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.     

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.     

Effect of Yb concentration on the upconversion of Er ion doped La2O3 nanocrystals under 980 nm excitation

The effect of Yb³⁺ concentration on the upconversion of La₂O₃:Yb³⁺, Er³⁺ nanocrystals was reported. Green (about at 530 and 549 nm) and red (around at 672 nm) upconversion emissions under 980 nm excitation were observed at room temperature. It was found that the ratio of green to red upconversion emission intensity is considered as a function of Yb³⁺ ion concentration. Of the samples doped with varying Er³⁺ or constant Er³⁺ ion concentration, it can be observed that the intensity ratio drastically decreases with an Yb³⁺ ion concentration increase and the Yb³⁺ ions concentration is around 3 mol% as the emission intensity ratio of green to red upconversion is close to 1.     

Up-conversion luminescence properties of Y2O2S:Yb,Er 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.     

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.     

Growth and spectral properties of Er:NaGd(WO4)2 crystal

A high optical quality Er³⁺-doped NaGd(WO₄)₂ single crystal with dimensions of ∅18 × 50 mm³ has been grown using the Czochralski method. The structure of the grown crystal was proved by X-ray powder diffraction. The accurate concentration of Er³⁺ ion in the crystal was measured. The absorption spectra, fluorescence spectra and fluorescence lifetime of the crystal were measured at room temperature. Green up-conversion luminescence has been observed when the crystal is excited at 965 nm.     

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.     

Up- and down-conversion luminescence in the oxyfluoride glass ceramics containing Ba2+1.5xYb1−xF7:Tb nanocrystals

Transparent oxyfluoride borosilicate glass ceramics containing Ba_2+1.5xYb_1−xF₇:Tb³⁺ nanocrystals were successfully prepared by a melt-quenching method with subsequent heat treatment. The precipitated crystalline phase in the glass matrix changed gradually from BaF₂ to Ba_2+1.5xYb_1−xF₇ with the increase of YbF₃ content, which was confirmed by the results of XRD, HRTEM and EDX measurements. The ultraviolet and visible up-conversion and near-infrared quantum cutting down-conversion emissions were observed and interpreted. These materials could be used to modify the solar spectrum and enhance the silicon solar cell efficiency by the up-conversion and down-conversion luminescence of Tb³⁺–Yb³⁺ couples in the oxyfluoride borosilicate glass ceramics.     

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.     

Optimized solvent-thermal preparation of NaYF4 :Yb3+, Er3+ up-conversion nanoparticles for application in solar cells

用溶剂热法合成Yb³⁺、Er³⁺共掺的NaYF₄ 纳米上转换材料, 研究了去离子水、乙醇两种反应溶剂对材料性能的影响. 用X射线衍射光谱、扫描电镜和荧光光谱等测试手段对材料性能进行了对比分析. 结果表明: 以乙醇为溶剂并加入一定比例的EDTA, 所制备的上转换材料能发射较强的、可被太阳电池吸收的可见光.     

Up-conversion emission in KGd(WO4)2 single crystals triply-doped with Er/Yb/Tm, Tb/Yb/Tm and Pr/Yb/Tm ions

Triply-doped single crystals KGd(WO₄)₂:Er³⁺/Yb³⁺/Tm³⁺, KGd(WO₄)₂:Tb³⁺/Yb³⁺/Tm³⁺ and KGd(WO₄)₂:Pr³⁺/Yb³⁺/Tm³⁺ were grown by the Top Seeded Solution Growth (TSSG) method, with an aim of getting efficient up-converted multicolored luminescence, which subsequently can be used for generation of white light. Such an aim determined the choice of the triply doped compounds: excitation of the Yb³⁺ ions in the infrared spectral region is followed by red, green and blue emission from other dopants. It was shown that all these systems exhibit multicolor up-conversion fluorescence under 980 nm laser irradiation. Detailed spectroscopic studies of their absorption and luminescence spectra were performed. From the analysis of the dependence of the intensity of fluorescence on the excitation power the conclusion was made about significant role played by the host’s conduction band and other possible defects of the KGd(WO₄)₂ crystal lattice in the up-conversion processes.     

Energy transfer in crystalline Er,Yb:Sc2O3

The use of Yb³⁺ as a sensitizer for Er³⁺ doped laser materials is a common technique because of the high Yb³⁺ absorption cross sections. Energy transfer processes from Yb³⁺ to Er³⁺ in Sc₂O₃ are studied by two different methods. Transfer parameters describing the interactions between Er³⁺ and Yb³⁺ ions are obtained on the one hand from the ratio of emitted photons around 1.55 μm by Er³⁺ ions and around 1 μm by Yb³⁺ ions at cw excitation of Yb³⁺, on the other hand by lifetime measurements of Yb³⁺ ions in the codoped samples. Laser experiments are performed to study the suitability of Er³⁺,Yb³⁺:Sc₂O₃ as a laser material. Comparisons with energy transfer in Er³⁺,Yb³⁺:glass are made.     

Design and achieving mechanism of upconversion white emission based on Yb/Tm/Er tri-doped KY3F10 nanocrystals

KY₃F₁₀:Yb³⁺/Tm³⁺/Er³⁺ upconversion nanocrystals are synthesized via a simple hydrothermal procedure. The nanocrystals emit the near equal energy white light with high brightness and favorable color balance when excited using a 980 nm continuous wave diode laser. The research of upconversion mechanism indicates that in addition to the energy transfer processes from Yb³⁺ to Tm³⁺ and Er³⁺, respectively, there exists a new process ¹G₄ (Tm³⁺) + ⁴I_11/2 (Er³⁺) → ³H₄ (Tm³⁺) + ⁴S_3/2 (Er³⁺).     

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.     

Effect of CdF2 addition on thermal stability and upconversion luminescence properties in Tm–Yb codoped oxyfluoride silicate glasses

Tm³⁺–Yb³⁺ codoped oxyfluoride silicate glasses suitable for upconversion laser has been fabricated. In this paper, effect of CdF₂ addition on thermal stability and upconversion luminescence properties in Tm³⁺–Yb³⁺ codoped oxyfluoride silicate glasses have been systematically investigated. The experimental results indicate that, with the substitution CdF₂ for PbF₂, the glass thermal stability increases and the UV cutoff edge moves to short-wave band slightly. With increasing CdF₂ content, the blue and red upconversion luminescence intensity increases slightly at first, and then increases rapidly. While the near infrared (NIR) upconversion emission intensity increases notably at first and then increases slightly. However, the blue and NIR luminescence intensity are much stronger than that of red, indicating these oxyfluoride silicate glasses are more preferable for blue and NIR emissions than red emission. The possible upconversion mechanisms for the blue, red and NIR fluorescence are also estimated and evaluated.     

VUV–UV spectroscopic properties of RE (RE = Ce, Eu and Tb)-doped KMLn(PO4)2 (M = Ca, Sr; Ln = Y, La, Lu)

The VUV excited luminescent properties of Ce³⁺, Eu³⁺ and Tb³⁺ in the matrices of KMLn(PO₄)₂ (M²⁺ = Ca, Sr; Ln³⁺ = Y, La, Lu) were investigated. The bands at about 155 nm in the VUV–UV excitation spectra are attributed to the host lattice absorption, which indicates that the optical band gap of KMLn(PO₄)₂ is about 8.0 eV. Ce³⁺-doped samples show typical Ce³⁺ emission in the range of 300–450 nm, and the energy transfer from host lattice to Ce³⁺ is efficient. For Eu³⁺-doped samples, the O²⁻–Eu³⁺ CTBs are observed to be at about 228 nm except KSrLu(PO₄)₂:Eu³⁺ (247 nm). As for Tb³⁺-doped samples, typical 4f → 5d absorption bands in the region of 175–250 nm were observed.     

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.     

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.     

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.     

Fabrication and optical properties of NUV-emitting SiO2–SrB4O7:Eu glass–ceramic thin films

SiO₂–SrB₄O₇:Eu²⁺ glass–ceramic thin films were fabricated for possible application in near ultraviolet (NUV) emitting devices. Nano-sized SrB₄O₇:Eu²⁺ powders were prepared by a Pechini-type sol–gel method and a subsequent ball-milling treatment. The powders showed NUV emissions centered at 367 nm, upon irradiation with UV of shorter wavelengths, due to an allowed 4f⁶5d¹ → 4f⁷ electronic transition of Eu²⁺ ions. The glass–ceramic thin films were prepared by dip-coating of tetraethylorthosilicate (TEOS) solutions dispersed with the nano-sized SrB₄O₇:Eu²⁺ powders and a subsequent heat-treatment. It was found that the glass–ceramic thin films had relatively high thermal stability up to 800 °C in terms of the Eu²⁺ emissions. SiO₂ layers surrounding SrB₄O₇:Eu²⁺ appeared to be effective for the surface passivation of the phosphor particles.