C-H-F氛围下金刚石薄膜的低温CVD生长过程分析

简小刚; 梁晓伟; 姚文山; 张毅; 张斌华; 陈哲; 陈茂林

doi:10.13394/j.cnki.jgszz.2023.0069

C-H-F氛围下金刚石薄膜的低温CVD生长过程分析

doi: 10.13394/j.cnki.jgszz.2023.0069

同济大学机械与能源工程学院, 上海 201804

基金项目: 国家自然科学基金（51275358）。

详细信息

作者简介:
简小刚，男，1975年生，博士、副教授。主要研究方向：涂层制备与性能检测。E-mail：jianxgg@tongji.edu.cn

中图分类号: TQ164; TG74
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- 被引次数: 0
出版历程
- 收稿日期: 2023-03-21
- 修回日期: 2023-05-11
- 网络出版日期: 2024-03-15
- 刊出日期: 2024-02-20

Analysis of low-temperature CVD growth process of diamond films in C-H-F atmosphere

School of Mechanical and Energy Engineering, Tongji University, Shanghai 201804, China

摘要

摘要: 基于第一性原理的密度泛函理论对C-H-F氛围下低温CVD金刚石薄膜的生长过程进行仿真分析，计算H、F原子在氢终止金刚石表面发生萃取反应的吸附能、反应热与反应能垒，并分析CF₃、CF₂、CF 3种生长基团在带有活性位点基底上的吸附。结果表明：与H原子相比，F原子更容易在氢终止金刚石表面萃出H，并以HF形式脱附，且在C-H-F氛围下有利于在低温时产生更多的活性位点；CF₃、CF₂、CF基团在吸附后的结构和吸附能绝对值都更有利于金刚石相的生成，适当提高CF₃、CF₂、CF基团的浓度有助于实现金刚石相的更高速率生长。
- CVD金刚石薄膜 /
- 氟 /
- 沉积机制 /
- 第一性原理 /
- 吸附 /
- 表面化学反应
Abstract: To better understand the growth mechanism of diamond films via low-temperature chemical vapor deposition in a C-H-F atmosphere, this paper employed density functional theory based on first principle. It calculated the adsorption energy, reaction heat, and reaction energy barrier of H and F atoms undergoing extraction reactions on the hydrogen-terminated diamond surface. Additionally, the analysis included the adsorption of CF₃, CF₂, and CF growth groups on the active site substrate. The results show that compared with H atoms, F atoms are more likely to extract H from the surface of hydrogen terminated diamond and desorb it in the form of HF. This process is advantageous for generating more active sites at low temperatures in a C-H-F atmosphere. Both the structure and the absolute value of the adsorption energy of CF₃, CF₂, and CF groups are more favorable for the generation of the diamond phase after adsorption. Increasing the concentration of CF₃, CF₂, and CF growth groups appropriately can facilitate the growth of diamond phase at a higher rate.
- CVD diamond film /
- fluorine /
- deposition mechanism /
- first-principles /
- adsorption /
- surface chemical reaction

HTML全文

图 1 C-H氛围下金刚石相形成机制

Figure 1. The mechanism of diamond phase formation under C–H atmosphere

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图 2 金刚石基底建模过程

Figure 2. Modeling process of diamond substrate

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图 3 基底模型

Figure 3. Substrate model

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图 4 粒子基团的吸附模型

Figure 4. Adsorption model of particle groups

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图 5 H、F原子吸附位置

Figure 5. H and F atomic adsorption positions

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图 6 H原子的萃取反应过渡态搜索

Figure 6. Transition state search for H atom abstraction reaction

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图 7 F原子的萃取反应过渡态搜索

Figure 7. Transition state search for F atom extraction reaction

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图 8 CF₃基团在生长基底上吸附后的结构

Figure 8. Structure of CF₃ group adsorbed on growth substrate

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图 9 CF₂基团在生长基底上吸附后的结构

Figure 9. Structure of CF₂ group adsorbed on growth substrate

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图 10 CF基团在生长基底上吸附后的结构

Figure 10. Structure of CF group adsorbed on growth substrate

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表 1 H、F原子在金刚石基底表面的吸附能

Table 1. Adsorption energy of H and F atoms on the diamond substrate surface

原子	E_ads / eV
H	−0.170 8
F	−2.092 8

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表 2 CF₃、CF₂、CF基团吸附后的键长、键角值

Table 2. Bond length and bond angle values after adsorption of CF₃, CF₂, and CF groups

参数	取值
参数	CF₃	CF₂	CF
HC-CCF_x吸附后键长 L₂ / nm	0.162 2	0.161 9	0.161 0
HCC-CF_x吸附后键长 L₁ / nm	0.158 4	0.150 5	0.148 8
F_x-1C-F键长 L₃ / nm	0.136 4	0.135 7	0.135 4
HCC键角 α / (°)	113.950	111.357	111.395
CCC键角 β / (°)	118.012	109.059	110.553

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表 3 CF₃、CF₂、CF、CH₃基团在生长基底的吸附能

Table 3. Adsorption energies of CF₃, CF₂, CF and CH₃ groups on growth substrate

基团	吸附能 E_ads / eV
CF₃	−3.7251
CF₂	−3.4282
CF	−3.5366
CH₃	−3.3260

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