Luminescent properties of Eu³⁺-doped BaZrO₃ phosphor for UV white light emitting diode

A novel orange phosphor Eu3+ doped barium zirconate(BaZrO3) was synthesized by conventional solid state reaction method and its crystal structure and luminescent properties were investigated in this paper.The X-ray diffraction patterns(XRD) showed that simple BaZrO3 phase was obtained.Monitoring at 596 nm,the excitation spectrum consisted of a broad band and a series of narrow bands and the stronger excitation peaks located at 275 and 393 nm,respectively.The emission spectrum excited by 393 nm UV light was composed of four narrow bands.The strongest emission was located at 596 nm.The appropriate concentration of Eu3+ was 0.025(molar fraction) for the highest emission intensity at 596 nm.The H3BO3 and ammonium were added as flux and the results showed that 2 wt.% NH4F ions was the optimal flux for BaZrO3:Eu3+.     

Intense blue-emitting Ca2PO4Cl:Eu2+ phosphor for near-ultraviolet converting white light-emitting diodes

A blue phosphor Ca₂PO₄Cl:Eu²⁺ (CAP:Eu²⁺) was synthesized by solid state reaction. The Ca₂PO₄Cl:Eu²⁺ exhibited high quantum efficiency and excellent thermal stability. The luminescent intensity of Ca₂PO₄Cl:Eu²⁺ was found to be 128% under excitation at 380 nm, 149% under 400 nm, and 247% under 420 nm as high as that of BaMgAl₁₀O₁₇:Eu²⁺. The optimal doping concentration was observed to 11 mol.% of CAP:Eu²⁺. The energy transfer between Eu²⁺ ions in CAP were occurred via electric multipolar interaction, and the critical transfer distance was estimated to be 1.26 nm. A mixture of blue-emitting Ca₂PO₄Cl:Eu²⁺, green-emitting (Ba,Sr)₂SiO₄:Eu²⁺ and red-emitting CaAlSiN₃:Eu²⁺ phosphors were selected in conjunction with 400 nm chip to fabricate white LED devices. The average color-rendering index R_a and correlated color temperature (T_c) of the white LEDs were found to be 93.4 and 4590 K, respectively. The results indicated that it was a promising candidate as a blue-emitting phosphor for the near-UV white light-emitting diodes.     

Effects of Sr²⁺ on structure and luminescent properties of BaAl₁₂O₁₉:Eu phosphors

Ba0.9-ySryAl12O19:Eu0.1 phosphors were prepared by sol-gel technique,the crystalline structures of samples characterized by XRD,and the luminescence properties were investigated.The influence of crystallographic positions on the luminescent properties of Sr2+-doped BaAl12O19:Eu was investigated in detail.The results indicated that the crystal lattice of BaAl12O19:Eu was not influenced by the Sr2+ and doping Sr2+ in BaAl12O19:Eu enhanced the luminescent properties of the phosphors at the proper concentration of Sr2+.With the increasing of concentration of Sr2+ doped in BaAl12O19:Eu,the relative luminescent intensity of Ba0.9-ySryAl12O19:Eu0.1 strengthened and blue-shifted.     

Synthesis and characterization of CaAl_xO_y:Eu²⁺ phosphors prepared using solution-combustion method

Europium-doped calcium aluminate(CaAlxOy:Eu2+) phosphors were obtained at low temperatures(500 oC) by the solution-combustion of corresponding metal nitrate-urea solution mixtures.The particle size and morphology and the structural and luminescent properties of the as-synthesized phosphors were examined by means of scanning electron microscopy(SEM),X-ray diffraction(XRD),Auger spectroscopy,transmission electron spectroscopy(TEM) and photoluminescence(PL).It was found that the Ca:Al molar ratios showed greatly influence not only on the particle size and morphology,but also on their PL spectra and structure.With the Ca:Al molar ratios increasing from 6:100 to 26:100,the structure of as-synthesized phosphor changed from CaAl12O19 to monoclinic CaAl2O4 and the dominant emitting light from red to blue,implying that the oxidation state of doped europium ions changed from trivalent to divalent due to the structure variation of host lattice.A blue phosphor with almost pure phase can be easily prepared by solution combustion method with suitable Ca:Al molar ratio.     

Electrospinning synthesis and luminescent properties of Lu₂O₃:Eu³⁺ nanofibers

One-dimensional Lu2O3:Eu3+ nanofibers were prepared by electrospinning followed by high-temperature calcinations.Thermogravimetric and differential thermal analysis,X-ray powder diffraction,Fourier transform infrared spectroscopy,scanning electron microscopy,photoluminescent spectra and decay curves were used to characterize the samples.Results showed that samples began to crystallize at ～500 oC and crystallized completely around 1000 oC.The average diameter of nanofibers(1000 oC annealed) was about 55 nm and the particle size of Lu2O3:Eu3+ increased with increasing annealing temperature.Under ultraviolet excitation,nanofibers exhibited typical red emission of Eu3+ in Lu2O3.The effect of heat-treatment temperature on luminescent properties of nanofibers was also discussed.     

Re-determination of the crystal structure of Ca₂Y₈Si₆O₂₆ and study on the luminescent properties of Ca₂Y₈Si₆O₂₆:Tb³⁺

The crystal structure of silicate oxyapatite Ca2Y8Si6O26 was indexed as hexagonal,space group P63/m,a=0.93515 nm,c=0.67872 nm,α=β=90°,γ=120°,V=0.5138692 nm3.Three strong peaks located at 32.079o,32.595o,and 50.104o with d=2.7903,2.74649,1.8194 was in accordance with,(112),and(213) planes.The optimum concentration of Tb3+ in Ca2Y8Si6O26 to yield highest photoluminescence intensity was 10 mol.% of Y3+.The corresponding excitation spectrum consisted of an intense broad band from 220 to 260 nm.The photoluminescence measurements showed that the green emission originated from 5D4-7F5 was predominant in the measured range with strong doublet lines at 543 and 549 nm.     

Photoluminescence study of SiO₂ coated Eu³⁺:Y₂O₃ core-shells under high pressure

Uniform core-shell Eu3+:Y2O3/SiO2 spheres were synthesized via precipitation and the Stber method.The structural transition of core-shell Eu3+:Y2O3/SiO2 was studied by using high pressure photoluminescence spectra.With pressure increasing,the emission intensities of 5D0→7F0,1,2 transitions of Eu3+ ions decreased and the transition lines showed a red shift.The relative luminescence intensity ratio of 5D0→7F2 to 5D0→7F1 transitions decreased with increasing pressure,indicating lowering asymmetry around Eu3+ ions.During compression,structural transformation for cores in the present core-shell Eu3+:Y2O3/SiO2 sample from cubic to monoclinic took place at 7.5 GPa,and then the monoclinic structure turned into hexagonal above 15.2 GPa.After the pressure was released,the hexagonal structure transformed back to monoclinic and the monoclinic structure was kept stable to ambient pressure.     

Luminescence properties of BaAl₁₂O₁₉:Tb,Ce and energy transfer between Ce³⁺,Tb³⁺

BaAl12O19:Tb,Ce phosphors were prepared by sol-gel technique,the crystalline structures of samples characterized by XRD,and the luminescence properties and energy transfer between Ce3+ and Tb3+ were investigated.The results indicated that the emission intensity and the excitation wavelength range of Tb3+ increased when Ce3+ was doped.It demonstrated that the Ce3+ added in the BaAl12O19:Tb could deliver energy to Tb3+,and Ce3+ was not luminous by itself.The relative emission intensity of Tb3+ at wavelength of 548 nm was the strongest by Tb3+/Ce3+ ratio of 2:1,when excited at 310 nm,which was the characteristic adsorption wavelength of Ce3+.     

Luminescence Properties of Eu~(2 ) and Mn~(2 ) Co-Doped Ca_8Mg(SiO_4)_4Cl_2

The green phosphor for white LED, Ca8Mg(SiO4)4Cl2∶Eu2+, Mn2+, was synthesized by high temperature solid state reaction under reducing atmosphere. During the process of the phosphor prepared, the excess CaCl2 can improve the intensity of emission. The experimental results indicate that there is an effective energy transfer from Eu2+ to Mn2+in Ca8Mg(SiO4)4Cl2 host. This kind of energy transfer may be due to resonance transfer, and this energy transfer is limited.     

Optimization of BaMgAl₁₀O₁₇:Eu²⁺ phosphors by the substitution of Si-N bonds for Al-O bonds

We proposed a simple method to improve the thermal stability of BaMgAl10O17:Eu2+(BAM) phosphors by the substitution of Si-N bonds for Al-O bonds in the host lattice.Both photoluminescence properties and thermal stability under ultraviolet(UV) and vacuum ultraviolet(VUV) excitation could be significantly improved through Si-N incorporation.After thermal degradation at 600 °C for 1 h in air atmosphere,the Si-N doped sample(Ba0.88Eu0.12MgAl9.97Si0.03O16.97N0.03) had the highest emission intensity which was 22% and 40% stronger than that of as-received sample under UV and VUV excitation,respectively.This could be attributed to the stable local structure surrounding the Eu2+ ions and the lower electronegativity of nitrogen.     

Size dependence of up-conversion luminescence of NaYF₄:Yb³⁺/Tm³⁺

Tm3+/Yb3+ codoped NaYF4 microcrystals were synthesized using a hydrothermal method.The bright upconversion light was observed under 980 nm excitation.The upconversion luminescence was systematically investigated at different Yb3+ concentrations and different reaction temperatures and time.The sample with 60% Yb3+ concentration and reacting at 180 oC for 24 h possessed the highest luminescent efficiency.The higher luminescent efficiency was contributed to a large surface area.The large surface area induced the large vibration mode by absorbed H2O and CO2.The larger vibration mode could enhance the energy transfer efficiency from the excited Yb3+ to Tm3+ by the process of phonon assisted energy transfer.     

Pressure effect on optical properties and structure stability of LaPO₄:Eu³⁺ hollow spheres

Uniform monoclinic monazite structure LaPO4:Eu3+ hollow spheres were s ynthesized via an attractive hydrothermal method owing to the higher yield and s implicity.Photoluminescence and Raman spectra of the sample were investigated u nder high pressure up to 26 GPa using diamond anvil cells.At ambient pressure,the sample exhibited same luminescent properties with that of bulk monazite LaPO 4:Eu3+.With the increase of pressure,the emission intensity of Eu3+ decreased and the half-widths of transition lines increased,while emission peaks showed a red shift toward longer wavelengths due to increase in crystal-field strength.No phase transformation appeared before amorphization for monoclinic LaPO4:Eu3+ hollow spheres,which was confirmed based on the analysis of high pressure Raman spectra.The large surface energy of hollow spheres was proposed to prevent the occurrence of phase transformation.     

Controlled synthesis and tunable luminescence of NaYF₄:Eu³⁺

High quality NaYF4:Eu3+ luminescent materials were successfully synthesized via a facile template technique by hydrothermal method.The samples were characterized by X-ray powder diffraction(XRD),transmission electron microscopy(TEM) and fluorescence spectroscopy(FS).The incorporating of Eu3+ ions into NaYF4 crystal lattice influenced the symmetry types of NaYF4 crystals,resulting in phase transformation of NaYF4 crystals between α and β phase.The pure hexagonal phase of branched NaYF4:Eu3+ was obtained as the Eu3+ concentration reached 15 mol.%.In addition,the luminescence color was tuned by changing the doping concentration of Eu3+ ions.     

Single-phase full-color Ba_3Lu_2（SiO_4）_3：Eu~（2＋） phosphor for white-light emitting diodes

we developed a new silicate-based full-color phosphor Ba3Lu2(SiO4)3:Eu2+ through solid state reaction.The host crystal structure was isostructural with Ca3Y2(SiO4)3 instead of garnet-type.The phosphor absorbed near-ultraviolet light from 250 to 400 nm,which was very suitable for a color converter of white LED that used UV-LED as the primary light source.The photoluminescence peak wavelength of Ba3Lu2(SiO4)3:Eu2+ was about 461 nm and a shoulder peak was around 522 nm,which resulted from the 5d-4f transition ...     

Combustion synthesis and luminescence properties of blue NaBaPO4:Eu2+ phosphor

The blue-emitting phosphor NaBaPO4:Eu2+ was prepared by the combustion method. The phase structure and microstructure of the as-prepared samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Under the excita-tion wavelength of 360 nm, the emission spectrum exhibited only one blue band centering at 435 nm, which was ascribed to the 4f65d1→4f7 transition on Eu2+ ions. Compared with the phosphor obtained by solid-state reaction method, the relative emission intensity of sample ob-tained by combustion method increased slightly. The decay times and the temperature dependence luminescence intensities (25-300 oC) were discussed in order to further investigate the potential applications. Furthermore, Eu2+-doped NaBaPO4 phosphor showed higher thermally sta-ble luminescence comparable to commercially available Y3Al5O12:Ce3+ (YAG:Ce3+) phosphor. All the investigated suggestions that Na-BaPO4:Eu2+ is a good phosphor candidate applied in white light emitting diode.     

Luminescence and Preparation of LED Phosphor Ca8Mg(SiO4)4Cl2:Eu2+

Calcium magnesium chlorosilicate doped by europium, Ca8Mg(SiO4)4Cl2:Eu2 , was prepared by the solid state reaction at high temperature. The compound obtained is pure Ca8Mg(SiO4)4Cl2 phase with cubic structure. Its average particle size is 5 μm, and it has good dispersity and morphological form. The excitation spectrum of Ca8Mg(SiO4)4Cl2:Eu2 is a wide band, which covers from 270 to 480 nm. The emission spectrum is also a wide band peaked at 510 nm. The luminescent intensity reaches to the maximum when the concentration of Eu2 is 2%. The wavelength of emission and excitation of the phosphor with various Eu2 contents keeps constant. This spectrum range matches violet and blue LED chips very well, and its strong luminescence intensity is suitable for a green phosphor of tricolor phosphor of white light LED.     

Luminescent properties of Ca2SiO4:Eu3+ red phosphor for trichromatic white light emitting diodes

The luminescent properties of Eu3 doped Ca2SiO4 red phosphors synthesized by the flux fusion reaction method were investigated. It was found that the excitation spectrum included two regions: the weak excitation band below 325 nm and strong narrow peaks above 325 nm. The main peak of the excitation band was located at 400 nm. The peaks located at 290 nm were assigned to the combination of the charge transfer transition of O-Eu, peaks above 325 nm (325, 385, 400, 470, 511, and 539 nm) were assigned to the f–f transitions of Eu3 . The emission spectrum was dominated by the red peak located at 612 nm due to the electric dipole transition of 5D0–7F2. In addition, the ef- fects of the Eu3 content and charge compensators of Li , Na , K , and Cl– ions on the emission intensity were investigated. The experiment results suggested that the strongest emission was obtained when the concentration of the Eu3 ions was 0.3 mol–1, and Li ions gave the best improvement to enhance the emission intensity. Ca2SiO4:Eu3 , Li was thus suitable for low-cost trichromatic white light emitting diodes (WLED) based on UV InGaN chip.     

Study on Ca8Mg(SiO4)4Cl2:Eu2+ Doped with Sr2+

Ca8Mg(SiO4)4Cl2:Eu2 phosphor doped with Sr2 cation for Ca2 partially, was synthesized by solid-state reaction at high temperature under reducing atmosphere, and its luminescent properties were investigated. The experimental results indicate that the emission intensity of the phosphor increases after being doped with a few amount of Sr2 ion. The emission peak of the phosphor blue shift to about 464 nm when the phosphor is doped with large quantity of Sr2 ions. The excitation spectrum indicates that the phosphor can be well excited by UV and blue light from 300 to 460 nm, and the phosphor was fitted well for the excitation by UV or blue-LED.     

Enhancement of photoluminescence of Ba2SiO4：Eu^2＋ by co-doping of La^3＋ or Y^3＋

Green light-emitting Ba2SiO4:Eu2+ phosphors co-doped with La or Y were synthesized by conventional solid-state reaction technique in reductive atmosphere (a mixture of 5% H2 and 95% N2). The results showed that the co-doping of La and Y could greatly enhance the fluorescence intensity of Ba2SiO4:Eu2+ phosphors. The optimum doping concentration expressed by the x value in (Ba0.985-1.5xREx)2SiO4: 0.03Eu2+ (RE=La or Y) was determined to be of 0.05. The excitation and emission peaks of all as-synthesized phosphors were wide bands. The excitation bands ranged from 250 to 400 nm, which matched well with the wavelength of near ultraviolet white light-emitting diodes (LED) chip and could be used as a potential candidate for the fabrication of white LED. The emission bands from 450 to 550 nm were typical 5d-4f transition emission of Eu2+ and displayed un-symmetry profiles because of the two substitution sites of Ba2+ with Eu2+.     

Photocatalytic degradation of pesticide residues with RE³⁺-doped nano-TiO₂

The photocatalytic degradation effects of carbofuran solution under concentration of 0.2,0.4,0.8 g/L Re3+-doped nano-TiO2 were studied.The highest degradation rate of 54.89% was obtained after 4 h degradation when the concentration of nano-TiO2 was 0.4 g/L.Then field trials of photocatalytic degradation with suspension nano-TiO2 were conducted.The photocatalytic degradation effect of organic phosphorus and carbamate pesticides in tomato leaves and soil with different concentratio catalyst(0,0.2,0.4,0.6,0.8 g/L) were studied.The results showed that nano-TiO2 could significantly increase photocatalytic degradation rate of pesticide residues in tomato leaves and soil.Pesticide residues degradation rate could be increased by 20%-30% on the tomato leaves and 15%-20% in soil,and the best concentration of photocatalytic degradation was 0.2-0.4 g/L.