同质外延生长ZnO单晶结构及光电性能的研究

人工晶体学报 ›› 2021, Vol. 50 ›› Issue (4): 768-775.

同质外延生长ZnO单晶结构及光电性能的研究

刘振华^1,2, 樊龙¹, 符亚军², 王进², 曹林洪², 吴卫东¹

1.中国工程物理研究院激光聚变研究中心,绵阳 621900;
2.西南科技大学材料科学与工程学院,绵阳 621010

收稿日期:2021-01-26 出版日期:2021-04-15 发布日期:2021-05-21
通讯作者: 曹林洪,教授。E-mail:hyclhg@yeah.net;吴卫东,教授。E-mail:wuweidongding@163.com
作者简介:刘振华(1994—),男,山西省人,硕士研究生。E-mail:1113594213@qq.com
基金资助:
中国工程物理研究院激光聚变研究中心基金(2018BB02);国家自然科学基金(11905199,2020YJ0333)

Structure and Photoelectric Properties of ZnO Single Crystal Grown by Homoepitaxy

LIU Zhenhua^1,2, FAN Long¹, FU Yajun², WANG Jin², CAO Linhong², WU Weidong¹

1. Laser Fusion Research Center, China Academy of Engineering Physics, Mianyang 621900, China;
2. School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010, China

Received:2021-01-26 Online:2021-04-15 Published:2021-05-21

摘要/Abstract

摘要： 本文报道了同质外延生长氧化锌(ZnO)单晶在高温氧气气氛退火前后的结构及光电特性。利用化学气相输运(CVT)法生长了红棕色的ZnO单晶,且进行高温氧气气氛退火处理后的ZnO单晶呈现无色透明状。通过X射线衍射仪(XRD)、X射线光电子能谱(XPS)、能谱仪(EDS)和拉曼(Raman)光谱测试分析了高温氧气气氛退火前后的ZnO单晶结构,讨论了退火对单晶内部缺陷类型及结构的影响。XRD测试表明ZnO单晶的生长方向为(002)方向。退火前后ZnO单晶的ω摇摆曲线半高宽分别为59″和31″,表明退火后单晶内缺陷显著减少;XPS和EDS能谱分析了退火前后ZnO单晶的成分和元素价态,结果表明高温氧气气氛处理后单晶内Zn和O元素含量比更接近理论值;通过Raman光谱分析了高温氧气气氛处理前后ZnO单晶的不同拉曼振动模式;通过紫外光谱数据分析,得到了退火前后ZnO单晶的光学禁带宽度分别为3.05 eV和3.2 eV;最后,通过Hall测试分析了高温氧气气氛退火处理前后ZnO单晶的电学性能参数,并深入讨论了退火前后ZnO单晶的低温电输运特性。

关键词: ZnO, 化学气相输运, 晶格氧, 禁带宽度, 载流子浓度, Hall效应

Abstract: The structure and photoelectric properties of ZnO single crystal grown by homoepitaxy before and after annealing was reported. The red-brown ZnO single crystals were grown by the chemical vapor transport (CVT) method. The ZnO single crystal annealed in a high-temperature oxygen atmosphere shows colorless and transparent. The structure of the ZnO single crystal before and after annealing was analyzed by XRD, XPS, EDS, and Raman. The effect of annealing on the defect type and structure of a single crystal was discussed. XRD results show that the growth direction of the ZnO single crystal is (002). The FWHM of ω-rocking curve of ZnO single crystal before and after annealing is 59″ and 31″, respectively. It indicates that the defects in the single crystal decrease significantly after annealing. The composition and valence of elements in the single crystal before and after annealing were analyzed by XPS and EDS, and the results show that the content ratio of Zn and O elements in the single crystal after high-temperature oxygen atmosphere treatment is closer to the theoretical value. Raman spectroscopy analyzed the high-temperature oxygen atmosphere. The different Raman vibration modes of ZnO single crystal before and after annealing were analyzed. Through UV spectrum data analysis, the optical band-gap of ZnO single crystal before and after annealing is obtained to be 3.05 eV and 3.2 eV, respectively. Finally, the ZnO single crystal’s electrical properties before and after annealing in a high-temperature oxygen atmosphere were analyzed by Hall test. The low-temperature electrical transport characteristics of ZnO single crystal before and after annealing were discussed in depth.

Key words: ZnO, chemical vapor transport, lattice oxygen, optical band-gap, carrier concentration, Hall effect

中图分类号:

刘振华, 樊龙, 符亚军, 王进, 曹林洪, 吴卫东. 同质外延生长ZnO单晶结构及光电性能的研究[J]. 人工晶体学报, 2021, 50(4): 768-775.

LIU Zhenhua, FAN Long, FU Yajun, WANG Jin, CAO Linhong, WU Weidong. Structure and Photoelectric Properties of ZnO Single Crystal Grown by Homoepitaxy[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(4): 768-775.

参考文献

[1] OHSHIMA E, OGINO H, NIIKURA I, et al. Growth of the 2-in-size bulk ZnO single crystals by the hydrothermal method[J]. Journal of Crystal Growth, 2004, 260(1/2): 166-170.
[2] TRIBOULET R. Growth of ZnO bulk crystals: a review[J]. Progress in Crystal Growth and Characterization of Materials, 2014, 60(1): 1-14.
[3] 袁海,刘正堂.原子层沉积Sn掺杂ZnO薄膜结构及光电性能的研究[J].人工晶体学报,2013,42(2):240-245.
YUAN H, LIU Z T. Structural, electrical and optical properties of Sn doped ZnO films deposited by atomic layer deposition[J]. Journal of Synthetic Crystals, 2013, 42(2): 240-245(in Chinese).
[4] NAUSE J, NEMETH B. Pressurized melt growth of ZnO boules[J]. Semiconductor Science and Technology, 2005, 20(4): S45-S48.
[5] EHRENTRAUT D, SATO H, KAGAMITANI Y, et al. Solvothermal growth of ZnO[J]. Progress in Crystal Growth and Characterization of Materials, 2006, 52(4): 280-335.
[6] FAN L, ZHANG Y J, PENG L P, et al. Crystal growth, finite element analysis and oxygen annealing of ZnO bulk crystal grown by low-temperature-gradient chemical vapor transport[J]. Ceramics International, 2020, 46(14): 23107-23115.
[7] 李新华,徐家跃.半导体ZnO单晶生长的技术进展[J].功能材料,2005,36(5):652-654+657.
LI X H, XU J Y. Technical progress on the growth of semiconductor ZnO crystals[J]. Journal of Functional Materials, 2005, 36(5): 652-654+657(in Chinese).
[8] LIU L, EDGAR J H. Substrates for gallium nitride epitaxy[J]. Materials Science and Engineering: R: Reports, 2002, 37(3): 61-127.
[9] NTEP J M, SAID HASSANI S, LUSSON A, et al. ZnO growth by chemical vapour transport[J]. Journal of Crystal Growth, 1999, 207(1/2): 30-34.
[10] LI X Y, WANG Y L, LIU W F, et al. Study of oxygen vacancies' influence on the lattice parameter in ZnO thin film[J]. Materials Letters, 2012, 85: 25-28.
[11] MIKAMI M, ETO T, WANG J F, et al. Growth of zinc oxide by chemical vapor transport[J]. Journal of Crystal Growth, 2005, 276(3/4): 389-392.
[12] FAN L, XIAO T T, ZHONG C J, et al. Seeded growth of bulk ZnO crystals in a horizontal tubular furnace[J]. CrystEngComm, 2019, 21(8): 1288-1292.
[13] WANG H H, BAEK S, SONG J, et al. Microstructural and optical characteristics of solution-grown Ga-doped ZnO nanorod arrays[J]. Nanotechnology, 2008, 19(7): 075607.
[14] PARK S M, IKEGAMI T, EBIHARA K. Effects of substrate temperature on the properties of Ga-doped ZnO by pulsed laser deposition[J]. Thin Solid Films, 2006, 513(1/2): 90-94.
[15] ARGUELLO C A, ROUSSEAU D L, PORTO S P S. First-order Raman effect in wurtzite-type crystals[J]. Physical Review, 1969, 181(3): 1351.
[16] WEI X C, ZHAO Y W, DONG Z Y, et al. Investigation of native defects and property of bulk ZnO single crystal grown by a closed chemical vapor transport method[J]. Journal of Crystal Growth, 2008, 310(3): 639-645.
[17] BUNDESMANN C, ASHKENOV N, SCHUBERT M, et al. Raman scattering in ZnO thin films doped with Fe, Sb, Al, Ga, and Li[J]. Applied Physics Letters, 2003, 83(10): 1974-1976.
[18] ASHKENOV N, MBENKUM B N, BUNDESMANN C, et al. Infrared dielectric functions and phonon modes of high-quality ZnO films[J]. Journal of Applied Physics, 2003, 93(1): 126-133.
[19] ZENG J N, LOW J K, REN Z M, et al. Effect of deposition conditions on optical and electrical properties of ZnO films prepared by pulsed laser deposition[J]. Applied Surface Science, 2002, 197/198: 362-367.
[20] YU J, WANG X M, WANG J, et al. Spacing-dependent nonlinear optical study of FePt nanoparticles composited films[J]. Journal of Alloys and Compounds, 2020, 832: 154870.
[21] SRIKANT V, CLARKE D R. Optical absorption edge of ZnO thin films: the effect of substrate[J]. Journal of Applied Physics, 1997, 81(9): 6357-6364.
[22] HONG S H, MUN J H, MIMURA K, et al. Effect of annealing in an O₂ atmosphere on the electrical properties of high-quality ZnO single crystals grown by seeded chemical vapor transport[J]. Journal of Ceramic Processing Research, 2012, 13(2): 105-109.
[23] HILSUM C, BARRIE R. Properties of p-type indium antimonide: i. electrical properties[J]. Proceedings of the Physical Society, 1958, 71(4): 676-685.