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.     

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.     

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.     

Upconversion luminescence enhancement in Yb3+/Tm3+-codoped Lu2O3 nanocrystals induced by doping with Li+ ions

Lutetium oxide (Lu2O3) nanocrystals doped with 2%Yb3+, 0.5%Tm3+, and various doping concentrations of Li+ (0, 3, 5, 7, 10, 12, and 15 mol%) were prepared by the sol-gel method. The dependence on different doping concentrations of Li+ ions of the structure, morphology, and the upconversion emission intensity of the Lu2O3:2%Yb3+, 0.5%Tm3+ nanocrystals was investigated. The obtained Lu2O3 nanocrystals were systematically characterized by X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), Fourier transformed infrared (FT-IR) spectra, Raman spectra, and upconversion spectra measurements. It was found that all the nanocrystals can be readily indexed to pure cubic phase of Lu2O3, indicating good crystallinity. The experimental results show that Li+ doping in Lu2O3:2%Yb3+, 0.5%Tm3+ nanocrystals can greatly enhance the upconversion emission intensity. The strong blue (490 nm) and the weak red (653 nm) emissions from the prepared nanocrystals were observed under 980 nm laser excitation, and attributed to the 1G4 --> 3H6 and 1G4 --> 3F4 transitions of Tm3+ ions, respectively. An simple analysis based on steady-state rate equations and a power-dependent study both indicate that the 1G4 levels can be populated by three-step energy transfer (ET) processes. The enhancement of the upconversion luminescence was suggested to be the consequence of the modification of the local field symmetry around the Tm3+ ion, reduced number of OH- groups, and the enlarged nanocrystal size induced by the Li+ ions.     

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.     

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.     

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.     

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.     

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.     

The properties of upconversion luminescence on YAIO3:Er(3+) nanophosphors with different Er(3+) concentrations

We report the properties of upconversion luminescence on Yttrium aluminum perovoskite (YAIO3) doped with trivalent erbium at concentrations of 1, 2, 3, 5 and 7 mol%. The samples were synthesized by solvo-thermal reaction method and the XRD patterns conforms that the YAP:Er(3+) nanophosphors have orthorhombic phase. Efficient green and red upconversion (UC) emission of YAP:Er(3+) nanophosphors was measured under the excitation of 975 nm continuous wave diode laser, and its dynamics and pump power dependence were investigated. As concentration of Er(3+) ion increased from 1 to 7 mol%, the red UC emission increased more rapidly. It is attributed to the energy transfer (4I(11/2) --> 4I(15/2):4I(13/2) --> 4F(9/2)) and to the cross relaxation (4S(3/2) --> 4I(9/2):4I(15/2) --> 4I(13/2)) between Er(3+) ions. In this case, the green and red emissions were yielding from quadratic to linear. These conclusions obtained are confirmed by theoretical investigations based on steady-state rate equations.     

Temperature-dependent photoluminescence spectra of Er-Tm codoped calcium boroaluminate glasses

The temperature dependence of photoluminescence (PL) spectra of Er-Tm codoped calcium boroaluminate (CABAL) glasses with different dopant concentrations was investigated under 15-298 K, by pumping at 795 nm. The intensities of three band emissions located at 1.46, 1.53, and 1.80 μm decreased monotonically when increasing the temperature from at lower concentrations. However, the emissions peaked at 1.80 μm increase with the increasing temperature at higher concentrations. This was attributed to the increasing of cross relaxation (CR) resulting from the high doping concentration of Tm ions. This was evidenced by the much shorter fluorescence lifetime of 56 μs for the 3F4 emission due to 3F4→3H6 transition for the CABAL glass codoped with 2.00 mol.% Tm2O3, in comparison with 185 μs for that of 0.2 mol.% Tm2O3. The energy transfer (ET) and CR processes between Er3+ and Tm3+ ions have been discussed at different doping concentrations and operating temperatures. The nonexponential character of the decays of 4I(13/2) and 3H4 with the increasing concentration indicated the occurring of a dipole-dipole quenching processes in the framework of a diffusion-limited regime. The average critical distances of CR between Tm3+ ions and ET between Er3+ and Tm3+ ions were approximately 1 nm.     

Effect of photonic bandgap on upconversion emission in YbPO4:Er inverse opal photonic crystals

We obtained upconversion (UC) light-emitting photonic materials (YbPO(4):Er) with an inverse opal structure by the self-assembly technique in combination with a solgel method. The effect of the photonic stopband on the UC luminescence of the (2)H(11/2), (4)S(3/2)→(4)I(15/2), and (4)F(9/2)→(4)I(15/2) transitions of Er(3+) has been observed in the inverse opals of the Er(3+)-doped YbPO(4). Significant suppression of the UC emission was detected if the photonic bandgap overlapped with the Er(3+) ions emission band, while enhancement of the UC emission occurs if the emission band appears at the edge of the bandgap.     

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.     

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.     

Ultraviolet upconversion fluorescence of Er3+ in Yb3+/Er3+-codoped Gd2O3 nanotubes

Under 980 nm excitation, room-temperature ultraviolet (UV) upconversion (UC) emissions of Er3+ from the 4G(9/2), 2K(13/2), and 2P(3/2) states were observed in Gd2O3:Yb3+/Er3+ nanotubes, which were synthesized via a simple wet-chemical route at low temperature and ambient pressure followed by a subsequent heat treatment at 800 degrees C. The experimental results exhibited that these UV emissions came from four-photon UC processes. In the Gd2O3:Yb3+/Er3+ nanocrystals, the energy transfers (ETs) from Yb3+ to Er3+ played important roles in populating the high-energy states of Er3+ ions. This material provides a possible candidate for building UV compact solid-state lasers or fiber lasers.     

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...     

Sequence lasing in a gain-switched Yb3+,Er(3+)-doped silica double-clad fiber laser

Experimental results relating to the gain-switched operation of a double-clad Yb3+,Er(3+)-doped silica fiber laser that is pulse pumped with the output from a flash-lamp-pumped Ti:sapphire laser are presented. For all the configurations of the fiber laser that we studied, the 2F5/2-->2F7/2 laser transition of the Yb3+ ion lased prior to laser emission from the 4I13/2-->4I15/2 transition of the Er3+ ion. To the best of our knowledge, this is the first reported operation of sequence lasing in the Yb3+,Er(3+)-codoped system. This succession of laser pulses deduced from the measurements of this investigation is a consequence of both the short intense pump pulse and the short 900-nm wavelength of the pump that does not overlap with any important excited-state absorption transitions. We believe that the predominant interionic interaction during the course of the pump pulse is the double-energy transfer to the Er3+ ion acting twice from the 2F5/2 energy level of the Yb3+ donor ion. A maximum total output of 1.65 mJ is obtained (1.38 mJ from the 2F5/2-->2F7/2 transition of Yb3+ and 0.27 mJ from the 4I13/2-->4I15/2 transition of Er3+) from a nonoptimized configuration of the fiber laser. The wavelength of the output from the fiber laser was measured to vary approximately linearly with fiber length from 1040 to 1046 nm for the Yb(3+)-based laser and 1535 to 1541 nm for the Er(3+)-based laser.     

Investigation on Yb3+∕Er3+∕Tm3+ tri-doped phosphate glass ceramic for white-light-emitting diode

Yb3+∕Er3+∕Tm3+ tri-doped phosphate glass ceramics were prepared by a high-temperature melting method and thermal treatment technology. Upconversion (UC) emissions of the Yb3+∕Er3+∕Tm3+ tri-doped phosphate glass ceramic samples were studied under 975 nm excitation. The glass ceramic samples can simultaneously generate blue, green, and red emissions. The multicolor emission obtained was tuned to white light by adjusting the Er3+ ion concentration. The emission color of the sample doped with 8 mol.% Er3+ ion is white to the naked eye, and CIE coordinates (x=0.316, y=0.354) of the sample are close to the standard equal energy white-light illumination (x=0.333, y=0.333). The material will be useful in developing the white-light-emitting diode.     

稀土掺杂上转换发光玻璃陶瓷的制备及性能

实验制备了一类含有SrF2∶Yb3+,Tm3+及SrF2∶Yb3+,Er3+的透明发光玻璃和玻璃陶瓷,对比研究了热处理工艺对玻璃陶瓷相组成、微观结构和光谱性能的影响规律。研究表明,玻璃陶瓷具有立方SrF2纳米晶相均匀分布于玻璃基体的复相结构,利用HRTEM可观测到SrF2纳米晶相的(111)晶面,其晶粒尺度在10~30nm之间,且该析晶相中富集有Yb3+/Tm3+和Yb3+/Er3+。基于此,玻璃陶瓷在980nm LD激光激发下的上转换发光强度较玻璃样品有较大提高。其上转换发光机制分别主要为Yb3+-Yb3+之间的合作上转换,Yb3+-Tm3+和Tm3+-Tm3+之间的交叉弛豫能量传递过程,以及Yb3+-Er3+之间的能量传递上转换。     

Luminescent properties of rare earth ions in one-dimensional oxide nanowires

Rare-earth doped one-dimensional oxide nanowires including LaPO4, La2O3, and Gd2O3 were synthesized by the hydrothermal method. Their luminescent properties including local environments, electronic transitions, energy transfer, and frequency up-conversion luminescence processes were systematically studied. In LaPO4:Eu and La2O3:Eu nanowires, different symmetry sites of Eu3+ ions were identified, which obviously differed from those of the corresponding micrometer-sized particles. This was attributed to crystal field degeneration in the fringe along the length axis. In LaPO4:Eu nanowires, the electronic transition rate of 5D1-sigmaJ7FJ increased approximately 2 times over that of the zero-dimensional nanoparticles and micrometer-sized particles, which was related to the variation of dipole field induced by shape anisotropy. Considering the nonradiative relaxations, meanwhile, the luminescent quantum efficiency for 5D1-sigmaJ7FJ transitions of Eu3+ in nanowires increased 100% over that in nanoparticles and 20% over that in micrometer particles. In Gd2O3:Eu3+, LaPO4:Ce3+, and LaPO4:Tb3+ nanowires and micrometer-sized particles, the electronic transition rate of rare earths had only a little variation. In LaPO4:Ce3+/Tb3+ nanowires, the energy transfer rate of Ce3+--> Tb3+ decreased 3 times compared to that in micrometer rods. Despite this, the brightness for the 5D4-7F5 green emissions of Tb3+ increased several times due to decreased energy transfer from the excited states higher than 5D4 to some defect levels. In Gd2O3:Er3+/Yb3+ nanocrystals, as the shape varied from nanopapers to nanowires, the relative intensity of up-conversion luminescence of 2H(11/2)/4S(3/2)-4I(15/2) and 4F(9/2)-4I(15/2) to the infrared down-conversion luminescence of 4I(13/2)-4I(15/2) increased remarkably, indicating efficient up-conversion luminescence. Our present results indicate that rare-earth-doped oxide nanowires is a type of new and efficient phosphors.