Synthesis of diamond co-doped with B and S under high pressure and high temperature and electrical properties of the synthesized diamond

Li Yong; Wang Ying; Li Shang-Sheng; Li Zong-Bao; Luo Kai-Wu; Ran Mao-Wu; Song Mou-Sheng

doi:10.7498/aps.68.20190133

Abstract

As is well known, diamond is extensively used in many fields, because of its excellent properties, such as its hardness, high thermal conductivity, high electron and hole mobility, high breakdown field strength and large band gap (5.4 eV). However, its application in semiconductor area needs to be further understood, because it is irreplaceable by conventional semiconductor materials, especially in the extreme working conditions. Furthermore, the preparation of n-type diamond semiconductors is still an unsolved problem. The reason is that an effective donor element has not yet been found. Recently, both the theoretical and experimental studies show that it is difficult to obtain n-type diamond semiconductor with excellent properties by doping single element in the synthetic system. In this paper, diamond single crystals co-doped with B and S are successfully synthesized in FeNiMnCo-C system at a pressure of 6.5 GPa and temperature ranging from 1280 ℃ to 1300 ℃, by using temperature gradient method. The impurity defects in the synthesized diamond single crystals are characterized by Fourier infrared absorption spectra and the results indicate that the corresponding characteristic absorption peaks of B and S are located at 1298 cm^–1 and 847 cm^–1, respectively. Furthermore, the absorption attributed to B-S group is not detected. The N concentration of the synthesized diamond crystals decreases to 195 ppm, resulting from the incorporation of B and S impurities into the diamond lattices. Additionally, the electrical properties of the typical diamond single crystals are measured in virtue of Hall effects at room temperature. The measurement results display that the electrical conductivity of the diamond doped with B is obviously enhanced, resulting from the involvement of the S when B addition amount is fixed in the synthesis system. Hall mobility of the corresponding diamond crystals increases from 12.5 cm^–2·V^–1·s^–1 to 760.87 cm^–2·V^–1·s^–1. And then, the relative proportion of S and B will determine the p/n properties of the obtained diamond. In order to further study the electrical properties of diamond, first-principles calculations are adopted and the theoretical calculation results show that the impurity elements involved in the obtained diamond can affect the band structures of the synthetic diamond crystals, which is consistent with the experimental result.

Keywords:

Authors and contacts

1.
Department of Physics and Electrical Engineering, Tongren University, Tongren 554300, China
2.
School of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo 454000, China

Corresponding author: Li Zong-Bao, zongbaoli1982@163.com

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 11604246), the Natural Science Foundation of Guizhou Province Education Department, China (Grant No. KY[2017]053), the Natural Science Foundation of Guizhou Province Science and Technology Agency, China (Grant No. [2018]1163), and the Outstanding Young Science and Technology Talents of Guizhou Province, China.

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References

[1]	王君卓, 李尚升, 宿太超, 胡美华, 胡强, 吴玉敏, 王健康, 韩飞, 于昆鹏, 高广进, 郭明明, 贾晓鹏, 马红安, 肖宏宇 2018 67 168101 Google Scholar Wang J Z, Li S S, Su T C, Hu M H, Hu Q, Wu Y M, Wang J K, Han F, Yu K P, Gao G J, Guo M M, Jia X P, Ma H A, Xiao H Y 2018 Acta Phys. Sin. 67 168101 Google Scholar
[2]	刘银娟, 贺端威, 王培, 唐明君, 许超, 王文丹, 刘进, 刘国端, 寇自力 2017 66 038103 Google Scholar Liu Y J, He D W, Wang P, Tang M J, Xu C, Wang W D, Liu J, Liu G D, Kou Z L 2017 Acta Phys. Sin. 66 038103 Google Scholar
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[13]	Katayama Yoshida H, Nishimatsu T, Yamamoto T, Orita N 2001 J. Phys.: Cond. Matter 13 8901 Google Scholar
[14]	Li Y, Jia X P, Ma H A, Zhang J, Wang F B, Chen N, Feng Y G 2014 CrystEngComm 16 7547 Google Scholar
[15]	肖宏宇, 秦玉琨, 隋永明, 梁中翥, 刘利娜, 张永胜 2016 65 070705 Google Scholar Xiao H Y, Qin Y K, Sui Y M, Liang Z Z, Liu L N, Zhang Y S, 2016 Acta Phys. Sin. 65 070705 Google Scholar
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[20]	Zhang J Q, Ma H A, Jiang Y P, Liang Z Z, Tian Y, Jia X P 2007 Diamond Relat. Mater. 16 283 Google Scholar
[21]	李勇, 李宗宝, 宋谋胜, 王应, 贾晓鹏, 马红安 2016 65 118103 Google Scholar Li Y, Li Z B, Song M S, Wang Y, Jia X P, Ma H A 2016 Acta Phys. Sin. 65 118103 Google Scholar
[22]	王应, 李勇, 李宗宝 2016 65 087101 Google Scholar Wang Y, Li Y, Li Z B 2016 Acta Phys. Sin. 65 087101 Google Scholar

Cited By

图 1 金刚石合成腔体示意图(1, 钢帽; 2, 石墨片; 3, 氯化钠管; 4, 陶瓷堵头; 5, 石墨加热管; 6, 触媒; 7, 碳源; 8, 绝缘管; 9, 晶种; 10, 叶蜡石)

Figure 1. Schematic of the cell for diamond synthesis (1, conductive ring; 2, graphite sheet; 3, NaCl tube; 4, ceramic cylinder and cover; 5, graphite heater; 6, catalyst; 7, carbon source; 8, insulation tube; 9, seed crystal; 10, pyrophyllite).

DownLoad: Full-Size Img PowerPoint

图 2 FeNiMnCo-C体系中所合成的金刚石光学照片

Figure 2. Optical images of diamond synthesized in FeNiMnCo-C system.

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图 3 硼硫协同掺杂金刚石的红外光谱　(a)添加1.2%硼和添加2.0%硫; (b)添加0.8%硼和添加2.0%硫

Figure 3. FTIR spectra of diamond co-doped with B and S: (a) With 1.2% B and 2.0% S additives; (b) with 0.8% B and 2.0% S additives.

DownLoad: Full-Size Img PowerPoint

图 4 金刚石能带结构　(a)未添加硼与硫; (b)添加2.0%硫; (c)添加1.2%硼和2.0%硫; (d)添加0.8%硼和2.0%硫

Figure 4. Band structures of the synthesized diamond: (a) Without B or S additive; (b) with 2.0% S additive; (c) with 1.2% B and 2.0% S additives; (d) with 0.8% B and 2.0% S additives.

DownLoad: Full-Size Img PowerPoint

表 1 金刚石合成参数

Table 1. Parameters of the synthetic experiments of diamond performed at 6.5 GPa in the FeNiMnCo-C system.

Sample	B/%	S/%	温度/℃	颜色
(a)	—	—	1280	黄色
(b)	—	2.0	1280	黄色
(c)	1.2	—	1280	黄黑色
(d)	1.2	2.0	1300	黑色
(e)	0.8	2.0	1290	黄色

DownLoad: CSV

表 2 金刚石样品的电学性能参数((a)未添加硼与硫, (b)添加2.0%硫, (c)添加1.2%硼, (d)添加1.2%硼和2.0%硫, (e)添加0.8%硼和2.0 %硫)

Table 2. Electrical performance parameters of the diamond samples measured at room temperature ((a) without B or S additives, (b) with 2.0 wt.% S additive, (c) with 1.2% B additive, (d) with 1.2% B and 2.0% S additives, (e) with 0.8% B and 2.0% S additives).

Sample	电阻率/Ω·cm	载流子浓度/cm^–3	迁移率/cm^–2·V^–1·s^–1	Hall系数
(a)	> 10⁸	—	—	—
(b)	4.417 × 10⁶	5.383 × 10⁹	262.853	–1.151 × 10⁹
(c)	3.665 × 10³	1.364 × 10¹⁶	12.5	4.586 × 10⁴
(d)	8.510	6.652 × 10¹⁴	760.870	6.475 × 10³
(e)	1.262 × 10⁶	8.738 × 10¹⁰	56.680	–7.153 × 10⁷

DownLoad: CSV

map

[1]	王君卓, 李尚升, 宿太超, 胡美华, 胡强, 吴玉敏, 王健康, 韩飞, 于昆鹏, 高广进, 郭明明, 贾晓鹏, 马红安, 肖宏宇 2018 67 168101 Google Scholar Wang J Z, Li S S, Su T C, Hu M H, Hu Q, Wu Y M, Wang J K, Han F, Yu K P, Gao G J, Guo M M, Jia X P, Ma H A, Xiao H Y 2018 Acta Phys. Sin. 67 168101 Google Scholar
[2]	刘银娟, 贺端威, 王培, 唐明君, 许超, 王文丹, 刘进, 刘国端, 寇自力 2017 66 038103 Google Scholar Liu Y J, He D W, Wang P, Tang M J, Xu C, Wang W D, Liu J, Liu G D, Kou Z L 2017 Acta Phys. Sin. 66 038103 Google Scholar
[3]	Li Y, Zhou Z X, Guan X M, Li S S, Wang Y, Jia X P, Ma H A 2016 Chin. Phys. Lett. 33 028101 Google Scholar
[4]	Banerjee A, Bernoulli D, Zhang H T, Yuen M F, Liu J B, Dong J C, Ding F, Lu J, Dao M, Zhang W J, Lu Y, Suresh S 2018 Science 360 300 Google Scholar
[5]	Wang J K, Li S S, Jiang Q W, Song Y L, Yu K P, Han F, Su T C, Hu M H, H Q, Ma H A, Jia X P, Xiao H Y 2018 Chin. Phys. B 27 088102 Google Scholar
[6]	Ekimov E A, Sidorov1 V A, Bauer E D, Mel'nik N N, Curro N J, Thompson J D, Stishov1 S M 2004 Nature 428 542 Google Scholar
[7]	Prawer S, Uzan-Sanay C, Braunstein G 1993 Appl. Phys. Lett. 63 2502 Google Scholar
[8]	Jackson K, Pederson M R, Harrison J G 1990 Phys. Rev. B 41 12641 Google Scholar
[9]	Cao G Z, Driessen F A J M, Bauhuis C J 1995 J. Appl. Phys. 78 3125 Google Scholar
[10]	Gong C S, Li S S, Zhang H R, Su T C, Hu M H, Ma H A, Jia X P, Li Y 2017 Int. J. Refract. Metals and Hard Mater. 66 116 Google Scholar
[11]	Yan B M, Jia X P, Sun S S, Zhou Z X, Fang C, Chen N, Li Y D, Li Y, Ma H A 2015 Int. J Refract. Metals and Hard Mater. 48 56 Google Scholar
[12]	Fang C, Jia X P, Sun S S, Yan B M, Li Y D, Chen N, Li Y, Ma H A 2016 High Pressure Res. 36 42 Google Scholar
[13]	Katayama Yoshida H, Nishimatsu T, Yamamoto T, Orita N 2001 J. Phys.: Cond. Matter 13 8901 Google Scholar
[14]	Li Y, Jia X P, Ma H A, Zhang J, Wang F B, Chen N, Feng Y G 2014 CrystEngComm 16 7547 Google Scholar
[15]	肖宏宇, 秦玉琨, 隋永明, 梁中翥, 刘利娜, 张永胜 2016 65 070705 Google Scholar Xiao H Y, Qin Y K, Sui Y M, Liang Z Z, Liu L N, Zhang Y S, 2016 Acta Phys. Sin. 65 070705 Google Scholar
[16]	秦杰明, 张莹, 曹建明, 田立飞, 董中伟, 李岳 2011 60 036105 Google Scholar Qin J M, Zhang Y, Cao J M, Tian L F, Dong Z W, Li Y 2011 Acta Phys. Sin. 60 036105 Google Scholar
[17]	Sumiya H, Toda N, Nishibayashi Y, Satoh S 1997 J. Crystal Growth 178 485 Google Scholar
[18]	Liang Z Z, Jia X P, Ma H A, Zang C Y, Zhu P W, Guan Q F, Kanda H 2005 Diamond Relat. Mater. 14 1932 Google Scholar
[19]	Ma L Q, Ma H A, Xiao H Y, Li S S, Li Y, Jia X P 2010 Chin. Sci. Bull. 55 677 Google Scholar
[20]	Zhang J Q, Ma H A, Jiang Y P, Liang Z Z, Tian Y, Jia X P 2007 Diamond Relat. Mater. 16 283 Google Scholar
[21]	李勇, 李宗宝, 宋谋胜, 王应, 贾晓鹏, 马红安 2016 65 118103 Google Scholar Li Y, Li Z B, Song M S, Wang Y, Jia X P, Ma H A 2016 Acta Phys. Sin. 65 118103 Google Scholar
[22]	王应, 李勇, 李宗宝 2016 65 087101 Google Scholar Wang Y, Li Y, Li Z B 2016 Acta Phys. Sin. 65 087101 Google Scholar

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