Abstract
Raman and IR spectra are recorded on NASICON type compounds in the 77K–900K temperature range. The NASICON structure domain of stability has been investigated in the M2O-M'O2-SiO2-P2O5 system (M=Li,Na,K,Ag - M′=Hf,Zr,Sc,Ti). Metastability phenomena have been pointed out. The different compounds have been synthesized in the form of powder using a sol-gel process and in the form of single crystals. Conductivity and DTA measurements are performed. From a spectroscopic and structural viewpoint NASICON framework can be described as a isolated tetrahedra sublattice where the M,M' cations fill cavities between tetrahedra. As different kinds of structural distortions of the R3c prototype structure are observed against filling of cavities, distortions occur against temperature: long range cation correlations and librational tetrahedra disorder are simultaneously observed; these features are related to phase transition occurence and to conducting properties. The influence of the “thermal history” and of impurities or dopants on the local order is pointed out.
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