Multicolor up-conversion emissions of Tm3+/Er3+/Yb3+ tri-doped YF3 phosphors

Tm3+/Er3+/Yb3+ tri-doped yttrium fluoride (YF3) phosphors were prepared by a facile hydrothermal method. X-ray topographic analysis found that the phosphors were crystallized products. Their sizes and morphologies were characterized by scanning electron microscopy (SEM, Hitachi S-4800), which indicated that most of the YF3 phosphors were hundreds of nanometers in size. Up-conversion (UC) spectra were recorded under 980-nm diode laser excitation at room temperature with a fluorescence spectrometer (Hitachi F-4500). Plenty of UC emissions of Tm3+ and Er3+ were observed from ultraviolet to red. For Tm3+ ions, a five-photon process (approximately 291 nm and approximately 347 nm), a four-photon process (approximately 362 nm and approximately 452 nm), and a three-photon process (approximately 475 nm) were identified in the UC spectra. The UC emissions from the Er3+ were: approximately 380 nm, approximately 408 nm, approximately 521 nm, approximately 537 nm, and approximately 652 nm. Therefore, cyan-white light can be observed by the naked eye at 980-nm excitation, even under low excitation power density. By comparing the UC spectra of the phosphors annealed at different temperatures, we found that the intensity of the UC luminescence increased as annealing temperature increased. Furthermore, the spectral dependencies on Tm3+ doped concentrations were studied. The energy transfer processes and fluorescence dynamics in the tri-doped system are currently being investigated.     

Up-conversion fluorescence of Tm3+ and Gd3+ in Yb3+/Tm3+ co-doped Gd2O3 nanocrystals

Through a co-precipitation method Gd(OH)3:20%Yb3+, 1%Tm3+ nanorods were synthesized. After sintered at 900 degrees C for 1 h in air, the as-prepared Gd(OH)3:20%Yb3+, 1%Tm3+ nanorods were converted into Gd2O3:20%Yb3+, 1% Tm3+ nanocrystals. Crystalline phases, sizes, and morphologies of the two samples were characterized by X-ray diffraction and field emission scanning electron microscope. The up-conversion (UC) fluorescence spectra of the Gd2O3:20%Yb3+, 1%Tm3+ nanocrystals were recorded by using a fluorescence spectrophotometer with a 980 nm continuous wave laser diode as excitation source. The nanocrystals not only present characteristic blue and ultraviolet (UV) UC emissions of activated Tm3+, but also show UV UC emissions of host Gd3+. The experimental study suggests that the excitation power has great effects on UC fluorescence properties and the energy transfer from Tm3+ to Gd3+ is very efficient.     

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     

Up-conversion emissions characteristics of non-aqueous sol-gel derived RE3Al5O12 nanocrystals

The RE3Al5O12 (REAG:Er3Al5O12, Er:Y3Al5O12 and Er:Yb3Al5O12) up-conversion (UC) nanocrystals have been prepared by the non-aqueous sol-gel method. The green and red UC emissions are attributed to the 2H(11/2), 4S(3/2) --> 4I(15/2) and 4F(9/2) --> 4I(15/2) transitions of Er3+, respectively, were obtained for all samples with a 975 nm semiconductor LD excitation. For Er3Al5O12 nanocrystals, the green and red UC emissions have similar intensities. Y and Yb ions have no evident effect on the peak positions, but strongly affected the intensities of the green and red UC emissions of the Er. A much higher intensity of the green relative to red UC emission was observed for Er:Y3Al5O12 nanocrystals, however, the red UC emission became predominant for Er:Yb3Al5O12 nanocrystals. It was suggested that the two-photon process was responsible for the green and red UC emissions mechanism for all the samples.     

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.     

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.     

Emission properties of hydrothermal Yb(3+), Er(3+) and Yb(3+), Tm(3+)-codoped Lu2O3 nanorods: upconversion, cathodoluminescence and assessment of waveguide behavior

Yb(3+) and Ln(3+) (Ln(3+) = Er(3+) or Tm(3+)) codoped Lu(2)O(3) nanorods with cubic Ia3 symmetry have been prepared by low temperature hydrothermal procedures, and their luminescence properties and waveguide behavior analyzed by means of scanning near-field optical microscopy (SNOM). Room temperature upconversion (UC) under excitation at 980 nm and cathodoluminescence (CL) spectra were studied as a function of the Yb(+) concentration in the prepared nanorods. UC spectra revealed the strong development of Er(3+) (4)F(9/2) → (4)I(15/2) (red) and Tm(3+) (1)G(4) → (3)H(6) (blue) bands, which became the pre-eminent and even unique emissions for corresponding nanorods with the higher Yb(3+) concentration. Favored by the presence of large phonons in current nanorods, UC mechanisms that privilege the population of (4)F(9/2) and (1)G(4) emitting levels through phonon-assisted energy transfer and non-radiative relaxations account for these observed UC luminescence features. CL spectra show much more moderate development of the intensity ratio between the Er(3+) (4)F(9/2) → (4)I(15/2) (red) and (2)H(11/2), (4)S(3/2) → (4)I(15/2) (green) emissions with the increase in the Yb(3+) content, while for Yb(3+), Tm(3+)-codoped Lu(2)O(3) nanorods the dominant CL emission is Tm(3+) (1)D(2) → (3)F(4) (deep-blue). Uniform light emission along Yb(3+), Er(3+)-codoped Lu(2)O(3) rods has been observed by using SNOM photoluminescence images; however, the rods seem to be too thin for propagation of light.     

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.     

Synthesis and up-conversion emissions of $$\hbox {Yb}^{3+}{/}\hbox {Er}^{3+}$$, $$\hbox {Yb}^{3+}{/}\hbox {Tm}^{3+}$$Yb3+/Tm3+ and $$\hbox {Yb}^{3+}{/}\hbox {Tm}^{3+}{/}\hbox {Gd}^{3+}$$Yb3+/Tm3+/Gd3+ co-doped $$\hbox {KLu}_{2}\hbox {F}_{7}$$KLu2F7

\(\hbox {Yb}^{3+}/\hbox {Er}^{3+}\), \(\hbox {Yb}^{3+}/\hbox {Tm}^{3+}\), or \(\hbox {Yb}^{3+}/\hbox {Tm}^{3+}/\hbox {Gd}^{3+}\) co-doped \(\hbox {KLu}_{2}\hbox {F}_{7}\) up-conversion (UC) materials were synthesized through a hydrothermal method or an additive-assisted hydrothermal method. The X-ray diffraction (XRD) results suggested that the materials crystallized in orthorhombic phase, yet, the potassium citrate (CitK) introduction affected immensely the crystalline purity of final material. The field emission scanning electron microscopy (FE-SEM) results suggested that the additive adding had effects on size and morphology of the material, which affected the UC emissions further. Green/red UC emissions of \(\hbox {Er}^{3+}\), UV/blue/IR UC emissions of \(\hbox {Tm}^{3+}\), and UV UC emissions of \(\hbox {Gd}^{3+}\) were observed in the orthorhombic phase of \(\hbox {KLu}_{2}\hbox {F}_{7}\) materials. The excitation power-dependent UC emissions illustrated that the UC emission intensity initially increased, then decreased with the increase in excitation power. At the same time, the variation rates of different transitions in \(\hbox {Er}^{3+}\) or \(\hbox {Tm}^{3+}\) are also different. In addition, the \(\hbox {Er}^{3+}\) or \(\hbox {Tm}^{3+}\) concentration-dependent UC emission results suggested that the optimal doping concentration of \(\hbox {Er}^{3+}\) is 2 mol% and \(\hbox {Tm}^{3+}\) is 0.5 mol% with the \(\hbox {Yb}^{3+}\) concentration fixed as 20 mol%. The experimental results suggest that the orthorhombic phase of \(\hbox {KLu}_{2}\hbox {F}_{7}\) should be a good host lattice for UC emitters.     

Ion-exchanged waveguide lasers in Er3+/Yb3+ codoped silicate glass

We investigated an Er(3+)/Yb(3+) codoped silicate glass as a host material for waveguide lasers operating near 1.5 mum. Spectroscopic properties of the glass are reported. Waveguide lasers were fabricated by K(+)-ion exchange from a nitrate melt. The waveguides support a single transverse mode at 1.5 mum. An investigation of the laser performance as a function of the Yb:Er ratio was performed, indicating an optimal ratio of approximately 5:1. Slope efficiencies of as great as 6.5% and output powers as high as 19.6 mW at 1.54 mum were realized. The experimental results are compared with a waveguide laser model that is used to extract the Er(3+) upconversion coefficients and the Yb(3+)-Er(3+) cross-relaxation coefficients. The results indicate the possibility of obtaining high-performance waveguide lasers from a durable silicate host glass.     

White up-conversion luminescent property in Re3+:Gd3Ga5O12 nanocrystals

Rare-earth ions doped Gd3Ga5O12 nanocrystals have been prepared by a propellant combustion synthesis method and their up-conversion properties were systematically investigated in this paper. XRD, SEM, TEM, and up-conversion emission spectra were used to characterize the synthesized nanocrystals. Energy transfer from Yb3+ to Er3+ and Tm3+ can occur simultaneously in the as-synthesized Gd3Ga5O12 nanocrystals. The up-conversion mechanisms and relevant energy transfer processes are discussed. A white light generation was observed when the Yb3+, Er3+ and Tm3+ were directly incorporated in the Gd3Ga5O12 lattice. And its calculated color coordinates is (0.35, 0.41) under the excitation at 974.5 nm. The bright white luminescent nanocrystals may have potential application in the field of lighting, displays and photonics.     

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.     

Fluorescence dynamics and rate equation analysis in Er3+ and Yb3+ doped double tungstates

The fluorescence dynamics in Er3+ and Yb3+ doped KGd(WO4)2 and KY(WO4)2 has been investigated. Lifetimes have been measured for the Yb (2F(5/2)), Er (4I(13/2)), and Er (4S(3/2)) levels around 1, 1.5, and 0.55 microm, respectively. The Yb (2F(5/2)) lifetimes show a decreasing trend toward the limiting Er (4I(11/2)) lifetime with increasing Er-to-Yb concentration ratio, whereas the Er (4I(13/2)) lifetimes are mostly unaffected by the doping concentrations. A rate equation analysis has been performed to explain the observed behavior and gain is calculated for a continuous-wave laser at 1.53 microm to find the optimum doping concentrations for high gain.     

Improved infrared emissions of Er(3+)-Tm3+ co-doped Al2O3 thin films: the role of cross relaxation among rare earth ions

We report the infrared emissions of Er(3+)-Tm3+ co-doped amorphous Al2O3 thin films pumped at 791 nm by a Ti:sapphire laser. The as-deposited films were annealed to improve the photoluminescence performance. Three cross relaxation channels among Er(3+)-Tm3+ and Tm(3+)-Tm3+ ions incorporated in the films were investigated as annealing temperature increases especially from 800 to 850 degrees C. In order to understand the Stark effect and cross relaxations, the photoluminescence spectra were deconvoluted by Gaussian fittings. Our results indicate that the luminescence intensity of 1.62 microm in comparison to 1.5 microm can be enhanced by the cross relaxation process [Er3+ (4I13/2) + Tm3+ (3H6) --> Er3+ (4I15/2) + Tm3+ (3F4)], and the longer-wavelength side of Er3+ emission can be improved by the CR process [Er3+ (4I15/2) + Tm3+ (3H4) --> Er3+ (4I3/2) + Tm3+ (3F4) at expense of the Tm3+ 1.47 microm emission which is also maybe quenched by the CR effect between themselves. These results suggest one possible approach to achieve broadband infrared emissions at the wavelength region of 1.45-1.65 microm from the Er(3+)-Tm3+ co-doped systems.     

纤维状中空结构NaYF4:Yb3+, Er3+上转换材料的 合成及防伪应用

采用水溶性聚合物聚乙烯亚胺(PEI)调介下的水热法,一步合成了具有纤维状中空结构的六方相NaYF4:Yb3+,Er3+上转换荧光材料,并将其作为荧光填料,通过流延成膜法制备了具有上转换荧光性能的壳聚糖/聚乙烯醇(CS/PVA)荧光复合薄膜.探究了PEI配体含量和反应体系pH值对合成的上转换材料的形貌、晶型和荧光性能的影响,以及壳聚糖/聚乙烯醇荧光复合薄膜中荧光填料的最佳掺杂量.研究结果表明,在PEI含量为0.3 g且反应体系pH=5的条件下,合成的产物为具有纤维状中空结构的六方相NaYF4:Yb3+,Er3+.荧光光谱表明,合成的NaYF4:Yb3+,Er3+上转换材料在980 nm激光激发下具有优异的荧光性能.当荧光填料的掺杂质量分数为3.0％时,制备的NaYF4:Yb3+,Er3+/(CS/PVA)荧光复合薄膜具有最佳的透明度和上转换荧光特性.     

铒单掺和铒/镱共掺氟氧玻璃的上转换发光性质研究

研究了室温下掺不同摩尔分数Er3+单掺和Er3+/Yb3+双掺的20GaF3-15InF3-17CdF2-15ZnF2-10SnF2-3P2O5-(20-x-y)PbF2-xErF3-yYbF3(x=0.1~0.4,y=1~4)氟氧玻璃的上转换发光性质。755nm激发下,在Er3+单掺系列玻璃中观察到紫色(410nm)、蓝色(465nm)和绿色(522nm、544nm)上转化发光,随着掺杂Er3+浓度的增大,各荧光强度增幅有变缓的趋势。980nm激发下,由于Yb3+的敏化作用,在Er3+/Yb3+双掺系列玻璃中观察到绿色(548nm、527nm)和红色(661nm)上转换发光,固定Er3+浓度,随着Yb3+浓度的增大,各荧光强度先增大后减小,当Yb3+、Er3+掺杂浓度比为15时发光强度最大。该氟氧玻璃具有比氟化物玻璃更好的抗析晶稳定性,掺稀土离子后在不同波长激发下可观察到明亮的红、绿色上转换荧光,是一种有潜质用于红、绿色上转换发光的材料。     

Synthesis and upconversion luminescence properties of CaF2:Yb3+/Tm3+ microspheres

CaF2:Yb3+/Tm3+ microspheres were synthesized by using a simple hydrothermal method. Their structures and morphologies were characterized by X-ray diffraction (XRD) and field-effective scanning electron microscopy (FESEM). The microspheres were formed from a large number of nanospheres with almost the same diameter after annealing. The growth mechanism of the microspheres was discussed. Strong ultraviolet (UV) and blue upconversion (UC) emission from the CaF2 microspheres was observed under 980 nm excitation. The enhancement of the UV UC emission was attributed to the size effect of the nanoscale particles.     

Upconversion luminescence properties of YF3:Yb3+, Er3+ nanoclusters

The synthesis, characterization, and spectroscopy of upconverting Yb3+/Er3+ codoped YF3 rod-like nanoclusters are presented. The YF3 nanoclusters were synthesized by a simple hydrothermal method. The clusters structure was characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Under 978 nm laser excitation, stronger blue (4F(5/2) --> 4I(15/2) and 2p(3/2) --> 4I(11/2)) and green (4S(3/2), 2H(11/2) --> 4I(15/2)) upconversion luminescence were observed at 978 nm. The measured intensity of upconversion luminescence was different when pump power changed, which shows that the blue and green upconversion luminescence come from three-photon and two-photon energy transfer processes, respectively.     

Yb3+、Er3+和Eu3+共掺杂TiO2纳米带的制备与表征

通过离子交换和水热两步合成过程简单制备了Yb3+、Er3+和Eu3+共掺杂锐钛矿型TiO2纳米带。该3种离子共掺杂未导致TiO2结构和形貌发生变化。光学特性测试结果表明,由于稀土离子掺杂浓度低,Eu3+掺杂未改变由Yb3+和Er3+产生的上转换发射峰位,但可观察到因上转换发光激发的Eu3+荧光发射峰;Eu3+荧光光谱也未受到Yb3+和Er3+掺杂的影响。通过对掺杂样品上转换发光机理的考察证实,上转换发光过程是双光子过程,但TiO2和Eu3+掺杂对此发光过程有明显影响。     

Synthesis and upconversion luminescence of uniform beta-NaYF4:Yb3+/Tm3+ hexagonal nanoplates

Yb3+ and Tm3+-codoped hexagonal-phase NaYF4 powders were prepared by a facile hydrothermal method. The results of X-ray powder diffraction (XRD) and scanning electron microscopy (SEM) showed that the as-prepared powders were well crystallized nanoplates with high size-uniformity. Under the excitation from a 980 nm laser diode, upconversion (UC) emissions centered at approximately 291 nm (1I6 --> 3H6), approximately 346 nm (1I6 --> 3F4), approximately 361 nm (1D2 --> 3H6), approximately 451 nm (1D2 --> 3F4), approximately 474 nm (1G4 --> 3H6), approximately 644 nm (1G4 --> 3F4), and approximately 799 nm (3H4 --> 3H6) were observed in the sample. Furthermore, the intensity dependence of UC emissions on excitation power was measured. The results indicated that populating the 1I6, 1D2, 1G4, and 3H4 states were five-photon, four-photon, three-photon, and two-photon UC processes, respectively.