Negative thermal expansion (NTE) is the phenomenon in which materials shrink rather than expand on heating. Although NTE had been previously observed in a few simple materials at low temperature, it was the realisation in 1996 that some materials have NTE over very wide ranges of temperature that kick-started current interest in this phenomenon. Now, nearly two decades later, a number of families of ceramic NTE materials have been identified. Increasingly quantitative studies focus on the mechanism of NTE, through techniques such as high-pressure diffraction, local structure probes, inelastic neutron scattering and atomistic simulation. In this paper we review our understanding of vibrational mechanisms of NTE for a range of materials. We identify a number of different cases, some of which involve a small number of phonons that can be described as involving rotations of rigid polyhedral groups of atoms, others where there are large bands of phonons involved, and some where the transverse acoustic modes provide the main contribution to NTE. In a few cases the elasticity of NTE materials has been studied under pressure, identifying an elastic softening under pressure. We propose that this property, called pressure-induced softening, is closely linked to NTE, which we can demonstrate using a simple model to describe NTE materials. There has also been recent interest in the role of intrinsic anharmonic interactions on NTE, particularly guided by calculations of the potential energy wells for relevant phonons. We review these effects, and show how anhamonicity affects the response of the properties of NTE materials to pressure.

A long-lived hot carrier population is critical in order to develop working hot carrier photovoltaic devices with efficiencies exceeding the Shockley–Queisser limit. Here, we report photoluminescence from hot-carriers with unexpectedly long lifetime (a few ns) in formamidinium tin triiodide. An unusual large blue shift of the time-integrated photoluminescence with increasing excitation power (150 meV at 24 K and 75 meV at 293 K) is displayed. On the basis of the analysis of energy-resolved and time-resolved photoluminescence, we posit that these phenomena are associated with slow hot carrier relaxation and state-filling of band edge states. These observations are both important for our understanding of lead-free hybrid perovskites and for an eventual future development of efficient lead-free perovskite photovoltaics.

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Enjoying great safety, high power, and high energy densities, all-solid-state batteries play a key role in the next generation energy storage devices. However, their development is limited by the lack of solid electrolyte materials that can reach the practically useful conductivities of 10 S/cm at room temperature (RT). Here, by exploring a set of lithium-rich antiperovskites composed of cluster ions, we report a lithium superionic conductor, LiSBF, that has an estimated 3D RT conductivity of 10 S/cm, a low activation energy of 0.210 eV, a giant band gap of 8.5 eV, a small formation energy, a high melting point, and desired mechanical properties. A mixed phase of the material, LiS(BF)Cl, with the same simple crystal structure exhibits an RT conductivity as high as 10 S/cm and a low activation energy of 0.176 eV. The high ionic conductivity of the crystals is enabled by the thermal-excited vibrational modes of the cluster ions and the large channel size created by mixing the large cluster ion with the small elementary ion.

Stimuli-responsive behaviors of flexible metal–organic frameworks (MOFs) make these materials promising in a wide variety of applications such as gas separation, drug delivery, and molecular sensing. Considerable efforts have been made over the last decade to understand the structural changes of flexible MOFs in response to external stimuli. Uniform pore deformation has been used as the general description. However, recent advances in synthesizing MOFs with non-uniform porous structures, i.e. with multiple types of pores which vary in size, shape, and environment, challenge the adequacy of this description. Here, we demonstrate that the CO 2 -adsorption-stimulated structural change of a flexible MOF, ZIF-7, is induced by CO 2 migration in its non-uniform porous structure rather than by the proactive opening of one type of its guest-hosting pores. Structural dynamics induced by guest migration in non-uniform porous structures is rare among the enormous number of MOFs discovered and detailed characterization is very limited in the literature. The concept presented in this work provides new insights into MOF flexibility.

Pressure and temperature dependence of the negative thermal expansion in Zn(CN)2 is fully investigated using molecular dynamics simulations with a built potential model. The advantage of this study allows us to reproduce the exotic behaviours of the material, including the negative thermal expansion (NTE), the reduction of NTE with elevated temperature, the pressure enhancement of NTE and the pressure-induced softening. Results of the study provide us detailed data to link the properties in the energy space and the real space, giving us insights to understand the properties and the connections between them.

Hybrid perovskites viewed as super alkali halides with alkali and halogen ions replaced by super alkalis and super halogens, respectively. The basic properties of these materials are determined by the bonding ionicity and effective ionic radii of the super-ions. New colorful hybrid perovskites can be invented with super-ions as the building block.

We show that the electronic properties, including the band gap, the gap deformation potential, and the exciton binding energy as well as the chemical stability of organic-inorganic hybrid perovskites can be traced back to their corresponding molecular motifs. This understanding allows one to quickly estimate the properties of the bulk semiconductors from their corresponding molecular building blocks. New hybrid perovskite admixtures are proposed by replacing halogens with superhalogens having compatible ionic radii. The mechanism of the boron-hydride based hybrid perovskite reacting with water is investigated by using a cluster model.