The tetragonal structure of nanocrystals in rare-earth doped oxyfluoride glass ceramics |
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Authors: | Hu Nan Yu Hua Zhang Ming Zhang Pan Wang Yazhou Zhao Lijuan |
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Institution: | Tianjin Key Lab of Photonics Material and Technology for Information Science, Ministry of Education, Nankai University, Tianjin, 300457, China. |
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Abstract: | Rare-earth doped oxyfluoride glasses and nanocrystalline glass ceramics have been prepared and studied by energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) aiming at investigating the structure and the symmetry of the nanocrystal as well as the site of the rare-earth ion. To solve the problem encountered by previous researchers due to glass host interference, we etched off glass matrix and released the fluoride nanocrystal, which is more convenient for EDS measurement. A tetragonal phase model with the chemical formula as PbREF(5) proved by quantitative EDS and XRD analyses has been proposed in this paper for the first time. Two specific crystalline phases with the same space group have been observed at 460 °C-500 °C and 520 °C-560 °C, respectively. Moreover, a super "pseudo-cubic" cell based on our tetragonal model may give a good explanation to the probable previous cubic-symmetry misunderstanding by researchers. Additionally, the thermodynamic mechanism of phase transition and the thermal stability related to the structure of nanocrystals in glass ceramics have been studied and supported by ab initio calculations and experimental methods. The structure and thermal stability of the nanocrystal and clear environment of the rare-earth ion reported here have far-reaching significance with respect to the optical investigations and further applications of rare-earth doped oxyfluoride glass ceramics. |
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