不同浓度Nb掺杂ZnO第一性原理研究

摘要/Abstract

摘要： 本文采用基于密度泛函理论的第一性原理计算了不同浓度Nb掺杂ZnO的能带结构及性能,并对本征ZnO、Al掺杂ZnO(AZO)和Nb掺杂ZnO(NZO)的模拟结果进行对比分析。结果表明:(1)NZO和AZO的带隙值均低于本征ZnO的带隙值,掺杂浓度(原子数分数)同为6.25%的NZO的带隙值低于AZO的带隙值。随着Nb掺杂浓度增高,NZO的导带底明显降低,态密度峰值降低,且Nb-4d态电子占据了费米能级的主要量子态。(2)随着掺杂浓度的增加,NZO和AZO吸收峰和介电函数峰均降低,且向低能区移动,其中,NZO吸收峰向低能区移动更明显,且介电函数虚部分别在0.42 eV和34.29 eV出现新的峰,主要是价带中Nb-4d和Nb-5p电子能级跃迁所致。掺杂浓度同为6.25%的NZO的静介电常数大于AZO的静介电常数,表明NZO极化能力更强,NZO可以更有效改善ZnO的光电性能。随着Nb掺杂浓度增加,NZO的吸收系数和介电函数虚部强度增加且向高能区移动。NZO的模拟结果为高价态元素Nb掺杂ZnO的实验研究工作及实际应用提供了理论参考。

关键词: 第一性原理, 能带结构, 掺杂, Nb掺杂ZnO, 态密度, 光学性质

Abstract: In this paper, the energy band structure and properties of Nb doped ZnO with different concentration were calculated based on the first-principle of density functional theory, and the simulation results of intrinsic ZnO, Al doped ZnO (AZO) and Nb doped ZnO (NZO) were compared and analyzed. The results show that: (1) the band gap values of NZO and AZO are lower than that of intrinsic ZnO, and the band gap values of NZO with the same concentration of 6.25% are lower than that of AZO. With the increase of Nb doping concentration, the conduction band bottom and the peak density of states of NZO decrease obviously, and Nb-4d electrons occupy the main quantum states of Fermi level. (2) With the increase of doping concentration, the absorption peaks and dielectric function peaks of NZO and AZO decrease, and move to the low energy region. Among them, the absorption peaks of NZO move more obviously to the low energy region, and the imaginary part of dielectric function has new peaks at 0.42 eV and 34.29 eV respectively, which is mainly due to the transition of Nb-4d and Nb-5p electronic energy levels in the valence band. The static dielectric constant of NZO with the same concentration of 6.25% is greater than that of AZO, which indicates that NZO has stronger polarization ability, and NZO can improve the photoelectric properties of ZnO more effectively. With the increase of Nb doping concentration, the absorption coefficient and the imaginary part strength of dielectric function of NZO increase and move to the high energy region. The theoretical simulation results of NZO provide a theoretical reference for the experimental research and practical application of high valence element Nb doped ZnO.

Key words: first-principle, energy band structure, doping, Nb doped ZnO, density of state, optical property

中图分类号:

O77⁺5
O469

王姝予, 李天微, 郝莹, 马颖, 刘鹏, 徐英起, 顾文梅. 不同浓度Nb掺杂ZnO第一性原理研究[J]. 人工晶体学报, 2022, 51(7): 1194-1201.

WANG Shuyu, LI Tianwei, HAO Ying, MA Ying, LIU Peng, XU Yingqi, GU Wenmei. First-Principles Study on Nb Doped ZnO with Different Concentration[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(7): 1194-1201.

参考文献

[1] RAJA M, MUTHUKUMARASAMY N, VELAUTHAPILLAI D, et al. Enhanced photovoltaic performance of quantum dot-sensitized solar cell fabricated using Al-doped ZnO nanorod electrode[J]. Superlattices and Microstructures, 2015, 80: 53-62.
[2] 孟甲,余春燕,贾伟,等.洋葱皮敏化ZnO太阳能电池的光电性能研究[J].人工晶体学报,2014,43(8):2028-2034.
MENG J, YU C Y, JIA W, et al. Study on photoelectric properties of ZnO solar cell sensitized by onion skin[J]. Journal of Synthetic Crystals, 2014, 43(8): 2028-2034(in Chinese).
[3] TSUKAZAKI A, OHTOMO A, ONUMA T, et al. Repeated temperature modulation epitaxy for p-type doping and light-emitting diode based on ZnO[J]. Nature Materials, 2005, 4(1): 42-46.
[4] RECH B, KLUTH O, REPMANN T, et al. New materials and deposition techniques for highly efficient silicon thin film solar cells[J]. Solar Energy Materials and Solar Cells, 2002, 74(1/2/3/4): 439-447.
[5] PUST S E, BECKER J P, WORBS J, et al. Electrochemical etching of zinc oxide for silicon thin film solar cell applications[J]. Journal of the Electrochemical Society, 2011, 158(7): D413.
[6] LIN Y C, YEN W T, SHEN C H, et al. Surface texturing of Ga-doped ZnO thin films by pulsed direct-current magnetron sputtering for photovoltaic applications[J]. Journal of Electronic Materials, 2012, 41(3): 442-450.
[7] LEE J M, YUN S J, KIM J K, et al. Texturing of Ga-doped ZnO transparent electrode for a-Si∶H thin film solar cells[J]. Electrochemical and Solid-State Letters, 2011, 14(11): B124.
[8] FAŸ S, STEINHAUSER J, NICOLAY S, et al. Polycrystalline ZnO∶B grown by LPCVD as TCO for thin film silicon solar cells[J]. Thin Solid Films, 2010, 518(11): 2961-2966.
[9] FAŸ S, STEINHAUSER J, OLIVEIRA N, et al. Opto-electronic properties of rough LP-CVD ZnO∶B for use as TCO in thin-film silicon solar cells[J]. Thin Solid Films, 2007, 515(24): 8558-8561.
[10] SAXENA N, MANZHI P, CHOUDHARY R J, et al. Performance optimization of transparent and conductive Zn_1-xAl_xO thin films for opto-electronic devices: an experimental & first-principles investigation[J]. Vacuum, 2020, 177: 109369.
[11] 彭丽萍,孟桂菊,徐凌.Al掺杂ZnO光学性能的第一性原理研究[J].高等函授学报(自然科学版),2007,20(4):39-42+44.
PENG L P, MENG G J, XU L. First principles study on optical properties of Al doped ZnO[J]. Journal of Higher Correspondence Education (Natural Sciences), 2007, 20(4): 39-42+44(in Chinese).
[12] 王延峰,张晓丹,黄茜,等.B掺杂ZnO透明导电薄膜的实验及理论研究[J].物理学报,2013,62(24):316-321.
WANG Y F, ZHANG X D, HUANG Q, et al. Experimental and theoretical investigation of transparent and conductive B doped ZnO film[J]. Acta Physica Sinica, 2013, 62(24): 316-321(in Chinese).
[13] 刘建军,陈三.Ga掺杂ZnO电子结构和吸收光谱的第一性原理研究[J].原子与分子物理学报,2010,27(3):575-580.
LIU J J, CHEN S. First-principles study on the electronic structures and absorption spectrum of Ga-doped ZnO[J]. Journal of Atomic and Molecular Physics, 2010, 27(3): 575-580(in Chinese).
[14] 王延峰,孟旭东,郑伟,等.V掺杂ZnO透明导电薄膜研究[J].物理学报,2016,65(8):344-350.
WANG Y F, MENG X D, ZHENG W, et al. Investigation of V doped ZnO transparent conductive oxide films[J]. Acta Physica Sinica, 2016, 65(8): 344-350(in Chinese).
[15] 贾晓芳,侯清玉,赵春旺.采用第一性原理研究钼掺杂浓度对ZnO物性的影响[J].物理学报,2017,66(6):067401.
JIA X F, HOU Q Y, ZHAO C W. Effect of Mo doping concentration on the physical properties of ZnO studied by first principles[J]. Acta Physica Sinica, 2017, 66(6): 067401(in Chinese).
[16] 方文玉,卫荣华,王晓雯,等.W掺杂ZnO电子结构与光学性质第一性原理计算[J].原子与分子物理学报,2019,36(4):682-687.
FANG W Y, WEI R H, WANG X W, et al. First-principles calculations on the electronic structures and optical properties of ZnO doped with W[J]. Journal of Atomic and Molecular Physics, 2019, 36(4): 682-687(in Chinese).
[17] SUZUKI A Y, NOSE K, UENO A, et al. High transparency and electrical conductivity of SnO₂∶Nb thin films formed through (001)-oriented SnO∶Nb on glass substrate[J]. Applied Physics Express, 2012, 5(1): 011103.
[18] 张敏明.透明导电氧化物半导体材料的量子化学计算与设计[D].北京:北京化工大学,2013.
ZHANG M M. Quantum chemistry design and calculation of transparent conductive oxide semiconductor materials[D]. Beijing: Beijing University of Chemical Technology, 2013(in Chinese).
[19] ERHART P, ALBE K. First-principles study of migration mechanisms and diffusion of oxygen in zinc oxide[J]. Physical Review B, 2006, 73(11): 115207.
[20] PAN F C, LIN X L, LI J, et al. The electronic structures and ferromagnetism of Cu-doped ZnO: the first-principle calculation study[J]. Journal of Superconductivity and Novel Magnetism, 2018, 31(7): 2103-2110.
[21] ZHOU C, LIU X, LI K, et al. Electronic and optical properties of Zn(Cu, V)O studied by first principles[J]. Optik, 2015, 126(23): 4731-4734.
[22] 伞海生,李斌,冯博学,等.由缺陷引起的Burstein-Moss和带隙收缩效应对CdIn₂O₄透明导电薄膜光带隙的影响[J].物理学报,2005,54(2):842-847.
SAN H S, LI B, FENG B X, et al. Effect on optical band-gap of transparent and conductive CdIn₂O₄ thin film due to defects-induced burstein-moss and band-gap narrowing characteristics[J]. Acta Physica Sinica, 2005, 54(2): 842-847(in Chinese).
[23] 郭连权,武鹤楠,刘嘉慧,等.ZnO能带及态密度的密度泛函理论研究[J].人工晶体学报,2009,38(2):440-444.
GUO L Q, WU H N, LIU J H, et al. Density functional theory study on energy band and density of states of ZnO[J]. Journal of Synthetic Crystals, 2009, 38(2): 440-444(in Chinese).
[24] DJURIC Z, LIVADA B, JOVIC V, et al. Quantum efficiency and responsivity of InSb photodiodes utilizing the Moss-Burstein effect[J]. Infrared Physics, 1989, 29(1): 1-7.
[25] 周爱萍,刘汉法,袁玉珍.氩气压强对直流磁控溅射法制备ZnO∶Nb透明导电薄膜性质的影响[J].真空科学与技术学报,2012,32(11):974-977.
ZHOU A P, LIU H F, YUAN Y Z. Growth and characterization of magnetron sputtered ZnO∶Nb films[J]. Chinese Journal of Vacuum Science and Technology, 2012, 32(11): 974-977(in Chinese).