Electron traps in Gd<Subscript>3</Subscript>Ga<Subscript>3</Subscript>Al<Subscript>2</Subscript>O<Subscript>12</Subscript>:Ce garnets doped with rare-earth ions

The curves of thermally stimulated luminescence of Gd₃Ga₃Al₂O₁₂:Ce³⁺ ceramics (a nominally pure sample and samples doped with rare-earth ions) are measured in the temperature range of 80–550 K. The depth and the frequency factor of electron traps established by Eu and Yb impurities are determined. An energy-level diagram of rare-earth ions in the bandgap of Gd₃Ga₃Al₂O₁₂ is presented.     

The influence of activation of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> polycrystalline matrices by Bi<Superscript>3+</Superscript> ions on the luminescence of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript>

The influence of activation of the Y₂O₃ matrix of the Y₂O₃:Eu³⁺ phosphor by Bi³⁺ ions on the luminescence of Eu³⁺ and Bi³⁺ ions in it and on conditions of the excitation energy transfer to luminescence centers is studied. It is shown that the presence of Bi³⁺ ions leads to the appearance of recombination luminescence with participation of bismuth ions at low concentrations (up to 6–8 at %) of the dominant activator europium and to an increase in the threshold of intrinsic concentration quenching of its luminescence.     

Pt/Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> composite nanotubes: Enhanced photoluminescence and application in dye-sensitized solar cells

Y(OH)3:Eu3+ nanotubes were synthesized using a facile hydrothermal method,and then,Pt particles were grown on the surface of the nanotubes using a combination of vacuum extraction and annealing.The resulting Pt/Y2O3∶Eu3+ composite nanotubes not only exhibited enhanced red luminescence under 255-or 468-nm excitation but could also be used to improve the efficiency of dyesensitized solar cells,resulting in an efficiency of 8.33％,which represents a significant enhancement of 11.96％ compared with a solar cell without the composite nanotubes.Electrochemical impedance spectroscopy results indicated that the interfacial resistance of the TiO2-dye|I3-/I-electrolyte interface of the TiO2-Pt/Y2O3:Eu3+ composite cell was much smaller than that of a pure TiO2 cell.In addition,the TiO2-Pt/Y2O3:Eu3+ composite cell exhibited a shorter electron transport time and longer electron recombination time than the pure TiO2 cell.     

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.     

Low temperature synthesis and photoluminescence of Ca<Subscript>3</Subscript>(VO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Eu<Superscript>3+</Superscript> nanocrystals with Li<Superscript>+</Superscript> addition

Different crystalline Ca₃(VO₄)₂ nanocrystals have been synthesized successfully via a facile low temperature method with lithium addition. After different ration of Li⁺ doping into the Ca₃(VO₄)₂: Eu³⁺ host, the crystallinity of the sample becomes different, resulting in different of luminescence intensity of the characteristic emission of Eu³⁺ ions. This approach provides economically viable route for large-scale synthesis of this kind of nanomaterials.     

Roles of doping ions in persistent luminescence of SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript>, RE<Superscript>3+</Superscript> phosphors

The polycrystalline Eu²⁺ and RE³⁺ co-doped strontium aluminates SrAl₂O₄:Eu²⁺, RE³⁺ were prepared by solid state reactions. The UV-excited photoluminescence, persistent luminescence and thermo-luminescence of the SrAl₂O₄:Eu²⁺, RE³⁺ phosphors with different composition and doping ions were studied and compared. The results showed that the doped Eu²⁺ ion in SrAl₂O₄:Eu²⁺, Dy³⁺ phosphors works as not only the UV-excited luminescent center but also the persistent luminescent center. The doped Dy³⁺ ion can hardly yield any luminescence under UV-excitation, but can form a electron trap with appropriate depth and greatly enhance the persistent luminescence and thermo-luminescence of SrAl₂O₄:Eu²⁺. Different co-doping RE³⁺ ions showed different effects on persistent luminescence. Only the RE³⁺ ion (e.g. Dy³⁺, Nd³⁺), which has a suitable optical electro-negativity, can form the appropriate electron trap and greatly improve the persistent luminescence of SrAl₂O₄:Eu²⁺. Based on above observations, a persistent luminescence mechanism, electron transfer model, was proposed and illustrated.     

Large enhancement of upconversion luminescence in Er<Superscript>3+</Superscript>/In<Superscript>3+</Superscript>:Ba<Subscript>0.85</Subscript>Ca<Subscript>0.15</Subscript>TiO<Subscript>3</Subscript> lead-free piezoelectric ceramics

A series of In³⁺-doped Ba_0.85Ca_0.15TiO₃:0.75%Er³⁺/xIn³⁺ (BCT:Er/xIn) lead-free piezoelectric ceramics with excellent upconversion luminescence were synthesized by the solid state reaction method. The effects of In³⁺ content on the crystal structure, ferroelectric, dielectric, piezoelectric, and upconversion luminescence properties were systematically studied. Under 980 nm excitation, a giant enhancement of the green emission (550 nm) by 10 times is achieved upon 2.5% mol In³⁺ doping, which is rarely observed in rare-earth ions-doped perovskite ferroelectric materials. The ultraviolet-visible-near infrared absorption measurements show that the In³⁺ doping may improve the dissolution of Er³⁺ ions and modify the isolate-/clustered-Er³⁺ ratio for x?≤?2.5%, resulting in the enhancement of the absorption cross-section, thereby contributing to the enhancement of green luminescence. Unfortunately, the In³⁺ doping suppresses the ferroelectric and piezoelectric properties of the BCT:Er/xIn ceramics. This problem can be resolved by adding a small amount (1 mol%) of Yb³⁺ to the BCT:Er/xIn ceramics to restore their good ferroelectric and piezoelectric properties. Such In³⁺ and rare-earth ions co-doped ceramics with greatly enhanced upconversion luminescence and good ferroelectricity and piezoelectricity may have potential applications in electro-optical devices.     

One-pot synthesis and strong near-infrared upconversion luminescence of poly(acrylic acid)-functionalized YF<Subscript>3</Subscript>:Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript> nanocrystals

This paper describes the synthesis of new upconverting luminescent nanoparticles that consist of YF₃:Yb³⁺/Er³⁺ functionalized with poly(acrylic acid) (PAA). Unlike the upconverting nanocrystals previously reported in the literature that emit visible (blue-green-red) upconversion fluorescence, these as-prepared nanoparticles emit strong near-infrared (NIR, 831 nm) upconversion luminescence under 980 nm excitation. Scanning electron microscopy, transmission electron microscopy, and powder X-ray diffraction were used to characterize the size and composition of the luminescent nanocrystals. Their average diameter was about 50 nm. The presence of the PAA coating was confirmed by infrared spectroscopy. The particles are highly dispersible in aqueous solution due to the presence of carboxylate groups in the PAA coating. By carrying out the synthesis in the absence of PAA, YF₃:Yb³⁺/Er³⁺ nanorice materials were obtained. These nanorice particles are larger (∼700 nm in length) than the PAA-functionalized nanoparticles and show strong typical visible red (668 nm), rather than NIR (831 nm), upconversion fluorescence. The new PAA-coated luminescent nanoparticles have the pottential be used in a variety of bioanalytical and medical assays involving luminescence detection and fluorescence imaging, especially in vivo fluorescence imaging, due to the deep penetration of NIR radiation.      

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.     

Facile and scalable synthesis of Ti<Subscript>5</Subscript>Si<Subscript>3</Subscript> nanoparticles via solid-state route in an autoclave

A novel method of the synthesis of titanium silicide nanoparticles via solid-state route in an autoclave at 700°C is reported. The reaction of titanium silicide could be described briefly as: 5TiO₂ + 3Si + 20Li = Ti₅Si₃ + 10Li₂O. XRD pattern indicated that the product was hexagonal Ti₅Si₃. The Ti₅Si₃particle size (about 20–40 nm) is confirmed by the TEM images. Furthermore, the thermal stability and oxidation resistance of the titanium silicide nanoparticles were also investigated.     

Ultrafine Cr-Doped Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Prepared by Detonation Synthesis

Data are presented on the phase composition, particle size distribution, EPR, and luminescence of ultrafine chromium-doped alumina powders prepared by detonation synthesis. The largest particles in the powders are shown to consist mainly of a Cr₂O₃ solid solution in α-Al₂O₃. The luminescence spectrum of fine particles shows, in addition to lines characteristic of ruby, extra lines which are tentatively attributed to Cr³⁺ ions incorporated substitutionally into θ-Al₂O₃.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 8, 2005, pp. 948–954.Original Russian Text Copyright © 2005 by Lyamkina, Chiganova, Slabko, Vorotynov, Taranova.     

Upconversion Luminescence of Gd<Subscript>2</Subscript>O<Subscript>3</Subscript> Nanocrystals Doped with Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> Ions

The upconversion luminescence (UCL) of nanocrystalline gadolinium oxide (Gd₂O₃) doped with Er³⁺ and Yb³⁺ ions has been studied in the temperature range of 90–400 K. The nanocrystals were synthesized by chemical vapor deposition and possessed a cubic crystalline structure with an average particle size within 48–57 nm. It is established that the USL intensity in the red (⁴F_9/2 → ⁴I_15/2 transition in Er3+ ion) and green (⁴S_3/2 → ⁴I_15/2 transition) spectral regions depends on the sample temperature and concentration of dopant ions, as well as on the additional structural defects (anion vacancies) created in the crystal lattice by the introduction of Zn²⁺ ions or irradiation with high-energy (10 MeV) electrons. The luminescence efficiency and spectrum of the upconversion phosphor are determined by energy transfer processes.     

Influence of microstructure on the luminescence properties of YVO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> nanoparticles

YVO₄:Eu³⁺ nanoparticles were synthesized by hydrothermal method at different conditions. The microstructures and photoluminescence (PL) properties of the as-prepared YVO₄:Eu³⁺ nanoparticles were investigated by X-ray powder diffraction, field emission scanning electron microscopy and PL spectroscopy. The detailed relationship between the microstructures and luminescence properties was investigated. It has been found that the crystallinity, the grain size and the duty factor of Eu³⁺ play important roles in influencing the luminescence properties. The article is published in the original.     

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.     

Effect of secondary heat treatment on the spectroscopic properties of Na<Subscript>2</Subscript>O-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

We have studied the optical absorption and luminescence spectra of 45Na₂O · xNb₂O₅ · (55 − x)P₂O₅ glasses containing 5, 10, 20, 25, 30, and 35 mol % Nb₂O₅. The results indicate that the absorption band around 26000 cm⁻¹, responsible for the yellow color of the glasses, is due to the [Nb^(5+)--O⁻] center and disappears upon secondary heat treatment. Heat treatment of europium-doped glasses increases the concentration of Eu³⁺ centers in an asymmetric environment, which is accompanied by an increase in luminescence efficiency. The reason for this is that the Eu³⁺ ions are located outside the niobate subsystem of the glass matrix. The europium in the glasses studied acts as a protector ion.     

Synthesis and properties of laser-active liquids POCl<Subscript>3</Subscript>-SbCl<Subscript>5</Subscript>-<Superscript>235</Superscript>UO<Stack><Subscript>2</Subscript><Superscript>2+</Superscript></Stack>-Nd<Superscript>3+</Superscript>

The effect of the synthesis conditions on the properties of inorganic laser-active liquids POCl₃-SbCl₅-²³⁵UO ₂ ²⁺ -Nd³⁺ is considered. The kinetic dependences of the U(IV) content and decay time of the Nd³⁺ luminescence in POCl₃-SbCl₅-²³⁵UO ₂ ²⁺ -Nd³⁺ solutions for various synthesis procedures at 380 K have been obtained. In POCl₃-SbCl₅-²³⁵UO ₂ ²⁺ -Nd³⁺ solutions, nonradiative energy transfer Nd³⁺ → U⁴⁺ is observed, and quenching of the Nd³⁺ luminescence is described by the Stern-Volmer law: k _q = (6.4 ± 0.6) × 10⁵ l mol^?1 s^?1. Laser liquids POCl₃-SbCl₅-²³⁵UO ₂ ²⁺ -Nd³⁺ with neodymium concentration of up to 0.7 M, uranyl concentration of up to 0.1 M, and decay time of the Nd³⁺ luminescence of up to 220 μs have been prepared for the first time.     

The comparison: photoluminescence and afterglow behavior in CaSnO<Subscript>3</Subscript>:Dy<Superscript>3+</Superscript> and Ca<Subscript>2</Subscript>SnO<Subscript>4</Subscript>:Dy<Superscript>3+</Superscript> phosphors

This paper reports the comparison of photoluminescence and afterglow behavior of Dy³⁺ in CaSnO₃ and Ca₂SnO₄ phosphors. The samples containing CaSnO₃ and Ca₂SnO₄ were prepared via solid-state reaction. The properties have been characterized and analyzed by utilizing X-ray diffraction (XRD), photoluminescence spectroscope (PLS), X-ray photoelectron spectroscopy (XPS), afterglow spectroscopy (AS) and thermal luminescence spectroscope (TLS). The emission spectra revealed that CaSnO₃:Dy³⁺ and Ca₂SnO₄:Dy³⁺ phosphors showed different photoluminescence. The Ca₂SnO₄:Dy³⁺ phosphor showed a typical ⁴F_9/2 to ⁶H_j energy transition of Dy³⁺ ions, with three significant emissions centering around 482, 572 and 670 nm. However, the CaSnO₃:Dy³⁺ phosphor revealed a broad T₁ → S₀ transitions of Sn²⁺ ions. The XPS demonstrate the existence of Sn²⁺ ions in CaSnO₃ phosphor caused by the doping of Dy³⁺ ions. Both the CaSnO₃:Dy³⁺ and Ca₂SnO₄:Dy³⁺ phosphors showed a typical triple-exponential afterglow when the UV source switched off. Thermal simulated luminescence study indicated that the persistent afterglow of CaSnO₃:Dy³⁺ and Ca₂SnO₄:Dy³⁺ phosphors was generated by the suitable electron or hole traps which were resulted from the doping the calcium stannate host with rare-earth ions (Dy³⁺).     

Anti-stokes luminescence of CsCdBr<Subscript>3</Subscript>:Tm crystals

Transmission and spontaneous photoluminescence excitation spectra of CsCdBr₃:Tm (1 and 2.5 at % Tm) crystals have been studied under different optical pumping conditions. The results demonstrate that the anti-Stokes luminescence intensity in the thulium-doped crystals is higher at the higher doping level. We have determined the resonance wavelengths of IR photons for two-photon excitation of visible luminescence in CsCdBr₃:Tm and identified the corresponding electronic transitions in thulium-related emission centers for Stokes and anti-Stokes luminescence.     

Microwave synthesis and luminescence properties of YVO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript>

Europium-doped YVO₄ phosphors have been synthesized using microwave radiation of 700 W power. The uniformity and high rate of microwave heating, as well as “nonthermal” effects of microwave radiation, considerably accelerate the decomposition of precursors and YVO₄:Eu³⁺ synthesis. The europium concentration was varied from 1 to 8 at %. The luminescence intensity of YVO₄:Eu³⁺ was shown to depend on Eu³⁺ concentration, with a maximum at 8 at % Eu³⁺. According to transmission electron microscopy data, the synthesized phosphors consist of nanoparticles 6 to 8 nm in size, with an appreciable degree of agglomeration.     

Synthesis of monodisperse NaYF4:Yb, Tm@SiO2 nanoparticles with intense ultraviolet upconversion luminescence

In this paper, the NaYF4:Yb, Tm upconversion (UC) nanoparticles (NPs) were synthesized using a solvothermal approach, and the core-shell structured NaYF4:Yb, Tm@SiO2 NPs, coated with a thin layer of SiO2 on the surface of the NaYF4:Yb, Tm NPs, were prepared by a typical St?ber method. X-ray diffraction (XRD), transmission electron microscopy (TEM), and luminescence spectroscopy were applied to characterize these samples. The obtained core-shell structured NaYF4:Yb, Tm@SiO2 NPs exhibited a perfect spherical morphology with narrow size distribution and smooth surfaces. Under 980 nm excitation, NaYF4:Yb, Tm and NaYF4:Yb, Tm@SiO2 samples showed intense ultraviolet UC luminescence, which originated from the 1D2 --> 3H6, 1I6 --> 3F4 transitions of Tm3+. These NPs have great potential for applications as fluorescent labels, imaging probes, optical storage, photodynamic therapy (PDT) in deep tissue, and solid-state lasers.