Synthesis and luminescent characterization of YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>:Tb<Superscript>3+</Superscript> phosphors

YAl₃(BO₃)₄:Tb³⁺ phosphors were fabricated by the sol–gel method. The phosphor showed prominent luminescence in green due to the magnetic dipole transition of ⁵D₄–⁷F₅. Structural characterization of the luminescent material was carried out with X-ray powder diffraction (XRD) analysis. Luminescence properties were analyzed by measuring the excitation and photoluminescence spectra. Photoluminescence measurements indicated that the phosphor exhibited bright green emission at about 541 nm under UV excitation. It is shown that the 11% of doping concentration of Tb³⁺ ions in YAl₃(BO₃)₄:Tb³⁺ phosphors is optimum.     

Liquid-phase epitaxy of NdAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> and Yb-doped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Epitaxial layers of NaAl₃(BO₃)₄ (NAB) and YAl₃(BO₃)₄〈Yb〉 (YAB〈Yb〉) containing up to 10 at % Yb have been grown by liquid-phase epitaxy on YAB substrates. Their growth kinetics have been studied at relative supersaturations of the high-temperature solution from 2 × 10^?2 to 16 × 10^?2. The ytterbium concentration in YAB〈Yb〉 has been shown to vary little during the epitaxial process. Near the edges of the substrate, the surface morphology of the layers is complicated by vicinals, which have a spiral form in the case of YAB〈Yb〉. On \(\{ 10\overline 1 1\} \) YAB substrates, homogeneous single-crystal NAB films have been grown.     

Synthesis and photoluminescence study of narrow-band UVB-emitting LiSr<Subscript>4</Subscript>(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>:Gd<Superscript>3+</Superscript>, Pr<Superscript>3+</Superscript> phosphor

A series of Pr³⁺, Gd³⁺ and Pr³⁺–Gd³⁺-doped inorganic borate phosphors LiSr₄(BO₃)₃ were successfully synthesized by a modified solid-state diffusion method. The crystal structures and the phase purities of samples were characterized by powder X-ray diffraction. Surface morphology of the sample was studied by scanning electronic microscopy (SEM). The optimal concentrations of dopant Gd³⁺ ions in compound LiSr₄(BO₃)₃ were determined through the measurements of photoluminescence (PL) spectra of phosphors. Gd³⁺-doped phosphors LiSr₄(BO₃)₃ show strong band absorption in UV spectral region and narrow-band UVB emission under the excitation of 276 nm was only due to ⁶P _J → ⁸S_7/2 transition of Gd³⁺ ions. The effect of Pr³⁺ ion on excitation of LiSr₄(BO₃)₃:Gd³⁺ was also studied. The excitation of LiSr₄(BO₃)₃:Gd³⁺, Pr³⁺ gives a broad-band spectra, which show very good overlap with the Hg 253.7 nm line. The photoluminescence spectra of LiSr₄(BO₃)₃ with different doping concentrations Pr³⁺ and keeping the concentration of Gd³⁺ constant at 0.03 mol have also been studied. The emission intensity of LiSr₄(BO₃)₃:Pr³⁺–Gd³⁺ phosphors increases with increasing Pr³⁺ doping concentration and reaches a maximum at 0.01 mol. From the photoluminescence study of LiSr₄(BO₃)₃:Gd³⁺, Pr³⁺ we conclude that there was efficient energy transfer from Pr³⁺→ Gd³⁺ ions in LiSr_4?x?y Pr _x Gd _y (BO₃)₃ phosphors.     

Luminescence properties and electronic structure of Sm<Superscript>3+</Superscript>-doped YAl<Subscript>3</Subscript>B<Subscript>4</Subscript>O<Subscript>12</Subscript>

The luminescence properties of Sm³⁺ ions in YAl₃B₄O₁₂ were studied upon synchrotron excitation in the 3.8–11 eV region. In addition to the 4f → 4f excitation bands, the excitation spectra of the Sm³⁺ emission contain broad bands at 6.1 and ~7.0 eV. These bands are attributed to charge transfer transition in Sm³⁺–O²⁻ complexes and 4f → 5d transition of Sm³⁺ ions, respectively. The optical absorption edge of YAl₃B₄O₁₂ was determined at 7.3 eV. A comparison with the results of electronic structure calculations on YAl₃B₄O₁₂ is also made.     

Liquid-phase epitaxy of single-crystal erbium-ytterbium codoped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> layers as key components of planar waveguides

YAl₃(BO₃)₄ (YAB) crystals 10 × 10 × 8 mm in dimensions were grown on point seeds from a potassium-trimolybdate-based high-temperature solution. The crystals were used as substrates for liquid-phase epitaxy of (Er,Yb):YAB single-crystal films 50 to 100 μm in thickness. The hexagonal cell parameters of nominally undoped and erbium-ytterbium codoped YAB were determined as functions of temperature by high-temperature X-ray diffraction and were used to evaluate the thermal expansion coefficients of the materials. We have demonstrated waveguiding and measured the optical loss in the films.     

Effect of the chemical nature of precipitants on the formation of ultrafine YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>:Ce powders

Ultrafine Ce³⁺-doped YAl₃(BO₃)₄ powders have been synthesized through coprecipitation using ammonia, ammonium bicarbonate, and ammonium oxalate as precipitants. We have studied the effect of the nature of the precipitants on the formation of YAl₃(BO₃)₄:Ce and its structural properties, morphology, and luminescence spectrum.     

Synthesis and properties of AgTi<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-based NASICON-type phosphates doped with Nb<Superscript>5+</Superscript>, Zr<Superscript>4+</Superscript>, and Ga<Superscript>3+</Superscript>

We have synthesized materials based on a silver titanium phosphate with partial substitution of tri-, tetra-, or pentavalent cations for titanium: Ag_1±x Ti_2−x M _x (PO₄)₃ (M = Nb⁵⁺, Ga³⁺) and AgTi_2−x Zr _x (PO₄)₃. The materials have been characterized by X-ray diffraction and impedance spectroscopy and have been shown to have small thermal expansion coefficients. Their ionic conductivity has been determined. Silver ions in these materials are difficult to replace with protons.     

Spectral parameters of Er<Superscript>3+</Superscript> ion in Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript>:KY(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal

The spectral parameters of Er³⁺ in Yb³⁺/Er³⁺:KY(WO₄)₂ crystal with space group C2/c have been investigated based on Judd-Ofelt theory. The spectral parameters were obtained: the intensity parameters are: ₂ = 6.33 × 10^–20 cm², ₄ = 1.35 × 10^–20 cm², ₆ = 1.90 × 10^–20 cm². The radiative lifetime and the fluorescence branch ratios were calculated. The emission cross section _e (at 1536 nm) is 2.0 × 10^–21 cm².     

Luminescence of BaSiO<Subscript>3</Subscript> crystals doped with Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript>

The Stokes and anti-Stokes luminescence of undoped and rare-earth-doped (Er³⁺ and Yb³⁺) BaSiO₃ has been studied in the temperature range 78–450 K under excitation at 10–1000 mV. The results indicate that the emission mechanism in BaSiO₃ crystals is hole recombination and that the anti-Stokes luminescence is due to consecutive sensitization; that is, the Yb³⁺ ions in the BaSiO₃ compound act as luminescence sensitizers, and the Er³⁺ ions, as activators.     

Emission analysis of Pr<Superscript>3+</Superscript> &; Ho<Superscript>3+</Superscript>: Ca<Subscript>4</Subscript>GdO(BO<Subscript>3</Subscript>)<Subscript>3</Subscript> powder phosphors

Emission spectral results of Pr³⁺ & Ho³⁺ ions doped Ca₄GdO(BO₃)₃ powder phosphors are reported here. XRD, SEM and FTIR measurements have been carried out for them. The emission spectrum of Pr³⁺: Ca₄GdO(BO₃)₃ has shown an emission transition ¹D₂ → ³H₄ at 606 nm with λ_exci = 480 nm (³H₄ → ³P₀) and Ho³⁺: Ca₄GdO(BO₃)₃ phosphor has shown an emission transition ⁵S₂ → ⁵I₈ at 549 nm with λ_exci = 447 nm (⁵I₈ → ⁵F₁). Emission performances of these two phosphors have been explained in terms of energy level diagrams.     

X-ray diffraction,optical absorption and emission studies on Er<Superscript>3+</Superscript>- and Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript>-doped Li<Subscript>3</Subscript>NbO<Subscript>4</Subscript> powder

Er³⁺(/Yb³⁺)-doped Li₃NbO₄ powder were prepared by thermally sintering mixtures of Er₂O₃ (0.5, 1.0 mol%), Yb₂O₃ (0, 0.5, 1.0 mol%), Li₂CO₃ (48–49 mol%) and Nb₂O₅ (50 mol%) at 1125, 1150 and 1450 °C over the durations of 8–22 h. The crystalline phases contained in these samples were determined by using X-ray diffraction and discussed in comparison with a vapor-transport-equilibration-treated (VTE-treated) Er(2.0 mol%):LiNbO₃ single crystal and ErNbO₄ powder previously reported. The results show that the X-ray patterns of the rare-earth-doped samples reveal little difference each other, but large differences with those of the VTE crystal and ErNbO₄ powder. The doped rare-earth ions Er³⁺ (and Yb³⁺) present in the powder as the ErNbO₄ (and YbNbO₄) phase(s). The possibility that the highly Er-doped LiNbO₃ crystal contains Li₃NbO₄ precipitates is small. Optical absorption and emission studies show that the only Er-doped Li₃NbO₄ powder shows similar absorption and emission characteristics with the pure ErNbO₄. The codopant Yb³⁺ ion enhances the 980-nm-upconversion emissions of Er³⁺ ions, results in remarkable spectral alterations at 0.98 μm region, and causes the alterations of relative absorbance and relative emission intensity of individual peaks or bands at 1.5 μm region. On the other hand, the Yb-codoping hardly affects the Er³⁺ energy structure and the lifetime of Er³⁺ ion at 1.5 μm. The measured lifetimes at 1.5 μm of Er³⁺ ions in the singly Er³⁺- and doubly Er³⁺/Yb³⁺-doped mixtures have a nearly same value of ∼ 1.5 ms. For the pure ErNbO₄ powder, the lifetime is prolonged to ∼2 ms perhaps due to radiation trapping effect.     

Spectral parameters of Nd3+ ion in Nd<Superscript>3+</Superscript>:LaCa<Subscript>4</Subscript>O(BO<Subscript>3</Subscript>)<Subscript>3</Subscript> crystal

The spectral parameters of Nd³⁺ ions in Nd:LaCa₄O(BO₃)₃ crystal have been investigated based on Judd-Ofelt theory. The spectral parameters were obtained: the intensity parameters Ω_λ are Ω₂ =1.98 × 10^–20 cm², Ω₄ =2.39 × 10^–20 cm², Ω₆ =1.38 × 10^–20 cm², the radioactive lifetime is 655 μs, the quantum efficiency is 10%, and the fluorescence branch ratios were calculated: β₁ = 0.51, β₂ = 0.42, β₃ = 0.066, β₄ = 0.003. Electronic Publication     

Beta-LaSc<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>: correction of the crystal structure

The published structure data of trigonal beta-LaSc₃(BO₃)₄ are incorrect because they are not compatible with the formula of the compound. After correcting the positional atom co-ordinates of one O atom the structure is found to be isotypic with CeSc₃(BO₃)₄ which crystallizes with the huntite CaMg₃(CO₃)₄ structure type.Response to paper, titled "Structure of medium temperature phase -LaSc₃(BO₃)₄ crystal," by He MY et al., published in MRI, vol. 2, issue 6, pp. 345–348, DOI     

NIR-excited NIR and visible luminescent properties of amphipathic YVO<Subscript>4</Subscript>: Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> nanoparticles

This article reports the luminescence properties of amphipathic YVO₄:Er³⁺/Yb³⁺ nanoparticles (average grain size ca. 20 nm) obtained by an oleate-aided hydrothermal process. Depending on the upconversion (UPC) and downconversion (DWC) processes, they show luminescence in the visible and near-infrared (NIR) regions, respectively, by 980-nm excitation. The sample doped with Er³⁺:2.5 mol% and Yb³⁺:10 mol% showed the highest luminescence intensity in both the visible and NIR regions as a result of efficient energy transfer from Yb³⁺ to Er³⁺ ions. The hydrothermal treatment greatly enhanced both the DWC and UPC luminescence efficiencies. This is due to the reduction in the concentration of surface defects and ligands, accompanied by grain growth. NIR Fluorescence microscopy revealed for the first time that DWC luminescence is sufficiently intense for application of these nanocrystals as a NIR bioprobe.     

Luminescence properties of Bi codoped and P codoped Ca<Subscript>3</Subscript>(VO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Eu<Superscript>3+</Superscript>

New red emitting phosphors, Ca₃(VO₄)₂:Eu³⁺,Bi³⁺, Ca₃((P,V)O₄)₂:Eu³⁺ were synthesized by low temperature solid-state reaction and characterized by X-ray diffraction, scanning electron microscopy, photoluminescence spectra and Fourier transform infrared spectroscopy. The results show that the red emission located at about 613 nm was ascribed to ⁵ D ₀-⁷ F ₂ transition of Eu³⁺. The effect of by Bi doping and by P doping was also investigated systematically.     

Pulsed cathodoluminescence of single-crystalline and pressed CaF<Subscript>2</Subscript>:Yb<Superscript>2+</Superscript>,Yb<Superscript>3+</Superscript>

We have studied the pulsed cathodoluminescence spectra and kinetics of CaF₂:Yb²⁺,Yb³⁺ (3 mol % YbF₃) single crystals and pressed samples under excitation with nanosecond electron pulses and determined the characteristic times and intensities of nanosecond and microsecond emission decay components at temperatures from 15 to 300 K. The results demonstrate that deformation pressing in vacuum at 1150°C followed by annealing in a CF₄ atmosphere at 1180°C has an insignificant effect on the emissive properties of CaF₂:Yb²⁺,Yb³⁺.     

Luminescent properties of Yb<Superscript>3+</Superscript>-doped hexagonal Ln<Subscript>3</Subscript>BWO<Subscript>9</Subscript> (Ln = Gd,Y)

We report the synthesis and spectroscopic characterization of polycrystalline Yb³⁺-doped (1, 2, and 5 at %) Ln₃BWO₉ (Ln = Gd and Y) borotungstates as candidate gain media for diode-pumped near-IR and visible solid-state lasers. Unpolarized luminescence and absorption spectra for the Yb^{3+ 2} F _7/2→² F _5/2 transition are measured at T = 77 and 300 K, the lifetime of the ² F _5/2 excited state is determined, and the emission cross section of the stimulated Yb^{3+ 2} F _5/2→² F _7/2 transition in these compounds is evaluated. Offering a combination of nonlinear optical and lasing properties, the Ln₃BWO₉ (Ln = Gd, Y) hexagonal borotung-states can be used as bifunctional media for diode-pumped lasers with nonlinear laser frequency self-conversion.     

Synthesis and luminescence properties of Tb<Superscript>3+</Superscript>-doped LiMgPO<Subscript>4</Subscript> phosphor

Polycrystalline sample LiMg_(1?x)PO₄:xTb³⁺ (x = 0.001, 0.002, 0.005, 0.01, 0.02) phosphor was synthesized via modified solid state method (MSSM). The prepared sample was characterized through XRD pattern (X-ray diffraction) and SEM (scanning electron microscope). Additionally, photoluminescence (PL), optically stimulated luminescence (OSL), thermoluminescence (TL) and other dosimetric properties including dose linearity, reusability and fading were studied. In OSL mode, sensitivity of prepared phosphor was found to be 2.7 times that of LiMgPO₄:Tb³⁺, B (BARC) phosphor and 4.3 times that of α-Al₂O₃:C (BARC) phosphor. The TL glow consists of overlapping peaks in temperature range of 50–400^°C and first peak (P₁) was observed at 150^°C, second peak (P₂) at 238^°C, third peak (P₃) at 291^°C and fourth peak (P₄) at 356^°C. The TL sensitivity of second peak (P₂) of LiMgPO₄:Tb³⁺ phosphor was compared with α-Al₂O₃:C (BARC) phosphor and found to be 100 times that of the α-Al₂O₃:C (BARC) phosphor. The minimum detectable dose (MDD) was found to be 5.6 μGy. Moreover, photoionization cross-sections, linearity, reusability, fading and kinetic parameters were calculated. Also, photoluminescence spectra of LiMgPO₄: Tb³⁺ shows characteristic green–yellow emission exciting at 224 nm UV source.     

Synthesis and crystal structure CoNi<Subscript>2</Subscript>(BO<Subscript>3</Subscript>)<Subscript>2</Subscript>

A new metal orthoborate compound, cobalt dinickel orthoborate, CoNi₂(BO₃)₂ has been successfully synthesized for the first time. The title compound was synthesized by thermally-induced solid-state chemical reaction at 900°C between the initial reagents of Co(NO₃)₂ · 6H₂O, Ni(NO₃)₂ · 6H₂O and H₃BO₃ which were mixed with the mol ratio of 1: 2: 2 respectively. The obtained product was structurally characterized by X-ray powder diffraction technique. It has been found that the CoNi₂(BO₃)₂ crystallizes in the kotoite type and isostructural with the compounds having the chemical formula M₃(BO₃)₂ where M—Mg, Co and Ni. The synthesized compound belongs to the orthorhombic crystal system with the refined unit cell parameters of a = 5.419(9) Å, b = 8.352(0) Å, c = 4.478(8) Å and Z = 2. The space group was determined as Pnmn. Further characterizations by FTIR, elemental analysis and thermal analysis were also performed.     

Tunable luminescence properties and energy transfer of single-phase Ca<Subscript>4</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>O: Dy<Superscript>3+</Superscript>, Eu<Superscript>2+</Superscript> multi-color phosphors for warm white light

The novel Ca_4?x(PO₄)₂O: xDy³⁺ and Ca_4?x?y(PO₄)₂O: xDy³⁺, yEu²⁺ multi-color phosphors were synthesized by traditional solid-state reaction. The crystal structure, particle morphology, photoluminescence properties and energy transfer process were investigated in detail. The X-ray diffraction (XRD) results demonstrate that the products showed pure monoclinic phase of Ca₄(PO₄)₂O when x < 0.1. The scanning electron microscopy (SEM) indicated that the phosphors were grain-like morphologies with diameters of ~ 3.7–7.0 μm. Under excitation of 345 nm, Dy³⁺-doped Ca₄(PO₄)₂O phosphors showed multi-color emission bands at 410, 481 and 580 nm originated from oxygen vacancies and Dy³⁺. Interestingly, Ca₄(PO₄)₂O: Dy³⁺, Eu²⁺ phosphors exhibited blue emission band at 481 nm and broad emission band from 530 to 670 nm covering green to red regions. The energy transfer process from Dy³⁺ to Eu²⁺ was observed for the co-doped samples, and the energy transfer efficiency reached to 60% when Eu²⁺ molar concentration was 8%. In particular, warm/cool/day white light with adjustable CCT (2800–6700 K) and high CRI (R_a > 85) can be obtained by changing the Eu²⁺ co-doping contents in Ca₄(PO₄)₂O: Dy³⁺, Eu²⁺ phosphors. The optimized Ca_3.952(PO₄)₂O: 0.04Dy³⁺, 0.008Eu²⁺ phosphor can achieve the typical white light with CCT of 4735 K and CRI of 87.