CVD金刚石膜应力的产生、抑制、应用及测量

doi:10.15541/jim20250094

摘要/Abstract

摘要：

金刚石具有优异的性能, 在光学、电子器件热管理及宽禁带半导体领域有着广阔的应用前景, 被誉为终代半导体。作为光学窗口, 需要大尺寸、厚度2 mm以上的CVD (Chemical Vapor Deposition, 化学气相沉积)金刚石自支撑厚膜; 在半导体散热中, 则需要4英寸(1英寸=2.54 cm)以上、100 μm厚的金刚石自支撑膜与GaN等半导体材料进行键合。但由于技术限制, 大面积CVD金刚石膜的合成及应用依旧存在较大困难。一方面, 沉积过程中应力会导致金刚石膜发生破裂; 另一方面, 残余应力会导致金刚石膜发生翘曲, 键合质量变差。因此, 控制金刚石膜的应力成为目前金刚石膜规模化、大范围应用的一个关键问题。本文综述了CVD金刚石应力的分类、来源以及影响应力的各种因素, 详细介绍了抑制金刚石膜应力的措施。同时, 总结了通过人为施加应力来改善金刚石性能的研究, 包括应力改变金刚石带隙、应力提高金刚石热导率等。最后, 给出了评价金刚石应力大小的方法及理论计算公式, 并分析了未来金刚石膜应力研究的趋势。

关键词: CVD金刚石, 膜应力, 应力抑制, 应力应用, 应力测量, 综述

Abstract:

Diamond with excellent properties and broad application prospects in the fields of thermal management of optics and electronic devices, and wide bandgap semiconductors, is known as the ultimate semiconductor. As an optical window, a large-sized CVD (chemical vapor deposition) diamond free-standing thick film with a thickness of ≥2 mm is required. In semiconductor heat dissipation, a diamond free-standing film with a diameter over 4 inches (1 inch=2.54 cm) and a thickness of 100 μm is required to bond with semiconductor materials such as gallium nitride (GaN). However, there still exist significant difficulties in synthesis and application of large-area CVD diamond films. On the one hand, stress during the deposition process can cause the diamond film to rupture. On the other hand, residual stress can cause the diamond film to warp, resulting in poor bonding quality. Therefore, controlling the stress of diamond films has become a key issue for the large-scale and widespread application of diamond films. This article summarizes the classification, sources, and influencing factors of CVD diamond stress, and provides a detailed introduction to measures for suppressing stress in diamond films. Furthermore, researches on improving diamond properties by artificially applying stress are summarized, including changing diamond bandgap and increasing diamond thermal conductivity under stress. Finally, a method and theoretical calculation formula for evaluating the stress magnitude of diamond are provided, and the future trend of stress research on diamond films is analyzed.

Key words: CVD diamond, film stress, stress restraint, stress application, stress measurement, review

中图分类号:

TQ174

李成明, 周闯, 刘鹏, 郑礼平, 赖泳机, 陈良贤, 刘金龙, 魏俊俊. CVD金刚石膜应力的产生、抑制、应用及测量[J]. 无机材料学报, 2025, 40(11): 1188-1200.

LI Chengming, ZHOU Chuang, LIU Peng, ZHENG Liping, LAI Yongji, CHEN Liangxian, LIU Jinlong, WEI Junjun. Stress in CVD Diamond Films: Generation, Suppression, Application, and Measurement[J]. Journal of Inorganic Materials, 2025, 40(11): 1188-1200.

图/表 10

图1 不同种类缺陷尺寸对比[11]

Fig. 1 Comparison of different types of defect sizes[11]

表1 常见衬底材料的热膨胀系数[12]

Table 1 Thermal expansion coefficients of common substrate materials[12]

Substrate material	Elastic modulus/GPa	Melting temperature/K	Coefficient of thermal expansion (polynomial interpolation)/(×10^-6, K^-1)
Si	130	1683	-2.15+2.47×10^-2T-3.82×10^-5T²+2.67×10^-8T³-6.87×10^-12T⁴
Mo	327	2888	4.31+0.002T
W	411	3660	2.78+0.01T-2.21×10^-5T²+1.93×10^-8T³-5.56×10^-12T⁴
Diamond	1050	—	-1.36+8.79×10^-3T+3.98×10^-7T²-6.18×10^-9T³+2.78×10^-12T⁴

图2 常见衬底材料热膨胀系数与温度的关系[12]

Fig. 2 Relationship between coefficient of thermal expansion and temperature of common substrate materials[12]

表2 金刚石与各种材料的晶格常数及晶格错配度

Table 2 Lattice constants and lattice mismatch of diamond with various materials

Material	Si (0.543 nm)	Mo (0.3147 nm)	W (0.3165 nm)	Diamond (0.357 nm)
Lattice mismatch	34.3%	13.4%	12.8%	—

图3 碳离子注入剂量与应力的关系[47]

Fig. 3 Relationship between carbon ion implantation dose and stress[47]

图4 退火时间与应力大小的关系[16]

Fig. 4 Relationship between annealing time and stress[16]

图5 水冷因数与热应力的关系[58]

Fig. 5 Relationship between water cooling coefficient and thermal stress[58]

图6 系统的总应力σtot分布及Al-Si-N中间层应力σAlSiN, 金刚石膜底部应力σbottom和顶部应力σtop[62]

Fig. 6 Distribution of the total stress σtot in the system and the stress σAlSiN in the Al-Si-N intermediate layer, as well as the bottom and top stress (σbottom, σtop) of the diamond film[62]

图7 不同尺度单轴拉伸应力下κ的温度依赖性[66]

Fig. 7 Temperature dependence of κ under uniaxial tensile stress at different scales[66]

图8 300 K下天然金刚石和纯金刚石的热导率κNat和κPure随压力的变化[67]

Fig. 8 Thermal conductivity κNat and κPure of natural diamond and pure diamond varied with pressure at 300 K[67]

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