七铝酸十二钙电子化合物研究进展

doi:10.11896/cldb.19050051

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Abstract In 2002, researchers at the Tokyo Institute of Technology synthesized a new inorganic mayenite electride—12CaO·7Al₂O₃:2e^- (hereinafter C12A7:e^-), as a potential transparent conductive oxide, which opened a new chapter in electride synthesis and utilization. Compared with other organic electrides, it has better chemical stability and can be stable in air below 450 ℃.This thermally stable electride has a number of potentially useful properties, such as air-stability, low work function, excellent performance in resisting poisoning, and metallic conductivity. Thermal stability and low reactivity with air make this material has a broad application prospect in electron emitter, optical device, catalyst support and other fields. Especially, C12A7:e^- has been found to have certain emission performance at low temperature and is very suitable as a electron emission material for low-power vacuum electronic devices. Compared with commercialized cathode materials, such as Ni(5.0 eV), Mo(4.6 eV) and LaB₆(2.67 eV), C12A7:e^-exhibits low work function (~2.4 eV). On the other hand, the strong chemical bond force in C12A7 crystal makes it have better ion bombardment resistance. The sputtering effect of ion bombardment on the cathode at work has an impact influence on the service life. Furthermore, the search for other inorganic electrides is a very promising area of study.
Due to the prolonged synthesis cycle and special encapsulation, in the past decade, substantial efforts have been devoted to seeking simple and efficient route to acquire the electride in desire forms. So far, various forms of mayenite electride have been realized, mainly including single crystal, thin film and polycrystalline. These researchers have been working to make full use of the advantages of C12A7:e^- applications while significantly reducing the preparation cycle and increasing the electron concentration. Now, the electron concentration of C12A7:e^- can reach 2.3×10²¹ cm^-3, which is close to the theoretical electron concentration of 2.33×10²¹ cm^-3.The conductivity at room temperature also jumped from 0.3 S·cm^-1 in 2002 to 1 380 S·cm^-1.
Since Hayashi found that C12A7:H^- can be changed from an insulator to an electrical conductor C12A7:e^- after being exposed to ultraviolet light, many scholars have been working on developing more efficient and rapid preparation methods. In 2003, Matsuishi et al. prepared C12A7:e^- with high electron concentration (2×10²¹ cm^-3) by Ca metal vapor reduction, but this method would form a dense CaO film on the sample surface and hinder the continuation of reduction, resulting in too long reduction time. After that, Hosono effectively reduced reduction time by replacing Ca metal with Ti, but metal vapor reduction could not reduce C12A7:e^- film. In 2006, the CO/CO₂ atmospheric reduction solved this problem, but the sample prepared had a low electron concentration (Ne~1.4×10¹⁹ cm^-3).Recently developed by our team of SPS combinate with Ti metal vapor reduction method and in-situ aluminothermic reduction process, can manufacture the high electron concentration (Ne~2.3×10²¹ cm^-3) C12A7:e^- block within 0.5 h. These two methods need the shortest reduction time, lowest cost, and are the easiest way to mass production in many preparation methods, they overcome many problem, such as the long preparation period, large energy consumption and low electron concentration, which laid a foundation for its large-scale application. However, those methods still has great limitations, because they can only be used to prepare C12A7:e^- polycrystalline block.
This paper summarizes the preparation methods of C12A7:e^- single crystal, thin film and polycrystalline, compares the advantages and disadvantages of each preparation method, analyzes the problems faced by the preparation of the material and prospects its application, in order to provide reference for finding a more rapid and effective preparation method.

Key words： C12A7:e^- electronic compound reduction single crystal block thin film

Published: 24 June 2020

CLC number:

TJ430.4

Fund:Beijing Municipal Natural Science Foundation, China (2112007) and the Fundamental Research Funds for the Central Universities, China (PXM2019-014204-500032)

About author:: Jie Chenreceived her B.E. degree in materials science from Liaocheng University in 2017. She is currently pursuing her master degree at the School of Materials Science and Engineering, Beijng University of Technology. Her research has focused on cathode materials that emits electrons.
Xin Zhang, January 2006 graduated from the Beijing University of Technology, he received his Ph.D. degree in engineering. In May of the same year, he began to engage in teaching and scientific research in the School of Material Science and Engineering, Beijing University of Technology, mainly research on the study of thermoelectric energy conversion materials and cat-hode materials. He successively presided over and participated in the National Natural Science Foundation of China, Beijing Natural Science Foundation of China, Beijing Middle-aged Backbone Teachers Program, etc. He has served as reviewer for international publications such as J. Appl. Phy., J. Alloy. Comp., J. Electr. Mater.

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	CHEN Jie
	ZHANG Xin
	LIU Hongliang
	XIAO Yixin
	LI Fan
	FENG Qi
	ZHAO Weikang
	LIU Yanqin
	ZHANG Jiuxing

Cite this article:

CHEN Jie,ZHANG Xin,LIU Hongliang, et al. Advances in the Study of C12A7:e^- Electride[J]. Materials Reports, 2020, 34(13): 13076-13083.

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http://www.mater-rep.com/EN/10.11896/cldb.19050051 OR http://www.mater-rep.com/EN/Y2020/V34/I13/13076

1 Wang Z, Pan Y, Dong T, et al. Applied Catalysis A: General, 2007, 320, 24.
2 Yang S, Kondo J N, Hayashi K, et al. Applied Catalysis A: General, 2004, 277(1), 239.
3 Imlach J A, Glasser L S D, Glasser F P. Cement and Concrete Research, 1971, 15(4), 157.
4 Jeevaratnam J, Glasser F P, Glasser L S D. Journal of the American Ceramic Society, 1964, 47(2), 105.
5 Hosono H, Abe Y. Inorganic Chemistry, 1987, 26, 1192.
6 Hosono H, Hayashi K, Hirano M. Journal of Materials Science, 2007, 42(6), 1872.
7 Fujita S, Suzuki K, Ohkawa M, et al. Chemistry of Materials, 2003, 15(1), 255.
8 Hayashi K, Matsuishi S, Kamiya T. Nature, 2002, 419, 462.
9 Hayashi K, Matsuishi S, Ueda N, et al. Chemistry of Materials, 2003, 15(9), 1851.
10 Sun J Q, Song C F, Ning S, et al. Acta Physico Chimica Sinica, 2009, 25(9), 1713.
11 Song C, Sun J, Qiu S, et al. Chemistry of Materials, 2008, 20(10), 3473.
12 Zhang M, Liu Y, Zhu H, et al. Physical Chemistry Chemical Physics, 2016, 18(28), 18697.
13 Kerrour W, Kabir A, Schmerber G, et al. Journal of Materials Science: Materials in Electronics, 2016, 27(10), 10106.
14 Adachi Y, Kim S W, Kamiya T, et al. Materials Science and Enginee-ring: B,2009, 161(1-3), 76.
15 Inoue Y, Kitano M, Kim S W, et al. ACS Catalysis, 2014, 4(2), 674.
16 Kitano M, Inoue Y, Yamazaki Y, et al. Nature Chemistry, 2012, 4(11), 934.
17 Honkala K, Hellman A, Remediakis I N, et al. Science, 2005, 307(5709), 555.
18 Ebbinghaus S G, Krause H, Syrowatka F. Crystal Growth & Design, 2013, 13(7), 2990.
19 Sushko P V, Shluger A L, Hayashi K, et al. Physical Review Letters, 2003, 91(12), 126401.
20 Kanbara S, Kitano M, Inoue Y, et al. Journal of the American Chemical Society, 2015, 137(45), 14517.
21 Sasao M, Moussaoui R, Kogut D, et al. Applied Physics Express, 2018, 11(6), 066201.
22 Hiraishi M, Kojima K M, Miyazaki M, et al. Physical Review B, 2016, 93(12), 121201.
23 Toda Y, Yanagi H, Ikenaga E, et al. Advanced Materials, 2007, 19(21), 3564.
24 Rand L P, Williams J D.In: 49th AIAA/ASME/SAE/ASEE Joint Propulsion Conference, United States, 2013, pp.4037.
25 Rand L P, Williams J D, Martinez R A. U.S. Patent, US1961702A1,2016.
26 Rand L P, Williams J D, Martinez R A. U.S. Patent,US7892458B2, 2017.
27 Zhao J P, Zhang X, Liu H L, et al. Crystal Research and Technology, 2018, 53(1), 1700201.
28 Sushko P V, Shluger A L, Hirano M, et al. Journal of the American Chemical Society, 2007, 129(4), 942.
29 Bertoni M I, Mason T O, Medvedeva J E, et al. Journal of Applied Phy-sics, 2007, 102(11), 113704.
30 Li F, Zhang X, Liu H L, et al. Journal of the American Ceramic Society, 2019, 102(3), 884.
31 Toda Y, Matsuishi S, Hayashi K, et al.Advanced Materials, 2004,16(8), 685.
32 Zhao J P, Zhang X, Liu H L, et al. Crystal Research and Technology, 2018, 53, 1700201.
33 Miyakawa M, Kim S W, Hirano M, et al. Journal of the American Che-mical Society, 2007, 129(23) 7270.
34 Souma S, Arakane T, Sato T, et al. Journal of the Physical Society of Japan, 2010, 79(10), 103704.
35 Kim S W, Matsuishi S, Nomura T, et al. Nano letters, 2007, 7(5), 1138.
36 Kondo J. In Solid State Physics, 1970, 23, 183.
37 Shimizu K, Ishikawa H, Takao D, et al. Nature, 2002, 419(6907), 597.
38 Christensen N E, Novikov D L. Physical Review B, 2006, 73(22), 224508.
39 Yabuuchi T, Matsuoka T, Nakamoto Y, et al. Journal of the Physical Society of Japan, 2006, 75(8), 083703.
40 Nurse R W, Welch J H, Majumdar A J. British Ceramic Society Transactions,1965, 64(9), 409.
41 Watauchi S, Tanaka I, Hayashi K, et al. Journal of Crystal Growth, 2002, 237, 801.
42 Yoon S G, Kim S W, Hirano M, et al. Crystal Growth and Design, 2008, 8(4), 1271.
43 Kurashige K, Toda Y, Matstuishi S, et al. Crystal Growth and Design, 2006, 6(7), 1602.
44 Matsuishi S, Toda Y, Miyakawa M, et al. Science, 2003, 301(5633), 626.
45 Kim S W, Hayashi K, Hirano M, et al. Journal of the American Ceramic Society, 2006, 89(10), 3294.
46 Miyakawa M, Hayashi K, Hirano M, et al. Advanced Materials, 2003, 15(13), 1100.
47 Toda Y, Miyakawa M, Hayashi K, et al. Thin Solid Films, 2003, 445(2), 309.
48 Miyakawa M, Hiramatsu H, Kamiya T, et al. Journal of Solid State Chemistry, 2010, 183(2), 385.
49 Miyakawa M, Hirano M, Kamiya T, et al. Applied Physics Letters, 2007, 90(18), 182105.
50 Hosono H, Toda Y, Hayashi K, et al. U S Patent, US8377413B2,2015.
51 Li F, Zhang X, Liu H L, et al. Vacuum, 2018, 158, 152.
52 Munir Z A, Anselmi-Tamburini U, Ohyanagi M. Journal of Materials Science, 2006, 41(3), 763.
53 Matsuishi S, Nomura T, Hirano M, et al. Chemistry of Materials, 2009, 21(13), 2589.
54 Matsuishi S, Kim S W, Kamiya T, et al. The Journal of Physical Chemistry, 2008, 112(12), 4753.
55 Sushko P V, Shluger A L, Hayashi K, et al. Physical Review Letters, 2003, 91(12), 126401.
56 Toda Y, Miyakawa M, Hayashi K, et al. Thin Solid Films, 2003, 445, 309.
57 Buchammagari H, Toda Y, Hirano M, et al. Organic Letters, 2007, 9(21), 4287.
58 Li J, Inagi S, Fuchigami T, et al. Electrochemistry Communications, 2014, 44, 45.
59 Hara M, Kitano M, Hosono H. ACS Catalysis, 2017, 7(4), 2313.
60 Watanabe S, Watanabe T, Ito K, et al. Science and Technology of Advanced Materials, 2011, 12(3), 034410.
61 Miyakawa N, Watanabe T, Watanabe S, et al. SID Symposium Digest of Technical Papers, 2011, 42(1), 762.
62 Hung L S, Tang C W, Mason M G. Applied Physics Letters, 1997, 70(2), 152.
63 Lian J R, Luo X, Chen W, et al. Chinese Physics Letters, 2014, 31(11), 118501.
64 Heil H, Steiger J, Karg S, et al. Journal of Applied Physics, 2001, 89(1), 420.
65 Hosono H, Kim J, Toda Y, et al. Proceedings of the National Academy of Sciences, 2017, 14(2), 233.