A new dedicated high-resolution high-throughput powder diffraction beamline has been built, fully commissioned, and opened to general users at the Advanced Photon Source. The optical design and commissioning results are presented. Beamline performance was examined using a mixture of the NIST Si and Al(2)O(3) standard reference materials, as well as the LaB6 line-shape standard. Instrumental resolution as high as 1.7 x 10(-4) (DeltaQQ) was observed.
A dedicated high-resolution high-throughput X-ray powder diffraction beamline has been constructed at the Advanced Photon Source (APS). In order to achieve the goals of both high resolution and high throughput in a powder instrument, a multi-analyzer detector system is required. The design and performance of the 12-analyzer detector system installed on the powder diffractometer at the 11-BM beamline of APS are presented.
Characteristics of nanoscale materials are often different from the corresponding bulk properties providing new, sometimes unexpected, opportunities for applications. Here we investigate the properties of 8 nm colloidal nanoparticles of MAPbBr3 perovskites and contrast them to the ones of large microcrystallites representing a bulk. X-ray spectroscopies provide an exciton binding energy of 0.32 ± 0.10 eV in the nanoparticles. This is 5 times higher than the value of bulk crystals (0.084 ± 0.010 eV), and readily explains the high fluorescence quantum yield in nanoparticles. In the bulk, at high excitation concentrations, the fluorescence intensity has quadratic behavior following the Saha-Langmuir model due to the nongeminate recombination of charges forming the emissive exciton states. In the nanoparticles, a linear dependence is observed since the excitation concentration per particle is significantly less than one. Even the bulk shows linear emission intensity dependence at lower excitation concentrations. In this case, the average excitation spacing becomes larger than the carrier diffusion length suppressing the nongeminate recombination. From these considerations we obtain the charge carrier diffusion length in MAPbBr3 of 100 nm.
At room temperature, the normal oxide spinels NiCr2O4 and CuCr2O4 are tetragonally distorted and crystallize in the I41/amd space group due to cooperative Jahn-Teller ordering driven by the orbital degeneracy of tetrahedral Ni 2+ (t 4 2 ) and Cu2 ). Upon cooling, these compounds undergo magnetic ordering transitions; interactions being somewhat frustrated for NiCr2O4 but not for CuCr2O4. We employ variable-temperature high-resolution synchrotron X-ray powder diffraction to establish that at the magnetic ordering temperatures there are further structural changes, which result in both compounds distorting to an orthorhombic structure consistent with the F ddd space group. NiCr2O4 exhibits additional distortion, likely within the same space group, at a yet-lower transition temperature of T = 30 K. The tetragonal to orthorhombic structural transition in these compounds appears to primarily involve changes in NiO4 and CuO4 tetrahedra.
Instrumentation for stroboscopic time-resolved diffraction studies at low temperatures is described. Exciting laser light is delivered to the crystal through an optical ®ber. During the diffraction experiment,¯uorescence from the sample is focused onto a ®ber optic bundle surrounding the laserlight ®ber, and monitored by a photodiode. A rotating slotted disk produces a pulsed X-ray beam with pulse frequencies suitable for the study of molecular excited states with lifetimes of 10 ms or longer. Synchronization of the laser-pump/X-ray-probe pulses is achieved through a trigger signal from a photosensor mounted on the rotating disk, or from an X-ray sensitive photodiode inserted in the beamstop. For the study of shorter-lived species the time structure of the synchrotron beam is to be used. Equations are derived for the maximum and average fractional excited-state populations as a function of lifetime, pulse frequency and the fraction of molecules being excited by the laser pulse.
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