Up-conversion luminescence of Er~(3+)-doped and Yb~(3+)/Er~(3+) co-doped 12CaO·7Al_2O_3 poly-crystals

The optical properties of Er3+-doped and Yb3+/Er3+ co-doped 12CaO·7Al2O3 (C12A7) poly-crystals, synthesized by high temperature solid state method, were investigated in detail. For Er3+-doped and Yb3+/Er3+ co-doped C12A7 poly-crystals, two main emission bands centered around 530/550 nm (green) and 660 nm (red) were observed under 980 nm diode laser excitation via an up-conversion process. The intensity of green up-conversion emission had a strong increase in Er3+ (1.0 mol.%, 1.5 mol.%, 3.0 mol.%), and the i...     

Up-conversion of Er3＋/yb3＋ co-doped transparent glass-ceramics containing Ba2LaF7 nanocrystals

The up-conversion of Er3+/Yb3+co-doped transparent glass-ceramics 50SiO2-10AlF3-5TiO2-30BaF2-4LaF3-0.5ErF3-0.5YbF3 containing Ba2 LaF7 nanocrystals under the changing of heat treatment temperature and time were investigated.The Ba2 LaF7 nanocrystals precipitated from the glass matrix was confirmed by X-ray diffraction(XRD).The structural investigation carried out by XRD and transmission electron microscopy(TEM) evidenced the formation of cubic Ba2 LaF7 nanocrystals with crystal size of about 14 nm.Comparing with the samples before heat treatment,the high efficiency up-conversion emission of Er3+/Yb3+co-doped samples was observed in the glass-ceramics under 980 nm laser diode excitation.The increase in red emission intensity bands was stronger than the green bands when the crystal size increased.The mechanism for the up-conversion process in the glass-ceramics and the reasons for the increase of Er3+/Yb3+co-doped up-conversion intensity after heat treatment were discussed.     

Up-conversion luminescence properties of Yb^3＋ and Ho^3＋ co-doped Bi3.84W0.16O6.24 powder synthesized by hydrothermal method

Using polyethylene glycol (PEG) as the surfactant, Bi3.84W0.16O6.24 up-conversion luminescence nano-crystal co-doped with Yb3+ and Ho3+ ions was synthesized by the hydrothermal method. The structure and properties of luminescence powder were studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). It was of cubic system when the sample was synthesized at a low temperature and the particle size was about 30 nm. The results showed that adding surfactants was useful to improve the powder agglomeration and the grain crystal was spherical. The green emission peak at 546 nm and red emission peak at 655 nm, corresponding to the ( 5F4, 5S2)→ 5 I 8 and the 5 F 5 → 5 I 8 transitions of Ho 3+ , respectively, were simultaneously observed at room temperature under excitation of 980 nm semiconductor laser. The up-conversion luminescence intensity was the strongest when the concentration ratio of Yb3+ /Ho3+ was 6:1 and the concentration of Ho 3+ ion was 1.5 mol.%. The up-conversion mechanism was also studied. The green and red emission peaks were the two-photon absorption according to the relationship between the pump power and the luminescence intensity.     

Luminescence properties of Tm^3＋/Yb^3＋, Er^3＋/Yb^3＋ and Ho^3＋/Yb^3＋ activated calcium tungstate

CaWO4 phosphor activated by the Tm3+/Yb3+,Er3+/Yb3+ and Ho3+/Yb3+ ions were synthesized by a traditional high-temperature solid-state method.The crystal structures and morphologies of the products were characterized by X-ray powders diffraction method(XRD) ,infrared spectra(FT-IR) and scanning electron microscopy(SEM) .The samples were found to show up-conversion luminescence properties.CaWO4 doped with Tm3+/Yb3+ showed blue luminescence characteristic of Tm(III) ion in the range of 460-485 nm,corresponding to the 1G4→3H6 electronic transition.CaWO4 doped with Er3+/Yb3+ showed strong green luminescence at 510-565 nm(2H11/2,4S3/2→4I15/2) and weak red luminescence at 640-685 nm(4F9/2→4I15/2) of Er(III) ion.CaWO4 doped with Ho3+/Yb3+ phosphor emitted green luminescence at 525-560 nm(5S2,5F4→5I8) and red luminescence at 630-670 nm(5F5→5I8) and at 730-770 nm(5S2,5F4→5I7) ,which is the characteristic of Ho(III) ion.     

Combustion synthesis and upconversion luminescence of CaSc_2O_4：Yb~（3＋）,Er~（3＋） nanopowders

Novel up-conversion (UC) luminescent nano-powders, CaSc2O4:Yb3+:Er3+ were prepared with a combustion method at an ignition temperature as low as 200 oC. The CaSc2O4:Yb3+,Er3+ nano-powder had an orthorhombic CaFe2O4-type structure, and showed sphere-like morphology with an average diameter of about 30 nm. It gave strong green (525, 552 nm) and red (652-674 nm) up-conversion luminescence due to the 2H11/2→4I15/2, 4S3/2→4I15/2 and 4F9/2→4I15/2 transitions of Er3+ under a 980 nm semiconductor laser excitation a...     

Energy transfer and frequency upconversion in Er~（3＋）-Yb~（3＋） codoped oxy-fluoro-tungstosilicate glasses

Er3+-Yb3+ codoped oxy-fluoro-tungstosilicate glasses with infrared-to-visible frequency upconversion luminescence were prepared by melting quenching in air.The effects of Er3+ doping on the optical properties of the samples were measured by means of techniques such as optical absorption spectra and photoluminescence spectra.The results showed that intense green and red signals centered at 546 and 665 nm,corresponding to the 4S3/2 → 4I15/2 and 4F9/2 → 4I15/2 transitions of Er3+ by a multiphoton stepwise phonon-assisted excited-state absorption process,respectively,were simultaneously observed by exciting the samples with a diode laser operating at 980 nm at room temperature.The upconversion process was found very sensitive to Er3+ content at a constant Yb2O3 content of 5 mol.%.With the increase of Er3+ content from 0.5% to 1.5%,the upconversion intensity increased gradually.Further increasing of Er3+ content to 3.0% resulted in a significant fluorescence quenching.Moreover,the possible upconversion mechanisms were discussed based on the energy-matching conditions and the quadratic dependence on excitation power.     

Spectroscopic investigations on Er3+/Yb3+-doped oxyfluoride glass ceramics containing YOF nanocrystals

Spectroscopic properties of Er3+/Yb3+-doped transparent oxyfluoride borosilicate glass ceramics containing YOF nanocrystals were systematically investigated. X-ray diffraction (XRD) confirmed the formation of YOF nanocrystals in the glassy matrix. Based on the Judd-Ofelt theory, the intensity parameters Ωi (i=2, 4, 6), spontaneous emission probability, radiative lifetime, radiative quantum efficiency and the effective emission bandwidth were investigated. The upconversion luminescence intensity of Er3+ ions in the glass ceramics increased significantly with the increasing crystallization temperature. The transition mechanisms of the green and red upconversion luminescence were ascribed to a two-photon process, and the blue upconversion luminescence was a three-photon absorption process.     

Preparation and characterization of Er3＋-Yb3＋-Ce3＋ co-doped transparent glass ceramic containing nano Cas（PO4）3F crystals

A transparent glass ceramic tri-doped with Ce3+/Er3+/Yb3+ was fabricated by the high-temperature melting technique and following heat-treatment.X-ray diffraction and transmission electron microscope results demonstrated that Ca5(PO4)3F(FAP) nanocrystals,possessed with preferable emission performances for the 1.54 m transition for doping Er3+,were homogeneously precipitated among the glass matrix with a mean size of 30 nm.Addition of Ce3+ greatly enhanced 1.54 m fluorescence of Er3+ by the cross relaxation energy transfer between Er3+ and Ce3+.Meanwhile,incorporation of Ce3+ dramatically decreased the visible upconversion emission intensity of glass ceramic than that of glass,suggesting that Ce3+ might incorporate into the FAP nanocrystals.The properties of this transparent glass ceramic showed the potential application as an efficient 980 nm pumped infrared laser medium.     

Energy transfer in Tb~（3＋）,Yb~（3＋） codoped Lu_2O_3 near-infrared downconversion nanophosphors

Tb3+ and Yb3+ codoped Lu2O3 nanophosphors were synthesized by the reverse-strike co-precipitation method. The obtained Lu2O3:Tb3+,Yb3+ nanophosphors were characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectra. The XRD results showed that all the prepared nanophosphors could be readily indexed to pure cubic phase of Lu2O3 and indicated good crystallinity. The Tb3+→Yb3+ energy transfer mechanisms in the UV-blue region in Lu2O3 nanophosphors were investigated. The experimental results showed that the strong visible emission around 543 nm from Tb3+ (5D4→7F5) and near-infrared (NIR) emission around 973 nm from Yb3+ (2F5/2→2F7/2) of Lu2O3:Tb3+,Yb3+ nanophosphors were observed under ultraviolet light excitation, respectively. Tb3+ could be effectively excited up to its 4f75d1 state and relaxed down to the 5D4 level, from which the energy was transferred cooperatively to two neighboring Yb3+. The Yb3+ concentration dependent luminescent properties and lifetimes of both the visible and NIR emissions were also studied. The lifetime of the visible emission decreased with the increase of Yb3+ concentration, verifying the efficient energy transfer from the Tb3+ to the Yb3+. Cooperative energy transfer (CET) from Tb3+ to Yb3+ was discussed as a possible mechanism for the near-infrared emission. When doped concentrations were 1 mol.% Tb3+ and 2 mol.% Yb3+, the intensity of NIR emission was the strongest.     

Enhancement of 1.54 μm emission in Er：LiNbO_3 crystal by codoping with Zn~（2＋） ions

The enhanced intensity and lengthened lifetime of 1.54 μm emission were observed for Er:LiNbO3 crystal codoped with Zn2+ ions.The ZnO codoping led to the reduction of the green upconversion emission in Er:LiNbO3 crystals.The decay trace of the 4S3/2→4I15/2 was ob-viously nonexponential for Er:LiNbO3 codoped with 0 and 3 mol.% ZnO,but became exponential for one codoped with 6 mol.% ZnO.The OH-absorption spectra showed after codoping with Zn2+ ions,the OH-absorption peaking position shifted from ~3495 to 3484 cm-1,and the absorption cross section decreased.These spectroscopic characteristics suggested that the improvement of 1.54 μm emission was attributed to the reduction of Er3+ cluster sites.     

Upconversion luminescence of Y2O3：Er^3＋ ,Yb^3＋ nanoparticles prepared by a homogeneous precipitation method

Y2O3： Er^3＋, Yb^3＋ nanoparticles were synthesized by a homogeneous precipitation method without and with different concentrations of EDTA 2Na. Upconversion luminescence spectra of the samples were studied under 980 nm laser excitation. The results of XRD showed that the obtained Y2O3：Er^3＋,Yb^3＋ nanoparticles were of a cubic structure. The average crystallite sizes calculated were in the range of 28-40 nm. Green and red upconversion emission were observed, and attributed to ^2H11/2,^4S3/2→^4I15/2 and ^4F9/2→^4I15/2 transitions of the ion, respectively. The ratio of the intensity of green emission to that of red emission drastically changed with a change in the EDTA 2Na concentration. In the sample synthesized without EDTA, the relative intensity of the green emission was weaker than that of the red emission. The relative intensities of green emission increased with the increased amount of EDTA 2Na used. The possible upconversion luminescence mechanisms were discussed.     

Growth and Optical Spectra of Zn：Er：LiNbO3 Crystals Using Bridgman Method

The growth of LiNbO₃ single crystal with Er³⁺ and Zn²⁺ co-doped using Bridgman method and its characteristic absorption spectra and fluorescence spectra were reported. Large-size crystals initially containing Zn²⁺ (3%) and Er³⁺ (0.6%) with good optical quality were obtained using optimized conditions such as a growth rate of 0.8 1.5 mm·h⁻¹ and a temperature gradient of about 30 35 °C · cm⁻¹ across the solid-liquid interface and the sealed platinum crucible. X-ray diffraction and differential thermal analysis (DTA) were used to characterize the crystals. The results indicate that the concentration of Er³⁺ ions in crystals, their absorption intensity, and their fluorescence intensity decrease from the bottom to the top in the crystals. However, for the upper part of the crystal, the up-conversion fluorescence intensity is higher than that of the lower part excited by an 800 or 970 nm pump. The effects of the crystal lattice, their structural defect and their effective segregation of Er³⁺ ions were discussed with respect to the variations of the up-conversion fluorescence intensity.     

Tm^3＋-doped tellurite glass with Yb^3＋ energy sensitized for broadband amplifier at 1400-1700 nm bands

A kind of novel experiment was disclosed as it possessed two bands of fluorescence emission at 1.4 and 1.6 μm, which were perfectly complimentary to the current C band of optic communication. The fluorescence was based on energy transfer and up-conversion processes between Tm^3＋ and Yb^3＋ under direct pumping of 975 nm LD. The spectra and lifetimes of Tm^3＋ fluorescence in the tellurite glass were described. The corresponding fluorescence characteristics and energy migration process were analyzed by the method of lifetime and intensity comparison. The mechanism of the up-conversion based IR fluorescence was presented upon analyzing the multi-photon pumping process. The potential advantages of Tm^3＋/Yb^3＋ co-doped tellurite glass as amplifier material were concluded.     

Preparation and Characterization Upconversion Luminescence Material of Yttrium Aluminate Doped with Rare Earth

Low phonon energy yttrium aluminate was adopted as matrix and the upconversion materials yttrium aluminate co-doped with Yb³⁺ and Er³⁺ was synthesized by solid-state reaction method. The X-ray diffraction spectra and the upconversion emission spectra of various samples were measured and the effect of Er³⁺ concentration, sensitization, fluxing agent and calcining temperature on the luminescence properties was studied. Research results showed that the sample could emit green light at 543 and 570 nm when excited 980 nm laser; the optimum concentration of Er³⁺ should be 1.0%; sensitization of Yb³⁺ could enhance luminescent effects of Er³⁺ obviously; the optimum content of F₃BO₃ fluxing agent should be 8% and the optimum calcining temperature should be 1500 °C.     

Effects of Bi3+ on down-/up-conversion luminescence,temperature sensing and optical transition properties of Bi3+/Er3+ co-doped YNbO4 phosphors

A series of YNbO₄:Bi³⁺ and YNbO₄:Bi³⁺/Er³⁺ phosphors were prepared by a conventional high temperature solid–state reaction method. The results of XRD and Rietveld refinement confirm that monoclinic phase YNbO₄ samples are achieved. The down-/up-conversion luminescence of Er³⁺ ions was investigated under the excitation of ultraviolet light (327 nm) and near infrared light (980 nm). Under 327 nm excitation, broad visible emission band from Bi³⁺ ions and characteristic green emission peaks from Er³⁺ ions are simultaneously observed, while only strong green emissions from Er³⁺ ions are detected upon excitation of 980 nm. Remarkable emission enhancement is observed in down-/up-conversion luminescence processes by introducing Bi³⁺ ions into Er³⁺-doped YNbO₄ phosphors. Pumped current versus up-conversion emission intensity study shows that two-photon processes are responsible for both the green and the red up-conversion emissions of Er³⁺ ion. Through the study of the temperature sensing property of Er³⁺ ion, it is affirmed that the temperature sensitivity is sensitive to the doping concentration of Bi³⁺ ions. By comparing the experimental values of the radiative transition rate ratio of the two green emission levels of Er³⁺ ions and the theoretical values calculated by Judd-Ofelt (J-O) theory, it is concluded that the temperature sensing property of Er³⁺ ions is greatly affected by the energy level splitting.     

Luminescence investigation of Eu~（3＋）-Bi~（3＋） co-doped CaMoO_4 phosphor

A series of Eu³⁺-Bi³⁺ co-doped CaMoO₄ red phosphors were synthesized via the solid-sate reaction method. The crystal structures of the obtained samples were identified by X-ray powder diffraction (XRD). The photoluminescence property was investigated, and the results showed that the intensity of excitation spectra and emission spectra could be changed with different doping ratios of Bi³⁺/Eu³⁺. The proposed explanation of these changes was from the energy transfer between Bi³⁺ and Eu³⁺ and the unbalanced charge from the substitution of Eu³⁺ and Bi³⁺ for Ca²⁺ in CaMoO₄. The obtained samples are a promising red light emitting phosphor for the needs of different excitation sources with near-UV and blue GaN-based chips.     

Three-photon-excited fluorescence of Tb-doped CaO-Al2O3-SiO2 glass by femtosecond laser irradiation

A near infrared to visible blue, green, and red upconversion luminescence in a Tb^3＋-doped CaO-Al2O3-SiO2 glass was studied, which was excited using 800 nm femtosecond laser irradiation. The upconversion luminescence was attributed to ^5D3→^7F5, ^5D3→^7F4, ^5D3→^7F3, ^5D4→^7F6, ^5D4→^7F5, ^5D4→^7F4, and ^5D4→^7F3 transitions of Tb^3＋. The relationship between upconversion luminescence intensity and the pump power indicated that a three-photon simultaneous absorption process was dominant in this upconversion luminescence. The intense red, green, and blue upconversion luminescence of Tb^3＋-doped CaO-Al2O3-SiO2 glass may be potentially useful in developing three-dimensional display applications.     

Extracting structural information from low symmetry crystal field parameterscase study： Er3＋ and Nd3＋ ions in YAIO3

The experimental monoclinic CF parameter (CFP) sets obtained by Duan et al. (Phys. Rev. B 75 (2007) 195130) for Er³⁺ and Nd³⁺ ions in YAlO₃ were reanalyzed. These CFPs fitted using R-approach, i.e. with the monoclinic second-rank CFP set to zero, and additionally with one six-rank CFP fixed to zero, turned out to be non-standard. In order to understand better the low symmetry aspects involved in the fitted CFPs and extract useful structural information inherent in monoclinic CFPs, an approach comprising four methods was utilized. First, superposition model (SPM) was applied to calculate CFPs in the crystallographic axis system. Second, the principal values for the SPM determined CFPs and the orientation of the principal axis system w.r.t. the crystallographic axis system were obtained using the procedure 3DD for diagonalization of the 2^nd-rank CFPs. Third, analysis of higher symmetry approximations, i.e. orthorhombic and tetragonal, was carried out using the pseudosymmetry axes method. Fourth, the closeness factors and norm ratios were employed for quantitative comparisons of various CFP sets. Partial results for Er³⁺ ions in YAlO₃ were presented here, whereas detailed results would be given in a follow-up paper.