Electronic and ionic conductivities in superionic Li4 C60

The 10 GHz microwave conductivity, σ(T) and high field, 222 GHz electron spin resonance (HF-ESR) of Li4C60 fulleride is measured in a wide temperature range. We suggest that the majority of ESR active sites and at least some of the charge carriers for σ(T) are electrons bound to a small concentration of surplus or vacancy ions in the polymer phase. Both σ(T) and the ESR line shape depend on ionic motion. A change of the activation energy of σ(T) at 125 K coincides with the onset of the ionic DC conductivity. The ESR line shape is determined mainly by Li ionic motion within octahedral voids below 150 K. At higher temperatures, fluctuations due to ionic diffusion change the environment of defects from axial to effectively isotropic on the ESR time scale. σ(T) data up to 700 K through the depolymerization transition confirm that the monomeric phase of Li4C60 is a metal.