Synthesis and Characterization of P-Doped Diamond Crystals in the FeNiCo-C System under High Temperature and High Pressure
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摘要: 为探究磷掺杂对金刚石晶体生长的影响，在5.5 GPa、1 300 ℃的条件下，将Fe3P掺入FeNiCo-C体系中，采用温度梯度法沿(111)晶面合成了磷掺杂金刚石单晶。对合成的金刚石样品进行傅里叶变换红外光谱、拉曼光谱、光致发光光谱以及X射线光电子能谱测试。随着Fe3P添加量的上升，金刚石晶体颜色逐渐变浅，晶体结构由八面体向六-八面体转变。金刚石晶体中氮杂质含量随着Fe3P添加量的上升呈下降趋势，原因是Fe3P的掺入改变了触媒特性，使触媒的氮溶解度增加，从而减少了进入金刚石内部的氮原子数量。磷掺杂会使金刚石晶体内应力增大，产生晶格畸变，降低金刚石质量，这一结论可通过金刚石拉曼峰位偏移和半高宽变化得到证实。磷原子的掺入不利于金刚石晶体中NV−色心的形成。X射线光电子能谱测试结果证实，磷元素成功进入金刚石晶体内部。研究成果可为完善磷掺杂金刚石晶体合成机理以及推动磷掺杂金刚石晶体的潜在应用提供参考。Abstract: To investigate the effects of phosphorus doping on diamond crystal growth, diamond single crystals doped with phosphorus were synthesized along the (111) plane using the temperature gradient method. The experiments were conducted under conditions of 5.5 GPa and 1 300 ℃, with Fe3P added into the FeNiCo-C system. The synthesized diamond samples were characterized by Fourier-transform infrared (FTIR) spectroscopy, Raman spectroscopy, photoluminescence (PL) spectroscopy, and X-ray photoelectron spectroscopy (XPS). With increasing Fe3P addition, the diamond color gradually lightens, and the crystal morphology changes from octahedral to hexoctahedral. Moreover, the addition of Fe3P alters the catalyst properties, leading to the increases of nitrogen solubility of the catalyst. Thus, fewer nitrogen atoms enter the diamond lattice, resulting in a decrease of nitrogen impurity content in the diamonds. Phosphorus doping increases internal stress and induces lattice distortion in the diamond crystal, resulting in degrading of the diamond quality. This conclusion is supported by the shift and broadening of the Raman peak. The incorporation of phosphorus atoms inhibits the formation of NV− centers in diamond crystals. XPS results confirm the successful incorporation of phosphorus into the diamond lattice. This study provides useful insights for understanding the synthesis mechanism of phosphorus-doped diamond crystals, and supports potential applications of phosphorus-doped diamond crystals.
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图 1 温度梯度法合成金刚石晶体腔体示意图
Figure 1. Schematic diagram of diamond growth cell via the temperature gradient method
图 2 添加不同质量分数Fe3P的金刚石晶体的光学显微照片
Figure 2. Optical micrographs of diamond crystals with different Fe3P mass fraction
图 3 不同Fe3P添加量金刚石单晶的红外光谱
Figure 3. FTIR spectra of diamond crystals synthesized under different Fe3P mass fraction
图 4 不同Fe3P质量分数金刚石单晶的(a) Raman光谱以及(b) 拉曼峰位和半高宽
Figure 4. (a) Raman spectra and (b) Raman peak positions and FWHM of diamond crystals synthesized under different Fe3P mass fraction
图 5 不同Fe3P添加量金刚石单晶的PL光谱
Figure 5. PL spectra of diamond crystals synthesized under different Fe3P content
图 6 Fe3P质量分数为2%的金刚石晶体的XPS光谱
Figure 6. XPS spectra of diamond crystals with Fe3P mass fraction of 2%
表 1 P掺杂金刚石晶体形貌及颜色
Table 1. Morphology and color of P-doped diamond crystals
Sample Mass fraction of Fe3P/% Morphology Color Inclusion A 1 Octahedron Yellow No B 2 Hexoctahedral Yellow Little C 4 Hexoctahedral Light yellow Little D 6 Hexoctahedral Light yellow Many E 8 Skeletal crystal Dark 
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表 2 P掺杂金刚石晶体的氮含量
Table 2. Nitrogen concentration of P-doped diamond crystals
Sample CN/10−6 A 387 B 157 C 134 D 111
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表 3 不同Fe3P质量分数的金刚石单晶的内应力
Table 3. Internal stress of diamond crystals synthesized under different Fe3P mass fraction
Sample σh/GPa A 0.052 B 0.107 C 0.149 D 0.194
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