Energy vs Charge Transfer in Manganese-Doped Lead Halide Perovskites.
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ABSTRACT:
SUBMITTER: Ricciarelli D
PROVIDER: S-EPMC8763376 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Large polarons are known to form in lead halide perovskites (LHPs). Photoinduced isolated polarons at low densities have been well-researched, but many-body interactions at elevated polaron densities, exceeding the Mott criterion (i.e., Mott polaron density), have remained elusive. Here, employing ultrafast terahertz spectroscopy, we identify a stable Mott polaron state in LHPs at which the polaron wavefunctions start to overlap. The Mott polaron density is determined to be ∼1018 cm-3, in good agreement with theoretical calculations based on the Feynman polaron model. The electronic phase transition across the Mott density is found to be universal in LHPs and independent of the constituent ions. Exceeding the Mott polaron density, excess photoinjected charge carriers annihilate quickly within tens to hundreds of picoseconds, before reaching the stable and long-lived Mott state. These results have considerable implications for LHP-based devices and for understanding exotic phenomena reported in LHPs.
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Project description:Metal halide perovskites are promising materials for future optoelectronic applications. One intriguing property, important for many applications, is the tunability of the band gap via compositional engineering. While experimental reports on changes in absorption or photoluminescence show rather good agreement for different compounds, the physical origins of these changes, namely the variations in valence and conduction band positions, are not well characterized. Here, we determine ionization energy and electron affinity values of all primary tin- and lead-based perovskites using photoelectron spectroscopy data, supported by first-principles calculations and a tight-binding analysis. We demonstrate energy level variations are primarily determined by the relative positions of the atomic energy levels of metal cations and halide anions and secondarily influenced by the cation-anion interaction strength. These results mark a significant step towards understanding the electronic structure of this material class and provides the basis for rational design rules regarding the energetics in perovskite optoelectronics.
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Project description:Abstract Doping and alloying are valuable tools for modifying and enhancing the properties and performance of lead halide perovskites. However, the effects of heterovalent doping with Sb3+ and Bi3+ cations are still a matter of current investigation. Due to the different charge of the dopants compared to the constituting Pb2+ ions, a simultaneous creation of defects is unavoidable and the influence of these defects and the actual metal substitution become entangled. Herein, we present the first 14–15 iodido metalates, (BED)4PbE2I16 (BED=N?benzylethylenediammonium; E=Sb (1), Bi (2)), which are model compounds for doped lead iodide perovskites and display surprisingly low band gaps of 2.01 (1) and 1.88?eV (2). Quantum chemical investigations show that this stems from a good electronic match between the PbI6 and EI6 units of the compounds. Our results provide a model system for doped perovskites, but also represent the first examples of a promising new class of metal halide materials. The electronic nature of Sb? and Bi?doped lead halide perovskites is an area of current scientific debate. Model compounds featuring [PbE2I16]8? (E=Sb, Bi) anions that represent precise cut?outs of doped perovskites are presented. The compounds display surprisingly low band gaps owing to an excellent electronic match between PbI6 and EI6 units and represent the first members of a promising new class of metal halide materials.
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Project description:Direct piezoelectric force microscopy (DPFM) is employed to examine whether or not lead halide perovskites exhibit ferroelectricity. Compared to conventional piezoelectric force microscopy, DPFM is a novel technique capable of measuring piezoelectricity directly. This fact is fundamental to be able to examine the existence of ferroelectricity in lead halide perovskites, an issue that has been under debate for several years. DPFM is used to detect the current signals, i.e. changes in the charge distribution under the influence of the scan direction and applied force of the atomic force microscope (AFM) tip in contact mode. For comparison, (i) we use DPFM on lead halide perovskites and well-known ferroelectric materials (i.e. periodically poled lithium niobate and lead zirconate titanate); and (ii) we conduct parallel experiments on MAPbI3 films of different grain sizes, film thicknesses, substrates, and textures using DPFM as well as piezoelectric force microscopy (PFM) and electrostatic force microscopy (EFM). In contrast to previous work that claimed there were ferroelectric domains in MAPbI3 perovskite films, our work shows that the studied perovskite films Cs0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17)3 and MAPbI3 are ferroelectricity-free. The observed current profiles of lead halide perovskites possibly originate from ion migration that happens under an applied electrical bias and in strained samples under mechanical stress. This work provides a deeper understanding of the fundamental physical properties of the organic-inorganic lead halide perovskites and solves a longstanding dispute about their non-ferroelectric character: an issue of high relevance for optoelectronic and photovoltaic applications.
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Project description:Lead halide perovskites open great prospects for optoelectronics and a wealth of potential applications in quantum optical and spin-based technologies. Precise knowledge of the fundamental optical and spin properties of charge-carrier complexes at the origin of their luminescence is crucial in view of the development of these applications. On nearly bulk Cesium-Lead-Bromide single perovskite nanocrystals, which are the test bench materials for next-generation devices as well as theoretical modeling, we perform low temperature magneto-optical spectroscopy to reveal their entire band-edge exciton fine structure and charge-complex binding energies. We demonstrate that the ground exciton state is dark and lays several millielectronvolts below the lowest bright exciton sublevels, which settles the debate on the bright-dark exciton level ordering in these materials. More importantly, combining these results with spectroscopic measurements on various perovskite nanocrystal compounds, we show evidence for universal scaling laws relating the exciton fine structure splitting, the trion and biexciton binding energies to the band-edge exciton energy in lead-halide perovskite nanostructures, regardless of their chemical composition. These scaling laws solely based on quantum confinement effects and dimensionless energies offer a general predictive picture for the interaction energies within charge-carrier complexes photo-generated in these emerging semiconductor nanostructures.
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Project description:Spintronics holds great potential for next-generation high-speed and low-power consumption information technology. Recently, lead halide perovskites (LHPs), which have gained great success in optoelectronics, also show interesting magnetic properties. However, the spin-related properties in LHPs originate from the spin-orbit coupling of Pb, limiting further development of these materials in spintronics. Here, we demonstrate a new generation of halide perovskites, by alloying magnetic elements into optoelectronic double perovskites, which provide rich chemical and structural diversities to host different magnetic elements. In our iron-alloyed double perovskite, Cs2Ag(Bi:Fe)Br6, Fe3+ replaces Bi3+ and forms FeBr6 clusters that homogenously distribute throughout the double perovskite crystals. We observe a strong temperature-dependent magnetic response at temperatures below 30 K, which is tentatively attributed to a weak ferromagnetic or antiferromagnetic response from localized regions. We anticipate that this work will stimulate future efforts in exploring this simple yet efficient approach to develop new spintronic materials based on lead-free double perovskites.
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