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.     

Polyol-mediated synthesis of water-soluble LaF3:Yb,Er upconversion fluorescent nanocrystals

Well-crystallized LaF₃:Yb,Er nanoparticles were prepared by the polyol method and three kinds of polyols (glycol, diethylene glycol and glycerol) were chosen as the reaction medium respectively. All of the obtained LaF₃:Yb,Er nanoparticles have roughly spherical shapes, and the average sizes of these nanoparticles ranged from 5 to 7 nm. These nanoparticles could be well dispersed in water or ethanol to form colloidal solutions. When these nanoparticles were excited by the 980 nm laser, several upconversion emissions were observed.     

Enhancement of upconversion luminescence of Er and Yb co-doped Y2O3 nanoparticle by Ag half-shell

Upconversion photoluminescence (PL) properties of single Y₂O₃ nanoparticles doped with Yb and Er (Y₂O₃:Yb,Er) with a Ag over-layer is studied. We traced the PL and light scattering images of individual nanoparticles by changing the thickness of a Ag over-layer. When the Ag thickness is relatively small and only the upper part of a nanoparticle is covered by Ag (Ag half-shell), the PL is strongly enhanced. On the other hand, when the Ag thickness is increased and a continuous Ag over layer is formed, the enhancement factor decreases. From the correlation between the enhancement factors of the upconversion PL and scattering intensities as well as the change of the PL lifetime, the mechanism of the PL enhancement is 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.     

Two-phase solvothermal synthesis of rare-earth doped NaYF4 upconversion fluorescent nanocrystals

The synthesis, characterization, and fluorescent spectra of rare-earth doped NaYF₄ upconversion nanocrystals are introduced in this paper. The nanocrystals were synthesized in the water-ethanol-oleic acid system via a two-phase solvothermal approach, by using rare-earth stearate as the precursor. The as-prepared nanocrystals were of hexagonal phase, strong UC fluorescent intensity, with an average size of about 25 nm, which have been characterized by TEM, SAED, powder XRD, and luminescence spectroscopy. The possible mechanism of this synthesis that the nucleation and growth of nanocrystals occurred at the solid-liquid interface was also discussed. The nanocrystals are hydrophilic, and expected to fulfil the demand for biological applications via further modification.     

An experimental design approach for hydrothermal synthesis of NaYF4: Yb3+, Tm3+ upconversion microcrystal: UV emission optimization

Ultraviolet (UV) emissions of hydrothermally synthesized NaYF₄: Yb³⁺, Tm³⁺ upconversion crystals were optimized using the response surface methodology experimental design. In these experimental designs, 9 runs, two factors namely (1) Tm³⁺ ion concentration, and (2) pH value were investigated using 3 different ligands. Introducing UV upconversion emissions as responses, their intensity were separately maximized. Analytical methods such as XRD, SEM, and FTIR could be used to study crystal structure, morphology, and fluorescent spectroscopy in order to obtain luminescence properties. From the photo-luminescence spectra, emissions centered at 347, 364, 452, 478, 648 and 803 nm were observed. Some results show that increasing each DOE factor up to an optimum value resulted in an increase in emission intensity, followed by reduction. To optimize UV emission, as a final result to the UV emission optimization, each design had a suggestion.     

Controlled synthesis of carbon-based alumina nanophosphors with tunable blue-green luminescence

Carbon-based alumina nanophosphors were prepared by a facile liquid process. The nanophosphors showed high photoluminescence properties, and tunable color emission from blue to green. The luminescent intensity and color were controlled by simply manipulating of polyethylene glycol and urea amounts, respectively. Oxygen deficiency, surface defects, and carboxylic impurities are considered to be possible emission mechanisms.     

Color tunability of upconversion emission in YBO3: Yb, Er inverse opal

Upconversion (C) light-emitting photonic band gap materials (YBO₃: Yb, Er) with inverse opal structure were prepared by a self-assembly technique in combination with a sol-gel method. The effect of the photonic stop-band on the upconversion luminescence of Er³⁺ ions has been investigated in the YBO₃: Yb, Er inverse opals. Significant suppression of the green or red UC emission was detected if the photonic band-gap overlaps with the Er³⁺ ions emission band. We successfully achieved the color tuning of the UC optical properties of the inverse opal by controlling the structure of the photonic crystal.     

Controllable synthesis of tetragonal LiScF4:Yb3+, Er3+ nanocrystals and its upconversion photoluminescence properties: Lithium scandium fluoride nanocrystals

Tetragonal rare-earth ions codoped LiScF₄ nanocrystals have been synthesized by a modified solvothermal method. The results revealed that the phase and morphology can be tailored through varying the synthesis conditions, such as reaction temperature and time. Meanwhile, the UC fluorescence emission spectra were measured. It turned out that the UC emission intensity can be significantly influenced by reaction temperature and time. Different from the NaYF₄:20%Yb³⁺,2%Er³⁺ nanocrystals that usually emit green emission, yellow color emission can be observed in the LiScF₄:20%Yb³⁺,2%Er³⁺ samples under 980 nm excitation, which illustrates that the obtained new phase LiScF₄ is suitable as a promising host for efficient UC fluorescence generation and tunable UC emission spectra. Moreover, the UC mechanism was investigated in detail.     

Luminescence properties of Yb:Er:KY3F10 nanophosphor and thermal treatment effects

In this work, we present the spectroscopic properties of KY₃F₁₀ nanocrystals activated with erbium and codoped with ytterbium ions. The most important processes that lead to the erbium upconversion of green and red emissions of Er³⁺ were identified. A time-resolved luminescence spectroscopy technique was employed to measure the luminescence decays of ⁴S_3/2 and ⁴F_9/2 excited levels of Er³⁺ and to determine the upconversion processes and the luminescence efficiencies of erbium in the visible. Analysis of the luminescence kinetics in Yb:Er:KY₃F₁₀ shows a rapid upconversion (Up₁) for the green emission with a time constant of 0.31 μs after pulsed laser excitation at 972 nm for as synthesized nanocrystals, which is faster than the time constant measured for the bulk crystal (23 μs). In addition, it is observed a second upconversion process (non-resonant) (Up₂) responsible for the red emission (Er³⁺), which competes with Up₁ process. However, the luminescence efficiency of the green emission (⁴S_3/2) is observed to be very low (1.6%) for the as synthesized nanocrystal (25 °C). Nevertheless, it increases with the nanopowder heat treatment reaching an efficiency of 99% (T = 550 °C) relative to the bulk crystal. Similar luminescence behavior was observed for the ⁴F_9/2 level (Er³⁺) that emits red emission. X-ray diffraction analysis of nanopowder by Rietveld method reveled that the mean crystallite size remains unchanged (8.3–12.3 nm) after thermal treatments with T ∼ 400 °C, while the ⁴S_3/2 luminescence efficiency strongly increases to 20%. The luminescence dynamics indicates that Er³⁺ ions distribution plays a determinant role in the luminescence efficiency of green and red emissions of Er³⁺ besides also the strong influence on the upconversions processes. The observed luminescence effect is caused by the non-uniform Er³⁺ (and Yb³⁺) ions distribution due to the nanocrystal grown, which introduces a concentration gradient that increases towards the nanoparticle surface. This concentration effect produces strong (Er × Er) cross-relaxations depleting the excited states populations of ⁴S_3/2 and ⁴F_9/2 levels and their luminescence efficiencies in KY₃F₁₀ nanocrystals. The concentration gradient is very accentuated in the as synthesized nanocrystal and gradually decreases with the thermal treatments where the dopant ions can migrate through the lattice towards the nanocrystal’s interior to get a more uniform and random distribution, which is reached after heat treatment to T = 550 °C.     

White light upconversion of nanocrystalline Er/Tm/Yb doped tetragonal Gd4O3F6

Er³⁺, Tm³⁺ and Yb³⁺ codoped gadolinium oxyfluoride nanoparticles were prepared in aqueous solution by a simple coprecipitation method, under alkaline conditions. After a suitable heat treatment at 500 °C, the nanocrystalline powders were found to be single phase tetragonal Gd₄O₃F₆ after a structural characterization using X-ray powder diffraction. Transmission electron microscopy images showed that the average size of the nanoparticles was approximately 50 nm. Following appropriate lanthanide ion doping, the nanocrystals show bright white light upconversion upon excitation at 980 nm using a diode laser as the excitation source.     

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.     

Strong upconversion luminescence in LiYMo2O8:Er,Yb towards efficiency enhancement of dye-sensitized solar cells

Strong green upconversion (UC) emissions induced by a 940 nm laser have been observed in a series of Er³⁺, Yb³⁺ co-doped LiYMo₂O₈ samples. The diffuse reflectance absorption spectra show that the co-doped samples can absorb the photons in the range of 900–1050 nm efficiently, demonstrating the excellent sensitization effect of Yb³⁺ ions. Based on power switched UC luminescence, UC mechanisms are discussed, and the emission spectra excited by 490 nm are also measured to give additional evidence. The results reveal that application of these phosphors may improve the conversion efficiency of DSSCs.     

Frequency upconversion of Tm and Yb codoped YLiF4 synthesized by hydrothermal method

In this paper, YLiF₄ codoped with Tm³⁺ and Yb³⁺ ions was synthesized by hydrothermal method. Yb³⁺ concentration is fixed at 1.5%, and Tm³⁺ concentration is changed from 0.1 to 0.4%. Intense upconversion luminescence is observed when the samples are excited by 980 nm. The dependence of upconversion luminescence on Tm³⁺ concentrations is presented. The results show that upconversion luminescence increases with the Tm⁺ concentration and gets its peak at 0.3 mol%. Under the excitation of 980 nm, the blue emission of 479 nm and the red emission of 647 nm are both duo to two photons process, and the UV emission of 361 nm is attributed to the three photons process. We also analyse the upconversion mechanism and process.     

Microwave hydrothermal synthesis and upconversion properties of NaYF4:Yb, Tm with microtube morphology

Efficient upconversion Yb³⁺ and Tm³⁺ codoped β-NaYF₄ is firstly synthesized via a novel and rapid microwave hydrothermal process. The as-prepared sample is characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The sample shows a microtube morphology, which may be formed by the curliness of flakes. It is found that NaYF₄:Yb³⁺, Tm³⁺ microtubes can be synthesized using microwave hydrothermal method in a much shorter reaction time compared with conventional hydrothermal method, and the upconversion fluorescent intensity is also greatly enhanced under 976 nm laser excitation. The energy transfer upconversion mechanisms and the possible reason for the enhancement of the fluorescent intensity are also proposed.     

The influence of Yb doping on the upconversion luminescence of Pr in aluminum oxide based powders prepared by combustion synthesis

The effect of ytterbium (Yb³⁺) doping on the upconversion (UC) emission of praseodymium (Pr³⁺) doped in aluminum oxide based powders prepared by combustion synthesis is reported for near-infrared excitation (λ = 980 nm). Our experimental results show that the crystalline structure and the UC emission changes with the Yb³⁺ concentration. The sample containing only Pr³⁺ (1.0 wt.%) did not show any UC signal and the UC emission profiles of the samples containing Pr³⁺ (1.0 wt.%) and Yb³⁺ (0.5, 2.0 wt.%) are quite different. The sample containing 0.5 wt.% of Yb³⁺ has five emission lines in the visible range associated to Pr³⁺ 4f–4f transitions, ³P₀ → ³H₄ (497 nm), ³P₀ → ³H₅ (525 and 550 nm), ³P₀ → ³H₆ (620 nm) and ³P₀ → ³F₂ (650 nm). We believe that the UC process has its origin in energy transfer from Yb³⁺ ions to Pr³⁺ ions in Pr_0.83Al_11.83O₁₉ phase. The sample containing 2.0 wt.% of Yb³⁺ has only one emission line in the visible range peaked at 507 nm which we believe has its origin in cooperative UC emission due to excited Yb³⁺ pairs in YbAlO₃ phase. The samples containing Yb³⁺ also present UC emission lines in the near-infrared which are assigned to intrinsic lattice defects.     

Controllable synthesis of NaYF(4) : Yb,Er upconversion nanophosphors and their application to in vivo imaging of Caenorhabditis elegans

β-NaYF(4) : Yb,Er upconversion nanoparticles (UCNPs) can emit bright green fluorescence under near-infrared (NIR) light excitation which is safe to the body and can penetrate deeply into tissues. The application of UCNPs in biolabeling and imaging has received great attention recently. In this work, β-NaYF(4) : Yb,Er UCNPs with an average size of 35 nm, uniformly spherical shape, and surface modified with amino groups were synthesized by a one-step green solvothermal approach through the use of room-temperature ionic liquids as the reactant, co-solvent and template. The as-prepared UCNPs were introduced into Caenorhabditis elegans (C. elegans) to achieve successful in vivo imaging. We found that longer incubation time, higher UCNP concentration and smaller UCNP size can make the in vivo fluorescence of C. elegans much brighter and more continuous along their body. The worms have no apparent selectivity on ingestion of the UCNPs capped with different capping ligands while having similar size and shape. The next generation of worms did not show fluorescence under excitation. In addition, low toxicity of the nanoparticles was demonstrated by investigating the survival rates of the worms in the presence of the UCNPs. Our work demonstrates the potential application of the UCNPs in studying the biological behavior of organisms, and lays the foundation for further development of the UCNPs in the detection and diagnosis of diseases.     

Er3+单掺与Er3+/Yb3+共掺Y2SiO5的上转换发光

报道了一种新的上转换发光材料X2型Y2SiO5:Er, Yb并研究了Yb3 浓度和泵浦功率对样品的上转换发光特性的影响:(1)随着Yb3 浓度的增加,绿、红光发射均呈先增强后减弱的变化,但相对于绿光发射,红光发射受Yb3 浓度的影响更剧烈,并且当12%(摩尔分数)Yb3 时,可以得到很纯的红光发射;(2)上转换发光强度与泵浦功率的关系表明,双光子吸收贡献样品的上转换发射.此外,讨论了可能的上转换机制.认为随着Yb3 浓度增加,Er3 的激发态吸收、Yb3 到Er3 的能量传递和Er3 的交叉弛豫对上转换发光的作用依次逐渐加强.     

Spectroscopy and frequency upconversion of Er ions in fluorotellurite glasses

In this work we report the optical properties and upconversion luminescence of Er³⁺ ions in TeO₂–WO₃–PbO–BaF₂ and TeO₂–TiO₂–Nb₂O₅–BaF₂ fluorotellurite glasses and their comparison with those of TeO₂–TiO₂–Nb₂O₅ glass. The optical properties of Er³⁺ ions have been established in terms of absorption and emission spectra and lifetime measurements. The 1.5 μm emission cross-section has been determined from the line shape of the emission spectrum and the calculated emission probability for the ⁴I_13/2 level. The highest emission cross section (6.9 × 10⁻²¹ cm²) corresponds to the TeO₂–TiO₂–Nb₂O₅–BaF₂ glass with a figure of merit for the bandwidth of 524.4 cm² nm. Upconversion emissions at 530, 548 nm, and 660 nm have been obtained under infrared excitation at 800 nm in the ⁴I_9/2 level and compared with those obtained under one photon excitation. The green emission corresponding to the ⁴S_3/2 → ⁴I_15/2 transition is dominant in all glasses. The excitation wavelength dependence of the upconverted luminescence together with its time evolution after infrared pulsed excitation suggest that energy transfer upconversion processes are responsible for the green upconversion luminescence.     

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.