The local thermal conductivity, thermal diffusivity, and volumetric heat capacity of cesium lead chloride perovskite thin films are mapped simultaneously and with highest spatial resolution by a scanning near-field thermal microscope. Both, the 3D phase (CsPbCl 3 ) and the 0D phase (Cs 4 PbCl 6 ) are investigated. For CsPbCl 3 thin films the variation of the thermal properties across the phase transitions in the range from room-temperature to 65°C are analyzed. While the thermal conductivity at room temperature is ultra-low, a significant increase of the thermal conductivity is found for the cubic phase of CsPbCl 3 (T>46°C). While only slight variations in the thermal conductivity are detectable for transitions from the monoclinic to the orthorhombic to the tetragonal phase, thermal diffusivity and volumetric heat capacity measurements are extremely sensitive to the amount of heat involved in the respective transition. It is shown that upon transition to the cubic phase of CsPbCl 3 thin films, the relative increase of the volumetric heat capacity is significantly higher than that of the thermal conductivity. Thus, the thermal diffusivity in the cubic phase becomes notably lower in comparison to that of the respective phase at room temperature. An increase of the volumetric heat capacity had been theoretically predicted earlier but could not be confirmed in previous experimental studies. The findings of our thermal analysis are of great general importance for fundamental material research and for the thermal design of thin-film devices based on CsPbCl 3 perovskites.

We investigate all-inorganic perovskite CsPb x Sn1–x Br3 thin films to determine the variations in the band gap and electronic structure associated with the Pb/Sn ratio. We observe that the band gap can be tuned between 1.86 eV (x = 0) and 2.37 eV (x = 1). Intriguingly, this change is nonlinear in x, with a bowing parameter of 0.9 eV; furthermore, a slight band gap narrowing is found for low Pb content (minimum x ∼ 0.3). The wide tunability of the band gap makes CsPb x Sn1–x Br3 a promising material, e.g., for a wide-gap subcell in tandem applications or for color-tunable light-emitting diodes. Employing photoelectron spectroscopy, we show that the valence band varies with the Pb/Sn ratio, while the conduction band is barely affected.

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The quality and the stability of devices prepared from polycrystalline layers of organic–inorganic perovskites highly depend on the grain sizes prevailing. Tuning of the grain size is either done during layer preparation or in a post-processing step. Our investigation refers to thermal imprint as the post-processing step to induce grain growth in perovskite layers, offering the additional benefit of providing a flat surface for multi-layer devices. The material studied is MAPbBr3; we investigate grain growth at a pressure of 100 bar and temperatures of up to 150 °C, a temperature range where the pressurized stamp is beneficial to avoid thermal degradation. Grain coarsening develops in a self-similar way, featuring a log-normal grain size distribution; categories like ‘normal’ or ‘secondary’ growth are less applicable as the layers feature a preferential orientation already before imprint-induced grain growth. The experiments are simulated with a capillary-based growth law; the respective parameters are determined experimentally, with an activation energy of Q ≈ 0.3 eV. It turns out that with imprint as well the main parameter relevant to grain growth is temperature; to induce grain growth in MAPbBr3 within a reasonable processing time a temperature of 120 °C and beyond is advised. An analysis of the mechanical situation during imprint indicates a dominance of thermal stress. The minimization of elastic energy and surface energy together favours the development of grains with (100)-orientation in MaPbBr3 layers. Furthermore, the experiments indicate that the purity of the materials used for layer preparation is a major factor to achieve large grains; however, a diligent and always similar preparation of the layer is equally important as it defines the pureness of the resulting perovskite layer, intimately connected with its capability to grow. The results are not only of interest to assess the potential of a layer with respect to grain growth when specific temperatures and times are chosen; they also help to rate the long-term stability of a layer under temperature loading, e.g. during the operation of a device.