氮氢共掺杂金刚石中氢的典型红外特征峰的表征

摘要

所有天然Ia型金刚石红外光谱中都存在3107 cm-1特征峰,而在金属触媒直接合成的金刚石红外光谱中没有检测出3107 cm-1特征峰.本文在6.3 GPa,1500◦C条件下,通过Fe70Ni30触媒中添加P3N5直接合成出具有3107 cm-1特征峰的氮氢共掺杂的金刚石.红外光谱分析表明,合成的金刚石中氢有两种存在形式：一种对应着乙烯基团>C＝CH2中C-H 键的伸缩振动(3107 cm-1)和弯曲振动(1450 cm-1)的吸收峰,另一种对应着sp3杂化C-H键的对称伸缩振动(2850 cm-1)和反对称伸缩振动(2920 cm-1)的吸收峰.通过分析发现,3107 cm-1吸收峰与金刚石中聚集态的氮原子有关,当金刚石中没有聚集态的氮元素时,即使氮含量高也不会出现3107 cm-1峰；并且2850和2920 cm-1附近的吸收峰比3107 cm-1附近的吸收峰更为普遍存在.这说明sp3杂化C-H键比乙烯基团的C-H键更广泛存在于金刚石中,从两者的峰值看,天然金刚石中的氢杂质主要以乙烯基团>C＝CH2存在.3107 cm-1吸收峰与聚集态的氮原子的这种存在关系为天然金刚石形成机制的研究提供了一种新思路,同时较低的合成条件也可能为氢与其他元素共掺杂合成具有n型半导体特性的金刚石提供一个较理想的合成环境.%The 3107 cm-1 peak is observed in the infrared absorption spectra of all types of Ia diamonds, but it has not been observed in the iron-based catalyst. A series of nitrogen and hydrogen-doped diamond crystals is successfully synthesized using P3N5 as the nitrogen source in a catalyst-carbon system at a lower pressure and temperature (6.3 GPa, 1500 ◦C). Fourier transform infrared micro-spectroscopy reveals that the hydrogen atoms existing in the synthesized diamond are in two forms. The one is attributed to the C-H bond stretching (3107 cm-1) and bending (1405 cm-1) vibrations of the vinylidene group (> C=CH2). The other is due to sp3 hybridization C-H bond symmetric (2850 cm-1) and anti-symmetric (2920 cm-1) vibrations. According to our result, we find that the 3107 cm-1 hydrogen absorption peak is related to the aggregated nitrogen in synthetic diamond. The 3107 cm-1 peak could not be observed in synthetic diamond without aggregated nitrogen, even if it has a high nitrogen concentration. And the hydrogen absorption peaks at 2920 and 2850 cm-1 are more widespread than the absorption peak at 3107 cm-1, this suggests that the sp3 C-H bond more widely exists in diamond than the vinylidene group (>C=CH2). Infrared spectra analysis indicates that the hydrogen impurity mainly exists in the natural diamond as vinylidene group as seen from the absorption peak intensity. We believe that our results provide a new way to study the formation mechanism of the natural diamond. Moreover, the ideal synthesis condition in our system supplies a possible way for us to design n-type diamond semiconductor.