A simple in-situ PZT oxide's decomposition: Realizing synergistic tailoring of electrical and thermal transport properties of BiCuSeO thermoelectric ceramics through band and phonon engineering

BiCuSeO, an oxide thermoelectric material with a superlattice structure, presents the advantages of affordability, low toxicity, and environmental friendliness . However, its intrinsic low electrical conductivity has impeded its possible applications. To address this challenge, we put tiny PbZr 0.52 Ti 0.48 O 3 (PZT) with varying weight percentages ( x  = 0, 5, 7, 9, 11) into BiCuSeO (BCSO) to fabricate thermoelectric nanocomposites . Through the spark plasma sintering process, PZT particles underwent in-situ decomposition, generating nano-sized second phases such as PbO 2 , TiO 2 , and PbZrO 3 , which are homogenously distributed within BCSO matrix (validated by XRD and TEM). The introduced PbO 2 , TiO 2 , and PbZrO 3 second phases served a dual purpose: inhibiting the grain growth of BCSO and introducing additional nano-grain boundaries. This resulted in more effective phonon scattering sites, thereby reducing lattice thermal conductivity . Simultaneously, the Pb element derived from PZT decomposition was doped into the Bi site of the BCSO matrix, causing a reduction in the band gap of BCSO from 0.49 eV to 0.388 eV and a significant increase in carrier concentration. Consequently, this doping enhanced the electrical conductivity of BCSO-based composites, with the composite with 11 wt% PZT additive amount exhibiting a remarkable 318-fold increase, reaching 550 S/cm compared to pristine BCSO. Notably, the composite with 7 wt% PZT additive amount achieved an exceptionally low lattice thermal conductivity of 0.333 W m −1  K −1 at 823 K. Through the synergistic optimization of electrical and thermal transport properties, the BCSO-based composite with 7 wt% PZT additive amount obtained a ZT value of ∼0.9 at 873 K, representing a 2.45-fold increase compared to pristine BiCuSeO. This straightforward method presents a cost-effective and scalable approach to enhance the thermoelectric performance of various materials, opening new avenues for potential commercial applications.