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.     

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.     

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.     

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.     

Enhanced red upconversion luminescence in Er-Tm codoped NaYF4 phosphor

This paper presents a study on the enhanced red upconversion (UC) luminescence via efficient energy transfer (ET) between Er3+ and Tm3+ in Er-Tm codoped NaYF4 microtubes. Er doped and Er-Tm codoped NaYF4 UC hollow microtubes have been synthesized using a hydrothermal method. Under 1560 nm excitation from a diode laser, the Er doped NaYF4 microtubes emitted dominant green UC luminescence while the Er-Tm codoped NaYF4 microtubes emitted dominant red UC luminescence, which implies the energy transfer between Er3+ and Tm3+ plays a key role in the enhanced red UC emissions. The red UC luminescence is significantly enhanced compared with the green UC luminescence with the increase of Tm3+ doping concentration. In addition, our experimental results show that the UC luminescence properties under 980 nm excitation are almost identical with that under 1560 nm excitation. Furthermore, the possible ET mechanism was proposed on the basis of our experimental results.     

Synthesis and characterization of upconverting NaYF4:Er3+, Yb3+ nanocrystals via thermal decomposition of stearate precursor

Er3+-Yb3+ codoped hexagonal NaYF4 nanocrystals were prepared via a method of thermal decomposition of stearate precursor. Their crystal structure, morphologies and photoluminescence (PL) properties were characterized by XRD, SEM, and fluorescence spectra. The hexagonal NaYF4:Er3+, Yb3+ nanocrystals could be well dispersed in cyclohexane to form a clear solution. Under 980 nm excitation, the solution of Er3+-Yb3+ codoped NaYF4 nanocrystals emits bright green upconversion fluorescence.     

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.     

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。     

Optical high temperature sensor based on enhanced green upconversion emissions in Er3+-Yb3+-Li+ codoped TiO2 powders

The Er3+-Yb3+-Li+ codoped TiO2 powders have been prepared by sol-gel method. The strong enhancement of green and red upconversion emissions were obtained for Er3+-Yb3+ codoped TiO2 by additional Li+ codoping and investigated using 976 nm semiconductor laser diode excitation. The enhanced upconversion emissions by the addition of Li+ resulted from the formation of Li compound with lower crystal field symmetry. The fluorescence intensity ratio (FIR) of green upconversion emissions from the transitions of 2H(11/2) --> 4I(15/2) and 4S(3/2) --> 4I(15/2) of Er3+ in the Er3+-Yb3+-Li+ codoped TiO2 has been studied as a function of temperature in the range of 300-925 K, and the maximum sensitivity was determined to be 0.0025 K(-1). Er3+-Yb3+-Li+ codoped TiO2 material with the highest operating temperature up to 925 K, has higher temperature sensitivity and fluorescence efficiency being a promising candidate for applications in optical high temperature sensor.     

Paramagnetism and improved upconversion luminescence properties of NaYF4:Yb,Er/NaGdF4 nanocomposites synthesized by a boiling water seed-mediated route

In a route boiling water served as reaction medium, a stoichiometric amount of rare-earth compound and fluoride are put into this system to form α-NaYF₄:Yb, Er nuclei. Then prepared sample is heated at elevated temperature to improve the fluorescence intensity, and next a NaGdF₄ shell grows on the surface of NaYF₄ nuclei. NaYF₄:Yb,Er/NaGdF₄ core–shell structured upconversion nanoparticles (CSUCNPs) have been successfully synthesized by above route. The use of boiling water decreases the cubic-to-hexagonal phase transition temperature of NaYF₄:Yb,Er to 350°C and increases its upconversion (UC) luminescence intensity. A heterogeneous NaGdF₄ epitaxially growing on the surface of Ln³⁺-doped NaYF₄ not only improves UC luminescence, but also creates a paramagnetic shell, which can be used as contrast agents in magnetic resonance imaging (MRI). The solution of CSUCNPs shows bright green UC fluorescence under the excitation at 980 nm in a power density only about 50 mW·cm^–2. A broad spectrum with a dominant resonance at g of about 2 is observed by the electron paramagnetic resonance (EPR) spectrum of CSUCNPs. Above properties suggest that the obtained CSUCNPs could be potential candidates for dual-mode optical/magnetic bioapplications.     

Color tunability of upconversion emission in YBO3: Yb, Er inverse opal

Upconversion (C) light-emitting photonic band gap materials (YBO₃: Yb, Er) with inverse opal structure were prepared by a self-assembly technique in combination with a sol-gel method. The effect of the photonic stop-band on the upconversion luminescence of Er³⁺ ions has been investigated in the YBO₃: Yb, Er inverse opals. Significant suppression of the green or red UC emission was detected if the photonic band-gap overlaps with the Er³⁺ ions emission band. We successfully achieved the color tuning of the UC optical properties of the inverse opal by controlling the structure of the photonic crystal.     

硫酸盐还原法制备La_2O_2S∶Yb,Er及其上转换发光性能

采用硫酸盐还原法制备了Yb、Er双掺的La2O2S粉体,考察了柠檬酸用量、前驱体煅烧温度、碳还原温度、Er3+离子浓度和Yb3+离子浓度对粉体的影响。分别采用X-射线衍射分析(XRD)、扫描电子显微镜(SEM)、比表面积分析(BET)、紫外可见光分光光度计(UVPC)和荧光光谱分析(PL)对粉体的相组成、形貌、颗粒尺寸、反射率和上转换发光性能进行表征。研究结果表明,800℃时可以得到纯相的La2(SO4)3;碳还原温度为900℃以上可以得到纯相的结晶较好的La2O2S;样品的粒径大约为100～200nm,颗粒存在一定的团聚;柠檬酸与硝酸盐的最佳摩尔比为1.5∶1;Er3+离子掺杂浓度为2mol%、Yb3+离子掺杂浓度为12mol%时粉体的上转换发光强度最强。     

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.     

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。     

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.     

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.     

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.     

NaYF4：Yb,Er红色上转换发光纳米粒子的合成

利用热分解方法在油酸和十八胺的混合溶剂中合成了红色上转换发光的α-NaYF4：Yb,Er纳米粒子,通过X射线衍射（XRD）、透射电镜（TEM）以及980nm激发下的上转换发光光谱等方法进行表征,结果发现,在溶剂油酸和十八胺混合溶剂中,虽然反应时间和温度不同,但产物均为立方相结构且光学性能几乎呈现纯的红色发射光,说明可以在很广泛的范围内合成具有良好的红色上转换发光的NaYF4：Yb,Er纳米粒子。     

Citric acid-assisted growth of lanthanide ions co-doped one-dimensional upconversion microcrystals and their photovoltaic applications

We report for the first time the preparation of Yb³⁺–Er³⁺ co-doped β-phase sodium gadolinium fluoride (NaGdF₄:Yb/Er) microcrystals using citric acid (CA) as a shape modifier and the application of NaGdF₄:Yb/Er to amorphous silicon solar cells. The proposed hydrothermal method was facile and eco-friendly. It was found that CA played a critical role in the shape evolution of the final products. The related synthesis mechanisms are discussed. Under 980 nm laser excitation, the optimized NaGdF₄:Yb/Er crystals exhibited strong upconversion (UC) emissions at visible wavelengths. Amorphous silicon thin film solar cells were designed and fabricated for investigating different UC configurations. In combination with a metallic back reflector, the cell with the front side UC layer achieved a six-fold improvement of the photocurrent while the cell with the rear side UC layer exhibited a ten-fold enhancement of the photocurrent, under 980 nm light, compared with the cell without upconverter.     

Hydrothermal synthesis of hexagonal lanthanide-doped LaF(3) nanoplates with bright upconversion luminescence

Hexagonal Yb/Er or Yb/Ho co-doped LaF(3) nanoplates with uniform morphology have been synthesized with an average diameter of ～15?nm. It was found that the coating reagent, hydrothermal temperature and time play critical roles in the control of the shape of the final products. A possible growth mechanism including ion exchange, 'burst-nucleation', and 'heat-up' growth is proposed. (1)H NMR spectra and Fourier transform infrared (FTIR) spectra indicate that the surface of the nanoplates is coated with oleic acid ligands. Those hexagonal nanoplates display the capability of forming self-assembled two-dimensional nanoarrays. Moreover, under continuous-wave excitation at 980?nm, the LaF(3):12%Yb,3%Er nanoplates exhibited bright orange emission (a combination of green between 515 and 556?nm and red between 640 and 675?nm) and the LaF(3):20%Yb,1%Ho nanoplates had nearly pure green upconversion luminescence between 530 and 554?nm. The intensity of upconversion luminescence increased with time and increase of the hydrothermal temperature. For the bright upconversion luminescence, the as-prepared samples show potential applications in color displays, the building of nanodevices and as biolabels.