Novel Upconversion Behavior in Ho3+‐Doped Transparent Oxyfluoride Glass‐Ceramics Containing NaYbF4 Nanocrystals

Novel Ho³⁺ doped highly transparent NaYbF₄ glass‐ceramics were successfully fabricated by melt‐quenching technique. Their structural and luminescent properties were systemically investigated by XRD, TEM, absorption spectra, upconversion spectra, and lifetime measurements. Excited by 980‐nm laser, samples exhibit characteristic emissions of Ho³⁺. Impressively, the luminescent color can be tuned easily from red for precursor glass to green for glass‐ceramics. Such novel phenomenon was elaborately investigated and is owing to the reduced multiphonon nonradiative relaxation and enhanced cross‐relaxation of Ho³⁺ in NaYbF₄ nanocrystals after crystallization. Our results indicate that NaYbF₄ transparent glass‐ceramics is an excellent host for upconversion.     

Elaboration,Structure, and Luminescence of Eu3+‐Doped BaLuF5‐Based Transparent Glass‐Ceramics

Novel Eu³⁺‐doped transparent oxyfluoride glass‐ceramics containing BaLuF₅ nanocrystals were successfully fabricated by melt‐quenching technique for the first time. Analyses of XRD patterns prove that the new precipitated glass‐ceramics are crystallized in cubic BaLuF₅ based on isostructural BaGdF₅. Intense red emissions observed in glass ceramics are attributed to the enrichment of Eu³⁺ ions into BaLuF₅ nanocrystals. Besides, obvious stark splitting emissions, low forced electric dipole ⁵D₀→⁷F₂ transition, and long decay lifetimes of Eu³⁺ ions also evidence the partition of Eu³⁺ ions into BaLuF₅ nanocrystals with low phonon energy. Such transparent material may find applications in photonics.     

Er3+ Ions‐Doped Germano‐Gallate Oxyfluoride Glass‐Ceramics Containing BaF2 Nanocrystals

Er³⁺ ions‐doped germano‐gallate oxyfluoride glass‐ceramic containing BaF₂ nanocrystals was prepared through conventional melt quenching and subsequent thermal treatment method. X‐ray diffraction patterns and transmission electron microscope images confirmed the formation of BaF₂ nanocrystals in glass‐ceramics. Preferential incorporation of Er³⁺ ions into the BaF₂ nanocrystals were confirmed by the absorption spectra and emission spectra, and enhanced upconversion emission and infrared emission were observed. Relatively high transmittance in the mid‐infrared region indicated great potential of this germano‐gallate oxyfluoride glass‐ceramics as host materials for the efficient mid‐infrared emission from rare‐earth ions.     

Phase evolution and photoluminescence in Er3+ doped glass ceramics containing lutetium oxyfluoride nanocrystals

Crystalline phase evolution through merely adjusting composition was achieved in silicate glass ceramics containing Lu_nO_n-1F_n+2 (n = 5–10) nanocrystals. Orthorhombic or cubic phase nanocrystals were precipitated in the aluminosilicate glass matrix after thermal treatment together with varying the Na₂O/NaF ratio. Oxyfluoride nanocrystals with quasi-spherical shape show homogenous and dense distribution in glass matrix by transmission electron microscopy measurement. Intense upconversion and mid-infrared emissions were realized in these glass ceramics compared to the precursor glass, and the emission spectral shapes, relative emission intensity and fluorescence decay curves of Er³⁺ in cubic LuOF embedded samples exhibit remarkable differences due to the crystal phase dependent effect in glass ceramics. These results indicate that the crystallization and luminescence properties of oxyfluoride glass ceramics could be modified through the alteration of glass composition, which could be used for the development of novel glass ceramics and design of luminescent properties.     

Germanate-based oxyfluoride transparent glass-ceramic embedded with Tm3+:Ca2YbF7 nanocrystals for high-performance optical thermometer

Germanate-based oxyfluoride transparent glass-ceramic functionalized by Tm³⁺:Ca₂YbF₇ nanocrystals was newly developed. The tremendously enhanced upconversion emission of ³F_2,3 energy levels by in situ crystallization was extremely beneficial for constructing optical thermometry involving the indirect thermally coupled energy levels (¹G₄ and ³F_2,3) of Tm³⁺ ions. Utilizing the fluorescence intensity ratio technique, the thermometry potentials of PG and GC8 were systematically evaluated based on the emissions from ³F_2,3 and ¹G₄ energy levels. The relative and absolute sensitivities, thermometry resolutions, and repeatabilities were superior to many reported materials. This work provides an avenue for precipitating ternary fluoride nanocrystals containing rare earths in germanate-based oxyfluoride glass, and proposes a promising way to achieve high performance optical thermometry based on the emissions from widely spaced energy levels.     

Effect of lanthanide doping on crystal phase and near-infrared to near-infrared upconversion emission of Tm doped KF–YbF3 nanocrystals

Tm³⁺ doped KF–YbF₃ nanocrystals were synthesized by a hydrothermal method using oleic acid as a stabilizing agent at 190 °C. The influence of Gd³⁺ and Sm³⁺ content on the phase structure and upconversion (UC) emission of the final products was investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and UC spectra. XRD analyses and TEM observations evidence that the phase and size of the as prepared Tm³⁺ doped KF–YbF₃ nanocrystals are closely related to the Gd³⁺ doping content. Without Gd³⁺ impurity, the undoped nanocrystals crystallize in orthorhombic KYb₂F₇ with an average diameter of 42 nm. When the Gd³⁺ doping is below 10 mol%, the orthorhombic KYb₂F₇ nanocrystals grow up. However, with Gd³⁺ addition beyond about 30 mol%, the complete phase transformation from orthorhombic KYb₂F₇ to cubic KGdF₄ occurs in the final products. Under the excitation of a 980 nm laser diode, the as prepared Tm³⁺ doped nanocrystals exhibit strong near-infrared UC emission at 800 nm. Particularly, the intensity of high energy UV and blue UC emissions of Tm³⁺ ions in Tm³⁺ doped KYb₂F₇ nanocrystals are selectively reduced compared to the NIR emission at 800 nm by co-doping a small amount of Sm³⁺ ions into the host matrix. Possible dynamic processes for UC emissions in Tm³⁺ doped nanocrystals are discussed in detail.     

Luminescence of Eu‐Doped Transparent LuPO4 Glass‐Ceramics

Dual valence Eu‐doped transparent glass‐ceramics containing LuPO₄ nanocrystals were fabricated by melt‐quenching technique in air atmosphere. Their luminescent properties were systematically investigated by excitation, emission spectra, and decay lifetime measurements. The prominent Stark splitting, low forced electric‐dipole ⁵D₀ – ⁷F₂ transition and long decay lifetimes of Eu^{3 +} emission for glass‐ceramics reveal the incorporation of Eu^{3 +} into LuPO₄ nanocrystals. The enhanced Eu^{2 +} emission and reduction mechanism of Eu^{3 +} to Eu^{2 +} after crystallization are discussed briefly. Our results indicate that transparent LuPO₄ glass‐ceramics may find applications in photonics.     

Near white light emission of Ce3+‐, Ho3+‐, and Sm3+‐doped oxyfluoride silicate glasses

The Ce³⁺‐, Ho³⁺‐, and Sm³⁺‐ single and co‐doped oxyfluoride silicate glasses for light emitting diodes are studied. These glasses were prepared by melt quenching method and their optical and structural properties were investigated by absorption spectra, photoluminescence spectra, Commission International de I'Eclairage chromaticity coordinates, X‐ray diffraction, and Fourier transform infrared spectra. It is found that the introduction of Al₂O₃ in glass composition can improve the emissions of Ho³⁺ and Sm³⁺. While the presence of B₂O₃ has the adverse effect and can suppress the emissions of Ho³⁺ and Sm³⁺. With substituting Na₂O for CaO in the glass compositions, CaF₂ crystals can be formed during the melt quenching process. We find the formation of CaF₂ crystals can change the emission behavior of Ho³⁺ and Sm³⁺ ions. White light emissions can be achieved in the glasses and the luminescence colors can be tuned by varying the concentrations of the doped rare‐earth ions and the composition of glass matrix. The Ce³⁺‐, Ho³⁺‐, and Sm³⁺‐doped oxyfluoride silicate glasses presented here demonstrate promising applications in the fields of light emitting diodes.     

Phase transitions and upconversion luminescence in oxyfluoride glass ceramics containing Ba4Gd3F17 nanocrystals

Novel transparent Er³⁺ doped oxyfluoride glass-ceramics containing Ba₄Gd₃F₁₇ nanocrystals were prepared by melt quenching followed by heat treatment of as-prepared glasses. The phase composition and microstructure were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Intense upconversion luminescence (UCL) was detected. Longer characteristic decay times and splitting of the luminescence bands compared to the precursor glass indicated the incorporation of erbium ions in the crystalline phase. The spectroscopic properties of glass ceramics were compared with single phase cubic and rhombohedral Ba₄Gd₃F₁₇ ceramics. The unit cell parameters and atomic positions in the rhombohedral phase were calculated using Rietveld refinement. The local environment of Er³⁺ and the phonon energy of both polymorphs were analyzed using luminescence and Raman spectroscopy. In the glass ceramics, a phase transition from distorted metastable fluorite to ordered rhombohedral Ba₄Gd₃F₁₇ was observed and resulted in the enhancement of the efficiency of UCL.     

Fabrication and Luminescence Properties of Transparent Glass‐Ceramics Containing Eu3+‐Doped TbPO4 Nanocrystals

Eu³⁺‐doped transparent phosphate precursor glasses and glass‐ceramics containing TbPO₄ nanocrystals were successfully fabricated by a conventional high‐temperature melt‐quenching technique for the first time. The formation of TbPO₄ nanocrystals was identified through X‐ray diffraction, transmission electron microscopy, high‐resolution transmission electron microscopy, selected‐area electron diffraction, and photoluminescence emission spectra. The obvious Stark splitting of ⁵D₀‐⁷F_J (J = 1, 2, 4) transitions of Eu³⁺and the increase of internal quantum efficiency indicate the incorporation of Eu³⁺ into TbPO₄ nanocrystals. Energy transfer from Tb³⁺ ions to Eu³⁺ ions was investigated using excitation and emission spectra at room temperature. The glass‐ceramics obtained have more efficient Tb³⁺ to Eu³⁺ energy transfer than the glass, and so serve as good hosts for luminescent materials.     

Enhanced up-conversion luminescence of Er:LaOF oxyfluoride borosilicate glass ceramics

Er³⁺-doped transparent oxyfluoride borosilicate glass ceramics containing LaOF nanocrystals have been obtained by the high temperature melt-quenching and subsequent heat treatment method. The formation of LaOF nanocrystals in the glass matrix was confirmed by XRD and TEM results. In comparison with the precursor glass, Er³⁺-doped transparent oxyfluoride glass ceramics containing LaOF nanocrystals exhibited efficient up-conversion luminescence. Especially, the green emission intensity was greatly enhanced about nearly 200 times and its up-conversion mechanism can be ascribed to a two-photon absorption process.     

Enhanced near-infrared to green upconversion from Er3+-doped oxyfluoride glass and glass ceramics containing BaGdF5 nanocrystals

In this work, effect of glass composition as well as ceramization on visible and near-infrared (NIR) luminescence properties along with their decay dynamics of Er³⁺ ions has been compared considering two different oxyfluoride glasses yielding BaF₂ and BaGdF₅ nanocrystals. Both the glass systems have exhibited an intense normal and upconversion green emission under ultraviolet (378 nm) and NIR (978 nm) excitations, respectively. A remarkable enhancement of these emission intensities is observed for gadolinium-(Gd) containing glasses. Interestingly, NIR fluorescence intensity from Er³⁺ ions at 1540 nm has showed marginal decrease in gadolinium-containing glass which is attributed to occurrence of strong excited-state absorption (ESA) due to higher fluorine content ensuing an augmentation of upconversion green emission with a concomitant decrease in NIR emission. The quadratic dependence of upconversion green emission intensity on its pump power for all the samples revealed biphotonic absorption process from ground-state ⁴I_15/2 to the excited-state ⁴I_11/2 followed by ESA of second photon to the ⁴F_7/2 level. The intense green upconversion emission as well as enhanced NIR fluorescence lifetimes indicate the suitability of these glass/glass ceramics for upconversion lasers and amplification in the third telecom window.     

Ordering of fluorite-type phases in erbium-doped oxyfluoride glass ceramics

In this study, novel transparent Er³⁺ doped glass ceramics were prepared from melt-quenched oxyfluoride glasses with general composition of Na₂O-NaF-BaF₂-YbF₃-Al₂O₃-SiO₂. The crystallization of fluorite (BaF₂, BaF₂-YbF₃, NaF-BaF₂-YbF₃ and Na_0.5-xYb_0.5+xF_2+2x) and distorted fluorite (rhombohedral Ba₄Yb₃F₁₇ and tetragonal NaF-BaF₂-YbF₃) phases was analysed in glass ceramics with different BaF₂ and YbF₃ ratio. The phase composition and microstructure were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Intense red upconversion luminescence (UCL) was detected under near-infrared excitation resulting from three photon upconversion followed by cross-relaxation between Er³⁺ and Yb³⁺ ions.The local environment of Er³⁺ ions in fluorite and distorted phases was analysed using site-selective spectroscopy. The Er³⁺ ions were found to act as nucleation centres in the glass ceramics containing BaF₂. The phase transition from metastable fluorite to rhombohedrally and tetragonally distorted fluorite phases was detected using Er³⁺ ions as a probe.     

Nonlinear negative transmittance at a CW 980‐nm laser diodes pumping in Yb3+:CaF2 nanocrystals‐embedded glass ceramics

Cooperative upconversion luminescence (CUCL) occurs in spectral regions in which single ions do not have energy levels. However, all results reported so far are concentrated on luminescence properties from Yb³⁺ ions‐doped various hosts. Here, we report the observation of nonlinear negative transmittance (NNT) at continuous‐wavelength (CW) 980‐nm laser diodes (LDs) pumping in silicate oxyfluoride glass ceramics (GCs)‐containing CaF₂:Yb³⁺ nanocrystals. The unique optical nonlinearity is analyzed based on energy‐level transitions, dynamic evolution, rate equation, and power transmission equation, which can be explained as the cooperative optical absorption for the intense CUCL of Yb³⁺ ions. The NNT in the CaF₂:Yb³⁺ nanocrystals‐embedded GCs can be tailored with the power of a CW 980‐nm LDs, which possesses potential for the development of future optical limiters and switches.     

Evolution of Strong Red Upconversion Luminescence in Er3+‐Containing Oxy‐Fluoride Glass and Glass‐Ceramics

The Er³⁺ concentration dependencies of upconversion luminescence in oxy‐fluoride glass and glass‐ceramics containing PbF₂ nanocrystals were investigated. Strong red emission from the ⁴F_9/2 → ⁴I_15/2 transition was observed with the addition of ~0.8 mol% Er³⁺ ions, whereas ~10 mol% of Er³⁺ is required to achieve such emission in several other crystalline hosts. Intensities of red emission further increased with the formation of nanocrystals through heat treatment. The Er³⁺ ions enriched in glass and segregated preferentially inside the PbF₂ nanocrystals that decreased the distance among Er³⁺ ions and thereby facilitated energy transfer.     

A new parameter for characterizing Eu3+ distribution in mixed-valence Eu-doped cubic LaF3-based transparent glass-ceramics

Mixed-valence Eu-doped transparent oxyfluoride glass-ceramics containing cubic LaF₃ nanocrystals were fabricated by traditional melt-quenching technique and consequent annealing processes. Their structural and luminescent properties were systemically investigated by X-ray diffraction (XRD), transmission electron microscopy, absorption, excitation, emission spectra, and fluorescence lifetime measurements. Analyses of XRD patterns prove that the new precipitated nanocrystals disperse in glass-ceramics crystallize in cubic LaF₃. The spectroscopic investigations show that Eu²⁺ ions have been incorporated into the LaF₃ nanocrystals preferentially, while Eu³⁺ ions still remain in the glass phase after crystallization. Based on the spectral results, a new parameter was defined to describe the changes of the environments of Eu³⁺ before and after crystallization more straightforwardly and more sensitively, where R_PG and R_GC represent the integrated intensity radio of ⁵D₀ → ⁷F₂ to ⁵D₀ → ⁷F₁ emissions of Eu³⁺ in PG and GC samples, respectively. Our investigation will not only enrich the understanding of fluoride nanocrystals-based oxyfluoride glass-ceramics, but also the distribution and luminescence behaviors of Eu³⁺ ions in them.     

Enhanced and Long‐Lived Near‐Infrared Luminescence of Er3+ Ions in Lead Borate Glass‐Ceramics Containing PbWO4 Nanocrystals

Lead tungstate PbWO₄ nanocrystals in transparent lead borate glass‐ceramics containing Er³⁺ ions were fabricated. Luminescence spectra at about 1530 nm due to main ⁴I_13/2–⁴I_15/2 laser transition of Er³⁺ ions were examined for glass samples before and after heat treatment. Near‐infrared luminescence of Er³⁺ ions in glass‐ceramics is enhanced and long‐lived in comparison to precursor glasses. It suggests that the Er³⁺ ions are partially incorporated into PbWO₄ crystalline phase.     

Reproducible X-ray excited luminescence performance with transparent Tb3+-doped NaGd2F7 scintillating glass ceramics

Oxyfluoride glass ceramics with low toxicity, high stability and strong X-ray excited luminescence intensity are introduced as scintillating material. Herein, a series of novel NaGd₂F₇:xTb³⁺ (x = 0, 0.1, 0.2, 0.3, 0.4) were synthesized through in situ growth self-crystallization. X-ray diffraction, fourier transform infrared spectrometer and transmission electron microscopy were measured to investigate the structure and morphology of NaGd₂F₇ glass ceramics. These investigations demonstrate that NaGd₂F₇ nanocrystals are uniformly distributed in glass matrix with 20–30 nm diameter. Photoluminescence and X-ray excitation spectra are greatly enhanced after further thermal treatment which verify better crystallization of NaGd₂F₇ glass ceramics. The X-ray excited luminescence of the GC2–640 sample can reach 143.8% of the commercial BGO. More importantly, the damaged material can be completely repaired by annealing at 350 °C for 30 min. Our investigation indicates that Tb-doped transparent NaGd₂F₇ glass ceramics are potential candidates of X-ray scintillating material.     

Energy transfer,tunable emission and optical thermometry in Tb3+/Eu3+ co-doped transparent NaCaPO4 glass ceramics

Tb³⁺/Eu³⁺ co-doped glass ceramics containing NaCaPO₄ nanocrystals were successfully synthesized via traditional melt-quenching route with further heat-treatment and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence spectroscopy. The energy transfer process of Tb³⁺→Eu³⁺ was confirmed by excitation and emission spectra and luminescence decay curves, and the energy transfer efficiency was also estimated. The results indicated that the efficient emission of Eu³⁺ was sensitized by Tb³⁺ under the excitation of 378 nm, realizing tunable emission in the transparent bulk glass ceramics containing NaCaPO₄ nanocrystals. Furthermore, optical thermometry was achieved by the fluorescence intensity ratio between Tb³⁺:⁵D₄→⁷F₅ (~542 nm) and Eu³⁺:⁵D₀→⁷F₂ (~612 nm). The maximum absolute sensitivity of 4.55% K⁻¹ at 293 K and the maximal relative sensitivity of 0.66% K⁻¹ at T=573 K for Tb³⁺/Eu³⁺ co-doped transparent NaCaPO₄ glass ceramic are obtained. It is expected that the investigated transparent NaCaPO₄ glass ceramics doped with Tb³⁺/Eu³⁺ have prospective applications in display technology and optical thermometry.     

Effect of ligand field symmetry on upconversion luminescence in heat‐treated LaBGeO5:Yb3+, Er3+ glass

In this paper, we report upconversion (UC) luminescence enhancement in LaBGeO₅:Yb³⁺, Er³⁺ glass‐ceramics (GCs), surface crystallized glass‐ceramics (SCGCs) and ceramics compared with the as‐melt glass fabricated by the conventional melt‐quenching technique. Based on structural investigations, we find that the nucleation and crystallization of trigonal stillwellite LaBGeO₅:Yb³⁺, Er³⁺ nanocrystals occur first at the glass surface before the following volume crystallization. The local site symmetry around rare earth (RE) ions which was evaluated using the Eu³⁺ ions as a probe together with Judd‐Ofelt theory calculations exhibits a clear increase with the devitrification of the glass. Consequently, complete crystallization of the glass leads to largest enhancement in the UC emissions of the LaBGeO₅:Yb³⁺, Er³⁺ ceramics. We ascribe the enhancement of UC luminescence in the LaBGeO₅:Yb³⁺, Er³⁺ GCs, SCGCs, and ceramics to the structural ordering and the improvement of site symmetry surrounding RE ions that minimizes the rate of nonradiative relaxation process.