Upconversion emissions in Yb<Superscript>3+</Superscript>–Tm<Superscript>3+</Superscript>-doped tellurite glasses excited at 976 nm

Intense Tm³⁺ blue upconversion emission has been observed in Tm³⁺–Yb³⁺ codoped oxyfluoride tellurite glass under excitation with a diode laser at 976 nm. Three emission bands centered at 475, 650 and 796 nm corresponding to the transitions ¹G₄→ ³H₆, ¹G₄→ ³H₄ and ³F₄→ ³H₆, respectively, simultaneously occur. The dependence of upconversion intensities on Tm³⁺ ions concentration and excitation power are investigated. For fixed Yb₂O₃ concentrations of 5.0 mol%, the maximum upconversion intensity was obtained with Tm₂O₃ concentration of about 0.1 mol%. The blue upconversion luminescence lifetimes of the Tm³⁺ transitions ¹G₄→ ³H₆ are measured. The results are evaluated by the possible upconversion mechanisms.     

Microstructure and upconversion luminescence of Yb<Superscript>3+</Superscript> and Ho<Superscript>3+</Superscript> co-doped BST thick films

Ba_0.8Sr_0.2TiO₃ (BST) thick films co-doped with Yb³⁺ and Ho³⁺ were fabricated by the screen printing techniques on alumina substrates. The structure and morphology of the BST thick films were studied by XRD and SEM, respectively. After sintered at 1240 °C for 100 min the BST thick films are polycrystalline with a perovskite structure. The upconversion luminescence properties of the RE-doped BST thick films under 800 nm excitation at room temperature were investigated. The upconversion emission bands centered at 470 and 534 nm corresponding to ⁵F₁ → ⁵I₈ and ⁵F₄ → ⁵I₈ transition, respectively were observed, and the upconversion mechanisms were discussed. The dependence of the upconversion emission intensity upon the Ho³⁺ ions concentration was also examined; the emission intensity reaches a maximum value in the sample with 2 mol% Yb³⁺ and 0.250 mol% Ho³⁺ ions. All the results show that the BST thick films co-doped with Yb³⁺ and Ho³⁺ may have potential use for photoelectric devices.     

Intense frequency upconversion luminescence in Yb<Superscript>3+</Superscript>/Tm<Superscript>3+</Superscript>-codoped oxychloride germanate glasses

Yb³⁺/Tm³⁺-codoped oxychloride germanate glasses for developing potential upconversion lasers have been fabricated and characterized. Structural properties were obtained based on the Raman spectra analysis, indicating that PbCl₂ plays an important role in the formation of glass network and has an important influence on the maximum phonon energies of host glasses. Intense blue and weak red emissions centered at 477 and 650 nm, corresponding to the transitions ¹G₄ → ³H₆ and ¹G₄ → ³H₄, respectively, were observed at room temperature. With increasing PbCl₂ content, the intensity of blue (477 nm) emission increases significantly, while the red (650 nm) emission increases slowly. The results indicate that PbCl₂ has more influence on the blue emissions than the red emission in oxychloride germanate glasses. The possible upconversion mechanisms are discussed and estimated. Intense blue upconversion luminescence indicates that these oxychloride germanate glasses can be used as potential host material for upconversion lasers.     

Synthesis of β–NaYF4: Yb3+, Tm3+ @ TiO2 and β–NaYF4: Yb3+, Tm3+ @ TiO2 @ Au nanocomposites and effective upconversion–driven photocatalytic properties

The β–NaYF₄: Yb³⁺, Tm³⁺ @ TiO₂ nanocomposite has been prepared by a facile hydrothermal method followed by the hydrolysis of TBOT, and then NaYF₄: Yb³⁺, Tm³⁺ @ TiO₂, HAuCl₄ and sodium citrate were put into an oil bath for reaction to obtain the β–NaYF₄: Yb³⁺, Tm³⁺ @ TiO₂ @ Au core–shell nanocomposite. XRD and HRTEM show that the samples exhibit the hexagonal phase NaYF₄, anatase TiO₂ and cubic Au, indicating that the core–shell phases of NaYF₄−TiO₂ or NaYF₄−TiO₂−Au coexist in these samples. EDS and XPS results show the presence of Na, Y, F, Ti, O and Au elements. When TiO₂ was coated on the surface of upconversion nanomaterials of NaYF₄: Yb³⁺, Tm³⁺, the photocatalytic activity was improved significantly, and the β–NaYF₄: Yb³⁺, Tm³⁺ @ TiO₂ nanocomposite gives the highest photodegradation efficiency for MB and RhB, and decomposes about 73% of MB or 80% of RhB within 4.5 h under simulated solar light irradiation respectively. When the ultraviolet light from simulated sunlight irradiation was removed by the addition of a UV filter, the β–NaYF₄: Yb³⁺, Tm³⁺ @ TiO₂ nanocomposite decomposes about 42% of MB or 48% of RhB within 4.5 h. It means that the upconversion–driven photocatalytic performance (decomposes 42% of MB or 48% of RhB) is more effective than UV light–driven photocatalytic performance (31% of MB or 32% of RhB) in the photodegradation process. In addition, the β–NaYF₄: Yb³⁺, Tm³⁺ @ TiO₂ @ Au core–shell nanocomposite does not exhibit the better photocatalytic activity, and the optimal research will be carried out in the future.     

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.     

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.     

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.     

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.     

Hydrothermal synthesis and photoluminescence properties of Y<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript>:Tb<Superscript>3+</Superscript> phosphors

This article presents the synthesis and photoluminescence (PL) properties of Y₂Zr₂O₇:Tb³⁺. The Tb³⁺-doped Y₂Zr₂O₇ zirconates were successfully synthesized by a hydrothermal process at 200 °C for 20 h. X-ray diffractometer (XRD) patterns revealed that all of the products were phase-pure with the fluorite structure. PL study showed that the Y₂Zr₂O₇:Tb³⁺ phosphors exhibited obvious PL emission peaks which located at 490, 545, 585, and 623 nm; the dominant emission located at 545 nm is assigned to ⁵D₄ → ⁷F₅ transition. Furthermore, Tb³⁺-doping concentration strongly affected the PL properties, and the quenching concentration is 5 at.%.     

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.     

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.     

Morphology and luminescent properties of Al<Superscript>3+</Superscript>/Mg<Superscript>2+</Superscript>-doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphor

Al³⁺/Mg²⁺ doped Y₂O₃:Eu phosphor was synthesized by the glycine-nitrate solution combustion method. In contrast to Y₂O₃:Eu which showed an irregular shape of agglomerated particles (the mean particle size >10 μm), the morphology of Al³⁺/Mg²⁺ doped Y₂O₃:Eu crystals was quite regular. Al³⁺/Mg²⁺ substituting Y³⁺ in Y₂O₃:Eu resulted in an obvious decrease of the particle size. Meanwhile, higher the Al³⁺/Mg²⁺ concentration, smaller the particle size. In particular, the introduction of Al³⁺ ion into Y₂O₃ lattice induced a remarkable increase of PL and CL intensity. While, for Mg²⁺ doped Y₂O₃:Eu samples, their PL and CL intensities decreased. The reason that causes the variation of PL and CL properties for Al³⁺ and Mg²⁺ doped Y₂O₃:Eu crystals was concluded to be related to sites of Al³⁺ and Mg²⁺ ions inclined to take and the difference of ion charge.     

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.     

Multicolor upconversion of Er3+/Tm3+/Yb3+ doped oxyfluoride glass ceramics

Er³⁺/Tm³⁺/Yb³⁺ tridoped oxyfluoride glass ceramics was synthesized in a general way. Under 980 nm LD pumping, intense red, green and blue upconversion was obtained. And with those primary colors, multicolor luminescence was observed in oxyfluoride glass ceramics with various dopant concentrations. The red and green upconversion is consistent with ⁴F_9/2 → ⁴I_15/2 and ²H_11/2, ⁴S_3/2 → ⁴I_15/2 transition of Er³⁺ respectively. While the blue upconversion originates from ¹G₄ → ³H₆ transition of Tm³⁺. This is similar to that in Er³⁺/Yb³⁺ and/or Tm³⁺/Yb³⁺ codoped glass ceramics. However the upconversion of Tm³⁺ is enhanced by the energy transfer between Er³⁺ and Tm³⁺.     

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.      

Synthesis of LaF3: Yb3+ ,Ln3+ nanoparticles with improved upconversion luminescence

Yb³⁺/Er³⁺ and Yb³⁺/Tm³⁺ co-doped LaF₃ nanoparticles with upconversion luminescence properties were prepared via the co-precipitation method, followed by heat treatment at different temperatures in the range of 180°C to 600°C. We investigated the influence of heat treatment temperatures on the size, morphology, and upconversion luminescence intensity of the nanoparticles. Significant increases of the particle size and upconversion luminescence intensity of the nanoparticles were observed with increasing heat treatment temperature. The upconversion mechanism of the LaF₃:Yb³⁺,Er³⁺ and LaF₃:Yb³⁺,Tm³⁺ nanoparticles was also discussed.     

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.     

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.     

A new yttrium oxysulfide-based multispectral IR phosphor activated with Nd<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> ions

We have identified the main general trends of variations in the spectral and kinetic properties of the Nd³⁺ and Yb³⁺ IR luminescence bands in (Y_0.99–xNd_0.01Yb_x)₂O₂S solid solutions under excitation at wavelengths of 0.810 and 0.940 µm. Using these results, we have developed the first multispectral IR phosphors with various relative intensities of the IR luminescence bands in the ranges 0.88–0.94, 0.94–1.06, 1.06–1.12, and 1.35–1.42 µm under excitation with 0.810-µm light and bright IR luminescence in the range 0.94–1.06 µm under excitation with 0.940-µm light.     

Recombination processes in the Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce<Superscript>3+</Superscript> scintillator

The roentgenoluminescence spectra, temperature-dependent activator luminescence, optically stimulated luminescence, and the effect of IR irradiation on the yield and spectral composition of the low-temperature roentgenoluminescence and thermoluminescence curves of the Y₃Al₅O₁₂:Ce³⁺ scintillator have been studied in the temperature range 85–295 K. The results, coupled with earlier data, suggest that the Ce³⁺ ions in the garnet crystal studied form Ce³⁺ p hole centers and increase the concentration of electronic F ^?-centers responsible for the IR stimulation band at 940 nm. The reduction in roentgenoluminescence yield on cooling Y₃Al₅O₁₂:Ce³⁺ to below 230 K is due to the significant localization of excited carriers at defects, which show up in thermoluminescence peaks and optical stimulation spectra. The low-temperature Ce³⁺ luminescence in Y₃Al₅O₁₂:Ce₃₊ seems to result from the recombination of activator-bound excitons.