Structure and cation distribution in perovskites with small cations at the A site: the case of ScCoO3

Abstract

We synthesize ScCoO₃ perovskite and its solid solutions, ScCo_1?xFe_xO₃ and ScCo_1?xCr_xO₃, under high pressure (6 GPa) and high temperature (1570 K) conditions. We find noticeable shifts from the stoichiometric compositions, expressed as (Sc_1?xM_x)MO₃ with x = 0.05–0.11 and M = Co, (Co, Fe) and (Co, Cr). The crystal structure of (Sc_0.95Co_0.05)CoO₃ is refined using synchrotron x-ray powder diffraction data: space group Pnma (No. 62), Z = 4 and lattice parameters a = 5.26766(1) Å, b = 7.14027(2) Å and c = 4.92231(1) Å. (Sc_0.95Co_0.05)CoO₃ crystallizes in the GdFeO₃-type structure similar to other members of the perovskite cobaltite family, ACoO₃ (A³⁺ = Y and Pr-Lu). There is evidence that (Sc_0.95Co_0.05)CoO₃ has non-magnetic low-spin Co³⁺ ions at the B site and paramagnetic high-spin Co³⁺ ions at the A site. In the iron-doped samples (Sc_1?xM_x)MO₃ with M = (Co, Fe), Fe³⁺ ions have a strong preference to occupy the A site of such perovskites at small doping levels.     

Magnetic properties of solid solutions between BiCrO3 and BiGaO3 with perovskite structures

Magnetic properties of BiCr_1−xGa_xO₃ perovskite-type solid solutions are reported, and a magnetic phase diagram is established. As-synthesized BiCrO₃ and BiCr_0.9Ga_0.1O₃ crystallize in a monoclinic (m) C2/c structure. The Néel temperature (T_N) decreases from 111 K in BiCrO₃ to 98 K in BiCr_0.9Ga_0.1O₃, and spin-reorientation transition temperature increases from 72 K in BiCrO₃ to 83 K in BiCr_0.9Ga_0.1O₃. o-BiCr_0.9Ga_0.1O₃ with a PbZrO₃-type orthorhombic structure is obtained by heating m-BiCr_0.9Ga_0.1O₃ up to 573 K in air; it shows similar magnetic properties with those of m-BiCr_0.9Ga_0.1O₃. T_N of BiCr_0.8Ga_0.2O₃ is 81 K, and T_N of BiCr_0.7Ga_0.3O₃ is 63 K. Samples with x = 0.4, 0.5, 0.6 and 0.7 crystallize in a polar R3c structure. Long-range antiferromagnetic order with weak ferromagnetism is observed below T_N = 56 K in BiCr_0.6Ga_0.4O₃, T_N = 36 K in BiCr_0.5Ga_0.5O₃ and T_N = 18 K in BiCr_0.4Ga_0.6O₃. BiCr_0.3Ga_0.7O₃ shows a paramagnetic behaviour because the Cr concentration is below the percolation threshold of 31%.     

Comparison of the homogeneous and the heterogenizing homogeneous Co3+ catalyst in the synthesis of organic peroxides

Abstract

Comparison of the homogeneous and heterogenizing homogeneous cobalt ion catalyst in the synthesis of organic peroxides was studied. The heterogenizing or immobilizing homogeneous cobalt ion catalyst was prepared by ion exchange of the cobalt ion on a polymer support. Acetaldehyde was used as the model compound for the comparison of the homogeneous and the heterogenizing homogeneous catalyst. The results indicate that both the selectivity and yield of peracetic acid by using the heterogenizing homogeneous catalyst is higher than that of using a homogeneous catalyst. The comparison of the reaction mechanism as well as the kinetics of using these two types of catalysts were also obtained.     

White light emission of Dy3+-doped and Dy3+:Yb3+-codoped oxyfluoride glass ceramics under 388-nm excitation

Dy³⁺-doped and Dy³⁺:Yb³⁺-codoped oxyfluoride glass ceramics have been prepared by high-temperature solid phase sintering method. The micrographs of scanning electron microscope show that a lot of nanorods are formed on the surface of Dy³⁺:Yb³⁺-codoped sample. The excitation spectra and emission spectra are measured, respectively, and intense photoluminescence peaks at 482 and 575 nm corresponding to the transitions of Dy³⁺ ions are found in single-doped samples under 388-nm excitation. For Dy³⁺:Yb³⁺-codoped oxyfluoride glass ceramics, the intensities at blue and green bands become weaker whereas the intensity at 695 nm gets stronger. The indirect sensitization is detailedly discussed and Commission Internationale de l′E-clairage chromaticity coordinates exhibit that two kinds of oxyfluoride glass ceramics are available candidates for the solid-state white light emission.     

Er~(3+)/Yb~(3+)/Tb~(3+)共掺氟氧锗酸盐玻璃上转化发光性质及机理研究(英文)

在980nm激发下,研究了Er3+、Yb3+和Tb3+单掺或共掺氟氧锗酸盐玻璃的上转换发光性质和机理.室温下,观察到了强的绿色和红色上转换发光,其发光中心位于524、546和658nm处,分别对应于Tb3+离子的5D4→7FJ(J=5和0)和Er3+离子的(2H11/2、4S3/2和4F9/2)→4I15/2跃迁.研究了TbF3、YbF3掺杂浓度以及激光功率对上转换发光强度的影响,讨论了Er3+、Yb3+和Tb3+之间的能量传递和上转换机理.     

Magnetic properties of solid solutions between BiCrO3 and BiGaO3 with perovskite structures

Abstract

Magnetic properties of BiCr_1?xGa_xO₃ perovskite-type solid solutions are reported, and a magnetic phase diagram is established. As-synthesized BiCrO₃ and BiCr_0.9Ga_0.1O₃ crystallize in a monoclinic (m) C2/c structure. The Néel temperature (T_N) decreases from 111 K in BiCrO₃ to 98 K in BiCr_0.9Ga_0.1O₃, and spin-reorientation transition temperature increases from 72 K in BiCrO₃ to 83 K in BiCr_0.9Ga_0.1O₃. o-BiCr_0.9Ga_0.1O₃ with a PbZrO₃-type orthorhombic structure is obtained by heating m-BiCr_0.9Ga_0.1O₃ up to 573 K in air; it shows similar magnetic properties with those of m-BiCr_0.9Ga_0.1O₃. T_N of BiCr_0.8Ga_0.2O₃ is 81 K, and T_N of BiCr_0.7Ga_0.3O₃ is 63 K. Samples with x = 0.4, 0.5, 0.6 and 0.7 crystallize in a polar R3c structure. Long-range antiferromagnetic order with weak ferromagnetism is observed below T_N = 56 K in BiCr_0.6Ga_0.4O₃, T_N = 36 K in BiCr_0.5Ga_0.5O₃ and T_N = 18 K in BiCr_0.4Ga_0.6O₃. BiCr_0.3Ga_0.7O₃ shows a paramagnetic behaviour because the Cr concentration is below the percolation threshold of 31%.     

Photoluminescence and doping mechanism of theranostic Eu3+/Fe3+ dual-doped hydroxyapatite nanoparticles

Theranostic nanoparticles currently have been regarded as an emerging concept of ‘personalized medicine’ with diagnostic and therapeutic dual-functions. Eu³⁺ doped hydroxyapatite (HAp) has been regarded as a promising fluorescent probe for in vivo imaging applications. Additionally, substitution of Ca²⁺ with Fe³⁺ in HAp crystal may endow the capability of producing heat upon exposure to a magnetic field. Here we report a preliminary study of doping mechanism and photoluminescence of Eu³⁺ and Fe³⁺ doped HAp nanoparticles (Eu/Fe:HAp). HAp with varied concentration of Eu³⁺ and Fe³⁺ doping are presented as Eu(10 mol%):HAp, Eu(7 mol%)-Fe(3 mol%):HAp, Eu(5 mol%)-Fe(5 mol%):HAp, Eu(3 mol%)-Fe(7 mol%):HAp, and Fe(10 mol%):HAp in the study. The results showed that the HAp particles, in nano-size with rod-like morphology, were successfully doped with Eu³⁺ and Fe³⁺, and the particles can be well suspended in cell culture medium. Photoluminescence analysis revealed that particles have prominent emissions at 536 nm, 590 nm, 615 nm, 650 nm and 695 nm upon excitation at a wavelength of 397 nm. Moreover, these Eu/Fe:HAp nanoparticles belonged to B-type carbonated HAp, which has been considered an effective biodegradable and biocompatible drug/gene carrier in biological applications.     

Luminescence behavior of Dy ions in lead borate glasses

Dy-doped lead borate glasses were studied. The luminescence spectra showed two characteristic bands at 480 and 573 nm due to ⁴F_9/2–⁶H_15/2 (blue) and ⁴F_9/2–⁶H_13/2 (yellow) transitions of Dy³⁺. The yellow/blue luminescence of trivalent dysprosium was analyzed as a function of the B₂O₃/PbO ratios, the activator (Dy³⁺) and the PbX₂ (X = F, Cl, Br) content.     

Significant reduction of upconversion emission in CaTiO3: Yb, Er inverse opals

Inverse opal photonic crystals of Yb³⁺, Er³⁺ co-doped CaTiO₃ (CaTiO₃: Yb, Er) were prepared using self-assembled polystyrene templates combined with the infiltration of sol-gel precursor. The influence of the photonic band gap on upconversion emission of Er³⁺ has been investigated in the CaTiO₃: Yb, Er inverse opals. Significant reduction of the upconversion emission was detected if the photonic band-gap overlaps with the Er³⁺ ions emission band.     

Local thermal effect at luminescent spot on upconversion luminescence in Y2O3:Er,Yb nanoparticles

Y₂O₃:Er³⁺,Yb³⁺ nanoparticles were synthesized using Pechini type sol-gel method and then characterized by XRD, TEM, SEM, Raman spectroscopy, and fluorescence spectrophotometer. Local temperature effect on upconversion luminescence intensities was theoretically analyzed and experimentally tested. These results indicate that a competition process between local temperature at luminescent spot and laser pump power density decides the development trend of upconversion luminescence intensity. Therefore, it can be concluded that the most intensive upconversion luminescence in Y₂O₃:Er³⁺,Yb³⁺ nanoparticles can be achieved at a certain pump power density, which should be slightly below a given constant value (the corresponding threshold of temperature).     

Infrared-to-visible conversion luminescence of Er ions in lead borate transparent glass-ceramics

Transparent glass-ceramics were successfully prepared during controlled heat treatment of lead borate glasses. The PbF₂ particles were dispersed into a borate glass matrix which was evidenced by X-ray diffraction analysis. The phase identification revealed that crystalline peaks can be related to the orthorhombic PbF₂ phase. Green up-conversion luminescence due to the ⁴S_3/2–⁴I_15/2 transition of Er³⁺ ions was registered. In comparison to the precursor glass the luminescence intensity was considerably higher, whereas the luminescence linewidth slightly decreased in the studied oxyfluoride transparent glass-ceramics. It indicated that a part of the trivalent erbium was incorporated into the PbF₂ crystalline phase.     

Photoluminescence properties of Y2O3:Tb and YBO3:Tb green phosphors synthesized by hydrothermal method

In this work, two Tb³⁺ activated green phosphors: Y₂O₃:Tb³⁺ and YBO₃:Tb³⁺ were prepared by hydrothermal method. Photoluminescence properties of both phosphors were studied in details. Both phosphors exhibit similar luminescent characteristics symbolized by the dominant green emission at 545 nm. Concentration quenching occurs at the Tb³⁺ concentration of 1.60 atomic% and 2.57 atomic% for Y₂O₃:Tb³⁺ and YBO₃:Tb³⁺, respectively. Luminescence decay properties were characterized to better understand the mechanism of concentration quenching. Based on the calculation, the concentration quenching in both phosphors was caused by the dipole–dipole interaction between Tb³⁺ ions.     

Temperature dependence of luminescence behavior in Er/Yb co-doped transparent phosphate glass ceramics

The effect of temperature on the luminescence intensity of up-conversion and near infrared in Er³⁺/Yb³⁺ co-doped phosphate glass ceramics has been investigated. Efficient green and red up-conversion luminescence and strong infrared fluorescence at 1.54 μm wavelength are observed under excitation of 975 nm. The fluorescence intensity is changing at different temperature and the results are explained with the level transitions in Er³⁺/Yb³⁺ co-doped system. Meanwhile, the lifetime of Er³⁺:⁴I_13/2 level corresponding to different operating temperature and pump power is also discussed, and the experimental results are fitted using multiphonon relaxation theory.     

White light generation in Al2O3:Ce:Tb:Mn films deposited by ultrasonic spray pyrolysis

Aluminium oxide (Al₂O₃) films doped with CeCl₃, TbCl₃ and MnCl₂ were deposited at 300 °C with the ultrasonic spray pyrolysis technique. The films were analysed using the X-ray diffraction technique and they exhibited a very broad band without any indication of crystallinity, typical of amorphous materials. Sensitization of Tb³⁺ and Mn²⁺ ions by Ce³⁺ ions gives rise to blue, green and red simultaneous emission when the film activated by such ions is excited with UV radiation. The overall efficiency of such energy transfer results to be about 85% upon excitation at 312 nm. Energy transfer from Ce³⁺ to Tb³⁺ ions through an electric dipole-quadrupole interaction mechanism appears to be more probable than the electric dipole-dipole one. A strong white light emission for the Al₂O₃:Ce³⁺(1.3 at.%):Tb³⁺(0.2 at.%):Mn²⁺(0.3 at.%) film under UV excitation is observed. The high efficiency of energy transfer from Ce³⁺ to Tb³⁺ and Mn²⁺ ions, resulting in cold white light emission (x = 0.30 and y = 0.32 chromaticity coordinates) makes the Ce³⁺, Tb³⁺ and Mn²⁺ triply doped Al₂O₃ film an interesting material for the design of efficient UV pumped phosphors for white light generation.     

Novel blue-emitting phosphor NaMg4(PO4)3:Eu, Ce with energy transfer

A blue-emitting phosphor of NaMg₄(PO₄)₃:Eu²⁺, Ce³⁺ was prepared by a combustion-assisted synthesis method. The phase formation was confirmed by X-ray powder diffraction measurement. Photoluminescence excitation spectrum measurements show that the phosphor can be excited by near UV light from 230 to 400 nm and presents a dominant luminescence band centered at 424 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions at room temperature. Effective energy transfer occurs in Ce³⁺/Eu²⁺ co-doped NaMg₄(PO₄)₃ due to large spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺, and Ce³⁺ plays a role as a sensitizer. Ce³⁺-Eu²⁺ co-doped NaMg₄(PO₄)₃ powders can possibly be applied as blue phosphors in the fields of lighting and display.     

Enhanced G4 emission in NaLaF4: Pr, Yb and charge transfer in NaLaF4: Ce, Yb studied by fourier transform luminescence spectroscopy

A high resolution luminescence study of NaLaF₄: 1%Pr³⁺, 5%Yb³⁺ and NaLaF₄: 1%Ce³⁺, 5%Yb³⁺ in the UV to NIR spectral range using a InGaAs detector and a fourier transform interferometer is reported. Although the Pr³⁺(³P₀ → ¹G₄), Yb³⁺(²F_7/2 → ²F_5/2) energy transfer step takes place, significant Pr³⁺¹G₄ emission around 993, 1330 and 1850 nm is observed. No experimental proof for the second energy transfer step in the down-conversion process between Pr³⁺ and Yb³⁺ can be given. In the case of NaLaF₄: Ce³⁺, Yb³⁺ it is concluded that the observed Yb³⁺ emission upon Ce³⁺ 5d excitation is the result of a charge transfer process instead of down-conversion.     

A red-emitting heavy doped phosphor Li6Y(BO3)3:Eu for white light-emitting diodes

A series of Eu³⁺ activated Li₆Y_1−xEu_x(BO₃)₃ (0.05 ? x ? 1) phosphors were synthesized by solid-state reaction method. The structures and photoluminescent properties of the phosphors were investigated at room temperature. The results of XRD patterns indicate that these phosphors are isotypic to the monoclinic Li₆Gd(BO₃)₃. The excitation spectra indicate that these phosphors can be effectively excited by near UV (370-410 nm) light. The red emission from transition ⁵D₀→⁷F₂ is dominant. The emission spectra exhibit strong red performance (CIE chromaticity coordinates: x = 0.65, y = 0.35), which is due to the ⁵D₀−⁷F_J transitions of Eu³⁺ ions. The relationship between the structure and the photoluminescent properties of the phosphors was studied. The concentration quenching occurs at x ≈ 0.85 under near UV excitation. Li₆Y(BO₃)₃:Eu³⁺ has potential application as a phosphor for white light-emitting diodes.     

Ce3+掺杂钛酸钡纳米管薄膜的制备与性能

以阳极氧化制备的TiO_2纳米管薄膜为模版,通过水热法制备了Ba_(1-x)Ce_xTiO_3(0≤x≤0.08)纳米管薄膜,研究了Ba_(1-x)Ce_xTiO_3的结构、表面形貌及其电性能。采用X射线衍射仪表征其晶体结构,采用扫描电子显微镜和透射电子显微镜观察其表面及断口形貌,采用宽频介电阻抗谱仪测试其介电性能。结果表明,在较为温和的条件下用水热法成功制备出立方相结构的Ba_(1-x)Ce_xTiO_3纳米管薄膜,纳米管孔径在80~95nm之间;将制备的Ba_(1-x)Ce_xTiO_3经退火后生成多晶的Ba1-xCexTiO3纳米管薄膜,且样品的管外径尺寸在90~100nm之间,管壁的厚度为25~30nm,介电常数在1kHz下最高可达472,介电损耗为0.41。     

Structural and optical properties of Er implanted AlN thin films: Green and infrared photoluminescence at room temperature

In this work erbium ions were implanted into AlN films grown on sapphire with fluence range: (0.5-2) × 10¹⁵ at/cm⁻², ion energy range: 150-350 keV and tilt angle: 0°, 10°, 20°, 30°. The optical and structural properties of the films are studied by means of photoluminescence and Raman spectroscopy in combination with Rutherford backscattering/channeling (RBS/C) measurements. The photoluminescence spectra of the Er³⁺ were recorded in the visible and infrared region between 9 and 300 K after thermal annealing treatments of the samples. The emission spectrum of the AlN:Er films consists of two series of green lines centered at 538 and 558 nm with typical Er³⁺ emission in the infrared at 1.54 μm. The green lines have been identified as Er³⁺ transitions from the ²H_11/2 and ⁴S_3/2 levels to the ⁴I_15/2 ground state. Different erbium centers in the matrix are suggested by the change of infrared photoluminescence relative intensity of some of the emission lines when different excitation wavelengths are used. The relative abundances of these centers can be varied by using different implantation parameters. The Raman and RBS/C measurements show good crystalline quality for all the studied films.     

Efficient Bi → Nd energy transfer in Gd2O3:Bi,Nd

Bi³⁺,Nd³⁺ co-doped Gd₂O₃ were prepared by solid state reaction and the optical properties were investigated. The results show that the near-infrared emission of Nd³⁺ ions is significantly enhanced by the introducing of Bi³⁺ in co-doped samples. An efficient energy transfer from Bi³⁺ to Nd³⁺ corresponds to the near-infrared emission enhancement. The energy transfer efficiency reaches 64.1% for the sample with the strongest near-infrared emission, which has the optimized doping concentrations of 0.5% for Bi³⁺ and 2% for Nd³⁺. The interesting optical properties make Bi³⁺,Nd³⁺ co-doped Gd₂O₃ promising as the luminescent down-conversion layers in front of c-Si solar cells to enhance the performance of the solar cells.