七铝酸十二钙电子化合物单晶的电输运及电子发射性能
|
摘要
采用放电等离子烧结–光学悬浮区域熔炼–高温活性金属Ti还原相结合的制备方法成功获得了[Ca24Al28O64]4+:4e-(C12A7:e-)单晶体。测试了C12A7:e-的电子浓度,在800～1 100℃温度范围内测试了C12A7:e-单晶体自由生长面的热电子发射性能。结果表明:以活性金属Ti作为还原剂,在1 100℃还原30 h后,获得了接近理论电子浓度最大值(2.1×1021 cm-3)的C12A7:e-单晶,室温下的电导率达到1.96×103S/cm。在1 100℃,电压为3.5 kV时,发射电流密度达到最大值1.25 A/cm~2,平均有效逸出功为1.81 eV,表现出良好的热发射性能。
A single crystal of [Ca_(24)Al_(28)O_(64)]~(4+):4e~-(C12A7:e-) was prepared via a spark plasma sintering(SPS)–floating zone(Fz)–Ti metal reduction method. The electron concentration of C12A7:e-was measured and its thermionic emission properties of free growth surface at 800-1 100 ℃ were also investigated. The results show that after the reduction treatment with Ti metal at 1 100 ℃ for 30 h, a C12A7:e-single crystal with a theoretical maximum electron concentration(2.1×1021 cm-3) is obtained, and the electrical conductivity at room temperature is 1.96×103 S/cm. The emission current density reaches a maximum value of 1.25 A/cm2 at 1 100 ℃ with a voltage of 3.5 kV. The average effective work function is 1.81 e V, showing a good thermionic emission performance.
A single crystal of [Ca_(24)Al_(28)O_(64)]~(4+):4e~-(C12A7:e-) was prepared via a spark plasma sintering(SPS)–floating zone(Fz)–Ti metal reduction method. The electron concentration of C12A7:e-was measured and its thermionic emission properties of free growth surface at 800-1 100 ℃ were also investigated. The results show that after the reduction treatment with Ti metal at 1 100 ℃ for 30 h, a C12A7:e-single crystal with a theoretical maximum electron concentration(2.1×1021 cm-3) is obtained, and the electrical conductivity at room temperature is 1.96×103 S/cm. The emission current density reaches a maximum value of 1.25 A/cm2 at 1 100 ℃ with a voltage of 3.5 kV. The average effective work function is 1.81 e V, showing a good thermionic emission performance.
引文
[1]HOSONO Hideo,HAYASHI Katsuro,HIRANO Masahiro.Active anion manipulation for emergence of active functions in the nanoporous crystal 12CaO·7Al2O3:a case study of abundant element strategy[J].J Mater Sci,2007,42:1872?1883.
[2]EBBINGHAUS S G,KRAUSE H,LEE D K,et al.Single crystals of C12A7(Ca12Al14O33)substituted with 1 mol%Iron[J].Cryst Growth Des,2014,14(5):2240?2245.
[3]MIYAKAWA M,KIM S W,HIRANO H,et al.Superconductivity in an Inorganic Electr-ide 12CaO·7Al2O3:e?[J].J Am Ceram Soc,2007,129(23):7270?7271.
[4]BERTONI M I,MASON T O,MEDVEDEVA J E.Conductivity and conduction mechanism in an ultraviolet light activated electronic conductor[J].Appl Phys,2005,97:103713?103716.
[5]LI J,HUANG F,WANG L,et al.Mechanistic for Hydroxy Anion Emission from the Modified 12CaO·7Al2O3 surface[J].J Phys Chem B,2005,109(30):14599?14603.
[6]宫璐,沈静,李全新.C12A7:O-材料抗菌性能及机理研究[J].无机材料学报,2010,25(9):942?946.GONG Lu,SHEN Jing,LI Quanxin.J Inorg Mater(in Chinese),2010,25(9):942?946.
[7]HAYASHI K,MATSUISHI S,KAMIYA T,et al.Light-induced conversion of an insulating refractory oxide into a persistent electronic conductor[J].Nature,2002,419:462?465.
[8]SUN J Q,SONG C F,NING S,et al.Features and mechanism of chlorine anion emission from microporous crystal C12A7-Cl?surface[J].Acta Phys-Chim Sin,2009,25(9):1713?1720.
[9]SONG C,SUN J,QIU S,et al.Atoic Fluorine anion storage emission material C12A7-F?and etching of Si and SiO2 by atomic fluorine[J].Chem Mater,2008,20(10):3473?3479.
[10]HAYASHI K,MATSUISHI S,UEDA N,et al.Maximum Incorporation of Oxygen Radicals,O?and O2?,into 12CaO·7Al2O3with a Nanoporous Structure[J].Chem Mater,2003,15(9):1851?1854.
[11]DYE James L.Electrons as anions[J].Science,2003,301:607?608.
[12]KIM.S W,MIYAKAWA M,HIRANO M,et al.Superconducting transition in electron-doped 12CaO·7Al2O3[J].Mater Trans,2008,49:1748?1752.
[13]TODA Yoshitake,KIM Sung Wng,HAYASHI Katsuro,et al.Intense thermal field electron emission from room-temperature stable electride[J].Appl Phys Lett,2005,87(25):254103(1?3).
[14]KIM S W,HAYASHI K,HIRANO M,et al.Electron carrier generation in a refractory oxide 12CaO·7Al2O3 by heating in reducing atmosphere:Conversion from an insulator to a persistent conductor[J].J Am Ceram Soc,2006,89(10):3294-3298.
[15]KIM S W,TODA Y,HIRANO M,et al.Synthesis of a room temperature stable 12CaO·7Al2O3 electride from the melt and its application as an electron field emitter[J].Chem Mater,2006,18:1938-1944.
[16]MATSUISHI S,TODA Y,MIYAKAWA M,et al.High-density electron anions in a nanoporous single crystal:[Ca24Al28O64]4+(4e?)[J].Science,2003,301:626?629.
[17]KIM S W,MATSUISHI S,NOMURA T,et al.Metallic state in a lime-alumina compound with nanoporous structure[J].Nano Lett,2007,7(5):1138?1143.
[18]江浩.C12A7:e?电子化合物的制备及发射性能研究[D].北京:北京工业大学,2017.JIANG Hao.Research on preparation and emission properties of C12A7:e?electride(in Chinese,dissertation).Beijing:Beijing University of Technology,2017.
[19]吴庆辉,唐慧丽,苏良碧,等.光学浮区法生长掺铟氧化镓单晶及其性能[J].硅酸盐学报,2017,45(4):548-552.WU Qinghui,TANG Huili,SU Liangbi,et al.J Chin Ceram Soc,2017,45(4):548-552.
[20]YOON S G,KIM S W,YOON D H,et al.Single crystal growth of nano-porous C12A7:e?by controlling melt state[J].J Nanosci Nanotechnol,2009,9:7345?7349.
[21]胡志方.真空蒸馏法制备高纯钙的热力学及工艺研究[D].北京:北京有色金属研究总院,2013.HU Zhifang.The thermodynamic and process of preparation of high purity calcium by vacuum distillation(in Chinese,dissertation).Beijing:General Research Institute for Nonferrous Metals,2013.
[22]ALI M M,NAGAO M,WATAUCHI S,et al.Floating zone growth and characterization of(Ca1?x Nbx)12Al14O33+6x(x=0.001)single crystals[J].ACS Omega,2016,1:1157-1163
[23]MATSUISHIS,NOMURA T,HIRANO M,et al.Direct synthesis of powdery inorganic electride[Ca24Al28O64]4+(e?)4 and determination of oxygen stoichiometry[J].Chem Mater,21:2589?2591.
[24]ZHAO Jiping,ZHANG Xin,LIU Hongliang,et al.Synthesis and Characterization of(Ca1?x Srx)12Al14O33 Electrides[J].Cryst Res Technol,2018,53:1700201.
[25]冯琦,张忻,刘洪亮,等.[Ca24Al28O64]4+:4e?电子化合物的制备及其电输运特性[J].物理学报,2018,67:047102.FENG Qi,ZHANG Xin,LIU Hongliang,et al.Acta Phys Sin(in Chinese),2018,67:047102.
[26]MATSUISHI S,NOMURA T,HIRANO M,et al.Direct synthesis of powdery inorganic electride[Ca24Al28O64]4+(e-)4 and determination of oxygen stoichiometry[J].Chem Mater,2009,21:2589?2591.
[27]张繁星,张忻,张久兴,等.悬浮区域熔炼法制备Ce PrB6单晶体及其热发射性能研究[J].无机材料学报,2014,29(10):1073?1076.ZHANG Fanxing,ZHANG Xin,ZHANG Jiuxing,et al.J Inorg Mater(in Chinese),2014,29(10):1073?1076.
[28]王杨,张忻,张久兴,等.低逸出功Ce1?xGdx B6单晶体的制备及其热发射性能[J].无机材料学报,2016,31(8):797?801.WANG Yang,ZHANG Xin,ZHANG Jiuxing,et al.J Inorg Mater(in Chinese),2016,31(8):797?801.
[2]EBBINGHAUS S G,KRAUSE H,LEE D K,et al.Single crystals of C12A7(Ca12Al14O33)substituted with 1 mol%Iron[J].Cryst Growth Des,2014,14(5):2240?2245.
[3]MIYAKAWA M,KIM S W,HIRANO H,et al.Superconductivity in an Inorganic Electr-ide 12CaO·7Al2O3:e?[J].J Am Ceram Soc,2007,129(23):7270?7271.
[4]BERTONI M I,MASON T O,MEDVEDEVA J E.Conductivity and conduction mechanism in an ultraviolet light activated electronic conductor[J].Appl Phys,2005,97:103713?103716.
[5]LI J,HUANG F,WANG L,et al.Mechanistic for Hydroxy Anion Emission from the Modified 12CaO·7Al2O3 surface[J].J Phys Chem B,2005,109(30):14599?14603.
[6]宫璐,沈静,李全新.C12A7:O-材料抗菌性能及机理研究[J].无机材料学报,2010,25(9):942?946.GONG Lu,SHEN Jing,LI Quanxin.J Inorg Mater(in Chinese),2010,25(9):942?946.
[7]HAYASHI K,MATSUISHI S,KAMIYA T,et al.Light-induced conversion of an insulating refractory oxide into a persistent electronic conductor[J].Nature,2002,419:462?465.
[8]SUN J Q,SONG C F,NING S,et al.Features and mechanism of chlorine anion emission from microporous crystal C12A7-Cl?surface[J].Acta Phys-Chim Sin,2009,25(9):1713?1720.
[9]SONG C,SUN J,QIU S,et al.Atoic Fluorine anion storage emission material C12A7-F?and etching of Si and SiO2 by atomic fluorine[J].Chem Mater,2008,20(10):3473?3479.
[10]HAYASHI K,MATSUISHI S,UEDA N,et al.Maximum Incorporation of Oxygen Radicals,O?and O2?,into 12CaO·7Al2O3with a Nanoporous Structure[J].Chem Mater,2003,15(9):1851?1854.
[11]DYE James L.Electrons as anions[J].Science,2003,301:607?608.
[12]KIM.S W,MIYAKAWA M,HIRANO M,et al.Superconducting transition in electron-doped 12CaO·7Al2O3[J].Mater Trans,2008,49:1748?1752.
[13]TODA Yoshitake,KIM Sung Wng,HAYASHI Katsuro,et al.Intense thermal field electron emission from room-temperature stable electride[J].Appl Phys Lett,2005,87(25):254103(1?3).
[14]KIM S W,HAYASHI K,HIRANO M,et al.Electron carrier generation in a refractory oxide 12CaO·7Al2O3 by heating in reducing atmosphere:Conversion from an insulator to a persistent conductor[J].J Am Ceram Soc,2006,89(10):3294-3298.
[15]KIM S W,TODA Y,HIRANO M,et al.Synthesis of a room temperature stable 12CaO·7Al2O3 electride from the melt and its application as an electron field emitter[J].Chem Mater,2006,18:1938-1944.
[16]MATSUISHI S,TODA Y,MIYAKAWA M,et al.High-density electron anions in a nanoporous single crystal:[Ca24Al28O64]4+(4e?)[J].Science,2003,301:626?629.
[17]KIM S W,MATSUISHI S,NOMURA T,et al.Metallic state in a lime-alumina compound with nanoporous structure[J].Nano Lett,2007,7(5):1138?1143.
[18]江浩.C12A7:e?电子化合物的制备及发射性能研究[D].北京:北京工业大学,2017.JIANG Hao.Research on preparation and emission properties of C12A7:e?electride(in Chinese,dissertation).Beijing:Beijing University of Technology,2017.
[19]吴庆辉,唐慧丽,苏良碧,等.光学浮区法生长掺铟氧化镓单晶及其性能[J].硅酸盐学报,2017,45(4):548-552.WU Qinghui,TANG Huili,SU Liangbi,et al.J Chin Ceram Soc,2017,45(4):548-552.
[20]YOON S G,KIM S W,YOON D H,et al.Single crystal growth of nano-porous C12A7:e?by controlling melt state[J].J Nanosci Nanotechnol,2009,9:7345?7349.
[21]胡志方.真空蒸馏法制备高纯钙的热力学及工艺研究[D].北京:北京有色金属研究总院,2013.HU Zhifang.The thermodynamic and process of preparation of high purity calcium by vacuum distillation(in Chinese,dissertation).Beijing:General Research Institute for Nonferrous Metals,2013.
[22]ALI M M,NAGAO M,WATAUCHI S,et al.Floating zone growth and characterization of(Ca1?x Nbx)12Al14O33+6x(x=0.001)single crystals[J].ACS Omega,2016,1:1157-1163
[23]MATSUISHIS,NOMURA T,HIRANO M,et al.Direct synthesis of powdery inorganic electride[Ca24Al28O64]4+(e?)4 and determination of oxygen stoichiometry[J].Chem Mater,21:2589?2591.
[24]ZHAO Jiping,ZHANG Xin,LIU Hongliang,et al.Synthesis and Characterization of(Ca1?x Srx)12Al14O33 Electrides[J].Cryst Res Technol,2018,53:1700201.
[25]冯琦,张忻,刘洪亮,等.[Ca24Al28O64]4+:4e?电子化合物的制备及其电输运特性[J].物理学报,2018,67:047102.FENG Qi,ZHANG Xin,LIU Hongliang,et al.Acta Phys Sin(in Chinese),2018,67:047102.
[26]MATSUISHI S,NOMURA T,HIRANO M,et al.Direct synthesis of powdery inorganic electride[Ca24Al28O64]4+(e-)4 and determination of oxygen stoichiometry[J].Chem Mater,2009,21:2589?2591.
[27]张繁星,张忻,张久兴,等.悬浮区域熔炼法制备Ce PrB6单晶体及其热发射性能研究[J].无机材料学报,2014,29(10):1073?1076.ZHANG Fanxing,ZHANG Xin,ZHANG Jiuxing,et al.J Inorg Mater(in Chinese),2014,29(10):1073?1076.
[28]王杨,张忻,张久兴,等.低逸出功Ce1?xGdx B6单晶体的制备及其热发射性能[J].无机材料学报,2016,31(8):797?801.WANG Yang,ZHANG Xin,ZHANG Jiuxing,et al.J Inorg Mater(in Chinese),2016,31(8):797?801.