二氧化碳对同质外延生长单晶金刚石内应力的影响

摘要/Abstract

摘要： 本文研究了在反应气体中引入不同浓度的CO₂对微波等离子体化学气相沉积(MPCVD)法同质外延生长单晶金刚石内应力的影响,并对其作用机理进行了分析。研究发现,随着CO₂浓度增加,单晶金刚石内应力逐渐减小,这是由于添加的CO₂提供了含氧基团,可以有效刻蚀金刚石生长过程中的非金刚石碳,并能够降低金刚石中杂质的含量,从而避免晶格畸变,减少生长缺陷,并最终表现为单晶金刚石内应力的减小,其中金刚石内应力以压应力的形式呈现。此外反应气体中加入CO₂可以降低单晶金刚石的生长速率和沉积温度,且在合适的碳氢氧原子比(5∶112∶4)下能够得到杂质少、结晶度高的单晶金刚石。

关键词: 单晶金刚石, MPCVD, 同质外延, 内应力, 二氧化碳

Abstract: In this paper, the effect of introducting different concentration CO₂ into reaction gas on the internal stress of single crystal diamond grown by microwave plasma chemical vapor deposition (MPCVD) homogeneous epitaxy was studied, and its mechanism was analyzed. Results show that with the increase of CO₂ concentration, the internal stress of single crystal diamond decreases gradually. This is because the added CO₂ provides oxygen containing groups, which can effectively etch the non-diamond carbon in the diamond growth process, and reduce the content of impurities in the diamond, so as to avoid lattice distortion and reduce growth defects. This ultimately shows the reduction of the internal stress of single crystal diamond, which is in the form of compressive stress. Besides, the addition of CO₂ in reaction gas can reduce the growth rate and deposition temperature of single crystal diamond, and single crystal diamond with less impurities and high crystallinity can be obtained at a suitable carbon hydrogen oxygen atomic ratio (5∶112∶4).

Key words: single crystal diamond, MPCVD, homogeneous epitaxy, internal stress, carbon dioxide

中图分类号:

TQ163

贾元波, 满卫东, 伍正新, 梁凯, 林志东. 二氧化碳对同质外延生长单晶金刚石内应力的影响[J]. 人工晶体学报, 2023, 52(1): 34-40.

JIA Yuanbo, MAN Weidong, WU Zhengxin, LIANG Kai, LIN Zhidong. Effect of Carbon Dioxide on Internal Stress of Single Crystal Diamond Grown by Homogeneous Epitaxy[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2023, 52(1): 34-40.

参考文献

[1] CHEN Y C, TZENG Y, CHENG A J, et al. Inkjet printing of nanodiamond suspensions in ethylene glycol for CVD growth of patterned diamond structures and practical applications[J]. Diamond and Related Materials, 2009, 18(2/3): 146-150.
[2] DE SIO A, DI FRAIA M, ANTONELLI M, et al. X-ray micro beam analysis of the photoresponse of an enlarged CVD diamond single crystal[J]. Diamond and Related Materials, 2013, 34: 36-40.
[3] MAMEDOV T N, BATURIN A S, BLANK V D, et al. Muonium in synthetic diamond[J]. Diamond and Related Materials, 2013, 31: 38-41.
[4] 王伟华,代兵,王杨,等.异质外延单晶金刚石的研究进展[J].中国科学:技术科学,2020,50(7):831-848.
WANG W H, DAI B, WANG Y, et al. Recent progress in hetero-epitaxial growth of the single-crystal diamond[J]. Scientia Sinica (Technologica), 2020, 50(7): 831-848(in Chinese).
[5] HARRIS D C. Properties of diamond for window and dome applications[C]//San Diego, CA, USA: SPIE′s 1994 International Symposium on Optics, Imaging, and Instrumentation. Proc SPIE 2286, Window and Dome Technologies and Materials IV, 1994, 2286: 218-228.
[6] 阳硕,满卫东,赵彦君,等.MPCVD法合成单晶金刚石的研究及应用进展[J].真空与低温,2015,21(3):131-138.
YANG S, MAN W D, ZHAO Y J, et al. Progress and applications of single crystal diamond synthesized by mpcvd[J]. Vacuum and Cryogenics, 2015, 21(3): 131-138(in Chinese).
[7] 宋修曦,马志斌,耿传文,等.不同温度下同质外延生长单晶金刚石的应力分析[J].人工晶体学报,2018,47(5):942-947.
SONG X X, MA Z B, GENG C W, et al. Stress analysis of homoepitaxial growth of single crystal diamond at different temperatures[J]. Journal of Synthetic Crystals, 2018, 47(5): 942-947(in Chinese).
[8] FENG Z B, CHAYAHARA A, YAMADA H, et al. Surface stress measurement with interference microscopy of thick homoepitaxial single-crystal diamond layers[J]. Diamond and Related Materials, 2010, 19(12): 1453-1456.
[9] 李一村,舒国阳,刘刚,等.MPCVD单晶金刚石初始及断续生长界面的表征与分析[J].人工晶体学报,2020,49(10):1765-1769.
LI Y C, SHU G Y, LIU G, et al. Characterization and analysis of the initial and intermittent growth interfaces of MPCVD single crystal diamond[J]. Journal of Synthetic Crystals, 2020, 49(10): 1765-1769(in Chinese).
[10] 熊刚,汪建华,翁俊,等.氢氧等离子体预处理对单晶金刚石刻蚀坑的研究[J].真空科学与技术学报,2017,37(9):909-915.
XIONG G, WANG J H, WENG J, et al. Homoepitaxial growth of diamond coatings on artificial diamond polished by H₂/O₂ plasma etching[J]. Chinese Journal of Vacuum Science and Technology, 2017, 37(9): 909-915(in Chinese).
[11] 夏禹豪.氮元素对单晶金刚石生长的影响[D].武汉:武汉工程大学,2019.
XIA Y H. Research on the effects of nitrogen on the growth of single crystal diamond[D]. Wuhan: Wuhan Institute of Technology, 2019(in Chinese).
[12] ROBINS L H, FARABAUGH E N, FELDMAN A. Line shape analysis of the Raman spectrum of diamond films grown by hot-filament and microwave-plasma chemical vapor deposition[J]. Journal of Materials Research, 1990, 5(11): 2456-2468.
[13] YAN C S, VOHRA Y K, MAO H K, et al. Very high growth rate chemical vapor deposition of single-crystal diamond[J]. Proceedings of the National Academy of Sciences of the United States of America, 2002, 99(20): 12523-12525.
[14] LIANG Q, YAN C S, MENG Y F, et al. Recent advances in high-growth rate single-crystal CVD diamond[J]. Diamond and Related Materials, 2009, 18(5/6/7/8): 698-703.
[15] DAS D, SINGH R N, BARNEY I T, et al. Effect of oxygen on growth and properties of diamond thin film deposited at low surface temperature[J]. Journal of Vacuum Science & Technology, A Vacuum, Surfaces, and Films, 2008, 26(6): 1487-1496.
[16] HARRIS S J, WEINER A M. Methyl radical and H-atom concentrations during diamond growth[J]. Journal of Applied Physics, 1990, 67(10): 6520-6526.
[17] TALLAIRE A, ACHARD J, SILVA F, et al. Oxygen plasma pre-treatments for high quality homoepitaxial CVD diamond deposition[J]. Physica Status Solidi (a), 2004, 201: 2419-2424.
[18] HEMLEY R J, MAO H K, YAN C S. Colorless single-crystal CVD diamond at rapid growth rate: US20070196263[P]. 2007-08-23.
[19] MOLLART T P, LEWIS K L. Optical-quality diamond growth from CO₂-containing gas chemistries[J]. Diamond and Related Materials, 1999, 8(2/3/4/5): 236-241.
[20] ZHANG Q, LI H, CHENG S, et al. The effect of CO₂ on the high-rate homoepitaxial growth of CVD single crystal diamonds[J]. Diamond & Related Materials, 2011, 20(4): 496-500.
[21] 赵玉成,邢广忠,王明智,等.金刚石中应力的定量测量与应用[J].人工晶体学报,2006,35(2):359-362.
ZHAO Y C, XING G Z, WANG M Z, et al. Quantitative measurement and application of stress in diamond[J]. Journal of Synthetic Crystals, 2006, 35(2): 359-362(in Chinese).
[22] PAL K S, MALLIK A K, DANDAPAT N, et al. Microscopic properties of MPCVD diamond coatings studied by micro-Raman and micro-photoluminescence spectroscopy[J]. Bulletin of Materials Science, 2015, 38(2): 537-549.
[23] 吕反修.金刚石膜制备与应用-上卷[M].北京:科学出版社,2014.
LYU F X. Preparation and application of diamond film. Volume 1[M]. Beijing: Science Press, 2014(in Chinese).
[24] LYON S A, NEMANICH R J, JOHNSON N M, et al. Microstrain in laser-crystallized silicon islands on fused silica[J]. Applied Physics Letters, 1982, 40(4): 316-318.
[25] MITSUHASHI M, KARASAWA S, OHYA S, et al. Dislocation of epitaxial CVD diamond and the characterization by Raman spectroscopy[J]. Applied Surface Science, 1992, 60/61: 565-572.
[26] STUART S A, PRAWER S, WEISER P S. Growth-sector dependence of fine structure in the first-order Raman diamond line from large isolated chemical-vapor-deposited diamond crystals[J]. Applied Physics Letters, 1993, 62(11): 1227-1229.
[27] KARASAWA S, MITSUHASHI M, OHYA S, et al. Crystal growth of epitaxial CVD diamond using ¹³C isotope and characterization of dislocations by Raman spectroscopy[J]. Journal of Crystal Growth, 1993, 128(1/2/3/4): 403-407.
[28] BAR-YAM Y, MOUSTAKAS T D. Defect-induced stabilization of diamond films[J]. Nature, 1989, 342(6251): 786-787.
[29] KNIGHT D S, WHITE W. Characterization of diamond films by Raman spectroscopy[J]. Journal of Materials Research, 1989, 4: 385-393.
[30] 张青,翁俊,刘繁,等.高功率微波等离子体对单晶金刚石同质外延生长的影响[J].表面技术,2022,51(6):364-373+398.
ZHANG Q, WENG J, LIU F, et al. Effect of high microwave power plasma on the homogeneous epitaxy growth of single crystal diamond[J]. Surface Technology, 2022, 51(6): 364-373+398(in Chinese).
[31] 屠菊萍,刘金龙,邵思武,等.高质量单晶金刚石的合成、结构与光学性能研究[J].光学学报,2020,40(6):205-212.
TU J P, LIU J L, SHAO S W, et al. Synthesis, structure, and optical properties of a high-quality single-crystal diamond[J]. Acta Optica Sinica, 2020, 40(6): 205-212(in Chinese).
[32] YIMING Z, LARSSON F, LARSSON K. Effect of CVD diamond growth by doping with nitrogen[J]. Theoretical Chemistry Accounts, 2014, 133(2): 1432.
[33] INSPEKTOR A, LIOU Y, MCKENNA T, et al. Plasma CVD diamond deposition in C-H-O systems[J]. Surface and Coatings Technology, 1989, 39/40: 211-221.