高温退火对PVT法生长的AlN晶体质量的影响

doi:10.15541/jim20220481

无机材料学报 ›› 2023, Vol. 38 ›› Issue (3): 343-349.DOI: 10.15541/jim20220481 CSTR: 32189.14.10.15541/jim20220481

高温退火对PVT法生长的AlN晶体质量的影响

俞瑞仙(), 王国栋, 王守志, 胡小波(), 徐现刚, 张雷()

山东大学深圳研究院，新一代半导体材料研究院, 晶体材料国家重点实验室, 济南 250100

收稿日期:2022-08-13 修回日期:2022-10-09 出版日期:2023-03-20 网络出版日期:2022-11-20
通讯作者: 胡小波, 教授. E-mail: xbhu@sdu.edu.cn;
张雷, 副教授. E-mail: leizhang528@sdu.edu.cn
作者简介:俞瑞仙(1987-), 男, 博士研究生. E-mail: yuruixian0001@126.com

Effect of High-temperature Annealing on AlN Crystal Grown by PVT Method

YU Ruixian(), WANG Guodong, WANG Shouzhi, HU Xiaobo(), XU Xiangang, ZHANG Lei()

The State Key Laboratory of Crystal Materials, Shandong University, Institute of Novel Semiconductors, Shenzhen Research Institute of Shandong University, Shandong University, Jinan 250100, China

Received:2022-08-13 Revised:2022-10-09 Published:2023-03-20 Online:2022-11-20
Contact: HU Xiaobo, professor. E-mail: xbhu@sdu.edu.cn;
ZHANG Lei, associate professor. E-mail: leizhang528@sdu.edu.cn
About author:YU Ruixian (1987-), male, PhD candidate. E-mail: yuruixian0001@126.com
Supported by:
Shenzhen Science and Technology Program(JCYJ20210324141607019);Natural Science Foundation of Shandong Province(ZR2022QF044);National Natural Science Foundation of China(52202265)

摘要/Abstract

摘要：

在PVT法生长AlN晶体的过程中, 很难保持理想的热力学平衡状态, 不可避免地会产生晶体缺陷。高温退火技术对提高晶体完整性十分有效，受到了广泛关注。本工作在N₂气氛环境下对PVT法生长的AlN晶片进行高温退火研究。为了评价退火前后AlN晶体的质量和结构变化情况, 进行了高分辨率X射线衍射(HRXRD)和拉曼光谱分析。通过室温光致发光(PL)和吸收光谱对AlN晶体的光学性质以及与杂质相关的带隙变化情况进行了表征。在1400~1800 ℃退火后, AlN晶体质量显著提高。1400 ℃退火后, (10-12)晶面的X射线摇摆曲线的半峰宽(FWHM)从104.04 arcsec减小到79.92 arcsec。随着退火温度升高, 吸收性能明显增强, 带隙增大, 说明高温退火处理有利于提高AlN晶体的质量。二次离子质谱(SIMS)结果表明, 退火过程降低了C杂质, 增加了AlN晶体的带隙, 这与光吸收结果一致。

关键词: 高温退火技术, AlN晶体, C杂质, 带隙

Abstract:

In the process of PVT growth of AlN crystals, there is difficult to maintain ideal thermodynamic equilibrium conditions, causing crystal defects being inevitably generated. High temperature annealing technology has received much attention due to their effectiveness in improving crystal integrity. In this paper, AlN samples grown by PVT method were annealed at high temperature in N₂ atmosphere. In order to evaluate the crystalline quality and structural perfection of AlN before and after thermal annealing, high-resolution X-ray diffraction (HRXRD) and Raman spectrum were carried out. In addition, the impurity related band gap changes in the optical properties of AlN crystals were characterized by room temperature photoluminescence (PL) and absorption spectra. The crystal quality of these AlN crystals was significantly improved after annealing at 1400-1800 ℃. The full width at half maximum (FWHM) of the (10¯12) plane X-ray rocking curve decreased from 104.04 to 79.92 arcsec (1 arcsec=0.01592°) after annealing at 1400 ℃. As the annealing temperature increases, the absorption was significantly enhanced and the band gap became larger, indicating that the annealing process was beneficial to improve the quality of AlN crystals. The results of secondary ion mass spectrometry (SIMS) demonstrate that the annealing process reduces the C impurity, resulting in an increase in band gap of AlN crystal, which is consistent with the results of optical absorption.

Key words: high temperature annealing technology, AlN crystal, C impurities, bandgap

中图分类号:

TB34

俞瑞仙, 王国栋, 王守志, 胡小波, 徐现刚, 张雷. 高温退火对PVT法生长的AlN晶体质量的影响[J]. 无机材料学报, 2023, 38(3): 343-349.

YU Ruixian, WANG Guodong, WANG Shouzhi, HU Xiaobo, XU Xiangang, ZHANG Lei. Effect of High-temperature Annealing on AlN Crystal Grown by PVT Method[J]. Journal of Inorganic Materials, 2023, 38(3): 343-349.

图/表 8

Fig. 1 Photos of AlN crystal sample (a) Bulk AlN crystal; (b) Polished AlN crystal

Fig. 2 Schematic view of high temperature annealing process (a) High temperature annealing furnace; (b) High temperature annealing process

Fig. 3 EBSD of AlN crystal sample (a) EBSD Kikuchi patterns of AlN crystal without annealing; (b) Band slop obtained from EBSD mapping date; (c) Pole figures of AlN without annealing

Fig. 4 XRD ω-scan rocking curves of AlN (10¯12) diffractions

Table 1 Calculated edge dislocations density(ρe) of AlN samples

Sample	(10¯12) FWHM/arcsec^*	Edge dislocations density, ρ_e/(×10⁷, cm^-2)
Raw	104.04	5.80
AlN-1400	79.92	3.42
AlN-1600	78.92	3.34
AlN-1800	97.2	5.06

Fig. 5 Raman spectra of AlN samples without and with annealing at different temperatures

Fig. 6 Optical absorption spectra of the AlN crystals with and without annealing (a) Absorption spectra of the AlN without and with annealing at different temperatures with right enlarged spectra showing an absorption peak at 634 nm; (b) Correlation curves of (αE)2 on E with inset showing the band gap of AlN without and with annealing at different temperatures

Fig. 7 SIMS depth profiles of AlN crystal without (a) and with annealing at 1600 ℃ (b)

参考文献 20

[1]	SUN M S, LI J F, ZHANG J C et al. The fabrication of AlN by hydride vapor phase epitaxy. Journal of Semiconductors, 2019, 40: 121803. DOI
[2]	YU R X, LIU G X, WANG G D et al. Ultrawide-bandgap semiconductor AlN crystals: growth and applications. J. Mater. Chem. C, 2021, 9: 1852. DOI URL
[3]	YU R X, CHEN C M, ZHANG L et al. Influence of different heater structures on the temperature field of AlN crystal growth by resistance heating. Materials, 2021, 14: 7441. DOI URL
[4]	ZHENG W, HUANG F, ZHENG R S, et al. Low-dimensional structure vacuum-ultraviolet-sensitive (λ<200 nm) photodetector with fast-response speed based on high-quality AlN micro/ nanowire. Adv. Mater., 2015, 27: 3921. DOI URL
[5]	CHEN Z L, LIU Z Q, WEI T B, et al. Improved epitaxy of AlN film for deep-ultraviolet light-emitting diodes enabled by graphene. Adv. Mater., 2019, 31: 1807345. DOI URL
[6]	LU T J, LIENHARD B, JEONG K Y, et al. Bright high-purity quantum emitters in aluminum nitride integrated photonics. ACS Photonics, 2020, 7: 2650. DOI URL
[7]	LIU X H, ZHANG J C, SU X J, et al. Fabrication of crack-free AlN film on sapphire by hydride vapor phase epitaxy using an in situ etching method. Appl. Phys. Exp., 2016, 9: 045501. DOI
[8]	KATAGIRI Y, KISHINO S, OKUURA K, et al. Low-pressure HVPE growth of crack-free thick AlN on a trench-patterned AlN template. J. Cryst. Growth, 2009, 311: 2831. DOI URL
[9]	HARTMANN C, DITTMAR A, WOLLWEBER J, et al. Bulk AlN growth by physical vapor transport. Semicond. Sci. Technol., 2014, 29: 084002. DOI URL
[10]	ZHUANG D, HERRO Z G, SCHLEAAER R, et al. Seeded growth of AlN single crystals by physical vapor transport. J. Cryst. Growth, 2006, 287: 372. DOI URL
[11]	GUGUSCHEV C, DITTMAR A, MOUKHINA E, et al. Growth of bulk AlN single crystals with low oxygen content taking into account thermal and kinetic effects of oxygen-related gaseous species. J. Cryst. Growth, 2012, 360: 185. DOI URL
[12]	TANIYASU Y, KASU M, MAKIMOTO T. Electrical conduction properties of n-type Si-doped AlN with high electron mobility (>100 cm²·V^-1·s^-1). Appl. Phys. Lett., 2004, 85: 4672. DOI URL
[13]	STRASSBURG M, SENAWIRATNE J, DIETZ N. The growth and optical properties of large, high-quality AlN single crystals. J. Appl. Phys., 2004, 96: 5870. DOI URL
[14]	HARTMANN C, WOLLWEBER J, DITTMAR A, et al. Preparation of bulk AlN seeds by spontaneous nucleation of freestanding crystals. Jpn. J. Appl. Phys., 2013, 52: 08JA06. DOI
[15]	WANG G D, ZHANG L, WANG Y, et al. Effect of temperature gradient on AlN crystal growth by physical vapor transport method. Cryst. Growth Des., 2019, 19: 6736. DOI URL
[16]	MOTAMEDI P, CADIEN K. Structural and optical characterization of low-temperature ALD crystalline AlN. J. Cryst. Growth, 2015, 421: 45. DOI URL
[17]	HARTMANN C, MATIWE L, WOLLWEBER J, et al. Favorable growth conditions for the preparation of bulk AlN single crystals by PVT. CrystEngComm, 2020, 22: 1762. DOI URL
[18]	COLLAZO R, XIE J, GADDY B, et al. On the origin of the 265 nm absorption band in AlN bulk crystals. Appl. Phys. Lett., 2012, 100: 191914. DOI URL
[19]	GADDY B E, BRYAN Z, BRYAN I, et al. The role of the carbon- silicon complex in eliminating deep ultraviolet absorption in AlN. Appl. Phys. Lett., 2014, 104: 202106. DOI URL
[20]	ZHAO L, YANG K, AI Y J, et al. Crystal quality improvement of sputtered AlN film on sapphire substrate by high-temperature annealing. J. Mater. Sci.: Mater. Electron., 2018, 29: 13766. DOI

高温退火对PVT法生长的AlN晶体质量的影响

Effect of High-temperature Annealing on AlN Crystal Grown by PVT Method

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 20

相关文章 15

编辑推荐

Metrics

本文评价

[1]	李腊, 沈国震. 二维MXenes材料在柔性光电探测器中的应用展望[J]. 无机材料学报, 2024, 39(2): 186-194.
[2]	孟雨婷, 王雪梅, 章淑娴, 陈志炜, 裴艳中. Bi₂Te₃基热电材料的单带和双带传输特性转变[J]. 无机材料学报, 2024, 39(11): 1283-1291.
[3]	张守超, 陈洪雨, 刘洪飞, 杨羽, 李欣, 刘德峰. 6H-SiC中子辐照肿胀高温回复及光学特性研究[J]. 无机材料学报, 2023, 38(6): 678-686.
[4]	徐家跃, 梁肖肖, 金敏, 曾海波, KIMURAHideo, 胡皓阳, 邵和助, 申慧, 田甜, 李海霞. 移动区熔法生长全无机钙钛矿型CsPbBr₃晶体及其性能研究[J]. 无机材料学报, 2018, 33(11): 1253-1258.
[5]	魏菁, 李汉超, 柯培玲, 汪爱英. 不同厚度四面体非晶碳薄膜的高通量制备及表征[J]. 无机材料学报, 2018, 33(11): 1173-1178.
[6]	敖伟栋, 刘妍, 马青山, 刘欢, 周斌, 郑霄家, 于东麒, 张文华. 垂直排列ReS_2(1-_x₎Se₂_x合金纳米片的控制合成及带隙调控[J]. 无机材料学报, 2018, 33(10): 1083-1088.
[7]	秦毅, 赵婷, 王波, 杨建锋. PECVD沉积和原位退火时间对h-BN薄膜组成及光学带隙的影响[J]. 无机材料学报, 2014, 29(7): 729-734.
[8]	刘峰, 陆毅青, 李永祥. 铋层状共生结构铁电体Bi₇Ti₄NbO₂₁的第一性原理计算[J]. 无机材料学报, 2014, 29(1): 38-42.
[9]	宋继梅, 胡海琴, 王秀芝, 赵绍娟, 师亚利, 任明松. Bi₂Mo_xW_1-xO₆固溶体的水热合成、表征及光催化性能[J]. 无机材料学报, 2013, 28(12): 1275-1280.
[10]	王博, 刘芳洋, 李劼, 赖延清, 张治安, 刘业翔. Co-Se 化合物薄膜的电沉积制备与表征[J]. 无机材料学报, 2011, 26(4): 403-410.
[11]	邓赞红, 方晓东, 陶汝华, 董伟伟, 周曙, 孟钢, 邵景珍. 沉积激光能量对 CuAlO₂ 薄膜光学性质的影响[J]. 无机材料学报, 2011, 26(3): 281-285.
[12]	李抗, 黄剑锋, 曹丽云, 王博, 施浙勇,李抗, 黄剑锋, 曹丽云, 王博, 施浙勇. 络合溶胶-凝胶法制备CuAlO₂微晶及其光学性能研究[J]. 无机材料学报, 2011, 26(3): 275-280.
[13]	范鑫烨,徐铁峰,沈祥,戴世勋,聂秋华,王训四,陈飞飞. GeS₂-Ga₂S₃-AgCl玻璃的光学特性研究[J]. 无机材料学报, 2010, 15(2): 191-195.
[14]	钟兰花,吴福根,李小玲,钟会林,钟韶. 二维声子晶体的对称性对声学带隙的影响[J]. 无机材料学报, 2006, 21(1): 29-34.
[15]	快素兰,章俞之,胡行方. 二氧化硅胶体晶体的制备及其光子带隙特性[J]. 无机材料学报, 2002, 17(1): 159-162.