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Metal oxide thin film, organic electroluminescence element including the thin film, solar cell, and thin film fabrication method NEW

外国特許コード F190009873
整理番号 J1014-06US2
掲載日 2019年7月29日
出願国 アメリカ合衆国
出願番号 201916270354
公報番号 20190172605
出願日 平成31年2月7日(2019.2.7)
公報発行日 令和元年6月6日(2019.6.6)
優先権データ
  • 特願2012-139197 (2012.6.20) JP
  • 特願2012-151848 (2012.7.5) JP
  • 特願2013-037851 (2013.2.27) JP
  • 特願2013-071154 (2013.3.29) JP
  • 特願2013-071163 (2013.3.29) JP
  • 2013JP66850 (2013.6.19) WO
  • 201414567047 (2014.12.11) US
発明の名称 (英語) Metal oxide thin film, organic electroluminescence element including the thin film, solar cell, and thin film fabrication method NEW
発明の概要(英語) Disclosed herein is an amorphous C12A7 electride thin film which has an electron density of greater than or equal to 2.0×1018 cm-3 and less than or equal to 2.3×1021 cm-3, and exhibits a light absorption at a photon energy position of 4.6 eV. Also disclosed herein is an amorphous thin film which is fabricated using a target made of a crystalline C12A7 electride, and containing an electride of an amorphous solid material includig calcium, aluminum, and oxygen, in which an Al/Ca molar ratio of the thin film is 0.5 to 4.7.
従来技術、競合技術の概要(英語) BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a C12A7 electride thin film fabrication method and a C12A7 electride thin film.
2. Description of the Related Art
Crystalline C12A7 has a representative composition expressed as 12CaO.7Al2O (hereinafter referred to as “C12A7”) and has a characteristic crystal structure including voids (cages) with diameters of about 0.4 nm that are linked three-dimensionally. The lattice framework forming the cages is positively charged and forms 12 cages per unit cell. One-sixth (⅙) of the cages are occupied by oxygen ions in order to satisfy an electrically neutral condition of the crystal. These oxygen ions are particularly referred to as free oxygen ions because they have properties chemically different from those of the other oxygen ions constituting the framework. Crystalline C12A7 is also denoted as [Ca24Al28O64]4+.2O2- (see F. M. Lea and C. H. Desch, The Chemistry of Cement and Concrete, 2nd ed., p. 52, Edward Arnold & Co., London, 1956).
Also, 12SrO.7Al2O3 (hereinafter referred to as “S12A7”) is known as an isomorphic compound of crystalline C12A7 and a mixed crystal compound of C12A7 and S12A7 containing Ca and Sr at a given mix ratio is also known (see O. Yamaguchi, A. Narai, K. Shimizu, J. Am. Ceram. Soc. 1986, 69, C36).
The inventors of the present invention, Hosono et al., have discovered that by subjecting crystalline C12A7 powder or a sintered body thereof to a heating process in a H2 atmosphere to cause the cages to contain H-ions and subsequently irradiating ultraviolet light thereon, the crystalline C12A7 powder or the sintered body may be arranged to contain electrons in the cages and be able to exhibit permanent conductive properties at room temperature (see WO 2005/000741). The electrons contained are loosely bound to the cages and can move freely in the crystals, and as such, crystalline C12A7 exhibits conductive properties.
Crystalline C12A7 having such conductive properties is referred to as a crystalline C12A7 electride. Because crystalline C12A7 electrides have a very low work function of about 2.4 eV, advantageous effects can be expected by applying crystalline C12A7 electrides to electron injection electrodes of organic EL (electroluminescence) elements and cold electron emission sources, or reducing agents used in chemical reactions, for example.
Generally, a crystalline C12A7 bulk is fabricated by performing a sintering process on crystalline C12A7 electride powder under a high-temperature reducing atmosphere (Patent Document 1). For example, the temperature of the sintering process may be about 1200° C.
Although the above conventional method may be effective for fabricating the crystalline C12A7 in bulk, the method is not suitable for fabricating a crystalline C12A7 electride thin film.
That is, in the case of fabricating a crystalline C12A7 electride thin film using a conventional method requiring a high temperature of about 1200° C., for example, materials that may be used as the substrate of the thin film may be limited to heat resistant materials. As a result, the combination of the types of materials that may be used for the thin film and the substrate may be very limited.
For example, a glass substrate is often used as a versatile substrate for various types of electrical devices and elements. However, the temperature limit for a glass substrate is about 700° C. at most. Accordingly, it would be difficult to form a crystalline C12A7 electride thin film on a glass substrate using a conventional fabrication method owing to the temperature limit of the glass substrate.
In light of the above, there is a growing demand for a technique for fabricating a C12A7 electride thin film under a low processing temperature to avoid or alleviate the above-described shortcomings.
特許請求の範囲(英語) [claim1-9]
1-9. (canceled)

[claim10]
10. A C12A7 electride thin film, wherein:
an electron density of the thin film is greater than or equal to 2.0×1018 cm-3 and less than or equal to 2.3×1021 cm-3;
the thin film exhibits light absorption at a photon energy position of 4.6 eV; and
the thin film is amorphous.

[claim11]
11. The thin film as claimed in claim 10, comprising:
calcium, aluminum, and oxygen;
wherein a calcium to aluminum molar ratio is 13:12 to 11:16.

[claim12]
12. The thin film as claimed in claim 10, wherein a light absorption value of the thin film at the photon energy position of 4.6 eV is greater than or equal to 100 cm-3.

[claim13]
13. The thin film as claimed in claim 10, wherein the thin film has a thickness less than or equal to 10 μm.

[claim14]
14. The thin film as claimed in claim 10, wherein the thin film is formed on a glass substrate.

[claim15]
15. (canceled)

[claim8]
16. An amorphous thin film, wherein:
the thin film is fabricated using a target made of a crystalline C12A7 electride;
the thin film comprises an electride of an amorphous solid material comprising calcium, aluminum, and oxygen; and
an Al/Ca molar ratio of the thin film is 0.5 to 4.7.

[claim9]
17. The thin film as claimed in claim 16 wherein:
the thin film exhibits an electron density of greater than or equal to 2.0×1018 cm-3 and less than or equal to 2.3×1021 cm-3; and
the thin film exhibits a exhibiting light absorption at a photon energy position of 4.6 eV.

[claim10]
18. The thin film as claimed in claim 16, wherein the thin film has an F+ center concentration of less than 5×1018 cm-3.

[claim11]
19. The thin film as claimed in claim 16, wherein a ratio of a light absorption coefficient of the thin film at a photon energy position of 3.3 eV with respect to a light absorption coefficient at a photon energy position of 4.6 eV is less than or equal to 0.35.
  • 発明者/出願人(英語)
  • HOSONO Hideo
  • TODA Yoshitake
  • HAYASHI Katsuro
  • ITO Setsuro
  • WATANABE Satoru
  • MIYAKAWA Naomichi
  • WATANABE Toshinari
  • ITO Kazuhiro
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
国際特許分類(IPC)
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