基于等离子体诊断的MPCVD单晶金刚石生长优化设计

doi:10.15541/jim20230164

无机材料学报 ›› 2023, Vol. 38 ›› Issue (12): 1405-1412.DOI: 10.15541/jim20230164 CSTR: 32189.14.10.15541/jim20230164

基于等离子体诊断的MPCVD单晶金刚石生长优化设计

李一村¹(), 郝晓斌¹, 代兵¹(), 文东岳¹, 朱嘉琦¹, 耿方娟¹, 乐卫平², 林伟群²()

1.哈尔滨工业大学航天学院, 哈尔滨 150000
2.深圳市恒运昌真空技术有限公司, 深圳 518000

收稿日期:2023-04-04 修回日期:2023-05-23 出版日期:2023-08-31 网络出版日期:2023-08-31
通讯作者: 代兵, 教授. E-mail: daibinghit@vip.126.com;
林伟群, 工程师. E-mail: fred.lin@csl-vacuum.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);深圳市科技计划(JSGG20201102162002006)

Optimization Design of MPCVD Single Crystal Diamond Growth Based on Plasma Diagnostics

LI Yicun¹(), HAO Xiaobin¹, DAI Bing¹(), WEN Dongyue¹, ZHU Jiaqi¹, GENG Fangjuan¹, YUE Weiping², LIN Weiqun²()

1. School of Astronautics, Harbin Institute of Technology, Harbin 150000, China
2. Shenzhen CSL Vacuum Science and Technology Co., LTD, Shenzhen 518000, China

Received:2023-04-04 Revised:2023-05-23 Published:2023-08-31 Online:2023-08-31
Contact: DAI Bing, professor. E-mail: daibinghit@vip.126.com;
LIN Weiqun, engineer. E-mail: fred.lin@csl-vacuum.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);Shenzhen Science and Technology Plan(JSGG20201102162002006)

摘要/Abstract

摘要：

微波等离子体化学气相沉积(Microwave plasma chemical vapor deposition, MPCVD)技术是制备大尺寸、高品质单晶金刚石的理想途径, 然而MPCVD单晶金刚石生长过程的复杂性与晶体生长需求的多样性难以对生长过程进行优化设计。针对此问题, 本研究提出了一种基于等离子体诊断技术的MPCVD单晶金刚石生长的系统性设计方法, 采用等离子体成像和光谱分析对微波等离子体进行量化诊断。并利用自主研发的MPCVD设备, 研究了腔室压力-微波功率-等离子体性状-衬底温度间的物理耦合特性和量化关系, 得到了不同参数下的等离子体有效长轴尺寸、基团浓度和分布、能量密度等数据, 以实验观测数据为基础拟合得到了单晶金刚石生长工艺图谱。根据此工艺图谱, 可以通过选择生长温度和所需生长面积来选取工艺参数, 且通过实验验证, 表明此图谱具有较强的指导意义, 预测参数误差小于5%。同时根据该图谱的预测, 研究了不同等离子体能量密度下的单晶金刚石生长情况, 在较低功率下(2600 W)也得到了较高的能量密度(148.5 W/cm³), 含碳前驱体的浓度也高于其他工艺条件, 因而获得了较高的生长速率(8.9 μm/h)。此套方法体系可以针对不同单晶金刚石生长需求进行有效的等离子体调控和工艺优化。

关键词: MPCVD, 单晶金刚石生长, 等离子体, 生长参数优化

Abstract:

Microwave plasma chemical vapor deposition (MPCVD) technology is an ideal way to prepare large size and high-quality single crystal diamonds. However, the complexity of MPCVD single crystal diamond growth and the diversity of crystal growth requirements make it difficult to optimize the growth process. To address this issue, a systematic design method for MPCVD single crystal diamond growth based on plasma diagnostic technology was proposed, using plasma imaging and spectral analysis to quantitatively diagnose microwave plasma. The physical coupling characteristics and quantitative relationship between pressure, microwave(MW) power, plasma properties, and substrate temperature were studied by using home-made MPCVD system. And the size of major axis, precursor group concentration and distribution, energy density, and other data of the plasma under different parameters were obtained. Based on experimental data, the growth process map of single crystal diamond was obtained. According to this map, we selected process parameters by growth temperature and growth area. Through experimental verification, it is shown that this map is usful for guiding prediction with parameter error of less than 5%. Simultaneously, based on the predicted map, growth of single crystal diamond under different plasma energy densitiesis studied. At lower power (2600 W), a higher energy density (148.5 W/cm³) was obtained, and the concentration of carbon containing precursors was higher than that of the other parameters, resulting in a higher growth rate (8.9 μm/h). By this method system, effective plasma control and process optimization can be carried out meeting for different single crystal diamond growth.

Key words: MPCVD, single crystal diamond growth, plasma, optimization of growth parameters

中图分类号:

TQ174

李一村, 郝晓斌, 代兵, 文东岳, 朱嘉琦, 耿方娟, 乐卫平, 林伟群. 基于等离子体诊断的MPCVD单晶金刚石生长优化设计[J]. 无机材料学报, 2023, 38(12): 1405-1412.

LI Yicun, HAO Xiaobin, DAI Bing, WEN Dongyue, ZHU Jiaqi, GENG Fangjuan, YUE Weiping, LIN Weiqun. Optimization Design of MPCVD Single Crystal Diamond Growth Based on Plasma Diagnostics[J]. Journal of Inorganic Materials, 2023, 38(12): 1405-1412.

图/表 10

图1 HITLH-2450M金刚石生长系统及等离子体诊断系统

Fig. 1 HITLH-2450M diamond growth system and plasma diagnostic system (a) Diagrammatic sketch; (b) Photograph of the system

图2 三种匹配模式下, 压力-功率参数曲线(a)和等离子体核心Hα谱线强度变化(b)

Fig. 2 Pressure-microwave power parameter curves (a) and Hα intensity of plasma central region (b) under three matching modes The abscissa in (b) corresponds to the 10 parameter observation points in (a)

图3 一定压力下, 反射功率随输入功率的变化曲线(a)和等离子体核心Hα谱线强度随输入功率变化曲线(b)

Fig. 3 At a certain pressure, change of reflected power (a) and change of Hα intensity (b) with input power The data at 17 kPa are selected for display, and the variation trend is similar under the other pressures

图4 最佳吸收匹配模式下各观测参数点等离子体中的原子氢浓度分布(其他模式下分布规律变化情况类似)

Fig. 4 Atomic hydrogen concentration distributions in plasma at various observation parameter points under optimal absorption matching mode with similar distribution pattern changes in other modes

图5 均匀增长与最佳吸收匹配下的等离子体量化分析

Fig. 5 Quantitative analysis of plasma in uniform increase and optimal absorption matching mode (a) Sizes of major axis and minor axis; (b) Eccentricity; (c) Volume; (d) Energy density

图6 恒定压力条件下等离子体长轴和短轴(a)、离心率(b)、体积(c)以及能量密度(d)随输入功率的变化曲线(选取气压为16 kPa的数据作为展示, 其余参数点变化趋势类似)

Fig. 6 Changes in plasma major axis and minor axis (a), eccentricity (b), volume (c), and energy density (d) with input power under constant pressure with data at 16 kPa showing the selected display, and variation trends being similar under different pressures

图7 MPCVD单晶金刚石生长工艺预测图谱

Fig. 7 Prediction map of MPCVD single crystal diamond growth process HITLH-2450M system, seed at 0.5 mm in thickness, under the conditions of 20 ℃ water-cooling, 9-17 kPa pressure, and 1600-4200 W microwave power

表1 根据工艺预测谱图选取的参数点及实际的单晶金刚石生长参数

Table 1 Parameter points selection based on the predicted map and growth parameters of actual single crystal diamond

Parameter	Sample 1	Sample 2	Sample 3
Preset growth temperature/℃	850	850	850
Preset major axis/mm	48	42	53
Predicted pressure- microwave power	14.2 kPa- 3140 W	15.6 kPa- 2600 W	12.8 kPa- 3500 W
Actual growth temperature/℃	867	860	835
Actual major axis/mm	47.5	41.2	52.8
Energy density/ (W·cm^-3)	121.3	148.5	115.2
Growth rate/(μm·h^-1)	8.5	8.9	8.2

图8 三个实验样品的等离子体生长环境照片(加装Hα滤镜)以及生长10 h后的表面光学显微形貌

Fig. 8 Photos of plasma growth environment of three samples (with Hα filter) and the surface optical micrographs after 10 h of growth (a, b) Sample 1; (c, d) Sample 2; (e, f) Sample 3

图9 单晶金刚石样品生长过程中的等离子体发射光谱

Fig. 9 Plasma emission spectra in the growth of single crystal diamond #1, # 2 and # 3 correspond to samples 1, 2, and 3, respectively

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基于等离子体诊断的MPCVD单晶金刚石生长优化设计

Optimization Design of MPCVD Single Crystal Diamond Growth Based on Plasma Diagnostics

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