纳米金刚石的结构、光学性能和热稳定性研究

人工晶体学报 ›› 2022, Vol. 51 ›› Issue (5): 920-925.

纳米金刚石的结构、光学性能和热稳定性研究

程学瑞^1,2, 皇甫战彪², 蔡玉乐¹, 武玺旺¹, 杨坤²

1.河南黄河旋风股份有限公司,许昌 461500;
2.郑州轻工业大学物理与电子工程学院,郑州 450002

收稿日期:2021-12-27 出版日期:2022-05-15 发布日期:2022-06-17
通讯作者: 杨坤,博士,教授。E-mail:yyyk2002@163.com
作者简介:程学瑞(1982—),男,河南省人,博士。E-mail:xrcheng@zzuli.edu.cn; 杨坤,郑州轻工业大学教授,硕士生导师。主要从事光学测量与传感和光谱分析研究,发展了高压条件下折射率、粘滞系数等物理量的原位测试技术,开展荧光探针、二维材料、纳米金刚石等功能材料的光学研究。现任中国光学学会光学测试专业委员会委员、河南省光学学会常务理事、河南省物理学会理事。
基金资助:
国家自然科学基金(12104415);河南省高等学校重点科研项目(21B140011)

Structure, Optical Properties and Thermal Stability of Nanodiamond

CHENG Xuerui^1,2, HUANGFU Zhanbiao², CAI Yule¹, WU Xiwang¹, YANG Kun²

1. Henan Huanghe Whirlwind Co.,Ltd, Xuchang 461500, China;
2. College of Physics and Electrical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, China

Received:2021-12-27 Online:2022-05-15 Published:2022-06-17

摘要/Abstract

摘要： 纳米金刚石兼具纳米材料和金刚石的双重特性,呈现出与微米金刚石、块体金刚石截然不同的特点。本文以不同尺寸金刚石样品为研究对象,采用扫描电镜、X射线衍射、光谱学、热重分析技术对其结构、光学性能和热稳定性进行研究。结果显示样品尺寸分别为300 μm、30 μm和100 nm,大尺寸样品结晶质量较好,富含孤氮杂质,为Ⅰb型金刚石。纳米金刚石样品结晶较差,含有少量石墨残留,并含有H₂O、N—H和C—H键,说明其表面存在诸多有机活性基团。大尺寸金刚石样品存在中性和带负电荷的氮空位缺陷,产生较强荧光,而纳米金刚石由于存在诸多的有机基团和表面缺陷,形成非辐射中心,导致荧光猝灭。大尺寸样品在300~525 nm具有较强吸收,而纳米金刚石样品在紫外-可见-近红外整个区域均呈现出较强吸收,透过率显著较低。随着颗粒尺寸的减小,金刚石的起始氧化温度逐渐下降,氧化速率降低,因此大颗粒尺寸金刚石样品具有更好的热稳定性。

关键词: 金刚石, 纳米金刚石, 颗粒尺寸, 缺陷, 热稳定性, 荧光, 拉曼光谱

Abstract: Nanodiamond combines the properties of both nanomaterials and diamond materials, resulting in different characteristics from that of micron and bulk diamond. In this work, the structure, optical properties and thermal stability of diamond samples with different sizes were studied by scanning electron microscopy, X-ray diffraction, spectroscopy techniques and thermogravimetric analysis. The results show that the sizes of three samples are 300 μm, 30 μm and 100 nm, respectively. Diamond samples with larger size present better crystal quality, and are confirmed to be Ⅰb type diamond because single nitrogen impurities are observed. In contrast, the crystallinity of nanodiamond samples is poor, and residual graphite is detected in nanodiamond samples from both XRD and Raman results. In addition, H₂O, N—H and C—H bonds are observed in nanodiamond, suggesting there may be many organic reactive groups on surface. Two emission peaks are observed in both samples of 300 μm and 30 μm, originated from two types of nitrogen vacancy defects with neutral and negative charge respectively. In contrast, no emission is observed for nanodiamond because of fluorescence quenching from nonradiative center originated from organic groups and surface defects in the nanodiamond. Diamond samples with large size have the intensive absorption in the range from 300 nm to 525 nm, while the nanodiamond sample show strong absorption in the entire UV-visible-NIR region resulting in much lower transmittance. With the decrease of particle size, both the initial oxidizing temperature and oxidizing rate gradually decline. As a result, larger size samples have better thermal stability.

Key words: diamond, nanodiamond, particle size, defect, thermal stability, fluorescence, Raman spectra

中图分类号:

程学瑞, 皇甫战彪, 蔡玉乐, 武玺旺, 杨坤. 纳米金刚石的结构、光学性能和热稳定性研究[J]. 人工晶体学报, 2022, 51(5): 920-925.

CHENG Xuerui, HUANGFU Zhanbiao, CAI Yule, WU Xiwang, YANG Kun. Structure, Optical Properties and Thermal Stability of Nanodiamond[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(5): 920-925.

参考文献

[1] 王芬芬,李剑云,靳玮.纳米金刚石表面修饰工艺研究[J].超硬材料工程,2020,32(3):25-31.
WANG F F, LI J Y, JIN W. Study on surface modification of nano diamond[J]. Superhard Material Engineering, 2020, 32(3): 25-31(in Chinese).
[2] 杨扬,张文军.一维纳米金刚石的制备、性质及应用[J].科学通报,2019,64(35):3665-3685.
YANG Y, ZHANG W J. One-dimensional diamond nanostructures: synthesis, properties and applications[J]. Chinese Science Bulletin, 2019, 64(35): 3665-3685(in Chinese).
[3] GORELIK V S, PYATYSHEV A Y. Raman scattering in diamond nano- and microcrystals, synthesized at high temperatures and high pressures[J]. Diamond and Related Materials, 2020, 110: 108104.
[4] SIMAKOV S K. Nano- and micron-sized diamond genesis in nature: an overview[J]. Geoscience Frontiers, 2018, 9(6): 1849-1858.
[5] YOSHIKAWA M, MORI Y, OBATA H, et al. Raman scattering from nanometer-sized diamond[J]. Applied Physics Letters, 1995, 67(5): 694-696.
[6] HAINSCHWANG T, NOTARI F, PAMIES G. The origin of color of 1330 nm center diamonds[J]. Diamond and Related Materials, 2020, 110: 108151.
[7] GORELIK V S, SKRABATUN A V, BI D X. Raman scattering of light in diamond microcrystals[J]. Crystallography Reports, 2019, 64(3): 428-432.
[8] 张金辉,李敬,郁建元.石墨烯/纳米金刚石复合电极性能研究[J].金刚石与磨料磨具工程,2021,41(4):31-35.
ZHANG J H, LI J, YU J Y. Properties of graphene/nano diamond composite electrode[J]. Diamond & Abrasives Engineering, 2021, 41(4): 31-35(in Chinese).
[9] YAN X R, LI X J, WANG X H, et al. Preparation and characterization of boron-doped nanodiamond[J]. Rare Metal Materials and Engineering, 2018, 47(12): 3634-3639.
[10] 冯园耀,李中豪,张扬,等.固态金刚石氮空位色心光学调控优化[J].物理学报,2020,69(14):228-233.
FENG Y Y, LI Z H, ZHANG Y, et al. Optimization of optical control of nitrogen vacancy centers in solid diamond[J]. Acta Physica Sinica, 2020, 69(14): 228-233(in Chinese).
[11] 文潮,金志浩,刘晓新,等.炸药爆轰合成纳米金刚石的拉曼光谱和红外光谱研究[J].光谱学与光谱分析,2005,25(5):681-684.
WEN C, JIN Z H, LIU X X, et al. Studies on nano-diamond prepared by explosive detonation by Raman and infrared spectroscopy[J]. Spectroscopy and Spectral Analysis, 2005, 25(5): 681-684(in Chinese).
[12] 刘云贵,吕政星,宋海鹏,等.金刚石荧光机制的研究及其对高压拉曼光谱测试的意义[J].高压物理学报,2019,33(4):37-42.
LIU Y G, LÜ Z X, SONG H P, et al. Fluorescence mechanism of diamond and the significance in high pressure Raman spectrometry[J]. Chinese Journal of High Pressure Physics, 2019, 33(4): 37-42(in Chinese).
[13] 王凯悦,朱玉梅,李志宏,等.氮掺杂金刚石{100}晶面的缺陷发光特性[J].物理学报,2013,62(9):449-453.
WANG K Y, ZHU Y M, LI Z H, et al. The defect luminescences of {100} sector in nitrogen-doped diamond[J]. Acta Physica Sinica, 2013, 62(9): 449-453(in Chinese).
[14] 王凯悦,李志宏,张博,等.光致发光光谱研究金刚石光学中心的振动结构[J].物理学报,2012,61(12):505-510.
WANG K Y, LI Z H, ZHANG B, et al. Investigation of vibronic structures of optical centres in diamond by photoluminescence spectra[J]. Acta Physica Sinica, 2012, 61(12): 505-510(in Chinese).
[15] 黄严阵,郝全新.用差热分析测定人造金刚石热稳定性的几点探讨[J].超硬材料与工程,1998(4):22-23+18.
HUANG Y Z, HAO Q X. Discussion on determination of thermal stability of synthetic diamond by differential thermal analysis[J]. Superhard materail engineering, 1998(4): 22-23+18(in Chinese).