Metal-halide perovskite semiconductors are of tremendous interest for a variety of applications. Only recently, solar cells based on a representative of this family have been certified with an efficiency in excess of 24%.[1] Aside from their remarkable success in photovoltaics, metal-halide perovskites are also highly promising as light emitters, e.g., in light-emitting diodes (LEDs) or lasers. [2][3][4] LEDs based on the fruit-fly of these compounds, i.e., methylammonium lead iodide (CH 3 NH 3 PbI 3 or MAPbI 3 ), and other related perovskites have been demonstrated with continuously increasing efficiency. [5][6][7] For lasers, there is the vision that perovskites may overcome/avoid the typical limitations and loss mechanisms present in organic gain media, such as triplet-singlet annihilation or absorption due to triplet excitons and
Cesium lead halide perovskites are of interest for light-emitting diodes and lasers. So far, thin-films of CsPbX 3 have typically afforded very low photoluminescence quantum yields (PL-QY < 20%) and amplified spontaneous emission (ASE) only at cryogenic temperatures, as defect related nonradiative recombination dominated at room temperature (RT). There is a current belief that, for efficient light emission from lead halide perovskites at RT, the charge carriers/excitons need to be confined on the nanometer scale, like in CsPbX 3 nanoparticles (NPs).Here, thin films of cesium lead bromide, which show a high PL-QY of 68% and low-threshold ASE at RT, are presented. As-deposited layers are recrystallized by thermal imprint, which results in continuous films (100% coverage of the substrate), composed of large crystals with micrometer lateral extension. Using these layers, the first cesium lead bromide thin-film distributed feedback and vertical cavity surface emitting lasers with ultralow threshold at RT that do not rely on the use of NPs are demonstrated. It is foreseen that these results will have a broader impact beyond perovskite lasers and will advise a revision of the paradigm that efficient light emission from CsPbX 3 perovskites can only be achieved with NPs.
Thermal management
in devices like solar cells, light-emitting
diodes, and lasers based on hybrid halide perovskite thin films is
expected to be of paramount importance for optimal performance and
reliability. As of yet, experimental data of thermal properties of
non-iodine-based hybrid halide perovskites is very scarce. Here the
thermal conductivity of methylammonium lead halide perovskite (CH3NH3PbX3 X= I, Br, and Cl) single crystals
and thin films is analyzed by scanning near-field thermal microscopy.
The thermal conductivity of CH3NH3PbX3 single crystals with X= I, Br, and Cl is found to be 0.34 ±
0.12, 0.44 ± 0.08, and 0.50 ± 0.05 W/(mK) at room temperature,
respectively. Strikingly, similar thermal conductivities are determined
for the corresponding thin-film samples. The thermal conductivity
of MAPbI3 in the cubic phase (T > 55
°C)
increases to (1.1 ± 0.1) W/(mK). In addition, the temperature
dependence of the thermal conductivities and of thermal expansion
coefficients of MAPbI3 around the phase transition from
the tetragonal to cubic phase is presented.
Aside from photovoltaics, metal-halide perovskite semiconductors have also emerged as attractive platform for LEDs and even lasers. For all of them, performance and operational stability are strongly influenced by thermally...
Perovskites have high potential for future electronic devices, in particular, in the field of opto-electronics. However, the electronic and optic properties of these materials highly depend on the morphology and thus on the preparation; in particular, highly crystalline layers with large crystals and without pinholes are required. Here, nanoimprint is used to improve the morphology of such layers in a thermal imprint step. Two types of material are investigated, MAPbI3 and MAPbBr3, with MA being methylammonium, CH3NH3+. The perovskite layers are prepared from solution, and the crystal size of the domains is substantially increased by imprinting them at temperatures of 100–150 °C. Although imprint is performed under atmospheric conditions which, in general, enhances the degradation, the stamp that covers the layer under elevated temperature is able to protect the perovskite largely from decomposition. Comparing imprinting experiments with pure annealing at a similar temperature and time proves this. Furthermore, imprint is capable of patterning the surface of the perovskite layers; lines and spaces of 150 nm width were reproducibly obtained under imprint at 150 °C. Moreover, a through-layer patterning is possible by using the partial cavity filling approach. Although not yet optimized, this simple way to define isolated perovskite patterns within a layer simply by thermal nanoimprint is of impact for the preparation of devices, as patterning of perovskite layers by conventional techniques is limited.
Local thermal conductivity, thermal diffusivity, and volumetric heat capacity of all-inorganic halide perovskite thin films are mapped simultaneously and with highest spatial resolution for the first time. These various thermal properties are detected by a scanning near-field thermal microscope operated at two different frequencies simultaneously. We apply this technique to analyze the thermal properties of halide perovskites on the nanoscale. In addition to an ultralow thermal conductivity of 0.43 ± 0.03 and 0.33 ± 0.02 W/(m•K), a low thermal diffusivity of 0.3 ± 0.1 mm 2 /s and a small heat capacity of 0.29 ± 0.9 and 0.18 ± 0.6 J/(g•K) are obtained for CsPbBr 3 and CsPb 2 Br 5 films, respectively. The findings of our thermal microscopy are of great general importance for the thermal design of thin-film devices based on halide perovskites, while the measurement technique itself is generally applicable for other thin-film optoelectronic materials.
This is the first report on a plasma enhanced spatial atomic layer deposition (APP-ALD) process at atmospheric pressure to grow conducting metallic Cu thin films from a carbene stabilized precursor.
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