Preparation and up‐conversion luminescence properties of LaOBr:Yb3+/Er3+ nanofibers via electrospinning

LaOBr:Yb³⁺/Er³⁺ nanofibers were synthesized for the first time by calcinating electrospun PVP/[La(NO₃)₃ + Er(NO₃)₃ + Yb(NO₃)₃ + NH₄Br] composites. The morphology and properties of the final products were investigated in detail using scanning electron microscopy (SEM), energy dispersion spectroscopy (EDS), X‐ray diffractometry (XRD) and fluorescence spectroscopy. The results indicate that LaOBr:Yb³⁺/Er³⁺ nanofibers are tetragonal in structure with a space group of P4/nmm. The diameter of LaOBr:Yb³⁺/Er³⁺ nanofibers is ~ 147 nm. Under the excitation of a 980‐nm diode laser, LaOBr:Yb³⁺/Er³⁺ nanofibers emit strong green and red up‐conversion emission centering at 519, 541 and 667 nm, ascribed to the ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴ F_9/2 → ⁴I_15/2 energy‐level transitions of Er³⁺ ions, respectively. The up‐conversion luminescent mechanism of LaOBr:Yb³⁺/Er³⁺ nanofibers is advanced. Moreover, near‐infrared emission of LaOBr:Yb³⁺/Er³⁺ nanofibers is obtained under the excitation of a 532‐nm laser. The formation mechanism of LaOBr:Yb³⁺/Er³⁺ nanofibers is proposed. LaOBr:Yb³⁺/Er³⁺ nanofibers could be important up‐conversion luminescent materials. Copyright © 2014 John Wiley & Sons, Ltd.     

Pure red upconverted and near-infrared luminescence properties of Er3+-doped SnO2 nanocrystals for lighting applications

Tin oxide (SnO₂) nanocrystalline powders doped with erbium ion (Er³⁺) in different molar ratios (0, 3, 5, and 7 mol%) were prepared using a solid-state reaction technique. These samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-visible absorption, visible upconversion, and near-infrared luminescence techniques. XRD analysis revealed the tetragonal rutile structure of SnO₂ and the average crystallite size was about 32 nm. From Tauc's plots, it was confirmed that the substitution of Er³⁺ ions into the SnO₂ host lattice resulted in the narrowing its band gap. Optical absorption bands at 520 and 654 nm correspond to the 4f electron transitions of Er³⁺ further confirming visible light absorption. Infrared luminescence spectra showed a broad band centred at 1536 nm which is assigned to the ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺. Visible upconverted emission spectra under 980 nm excitation exhibit a strong red luminescence with a main peak at 672 nm which is attributed to the ⁴F_9/2 → ⁴I_15/2 transition of Er³⁺. Power-dependent upconversion spectra confirmed that two photons participated in the upconversion mechanism. Enhancement in the intensities of both visible and infrared luminescence was observed when raising the concentration. The results pave the way for the potential applications of these nanocrystalline powders in energy harvesting applications such as infrared light upconverting layer in solar cells, light emitting diodes, infrared broadband sources and amplifiers, and biological labelling.     

Infrared and visible emissions of rare‐earth‐doped CeO2 phosphor

This paper reports the synthesis and characterization of Er³⁺‐doped CeO₂ phosphor with variable concentrations of erbium. The sample was synthesized using a solid‐state reaction method, which is useful for the large‐scale production of phosphors and is also eco‐friendly. The prepared sample was characterized using an X‐ray diffraction (XRD) technique. The XRD pattern confirmed that sample has the pure cubic fluorite crystal structure of CeO₂. The crystallite size of the prepared phosphor was determined by Scherer's formula and the crystallite size giving an intense XRD peak is 40.06 nm. The surface morphology of the phosphor was determined by field emission gun scanning electron microscopy (FEGSEM). From the FEGSEM image, good surface morphology with some agglomerates was found. The functional group in the prepared sample was analysed by Fourier transform infrared (FTIR) spectroscopy. All samples prepared with variable concentrations of Er³⁺ (0.1–2 mol%) were studied by photoluminescence analysis and it was found that the excitation spectra of the prepared phosphor shows broad excitation centred at 251 nm. Emission spectra at different concentrations of Er³⁺ show strong peaks at 413 and 470 nm and a weaker peak at 594 nm. The dominant peaks at 413 and 470 nm are caused by the allowed electronic transition ⁴S_3/2 → ⁴I_15/2 and the weaker transition at 594 nm is due to the transition ⁴ F_9/2 → ⁴I_15/2. Spectrophotometric determinations of peaks were evaluated using the Commission Internationale de I'Eclairage (CIE) technique. The emission spectra were also observed using an infrared (IR) laser 980 nm source, and three distinct peaks were found in the IR region at 848, 870 and 980 nm. The prepared phosphor has utility for application in display devices. Copyright © 2015 John Wiley & Sons, Ltd.     

Down-conversion luminescence and temperature sensing characteristics of LaSrGaO4:Er3+

Erbium(III) ion (Er³⁺) has abundant energy levels that can emit light covering a quite broad wavelength range in many hosts. Here we synthesized LaSrGaO₄:Er³⁺ phosphors by a high-temperature solid-state method. Upon excitation at the ultraviolet (UV) band, LaSrGaO₄:Er³⁺ phosphors could emit green, red and near-infrared emission simultaneously. The temperature dependent emission characteristics of the as-prepared samples was then studied and two kinds of luminescent ratiometric thermometry were constructed. The first one is on the basis of two green emission bands that stems from the ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions of Er³⁺. The intensity ratio between these two emission bands was found to follow well with the Boltzmann distribution, and its maximum relative sensitivity was calculated to be 0.84% K⁻¹ at 299 K. The other one depends on the ⁴F_9/2 → ⁴I_15/2 transition of Er³⁺ and self-luminescence of the host LaSrGaO₄, considering that these two emission lines have different temperature response. The relative sensitivity of this type of luminescence intensity ratio (LIR) thermometry could reach 1.86% K⁻¹ at 299 K, we have successfully developed materials with one of the largest relative sensitivities to date, which provides some basis for the subsequent development of a new type of non-contact temperature sensor.     

Erbium(III) ion-doped borate-based glasses for 1.53 μm broad band applications

Novel erbium(III) ion-doped borate-based glasses (Er³⁺:BCNF) by conventional melt-quenching technique were designed and synthesized. The glasses were characterized for their structural, vibrational and spectroscopic properties. The nephelauxetic ratio, bonding parameters, and Judd–Ofelt (JO) intensity parameters (Ω_λ λ = 2, 4 and 6) were determined by using absorption spectrum of 1 mol% Er₂O₃ doped glass. These JO parameters were utilized to derive radiative properties for various excited states of erbium(III) ions. Emission cross-section for ⁴I_13/2 → ⁴I_15/2 transition of erbium(III) ions was computed through McCumber theory. The decay curves for (²H_11/2, ⁴S_3/2) and ⁴I_13/2 levels were recorded and analysed. All the results of Er³⁺:BCNF glasses revealed that the studied glasses are efficient and thermally stable and could be suitable for display devices, optical amplification and green laser applications.     

Optical analysis of RE3+ (RE = Nd or Er):B2O3–P2O5–CaF2–ZnO–(Li2O/Na2O/K2O) glasses

Calcium boro fluoro zinc phosphate glasses modified using alkali oxide and doped with Nd³⁺ and Er³⁺ ions with the chemical composition of 69.5 (B₂O₃) + 10 (P₂O₅) + 10 (CaF₂) + 5 (ZnO) + 5 (Na₂O/Li₂O/K₂O) + 0.5 (Er₂O₃/Nd₂O₃) were prepared using a conventional melt quenching technique. The results of X-ray diffraction patterns indicated the amorphous nature of all the prepared glasses. The visible–near-infrared red (NIR) absorption spectra of these glasses were analyzed systematically. The NIR emission spectra of Er³⁺ and Nd³⁺:calcium boro fluoro zinc phosphate glasses showed prominent emission bands at 1536 nm (⁴I_13/2→⁴I_15/2) and 1069 nm (⁴F_3/2→⁴I_11/2) respectively with λ_exci = 514.5 nm (Ar⁺ laser) as the excitation source.     

Plasmonic Coupling in Er3+:Au Tellurite Glass

In this paper, we report on luminescence and absorbance effects of Er⁺³:Au-doped tellurite glasses synthesized by a melting-quenching and heat treatment technique. After annealing times of 2.5, 5.0, 7.5, and 10.0 h, at 300 °C, the gold nanoparticles (GNP) effects on the Er⁺³ are verified from luminescence spectra and the corresponding levels lifetime. The localized surface plasmon resonance around 800 nm produced a maximum fluorescence enhancement for the band ranging from 800 to 840 nm, corresponding to the transitions ⁴H_11/2 → ⁴I_13/2 (805 nm) and ⁴S_3/2 → ⁴I_13/2 (840 nm), with annealing time till 7.5 h. The measured lifetime of the levels ⁴H_11/2 and ⁴S_3/2 confirmed the lifetime reduction due to the energy transfer from the GNP to Er⁺³, causing an enhanced photon emission rate in these levels.     

Thermal Characterization,Crystal Field Analysis and In-Band Pumped Laser Performance of Er Doped NaY(WO4)2 Disordered Laser Crystals

Undoped and Er-doped NaY(WO₄)₂ disordered single crystals have been grown by the Czochralski technique. The specific heat and thermal conductivity (κ) of these crystals have been characterized from T = 4 K to 700 K and 360 K, respectively. It is shown that κ exhibits anisotropy characteristic of single crystals as well as a κ(T) behavior observed in glasses, with a saturation mean free phonon path of 3.6 Å and 4.5 Å for propagation along a and c crystal axes, respectively. The relative energy positions and irreducible representations of Stark Er³⁺ levels up to ⁴G_7/2 multiplet have been determined by the combination of experimental low (<10 K) temperature optical absorption and photoluminescence measurements and simulations with a single-electron Hamiltonian including both free-ion and crystal field interactions. Absorption, emission and gain cross sections of the ⁴I_13/2↔⁴I_15/2 laser related transition have been determined at 77 K. The ⁴I_13/2 Er³⁺ lifetime (τ) was measured in the temperature range of 77–300 K, and was found to change from τ (77K) ≈ 4.5 ms to τ (300K) ≈ 3.5 ms. Laser operation is demonstrated at 77 K and 300 K by resonantly pumping the ⁴I_13/2 multiplet at λ≈1500 nm with a broadband (FWHM≈20 nm) diode laser source perfectly matching the 77 K crystal ⁴I_15/2 → ⁴I_13/2 absorption profile. At 77 K as much as 5.5 W of output power were obtained in π-polarized configuration with a slope efficiency versus absorbed pump power of 57%, the free running laser wavelength in air was λ≈1611 nm with the laser output bandwidth of 3.5 nm. The laser emission was tunable over 30.7 nm, from 1590.7 nm to 1621.4 nm, for the same π-polarized configuration.     

Synthesis of NaYF(4):Yb/Er/Gd up-conversion luminescent nanoparticles and luminescence resonance energy transfer-based protein detection

High-quality NaYF₄:Yb/Er/Gd up-conversion nanoparticles (UCNPs) were first synthesized by a solvothermal method using rare earth stearate, sodium fluoride, ethanol, water, and oleic acid as precursors. Doped Gd³⁺ ions can promote the transition of NaYF₄ from cubic to hexagonal phase, shorten the reaction time, and reduce the reaction temperature without reducing the luminescence intensity of NaYF₄:Yb/Er UCNPs. X-ray diffraction, infrared spectroscopy, transmission electron microscopy, and luminescence spectroscopy were applied to characterize the UCNPs. The nanoparticles exhibited small size and excellent green up-conversion photoluminescence, making them suitable for biological applications. After the surfaces of NaYF₄:Yb/Er/Gd UCNPs were modified with amino groups through the Stöber method, they could be brought close enough to the analytically important protein called R-phycoerythrin (R-PE) bearing multiple carboxyl groups so that energy transfer could occur. A luminescence resonance energy transfer (LRET) system was developed using NaYF₄:Yb/Er/Gd UCNPs as an energy donor and R-PE as an energy acceptor. As a result, a detection limit of R-PE of 0.5 μg/ml was achieved by the LRET system with a relative standard deviation of 2.0%. Although this approach was first used successfully to detect R-PE, it can also be extended to the detection of other biological molecules.     

Optical analysis of RE3+ (RE = Pr3+, Er3+ and Nd3+):cadmium lead boro tellurite glasses

This article reports on the optical characterization of Pr³⁺‐, Er³⁺‐ and Nd³⁺‐doped cadmium lead boro tellurite (CLBT) glasses prepared using the melt quenching method. The visible–near infrared (Vis–NIR) absorption spectra of these glasses were analyzed systematically. On measuring the NIR emission spectra of Er³⁺:CLBT glasses, a broad emission band centered at 1536 nm (⁴I_13/2 → ⁴I_15/2) was observed, as were three NIR emission bands at 900 nm (⁴F_3/2 → ⁴I_9/2), 1069 nm (⁴F_3/2 → ⁴I_11/2) and 1338 nm (⁴F_3/2 → ⁴I_13/2) from Nd³⁺:CLBT glasses and an NIR emission band at 1334 nm (¹G₄ → ³H₅) from Pr³⁺:CLBT glasses at an excitation wavelength (λ_ex) of 514.5 nm (Ar⁺ laser). Copyright © 2016 John Wiley & Sons, Ltd.     

Effect of Bi3+ addition on the upconversion luminescence properties of NaYbF4:Er

In this study, Bi³⁺ incorporation in NaYbF₄:Er lattice and its influence on upconversion luminescence properties have been investigated in detail using techniques such as temperature‐dependent luminescence, Fourier transform infrared spectroscopy and X‐ray diffraction (XRD). The study was carried out to develop phosphors with improved upconversion luminescence. From photoluminescence and lifetime measurements it is inferred that luminescence intensity from NaYbF₄:Er increases with Bi³⁺ addition. The sample containing 50 at.% Bi³⁺ ions exhibited optimum upconversion luminescence. Increased distance between Yb³⁺–Yb³⁺ and Er³⁺–Er³⁺ due to Bi³⁺ incorporation into the lattice and associated decrease in the extent of dipolar interaction/self‐quenching are responsible for increase in lifetime values and luminescence intensities from Er³⁺ ions. Incorporation of Bi³⁺ into NaYbF₄:Er lattice reduced self‐quenching among Yb³⁺–Yb³⁺ions and this facilitated energy transfer from Yb³⁺ to Er³⁺. This situation also explains decrease in the extent of temperature‐assisted quenching of emission from thermally coupled ²H_11/2 and ⁴S_3/2 levels of Er³⁺. Based on Rietveld refinement of XRD patterns it was confirmed that a maximum of 10 at.% of Bi³⁺added was incorporated into the NaYbF₄:Er lattice and the remaining complex co‐exists as a BiOF phase. These results are of significant interest in the area of development of phosphors based on Yb³⁺–Er³⁺ upconversion luminescence.     

Structural,morphological, and photoluminescence properties of RE (RE = Dy3+, Eu3+, Sm3+)-doped CaAlBO4 phosphor synthesized by combustion method

The CaAlBO₄:RE (RE = Dy³⁺, Eu³⁺, Sm³⁺) phosphor were prepared via combustion synthesis and studied by X-ray diffraction (XRD), Fourier-transform infrared (FTIR) analysis, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), photoluminescence (PL) spectra and CIE coordinates. The phase formation of the obtained phosphor was analyzed by XRD and the result was confirmed by standard PDF Card No. 1539083. XRD data successfully indicated pure phase of CaAlBO₄ phosphor. The crystal structure of CaAlBO₄ phosphor is orthorhombic with space group Ccc2 (37). The SEM image of CaAlBO₄ phosphor reveals an agglomerated morphology and non-uniform particle size. The EDS image provides evidence of the elements present and the chemical makeup of the materials. Under the 350 nm excitation, the emission spectrum of Dy³⁺ activated CaAlBO₄ phosphor consists of two main groups of characteristic peaks located at 484 and 577 nm which are ascribed to ⁴F_9/2 → ⁶H_15/2 and ⁴F_9/2 → ⁶H_13/2 transition of Dy³⁺ respectively. The PL emission spectra of CaAlBO₄:Eu³⁺ phosphor shows characteristics bands observed around 591 and 613 nm, which corresponds to ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂ transition of Eu³⁺ respectively, upon 395 nm excitation wavelength. The emission spectra of Sm³⁺ activated CaAlBO₄ phosphor shows three characteristic bands observed at 565, 601 and 648 nm which emits yellow, orange and red color. The prominent emission peak at the wavelength 601 nm, which is attributed to ⁴G_5/2 → ⁶H_7/2 transition, displays an orange emission. The CIE color coordinates of CaAlBO₄:RE (RE = Dy³⁺, Eu³⁺, Sm³⁺) phosphor are calculated to be (0.631, 0.368), (0.674, 0.325) and (0.073, 0.185). As per the obtained results, CaAlBO₄:RE (RE = Dy³⁺, Eu³⁺, Sm³⁺) phosphor may be applicable in eco-friendly lightning technology.     

Photoluminescence properties of aeschynite‐type LaNbTiO6:RE3+ (RE = Tb,Dy, Ho) down‐converting phosphors

In this study, a series of LaNbTiO₆:RE³⁺ (RE = Tb, Dy, Ho) down‐converting phosphors were synthesized using a modified sol–gel combustion method, and their photoluminescence (PL) properties were investigated as a function of activator concentration and annealing temperature. The resultant particles were characterized using X‐ray diffraction, transmission electron microscopy, scanning electron microscopy, UV/Vis diffuse reflectance spectroscopy and PL spectra. The highly crystalline LaNbTiO₆:RE³⁺ (RE = Tb, Dy, Ho) phosphors with an average size of 200–300 nm obtained at 1100°C have an orthorhombic aeschynite‐type structure and exhibit the highest luminescent intensity in our study range. The emission spectra of LaNbTiO₆:RE³⁺ (RE = Tb, Dy, Ho) phosphors under excitations at UV/blue sources are mainly composed of characteristic peaks arising from the f–f transitions of RE³⁺, including 489 nm (⁵D₄ → ⁷F₆) and 545 nm (⁵D₄ → ⁷F₅) for Tb³⁺, 476 and 482 nm (⁴F_9/2 → ⁶H_15/2) and 571 nm (⁴F_9/2 → ⁶H_13/2) for Dy³⁺, and 545 nm (⁵F₄ + ⁵S₂ → ⁵I₈) for Ho³⁺, respectively. The luminescent mechanisms were further investigated. It can be expected that these phosphors are of intense interest and potential importance for many optical applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Magnetic nanobead-based immunoassay for the simultaneous detection of aflatoxin B1 and ochratoxin A using upconversion nanoparticles as multicolor labels

A novel and sensitive immunoassay for the simultaneous detection of aflatoxin B₁ (AFB₁) and ochratoxin A (OTA) in food samples was developed by using artificial antigen-modified magnetic nanoparticles (MNPs) as immunosensing probes and antibody functionalized upconversion nanoparticles (UCNPs) as signal probes. NaY_0.78F₄:Yb_0.2, Tm_0.02 and NaY_0.28F₄:Yb_0.7,Er_0.02 UCNPs were prepared and functionalized, respectively, with immobilized monoclonal anti-AFB₁ antibodies and anti-OTA antibodies as signal probes. Based on a competitive immunoassay format, the detection limit for both AFB₁ and OTA under optimal conditions was as low as 0.01 ng mL⁻¹, and the effective detection range was from 0.01 to 10 ng mL⁻¹. The proposed method was successfully applied to measure AFB₁ and OTA in naturally contaminated maize samples and compared to a commercially available ELISA method. The high sensitivity and selectivity of this method is due to the magnetic separation and concentration effect of the MNPs, the high sensitivity of the UCNPs, and the different emission lines of Yb/Tm and Yb/Er doped NaYF₄ UCNPs excited by 980 nm laser. Multicolor UCNPs have the potential to be used in other applications for detecting toxins in the field of food safety and other fields.     

Solution studies of lanthanide (III) complexes based on 1,1,1,5,5,5-hexafluoro-2,4-pentanedione and 1,10-phenanthroline Part-I: Synthesis, H NMR, 4f-4f absorption and photoluminescence

Solution studies on the complexes of the type [Ln(hfaa)₃(phen)₂] (Ln = La, Pr and Nd) and [Ln(hfaa)₃phen] (Ln = Nd, Ho, Er and Yb; hfaa stands for the anion of 1,1,1,5,5,5-hexafluoro-2,4-pentanedione and phen stands for 1,10-phenanthroline) are presented. These complexes are synthesized in high yields by an in situ method in which hfaa, ammonium hydroxide, lanthanide chlorides and phen were allowed to react in 3:3:1:1 molar ratio in ethanol. In the case of neodymium both eight- and ten-coordinate complexes are isolated. The paramagnetic shifts of the methine protons of β-diketone have their sign opposed to those of paramagnetic shifts of phen protons and the shifts are dominated by dipolar interactions. The inter- and intramolecular shift ratios have been calculated and discussed. The 4f-4f absorption spectra of the complexes of Pr, Nd, Ho and Er are analyzed. The eight- and ten-coordinate neodymium complexes display distinctively different band shapes of the ⁴G_5/2,²G_7/2 ← ⁴I_9/2 hypersensitive transition. The efficient energy transfer from ligand to Pr(III) is reflected by strong red luminescence of this complex at room temperature.     

Influence of Er3+ concentration on the photoluminescence characteristics and excitation mechanism of Gd2O3:Er3+ phosphor synthesized via a solid‐state reaction method

An Er³⁺‐doped phosphor of Gd₂O₃ (Gd₂O₃:Er³⁺) was prepared using a conventional solid‐state reaction method. The structure and particle size were determined from X‐ray powder diffraction measurements. The average particle size of the phosphor was in between 20 and 50 nm. The particle size and structure of the phosphor were further confirmed by transmission electron microscopy (TEM) analysis. Luminescence spectra were recorded under excitation wavelengths of 275, 380, 515 and 980 nm. The visible upconversion and downconversion luminescence spectra of the Gd₂O₃:Er³⁺ phosphor were investigated as a function of Er³⁺ ion concentration. The upconverted emission at 980 nm excitation shows enhanced red emission with respect to green emission as the dopant concentration increased. Similar results were observed for downconversion emission under 275 and 380 nm excitation wavelengths. The mechanisms responsible for populating the ⁴S_3/2 and ⁴ F_9/2 levels, for green and red emissions, respectively, are different for different excitations and for different concentrations of Er³⁺. Copyright © 2014 John Wiley & Sons, Ltd.     

Heterobinuclear Zn‐Ln (Ln = La,Nd, Eu,Gd, Tb,Er and Yb) complexes based on asymmetric Schiff‐base ligand: synthesis,characterization and photophysical properties

With a novel asymmetric Schiff‐base zinc complex ZnL (H₂L = N‐(3‐methoxysalicylidene)‐N′‐(5‐bromo‐3‐methoxysalicylidene)phenylene‐1,2‐diamine), obtained from phenylene‐1,2‐diamine, 3‐methoxysalicylaldehyde and 5‐bromo‐3‐methoxysalicylaldehyde, as the precursor, a series of heterobinuclear Zn‐Ln complexes [ZnLnL(NO₃)₃(CH₃CN)] (Ln = La, 1; Ln = Nd, 2; Ln = Eu, 3; Ln = Gd, 4; Ln = Tb, 5; Ln = Er, 6; Ln = Yb, 7) were synthesized by the further reaction with Ln(NO₃)₃·6H₂O, and characterized by Fourier transform‐infrared, fast atom bombardment mass spectroscopy and elemental analysis. Photophysical studies of these complexes show that the strong and characteristic near‐infrared luminescence of Nd³⁺, Yb³⁺and Er³⁺ with emissive lifetimes in the microsecond range has been sensitized from the excited state of the asymmetric Schiff‐base ligand due to effective intramolecular energy transfer; the other complexes do not show characteristic emission due to the energy gap between the chromophore and lanthanide ions. Copyright © 2012 John Wiley & Sons, Ltd.     

Assembly and upconversion luminescence of lanthanide-organic frameworks with mixed acid ligands

Three new lanthanide coordination polymers based on mixed acid ligands [Ln(oba)(ox)_0.5(H₂O)₂]_n (Ln = Y (1); Er (2); Yb (3). H₂oba = 4,4′-oxybis (benzoic acid); H₂ox = oxalic acid) were prepared by hydrothermal reactions and characterized by single-crystal X-ray diffraction. In these complexes, lanthanide ions are bridged by oba ligands to form 1D double-stranded chains, which are further connected by ox ligands, resulting in the formation of 2D (4,4) grids. The upconversion emission of the Y:Er-Yb co-doped coordination polymer was studied and the unusual blue emission for the Er(III) complexes was observed, which arises from the ²H_9/2 → ⁴I_15/2 transition and can be explained by three-photon excitation mechanism which is mostly phonon-dependent. The introduction of the oxalate anion without high-energy vibrational groups is beneficial to the increasing intensity of upconversion fluorescence. The magnetic properties of complexes 2 and 3 were investigated. The decrease of χ_MT over the temperature range of 300-2 K and the negative value of θ are due primarily to the splitting of the ligand field of the Er^III and Yb^III ions together with the possible weak antiferromagnetic coupling between the rare earth ions.     

Optical properties of CaAl(SO4)2Br:RE (RE = Dy,Eu, Ce) novel phosphors

A new phosphor CaAl(SO₄)₂Br doped with Dy, Ce and Eu is reported. Rare earth (Dy, Eu and Ce)‐doped polycrystalline CaAl(SO₄)₂Br phosphors were prepared using a wet chemical reaction method and studied for X‐ray diffraction and photoluminescence (PL) characteristics. Dy³⁺ emission in the CaAl(SO₄)₂Br lattice was observed at 484 and 574 nm in the blue and yellow regions of the spectrum, which are assigned to ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transitions of the Dy³⁺ ion, respectively. While the PL emission spectra of CaAl(SO₄)₂Br:Ce phosphor showed Ce³⁺ emission at 347 nm due to 5d → 4f transition of the Ce³⁺ ion. In a CaAl(SO₄)₂Br:Eu lattice, Eu³⁺ emissions were observed at 593 and 617 nm, coming from the ⁵D₀ → ⁷ F₁ and ⁵D₀ → ⁷ F₂ electron transitions, respectively. The PL study showed that the intensity of electric dipole transition at 617 nm dominates over that of magnetic dipole transition at 590 nm. The maximum PL intensity was obtained for a 1 mol% concentration of Eu³⁺ in CaAl(SO₄)₂Br host lattice. The results showed that the material may be a promising candidate as a blue‐, yellow‐ and red‐emitting phosphor. Copyright © 2013 John Wiley & Sons, Ltd.