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⁺).     

Hydrothermal synthesis of blue-emitting YPO<Subscript>4</Subscript>:Yb<Superscript>3+</Superscript> nanophosphor

The blue-emitting YPO₄ phosphors doped with Yb³⁺ were prepared by a simple hydrothermal method. All the products were characterized by XRD and TEM, which revealed that they were zircon structure with leaf-like morphology. According to the analysis of photoluminescence spectra, upon ultraviolet (275 nm) excitation, the Yb³⁺ doped YPO₄ phosphor showed an intense blue emission composed of two main bands at 420 and 620 nm assigned to charge transfer state (CTS) → ²F_5/2 and CTS → ²F_7/2, respectively. Moreover, the optimum doping concentration of Yb³⁺ in YPO₄ phosphor was 1%, which exhibited the maximum emission intensity. The possible physical mechanism of concentration quenching was discussed, and the critical transfer distance determined to be 23.889 Å. In particular, the color purity of the as-synthesized Yb³⁺ doped YPO₄ phosphor was as high as 83%, which made it an excellent candidate for blue-emitting materials.     

Cr<Superscript>3+</Superscript> activated Zn<Subscript>3</Subscript>Al<Subscript>2</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript>: a novel near-infrared long persistent phosphor

The near-infrared (NIR) long persistent phosphors have gained considerable attention owing to the potential applications in in vivo imaging. A novel NIR long-persistent phosphors Zn₃Al₂Ge₃O₁₂:Cr³⁺ was successfully synthesized by a high temperature solid-state reaction. The luminescent properties and the afterglow behaviors of the Zn₃Al₂Ge₃O₁₂:Cr³⁺ were investigated in detail. On the basis of thermoluminescence analyses, the mechanism of the persistent afterglow of the phosphors was also discussed briefly. The afterglow duration of this phosphor can last more than 12 h with the 650–750 nm emission range after stoppage of 254 nm ultraviolet light irradiation. Specifically, the persistent luminescence intensity and duration were regulated by changing Cr³⁺ doping concentration. All the results indicate that the Cr³⁺ activated Zn₃Al₂Ge₃O₁₂ has promising potential of practical applications.     

Ultraviolet upconversion luminescence in Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Yb<Superscript>3+</Superscript>,Tm<Superscript>3+</Superscript> nanocrystals and its application in photocatalysis

Infrared-to-ultraviolet upconversion luminescence agent Y₂O₃:Yb³⁺,Tm³⁺ was prepared by a combustion method using citrate as a fuel/reductant. The prepared sample was characterized by X-ray diffraction, SEM, and fluorescence spectrophotometer. Two unusual ¹I₆ → ³H₆ (~297 nm) and ¹D₂ → ³H₆ (~363 nm) emissions from Tm³⁺ ions were observed at room temperature under 980-nm laser excitation. The change of upconversion emission intensity depending on the Yb³⁺ concentrations was discussed. The results showed that modest Yb³⁺ doping could make the upconversion emission of Tm³⁺ intense, and high Yb³⁺ concentrations might lead to fluorescence quenching. Moreover, the influence of ultraviolet upconversion luminescence on the photodegradation of methyl orange aqueous solution under solar light irradiation in the presence of TiO₂ catalyst doped with Y₂O₃:Yb³⁺,Tm³⁺ was also investigated. It was concluded from the experiment of this study that TiO₂/Y₂O₃:Yb³⁺,Tm³⁺ composite had higher photocatalytic activity than pure TiO₂ under solar light. This study would make TiO₂ utilize sunlight more efficiently and accelerate the practical application of photocatalytic technology in water treatment region.     

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.     

Study of the effect of Li<Superscript>+</Superscript> concentration on the photoluminescence properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphors

Y₂O₃:Eu³⁺ phosphors were prepared by hydrothermal method. Effect of the doping concentration of Eu³⁺ on the photoluminescence properties of Y₂O₃:Eu³⁺ phosphor was studied in details. It was found that the strongest emission intensity is achieved as atomic ratio of Y³⁺ to Eu³⁺ is 8. As concentration of Eu³⁺ exceeds the critical concentration, the emission intensity decreases dramatically due to the concentration quenching of Eu³⁺. Also, the effect of Li⁺ on the photoluminescence performance of the Y₂O₃:Eu³⁺ phosphor is studied in this work. According to the results, the doping of Li⁺ may greatly improve the PL performance of the Y₂O₃:Eu³⁺ phosphors due to the flux effect and improved crystallinity caused by the doping of Li⁺.     

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.     

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.     

Combusion synthesis,structural and photo-physical characteristics of Eu<Superscript>2+</Superscript> and Dy<Superscript>3+</Superscript> co-doped SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript> phosphor nanopowders

In this research, we reported the synthesis of Eu²⁺ and Dy³⁺ co-doped SrAl₂O₄ phosphor nanopowders with high brightness and long afterglow by urea-nitrate solution combustion synthesis (SCS) at 600 °C, followed by heating the resultant combustion ash at 1,200 °C in a weak reductive atmosphere (5% H₂ + 95% N₂). The broad-band UV-excited luminescence of the SrAl₂O₄: Eu²⁺, Dy³⁺ nanopowders was observed at λ _max = 517 nm due to transitions from the 4f⁶5d¹ to the 4f⁷ configuration of the emission center (Eu²⁺ ions). The excitation spectra consist of 240- and 254 nm broad peaks. Finally, it was found that the optimum ratio of urea is 2.5 times higher than theoretical quantities for the best emission condition of SrAl₂O₄: Eu²⁺, Dy³⁺ phosphor nanopowders.     

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.     

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.     

Influence of Mn<Superscript>2+</Superscript> on the up-conversion emission performance of Mn<Superscript>2+</Superscript>, Yb<Superscript>3+</Superscript>, Er<Superscript>3+</Superscript>: ZnWO<Subscript>4</Subscript> green phosphors

The Mn²⁺, Yb³⁺, Er³⁺: ZnWO₄ green phosphors are synthesized successfully through the high temperature solid state reaction method. The micro-structure and morphology have been investigated by means of XRD and EDS. The doped concentrations of Mn²⁺, Yb³⁺, Er³⁺ are measured by ICP. The absorption spectra and emission spectra with different doped concentrations of Mn²⁺ are presented to reveal the influence of Mn²⁺ on the green up-conversion performance. Excited with 970 nm LED, the up-conversion emission peak at 547 nm is obtained and the CIE spectra as well as the green light photo are also presented. The results indicate that the Mn²⁺ ions play the role of the luminescence adjustment in the up-conversion process, which can improve the up-conversion green emission intensity effectively. The luminescence adjustment mechanism of Mn²⁺ ions in Mn²⁺, Yb³⁺, Er³⁺: ZnWO₄ green phosphors has been discussed. The crystal parameters of Dq, B and C are calculated to evaluate the energy level split effect.     

Highly efficient cooperative up-conversion of Yb<Superscript>3+</Superscript> in NaYF<Subscript>4</Subscript>

Strong blue cooperative up-conversion emission around 475 nm has been observed in Yb³⁺-doped hexagonal NaYF₄. The influence of concentration of the Yb³⁺ ion on the luminescence intensity is investigated. It is found that the sample shows the strongest cooperative luminescence when the Yb³⁺ ion concentration is 75%. The investigation shows that hexagonal NaYbF₄ is an efficient blue up-converted phosphor, which might be potentially applicable in three-dimensional solid-state fluorescence display.     

Crystal structure and luminescence property of a single-phase white light emission phosphor Sr<Subscript>3</Subscript>YNa(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>F:Dy<Superscript>3+</Superscript>

A series of single-phase Sr₃YNa(PO₄)₃F:Dy³⁺ phosphors were successfully synthesized via a conventional solid state reaction process. The powder X-ray diffraction patterns were utilized to confirm the phase composite and crystal structure. The phosphor could be excited by the ultraviolet visible light in the region from 300 to 420 nm, and it shown two dominant emission bands peaking at 484 nm (blue light) and 580 nm (yellow light) which originated from the transitions of ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 of Dy³⁺, respectively. The optimum dopant concentration of Dy³⁺ ions was confirmed to be 7 mol% in Sr₃YNa(PO₄)₃F:Dy³⁺ system and the concentration quenching mechanism is dipole–dipole interaction. The lifetime values of Dy³⁺ ions at different concentrations (x?=?0.03, 0.05, 0.07, 0.09 and 0.11) were determined to be about 0.855, 0.759, 0.686, 0.606 and 0.546 ms, respectively. The thermal stability of luminescence of Sr₃YNa(PO₄)₃F:0.07Dy³⁺ phosphor was also investigated and the activated energy was deduced to be 0.228 eV, which shows good thermal stability. The chromaticity coordinates fall in the white-light region calculated by the emission spectrum. These results show that Sr₃YNa(PO₄)₃F:Dy³⁺ phosphor can be a promising white emitting phosphor for white LEDs.     

Green and red upconversion emissions of Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript>-codoped SrTiO<Subscript>3</Subscript> powder prepared by a polymeric precursor method

Ultrafine Er³⁺/Yb³⁺-codoped SrTiO₃ (SEYT) powders in cubic form have been prepared by a poly-meric precursor method. The single phase perovskite for the obtained material was observed at low temperature. An efficient infrared-to-visible conversion in SEYT perovskite will be reported. Visible emissions at 550 and 663 nm corresponding to the ²S_3/2 − ⁴I_15/2 and ⁴F_9/2 − ⁴I_15/2 transitions, respectively, were observed under continuous wave excitation at 980 nm. An enhancement of the visible upconversion luminescence in Er³⁺/Yb³⁺ codoped samples was confirmed due to efficient energy transfer from Yb³⁺ to Er³⁺ ions. The quadratic pump power dependence of these emissions indicated the contribution of two photons to the upconversion process. The text was submitted by the authors in English.     

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.     

Persistent luminescence of Zn<Subscript>2</Subscript>GeO<Subscript>4</Subscript>:Mn<Superscript>2+</Superscript>/Pr<Superscript>3+</Superscript> phosphors

Zn₂GeO₄, Zn₂GeO₄:Mn²⁺, Zn₂GeO₄:Pr³⁺ and Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphors were fabricated by a solid state reaction. The phase and luminescent properties of the fabricated phosphors were investigated. The XRD patterns show that all of the fabricated phosphors have an orthorhombic structure. The fabricated Zn₂GeO₄ shows an emission band in the range of 350–550 nm. The fabricated Zn₂GeO₄:Mn²⁺ and Zn₂GeO₄:Pr³⁺ phosphors show emission bands corresponding to Mn²⁺ and Pr³⁺ ions, respectively. The fabricated Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphor shows the emission band results from Mn²⁺ and the codoped Pr³⁺ enhances the emission intensity of Mn²⁺. Moreover, Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphor exhibits longer decay time than that of Zn₂GeO₄:Mn²⁺. The higher intensity and longer lifetime of Mn²⁺ emission are induced by the energy transfer from Pr³⁺ of various vacancies to Mn²⁺ in Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphors.     

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⁺.     

Color-tunable luminescence properties of Sm<Superscript>3+</Superscript>/Dy<Superscript>3+</Superscript> co-doped NaLa(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> phosphors and their energy transfer mechanism

The Sm³⁺, Dy³⁺ doped and Sm³⁺/Dy³⁺ co-doped NaLa(MoO₄)₂ spherical phosphors were hydrothermally synthesized by the EDTA-2Na mediated method. Under the excitation of 297 nm, the quenching concentration of Sm³⁺ in NaLa(MoO₄)₂ host was determined to be 13%, and the concentration quenching mechanism was discussed to be the electric quadrupole–quadrupole interaction. After Sm³⁺ and Dy³⁺ ions were co-doped into the NaLa(MoO₄)₂ host, the energy transfer behaviors resulted from Dy³⁺ to Sm³⁺ ions were investigated by the help of the luminescent spectra of the obtained phosphors. By varying co-doping concentrations of Sm³⁺/Dy³⁺ ions, the emission color of NaLa(MoO₄)₂:Sm³⁺/Dy³⁺ can be tuned from reddish-orange, pink and white to bluish-green. The CIE chromaticity coordinate, the correlated color temperature and the quantum efficiency of NaLa_0.87(MoO₄)₂:1%Sm³⁺, 12%Dy³⁺ were calculated to be (0.356, 0.320), 4353 K and 20%, respectively. Furthermore, in the temperature-dependent analysis, it presented good thermal stability, which can become a promising single-phased white-emitting phosphor for white LEDs devices. Based on these results, the possible energy transfer mechanism between Dy³⁺ and Sm³⁺ in NaLa(MoO₄)₂:Sm³⁺/Dy³⁺ was also proposed.     

Effect of coactivation with Dy<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> ions on the efficiency of energy storage in Lu<Subscript>2</Subscript>SiO<Subscript>5</Subscript>:Ce<Superscript>3+</Superscript> crystals

Cerium-activated lutetium oxyorthosilicate Lu₂SiO₅:Ce³⁺ (LSO:Ce) and coactivated LSO:Ce,Dy and LSO:Ce,Yb crystals have been synthesized by the sol-gel technique. It is shown that the introduction of coactivator (Yb and Dy) ions influences the energy storage in LSO:Ce, thus making it possible to control the afterglow and thermoluminescence in these crystals. The observed effect is related to the electron properties of coactivator ions (donor against acceptor), which determine the recharge of electron traps in LSO crystals.