[Ca24Al28O64]4+(4e–)电子化合物的直接合成及热发射性能

李凡; 张忻; 张久兴

doi:10.7498/aps.68.20190070

摘要

[Ca₂₄Al₂₈O₆₄]⁴⁺(4e^–)电子化合物是一种具有高载流子密度、低逸出功的透明导电氧化物, 但是繁琐的制备步骤、苛刻的工艺条件极大地限制了其实际应用. 本文以特定化学计量比的Ca₁₂Al₁₄O₃₃+CaAl₂O₄两相为前驱体, 在放电等离子烧结系统里通过原位钙热反应成功制备了多晶C12A7:e^–. 在烧结温度为1100 ℃, 保温时间为10 min的条件下, 其电子浓度基本达到理论最大值~2.3×10²¹ cm^–3, 在2.5 eV处出现明显的紫外吸收峰, 致密度可达99%以上. 同时用顺磁共振谱仪分析了其电子结构, 结果呈Dyson特性, 这些结果充分证明了电子有效地注入到笼腔结构中. 热电子发射测试结果显示: 在阴极温度为1373 K, 外加电场为35000 V/cm的条件下, C12A7:e^–的热发射电流密度为1.75 A/cm², 有效逸出功为2.07 eV. 该工艺提供了一种新型的电子注入方法, 大幅度缩短了制备周期使大规模生产成为可能.

关键词:

C12A7:e^– /
钙热反应 /
热发射

Abstract

[Ca₂₄Al₂₈O₆₄]⁴⁺(4e^–) eletride, as the first room-temperature stable inorganic electride, has attracted intensive attention because of its fascinating chemical, electrical, optical, and magnetic properties. However, it usually needs synthesizing through a complicated multistep process involving high temperature (e.g., 1350 °C), severe reduction (e.g., 700–1300 ℃ for up to 240 h in Ca or Ti metal vapor atmosphere) and post-purification. Owing to the H₂O sensitivity of mayenite, the post-purification is quite troublesome once impurities are introduced. High-density, loosely bound encaged electrons with a low work function make it promise to possess practical applications. Therefore the facile method of massively producing the high-quality C12A7:e^– with high Ne is extremely desired. In this work, C12A7:e^– bulks are for the first time synthesized by simple spark plasma sintering process directly from a mixture of C12A7, CA and Ca powders under milder conditions (e.g., sintered at 1070 ℃ for 10 min in a vacuum). The obtained electride, which exhibits a relative density of 99%, an electron concentration of ~2.3×10²¹ cm^–3 and an obvious absorption peak at 2.5 eV, is obtained via SPS process at 1100 ℃ for 10 min. Electronic structure is also investigated by electron paramagnetic resonance. The occurrence of Dysonian characteristic, a typical feature of good electronic conductors, strongly suggests that the electrons are trapped in mayenite cavities. Furthermore, the obtained C12A7:e^– exhibits good sinterabilty on a crystal scale of 5–40 μm. Thermionic emission test results show that the thermionic emission begins to occur at 700 K and a large current density of 1.75 A/cm² is obtained in the electron thermal emission from a flat surface of the polycrystalline C12A7:e^– with an effective work function of 2.09 eV for a temperature of 1373 K with an applied electric field of ~35000 V/cm in a vacuum. Owing to no external reductant is needed, this developed route exhibits notable superiority over the conventional reduction method for phase-pure C12A7:e^–. Therefore, these results not only suggest a novel precursor for fabricating mayenite electride but also make it possible to produce efficiently the electride in large volume.

Keywords:

作者及机构信息

1.
北京工业大学材料科学与工程学院, 北京　100124

2.
合肥工业大学材料科学与工程学院, 合肥　230009

通信作者: 张忻, zhxin@bjut.edu.cn

基金项目: 国家自然科学基金(批准号: 51371010, 51572066, 50801002) 资助的课题

Authors and contacts

1.
College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China

2.
School of Materials Science and Engineering, Hefei University of Technology, Hefei 230009, China

Corresponding author: Zhang Xin, zhxin@bjut.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 51371010, 51572066, 50801002)

文章全文 : translate this paragraph

参考文献

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施引文献

图 1 C12A7+CA混合前驱体烧结前后XRD与实物照片

Fig. 1. Powder X-ray diffraction patterns of precursor before and after SPS process, insets are digital pictures of the precursor and the obtained electride.

下载: 全尺寸图片幻灯片

图 2 C12A7:e^–扫描照片

Fig. 2. SEM images of the sintered C12A7:e^– ceramic.

下载: 全尺寸图片幻灯片

图 3 (a) 样品的顺磁共振图谱; (b) 样品的紫外吸收光谱

Fig. 3. (a) EPR spectra of the sintered C12A7 bulk; (b) optical absorption spectra of the sintered C12A7:e^– powders.

下载: 全尺寸图片幻灯片

图 4 (a) 不同温度下发射电流密度随电场强度的变化; (b) 零场电流密度的拟合直线; (c) Richardson直线; (d) 发射稳定性曲线

Fig. 4. (a) Emission current density as a function of electric field at various in the range of 973 to 1373 K; (b) Schottky plots at various temperatures, fitting of the curves result in zero field emission current density at each temperature; (c) Richardson plot of the sample; (d) scatter plot of the emission current density versus time.

下载: 全尺寸图片幻灯片

map

[1]	Dye J L 2009 Acc. Chem. Res. 42 1564 Google Scholar
[2]	Kim S W, Hosono H 2012 Philos. Mag. 92 2596 Google Scholar
[3]	Jiang D, Zhao Z Y, Mu S L, Qian H J, Tong J H 2018 Inorg. Chem. 58 960
[4]	Khan K, Tareen A K, Elshahat S, Yadav A, Khan U 2018 Dalton Trans. 47 3819 Google Scholar
[5]	Matsuishi S, Toda Y, Miyakawa M 2003 Science 301 626 Google Scholar
[6]	刘洪亮, 张忻, 王杨, 肖怡新, 张久兴 2018 67 048101 Google Scholar Liu H L, Zhang X, Wang Y, Xiao Y X, Zhang J X 2018 Acta Phys. Sin. 67 048101 Google Scholar
[7]	Kitano M, Inoue Y, Yamazaki Y, Fumitaka H, Shinji K, Satoru M, Toshiharu Y, Sung W K, Michikazu H, Hideo H 2012 Nat. Chem. 4 934 Google Scholar
[8]	Kim S W, Hayashi K, Hirano M, Hosono H, Tanaka I 2006 J. Am. Ceram. Soc. 89 3294 Google Scholar
[9]	Kitano M, Kanbara S, Inoue Y, Kuganathan N, Sushko P V, Yokoyama T, Hara M, Hosono H 2015 Nat. Commun. 6 6731 Google Scholar
[10]	Hara M, Masaaki K, Hosono H 2017 ACS Catal. 7 2313 Google Scholar
[11]	Ding Y F, Zhao Q Q, Yu Z L, Zhao Y Q, Liu B, He P B, Zhou H, Li K L, Yin S F, Cai M Q 2019 J. Mater. Chem. C 7 7433 Google Scholar
[12]	Zhao Y Q, Wang X, Liu B, Yu Z L, He P B, Wan Q, Cai M Q, Yu H L 2018 Org. Electron. 53 50 Google Scholar
[13]	Dye J L 2003 Science 301 607 Google Scholar
[14]	Toda Y, Kim S W, Hayashi K, Hirano M, Kamiya T, Hosono H, Yasuda H 2005 Appl. Phys. Lett. 87 254103 Google Scholar
[15]	Yu Z L, Ma Q R, Liu B, Zhao Y Q, Wang L Z, Zhou H, Cai M Q 2017 J. Phys. D: Appl. Phys. 50 465101 Google Scholar
[16]	Zhao Y Q, Ma Q R, Liu B, Yu Z L, Yang J L, Cai M Q 2018 Nanoscale 10 8677 Google Scholar
[17]	Deng X Z, Zhao Q Q, Zhao Y Q, Cai M Q 2019 Current Appl. Phys. 19 279 Google Scholar
[18]	Kim K B, Kikuchi M, Miyakawa M, Yanagi H, Kamiya T, Hirano M, Hosono H 2007 J. Phys. Chem. C 111 8403 Google Scholar
[19]	Kou X C, Kronmüller H, Givord D, Rossignol M F 1994 Phys. Rev. B 50 3849 Google Scholar
[20]	Matsuishi S, Nomura T, Hirano M, Kodama K, Shamoto S I, Hosono H 2009 Chem. Mater. 21 2589 Google Scholar
[21]	Kim S W, Matsuishi S, Nomura T, Kubota Y, Takata M, Hayashi K, Hosono H 2007 Nano Lett. 7 1138 Google Scholar
[22]	Hosono H, Hayashi K, Hirano M 2007 J. Mater. Sci. 42 1872 Google Scholar
[23]	Sushko P V, Shluger A, Hayashi K, Hirano M, Hosono H 2003 Phys. Rev. Lett. 9 126401
[24]	Miyakawa M, Toda Y, Hayashi K, Hirano M, Kamiya T, Matsunami N, Hosono H 2005 J. Appl. Phys. 97 023510 Google Scholar
[25]	Woomer A H, Druffel D L, Sundberg J D, Pawlik J T, Warren S C 2019 J. Am. Ceram. Soc. 141 10300
[26]	冯琦, 张忻, 刘洪亮, 赵吉平, 李凡, 张久兴 2018 67 047102 Google Scholar Feng Q, Zhang X, Liu H L, Zhao J P, Xiao Y X, Li F, Zhang J X 2018 Acta Phys. Sin. 67 047102 Google Scholar
[27]	Duan J, Zhou T, Zhang L, Du J G, Jiang G, Wang H B 2015 Chin. Phys. B 24 096201 Google Scholar
[28]	Yu Z, Okoronkwo M U, Sant G N, Misture S T, Wang B 2019 J. Phys. Chem. C 123 11982 Google Scholar
[29]	Matsuishi S, Kim S W, Kamiya T, Hirano M, Hosono H 2008 J. Phys. Chem. C 112 4753 Google Scholar
[30]	Li F, Zhang X, Liu H L, Zhao J P, Xiao Y X, Zhang J X 2019 J. Am. Ceram. Soc. 102 884
[31]	Li F, Zhang X, Liu H L, Zhao J P, Xiao Y X, Zhang J X 2018 Vacuum 158 152 Google Scholar
[32]	包黎红, 那仁格日乐, 特古斯, 张忻, 张久兴 2013 62 196105 Google Scholar Bao L H, Narengerile, Tegus O, Zhang X, Zhang J X 2013 Acta Phys. Sin. 62 196105 Google Scholar
[33]	Konovalov S, Zagulyaev D, Chen X Z, Gromov V, Ivanov Y 2017 Chin. Phys. B 26 126203 Google Scholar
[34]	Xue J J, Cai Q, Zhang B H, Gei M, Chen D J, Zhi T, Chen J W, Wang L H, Zhang R, Zhen Y D 2017 Chin. Phys. B 26 116801 Google Scholar
[35]	Zhou S, Zhang J, Liu D, Lin Z, Huang Q, Bao L, Ma R, Wei Y 2010 Acta Mater. 58 4978 Google Scholar
[36]	Zhao G P, Zhao M G, Lim H S, Feng Y P, Ong C K 2005 Appl. Phys. Lett. 87 162513 Google Scholar

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[Ca₂₄Al₂₈O₆₄]⁴⁺(4e^–)电子化合物的直接合成及热发射性能