TOP > 外国特許検索 > CRYSTAL CONTAINING COPPER HALIDE, AND METAL HALIDE AND/OR AMMONIUM HALIDE, CRYSTALLINE THIN-FILM, PRECURSOR SOLUTION THEREOF, AND METHOD FOR PRODUCING CRYSTALLINE THIN-FILM

CRYSTAL CONTAINING COPPER HALIDE, AND METAL HALIDE AND/OR AMMONIUM HALIDE, CRYSTALLINE THIN-FILM, PRECURSOR SOLUTION THEREOF, AND METHOD FOR PRODUCING CRYSTALLINE THIN-FILM NEW

外国特許コード F200010203
整理番号 (S2019-0108-N0)
掲載日 2020年7月30日
出願国 世界知的所有権機関(WIPO)
国際出願番号 2019JP048340
国際公開番号 WO 2020122075
国際出願日 令和元年12月10日(2019.12.10)
国際公開日 令和2年6月18日(2020.6.18)
優先権データ
  • 特願2018-232936 (2018.12.12) JP
発明の名称 (英語) CRYSTAL CONTAINING COPPER HALIDE, AND METAL HALIDE AND/OR AMMONIUM HALIDE, CRYSTALLINE THIN-FILM, PRECURSOR SOLUTION THEREOF, AND METHOD FOR PRODUCING CRYSTALLINE THIN-FILM NEW
発明の概要(英語) The present invention provides a crystal which exhibits favorable conductivity, can be produced at a processing temperature which is lower than that of the prior art, and contains a copper halide and also contains a halide of a metal selected from the group consisting of alkali metals, magnesium and zinc and/or an ammonium halide. The present invention also provides a transparent crystalline thin-film, a precursor solution thereof, and a method for producing a crystalline thin-film. This crystalline thin-film contains a copper halide and also contains a halide of a metal selected from the group consisting of alkali metals, magnesium and zinc and/or an ammonium halide. The mole ratio of the copper halide to the metal halide and/or ammonium halide is in the range of 100:1 to 100:30.
従来技術、競合技術の概要(英語) BACKGROUND ART
The discovery of high photoelectric conversion efficiency, a perovskite-type solar cell for practical use of the study are performed at the world. A perovskite-type solar cell, a perovskite crystal film is formed, light responsible for charge separation.
This perovskite is for a solar cell, ITO or FTO is, excellent in low resistivity as an electrode from a transparent conductive material can be used widely. FTO and ITO as a candidate for an alternative material, copper halide, CuI is copper iodide in particular has attracted attention. CuI is copper iodide, the visible-light transmittance of the first function as the transparent conductive film (Non-Patent Document 1) are known. For example, deposition of a copper thin film was prepared by an iodine vapor-iodide, the volume resistivity is shown in 0.01Ωcm. In addition, copper iodide (non-patent document 2) is, solution coating, and laminating the low-temperature heat treatment, a perovskite type such as solar cells or organic thin film solar cell is excellent as an electron blocking layer (hole conduction) in the transparent p-type semiconductor can be seen, is attracting attention.
On the other hand, copper iodide, solution coating, a thin film transistor (TFT) can be manufactured at a low-temperature heat treatment (non-patent document 4) an organic light emitting diode (OLED) a transparent p-type (non-patent document 5) has been expected as a semiconductor thin film.
However, copper iodide, easily available at low cost, and printing, for application in a common solvent such as alcohol can be handled safely-soluble. Therefore, even from the non-patent document 2 as shown in 5, such as a liquid or the use of expensive special dipropylsulphide, toxicity concerns must use a large amount of chlorobenzene. In addition, the solubility is not sufficient.
On the other hand, A.R. Zainum et al., 3 in acetonitrile (TMED) was added and the tertiary amines of the diamine, the particles is decreased to 1.5nm, crystallization of the CuI solution is suppressed, an acetonitrile solution of CuI in 50°C containing TMED and added dropwise to the heated glass substrate, a transparent thin film is obtained CuI. Is a scanning electron microscope (SEM image) image, an acetonitrile solution of CuI TMED does not contain the case of using an infinite number of void generated in the exposed substrate is improved and it is possible to obtain dense films have been reported (Non-Patent Document 6). However, the thickness of the coating film is not shown, a thin film solar cell is used as a transparent p-type semiconductor layer (100nm or less) in a desired film thickness of the dense film cannot be determined whether or not it is possible to fabricate.
W.Y. Chen et al., on the FTO substrate was prepared in an acetonitrile solution of CuI may be spin-coated, by a small island-like crystallization, incomplete coating FTO occurs, the leakage current of the perovskite-type solar cell has been shown to cause (non-patent document 7). As described above, CuI is copper iodide represented by, a solar cell, furthermore, in the thin film transistor, low cost and high performance p-type semiconductor thin film used as a transparent value is getting much attention.
In addition, in recent years, copper iodide (II) complex, inexpensive and safe handling of the alcohol in the precursor solution made of a general-purpose and dissolved in a solvent, coating solution, by thermal decomposition, has been reported to produce a film.
For example, a trivalent ion of copper +2, and ethanolamine, and iodide ion is coordinated by the coordination compound, copper iodide 110°C or more by heat treatment of the peak derived from the X-ray diffraction (XRD) powder has been reported (Non-Patent Document 8). However, the generated voids in the film and the like are often, and has a film thickness of 780-850nm, a transparent p-type semiconductor layer of a solar cell or thin film transistor is used as the film thickness required in a case where (100nm or less) is not satisfied.
Further, a trivalent ion of copper +2, and ethanolamine, and iodide ion is coordinated to the coordination compound by mixing CuBr, 170°C can be formed of a thin film have been reported (Non-Patent Document 9). However, in this document, in this case of the thin film, and a thickness of 200-300nm, a low transmittance. In addition, the band gap change is only described, the conductive is no description.
Furthermore, the copper +2 a trivalent ion, alkanolamines, and iodide ion is coordinated with a coordination compound, or a trivalent ion of copper +2, a tertiary or quaternary alkyl amine and alcohol 1 2, and the iodide ion or iodide ion is coordinated false is made, by preparing a copper iodide, uniform precursor solution has been developed. The precursor solution, a heat treatment at 150-200 ° C. or less in, the light transmittance of the wavelength at 450-800nm is 80% or more, and the volume resistance in a low resistance value of 0.08-0. for a crystalline thin film have been reported (Patent Document 1). However, due to thermal decomposition of 150°C or more in the step of the method, a low melting point PET film cannot be used for inexpensive.
  • 出願人(英語)
  • ※2012年7月以前掲載分については米国以外のすべての指定国
  • YAMAGATA UNIVERSITY
  • 発明者(英語)
  • KURIHARA, Masato
  • ISHIZAKI, Manabu
国際特許分類(IPC)
指定国 National States: AE AG AL AM AO AT AU AZ BA BB BG BH BN BR BW BY BZ CA CH CL CN CO CR CU CZ DE DJ DK DM DO DZ EC EE EG ES FI GB GD GE GH GM GT HN HR HU ID IL IN IR IS JO JP KE KG KH KN KP KR KW KZ LA LC LK LR LS LU LY MA MD ME MG MK MN MW MX MY MZ NA NG NI NO NZ OM PA PE PG PH PL PT QA RO RS RU RW SA SC SD SE SG SK SL SM ST SV SY TH TJ TM TN TR TT TZ UA UG US UZ VC VN ZA ZM ZW
ARIPO: BW GH GM KE LR LS MW MZ NA RW SD SL SZ TZ UG ZM ZW
EAPO: AM AZ BY KG KZ RU TJ TM
EPO: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
OAPI: BF BJ CF CG CI CM GA GN GQ GW KM ML MR NE SN ST TD TG

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