等离子体聚集装置下的高能量密度单晶金刚石快速生长研究

doi:10.15541/jim20220633

无机材料学报 ›› 2023, Vol. 38 ›› Issue (3): 303-309.DOI: 10.15541/jim20220633 CSTR: 32189.14.10.15541/jim20220633

等离子体聚集装置下的高能量密度单晶金刚石快速生长研究

李一村¹(), 刘雪冬¹, 郝晓斌¹, 代兵¹(), 吕继磊², 朱嘉琦¹

1.哈尔滨工业大学航天学院, 哈尔滨 150000
2.湖北碳六科技有限公司, 宜昌 443000

收稿日期:2022-10-27 修回日期:2022-12-18 出版日期:2023-03-20 网络出版日期:2023-01-11
通讯作者: 代兵, 教授. E-mail: daibinghit@vip.126.com
作者简介:李一村(1996-), 男, 博士研究生. E-mail: 741624995@qq.com
基金资助:
国家自然科学基金(52072087);国家重点研发计划(2020YFA0709700);黑龙江省自然科学基金(YQ2020E008)

Rapid Growth of Single Crystal Diamond at High Energy Density by Plasma Focusing

LI Yicun¹(), LIU Xuedong¹, HAO Xiaobin¹, DAI Bing¹(), LYU Jilei², ZHU Jiaqi¹

1. School of Astronautics, Harbin Institute of Technology, Harbin 150000, China
2. Hubei Carbon Six Science and Technology Co., Ltd, Yichang 443000, China

Received:2022-10-27 Revised:2022-12-18 Published:2023-03-20 Online:2023-01-11
Contact: DAI Bing, professor. E-mail: daibinghit@vip.126.com
About author:LI Yicun (1996-), male, PhD candidate. E-mail: 741624995@qq.com
Supported by:
National Natural Science Foundation of China(52072087);National Key R&D Program of China(2020YFA0709700);Natural Science Foundation of Heilongjiang Province(YQ2020E008)

摘要/Abstract

摘要：

单晶金刚石是一种性能优异的晶体材料, 在先进科学领域具有重要的应用价值。在微波等离子体化学气相沉积(Microwave plasma chemical vapor deposition, MPCVD)单晶金刚石生长中, 如何提高晶体的生长速率一直是研究者们关注的重点问题之一, 而采用高能量密度的等离子体是提高单晶金刚石生长速率的有效手段。在本研究中, 首先通过磁流体动力学(Magnetohydrodynamic, MHD)模型仿真计算, 优化设计了特殊的等离子体聚集装置; 随后基于模拟结果进行生长实验, 采用光谱分析和等离子体成像对等离子体性状进行了研究, 制备了单晶金刚石生长样品; 并通过光学显微镜、拉曼光谱对生长样品进行测试。模拟结果显示, 聚集条件下的核心电场和电子密度是普通条件下的3倍; 生长实验结果显示, 在常规的微波功率(3500 W)、生长气压(18 kPa)下得到的高能量密度(793.7 W/cm³)的等离子体与模型计算结果吻合。高能量密度生长条件并不会对生长形貌产生较大影响, 但加入一定量氮气能够显著改变生长形貌, 并对晶体质量产生影响。采用这种方法, 成功制备了高速率(97.5 μm/h)单晶金刚石。不同于通过增大生长气压来获得高能量密度的途径, 本研究在常规的生长气压和微波功率下也可以生长高能量密度单晶金刚石。

关键词: MPCVD单晶金刚石生长, 高能量密度, 高生长速率, 等离子体仿真

Abstract:

Single crystal diamond is a kind of crystal material with excellent performance, which has important application value in advanced scientific field. In the field of single crystal diamond growth by microwave plasma chemical vapor deposition (MPCVD), improvement of crystal growth rate is still a key challenge, although corrent high energy density plasma has been a ralatively effective method. In this work, a special plasma focusing structure was designed through magnetohydrodynamic (MHD) model simulation which then was used in the growth experiment based on the simulation. The plasma properties were studied by means of spectral analysis and plasma imaging, and late on single crystal diamond samples were synthesized. The simulation results show that the core electric field and electron density under focusing conditions were 2 times higher than those under normal conditions. The growth experiment results show that plasma with high energy density (793.7 W/cm³) is obtained under conventional microwave power (3500 W) and growth pressure (18 kPa), which is consistent with the model calculation results. We find that a certain amount of nitrogen instead of high energy density growth conditions can significantly change the growth morphology and affect the quality of the crystal. With those findings, we realize the growth rate of single crystal diamond up to 97.5 μm/h. Different from the way to obtain high energy density by increasing the growth pressure, single crystal diamond can be synthesized with high energy density under normal growth pressure and microwave power.

Key words: MPCVD single crystal diamond growth, high energy density, high growth rate, plasma simulation

中图分类号:

TQ174

李一村, 刘雪冬, 郝晓斌, 代兵, 吕继磊, 朱嘉琦. 等离子体聚集装置下的高能量密度单晶金刚石快速生长研究[J]. 无机材料学报, 2023, 38(3): 303-309.

LI Yicun, LIU Xuedong, HAO Xiaobin, DAI Bing, LYU Jilei, ZHU Jiaqi. Rapid Growth of Single Crystal Diamond at High Energy Density by Plasma Focusing[J]. Journal of Inorganic Materials, 2023, 38(3): 303-309.

图/表 8

表1 单晶金刚石样品生长实验的条件

Table 1 Conditions for the growth experiment of single crystal diamond samples

Sample	Substrate type	N₂ concentration/ (μL·L^-1)	Growth rate/ (μm·h^-1)
S1	molybdenum disk	0	9.5
S2	focusing structure	0	32.2
S3	molybdenum disk	300	20.1
S4	focusing structure	300	97.5

图1 3500 W, 18 kPa条件下舱体内电场强度和电子密度的分布情况仿真结果

Fig. 1 Simulation results of the distribution of electric field and electron density in the reaction chamber at 3500 W and 18 kPa (a) Electric field distribution with molybdenum disk; (b) Electric field distribution with focusing structure; (c) Electron density distribution with molybdenum disk; (d) Electron density distribution with focusing structure

图2 两种条件下等离子体的实际观测图(微波功率3500 W, 舱体气压18 kPa, 加装Hα滤镜)

Fig. 2 Observation maps of plasma under two conditions (MW power 3500 W, pressure 18 kPa, with Hα filter) (a, b) Molybdenum disk condition; (c, d) Focusing structure condition; (a, c) are the light intensity contour plots of observation maps (b, d)

图3 不同功率-气压条件下的等离子体核Hα(656 nm)谱线强度

Fig. 3 Hα (656 nm) intensity of plasma under different power and pressure conditions Data points in the horizontal axis represent different power-pressure parameters. Data point 1 is the initial parameter (900 W-5 kPa), and then the power and pressure of each data point increase by 200 W and 1 kPa successively until the final growth conditions (3500 W-18 kPa)

图4 样品生长的实际情况

Fig. 4 Photos of growth of samples (a) S1 (molybdenum disk); (b) S2 (focusing structure); The growth of S3 and S4 samples is similar

图5 不同样品生长过程中的等离子体发射光谱

Fig. 5 OE spectra during growth of different samples (a) OE spectra of sample S1, S2, S3 and S4 during the growth experiments; (b) Magnified OE spectra around the CN (388 nm) band; 1 ppm=1 μL/L; Colorful figures are available on website

图6 单晶金刚石样品的表面生长形貌的光学显微照片

Fig. 6 Optical microscopic images of surface morphologies of sample after growth (a) S1; (b) S2; (c) S3; (d) S4

图7 S1、S2、S3、S4单晶金刚石生长样品的中心区域拉曼光谱

Fig. 7 Central region Raman spectra of sample S1, S2, S3, S4 after growth (excited by 532 nm wavelength laser)

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等离子体聚集装置下的高能量密度单晶金刚石快速生长研究

Rapid Growth of Single Crystal Diamond at High Energy Density by Plasma Focusing

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