Electronic Instability and Anharmonicity in SnSe

The binary compound SnSe exhibits record high thermoelectric performance, largely because of its very low thermal conductivity. The origin of the strong phonon anharmonicity leading to the low thermal conductivity of SnSe is investigated through first-principles calculations of the electronic structure and phonons. It is shown that a Jahn-Teller instability of the electronic structure is responsible for the high-temperature lattice distortion between the Cmcm and Pnma phases. The coupling of phonon modes and the phase transition mechanism are elucidated, emphasizing the connection with hybrid improper ferroelectrics. This coupled instability of electronic orbitals and lattice dynamics is the origin of the strong anharmonicity causing the ultralow thermal conductivity in SnSe. Exploiting such bonding instabilities to generate strong anharmonicity may provide a new rational to design efficient thermoelectric materials

Orbital-Energy Splitting in Anion Ordered Ruddlesden-Popper Halide Perovskites for Tunable Optoelectronic Applications

The electronic orbital characteristics at the band edges plays an important role in determining the electrical, optical and defect properties of perovskite photovoltaic materials. It is highly desirable to establish the relationship between the underlying atomic orbitals and the optoelectronic properties as a guide to maximize the photovoltaic performance. Here, using first-principles calculations and taking anion ordered Ruddlesden-Popper (RP) phase halide perovskites Cs$_{n+1}$Ge$_n$I$_{n+1}$Cl$_{2n}$ as an example, we demonstrate how to rationally optimize the optoelectronic properties (e.g., band gap, transition dipole matrix elements, carrier effective masses, band width) through a simple band structure parameter. Our results show that reducing the splitting energy $|\Delta c|$ of p orbitals of B-site atom can effectively reduce the band gap and carrier effective masses while greatly improving the optical absorption in the visible region. Thereby, the orbital-property relationship with $\Delta c$ is well established through biaxial compressive strain. Finally, it is shown that this approach can be reasonably extended to several other non-cubic halide perovskites with similar p orbitals characteristics at the conduction band edges. Therefore, we believe that our proposed orbital engineering approach provides atomic-level guidance for understanding and optimizing the device performance of layered perovskite solar cells

External uniform electric field removing flexoelectric effect in epitaxial ferroelectric thin films

Using the modified Landau-Ginsburg-Devonshire thermodynamic theory, it is found that the coupling between stress gradient and polarization, or flexoelectricity, has significant effect on ferroelectric properties of epitaxial thin films, such as polarization, free energy profile and hysteresis loop. However, this effect can be completely eliminated by applying an optimized external, uniform electric field. The role of such uniform electric field is shown to be the same as that of an ideal gradient electric field which can suppress the flexoelectricty effect completely based on the present theory. Since the uniform electric field is more convenient to apply and control than gradient electric field, it can be potentially used to remove the flexoelectric effect induced by stress gradient in epitaxial thin films and enhance the ferroelectric properties.Comment: 5 pages, 3 figure