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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 ℃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CH 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CH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CH键比乙烯基团的CH 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 ℃). 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 CH bond stretching (3107 cm-1) and bending (1405 cm-1) vibrations of the vinylidene group (C＝CH2). The other is due to sp3 hybridization CH 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 CH 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.
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Keywords:
- diamond /
- nitrogen and hydrogen co-doped diamond crystals /
- Fourier transform infrared spectra
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[2] Zhang W J, Wu Y, Wong W K, Meng X M, Chan C Y, Bello I, Lifshitz Y, Lee S T 2003 Appl. Phys. Lett. 83 3365
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[19] Zhang Z F, Jia X P, Sun S S, Liu X B, Li Y, Yan B M, Ma H A 2013 Int. J. Refractory Metals Hard Mater. 38 111
[20] Li Y, Jia X P, Hu M H, Liu X B, Yan B M, Zhou Z X, Zhang Z F, Ma H A 2012 Chin. Phys. B 21 058101
[21] Ma H A, Jia X P, Chen L X, Zhu P W, Guo W L, Guo X B, Wang Y D, Li S Q, Zou G T, Bex P 2002 J. Phys. Condens. Matter 14 11269
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[1] Kim Y D, Choi W, Wakimoto H, Usami S, Tomokage H, Ando T 1999 Appl. Phys. Lett. 75 3219
[2] Zhang W J, Wu Y, Wong W K, Meng X M, Chan C Y, Bello I, Lifshitz Y, Lee S T 2003 Appl. Phys. Lett. 83 3365
[3] Wang J, Chen G, Chatrathi M P, Fujishima A, Tryk D A, Shin D 2003 Anal. Chem. 75 935
[4] Shin D, Sarada B V, Tryk D A, Fujishima A, Wang J 2003 Anal. Chem. 75 530
[5] Hu M H, Ma H A, Yan B M, Zhang Z F, Li Y, Zhou Z X, Qin J M, Jia X P 2012 Acta Phys. Sin. 61 078102 (in Chinese) [胡美华, 马红安, 颜丙敏, 张壮飞, 李勇, 周振翔, 秦杰明, 贾晓鹏 2012 61 078102]
[6] Koizumi S, Watanabe K, Hasegawa M, Kanda H 2001 Science 292 1899
[7] Yu B D, Miyamoto Y, Sugino O 2000 Appl. Phys. Lett. 76 976
[8] Polyakov V I, Rukovishnikov A I, Rossukanyi N M, Ralchenko V G 2001 Diam. Relat. Mater. 10 593
[9] Zhang Z F, Jia X P, Liu X B, Hu M H, Li Y, Yan B M, Ma H A 2012 Chin. Phys. B 21 038103
[10] Liang Z Z, Kanda H, Jia X P, Ma H A, Zhu P W, Guan Q F, Zang C Y 2006 Carbon 44 913
[11] Chrenko R M, McDonald R S, Darrow K A 1967 Nature 213 474
[12] Runciman W A, Carter T 1971 Solid St. Commun. 9 315
[13] Woods G S, Collins A T 1983 J. Phys. Chem. Solids 44 471
[14] Palyanov Y N, Kupriyanov I N, Borzdov Y M, Sokol A G, Khonkhryakov A F 2009 Cryst. Growth. Des. 9 2922
[15] Meng Y F Yan C S, Lai J, Krasnicki S, Shu H Y, Yu T, Liang Q, Mao H K, Hemley R J 2008 Proc. Natl. Acad. Sci. USA 105 17620
[16] Charles S J, Butler J E, Feygelson B N, Newton M E, Carroll D I, Steeds J W, Darwish H, Yan C S, Mao H K, Hemley R J 2004 Phys. Status Solidi A 201 2473
[17] Borzdov Y, Pal'yanov Y, Kupriyanov I, Gusev V, Khokhryakov A, Sokol A, Efremov A 2002 Diam. Relat. Mater. 11 1863
[18] Kiflawi I, Fisher D, Kanda H, Sittas G 1996 Diam. Relat. Mater. 5 1516
[19] Zhang Z F, Jia X P, Sun S S, Liu X B, Li Y, Yan B M, Ma H A 2013 Int. J. Refractory Metals Hard Mater. 38 111
[20] Li Y, Jia X P, Hu M H, Liu X B, Yan B M, Zhou Z X, Zhang Z F, Ma H A 2012 Chin. Phys. B 21 058101
[21] Ma H A, Jia X P, Chen L X, Zhu P W, Guo W L, Guo X B, Wang Y D, Li S Q, Zou G T, Bex P 2002 J. Phys. Condens. Matter 14 11269
[22] Coudberg P, Catherine Y 1987 Thin Solid Films 146 93
[23] McNamara K M, Williams B E, Gleason K K, Scruggs B E 1994 J. Appl. Phys. 76 2466
[24] Field J E 1992 The Properties of Natural and Synthetic Diamond (London: Academic) pp36-41, 81-179
[25] Kanda H, Akaishi M Yamaoka S 1999 Diam. Relat. Mater. 8 1441
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