Development of Cu2SnS3 based thermoelectric materials and devices

Commercially available high-performance thermoelectric materials are often rare or toxic and therefore unsustainable. The present thesis work makes a case for eco-friendly, earth-abundant, and non-toxic p-type ceramic Cu2SnS3 (CTS, hereafter) and, in general, the use of disordered materials for thermoelectric applications. The detailed study of polymorphism, synthesis conditions, porosity, grain size, and doping provides a systematic and in-depth experimental and computational analysis of thermoelectric properties and stability of CTS. These results can be generalized for numerous thermoelectric materials and other applications. Moreover, a case for functioning thermoelectric generators using non-toxic and cost-effective materials is also presented. The thesis begins with a brief introduction to thermoelectricity, followed by a literature review and justification of the choice of the subject. The second chapter puts forward a novel approach to stabilize a disordered CTS polymorph without any chemical alteration through high-energy reactive ball milling. The third chapter deals with the stability of disordered samples under different synthesis and sintering conditions, highlighting the effect of synthesis environment, microstructure, and porosity. The fourth chapter employed a novel, facile, and cost-effective two-step synthesis method (high-energy ball milling combined with spark plasma sintering) to synthesize CTS bulk samples. The two-step synthesis method was able to constrain the CTS grain growth in the nanometric range, revealing the conductive nature of the CTS surfaces. The next chapter explores combining the two-step synthesis method with Ag substitution at the Sn lattice site to improve CTS's thermoelectric performance further. In the final stages of the thesis work, thin film thermoelectric generators were fabricated using CTS and similar chalcogenides, demonstrating power output comparable to existing thermoelectric materials used in the medium temperature range. The final chapter summarizes outlooks and future perspectives stemming from this research work.