Detailed investigations of the photoluminescence properties of
Mn4+
(3d3) ions
in YAlO3
have been performed in the temperature range 10–600 K. The luminescence of
Mn4+
ions due to the transition consists of two zero-phonon lines
(R
lines) at 691.3 and 692.7 nm, which became visible only at low temperature, and their vibronic
sidebands that cover the range of 660–740 nm. The thermal quenching of the luminescence
intensity due to the non-radiative decay occurs at temperatures above 420 K. The
temperature dependence of the luminescence decay time shows a quasi-linear decrease from
τ = 4.9
to 1.6 ms in the temperature range from 90 to 420 K (with a temperature coefficient
−0.01 ms K−1) that
makes YAlO3:Mn
a potentially good phosphor for a fibre optic fluorescence thermometer in
this temperature range. The high-pressure low-temperature luminescence
measurements in a diamond-anvil cell reveal similar pressure coefficients for
Mn4+ and
Cr3+ dopant
ions in YAlO3,
equal to 1.16 cm−1 kbar−1
and 1.08 cm−1 kbar−1, respectively.
A thorough consideration of the relation between the lattice parameters of 185 binary and ternary spinel compounds, on one side, and ionic radii and electronegativities of the constituting ions, on the other side, allowed for establishing a simple empirical model and finding its linear equation, which links together the above-mentioned quantities. The derived equation gives good agreement between the experimental and modeled values of the lattice parameters in the considered group of spinels, with an average relative error of about 1% only. The proposed model was improved further by separate consideration of several groups of spinels, depending on the nature of the anion (oxygen, sulfur, selenium/tellurium, nitrogen). The developed approach can be efficiently used for prediction of lattice constants for new isostructural materials. In particular, the lattice constants of new hypothetic spinels ZnRE 2 O 4 , CdRE 2 S4, CdRE 2 Se 4 (RE=rare earth elements) are predicted in the present paper. In addition, the upper and lower limits for the variation of the ionic radii, electronegativities and certain their combinations were established, which can be considered as stability criteria for the spinel compounds. The findings of the present paper offer a systematic overview of the structural properties of spinels and can serve as helpful guides for synthesis of new spinel compounds.3
The hydrostatic pressure dependence of photoluminescence, dE PL / dp, of In x Ga 1−x N epilayers has been measured in the full composition range 0 Ͻ x Ͻ 1. Furthermore, ab initio calculations of the band gap pressure coefficient dE G / dp were performed. Both the experimental dE PL / dp values and calculated dE G / dp results show pronounced bowing and we find that the pressure coefficients have a nearly constant value of about 25 meV/GPa for epilayers with x Ͼ 0.4 and a relatively steep dependence for x Ͻ 0.4. On the basis of the agreement of the observed PL pressure coefficient with our calculations, we confirm that band-to-band recombination processes are responsible for PL emission and that no localized states are involved. Moreover, the good agreement between the experimentally determined dE PL / dp and the theoretical curve of dE G / dp indicates that the hydrostatic pressure dependence of PL measurements can be used to quantify changes of the band gap of the InGaN ternary alloy under pressure, demonstrating that the disorder-related Stokes shift in InGaN does not induce a significant difference between dE PL / dp and dE G / dp. This information is highly relevant for the correct analysis of pressure measurements.
Lanthanum orthovanadate (LaVO4) is the only stable monazite-type rare-earth orthovanadate. In the present paper the equation of state of LaVO4 is studied using in situ high-pressure powder diffraction at room temperature, and ab initio calculations within the framework of the density functional theory. The parameters of a second-order Birch-Murnaghan equation of state, i.e. those fitted to the experimental and theoretical data, are found to be in perfect agreement - in particular, the bulk moduli are almost identical, with values of 106 (1) and 105.8 (5) GPa, respectively. In agreement with recent reported experimental data, the compression is shown to be anisotropic. Its nature is comparable to that of some other monazite-type compounds. The softest compression direction is determined.
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