Facile synthesis of β-NaYF4:Ln3+ (Ln = Eu, Tb, Yb/Er, Yb/Tm) microcrystals with down- and up-conversion luminescence

β-NaYF₄:Ln³⁺ (Ln = Eu, Tb, Yb/Er, Yb/Tm) hexagonal microrods have been successfully synthesized through a facile molten salt method without any surfactant. X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy, high-resolution transmission electron microscopy, and photoluminescence spectra were used to characterize the samples. It is found that at a preferred reaction temperature of 400 °C, the structure of β-NaYF₄ can gradually transform from microtubes to microrods as reaction time extends from 0.5 to 4 h. Furthermore, as the molar ratio of NaF:RE³⁺ (RE represents the total amount of Y³⁺ and the doped rare earth elements such as Eu³⁺, Tb³⁺, Yb³⁺/Er³⁺, or Yb³⁺/Tm³⁺) increased, the phase of sample transforms from YF₃ into NaYF₄. Under the excitation of 395 nm ultraviolet light, β-NaYF₄:5 %Eu³⁺ shows the emission lines of Eu³⁺ corresponding to ⁵D_0-3 → ⁷F _J (J = 1–4) transitions from 400 to 700 nm, resulting in red down-conversion (DC) light emission. When doped with 5 % Tb³⁺ ions, the strong DC fluorescence corresponding to ⁵D₄ → ⁷F _J (J = 6, 5, 4, 3) transitions with ⁵D₄ → ⁷F _J (green emission at 544 nm) being the most prominent group that has been observed. Moreover, upon 980 nm laser diode excitation, the Yb³⁺/Er³⁺- and Yb³⁺,Tm³⁺- co-doped β-NaYF₄ samples exhibit bright yellow and blue upconversion (UC) luminescence, respectively, by two- or three-photon UC process. The luminescence mechanisms for the doped lanthanide ions were thoroughly analyzed.     

Synthesis and luminescence properties of Yb3+–Er3+ co-doped LaOCl nanostructures

LaOCl:Yb³⁺, Er³⁺ nanofibers and hollow nanofibers were prepared by electrospinning combined with a double-crucible chlorination technique using NH₄Cl as chlorinating agent. X-ray powder diffraction analysis indicated that LaOCl:Yb³⁺, Er³⁺ nanostructures were tetragonal with space group P4/nmm. Scanning electron microscope analysis and histograms revealed that diameters of LaOCl:Yb³⁺, Er³⁺ nanofibers and hollow nanofibers, respectively, were 117.87 ± 15.48 and 141.09 ± 17.10 nm under the 95 % confidence level. Up-conversion (UC) emission spectra analysis manifested that LaOCl:Yb³⁺, Er³⁺ nanostructures exhibited strong green and red UC emission centering at 526, 548, and 671 nm, respectively, attributed to ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2, and ⁴F_9/2 → ⁴I_l5/2 transitions of Er³⁺ ions under the excitation of a 980-nm diode laser. It was found that the relative intensities of green and red emissions vary obviously with the addition of Yb³⁺ ions, and the optimized molar ratio of Yb³⁺ to Er³⁺ was 10:1 in the as-prepared nanofibers. Moreover, the near-infrared characteristic emissions of LaOCl:Yb³⁺, Er³⁺ nanostructures were achieved under the excitation of a 532-nm laser. CIE analysis demonstrated that color-tuned luminescence can be obtained by changing doping concentration of Yb³⁺ (and/or Er³⁺) ions and morphologies of nanomaterials, which could be applied in the fields of optical telecommunication and optoelectronic devices. The UC luminescent mechanism and the formation mechanisms of LaOCl:Yb³⁺, Er³⁺ nanofibers and hollow nanofibers were also proposed.     

Synthesis and properties of LnBaFeCoO5 + δ (Ln = Nd, Sm, Gd)

LnBaFeCoO_{5 + δ} (Ln = Nd, Sm, Gd) layered oxides have been synthesized and their crystal structure, thermal stability, thermal expansion, electrical conductivity, thermoelectric power, and magnetic susceptibility have been studied. The oxides have a tetragonal structure (sp. gr. P4/mmm) with unit-cell parameters a = 0.3909(2) nm and c = 0.7695(6) nm for Ln = Nd (δ = 0.65), a = 0.3908(3) nm and c = 0.7662(6) nm for Ln = Sm (δ = 0.37), and a = 0.3908(2) nm and c = 0.7613(6) nm for Ln = Gd (δ = 0.37). The LnBaFeCoO_{5 + δ} compounds are antiferromagnetic p-type semiconductors. With decreasing Ln³⁺ ionic radius, their electrical conductivity and linear thermal expansion coefficient decrease and their thermoelectric power and antiferromagnetic ordering temperature increase. Near 518–653 K, the linear thermal expansion coefficient of the LnBaFeCoO_{5 + δ} oxides increases from (12.9–16.6) × 10^?6 to (19.3–26.5) × 10^?6 K^?1, which is due to the release of weakly bound oxygen from the oxides. We have determined parameters of charge transport in the [Fe(Co)O₂] layers in the crystal structure of the LnBaFeCoO_{5 + δ} phases.     

Sol–gel auto-combustion synthesis of PVP/CoFe2O4 nanocomposite and its magnetic characterization

Poly(vinyl pyrrolidone)/CoFe₂O₄ nanocomposite has been fabricated by a sol–gel auto-combustion method. Poly(vinyl pyrrolidone) was used as a reducing agent as well as a surface capping agent to prevent particle aggregation and stabilize the particles. The average crystallite size estimated from X-ray line profile fitting was found to be 20 ± 7 nm. The high field irreversibility and unsaturated magnetization behaviours indicate the presence of the core–shell structure in the sample. The exchange bias effect observed at 10 K suggests the existence of the magnetically aligned core surrounded by spin-disordered surface layer. The reduced remanent magnetization value of 0.6 at 10 K (higher than the theoretical value of 0.5) shows the PVP/CoFe₂O₄ nanocomposite to have cubic magnetocrystalline anisotropy according to the Stoner–Wohlfarth model.     

Structural,dielectric and electrical properties of Sol–gel auto-combustion technic of CuFeCr0.5Ni0.5O4 ferrite

Journal of Materials Science - The CuFeCr0.5Ni0.5O4 (CFO) compound was synthesized using sol–gel reaction combustion technic. The structural analysis showed that the obtained composites have...     

Synthesis and luminescence properties of Yb3+–Er3+ co-doped LaOCl nanobelts via electrospinning combined with chlorination technique

LaOCl:Yb³⁺, Er³⁺ nanobelts were prepared by electrospinning combined with a double-crucible chlorination technique using NH₄Cl as chlorinating agent. X-ray powder diffraction analysis indicated that LaOCl:Yb³⁺, Er³⁺ nanobelts were tetragonal with space group P4/nmm. Scanning electron microscope analysis and histograms revealed that width of LaOCl:Yb³⁺, Er³⁺ nanobelts was 6.12 ± 0.18 μm under the 95% confidence level, and the thickness was 113 nm. Transmission electron microscope observation showed that as-obtained LaOCl:Yb³⁺, Er³⁺ nanobelts were composed of nanoparticles. LaOCl:Yb³⁺, Er³⁺ nanobelts emitted strong green and red up-conversion emission centring at 523, 551 and 667 nm, respectively, attributed to ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_l5/2 transitions of Er³⁺ under the excitation of a 980-nm diode laser (DL) excitation. Moreover, the near-infrared characteristic emission of LaOCl:Yb³⁺, Er³⁺ nanobelts was achieved under the excitation of a 532-nm laser. Commission Internationale de L'Eclairage analysis demonstrated that colour-tuned luminescence can be obtained by changing doping concentration of Yb³⁺ and Er³⁺, which could be applied in the fields of optical telecommunication and optoelectronic devices. The up-conversion luminescent mechanism and the formation mechanism of LaOCl:Yb³⁺, Er³⁺ nanobelts were also proposed.     

Sol–gel combustion synthesis of nanocrystalline LaMnO<Subscript>3</Subscript> powders and photocatalystic properties

A novel LaMnO₃ photocatalyst with perovskite structure was prepared by sol–gel combustion method. The combustion reaction mechanisms of nanocrystalline LaMnO₃ powders were investigated by thermal analysis, infrared spectra, and X-ray diffraction technique. The results showed that the gels exhibited self-propagating behavior after ignition in air. Nanocrystalline LaMnO₃ powders can be synthesized in one step by using sol–gel combustion synthesis. The photocatalytic activity of the LaMnO₃ powders were evaluated by degradation of methyl orange (MO) in water under UV light irradiation. The results showed that the LaMnO₃ powders exhibit good photocatalytic activities under UV light irradiation. The degradation percentage after 36 h on LaMnO₃ powders was about 76%.     

Visible luminescence properties of Er3+–Pr3+ codoped fluorotellurite glasses

Er³⁺ and Pr³⁺ codoped fluorotellurite glasses has been synthesized. The PL spectrum revealed that the intensity of Er³⁺ characteristic emission was enhanced as Pr³⁺ concentration increased. Due to small mismatch between the energy level of Er³⁺: ⁴F_7/2 and Pr³⁺: ³P₀ resonant energy was possibly transferred between them. While Pr³⁺ concentration kept increasing, both Pr³⁺ and Er³⁺ concentration quenching occurred. These glasses with the controllable CIE coordinates might be a potential candidate for the widely application such as solid state multicolor display.     

Preparation and luminescence properties of glass–ceramics containing Sm3+-doped hexagonal NaGdF4 crystals

Rare earth-doped hexagonal NaGdF₄ nanocrystals were precipitated from a glass. The glass with the mol% composition 70.1SiO₂·4.3Al₂O₃·1.8AlF₃·2.3Na₂O·18.5NaF·3.0Gd₂O₃ doped with 8 × 10¹⁹ Sm³⁺ ions per cm³ was already phase separated after casting. The formed droplets enriched in rare earths and fluoride had sizes in the range mainly from 50 to 90 nm. During annealing at temperatures ≥600 °C, multi core particles of hexagonal NaGdF₄ were formed inside the amorphous droplet phase. The fluorescence spectra show that Sm³⁺ is incorporated into the NaGdF₄ lattice. This is confirmed by electron dispersive X-ray analyzes performed in a transmission electron microscope.     

Au-modified silicon nanowires for surface-enhanced fluorescence of Ln3+ (Ln = Pr, Nd, Ho, and Er)

The interaction of the surface plasmons of gold nanoparticles on silicon nanowires with fluorophores, lanthanide ions (praseodymium ions, Pr³⁺, neodymium ions Nd³⁺, holmium ions Ho³⁺, and erbium ions Er³⁺) was investigated. In the presence of Au/Si nanomaterials, the fluorescence peaks were significantly enhanced, which resulted in about 2 orders of magnitude enhancement. The photoluminescence studies revealed that the enhanced fluorescence originates from the local field enhancement around Ln³⁺ ions, caused by the electronic plasmons resonance of the gold nanoparticles. Results showed that this Au/Si nanostructure had larger enhancement factor than that caused by unsupported Au nanoparticles. These results might be explained by the local field overlap originated from the closed and fixed gold nanoparticles on silicon nanowires.     

Controllable synthesis and luminescence of YPO<Subscript>4</Subscript>:Ln<Superscript>3+</Superscript> (Ln = Eu and Sm) nanotubes

YPO₄:Ln³⁺ (Ln = Eu and Sm) nanotubes were synthesized by a precipitation process in the presence of SDS. The XRD results showed that all samples have a xenotime type tetragonal structure, indicating that doped rare earth ions have no influence on the phase. The SEM and TEM images showed that all samples are nanotubes. On basis of the morphology of samples and the properties of SDS, the possible formation mechanism was speculated. YPO₄:Eu³⁺ and YPO₄:Sm³⁺ nanotubes showed characteristic emission bands of Eu³⁺ and Sm³⁺ ions, respectively. For YPO₄:Eu³⁺/Sm³⁺ nanotubes, the codoping Sm³⁺ ions can enhance the emission intensity of Eu³⁺ ions.     

Emission (Gd3+ and Sm3+) and ESR (Gd3+) studies of La1−xLnxB3O6 (Ln = Gd,Sm; 0 ≤ x ≤ 0.2 for Gd; 0 ≤ x ≤ 0.1 for Sm) phosphors

Polycrystalline powders of rare-earth doped La_1?xGd_xB₃O₆ (0?≤?x?≤?0.2) and La_1?xSm_xB₃O₆ (0.0?≤?x?≤?0.1) phosphors were successfully prepared by a B₂O₃ flux method. All the phosphor samples are well characterized by powder X-ray diffraction (XRD), infrared (IR), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) methods and fluorescence lifetime of Sm³⁺ ion. The XRD patterns show that La_1?xM_xB₃O₆ (M?=?Gd and Sm) adopt monoclinic with the I2/a space group. The SEM–EDS results confirmed the doping of Gd and Sm into LaB₃O₆ lattice. The IR and Raman spectra of these solid solutions gave distinctive bands corresponding to planar BO₃ and tetrahedral BO₄ groups. The photoluminescence (PL) spectra of La_1?xGd_xB₃O₆ gave a strong emission band, ⁶P_J?→?⁸S_7/2, at 310 nm. The PL spectra of La_1?xSm_xB₃O₆ phosphor showed orange-red emission at 598 nm when excited using light of wavelength of 402 nm. The results were obtained by the transition ⁴G_5/2?→?⁶H_7/2 of Sm³⁺ ions. The influence of dopant concentration on the emission profiles was studied. The ESR spectra of La_1?xGd_xB₃O₆ (x?=?0.02) gave a typical U-spectrum and spin-Hamiltonian parameters are deduced.

     

Sol–gel synthesis of long-lasting phosphors CdSiO3: Mn2+, RE3+ (RE = Tb,Eu, Nd) and luminescence mechanism research

Mn²⁺ and RE³⁺ (RE = Tb, Eu, Nd) co-doped CdSiO₃ orange phosphors were prepared at 1050 °C by a sol–gel method. The phase and crystallinity of the synthesized materials were investigated by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The luminescence characteristics were analyzed using photoluminescence (PL) spectra, afterglow decay curves, long-lasting phosphorescence spectra, and thermoluminescence (TL) spectra. Due to the difference in co-doped rare earth ionic radii, it varied greatly in trap density and trap depth caused by the different defects deriving from RE³⁺ ions co-doping into the CdSiO₃: Mn²⁺ host. The afterglow intensity and time for these samples increased as follows: CdSiO₃: Mn²⁺0.2%, Nd³⁺0.8% < CdSiO₃: Mn²⁺0.4%, Tb³⁺0.8% < CdSiO₃: Mn²⁺0.4%, Eu³⁺0.3%. CdSiO₃: Mn²⁺0.4%, Eu³⁺0.3% had the best afterglow properties, which could be due to the proper traps formed by Eu³⁺ ions co-doping into the host. The role of RE³⁺ co-doped into the CdSiO₃: Mn²⁺ matrix and the possible long-lasting phosphorescence process was also discussed in this paper.