Semiconducting lead halide perovskites (LHPs) have not only become prominent thin-film absorber materials in photovoltaics but have also proven to be disruptive in the field of colloidal ...semiconductor nanocrystals (NCs). The most important feature of LHP NCs is their so-called defect-tolerance—the apparently benign nature of structural defects, highly abundant in these compounds, with respect to optical and electronic properties. Here, we review the important differences that exist in the chemistry and physics of LHP NCs as compared with more conventional, tetrahedrally bonded, elemental, and binary semiconductor NCs (such as silicon, germanium, cadmium selenide, gallium arsenide, and indium phosphide). We survey the prospects of LHP NCs for optoelectronic applications such as in television displays, light-emitting devices, and solar cells, emphasizing the practical hurdles that remain to be overcome.
Two- and three-dimensional lead-halide perovskite (LHP) materials are novel semiconductors that have generated broad interest owing to their outstanding optical and electronic properties. ...Characterization and understanding of their atomic structure and structure–property relationships are often nontrivial as a result of the vast structural and compositional tunability of LHPs as well as the enhanced structure dynamics as compared with oxide perovskites or more conventional semiconductors. Nuclear magnetic resonance (NMR) spectroscopy contributes to this thrust through its unique capability of sampling chemical bonding element-specifically (1/2H, 13C, 14/15N, 35/37Cl, 39K, 79/81Br, 87Rb, 127I, 133Cs, and 207Pb nuclei) and locally and shedding light onto the connectivity, geometry, topology, and dynamics of bonding. NMR can therefore readily observe phase transitions, evaluate phase purity and compositional and structural disorder, and probe molecular dynamics and ionic motion in diverse forms of LHPs, in which they can be used practically, ranging from bulk single crystals (e.g., in gamma and X-ray detectors) to polycrystalline films (e.g., in photovoltaics, photodetectors, and light-emitting diodes) and colloidal nanocrystals (e.g., in liquid crystal displays and future quantum light sources). Herein we also outline the immense practical potential of nuclear quadrupolar resonance (NQR) spectroscopy for characterizing LHPs, owing to the strong quadrupole moments, good sensitivity, and high natural abundance of several halide nuclei (79/81Br and 127I) combined with the enhanced electric field gradients around these nuclei existing in LHPs as well as the instrumental simplicity. Strong quadrupole interactions, on one side, make 79/81Br and 127I NMR rather impractical but turn NQR into a high-resolution probe of the local structure around halide ions.
Low-dimensional metal halides have been researched as optoelectronic materials for the past two decades. Zero-dimensional halides of ns2 elements (Sn, Pb, Sb) have recently gained attention as highly ...efficient broadband light emitters. These compounds comprise discrete metal halide centers, isolated by bulky organic cations. Herein, we report isostructural halide complexes of Ge(II), Sn(II), and Pb(II) with a 1-butyl-1-methyl-piperidinium cation (Bmpip), featuring unusual disphenoidal coordination with a highly stereoactive lone pair. Spectrally broad, bright emission from highly localized excitons, with quantum efficiencies of up to 75%, is observed in blue to red spectral regions for bromides (for Pb, Sn, and Ge, respectively) and extends into the near-infrared for Bmpip2SnI4 (peak at 730 nm). In the case of Sn(II) and Ge(II), both singlet and triplet excitonic emission bands have been observed. Furthermore, Bmpip2SnBr4 and Bmpip2PbBr4 exhibit X-ray-excited luminescence (radioluminescence) with brightness being commensurate with that of a commercial inorganic X-ray scintillator (NaI:Tl).
Postsynthetic chemical transformations of colloidal nanocrystals, such as ion-exchange reactions, provide an avenue to compositional fine-tuning or to otherwise inaccessible materials and ...morphologies. While cation-exchange is facile and commonplace, anion-exchange reactions have not received substantial deployment. Here we report fast, low-temperature, deliberately partial, or complete anion-exchange in highly luminescent semiconductor nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, I). By adjusting the halide ratios in the colloidal nanocrystal solution, the bright photoluminescence can be tuned over the entire visible spectral region (410–700 nm) while maintaining high quantum yields of 20–80% and narrow emission line widths of 10–40 nm (from blue to red). Furthermore, fast internanocrystal anion-exchange is demonstrated, leading to uniform CsPb(Cl/Br)3 or CsPb(Br/I)3 compositions simply by mixing CsPbCl3, CsPbBr3, and CsPbI3 nanocrystals in appropriate ratios.
Finding narrow-band light emitters for the visible spectral region remains an immense challenge. Such phosphors are in great demand for solid-state lighting and display application. In this context, ...green luminescence from tetrahedrally coordinated Mn(II) is an attractive research direction. While the oxide–ligand environment had been studied for decades, much less systematic efforts have been undertaken with regard to halide coordination, especially in the form of fully inorganic halide matrixes. In this study, we synthesized a series of hybrid organic–inorganic Mn(II) halides as well as a range of fully inorganic Zn halide hosts (chlorides, bromides, iodides) doped with Mn(II). In the latter, tetrahedral coordination is attained via substitutional doping owing to the tetrahedral symmetry of Zn sites. We find that the choice of the halide as well as subtle details of the crystal structure profoundly govern the photoluminescence peak positions (500–550 nm range) and emission line widths (40–60 nm) as well as radiative lifetimes (shorter for iodides) through the altered ligand-field effects and degrees of spin–orbit coupling. The photoluminescence quantum yields were as high as 70–90%. The major hurdle for the practical use of these compounds lies in their low absorption coefficients in the blue spectral regions.
We report colloidal synthesis of antimony (Sb) nanocrystals with mean size tunable in the 10–20 nm range and with narrow size distributions of 7–11%. In comparison to microcrystalline Sb, 10 and 20 ...nm Sb nanocrystals exhibit enhanced rate-capability and higher cycling stability as anode materials in rechargeable Li-ion and Na-ion batteries. All three particle sizes of Sb possess high and similar Li-ion and Na-ion charge storage capacities of 580–640 mAh g–1 at moderate charging/discharging current densities of 0.5–1C (1C-rate is 660 mA g–1). At all C-rates (0.5–20C, e.g. current densities of 0.33–13.2 Ag1–), capacities of 20 nm Sb particles are systematically better than for both 10 nm and bulk Sb. At 20C-rates, retention of charge storage capacities by 10 and 20 nm Sb nanocrystals can reach 78–85% of the low-rate value, indicating that rate capability of Sb nanostructures can be comparable to the best Li-ion intercalation anodes and is so far unprecedented for Na-ion storage.
This study depicts the influence of the Rashba effect on the band-edge exciton processes in all-inorganic CsPbBr3 perovskite single colloidal nanocrystal (NC). The study is based on magneto-optical ...measurements carried out at cryogenic temperatures under various magnetic field strengths in which discrete excitonic transitions were detected by linearly and circularly polarized measurements. Interestingly, the experiments show a nonlinear energy splitting between polarized transitions versus magnetic field strength, indicating a crossover between a Rashba effect (at the lowest fields) to a Zeeman effect at fields above 4 T. We postulate that the Rashba effect emanates from a lattice distortion induced by the Cs+ motion degree of freedom or due to a surface effect in nanoscale NCs. The unusual magneto-optical properties shown here underscore the importance of the Rashba effect in the implementation of such perovskite materials in various optical and spin-based devices.
The quest for cost‐effective and TWh‐scale stationary energy storage systems has caused a surge of research on novel post‐Li‐ion batteries that consist solely of abundant chemical elements. ...Nonaqueous Al batteries, inter alia, are appealing as an inexpensive electrochemical technology owing to the high natural abundance of aluminum. A critical assessment of the literature on Al batteries, however, points to numerous misconceptions in this field. The latter is primarily linked to the false assessment of the charge storage redox reactions occurring upon cycling of Al batteries. To ensure the constructive progress of Al batteries, in this essay, the current scientific understanding of the operational mechanisms of two commonly studied Al battery systems, Al‐ion and Al dual‐ion batteries are summarized. Furthermore, the main pitfalls in interpretation and reporting of the electrochemical performance of Al cathode materials and cell‐level energy densities of Al batteries are clarified along with core challenges currently limiting their development. Toward this end, the subject of the charge storage balancing of Al dual‐ion batteries is discussed.
This essay summarizes the current scientific understanding of operational mechanisms of the two most commonly studied Al battery systems, as Al‐ion and Al dual‐ion batteries. Furthermore, it outlines the main pitfalls in interpretation and reporting of the electrochemical performance of Al cathode materials and cell‐level energy densities of Al batteries along with the core challenges currently limiting their development.
Graphite dual-ion batteries represent a potential battery concept for large-scale stationary storage of electricity, especially when constructed free of lithium and other chemical elements with ...limited natural reserves. Owing to their non-rocking-chair operation mechanism, however, the practical deployment of graphite dual-ion batteries is inherently limited by the need for large quantities of electrolyte solutions as reservoirs of all ions that are needed for complete charge and discharge of the electrodes. Thus far, lithium-free graphite dual-ion batteries have employed moderately concentrated electrolyte solutions (0.3-1 M), resulting in rather low cell-level energy densities of 20-70 Wh kg
. In this work, we present a lithium-free graphite dual-ion battery utilizing a highly concentrated electrolyte solution of 5 M potassium bis(fluorosulfonyl)imide in alkyl carbonates. The resultant battery offers an energy density of 207 Wh kg
, along with a high energy efficiency of 89% and an average discharge voltage of 4.7 V.
PDF
