Spectral Characteristic and Colour Mechanism of Fancy Coloured CVD Diamonds—Take Blue and Pink CVD Diamonds for Example
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摘要:
化学气相沉积(CVD)技术被广泛应用于钻石的合成。CVD钻石在供应能力、品质、成本和技术创新等方面均表现出显著的优势，为钻石市场带来了广阔的应用前景。颜色的多样性是钻石魅力的重要组成部分，而钻石的颜色成因机制一直是研究的热点问题。本研究选取6颗彩色CVD钻石(4颗粉色和2颗蓝色)样品为例, 通过常规宝石学仪器、DiamondViewTM、傅里叶变换红外光谱仪、GEM-3000紫外-可见珠宝检测仪、激光拉曼光谱仪、超景深显微镜等仪器对其进行测试，探讨其谱学特征及呈色机理，获得如下认识：(1)蓝色CVD钻石样品的内部不可见包裹体，在DiamondViewTM下未见层状生长结构。粉色CVD钻石样品具有细小黑色包裹体，短波紫外荧光下具强橙红色荧光，在DiamondViewTM下样品A01-A03可见明显层状生长结构。样品A04未见生长结构特征。层状生长结构和紫外荧光特征可以作为初步判定CVD钻石的依据(图 1)；(2)蓝色CVD钻石样品A05和A06的红外光谱特征显示其具有H1a心(1 450 cm-1)，紫外吸收光谱显示具有GR1色心(741 nm)。粉色CVD钻石样品A03在红外光谱中显示1 330 cm-1的孤氮吸收峰，样品A01、A02、A04则无氮原子存在形式的相关表征。粉色CVD钻石样品A01-A04的紫外光谱显示存在[N-V]0(579 nm)缺陷、[Si-V]-(737 nm)缺陷以及[Si-V]0(945 nm)的相关吸收。所有CVD钻石样品在拉曼光谱中均显示1 335 cm-1的钻石拉曼本征峰(图 2-图 4)；(3)蓝色CVD钻石样品为工艺过程中加入B元素造成了红光到蓝光逐渐减弱的吸收，与GR1色心缺陷、经辐照处理后再经退火处理导致的H1a心和以617 nm为中心的吸收带导致在短波蓝光区产生明显的透射等共同作用导致其呈蓝色。粉色CVD钻石样品的呈色与N元素等晶格缺陷有关, 样品A01-A04具有[N-V]0和[Si-V]-/0缺陷，样品A03的氮杂质为替代氮。
Abstract:Chemical vapor deposition (CVD) technology is widely used in the synthesis of diamond. CVD diamonds have shown significant advantages in terms of supply capacity, quality, cost and technological innovation, which has brought broad application prospects to the diamond market. The diversity of colours is an important part of the charm of diamonds, and the colour mechanism of CVD diamond always has been a hot issue. In this study, the spectral characteristics and colour mechanism of six fancy coloured CVD diamond samples (four pink samples and two blue samples) were studied using conventional gemmological tests, DiamondViewTM, FTIR, UV-Visible jewelry detector, laser Raman spectrometer and ultra-depth microscope. The following understandings were obtained: (1) Invisible inclusions in blue CVD diamond samples under 45× magnification, and there is no layered growth structure under DiamondViewTM. The pink CVD diamond samples have fine black inclusions and strong orange-red fluorescence (SW). The pink samples A01-A03 under DiamondViewTM show obvious layered growth structure, while pink sample A04 has no structural characteristics. The layered growth structure and ultraviolet fluorescence characteristics can be used as the basis for preliminary determination of CVD diamonds, as shown in Fig. 1; (2) The infrared spectra of the blue CVD diamond samples A05 and A06 have H1a centers (1 450 cm-1), and the UV-Visible spectrum results show GR1 colour centers (741 nm). The pink CVD diamond sample A03 shows 1 330 cm-1 solitary nitrogen absorption peak in the infrared spectrum. The pink samples A01, A02 and A04 have no relevant characterization of the existence form of nitrogen atoms in the infrared spectrum, while samples A01-A04 show [N-V]0 (579 nm) defect, [Si-V]- (737 nm) defect and [Si-V]0 (945 nm) related absorption in the UV-Visible spectrum. Raman spectra of all CVD diamond samples show 1 335 cm-1 diamond Raman characteristic peak, as shown in Fig. 2, Fig. 3 and Fig. 4; (3)The blue CVD diamond sample is the absorption from red light to blue light gradually weakened due to the addition of boron in the process. It has the same effect with GR1 colour center defect, H1a center caused by irradiation and annealing treatment, and the absorption band centered at 617 nm, which will lead to obvious transmission in the short wave blue light region, resulting in the blue. The colour of the pink CVD diamond sample is related to the lattice defects of nitrogen, while the samples A01-A04 have defects of [N-V]0 and [Si-V]-/0, and the nitrogen impurity in sample A03 is substituted nitrogen.
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图 1 彩色CVD钻石样品的内部包裹体及其在DiamondViewTM下的图片
Figure 1. Inclusions of fancy coloured CVD diamond samples and pictures under DiamondViewTM
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图 3 CVD钻石样品A01-A06的紫外-可见吸收光谱
Figure 3. Ultraviolet-Visible absorption spectra of CVD diamond samples A01-A06
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