硼协同掺杂金刚石单晶的高温高压合成

人工晶体学报 ›› 2022, Vol. 51 ›› Issue (5): 830-840.

所属专题：超硬材料与特殊环境晶体生长技术

硼协同掺杂金刚石单晶的高温高压合成

王志文¹, 马红安¹, 陈良超², 蔡正浩¹, 贾晓鹏¹

1.吉林大学超硬材料国家重点实验室,长春 130012;
2.郑州大学材料物理教育部重点实验室,郑州 450052

收稿日期:2022-02-10 出版日期:2022-05-15 发布日期:2022-06-17
通信作者: 贾晓鹏,教授。E-mail:jiaxp@jlu.edu.cn
作者简介:王志文(1999—),男,山东省人,硕士研究生。E-mail:1505000191@qq.com; 贾晓鹏,教育部“重大人才工程奖励计划”特聘教授,吉林大学唐敖庆学者卓越教授,博士生导师,《金刚石与磨料磨具工程》《超硬材料工程》等学术刊物编委。1996年于日本国立筑波大学获得工学博士学位。1999年12月作为教育部特聘教授回到吉林大学超硬材料国家重点实验室工作至今。研究方向为超硬和多功能材料的高温高压合成与应用。在宝石级金刚石、高品级工业金刚石、立方氮化硼,以及热电材料和功能陶瓷等的高温高压合成与应用研究领域,取得了一系列的创新成果。部分研究成果已实现了工业化生产,为企业发展提供了坚强的技术支持。在其研究领域权威学术杂志期刊上已发表国际期刊学术论文200余篇,获多项发明专利,作为项目负责人主持了多项国家自然科学基金项目。
基金资助:
国家自然科学基金(51772120,51872112,11804305,11604246);中央高校基本科研业务费专项资金

HPHT Synthesis of Boron Co-Doped Single Crystal Diamond

WANG Zhiwen¹, MA Hongan¹, CHEN Liangchao², CAI Zhenghao¹, JIA Xiaopeng¹

1. State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012, China;
2. Key Laboratory of Material Physics of Ministry of Education, Zhengzhou University, Zhengzhou 450052, China

Received:2022-02-10 Online:2022-05-15 Published:2022-06-17

摘要/Abstract

摘要： 金刚石是一种具有优异性能的极限性超硬多功能材料。人工合成的金刚石可通过掺杂的方式使其具有各种独特的性质。掺硼金刚石兼具p型半导体的导电特性和金刚石自身优良的物理和化学性能,在国防、医疗、勘探、科研等领域具有极高的应用价值。本文基于本课题组高温高压(HPHT)法合成的系列掺硼金刚石以及硼协同掺杂金刚石单晶,进行了硼掺杂金刚石、硼氢协同掺杂金刚石以及硼氮协同掺杂金刚石的合成和性能特征等方面的研究。通过表征合成样品在光学、电学方面的性能,探讨了不同掺杂添加剂对合成金刚石性能的影响,为合成高性能的半导体金刚石提供了思路。

关键词: 掺硼金刚石, 高温高压, 超硬材料, 晶体生长, 协同掺杂, 霍尔效应, 半导体金刚石

Abstract: Diamond is a superhard and multi-functional material with excellent properties. Synthetic diamond can own unique properties by doping. Boron-doped diamond has both conductive characteristics of p-type semiconductor and excellent physical and chemical properties. It has wide application value in national defense, medical treatment, exploration, scientific research and other fields. Based on boron-doped diamond and boron co-doped diamond single crystals synthesized by high pressure and high temperature (HPHT) method in our laboratory, the synthesis and properties of boron-doped diamond, boron-hydrogen co-doped diamond and boron-nitrogen co-doped diamond are discussed. The influence of different additives on the synthesis properties of the synthetic diamonds through the optical and electrical characterization are analyzed, which provides some ideas for further synthesizing high-performance semiconductor diamonds.

Key words: boron-doped diamond, HPHT, superhard material, crystal growth, co-doping, Hall effect, semiconductor diamond

中图分类号:

TQ163

王志文, 马红安, 陈良超, 蔡正浩, 贾晓鹏. 硼协同掺杂金刚石单晶的高温高压合成[J]. 人工晶体学报, 2022, 51(5): 830-840.

WANG Zhiwen, MA Hongan, CHEN Liangchao, CAI Zhenghao, JIA Xiaopeng. HPHT Synthesis of Boron Co-Doped Single Crystal Diamond[J]. Journal of Synthetic Crystals, 2022, 51(5): 830-840.

参考文献

[1] LIANG Z Z, KANDA H, JIA X, et al. Synthesis of diamond with high nitrogen concentration from powder catalyst-C-additive NaN₃ by HPHT[J]. Carbon, 2006, 44(5): 913-917.
[2] UMEZAWA H, NAGASE M, KATO Y, et al. High temperature application of diamond power device[J]. Diamond and Related Materials, 2012, 24: 201-205.
[3] FANG S, MA HONGAN, CAI Z H, et al. Study on the characteristics of Ib diamond crystals synthesized with Fe₃O₄ doped in an Fe-Ni-C system[J]. CrystEngComm, 2020, 22(22): 3854-3862.
[4] FANG C, JIA X P, CHEN N, et al. Crystal growth and characterization of hydrogen-doped single diamond with Fe(C₅H₅)₂ additive[J]. Acta Physica Sinica, 2015, 64(12): 128101.
[5] HUMBLE P. The structure and mechanism of formation of platelets in natural type Ia diamond[J]. Proceedings of the Royal Society of London A Mathematical and Physical Sciences, 1982, 381(1780): 65-81.
[6] GEIS M W, TWICHELL J C, EFREMOW N N, et al. Comparison of electric field emission from nitrogen-doped, type Ib diamond, and boron-doped diamond[J]. Applied Physics Letters, 1996, 68(16): 2294-2296.
[7] 肖宏宇.优质克拉级金刚石大单晶的高温高压合成[D].长春:吉林大学,2010.
XIAO H Y. Growth of high-quality large diamond single crystals in carats grade under HPHT[D]. Changchun: Jilin University, 2010(in Chinese).
[8] KALISH R. The search for donors in diamond[J]. Diamond and Related Materials, 2001, 10(9/10): 1749-1755.
[9] SIDOROV V A, EKIMOV E A, BAUER E D, et al. Superconductivity in boron-doped diamond[J]. Diamond and Related Materials, 2005, 14(3/4/5/6/7): 335-339.
[10] EKIMOV E A, SIDOROV V A, BAUER E D, et al. Superconductivity in diamond[J]. Nature, 2004, 428(6982): 542-545.
[11] YANG N J, YU S Y, MACPHERSON J V, et al. Conductive diamond: synthesis, properties, and electrochemical applications[J]. Chemical Society Reviews, 2019, 48(1): 157-204.
[12] WOOD G F, ZVORISTE-WALTERS C E, MUNDAY M G, et al. High pressure high temperature synthesis of highly boron doped diamond microparticles and porous electrodes for electrochemical applications[J]. Carbon, 2021, 171: 845-856.
[13] PICKETT W E. Negative electron affinity and low work function surface: cesium on oxygenated diamond (100)[J]. Physical Review Letters, 1994, 73(12): 1664-1667.
[14] HEIM C, UREÑA DE VIVANCO M, RAJAB M, et al. Rapid inactivation of waterborne bacteria using boron-doped diamond electrodes[J]. International Journal of Environmental Science and Technology, 2015, 12(10): 3061-3070.
[15] RAJAB M, HEIM C, LETZEL T, et al. Electrochemical disinfection using boron-doped diamond electrode-the synergetic effects of in situ ozone and free chlorine generation[J]. Chemosphere, 2015, 121: 47-53.
[16] LI J H, WANG Q L, LIU Y F, et al. Boron/nitrogen co-doped diamond electrode for highly efficient electrochemistry detection of aniline[J]. Functional Diamond, 2021, 1(1): 135-142.
[17] CHEN Y H, GAO X L, LIU G S, et al. Correlation of the role of boron concentration on the microstructure and electrochemical properties of diamond electrodes[J]. Functional Diamond, 2021, 1(1): 197-204.
[18] LIU X B, CHEN X, SINGH D J, et al. Boron-oxygen complex yields n-type surface layer in semiconducting diamond[J]. Proceedings of the National Academy of Sciences of the United States of America, 2019, 116(16): 7703-7711.
[19] ZHOU D L, TANG L, GENG Y W, et al. First-principles calculation to n-type LiN co-doping and Li doping in diamond[J]. Diamond and Related Materials, 2020, 110: 108070.
[20] LI Z B, LI Y, WANG Y, et al. Synergistic effect in B and N co-doped Ⅰb-type diamond single crystal: a density function theory calculation[J]. Canadian Journal of Physics, 2016, 94(9): 929-932.
[21] WU Y Z, TONG J W, RUAN L X, et al. N-type diamond semiconductor induced by co-doping selenium and boron[J]. Computational Materials Science, 2021, 196: 110515.
[22] 马利秋.高温高压下掺硼宝石级金刚石的合成[D].长春:吉林大学,2009.
MA L Q. The synthesis of gem diamond crystals with boron-doped under HPHT[D]. Changchun: Jilin University, 2009 (in Chinese).
[23] 苗辛原.硼氮共掺杂金刚石的高温高压合成与杂质行为研究[D].长春:吉林大学,2020.
MIAO X Y. HPHT synthesis and impurities research of boron and nitrogen co-doped diamonds[D]. Changchun: Jilin University, 2020(in Chinese).
[24] BERNARD M, BARON C, DENEUVILLE A. About the origin of the low wave number structures of the Raman spectra of heavily boron doped diamond films[J]. Diamond and Related Materials, 2004, 13(4/5/6/7/8): 896-899.
[25] MORTET V, ŽIVCOVÁ Z V, TAYLOR A, et al. Insight into boron-doped diamond Raman spectra characteristic features[J]. Carbon, 2017, 115: 279-284.
[26] BLANK V D, DENISOV V N, KIRICHENKO A N, et al. Raman scattering by defect-induced excitations in boron-doped diamond single crystals[J]. Diamond and Related Materials, 2008, 17(11): 1840-1843.
[27] 赵占东.不同金属溶剂体系合成B-H共掺杂金刚石单晶[D].长春:吉林大学,2021.
ZHAO Z D. Synthesis of B-H co-doped diamond single crystals in differentmetal solvent systems[D]. Changchun: Jilin University, 2021(in Chinese).
[28] TEUKAM Z, CHEVALLIER J, SAGUY C, et al. Shallow donors with high n-type electrical conductivity in homoepitaxial deuterated boron-doped diamond layers[J]. Nature Materials, 2003, 2(7): 482-486.
[29] 李勇. 氢协同掺杂大尺寸金刚石单晶的高温高压合成与表征[D].长春:吉林大学,2013.
LI Y. The synthesis and characterization of H co-doped diamond large single crystal under high pressure and high temperature[D]. Changchun: Jilin University, 2013(in Chinese).
[30] MAVRIN B N, DENISOV V N, POPOVA D M, et al. Boron distribution in the subsurface region of heavily doped Ⅱb type diamond[J]. Physics Letters A, 2008, 372(21): 3914-3918.
[31] BLANK V D, KUZNETSOV M S, NOSUKHIN S A, et al. The influence of crystallization temperature and boron concentration in growth environment on its distribution in growth sectors of type IIb diamond[J]. Diamond and Related Materials, 2007, 16(4/5/6/7): 800-804.
[32] 周振翔.多元掺杂体系下金刚石大单晶合成的研究[D].长春:吉林大学,2015.
ZHOU Z X. Study on the effect of several elements synergistic doped on the synthesis of large single diamond crystals[D]. Changchun: Jilin University, 2015(in Chinese).
[33] BOGDANOWICZ R, RYL J. Structural and electrochemical heterogeneities of boron-doped diamond surfaces[J]. Current Opinion in Electrochemistry, 2022, 31: 100876.
[34] LI R B. A molecular dynamics study of boron and nitrogen in diamond[J]. Solid State Communications, 2005, 135(3): 155-157.
[35] MIAO X Y, CHEN L C, MA H A, et al. High-pressure and high-temperature treatment of N-rich B-doped diamonds[J]. CrystEngComm, 2019, 21(26): 3961-3965.
[36] HU M H, BI N, LI S S, et al. Synthesis and characterization of boron and nitrogen co-doped diamond crystals under high pressure and high temperature conditions[J]. CrystEngComm, 2017, 19(31): 4571-4575.
[37] DE WEERDT F, COLLINS A T. Determination of the C defect concentration in HPHT annealed type ⅠaA diamonds from UV-VIS absorption spectra[J]. Diamond and Related Materials, 2008, 17(2): 171-173.
[38] MIAO X Y, MA H A, ZHANG Z F, et al. Synthesis and characterizations of boron and nitrogen co-doped high pressure and high temperature large single-crystal diamonds with increased mobility[J]. Chinese Physics B, 2021, 30(6): 068102.
[39] FANG C, JIA X P, SUN S S, et al. Studying the effect of hydrogen on diamond growth by adding C₁₀H₁₀Fe under high pressures and high temperatures[J]. High Pressure Research, 2016, 36(1): 42-54.
[40] ZHANG H, LI S S, SU T C, et al. Large single crystal diamond grown in FeNiMnCo-S-C system under high pressure and high temperature conditions[J]. Chinese Physics B, 2016, 25(11): 118104.
[41] ZHANG H, LI S S, SU T C, et al. Synthesis of N-type semiconductor diamonds with sulfur, boron co-doping in FeNiMnCo-C system at high pressure and high temperature[J]. Chinese Physics B, 2017, 26(5): 058102.
[42] 陈宁.硫(氢)掺杂金刚石单晶的高压合成及金刚石色心研究[D].长春:吉林大学,2018.
CHEN N. Synthesis and color center research of S(H) doped diamond under high pressure[D]. Changchun: Jilin University, 2018(in Chinese).

编辑推荐

Metrics

阅读次数

全文

255

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	0	0	0	255

来源	本网站	其他网站

次数	254	1
比例	100%	0%

摘要

169

最新录用	在线预览	正式出版

0	0	169

	来源	本网站

	次数	169
	比例	100%

硼协同掺杂金刚石单晶的高温高压合成

HPHT Synthesis of Boron Co-Doped Single Crystal Diamond

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	许万里, 甘云海, 李悦文, 李彬, 郑有炓, 张荣, 修向前. 高均匀性6英寸GaN厚膜的高速率HVPE生长研究[J]. 人工晶体学报, 2025, 54(1): 11-16.
[2]	孙元龙, 胡子钰, 郑国宗. 大尺寸CH₃NH₃PbBr₃晶体生长和光电性能表征[J]. 人工晶体学报, 2024, 53(8): 1313-1318.
[3]	马启司, 刘江高, 折伟林, 曹聪, 张立超, 赵超, 范叶霞, 周振奇. 基于CGSim模拟的炉膛空气对流对碲锌镉晶体生长温场影响研究[J]. 人工晶体学报, 2024, 53(8): 1344-1351.
[4]	凌昊, 徐乐, 陈思贤, 唐远之, 孙海滨, 郭学, 冯玉润, 胡强强. 溶液法生长大尺寸CsCu₂I₃钙钛矿单晶及其光学性能研究[J]. 人工晶体学报, 2024, 53(7): 1121-1126.
[5]	肖宏宇, 李勇, 田昌海, 张蔚曦, 王强, 肖政国, 王应, 金慧, 鲍志刚, 周振翔. Ib型金刚石单晶生长及合成腔体温度场分布研究[J]. 人工晶体学报, 2024, 53(6): 959-966.
[6]	艾家辛, 万洪平, 钱俊兵, 韦华. VGF法磷化铟单晶炉加热器对炉内热场分布影响的研究[J]. 人工晶体学报, 2024, 53(5): 781-791.
[7]	邢佳斌, 李威, 贾松岩, 马亚丽, 李雪, 郑强. 低温碳化法制备高分散性纳米碳酸钙的研究[J]. 人工晶体学报, 2024, 53(5): 864-872.
[8]	黄昌保, 胡倩倩, 朱志成, 李亚, 毛长宇, 徐俊杰, 吴海信, 倪友保. 中长波Cr²⁺/Fe²⁺∶CdSe激光晶体生长及元件制备[J]. 人工晶体学报, 2024, 53(4): 551-553.
[9]	秦峰, 吴金杰, 邓宁勤, 焦志伟, 朱伟峰, 汤显强, 赵瑞. 基于溶液法制备卤化铅钙钛矿的直接型辐射探测器研究进展[J]. 人工晶体学报, 2024, 53(4): 554-571.
[10]	曹聪, 刘江高, 范叶霞, 李振兴, 周振奇, 马启司, 牛佳佳. 碲锌镉晶体生长温度梯度与界面形状稳定性关系的研究[J]. 人工晶体学报, 2024, 53(4): 641-648.
[11]	郝敬林, 邓丽芬, 王凯悦, 宋惠, 江南, 西村一仁. 高温高压合成掺杂金刚石研究进展[J]. 人工晶体学报, 2024, 53(2): 194-209.
[12]	王坤元, 梁小燕, 闵嘉华, 张继军. 原位热处理对碲锌镉晶体质量和性能的影响[J]. 人工晶体学报, 2024, 53(12): 2079-2084.
[13]	李冬梅, 周俊, 吴非凡, 吕家波, 肖黎, 龚恒翔. 静电场对超声雾化热解喷涂制备TiO₂薄膜的影响研究[J]. 人工晶体学报, 2024, 53(12): 2173-2180.
[14]	任永春, 李健达, 曹笑, 黄燚, 张帆, 张宁, 薛艳艳, 王庆国, 唐慧丽, 徐晓东, 董永军, 徐军. 高熔点稀土氧化物激光晶体的研究进展[J]. 人工晶体学报, 2024, 53(11): 1829-1839.
[15]	郭俊, 刘坚, 王泽彬, 陈鹏, 宋青松, 马杰, 王庆国, 徐晓东, 徐军. Nd∶ASL单晶光纤的生长、光谱和激光性能研究[J]. 人工晶体学报, 2024, 53(11): 1877-1883.