-voltage curve of the prepared element is shown in FIG. 1, and the measurement results of the photoelectric conversion characteristics are shown in Table 1.
（光電変換特性の測定）
実施例１及び比較例１で得られたペロブスカイト太陽電池素子を、ＪＩＳ ８９１２ クラスＡに準拠したＡＭ１．５Ｇ、１００ｍＷ／ｃｍ２のソーラーシミュレータ（メーカー名：山下電装社、型番：ＹＳＳ−５０Ａ）を用いて光を照射しながら、ソースメーター（メーカー名：株式会社 エーディーシー 型番：６２４０Ａ）を用いて電流―電圧測定を行い、短絡電流密度（ＪＳＣ）、開放電圧（ＶＯＣ）及びフィルファクター（ＦＦ）を求めた。さらに、これらから（式１）により変換効率（Ｅｆｆ）を算出した。
(Measurement of photoelectric conversion characteristics)
Perovskite solar cell elements obtained in Example 1 and Comparative Example 1 were compared with a solar simulator (Manufacturer name: Yamashita Densha Co., model number: YSS-50A) of AM 1.5 G, 100 mW / cm 2 conforming to JIS 8912 class A. Measure the current-voltage using a source meter (Manufacturer name: ADC Model number: 6240A) while irradiating with light, and short circuit current density (J SC ), open circuit voltage (V OC ) and fill factor ( I asked for FF). Furthermore, the conversion efficiency (Eff) was calculated from these by (Formula 1).
変換効率（％）＝ＪＳＣ（ｍＡ／ｃｍ２）×ＶＯＣ（Ｖ）×ＦＦ（％） （式１）
結果を表１に示す。表から明らかなように、実施例１の素子は比較例１の素子よりも高い変換効率を示した。
Conversion efficiency (%) = J SC (mA / cm 2) × V OC (V) × FF (%) (Equation 1)
The results are shown in Table 1. As apparent from the table, the device of Example 1 exhibited higher conversion efficiency than the device of Comparative Example 1.
Claims (5)
ＴｉｘＯｙ（ＯＲ）ｚ （１）
（式中、ｘは３以上１００以下の整数、ｙは１以上の整数、ｚは２以上の整数である。ただし、ｘ、ｙ及びｚは、４ｘ＝２ｙ＋ｚを満たすものとする。Ｒは同一又は相異なって、水素原子、アルキル基、アリール基を表す。ただし、Ｒはヘテロ原子を含む官能基を含有していてもよい。）で示されるチタン酸化物クラスター化合物及び有機溶媒を含んでなる成膜溶液を基板上に塗布して加熱した酸化物膜を含んでなるコンパクト層。 General formula (1)
Ti x O y (OR) z (1)
(Wherein x is an integer of 3 to 100, y is an integer of 1 or more, z is an integer of 2 or more, provided that x, y and z satisfy 4x = 2y + z, and R is the same. Or different from each other, each representing a hydrogen atom, an alkyl group, or an aryl group, provided that R represents a titanium oxide cluster compound represented by the following formula) and an organic solvent: A compact layer comprising an oxide film obtained by applying a film forming solution onto a substrate and heating it.
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| CN112250107A (en) * | 2020-10-21 | 2021-01-22 | 华北电力大学 | Single crystal diamond-shaped titanium dioxide nano-particles and preparation method thereof, and titanium dioxide slurry and application thereof |
| CN112920213A (en) * | 2021-01-27 | 2021-06-08 | 淮阴工学院 | Organic dye containing silicon fused pentacyclic bridging, and preparation method and application thereof |
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