Microscopic Mechanisms of Glass-Like Lattice Thermal Transport in Cubic Cu${}_{12}$Sb${}_4$S${}_{13}$ Tetrahedrites

Abstract

Materials based on cubic tetrahedrites (Cu${}_{12}$Sb${}_4$S${}_{13}$) are useful thermoelectrics with unusual thermal and electrical transport properties, such as very low and nearly temperature-independent lattice thermal conductivity (${\kappa }_L$). We explain the microscopic origin of the glass-like ${\kappa }_L$ in Cu${}_{12}$Sb${}_4$S${}_{13}$ by explicitly treating anharmonicity up to quartic terms for both phonon energies and phonon scattering rates. We show that the strongly unstable phonon modes associated with trigonally coordinated Cu atoms are anharmonically stabilized above approximately $100$ K and continue hardening with increasing temperature, in accord with experimental data. This temperature induced hardening effect reduces scattering of heat carrying acoustic modes by reducing the available phase space for three-phonon processes, thereby balancing the conventional $\propto T$ increase in scattering due to phonon population and yielding nearly temperature-independent ${\kappa }_L$. Furthermore, we find that very strong phonon broadening lead to a qualitative breakdown of the conventional phonon-gas model and modify the dominant heat transport mechanism from the particle-like phonon wave packet propagation to incoherent tunneling described by off-diagonal terms in the heat-flux operator, which are typically prevailing in glasses and disordered crystals. Our work paves the way to a deeper understanding of glass-like thermal conductivity in complex crystals with strong anharmonicity.

References in corpus (3)

• Impact of Rattlers on Thermal Conductivity of a Thermoelectric Clathrate: A First-Principles Study
• First-Principles Lattice Dynamics Method for Strongly Anharmonic Crystals
• Anharmonic phonon spectra of PbTe and SnTe in the self-consistent harmonic approximation

Cited by in corpus (22)

• Unravelling Ultralow Thermal Conductivity in Double Perovskite Cs2AgBiBr6: Dominant Wave-like Phonon Tunnelling, Strong Quartic Anharmonicity and Lattice Instability
• Many-body Green's function approach to lattice thermal transport
• A Unified Understanding of Minimum Lattice Thermal Conductivity
• Correlation between vibrational anomalies and emergent anharmonicity of local potential energy landscape in metallic glasses
• Machine learning for predicting ultralow thermal conductivity and high ZT in complex thermoelectric materials
• Ultra-low glassy thermal conductivity and controllable, promising thermoelectric properties in crystalline o-CsCu5S3
• Spin-phonon scattering-induced low thermal conductivity in a van der Waals layered ferromagnet Cr${}_2$Si${}_2$Te${}_6$
• Efficient Cross-layer Thermal Transport with Atypical Glassy-like Phenomena in Crystalline CsCu${}_4$Se${}_3$
• Hierarchical Characterization of Thermoelectric Performance in Copper-Based Chalcogenide CsCu${}_3$S${}_2$: Unveiling the role of Anharmonic Lattice Dynamics
• Thermal conductivity of MgO in giant planetary interior conditions predicted by deep potential
• Ineffectiveness of Formamidine in Suppressing Ultralow Thermal Conductivity in Cubic Hybrid Perovskite FAPbI3
• Copper delocalization leads to ultralow thermal conductivity in chalcohalide CuBiSeCl2
• Diffuson-Dominated Thermal Transport Crossover from Ordered to Liquid-like Cu${}_3$BiS${}_3$:The Negligible Role of Ion Hopping
• Accelerated Discovery of Crystalline Materials with Record Ultralow Lattice Thermal Conductivity via a Universal Descriptor
• Bonding Hierarchy and Coordination Interaction Leading to High Thermoelectricity in Wide Bandgap TlAgI2
• API Phonons: Python Interfaces for Phonon Transport Modeling
• Unique Hierarchical Rotational Dynamics Induces Ultralow Lattice Thermal Conductivity in Cyanide-bridged Framework Materials
• s-d coupling enhanced phonon anharmonicity in copper-based compounds
• Exploring low lattice thermal conductivity materials using chemical bonding principles
• Anomalous Reversal of Stability in Mo-containing Oxides: A Difficult Case Exhibiting Sensitivity to DFT+U and Distortion
• Role of octahedral tilting induced acoustic softening on limiting thermal transport in SrSnO3
• Data-Driven Exploration and Insights into Temperature-Dependent Phonons in Inorganic Materials