粉色CVD合成钻石的光致变色及光谱特征

doi:10.3964/j.issn.1000-0593(2025)11-3190-08

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摘要：无色合成钻石可经高温高压、辐照、低温退火多阶段处理形成NV色心而呈粉色，少量化学气相沉积法（CVD）合成钻石有NVH⁰与SiV^-色心致粉色。不同机理致粉色合成钻石经短波紫外线（225 nm）照射后发生变色，选取粉色CVD合成钻石进行短波紫外线（225 nm）与钻石分级荧光灯（6 500 K）照射实验，分析颜色变化、恢复时长及照射前后红外光谱（IR）、紫外-可见光谱（UV-Vis）、光致发光光谱（PL）特征，结果显示：样品在短波紫外线（225 nm）照射后，明度降低，整体变灰，颜色恢复需7～30 min；IR有极弱的N⁺_s所致1 332与950 cm^-1吸收峰/带，N⁰_s所致1 344与1 130 cm^-1吸收峰/带，显示样品含氮量极低，可归为Ⅱa型，短波紫外线（225 nm）照射后，1 344 cm^-1增强，1 332 cm^-1减弱；UV-Vis显示样品为NV色心致粉色，短波紫外线（225 nm）照射后，637 nm（NV^-）吸收强度变弱，NV⁰与NV^-吸收强度与各自吸收边带中心位置的变化，是颜色发生变化的主要原因；PL可见强575与637 nm发光峰，NV⁰峰强度为NV^-的2.5～6.5倍，多数样品见弱736.6与736.9 nm双峰（SiV^-），短波紫外线（225 nm）照射后NV⁰、NV^-与SiV^-强度呈不同程度降低，NV^-与其发光边带最明显，指示NV⁰、NV^-与SiV^-色心浓度呈不同程度降低，NV^-降低最为明显。综合分析认为，样品经短波紫外线（225 nm）照射，存在N⁺+NV^-↔N⁰+NV⁰与N⁺+SiV^-↔N⁰+SiV⁰，以及N⁰+NV⁰↔N^-+NV⁺或X^+/0+NV⁰↔X^0/-+NV⁺，导致部分NV⁰形成无光谱特征的NV⁺；NV^0/-色心的零声子线强度和吸收边带中心变化，导致样品颜色发生变化，白色光照可使其颜色恢复至初始状态。

关键词：粉色CVD合成钻石；NV色心；光致变色；光谱特征

Abstract：The formation of NV color centers in colorless synthetic diamonds involves multi-stage processes, including high-temperature, high-temperature high-pressure treatment, irradiation, and low-temperature annealing, resulting in a pink hue. Additionally, a small number of synthetic diamonds produced by the chemical vapor deposition (CVD) method may exhibit a pink color due to the presence of NVH⁰ and SiV^- color centers. Pink synthetic diamonds undergo a photochromic effect when exposed to short-wave ultraviolet radiation at 225 nm. An experimental study was condu cted on pink CVD synthetic diamonds by exposing them to short-wave ultraviolet radiation and diamond grading fluorescent lamps (6 500 K). The analysis focused on color changes, recovery times, and the characteristics of infrared (IR) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, and photoluminescence (PL) spectroscopy before and after exposure. The findings revealed that: After exposure to short-wavelength ultraviolet radiation, the samples exhibited a decrease in brightness, turning overall grayish, with color restoration occurring within 7 to 30 minutes. The infrared (IR) spectra displayed extremely weak absorption peaks/bands at 1 332 and 950 cm^-1 attributed to N⁺_s, as well as peask/bands at 1 344 and 1 130 cm^-1 attributed to N^-_s, indicating an extremely low nitrogen content in the samples, classifying them as type IIa. Following short-wavelength UV exposure, the peak at 1 344 cm^-1 intensified, while the peak at 1 332 cm^-1 weakened. The UV-Vis spectra confirmed that the pink color of the samples was due to NV color centers. After short-wavelength UV exposure, the absorption intensity at 637 nm (NV^-) weakened. Changes in the absorption intensities of NV⁰ and NV^- color centers, along with shifts in the centers of their respective absorption edge bands, were identified as the primary reasons for the color alterations. The PL spectra exhibited prominent luminescent peaks at 575 and 637 nm, attributed to NV⁰ and NV^-, respectively. The intensity of the NV⁰ peak was 2.5 to 6.5 times that of the NV^- peak. In most samples, weak double peaks at 736.6 and 736.9 nm (SiV^-) were also observed. After exposure to short-wavelength ultraviolet radiation, the luminescent peak intensities of NV⁰, NV^-, and SiV^- decreased to varying degrees, with the most pronounced decrease observed for NV⁰ and its luminescent sideband. This indicates that short-wavelength UV exposure caused a redu ction in the concentration of NV⁰, NV^-, and SiV^- color centers to varying extents, with NV^- experiencing the most significant decrease, suggesting its greatest instability under 225 nm UV light. Based on a comprehensive analysis, the samples are classified as pink due to NV color centers. Upon exposure to 225 nm UV radiation, rea ctions such as N⁺+NV^-↔N⁰+NV⁰ and N⁺+SiV^-↔N⁰+SiV⁰ occur, as well as N⁰+NV⁰↔N^-+NV⁺ or X^+/0+NV⁰↔X^0/-+NV⁺, leading to the formation of NV⁺. Changes in the zero-phonon line intensity and the center of the absorption edge band of NV^0/- color centers result in significant color of the samples. Exposure to white light was found to restore the color of the samples to their original state.

Key words：Pink CVD synthetic diamond; NV color center; Photochromism; Spectral characteristics

收稿日期: 2025-02-13 修订日期: 2025-08-15

中图分类号:

O77+3

基金资助: 国家自然科学基金项目(41403032)，广州市宝玉石及首饰材料创新团队项目（202235328），广州市教育局产教融合项目（2024312302），广州职业技术大学重大科研项目（2024KJ01）资助

通讯作者: 岳素伟，李坤 E-mail: yuesw@gzpyp.edu.cn; Lik@gzpyp.edu.cn

作者简介: 岳素伟，1985年生，广州职业技术大学珠宝学院教授 e-mail: yuesw@gzpyp.edu.cn

引用本文:

岳素伟，李坤，高诗佳，金莉莉. 粉色CVD合成钻石的光致变色及光谱特征[J]. 光谱学与光谱分析, 2025, 45(11): 3190-3197.
YUE Su-wei, LI Kun, GAO Shi-jia, JIN Li-li. Photochromism and Its Spectral Characteristics of Pink CVD Synthetic Diamond. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(11): 3190-3197.

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https://www.gpxygpfx.com/CN/10.3964/j.issn.1000-0593(2025)11-3190-08 或 https://www.gpxygpfx.com/CN/Y2025/V45/I11/3190

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