CVD合成蓝色钻石的显微特征及谱学特征

Microscopic and Spectroscopic Characteristics of CVD Synthetic Blue Diamond

  • 摘要: 天然蓝色钻石产量稀少且价格昂贵,主要流通于高端拍卖市场。随着市场需求增长,合成及改色处理的蓝色钻石逐渐进入人们的视野。目前,常见的高温高压法(HPHT)合成的掺硼蓝色钻石常因生长分区形成了十字形的颜色分布特征,人工辐照改色蓝色Ⅰa型钻石的蓝绿色调受N3和GR1两个色心的强弱控制,Ⅱa型钻石辐照后颜色主要受GR1色心控制,同时GR2-8色心辅助致色,因无法人为定量控制色心的强弱,颜色具有不稳定性。化学气相沉积法(CVD)合成钻石在硼元素掺杂致色的浓度、均匀程度及一致性调控方面更具优势,但由于其生长难度较大,目前少见CVD法生长合成蓝色钻石的报道。本研究通过放大检查、紫外-可见吸收光谱、红外光谱、拉曼光谱以及光致发光光谱对一颗CVD合成的蓝色钻石进行一系列光学无损表征测试,并与天然蓝色钻石和辐照改色蓝色钻石对比。结果发现, CVD合成的含硼蓝色钻石与天然蓝色钻石颜色相近,颜色分布较为均匀,内部干净,少数有羽状纹和暗色物质;紫外-可见光谱吸收特征与天然蓝色钻石相似,但区别于辐照处理蓝色钻石的GR1色心吸收带(741 nm);红外光谱表明样品为Ⅱb型钻石,1 290 cm-1和2 458 cm-1处与硼相关吸收峰与天然蓝钻的2 455 cm-1和2 802 cm-1处吸收峰以及辐照改色蓝色钻石中由H1a心引起的1 450 cm-1处吸收峰存在差异,且三声子区(>3 000 cm-1)的波动表明硼含量高;CVD合成蓝色钻石的拉曼光谱在1 332 cm-1处的金刚石本征峰因硼掺杂呈现不对称;光致发光光谱测试结果表明,样品存在NV0缺陷(575 nm)、NV-缺陷(637 nm)以及SiV-缺陷(737 nm)。

     

    Abstract: Natural blue diamonds are produced in very small quantities and command extremely high prices, mostly appearing in the auction market. With the increasing demand for blue diamonds, some synthetic or colour modified blue diamonds came into people's view. At present, common boron-doped blue diamond synthesized by high temperature and high pressure (HPHT) method tend to have a cross-shaped colour distribution characteristic of growth zoning. Irradiated type Ia blue diamonds display blue-green hues controlled by the relative intensities of N3 and GR1 colour centers. Irradiated type Ⅱa diamonds primarily show GR1-dominated colouration with GR2-8 colour centers as auxiliary contributors, so we can't control the intensity of the colour center in an artificial and quantitative way, which results in the colour being unstable. Diamond synthesized by chemical vapor deposition (CVD) has distinct advantages in controlling doped boron element concentration and maintaining uniformity and consistency. However, due to the difficulty of its growth, there are few reports of blue diamonds synthesized by CVD. In this study, a blue diamond synthesized by CVD was performed a series of optical non-destructive characterization tests by magnification examination, ultraviolet-visible spectrophotometer, infrared spectrometer, Raman spectrometer, and photoluminescence spectrometer. Comparing with irradiation modified and HPHT blue diamonds, this boron doped blue diamond synthesized by CVD was similar to natural blue diamonds in colour, with a more uniform colour distribution, clean inclusion, and a few feather and dark substances. UV-Vis spectra showed that the absorption features of the CVD synthetic blue diamonds are similar to the natural blue diamonds but distinct from the GR1 center absorption band (741nm) in irradiation-treated diamonds. The infrared spectra revealed the sample to be a type Ⅱ b diamond. The boron-related absorption peaks at 1 290 cm-1 and 2 458 cm-1 differed from the 2 455 cm-1 and 2 802 cm-1 peaks observed in natural blue diamonds, as well as the 1 450 cm-1 peak associated with the H1a defect center in radiation-treated blue diamonds. Additionally, fluctuations in the three-phonon region (>3 000 cm-1 ) suggested a high boron content. Raman spectra exhibited 1 332 cm-1 diamond intrinsic asymmetry peak resulting from boron doping. Photoluminescence spectroscopy tests revealed the presence of NV0 defects (575 nm), NV-defects (637 nm), and SiV-defects (737 nm).

     

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