Novel phosphors of Eu^3＋, Tb^3＋ or Tm^3＋ activated LaBGeO5

Rare earth borogermanates as a group of stable compounds provided various potential properties important for modern sciences. Among the properties of interests, luminescence was manifested due to the variability of rare earth elements and the compounds constituted an important group of potential candidate. In this work, novel phosphors of Eu³⁺, Tb³⁺ or Tm³⁺ doped LaBGeO₅ with the stillwellite type structure were synthesized by the solid state reaction method. Their X-ray and UV excitation luminescent properties showed that LaBGeO₅ was an excellent host lattice for the luminescence of Eu³⁺, Tb³⁺ and Tm³⁺. The LaBGeO₅:Eu³⁺, LaBGeO₅:Tb³⁺ and LaBGeO₅:Tm³⁺ presented bright red, green and blue emission light for both UV and X-ray excitation.     

Energy transfer from Ce~(3+) to Tb~(3+) and Eu~(3+) in zinc phosphate glasses

Ce3+,Eu3+ and Tb3+ singly doped and Ce3+/Eu3+ and Ce3+/Tb3+ co-doped zinc phosphate glasses were prepared by sintering P2O5,ZnO,Ce2(C2O4)3·10H2O and Eu2O3/Tb4O7 mixtures at 1200 °C in the air for 2 h and then annealing at 450 °C for 10 h.The obtained glasses were homogeneous and transparent.The glasses without Ce3+ were colorless and those with Ce3+ showed slightly yellow.The singly doped glasses showed strong emissions and excitations from doped trivalent rare earth ions.Strong energy transfer from Ce3+ to Tb3+ was observed for Ce3+/Tb3+ coped samples.There were also some very weak evidences for the energy transfer from Ce3+ to Eu3+.     

Photoluminescence of SrGdGa_3O_7∶RE (RE=Ce~(3 ), Pr~(3 ), Tb~(3 )) under VUV-UV Excitation

SrGdGa3 O7belongstothelargefamilieswhosegeneralchemicalformulaisAMM′3 O7(A =Ca ,Sr ,Ba ;M =La ,Gd ,Y ;M′ =Al,Ga) .Thesecom poundshavemelilitestructure .Structuralinvestiga tionsindicatethatSrGdGa3 O7formstetragonalcrystalswithspacegroupP 4 2 1m .Theunit…     

Luminescence characteristics of Ca_4YO(BO_3)_3 doped with Bi~(3+),Dy~(3+) and Pr~(3+) ions

The photoluminescence(PL) properties of Ca4YO(BO3)3 doped with Bi3+,Dy3+,and Pr3+ ions were investigated.These compounds were prepared using a typical solid-state reaction.The excitation and emission spectra were measured using a spectrofluorometer.For Ca4YO(BO3)3:Bi3+,the excitation spectrum showed the bands at about 228,309,and 370 nm which correspond to the 1S0→1P1 transition and the 1S0→3P1 transition of Bi3+ ions.The emission band at 390 nm corresponded to the 3P1→1S0 transition of Bi3+ ions.For Ca4YO(BO3)3:Bi3+,Dy3+,energy transfer occurred from Bi3+ to Dy3+ somewhat.In Ca4YO(BO3)3:Bi3+,Dy3+,Pr3+,the excitation band at 367 nm was enhanced obviously due to the energy migration from Bi3+ to Pr3+,which converted efficiently the emission of semiconductor InGaN based light-emitting diode(LED).Therefore,the emission of Dy3+ ions was enhanced due to the energy migration from the process of Bi3+→Pr3+→Dy3+.It resulted in the good color rendering.     

Luminescence properties of Tm^3＋/Yb^3＋, Er^3＋/Yb^3＋ and Ho^3＋/Yb^3＋ activated calcium tungstate

CaWO4 phosphor activated by the Tm3+/Yb3+,Er3+/Yb3+ and Ho3+/Yb3+ ions were synthesized by a traditional high-temperature solid-state method.The crystal structures and morphologies of the products were characterized by X-ray powders diffraction method(XRD) ,infrared spectra(FT-IR) and scanning electron microscopy(SEM) .The samples were found to show up-conversion luminescence properties.CaWO4 doped with Tm3+/Yb3+ showed blue luminescence characteristic of Tm(III) ion in the range of 460-485 nm,corresponding to the 1G4→3H6 electronic transition.CaWO4 doped with Er3+/Yb3+ showed strong green luminescence at 510-565 nm(2H11/2,4S3/2→4I15/2) and weak red luminescence at 640-685 nm(4F9/2→4I15/2) of Er(III) ion.CaWO4 doped with Ho3+/Yb3+ phosphor emitted green luminescence at 525-560 nm(5S2,5F4→5I8) and red luminescence at 630-670 nm(5F5→5I8) and at 730-770 nm(5S2,5F4→5I7) ,which is the characteristic of Ho(III) ion.     

Biosorption of La^3＋ and Ce^3＋ by Agrobacterium sp.HN1

The Agrobacterium sp.HN1 was isolated from the soil and used to adsorb rare earth ions La3+ and Ce3+.The results showed that the pretreatments of Agrobacterium sp.HN1 did not enhance the adsorption of La3+ and Ce3+.The pH,temperature,time and bacterial age affected the dynamics of adsorption of La3+ and Ce3+.The optimum adsorption conditions for Agrobacterium sp.HN1 were as follows:15 mg/L La3+ of initial concentration,10 mg/L Ce3+,300 mg/L(dry wt.cell) biomass for sorption,6.8 pH,30 oC temperature,150 r/min rotational speed,2 h adsorption time and 28 h bacterial age.The adsorption kinetics of La3+ and Ce3+ for Agrobacterium sp.HN1 followed the pseudo-second order equation.     

Humidity sensing properties of La^3＋ and K^＋ co-doped Ti0.9Sn0.1O2 thin films

The humidity sensing properties of La3+ and K+ co-doped Ti0.9Sn0.1O2 thin films were investigated. The humidity sensitive thin films were prepared by sol-gel method on alumina substrates. The sensing behaviors of thin films were inspected at different sintering temperatures by constructing a humidity-impedance measuring system. It was found that the addition of rare earth ion La3+ and alkali ion K+ was beneficial for improving the humidity sensitive properties of the samples and La0.003K0.5Ti0.9Sn0.1O2 sintered at 500 ℃ for 4 h showed the best humidity sensing properties. The impedance of this thin film decreased from 109 to 104 Ω with excellent linearity in the humidity range of 11%-95%. Narrow hysteresis loop, prominent stability and high sensitivity were obtained. The effects of dopant con-tent and doping mechanism on humidity sensitivity were also discussed in terms of segregation of rare earth ions at grain boundaries and granularity of crystalline and influence of K+ on the decrease in the intrinsic resistance of the materials, and increase in the number of wa-ter adsorption sites.     

Efficient near-infrared quantum cutting by Ce~（3＋）-Yb~（3＋） couple in GdBO_3 phosphors

Ce3+ and Yb3+ co-activated GdBO3 phosphors were prepared by a conventional solid-state reaction method. X-ray powder diffraction, photoluminescent spectra and decay curves were used to characterize their structural and luminescent properties. An efficient near-infrared (NIR) quantum cutting (QC) from the phosphors was observed, which involved the emission of two low-energy NIR photons (around 971 nm) from an absorbed ultra-violet (UV) photon at 358 nm via a cooperative energy transfer (CET) from Ce3+ to Yb3+ ions. The theoretical quantum efficiency was calculated and the maximum efficiency approached up to 164% before reaching the critical concentration quenching threshold. Our results demonstrated that these phosphors might find potential application in improving the efficiency of silicon based solar cells.     

Preparation and photocatalytic activity of La~(3+) and Eu~(3+) co-doped TiO_2 nanoparticles: photo-assisted degradation of methylene blue

Rare earth ions La3+ and Eu3+ co-doped TiO2 photocatalyst (La-Eu/TiO2) was prepared by sol-gel method, and characterized by various techniques such as X-ray diffraction (XRD), specific surface area and porosity (BET and BJH), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), UV-vis diffuse reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the La-Eu/TiO2 was evaluated by the degradation of methylene blue (MB) ...     

Structural studies of BaTiO3：Er3＋ and BaTiO3：Yb3＋ powders synthesized by hydrothermal method

Erbium and ytterbium doped barium titanate nanopowders were prepared using the hydrothermal method. A barium titanate structure doped with rare earth ions manifested new characteristics and improved the field of application of optical devices such as trichromatic tubes, LCD displays, lamps, and infrared lasers. In this work, BaTiO3：Er3＋ and BaTiO3：Yb3＋ were prepared using barium chloride [BaCl2], titanium butoxide [C16H36O4Ti], erbium chloride [ErCl3] and ytterbium chloride [YbCl3] as precursors. Anhydrous methanol was employed as a solvent. Metallic potassium was used to promote solubility in the system and increase the pH to 13. This method yielded the formation of a predominantly cubic structure in both Er3＋ and Yb3＋ doped BaTiO3 powders. Characteristic bondings of BaTiO3 were observed with FT-IR spectroscopy. The predominantly cubic structure was confirmed by X-ray diffraction and micro-Raman analyses. The particle size（～30 nm） was estimated using the Scherrer equation and X-ray diffraction data. The results were presented and discussed.     

Humidity sensing properties of La~(3+)/Ce~(3+)-doped TiO_2-20 wt.% SnO_2 thin films derived from sol-gel method

The humidity sensing properties of La3+/Ce3+-doped TiO2-20 wt.%SnO2 thin films were studied.Sol-gel method was employed to prepare the films on alumina substrates.By constructing a humidity-impedance measuring system,the sensing behaviors were inspected for the films sintered at different temperatures.Experimental results showed that,0.5 wt.% of La2O3 or Ce2O3 doped films sintered at 500 °C for 2 h had the best humidity sensing properties,the impedance decreasing from 109 ? to below 104 ? in the humidity range of 15-95 RH%.Moreover,Ce3+-doping had better humidity sensing properties than La3+-doping.The doping mechanism was discussed in terms of phase composition,granularity of crystalline and segregation of rare earth ions at grain boundaries.     

Sensitizing effect of Nd~(3+) on Tb~(3+) activated ZrP_2O_7 long persistent phosphor materials

The long persistent phosphors of Zr_(0.97)P_2 O_7:0.018 Tb~(3+),0.012 Nd3+with Nd~(3+)as sensitized ions and Tb~(3+)as emission centers were synthesized using high temperature solid state reaction.The crystal structure and defects,excitation and emission spectra,decay curves and thermoluminescence(TL) curves of the phosphors were investigated.The synthesized Zr_(0.97)P_2 O_7:0.018 Tb3+,0.012 Nd3+is essentially in line with the standard card PDF#49-1079.The emission band with main peak at 548 nm exhibits the characteristic transitions of ~5 D_3-~7 F_j(j=5,4) and ~5 D3-~7 F_j(j=6,5,4,3) of Tb~(3+).The analysis of excitation and emission spectra shows that there exists the overlap between the emission peaks of Nd~(3+)at 466 and 485 nm and the excitation of Tb3+at 443 and 485 nm,and the energy transfer from Nd3+to Tb3+plays an important role in the improvement of luminescence properties.The decay curves shows that Zr_(0.97)P_2 O_7:0.018 Tb3+,0.012 Nd3+has longer afterglow time than ZrP_2 O_7 and Zr_(0.982)P_2 O_7:0.018 Tb3+.Additionally,the TL curves indicate that the trap depth at 0.72 eV in Zr_(0.97)P_2 O_7:0.018 Tb~(3+),0.012 Nd3+is to the benefit of the afterglow time.The possible luminescence mechanism of ZrP_2 O_7:Tb~(3+),Nd3+is proposed on the basis of the XPS spectra,EPR spectra,excitation and emission spectra,decay curves,TL curves and the analysis of defect equations.     

A novel blue-purple Ce~(3+) doped whitlockite phosphor:Synthesis,crystal structure,and photoluminescence properties

At present,the rare earth(RE) ions doped phosphors have attracted more and more attention because of their excellent properties.In this paper,a series of novel blue-purple β-Ca_3(PO_4)_2:Ce~(3+) phosphors were synthesized by a high temperature solid phase method.The X-ray diffraction(XRD),infrared spectrum,energy dispersive spectroscopy(EDS),scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),photoluminescence excitation and emission spectra were used to investigate the crystal structure,composition and the luminescent properties of the resulting samples.The phosphor shows a strong absorption in the ultraviolet band.Under the excitation of 269 nm,the phosphor emits a strong purple fluorescence ranging from 360 to 520 nm.When Ce~(3+) doping content is 0.07 mol,the strongest luminescence intensity is reached,and the concentration quenching mechanism is dipole-dipole(d-d)interaction for Ce~(3+) based on Dexter theory.     

Optically stimulated luminescence of Dy~(3+)-doped NaCaPO_4 glass-ceramics

Dy~(3+)-doped glass-ceramics containing NaCaPO_4 crystals were successfully fabricated by heat treatment at base glass,and the luminescence properties were investigated for potential applications in radiation measurements.The photo luminescence(PL) excitation and emission spectra exhibit transitions related to Dy~(3+) ions corresponding to the strongest excitation and emission wavelengths at 351 and 575 nm,respectively.The CW-OSL properties as a function of dopant concentration,pre-heating temperature,pre-heating time and signal fading were investigated.The most appropriate Dy~(3+)ion concentration was found to be 0.25 mol%.The TL glow curves have a broad peak feature peaking at 195±5 ℃.The fading of the OSL signal would keep stable in five days with the intensity value of about 76.11%.The samples also exhibit good signal reusability and a broad linear dose response range(0.02-1000 Gy).     

Specific features of Eu~(3+) and Tb~(3+) magnetooptics in gadolinium-gallium garnet (Gd_3Ga_5O_(12))

We reported magnetooptical properties of Eu3+(4f(6)) and Tb3+(4f(8)) in single crystals of Gd3Ga5O12 (GGG), Y3Ga5O12 (YGG), and Eu3+(4f(6)) in Eu3Ga5O12 (EuGG) for both ions occupying sites of D2 symmetry in the garnet structure. Absorption, luminescence, and magnetic circular polarization of luminescence (MCPL) spectra of Tb3+ in GGG and YGG and absorption and magnetic circular dichroism (MCD) of Eu3+ in EuGG were studied. The data were obtained at 85 K and room temperature (RT). Magnetic susceptibility of...     

CsBaB_3O_6:Eu~(3+) red-emitting phosphors for white LED and FED:Crystal structure,electronic structure and luminescent properties

Recently,borate compounds have received much attention in the field of rare earth doped phosphors due to their excellent luminescent performance.In this work,to explore the potential in LED and FED applications,the CsBaB_3 O_6:Eu~(3+) phosphor was investigated in detail by using Rietveld refinement,DFT calculations,photoluminescent and cathodoluminescent spectra.As a result,CsBaB_3 O_6 has a planar stacked three-dimensional layered structure.Under the excitation of 395 nm n-UV light and electron beam,CsBaB_3 O_6:Eu~(3+) phosphor exhibits a typical red emission of Eu~(3+).A good thermal stability and good resistance to saturation and degradation were observed in the CsBaB_3 O_6:Eu~(3+) phosphor.The related photoluminescent and cathodoluminescent mechanisms were studied.The results indicate that CsBaB_3 O_6:Eu~(3+) phosphor has potential in multifunctional applications.     

稀土固体超强酸Gd3+-SO2-4/ZrO2催化合成乙酸正丁醋

采用乙酸、正丁醇为原料,以固体超强酸Gd3+-SO24-/ZrO2作为催化剂,催化合成乙酸正丁酯。用固体超强酸Gd3+-SO42-/ZrO2和SO24-/ZrO2进行催化活性对比试验,考察浸渍硫酸浓度、浸渍时间、焙烧温度对催化剂活性的影响以及原料酸醇比、反应时间、催化剂用量对酯化率的影响,从而确定固体超强酸的最佳制备条件。试验结果表明:在反应温度105～110℃,催化剂用量1.5g,n(正丁醇)∶n(乙酸)=2.5∶1,反应时间2.5h条件下,酯化率可达98.86%;催化剂重复使用效果明显;加Gd3+的固体超强酸的催化活性明显增强。     

Enhanced afterglow performance of CaAl_2O_4:Eu~(2+),Nd~(3+) phosphors by co-doping Gd~(3+)

In order to effectively improve the afterglow properties of CaAl_2 O_4:Eu~(2+),Nd~(3+) phosphors,a series of Ca_(0.982-x)Al_2 O_4:0.012 Eu~(2+),0.006 Nd~(3+),xGd~(3+)(x=0,0.012,0.024,0.036,0.048,0.060 mol) phosphors were prepared by a high-temperature solid-phase approach.Crystalline composition and microstructure were characterized by XRD,TEM,HRTEM,and XPS,luminescence properties were systematically analyzed by fluorescence spectra,afterglow decay curves and TL glow curve.Results show that all of Ca_(0.982-x)Al_2 O_4:0.012 Eu~(2+),0.006 Nd~(3+),xGd~(3+)phosphors belong to monoclinic CaAl_2 O_4,without other cystalline phase.The blue emission at 442 nm is observed,which is assigned to the 4 f~65 d→4 f~7 transition of Eu~(2+) ions.Doping with appropriate amount of Gd~(3+) ions(x=0.036 mol) significantly improves the afterglow properties of phosphors,but the excessive doping of Gd~(3+) induces the fluorescent quenching.The doping of moderate Gd3+changes the traps states,the trap depth varies from 0.598 to 0.644 eV and the trap concentration is also greatly improved,thus significantly improving afterglow performance.     

Effect of Gd~(3+)-,Pr~(3+)-or Sm~(3+)-substituted cobalt-zinc ferrite on photodegradation of methyl orange and cytotoxicity tests

Gd~(3+)-,Pr~(3+)-or Sm~(3+)-doped Co-Zn(Co_(0.5)Zn_(0.5)Fe_2 O_4) magnetic ferrites(i.e.,Co_(0.5)Zn_(0.5)Gd_(0.1)Fe_(1.9)O_4,Co_(0.5)Zn_(0.5)Pr_(0.1)Fe_(1.9)O_4 and Co_(0.5)Zn_(0.5)Sm_(0.1)Fe_(1.9)O_4) were prepared using a facile sol-gel approach,and the structure,surface morphology and chemical composition of the products were studied by means of scanning electron microscopy(SEM),energy dispersive X-ray analysis(EDX),X-ray diffraction(XRD),UVvisible diffuse reflectance spectroscopy(DRS),photoluminescence(PL) spectroscopy,Fourier transform infrared spectroscopy(FT-IR) and vibrating sample magnetometer(VSM) spectroscopy.XRD patterns show the Co-Zn product is composed of cubic spinel phases with few impurities or secondary phases,and the average crystallite sizes of the samples are determined to be approximately～51—80,～99—181,～68—103 and～83—133 nm.Also the coercivity and remnant and saturation magnetizations,evaluated by vibrating sample magnetometer(VSM),are found to increase linearly with the incorporation of Gd3+,Pr3+and Sm3+in the product formulation.The CO_(1-x)Zn_xFe_(2-y)R_yO_4 photocatalyst sample is found to display a red shift in its absorption,and exhibits outstanding photocatalytic effects in the degradation of MO under ultraviolet(UV) light.This is attributed to the reduction of the band gap of cobalt-zinc ferrite due to the presence of rare earth ions.Further in vitro evaluations of the cytotoxic effects of the synthesized nanoparticles were performed on a HeLa cell line.     

ScF_3的水热法制备及掺Ce~(3+)光谱性质研究

首次用低温水热法制备了ScF_3晶体及其掺杂Ce~(3+)的粉体.通过X射线粉末衍射(XRD),扫描电镜(SEM),荧光光谱(FS)对样品进行了表征.结果表明,所用氟化物的种类和反应温度对ScF_3的制备至关重要.以NaF作为原料更容易得到纯的ScF_3.当水热温度为120℃时,产物为ScF_3晶体,而温度升高至180℃时则为NaScF4复合氟化物.所制备的ScF_3呈针尖棒状放射形.考察了ScF_3:Ce~(3+)粉体荧光光谱性质,讨论了其与同类型的稀土氟化物的荧光光谱的比较.