In this study, we developed a user-friendly automatic powder diffraction measurement system for Debye-Scherrer geometry using a capillary sample at beamline BL02B2 of SPring-8. The measurement system consists of six one-dimensional solid-state (MYTHEN) detectors, a compact auto-sampler, wide-range temperature control systems, and a gas handling system. This system enables to do the automatic measurement of temperature dependence of the diffraction patterns for multiple samples. We introduced two measurement modes in the MYTHEN system and developed new attachments for the sample environment such as a gas handling system. The measurement modes and the attachments can offer in situ and/or time-resolved measurements in an extended temperature range between 25 K and 1473 K and various gas atmospheres and pressures. The results of the commissioning and performance measurements using reference materials (NIST CeO 674b and Si 640c), VO and TiO, and a nanoporous coordination polymer are presented.
BiCh2-based compounds (Ch: S, Se) are a new series of layered superconductors, and the mechanisms for the emergence of superconductivity in these materials have not yet been elucidated. In this study, we investigate the relationship between crystal structure and superconducting properties of the BiCh2-based superconductor family, specifically, optimally doped Ce1−xNdxO0.5F0.5BiS2 and LaO0.5F0.5Bi(S1−ySey)2. We use powder synchrotron X-ray diffraction to determine the crystal structures. We show that the structure parameter essential for the emergence of bulk superconductivity in both systems is the in-plane chemical pressure, rather than Bi-Ch bond lengths or in-plane Ch-Bi-Ch bond angle. Furthermore, we show that the superconducting transition temperature for all REO0.5F0.5BiCh2 superconductors can be determined from the in-plane chemical pressure.
All-inorganic perovskites have emerged as a new class of phosphor materials owing to their outstanding optical properties. Zero-dimensional inorganic perovskites, in particular the CsPbBr-related systems, are inspiring intensive research owing to the high photoluminescence quantum yield (PLQY) and good stability. However, synthesizing such perovskites with high PLQYs through an environment-friendly, cost-effective, scalable, and high-yield approach remains challenging, and their luminescence mechanisms has been elusive. Here, we report a simple, scalable, room-temperature self-assembly strategy for the synthesis of CsPbBr/CsPbBr perovskite composites with near-unity PLQY (95%), high product yield (71%), and good stability using low-cost, low-toxicity chemicals as precursors. A broad range of experimental and theoretical characterizations suggest that the high-efficiency PL originates from CsPbBr nanocrystals well passivated by the zero-dimensional CsPbBr matrix that forms based on a dissolution-crystallization process. These findings underscore the importance in accurately identifying the phase purity of zero-dimensional perovskites by synchrotron X-ray technique to gain deep insights into the structure-property relationship. Additionally, we demonstrate that green-emitting CsPbBr/CsPbBr, combined with red-emitting KSiF:Mn, can be used for the construction of WLEDs. Our work may pave the way for the use of such composite perovskites as highly luminescent emitters in various applications such as lighting, displays, and other optoelectronic and photonic devices.
The nature of the unconventional ordered phase occurring in CeRu2Al10 below T0 = 27 K was investigated by neutron scattering. Powder diffraction patterns show clear superstructure peaks corresponding to forbidden (h + k)-odd reflections of the Cmcm space group. Inelastic neutron scattering experiments further reveal a pronounced magnetic excitation developing in the ordered phase at an energy of 8 meV. The low-temperature behavior of intermetallic cerium compounds can be broadly typified in terms of the competition between several interaction channels (intra-atomic couplings, on-site Coulomb repulsion, hybridiza-tion between local f-electron states and itinerant conduction-band states), forming the basis of the well-known and highly successful Anderson model. 1 However, there has also been continued interest in Ce-based materials which do not seem to fit into this general framework. Among those are, for instance, the "Kondo insula-tors", as well as various compounds exhibiting multipole ordering 2 or other types of elusive "hidden order" transitions. One example of such unconventional ordering properties has been discovered very recently by Strydom 3 in the ternary compound CeRu 2 Al 10. CeRu 2 Al 10 is an YbFe 2 Al 10-type orthorhombic compound belonging to the Cmcm space group, with room-temperature lattice constants a = 9.1272Å1272Å, b = 10.282Å 282Å, and c = 9.1902Å1902Å. It has been described as a "cage" crystal structure, in which Ce atoms are separated from each other by an exceptionally large distance of 5.2 ˚ A. From the lattice constants, the Ce valence state was estimated to be close to 3+. The transport properties below room temperature are indicative of a gap in the electronic structure, 3 although the Hall effect still suggests a dominant metallic character. In this regime, the material exhibits considerable magnetic anisotropy (a: easy axis, b: hard axis). 4-6 Upon application of pressure, the system rapidly changes, first to a Kondo insulator, then to a metal above 5 GPa. 4 The striking feature of this compound is the phase transition taking place at T 0 = 27 K, which causes pronounced anomalies in various physical properties. Whereas the origin of this transition remains highly controversial, there is growing evidence that it cannot reduce to a conventional ordering of local Ce magnetic moments. The transition temperature is far too high in view of the large Ce-Ce distance and, more specifically, of the magnetic ordering temperature of 16.5 K found in GdRu 2 Al 10. 4 The drop in the magnetic susceptibility below T 0 occurring for all three magnetic field orientations H a, b, c, with an exponential behavior χ = χ 0 + A exp(−∆/T) and ∆ ∼ 100 K, is also difficult to reconcile with the behavior expected for an antiferromagnet. 4,7 Finally, 27 Al NQR/NMR experiments did not find the splitting of peaks below T 0 expected for a static order of Ce magnetic moments. 8 Alternative mechanisms such as charge-or spin-density-wave formation also have serious shortcomings. 4,8 Recently, Tanida et al. 5,7 sugge...
Cesium lead halide perovskite nanocrystals (NCs) have emerged as promising luminescent materials for a range of applications. However, the creation of highly luminescent violet-emitting CsPbCl3 NCs mostly relies on doping of a limited number of small-sized metal ions or post-synthetic surface treatment of NCs. Alkaline-earth (AE) metals (e.g., Ca2+, Sr2+, and Ba2+) have been proposed to be able to substitute Pb2+ in halide perovskites, yet it remains incompletely understood whether AE metal ions can be incorporated into the perovskite lattice or can be merely situated at the surface. Here, we explore the possibility of using AE metal ions for the suppression of the formation of trap centers, which leads us to develop a one-pot synthetic passivation strategy to boost the violet-emitting efficiency of CsPbCl3 NCs through the creation of a Ca2+/Sr2+ involved passivation layer. The photoluminescence quantum yield of violet emission reaches 77.1% by incorporating an optimal amount of Ca2+. A wide range of optical and structural characterizations, coupled with first-principles calculations, aid in clarifying the underlying mechanism for the AE-metal-dependent passivation of CsPbCl3 NCs. Specifically, based on the experimental and theoretical results, a model is proposed for the observed abnormal incorporation phenomenon of AE2+ ions in NCs (i.e., Ba2+ can be incorporated into the core of NCs, Ca2+/Sr2+ can only be at/near the surface, while Mg2+ can neither be in the core nor at the surface). We believe that the knowledge gained here may not only offer a new perspective to obtain high-efficiency violet-emitting perovskite NCs through a one-pot synthetic passivation but can also help elucidate the functions that AE2+ ions play in the optimization of perovskite optoelectronic devices.
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