UVC Stokes and Anti-Stokes Emission of Ca9Y(PO4)7 Polycrystals Doped with Pr3+ Ions.

The recent COVID-19 pandemic has made everyone aware of the threat of viruses and the growing number of antibiotic-resistant bacteria. It has become necessary to find new methods to combat these hazards. One tool that could be used is UVC radiation, i.e., 100-280 nm. Currently, the available sources of this light are mercury vapor lamps. However, the modern world requires more compact, mercury-free, and less energy-consuming light sources. This work presents the results of our research on a new material in which efficient UVC radiation was obtained. Here, we present the results of research on Ca9Y(PO4)7 polycrystals doped with Pr3+ ions prepared using the solid-state method. The absorption, excitation, emission, and emission decay profiles of praseodymium(III) ions were measured and analyzed. The upconversion emission in the UVC region excited by blue light was observed. Parameters such as energy bandgap, refractive index, and thermal stability of luminescence were determined. The studied phosphate-based phosphor possesses promising characteristics that show its potential in luminescent applications in future use in medicine or for surface disinfection.

UVC Up-Conversion and Vis-NIR Luminescence Examined in SrO-CaO-MgO-SiO2 Glasses Doped with Pr3.

The application of ultraviolet-C light in the field of surface treatment or photodynamic therapy is highly prospective. In this regard, the stable fluorescent silicate SrO-CaO-MgO-SiO2-Pr2O3 glasses able to effectively convert visible excitation on the ultraviolet praseodymium emission were fabricated and examined. An unusual wide-range visible-to-UVC up-conversion within 240-410 nm has been achieved in Pr3+-doped glasses, revealing their potential advantage in different sophisticated disinfection technologies. The integrated emission intensity was studied as a function of light excitation power to assess a mechanism attributed to UVC luminescence. Especially, it was revealed that the multicomponent silicate glass qualities and praseodymium 3PJ excited state peculiarities are favorable to obtaining useful broadband ultraviolet up-converted luminescence. The glass dispersion qualities were determined between 450-2300 nm. The impact of praseodymium concentration on Vis-NIR spectroscopic glass qualities was evaluated employing absorption spectra, emission spectra, and decay curves of luminescence associated with two involved praseodymium excited states. Especially, efficient interionic interactions can be inferred by investigating the decrease in 1D2 state experimental lifetime in the heavily doped samples. Examination of absorption spectra as a function of temperature implied that excitation at 445 nm should be quite effective up to T = 625 K. Contrary to this, temperature elevation gives rise to a moderate lowering of the visible praseodymium luminescence.

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.

Luminescence Properties of an Orthorhombic KLaF4 Phosphor Doped with Pr3+ Ions under Vacuum Ultraviolet and Visible Excitation.

Fluorides have a wide bandgap and therefore, when doped with the appropriate ions, exhibit emissions in the ultraviolet C (UVC) region. Some of them can emit two photons in the visible region for one excitation photon, having a quantum efficiency greater than 100%. In a novel exploration, praseodymium (Pr3+) ions were introduced into KLaF4 crystals for the first time. The samples were obtained according to a high-temperature solid-state reaction. They exhibited an orthorhombic crystal structure, which has not been observed for this lattice yet. The optical properties of the material were investigated in the ultraviolet (UV) and visible ranges. The spectroscopic results were used to analyze the Pr3+ electronic-level structure, including the 4f5d configuration. It has been found that KLaF4:Pr3+ crystals exhibit intense luminescence in the UVC range, corresponding to multiple 4f → 4f transitions. Additionally, under vacuum ultraviolet (VUV) excitation, distinct transitions, specifically 1S0 → 1I6 and 3P0 → 3H4, were observed, which signifies the occurrence of photon cascade emission (PCE). The thermal behavior of the luminescence and the thermometric performance of the material were also analyzed. This study not only sheds light on the optical behavior of Pr3+ ions within a KLaF4 lattice but also highlights its potential for efficient photon management and quantum-based technologies.

Upconversion Luminescence Properties of Pr3+-Doped BaYF5 Nanoparticles Prepared by Microwave Hydrothermal Method.

Pure and Pr3+-doped BaYF5 nanoparticles were synthesized by the microwave hydrothermal method. The nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and optical spectroscopy. The XRD and TEM confirm that the average size of nanoparticles is in the range of 26-37 nm. The optical excitation and luminescence spectra of BaYF5:Pr3+ nanoparticles are presented in the visible and ultraviolet (UV) range. It has been verified that Pr3+ ions are capable of emitting UV-C photons when excited by a 444 nm laser. This emission arises from a two-photon energy-transfer upconversion mechanism. The concentration dependence of the upconversion luminescence of BaYF5:Pr3+ was studied.

Effect of A-Cation Radius on the Structure, Luminescence, and Temperature Sensing of Double Perovskites A2MgWO6 Doped with Dy3+ (A = Ca, Sr, Ba).

Herein, we report a case of A2MgWO6 (A = Ca, Sr, Ba) doped with 2%Dy3+, 2%Li+, in which the influences of the cation substitution are exhibited through the crystal structure, the charge transfer band (O2--W6+), the emission spectrum, the color of the luminescence, and the luminescent decay time. The substitution of Ca2+ and Sr2+ ions for larger ions (Ba2+) led to the crystal structure alteration from cubic to monoclinic and tetragonal, respectively. These structure changes also lowered the crystallography symmetry site of Dy3+, tuned the color of the emitted light from the whitish to yellowish region, and caused a blue shift of the CTB. Furthermore, a significant decline in the lifetime of the 4F9/2 → 6H13/2,15/2 transitions was noticed, from 748, 199, to 146 µs corresponding to Ba, Sr, Ca sample owing to the reduction in the local symmetry of Dy3+. Moreover, the thermal sensing properties of 2%Dy3+-doped samples were investigated based on the fluorescence intensity ratio technique in the range of 80-325 K. Under 266 nm excitation wavelength, the maximum relative sensitivity of the investigated samples was remarkably enhanced from 2.26%/K, 3.04%/K, to 4.38%/K corresponding to Ba, Ca, and Sr samples, respectively. In addition to providing a comprehensive understanding of the effects of compositional modifications on the optical properties, the results also present a viable pathway to manipulate the temperature sensing performance.

Highly Stable White Light Emission from III-Nitride Nanowire LEDs Utilizing Nanostructured Alumina-Doped Mn4+ and Mg2.

In this report, red-emitting alumina nanophosphors doped with Mn4+ and Mg2+ (Al2O3:Mn4+, Mg2+) are synthesized by a hydrothermal method using a Pluronic surfactant. The prepared samples are ceramic-sintered at various temperatures. X-ray diffraction shows that Al2O3:Mn4+, Mg2+ annealed at 500 °C exhibits a cubic γ-Al2O3 phase with the space group Fd3m-227. The tetragonal δ-Al2O3 and rhombohedral α-Al2O3 phase is obtained at 1000 and 1300 °C, respectively. Cube-like nanoparticles in a size of ∼40 nm are observed for the alumina heated at 500-1000 °C. The size and red-emitting intensity of the phosphors remarkably increased with annealed temperature ∼1300 °C. Emission spectra of the phosphors show strong peaks at 678 and 692 nm due to 2 E g → 4 A 2 transitions of the Mn4+ ion, under a light excitation of 460 nm. A strong zero-phonon line (ZPL) emission is observed in the luminescence spectra of δ-Al2O3:Mn4+, Mg2+ at 298 K, whereas a weak one is observed in those of α- and γ-Al2O3:Mn4+, Mg2+. The alumina phosphors exhibited an excellent waterproof ability during 60 days in water and good thermal stability in the range of 77-573 K. A warm-white light-emitting diode (WLED) fabricated using In x Ga1-x N nanowire chips with Al2O3:Mn4+, Mg2+ red-emitting nanophosphors presents a high color rendering index of ∼95.1 and a low correlated color temperature of ∼4998 K. Moreover, the current-voltage characteristic of the nanowire LEDs could be improved using Al2O3:Mn4+, Mg2+ nanophosphors which is attributed to the increased heat dissipation in the nanowire LEDs.

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.

Passive radiant cooling without sacrificing the aesthetics of objects.

Photonic-engineered passive radiative cooling built into decorative climate-controlled enclosures reduces the active power consumption of the existing enclosure without sacrificing its aesthetics.

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.