Tailoring Polaron Dimensions in Lead-Tin Hybrid Perovskites.

Charge carriers in the soft and polar perovskite lattice form so-called polaron quasiparticles, charge carriers dressed with a lattice deformation. The spatial extent of a polaron is governed by the material's electron-phonon interaction strength, which determines charge carrier effective mass, mobility, and the so-called Mott polaron density, that is, the maximum stable density of charge carriers that a perovskite can support. Despite its significance, controlling polaron dimensions has been challenging. Here, experimental substantial tuning of polaron dimensions is reported by lattice engineering, through Pb/Sn substitution in CH3NH3SnxPb1-xI3. The polaron dimension is deduced from the Mott polaron density, which can be composition-tuned over an order of magnitude, while charge carrier mobility occurs through band transport, and remains substantial across all compositions, ranging from 10 s to 100 s cm2 V s-1 at room temperature. The effective modulation of polaron size can be understood by considering the bond asymmetry after carrier injection as well as the random spatial distribution of Pb/Sn ions. This study underscores the potential for tailoring polaron dimensions, which is crucial for optimizing applications prioritizing either high charge carrier density or high mobility.

In Situ Annealing Effect on Thermally Co-Evaporated CsPbI2Br Thin Films Studied via Spectroscopic Ellipsometry.

All-inorganic cesium lead halide perovskites possess excellent thermal stability, a feature that renders them highly favorable for optoelectronic applications with an elevated thermal budget. Employing a coevaporation approach for their deposition holds promise for manufacturing at an industrial level, owing to improvements in device scalability and reproducibility. For unlocking the full potential of vacuum-evaporated perovskite thin films, it is crucial to delve deeper into their crystallization process, which, as a solid-state reaction, has been less investigated compared to the crystallization process of, most commonly used, solution-based methods. In this work, we employ spectroscopic ellipsometry, a nondestructive, high speed, and high accuracy characterization method, to study the real time annealing effect on thermally coevaporated CsPbI2Br thin films in a temperature range between 25 and 300 °C. We achieve this by developing a singular dynamic model that can be fitted in real time as a function of temperature, providing insights into how thermal annealing influences the perovskite film's morphology and optical constants. Based on the latter, we derive the temperature dependence of the thermo-optic coefficient and Urbach energy as well as analyze the interband transition energies via critical point analysis. We demonstrate that the γ- to ß-phase transition can be identified through a pronounced shift in the bandgap energy, whereas the ß- to α-phase transition can be discerned by a sharp increase in the film's roughness. We corroborate the obtained fit results with additional in- and ex situ measurements, such as in situ grazing incidence wide-angle X-ray scattering, atomic force microscopy, reflectance/transmittance, and profilometry.

Oxygen-Mediated (0D) Cs4PbX6 Formation during Open-Air Thermal Processing Improves Inorganic Perovskite Solar Cell Performance.

The desire to commercialize perovskite solar cells continues to mount, motivating the development of scalable production. Evaluations of the impact of open-air processing have revealed a variety of physical changes in the fabricated devices─with few changes having the capacity to be functionalized. Here, we highlight the beneficial role of ambient oxygen during the open-air thermal processing of metastable γ-CsPbI3-based perovskite thin films and devices. Physiochemical-sensitive probes elucidate oxygen intercalation and the formation of Pb-O bonds in the CsPbI3 crystal, entering via iodine vacancies at the surface, creating superoxide (O2-) through electron transfer reactions with molecular oxygen, which drives the formation of a zero-dimensional Cs4PbI6 capping layer during annealing (>330 °C). The chemical conversion permanently alters the film structure, helping to shield the subsurface perovskite from moisture and introduces lattice anchoring sites, stabilizing otherwise unstable γ-CsPbI3 films. This functional modification is demonstrated in γ-CsPbI2Br perovskite solar cells, boosting the operational stability and photoconversion efficiency of champion devices from 12.7 to 15.4% when annealed in dry air. Such findings prompt a reconsideration of glovebox-based perovskite solar cell research and establish a scenario where device fabrication can in fact greatly benefit from ambient oxygen.

Noble-Metal-Free High-Entropy Alloy Nanoparticles for Efficient Solar-Driven Photocatalytic CO2 Reduction.

Metal nanoparticle (NP) cocatalysts are widely investigated for their ability to enhance the performance of photocatalytic materials; however, their practical application is often limited by the inherent instability under light irradiation. This challenge has catalyzed interest in exploring high-entropy alloys (HEAs), which, with their increased entropy and lower Gibbs free energy, provide superior stability. In this study, 3.5 nm-sized noble-metal-free NPs composed of a FeCoNiCuMn HEA are successfully synthesized. With theoretic calculation and experiments, the electronic structure of HEA in augmenting the catalytic CO2 reduction has been uncovered, including the individual roles of each element and the collective synergistic effects. Then, their photocatalytic CO2 reduction capabilities are investigated when immobilized on TiO2. HEA NPs significantly enhance the CO2 photoreduction, achieving a 23-fold increase over pristine TiO2, with CO and CH4 production rates of 235.2 and 19.9 µmol g-1 h-1, respectively. Meanwhile, HEA NPs show excellent stability under simulated solar irradiation, as well high-energy X-ray irradiation. This research emphasizes the promising role of HEA NPs, composed of earth-abundant elements, in revolutionizing the field of photocatalysis.

Phase-engineering compact and flexible CsPbBr3 microcrystal films for robust X-ray detection.

All-inorganic CsPbBr3 perovskites have gained significant attention due to their potential in direct X-ray detection. The fabrication of stable, pinhole-free thick films remains challenging, hindering their integration in durable, large-area high-resolution devices. In this study, we propose a facile strategy using a non-conductive polymer to create a flexible, compact thick film under ambient conditions. Furthermore, we investigate the effect of introducing the 2D CsPb2Br5 phase into CsPbBr3 perovskite crystals on their photophysical properties and charge transport. Upon X-ray exposure, the devices consisting of the dual phase exhibit improved stability and more effective operation at higher voltages. Rietveld refinement shows that, due to the presence of the second phase, local distortions and Pb-vacancies are introduced within the CsPbBr3 lattice. This in turn presumably increases the ion migration energy barrier, resulting in a very low dark current and hence, enhanced stability. This feature might benefit local charge extraction and, ultimately, the X-ray image resolution. These findings also suggest that introducing a second phase in the perovskite structure can be advantageous for efficient photon-to-charge carrier conversion, as applied in medical imaging.

Emergence of a Non-Van der Waals Magnetic Phase in a Van der Waals Ferromagnet.

Manipulation of long-range order in 2D van der Waals (vdW) magnetic materials (e.g., CrI3 , CrSiTe3 ,etc.), exfoliated in few-atomic layer, can be achieved via application of electric field, mechanical-constraint, interface engineering, or even by chemical substitution/doping. Usually, active surface oxidation due to the exposure in the ambient condition and hydrolysis in the presence of water/moisture causes degradation in magnetic nanosheets that, in turn, affects the nanoelectronic /spintronic device performance. Counterintuitively, the current study reveals that exposure to the air at ambient atmosphere results in advent of a stable nonlayered secondary ferromagnetic phase in the form of Cr2 Te3 (TC2 ≈160 K) in the parent vdW magnetic semiconductor Cr2 Ge2 Te6 (TC1 ≈69 K). The coexistence of the two ferromagnetic phases in the time elapsed bulk crystal is confirmed through systematic investigation of crystal structure along with detailed dc/ac magnetic susceptibility, specific heat, and magneto-transport measurement. To capture the concurrence of the two ferromagnetic phases in a single material, Ginzburg-Landau theory with two independent order parameters (as magnetization) with a coupling term can be introduced. In contrast to the rather common poor environmental stability of the vdW magnets, the results open possibilities of finding air-stable novel materials having multiple magnetic phases.

A combined study on structural, magnetic and specific heat on double perovskite iridates Ln2CoIrO6[Ln = Pr, Nd].

We report rich magnetic behavior for Co-Ir based double perovskites consisting of different rare earth cations Pr and Nd: Pr2CoIrO6(PCIO) and Nd2CoIrO6(NCIO). Both oxides show an antisite disorder of 10% and a ferrimagnetic transition,TFiMaround 96 K and 98 K respectively. The long range magnetic ordering is arising from the canted antiferromagnetic ordering between the Co2+and Ir4+ions. A prominent peak around 27 K in magnetization data of NCIO indicates that the total moment of Nd ion is antiferromagnetically coupled to the Co-Ir sublattice. The long range order of the Nd sublattice is corroborated by the evidence of an anomaly in specific heat at very low temperature. The compounds exhibit a maximum change of magnetic entropy of 0.57 (0.48) J kg.K-1atTFiMin a magnetic field of 5 T. The strong spin-orbit coupling in 5dstates of Ir and cation disorder lead to the Mott insulating phase as found from the analysis of temperature dependent resistivity. These unique behaviors suggest an interesting interplay between localized Pr/Nd-4f, itinerant Co-3dand Ir-5delectrons.

Magnetic and transport properties of the mixed 3d-5d-4fdouble perovskite Sm2CoIrO6.

Iridium-based double perovskites having mixed 3d-5d-4fmagnetic sub-lattices are expected to exhibit exotic magnetic phenomenon. In this paper, we report a study of structural, magnetic and transport properties of the mixed 3d-5d-4fdouble perovskite Sm2CoIrO6(SMCO), which crystallizes in monoclinic structure with space groupP21/nand the crystal symmetry remains same throughout the measured temperature down to 15 K. High resolution synchrotron x-ray diffraction reveals an isostructural phase transition around 104 K. Magnetization measurements on polycrystalline samples indicate that SMCO orders ferrimagnetically atTFiM= 104 K; while, a second transition is observed below 10 K due to the rare-earth (Sm3+) ordering. The ferrimagnetic transition is well-understood by Néel's two-sublattice model, which is primarily ascribed to antiferromagnetic coupling between Co2+and Ir4+sub-lattices. Electronic transport measurement shows the insulting behaviour of SMCO, which follows Mott variable-range hopping conduction mechanism. However, dielectric measurements as a function of temperature rules out the presence of magneto dielectric coupling in this compound.