Enhanced Seebeck coefficient from carrier-induced vibrational softening

Through their electron-lattice interactions, localized carriers reduce vibrational stiffness constants in their surroundings. States with a large electronic polarizability (e.g., multiatomic localized states and states of a singlet bipolaron formed of degenerate electronic orbitals) induce exceptionally large softening. This carrier-induced softening augments the Seebeck coefficient of solids whose carriers hop between these localized states through two separate effects. One enhancement is due to a localized carrier inducing an increase in a solid's vibrational entropy. The other contribution is proportional to the vibrational energy transferred with a carrier as it hops. Both softening contributions are independent of the carrier density. The magnitudes and temperature dependencies of these contributions to the Seebeck coefficient indicate the electronic polarizabilities of the localized states and the vibrational modes to which they are coupled. Measured softening enhancements of Seebeck coefficients are sometimes large enough (e.g., > 200 mu V/K measured at 300 K in boron carbides) to significantly increase the efficiency of thermoelectric energy conversion. [S0163-1829(99)02109-8].