Experimental study on synthesis of single crystal diamond by hot filament chemical vapor deposition method
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摘要: 热丝化学气相沉积法沉积区域可达12英寸(30.48 cm)，其具备大批量生产单晶金刚石的潜力。采用尺寸为3 mm×3 mm×1 mm，(100)取向的单晶金刚石为基体，利用热丝化学气相沉积法以甲烷和氢气为前驱体，同时通入少量氮气进行同质外延生长。结果表明，在热丝温度为2200 ℃、碳源浓度为4%、腔体气压为4 kPa的条件下，单晶金刚石以3.41 μm/h的速度生长，表面无多晶、破口、孔洞等缺陷；外延层X射线衍射光谱在(400)面处峰值的半高宽为0.11°，低于基体的半高宽0.16°，证明外延层具有较高的晶体质量；氮气的引入可以提升单晶金刚石的生长速度，同时降低外延层的晶体质量，较高的氮气浓度还会使得单晶金刚石的生长模式转为岛状生长。Abstract: The deposition area of the hot filament chemical vapor deposition (HFCVD) method can reach 12 inches, which has the potential to produce larger-sized single crystal diamonds. In this study, single crystal diamond with a size of 3 mm × 3 mm × 1 mm and (100) orientation was used as the substrate. Homoepitaxial growth was carried out using the HFCVD method with methane and hydrogen as precursors, and a small amount of nitrogen gas. The results show that under the conditions of a filament temperature of 2200 °C, a carbon source concentration of 4%, and a chamber pressure of 4 kPa, single crystal diamond grows at a rate of 3.41 μm/h. The surface of the diamond exhibits no defects such as polycrystals, cracks, or holes. The full width half maximum (FWHM) of the epitaxial layer’s X-ray diffraction spectrum at the (400) peak is 0.11°, which is lower than that of the substrate at 0.16°, indicating that the crystal quality of the epitaxial layer is higher than that of the substrate. The introduction of nitrogen can increase the growth rate of single crystal diamond, although it reduces the crystal quality of the epitaxial layer. A higher nitrogen concentration can also shift the growth mode of single crystal diamond change to island growth.
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图 1 HFCVD单晶外延层Raman光谱与MPCVD单晶基体Raman光谱
Figure 1. Raman spectrum of HFCVD single crystal epitaxial layer and Raman spectrum of MPCVD single crystal substrate
图 2 不同热丝温度条件下单晶金刚石截面Raman mapping面扫描图像及表面Raman点扫描图像
Figure 2. Raman mapping image of single crystal diamond cross section under the different condition of filament temperature and Raman point scanning image of surface
图 3 不同热丝温度条件下单晶金刚石表面形貌
Figure 3. Surface morphology of single crystal diamond under the different condition of filament temperature
图 4 不同碳源浓度条件下单晶金刚石截面Raman mapping面扫描图像及表面Raman点扫描图像
Figure 4. Raman mapping image of single crystal diamond cross section under the different condition of carbon source concentration and Raman point scanning image of surface
图 5 不同碳源浓度条件下单晶金刚石表面形貌
Figure 5. Surface morphology of single crystal diamond under the different condition of carbon source concentration
图 6 不同腔体压力条件下单晶金刚石截面Raman mapping面扫描图像及表面Raman点扫描图像
Figure 6. Raman mapping image of single crystal diamond cross section under the different condition of pressure and Raman point scanning image of surface
图 7 不同腔体压力条件下单晶金刚石表面形貌
Figure 7. Surface morphology of single crystal diamond under the different condition of pressure
图 8 MPCVD单晶金刚石基体和HFCVD单晶金刚石外延层 XRD谱图
Figure 8. XRD spectra of MPCVD single crystal diamond substrate HFCVD single crystal diamond epitaxial layer
图 9 不同氮气流量条件下单晶金刚石截面Raman mapping面扫描图像及表面Raman点扫描图像
Figure 9. Raman mapping image of single crystal diamond cross section under the different condition of nitrogen flow and Raman point scanning image of surface
图 10 不同氮气流量条件下单晶金刚石表面形貌
Figure 10. Surface morphology of single crystal diamond under the different condition of nitrogen flow rate
图 11 氮气流量0.02 sccm条件下单晶金刚石XRD谱图
Figure 11. XRD spectra of single crystal diamond at nitrogen flow rate of 0.02 sccm
图 12 氮气流量0.02 sccm条件下单晶金刚石PL光谱
Figure 12. PL spectrum of single crystal diamond at nitrogen flow rate of 0.02 sccm
表 1 HFCVD法制备单晶金刚石单因素实验方案
Table 1. Single-factor experimental scheme for preparing single crystal diamond by HFCVD method
编号 热丝温度/
℃碳源浓度/
%腔体压力/
kPa氮气流量/
sccm生长速度/
(μm·h−1)1 2000 4 4 0 0.45 2 2200 4 4 0 3.41 3 2400 4 4 0 4.55 4 2200 2 4 0 2.84 5 2200 4 4 0 3.41 6 2200 6 4 0 3.63 7 2200 4 2 0 — 8 2200 4 4 0 3.41 9 2200 4 6 0 2.95 10 2200 4 4 0 3.41 11 2200 4 4 0.02 5.91 12 2200 4 4 0.04 6.45 
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