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.     

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.     

Efficient dual‐mode up‐conversion and down‐shifting emission in β‐NaYF4:Yb3+,Er3+ microcrystals via ion exchange

We report efficient dual‐mode up‐conversion (UC) and down‐shifting (DS) emission in a single Yb³⁺/Er³⁺‐co‐doped β‐NaYF₄ microcrystals with controlled morphology and size via a simple Na⁺ ion‐exchange modification (IEM) method. IEM well preserves the crystal structure and monodispersed morphology of hydrothermal‐synthesized β‐NaYF₄. Meanwhile, IEM gives rise to the significant enhancement of UC emission intensity up to 3800 times and strongly enhanced DS emission intensity of Er³⁺ and Yb³⁺ by several times in β‐NaYF₄:Yb³⁺,Er³⁺ microcrystals. IEM also strongly prolongs the DS emission lifetimes of Er³⁺ and Yb³⁺ in visible and near‐infrared region. The enhanced UC and DS emission intensities and prolonged lifetimes in β‐NaYF₄:Yb³⁺,Er³⁺ are mainly ascribed to the dispersing of localized Yb³⁺ and Er³⁺ clusters during IEM.     

Preparation,Structure, and Up‐Conversion Luminescence of Yb3+/Er3+ Codoped SrIn2O4 Phosphors

SrIn₂O₄, which shows lower phonon energy than CaIn₂O₄, is not only a good photocatalyst but also can be an excellent up‐conversion (UC) host to exhibits UC luminescence. In this work, Yb³⁺ and/or Er³⁺ doped SrIn₂O₄ phosphors were synthesized, and their UC luminescence properties were studied and compared with those in the CaIn₂O₄ host. The structure of SrIn₂O₄: 0.01Er³⁺ and SrIn₂O₄: 0.1Yb³⁺/0.01Er³⁺ samples were refined by the Rietveld method and found to that SrIn₂O₄: 0.1Yb³⁺/0.01Er³⁺ showed increasing unit cell parameters and cell volume, indicating In³⁺ sites were substituted successfully by Yb³⁺ and/or Er³⁺ ions. From the UC luminescence spectra and diffuse reflection spectra, Er³⁺‐doped SrIn₂O₄ showed very weak luminescence due to ground state absorption of Er³⁺; Yb³⁺/Er³⁺ codoped SrIn₂O₄ presented strong green (550 nm) and red (663 nm) UC emissions which were assigned to energy transfer from Yb³⁺ transition ²F_7/2→²F_5/2 to the Er³⁺ transition ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2. Comparing with CaIn₂O₄, Yb³⁺/Er³⁺ codoped SrIn₂O₄ showed obvious advantages with higher UC luminescent intensity. The pumping powers study showed that UC emissions in Yb³⁺/Er³⁺ codoped SrIn₂O₄ were attributed to energy transfer of Yb³⁺→Er³⁺ with a two‐photon process. The possible UC luminescent mechanism of Yb³⁺/Er³⁺‐doped SrIn₂O₄ was discussed.     

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.     

Color‐Tunable Up‐Conversion Emission and Infrared Photoluminescence and Dielectric Relaxation of Er3+/Yb3+ Co‐Doped Bi2Ti2O7 Pyrochlore Thin Films

The color‐tunable up‐conversion (UC) emission and infrared photoluminescence and dielectric relaxation of Er³⁺/Yb³⁺ co‐doped Bi₂Ti₂O₇ pyrochlore thin films prepared by a chemical solution deposition method have been investigated. The pyrochlore phase structure of Bi₂Ti₂O₇ can be stabilized by Er³⁺/Yb³⁺ co‐doping. Intense color‐tunable UC emission and infrared photoluminescence can be detected on the thin films excited by a 980 nm diode laser. Two UC emission bands centered at 548 and 660 nm in the spectra can be assigned to ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ ions, respectively. A Stokes infrared emission centered at 1530 nm is due to ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺ ions. The dependence of UC emission intensity on pumping power indicates that the UC emission of the thin films is a two‐photon process. The thin films also exhibit a relatively high dielectric constant and a low dissipation factor as well as a good bias voltage stability. Temperature‐ and frequency‐dependent dielectric relaxation has been confirmed. This study suggests that Er³⁺/Yb³⁺ co‐doped Bi₂Ti₂O₇ thin films can be applied to new multifunctional photoluminescence dielectric thin‐film devices.     

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.     

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.     

Upconversion luminescence properties of NaBi(MoO4)2:Ln3+, Yb3+ (Ln = Er,Ho) nanomaterials synthesized at room temperature

Studies on lanthanide ions doped upconversion nanomaterials are increasing exponentially due to their widespread applications in various fields such as diagnosis, therapy, bio-imaging, anti-counterfeiting, photocatalysis, solar cells and sensors, etc. Here, we are reporting upconversion luminescence properties of NaBi(MoO₄)₂:Ln³⁺, Yb³⁺ (Ln = Er, Ho) nanomaterials synthesized at room temperature by simple co-precipitation method. Diffraction and spectroscopic studies revealed that these nanomaterials are effectively doped with Ln³⁺ ions in the scheelite lattice. DR UV–vis spectra of these materials exhibit two broad bands in the range of 200–350 nm correspond to MoO₄²⁻ charge transfer, s-p transition of Bi³⁺ ions and sharp peaks due to f-f transition of Ln³⁺ ions. Upconversion luminescence properties of these nanomaterials are investigated under 980 nm excitation. Doping concentration of Er³⁺ and Yb³⁺ ions is optimized to obtain best upconversion photoluminescence in NaBi(MoO₄)₂ nanomaterials and is found to be 5, 10 mol % for Er³⁺, Yb³⁺, respectively. NaBi(MoO₄)₂ nanomaterials co-doped with Er³⁺, Yb³⁺ exhibit strong green upconversion luminescence, whereas Ho³⁺, Yb³⁺ co-doped materials show strong red emission. Power dependent photoluminescence studies demonstrate that emission intensity increases with increasing pump power. Fluorescence intensity ratio (FIR) and population redistribution ability (PRA) of ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 transitions of Er³⁺ increases with increasing the Yb³⁺ concentration. Also, these values increase linearly with increasing the pump power up to 2 W. It reveal that these thermally coupled energy levels are effectively redistributed in co-doped samples due to local heating caused by Yb³⁺.     

Effects of Er3+ concentration on down-/up-conversion luminescence and temperature sensing properties in NaGdTiO4: Er3+/Yb3+ phosphors

Usually, Er³⁺ doping concentration effect on the temperature sensing properties of Er³⁺ containing materials is ignored. In this work, we demonstrated the influence of Er³⁺ concentration and excitation path on the spectral and temperature sensing properties in Er³⁺, Yb³⁺ co-doped NaGdTiO₄ system. The NaGdTiO₄: Er³⁺/Yb³⁺ phosphors were prepared by a high temperature solid state reaction method. Different spectral patterns for down- and up-conversion processes were observed and ascribed to the different excitation and population routes. The concentration quenching behaviors for down- and up-conversion processes were explained via cross relaxations between Er³⁺ ions. Most importantly, the Er³⁺ concentration dependent optical temperature sensing performance was observed and experimentally explained as a fact that the optical transition rate of Er³⁺ in different samples was changed with various Er³⁺ doping concentration.     

Upconversion emission,cathodoluminescence and temperature sensing behaviors of Yb3+ ions sensitized NaY(WO4)2:Er3+ phosphors

A series of Yb³⁺ ions sensitized NaY(WO₄)₂:Er³⁺ phosphors were synthesized through a solid-sate reaction method. The X-ray diffraction (XRD), upconversion (UC) emission and cathodoluminescence (CL) measurments were applied to characterize the as-prepared samples. Under the excitation of 980 nm light, bright green UC emissions corresponding to (²H_11/2,⁴S_3/2)→⁴I_15/2 transitions of Er³⁺ ions were observed and the UC emission intensities showed an upward trend with increasing the Yb³⁺ ion concentration, achieving its optimum value at 25 mol%. Furthermore, the temperature sensing behavior based on the thermally coupled levels (²H_11/2,⁴S_3/2) of Er³⁺ ions was analyzed by a fluorescence intensity ratio technique. It was found that the obtained samples can be operated in a wide temperature range of 133–773 K with a maximum sensitivity of approximately 0.0112 K⁻¹ at 515 K. Ultimately, strong CL properties were observed in NaY(WO₄)₂:0.01Er³⁺/0.25Yb³⁺ phosphors and the CL emission intensity increased gradually with the increment of accelerating voltage and filament current.     

Spectral management and energy‐transfer mechanism of Eu3+‐doped β‐NaGdF4:Yb3+,Er3+ microcrystals

β‐NaGdF₄:Yb³⁺,Er³⁺ upconversion (UC) microcrystals were prepared by a facile hydrothermal process with the assistance of ethylene diamine tertraacetic acid (EDTA). The β‐NaGdF₄ UC microcrystal morphology was controlled by changing the doses of EDTA and NaF. Uniform hexagonal structure can be obtained at the 2 mmol EDTA and 9‐10 mmol NaF. The UC emissions of β‐NaGdF₄:Yb³⁺,Er³⁺ microcrystals were tuned by the variation of Eu³⁺ doping level (0%‐5%), where the red/green intensity ratio decreased with the Eu³⁺ concentration increase. It was found on the base of rate equations that with the Eu³⁺ doping, the energy back transfer process ²H_11/2/⁴S_3/2 (Er³⁺) → ⁴I_13/2 (Er³⁺) decreased. In addition, an energy‐transfer process from ⁴F_7/2 (Er³⁺) to ⁵D₁ (Eu³⁺) and a cross relaxation process of ⁷H_9/2 (Er³⁺) + ⁵D₀ (Eu³⁺) → ⁴F_7/2 (Er³⁺) + ⁵D₂ (Eu³⁺) were proposed and verified by rate equations, which dominated the energy‐transfer mechanism between Er³⁺ and Eu³⁺, resulted in the spectra tuning of β‐NaGdF₄:Yb³⁺,Er³⁺. The results suggested that the color tuning of β‐NaGdF₄:Yb³⁺,Er³⁺,Eu³⁺ UC microcrystals would have potential applications in such fields as flat‐panel displays, solid‐state lasers, and photovoltaics.     

Visible up-conversion luminescence of CaWO<Subscript>4</Subscript>: Er<Superscript>3+</Superscript>,Yb<Superscript>3+</Superscript> and emission enhancement by tri-doping of Li<Superscript>+</Superscript> ions

Er³⁺,Yb³⁺ co-doped CaWO₄ polycrystalline powders were prepared by a solid-state reaction and their up-conversion (UC) luminescence properties were investigated in detail. Under 980 nm laser excitation, CaWO₄: Er³⁺,Yb³⁺ powder exhibited green UC emission peaks at 530 and 550 nm, which were due to the transitions of Er³⁺ (²H_11/2)→Er³⁺ (⁴I_15/2) and Er³⁺ (⁴S_3/2)→Er³⁺ (⁴I_15/2), respectively. Effects of Li+ tri-doping into CaWO₄: Er³⁺,Yb³⁺ were investigated. The introduction of Li⁺ ions reduced the optimum calcinations temperature about 100 °C by a liquid-phase sintering process and the UC emission intensity was remarkably enhanced by Li⁺ ions, which could be attributed to the lowering of the symmetry of the crystal field around Er³⁺ ions.     

Emission from Mo‐O charge‐transfer state and Yb3+ emission in Eu3+‐doped and nondoped molybdates under UV excitation

Molybdates of Li⁺ and Yb³⁺ are studied to investigate the luminescence under UV excitation. LiYb(MoO₄)₂ and Eu³⁺‐doped LiYb₁‐_xEux(MoO₄)₂ (x=001–1.0) phosphors were synthesized by solid state reaction under mixing of Eu₂O₃, Yb₂O₃, Li₂CO₃ and MoO₂ in air atmosphere. Two broad absorption bands centered at 333 and 236 nm are observed in LiYb(MoO₄)₂ compound. They are attributed to the ¹A₁→¹T₁ and ¹T₂ transitions due to the O^2?→Mo⁶⁺ electron transfers in MoO₄ tetrahedron. An emission band with a peak at about 440 nm is found, which is attributed to the ³T₁→¹A₁ transition of MoO₄. Appearance of near‐infrared (NIR) Yb³⁺ emission observed under UV excitation is understood by the MoO₄→Yb³⁺ Foerster‐Type energy transfer due to spectral overlap between the low‐energy tail of the broad 440 nm emission band and the high‐energy tail of the broad Yb³⁺ absorption band and due to short Yb³⁺‐MoO₄ distance. Yb³⁺ emission observed in LiYb_1?xEu_x(MoO₄)₂ by Eu³⁺ excitation is understood by the Eu³⁺→Yb³⁺ energy transfer by cross‐relaxation (CR) process between the ⁵D₀→⁷F₆ Eu³⁺ transition and the ²F_7/2→²F_5/2 Yb³⁺ transition. The CR efficiency shows maximum efficiency of 0.24 at x=0.15 of higher acceptor Yb³⁺ concentration than donor Eu³⁺ concentration. Three Yb³⁺ emission bands with peaks at 994, 1002, and 1023 nm are observed, depending on the excitation wavelength. This is explained by less‐shielded 4f electrons of Yb³⁺ by the 5s²5p⁶ outermost electron shells, which are also responsible for unusual broadband Yb³⁺ absorption and emission. From appearance of NIR Yb³⁺ emission under excitation by not only UV light but also red light, these compounds are expected to be suitable for efficient photovoltaic application to Si‐based solar cells.     

Highly Sensitive Optical Thermometry of Yb3+‐Er3+ Codoped AgLa(MoO4)2 Green Upconversion Phosphor

Er³⁺–Yb³⁺ codoped AgLa(MoO₄)₂ phosphors with intense green emission from ²H_11/2/⁴S_3/2 → ⁴I_15/2 transitions and negligible red emission from ⁴F_9/2 → ⁴I_15/2 transition of Er³⁺ were synthesized by sol–gel process. Its temperature sensing performance was evaluated based on the temperature dependence of fluorescence intensity ratio (FIR) of two green emission bands in the range 300–510 K. The maximum sensitivity of AgLa(MoO₄)₂: 0.02Er³⁺/0.4Yb³⁺ is approximately 0.018 K^?1 at 480 K, which is much higher than those of reported samples based on green emissions of Er³⁺. Result suggests that AgLa(MoO₄)₂: Er³⁺/Yb³⁺ has a great potential application in optical temperature sensors.     

A Novel Multifunctional Upconversion Phosphor: Yb3+/Er3+ Codoped La2S3

Yb³⁺/Er³⁺ codoped La₂S₃ upconversion (UC) phosphors have been synthesized using high‐temperature solid‐state method. Under 971‐nm excitation, the maximum luminescence power can reach 0.64 mW at the excitation power density of 16 W/cm² and an absolute power yield of 0.36% was determined by an absolute method at the excitation power density of 3 W/cm², and the quantum yield of La₂S₃:Yb³⁺, Er³⁺ (green ~0.18%, red ~0.03%, integration ~0.21) was comparable to that of NaYF₄:Yb³⁺, Er³⁺ nanocrystals (integration ~0.005–0.30). Frequency upconverted emissions from two thermally coupled excited states of Er³⁺ were recorded in the temperature range 100–900 K. The maximum sensitivity of temperature sensing is 0.0075 K^?1. As the excitation power density increases, the temperature of host materials rapidly rises and the top temperature can reach to 600 K. Given the intense UC emission, high sensitivity, as well as good photothermal stability, La₂S₃:Yb³⁺/Er³⁺ phosphor can become a promising composite material for photothermal ablation of cancer cells possessing the functions of temperature sensing and in vivo imaging.     

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.     

Microwave Sol–Gel Synthesis of CaGd2(MoO4)4:Er3+/Yb3+ Phosphors and Their Upconversion Photoluminescence Properties

CaGd₂(MoO₄)₄:Er³⁺/Yb³⁺ phosphors with the doping concentrations of Er³⁺ and Yb³⁺ (x = Er³⁺ + Yb³⁺, Er³⁺ = 0.05, 0.1, 0.2, and Yb³⁺ = 0.2, 0.45) have been successfully synthesized by the microwave sol–gel method, and the crystal structure refinement and upconversion photoluminescence properties have been investigated. The synthesized particles, being formed after heat‐treatment at 900°C for 16 h, showed a well‐crystallized morphology. Under the excitation at 980 nm, CaGd₂(MoO₄)₄:Er³⁺/Yb³⁺ particles exhibited strong 525 and 550‐nm emission bands in the green region and a weak 655‐nm emission band in the red region. The Raman spectrum of undoped CaGd₂(MoO₄)₄ revealed about 15 narrow lines. The strongest band observed at 903 cm^?1 was assigned to the ν₁ symmetric stretching vibration of MoO₄ tetrahedrons. The spectra of the samples doped with Er and Yb obtained under 514.5 nm excitation were dominated by Er³⁺ luminescence preventing the recording Raman spectra of these samples. Concentration quenching of the erbium luminescence at ²H_11/2→⁴I_15/2 and ⁴S_3/2→⁴I_15/2 transitions in the CaGd₂(MoO₄)₄:Er³⁺/Yb³⁺ crystal structure was established to be approximately at the 10 at.% doping level.     

Bright red upconversion luminescence from Er3+ and Yb3+ co-doped ZnO-TiO2 composite phosphor powder

ZnO-TiO₂ composites co-doped with Er³⁺ and Yb³⁺ ions were successfully synthesized by powder-solution mixing method and their upconversion (UC) luminescence was evaluated. The effect of firing temperature, ZnO/TiO₂ mixing ratio, and dopant concentration ranges on structural and UC luminescence properties was investigated. The crystal structure of the product was studied and calculated in detail by means of X-ray diffraction (XRD). Also, the site preference of Er³⁺ and Yb³⁺ ions in the host material was considered and analyzed based on XRD results and UC luminescence characteristics. Brightest UC luminescence was observed in the ZnO-TiO₂:Er³⁺,Yb³⁺ phosphor fired at 1300 °C in which the system consisted of mixed phases; Zn₂TiO₄, TiO₂, RE₂Ti₂O₇ and RE₂TiO₅ (RE = Er³⁺ and/or Yb³⁺). Under the excitation of a 980 nm laser, the two emission bands were detected in the UC emission spectrum, weak green band centered at 544 and 559 nm, and strong red band centered at 657 and 675 nm wavelengths in accordance with ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ ion, respectively. The simple chemical formula equations, for explaining the site preference of Er³⁺ and Yb³⁺ ions in host crystal matrix, were generated by considering the Zn₂TiO₄ crystal structure, its crystal properties, and the effect of Er³⁺ and Yb³⁺ ions to the host crystal matrix. The UC emission intensity of the products was changed by varying ZnO/TiO₂ mixing ratios, and Er³⁺ and Yb³⁺ concentrations. The best suitable condition for emitting the brightest UC emission was 1ZnO:1TiO₂ doped with 3 mol% Er³⁺, 9 mol% Yb³⁺ fired at 1300 °C for 1 h.