Designing Spin-Crossover Systems to Enhance Thermopower and
Thermoelertic Figure-of-Merit in Paramagnetic Materials
Abstract
Thermoelectric materials, capable of converting temperature gradients
into electrical power, have been traditionally limited by a trade-off
between thermopower and electrical conductivity. This study introduces a
novel, broadly applicable approach that enhances both the spin-driven
thermopower and the thermoelectric figure-of-merit (zT) without
compromising electrical conductivity, using temperature-driven spin
crossover. Our approach, supported by both theoretical and experimental
evidence, is demonstrated through a case study of chromium
doped-manganese telluride, but is not confined to this material and can
be extended to other magnetic materials. By introducing dopants to
create a high crystal field and exploiting the entropy changes
associated with temperature-driven spin crossover, we achieved a
significant increase in thermopower, by approximately 136 μV/K,
representing more than a 200% enhancement at elevated temperatures
within the paramagnetic domain. Our exploration of the bipolar
semiconducting nature of these materials reveals that suppressing
bipolar magnon/paramagnon-drag thermopower is key to understanding and
utilizing spin crossover-driven thermopower. These findings, validated
by inelastic neutron scattering, X-ray photoemission spectroscopy,
thermal transport, and energy conversion measurements, shed light on
crucial material design parameters. We provide a comprehensive framework
that analyzes the interplay between spin entropy, hopping transport, and
magnon/paramagnon lifetimes, paving the way for the development of
high-performance spin-driven thermoelectric materials.