Successive Phase Transitions and High Ionic Conductivity of Trichlorogermanate (II) Salts as Studied by 35C1 NQR and Powder X-Ray Diffraction

Abstract

Abstract A series of trichlorogermanate(II) salts (AGeCl3, A = Rb, Cs, CH3N H3, and (CH3)4N) have been synthesized and characterized by 35Cl NQR , 35Cl NMR , AC conductivity, DTA, and X-ray diffraction techniques. In the temperature range studied two, two, five, and four phases were confirmed for the Rb, Cs, CH3NH3, and (CH3)4N salts, respectively. From the 35Cl NQR and structural data, isolated pyramidal GeCl3 anions were recognized in the low temperature phases. With increasing temperature the relaxation times of the 35Cl NQR decreased exponentially and the signals disappeared far below the melting point. This suggests that the reorientation of the anion about the pseudo three-fold axis is excited. With further increase in temperature, the ionic conductivity of CH3NH3GeCl3 and (CH3)4NGeCl3 increased drastically at the phase transitions to their cubic perovskite phases (CH3NH3GeCl3:σ= 10-1 Sm-1 at 400 K, (CH3)4NGeCl3: σ = 5 x 10-2 Sm-1 at 420 K). The mobile ion was confirmed to be the chloride ion by means of 35Cl NMR and X-ray diffraction.