Exposing the hidden influence of selection rules on phonon-phonon scattering by pressure and temperature tuning.

Selection rules act to restrict the intrinsic anharmonic interactions between phonons in all crystals. Yet their influence on phonon propagation is hidden in most materials and so, hard to interrogate experimentally. Using ab initio calculations, we show that the otherwise invisible impact of selection rules on three-phonon scattering can be exposed through anomalous signatures in the pressure (P) and temperature (T) dependence of the thermal conductivities, κ, of certain compounds. Boron phosphide reveals such underlying behavior through an exceptionally sharp initial rise in κ with increasing P, which may be the steepest of any material, and also a peak and decrease in κ at high P. These features are in stark contrast to the measured behavior for many solids, and they occur at experimentally accessible conditions. These findings give a deep understanding of phonon lifetimes and heat conduction in solids, and motivate experimental efforts to observe the predicted behavior.

Ultrahigh thermal conductivity in isotope-enriched cubic boron nitride.

Materials with high thermal conductivity (κ) are of technological importance and fundamental interest. We grew cubic boron nitride (cBN) crystals with controlled abundance of boron isotopes and measured κ greater than 1600 watts per meter-kelvin at room temperature in samples with enriched 10B or 11B. In comparison, we found that the isotope enhancement of κ is considerably lower for boron phosphide and boron arsenide as the identical isotopic mass disorder becomes increasingly invisible to phonons. The ultrahigh κ in conjunction with its wide bandgap (6.2 electron volts) makes cBN a promising material for microelectronics thermal management, high-power electronics, and optoelectronics applications.

Non-monotonic pressure dependence of the thermal conductivity of boron arsenide.

Recent experiments demonstrate that boron arsenide (BAs) is a showcase material to study the role of higher-order four-phonon interactions in affecting heat conduction in semiconductors. Here we use first-principles calculations to identify a phenomenon in BAs and a related material - boron antimonide, that has never been predicted or experimentally observed for any other material: competing responses of three-phonon and four-phonon interactions to pressure rise cause a non-monotonic pressure dependence of thermal conductivity, κ, which first increases similar to most materials and then decreases. The resulting peak in κ shows a strong temperature dependence from rapid strengthening of four-phonon interactions relative to three-phonon processes with temperature. Our results reveal pressure as a knob to tune the interplay between the competing phonon scattering mechanisms in BAs and similar compounds, and provide clear experimental guidelines for observation in a readily accessible measurement regime.

Fermi Surface Nesting and Phonon Frequency Gap Drive Anomalous Thermal Transport.

The lattice thermal conductivity, k_{L}, of typical metallic and nonmetallic crystals decreases rapidly with increasing temperature because phonons interact more strongly with other phonons than they do with electrons. Using first principles calculations, we show that k_{L} can become nearly independent of temperature in metals that have nested Fermi surfaces and large frequency gaps between acoustic and optic phonons. Then, the interactions between phonons and electrons become much stronger than the mutual interactions between phonons, giving the fundamentally different k_{L} behavior. This striking trend is revealed here in the group V transition metal carbides, vanadium carbide, niobium carbide, and tantalum carbide, and it should also occur in several other metal compounds. This work gives insights into the physics of heat conduction in solids and identifies a new heat flow regime driven by the interplay between Fermi surfaces and phonon dispersions.

Unusual high thermal conductivity in boron arsenide bulk crystals.

Conventional theory predicts that ultrahigh lattice thermal conductivity can only occur in crystals composed of strongly bonded light elements, and that it is limited by anharmonic three-phonon processes. We report experimental evidence that departs from these long-held criteria. We measured a local room-temperature thermal conductivity exceeding 1000 watts per meter-kelvin and an average bulk value reaching 900 watts per meter-kelvin in bulk boron arsenide (BAs) crystals, where boron and arsenic are light and heavy elements, respectively. The high values are consistent with a proposal for phonon-band engineering and can only be explained by higher-order phonon processes. These findings yield insight into the physics of heat conduction in solids and show BAs to be the only known semiconductor with ultrahigh thermal conductivity.