Small polaron hopping conduction mechanism in Ni-doped LaFeO₃

Abstract

The electrical transport properties of LaFe_{1− x} Ni _x O₃ (0.1 ≤ x ≤ 0.6) bulk samples were investigated over a wide temperature range, i.e. 9–300 K. Powder x-ray diffraction patterns at room temperature showed that all samples were formed in a single phase. However, a structural transformation was observed from orthorhombic (Pnma) to rhombohedral crystal symmetry at x > 0.5 in Ni-doped samples, which is supported by the electrical transport analysis. Temperature-dependent resistivity data were fitted using Mott's variable-range hopping model for a limited range of temperatures to calculate the hopping distance and the density of states at Fermi level. It was found that all parameters vary systematically with an increase in Ni concentration. Moreover, the resistivity data were also fitted using the small polaron hopping (SPH) model. The non-adiabatic SPH conduction mechanism is followed up to 50% Ni concentration, whereas an adiabatic hopping conduction mechanism is active above it. Such a change in the conduction mechanism is accompanied by subtle electronically induced structural changes involving Fe³⁺–O–Fe³⁺ and Fe³⁺–O–Ni³⁺ bond angles and bond lengths. Thus, we suggest that the transport properties can be explained according to the additional delocalization of charge carriers induced by Ni doping.

Keywords:

• polaron hopping
• orthorhombic phase
• variable-range hopping model
• density of states
• electron–phonon interaction

Acknowledgements

Authors J.P. Srivastava and M.W. Khan are thankful to CSIR for financial support under Emeritus Scheme and RAship, respectively.