Up-conversion luminescence properties of Y2O2S:Yb3+,Er3+ nanophosphors

Up-converting yttrium oxysulfide nanomaterials doped with ytterbium and erbium (Y₂O₂S:Yb³⁺,Er³⁺) were prepared with the flux method. The precursor oxide materials were prepared using the combustion synthesis. The morphology of the oxysulfides was characterized with transmission electron microscopy (TEM). The particle size distribution was 10–110 nm, depending on the heating temperature. According to the X-ray powder diffraction (XPD), the crystal structure was found hexagonal and the particle sizes estimated with the Scherrer equation agreeded with the TEM images. Upon the 970 nm infrared (IR) laser excitation, the materials yield moderate green ((²H_11/2, ⁴S_3/2) → ⁴I_15/2 transition) and strong red (⁴F_9/2 → ⁴I_15/2) luminescence. The green luminescence was enhanced with respect to the red one by an increase in both the crystallite size and erbium concentration due to the cross-relaxation (CR) processes. The most intense up-conversion luminescence was achieved with x_Yb and x_Er equal to 0.10 and 0.005, respectively. Above these concentrations, concentration quenching occurred.     

Emissions properties of Ho: I7 → I8 transition sensitized by Er and Yb in fluorophosphate glasses

Emission properties of Ho³⁺ at 2.0 μm and the energy transfer mechanism between Yb³⁺, Er³⁺ and Ho³⁺ ions in fluorophosphate glasses are investigated. The measured emission spectra show that the ⁵I₇ → ⁵I₈ transition of Ho³⁺ upon 980 nm laser diode excitation is strong. Judd–Ofelt intensity parameters (Ω_λ, λ = 2, 4, 6), spontaneous transition probability (A_rad), radiative lifetime (τ_r), absorption cross section (σ_a), stimulated emission cross section (σ_e) and FWHM ×  for the transition of Ho³⁺: ⁵I₇ → ⁵I₈ are calculated and discussed. The obtained results show that the present Yb³⁺/Er³⁺/Ho³⁺ triply-doped fluorophosphate glass can be identified to be a promising material at 2.0 μm emission.     

Excited state absorption cross sections of I13/2 of Er in ZBLAN

Optical transition intensity parameters of Er³⁺ in ZBLAN were carefully calculated, and the obtained results were compared with those reported by others. The emission cross sections of ⁴S_3/2 → ⁴I_13/2 and ⁴I_11/2 → ⁴I_13/2 transitions were confirmed according to the Fuchtbauer–Ladenburg (FL) formula. The excited state absorption cross sections for ⁴I_13/2 → ⁴S_3/2 and ⁴I_13/2 → ⁴I_11/2 transitions were derived by using the reciprocity relationship in the framework of McCumber theory. The laser gain properties of ⁴S_3/2 → ⁴I_13/2 and ⁴I_11/2 → ⁴I_13/2 transitions were discussed.     

Sol-gel synthesis and green upconversion luminescence in BaGd2(MoO4)4:Yb,Er phosphors

Yb³⁺/Er³⁺ codoped BaGd₂(MoO₄)₄ phosphor powders were prepared by the Sol-gel method and the upconversion luminescence properties were investigated in detail. Under 980 nm semiconductor laser excitation, BaGd₂(MoO₄)₄:Yb³⁺,Er³⁺ phosphor exhibits green upconversion luminescence with peaks at 530 and 550 nm, which are due to the transitions of Er³⁺ (²H_11/2) → Er³⁺ (⁴I_15/2) and Er³⁺ (⁴S_3/2) → Er³⁺ (⁴I_15/2), respectively. Both of the two green emission lines are produced by populating Er³⁺ ions to the excited state through a two-photon process. By monitoring the intensities of the green upconversion luminescence, the optimum conditions for the Sol-gel synthesis were determined when the molar ratio of citric acid to total chelate metal cations was 2:1 and the sintering temperature was at 1073 K. The concentration quenching effect for Er³⁺ was found at the optimum doping concentration of 6 mol%, and the critical distance for the neighboring Er³⁺ was determined to be about 21.5 Å.     

Synthesis and upconversion luminescence properties of Yb/Er codoped BaGd2(MoO4)4 powder

Synthesis and upconversion luminescence properties of the new BaGd₂(MoO₄)₄:Yb³⁺,Er³⁺ phosphor were reported in this paper. The phosphor powder was obtained by the traditional high temperature solid-state method, and its phase structure was characterized by the XRD pattern. Based on the upconversion luminescence properties studies, it is found that, under 980 nm semiconductor laser excitation, BaGd₂(MoO₄)₄:Yb³⁺,Er³⁺ phosphor exhibits intense green upconversion luminescence, which is ascribed to ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transition of Er³⁺. While the observed much weaker red emission is due to the non-radiative relaxation process of ⁴S_3/2 → ⁴F_9/2 and ⁴F_9/2 → ⁴I_15/2 transition originating from the same Er³⁺. The concentration quenching effects for both Yb³⁺ and Er³⁺ were found, and the optimum doping concentrations of 0.5 mol% Yb³⁺ and 0.08 mol% Er³⁺ in the new BaGd₂(MoO₄)₄ Gd³⁺ host were established.     

Structure and up-conversion luminescence in sol–gel derived Er–Yb co-doped SiO2:PbF2 nano-glass–ceramics

Transparent oxyfluoride nano-glass–ceramics 90(SiO₂)10(PbF₂) co-doped with 0.3 Yb³⁺ and 0.1 Er³⁺ (mol%) have been prepared by thermal treatment of precursor sol–gel glasses. X-ray diffraction and high resolution transmission electron microscopy analysis pointed out a precipitation of cubic β-PbF₂ nanocrystals of certain diameter in nano-glass–ceramics varying from 10 to 20 nm depending on heat treatment conditions. The incorporation of Yb³⁺ and Er³⁺ dopants in these nanocrystals has been confirmed by signatures of luminescence spectroscopy. Up-conversion luminescence pumped at 980 nm has been detected. Colour tuneability of up-conversion luminescence varying pump power has been analyzed in terms of standard chromaticity diagram. This tuneability opens applications for up-conversion phosphors and three-dimensional optical recording.     

Structural evolution and its influence on luminescence of SiO2–SrF2–ErF3 glass ceramics prepared by sol–gel method

Er³⁺ doped SrF₂–SiO₂ transparent glass ceramics were prepared by sol–gel method and heat treatment. The decomposition of Sr²⁺–CF₃COO⁻ and the formation of SrF₂ nano-crystals were found to proceed synchronously in the xerogel. After crystallization of the xerogel, SrF₂ nano-crystals with 8–10 nm in size distributed homogenously among the glassy matrix, and the microstructure of the glass ceramic was stable under and at the temperature of 800 °C probably due to interfacial interaction between nano-crystals and glassy matrix. When heat-treated at 800 °C, the chemically bonded water in the sample was eliminated, resulting in the appearance of the visible luminescence bands of ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions.     

Spectral analysis of RE (RE = Sm, Dy, and Tm): P2O5–Al2O3–Na2O glasses

Phosphate glasses in the compositions of 70P₂O₅–15Al₂O₃–14Na₂O–1RE³⁺ (RE = Sm, Dy, and Tm) (mol%) were prepared by melt-quenching technique and characterized optically. The differential thermal analysis (DTA) profile of the host glass was carried out to confirm its thermal stability. For all the glasses absorption, photoluminescence and decay measurements have also been carried out. These glasses have shown strong emission and absorption bands in visible and near-infrared (NIR) region. From the measured absorption spectra, Judd–Ofelt (J–O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. For Sm³⁺ doped glass, four emission bands centered at 562 nm (⁴G_5/2 → ⁶H_5/2), 598 nm (⁴G_5/2 → ⁶H_7/2), 644 nm (⁴G_5/2 → ⁶H_9/2), and 704 nm (⁴G_5/2 → ⁶H_11/2) have been observed with 402 nm (⁶H_5/2 → ⁴F_7/2) excitation wavelength. Of them, 598 nm (⁴G_5/2 → ⁶H_7/2) has shown a bright orange emission. With regard to Dy³⁺ doped glass, a blue emission band centered at 486 nm (⁴F_9/2 → ⁶H_15/2) and a bright yellow emission at 575 nm (⁴F_9/2 → ⁶H_13/2) have been observed, apart from 662 nm (⁴F_9/2 → ⁶H_11/2) emission transition with an excitation at 388 nm (⁶H_15/2 → ⁴I_13/2,⁴F_7/2) wavelength. Emission bands of 650 nm (¹G₄ → ³F₄) and 785 nm (¹G₄ → ³H₅) transitions for the Tm³⁺ doped glass, with an excitation wavelength at 466 nm (³H₆ → ¹G₄), have also been observed. The stimulated emission cross-sections of all the emission bands of RE³⁺ glasses (RE = Sm, Dy, and Tm) have been computed based on their measured full-width at half maximum (FWHM, Δλ) and measured lifetimes (τ_m).     

Up-conversion luminescence of the NaYF4:Yb3+,Er3+ nanomaterials prepared with the solvothermal synthesis

Up-converting NaYF₄:Yb³⁺,Er³⁺ (x_Yb: 0.20, x_Er: 0.02) nanomaterials were prepared with a microwave assisted solvothermal synthesis to study how the synthesis parameters affect the structure and up-conversion luminescence of the materials and thus their usability as labels in biomedical applications. The purity of the materials was studied with Fourier transform infra-red (FT-IR) spectroscopy and the particle size and morphology with transmission electron microscopy (TEM). The crystal structure was characterized with X-ray powder diffraction (XPD) and the crystallite sizes were calculated with the Scherrer formula. Up-conversion luminescence and luminescence decays were studied with near infra-red (NIR) laser excitation at 970 nm.The presence of the oleic acid was observed in the FT-IR spectra. The TEM images showed small quasi-spherical nanoparticles as well as long nanorods. The XPD measurements revealed that both cubic and hexagonal forms of NaYF₄ were present in the materials. The crystallite sizes ranged from ca. 20 to over 150 nm for the cubic and hexagonal phases, respectively. The characteristic up-conversion luminescence of Er³⁺ in red (640–685 nm; ⁴F_9/2 → ⁴I_15/2) and green (515–560 nm; ²H_11/2, ⁴S_3/2 → ⁴I_15/2 transitions) wavelengths was observed. The most intense luminescence and the longest luminescence emission lifetime were obtained with the material annealed for 12 h at 177 °C with 1.8 MPa pressure due to the predominance of the well-crystallized hexagonal form of NaRF₄ (R: Y, Yb, Er).     

Preparation and upconversion property of TeO2:Er/Yb nanoparticles

Different crystal structure of TeO₂ nanoparticles were used as the host materials to prepare the Er³⁺/Yb³⁺ ions co-doped upconversion luminescent materials. The TeO₂ nanoparticles mainly kept the original morphology and phase after having been co-doped the Er³⁺/Yb³⁺ ions. All the as-prepared TeO₂:Er³⁺/Yb³⁺ nanoparticles showed the green emissions (525 nm, 545 nm) and red emission (667 nm) under 980 nm excitation. The green emissions at 525 nm, 545 nm and red emission at 667 nm were attributed to the ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of the Er³⁺ ions, respectively. For the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, three-photon process involved in the green (²H_11/2 → ⁴I_15/2) emission, while two-photon process involved in the green (⁴S_3/2→⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. For the β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, two-photon process involved in the green (²H_11/2 → ⁴I_15/2), green (⁴S_3/2 → ⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. It suggested that the crystal structure of TeO₂ nanoparticles had an effect on transition processes of the Er³⁺/Yb³⁺ ions. The emission intensities of the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles and β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles were much stronger than those of the (α + β)-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles.     

Luminescence properties of Ca0.65La0.35F2.35:Yb, Er with enhanced red emission via upconversion

Yb³⁺/Er³⁺ codoped Ca_0.65La_0.35F_2.35 materials with intense red emission via upconversion were prepared by a high temperature solid-state method. Based on the upconversion luminescence properties investigations, it was found that, under 980 nm excitation, Ca_0.65La_0.35F_2.35:20 mol.%Yb³⁺, xEr³⁺ showed intense red upconversion luminescence, which was ascribed to ⁴F_9/2 → ⁴I_15/2 transition of Er³⁺, although both green and red emissions could be detected. It was also found that the green and red emissions originated the two photon processes, and the ground-state absorption (GSA), excited-state absorption (ESA) and energy transfer (ET) processes between Er³⁺/Yb³⁺ ions and Er³⁺/Er³ ions were involved in the enhanced red emission mechanism.     

Influence of Ce on the luminescence properties of Er/Yb:YVO4 crystals

YVO₄ single crystals doped with Ce³⁺, Er³⁺ and Yb³⁺ ions were grown by the Czochralsski technology. The luminescence properties of Er³⁺/Yb³⁺:YVO₄ single crystals with different concentration of Ce³⁺ were studied, and the energy transfer mechanism between Er³⁺, Yb³⁺ and Ce³⁺ was discussed based on their energy level properties. The branching ratios of the ⁴I_11/2 → ⁴I_13/2 transition in different samples were calculated. The results indicate that codopants of Ce³⁺ greatly enhance the population rate of the ⁴I_13/2 level due to the fast resonant energy transfer between Er³⁺ and Ce³⁺, i.e., ⁴I_11/2(Er³⁺) + ²F_7/2(Ce³⁺) → ⁴I_13/2(Er³⁺) + ²F_5/2(Ce³⁺).     

Up-conversion processes in NaLaF4:Er

Structural and spectroscopic investigation of NaLaF₄:Er³⁺ material at different doping concentrations is presented. X-ray diffraction patterns, up-conversion luminescence spectra and decay curves for ²H_9/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 optical transitions in the material are shown and possible excitation routes are discussed. Raman spectrum for the undoped material is presented and the effective phonon energy of the material is estimated. Based on the obtained results application of rare-earth doped NaLaF₄ in the field of up-conversion phosphors is evaluated.     

Temperature dependence of luminescence behavior in Er/Yb co-doped transparent phosphate glass ceramics

The effect of temperature on the luminescence intensity of up-conversion and near infrared in Er³⁺/Yb³⁺ co-doped phosphate glass ceramics has been investigated. Efficient green and red up-conversion luminescence and strong infrared fluorescence at 1.54 μm wavelength are observed under excitation of 975 nm. The fluorescence intensity is changing at different temperature and the results are explained with the level transitions in Er³⁺/Yb³⁺ co-doped system. Meanwhile, the lifetime of Er³⁺:⁴I_13/2 level corresponding to different operating temperature and pump power is also discussed, and the experimental results are fitted using multiphonon relaxation theory.     

Infrared to visible upconversion luminescence in Er/Yb co-doped CeO2 inverse opal

Infrared to visible upconversion luminescence has been investigated in Er³⁺/Yb³⁺ co-doped CeO₂ inverse opal. Under the excitation of 980 nm diode lasers, visible emissions centered at 525, 547, 561, 660 and 680 nm are observed, which are assigned to the Er³⁺ transitions of ²H_11/2 → ⁴I_15/2 (525 nm), ⁴S_3/2 → ⁴I_15/2 (547, 561 nm), ⁴F_9/2 → ⁴I_15/2 (660 and 680 nm), respectively. The effect of photonic band gap on the upconversion luminescence intensity was also obtained. Additionally, the upconversion luminescence mechanism was studied. The dependence of Er³⁺ upconversion emission intensity on pump power reveals that it is a two-photon excitation process.     

Luminescence properties of Sn2P2Se6 crystals

A large family of Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) semiconductor-ferroelectric crystals were obtained by the Bridgman technique. The photoluminescence properties of the Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) family crystals strongly depend on their chemical composition, excitation energy and temperature. The influence of the Pb → Sn and S → Se isovalent substitutions on the luminescence properties of a crystal with the Sn₂P₂Se₆ basic composition was investigated. A broad emission band observed in the Sn₂P₂Se₆ crystal with a maximum roughly at 600 nm (at T = 8.6 K) was assigned to a band-to-band electron-hole recombination, whereas broad emission bands, peaked near 785 nm (at T = 8.6 K) and 1025 nm (at T = 44 K) were assigned to an electron-hole recombination from defect levels localised within the bandgap. Possible types of recombination defect centres and specific mechanisms of luminescence in the Sn₂P₂Se₆ semiconductor-ferroelectric crystals were considered and discussed on the basis of the obtained results and the referenced data.     

Effect of Mg and Ti doping on the luminescence of Y2O2S:Eu

The Y₂O₂S:Eu³⁺,Mg²⁺,Ti^IV (x_Eu = 0.028, x_Mg = 0.086, x_Ti = 0.03) materials were prepared with the flux fusion method. According to X-ray powder diffraction, the materials had the hexagonal crystal structure. The emission of Y₂O₂S:Eu³⁺,Mg²⁺,Ti^IV was centered at 627 nm (λ_exc : 250 nm) due to the ⁵D₀ → ⁷F₂ transition of Eu³⁺. The excitation spectra (λ_em : 627 nm) showed broad bands at 240 and 320 nm due to the O²⁻ → Eu³⁺ and S²⁻ → Eu³⁺ charge transfer transitions, respectively. The latter band can also overlap with the Ti → Eu³⁺ energy transfer. In the excitation spectra with synchrotron radiation, in addition to the O²⁻ → Eu³⁺ and S²⁻ → Eu³⁺ charge transfer transitions, excitation over the band gap was observed at 4.8 eV (258 nm). The red persistent luminescence due to the ⁵D₀ → ⁷F₂ emission from Eu³⁺ residing in the regular Y³⁺ site of the host was ca. 10 min with 1 min fluorescent lamp irradiation. In addition, a very broad band was observed at 600 nm probably due to the Ti³⁺ emission.     

Er:YAl3(BO3)4 glassy thin films from polymeric precursor and sol-gel methods: Waveguides for integrated optics

This paper presents the characterization of single-mode waveguides for 980 and 1550 nm wavelengths. High quality planar waveguide structure was fabricated from Y_1 − xEr_xAl₃(BO₃)₄ multilayer thin films with x = 0.02, 0.05, 0.1, 0.3, and 0.5, prepared through the polymeric precursor and sol-gel methods using spin-coating. The propagation losses of the planar waveguides varying from 0.63 to 0.88 dB/cm were measured at 632.8 and 1550 nm. The photoluminescence spectra and radiative lifetimes of the Er^{3+ 4}I_13/2 energy level were measured in waveguiding geometry. For most samples the photoluminescence decay was single exponential with lifetimes in between 640 μs and 200 μs, depending on the erbium concentration and synthesis method. These results indicate that Er doped YAl₃(BO₃)₄ compounds are promising for low loss waveguides.     

Up-conversion luminescence of trivalent-rare-earth ion-doped LnTaO4 (Ln = Y, Gd, La)

The up-conversion luminescence properties of trivalent-rare-earth ion-doped orthotantalates are studied under 980 nm laser diode excitation. The results indicate that YTaO₄:Tm³⁺/Yb³⁺ emits blue and strong infrared emissions respectively corresponding to ¹G₄→³H₆ and ³H₄→³H₆ transitions of Tm³⁺ ions, while YTaO₄:Er³⁺/Yb³⁺ produces strong green and weak red emissions, resulting from ²H_11/2/⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions of Er³⁺ ions, respectively. In contrast to three excellent up-conversion phosphors, viz. NaYF₄:Er³⁺/Yb³⁺, Y₂O₂S:Er³⁺/Yb³⁺ and Y₂O₃:Er³⁺, YTaO₄:Er³⁺/Yb³⁺ shows not only strong green emission, but also larger intensity ratio of green to red emission. In addition, it is found that LaTaO₄: Er³⁺/Yb³⁺ shows the minimum quenching concentration of Yb³⁺ and weakest up-conversion emission intensity, and the main peak presents blue shift (8 nm/556 nm) as compared with YTaO₄:Er³⁺/Yb³⁺ and GdTaO₄:Er³⁺/Yb³⁺. The distinct luminescent characteristics of LaTaO₄: Er³⁺/Yb³⁺ can be attributed to the larger difference of radius between doped ion and La³⁺ ion.