Si–Ge is a well-known disordered alloy exhibiting
high anharmonicity.
These two features, disorder and anharmonicity, arise due to the unique
nature of bonding instead of structural complexity and are beneficial
as they limit the thermal conduction and are widely used in high-temperature
thermoelectric applications. In this regard, a comprehensive understanding
of the nature of interatomic bonds and the calculation of the Grüneisen
parameter, which is a characteristic metric of anharmonicity, of the
individual bond are essential to design a crystalline solid along
with the development of a high-throughput thermoelectric alloy exhibiting
ultralow lattice thermal conductivity. Here, we demonstrate the origin
of the low lattice thermal conductivity, κl, of ∼0.8
and 0.4 Wm–1 K–1 for the transition-metal
(Ni and Cr)-doped Si–Ge alloy, respectively, due to the difference
in the anharmonic pair potential achieved using synchrotron-based
X-ray absorption fine structure spectroscopy. The technique enables
the determination of the Grüneisen parameter of the individual
bond in the alloy and thus reveals the unpaired electron-induced bond
anharmonicities and bonding heterogeneity. The technique also determines
the bond Grüneisen parameter more precisely in comparison to
the values obtained from the speed of sound, as the latter neglects
the existence of the soft TO mode, which also contributes to lattice
dynamics. Thus, the synergistic presence of (i) heteroatoms as point
scatters (mass contrast), (ii) bonding anharmonicities, and (iii)
electron–phonon scattering suppresses the lattice thermal conductivity
beyond the theoretical alloy limit. Furthermore, the analysis imparts
a conception for the estimation of the bond Grüneisen parameter
through the acquisition and analysis of extended X-ray analysis of
fine structure (EXAFS) spectra.