Search Results (16)

Thermally enhanced upconversion luminescence (UCL), also known as negative thermal quenching of UCL, denotes a continuous increase in the UCL emission intensity of a particular phosphor with a rising temperature. In recent years, the thermal enhancement of UCL has attracted extensive research attention, with numerous reports detailing this effect in phosphors characterized by varying particle sizes, architectures, and compositions. Several hypotheses have been formulated to explain the underlying mechanisms driving this thermal enhancement. This paper rigorously examines thermally enhanced UCL in fluoride nanoparticles by addressing two key questions: (1) Is the thermal enhancement of UCL an intrinsic feature of these nanoparticles? (2) Can the proposed mechanisms explaining this enhancement be unequivocally supported by the existing literature? Upon analyzing a compilation of experimental observations alongside the concurrent phenomena occurred during spectral measurements, it is postulated that thermally enhanced UCL intensity is likely a consequence of multiple extrinsic factors operating simultaneously at elevated temperatures, rather than being an intrinsic property of nanoparticles. These factors include moisture desorption, laser-induced local heating, and lattice thermal expansion. The size-dependent properties of nanoparticles, such as surface-to-volume ratio, thermal expansion coefficient, and quantum yield, are the fundamental reasons for the size-dependent thermal enhancement factor of UCL. Temperature-dependent emission spectral intensity is not a dependable indicator for assessing the thermal quenching properties of phosphors. This is because it is influenced not only by the phosphor’s quantum yield, but also by various extrinsic factors at high temperatures. The nonlinear nature of UCL further magnifies the impact of these extrinsic factors. Full article

In this study, the mechanochemical preparation of nanocrystalline CaF₂:Sm³⁺ by ball milling calcium acetate hydrate, samarium (III) acetate hydrate, and ammonium fluoride is reported. The photoluminescence of the as-prepared CaF₂:Sm³⁺ shows predominantly Sm^3+ 4G_5/2 → ⁶H_J(J = 5/2, 7/2, 9/2, and 11/2) f-f luminescence, but intense electric dipole allowed 4f⁵5d (T_1u) → 4f^6 7F₁ (T_1g) luminescence by Sm²⁺ was generated upon X-irradiation. In comparison with the co-precipitated CaF₂:Sm³⁺, the conversion of Sm³⁺$\to$ Sm²⁺ in the ball-milled sample upon X-irradiation is significantly lower. Importantly, the present results indicate that the crystallite size and X-ray storage phosphor properties of the lanthanide-doped nanocrystalline CaF₂ can be modified by adjusting the ball milling time, dopant concentration and post-annealing treatment, yielding crystallite sizes as low as 6 nm under specific experimental conditions. Full article

Excitation wavelength controllable lanthanide upconversion allows for real-time manipulation of luminescent color in a composition-fixed material, which has been proven to be conducive to a variety of applications, such as optical anti-counterfeiting and information security. However, current available materials highly rely on the elaborate core–shell structure in order to ensure efficient excitation-dependent energy transfer routes. Herein, multicolor upconversion luminescence in response to both near-infrared I and near-infrared II (NIR-I and NIR-II) excitations is realized in a novel but simple NaYGeO₄:Yb³⁺/Er³⁺ phosphor. The remarkably enhanced red emission ratio under 1532 nm excitation, compared with that under 980 nm excitation, could be attributed to the Yb³⁺-mediated cross-relaxation energy transfers. Moreover, multi-wavelength excitable temperature-dependent (295–823 K) upconversion luminescence realizes a ratiometric thermometry relying on the thermally coupled levels (TCLs) of Er³⁺. Detailed investigations demonstrate that changing excitation wavelength makes little difference for the performances of TCL-based ratiometric thermometry of NaYGeO₄:Yb³⁺/Er³⁺. These findings gain more insights to manipulate cross-relaxations for excitation controllable upconversion in single activator doped materials and benefit the cognition of the effect of excitation wavelength on ratiometric luminescence thermometry. Full article

Gallium oxide (Ga₂O₃) is an emerging wide bandgap semiconductor promising a wide range of important applications. However, mass production of high-quality crystalline Ga₂O₃ still suffers from limitations associated with poor reproducibility and low efficiency. Low-temperature-grown amorphous Ga₂O₃ demonstrates comparable performance with its crystalline counterparts. Lanthanide Er³⁺-doped Ga₂O₃ (Ga₂O₃: Er) possesses great potential for developing light-emitting devices, photodetectors, solid-state lasers, and optical waveguides. The host circumstance can exert a crystal field around the lanthanide dopants and strongly influence their photoluminescence properties. Here, we present a systematical study of the impact of amorphous-to-crystalline transition on the upconversion photoluminescence in Ga₂O₃: Er thin films. Through controlling the growth temperature of Ga₂O₃: Er films, the upconversion luminescence of crystalline Ga₂O₃: Er thin film is strongly enhanced over 100 times that of the amorphous Ga₂O₃: Er thin film. Moreover, the variation of photoluminescence reflects the amorphous-to-crystalline transformation of the Ga₂O₃: Er thin films. These results will aid further designs of favorable optoelectronic devices integrated with lanthanide-doped Ga₂O₃ thin films. Full article

The study provides novel insights into the crystal–chemical and optical characteristics of frankamenite. Frankamenite belongs to a special group (canasite group) of the complex alkaline Ca-(K)-(Na) silicates, and it was found in charoitites from the only known location, Murun Massif, Eastern Siberia, Russia. The crystal–chemical, vibrational, and optical properties of frankamenite were investigated by combining electron probe microanalysis (EPMA), single-crystal X-ray diffraction (SCXRD), infrared (IR) absorption, Raman, UV-Visible absorption, and electron spin resonance (ESR) spectroscopy. The behavior of the peaks in the IR spectra was also studied using ab initio calculations. Detailed characteristics of the internal composition and structure of the mineral species were described, and vibrational and optical properties based on these peculiarities were interpreted. The thermally stimulated reorientation of the H₂O molecules and OH⁻ groups was studied by thermo-Raman spectroscopy. Octahedral cationic positions can be readily doped with transition metal and lanthanide ions that provide a promising opportunity to adjust the Ce³⁺ luminescence. Hence, frankamenite is a potential material for ion exchange, novel phosphors, and luminophores. Full article

Nanophosphors are widely used, especially in biological applications in the first and second biological windows. Currently, nanophosphors doped with lanthanide ions (Ln³⁺) are attracting much attention. However, doping the matrix with lanthanide ions is associated with a narrow luminescence bandwidth. This paper describes the structural and luminescence properties of co-doped LaPO₄ nanophosphors, fabricated by the co-precipitation method. X-ray structural analysis, scanning electron microscope measurements with EDS analysis, and luminescence measurements (excitation 395 nm) of LaPO₄:Eu³⁺/Nd³⁺ and LaPO₄:Eu³⁺/Nd³⁺/Yb³⁺ nanophosphors were made and energy transfer between rare-earth ions was investigated. Tests performed confirmed the crystal structure of the produced phosphors and deposition of rare-earth ions in the structure of LaPO₄ nanocrystals. In the range of the first biological window (650–950 nm), strong luminescence bands at the wavelengths of 687 nm and 698 nm (⁵D₀ → ⁷F₄:Eu³⁺) and 867 nm, 873 nm, 889 nm, 896 nm, and 907 nm (⁴F_3/2 → ⁴I_9/2:Nd³⁺) were observed. At 980 nm, 991 nm, 1033 nm (²F_5/2 → ²F_7/2:Yb³⁺) and 1048 nm, 1060 nm, 1073 nm, and 1080 nm (⁴F_3/2 → ⁴I_9/2:Nd³⁺), strong bands of luminescence were visible in the 950 nm–1100 nm range, demonstrating that energy transfer took place. Full article

A polyester resin was strengthened with electrospun glass nanofibers to create long-lasting photochromic and photoluminescent products, such as smart windows and concrete, as well as anti-counterfeiting patterns. A transparent glass@polyester (GLS@PET) sheet was created by physically immobilizing lanthanide-doped aluminate (LA) nanoparticles (NPs). The spectral analysis using the CIE Lab and luminescence revealed that the transparent GLS@PET samples turned green under ultraviolet light and greenish-yellow in the dark. The detected photochromism can be quickly reversed in the photoluminescent GLS@PET hybrids at low concentrations of LANPs. Conversely, the GLS@PET substrates with the highest phosphor concentrations exhibited sustained luminosity with slow reversibility. Transmission electron microscopic analysis (TEM) and scanning electron microscopy (SEM) were utilized to examine the morphological features of lanthanide-doped aluminate nanoparticles (LANPs) and glass nanofibers to display diameters of 7–15 nm and 90–140 nm, respectively. SEM, energy-dispersive X-ray spectroscopy (EDXA), and X-ray fluorescence (XRF) were used to analyze the luminous GLS@PET substrates for their morphology and elemental composition. The glass nanofibers were reinforced into the polyester resin as a roughening agent to improve its mechanical properties. Scratch resistance was found to be significantly increased in the created photoluminescent GLS@PET substrates when compared with the LANPs-free substrate. When excited at 368 nm, the observed photoluminescence spectra showed an emission peak at 518 nm. The results demonstrated improved hydrophobicity and UV blocking properties in the luminescent colorless GLS@PET hybrids. Full article

Upconversion materials capable of converting low-energy excitation photons into high-energy emission photons have attracted considerable interest in recent years. However, the low upconversion luminescence seriously hinders the application of upconversion phosphors. Heavy lanthanide doping without concentration quenching represents a direct and effective method to enhance the emission intensity. In this study, Er³⁺ heavy doped Gd₂(MoO₄)₃ phosphor with a monoclinic phase was prepared by a sol–gel process. Under excitation at 976 nm, Gd₂(MoO₄)₃:Er³⁺ phosphor emitted remarkably intense green emission, and Er³⁺ concentration up to 20 mol% did not cause concentration quenching. Here, we discuss the upconversion mechanism and concentration quenching. When the Er³⁺ concentration was in the range of 30–60 mol%, the concentration quenching was governed by the electric dipole–dipole interaction, and when the concentration was greater than 60 mol%, the concentration quenching was controlled by the exchange interactions. The result provides a schematic basis for identifying a phosphor host with heavy lanthanide doping. Full article

The elucidation of local structure, excitation-dependent spectroscopy, and defect engineering in lanthanide ion-doped phosphors was a focal point of research. In this work, we have studied Eu³⁺-doped BaZrO₃ (BZOE) submicron crystals that were synthesized by a molten salt method. The BZOE crystals show orange–red emission tunability under the host and dopant excitations at 279 nm and 395 nm, respectively, and the difference is determined in terms of the asymmetry ratio, Stark splitting, and intensity of the uncommon ⁵D₀ → ⁷F₀ transition. These distinct spectral features remain unaltered under different excitations for the BZOE crystals with Eu³⁺ concentrations of 0–10.0%. The 2.0% Eu³⁺-doped BZOE crystals display the best optical performance in terms of excitation/emission intensity, lifetime, and quantum yield. The X-ray absorption near the edge structure spectral data suggest europium, barium, and zirconium ions to be stabilized in +3, +2, and +4 oxidation states, respectively. The extended X-ray absorption fine structure spectral analysis confirms that, below 2.0% doping, the Eu³⁺ ions occupy the six-coordinated Zr⁴⁺ sites. This work gives complete information about the BZOE phosphor in terms of the dopant oxidation state, the local structure, the excitation-dependent photoluminescence (PL), the concentration-dependent PL, and the origin of PL. Such a complete photophysical analysis opens up a new pathway in perovskite research in the area of phosphors and scintillators with tunable properties. Full article

Photopolymer resins used in stereolithographic 3D printing are limited to penetration depths of less than 1 mm. Our approach explores the use of near-infrared (NIR) to visible upconversion (UC) emissions from lanthanide-based phosphors to initiate photopolymer crosslinking at a much higher depth. This concept relies on the use of invisibility windows and non-linear optical effects to achieve selective crosslinking in photopolymers. SLA resin formulation capable of absorbing light in the visible region (420–550 nm) was developed, in order to take advantage of efficient green-UC of Er³⁺/Yb³⁺ doped phosphor. NIR-green light UC shows versatility in enhancing curing depths in laser patterning. For instance, a structure with a curing depth of 11 ± 0.2 mm, cured width of 496 ± 5 µm and aspect ratios of over 22.2:1 in a single pass via NIR-green light UC. The penetration depth of the reported formulation approached 39 mm. Therefore, this technique would allow curing depths of up to 4 cm. Moreover, it was also demonstrated that this technique can initiate cross-linking directly at the focal point. This shows the potential of NIR-assisted UC as a low-cost method for direct laser writing in volume and 3D printing. Full article

Light-emitting phosphors, doped with lanthanide ions of Tb(III) and Sm(III) of the type Gd_1.97−y Sm_yTb_0.03(MoO₄)₃ (y = 0.01–0.11, step 0.02) and Gd_1.95−xSm_0.05Tb_x(MoO₄)₃ (x = 0.01–0.09, step 0.02), were synthesized and characterized by X-ray diffraction, UV-Vis spectroscopy, scanning and transmitting electron microscopy (SEM, TEM) as well as photoluminescence spectroscopy. The effect of the doping content of Tb/Sm was followed. The unit cell parameters for Gd_1.97−ySm_yTb_0.03(MoO₄)₃ and Gd_1.95−xSm_0.05Tb_x(MoO₄)₃ changed with the increase in the Tb/Sm content. The microstrain values also increased, proposing an increased concentration of defects. The mean particle size was estimated to be approximately 0.6 µm. Based on a Williamson–Hall plot, the size of the crystallites was determined to be in the range of 42–60 nm for modified and pure Gd₂(MoO₄)₃ samples, respectively. The samples excited at 406 nm exhibited characteristic emission lines of Sm (485, 555, 646 nm). The host material Gd₂(MoO₄)₃ emission in visible light was explained by the crystal structure defects, namely, oxygen vacancies. The CIE x/y color coordinates of the phosphors were determined and the related points were located in the green-yellow/pale yellow region of the visible light. The excited state lifetimes were determined for both groups of the samples, showing values in the millisecond range and indicating the samples as promising phosphors. Full article

Near infrared (NIR) light offers high transparency in biological tissue. Recent advances in NIR fluorophores including organic dyes and lanthanide-doped inorganic nanoparticles have realized the effective use of the NIR optical window for in vivo bioimaging and photodynamic therapy. The narrow energy level intervals used for electronic transition that involves NIR light, however, give rise to a need for guidelines for reducing heat emission in luminescence systems, especially in the development of organic/inorganic hybrid structures. This review presents an approach for employing the polarity and vibrational energy of ions and molecules that surround the luminescence centers for the development of such hybrid nanostructures. Multiphonon relaxation theory, formulated for dealing with heat release in ionic solids, is applied to describe the vibrational energy in organic or molecular systems, referred to as phonon in this review, and we conclude that surrounding the luminescence centers either with ions with low vibrational energy or molecules with small chemical polarity is the key to bright luminescence. NIR photoexcited phosphors and nanostructures in organic/inorganic mixed systems, designed based on the guidelines, for photodynamic therapy are reviewed. Full article

Lanthanide-activated alkaline earth aluminate phosphors are excellent luminescent materials that are designed to overcome the limitations of conventional sulfide-based phosphors. The increasing research attention on these phosphors over the past decade has led to a drastic improvement in their phosphorescence efficiencies and resulted in a wide variety of phosphorescence colors, which can facilitate applications in various areas. This review article discusses the development of lanthanide-activated alkaline earth aluminate phosphors with a focus on the various synthesis methods, persistent luminescence mechanisms, activator and coactivator effects, and the effects of compositions. Particular attention has been devoted to alkaline earth aluminate phosphors that are extensively used, such as strontium-, calcium-, and barium-based aluminates. The role of lanthanide ions as activators and coactivators in phosphorescence emissions was also emphasized. Finally, we address recent techniques involving nanomaterial engineering that have also produced lanthanide-activated alkaline earth aluminate phosphors with long-persistent luminescence. Full article

For many optoelectronic applications, it is desirable for the lanthanide-doped phosphors to have broad excitation spectrum. The excitation mechanism of the lanthanide-doped YVO₄, a high quantum efficient lasing material, primarily originates from the energy transfer process from the host VO₄³⁻ complexes to the lanthanide ions, which has an excitation spectral bandwidth range of 230–330 nm. For applications in silicon solar cells, such phosphors can convert ultraviolet light to visible light for more efficient power generation, but this spectral range is still not broad enough to cover the entire ultraviolet spectrum of solar light. In this work, a novel core-shell and inorganic–organic hybridization strategy has been employed to fabricate Eu³⁺-doped YVO₄ nanoparticles to broaden their photoluminescence excitation spectral bandwidth to the range of 230–415 nm, covering the entire ultraviolet spectrum of solar light and enabling their potential applications in silicon solar cells. Full article

Due to the high atomic number of lutetium and the low phonon energy of the fluoride matrix, Lu-based fluoride nanoparticles doped with active lanthanide ions are potential candidates as bioprobes in both X-ray computed tomography and luminescent imaging. This paper shows a method for the fabrication of uniform, water-dispersible Eu³⁺:(H₃O)Lu₃F₁₀ nanoparticles doped with different Eu contents. Their luminescent properties were studied by means of excitation and emission spectra as well as decay curves. The X-ray attenuation capacity of the phosphor showing the highest emission intensity was subsequently analyzed and compared with a commercial contrast agent. The results indicated that the 10% Eu³⁺-doped (H₃O)Lu₃F₁₀ nanoparticles fabricated with the proposed polyol-based method are good candidates to be used as dual probes for luminescent imaging and X-ray computed tomography. Full article