Unravelling the luminescence spectrum of garnet grossular var. tsavorite: The role of chromium (III), manganese (II) and misattribution of vanadium (II)

IF 3.3 3区物理与天体物理 Q2 OPTICS

Journal of Luminescence Pub Date : 2024-10-11 DOI:10.1016/j.jlumin.2024.120936

A. Idini , R. Argazzi , F. Frau , M. Fantauzzi , C. Angeli

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引用次数: 0

Abstract

Gem quality garnet var. tsavorite from Tanzania is investigated by means of SEM-EDS, XPS and fluorescence spectroscopy to decipher its luminescence spectrum. The EDS analysis confirms that the main constituents of the tsavorite samples from Tanzania are those of grossularia (i.e. Ca, Al, Si, O), with V, Mn, Cr, Ti and Mg as minor but characteristic elements (particularly V, Mn and Cr) of the tsavorite variety. The XPS analysis shows that the oxidation state of Mn is +2 and that of V is +3. The luminescence of tsavorite in the yellow region (591 nm) is originated by Mn²⁺ in dodecahedral coordination (D₂ point symmetry) while the luminescence in the red region (690–750 nm) is originated by Cr³⁺ in octahedral coordination (O_h point symmetry) in a strong crystal field. Contrary to what is often reported in the literature, this study demonstrates that V²⁺ (or other 3d transition metal ions as well) is not responsible for the red emissions of tsavorite.

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揭示石榴石毛玻璃变种沙弗莱石的发光光谱：铬（III）、锰（II）的作用和钒（II）的错误归属

通过 SEM-EDS、XPS 和荧光光谱对坦桑尼亚出产的宝石级石榴石变种沙弗莱石进行了研究，以破译其发光光谱。EDS 分析证实，坦桑尼亚的沙弗莱石样本的主要成分是毛玻璃（即 Ca、Al、Si、O），V、Mn、Cr、Ti 和 Mg 是次要但具有沙弗莱石特征的元素（尤其是 V、Mn 和 Cr）。XPS 分析表明，锰的氧化态为 +2，钒的氧化态为 +3。沙弗莱石在黄色区域（591 纳米）的发光是由十二面体配位（D2 点对称）的 Mn2+ 发出的，而在红色区域（690-750 纳米）的发光则是由八面体配位（Oh 点对称）的 Cr3+ 在强晶场中发出的。与文献中经常报道的情况相反，这项研究表明 V2+（或其他 3d 过渡金属离子）并不是沙弗莱石发出红光的原因。

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来源期刊

Journal of Luminescence 物理-光学

CiteScore

6.70

自引率

13.90%

发文量

850

审稿时长

3.8 months

期刊介绍： The purpose of the Journal of Luminescence is to provide a means of communication between scientists in different disciplines who share a common interest in the electronic excited states of molecular, ionic and covalent systems, whether crystalline, amorphous, or liquid. We invite original papers and reviews on such subjects as: exciton and polariton dynamics, dynamics of localized excited states, energy and charge transport in ordered and disordered systems, radiative and non-radiative recombination, relaxation processes, vibronic interactions in electronic excited states, photochemistry in condensed systems, excited state resonance, double resonance, spin dynamics, selective excitation spectroscopy, hole burning, coherent processes in excited states, (e.g. coherent optical transients, photon echoes, transient gratings), multiphoton processes, optical bistability, photochromism, and new techniques for the study of excited states. This list is not intended to be exhaustive. Papers in the traditional areas of optical spectroscopy (absorption, MCD, luminescence, Raman scattering) are welcome. Papers on applications (phosphors, scintillators, electro- and cathodo-luminescence, radiography, bioimaging, solar energy, energy conversion, etc.) are also welcome if they present results of scientific, rather than only technological interest. However, papers containing purely theoretical results, not related to phenomena in the excited states, as well as papers using luminescence spectroscopy to perform routine analytical chemistry or biochemistry procedures, are outside the scope of the journal. Some exceptions will be possible at the discretion of the editors.