Luminomagnetic Nd3+ doped fluorapatite coated Fe3O4 nanostructures for biomedical applications

Luminomagnetic nanostructured Nd³⁺ doped fluorapatite (FAP) coated Fe₃O₄ nanoparticles were produced by hydrothermal method. X-ray diffraction analysis indicates that the prepared nanoparticles contain both FAP and Fe₃O₄ phases. Electron microscope analysis shows the formation of nanoparticles of Fe₃O₄ encased in rod shaped FAP nanoparticles of average length 40 nm. Magnetic measurements confirm the room temperature superparamagnetic nature of the nanoparticles with saturation magnetization value up to 7.8 emu/g. The prepared nanoparticles display strong near infrared (NIR) emission at 1060 nm under 800 nm excitation. Cell viability studies for 72 hour demonstrate the survival rate of over 84% with 500 μg/mL concentration indicating the good cytocompatibility of the prepared materials. The present Nd³⁺ doped FAP coated Fe₃O₄ nanostructure provides an excellent multifunctional platform for diagnostics and therapeutic applications.     

Near white light emission of Ce3+‐, Ho3+‐, and Sm3+‐doped oxyfluoride silicate glasses

The Ce³⁺‐, Ho³⁺‐, and Sm³⁺‐ single and co‐doped oxyfluoride silicate glasses for light emitting diodes are studied. These glasses were prepared by melt quenching method and their optical and structural properties were investigated by absorption spectra, photoluminescence spectra, Commission International de I'Eclairage chromaticity coordinates, X‐ray diffraction, and Fourier transform infrared spectra. It is found that the introduction of Al₂O₃ in glass composition can improve the emissions of Ho³⁺ and Sm³⁺. While the presence of B₂O₃ has the adverse effect and can suppress the emissions of Ho³⁺ and Sm³⁺. With substituting Na₂O for CaO in the glass compositions, CaF₂ crystals can be formed during the melt quenching process. We find the formation of CaF₂ crystals can change the emission behavior of Ho³⁺ and Sm³⁺ ions. White light emissions can be achieved in the glasses and the luminescence colors can be tuned by varying the concentrations of the doped rare‐earth ions and the composition of glass matrix. The Ce³⁺‐, Ho³⁺‐, and Sm³⁺‐doped oxyfluoride silicate glasses presented here demonstrate promising applications in the fields of light emitting diodes.     

UV–VIS absorption and NIR‐stimulated emission of Nd3+: PVA films

Neodymium‐doped polyvinyl alcohol films were prepared and the optical properties of the films were investigated. By applying Judd–Ofelt theory, the Ω parameters were obtained from the absorption spectrum. Various radiative parameters like transition probability for each level (A_J), total transition probability (A_T), branching ratio (β_R), radiative lifetime (τ_rad), and absorption cross‐section (σ_A) were calculated. The theoretically obtained branching ratio and integrated absorption cross‐section are found to be greater for the transition ⁴F_3/2 → ⁴I_11/2. From the emission spectrum peaked at 1064‐nm stimulated emission cross‐section (σ_E), the line width (Δλ_eff) is calculated to be 6.21 × 10^?21 cm² and 41 nm, respectively. Further the variation of the optical gain with the length of the film was studied and the slope efficiency (η = 8.5%) was determined from laser measurements. These results clearly support the potentiality of the Nd³⁺: polyvinyl alcohol films in realizing optical amplification and stimulated emission. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Pr3+/Yb3+:PLZT ferroelectric ceramics for near‐infrared radiation at 1340 nm

The near‐infrared luminescence properties of Pr³⁺/Yb³⁺:PLZT ferroelectric ceramics have been examined for the first time. Independently, upon either 450 nm (Pr³⁺) or 980 nm (Yb³⁺) excitation, luminescence centered at 1340 nm was observed, which corresponds to the ¹G₄→³H₅ transition of Pr³⁺. Several spectroscopic parameters for the ¹G₄→³H₅ transition of Pr³⁺ ions were determined. The average product of emission cross section and radiative lifetime were relatively large for all x/65/35 PLZT samples (x=6‐10) studied, with values close to 105±2 (×10^?26 cm²·s). These spectroscopic investigations indicate that Pr³⁺/Yb³⁺:PLZT ferroelectric ceramics are promising candidate for efficient sources emitting near‐infrared radiation at 1340 nm.     

Structural insights in Dy3+‐doped β‐Tricalcium phosphate and its multimodal imaging characteristics

A series of Dysprosium (Dy³⁺) doped β‐Tricalcium phosphate [β‐TCP, β‐Ca₃(PO₄)₂] were developed for applications in magnetic resonance imaging (MRI) and computed tomography (CT). Characterization studies confirmed the Dy³⁺ occupancy at Ca²⁺(1), Ca²⁺(2), and Ca²⁺(3) lattice sites of β‐Ca₃(PO₄)₂ and its substitution limit was determined as 4.35 mol%. The transitions from the ⁶H_15/2 ground state to various excited energy levels is validated by the characteristic absorption peaks of Dy³⁺. Luminescence studies inferred two intense bands at 480 and 572 nm due to ⁴F_9/2→⁶H_15/2 (blue) and ⁴F_9/2→⁶H_13/2 (yellow) transitions of Dy³⁺. The paramagnetic and nontoxic behavior of Dy³⁺‐doped β‐Ca₃(PO₄)₂ were confirmed from magnetic and MTT tests, respectively. Dy³⁺ in the host induces a high X‐ray absorption ability for X‐ray computed tomography (CT) and showed efficient contrast T₂‐enhancing modality. Thus the proposed system could be used as a promising probe for multimodality with optical imaging, computed tomography and magnetic resonance imaging.     

REVO4‐Based Nanomaterials (RE = Y,La, Gd,and Lu) as Hosts for Yb3+/Ho3+, Yb3+/Er3+, and Yb3+/Tm3+ Ions: Structural and Up‐Conversion Luminescence Studies

Rare‐earth vanadates of the form REVO₄ (RE = Y, La, Gd, and Lu) doped by Yb³⁺/Ho³⁺, Yb³⁺/Er³⁺_, or Yb³⁺/Tm³⁺ lanthanide ions were successfully synthesized using the sol–gel method and annealing at 600°C in an air atmosphere. The structure and morphology of the prepared nanocrystals were investigated by X‐ray diffraction, thermogravimetric analysis, transmission electron microscopy, and energy‐dispersive X‐ray spectroscopy. All prepared materials were homogenous and had nanosized dimensions. Their elemental compositions were confirmed by optical emission spectrometry. Spectroscopic analysis of the materials was carried out by measuring excitation and emission spectra, luminescence decays, and dependence between the intensity of the luminescence and the laser energy. Following effective excitation by NIR radiation, Ln³⁺ co‐doped vanadate matrices exhibited a strong up‐conversion (UC) luminescence. Differences in spectroscopic properties between monoclinic LaVO₄ and tetragonal YVO₄, GdVO₄, or LuVO₄ doped by Ln³⁺ ions were observed, indicating the influence of the crystal structure on the UC emission. Drawing conclusions from these spectroscopic investigations, the UC mechanisms were proposed, including energy‐transfer processes between Yb³⁺ ions and emitting ions.     

Thermal effects of Er3+/Yb3+‐doped NaYF4 phosphor induced by 980/1510 nm laser diode irradiation

The thermal effects of Er/Yb‐doped NaYF₄ phosphor induced by 980/1510 nm laser diode irradiation were intuitively and contrastively investigated using an infrared thermal imaging technology with real‐time online monitoring. The Yb³⁺/Er³⁺ codoped materials have strong thermal effects and high‐temperature elevation under 980 nm irradiation. However, the severe thermal effects of materials with higher Er³⁺ ion doping concentration are remarkably attributed to the cross relaxation between the Er³⁺ ions under 980 nm irradiation. The energy transfer between Er³⁺ and Yb³⁺ ions in Er³⁺/Yb³⁺‐codoped materials also contributes to the thermal effects under 1510 nm laser diode irradiation. Under the same testing conditions, the temperature elevation ?T of samples induced by 1510 nm laser diode irradiation is lower than that induced by 980 nm laser diode irradiation. The temperature rising rate and elevation ?T value of samples depend on the ion doping concentration and power density of the laser diode excitation. The internal temperature of the samples exhibits deep temperature gradient under 980/1510 nm laser diode irradiation. By comparing the two kinds of thermometry methods, the temperature value calculated by fluorescence intensity ratio is almost similar to that obtained through infrared thermal imaging technology under higher excitation power pumping.     

Enhancement of the luminescent intensity of the novel system containing Eu3+‐β‐diketonate complex doped in the epoxy resin

Photoluminescent properties of the europium tris(thenoyltrifluoroacetonate) dihydrate [Eu(TTA)₃(H₂O)₂] incorporated in epoxy resin in the solid state are reported. The polymeric Eu³⁺ complex and the precursor compound were characterized by elemental analysis, thermogravimetry (TG), differential scanning calorimetry (DSC), infrared spectroscopy, nuclear magnetic resonance (NMR), and electronic spectroscopy. Due to efficient energy transfer from the polymer to the rare earth ion, the polymer phosphorescence intensity was observed to decrease with an increase of the Eu³⁺ ion concentration. High values of the Ω₂ intensity parameter were obtained, reflecting the hypersensitive character of the ⁵D₀ → ⁷F₂ transition and indicating that the Eu³⁺ ions are in a highly polarizable chemical environment. This is consistent with systems containing epoxy resin that generally show a higher value for the Ω₄ parameter as a consequence of the difference in the basicity of the oxygen donor from the polymer. Lifetime measurement (τ = 0.442 ms) suggests that the Eu³⁺ luminescence has a higher efficiency than in the case of hydrated compound (τ = 0.260 ms). The emission quantum efficiency shows higher luminescence for the polymer containing 1% of Eu³⁺‐β‐diketonate complex. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2716–2726, 2002     

Tb3＋自敏化效应与Gd3＋-Tb3＋能量转移对硅酸盐玻璃发光性能的影响

研究了Tb3+自敏化效应与Gd3+-Tb3+能量转移对硅酸盐玻璃发光性能的影响.结果表明,随着Tb3+掺杂量的增加,Tb3+的400～450 nm蓝色荧光发射减弱,而485 nm和545 nm绿光发射增强.Tb3+掺杂硅酸盐玻璃中,Tb3+之间存在能量转移,产生自敏化效应,这种转移是由Tb3+之间电偶极-电四极的相互作用引起的共振能量转移.Gd3+通过Gd3+-Tb3+间的能量转移对Tb3+的发光起敏化作用,这种能量转移主要是偶极与偶极相互作用引起的共振转移.     

Hydrothermal formation and up‐conversion luminescence of Er3+‐doped GdNbO4

The effect of concentration of Er³⁺ on the up‐conversion and photoluminescence properties of Gd_1.00?xEr_xNbO₄, x=0‐0.50 which has monoclinic fergusonite‐type structure as a main phase has been investigated, using a processing technique based on hydrothermal method. Under weakly basic hydrothermal condition at 240°C for 5 hours, a single phase of fergusonite‐type Gd_1.00?xEr_xNbO₄ solid solution was directly formed as nanocrystals by the substitutional incorporation of Er³⁺ into GdNbO₄ because of the gradual and linear decrease in the lattice parameters of the monoclinic phase corresponding to the Vegard's Law. The gadolinium niobate doped with 2 mol% Er³⁺, Gd_0.98Er_0.02NbO₄ after heating at 1300°C for 1 hour, which has nanocrystalline structure whose crystallite size is around 29 nm, exhibits the highest photoluminescence intensity in the green spectral region, 515‐560 nm under excitation at wavelength of 254 nm. On the other hand, the up‐converted luminescence intensity of the niobate nanocrystals becomes the maximum at the concentration of 20 mol% Er³⁺, Gd_0.80Er_0.20NbO₄ under excitation at 980 nm. These results demonstrate that the material, Er³⁺‐doped GdNbO₄ nanocrystals prepared through hydrothermal route and postheating has potential for up‐converting phosphor.     

Nd3＋、Er3＋、Gd3＋和La3＋对超氧化物歧化酶活性的影响

通过研究Nd3＋、Er3＋、Gd3＋和La3＋稀土离子对枯草芽孢杆菌在生长过程中所产的超氧化物歧化酶活性的影响,来探讨稀土可能会导致生物体发生氧化损伤。利用改良的邻苯三酚自氧化法测定超氧化物歧化酶活性。结果表明：4种稀土离子对其细胞中超氧化物歧化酶活性均有抑制作用,且Nd3＋的抑制作用较其它3种稀土离子要强,故一定浓度的稀土离子很有可能会导致生物体发生氧化损伤。4种稀土离子的浓度不同影响有所不同,总的来说,稀土离子的浓度越大,对枯草杆菌抗氧化的抑制作用越明显,损伤毒性作用越强。     

Light‐induced electrons suppressed by Eu3+ ions doped in Ca11.94−xSrxAl14O33 caged phosphors for LED and FEDs

Control of light‐induced electron generation is of vital importance for the application of caged phosphors. For Eu‐doped Ca_11.94?xSr_xAl₁₄O₃₃ caged phosphors, the suppressed effect of strontium doping on the light‐induced electrons is observed compared to the europium‐free Ca_11.94?xSr_xAl₁₄O₃₃ phosphors. In the presence of europium ions, Sr doping will promote the reduction of Eu³⁺ to Eu²⁺. The Rietveld refinement suggests that unit cell volumes of the Ca_11.94?xSr_xAl₁₄O₃₃:Eu_0.06 samples are expanded when Ca²⁺ ions are replaced by Sr²⁺ ions. The absorption and FTIR transmittance spectra confirm that the competitive reaction of encaged O^2? anions with H₂ is suppressed. For the sample (x=0.48), the higher thermal activation energy (~0.40 eV) for luminescence quenching can be attributed to the more rigid framework structure after Sr doping. For Ca_11.94?xSr_xAl₁₄O₃₃:Eu_0.06 phosphors, their emission colours are tuned from red to purple upon 254 nm excitation and from pink to blue under electron beam excitation through Sr substitution. The insight gained from this work may have a significant guiding to design new phosphors for LED and FEDs and novel nanocaged mutifunctional materials.     

A novel dazzling Eu3+‐doped whitlockite‐type phosphate red‐emitting phosphor for white light‐emitting diodes

A series of novel red‐emitting Ca₈ZnLa_1?xEu_x(PO₄)₇ phosphors were successfully synthesized using the high‐temperature solid‐state reaction method. The crystal structure, photoluminescence spectra, thermal stability, and quantum efficiency of the phosphors were investigated as a function of Eu³⁺ concentration. Detailed analysis of their structural properties revealed that all the phosphors could be assigned as whitlockite‐type β‐Ca₃(PO₄)₂ structures. Both the PL emission spectra and decay curves suggest that emission intensity is largely dependent on Eu³⁺ concentration, with no quenching as the Eu³⁺ concentration approaches 100%. A dominant red emission band centered at 611 nm indicates that Eu³⁺ occupies a low symmetry sites within the Ca₈ZnLa(PO₄)₇ host lattice, which was confirm by Judd‐Ofelt theory. Ca₈ZnLa_1?xEu_x(PO₄)₇ phosphors exhibited good color coordinates (0.6516, 0.3480), high color purity (~96.3%), and high quantum efficiency (~78%). Temperature‐dependent emission spectra showed that the phosphors possessed good thermal stability. A white light‐emitting diode (LED) device were fabricated by integrating a mixture of obtained phosphors, commercial green‐emitting and blue‐emitting phosphors into a near‐ultraviolet LED chip. The fabricated white LED device emits glaring white light with high color rendering index (83.9) and proper correlated color temperature (5570 K). These results demonstrate that the Ca₈ZnLa_1?xEu_x(PO₄)₇ phosphors are a promising candidate for solid‐state lighting.     

Green luminescence system containing a Tb3+‐β‐diketonate complex doped in the epoxy resin as sensitizer

Photoluminescent properties of the terbium tris(acetylacetonate)tetrahydrated [Tb(acac)₃(H₂O)₄], doped in the epoxy resin, in the solid state are reported. The polymeric Tb³⁺ system and the precursor terbium complex were characterized by elemental analysis, thermogravimetry, differential scanning calorimetry, and infrared and electronic spectroscopy. The excitation and emission spectra of the samples containing the Tb³⁺ complex doped diglycidyl epoxy resin were recorded at 298 and 77 K and exhibited the characteristic bands arising from the ⁵D₄ → ⁷F_J transitions (J = 6–0). The system shows an increase in the luminescence intensity with the increase in the Tb³⁺ complex in the 1, 5, and 10% concentrations due to the energy transfer from the polymer to the rare earth ion. On the other hand, the concentration quenching of luminescence of polymer doped with 15% of the Tb³⁺ complex was observed. The lifetime measurements (τ = 0.81, 0.80, 0.79, and 0.78 ms) decrease with the increase of Tb³⁺‐complex concentration (1, 5, 10, and 15%) doped in polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 865–870, 2004     

Synthesis and luminescent properties of Sr4−xSi3O8Cl4: xEu3+ red phosphor by hydrothermal method

Sr_4‐xSi₃O₈Cl₄:xEu³⁺ (SSOC:Eu³⁺) phosphors were successfully synthesized by hydrothermal method. The crystallization of this phosphor was analyzed by means of X‐ray diffraction patterns. The size and morphology were recorded using SEM patterns of samples. And the PLE and PL spectra were characterized by a PL spectrophotometer. Excited by 394 nm UV light, the intense red emission is recognized in SSOC:Eu³⁺ phosphor and the main emission peak located at 620 nm. The influences of Eu³⁺ concentration, pH value of reaction solution, and charge compensator on PL spectra of SSOC:Eu³⁺ phosphors were investigated. The results revealed that this red phosphor had potential applications for white LEDs.     

Synthesis,structural characterization,and photoluminescence properties of Eu3+‐doped Mg3‐xEux(BO3)2 phosphor

Eu³⁺‐doped Mg_3‐xEu_x(BO₃)₂ (x = 0.000, 0.005, 0.010, 0.020, 0.050, and 0.100) phosphors were synthesized for the first time by solution combustion synthesis method, which is a fast synthesis method for obtaining nano‐sized borate powders. The optimization of the synthesis conditions of phosphor materials was performed by TG/DTA method. These phosphors were characterized by XRD, FTIR, SEM‐EDX, and photoluminescence, PL analysis. The XRD analysis exhibited that all of the prepared ceramic compounds have been crystallized in orthorhombic structure with space group Pnnm. Also, the influence of europium dopant ions on unit cell parameters of host material was analyzed using Jana2006 program and the crystalline size was determined by Debye‐Scherrer's formula. The luminescence properties of all Eu³⁺‐doped samples were investigated by excitation and emission spectra. The excitation spectra of Mg_3‐xEu_x(BO₃)₂ phosphors show characteristic peak at 420 nm in addition to other characteristic peaks of Eu³⁺ under emission at 613 nm. The emission spectra of Eu³⁺‐doped samples indicated most intensive red emission band dominated at 630 nm belonging to ⁵D₀→⁷F₂ magnetic dipole transition. Furthermore, the optimum or quenching concentration of Eu³⁺ ion has been determined as x = 0.010 showed the maximum emission intensity when it was excited at 394 nm.     

Ligand‐field splitting of the energy levels of Nd3+ (4f3) in 2‐hydroxyethyl methacrylate polymer (HEMA)

Detailed absorption spectra of trivalent neodymium (Nd³⁺) in 2‐hydroxyethyl methacrylate polymer (HEMA) are reported at cryogenic temperatures and at wavelengths between 440 and 900 nm. The Nd³⁺ spectra are confirmed by comparison with spectra of HEMA samples prepared without inclusion of the rare earth ion. The structure observed on the absorption bands can be interpreted in terms of the ligand‐field (crystal‐field) splitting of the energy levels of Nd³⁺ (4f³) for multiplet manifolds, ⁴F_3/2, ⁴F_5/2, ²H_9/2, ⁴F_7/2, ⁴S_3/2, ⁴F_9/2, ²H_11/2, ⁴G_5/2, ²G_7/2, ⁴G_7/2, and ²K_13/2. The Nd³⁺ ions are complexed as species made up of nitrate anions and H₂O molecules that come from the neodymium nitrate hydrate salt used in the preparation of the doped HEMA sample. The local symmetry of the Nd³⁺ ion in HEMA is very low (possibly C_S), and a number of different environments are likely for the neodymium species in the HEMA structure. We have calculated the ligand‐field splitting of the Nd³⁺ energy levels using a point charge/dipole model for one such possible species, Nd(NO₃)₃ · xH₂O^? (x = 5–6). The results of the model give an agreement of 10 cm^?1 (rms) between 43 observed‐to‐calculated ligand‐field (Stark) levels. Comparisons between these same calculated levels and observed levels obtained for Nd³⁺ in crystalline hydrated nitrate salts and certain Nd³⁺‐doped glasses also give good agreement and support a better understanding of the environment of Nd³⁺ in a polymeric structure. Copyright © 2006 Society of Chemical Industry     

Some features of thermophysical properties of γ‐Gd2S3 ceramics based on real structure

The heat capacity C_p, thermal diffusivity χ_T, and lattice thermal conductivity κ_latt of ceramic solid solutions of sesquisulfides Gd_3‐xV_Gd,xS₄ (0 < x < 0.33) in the temperature range 300‐700 K has been studied. Changing the real structure, namely the concentrations of vacancies (N_V) and deformation (N_Dc) centers of polycrystals, significantly decreases κ_latt. A deviation of composition from the stoichiometry 2:3 is accompanied by an increase in the specific area of the crystallite boundaries per unit volume, and, hence, the concentration of deformation centers D_C increases. This observation was confirmed by examining the short‐range order disturbance of the lattice and symmetry environment of the Gd³⁺ and S^2? environment by Raman spectroscopy and the magnetic susceptibility Faraday method. Therefore the thermal diffusivity of gadolinium sesquisulfide is reduced because of the mean free path of phonons decrease. As a result, the thermal conductivity of the polycrystalline samples is reduced by 10%.     

Erbium(III)‐doped polyurethaneureas: Novel broadband ultraviolet‐to‐visible converters

Novel, polymeric UV‐to‐visible converters were prepared by doping elastomeric poly(ether‐urethaneurea) copolymers with 5–25% by weight of ErCl₃ 6H₂O, corresponding to Er³⁺ concentrations of 2.19 to 10.86% by weight. When excited in the UV at 355 nm, the doped films generated a very broad, continuous visible luminescence between 400 and 750 nm. Preparation and spectroscopic characterization of the samples are discussed in detail. The color coordinates, color temperature, color rendering index of the samples, and the degree of overlap of their emission bands with the spectral response of the eye were determined. The color rendering index of samples is in the 57–70 range. The sample containing 2.19% by weight of Er³⁺ was found to give the color coordinates closest to the white‐source region and the highest color rendering index. The color temperatures of the samples were in the 5093–5540 K range. Overlap between the emission bands and the spectral response of the eye improved with increasing erbium concentration. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dy3+‐Doped Selenide Chalcogenide Glasses: Influence of Dy3+ Dopant‐Additive and Containment

This work reports on process‐induced impurities in rare‐earth ion: Dy³⁺‐doped selenide chalcogenide glasses, which are significant materials for active photonic devices in the mid‐infrared region. In particular, the effect of contamination from the silica glass ampoule containment used in chalcogenide glass synthesis is studied. Heat‐treating Dy‐foil‐only, and DyCl₃‐only, separately, within evacuated silica glass ampoules gives direct evidence of silica ampoule corrosion by the rare‐earth additives. The presence of [Ga₂Se₃] associated with [Dy] on the silica glass ampoule that has been contact with the chalcogenide glass during glass melting, is reported for the first time. Studies of 0–3000 ppmw Dy³⁺‐doped Ge_16.5As₉Ga₁₀Se_64.5 glasses show that Dy‐foil is better than DyCl₃ as the Dy³⁺ additive in Ge‐As‐Ga‐Se glass in aspects of avoiding bulk crystallization, improving glass surface quality and lowering optical loss. However, some limited Dy/Si/O related contamination is observed on the surfaces of Dy‐foil‐doped chalcogenide glasses, as found for DyCl₃‐doped chalcogenide glasses, reported in our previous work. The surface contamination indicates the production of Dy₂O₃ and/or [≡Si‐O‐Dy=]‐containing particles during chalcogenide glass melting, which are potential light‐scattering centers in chalcogenide bulk glass and heterogeneous nucleation agents for α‐Ga₂Se₃ crystals.