One-step synthesis and luminescent properties of nanocrystalline YVO4:Eu3+ powders

In this paper, nanocrystalline YVO4:Eu3+ powders have been successfully synthesized via high-temperature solution-phase synthesis process. The nanocrystalline YVO4:Eu3+ particles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV/Nis absorption spectra and luminescence spectra, luminescence decay curve and Fourier transform infrared (FT-IR), X-ray photoelectron spectra (XPS) respectively. The as-prepared nanocrystalline YVO4:Eu3+ particles are well crystallized with ellipsoidal morphology. The emission of YVO4:Eu3+ particles show emission originating from the 5D0 level, with 5D0-7F2 at 616 nm as the most prominent group. The excitation spectrum fits basically with the absorption spectrum from the vanadate ions. FT-IR and XPS spectra indicate that the surface ligands of nanocrystalline particles were oleic acid and oleylamine. The lifetime for the luminescence of Eu3+ in the as-prepared YVO4:Eu3+ samples are shorter than that of the bulk material due to the absorption of organic ligands on the nanoparticle surface.     

The sol-gel process synthesis of GdAl3(BO3)4:Eu3+ nanophosphors

GdAl3(BO3)4:Eu3+ red phosphors were prepared using citric acid as complex agent by sol-gel technique. The preparation conditions of the precursor synthesis, including crystallization temperature and crystallization time were investigated. Their structure and luminescence properties were characterized by X-ray diffraction (XRD) analysis and fluorescence spectrometry. The results showed that GdAl3(BO3)4:Eu3+ phosphor crystallized at 960 degrees C for 2 h have been synthesized by sol-gel method. The phosphor is distributed into hexagonal system and the lattice parameters are a = 9.2992 nm c = 7.2577 nm. The excitation spectrum of Gd(0.95)Al3(BO3)4:Eu(0.05)3+ samples is complex and the frequency scale is wide. It consists of a number of main excitation transitions namely 8S(7/2) --> 6IJ (270 nm) of Gd3+, and the others 7F0 --> 5L6 (400 nm), 7F0 --> 5D2 (472 nm) and 7F0 --> 5D1 (542 nm) of Eu3+. The main emission peaks are 614 nm and 619 nm, which are the characteristic emission peaks of Eu3+. These emission peaks correspond to the transition from 5D0 to 7F2 of Eu3+. The shape and the wavelength range of the emission spectrum are similar when the sample was excited by different excitation spectrum. Only the relative intensity of the emission peaks is different from each other.     

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.     

Broadband downconversion in Bi3+, Yb3+-Co-doped YVO4 phosphor

Yttrium vanadate phosphors co-doped with Bi3+ and Yb3+ ions have been prepared via the solid-state reaction. The phosphors were characterized by various methods including X-ray diffraction, photoluminescence excitation and photoluminescence spectra. Upon ultraviolet (UV) light excitation, an intense near-infrared (NIR) emission of Yb3+ corresponding to the transition of 2F(5/2) --> 2F(7/2) peaking at 985 nm was observed as a result of energy transfer from O2(-)-V5+ or Bi3+-V5+ charge transfer state (CTS) to Yb3+. A broad excitation band ranging from 250 to 375 nm was recorded when the Yb3+ emission was monitored, which suggests an efficient energy transfer from CTS to Yb3+ ions. The dependence of Yb3+ doping concentration on the visible emission, the NIR emission and decay lifetime has been investigated. The results of visible and NIR spectral evolution with temperature indicate that the mechanism for the NIR-emission is mainly phonon-assisted energy transfer at room temperature, while the mechanism is mainly cooperative energy transfer at low temperature. The YVO4:Bi3+, Yb3+ phosphor has prospects for realizing high efficiency crystalline Si solar cells by converting broadband UV energy into NIR light.     

Eu-doped titania nanofibers: processing, thermal behaviour and luminescent properties

Undoped and Europium-doped titania nanofibers have been fabricated by electrospinning technique, using a single multielement Titanium/Europium source. In this communication we present the synthesis, structural and spectroscopic characterisation of Eu-doped TiO2 nanofibers starting from polyvinylpyrrolidone, titanium tetraisopropoxide (Ti(OiPr)4) and Eu(hfa)3 x diglyme (Hhfa = 1,1,1,5,5,5-hexafluoroacetyacetone, diglyme = CH3O(CH2CH2O)2CH3). The chosen system allowed to investigate a wide compositional range, i.e., from 3 to 10% mol of Eu3+. Microstructure was studied by means of scanning electron microscopy (SEM), thermal behaviour followed by thermogravimetric and differential thermal analysis (TG-DTA). Phase analysis was performed by means of X-ray diffraction (XRD) and high temperature X-ray diffraction analysis (HT-XRD) up to 1100 degrees C. Luminescence properties were investigated by means of luminescence spectroscopy, using a laser excitation source at 395 nm. All electrospun materials consisted of randomly oriented nanofibers of fairly uniform diameter. The average fiber size was 80-100 nm and 40 nm for, respectively, Eu-doped and undoped TiO2 calcinated at 500 degrees C. The presence of Europium shifted toward higher values either the crystallization temperature of anatase and the anatase to rutile phase transition, the latter being accompanied by the formation of the Eu2Ti2O7 phase. The doped samples showed a strong luminescence of Eu3+ ions. The emission spectra were dominated by the 5D0 --> 7F2 emission, suggesting a notable distortion around the Eu3+ ions. The broadening of the bands pointed to the presence of a relevant inhomogeneous disorder around the Eu3+ sites. The Eu3+ doped TiO2 nanofibers showed a higher emission intensity with respect to the PVP/TiO2 ones.     

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.     

Microstructure and environment dependence of 2H11/2 --> 4I15/2 upconversion emission in YVO4:Er3+, Yb3+ nanocrystals

Upconversion emission of different nanocrystalline YVO4:Er3+, Yb3+ synthesized by a hydrothermal process at low temperature was studied under 980 nm excitation where green [(2H11/2, 4S3/2) --> 4I15/2] and red (4F9/2 --> 4I15/2) emissions demonstrate sensitivity to the local environments of Er3+. Small particle size, high Yb3+ concentration, or high temperature favors the emission of the 2H11/2 --> 4I15/2 transition. Both XRD patterns and Raman spectra have confirmed that crystal lattice distortion of YVO4:Er3+, Yb3+ nanocrystals is more serious when the nanoparticle size is decreasing or Yb3+ concentration is increasing. This distortion is thought to play a key role in the observed spectral properties, which might lead to a new route to improve the monochromatic upconversion emission efficiency in these nanocrystals.     

表面效应对YAG:Eu3+纳米晶发光特性的影响研究

分别采用沉淀法和燃烧法制备了YAG:1%Eu3+纳米晶粉末,用XRD和TEM对样品进行了结构分析和形貌表征。室温光谱分析表明,其发射主峰位于590nm,来源于5 D0→7F1跃迁,另外来源于5 D0→7F4跃迁的709nm发射也较强。另外发现,燃烧法制备的样品在不同激发波长激发时,发射光谱峰形有显著变化。对沉淀法制备的纳米微粒经盐酸"浸蚀"表面修饰后,发现395nm激发时,676nm和693nm发光显著增强,而且693nm发射的激发谱中存在两个宽激发带。对表面修饰后样品的变温发光特性研究发现,随着温度的降低,676nm发射显著增强,而693nm发射显著减弱。对于上述现象通过纳米微粒的表面效应和缺陷态进行了分析和解释。     

Energy transfer mechanisms in Yb3+-doped GdVO4 near-infrared downconversion nanophosphor

Yb3+-doped GdVO4 nanophosphor was prepared by the co-precipitation method. Under ultraviolet (UV) light excitation, strong near-infrared (NIR) emission of Yb3+ (2F(5/2) --> 2F(7/2)) around 980 nm was observed. Owing to the host absorption of GdVO4, a broad excitation band ranging from 250 to 350 nm was recorded when the Yb3+ emission was monitored, which suggests an efficient energy transfer from the host to the Yb3+ ions. The concentration dependence of the visible vanadate emission and the Yb3+ emission was investigated. The decay curve of the vanadate emission was measured under the excitation of a 266 nm pulsed laser. The decay time of the vanadate emission at 500 nm was remarkably reduced by introducing Yb3+, further verifying that the energy transfer from the vanadate host to the Yb3+ ions was very efficient. Cooperative energy transfer (CET) is discussed as the possible energy transfer process. The temperature dependence of the emission intensity and decay time were also investigated for our further discussion.     

Synthesis and luminescence properties of Sr2SiO4: Eu3+, Dy3+ phosphors by the sol-gel method

The Sr2SiO4:Eu3+, Dy3+ phosphors for white light emitting diodes (LEDs) were synthesized by the sol-gel method. The microstructure and luminescent properties of the obtained Sr2SiO4:Eu3+, Dy3+ particles were well characterized. The results demonstrate that the Sr2SiO4:Eu3+, Dy3+ particles, which have spherical morphology, emitted an intensive white light emission under excitation at 386 nm. The phosphors show three emission peaks: the blue emission at 486 nm corresponding to the 4F(9/2)-6H(15/2) transition of Dy3+, the yellow emission at 575 nm corresponding to the 4F(9/2)-6H(13/2) transition of Dy3+, and the red emission at 615 nm corresponding to the 5D0-7F2 transition of Eu3+. At the same time, the effect of Eu3+ concentration on the emission intensities of Sr2SiO4:Eu3+, Dy3+ was investigated in detail. The phosphors used for white LEDs were obtained by combining near ultraviolet (NUV) light (386 nm) with Sr2SiO4:0.04Dy3+, 0.01Eu3+ phosphors with the characteristic of Commission Internationale de l'Eclairage (CIE) chromaticity coordinate (x, y) of (0.33, 0.34), and color temperature Tc of 5,603 K. In addition, the effect of the charge compensators (Li+, Na+, and K+ ions) on the photoluminescence (PL) emission intensities were studied.     

Enhanced ultraviolet upconversion luminescence of Tm and Yb codoped ZrF4-BaF2-LaF3-AlF3-NaF glass

Ultraviolet (UV) upconversion (UC) luminescence properties of Tm3+ ions sensitized by Yb3+ ions in ZrF4-BaF2-LaF3-AlF3-NaF (ZBLAN) glass were studied in detail. Under the excitation from a 980 nm continuous wave (CW) diode laser, red, blue, and even UV emissions were observed in the fluorozirconate glass. Several fluorescence bands appeared in the UC emission spectrum from 292.8 nm to 805.8 nm. The UC emission peaks at 291 nm, 347 nm, 363 nm, 454 nm, 475 nm, 647 nm, 687 nm, and 804 nm correspond to the transitions of 1I6 --> 3H6, 1I6 --> 3F4, 1D2 --> 3H6, 1D2 --> 3F4, 1G4 --> 3H6, 1G4 --> 3F4, 3F3 --> 3H6, and 3H4 --> 3H6, respectively. Experimental results of intensity dependence of the up-converted fluorescence on the pump power indicate a five-photon excitation scheme of 1I6 energy level.     

Luminescent properties of La3PO7:Eu3+ nanoparticles

La3PO7:Eu3+ samples were prepared by combustion and annealing and characterized by X-ray diffraction and transmission electron microscopy. It was found that the average size of the particles is about 80 nm. The red emission from the 5D0 --> 7F2 transition of the Eu3+ ions under ultraviolet light excitation is much stronger than the orange emission from the 5D0 --> 7F1 transition. The emission spectra, charge transfer band, laser selective excitation spectra, and time-resolved spectra indicate that symmetry of the local environment of Eu3+ lacks an inversion center and Eu3+ ions occupy at least two types of sites in the La3PO7 crystal. The superior color chromaticity compared to other phosphates and borates doped with Eu3+ means La3PO7:Eu3+ may have potential as a luminescent material.     

CaMoO4:x%Yb3+: a novel near-infrared quantum-cutting phosphors via cooperative energy transfer

An efficient near-infrared (NIR) dowmconversion (DC) has been demonstrated in the CaMoO4:Yb3+ phosphors. Very strong NIR emission around 998 nm from the 2F(7/2) --> 2F(5/2) transition of the Yb3+ has been observed under ultraviolet excitation. A similar broad excitation band due to the absorption of the host CaMoO4 has been recorded when the NIR emission of Yb3+ and the visible molybdate (MoO4(-2)) emission are monitored, which suggests an efficient energy transfer (ET) from the host to the Yb3+. The Yb3+ concentration-dependent luminescence properties and lifetimes of both the visible and NIR emissions have also been studied. The lifetime of the molybdate emission decreases rapidly with the increasing Yb3+ concentration, further verifying the efficient ET from the host to the Yb3+. Moreover, the low temperature measurements have also been carried out to investigate the ET mechanism in the phosphors. A cooperative energy transfer (CET) mechanism has been proposed to rationalize the DC effect. The newly studied CaMoO4:Yb3+ DC phosphors, which can convert the broadband emission of the MoO4(2-) into NIR emission of Yb3+ with a twofold increase in the photon number will have potential application in greatly enhancing the response of silicon-based solar cells with a relatively higher Yb3+ quenching concentration.     

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%.     

Hydrothermal synthesis and size-enhanced chromaticity of Sr2ZnSi2O7:Eu3+ nanoparticles

Red phosphor Sr2ZnSi2O7:Eu3+ nanoparticles with an average diameter of 20 nm were successfully synthesized via a low-temperature hydrothermal route in order to understand the underlying relationship between size and luminescent properties. The nanometer-sized particles result in a distinct improvement in chromaticity and a high quenching concentration. According to emission spectra, the relative intensity of the 5D0 --> 7F2 to 5D0 --> 7F1 transitions in nanometer-sized phosphors is higher than that of the corresponding bulk material. The better chromaticity results from the more distorted lattices and relatively lower crystal symmetry around the Eu3+ ions, which is ascribed to the large surface area due to the nanometer size of the phosphor. Moreover, the nanometer-sized Sr2ZnSi2O7:Eu3+ red phosphor exhibits a shorter fluorescent lifetime and a blue-shift in excitation spectra compared to that of its bulk counterpart. These results indicate that size-induced enhancement of luminescent properties is an efficient way to obtain red phosphors with better chromaticity.     

Multipass pumped Nd-based thin-disk lasers: continuous-wave laser operation at 1.06 and 0.9 microm with intracavity frequency doubling

The laser performances of the 1.06 microm (4)F(3/2) --> (4)I(11/2) four-level transition and of the 0.9 microm (4)F(3/2) --> I(9/2)4 quasi-three-level transition were investigated using multipass pumped Nd-based media in thin-disk geometry. When pumping at 0.81 microm into the (4)F(5/2) level, continuous-wave laser operation was obtained with powers in excess of 10 W at 1.06 microm, in the multiwatt region at 0.91 microm in Nd:YVO(4) and Nd:GdVO(4), and at 0.95 microm in Nd:YAG. Intracavity frequency-doubled Nd:YVO(4) thin-disk lasers with output powers of 6.4 W at 532 nm and of 1.6 W at 457 nm were realized at this pumping wavelength. The pumping at 0.88 microm, which is directed into the (4)F(3/2) emitting level, was also employed, and Nd:YVO(4) and Nd:GdVO(4) thin-disk lasers with ~9 W output power at 1.06 microm and visible laser radiation at 0.53 microm with output power in excess of 4 W were realized. Frequency-doubled Nd:vanadate thin-disk lasers with deep blue emission at 0.46 microm were obtained under pumping directly into the (4)F(3/2) emitting level.     

稀土掺杂双钙钛矿结构红色荧光粉的制备及其发光性能

采用高温固相反应法制备了Sr_(2-x)BaxMgMoO_6∶Eu~(3+)(x=0~1)双钙钛矿结构红色荧光粉。探讨了预处理及煅烧制度、Ba取代量对Sr_(2-x)BaxMgMoO_6∶Eu~(3+)荧光粉的相结构和发光性能的影响。Sr_2Mg_(0.94)Eu_(0.06)MoO_6荧光粉最佳制备工艺为:在700℃下预处理1h再升温至1050℃预处理1h并随炉降温后研细,再在1300℃煅烧4h,所得样品主相为双钙钛矿结构的Sr2MgMoO6四方相。其最强发光峰位于617nm附近,对应于Eu3+的5D0→7F2电偶极跃迁。随着Ba2+对Sr2+的取代量的增加晶体对称性提高,晶体结构由四方相变为立方相,样品的激发峰强度显著提高。由于晶体对称性的提高,抑制了荧光粉在617nm处5D0→7F2红光发射,其发光由电偶极跃迁占主导转变为磁偶极跃迁占主导。     

Preparation and luminescence properties of La6MoO12:Eu3+/PVA nanofibers by Pechini/electrospinning process

The 20% concentration Eu3+-based red-emitting phosphor, nano-sized La6MoO12:Eu3+ was prepared by the Pechini method. X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG-DTA), scanning electron microscopy (SEM), photoluminescence (PL), and decay curves were used to characterize the resulting samples. The phosphor can be efficiently excited by near UV light and exhibits an intense red luminescence corresponding to the electric dipole transition 5D0 --> 7F2 at 615 nm. When the phosphor was mixed into poly(vinyl alcohol) aqueous solution, the fluorescent nanofibers could be prepared by electrospinning process. It was suggested that the La6MoO12:Eu3+ phosphor would be a promising red component for solid-state lighting devices based on InGaN or GaN light-emitting diodes.     

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.