Search

Computational models are employed to analyze residual chemical stresses arising from compositional variations in europium-doped BaBrCl crystals grown by the vertical Bridgman method. We find that significant chemical stress is produced by radial segregation of Eu in this system. In particular, the distribution of normal stresses is set by the radial concentration gradient, whose changing sign produces surface states in tension or compression. Crack opening from surface flaws will be promoted or suppressed by tensile or compressive surface stresses, respectively. Thus, crystal growth processing strategies that change the radial dopant concentration gradients are posited to affect the propensity for cracking. For this system, surface stresses are changed from states of tension to compression when the growth rate is increased, thus improving the chances to avoid cracking—a strategy that defies classical wisdom that dictates slower growth to improve outcomes. Similar strategies affecting segregation may prove beneficial to tailor chemical stress fields to reduce cracking in other crystal growth systems.

BaBrCl:Eu is a promising scintillator material; however, the crystal growth yield must be improved for it to become commercially viable. This study measures strain accumulations in the crystal lattice which can contribute to cracking during post-growth cooling. Neutron diffraction is used to measure the crystal structure of undoped and 5 mol% europium-doped BaBrCl from 303 to 1073 K, approaching the melting point. Rietveld analysis of these data provides the temperature dependence of the thermal and chemical strain in BaBrCl. In particular, anisotropic thermal expansion is measured, with expansion along the b axis nearly double the expansion along the a and c axes. Additionally, the chemical strain from the incorporation of europium atoms peaks around 673 K, explaining cracking frequently observed in that temperature range.

A key to the unique combination of electronic and optical properties in halide perovskite materials lies in their rich structural complexity. However, their radiation sensitive nature limits nanoscale structural characterization requiring dose efficient microscopic techniques in order to determine their structures precisely. In this work, we determine the space-group and directly image the Br halide sites of CsPbBr3, a promising material for optoelectronic applications. Based on the symmetry of high-order Laue zone reflections of convergent-beam electron diffraction, we identify the tetragonal (I4/mcm) structural phase of CsPbBr3 at cryogenic temperature. Electron ptychography provides a highly sensitive phase contrast measurement of the halide positions under low electron-dose conditions, enabling imaging of the elongated Br sites originating from the out-of-phase octahedral rotation viewed along the [001] direction of I4/mcm persisting at room temperature. The measurement of these features and comparison with simulations yield an octahedral rotation angle of 6.5°(±1.5°). The approach demonstrated here opens up opportunities for understanding the atomic scale structural phenomena applying advanced characterization tools on a wide range of radiation sensitive halide-based all-inorganic and hybrid organic-inorganic perovskites.

Luminescence-kinetics studies of Ce3+-doped GdP3O9 metaphosphate, which was prepared by a melt-solution technique, are performed using time-resolved luminescence spectroscopy techniques at T = 4.2-300 K. The processes of energy migration along the Gd3+ sub-lattice and energy transfer between Gd3+ and Ce3+ ions are investigated. At low temperatures, the emission of Gd3+ is caused by the radiative decay of its lowest-energy relaxed excited 6P7/2 state, and the Gd3+ ? Ce3+ energy transfer is absent. As the temperature increases, the thermally stimulated population of the higher energy 6P5/2, 6P3/2 levels of the Gd3+ 6PJ-excited state takes place, which reveals itself in a higher energy shift of the Gd3+ 6P5/2 excited level at T <150K is suggested to be responsible for the increase in probability of energy migration along the Gd6PJ ? 8S7/2 emission band. The phonon-assisted population of the Gd3+ 6P5/2 excited level at T <150K is suggested to be responsible for the increase in probability of energy migration along the Gd3+ sub-lattice followed by the Gd3+ ? Ce3+ energy transfer at T >150K takes place owing to the thermally stimulated population of the highest-energy 6P3/2 excited level together with the lower energy shift of the Ce3+ ? Ce3+ energy transfer at T >150K takes place owing to the thermally stimulated population of the highest-energy 6P3/2 excited level together with the lower energy shift of the Ce3+ 4f-5d1 absorption band. Unlike the Gd3+ ? Ce3+ transfer, the reverse Ce3+ ? Gd3+ energy transfer is observed at any temperature. [ABSTRACT FROM AUTHOR]

Neutrons are known to be unique probes in situations where other types of radiation fail to penetrate samples and their surrounding structures. In this paper it is demonstrated how thermal and cold neutron radiography can provide time-resolved imaging of materials while they are being processed ( e.g. while growing single crystals). The processing equipment, in this case furnaces, and the scintillator materials are opaque to conventional X-ray interrogation techniques. The distribution of the europium activator within a BaBrCl:Eu scintillator (0.1 and 0.5% nominal doping concentrations per mole) is studied in situ during the melting and solidification processes with a temporal resolution of 5-7 s. The strong tendency of the Eu dopant to segregate during the solidification process is observed in repeated cycles, with Eu forming clusters on multiple length scales (only for clusters larger than ∼50 µm, as limited by the resolution of the present experiments). It is also demonstrated that the dopant concentration can be quantified even for very low concentration levels (∼0.1%) in 10 mm thick samples. The interface between the solid and liquid phases can also be imaged, provided there is a sufficient change in concentration of one of the elements with a sufficient neutron attenuation cross section. Tomographic imaging of the BaBrCl:0.1%Eu sample reveals a strong correlation between crystal fractures and Eu-deficient clusters. The results of these experiments demonstrate the unique capabilities of neutron imaging for in situ diagnostics and the optimization of crystal-growth procedures.

LiYP(4)O(12) polyphosphate doped with Ce(3+) ions was prepared by the melt solution technique. The crystal structure, interatomic distances, and atom coordination numbers were determined using x-ray powder diffraction. A study of the spectral-kinetic luminescent properties was performed employing excitation with pulsed radiation from a synchrotron (UV-VUV range) and a laboratory x-ray source. The characteristics of Ce(3+) luminescence, namely the emission doublet maxima at 3.97 and 3.72 eV and the 4f-5d excitation maxima at 4.20, 5.11, 5.40, 5.65 and 6.55 eV, are discussed in terms of crystal field splitting in a low-symmetry site of the LiYP(4)O(12) host lattice. The location of the Ce(3+) energy levels with respect to the valence and conduction bands of the LiYP(4)O(12) host is estimated from the temperature dependence of the decay time measured for Ce(3+) 5d-4f luminescence.