Influence of B<sub>2</sub>S<sub>3 </sub>additive on [111]-oriented diamond crystal synthesized under high pressure condition

WANG Shuai; KANG Ruwei; LI Yong; XIAO Hongyu; WANG Ying; RAN Maowu; MA Hongan

doi:10.7498/aps.74.20250028

Abstract

Diamond is a kind of extremely functional material, which is widely used in the fields of industry, science and technology, military defense, medical and health, jewelry, and others. However, its application in the semiconductor field is still limited, because its electrical transport performance has not yet met the requirements of semiconductor devices. In order to improve the electrical transport performance of diamond as much as possible, the synthesis of diamond single crystal is studied by adding B₂S₃ to the synthesis system using temperature gradient growth (TGG) method at a pressure of 6.5 GPa in this work. The growth rate of the synthesized diamond crystal decreases from 2.19 mg/h to 1.26 mg/h, indicating that the growth rate of diamond is dependent not only on the growth driving force, but also on the impurity element in the synthetic cavity. Additionally, with the increase of additive dosage, the color of the synthesized diamond crystal changes from yellow to baby blue . Raman measurement results indicate that the obtained diamond appears as a single sp³ hybrid phase without the sp³ hybrid graphite phase. However, the corresponding Raman characteristic peak of the as-grown diamond crystal is located at about 1331 cm^–1 and tends to move towards low wave number. According to Fourier Transform Infrared Spectrometer (FTIR) measurement results, the absorption peaks at 1130 cm^–1 and 1344 cm^–1 are attributed to nitrogen defects. It is found that the nitrogen defect concentration of the synthesized diamond crystal decreases gradually from about 300×10^–6 to 60×10^–6. Furthermore, the electrical transport performance of the synthesized diamond is characterized by Hall effect measurement. Diamond has insulating properties due to the absence of any additives in the synthetic cavity. However, the results indicate that when B₂S₃ is introduced into the synthetic system as additive, there is almost no difference in carrier Hall mobility, but the difference in carrier concentration is as high as two orders of magnitude. Furthermore, the resistivity of the synthesized [111]-oriented diamond crystal decreases to 45.4 Ω·cm, due to the addition of B₂S₃ to the synthesis system. However, it is worth noting that the resistivity of the diamond crystal synthesized with 0.002 g B₂S₃ and Ti/Cu additives in the synthesis system drops sharply to 0.43 Ω·cm. Therefore, the nitrogen defects in diamond will have an important effect on its conductivity. It provides an important experimental basis for applying diamond to semiconductor field.

Keywords:

Authors and contacts

1.
Department of Physics and Electrical Engineering, Tongren University, Tongren 554300, China
2.
State Key Laboratory of High Pressure and Superhard Materials, JilinUniversity, Changchun 130012, China

Corresponding author: LI Yong, likaiyong6@163.com ; MA Hongan, maha@jlu.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 12064038), the Foundation for Excellent Scholars of Guizhou Province, China (Grant No. GCC[2023]087), and the Science and Technology Department of Guizhou Province, China (Grant Nos. ZK[2021]021, ZK [2023] 467).

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References

[1]	Bhattacharyya P, Chen W, Huang X, et al. 2024 Nature 627 73 Google Scholar
[2]	Tong K, Zhang X, Li Z H, et al. 2024 Nature 626 79 Google Scholar
[3]	Rodrigo M A, Canizares P, Carretero A S, Saez C 2010 Catal. Today 151 173 Google Scholar
[4]	Zhang D X, Zhao Q, Zang J H, Lu Y J, Dong L, Shan C X 2018 Carbon 27 170
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[22]	Li Y, Tan D B, Wang Q, Xiao Z G, Tian C H, Chen L 2020 Chin. Phys. B 29 098103 Google Scholar
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图 1 金刚石高温高压合成的组装剖面示意图　1, 导电钢帽; 2, 白云石; 3, 石墨管; 4, 叶蜡石; 5, 石墨; 6, 触媒; 7, 籽晶; 8, 绝缘材料

Figure 1. Schematic diagram of the cell for diamond HPHT synthesis: 1, conductive ring; 2, dolomite; 3, graphite heater; 4, pyrophyllite; 5, carbon source; 6, catalyst; 7, seed crystal; 8, insulation materials.

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图 2 温度梯度产生示意图

Figure 2. Schematic diagram of the temperature gradient generated.

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图 3 金刚石样品光学照片　(a) 无添加剂; (b)添加0.01 g B₂S₃; (c) 添加0.03 g B₂S₃; (d) 添加0.002 g B₂S₃+钛/铜

Figure 3. Optical morphology of the synthesized diamond crystals: (a) Without any additive; (b) with 0.01 g B₂S₃ additive; (c) with 0.03 g B₂S₃ additive; (d) with 0.002 g B₂S₃ + Ti/Cu additives.

DownLoad: Full-Size Img PowerPoint

图 4 金刚石晶体Raman光谱

Figure 4. Raman spectra of the obtained diamond crystals.

DownLoad: Full-Size Img PowerPoint

图 5 金刚石样品FTIR光谱

Figure 5. FTIR spectra of the synthesized diamond crystals

DownLoad: Full-Size Img PowerPoint

表 1 金刚石合成实验参数

Table 1. Experimental parameters for diamond synthesis.

金刚石样品	B₂S₃/g	合成温度/℃	生长时间/h	形貌	生长速率/(mg·h^–1)
1	—	1330	21	六八面体	2.19
2	0.01	1330	21	六八面体	1.98
3	0.03	1325	21	六八面体	1.83
4	0.002+Ti/Cu	1335	21	六八面体	1.26

DownLoad: CSV

表 2 金刚石晶体Raman测试结果

Table 2. Raman measurement results of the synthesized diamond crystals.

金刚石样品	特征峰位/cm^–1	FWHM/cm^–1	内应力/MPa
1	1330.9	5.3370	382
2	1330.9	5.3175	382
3	1131.0	5.4276	347
4	1330.4	5.2285	555

DownLoad: CSV

表 3 金刚石电输运性能参数

Table 3. Electric transport performance parameters of the obtained diamond crystals.

样品	B₂S₃/ g	电阻率/ (Ω·cm)	载流子浓度/ cm^–3	迁移率/ (cm^–2·v^–1·s^–1)	类型
1	—	—	—	—	—
2	0.01	8.98×10	6.63×10¹⁴	1.05×10²	p
3	0.03	4.54×10	2.81×10¹⁴	4.88×10²	p
4	0.002+Ti/Cu	4.33×10^–1	3.39×10¹⁶	4.25×10²	p

DownLoad: CSV

[1]	Bhattacharyya P, Chen W, Huang X, et al. 2024 Nature 627 73 Google Scholar
[2]	Tong K, Zhang X, Li Z H, et al. 2024 Nature 626 79 Google Scholar
[3]	Rodrigo M A, Canizares P, Carretero A S, Saez C 2010 Catal. Today 151 173 Google Scholar
[4]	Zhang D X, Zhao Q, Zang J H, Lu Y J, Dong L, Shan C X 2018 Carbon 27 170
[5]	Huang G F, Jia X P, Li Y, Hu M H, Li Z C, Yan B M, Ma H A 2011 Chin. Phys. B 20 78103 Google Scholar
[6]	Li Y, Chen X Z, Ran M W, She Y C, Xiao Z G, Hu M H, Wang Y, An J 2022 Chin. Phys. B 31 046107 Google Scholar
[7]	Li Y, Jia X P, Hu M H, Liu X B, Yan B M, Zhou Z X, Fang C, Zhang Z F, Ma H A 2012 Chin. Phys. B 21 058101 Google Scholar
[8]	Li Y, Jia X P, Song M S, Ma H A, Z X, Fang C, Wang F B, Chen N, Wang Y 2015 Mod. Phys. Lett. B 29 1550162
[9]	Du J B, Liu H Z, Yang N, Chen X Z, Zong W J 2023 Appl. Surf. Sci. 637 157882 Google Scholar
[10]	Li Y, Liao J H, Wang Y, She Y C, Xiao Z G, An J 2020 Opt. Mater. 101 109735 Google Scholar
[11]	Song Y W, Fang C, Mu Y H, Li Y D, Shen W X, Zhang Z F, Zhang Y W, Qang Q Q, Wan B, Chen L C, Jia X P 2023 CrystEngComm 25 357 Google Scholar
[12]	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
[13]	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
[14]	肖宏宇, 李勇, 鲍志刚, 佘彦超, 王应, 李尚升 2023 物理学报 72 020701 Google Scholar Xiao H Y, Li Y, Bao Z G, She Y C, Wang Y, Li S S 2023 Acta Phys. Sin. 72 020701 Google Scholar
[15]	Gheeraert E, Koizumi S, Teraj T, Kanda H, Nesladek M 2000 Diamond Relat. Mater. 9 948 Google Scholar
[16]	Jackson K, Pederson M R, Harrison J G 1990 Phys. Rev. B 41 12641 Google Scholar
[17]	Katayama-Yoshida H, Nishimatsu T, Yamamoto T, Orita N 2001 J. Phys. Conderns. Matter 13 8901 Google Scholar
[18]	Liu X B, Chen X, Singh D J, Stern R A, Wu J S, Petitgrard S, Bina C R, Jacobsen S D 2019 PANS 116 7703 Google Scholar
[19]	Hu X J, Li R B, Shen H S, Dai Y B, He X C 2014 Carbon 42 1501
[20]	Li Y, Jia X P, Ma H A, Zhang J, Wang F B, Chen N, Feng Y G 2014 CrystEngComm 16 7547 Google Scholar
[21]	马利秋, 马红安, 肖宏宇, 李尚升, 李勇, 贾晓鹏 2010 科学通报 55 418 Ma L Q, Ma H A, Xiao H Y, Li S S, Li Y, Jia X P 2010 Chin. Sci. Bull. 55 418
[22]	Li Y, Tan D B, Wang Q, Xiao Z G, Tian C H, Chen L 2020 Chin. Phys. B 29 098103 Google Scholar
[23]	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
[24]	Catledge S A, Vohra Y K, Ladi R, Rai G 1996 Diam. Relat. Mater. 5 1159 Google Scholar
[25]	Li Y, Jia X P, Yan B M, Zhou Z X, Fang C, Zhang Z F, Sun S S, Ma H A 2012 J. Crys. Growth 359 49 Google Scholar

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Influence of B₂S₃additive on [111]-oriented diamond crystal synthesized under high pressure condition

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Corresponding author: LI Yong, likaiyong6@163.com ; MA Hongan, maha@jlu.edu.cn

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Influence of B2S3 additive on [111]-oriented diamond crystal synthesized under high pressure condition

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Corresponding author: LI Yong, likaiyong6@163.com ; MA Hongan, maha@jlu.edu.cn

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Influence of B₂S₃additive on [111]-oriented diamond crystal synthesized under high pressure condition