Highly Sensitive Temperature Sensors Resulting from the Luminescent Behavior of Sm3+-Doped Ba2MgMoO6 High-Symmetry Double-Perovskite Molybdate Phosphors.

We present double-perovskite molybdate with the formula of Ba2MgMoO6 doped with Sm3+ ions as a potential red phosphor to improve the color characteristics of white-light-emitting dioded (wLEDs). The new orange-red phosphor was synthesized using the co-precipitation (CP) method, and then its structural and spectroscopic properties were determined. Red emission at 642.6 nm dominates, which results from the electric dipole (ED) transition of the 4G5/2 → 6H9/2 type, and the materials are characterized by short luminescence decay times. BMM:Sm3+ is, to our best knowledge, the clearest example of dominant red emission of Sm3+ resulting from the location of the dopant in octahedral sites of high-symmetry cubic structure. In the sample containing 0.1% Sm3+, Sm3+ ions are located in both Mg2+ and Ba2+ sites, while at higher concentrations the Ba2+ site is less preferable for doping, as a result of which the emission becomes more uniform and single-site. The relative sensitivity calculated from FIR has a maximum of 2.7% K-1 at -30 °C and another local maximum of 1.6% K-1 at 75 °C. Such value is, to the best of our knowledge, one of the highest achieved for luminescent thermometry performed using only Sm3+ ions. To sum up, the obtained materials are good candidates as red phosphor to improve the color characteristics of wLEDs, obtaining a color-rendering index (CRI) of 91 and coordinated color temperature (CCT) of 2943 K, constituting a warm white emission. In addition to this, a promising precedent for temperature sensing using high-symmetry perovskite materials is the high sensitivity achieved, which results from the high symmetry of the BMM host.

Influence of Sintering Parameters on Spectroscopic Properties of BMW: Eu3+ Ceramic Materials Prepared by HPLT Technique.

In this work, Ba2MgWO6: Eu3+ (BMW: Eu3+) ceramic materials with a double perovskite structure were sintered using the High-Pressure Low-Temperature sintering (HPLT) technique. As part of the research, the influence of pressure (CP), sintering temperature (CT), and sintering time (CTS) on the structure and luminescence of the doped BMW were determined. Structural analysis via XRD and SEM + EDS and spectroscopic analysis via emission and excitation spectra, decay time, and absorption spectra of the obtained ceramics were performed. Dense double perovskite ceramics were obtained with a cubic structure with optimal sintering parameters: T = 500 °C, p = 8 GPa, and t = 1 min. The increase in temperature caused an increased extinction of the luminescence due to the diffusion of carbon into the ceramics. The increase in pressure led to the formation of the amorphous phase, which increased the speed of non-radiative transitions and also led to the extinction of the luminescence. The increase in sintering time from 1 to 3 min enhanced the luminescence output, but when the ceramic was sintered for 5 min, the luminescence was quenched, most likely by increasing the rate of the non-radiative process, as evidenced by reduced decay time.

On how the mechanochemical and co-precipitation synthesis method changes the sensitivity and operating range of the Ba2Mg1-xEuxWO6 optical thermometer.

The suitability of Ba2MgWO6 (BMW) double perovskite doped with Eu3+ for the construction of an optical thermometer was tested. It has been shown that by controlling the conditions of BMW synthesis, the sensitivity of the optical thermometer and the useful range of its work can be changed. Pure BMW and doped with Eu3+ samples were prepared using the mechano-chemical and co-precipitation methods. Both the absolute sensitivity and the relative sensitivity in relation to the synthesis route were estimated. The findings proved that the relative sensitivity can be modulated from 1.17%K-1 at 248 K, to 1.5%K-1 at 120 K for the co-precipitation and the mechanochemical samples, respectively. These spectacular results confirm the applicability of the Ba2MgWO6: Eu3+ for the novel luminescent sensors in high-precision temperature detection devices. The density-functional theory was applied to elucidate the origin of the host emission.

Effect of Ceramic Formation on the Emission of Eu3+ and Nd3+ Ions in Double Perovskites.

Herein, the structure, morphology, as well as optical properties of the powder and ceramic samples of Ba2MgWO6 are presented. Powder samples were obtained by high temperature solid-state reaction, while, for the ceramics, the SPS technique under 50-MPa pressure was applied. The morphology of the investigated samples showed some agglomeration and grains with a submicron size of 490-492 µm. The theoretical density and relative density of ceramics were calculated using the Archimedes method. The influence of sample preparation on the position, shape, and character of the host, as well as dopants emission was investigated. Sample sintering enhances regular emission of WO6 groups causing a blue shift of Ba2MgWO6 emission. Nonetheless, under X-ray excitation, only the green emission of inversion WO6 group was detected. For the ceramic doped with Eu3+ ions, the emission of both host and dopant was detected. However, for the powder efficient host to activator energy, the transfer process occurred, and only the magnetic dipole emission of Eu3+ was detected. The intensity of Nd3+ ions of Ba2MgWO6 powder sample is five times higher than for the ceramic. The sintering process reduces inversion defects and creates a highly symmetrical site of neodymium ions. The emission of Ba2MgWO6:Nd3+ consists of transitions from the 4F3/2 excited level to the 4IJ multiplet states with the dominance of the 4F3/2→4I11/2 one. The spectroscopic quality parameter and branching ratio of Nd3+ emission are presented.