Mg掺杂调制铜铁矿结构CuAlO2多晶的微结构和电热传导

摘要/Abstract

摘要： 采用固相反应法制备铜铁矿结构的CuAl_1-xMg_xO₂ (x=0、0.005、0.01、0.02、0.03、0.04)多晶,研究了Mg掺杂对CuAlO₂多晶结构和性能的影响。Mg掺杂量x从0增加到0.02,样品均为菱方R3m单相,密度依次提高;所有样品呈半导体的热激活电输运行为,x=0.02样品在室温下的电阻率是未掺杂样品的1/19,热激活能显著下降(x=0时,ρ_{300 K}~5.54 Ω·m,E_a~0.328 eV;x=0.02时,ρ_{300 K}~0.29 Ω·m,E_a~0.218 eV),载流子浓度增加1个量级,主要因为Mg²⁺取代Al³⁺,引入新的受主能级。x>0.02时,MgAl₂O₄尖晶石杂相出现,使其电导率和热导率降低。CuAl_1-xMg_xO₂多晶的晶格热导率在总热导率中占绝对优势,且随温度升高(300~500 K)而下降,晶格热导Callaway模型模拟表明,所有样品的热阻主要源于点缺陷-声子散射。与x=0相比,x=0.02样品的室温热导率增大1倍(κ~13.065 0 W/(m·K)),声速增大,点缺陷-声子散射减弱,分析认为掺Mg形成强的Mg—O键,提高了晶体的弹性模量和声子频率,减弱了本征点缺陷、Mg掺杂引起的质量波动和应变场波动对声子的散射,同时Mg掺杂样品的密度提高也有利于增加热导率。

关键词: CuAl_1-xMg_xO₂多晶, 微结构, 电阻率, 晶格热导率, 点缺陷-声子散射, Mg—O键

Abstract: The CuAl_1-xMg_xO₂ (x=0, 0.005, 0.01, 0.02, 0.03, 0.04) polycrystals with delafossite structure were prepared by solid state reaction. The effects of Mg doping on structure and properties of CuAlO₂ polycrystals were studied. With the Mg doping amount x increasing from 0 to 0.02, the samples are of rhombohedral single phase with the space group of R3m, and density increases gradually. All samples exhibit the thermally activated electrical transport behavior of semiconductor, for x=0.02 sample, the room temperature resistivity is 1/19 of undoped sample, and the thermal activation energy decreases significantly (x=0, ρ_{300 K} ~5.54 Ω·m, E_a~0.328 eV; x=0.02, ρ_{300 K}~0.29 Ω·m, E_a~0.218 eV), the carrier concentration increased by 1 order of magnitude, as a result of the Al³⁺ is substituted by Mg²⁺, the new acceptor energy level is introduced. When x is greater than 0.02, the impurity phase of spinel MgAl₂O₄ increases, which leads to the drop of electrical conductivity and thermal conductivity. The lattice thermal conductivities of CuAl_1-xMg_xO₂ polycrystals are absolutely dominant in total thermal conductivity, and decrease as the temperature (300~500 K) increases. The simulation results of the Callaway model demonstrate that the point defect-phonon scattering makes a major contribution to thermal resistance of all samples. Compared with x=0, the room temperature thermal conductivity is doubled (κ~13.065 0 W/(m·K)), while the sound velocity increases and the point defect-phonon scattering weakens when x=0.02. The analysis shows that the strong Mg—O bond is formed by Mg-doping, which improves the elastic modulus of crystal and the phonon frequency, while the scattering between point defects and phonon is weakenes, the point defects include intrinsic point defect, the mass fluctuation and strain field fluctuation caused by Mg doping. The increase of density by Mg doping is also beneficial for thermal conductivity.

Key words: CuAl_1-xMg_xO₂ polycrystal, microstructure, electrical resistivity, lattice thermal conductivity, point defect-phonon scattering, Mg—O bond

中图分类号:

TB34

李毅, 武浩荣, 胡一丁, 孟佳源, 宋宏远, 唐艳艳, 黎振华, 陈亮维, 刘斌, 虞澜. Mg掺杂调制铜铁矿结构CuAlO₂多晶的微结构和电热传导[J]. 人工晶体学报, 2022, 51(8): 1422-1430.

LI Yi, WU Haorong, HU Yiding, MENG Jiayuan, SONG Hongyuan, TANG Yanyan, LI Zhenhua, CHEN Liangwei, LIU Bin, YU Lan. Modulation of Mg Doping on Microstructure and Electro-Thermal Conduction of CuAlO₂ Polycrystals with Delafossite Structure[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(8): 1422-1430.

参考文献

[1] 徐慢,夏冬林,赵修建.透明导电氧化物薄膜材料及其制备技术研究进展[J].材料导报,2006,20(S2):312-314+322.
XU M, XIA D L, ZHAO X J. Progress in transparent conductive oxide films and preparation technology[J]. Materials Review, 2006, 20(S2): 312-314+322(in Chinese).
[2] 沈艳,刘丹丹,宋世金,等.透明导电CuCr_1-xMg_xO₂(x=0～0.08)薄膜的固溶度扩展和c轴外延生长[J].材料导报,2021,35(10):10008-10012.
SHEN Y, LIU D D, SONG S J, et al. Solid solubility extension and c-axis epitaxial growth of transparent conductive CuCr_1-xMg_xO₂(x=0~0.08) thin films[J]. Materials Reports, 2021, 35(10): 10008-10012(in Chinese).
[3] 刘文婷,张赟,吴漫漫,等.Cu基铜铁矿结构透明导电氧化物薄膜的研究进展[J].材料导报,2014,28(3):28-32.
LIU W T, ZHANG Y, WU M M, et al. Research progress of Cu-based transparent conductive oxide thin films with delafossite structure[J]. Materials Review, 2014, 28(3): 28-32(in Chinese).
[4] YANAGI H, INOUE S I, UEDA K, et al. Electronic structure and optoelectronic properties of transparent p-type conducting CuAlO₂[J]. Journal of Applied Physics, 2000, 88(7): 4159.
[5] 岳锡华,赵屹,张维佳.ITO透明导电膜的制备及性能[J].航空学报,1996,17(1):57-63.
YUE X H, ZHAO Y, ZHANG W J. Preparation and properties of ITO transparent conducting films[J]. Acta Aeronautica et Astronautica Sinica, 1996, 17(1): 57-63(in Chinese).
[6] 裴志亮,谭明晖,陈猛,等.透明导电氧化物ZnO: Al(ZAO)薄膜的研究[J].金属学报,2000,36(1):72-76.
PEI Z L, TAN M H, CHEN M, et al. Study of transparent conductive oxide ZnO: Al(ZAO) films[J]. Acta Metallrugica Sinica, 2000, 36(1): 72-76(in Chinese).
[7] 宁洁.射频磁控溅射法制备氧化锡基透明导电氧化物薄膜[D].鞍山:辽宁科技大学,2014.
NING J. Doped tin oxide transparent conductive films prepared by RF magnetron sputtering[D]. Anshan: University of Science and Technology Liaoning, 2014(in Chinese).
[8] KAWAZOE H, YASUKAWA M, HYODO H, et al. P-type electrical conduction in transparent thin films of CuAlO₂[J]. Nature, 1997, 389(6654): 939-942.
[9] HAMADA I, KATAYAMA-YOSHIDA H. Energetics of native defects in CuAlO₂[J]. Physica B: Condensed Matter, 2006, 376/377: 808-811.
[10] TANG Y Y, QIN M, HU Y D, et al. Solid solubility of Mg and enhanced electrical conduction in the C-axis orientation of CuCr_1-xMg_xO₂ polycrystals[J]. Journal of Asian Ceramic Societies, 2020, 8(2): 537-541.
[11] DONG G B, ZHANG M, LAN W, et al. Structural and physical properties of Mg-doped CuAlO₂ thin films[J]. Vacuum, 2008, 82(11): 1321-1324.
[12] RUTTANAPUN C, MAENSIRI S. Effects of spin entropy and lattice strain from mixed-trivalent Fe³⁺/Cr³⁺ on the electronic, thermoelectric and optical properties of delafossite CuFe_1-xCr_xO₂(x = 0.25, 0.5, 0.75)[J]. Journal of Physics D: Applied Physics, 2015, 48(49): 495103.
[13] HU Y D, LI Y, WU H R, et al. Laser-induced transverse voltage effect in c-axis inclined CuCr_0.98Mg_0.02O₂ thin films with dominant phonon thermal conductivity[J]. Journal of Applied Physics, 2021, 130(14): 143104.
[14] 宋世金.错层Ca₃Co₄O₉的光热感生横向电压和热电输运各向异性研究[D].昆明:昆明理工大学, 2018.
SONG S J. Photothermally induced transverse voltage and thermoelectric transport anisotropy of staggered Ca₃Co₄O₉[D]. Kunming, China: Kunming University of Science and Technology, 2018(in Chinese).
[15] KUROTORI T, SUGIHARA S. Thermoelectric properties of CuAl_1-xM_xO₂ (M=Zn, Ca)[J]. Materials Transactions, 2005, 46(7): 1462-1465.
[16] YANAGIYA S, VAN NONG N, XU J, et al. The effect of (Ag, Ni, Zn)-addition on the thermoelectric properties of copper aluminate[J]. Materials, 2010, 3(1): 318-328.
[17] ONO Y, SATOH K I, NOZAKI T, et al. Structural, magnetic and thermoelectric properties of delafossite-type oxide, CuCr_1-xMg_xO₂(0≤x≤0.05)[J]. Japanese Journal of Applied Physics, 2007, 46(3A): 1071-1075.
[18] 梁英教,车荫昌.无机物热力学数据手册[M].沈阳:东北大学出版社,1993.
LIANG Y J, CHEN Y C. Handbook of inorganic thermodynamics data [M]. Shenyang, China. Northeastern University Press, 1993(in Chinese).
[19] CHEN L, HU M Y, WU P, et al. Thermal expansion performance and intrinsic lattice thermal conductivity of ferroelastic RETaO₄ ceramics[J]. Journal of the American Ceramic Society, 2019, 102(8): 4809-4821.
[20] LIU C, REN F, WANG H, et al. Solid-state synthesis and some properties of magnesium-doped copper aluminum oxides[J].MRS Online Proceedings Library, 2010, 1218(1): 1-6.
[21] 麦海翔,梁毅枫,梁守智,等.P型氧化物半导体CuAlO₂粉末的制备工艺及掺杂[J].材料科学与工程学报,2015,33(3):391-395.
MAI H X, LIANG Y F, LIANG S Z, et al. Preparation and doping of CuAlO₂ powder as P-type oxides semiconductor[J]. Journal of Materials Science and Engineering, 2015, 33(3): 391-395(in Chinese).
[22] LAN W, ZHANG M, DONG G B, et al. Improvement of CuAlO₂ thin film electrical conduction by the anisotropic conductivity[J]. Journal of Materials Research, 2007, 22(12): 3338-3343.
[23] PARK K, KO K Y, SEONG J K, et al. Microstructure and high-temperature thermoelectric properties of polycrystalline CuAl_1-xMg_xO₂ ceramics[J]. Journal of the European Ceramic Society, 2007, 27(13/14/15): 3735-3738.
[24] ZOU Y S, WANG H P, ZHANG S L, et al. Structural, electrical and optical properties of Mg-doped CuAlO₂ films by pulsed laser deposition[J]. RSC Advances, 2014, 4(78): 41294-41300.
[25] LIU R J, LI Y F, YAO B, et al. Shallow acceptor state in Mg-doped CuAlO₂ and its effect on electrical and optical properties: an experimental and first-principles study[J]. ACS Applied Materials & Interfaces, 2017, 9(14): 12608-12616.
[26] PELLS G P. Radiation-induced degradation of the intrinsic electrical conductivity of MgAl₂O₄ and Al₂O₃[J]. Journal of Nuclear Materials, 1991, 184(3): 177-182.
[27] 倪成明.钛酸钙/镁铝尖晶石热导率非平衡分子动力学计算研究[D].大连:大连理工大学,2018.
NI C M. Thermal conductivity of CaTiO₃/MgAl₂O₄: a non-equilibrium molecular dynamics caculation[D]. Dalian: Dalian University of Technology, 2018(in Chinese).
[28] LIU M S, LIN M C C, HUANG I T, et al. Enhancement of thermal conductivity with carbon nanotube for nanofluids[J]. International Communications in Heat and Mass Transfer, 2005, 32(9): 1202-1210.
[29] CHO J Y, SHI X, SALVADOR J R, et al. Thermoelectric properties and investigations of low thermal conductivity in Ga-doped Cu₂GeSe₃[J]. Physical Review B, 2011, 84(8): 085207.
[30] ZHOU T, LENOIR B, COLIN M, et al. Promising thermoelectric properties in Ag_xMo₉Se₁₁ compounds (3.4≤x≤3.9)[J]. Applied Physics Letters, 2011, 98(16): 162106.
[31] SHEN J J, FANG T, FU T Z, et al. Lattice thermal conductivity in thermoelectric materials[J]. Journal of Inorganic Materials, 2019, 34(3): 260.
[32] ZHANG X Y, PEI Y Z. Manipulation of charge transport in thermoelectrics[J]. Npj Quantum Materials, 2017, 2: 68.
[33] MUTA H, KANEMITSU T, KUROSAKI K, et al. Substitution effect on thermoelectric properties of ZrNiSn based half-Heusler compounds[J]. Materials Transactions, 2006, 47(6): 1453-1457.
[34] NOZAKI T, HAYASHI K, KAJITANI T. Mn-substitution effect on thermal conductivity of delafossite-type oxide CuFeO₂[J]. Journal of Electronic Materials, 2010, 39(9): 1798-1802.
[35] SLACK G A, GALGINAITIS S. Thermal conductivity and phonon scattering by magnetic impurities in CdTe[J]. Physical Review, 1964, 133(1A): A253-A268.

Mg掺杂调制铜铁矿结构CuAlO₂多晶的微结构和电热传导

Modulation of Mg Doping on Microstructure and Electro-Thermal Conduction of CuAlO₂ Polycrystals with Delafossite Structure

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	左芬, 翟章印. n型GaAs欧姆接触电极制备工艺[J]. 人工晶体学报, 2022, 51(4): 606-610.
[2]	李东珂, 陈佳明, 孙腾, 翟章印, 陈贵宾. 磷/硼共掺杂纳米硅的微观结构与光电性质[J]. 人工晶体学报, 2022, 51(1): 35-41.
[3]	廖杨芳, 谢泉. 溅射功率和溅射时间对Mg₂Si纳米晶薄膜结构和电阻率的影响[J]. 人工晶体学报, 2021, 50(9): 1675-1680.
[4]	王泽岩, 王朋, 刘媛媛, 郑昭科, 程合锋, 黄柏标. 基于晶体学原理的高效光催化材料的设计与制备[J]. 人工晶体学报, 2021, 50(4): 685-707.
[5]	杨云, 史新月, 吴红亚, 秦胜建, 张光磊. SiO₂气凝胶分子动力学模拟研究进展[J]. 人工晶体学报, 2021, 50(2): 397-406.
[6]	王小美, 王昭, 郝凌云, 张小娟, 刘楚. 基于光子晶体的结构色隐形眼镜的构建及应用[J]. 人工晶体学报, 2021, 50(11): 2164-2172.
[7]	邹征刚, 刘振, 龚国亮, 孙益坚, 温和瑞, 钟玖平. Ce³⁺∶GdLu₂Al₅O₁₂/Al₂O₃共晶微结构及其发光性能[J]. 人工晶体学报, 2021, 50(10): 1963-1970.
[8]	耿志明;狄琛;方轲;詹若男;袁紫媛;颜学俊;芦红;卢明辉;陈延峰. 人工晶体的微结构调控热输运研究[J]. 人工晶体学报, 2020, 49(9): 1569-1582.
[9]	钟良伟;郭纪林;曾志鹏;曾效舒. 艾奇逊炉提纯碳纳米管的组织结构性能表征[J]. 人工晶体学报, 2020, 49(7): 1272-1280.
[10]	郭凯红;赵铮;许卫锴. 基于进化算法的一维多相声子晶体拓扑优化设计[J]. 人工晶体学报, 2020, 49(6): 1083-1087.
[11]	刘强;刘阳;韦家蓓;谢腾飞;李江. Yb:CaF2透明陶瓷的制备与性能研究[J]. 人工晶体学报, 2020, 49(5): 799-803.
[12]	吕健, 王宏建, 曹佐, 袁莉娟, 李冰, 左飞, 周锐, 谢庆丰, 林华泰. ZrO₂陶瓷显微结构对绿光飞秒激光加工过程的协同效应[J]. 人工晶体学报, 2020, 49(2): 305-311.
[13]	仇满德;崔炎龙;商梦莉;边旭. CTAB辅助制备环状MoS2晶体及微结构调控[J]. 人工晶体学报, 2019, 48(3): 398-404.
[14]	商梦莉;仇满德;边旭. 金属有机骨架ZIF-67材料的合成及微结构调控研究[J]. 人工晶体学报, 2019, 48(12): 2228-2234.
[15]	郭会师;李文凤;高振禄;马丽君;桂阳海. 热处理温度对SiC纳米材料形貌和发光性能的影响[J]. 人工晶体学报, 2019, 48(11): 2119-2122.