Isochemical crystallization in condensed borate LaMgB5O10 glass-ceramics doped with optical probe Eu3.

The isochemical glass-ceramics doped with Eu3+ were prepared by the heat treatment of lanthanum magnesium borate glass. The crystalline phase was chemically identical to a glass matrix and consisted of condensed borate LaMgB5O10. The isochemical crystallization process begins with the formation of rings by BO4 groups. The emergence of ordered crystalline phase gives rise to intense charge transfer absorption of Eu3+, allowing the efficient luminescence under UV. The analysis of Judd-Ofelt parameters and comparison to purely crystalline samples obtained by solid-state synthesis reveal a switch of parameter relations from Ω2 > Ω4 for glass to Ω2 < Ω4 for crystals but also a maximum value of Ω6 for glass-ceramic sample, which indicates enhanced structural rigidity and results in superior luminescence output. The quantum yield measurements confirmed higher luminescence efficiency for glass-ceramics compared to both pure glass and pure crystalline samples.

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.

Exploration of the Temperature Sensing Ability of La2MgTiO6:Er3+ Double Perovskites Using Thermally Coupled and Uncoupled Energy Levels.

This work aimed to explore the temperature-sensing performance of La2MgTiO6:Er3+ double perovskites based on thermally coupled and uncoupled energy levels. Furthermore, the crystal structure, chemical composition, and morphology of the samples were investigated by powder X-ray diffraction, energy-dispersive X-ray spectroscopy, and scanning electron microscopy, respectively. The most intense luminescence was observed for the sample doped with 5% Er3+. The temperature-dependent emission spectra of La2MgTiO6:5% Er3+ were investigated in the wide range of 77-398 K. The highest sensitivity of the sample was equal to 2.98%/K corresponding to the thermally coupled energy level 2H11/2 → 4I15/2 and 4S3/2 → 4I15/2 as compared to 1.9%/K, obtained for the uncoupled energy level 2H11/2 → 4I15/2 and 2H9/2 → 4I15/2. Furthermore, the 300 K luminescent decay profiles were analyzed using the Inokuti-Hirayama model. The energy transfer among Er3+ ions was mainly regulated by the dipole-dipole mechanism. The critical transfer distance R0, critical concentration C0, energy transfer parameter Cda, and energy transfer probability Wda were 9.81 Å, 2.53×1020 ions·cm-3, 5.38×10-39 cm6·s-1, and 6020 s-1, respectively.

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.

Temperature sensitivity modulation through changing the vanadium concentration in a La2MgTiO6:V5+,Cr3+ double perovskite optical thermometer.

To fulfil the requirements of operating at low temperature in a harsh environment, the investigation on optical thermometers plays an increasingly important role. In this work, the influence of vanadium concentration on the capability of temperature readout by La2MgTiO6:V5+,Cr3+ luminescent thermometers was investigated for the first time. The presence of V3+ and V5+ was verified by XPS and absorption measurements. In the emission spectra, a blue-green emission region was assigned to both host and V5+ emission. Moreover, a spin-forbidden emission of Cr3+ ions was also detected. Vanadium ions in the +3 oxidation state do not exhibit luminescence, but play a role as a charge compensator. The highest emission intensity was obtained from the sample doped with 0.1% V. Besides, with increasing vanadium concentration, a redshift in the maximum position of the spectrum was observed corresponding to a movement from the greenish blue to yellowish green region in the CIE1931. It was shown that the relative sensitivity (Sr) and the temperature operating range can be easily modified by changing the concentration of vanadium ions. In particular, the outstanding relative sensitivities of 1.71% K-1 (at 187 K) and 1.96% K-1 (at 165 K) obtained from La2MgTiO6:0.1%V5+,Cr3+ and La2MgTiO6:0.05%V5+,Cr3+ demonstrated the enormous potential of this material for thermal sensing application.

Deep red fluoride dots-in-nanoparticles for high color quality micro white light-emitting diodes.

In this study, a novel nanostructure of fluoride red emitting phosphor is synthesized via soft templates. K2SiF6:Mn4+ nanocrystals in the range of 3-5 nm diameter are found inside the porous K2SiF6:Mn4+ nanoparticle hosts, forming unique dots-in-nanoparticles (d-NPs) structures with controlled optical properties. The porous K2SiF6:Mn4+ d-NPs exhibit a sharp and deep red emission with an excellent quantum yield of ∼95.9%, and ultra-high color purity with the corresponding x and y in the CIE chromaticity coordinates are 0.7102 and 0.2870, respectively. Moreover, this nanophosphor possesses good thermal stability in range of 300 K-500 K, under light excitation of 455 nm. The K2SiF6:Mn4+ d-NPs are covered onto a surface of 100×100 µm2 blue-yellow InxGa1-xN nanowire light-emitting diode (LED) to make warm white LEDs (WLEDs). The fabricated WLEDs present an excellent color rendering index of ∼95.4 and a low correlated color temperature of ∼3649 K. Porous K2SiF6:Mn4+ d-NPs are suggested as a potential red component for high color quality micro WLED applications.

Synthesis, Structure, Morphology, and Luminescent Properties of Ba2MgWO6: Eu3+ Double Perovskite Obtained by a Novel Co-Precipitation Method.

Eu3+ doped Ba2MgWO6 (BMW) double-perovskite was successfully synthesized for the first time by the co-precipitation method. The synthesis procedure, crystal structure, as well as morphology of obtained samples are presented. Domination of the 5D0-7F1 magnetic-dipole over forced electric-dipole transitions in the emission spectra indicates that Eu3+ ions are located in the high symmetry site with inversion center. Only one emission line assigned to the 5D0-7F0 transition was observed, confirming that europium substituted for only one host cation site. The photoluminescence excitation (PLE) spectrum is dominated by a strong and broad band related to the O2- → Eu3+ and O2- → W6+ charge transfer. The decay of the emission from the 5D0 and 5D1 levels was investigated. The temperature-dependent emission spectra showed that the T0.5 is equal to 350 K. Extinguishing mechanisms of the Eu3+ luminescence in the studied host are discussed.

The effect of K+ cations on the phase transitions, and structural, dielectric and luminescence properties of [cat][K0.5Cr0.5(HCOO)3], where cat is protonated dimethylamine or ethylamine.

We report the synthesis, crystal structure, and dielectric, vibrational and emission spectra of two novel heterometallic perovskite-type metal-organic frameworks (MOFs) of the following formula: [(CH3)2NH2][K0.5Cr0.5(HCOO)3] (DMAKCr) and [C2H5NH3][K0.5Cr0.5(HCOO)3] (EtAKCr). DMAKCr crystallizes in a trigonal structure (R3[combining macron] space group) and undergoes an order-disorder phase transition to the monoclinic system (P1[combining macron] space group) at about 190 K. The dielectric studies confirm the presence of first-order relaxor-like structural transformation. In the high-temperature phase, the dimethylammonium cations are dynamically disordered over three equal positions and upon cooling the dynamical disorder evolves into a two-fold one. This partial ordering is accompanied by a small distortion of the metal-formate framework. EtAKCr crystallizes in a monoclinic structure (P21/n space group) with ordered EtA+ cations and does not experience any phase transition. The differences in the thermal behavior caused by the substitution of Na+ ions by larger K+ ions in the [cat]MIMIII (cat = DMA+, EtA+, MI = Na+, K+ and MIII = Cr3+ and Fe3+) heterometallic MOF family are discussed taking into account the impact of the hydrogen bond (HB) pattern and other factors affecting the stability of metal-formate frameworks. The optical studies show that DMANaCr and EtAKCr exhibit Cr3+-based emission characteristics for intermediate ligand field strength.

Phase transitions and chromium(iii) luminescence in perovskite-type [C2H5NH3][Na0.5CrxAl0.5-x(HCOO)3] (x = 0, 0.025, 0.5), correlated with structural, dielectric and phonon properties.

We report the synthesis, crystal structure, dielectric, vibrational and emission spectra of heterometallic MOFs, [C2H5NH3][Na0.5Cr0.5(HCOO)3] (EtANaCr), [C2H5NH3][Na0.5Al0.5(HCOO)3] (EtANaAl) and [C2H5NH3][Na0.5Al0.475Cr0.025(HCOO)3] (EtANaAlCr). These compounds crystallize in non-centrosymmetric monoclinic polar structures (space group Pn) and undergo order-disorder phase transitions upon heating to the monoclinic centrosymmetric structure (space group P21/n) at 369 (EtANaAl) and 373 K (EtANaCr). In principle, they are ferroelectric below these temperatures. In the high-temperature phase, ethylammonium (EtA+) cations are dynamically disordered over two symmetrically independent positions while upon cooling they begin to order. The ordering is accompanied by distortion of the metal formate framework. The hydrogen bonds (HBs) between the NH3+ group and NaO6 octahedral units are more robust than between the NH3+ group and CrO6 (AlO6) octahedral units and this feature explains a much stronger distortion of the former units and a weak effect of a trivalent cation type on the phase transition temperature. The dielectric studies have confirmed the occurrence of phase transitions of dipolar character and dipole relaxation processes. The optical studies show that EtANaCr and EtANaAlCr exhibit efficient Cr(iii)-based emission characteristics for intermediate-ligand field strength.

Synthesis and characterization of [(CH3)2NH2][Na0.5Cr0.5(HCOO)3]: a rare example of luminescent metal-organic frameworks based on Cr(III) ions.

A novel formate [(CH3)2NH2][Na0.5Cr0.5(HCOO)3] (DMNaCr) was prepared by a solvothermal method. This compound crystallizes in the perovskite-type metal formate framework (space group R3[combining macron]) with disordered dimethylammonium (DMA(+)) cations. X-ray diffraction, DSC, Raman and IR studies show that in contrast to the isostructural iron analogue [(CH3)2NH2][Na0.5Fe0.5(HCOO)3] (DMNaFe), DMNaCr does not exhibit any structural phase transition at low temperatures. This behavior has been attributed to the smaller flexibility of the perovskite-like framework in DMNaCr when compared with that of DMNaFe. Dielectric permittivity data reveal pronounced dielectric relaxation that is attributed to the dynamical rotation of DMA(+) ions. Electron absorption and photoluminescence studies show that this material exhibits efficient emission at low temperatures. A detailed analysis of the optical properties shows that chromium ions are located at the site of intermediate crystal field strength with Dq/B = 2.29.