Defect mediated structural, optical, electrical and mechanical properties of mechano-synthesized PbTe nanostructure as a superior thermoelectric material: Correlation among electrical, mechanical and optical properties

This work reports on the formation of anti-site defects in mechanically alloyed PbTe samples and their anomalous effects on the optical and electrical properties of the sample. PbTe nanoparticles have been synthesised by mechanical alloying of the elemental Pb and Te powders mixed in stoichiometric ratio under an inert (Ar) atmosphere for different time durations. The structural and microstructural characterisations have been carried out by analysing X-ray diffraction (XRD) patterns, field-emission scanning electron mi-croscope (FESEM), and high-resolution transmission electron microscope (HRTEM) images. The elemental composition has been revealed from the energy-dispersive X-Ray (EDX) spectrum. The phase pure cubic PbTe is formed within just 30 min of milling. The Rietveld analysis of XRD patterns, FESEM, and HRTEM images revealed the crystallite size reduction and the increase in r.m.s. lattice strain with the increase in milling durations. Inclusions of more and more anti-site defects of type [PbTe] with increasing milling time are reflected in the expansion of the cubic lattice parameter with milling durations. Fourier-transform infrared (FTIR) spectrum reveals that PbTe is a narrow bandgap semiconductor, and the bandgap shows a redshift with increased milling time and reduced crystallite size. This anomalous behaviour of the optical bandgap with reduced particle size is well explained by Urbach tailing due to increased defects in the more extended milled sample. The positions of the conduction and valence bands in the milled PbTe samples are determined for different milling times. The DC conductivity study also shows anomalous behaviour; elec-trical conductivity increases with particle size reduction in more extended milling time samples. It is re-solved by considering that the carrier concentration increases with a longer milling time due to induced anti-site defects while milling. It results in bandgap reduction with milling durations and shows the pre-dominant effect of electronic conductivity over ionic conductivity. The conduction mechanism is explained as per the Pertritz model, and the dependence of activation energies on particle size and temperature has been explained in detail. The Vickers hardness of the milled samples is determined, and its variation with grain size is explained with the Hall-Petch relation. The improved electrical conductivity with increased milling is also manifested in the measured hardness values. (c) 2022 Elsevier B.V. All rights reserved.