First-principles study of structure,mechanical and optical properties of La-and Sc-doped Y_2O_3

The electronic,mechanical and optical properties of La-and Sc-doped Y_2O_3 were investigated using firstprinciples calculations.Two doping sites of Sc and La in Y_2O_3 were modeled.The calculated values of the energy of formation show that the most energetically favorable site for a La atom in Y_2O_3 is a d-site Y atom,while for Sc a b-site Y atom is the more stable position.The calculated band gap shows a slight decrease with increasing La or Sc concentration.The calculated results for the mechanical and optical properties of Y_(2-x)R_xO_3(R = Sc or La,0x ≤ 0.1875)show that La-or Sc-doped Y_2O_3 would have enhanced strength,and thus an ability of resisting external shocks,and increased hardness and mechanical toughness.These improved mechanical properties are achieved without sacrificing the optical properties of the doped compounds.So the doping of La or Sc in Y_2O_3 is permissible in the preparation of Y_2O_3 transparent ceramics,of course,doping of La or Sc will benefit the sintering of transparent ceramics.     

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.     

Synthesis,upconversion luminescence and optical heating of hexagonal NaGdF4:Yb3+,Er3+

An optical heater based on hexagonal NaGdF_4:Yb~(3+)/Er~(3+) is reported. XRD, SEM and EDS characterization results show that F~-/Ln~(3+) can not only control the phase composition, particle size and morphology, but also affect the effective doping concentration of Yb~(3+) and Er~(3+).When F~-/Ln~(3+) is 12/1, the strongest upconversion luminescence is obtained. Based on the luminescent temperature sensing behavior of Er~(3+),the photo-thermal conversion performance was investigated. The results indicate that the temperature of irradiation spot is linearly dependent on the power density, and the photo-thermal responsivity is determined to be 3.3K·cm~2/W. Also, it is found that the photo-thermal conversion efficiency can be regulated by changing the Yb~(3+) doping concentration. Compared with the nano-gold, copper sulfide and carbon nanotubes, the NaGdF_4:Yb~(3+)/Er~(3+) has the triple functions of upconversion luminescence, temperature sensing, and photo-thermal conversion, and may therefore be a promising optical heater for photo-thermal therapy of tumors.     

Spectroscopic properties of Er3+-doped fluoroindate glasses

The optical and thermal properties of a new class of fluoroindate glass with different erbium contents were investigated via Raman, transmission, and fluorescence spectroscopies, fluorescence decay curve analysis, and differential scanning calorimetry. The strength parameters of the samples were calculated using the Judd–Ofelt theory. The mid-infrared luminescence properties of erbium-doped fluoroindate glasses were studied, and a strong emission at 2.7 μm was obtained. Compared with the traditional ZBLAN glass, this glass has excellent emission properties, especially a longer fluorescence lifetime (7.09 ms) and larger emission cross-section (6.95 × 10^?21 cm²) at 2.7 μm. The results indicate that fluoroindate glass is an attractive host for mid-infrared lasers and as a gain medium for optical amplifier applications.     

Structural and optoelectronic properties of CsLnZnTe3(Ln=La,Pr,Nd and Sm)

Zinc telluride is a versatile wide band gap semiconductor used in many applications.But it has certain limitations like large dimensions and large band gaps.Introducing alkali metal to its bulk lattice(3D) can reduce its dimensions and lanthanide can produce a red shift in the energy gap by converting it into quaternary compounds.The alkali and lanthanide incorporated quaternary zinc tellurides CsLnZnTe₃(Ln =La,Pr,Nd and Sm) form layered crystal structure in which_∞²     

Structure and luminescence properties of color-tunable phosphor Sr2La3(SiO4)3F:Tb3+,Sm3+

A series of single-phase and color-tunable phosphors Sr₂La₃(SiO₄)₃F:0.15Tb³⁺,xSm³⁺(SLSOF:0.15Tb³⁺,xSm³⁺) was prepared using solid-state route.The X-ray diffraction(XRD) was used to characterize the phase of the as-prepared samples.The synthesized phosphors have apatite-type structure without other impurities.Sm³⁺ and Tb³⁺ ions substitute La³⁺ into the lattice and form a single...     

Er3+/Yb3+/Li+/Zn2+: Gd2(MoO4)3 upconverting nanophosphors in optical thermometry

Er~(3+)-Yb~(3+)-Li~+:Gd_2(MoO_4)_3 and Er~(3+)-Yb~(3+)-Zn~(2+):Gd_2(MoO_4)_3 nanophosphors, synthesized by chemical co-precipitation technique were characterized through XRD,FESEM,dynamic light scattering(DLS),diffuse reflectance, photoluminescence, photometric and decay time analysis. The enhancement of about～28, ～149 and ～351 times in the green upconversion emission band is observed for the optimized Er~(3+)-Yb~(3+),Er~(3+)-Yb~(3+)-Li~+ and Er~(3+)-Yb~(3+)-Zn~(2+):Gd_2(MoO_4)_3 nanophosphors in comparison to the singly Er~(3+) doped nanophosphors. The electric dipole-dipole interaction is found to be responsible for the concentration quenching. The temperature dependent behaviour of the two green thermally coupled levels of the Er~(3+) ions based on the fluorescence intensity ratio technique was studied. The maximum sensor sensitivity ～38.7 × 10~(-3) K~(-1) at 473 K for optimized Er~(3+)-Yb~(3+)-Zn~(2+) codoped Gd_2(MoO_4)_3 nanophosphors is reported with maximum population redistribution ability～88% among the ~2H_(11/2) and ~4S_(3/2) levels.     

Highly sensitive up-conversion phosphor for optical thermometry:CaLaAl_3O_7:Er~(3+)/Yb~(3+)

Herein, we reported Er~(3+)/Yb~(3+) co-doped CaLaAl_3O_7 up-conversion phosphors synthesized via solid state reaction, which was further explored as a new optical thermometry. The luminescent properties of Er~(3+) or Er~(3+)/Yb~(3+) doped CaLaAl_3O_7 phosphor was studied in detail. The two-photon process for the green emissions of Er~(3+) were confirmed by the power-dependent luminescence. The up-conversion optical temperature sensing performances of the Er~(3+)/Yb~(3+)-codoped CaLaAl_3O_7 phosphor were investigated based on the FIR technique. The maximum sensitivity of this phosphor can reach about 0.00345 K~(-1) at 453 K, which reveals this phosphor can be a promising candidate for optical thermometry devices.     

Effective regulation of electronic structures and luminescence properties of LiGd9(SiO4)6-x(GeO4)xO2:Dy3+ phosphors by tetrahedral substitution

A series of Dy³⁺-activated phosphors with the general formula LiGd₉(SiO₄)_6-x(GeO₄)_xO₂:Dy₃₊(0 ≤ x≤ 3)characterized by an apatite-type structure were successfully synthesized via a simple solid-state technique involving a partial substitution of [SiO₄]^4-with [GeO₄]^4- species.The effects of homovalent[GeO₄]^4--[SiO₄]^4- substit...     

Structural and electronic properties of bastnaesite and implications for surface reactions in flotation

The structural and electronic properties of bastnaesite were studied by using the first-principles method based on the density functional theory(DFT).The geometry structure of bastnaesite was first optimized,and then the Mulliken populations,electron density and density of states were calculated and further analyzed in detail.The calculation results reveal that it mainly ruptures along the ionic Ce-O and Ce-F bonds during the cleavage of bastnaesite,leaving≡Ce~+,≡F~-and≡CO_3~-dangling bonds exposed on the cleavage surface of bastnaesite.Combined with contact angle measurement,surface complexation theory and XPS analysis,the implications of structural and electronic properties on bastnaesite flotation reactions were studied.The hydration of exposed strong ionic bond on cleavage surface results in hydrophilic surface.According to surface complexation theory,the formed surface groups are≡CeOH~0,≡CO_3 H~0 and≡FH~0 groups.The investigated metal ions and flotation reagents complex with surface≡CeOH~0 groups,while≡CO_3 H~0 and≡FH~0 groups are not involved in the complexation.The high activity of Ce atoms facilitates these surface reactions.     

Low-temperature NH_3-SCR of NO_x over MnCeO_x/TiO_2 catalyst:Enhanced activity and SO_2 tolerance by modifying TiO_2 with Al_2O_3

A series of TiO_2-Al_2 O_3 composites with Al/Ti molar ratios of 0.1,0.2,and 0.4 were synthesized by a coprecipitation method and used as supports to prepare supported MnCeO_x catalysts by an impregnation method.The physico-chemical properties of the samples were extensively characterized by N2 physisorption,X-ray diffraction,Raman spectroscopy,scanning electron micro scopy and energy-dispersive Xray spectroscopy element mapping,X-ray photoelectron spectroscopy,H_2-temperature programmed reduction,ammonia temperature programmed desorption,and in-situ diffuse reflectance infrared Fourier transform spectroscopy.The catalytic activity and resistance to water vapor and SO_2 of the asprepared catalysts for the SCR of NO_x with NH3 were evaluated at 50-250℃ and GHSV of 80000 mL/(g_(cat)·h).The results reveal that MnCeO_x/TiO_2-Al_2 O_3 exhibits higher activity and better SO2 tolerance than MnCeO_x/TiO_2.Combining with the characterization results,the enhanced activity and SO2 tolerance of MnCeO_x/TiO_2-Al_2 O_3 can be mainly attributed to higher relative concentrations of Mn~(4+)and chemisorbed oxygen species,stronger reducibility,and larger adsorption capacity for NH3 and NO,which originate from the larger specific surface area and pore volume,higher dispersion of Mn and Ce species compared with MnCeO_x/TiO_2.Moreover,in situ DRIFTS was used to investigate the reaction mechanism,and the results indicate that the NH3-SCR reaction over MnCeO_x/TiO_2 and MnCeO_x/TiO_2-Al_2 O_3 takes place by both the E-R and L-H mechanisms.     

Y4GeO8:Er3+,Yb3+ up-conversion phosphors for optical temperature sensor based on FIR technique

Herein, we reported novel Y₄GeO₈:Er³⁺,Yb³⁺ phosphors elaborated via conventional solid-state reaction, and we further explored their properties as optical thermometer by using fluorescence intensity ratio (FIR) method complemented by detailed analysis on crystal structure, up-conversion luminescence and energy transfer from Yb³⁺ to Er³⁺. Upon 980 nm laser excitation, Y₄GeO₈:Er³⁺,Yb³⁺ phosphors present 525, 547 and 659 nm emission bands assigned to the characteristic transitions of Er³⁺. Furthermore, Y₄GeO₈:Er³⁺,Yb³⁺ samples show outstanding temperature sensing performances. To be specific, the minimal temperature resolution is 0.03 K (303 K), and the relative sensitivity of FIR can be up to 1.152%/K (303 K). Hence, Y₄GeO₈:Er³⁺,Yb³⁺ phosphors can be possible candidates for thermometry devices.     

Improving luminescence and thermometric performance of Ba2CaWO6:Er3+ by tri-doping with Yb3+ and Na+

The Er³⁺doped double perovskite Ba₂ CaWO₆ crystal is a promising ratiometric thermometer based on the fluorescence intensity ratio(FIR) of transitions from ² H_11/2 and ⁴ S_3/2to the lowered ⁴ I_15/2 level.However,the Ca²⁺vacancy defect caused by the charge difference between rare-earth ions and the substituted alkaline-earth ions gives rise to the non-radiative probability and limits the t...     

Characterization and photoluminescence of Lu_2O_3-Eu~（3＋） nano-phosphor prepared by modified solution combustion method

Nanoscale Lu2O3:Eu3+ phosphor was prepared by a modified solution combustion method using urea and acrylamide monomer.The particle sizes and photoluminescent properties of nano-phosphor were closely related to the molar ratio of urea-to-RE nitrates and acrylamide monomer-to-RE nitrates.The as-prepared samples with the sizes of 9.6-11.6 nm were characterized by X-ray diffraction,scanning electron microscopy,transmission electron microscopy and energy dispersive spectrometer.Lu2O3:Eu3+ nano-phosphor that depicted high photoluminescence in the size around 10 nm was reported.Compared with the sample prepared by solid state reaction,the photoluminescence of sample was increased sufficiently to be 45.1%.The emission spectra of the samples presented the typical emission from 5D0 level to 7FJ(J=0,1,2,3,4) level of the Eu3+ ion.     

Promising light converting BaMoO4:Er3+-Tm3+-Yb3+ phosphors for display and optical temperature sensing

Er³⁺-Tm³⁺-Yb³⁺ tri-doped BaMoO₄ phosphors were synthesized by co-precipitation technique and characterized by X-ray diffraction analysis, absorption study and field emission scanning electron microscopy analysis. Upconversion as well as downconversion luminescence studies were performed by using near infrared (980 nm) and ultraviolet (380 nm) excitations. Energy level diagram, pump power dependence and colour coordinate study were utilized to describe the multicolor upconversion emission properties. Under single 980 nm diode laser excitation the dual mode sensing behaviour is realized via Stark sublevels and thermally coupled energy levels of the Tm³⁺ and Er³⁺ ions in the prepared tri-doped phosphors. A comparative fluorescence intensity ratio analysis for integrated emission intensities arising from the Stark sublevels {¹G_4(a) and ¹G_4(b)} and thermally coupled energy levels {²H_11/2 and ⁴S_3/2} of the Tm³⁺ and Er³⁺ ions, respectively was carried out in the prepared tri-doped BaMoO₄ phosphors. The maximum sensitivity for thermally coupled energy levels of the Er³⁺ and Stark sublevels of the Tm³⁺ ion was reported. The developed phosphors could be useful in the display devices and optical thermometric applications.     

Tunable electronic band structure,luminescence properties and thermostability of(Gd_(1-x)La_x)_2Si_2O_7:Ce scintillator by adjusting La/Gd ratio

Mixed crystal strategy is an effective approach of improving the luminescence properties of optical materials and has been adopted widely in many systems.In this paper,the La-mixed Gd_2 Si_2 O_7:Ce polycrystalline samples were successfully synthesized by a sol-gel method.The crystal structure and luminescence properties were confirmed and discussed by XRD,UV-Vis luminescence spectra,and XEL,respectively.The vacuum ultraviolet excitation spectra and thermoluminescence glow curves were also systematically investigated and discussed at varied temperature.A combination of the first-principles calculations and optical characterization experiments was employed to study the electronic band structure of host material,revealing that the band gap is narrowed and the 5 d_1 level of Ce~(3+) shifts to higher energy as the La content increases.The luminescence the rmo-stability and activation energy were also measured and calculated.It indicates that thermo-stability is strongly dependent on the La concentration.An effective approach is developed to tune the electronic band structure,luminescence properties and thermostability of(Gd_(1-x)La_x)_2 Si_2 O_7:Ce scintillator by adjusting La/Gd ratio.     

Mechanism for transmittance light tunable property of nanocrystalline Eu-doped SmB_6:Experimental and first-principles study

Binary nanocrystalline rare-earth hexaboride is regarded as one of the promising optical absorption materials that possess the high transparency for visible light and the strong absorption for NIR due to the effects of localized surface plasmon resonance.In present work,we experimentally investigated the structural and optical absorption of ternary nanocrystalline Eu-doped SmB_6 powder.As a result,it is found that the reaction temperature as an important factor not only refines the grain size,but also improves the powder dispersion of synthesized samples.The optical absorption results reveal that the transmittance wavelength of nanocrystalline SmB_6 increases from 696 nm to exceeding 1000 nm with the Eu doping content increasing to x=0.8.Theo retically,in order to study the transmittance wavele ngth tunable mechanisms of nanocrystalline Eu-doped SmB_6,the electronic structure,density of states and energy loss function were calculated by first-principle calculation.It shows that the En~(2+) doping into SmB_6 effectively reduces the plasma frequency excitation energy from 1.48 to 1.25 eV and leads to the transmittance wavelength redshift toward a higher wavelength.Based on above meaningful studies,present work is helpful for extension of optical applications of nanocrystalline SmB_6 powder.     

La~(3+) doped LiCo_(0.25)Zn_(0.25)Fe_2O_4 spinel ferrite nanocrystals:Insights on structural,optical and magnetic properties

This paper addresses the manipulation of structural,morphology,optical and magnetic properties of LiCo_(0.25)Zn_(0.25)Fe_2 O_4 ferrite via incorporation of different proportions of La~(3+) at the expense of iron ions using a sol-gel method.The samples were characterized using the X-ray diffraction technique(XRD),Fourier transform infrared(FT-IR) spectroscopy,the energy dispersive X-ray spectra(EDX),inductively coupled plasma optical emission spectroscopy(ICP-OES),high resolution scanning electron microscopy(SEM),Brunauer-Emmett-Teller(BET) surface area analysis,ultraviolet-diffuse reflectance spectroscopy(UV-DRS),and vibrating sample magnetometer(VSM) technique.The Rietveld refinements of the samples indicate that at higher concentrations of La3+,nanostructures with dual phase,i.e.cubic spinel and orthorhombic LaFeO_3 perovskite with space group(Pbnm) appear.Optical studies show that the energy band gap(E_g) of the bare LiCo_(0.25)Zn_(0.25)Fe_2 O_4 ferrite sample(2.18 eV) reaches up to 2.47 eV at x=0.06 and above this concentration,it drops sharply to 2.00 eV.Although the saturation magnetization and the coercivity of LiCo_(0.25)Zn_(0.25)La_xFe_(2-x)O_4 are lower than that of LiCo_(0.25)Zn_(0.25)Fe_2 O_4 NPs.Overall,the superparamagnetic nature and low values of saturation magnetization and coercivity of LiCo_(0.25)Zn_(0.25)La_xFe_(2-x)O_4 NPs are suitable to be applied in transformers core.     

Preparation and luminescent properties of CaF2:Ln3+ (Ln:Er,Er/Yb)/Nafion composite films

In this work, CaF_2:Ln~(3+)(Ln:Er,Er/Yb)/Nafion composite films were prepared using Nafion as modifications and matrices by dripping method. The composite films were characterized by Fourier transform infrared spectroscopy(FT-IR), X-ray diffraction(XRD) and scanning electron microscopy(SEM). Composite films are transparent and CaF_2:Ln~(3+)(Ln:Er,Er/Yb) nanoparticles are well dispersed in Nafion films.The thicknesses of CaF_2:Er~(3+)/Nafion and CaF_2:Er~(3+),Yb~(3+)/Nafion composite film are about 77 and 73 μm,respectively. The nanoparticles in composite film possess cubic phase. CaF_2:Er~(3+),Yb~(3+)/Nafion composite film has stronger characteristic emission of Er~(3+) around 1530 nm with full width at half-maximum(FWHM) of 73 nm and longer luminescence lifetimes of 22.04 μs(25.03%) and 100.77 μs(74.97%).     

Structural and optical properties of Dy~(3+):YAlO_3 phosphors for yellow light-emitting diode applications

The spectroscopic properties of a series of Dy~(3+) single-doped and Dy~(3+)/Nd~(3+),Dy~(3+)/Tb~(3+),and Dy~(3+)/Tm~(3+)co-doped YAlO_3(yttrium aluminum perovskite,YAP) phosphors were investigated and compared through the measurements of optical absorption,emission spectra,and fluorescence decay curves.For the Dy~(3+) ion single-doped samples,the intensity of each absorption band increases with an increment in Dy~(3+) ion doping concentration,and the identified strong absorption peak at 447 nm indicates that Dy~(3+):YAP phosphors are suitable to be pumped by a blue laser diode(LD).For all co-doped samples,absorption peaks of Dy~(3+) ion along with some of the absorption bands of Nd~(3+),Tb~(3+),and Tm~(3+) ions are observed.Under 351 and 447 nm excitation,a prominent emission peak at 572 nm was obtained in all the samples,corresponding to Dy~(3+):~4 F_(9/2)→~6 H_(13/2) transition.Here,2 at% Dy~(3+):YAP phosphor exhibits the highest yellow emission intensity under 447 nm pumping.Among the three kinds of Dy~(3+) co-doped phosphors,Dy~(3+)/Tb~(3+):YAP phosphor possesses the dominant yellow emission.The fluorescence decay curves show exponential behaviour and are fitted well.The Commission International de L'Eclairage(CIE)chromaticity coordinates were calculated following the respective emission spectra,and it is found that all the coordinates locate in the yellow region.The energy transfer(ET) processes were investigated and the concentration quenching mechanism was discussed.The obtained results suggest that Dy~(3+)-activated YAP phosphors are good candidates for yellow LED applications.