Synthesis and Characterization of Monodispersed SiO2@Y3Al5O12:Er3+ Core-Shell Particles

Submicron core-shell structure particles SiO₂@Y₃Al₅O₁₂:Er³⁺, which silica spherical particles was coated with an yttrium aluminum garnet (Y₃Al₅O₁₂) layer doped with Er³⁺, were prepared by the modified Pechini-Type sol-gel method for the first time. The structure and morphology of samples were detected by the X-ray powder diffraction (XRD) measurement, field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM), respectively. The results indicate that well-crystallized garnet nanocrystallines were formed on the surface of the silica particles. The luminescent spectra in near infrared and visible region of the core-shell structured SiO₂@Y₃Al₅O₁₂:Er³⁺ powders were also investigated and compared with those of the pure Y₃Al₅O₁₂:Er³⁺ and the Er³⁺ doped silicate glass. The results show that mono-dispersed SiO₂@Y₃Al₅O₁₂:Er³⁺ core-shell spherical particles with the near infrared, red and green luminescent emissions under the excitation of 980 nm laser diode have been successfully synthesized.     

Investigation of luminescence spectra of the Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> and Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce single-crystal films

The luminescence spectra of single-crystal films and bulk crystals of yttrium-aluminum garnet Y₃Al₅O₁₂ and Ce³⁺-activated Y₃Al₅O₁₂ were investigated. It was shown that the room-temperature luminescence intensity of the Ce³⁺-free single-crystal Y₃Al₅O₁₂ film was considerably lower than that of the bulk crystals, while the luminescence intensity of the Ce³⁺ ions in the Y₃Al₅O₁₂:Ce films was considerably higher than that one for the corresponding bulk crystal.     

Photolumiscent Properties of Nanorods and Nanoplates Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript>

Nanorods and nanoplates of Y₂O₃:Eu³⁺ powders were synthesized through the thermal decomposition of the Y(OH)₃ precursors using a microwave-hydrothermal method in a very short reaction time. These powders were analyzed by X-ray diffraction, field emission scanning electron microscopy, Fourrier transform Raman, as well as photoluminescence measurements. Based on these results, these materials presented nanoplates and nanorods morphologies. The broad emission band between 300 and 440 nm ascribed to the photoluminescence of Y₂O₃ matrix shifts as the procedure used in the microwave-hydrothermal assisted method changes in the Y₂O₃:Eu³⁺ samples. The presence of Eu³⁺ and the hydrothermal treatment time are responsible for the band shifts in Y₂O₃:Eu³⁺ powders, since in the pure Y₂O₃ matrix this behavior was not observed. Y₂O₃:Eu³⁺ powders also show the characteristic Eu³⁺ emission lines at 580, 591, 610, 651 and 695 nm, when excited at 393 nm. The most intense band at 610 nm is responsible for the Eu³⁺ red emission in these materials, and the Eu³⁺ lifetime for this transition presented a slight increase as the time used in the microwave-hydrothermal assisted method increases.     

Laser performance of holmium-doped Lu<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> and (Lu,Y)<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> crystals pumped by Tm:fiber laser

Optical properties of Ho³⁺-doped Lu₃Al₅O₁₂ and (Lu,Y)₃Al₅O₁₂ crystals were investigated and compared. Substitution of Y for Lu in the host garnet Lu₃Al₅O₁₂ results in broad absorption and emission spectra, and improvements in the laser behavior of Ho³⁺. Pumped by Tm:fiber laser, a maximum output power of 5.02 and 5.73 W of Ho-doped Lu₃Al₅O₁₂ and (Lu,Y)₃Al₅O₁₂ have been obtained, respectively. The center lasing wavelength are 2124.5 and 2123.0 nm for Lu₃Al₅O₁₂ and (Lu,Y)₃Al₅O₁₂, respectively.     

Effect of composition disorder on the electron paramagnetic resonance spectrum of the thermally populated excited state of Er<Superscript>3+</Superscript> ions in YLuAG mixed garnets

The results of investigation of electron paramagnetic resonance of Er³⁺ ions in the thermally populated first excited state in (Y_{1 − x} Lu _x )₃Al₅O₁₂ (YLuAG) mixed yttrium-lutetium garnet single crystals (0 ≤ x ≤ 1) are considered. In composition-disordered YLuAG, a number of new (as compared to Y₃Al₅O₁₂ (YAG)) Er³⁺ paramagnetic centers are detected; these centers appear due to a change in the crystal field symmetry and magnitude upon isomorphic substitution of Lu³⁺ for Y³⁺ in the yttrium sublattice of garnets. The origin of new paramagnetic centers is established and their formation probability is calculated.     

Eu<Superscript>3+</Superscript> As a Luminescent Probe for Studying the Structure of R<Subscript>2</Subscript>O<Subscript>3</Subscript> Materials (R = Y,Eu, and Gd)

Spectra of Eu³⁺ in various dielectric matrices (Gd₂O₃:Eu³⁺, Y₂O₃:Eu³⁺, Eu₂O₃, and mSiO₂/Gd₂O₃:Eu³⁺ mesoporous particles) are studied by local cathodoluminescence. The results allowed identification of the local environment of Er³⁺ ions in amorphous samples and detection of the monoclinic Eu₂O₃ phase impurity in samples with yttrium oxide. The cathodoluminescence spectra of chemically pure Y₂O₃, Eu₂O₃, and Gd₂O₃ are recorded. Conclusions about the structural features of the materials are made and confirmed by other methods (XRD and EPMA).     

Up-conversion emissions of Er<Superscript>3+</Superscript>-Yb<Superscript>3+</Superscript> codoped Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles by the arc discharge synthesis method

The Er³⁺-Yb³⁺ codoped Al₂O₃ nanoparticles with an average particle size of about 50 nm have been synthesized by an arc discharge synthesis method. The green and red up-conversion emissions centered at about 526, 547 and 677 nm, corresponding respectively to the ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions of Er³⁺, were detected by a 978-nm semiconductor laser diode excitation. The Annealing has evident effect on the up-conversion emissions of the samples: The red up-conversion emission is noticeable before annealing; however, the green up-conversion emission becomes predominant after annealing. The mixture of (Er,Yb)₃Al₅O₁₂ and α-(Al,Er,Yb)₂O₃ phases is more favorable for green up-conversion emissions due to an enhancement of the ESA (I) of ⁴I_11/2+a photon→⁴F_7/2 and ET (III) of ²F_5/2(Yb³⁺)+⁴I_11/2(Er³⁺)→²F_7/2(Yb³⁺)+⁴F_7/2(Er³⁺) processes. The two-photon absorption up-conversion process is involved in the green and red up-conversion emissions. The results have proved that arc discharge synthesis is a new promising preparation technology for optical materials. Supported by National Natural Science Foundation of China (Grant No. 10804015), the Scientific Research Foundation for Doctor of Liaoning Province (Grant No. 20071095), and the Educational Committee Foundation of Liaoning Province (Grant No. 2008123)     

Improvement of sonocatalytic activity of TiO2 by using Yb,N and F-doped Er3+:Y3Al5O12 for degradation of organic dyes

In this study, several up-conversion luminescence agents (Er³⁺:Y₃Al₅O₁₂, Er³⁺:Yb_0.2Y_2.79Al₅O₁₂, Er³⁺:Yb_0.2Y_2.79Al₅N_0.01O_11.99, Er³⁺:Yb_0.2Y_2.79Al₅F_0.01O_11.99 and Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98) were synthesized using sol–gel method. And then, the corresponding sonocatalyst (Er³⁺:Y₃Al₅O₁₂/TiO₂, Er³⁺:Yb_0.2Y_2.79Al₅O₁₂/TiO₂, Er³⁺:Yb_0.2Y_2.79Al₅N_0.01O_11.99/TiO₂, Er³⁺:Yb_0.2Y_2.79Al₅F_0.01O_11.99/TiO₂ and Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98/TiO₂ coated composites) were prepared by sol–gel coating process. The synthesized up-conversion luminescence agents and their coated composites were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). And that, the sonocatalytic activities were detected through the degradation of Azo Fuchsine (AF) dye in aqueous solution by UV–vis spectroscopy. Some key influences such as heat-treated temperature and heat-treated time on the sonocatalytic activity of Er³⁺:Yb_aY_2.99−aN_xF_yAl₅O_12−x−y/TiO₂ coated composite, as well as ultrasonic irradiation time and initial dye concentration on the sonocatalytic degradation were studied. The results showed that the doping of Yb, N and F into Er³⁺:Y₃Al₅O₁₂/TiO₂ significantly enhanced the sonocatalytic activity of Er³⁺:Y₃Al₅O₁₂/TiO₂ coated composite in the degradation of organic dyes. Particularly, Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98/TiO₂ coated composites with 3:7 M ratio heat-treated at 550 °C for 60 min showed the highest sonocatalytic activity. At last, the experiments also indicated that the Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98/TiO₂ coated composites has a good sonocatalytic activity to degrade other organic dyes under ultrasonic irradiation.     

Intensities of hypersensitive transitions in garnet crystals doped with Er<Superscript>3+</Superscript> ions

We examine the oscillator strengths and the intensity parameters Ω _t (t = 2, 4, 6) of yttrium-aluminum, scandium-containing, and gallium garnet crystals doped with Er³⁺ ions. A comparative analysis of the oscillator strengths and the intensity parameters Ω _t (t = 2, 4, 6) of garnets with different contents of Al³⁺ and Sc³⁺ ions (Gd_2.4Er_0.5Sc_1.8Al_3.3O₁₂, Gd_2.4Er_0.5Sc_1.9Al_3.2O₁₂, Gd_2.4Er_0.5Sc_2.0Al_3.1O₁₂) is performed, as a result of which the oscillator strengths and the intensity parameters Ω _t (t = 2, 4, 6) of these crystals are shown to have close values. We find that Ca₃(NbGa)₅O₁₂ crystals doped with Er³⁺ ions are characterized by highest values of the oscillator strengths for hypersensitive transitions and of the intensity parameter Ω₂ of Er³⁺ ions compared to the values of these quantities in the examined garnet crystals, which is determined by the fact that the symmetry of the local environment of Er³⁺ ions in these crystals is C ₁, C ₂, or C _2ν. We reveal that, as the concentration of Er³⁺ ions in these crystals increases from 1 to 39 at %, both the oscillator strength of the hypersensitive transition ⁴ I _15/2 → ² H _11/2 of Er³⁺ ions and their intensity parameter Ω₂ tend to decrease, which can be related to an increase in the relative fraction of Er³⁺ ions with higher symmetry of the local environment.     

Intense Upconversion Luminescence of Yb<Superscript>3+</Superscript>-Er<Superscript>3+</Superscript> in Li<Subscript>2</Subscript>O Content Tungsten-tellurite Glasses

The Er³⁺ -Yb³⁺ codoped in Li₂O content tungsten -tellurite (TWL) transparent glasses are synthesized and measured the absorption, Raman and upconversion luminescence (UPL) spectra. At room temperature intense green emission peak at 560 nm ( ⁴S_3/2→⁴I_15/2) and red emission peak at 670 nm ( ⁴F_9/2→⁴I_15/2) of Er³⁺ observed even at minimum 86 mW pumping power of infrared 980 nm excitation. For structure of the TWL glass, Raman spectrum result revealed that an important role of WO₃ in the formation of glass network linkage with Li₂O. Under this influence estimated lifetime of the ⁴I_11/2 of Er³⁺ was 1.89 μs and due to lower phonon energy of the glass produce strong upconversion signal. The effect of Er₂O₃ concentration on emission intensity result indicated that green emission intensity initially increase in compare to red emission. Under the 980 nm pump power variation measured the relatively increases the red emission to the green emission intensity and analyze the possible upconversion mechanism and process.     

Enhanced photoluminescence of Ca<Subscript>2</Subscript>Al<Subscript>2</Subscript>SiO<Subscript>7</Subscript>:Eu<Superscript>3+</Superscript> by charge compensation method

The effect of compensator on optical properties of Ca₂Al₂SiO₇:Eu³⁺ is systematically investigated by the X-ray powder diffraction, photo-luminescence (PL) properties and lifetime. It is obviously observed that the PL intensity of Eu³⁺ under 394 nm excitation increases in the order of Ca_1.86Eu_0.14Al₂SiO₇ (CAS), Ca_1.72Na_0.14Eu_0.14Al₂SiO₇ (CASNa) and Ca_1.86Eu_0.14Al_2.14Si_0.86O₇ (CASAl), the intensity of Eu³⁺ are 100%, 134%, 184%, and the lifetime of Eu³⁺ are 0.75 ms, 1.28 ms and 1.39 ms, respectively. A charge compensation model is proposed to explain the changes in the emission intensity and lifetime of Eu³⁺ in Ca₂Al₂SiO₇ with different compensation methods. PACS 78.55.-m; 61.72.Ji; 61.43.Gt; 42.70.-a; 74.62.Dh     

Energy transfer from the host to Er<Superscript>3+</Superscript> dopants in semiconductor SnO<Subscript>2</Subscript> nanocrystals segregated in sol–gel silica glasses

Undoped and Er³⁺-doped glass–ceramics of composition (100−x)SiO₂–xSnO₂, with x = 5 or 10 and with 0.4 or 0.8 mol% of Er³⁺ ions, were synthesised by thermal treatment of precursor sol–gel glasses. Structural studies were developed by X-Ray Diffraction. Wide band gap SnO₂ semiconductor quantum-dots embedded in the insulator SiO₂ glass are obtained. The mean radius of the SnO₂ nanocrystals, ranging from 2 to 3.2 nm, is comparable to the exciton Bohr radius. The luminescence properties have been analysed as a function of sample composition and thermal treatment. The results show that Er³⁺ ions are partially partitioned into the nanocrystalline phase. An efficient UV excitation of the Er³⁺ ions by energy transfer from the SnO₂ nanocrystal host is observed. The Er³⁺ ions located in the SnO₂ nanocrystals are selectively excited by this energy transfer mechanism. On the other hand, emission from the Er³⁺ ions remaining in the silica glassy phase is obtained by direct excitation of these ions.     

Luminescence and scintillation properties of Y<Subscript>3</Subscript>A<Subscript>l5</Subscript>O<Subscript>12</Subscript>:Ce single crystals and single-crystal films

Luminescence and scintillation properties of Y₃A_l5O₁₂:Ce single crystals grown from the melt by the Czochralski and horizontal directed crystallization methods in various gas media and Y₃A_l5O₁₂:Ce single-crystal films grown by liquid-phase epitaxy from a melt solution based on a PbO-B₂O₃ flux have been comparatively analyzed. The strong dependence of scintillation properties of Y₃A_l5O₁₂:Ce single crystals on their growth conditions and concentrations of Y_Al antisite defects and vacancy defects has been established. Vacancy defects are involved in Ce³⁺ ion emission excitation as the centers of intrinsic UV luminescence and trapping centers. It has been shown that Y₃A_l5O₁₂:Ce single-crystal films are characterized by faster scintillation decay kinetics than single crystals and a lower content of slow components in Ce³⁺ ion luminescence decay during high-energy excitation due to the absence of Y_Al antisite defects in them and low concentration of vacancy defects. At the same time, the light yield of Y₃A_l5O₁₂:Ce single-crystal films is comparable to that of single crystals grown by directed crystallization due to the quenching effect of the Pb²⁺ ion impurity as a flux component and is slightly lower (∼25%) than the light yield of single crystals grown by the Czochralski method.     

Flame-synthesized Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Tb<Superscript>3+</Superscript> nanocrystals as spectral converting materials

In flame spray pyrolysis (FSP), the generation of uniform nanoparticles can be quite challenging due to difficulties in controlling droplet sizes during liquid spraying and uneven flame temperature. Here, we report a method to produce relatively uniform nanocrystals of a Tb³⁺ doped Y₂O₃ phosphor. In ethanol, metal nitrate precursors were simply mixed with organic surfactants to form a homogeneous solution which was then subjected to FSP. Depending on relative concentrations of the surfactant (oleic acid) to the metal precursors (yttrium and terbium nitrates), different sizes and morphologies of Y₂O₃:Tb³⁺ particles were obtained. By adjusting the surfactant concentration, Y₂O₃:Tb³⁺ crystals as small as 20~25 nm were acquired. X-ray diffraction and transmittance electron microscopy were used to prove that as-synthesized nanoparticles were highly crystalline due to the high temperature of FSP. X-ray photoelectron spectroscopy revealed that terbium dopants were well distributed throughout Y₂O₃ particles and a small portion of carbonate impurities were remained on the surface of particles, presumably originated from incomplete combustion of the organic surfactants. Photoluminescence (PL) spectra of Y₂O₃:Tb³⁺ nanocrystals exhibited a green light emission ensuring that the terbium doping was successfully occurred. However, when post-annealing was performed on the nanocrystals, their PL was dramatically enhanced indicating that quenching centers such as carbonate impurities and surface defects may have been removed by the annealing process. Owing to the continuous processability of FSP, this current method can be a practical way to produce nanoparticles in a large quantity. The obtained Y₂O₃:Tb³⁺ nanocrystals were used to fabricate a transparent film with poly-ethylene-co-vinyl acetate (poly-EVA) polymer, which was suitable for a spectral converting layer for a solar cell.

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Morphology-dependent luminescence behavior of Y<Subscript>2-x</Subscript>Gd<Subscript>x</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> thin-film phosphors grown by a laser ablation

Y_2-xGd_xO₃:Eu³⁺ luminescent thin films have been grown on Al₂O₃(0001) substrates using pulsed laser deposition. Films grown under different deposition conditions have been characterized using microstructural and luminescence measurements. The crystallinity, surface morphology and photoluminescence (PL) of the films are highly dependent on the amount of Gd present. The photoluminescence (PL) brightness data obtained from Y_2-xGd_xO₃:Eu³⁺ films grown under optimized conditions have indicated that Al₂O₃(0001) is one of the most promising substrates for the growth of high-quality Y_2-xGd_xO₃:Eu³⁺ thin-film red phosphors. In particular, the incorporation of Gd into the Y₂O₃ lattice could induce a remarkable increase of PL. The highest emission intensity was observed with Y_1.35Gd_0.60Eu_0.05O₃, whose brightness was increased by a factor of 3.1 in comparison with that of Y₂O₃:Eu³⁺ films. This phosphor may be promising for application in flat-panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w     

Intense White Luminescence from Combustion Synthesized Ca<Subscript>12</Subscript>Al<Subscript>14</Subscript>O<Subscript>33</Subscript>: Yb<Superscript>3+</Superscript>/Yb<Superscript>2+</Superscript> Single Phase Phosphor

The Ca₁₂Al₁₄O₃₃: Yb³⁺/Yb²⁺ single phase nano-phosphor has been synthesized through combustion route and its luminescence and lifetime studies have been carried out up to 20 K using 976 and 266 nm excitations. The samples heated in open atmosphere have shown the presence of Yb in Yb³⁺ and Yb²⁺ states. The 976 nm excitation results a cooperative upconversion emission at 486 nm due to the Yb³⁺ state and a broad band in the blue region and has been assigned to arise from the defect centers. The 266 nm excitation on the other hand results a broad emission band even from as-synthesized phosphor without doping of Yb, the width of which increases in presence of Yb due to the emission from Yb²⁺ ions formed in heated samples. The white emission covers almost whole visible region with bandwidth 190 nm. The ions in Yb²⁺ state has been found to increase with the increase in heating temperature up to 1,273 K. A back conversion of Yb²⁺ to Yb³⁺ has been observed for higher temperatures. Effect of boric and phosphoric acids as flux on the emission properties of Yb³⁺ and Yb²⁺ states have been examined and discussed. Quantum yield of emission has also been determined for different samples.     

Green,blue, red,near-infrared up-conversion luminescence of Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript>/Tm<Superscript>3+</Superscript> co-doped YVO<Subscript>4</Subscript> nanoparticles

YVO₄:Yb³⁺,Er³⁺; YVO₄:Yb³⁺,Tm³⁺; and YVO₄:Yb³⁺,Er³⁺,Tm³⁺ were all synthesized via sol-gel method with a subsequent thermal treatment. Specifically, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ phosphors were prepared with different annealing temperatures to study the influence of temperature. The transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffractometer (XRD), and photoluminescent (PL) spectrofluorometer were used to investigate the morphology, crystal structure, and up-conversion luminescent properties of all samples. In summary, all samples were granular-like nanoparticles and well crystallized with the same tetragonal phase as YVO₄. Under the irradiation at 980 nm, YVO₄:Yb³⁺,Er³⁺ phosphors can generate green emission at 525 and 553 nm and red emission at 657 nm, while YVO₄:Yb³⁺,Tm³⁺ phosphors can generate blue emission at 476 nm, red emission at 648 nm, and near-infrared emission at 800 nm. Notably, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ samples can exhibit green emission, blue emission, red emission, and near-infrared emission at the same time, which might endow the as-prepared samples with potential applications in many fields, such as luminous paint, infrared detection, and biological label.     

The influence of the specific surface of grains on the luminescence properties of Nd<Superscript>3+</Superscript>-doped Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> nanopowders

Nd³⁺:Y₃Al₅O₁₂ (Nd:YAG) powders were prepared by the Pechini method in the temperature range of 800 to 1400 °C. The pure garnet phase of the obtained materials was confirmed by XRD studies. The size of the grains was controlled by the annealing temperature of the samples. Their morphologies were investigated by TEM and porosity measurements (BET). The effect of annealing temperature on the morphology and luminescence properties of Nd:YAG nanocrystallites was studied, and the results were compared to the properties of a Nd:YAG single crystal. A significant enhancement of the ⁴F_3/2→⁴I_9/2/⁴F_3/2→⁴I_11/2 intensity ratio with decreasing grain size was observed. It was found that the decay times of the Nd³⁺ luminescence depends on the specific surface and is significantly longer for well crystallized nanocrystalline grains than for single crystals having the same concentration of Nd³⁺ ions. The role of crystallinity and specific surface on the radiative processes is analyzed. PACS 78.55.-m; 78.20.Ci; 78.67.Bf; 78.68.+m     

Concentration quenching anomalies of activated Y<Subscript>2</Subscript>SiO<Subscript>5</Subscript>:Pr<Superscript>3+</Superscript> nanocrystal luminescence

For the fist time in Y₂SiO₅:Pr³⁺ nanocrystals, the ordered stage in the ¹ D ₂ luminescence decay curves for Pr³⁺ ions has been observed at anomalously low doped ion concentration (0.5 at %). This effect is caused by preferred location of the activator ions in the near-surface layer of the nanocrystal that provides the relaxation of elastic tension arising due to the difference of ionic radii of Pr³⁺ and Y³⁺ ions. Concentration quenching of Pr³⁺ luminescence is caused by the cooperative cross-relaxation.