Materials with very low thermal conductivity are of high interest for both thermoelectric and optical phase-change applications. Synthetic nanostructuring is most promising to suppress thermal conductivity by scattering phonons, but challenges remain
in producing bulk samples. We show that in crystalline AgSbTe$_2$, a spontaneously-forming nanostructure leads to a suppression of thermal conductivity to a glass-like level. Our mapping of the phonon mean-free-paths provides a novel bottom-up microscopic account of thermal conductivity, and also reveals intrinsic anisotropies associated with the nanostructure. Ground-state degeneracy in AgSbTe$_2$ leads to the natural formation of nanoscale domains with different orderings on the cation sublattice, and correlated atomic displacements, which efficiently scatter phonons. This mechanism is general and points to a new avenue in nano-scale engineering of materials, to achieve low thermal conductivities for efficient thermoelectric converters and phase-change memory devices.
The phonon density of states (DOS) and magnetic excitation spectrum of polycrystalline BiFeO$_3$ were measured for temperatures $200 leq T leq 750,$K, using inelastic neutron scattering (INS). Our results indicate that the magnetic spectrum of BiFeO$
_3$ closely resembles that of similar Fe perovskites, such as LaFeO$_3$, despite the cycloid modulation in BiFeO$_3$. We do not find any evidence for a spin gap. A strong $T$-dependence of the phonon DOS was found, with a marked broadening of the whole spectrum, providing evidence of strong anharmonicity. This anharmonicity is corroborated by large-amplitude motions of Bi and O ions observed with neutron diffraction. These results highlight the importance of spin-phonon coupling in this material.
Understanding the microscopic processes affecting the bulk thermal conductivity is crucial to develop more efficient thermoelectric materials. PbTe is currently one of the leading thermoelectric materials, largely thanks to its low thermal conductivi
ty. However, the origin of this low thermal conductivity in a simple rocksalt structure has so far been elusive. Using a combination of inelastic neutron scattering measurements and first-principles computations of the phonons, we identify a strong anharmonic coupling between the ferroelectric transverse optic (TO) mode and the longitudinal acoustic (LA) modes in PbTe. This interaction extends over a large portion of reciprocal space, and directly affects the heat-carrying LA phonons. The LA-TO anharmonic coupling is likely to play a central role in explaining the low thermal conductivity of PbTe. The present results provide a microscopic picture of why many good thermoelectric materials are found near a lattice instability of the ferroelectric type.
The {57}Fe-specific phonon density of states of Ba(Fe(1-x)Co(x))2As2 single crystals (x=0.0, 0.08) was measured at cryogenic temperatures and at high pressures with nuclear-resonant inelastic x-ray scattering. Measurements were conducted for two diff
erent orientations of the single crystals, yielding the orientation-projected {57}Fe-phonon density of states (DOS) for phonon polarizations in-plane and out-of-plane with respect to the basal plane of the crystal structure. In the tetragonal phase at 300 K, a clear stiffening was observed upon doping with Co. Increasing pressure to 4 GPa caused a marked increase of phonon frequencies, with the doped material still stiffer than the parent compound. Upon cooling, both the doped and undoped samples showed a stiffening, and the parent compound exhibited a discontinuity across the magnetic and structural phase transition. These findings are generally compatible with the changes in volume of the system upon doping, increasing pressure, or increasing temperature, but an extra softening of high-energy modes occurs with increasing temperature. First-principles computations of the phonon DOS were performed and showed an overall agreement with the experimental results, but underestimate the Grueneisen parameter. This discrepancy is explained in terms of a magnetic Grueneisen parameter, causing an extra phonon stiffening as magnetism is suppressed under pressure.
