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.     

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.     

Efficient dual mode multicolor luminescence in a lanthanide doped hybrid nanostructure: a multifunctional material

The present work deals with inorganic-organic hybrid nanostructures capable of producing intense visible emission via upconversion (UC), downconversion (DC), and energy transfer (ET) processes which show the potential of the material as a luminescent solar collector (LSC), particularly to improve the efficiency of silicon solar cells. To achieve this, Gd2O3:Yb3+/Er3+ phosphor (average particle size～35 nm) and a Eu(DBM)3Phen organic complex have been synthesized separately and then the hybrid structure has been developed using a simple mixing procedure. Intense UC emission (in the red, green, and blue regions) due to Er3+ is observed on near infrared (976 nm) excitation which shows color tunability with input pump power. In contrast, intense red emission of Eu3+ is observed on ultaviolet (UV) (355 nm) excitation. The feasibility of energy transfer from Er3+ ions to Eu3+ ions has also been noted. These excellent optical properties are retained even if the particles of the hybrid nanostructure are dispersed in liquid medium, which also makes it suitable for security ink purposes.     

Er3+/Yb3+掺杂NaGd(WO4)2粉体的制备与发光性能

采用水热法成功制备了Er~(3+)/Yb~(3+)双掺杂的NaGd(WO_4)_2纳米粉体,研究了不同络合剂、水热温度对样品形貌和结构的影响。测量了不同Er~(3+)掺杂浓度样品的可见上转换和近红外发射光谱。结果表明:在980nm LD激发下,可观测到样品强烈的绿色上转换发光,对应Er~(3+)的~2H_(11/2)→~4I_(15/2)(530nm)和~4S_(3/2)→~4I_(15/2)(552nm)跃迁,以及较弱的红色上转换和近红外发光,分别对应Er~(3+)的~4F_(9/2)→4I15/2(656nm)和~4I_(13/2)→~4I_(15/2)(1 532nm)跃迁。且随着Er~(3+)掺杂浓度的增加,样品的上转换红绿光和1.54μm附近的近红外光均呈现出先增大后减小的趋势。样品的激发和发射光谱显示,在378nm处的激发峰最强,对应Er~(3+)的~4I_(15/2)→~4 G_(11/2)能级跃迁,最强发射峰位于552nm。根据泵浦功率与发光强度的关系可以得出,红光和绿光的发射主要为双光子吸收过程,但红光还包含了一定的单光子吸收成分。     

Structural and luminescence properties of Ho(3+)/Yb(3+)-doped Lu3Ga5O12 nano-garnets for phosphor applications

Lu3Ga5O12 nano-garnet powders doped with Ho(3+)/Yb(3+) ions have been prepared using a citrate sol-gel technique. The structural and morphological properties have been investigated by X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy. The materials are found to exist in single phase of cubic garnet structure with an average particle size of around 45 nm. The Ho(3+)/Yb(3+)-doped Lu3Ga5O12 nano-garnet powders give rise to an intense green and weak red emission of Ho3+ ions under 457.5 nm direct excitation. Moreover, when the Yb3+ ions are excited at 950 nm a very bright green luminescence of the Ho3+ ions is observed by the naked eyes even for such low laser power as 10 mW and the intensity of the red emission have been increased compared to that found under direct excitation of the Ho3+ ions. The power dependency and dynamics of the infrared-to-visible upconverted luminescence confirm the existence of different two-photon energy transfer processes. All these results have been compared with those obtained for other garnets doped with similar lanthanide ions which suggest that the Lu3Ga5O12 nano-garnets are potential materials for light emitting devices.     

热处理制度对Pr3+-Yb3+掺杂氟氧微晶玻璃光谱特性的影响

氟氧化物微晶玻璃具有良好的机械性能、化学稳定性和优异的发光性能,是作为量子剪裁的理想介质材料。本文选择55SiO2-5Na2O-20Al2O3-20CaF2作为稀土掺杂的基础玻璃,通过对玻璃进行不同的热处理从而获得了不同的Pr3+-Yb3+共掺微晶玻璃。通过吸收光谱、发射光谱和荧光衰减曲线的比较,发现升高热处理温度或延长保温时间会导致近红外区域的发射峰增强,Pr3+的荧光寿命降低,且计算表明,Pr3+-Yb3+之间的能量传递效率增加了。     

P2O3-B2O3-Al2O3-SrO-BaO玻璃中Yb3+非辐射能量转移下Er3+离子的增强发射

本文研究了共掺Er3 +/Yb3 +P2 O3 -B2 O3 -Al2 O3 -SrO -BaO玻璃的能量转移过程。实验中制备了高掺杂Yb3 +离子的双掺Er3 +/Yb3 +的磷酸盐玻璃样品。在Er3 +/Yb3 +掺杂比率 >1 :1 8(mol% )时 ,观测到了基于Yb3 +离子至Er3 +离子能量转移下Er3 +( 4 I13 / 2 →4I15 / 2 )的增强发射和Yb3 +( 2 F7/ 2 →2 F5 / 2 )发射的减弱 ,当Yb3 +离子掺杂浓度超过 2 .1× 1 0 2 1ions/cm3 时 (Er3 +/Yb3 +≤ 1 :1 8,mol% ) ,由于Yb3 +离子的自淬灭效应 ,Er3 +离子的发射强度降低。实验中得到了Yb3 +离子的最佳掺杂浓度为1 .74× 1 0 2 1ions/cm3     

Emission Properties of Yb3+/Er3+ Doped TeO2-WO3-ZnO Glasses for Broadband Optical Amplifiers

The YbS /Er3 doped TeO2-WO3-ZnO glasses were prepared. The absorption spectra, emission spectra and fluorescence lifetime of Era at 1.5μm, excited by 970 nm were measured. The influence of Er2Oa, Yb2Oa and Ohcontents on emission properties of Era at 1.5 μm was investigated. The optimum doping concentrations for Era and Yba is around 3.34× 1020 ions/cma and 6.63×1020 ions/cma, respectively. The peak emission cross section is 0.83～0.87 pm2. With the increasing concentration of Yba , the FWHM of Era emission at 1.5 μm in the glass increases from 77 nm to 83 nm. The results show that Yba /Era doped meO2-Woa-ZnO glasses are promising candidate for Era -doped broadband optical amplifier.     

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.     

Enhanced near-infrared quantum cutting in CaMoO4:Yb phosphors induced by doping with Li ions for improving solar cells efficiency

The near-infrared (NIR) quantum cutting (QC) CaMoO₄:Yb³⁺ phosphors co-doped with Li⁺ ions were synthesized by the sol–gel methods. The dependence of the structure, morphology, photoluminescence (PL) and downconversion (DC) quantum efficiency on the Li⁺ doping concentration have been investigated in details. It was demonstrated that the CaMoO₄:Yb³⁺ phosphors with appropriate concentration of the Li⁺ ions show improved crystallinity and remarkable increase of the NIR emission from the Yb³⁺ ions, if compared with the Li⁺-free samples. The enhancement of the NIR emission and DC quantum efficiency was suggested to be a consequence of the improved crystallinity and stronger absorption of the host due to the [MoO₄] tetrahedra distortion induced by the Li⁺ ions. Cooperative energy transfer (CET) from the host to the Yb³⁺ ions is discussed as a possible mechanism for the NIR emission enhancement. Excellent luminescence properties of the Li⁺ doped CaMoO₄:Yb³⁺ phosphor demonstrate its potential application as a better QC layer to increase the energy conversion efficiency of the Si-based solar cells.     

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.     

Structural and optical properties of NaY(WO4)2:Tm3+,Yb3+ and NaY(WO4)2:Tm3+,Er3+,Yb3+ powders synthesized by the high-temperature solid-state method

Journal of Materials Science: Materials in Electronics - The NaY(WO4)2:Tm3+,Yb3+ (NYW:Tm3+,Yb3+) and NaY(WO4)2:Tm3+,Er3+,Yb3+ (NYW:Tm3+,Er3+,Yb3+) powders have been synthesized by the...     

Zn2+掺杂诱导Eu3+激活BiOCl层状半导体的反常发光性能研究

采用固相法在500℃下成功制备Zn²⁺掺杂BiOCl:Eu³⁺层状半导体, 并研究了Zn²⁺ (0~20mol%)掺杂对Eu³⁺激活BiOCl层状半导体发光性能的影响。利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、傅里叶变换红外光谱(FT-IR)、激发-发射光谱、荧光寿命衰减曲线对样品的结构和性能进行表征。研究发现, 随Zn²⁺掺杂浓度增大, BiOCl晶体结构不变, Eu³⁺荧光寿命延长, 但发光强度却出现先减后增的反常现象。综合分析表明这可能与BiOCl特殊的层状结构有关。通过XRD和XPS的表征可以推断: 当Zn²⁺掺杂浓度≤10mol%, Zn²⁺在BiOCl中掺杂方式以晶胞层间隙掺杂为主; 当Zn²⁺掺杂浓度>10mol%后, 掺杂方式逐渐向取代掺杂转变。两种掺杂机制对Eu³⁺荧光寿命的改变以及形成缺陷对基质能量传递效率的影响可能是形成上述反常现象的主要原因。研究结果有助于认识稀土掺杂层状半导体的发光性能及影响规律, 并对Eu³⁺掺杂BiOCl这类新型发光材料的开发设计具有指导意义。     

Improved photoluminescence and ferroelectric properties of (Bi(3.6)Eu(0.4))Ti₃O₁₂ thin films via Li+ doping

(Bi(3.6)Eu(0.4))Ti?O?? (BEuT) thin films with different Li+ doping contents were prepared on fused silica and Pt/Ti/SiO?/Si substrates by chemical solution deposition, and the effects of Li+ doping contents on the photoluminescence and ferroelectric properties of the thin films were investigated in detail. The results showed that an appropriate amount of Li+ doping could effectively improve emission intensities for two characteristic Eu3+ emission transitions of ?D?→?F? (594 nm) and ?D?→?F? (617 nm) compared with BEuT thin films without Li doping. This photoluminescence improvement can be attributed to the dual roles of Li+ ions, one of which is that Li ions can act as co-activators which are helpful to the energy transfer from the host to the Eu3+ ions, leading to a higher quantum yield; the other is that Li ion doping can induce local distortion of crystal field surrounding the Eu3+ activator because Bi3+ and Li+ ions have different ionic radii. In addition, the Li+-doped BEuT thin films had larger remanent polarization than BEuT thin films without Li doping prepared under the same experimental conditions. These results suggest that Li+ doping is an effective way to improve photoluminescence and ferroelectric properties of the (Bi,Eu)?Ti?O?? thin films.     

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+.     

Photoluminescence spectra tuning of Eu2+ activated orthosilicate phosphors used for white light emitting diodes

Divalent europium activated alkaline earth orthosilicate M₂SiO₄ (M = Ba, Sr, Ca) phosphors were synthesized through solid-state reaction technique and their luminescent properties were investigated. Photoluminescence emission spectra of Sr₂SiO₄:Eu²⁺ phosphor was tuned by substitution of Sr²⁺ with 10 mol% Ca²⁺ or Mg²⁺. Two emission bands originated from the 4f–5d transition of Eu²⁺ ion doped into different cation sites in the M₂SiO₄ host lattice were observed under ultraviolet excitation. The Sr₂SiO₄:Eu²⁺ phosphor showed a blue and a green broad emission bands peaked around 475 and 555 nm with some variation for different Eu²⁺ doping concentration. When 10 mol% of Sr²⁺ was substituted by Ca²⁺ or Mg²⁺, the blue emission band blue-shifted to 460 nm and the green emission band shifted to even longer wavelength. An energy loss due to energy transfer from one Eu²⁺ to another Eu²⁺ ion, changing of the crystal field strength and covalence in the host lattice together were assigned for the tuning effect. With an overview of the excitation spectra and the emission spectra in blue and green-yellow color, these co-doped phosphors can become a promising phosphor candidate for white light-emitting-diodes (LEDs) pumped by ultraviolet chip.     

Eu2+离子在Sr2Al6O11基磷光体中发光行为的研究

研究了不同Eu掺杂浓度对Sr2Al6O11基磷光体发光性能的影响。结果发现，当Eu掺杂浓度低于0.01mol时，在其发射光谱中存在403和493nm的主发射峰，对应着Sr2Al6O11基质中Sr的两种不同位置Sr1和Sr2位。随着Eu掺杂浓度增加，由于能量传递作用，导致403nm的发射峰消失，493nm的发射峰增强。余辉衰减曲线表明，未掺杂Dy的磷光体没有余辉性能，当Eu掺杂量在0.01mol时，余辉性能最好，进一步提高Eu的掺杂量，由于浓度猝灭作用，导致发光性能下降。     

Tb3+-Yb3+共掺氟氧化物微晶玻璃的发光特性及其外量子效率的评价

本研究制备了Tb3+-Yb3+共掺杂含CaF2纳米晶相的氟氧化物透明微晶玻璃,并通过XRD验证了CaF2纳米晶的形成。基于Tb3+对Yb3+的协同能量传递,通过激发Tb3+∶5D4能级可观察到由Yb3+∶2F5/2→2F7/2跃迁引起的950~1100nm近红外发射。利用积分球测试系统评价了Yb3+在玻璃及微晶玻璃体系中的外量子效率,数据表明经过热处理后Yb3+的外量子效率有明显的增加,这是由于在微晶玻璃体系中掺杂的Tb3+离子和Yb3+离子富集在具有低声子能量的CaF2晶相从而获得了更有效的能量传递而引起的。同时利用Tb3+荧光寿命计算获得了材料的内量子效率,其值远大于外量子效率,这是由计算过程中的诸多近似所导致。     

Hydrothermal synthesis and luminescence behavior of lanthanide-doped GdF/sub 3/ nanoparticles

The lanthanide-doped GdF/sub 3/ nanoparticles have been produced by a simply hydrothermal synthesis procedure. The excitation and emission spectra of the Eu/sup 3+/-doped GdF/sub 3/ nanoparticles showed that the excitation energy of Gd/sup 3+/ is efficiently transferred to Eu/sup 3+/ in the Eu/sup 3+/-doped GdF/sub 3/ nanoparticles. Due to very low phonon energies of GdF/sub 3/ matrix, the /sup 5/D/sub 1/ emission of Eu/sup 3+/ ions in the Eu/sup 3+/-doped GdF/sub 3/ nanoparticles can be observed at room temperature when the doping concentration of Eu/sup 3+/ ions is lower than 15 mol%. The luminescence intensity of the Eu/sup 3+/-doped GdF/sub 3/ nanoparticles increased with increasing concentration of Eu/sup 3+/ ions and reached a maximum at approximately 15 mol%. The Er/sup 3+/-doped GdF/sub 3/ nanoparticles exhibit the typical emission spectra of Er/sup 3+/ in the near-infrared region. The upconversion emission of the Er/sup 3+//Yb/sup 3+/ codoped GdF/sub 3/ nanoparticles can also be observed. However, the upconversion emission intensity of the Er/sup 3+//Yb/sup 3+/-codoped GdF/sub 3/ nanoparticles was much weaker than that of the Er/sup 3+//Yb/sup 3+/-codoped GdF/sub 3/ bulk crystal.     

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。