Ib型金刚石单晶生长及合成腔体温度场分布研究

人工晶体学报 ›› 2024, Vol. 53 ›› Issue (6): 959-966.

Ib型金刚石单晶生长及合成腔体温度场分布研究

肖宏宇¹, 李勇¹, 田昌海¹, 张蔚曦¹, 王强¹, 肖政国¹, 王应¹, 金慧¹, 鲍志刚², 周振翔³

1.铜仁学院物理与电子工程系,铜仁 554300;
2.洛阳理工学院数理部,洛阳 471023;
3.北京中材人工晶体研究院有限公司,北京 100018

收稿日期:2024-01-16 出版日期:2024-06-15 发布日期:2024-06-20
通信作者: 李勇,博士,教授。E-mail:likaiyong6@163.com
作者简介:肖宏宇(1981—),男,吉林省人,博士。E-mail:xiaohy0205@163.com
基金资助:
国家自然科学基金(12064038);贵州省科技厅项目(黔科合基础-ZK〔2023〕一般467,ZK〔2021〕重点019,ZK〔2021〕一般021,ZK〔2021〕一般034,ZK〔2021〕一般031,ZK〔2023〕重点049);铜仁学院科研启动基金(trxyDH2221)

Study on the Growth of Type-Ib Diamond Single Crystal and the Temperature Field Distribution in the Synthesis Cavities

XIAO Hongyu¹, LI Yong¹, TIAN Changhai¹, ZHANG Weixi¹, WANG Qiang¹, XIAO Zhengguo¹, WANG Ying¹, JIN Hui¹, BAO Zhigang², ZHOU Zhenxiang³

1. Department of Physics and Electrical Engineering, Tongren University, Tongren 554300, China;
2. Department of Mathematics and Physics, Luoyang Institute of Science and Technology, Luoyang 471023, China;
3. Beijing Sinoma Snythetic Crystals Co., Ltd., Beijing 100018, China

Received:2024-01-16 Online:2024-06-15 Published:2024-06-20

摘要/Abstract

摘要： 本文利用六面顶压机,在5.7 GPa、1 560~1 600 K的压力温度条件下,分别采用15 mm和30 mm两种尺寸合成腔体,系统开展了Ib型金刚石单晶的晶体生长工作,并借助于有限元法对两种尺寸合成腔体的温度场分布进行了研究。首先,借助于有限元法分别对两种尺寸合成腔体的触媒温度场分布进行了模拟。模拟结果揭示了30 mm合成腔体温度场的均匀性要明显优于15 mm合成腔体。其次,金刚石晶体生长实验结果表明,采用15 mm合成腔体很难实现质量超过1.2 ct(1 ct=0.2 g)的优质Ib型金刚石单晶的生长,而30 mm合成腔体更适合用于生长大尺寸优质Ib型金刚石单晶。再次,扫描电子显微镜表面形貌测试结果表明,合成腔体尺寸的扩大不会对Ib型金刚石单晶的表面结晶质量产生显著影响。最后,拉曼光谱的测试结果表明,除了多晶金刚石的结晶质量较差,本研究两种腔体合成的其他金刚石单晶测试样品均具有较好的结晶质量。本研究对宝石级金刚石单晶大尺寸合成腔体的设计、大尺寸金刚石单晶的生长,以及多晶种法金刚石单晶合成技术的完善均具有一定的学术参考价值。

关键词: Ib型金刚石, 高温高压, 温度梯度法, 触媒, 温度场, 多晶

Abstract: In this paper, type-Ib diamond single crystals, using two different sizes of synthesis cavities of 15 mm and 30 mm, were synthesized under 5.7 GPa, 1 560~1 600 K, and the temperature field distributions of the two sizes of synthesis cavities were studied using finite element method (FEM). Firstly, the temperature field distributions of two different sizes of synthesis cavities were simulated using finite element method. The average radial temperature gradient and average axial temperature gradient of the 15 mm synthesis cavity are 0.573 and 5.700 K/mm, respectively. The average radial temperature gradient and average axial temperature gradient of the 30 mm cavity are 0.093 and 2.280 K/mm, respectively. The simulation results reveal that the uniformity of the temperature field in the 30 mm synthesis cavity is significantly better than that in the 15 mm synthesis cavity. Secondly, the reproducible growth of high-quality type-Ib diamond large single crystals was achieved using both synthesis cavities mentioned above. The 15 mm synthetic cavity is difficult to achieve the growth of high-quality type-Ib diamond single crystals weighing more than 1.2 ct (1 ct=0.2 g), while the 30 mm synthetic cavity is more suitable for the growth of large-size high-quality type-Ib diamond single crystals. Furthermore, the scanning electron microscopy (SEM) test results show that the surface flatness of high-quality type-Ib diamond single crystals grown using two different sizes of synthesis cavities in this study is good, and the expansion of the synthesis cavity has no significant effect on the crystal quality of Ib diamond single crystal surface. Finally, Raman spectrum test results show that the crystal quality of polycrystalline diamond deteriorates, and other diamond single crystal samples synthesized by two kinds of synthesis cavity in this study have better crystal quality. This research has certain academic reference value for the design of large size synthesis cavity of gem grade diamond single crystal, the growth of large size diamond single crystal, and the perfection of polycrystalline diamond single crystal synthesis technology.

Key words: type-Ib diamond, high pressure and high temperature, temperature gradient method, catalyst, temperature field, polycrystal

中图分类号:

TQ163

肖宏宇, 李勇, 田昌海, 张蔚曦, 王强, 肖政国, 王应, 金慧, 鲍志刚, 周振翔. Ib型金刚石单晶生长及合成腔体温度场分布研究[J]. 人工晶体学报, 2024, 53(6): 959-966.

XIAO Hongyu, LI Yong, TIAN Changhai, ZHANG Weixi, WANG Qiang, XIAO Zhengguo, WANG Ying, JIN Hui, BAO Zhigang, ZHOU Zhenxiang. Study on the Growth of Type-Ib Diamond Single Crystal and the Temperature Field Distribution in the Synthesis Cavities[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(6): 959-966.

参考文献

[1] STRONG H M. Catalytic effects in the transformation of graphite to diamond[J]. The Journal of Chemical Physics, 1963, 39(8): 2057-2062.
[2] LIU X B, CHEN X, SINGH D J, et al. Boron-oxygen complex yields n-type surface layer in semiconducting diamond[J]. Proceedings of the National Academy of Sciences of the United States of America, 2019, 116(16): 7703-7711.
[3] ZHANG Z F, JIA X P, LIU X B, et al. Synthesis and characterization of a single diamond crystal with a high nitrogen concentration[J]. Chinese Physics B, 2012, 21(3): 038103.
[4] SUMIYA H. Thermally activated deformation under knoop indentations in super-hard directions of high-quality synthetic type-IIa diamond crystals[J]. Diamond and Related Materials, 2006, 15(10): 1576-1579.
[5] BUNDY F P, HALL H T, STRONG H M, et al. Man-made diamonds[J]. Nature, 1955, 176(4471): 51-55.
[6] BUNDY F P, BASSETT W A, WEATHERS M S, et al. The pressure-temperature phase and transformation diagram for carbon; updated through 1994[J]. Carbon, 1996, 34(2): 141-153.
[7] EL-HAJJ H, DENISENKO A, KAISER A, et al. Diamond MISFET based on boron delta-doped channel[J]. Diamond and Related Materials, 2008, 17(7/8/9/10): 1259-1263.
[8] NADOLINNY V A, KOMAROVSKIKH A Y, PALYANOV Y N, et al. EPR study of germanium-vacancy defects in diamonds[J]. Journal of Structural Chemistry, 2016, 57(5): 1041-1043.
[9] KOMAROVSKIKH A, NADOLINNY V, PALYANOV Y, et al. EPR study of the hydrogen center in HPHT diamonds grown in carbonate medium[J]. Physica Status Solidi Applied Research, 2014, 211(10): 2274-2278.
[10] 李勇, 廖江河, 王应, 等. 硫脲掺杂金刚石的高温高压合成及FT-IR光谱研究[J]. 人工晶体学报, 2020, 49(7): 1176-1179+1207.
LI Y, LIAO J H, WANG Y, et al. Synthesis of diamond crystal with CH₄ N₂S additive at HPHT conditions and the study of FT-IR spectra[J]. Journal of Synthetic Crystals, 2020, 49(7): 1176-1179+1207 (in Chinese).
[11] LI Y, LIAO J H, WANG Y, et al. An innovation in obtaining the aggregation N of the synthesized diamond under HPHT conditions[J]. Optical Materials, 2020, 101: 109735.
[12] FANG C, SHEN W X, ZHANG Y W, et al. Si doping effects on the growth of large single-crystal diamond in a Ni-based metal catalyst system under high pressure and high temperature[J]. Crystal Growth & Design, 2019, 19(7): 3955-3961.
[13] 肖宏宇, 李勇, 鲍志刚, 等. 触媒组分对高温高压金刚石大单晶生长及裂纹缺陷的影响[J]. 物理学报, 2023, 72(2): 020701.
XIAO H Y, LI Y, BAO Z G, et al. Effect of catalyst composition on growth and crack defects of large diamond single crystal under high temperature and pressure[J]. Acta Physica Sinica, 2023, 72(2): 020701 (in Chinese).
[14] 王蒙召, 许安涛, 李尚升, 等. FeNi、NiMnCo及其复合触媒中Ⅰb型金刚石的生长特性[J]. 人工晶体学报, 2021, 50(11): 2060-2066.
WANG M Z, XU A T, LI S S, et al. Growth characteristics of type Ib diamonds in FeNi, NiMnCo and their composite catalysts[J]. Journal of Synthetic Crystals, 2021, 50(11): 2060-2066 (in Chinese).
[15] GUO M M, LI S S, HU M H, et al. Growth characteristics of type IIa large single crystal diamond with Ti/Cu as nitrogen getter in FeNi-C system[J]. Chinese Physics B, 2020, 29(1): 018101.
[16] 陈珈希, 张喜云, 李尚升, 等. 碳酸钙掺杂对Ⅰb型金刚石沿不同晶面生长行为的影响[J]. 人工晶体学报, 2021, 50(11): 2053-2059.
CHEN J X, ZHANG X Y, LI S S, et al. Effect of CaCO₃ doping on growth behavior of type Ⅰb diamond along different crystal faces[J]. Journal of Synthetic Crystals, 2021, 50(11): 2053-2059 (in Chinese).
[17] SATO Y, MIYAJIMA K, SHIKATA S. Complete analysis of dislocations in single crystal diamonds[J]. Diamond and Related Materials, 2022, 126: 109129.
[18] YELISSEYEV A P, ZHIMULEV E I, KARPOVICH Z A, et al. Characterization of the nitrogen state in HPHT diamonds grown in an Fe-C melt with a low sulfur addition[J]. CrystEngComm, 2022, 24(24): 4408-4416.
[19] CAI Z H, LI M, CHEN L C, et al. Study on the effect of N-H-O co-doping on diamond growth and its mechanism under HPHT by FeNi solvent[J]. CrystEngComm, 2022, 24: 1773-1781.
[20] HAN F, LI S S, JIA X F, et al. Inclusions in large diamond single crystals at different temperatures of synthesis[J]. Chinese Physics B, 2019, 28(2): 028103.
[21] LI Z C, JIA X P, HUANG G F, et al. FEM simulations and experimental studies of the temperature field in a large diamond crystal growth cell[J]. Chinese Physics B, 2013, 22(1): 014701.