超纳米金刚石薄膜的快速生长及结构分析

位少博; 王兵; 熊鹰

doi:10.13394/j.cnki.jgszz.2022.0122

超纳米金刚石薄膜的快速生长及结构分析

doi: 10.13394/j.cnki.jgszz.2022.0122

位少博^{1, 2,},
王兵^1, ,,
熊鹰¹

1.
西南科技大学材料与化学学院, 四川绵阳 621010
2.
西南科技大学，环境友好能源材料国家重点实验室, 四川绵阳 621010

基金项目: 四川省省院省校合作项目（2021YFSY0029）

详细信息

作者简介:
位少博，男，1996年生，硕士。主要研究方向：超纳米金刚石薄膜。E-mail：529273244@qq.com

通讯作者:
王兵，男，1967生，博士、教授。主要研究方向：薄膜材料/功能材料。E-mail：wangbing67@163.com

中图分类号: TB74；TB144；TQ164
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出版历程
- 收稿日期: 2022-08-08
- 修回日期: 2022-09-24
- 录用日期: 2022-09-29
- 刊出日期: 2023-04-20

Research on the rapid growth and structure of ultra-nanocrystalline diamond thin films

WEI Shaobo^{1, 2
,},
WANG Bing^{1
, ,},
XIONG Ying¹

1.
School of Materials and Chemistry, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China
2.
State Key Laboratory of Environmentally Friendly Energy Materials, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China

摘要

摘要: 采用微波等离子体化学气相沉积（microwave plasma chemical vapor deposition，MPCVD）技术，通过调节微波功率制备不同温度条件下的超纳米金刚石（ultrananocrystalline diamond，UNCD）薄膜。比较分析反应源激活功率及基体温度对UNCD膜生长和组成结构的影响，以期获得高质量UNCD膜材的快速生长工艺技术。采用SEM、XRD、Raman等方法分析表征UNCD薄膜的形貌结构、物相组成和生长速率，同时通过OES光谱监测UNCD薄膜沉积过程中的生长基团状态。结果表明：UNCD薄膜沉积的基体温度范围在450～650 ℃，且随着功率和基体温度增加，OES光谱中CN、C₂基团峰值强度增强，生长速率从0.82 μm/h上升到6.62 μm/h；膜材中晶粒尺寸稍有增加，但平均晶粒尺寸均小于10.00 nm，且表面更加平整光滑，形成更有利于力学性能的表面形貌。因此，采用二异丙胺液态小分子为反应源，同时施加更高的微波功率，在更高的基体温度下沉积是快速生长高质量UNCD膜的有效工艺途径。
- UNCD薄膜 /
- MPCVD /
- 基体温度 /
- 生长速度；晶粒尺寸
Abstract: Ultra-nanocrystalline diamond (UNCD) films were prepared by microwave plasma chemical vapour deposition (MPCVD) at different temperature conditions by adjusting the microwave power. The effects of the activation power of the reaction source and effects of the temperature of the substrate on the growth and composition of the UNCD films were compared and analysed in order to obtain the technique to rapidly grow high-quality UNCD films. SEM, XRD and Raman methods were used to characterise the morphological structure, phase composition and growth rate of the UNCD films, while OES spectroscopy was used to monitor the state of the growth groups during the deposition of the UNCD films. The results showed that the deposition temperature of the UNCD films ranged from 450 to 650 ℃; that the peak intensity of CN and C₂ groups in the OES spectra increased with the increase of power and substrate temperature; that the growth rate increased from 0.82 μm/h to 6.62 μm/h; and that the grain size in the films increased. The average grain size was less than 10.00 nm, and the surface was flatter and smoother, forming a surface profile more favourable to the mechanical properties. Therefore, the use of diisopropylamine liquid small molecules as the reaction source, together with the application of higher microwave power and deposition at higher substrate temperatures, is an effective way to mushroom high-quality UNCD films.
- UNCD film /
- MPCVD /
- substrate temperature /
- growth rate; grain size

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图 1 MPCVD设备

Figure 1. MPCVD equipment

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图 2 不同微波功率及温度下生长的UNCD薄膜的SEM图

Figure 2. SEM images of UNCD films grown at different different microwave power and temperatures

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图 3 不同功率及温度下所得薄膜的XRD图

Figure 3. XRD patterns of the obtained films under different power and temperature

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图 4 不同功率及温度下UNCD薄膜的Raman光谱

Figure 4. Raman spectra of UNCD films under different power and temperature

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图 5 不同功率及温度下UNCD薄膜的I_D/I_G值

Figure 5. I_D/I_G values of UNCD films at different power and temperature

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图 6 不同功率及温度下UNCD薄膜的ICP-OES光谱图

Figure 6. ICP-OES spectra of UNCD films under different power and temperature

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表 1 UNCD薄膜制备工艺参数

Table 1. Preparation process parameters of UNCD films

参数名称	数值
功率 P / kW	3.0	3.5	4.0	4.5	5.0
温度 θ / ℃	450	500	550	600	650
压力 p / kPa	11.3	11.3	11.3	11.3	11.3
C₆H₁₅N流量 Q₁ / (mL·min⁻¹)	8	8	8	8	8
H₂流量 Q₂ / (mL·min⁻¹)	160	160	160	160	160

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表 2 不同微波功率及温度下沉积薄膜的厚度及生长速度

Table 2. Thickness and growth rate of deposited films under different microwave power and temperature

参数名称	数值
功率 P / kW	3.0	3.5	4.0	4.5	5.0
温度 θ / ℃	450	500	550	600	650
3 h沉积厚度 h / μm	2.417	7.349	13.310	14.460	19.870
生长速率 v / （μm·h⁻¹）	0.81	2.45	4.44	4.82	6.62

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表 3 不同温度下UNCD薄膜的晶粒尺寸

Table 3. Grain size of UNCD films at different temperatures

功率 p/kW	温度 θ / ℃	衍射峰位 2θ / (°)	半峰宽 B / (cm⁻¹)	由不同衍射峰所得晶粒尺寸 d / nm	平均晶粒尺寸 d₁ / nm
3.0	450	44.05	2.15	4.14	8.83
		75.98	0.82	12.75
		92.02	1.24	9.59
3.5	500	43.86	1.20	7.42	8.73
		75.42	1.09	9.56
		91.49	1.29	9.20
4.0	550	43.92	1.05	8.46	9.20
		75.43	1.05	9.98
		91.58	1.29	9.17
4.5	600	43.88	0.95	9.32	9.34
		75.38	1.10	9.45
		91.52	1.28	9.24
5.0	650	44.38	1.01	8.86	8.98
		76.02	1.12	9.35
		92.19	1.37	8.72

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