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.     

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.     

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.     

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.     

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.     

Preparation, characterization and spectroscopy of Eu3+ in Gd2O3 nanorods

Eu3+:Gd2O3 nanorods were prepared by a hydrothermal method. X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and Fourier transform-infrared spectroscopy were used to characterize the resulting samples. Emission and excitation spectra were studied using xenon excited spectroscopic experiments at 10 K. Energy transfer from Gd3+ to Eu3+, from the band gap of the host to Eu3+, and from Eu3+ (S6) to Eu3+ (C2) was observed. The energy levels of Eu3+ at the C2 site of cubic Gd2O3 were experimentally determined according to the fluorescence spectra at 10 K, and fit well with the theoretical values. The standard deviation for the optimal fit was 12.9 cm(-1). The fluorescent lifetime of 5D0 (2.3 ms at 295 K) was unusually longer than that of the bulk counterparts (0.94 ms), indicating a small filling factor (0.55) for the nanorod volume. However the lifetime of 5D1 was much shorter than that of the bulk counterparts, 65 micros at 10 K, 37 micros at 295 K.     

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.     

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.     

Strong photoluminescence through up and down conversion in Tm(3+)/Ho(3+):LaOF nanoparticles

Efficient up and down frequency conversions in Tm(3+) and Ho(3+) doped LaOF tetragonal nanocrystals have been investigated. Bright fluorescence emissions are obtained in co-doped Tm(3+)/Ho(3+):LaOF tetragonal nanocrystals through UV and infrared excitation. Green florescence from doped Ho(3+) ions, which can be clearly seen with bared eyes, is obtained when Tm(3+) ion is excited. Specific mechanism of the cross relaxation between doped ions is explored through spectroscopic measurements in time and frequency domains. About 90% energy transfer efficiency is obtained when the weak radiative and nonradiative relaxations are neglected.     

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.     

Self-assembly of Yb3+-Tm3+ co-doped YF3 elongated nanocrystals into nanobundles of straw and up-conversion fluorescence

The hierarchical self-assembly of Yb3+ and Tm3+ co-doped YF3 elongated nanocrystals (NCs) into nanobundles of straw were synthesized through a facile hydrothermal route. The formational mechanisms of regular aggregates of the building blocks were studied. Ultraviolet (UV)-blue upconversion emissions of Tm3+ were recorded under 980-nm excitation by the Yb3+ sensitizer. The relatively bright blue emission indicated that the bundles have the potential for applications such as short-wavelength solid-state lasers and display devices.     

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.     

Structure and Luminescence Properties of Gd2(WO4)3 and Gd2(WO4)3:Tm3+,Yb3+ Nanopowders Prepared by Solid-State Sintering and the Pechini Methods

Inorganic Materials - Gd2(WO4)3 and Gd2(WO4)3:0.5% Tm3+, 10% Yb3+ nanopowders have been prepared by the Pechini method and solid-state sintering. According to X-ray diffraction results, the...     

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.     

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.     

Eu3+掺杂β-NaYF4∶20%Yb3+, 0.5%Tm3+的合成与双频光转换性能

采用高温溶剂热法合成了Eu3+掺杂的双频转换发光材料β-NaYF4∶20%Yb3+,0.5%Tm3+,并使用X射线衍射仪(XRD)、场发射扫描电镜(FESEM)和光致发光谱(PL)仪对所制备样品的物相结构、形貌特征和发光性质进行了表征,通过分析发光原理,解释了上、下转换发光的竞争机制,并探讨了稀土离子Tm3+与Eu3+之间的能量转移。结果表明:所合成的β-NaYF4∶20%Yb3+,0.5%Tm3+,xEu3+为纯六方相晶体,结晶良好,颗粒尺寸在200nm左右。改变Eu3+的掺杂浓度后晶格结构没有发生明显变化,样品可在394nm和980nm光的激发下,分别发生下转换和上转换发光。     

Synthesis of colloidal upconverting NaYF4: Er3+/Yb3+ and Tm3+/Yb3+ monodisperse nanocrystals

The synthesis, characterization, and spectroscopy of upconverting lanthanide-doped NaYF4 nanocrystals (NCs) is presented. The monodisperse cubic NaYF4 NCs were synthesized via a thermal decomposition reaction of trifluoroacetate precusors in a mixture of technical grade chemicals, octadecene and the coordinating ligand oleic acid. In this straightforward method, the dissolved precursors are added slowly to the reaction solution through a stainless-steel canula resulting in highly luminescent nanocrystals with an almost monodisperse particle size distribution. The NCs were characterized through the use of transmission electron microscopy, selected area electron diffraction, 1H NMR, powder X-ray diffraction, and high-resolution luminescence spectroscopy. The NaYF4 NCs are capable of being of dispersed in nonpolar organic solvents thus forming colloidally stable solutions. The colloids of the Er3+, Yb3+ and Tm3+, Yb3+ doped NCs exhibit green/red and blue upconversion luminescence, respectively, under 980 nm laser diode excitation with low power densities.     

Controllable multicolor upconversion luminescence of lanthanide doped NaGdF4 nanocrystals through single laser excitation at 980 nm

Room temperature multicolor Upconversion (UC) luminescence in Yb3+, Tm3+, Er3+ ions doped NaGdF4 nanocrystals have been successfully synthesized by a hydrothermal method. As-prepared nanocrystals are highly crystalline and well-dispersed in cyclohexane to form stable and clear colloidal solutions, which demonstrates strong emission properties with a single laser excitation at 980 nm. The multicolor light consists of blue, green, and red UC radiations that correspond to transitions 1G4 --> 3H6 of Tm3+, 2H(11/2)/4S(3/2) --> 4I(15/2), and 4F(9/2) --> 4I(15/2) of Er3+ ions, respectively. The UC mechanisms were proposed based on spectral, kinetic, and pump power dependence analyses.     

Study on luminescent properties of Eu3+ doped Gd2WO6, Gd2W2O9 and Gd2(WO4)3 nanophosphors prepared by co-precipitation

Eu3+ doped Gd2WO6, Gd2W2O9 and Gd2(WO4)3 nanophosphors with different concentrations have been prepared by co-precipitation. XRD (X-ray diffraction) and SEM (scanning electron microscopy) were used to investigate the structure and morphology. The emission spectra, excitation spectra and fluorescence decay curves were measured, and partial J-O parameters and quantum efficiencies of Eu3+ 5D0 energy level were calculated. Furthermore, concentration quenching curves of Eu3+ in different hosts were drawn. The photoluminescent properties of Eu3+ doped Gd2WO6, Gd2W2O9 and Gd2(WO4)3 nanophosphors have been studied. The results indicate that Eu3+ 5D0-7F2 red luminescence can be effectively excited by 395 nm and 465 nm in Gd2WO6 and Gd2W2O9 hosts, similar to the familiar Gd2(WO4)3:Eu. Especially Gd2W2O9:Eu has strong red emission and high quenching concentration, so it has potential applications for trichromatic white LED as red fluorescent materials.     

Size dependent ultraviolet upconversion in single YF3:Yb3+/Tm3+ particles

Yb3+-Tm3+ codoped YF3 bulk material was synthesized through a facile high-temperature calcinations method. By grinding and selecting, the particles with different desired sizes in microns were obtained. Under 980 nm excitation, optical upconversion (UC) from near-infrared (NIR) to ultraviolet (UV) was studied for each group of particles for the effect of their size on UC. Comparing with the bulk sample, the micro-size particles exhibited strong ability for NIR-to-UV UC. With the particle size decreasing from 800 microm to 20 microm, their UV emission intensities increased rapidly. Two possible mechanisms were proposed and discussed for clarifying the small size effect (SSE).