Water-soluble Yb, Tm codoped NaYF4 nanoparticles: Synthesis, characteristics and bioimaging

Water soluble NaYF₄ nanocrystals codoped with 20 mol% Yb³⁺, 0.5 mol% Tm³⁺ were prepared by a facile solvothermal approach using polyvinylpyrrolidone (PVP) as a surfactant. The upconversion NaYF₄ nanocrystals were pure cubic phase with an average size of ∼40 nm. They could be well redispersed in water to form a clearly transparent solution without obvious precipitation. With the excitation of a 980-nm diode laser, the nanocrystal solution presents bright violet and blue upconversion luminescence. These upconversion nanoparticles (UCNPs) were incubated with HeLa cells at 37 °C for 24 h, and bright blue upconversion luminescence were observed from the UCNPs endocytosed into the HeLa cells on a microscope equipped with a 980-nm fiber laser. These results indicated that the UCNPs had potential applications for biological imaging as luminescent probes.     

White light emission in Tm/Er/Yb tri-doped Y2O3 transparent ceramic

Tm³⁺/Er³⁺/Yb³⁺ triply doped Y₂O₃ transparent ceramics were fabricated by solid state reaction and characterized from the point of view of white light upconversion luminescence. All the samples exhibited high transparency not only in near-infrared band but also in visible region. Strong red (Er³⁺: ⁴F_9/2 → ⁴I_15/2), green (Er³⁺: ²H_11/2, ⁴S_3/2 → ⁴I_15/2) and blue (Tm³⁺: ¹G₄ → ³H₆) upconversion emissions have been observed under 980 nm excitation at room temperature. By varying the concentration of Er³⁺ ion, various colors of upconversion luminescence (pure blue, bluish green, pure green and yellowish green), including white light with CIE-X = 0.295 and CIE-Y = 0.312, can be easily achieved.     

Sensitized high-order ultraviolet upconversion emissions of Gd by Er in NaYF4 microcrystals

High-order ultraviolet (UV) upconversion (UC) emissions of Gd³⁺ and Er³⁺ ions were observed in NaYF₄:Yb³⁺/Gd³⁺/Er³⁺ microcrystals under 980 nm excitation. These UC emissions came from six- and five-photon UC processes at low pump power range, which were confirmed by the pumping power dependences of UC fluorescence intensities. In these high-order UC processes, energy transfer (ET) processes of Er³⁺ → Gd³⁺ played crucial roles in populating the excited states of Gd³⁺ ions. Experiments on concentration variation and dynamic analysis revealed the ET processes between Er³⁺ and Gd³⁺ in detail. Some of possible population routes for populating excited Gd³⁺ ions were proposed based on spectral and dynamic analysis.     

Upconversion luminescence in Er/Yb codoped Y2CaGe4O12

Calcium yttrium tetrametagermanates Y₂CaGe₄O₁₂ doped with Er³⁺ and Er³⁺/Yb³⁺ reveal upconversion emission in visible spectral range under near-infrared excitation, λ_ex = 980 nm. For the solid solution Er_xY_2−xCaGe₄O₁₂ concentration dependencies for the green and red lines of the visible emission around 526 nm (²H_11/2 → ⁴I_15/2), 545 nm (⁴S_3/2 → ⁴I_15/2) and 670 nm (⁴F_9/2 → ⁴I_15/2) show the optimal value for the sample x = 0.2. The power dependence of the visible luminescence measured at room temperature in the low-power limit indicates two-photon upconversion process. Direct intensification of the upconversion emission signals has been achieved by ytterbium sensitizing. The other upconversion excitation mechanism in Y₂CaGe₄O₁₂:Er³⁺ is discussed for an 808 nm incident laser irradiation. A scheme of excitation and emission routes involving ground/excited state absorption, energy transfer upconversion, nonradiative multiphonon relaxation processes in trivalent lanthanide ions in Y₂CaGe₄O₁₂:Er³⁺ and Y₂CaGe₄O₁₂:Er³⁺, Yb³⁺ has been proposed. Conditions for visible emission occurrence under quasi-resonance λ_ex = 1064 nm excitation depending on pump power values are considered. In the low-power regime only near-infrared emission caused by the transition ⁴I_13/2 → ⁴I_15/2 in erbium ions has been detected.     

Effect of Yb concentration on the structures and upconversion luminescence properties of Y2O3:Er ultrafine phosphors

Y₂O₃:Er³⁺ ultrafine phosphors with a varying Yb³⁺ ion concentration were prepared by a urea homogeneous precipitation method. The results of XRD show that all the samples are of a pure cubic structure and the average crystallite sizes can be calculated as 45, 34, and 28 nm for Y₂O₃:Er³⁺ ultrafine phosphors with Yb³⁺ ion concentrations of 0, 10%, and 20%, respectively. The lattice constant and cell volume of the ultrafine phosphors decrease with enhancing Yb³⁺ ion concentration. The upconversion luminescence spectra of all the samples were studied under 980 nm laser excitation. The strong green and red upconversion emission were observed, and attributed to the ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺, respectively. The intensity of red emission increases with increasing Yb³⁺ ion concentration. The effect of Yb³⁺ ion concentration on the structures and upconversion luminescence mechanism were discussed.     

Polarized spectral analysis of Er ions in Er:LiGd(MoO4)2 crystal

The Er³⁺:LiGd(MoO₄)₂ crystal with Ø21 × 33 mm³ was grown by the Czochralski technique, and the absorption spectra, the fluorescence spectra and the fluorescence decay curves were measured at room temperature. Some spectroscopic parameters, such as the parameters of oscillator strengths, the spontaneous transition probabilities, the fluorescence branching ratios, the radiative lifetimes and the emission cross-sections were estimated based on Judd-Ofelt theory and Füchtbauer-Ladenburg method. The infrared emission at 1450-1650 nm, due to ⁴I_13/2 → ⁴I_15/2 transition and the visible emission at 520-569 nm corresponding to ²H_11/2,⁴S_3/2 → ⁴I_15/2 transition were observed in Er³⁺:LiGd(MoO₄)₂ crystals under 979 nm excitation at room temperature. The emission cross-sections are 4.37 × 10⁻²⁰ cm² at 553 nm and 0.584 × 10⁻²⁰ cm² at 1561 nm for π-polarization, and the following measured lifetimes are 4.57 ms and 10.74 μs. The upconversion emissions were attributed to energy transfer between Er³⁺ ions and the excited state absorption.     

Efficient first-order resonant near-infrared quantum cutting in β-NaYF4:Ho,Yb

We demonstrated an efficient two-photon near-infrared (NIR) quantum cutting (QC) in Ho³⁺-Yb³⁺ co-doped hexagonal β-NaYF₄, which could efficiently convert an incident high-energy photon in the wavelength region of 300-550 nm into two NIR photons. Underlying mechanism for the two-photon NIR-QC process is analyzed in terms of static and dynamic photoemission and monitored excitation spectra. It is found that NIR-QC can occur through two possible energy transfer (ET) approaches: (i) the excited Ho³⁺:⁵F₃ state may simultaneously excite two Yb³⁺ neighbors via a cooperative ET process, and (ii) the NIR-QC can be feasibly induced by a first Ho³⁺(⁵S₂,⁵F₄) + Yb³⁺(²F_7/2) → Ho³⁺(⁵I₆) + Yb³⁺(²F_5/2) resonant ET process and a sequential ⁵I₆ → ⁵I₈ transition of Ho³⁺. This novel NaYF₄:Ho³⁺,Yb³⁺ NIR-QC phosphor, may explore a new approach to maximize the performance of solar cells.     

Solvothermal synthesis of monodisperse ultrasmall cubic-structure Ba2YbF7 nanocrystals with intense upconversion

A series of monodisperse ultrasmall Ba₂YbF₇ nanocrystals with intense upconversion emission were synthesized via a facile solvothermal method by using oleic acid as capping ligands. X-ray diffraction (XRD) and transmission electron microscopy (TEM) assays revealed that the as-synthesized Ba₂YbF₇ nanocrystals are of cubic structure, rather than the reported tetragonal structure. The cell parameter of the particles is 5.918 Å. The Er³⁺ or Tm³⁺ doped Ba₂YbF₇ nanocrystals with the size of sub-10 nm can give an intense upconversion emission under the 980 nm laser excitation and the upconversion processes were discussed. The Ba₂YbF₇ nanocrystals show a potential application as a bioimaging agent.     

Controllable synthesis of bifunctional NaYF4:Yb/Ho@SiO2/Au nanoparticles with upconversion luminescence and high X-ray attenuation

A novel type of bifunctional water-soluble NaYF₄:Yb³⁺/Ho³⁺@SiO₂/Au nanocomposite is fabricated by a facile layer-by-layer technology in which the mercapto-silica shell is used as the functional layer coating on the central NaYF₄:Yb³⁺/Ho³⁺ nanocrystals. Then by adjusting the mole ratio of the Au nanoparticles to the NaYF₄:Yb³⁺/Ho³⁺@SiO₂ nanoparticles, control of the gold loading on the upconversion nanocrystal surface is achieved. The fabricated nanocomposites inherit the excellent physical and chemical properties from their building blocks, simultaneously exhibiting upconversion luminescence and high X-ray attenuation and as well are easily modified with various molecules. These properties render the synthesized NaYF₄:Yb³⁺/Ho³⁺@SiO₂/Au nanocomposite not only useful as a multimodality contrast agent to increase the efficiency of molecular imaging but also has the potential of in situ curing of diseases.     

A study on microstructure and luminescent properties of oxyfluoride silicate glass-ceramics with (Ho,Yb):NaYF4 crystallites

Glass-ceramics containing NaYF₄ nanocrystals were prepared by heat-treatment from oxyfluoride silicate-based glass doped with Ho³⁺ and Yb³⁺ ions. The formation of crystalline fluoride phase was confirmed by X-ray diffraction and transmission electron microscopy. Absorption and emission spectra revealed that a fraction of Ho³⁺ and Yb³⁺ ions is incorporated into the NaYF₄ ordered lattice influencing spectroscopic features of glass-ceramics in comparison with those of precursor glass. Green up-conversion emission (545 nm) originating in the ⁵S₂ level in glass-ceramics and up-converted red emission (650 nm) originating in the ⁵F₅ level in as-melted glass were observed under optical pumping into Yb³⁺ absorption band and analyzed. Although both emissions in both materials are achieved by two-photon excitations, the relation between green and red emission intensity in glass-ceramics and glass implies that processes relevant to up-conversion phenomena are different. Based on a careful analysis of relaxation dynamics of Ho³⁺ and Yb³⁺ excited states, the mechanisms involved in conversion of the infrared radiation into the visible emission in these materials are proposed and discussed.     

Infrared spectroscopic properties of Tm, Ho:NaY(WO4)2 single crystals

Singly doped and Tm³⁺/Ho³⁺ co-doped NaY(WO₄)₂ single crystals were grown successfully by Czochralski method. The room temperature polarized absorption and fluorescence spectra as well as the decay curves were measured. Spectroscopic parameters related to the laser operation around 2.0 μm via the ³F₄ → ³H₆ (Tm³⁺) and ⁵I₇ → ⁵I₈ (Ho³⁺) transitions have been evaluated. The energy level scheme and energy transfer processes of Tm³⁺ and Ho³⁺ were analyzed.     

Thermal, mechanical, and upconversion properties of Er/Yb co-doped titanate glass prepared by levitation method

A novel Er³⁺/Yb³⁺ co-doped titanate glass sphere with diameter of 3.5 mm has been successfully fabricated by levitation method. Its thermal stability, mechanical property and upconversion behavior were investigated. The glass transition temperature T_g, onset crystallization temperature T_c, and peak crystallization temperature T_p, are as high as 820, 895 and 902 °C, respectively. Its Vickers hardness is found to be up to 7.85 GPa. Intense green and red upconversion emissions were obtained in this glassy sample upon 980 nm excitation. The results illustrate good potential of this class of material for practical application in frequency upconversion device. In addition, it is found that heating treatment above T_p can reduce the efficiency of upconversion fluorescence as well as deteriorate the mechanical property, due to the occurrence of La₄Ti₉O₂₄ crystals.     

Phase and luminescent intensity control of hydrophilic rare-earth up-converting nanophosphors prepared by one-pot solvothermal synthesis

Rare-earth up-converting nano-phosphors (RUNPs) have wide applications, and most of these applications require hydrophilic RUNPs with high up-converting luminescence efficiency. In this work, we report a simultaneous control of the phase and luminescent intensity of hydrophilic Gd³⁺ doped NaYF₄:Yb/Er nanoparticles with diameters of 40-100 nm, which were prepared by a facile one-pot solvothermal synthesis with ethylene glycol as the solvent and poly(vinylpyrrolidone) as the ligands at 220 °C for different time. When reaction time is 3 h, the increase of Gd³⁺ dopant concentration from 0 to 30 mol% results in the transformation from cubic to hexagonal phase, and pure hexagonal phase NaYF₄:Yb/Er nanoparticles can be obtained with Gd³⁺ dopant concentration up to 30 mol%. Gd³⁺ dopant concentration at 15 mol% leads to a maximal luminescent intensity in a wide dopant range of 0-80 mol%. Furthermore, the increase of reaction time from 3 to 24 h favors the formation of hexagonal phase samples and therefore improves greatly luminescence intensity. 15 mol% Gd³⁺ doped NaYF₄:Yb/Er nanoparticles prepared for 24 h exhibit the highest upconverting luminescence intensity which is almost 11 times as strong as that of ones prepared for 3 h and almost 28 times as strong as that of hexagonal phase NaGdF₄:Yb/Er (namely NaYF₄:Yb/Er sample with 80 mol% Gd³⁺ prepared for 3 h). Due to its small size, high hydrophilicity and excellent up-converting luminescence, this 15 mol% doped NaYF₄:Yb/Er sample has great superiority for biological applications.     

Structure and upconversion luminescence properties of BaYF5:Yb, Er nanoparticles prepared by different methods

BaYF₅:Yb³⁺, Er³⁺ (BYF) upconversion (UC) luminescence nanoparticles have been prepared using co-precipitation and hydrothermal techniques, respectively. Two different fluoride sources were used to synthesize BYF by the hydrothermal method, and the sizes of the as-prepared spherical particles were about 30 nm (NH₄BF₄ as a fluoride source) and 100 nm (NH₄HF₂ as a fluoride source), respectively. While the nanoparticles prepared by the co-precipitation method are irregular, many clusters and agglomerates can be seen. The UC fluorescence has been realized in all the as-prepared BYF samples upon 980 nm excitation. It is found that their luminescence spectra depend strongly upon the preparation method. Factors affecting the upconversion fluorescent intensity have been also studied. The UC emission transitions for ⁴F_9/2-⁴I_15/2 (red), ²H_11/2-⁴I_15/2 (green) and ⁴S_3/2-⁴I_15/2 (green) in the Yb³⁺/Er³⁺ codoped BYF nanoparticles depending on pumping power have also been discussed.     

Upconversion luminescence of Yb/Tb/Er-doped fluorosilicate glass ceramics containing SrF2 nanocrystals

Yb³⁺/Tb³⁺/Er³⁺-doped transparent alkaline earth fluorosilicate glass ceramics containing SrF₂ nanocrystals were prepared and their microstructures and spectroscopic properties were investigated. The formation of SrF₂ nanocrystals enriched with Yb³⁺/Tb³⁺/Er³⁺ in the glass ceramics was confirmed by XRD, HRTEM and SAED. The glass ceramics exhibited intense upconversion luminescence behaviors, owing to efficient energy transfers from Yb³⁺ to Er³⁺ and Tb³⁺ and low phonon assistant non-radiative transition probabilities of excited Er³⁺ and Tb³⁺. The upconversion could be enhanced significantly by increasing the annealing temperature and the luminescence color could be adjusted by varying the Yb³⁺/Tb³⁺/Er³⁺ ratio. Upconversion of Er³⁺ could be described as sequential energy transfer from single Yb³⁺ to single Er³⁺, while upconversion of Tb³⁺ described as cooperative energy transfer from double Yb³⁺ to single Tb³⁺.     

Effect of Bi doping on the quenching concentration of H11/2/S3/2 level of Er

Bi³⁺ and Er³⁺ codoped Y₂O₃ was prepared by sol-gel method. The upconversion emission was investigated under 980 nm excitation. For samples without Bi³⁺, the quenching concentration of ²H_11/2/⁴S_3/2 level of Er³⁺ is 3.0 mol%. However, by 1.5 mol% Bi³⁺ doping the quenching concentration increases to 5.0 mol%; meanwhile, the green emission is enhanced 1.9 times. The results indicate that both the quenching concentration and the emission intensity of ²H_11/2/⁴S_3/2 level can be increased by Bi³⁺ doping.     

Enhancement of upconversion luminescence of Y2O3:Er nanocrystals by codoping Li-Zn

The upconversion (UC) luminescence in sol-gel synthesized Li⁺, Zn²⁺, or Li⁺-Zn²⁺ codoped Y₂O₃:Er³⁺ nanocrystals were investigated under the excitation of a 970 nm diode laser. Compared to undoped Y₂O₃:Er³⁺ samples, proper doping of Li⁺-Zn²⁺ leads to an drastic increase of the UC luminescence centered at 560 nm by a factor of 28. The UC luminescence enhancement is a result of the increased lifetime of the intermediate state ⁴I_11/2 (Er). The intensity ratio of the green over red emissions (green/red) is also affected by the codoping of Zn²⁺, Li⁺ and Li⁺-Zn²⁺ ions. Our results demonstrated that the Li⁺-Zn²⁺ codoping in Y₂O₃:Er³⁺ phosphors produced remarkable enhancement of the UC luminescence and green/red ratio, making this nanocrystal a promising candidate for photonic and biological applications.     

Spectroscopic properties of Yb and Er ions in heavy metal glasses

Selected heavy metal glasses containing Yb³⁺ and Er³⁺ ions have been studied. Near-infrared luminescence spectra at 1.53 μm and up-conversion spectra of Er³⁺ ions were registered under excitation of Yb³⁺ ions by 975 nm diode laser line. The luminescence bands correspond to ⁴I_13/2-⁴I_15/2 (NIR), ⁴S_3/2-⁴I_15/2 (green) and ⁴F_9/2-⁴I_15/2 (red) transitions of Er³⁺, respectively. The optical transitions of rare earth ions have been examined as a function of glass host. The unusual large spectral linewidth nearly close to 110 nm for ⁴I_13/2-⁴I_15/2 transition of Er³⁺ ions in Yb-Er co-doped lead borate glass was obtained, whereas long-lived NIR luminescence at 1.53 μm was detected in lead germanate glass. The NIR luminescence and up-conversion phenomena strongly depend on stretching vibrations of glass host, which was confirmed by FT-IR spectroscopy.     

Tunable red-green-blue multicolor luminescence in Yb/Tm/Ho:Gd3Ga5O12 nano-crystals

The Yb³⁺/Tm³⁺/Ho³⁺: Gd₃Ga₅O₁₂ nano-crystals have been successfully prepared via a citric acid complex procedure. The luminescence spectra were measured and the up-conversion processes were discussed. By means of adjusting the doping concentrations of Yb³⁺/Tm³⁺/Ho³⁺, the red-green-blue up-conversion luminescence changed obviously. Results indicated that the ratio of red-green-blue up-conversion emissions enhanced heavily with the increasing concentrations of Tm³⁺ doped in the Yb³⁺/Tm³⁺/Ho³⁺:Gd₃Ga₅O₁₂ nano-crystals, which was rooted in the three-photon resonant cross relaxation processes(¹G₄ (Tm) + ⁵I₇ (Ho) → ³H₅ (Tm) + ⁵S₂ (Ho)). The tunable red-green-blue luminescence could be used in the fields of display, illumination, and photonics such as the white light generation.