稀土掺杂复式钨酸盐纳米晶体的制备及发光性能

应用水热合成技术制备了稀土掺杂复式钨酸盐NaRe（WO4）2（Re=La,Y,Gd）纳米晶体,水热合成温度随Re^3＋种类的不同而呈现较大的差异.稀土离子在NaRe（WO4）2纳米晶体中处于非反演对称中心位置.在980nm红外光激发下,Yb^3＋和Er^3＋共掺的NaRe（WO4）2纳米晶体可产生明显的绿色上转换发光,发光机理为双光子过程.     

Development of a terbium complex-based luminescent probe for imaging endogenous hydrogen peroxide generation in plant tissues

A highly sensitive Tb(3+) complex-based luminescent probe, N,N,N(1),N(1)-[2,6-(3'-aminomethyl-1'-pyrazolyl)-4-(3',4'-diaminophenoxy)methylene-pyridine] tetrakis(acetate)-Tb(3+) (BMTA-Tb(3+)), has been designed and synthesized for the recognition and detection of hydrogen peroxide (H(2)O(2)) in aqueous solutions. This probe is almost nonluminescent because the Tb(3+) luminescence is effectively quenched by the electron-rich moiety, diaminophenyl, on the basis of the photoinduced electron transfer (PET) mechanism. In the presence of peroxidase, the probe can react with H(2)O(2) to cause the cleavage of the diaminophenyl ether, which affords a highly luminescent Tb(3+) complex, N,N,N(1),N(1)-[2,6-bis(3'-aminomethyl-1'-pyrazolyl)-4-hydroxymethyl-pyridine] tetrakis(acetate)-Tb(3+) (BHTA-Tb(3+)), accompanied by a 39-fold increase in luminescence quantum yield with the increase of luminescence lifetime from 1.95 to 2.76 ms. The dose-dependent luminescence enhancement of the probe shows a good linearity with a detection limit of 3.7 nM for H(2)O(2), which is approximately 14-fold lower than those of the commonly used fluorescent probes. The probe was used for the time-resolved luminescence imaging detection of the oligosaccharide-induced H(2)O(2) generation in tobacco leaf epidermal tissues. On the basis of the probe, a background-free time-resolved luminescence imaging method for detecting H(2)O(2) in complicated biological systems was successfully established.     

Time-resolved spectroscopy of intrinsic luminescence of Y3Ga5O12 and (LaLu)3Lu2Ga3O12 single crystals

The nature of intrinsic luminescence of Y₃Ga₅O₁₂ (YGG) and (LaLu)₃Lu₂Ga₃O₁₂ (LLGG) single crystals grown from a melt was determined. In the case of a YGG single crystal containing Y_Ga antisite defects with a concentration of 0.25–0.275 at.% the intrinsic luminescence was considered as a superposition of luminescence of self-trapped excitons (STE), luminescence of excitons localized near antisite defects (LE(AD) centers) and luminescence caused by a recombination of an electron with a hole captured at Y_Ga antisite defects. Due to a large (2–3%) concentration of Lu_La antisite defects in LLGG single crystals the intrinsic luminescence was a superposition mainly of the LE(AD) center emission and the recombination luminescence of Lu_La antisite defects. The energy structure of the mentioned centers in YGG and LGGG hosts was determined from the excitation spectra of their luminescence under excitation by synchrotron radiation in the range of the fundamental absorption edge of these garnets.     

Time-resolved spectroscopy of intrinsic luminescence of Y3Ga5O12 and (LaLu)3Lu2Ga3O12 single crystals

The nature of intrinsic luminescence of Y₃Ga₅O₁₂ (YGG) and (LaLu)₃Lu₂Ga₃O₁₂ (LLGG) single crystals grown from a melt was determined. In the case of a YGG single crystal containing Y_Ga antisite defects with a concentration of 0.25–0.275 at.% the intrinsic luminescence was considered as a superposition of luminescence of self-trapped excitons (STE), luminescence of excitons localized near antisite defects (LE(AD) centers) and luminescence caused by a recombination of an electron with a hole captured at Y_Ga antisite defects. Due to a large (2–3%) concentration of Lu_La antisite defects in LLGG single crystals the intrinsic luminescence was a superposition mainly of the LE(AD) center emission and the recombination luminescence of Lu_La antisite defects. The energy structure of the mentioned centers in YGG and LGGG hosts was determined from the excitation spectra of their luminescence under excitation by synchrotron radiation in the range of the fundamental absorption edge of these garnets.     

Optically stimulated luminescence signals of polymineral fine grains in the JSC Mars-1 soil simulant sample

The results of various experiments which characterise the optically stimulated luminescence (OSL) signals from polymineral fine grains of a Martian soil simulant sample (JSC Mars-1) are presented. The blue-green stimulated luminescence signal has greater thermal stability than the infrared stimulated luminescence signal for pre-heat temperatures between 250 degrees C and 400 degrees C. Fading tests over a 2 month storage period at 20 degrees C indicate that in some aliquots of JSC Mars-1 both the blue-green stimulated luminescence and the infrared stimulated luminescence signals fade by as much as 50%, whereas in others there is no evidence of significant fading. Dose recovery experiments demonstrate that equivalent dose (measured/given) ratio varies from aliquot to aliquot, and the underestimation in dose is less than 5% for at least one aliquot, for both the infrared and blue-green stimulated luminescence signals.     

Influence of oxidized layer on operating voltage and luminance of nanocrystalline silicon electroluminescent device

A direct current (DC) operating voltage and luminescence property of red electroluminescent (EL) devices with and/or without a silicon dioxide (SiO2) layer at interface between nanocrystalline Si (nc-Si) region and Si substrate has investigated. The removal of SiO2 layer in the EL device led to the lowering of DC operating voltage from 4.0 up to 2.0 V and the increase of luminescence intensity more than one order of magnitude. The external quantum efficiency of red luminescence from the EL device without the SiO2 layer at the DC operating voltage of 3.0 V was 0.5%. These were realized by the efficient and easy injection of carriers to the radiative recombination centers in the nc-Si region due to the removal of SiO2 layer. These results indicate that the removal of SiO2 layer is drastically improved the DC operating voltage and luminescence intensity for the nc-Si based EL device.     

Temperature dependence of up-conversion luminescence and photoluminescence of Mn2+ in ZnS:Mn2+ nanoparticles

The photoluminescence (excited at both 300 nm and 383.5 nm) and up-conversion luminescence (excited at 767 nm) of the Mn2+ 4T1-->6A1 transition in both bulk and ZnS:Mn2+ nanoparticles have been measured as a function of temperature. The Mn2+ emission spectra shift monotonically to longer wavelengths at lower temperatures, whereas the intensity change of the luminescence is more complex. The complicated temperature behavior is explained by considering the processes of nonradiation relaxation via phonon coupling, exciton thermal dissociation (binding energy), energy transfer, carrier trapping, and the temperature change of the absorption spectra. The fact that the temperature dependence of the 767 nm excited up-conversion luminescence is the same as the 383.5 nm excited photoluminescence in both bulk and nanoparticles supports the conclusion that the up-conversion luminescence is due to two-photon absorption.     

纳米ZrO_2/(1-n)SiO_2-nAl_2O_3介孔复合作的制备与光致发光

采用溶胶-凝胶法和超临界干燥技术制备了（1－n）SiO2－nAl2O3（n=0、001、0.1）混合气凝胶体系，并以此作为载体，成功地将纳米ZrO2粒子组装到（1—n）SiO2－nAl2O3介孔体系中，而形成纳米ZrO2／（1—n）SiO2－nAl2O3介孔复合材料．光致发光光谱研究表明，室温下以316um（392eV）波长激发时，纳米ZrO2粒子540um（230eV）荧光峰，在介孔复合体中将蓝移至400um（310eV）左右，蓝移量140um；其光致荧光峰的相对强度亦随Al2O3的掺入量不同而不同．对产生上述光谱性质变化的机理进行了初步探讨．     

A real-time,fibre optic dosimetry system using Al2O3 fibres

Al2O3:C optical fibres were examined for potential use as real-time luminescence dosemeters for use in radiotherapy applications. The dosimetric properties of the fibres were studied in order to determine their usefulness as luminescence dosemeters. The measurements were performed by connecting the Al2O3:C fibres to a standard fused silica optical fibre and the optically stimulated luminescence (OSL) and radioluminescence (RL) were measured through the fibre. The OSL and RL responses of the Al2O3 fibre probes were measured during irradiation to determine the potential of the Al2O3:C fibres in a real-time fibre optic dosimetry system.     

High pressure luminescence and time resolved spectra of La2Be2O5:Pr

We present luminescence, luminescence excitation and luminescence time resolved spectra of La₂Be₂O₅:Pr³⁺ system. We used high pressure spectroscopy approaches, with high pressure applied in diamond anvil cell (DAC) and sapphire anvil cell (SAC), for detailed analysis of luminescence related to the 4f5d → 4f² and 4f² → 4f² transitions. We present effect of up-converted luminescence related to 4f5d → 4f² transition excited with 488 nm. We also discussed possibility of existence of praseodymium trapped exciton (PTE) states in La₂Be₂O₅:Pr³⁺ system. Lack of the PTE is attributed to high quantity of bulk modulus of this material.     

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.     

Persistent luminescence of Eu and Dy doped barium aluminate (BaAl2O4:Eu,Dy) materials

Polycrystalline Eu²⁺ and Dy³⁺ doped barium aluminate materials, BaAl₂O₄:Eu²⁺,Dy³⁺, were prepared with solid state reactions at temperatures between 700 and 1500 °C. The influence of the thermal treatments on the stability, homogeneity and structure as well as to the UV-excited and persistent luminescence of the materials was investigated by X-ray powder diffraction, SEM imaging and infrared spectroscopies as well as by steady state luminescence spectroscopy and persistent luminescence decay curves, respectively. The IR spectra of the materials prepared at 250, 700, and 1500 °C follow the formation of BaAl₂O₄ composition whereas the X-ray powder diffraction of compounds revealed how the hexagonal structure was obtained. The morphology of the materials at high temperatures indicated important aggregation due to sintering. The luminescence decay of the quite narrow Eu²⁺ band at ca. 500 nm shows the presence of persistent luminescence after UV irradiation. The dopant (Eu²⁺) and co-dopant (Dy³⁺) concentrations affect the crystallinity and luminescence properties of the materials.     

Cathodoluminescence of rare earth implanted Ga2O3 and GeO2 nanostructures

Rare earth (RE) doped gallium oxide and germanium oxide micro- and nanostructures, mostly nanowires, have been obtained and their morphological and optical properties have been characterized. Undoped oxide micro- and nanostructures were grown by a thermal evaporation method and were subsequently doped with gadolinium or europium ions by ion implantation. No significant changes in the morphologies of the nanostructures were observed after ion implantation and thermal annealing. The luminescence emission properties have been studied with cathodoluminescence (CL) in a scanning electron microscope (SEM). Both β-Ga(2)O(3) and GeO(2) structures implanted with Eu show the characteristic red luminescence peak centered at around 610 nm, due to the (5)D(0)-(7)F(2) Eu(3+) intraionic transition. Sharpening of the luminescence peaks after thermal annealing is observed in Eu implanted β-Ga(2)O(3), which is assigned to the lattice recovery. Gd(3+) as-implanted samples do not show rare earth related luminescence. After annealing, optical activation of Gd(3+) is obtained in both matrices and a sharp ultraviolet peak centered at around 315 nm, associated with the Gd(3+) (6)P(7/2)-(8)S(7/2) intraionic transition, is observed. The influence of the Gd ion implantation and the annealing temperature on the gallium oxide broad intrinsic defect band has been analyzed.     

Synthesis and luminescence properties of lanthanide (III)-doped YF3 nanoparticles

Synthesis process and luminescence properties of trivalent lanthanide ions (Ln3+) doped YF3 nanoparticles have been investigated. To synthesis Ln(3+)-doped YF3 nanoparticles, the mixture of (YCl3 x nH2O + LnCl3 x nH2O), and NH4F was hydrothermal treated at 180 degrees C in a Teflon-liner auto-clave or heated at higher temperatures (400 degrees C - 600 degrees C) in a stove. The XRD patterns showed that the Ln(3+)-doped orthorhombic YF3 nanoparticles with no second phase have been prepared. The solid solution Y(1-x)Eu(x)F3 (x = 0 - 0.4) nanoparticles have been synthesized. The luminescence concentration quenching resulted from resonance energy transfer between neighboring Eu3+ ions occurred at higher Eu3+ concentrations (30 mol%). The upconversion luminescence of Er(3+)-Yb3+ codoped YF3 nanoparticles under 980 nm excitation has also been observed. With increase of heated temperature, the size of the Er(3+)-Yb3+ codoped YF3 nanoparticles increased gradually, and upconversion luminescence intensity increased significantly.     

Ho~(3+)上转换发光在染料敏化太阳能电池中的应用

以水热和高温煅烧相结合的方法制备了掺Ho3+的TiO2上转换发光层,并将其组装在染料敏化太阳能电池中.通过XRD、荧光光谱仪、UV-vis和电池的光电性能测试,来分析上转换发光层的发光机理及其加入后对染料敏化太阳能电池性能的影响.结果表明,上转换发光层的引入有效地提高了DSSC的光电性能,在80mW/cm2红外光照射下最高光电转换效率达到了0.12‰,比未加上转换发光层的DSSC提高了360%.     

Introduction of the benzoquinoline ancillary ligand to the iridium complexes for organic light-emitting diodes

The new iridium complexes, Ir(C^N)2(bq), (C^N = ppy, F2-ppy, 2,3-dpqx-F2 or 4-Me-2,3-dpq) were prepared and their luminescence properties were investigated, where ppy, F2-ppy, 2,3-dpqx-F2, 4-Me-2,3-dpq and bq represent 2-phenylpyridine, 2-(4',6'-difluorophenyl)-pyridine, 2,3-bis (4'-fluorophenyl)quinoxaline, 4-methyl-2,3-diphenylquinoline and 10-hydroxybenzoquinoline ligands, respectively. We expected that the relative energy levels of the main ligands (C^N) and ancillary ligand, bq, in the complexes could determine the possibility of interligand energy transfer (ILET) in the complexes and thereby luminescence properties. The main ligands, F2-ppy and 2,3-dpqx-F2, which have drastically different energy gaps between the HOMO and LUMO energy levels were chosen and their complexes were synthesized. The photoabsorption, photoluminescence and electroluminescence of the complexes were studied. Ir(ppy)2(bq), Ir(F2-ppy)2(bq) Ir(2,3-dpqx-F2)2(bq) and Ir(4-Me-2,3-dpq)2(bq) exhibited the luminescence maxima between 600-694 nm and their efficiencies were affected by the main ligands. While Ir(ppy)2(bq) and Ir(F2-ppy)2(bq) showed relatively high luminous efficiencies (> 10 cd/A), Ir(2,3-dpqx-F2)(bq) had poor luminous efficiency (0.30 cd/A). The electrochemical properties were studied to support ILET in the ppy-based iridium complexes. Their luminescence performances were compared with those of the complexes containing acetylacetonate (acac) ancillary ligand which are not allowed to have ILET.     

Persistent luminescence of Eu2+ and Dy3+ doped barium aluminate (BaAl2O4:Eu2+,Dy3+) materials

Polycrystalline Eu²⁺ and Dy³⁺ doped barium aluminate materials, BaAl₂O₄:Eu²⁺,Dy³⁺, were prepared with solid state reactions at temperatures between 700 and 1500 °C. The influence of the thermal treatments on the stability, homogeneity and structure as well as to the UV-excited and persistent luminescence of the materials was investigated by X-ray powder diffraction, SEM imaging and infrared spectroscopies as well as by steady state luminescence spectroscopy and persistent luminescence decay curves, respectively. The IR spectra of the materials prepared at 250, 700, and 1500 °C follow the formation of BaAl₂O₄ composition whereas the X-ray powder diffraction of compounds revealed how the hexagonal structure was obtained. The morphology of the materials at high temperatures indicated important aggregation due to sintering. The luminescence decay of the quite narrow Eu²⁺ band at ca. 500 nm shows the presence of persistent luminescence after UV irradiation. The dopant (Eu²⁺) and co-dopant (Dy³⁺) concentrations affect the crystallinity and luminescence properties of the materials.     

Yttrium silicate and oxonitridosilicate luminescent materials from a silicone resin and nano-sized fillers

Yttrium silicate and oxonitridosilicate ceramic powders have been successfully prepared by heat treatment, at 1300–1400 °C, of a silicone resin embedding Y₂O₃ nano-sized particles as reactive fillers. Nano-sized RE-oxides (Eu₂O₃, CeO₂), used as secondary additives, promoted the development of apatite phase, in both air and N₂ atmosphere. For treatments in nitrogen, the only crystal phase consisted of yttrium nitrogen apatite, mixed with amorphous silicon oxycarbide (SiOC). Eu-doped and Ce-doped yttrium silicates were characterized by means of UV–visible luminescence and ion beam induced luminescence (IBIL). Strong luminescence features were observed, depending on the conditions of thermal treatment.     

The influence of activation of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> polycrystalline matrices by Bi<Superscript>3+</Superscript> ions on the luminescence of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript>

The influence of activation of the Y₂O₃ matrix of the Y₂O₃:Eu³⁺ phosphor by Bi³⁺ ions on the luminescence of Eu³⁺ and Bi³⁺ ions in it and on conditions of the excitation energy transfer to luminescence centers is studied. It is shown that the presence of Bi³⁺ ions leads to the appearance of recombination luminescence with participation of bismuth ions at low concentrations (up to 6–8 at %) of the dominant activator europium and to an increase in the threshold of intrinsic concentration quenching of its luminescence.     

Thermo-and photostimulated luminescence of CaI<Subscript>2</Subscript>-based crystals

We systematize earlier and new data on the effect of oxygen and hydrogen impurities on recombination processes in CaI₂ crystals by jointly examining their roentgeno-, thermo-, and photostimulated luminescence spectra. The 90-K emission spectra of CaI₂ crystals are shown to consist of at least five bands. The 395-nm emission is assumed to be due to radiative decay of (HI)* heteronuclear excitons. The 520-nm luminescence is attributable to iodine-vacancy-bound anion excitons. The thermostimulated luminescence peaks observed in the temperature range 90–150 K are due to the thermal dissociation of V _k and H hole centers. The 90-K photostimulated luminescence of CaI₂-based crystals is shown to be excited in the electronic stage of the recombination process.