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1.
Inorg Chem ; 57(15): 9086-9095, 2018 Aug 06.
Artículo en Inglés | MEDLINE | ID: mdl-30010331

RESUMEN

Strontium tantalum oxynitrides were prepared within the nominal composition range of 1.0 ≤ x ≤ 2.0, where x = Sr/Ta atomic ratio. A gradual structural transition was observed between the perovskite SrTaO2N and the Ruddlesden-Popper phase Sr2TaO3N with increasing SrO content. X-ray diffraction analyses showed that a single-phase perovskite was obtained up to x = 1.1, after which Sr2TaO3N gradually appeared at x ≥ 1.25. High-resolution scanning transmission electron microscopy observations identified the gradual intergrowth of a Ruddlesden-Popper Sr2TaO3N type planar structure interwoven with the perovskite crystal lattice upon increasing x. The crystal lattice at x = 1.4 was highly defective and consisted primarily of perovskite intergrown with a large amount of the Ruddlesden-Popper phase structure. This Ruddlesden-Popper phase layer intergrowth is a characteristic of an oxynitride perovskite rather than the Ruddlesden-Popper defects previously reported in oxide perovskites. Partial substitution of Ta with Sr was also evident in this perovskite lattice. Just below x = 2, a perovskite-type structure was intergrown as defects in the Ruddlesden-Popper Sr2TaO3N. Characterization of Sr2TaO3N in ambient air was challenging due to its moisture sensitivity. Thermal analysis demonstrated that this material was relatively stable up to approximately 1400 °C in comparison with SrTaO2N perovskite, especially under nitrogen. Sr2TaO3N could keep its structure in a sealed tube, and some amount of SrCO3 was observed in XRD after 10 days of exposure to 75% relative humidity under prior ambient conditions. A compact of this material had a relative density of 96% after sintering at 1400 °C under 0.2 MPa of nitrogen, even though a drastic loss of nitrogen was previously reported for a SrTaO2N perovskite under these same conditions. Postammonolysis of the Sr2TaO3N ceramics was not required prior to studying its dielectric behavior. This is in contrast to the SrTaO2N perovskite, which requires postammonolysis to recover its stoichiometric composition and electrical insulating properties.

2.
Appl Spectrosc ; 63(2): 185-91, 2009 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-19215648

RESUMEN

A method to determine the in-plane cathodoluminescence (CL) probe response function (PRF) (i.e., the function characterizing the in-plane luminescence intensity distribution within the electron probe volume) is proposed, which is based on "perturbing" the spectral position of a selected luminescence band using a highly graded stress field. The method is applied to the stress field developed ahead of the tip of an equilibrium crack in three different cases of CL bands, which arise from different structural phenomena: (i) the F(+) (oxygen excess) defect band in a nominally stoichiometric sapphire (alpha-Al(2)O(3)) single crystal; (ii) the chromophoric R-line in ruby lattice (alpha-Al(2-x)Cr(x)O(3)); and (iii) the near band-gap line in n-type GaN semiconductor crystal. A computer-aided data restoration procedure was applied to rationalize data retrieved from crack-tip line scans performed at different acceleration voltages. For the excitonic band-gap in GaN and for F(+) emission in sapphire the CL probe in the electron focal plane was found to be comparable, but not necessarily coincident, in size to the electron probe. On the other hand, the occurrence of self-absorption in the case of R-line photons in ruby resulted in a significantly broadened CL probe with respect to the average scattering length of electrons.

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