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.     

Optical Temperature Sensing Behavior of High‐Efficiency Upconversion: Er3+–Yb3+ Co‐Doped NaY(MoO4)2 Phosphor

A class of Yb³⁺/Er³⁺ co‐doped NaY(MoO₄)₂ upconversion (UC) phosphors have been successfully synthesized by a facile hydrothermal route with further calcination. The structural properties and the phase composition of the samples were characterized by X‐ray diffraction (XRD). The UC luminescence properties of Yb³⁺/Er³⁺ co‐doped NaY(MoO₄)₂ were investigated in detail. Concentration‐dependent studies revealed that the optimal composition was realized for a 2% Er³⁺ and 10% Yb³⁺‐doping concentration. Two‐photon excitation UC mechanism further illustrated that the green enhancement arised from a novel energy‐transfer (ET) pathway which entailed a strong ground‐state absorption of Yb³⁺ ions and the excited state absorption of Yb³⁺–MoO₄^2? dimers, followed by an effective energy transfer to the high‐energy state of Er³⁺ ions. We have also studied the thermal properties of UC emissions between 303 and 523 K for the optical thermometry behavior under a 980 nm laser diode excitation for the first time. The higher sensitivity for temperature measurement could be obtained compared to the previous reported rare‐earth ions fluorescence based optical temperature sensors. These results indicated that the present sample was a promising candidate for optical temperature sensors with high sensitivity.     

Synthesis and Up‐conversion Luminescence of Yb3+/Ln3+ (Ln = Er,Tm, Ho) Co‐Doped Strontium Cerate by Pechini Method

Novel up‐conversion (UC) luminescent nanopowders, Sr₂CeO₄:Yb³⁺,Ln³⁺ (Ln = Er, Tm, Ho) were prepared with Pechini method. The Sr₂CeO₄:Yb³⁺,Ln³⁺ (Ln = Er, Tm, Ho) nanopowders had an orthorhombic crystal structure, and showed olive‐like morphology with the length of about 260 nm and width of about 130 nm. Under 980 nm lazer excitation, the Sr₂CeO₄:Yb³⁺/Er³⁺, Sr₂CeO₄:Yb³⁺/Tm³⁺, and Sr₂CeO₄:Yb³⁺/Ho³⁺ nanophosphors exhibit strong green, blue, and green UC luminescence, respectively. The luminescence mechanisms for the doped lanthanide ions were thoroughly analyzed.     

Transmission electron microscopic and optical spectroscopic studies of Ni2+/Yb3+/Er3+/Tm3+ doped dual‐phase glass‐ceramics

Ni²⁺/Yb³⁺/Er³⁺/Tm³⁺ codoped transparent glass‐ceramics (GCs) containing both hexagonal β‐YF₃ and spinel‐like γ‐Ga₂O₃ dual‐phase nanoparticles (NCs) are synthesized by melt‐quenching and subsequent heating procedures. Two techniques of transmission electron microscopy (TEM) nanoanalytics and optical spectroscopy are conjugated to understand the distribution of the rare‐earth ions (REs) and transition metals (TMs) in the nanostructured GCs. It is found that the REs are located predominantly in β‐YF₃, whereas the TMs in γ‐Ga₂O₃ NCs. As a result, energy transfer (ET) between the REs and TMs is considerably suppressed due to the large spatial separation (> 3 nm), but it is enhanced between the REs partitioned in the β‐YF₃ NCs. This has important implications for intended and demanding photoluminescence functions. For example, an ultrabroadband near‐infrared (NIR) emission in the wavelength region of 1000‐2000 nm covering the entire telecommunications window is observed for the first time. Meanwhile, intense upconversion (UC) emissions covering the 3 primary colors and locating in the first biological window can be also recorded under excitation by a single pump source at 980 nm.     

REVO4‐Based Nanomaterials (RE = Y,La, Gd,and Lu) as Hosts for Yb3+/Ho3+, Yb3+/Er3+, and Yb3+/Tm3+ Ions: Structural and Up‐Conversion Luminescence Studies

Rare‐earth vanadates of the form REVO₄ (RE = Y, La, Gd, and Lu) doped by Yb³⁺/Ho³⁺, Yb³⁺/Er³⁺_, or Yb³⁺/Tm³⁺ lanthanide ions were successfully synthesized using the sol–gel method and annealing at 600°C in an air atmosphere. The structure and morphology of the prepared nanocrystals were investigated by X‐ray diffraction, thermogravimetric analysis, transmission electron microscopy, and energy‐dispersive X‐ray spectroscopy. All prepared materials were homogenous and had nanosized dimensions. Their elemental compositions were confirmed by optical emission spectrometry. Spectroscopic analysis of the materials was carried out by measuring excitation and emission spectra, luminescence decays, and dependence between the intensity of the luminescence and the laser energy. Following effective excitation by NIR radiation, Ln³⁺ co‐doped vanadate matrices exhibited a strong up‐conversion (UC) luminescence. Differences in spectroscopic properties between monoclinic LaVO₄ and tetragonal YVO₄, GdVO₄, or LuVO₄ doped by Ln³⁺ ions were observed, indicating the influence of the crystal structure on the UC emission. Drawing conclusions from these spectroscopic investigations, the UC mechanisms were proposed, including energy‐transfer processes between Yb³⁺ ions and emitting ions.     

Investigation on Crystallization and Optical Properties of Ca1−xLaxF2+x Glass‐Ceramics

Transparent oxyfluoride glass‐ceramics containing Er³⁺, Yb³⁺:Ca_1?xLa_xF_2+x nanocrystals, which may have potential applications in the fields of solid‐state laser and luminescence, were prepared. Crystallization of Ca_1?xLa_xF_2+x and behavior of Yb³⁺ and Er³⁺ during the heat treatment was investigated. Results showed that alumina content had a significant effect on crystallization of Ca_1?xLa_xF_2+x in the SiO₂–Al₂O₃–CaF₂–LaF₃ system. Due to the size of phase‐separated areas, the size of the crystals during the heat treatment did not change significantly. After crystallization of Ca_1?xLa_xF_2+x in the glass, the majority of Er³⁺ ions incorporated into the Ca_1?xLa_xF_2+x crystals during the heat‐treatment process. Time‐resolved luminescence of Er³⁺ ions in the samples around 842 nm showed that the solubility of Er³⁺ ions in Ca_1?xLa_xF₃ crystals is higher than pure CaF₂ crystals. The glass undergoes an enormous phase separation, which keeps the Yb³⁺ ions within the other separated phase. Therefore, only at high temperatures (790°C) or with a long heat‐treatment time (72 h), there is a possibility for Yb³⁺ ions to be incorporated into the fluorine phase.     

Pr3+/Yb3+:PLZT ferroelectric ceramics for near‐infrared radiation at 1340 nm

The near‐infrared luminescence properties of Pr³⁺/Yb³⁺:PLZT ferroelectric ceramics have been examined for the first time. Independently, upon either 450 nm (Pr³⁺) or 980 nm (Yb³⁺) excitation, luminescence centered at 1340 nm was observed, which corresponds to the ¹G₄→³H₅ transition of Pr³⁺. Several spectroscopic parameters for the ¹G₄→³H₅ transition of Pr³⁺ ions were determined. The average product of emission cross section and radiative lifetime were relatively large for all x/65/35 PLZT samples (x=6‐10) studied, with values close to 105±2 (×10^?26 cm²·s). These spectroscopic investigations indicate that Pr³⁺/Yb³⁺:PLZT ferroelectric ceramics are promising candidate for efficient sources emitting near‐infrared radiation at 1340 nm.     

Enhanced Sunlight Excited 1‐μm Emission in Cr3+–Yb3+ Codoped Transparent Glass‐Ceramics Containing Y3Al5O12 Nanocrystals

Cr³⁺–Yb³⁺ codoped transparent glass‐ceramics containing Y₃Al₅O₁₂ nanocrystals were prepared by heat treatment of as‐prepared glass sample and characterized by X‐ray diffraction and transmission electron microscopy. The efficient energy transfer from Cr³⁺ to Yb³⁺ ions through multi‐phonon‐assisted process was confirmed by the luminescence spectrum and fluorescent lifetime measurements. When excited by the lights from a solar simulator in the wavelength region of 400–800 nm, greatly enhanced near‐infrared emission around 1 μm was achieved from Cr³⁺–Yb³⁺ codoped glass ceramic compared with that from as‐prepared glass and Ce³⁺–Yb³⁺ codoped glass ceramic. These results demonstrate that the Cr³⁺–Yb³⁺ codoped glass ceramic is a promising material for enhancement of the efficiency of solar energy utilization.     

Stannum-(II) dopant effects on morphology evolution and upconversion performance of Yb3+/Er3+:NaGdF4 crystals

Hexagonal Yb³⁺/Er³⁺:NaGdF₄ nanocrystals codoped with Sn²⁺ ions were prepared via a modulated solvothermal method. Upon introducing 25mol% Sn²⁺ ions into the host lattice by substituting Gd³⁺ ions, a portion of Yb³⁺/Er³⁺:NaGdF₄ nanocrystals was converted into nanorods. Meanwhile, the upconversion (UC) luminescence intensity of 542 nm and 652 nm were intensified by 24 and 33 times respectively, when compared with samples without Sn²⁺ ions doping. The effect of Sn²⁺ ions doping content on the morphology and UC emission performances of Yb³⁺/Er³⁺:NaGdF₄ nanocrystals were discussed in detail. The enhancement of UC luminescence intensity could be attributed to the growth of UC nanocrystals and the low crystal local symmetry around Yb³⁺/Er³⁺ ion pairs. This study may be beneficial for fabricating high-performance UC materials and realizing their practical applications.     

Wide‐range thermometry based on green up‐conversion luminescence of K3LuF6:Yb3+/Er3+ bulk oxyfluoride glass ceramics

Yb³⁺/Er³⁺ ions codoped bulk glass ceramics (GC) with embedded monoclinic K₃LuF₆ nanocrystals are reported for potential temperature‐sensing application by using the fluorescence intensity ratio method. Such GC with good transparency and enhanced up‐conversion were prepared by the simple conversional melt‐quenching method and subsequent annealing process. Optical, structural, and temperature‐sensing up‐conversion properties were characterized systematically. Optical spectroscopy analysis confirms the incorporation of Yb³⁺/Er³⁺ into the K₃LuF₆ crystalline lattice, resulting in enhanced up‐conversion luminescence. Compared to other Er³⁺‐doped typical systems, Er³⁺ ions in K₃LuF₆ GC present large energy gap (870 cm^?1) and high relative sensitivity (37.6 × 10^?4 K^?1 at 625 K), revealing that K₃LuF₆:Yb³⁺/Er³⁺ GC can be excellent candidates for optical thermometers.     

The effect of Li+ incorporation in Yb3+-Nd3+ co-doped CaF2 phosphors over the NIR photoluminescence emission excited under visible light

The structural and optical characteristics of Nd³⁺-Yb³⁺ doped CaF₂ phosphors with and without the addition of Li⁺ ions are described in this work. The phosphors synthetized by hydrothermal and co-precipitation methods showed near-infrared (NIR) luminescence emission associated with inter-electronic transition of the Yb³⁺ ion in the range of 900–1050 nm via energy transfer process from Nd³⁺ ions under visible light excitation. The addition of Li⁺ to these phosphors resulted in an improvement of the NIR luminescence intensity by a factor up to 5. The effect of the incorporation of Li⁺ ions into the CaF₂ crystallite structure, the reduction of luminescence quenching states, as well as the energy transfer mechanism involved are discussed.     

Upconversion Luminescence and Energy‐Transfer Mechanism of NaGd(MoO4)2: Yb3+/Er3+ Microcrystals

Uniform and well‐crystallized NaGd(MoO₄)₂: Yb³⁺/Er^{3 +} microcrystals with tetragonal plate morphology were synthesized by a facile hydrothermal method. The structure and phase purity of the samples were identified by powder XRD analysis. The steady‐state and transient luminescence spectra were measured and analyzed. Under 980 nm excitation, intense green luminescence at 531 and 553 nm, and red luminescence at 657 and 670 nm were observed. The optimum doping concentrations for Yb³⁺ and Er³⁺ are determined to be 20% and 1% in NaGd(MoO₄)₂ tetragonal plate microcrystals. With increasing Yb³⁺ doping concentrations, the total integral emission intensities increase first and then decrease. The red/green intensity ratio of NaGd(MoO₄)₂: Yb³⁺/Er³⁺ microcrystals increases from 0.4 to 1.0 with the increase in Yb³⁺ concentrations. Based on the energy level diagram, the energy‐transfer mechanisms are investigated in detail according to the double logarithmic plot of upconversion intensities versus pump powers. The energy‐transfer mechanisms for green and red upconversion luminescence are ascribed to two‐photon processes at lower Yb³⁺ concentrations, and involve high‐Yb³⁺‐induced one‐photon processes at higher Yb³⁺ concentrations. For the red upconversion luminescence, energy back‐transfer process, that is, ⁴S_3/2 (Er³⁺) + ²F_7/2 (Yb³⁺) → ⁴I_13/2 (Er³⁺) + ²F_5/2 (Yb³⁺), is dominant at higher Yb³⁺ concentrations. Theoretical model of the energy‐transfer mechanisms based on rate equations is established, which agrees well with the experimental results.     

Molecular‐Like Ag Clusters and Eu3+ Co‐Sensitized Efficient Broadband Spectral Modification with Enhanced Yb3+ Emission

AgNO₃/EuF₃/YbF₃ tri‐doped oxyfluoride glass was prepared by a melt‐quenching method, in which a high‐efficient broadband spectral modification can be realized due to the simultaneous energy‐transfer processes of Eu³⁺→Yb³⁺, molecular‐like Ag (ML‐Ag) clusters→Yb³⁺, and ML‐Ag clusters→Eu³⁺→Yb³⁺. The spectral measurements indicated that besides the F‐center brought by the fluorides, the formation of the ML‐Ag clusters and the evolution of silver species within the glass matrix were also closely related to the introduction of Eu³⁺ and Yb³⁺ ions and which in return greatly affected the luminescence properties of these rare‐earth ions. As the UV‐visible irradiation in the wavelength region of 250–600 nm can be efficiently converted into near‐infrared emission around 1000 nm in the AgNO₃/EuF₃/YbF₃ tri‐doped glass, which thus has promising application in enhancing the photovoltaic conversion efficiency of the silicon solar cell.     

Thermal effects of Er3+/Yb3+‐doped NaYF4 phosphor induced by 980/1510 nm laser diode irradiation

The thermal effects of Er/Yb‐doped NaYF₄ phosphor induced by 980/1510 nm laser diode irradiation were intuitively and contrastively investigated using an infrared thermal imaging technology with real‐time online monitoring. The Yb³⁺/Er³⁺ codoped materials have strong thermal effects and high‐temperature elevation under 980 nm irradiation. However, the severe thermal effects of materials with higher Er³⁺ ion doping concentration are remarkably attributed to the cross relaxation between the Er³⁺ ions under 980 nm irradiation. The energy transfer between Er³⁺ and Yb³⁺ ions in Er³⁺/Yb³⁺‐codoped materials also contributes to the thermal effects under 1510 nm laser diode irradiation. Under the same testing conditions, the temperature elevation ?T of samples induced by 1510 nm laser diode irradiation is lower than that induced by 980 nm laser diode irradiation. The temperature rising rate and elevation ?T value of samples depend on the ion doping concentration and power density of the laser diode excitation. The internal temperature of the samples exhibits deep temperature gradient under 980/1510 nm laser diode irradiation. By comparing the two kinds of thermometry methods, the temperature value calculated by fluorescence intensity ratio is almost similar to that obtained through infrared thermal imaging technology under higher excitation power pumping.     

High Nd3+→Yb3+ energy transfer efficiency in tungsten‐tellurite glass: A promising converter for solar cells

This work reports on the energy transfer efficiency for Nd³⁺/Yb³⁺ co‐doped tellurite glasses (80TO₂‐20WO₃, in mol%,). The correlation between Yb³⁺ ion concentration and the downconversion mechanism was investigated using optical and thermal lens spectroscopies, which enabled investigation of the radiative and nonradiative processes, respectively, involved in energy transfer from neodymium to ytterbium. The Nd³⁺ near‐infrared fluorescence disappeared almost entirely when the maximum concentration of Yb³⁺ ions (4 mol%) was doped into the host. In contrast, there was a corresponding increase in the ytterbium emission at around 980 nm. When ytterbium was added, there was also a simultaneous reduction in the amount of heat generated by the sample due to a reduction in the nonradiative decay rate, corroborating the suspected high energy transfer efficiency of Nd³⁺→Yb³⁺. The results indicate that tungsten‐tellurite glasses may be of potential use in solar cells for matching the solar emission spectrum to the semiconductor cell.     

Intense upconversion luminescence and energy‐transfer mechanism of Ho3+/Yb3+ co‐doped SrLu2O4 phosphor

A series of novel SrLu₂O₄: x Ho³⁺, y Yb³⁺ phosphors (x=0.005‐0.05, y=0.1‐0.6) were synthesized by a simple solid‐state reaction method. The phase purity, morphology, and upconversion luminescence were measured by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) spectroscopy. The doping concentrations and sintering temperature were optimized to be x=0.01, y=0.5 and T=1400°C to obtain the strongest emission intensity. Under 980 nm laser diode excitation, the SrLu₂O₄:Ho³⁺, Yb³⁺ phosphors exhibit intense green upconversion (UC) emission band centered at 541 nm (⁵F₄,⁵S₂→⁵I₈) and weak red emission peaked at 673 nm (⁵F₅→⁵I₈). Under different pump‐power excitation, the UC luminescence can be finely tuned from yellow‐green to green light region to some extent. Based on energy level diagram, the energy‐transfer mechanisms are investigated in detail according to the analysis of pump‐power dependence and luminescence decay curves. The energy‐transfer mechanisms for green and red UC emissions can be determined to be two‐photon absorption processes. Compared with commercial NaYF₄:Er³⁺, Yb³⁺ and common Y₂O₃:Ho³⁺, Yb³⁺ phosphors, the SrLu_1.49Ho_0.01Yb_0.5O₄ sample shows good color monochromaticity and relatively high UC luminescence intensity. The results imply that SrLu₂O₄:Ho³⁺, Yb³⁺ can be a good candidate for green UC material in display fields.     

Tailorable Multicolor Up‐conversion Emissions in Tm3+/Ho3+/Yb3+ Co‐Doped LiLa(MoO4)2

Using a modified sol–gel method, LiLa(MoO₄)₂: Tm³⁺/Ho³⁺/Yb³⁺ phosphors with tailorable up‐conversion (UC) emission colors were prepared. Under the excitation of a 980 nm laser diode, up‐conversion red and green emissions in Ho³⁺/Yb³⁺ co‐doped and blue emission in Tm³⁺/Yb³⁺ co‐doped LiLa(MoO₄)₂ were observed, respectively. The intensities of the RGB (red, green, and blue) emissions could be controlled by varying concentrations of Tm³⁺ or Ho³⁺, and the optimal composition was also determined. In Tm³⁺/Ho³⁺/Yb³⁺ co‐doped LiLa(MoO₄)₂, the UC emission colors could be tuned from blue through white to yellow by adjusting the concentrations of Tm³⁺ or Ho³⁺. The UC excitation mechanisms were also investigated based on the power dependence of UC luminescence intensity.     

Energy‐Transfer Modulation for Enhanced Photocatalytic Activity of Near‐Infrared Upconversion Photocatalyst

One of the major challenges of near‐infrared upconversion photocatalyst concerns strengthening the cooperation between Rare‐earth (RE) ions and semiconductor materials for enhancing NIR photocatalytic activity. Herein, the basic energy‐transfer (ET) process between RE ions and semiconductor materials is discussed and the appropriate mode, nonradiative ET, is proposed for efficiently coupling them. As an example, a novel NIR‐based UC photocatalyst, CaIn₂O₄:Yb³⁺,Tb³⁺ was designed and successfully fabricated, which exhibited high photocatalytic activity under 980 nm irradiation. The present report highlights the potential of ET tuning between RE ions and semiconductors toward high performance of NIR photocatalysis.     

Effect of glass-ceramics network intermediate Al2O3 content on up-conversion luminescence in Er3+/Yb3+ co-doped NaYF4 oxy-fluoride glass-ceramics

Effect of alumina as a glass network intermediate on the up-conversion luminescence (UCL) in NaYF₄:Er³⁺/Yb³⁺ co-doped oxy-fluoride glass-ceramics (GCs) was investigated. Combinations of smaller NaYF₄ nanocrystals (10 and 13 nm) and lower Al₂O₃ contents (5% and 10%), as well as larger NaYF₄ nanocrystals (26 and 40 nm) and higher lower Al₂O₃ contents (15% and 20%) were prepared after heat-treatment, respectively. The glass network of intermediate partial replacement of SiO₂ with Al₂O₃ was investigated, and the consequence on the response to the up-conversion of the lanthanide ions was also studied. The UCL properties of Er³⁺ ions were changed in accordance with the addition of Al₂O₃, the red UCL intensity decreased with an increased Al₂O₃ concentration, while the green emission intensity showed opposite tendency. Our results showed that adding Al₂O₃ to 20 mol% is an effective strategy to simultaneous control of the magnitude and luminescence properties of lanthanide ion doped GCs.