MPCVD金刚石薄膜微波功率和沉积压力匹配性研究

人工晶体学报 ›› 2022, Vol. 51 ›› Issue (5): 910-919.

MPCVD金刚石薄膜微波功率和沉积压力匹配性研究

张帅¹, 安康^1,2, 邵思武¹, 黄亚博¹, 杨志亮¹, 陈良贤¹, 魏俊俊^1,2, 刘金龙^1,2, 郑宇亭^1,2, 李成明^1,2

1.北京科技大学新材料技术研究院,北京 100083;
2.北京科技大学顺德研究生院,佛山 528399

收稿日期:2022-02-25 出版日期:2022-05-15 发布日期:2022-06-17
通讯作者: 安康,博士。E-mail:ank_diamond@163.com; 李成明,博士,教授。E-mail:chengmli@mater.ustb.edu.cn
作者简介:张帅(1997—),男,陕西省人,硕士研究生。E-mail:18811308896@163.com; 安康,北京科技大学新材料技术研究院、钢铁冶金新技术国家重点实验室和顺德研究生院博士后。2012年开始从事金刚石装备设计制造、沉积及加工工艺研究。主持和参与国家自然科学基金、国家重点研发计划等项目多项。在Ceramics International、Diamond and Related Materials、Plasma Science and Technology等期刊发表文章多篇,授权发明专利多项。李成明,北京科技大学教授,主要从事CVD金刚石膜与CVD金刚石单晶制备及其功能应用研究。先后主持和参与国家重大专项(子项目)、国家重点研发计划、国际政府间合作项目欧洲地平线计划2020、国家“863”计划、国家“973”计划、国家自然科学基金等项目30多项。发表学术论文300余篇,授权国家发明专利70余项。主持研究的金刚石扩热板应用于北斗卫星系列,获得2019年教育部技术发明一等奖。获得其他省部级奖3项。
基金资助:
国家磁约束核聚变能发展研究专项资助(2019YFE100200);国家自然科学基金(52102034);中央高校基本科研业务费(FRF-MP-20-48);北京科技大学顺德研究生院博士后研究经费(2020BH015)

Microwave Power and Deposition Pressure Matching of MPCVD Diamond Films

ZHANG Shuai¹, AN Kang^1,2, SHAO Siwu¹, HUANG Yabo¹, YANG Zhiliang¹, CHEN Liangxian¹, WEI Junjun^1,2, LIU Jinlong^1,2, ZHENG Yuting^1,2, LI Chengming^1,2

1. Institute of Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China;
2. Shunde Graduate School, University of Science and Technology Beijing, Foshan 528399, China

Received:2022-02-25 Online:2022-05-15 Published:2022-06-17

摘要/Abstract

摘要： 微波等离子体化学气相沉积(MPCVD)法制备的高质量金刚石在很多领域均有广泛应用前景。本研究采用9 kW微波功率,分别在13 kPa、14 kPa、15.5 kPa、17 kPa的腔室压力下进行薄膜沉积实验,发现在15.5 kPa、17 kPa的腔室压力下沉积的薄膜在中心区域出现异常生长情况,具体表现为中心存在明显的阶梯式凸起。为揭示薄膜中心出现异常沉积的原因,使用SEM和Raman分析薄膜表面形貌和质量,通过数值模拟进行沉积过程建模计算和分析功率密度和流场分布。结果表明在相同功率下,提高腔室压力,压缩等离子体,因平均自由程较短,扩散能力不足,将导致衬底中心区域比边缘区域更易密集生长,金刚石薄膜中心区域出现明显的阶梯。同时,薄膜整体的生长速率、均匀性、质量均会在超过压力极值后降低。

关键词: 金刚石薄膜, MPCVD, 沉积压力, 微波功率, 均匀性, 数值模拟

Abstract: High-quality diamond prepared by microwave plasma chemical vapor deposition (MPCVD) has application prospects in many high-precision fields. The film deposition experiments were carried out using microwave power 9 kW. The chamber pressures are 13 kPa, 14 kPa, 15.5 kPa, and 17 kPa, respectively. It was found that the deposited films under pressure of 15.5 kPa and 17 kPa exhibit abnormal growth in the central region, which is manifested as an obvious stepped bulge in the center. Surface morphology and film quality of the film were analyzed by SEM and Raman in order to reveal the reason for the abnormal deposition in the center of the film. Meanwhile, the deposition process was modeled, the power density and flow field distribution were calculated and analyzed by numerical simulation. The results show that at the same power, increasing the chamber pressure and compressing the plasma will lead to more dense growth in the central region of the film than that in the edge region and obvious steps in the central region of the diamond film, due to the short mean free path and insufficient diffusion capacity. The overall growth rate, uniformity and quality of the film will decrease after exceeding pressure limit.

Key words: diamond film, MPCVD, deposition pressure, microwave power, uniformity, numerical simulation

中图分类号:

TQ163
TB383

张帅, 安康, 邵思武, 黄亚博, 杨志亮, 陈良贤, 魏俊俊, 刘金龙, 郑宇亭, 李成明. MPCVD金刚石薄膜微波功率和沉积压力匹配性研究[J]. 人工晶体学报, 2022, 51(5): 910-919.

ZHANG Shuai, AN Kang, SHAO Siwu, HUANG Yabo, YANG Zhiliang, CHEN Liangxian, WEI Junjun, LIU Jinlong, ZHENG Yuting, LI Chengming. Microwave Power and Deposition Pressure Matching of MPCVD Diamond Films[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(5): 910-919.

参考文献

[1] 李成明,陈良贤,刘金龙,等.直流电弧等离子体喷射法制备金刚石自支撑膜研究新进展[J].金刚石与磨料磨具工程,2018,38(1):16-27.
LI C M, CHEN L X, LIU J L, et al. Recent progress of free-standing diamond films prepared by DC arc plasma jet method[J]. Diamond & Abrasives Engineering, 2018, 38(1): 16-27(in Chinese).
[2] KOPOSOVA E V, MYASNIKOVA S E, PARSHIN V V, et al. The absorption investigation in CVD-diamond plates and windows at 50~200 GHz[J]. Diamond and Related Materials, 2002, 11(8): 1485-1490.
[3] ASMUSSEN J, REINHARD D. Diamond films handbook: chapter 10 [M]. New York: Marcell Dekker Inc, 2002.
[4] REINHARD D K, GROTJOHN T A, BECKER M, et al. Fabrication and properties of ultranano, nano, and microcrystalline diamond membranes and sheets[J]. Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, 2004, 22(6): 2811.
[5] 李义锋.新型高功率MPCVD装置研制与金刚石膜高效沉积[D].北京:北京科技大学,2015.
LI Y F. Design of high power MPVCD reactors and synthesis of high quality diamond films[D]. Beijing: University of Science and Technology Beijing, 2015(in Chinese).
[6] 吕反修.CVD金刚石膜的产业化应用与目前存在的问题[J].新材料产业,2003(7):63-67.
LYU F X. Development of a new type of high-power MPCVD device and efficient deposition of diamond films [J]. Advanced Materials Industry, 2003(7): 63-67(in Chinese).
[7] MCCLARENCE E. Novel solid-state laser design based on E6 synthetic diamond opens up new applications[J]. Diamond Intelligence Briefs, 2008, 23(528): 4978.
[8] SAHLI S, ASLAM D M. Ultra-high sensitivity intra-grain poly-diamond piezoresistors[J]. Sensors and Actuators A: Physical, 1998, 71(3): 193-197.
[9] TRISCHUK W, et al. Diamond particle detectors for high energy physics[J]. Nuclear and Particle Physics Proceedings, 2016, 273/274/275: 1023-1028.
[10] ULCZYNSKI M J, WRIGHT B, REINHARD D K. Diamond-coated glass substrates[J]. Diamond and Related Materials, 1998, 7(11/12): 1639-1646.
[11] AN K, ZHANG S, SHAO S W, et al. Effects of the electric field at the edge of a substrate to deposit a Ø100 mm uniform diamond film in a 2.45 GHz MPCVD system[J]. Plasma Science and Technology, 2022, 24(4): 045502.
[12] HEI L F, LIU J, LI C M, et al. Fabrication and characterizations of large homoepitaxial single crystal diamond grown by DC arc plasma jet CVD[J]. Diamond and Related Materials, 2012, 30: 77-84.
[13] LU F X, TANG W Z, HUANG T B, et al. Large area high quality diamond film deposition by high power DC arc plasma jet operating at gas recycling mode[J]. Diamond and Related Materials, 2001, 10(9/10): 1551-1558.
[14] 谈耀麟.CVD金刚石应用前景探讨[J].超硬材料工程,2009,21(4):49-53.
TAN Y L. Discussion on the prospect for the applications of CVD diamond[J]. Superhard Material Engineering, 2009, 21(4): 49-53(in Chinese).
[15] SILVA F, HASSOUNI K, BONNIN X, et al. Microwave engineering of plasma-assisted CVD reactors for diamond deposition[J]. Journal of Physics Condensed Matter: an Institute of Physics Journal, 2009, 21(36): 364202.
[16] MOKUNO Y, CHAYAHARA A, SODA Y, et al. High rate homoepitaxial growth of diamond by microwave plasma CVD with nitrogen addition[J]. Diamond and Related Materials, 2006, 15(4/5/6/7/8): 455-459.
[17] TALLAIRE A, ROND C, BÉNÉDIC F, et al. Effect of argon addition on the growth of thick single crystal diamond by high-power plasma CVD[J]. Physica Status Solidi (a), 2011, 208(9): 2028-2032.
[18] 李一村,郝晓斌,代兵,等.MPCVD单晶金刚石高速率和高品质生长研究进展[J].人工晶体学报,2020,49(6):979-989.
LI Y C, HAO X B, DAI B, et al. Research progress on high rate and high quality growth of MPCVD single crystal diamond[J]. Journal of Synthetic Crystals, 2020, 49(6): 979-989(in Chinese).
[19] 安康,刘小萍,李晓静,等.新型高功率MPCVD金刚石膜装置的数值模拟与实验研究[J].人工晶体学报,2015,44(6):1544-1550.
AN K, LIU X P, LI X J, et al. Numerical simulation and experimental study of a novel high-power microwave plasma CVD reactor for diamond films deposition[J]. Journal of Synthetic Crystals, 2015, 44(6): 1544-1550(in Chinese).
[20] 梁天,汪建华,翁俊,等.高气压对MPCVD沉积金刚石薄膜的影响[J].真空与低温,2018,24(1):54-59.
LIANG T, WANG J H, WENG J, et al. Influence of high pressureon mpcvd deposition of diamond films[J]. Vacuum and Cryogenics, 2018, 24(1): 54-59(in Chinese).
[21] 孟宪明,王凤英,黑立富,等.沉积参数对化学气相沉积纳米金刚石薄膜的影响[J].材料科学与工艺,2009,17(3):393-396+401.
MENG X M, WANG F Y, HEI L F, et al. Effects of deposition parameters on CVD nanocrystalline diamond thin films[J]. Materials Science and Technology, 2009, 17(3): 393-396+401(in Chinese).
[22] 王心洋,曹光宇,黄翀.微波等离子体化学气相沉积设备微波系统的仿真优化与验证[J].人工晶体学报,2020,49(10):1896-1903+1910.
WANG X Y, CAO G Y, HUANG C. Simulation optimization and verification of a microwave system for microwave plasma chemical vapor deposition device[J]. Journal of Synthetic Crystals, 2020, 49(10): 1896-1903+1910(in Chinese).
[23] LI Y F, SU J J, LIU Y Q, et al. A circumferential antenna ellipsoidal cavity type MPCVD reactor developed for diamond film deposition[J]. Diamond and Related Materials, 2015, 51: 24-29.
[24] YU S W, WANG R, ZHENG K, et al. Influence of power density on high purity 63 mm diameter polycrystalline diamond deposition inside a 2.45 GHz MPCVD reactor[J]. Journal of Physics D: Applied Physics, 2016, 49(35): 355202.
[25] 苏静杰.新型MPCVD装置的设计及金刚石膜的制备与介电性能研究[D].北京:北京科技大学,2015.
SU J J. Design of novel MPCVD device and preparation of diamond films with the dielectric properties research[D]. Beijing: University of Science and Technology Beijing, 2015(in Chinese).
[26] PLEULER E, WILD C, FÜNER M, et al. The CAP-reactor, a novel microwave CVD system for diamond deposition[J]. Diamond and Related Materials, 2002, 11(3/4/5/6): 467-471.