Nanostructured CaWO4, CaWO4:Eu3+ and CaWO4:Tb3+ particles: sonochemical synthesis and luminescent properties

Nanostructured CaWO4, CaWO4:Eu3+, and CaWO4:Tb3+ phosphor particles were synthesized via a facile sonochemical route. X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, photoluminescence, low voltage cathodoluminescence spectra, and photoluminescence lifetimes were used to characterize the as-obtained samples. The X-ray diffraction results indicate that the samples are well crystallized with the scheelite structure of CaWO4. The transmission electron microscopy and field emission scanning electron microscopy images illustrate that the powders consist of spherical particles with sizes from 120 to 160 nm, which are the aggregates of even smaller nanoparticles ranging from 10 to 20 nm. Under UV light or electron beam excitation, the CaWO4 powder exhibited a blue emission band with a maximum at 430 nm originating from the WO4/2- groups, while the CaWO4:Eu3+ powder showed red emission dominated by 613 nm ascribed to the 5D0 --> 7F2 of Eu3+, and the CaWO4:Tb3+ powders showed emission at 544 nm, ascribed to the 5D4 --> 7F5 transition of Tb3+. The PL excitation and emission spectra suggest that the energy is transferred from WO4/2- to Eu3+ CaWO4:Eu3+ and to Tb3+ in CaWO4:Tb3+. Moreover, the energy transfer from WO4/2- to Tb3+ in CaWO4:Tb3+ is more efficient than that from WO4/2- to EU3+ in CaWO4:Eu3+. This novel and efficient pathway could open new opportunities for further investigating the novel properties of tungstate materials.     

Optical spectroscopy of Eu3+ ions in tetragonal ZrO2 nanocrystals

A facile solvothermal method was introduced to incorporate Eu3+ ions into the monodisperse tetragonal ZrO2 nanocrystals (NCs) with small size of approximately 4 nm. The optical properties for Eu3+ doped ZrO2 NCs were investigated in detail by using the photoluminescence (PL) spectroscopy at room and low temperatures. Intense red emissions from Eu3+ ions could be achieved via the host sensitization, which was found to be much more efficient than the direct excitation of lanthanide ions. Moreover, multiple sites of Eu3+ as well as the host-to-Eu3+ energy transfer were also revealed based on the PL analyses.     

Nanostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles: polyol-mediated synthesis and luminescent properties

Nano-submicrostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles were prepared by polyol method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FT-IR), thermogravimetry-differential thermal analysis (TG-DTA), photoluminescence (PL), cathodo-luminescence (CL) spectra and PL lifetimes. The results of XRD indicate that the as-prepared samples are well crystallized with the scheelite structure of CaWO4. The FE-SEM images illustrate that CaWO4 and CaWO4 : Pb2+ and CaWO4 : Tb3+ powders are composed of spherical particles with sizes around 260, 290, and 190 nm respectively, which are the aggregates of smaller nanoparticles around 10-20 nm. Under the UV light or electron beam excitation, the CaWO4 powders exhibits a blue emission band with a maximum at about 440 nm. When the CaWO4 particles are doped with Pb2+, the intensity of luminescence is enhanced to some extent and the luminescence band maximum is red shifted to 460 nm. Tb(3+)-doped CaWO4 particles show the characteristic emission of Tb3+ 5D4-7FJ (J = 6 - 3) transitions due to an energy transfer from WO4(2-) groups to Tb3+.     

Self-assembled peanut-like Ln3+ (Ln = Tb, Sm, Eu) doped NaLa(WO4)2: phase control and its relevance to luminescence modification

Ln3+ (Ln = Tb, Sm, Eu) doped NaLa(WO4)2 peanuts were successfully self-assembled by a facile EDTA assisted hydrothermal treatment. EDTA played critical roles in the phase and morphology control, which regulated the phase transformation from monoclinic La2(WO4)3 flowers to tetrahedral NaLa(WO4)2 peanuts. La2(WO4)3:Tb3+ exhibited two broad excitation bands at 280 and 340 nm, which are related to the normal and perturb sites of WO4(2-). However, the excitation band for NaLa(WO4)2:Tb3+ shifted to near ultraviolet region and showed only one broad excitation band originating from perturb sites. Under ultraviolet excitation, La2(WO4)3:Tb3+ displayed green light and NaLa(WO4)2:Tb3+ showed blue-green light consisting of WO4(2-) self-activated blue emission and the characteristic Tb3+ emission. It can be clearly seen that the blue emission of WO4(2-) was not sufficiently quenched in NaLa(WO4)2 as that in La2(WO4)3, because the distortions of crystalline lattice for NaLa(WO4)2 may alter the energy migration processes. When doping with Sm3+ and Eu3+, NaLa(WO4)2 peanuts exhibited white color emission which may find practical applications in solid state lighting devices.     

Sensitized upconversion emissions of Tb3+ by Tm3+ in YF3 and NaYF4 nanocrystals

Yb3+-Tm3+-Tb3+-codoped YF3 and NaYF4 nanocrystals (NCs) were synthesized using a simple hydrothermal method. Under 980 nm excitation, violet and ultraviolet upconversion (UC) emissions of 5D3 --> 7FJ (J = 6, 5, 4) and 5D4 --> 7FJ (J = 6, 5, 4, 3) of Tb3+ ions were observed with the fluoride NCs. In the Yb-Tm-Tb codoped NCs, energy transfer (ET) processes from Tm3+ to Tb3+ were proposed to be the main mechanisms for the UC emissions of Tb3+ ions. They are more efficient than the phonon assisted cooperative sensitization of the Yb3+ couple proposed previously for similar material system. The analysis of power dependence indicated that populating the 5D4 level of the Tb3+ ions was a four photon UC process, which demonstrated the existence of the two step ET process of Yb3+ --> Tm3+ --> Tb3+. It was also found that UC luminescence properties of Tb3+ ions were sensitive to crystal structures.     

Study on luminescence behavior of BaAl12O19:Tb, Eu

BaAl12O19:Tb, Eu phosphors were prepared by sol-gel technique. The luminescence properties and the energy transfer between Eu2+ and Tb3+ were investigated. For BaAll2O19:Tb phosphor, the strongest excitation peak and emission peak produced from Tb3+ transition of 5D4-7F5 were at 240 nm and at 550 nm respectively, while the peak shape was narrow and peak intensity was large. The Eu2+ added in the BaAl12O19:Tb induced energy transfer to Tb3+ and different color luminescence from blue (400 nm) to green (570 nm) was obtained by changing the ratio of Tb3+/Eu2+ with excitation at 240 nm.     

Luminescence properties of nano-crystalline Ba3MgSi2O8:Eu2+, Mn2+ phosphors

Ba3MgSi2O8:Eu2+, Mn2+ phosphors were synthesized by the sol-gel method and high temperature solid-state reaction method, respectively. XRD (X-ray diffraction), FT-IR (Fourier transform infrared spectroscopy), PL (photoluminescence spectra), and PLE (photoluminescence excitation spectra) were measured to characterize the samples. Emission and excitation spectra of our Ba3MgSi2O8:Eu2+, Mn2+ phosphors monitored at 441, 515, and 614 nm are depicted in the paper. The emission intensities of 441 and 515 nm emission bands increase with increasing Eu2+ concentration, while the peak intensity of the 614 nm band increases with increasing Mn2+ concentration. We conclude that the 515 nm emission band is attributed to the 4f(6)5d transition of Eu2+ ions substituted by Ba2+ sites in Ba2SiO4. The 441 nm emission band originates from Eu2+ ions, while the 614 nm emission band originates from Mn2+ ions of Ba3MgSi2O8:Eu2+, Mn2+. Nano-crystalline Ba3MgSi2O8:Eu2+, Mn2+ phosphors prepared by the sol-gel method show higher color rendering and better color temperature in comparison with the samples prepared by high temperature solid-state reaction method.     

Eu3+对Na3Gd2(BO3)3∶Tb3+发光性能的影响及其能量传递

采用高温固相法制备了Na_3Gd_2(BO_3)_3∶Tb~(3+),Eu~(3+)荧光粉,并对样品的物相组成、微观形貌、发光性能和能量传递进行了分析。结果表明,Na_3Gd_(2-x)(BO_3)_3∶xTb~(3+)荧光粉在紫外和近紫外区域有较强的激发峰,在368nm波长激发下,发射光呈绿色,Tb~(3+)最佳掺杂量为x=0.04。随着在Na_3Gd_(1.96)(BO_3)_3∶0.04Tb~(3+)中掺入Eu~(3+),Tb~(3+)对Eu~(3+)产生了以电偶极-电偶极相互作用为主的能量传递,且传递效率随Eu~(3+)掺杂量的增加而逐渐增大。发射光谱中Tb~(3+)的发射峰强度逐渐减弱,而Eu~(3+)的发射峰强度逐渐增强,导致Na_3Gd_(1.96-y)(BO_3)_3∶0.04Tb~(3+),yEu~(3+)荧光粉发光颜色由绿色向橙色变化。     

Preparation and luminescent properties of YVO4:Eu3+ nanofibers by electrospinning

This paper describes a procedure based on electrospinning for generating europium-doped yttrium vanadate (YVO4:Eu3+) nanofibers with diameters ranging from 30 to 50 nm. The YVO4:Eu3+ nanofibers were obtained through calcining precursory nanofibers, which were prepared through the electrospinning method. Suitable electrospinning parameters, such as concentration of PVP in solution, spinneret tip-to-collector plate distance (TCD), and applied voltage between spinneret and collector plate, are used to obtain thinner and more uniform precursory nanofibers of YVO4:Eu3+, which is important for preparing smaller diameter pure YVO4:Eu3+ nanofibers. The luminescent properties of the YVO4:Eu3+ nanofibers including excitation and emission spectra and fluorescence lifetime were studied. The excitation spectrum shows a broad band extending from 200 to 350 nm, which corresponds to the strong vanadate absorption in YVO4:Eu3+. The emission spectrum is dominated by the red 5D0 --> 7F2 hypersensitive transition of Eu3+. The fluorescence lifetime of Eu3+ 5D0 --> 7F2 (619 nm) is determined to be 493 micros at room temperature, which is basically in accordance with that in the bulk (521 micros).     

Luminescence and energy transfer characteristics of Ce3+- and Tb3+-codoped nanoporous 12CaO 7Al2O3 phosphors

The novel green-emitting phosphors of 12CaO 7Al2O3:Ce3+ , Tb3+ (C12A7:Ce3+, Tb3+) were synthesized by a solid-state reaction. Upon the excitation of Ce3+ at 350 nm, the C12A7:Ce3+, Tb3+ phosphor shows intense green emissions located at 543 nm assigning to 5D4-7F5 transitions of Tb3+ ions, and weak blue emissions centered at 434 nm due to the transitions of Ce3+ 5d-4f. The photoluminescence (PL) intensity of Ce3+ decrease with increasing Tb3+ concentration, indicating the effective energy transfer (ET) occurred from Ce3+ to Tb3+ in C12A7:Ce3+, Tb3+. The ET efficiency between Ce3+ and Tb3+ in the optimum composition reaches to 99%. Based on Dexter's ET theory, we have demonstrated that the efficient ET is a resonant type via dipole-dipole mechanism with an energy transfer critical distance of 4.02 A. Our results suggested that C12A7:Ce3+, Tb3+ phosphor would be a promising green-emitting phosphor for UV-converting white light-emitting diodes.     

Er3+ -doped anatase TiO2 nanocrystals: crystal-field levels, excited-state dynamics, upconversion, and defect luminescence

A comprehensive survey of electronic structure and optical properties of rare-earth ions embedded in semiconductor nanocrystals (NCs) is of vital importance for their potential applications in areas as diverse as luminescent bioprobes, lighting, and displays. Er3+ -doped anatase TiO2 NCs, synthesized via a facile sol-gel solvothermal method, exhibit intense and well-resolved intra-4f emissions of Er3+ . Crystal-field (CF) spectra of Er3+ in TiO2 NCs are systematically studied by means of high-resolution emission and excitation spectra at 10-300 K. The CF analysis of Er3+ assuming a site symmetry of C(2v) yields a small root-mean-square deviation of 25.1 cm(-1) and reveals the relatively large CF strength (549 cm(-1) ) of Er3+, thus verifying the rationality of the C(2v) symmetry assignment of Er3+ in anatase TiO2 NCs. Based on a simplified thermalization model for the temperature-dependent photoluminescence (PL) dynamics from (4) S(3/2) , the intrinsic radiative luminescence lifetimes of (4) S(3/2) and (2) H(11/2) are experimentally determined to be 3.70 and 1.73 μs, respectively. Green and red upconversion (UC) luminescence of Er3+ can be achieved upon laser excitation at 974.5 nm. The UC intensity of Er3+ in Yb/Er-codoped NCs is found to be about five times higher than that of Er-singly-doped counterparts as a result of efficient Yb3+ sensitization and energy transfer upconversion (ETU) evidenced by its distinct UC luminescence dynamics. Furthermore, the origin of defect luminescence is revealed based on the temperature-dependent PL spectra upon excitation above the TiO2 bandgap at 325 nm.     

白光LED用钨酸盐红色荧光粉的制备及发光特性

采用高温固相法制备了NaY(WO4)2:Eu3+发光材料。分别用X射线粉末衍射(XRD)、发光光谱(PL)等手段研究了发光粉的晶体结构以及发光性能。XRD结果表明,Eu3+掺杂浓度达到25%(摩尔分数)时,仍然能够形成纯相的NaY(WO4)2:Eu3+多晶粉末。NaY(WO4)2:Eu3+的激发光谱由强度很大的宽激发带(220～300nm)和锐线谱(峰值位于393nm和465nm)组成,其中宽激发带源于O2-→W6+和O2-→Eu3+电荷转移,锐线谱属于Eu3+的4f-4f跃迁吸收,发射光谱显示随Eu3+浓度的增大,NaY(WO42):Eu3+光发射强度逐渐增大,当Eu3+浓度为20%时,发射强度达到最大,随后出现浓度猝灭。     

Molten salt synthesis and luminescent properties of YVO4:Ln (Ln = Eu3+, Dy3+) nanophosphors

Eu3+ and Dy(3+)-doped YVO4 nanocrystallites were successfully prepared at 400 degrees C in equal moles of NaNO3 and KNO3 molten salts. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, transmission electronic microscopy (TEM), photoluminescence (PL) spectrum and lifetime were used to characterize the nanocrystallites. XRD results demonstrate that NaOH concentration and annealing temperature play important roles in phase purity and crystallinity of the nanocrystallites, the optimum NaOH concentration and annealing temperature being 6:40 and 400 degrees C respectively. TEM micrographs show the nanocrystallites are well crystallized with a cubic morphology in an average grain size of about 18 nm. Upon excitation of the vanadate group at 314 nm, YVO4:Eu3+ and YVO4:Dy3+ nanocrystallites exhibit the characteristic emission of Eu3+ and Dy3+, which indicates that there is an energy transfer from the vanadate group to the rare earth ions. Moreover, the structure and luminescent properties of the nanocrystallites were compared with their bulk counterparts with same composition in detail.     

Molten salt synthesis and luminescent properties of YVO4:Ln (Ln = Eu3+, Dy3+) nanophosphors

Eu3+ and Dy(3+)-doped YVO4 nanocrystallites were successfully prepared at 400 degrees C in equal moles of NaNO3 and KNO3 molten salts. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, transmission electronic microscopy (TEM), photoluminescence (PL) spectrum and lifetime were used to characterize the nanocrystallites. XRD results demonstrate that NaOH concentration and annealing temperature play important roles in phase purity and crystallinity of the nanocrystallites, the optimum NaOH concentration and annealing temperature being 6:40 and 400 degrees C respectively. TEM micrographs show the nanocrystallites are well crystallized with a cubic morphology in an average grain size of about 18 nm. Upon excitation of the vanadate group at 314 nm, YVO4:Eu3+ and YVO4:Dy3+ nanocrystallites exhibit the characteristic emission of Eu3+ and Dy3+, which indicates that there is an energy transfer from the vanadate group to the rare earth ions. Moreover, the structure and luminescent properties of the nanocrystallites were compared with their bulk counterparts with same composition in detail.     

Sr0.95Zn0.05Se:Eu2+ and CdSe/ZnS nanocrystals hybrid phosphors for enhancing color rendering index of white light emitting diode

In this study, the yellow emitting cubic structure of Sr0.95Zn0.05Se:Eu2+ phosphors were prepared by high temperature solid state reaction. The Sr0.95Zn0.05Se:Eu2+ phosphors exhibited strong excitation intensity under 400-460 nm region, and broad band emission appeared at around 545-600 nm due to the d-f transition of Eu2+. To enhance the red emission, HDA/TOP/TOPO capped CdSe/ZnS NCs were synthesized via fast nucleation and slow growth method. The narrow emission peak was located at 615 nm with 69% of high quantum yield. Bright white emission was generated by combining a 460 nm InGaN LED chip with CdSe/ZnS NCs and Sr0.95Zn0.05Se:Eu2+ hybrid phosphors. The fabricated white LEDs showed warm white light with acceptable CIE chromaticity coordinate variation from (0.343, 0.255) at 20 mA to (0.335, 0.250) at 50 mA. The addition of CdSe/ZnS NCs contributed to the extension of white light spectrum by supplement of the red region. The color rendering index was largely enhanced from 41.7 to 79.7 compared to the Sr0.95Zn0.05Se:Eu2+ based phosphors white LED.     

Eu2+、Dy3+、Li+共掺杂CaSi2O2N2荧光粉的发光性能

采用高温固相反应法制备了一系列白光LED用CaSi2O2N2:0.05Eu2+,xDy3+,xLi+(0≤x≤0.03)荧光粉.利用X射线衍射仪对样品的物相结构进行了分析,结果表明:Dy3+和Li+离子的掺入没有改变CaSi2O2N2:Eu2+荧光粉的主晶相.利用荧光光谱仪对样品的发光性能进行了测试,发现所有样品的激发光谱均覆盖了从近紫外到蓝光的较宽范围,400 nm激发下得到的发射光谱为宽波段的单峰,峰值位于545 nm左右,是Eu2+离子5d-4f电子跃迁引起的.Dy3+离子掺杂可以提高CaSi2O2N2:Eu2+荧光粉的发光强度,Dy3+与Li+共掺杂可进一步提高荧光粉的发光强度,当Dy3+和Li+的掺杂量为1mol%时,荧光粉的发光强度达到最大值,是单掺杂Eu2+的荧光粉发光强度的157%.     

Luminescence properties of nano-sized Sr2MgSiO5: Eu2+, Mn2+ phosphors prepared by the sol-gel method

Nano-sized Sr2MgSiO5:Eu2+, Mn2+ phosphor was synthesized by the sol-gel method. The preparation conditions of the precursor were determined. The effect of Eu2+ and Mn2+ content on the luminescence intensity was studied. X-ray diffraction (XRD), photoluminescence spectra (PL), and photoluminescence excitation spectra (PLE) were used to characterize the samples. The results showed that the excitation bands ranged from 250 to 450 nm, and their peaks positioned around 365 nm. The emission spectrum consists of three bands: blue, green, and red, respectively. The blue and green emission bands originate from the center of the Eu2+, while the red emission band is attributed to the energy transfer from Eu2+ to Mn2+. White light can be obtained by mixing the three emission colors. The experiment results show that the Sr2MgSiO5:Eu2+, Mn2+ is a single host phosphor with superior properties for use in white light emitting diodes (white LED).     

Facile synthesis and luminescence characteristics of high-quality CdS: Eu/ZnS core/shell nanocrystals with biocompatibility

In this paper, we report a facile method to synthesize high quality CdS: Eu nanocrystals (NCs) and CdS: Eu/ZnS NCs with strong photoluminescence (PL). The influence of various experimental variables including the concentration of Eu3+ ions, the reaction time and the reaction temperature were investigated systematically. In addition, the PL properties of CdS: Eu NCs exhibited pH sensitive. Under the acid condition, pH value of the CdS: Eu NCs solution played an important role in determining PL emission intensity. However, under the alkaline condition, the obtained CdS: Eu NCs exhibited a tunable PL emission wavelength (from 490 nm to 610 nm) when pH value was adjusted from pH 7 to 10. After coating with ZnS shell, the CdS: Eu/ZnS NCs showed enhanced PL intensity compare with one of the CdS: Eu NCs. The CdS: Eu NCs and CdS: Eu/ZnS NCs were characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). In addition, the biocompatibility of these NCs was measured by hemolytic test, which indicated that CdS: Eu/ZnS NCs were more biocompatible than CdS: Eu NCs at the same conditions. It can be expected that CdS: Eu/ZnS NCs are promising biolabeling materials.     

Tunable luminescence and energy transfer properties of Sr₃AlO₄F:RE³+ (RE = Tm/Tb, Eu, Ce) phosphors

Sr(3)AlO(4)F:RE(3+) (RE = Tm/Tb, Eu, Ce) phosphors were prepared by the conventional solid-state reaction. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), photoluminescence (PL) spectra, as well as lifetimes were utilized to characterize samples. Under the excitation of UV light, Sr(3)AlO(4)F:Tm(3+), Sr(3)AlO(4)F:Tb(3+), and Sr(3)AlO(4)F:Eu(3+) exhibit the characteristic emissions of Tm(3+) ((1)D(2)→(3)F(4), blue), Tb(3+) ((5)D(4)→(7)F(5), green), and Eu(3+) ((5)D(0)→(7)F(2), red), respectively. By adjusting the doping concentration of Eu(3+) ions in Sr(3)AlO(4)F:0.10Tm(3+), 0.10Tb(3+), zEu(3+), a white emission in a single composition was obtained under the excitation of 360 nm, in which an energy transfer from Tb(3+) to Eu(3+) was observed. For Sr(3)AlO(4)F:Ce(3+),Tb(3+) samples, the energy transfer from Ce(3+) to Tb(3+) is efficient and demonstrated to be a resonant type via a dipole-quadrupole interaction by comparing the experimental data and theoretical calculation. Furthermore, the critical distance of the Ce(3+) and Tb(3+) ions has also been calculated to be 9.05 ?. The corresponding luminescence and energy transfer mechanisms have been proposed in detail. These phosphors might be promising for use in near-UV LEDs.     

Polyol-mediated synthesis and photoluminescent properties of Ce3+ and/or Tb3+-doped LaPO4 nanoparticles

Rare-earth ion (Ce3+, Tb3+) doped LaPO4 nanoparticles were prepared by the polyol method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), UV-vis absorption spectroscopy, photoluminescence (PL) spectroscopy, and lifetimes. The results of XRD indicate that the as-prepared nanoparticles are well-crystallized at 160 degrees C and assigned to the monoclinic monazite structure of the LaPO4 phase. The obtained LaPO4:Ce3+, Tb3+ nanoparticles are spherical with narrow size distribution and average size of 20 nm. The doped rare-earth ions show their characteristic emission in LaPO4 nanoparticles, i.e., Ce3+ 5d-4f and Tb3+ 5D4-7FJ (J = 6-3) transitions, respectively. The optimum doping concentration for Tb3+ in La(0.8-x)Ce0.2TbxPO4 nanoparticles is determined to be 15 mol% (x = 0.15). The luminescence decay curves of Ce3+ in LaPO4:Ce3+ and LaPO4:Ce3+, Tb3+ nanoparticles present a single-exponential behavior, and the lifetimes (tau) of Ce3+ decrease with increasing Tb3+ concentrations (at the constant Ce3+ concentration) in LaPO4:Ce3+, Tb3+ nanoparticles due to the energy transfer from Ce3+ to Tb3+. The energy-transfer efficiency from Ce3+ to Tb3+ was calculated, which depends on the doping concentrations of Tb3+ if the concentration of Ce3+ is fixed.