Luminescence enhancement of rare earth ions by metal nanostructures

Well-ordered metal structures, i.e. arrays of nanosized tips on silver surface for studies of the luminescence enhancement of absorbed media with rare earth ions were used. These arrays were prepared by the metal evaporation on track membranes. Calculations of reso- nanee frequencies of tips regarded as semispheroids were done taking into account the interaction between dipoles of tips. They were used to discuss experimental results for media with Eu（NO3）3·6H2O salt basing on data for bulk silver dielectric function.

Structure and Luminescent Enhancement Effect of Na_5Eu(MoO_4)_4 by Doping(WO_4)^(2-)

The luminescent enhancement effect of Na_5Eu(MoO_4)_4 by doping(WO_4)^(2-) has been studied. When the value x in Na_5Eu(Mo_(1-x)W_xO_4)_4 is in 0<x<0.21,its photoluminescent spectrum is near to that of Na_5Eu(MoO_4)_4,but its luminescent intensity increases.When x=0.033,the intensity is increased by about 30%.According to the X-ray diffraction analysis,W ions get into the lattice and occupy the sites of the Mo ions.The change of crystal environment of Eu^(3+) may result in the luminescent enhancement.

Enhanced Luminescence of InGaN-Based 395 nm Flip-Chip Near-Ultraviolet Light-Emitting Diodes with Al as N-Electrode

High-reflectivity Al-based n-electrode is used to enhance the luminescence properties of InGaN-based 395nm flip-chip near-ultraviolet （UV） light-emitting diodes. The Al-only metal layer could form the Ohmic contact on the plasma etched n-GaN by means of chemical pre-treatment, with the lowest specific contact resistance of 2.211 × 10^-5 Ω. cm2. The AI n-electrodes enhance light output power of the 395 nm flip-chip near-UV light-emitting diodes by more than 33% compared with the Ti/AI n-electrodes. Meanwhile, the electrical characteristics of these chips with two types of n-electrodes do not show any significant discrepancy. The near-field light distribution measurement of packaged chips confirms that the enhanced luminescence is ascribed to the high refleetivity of the Al electrodes in the UV region. After the accelerated aging test for over 1000 h, the luminous degradation of the packaged chips with Al n-electrodes is less than 3%, which proves the reliability of these chips with the Al-based electrodes. Our approach shows a simplified design and fabrication of high-refleetivity n-electrode for flip-chip near-UV light emitting diodes.

Fast Diagnosis of Gonorrhea With Enhanced Luminescence Enzyme Immunoassay

Objective:To evaluate the value of enhanced luminescence enzyme immunoassay in the diagnosis of Neisseria gonorrhea(NG) infection. Methods: Anti-catalase antibody for Neisseria gonorrheae combined with enhanced luminescence enzyme immunoassay were used to test for N. gonorrhea. Results: A minimum of 1×10^4/CFU of GC in genital tract secretions or urine could be detected with the technique of luminescence enzyme immunoassay. Conclusion : The enhanced luminescence enzyme immunoassay has the advantage of high sensitivity and specificity for diagnosing NG from genitourinary tract secretion and urine.

Enhanced red luminescence of Ca_(3)Si_(2−x)M_(x)O_(7):Eu^(3+)(M=Al,P)phosphors via partial substitution of Si^(4+) for applications in white light-emitting diodes

A red-emitting phosphor Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) with partial Al^(3+)/P^(5+) substitution on Si^(4+) was synthesized via a simple solid-state method,and the effects of the introduction of the M^(3+/5+)(M=Al,P)ions on the crystal structure and photoluminescence performance of Ca_(2.91)Si_(2−x)M_(x)O_(7):0.09Eu^(3+) phosphors were investigated.The X-ray diffraction(XRD),energy-dispersive X-ray spectroscopy(EDS),and X-ray photoelectron spectroscopy(XPS)results revealed that the structure of Ca_(3)Si_(2)O_(7) remained the same after the introduction of Al^(3+) and P^(5+) ions.The characteristic emission of Eu^(3+)-doped Ca_(3)Si_(2−x)M_(x)O_(7) phosphors exhibited two main peaks at 617 nm(red)and 593 nm(orange)under excitation at 394 nm,which originated from the^(5)D_(0)→^(7)F_(2)and^(5)D_(0)→^(7)F_(1) electron transitions of Eu^(3+) ions.After the partial substitution of Al^(3+) and P^(5+),the red emission intensities of the Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) phosphors were significantly enhanced by 1.88-and 1.42-fold,respectively,which is attributed to the crystal-field effect around Eu^(3+).Meanwhile,the luminescence intensities of the Ca_(2.91)Si_(1.96)Al_(0.04)O_(7):0.09Eu^(3+) and Ca_(2.91)Si_(1.94)P_(0.06)O_(7):0.09Eu^(3+) phosphors at 210℃ were 79.36%and 77.53%of those at 30°C,respectively,indicating their excellent thermal stability.Moreover,the as-prepared Ca_(2.91)Si_(1.96)Al_(0.04)O_(7):0.09Eu^(3+)and Ca_(2.91)Si_(1.94)P_(0.06)O_(7):0.09Eu^(3+) red-emitting phosphors were combined with a near-ultraviolet chip of 395 nm to fabricate red-light-emitting diode(LED)and white(w)-LED devices with excellent chromaticity features.In summary,Al^(3+)/P^(5+)-substituted Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) can serve as red-emitting phosphors for applications in w-LEDs.

Nano-effect enhanced cooperative luminescence of Yb^(3+) clusters in bulk materials

In order to improve the multi-ion cooperative transition, we proposed and exploited a novel nanoscale effect, namely the nanoshell effect in bulk materials. Based on the effect, an optimal material structure was designed by coating the surfaces of Ca F_(2):Yb^(3+)micron size particles with ZrO_(2). An about 2 times higher intensity of cooperative luminescence is observed upon laser excitation at 980 nm. Dynamical analysis exhibits that the novel effect plays a key role in improving the performance of cooperative transitions. Our results also suggest that the nanoshell effect in bulk materials is likely to be significant in some special cases, which have not been reported yet in the literature.

YPO_4 nanocrystals: preparation and size-induced lattice symmetry enhancement

YPO4 and Eu doped YPO4 nanocrystals were prepared via a simple hydrothermal method. The phase purity, rnicrostructure, surface absorbed water and luminescence properties were characterized with X-ray diffraction （XRD）, transmission electron microscopy （TEM）, fluorescence spectrum, infrared spectroscopy, Raman spectroscopy and thermogravimetry analysis（TGA）. Combined with XRD and TEM analysis, it was found that YPO4 nanocrystals crystallized into a single phase of tetragonal （141/amd） zircon structure. YPO4 nanocrystals showed a size reduction with the reaction temperature decreasing. Considering the XRD, IR and Raman results, a lattice expansion and the unit cell symmetry enhancement were observed with the particle size decreasing. A dipole to dipole interaction model was applied to investigate the relationship of the variation of microstrucmre and the particle size. The emission spectrum of Eu doped YPO4 nanocrystals was also presented and the emission bands were clearly ascribed to the f to f transitions of Eu^3＋.

稀土激活的荧光热增强材料研究进展

自从尺寸依赖的上转换荧光热增强现象在稀土激活的纳米荧光材料中被发现以来,开发具有显著荧光热增强效应的稀土荧光材料俨然成为了一个研究热点。近期的探索发现荧光热增强效应在非纳米尺度稀土荧光材料体系以及非上转换发光过程中均可实现,这进一步拓展了这一有趣光学现象的应用场景。本文总结和归纳了稀土激活荧光热增强材料的最新研究进展,概述了所提出的几类机理以及稀土荧光热增强材料的潜在应用场景,并展望了该类材料的研究发展方向。

Defect elimination to enhance photoluminescence and optical transparency of Pr-doped ceramics for self-calibrated temperature feedback windows

Pr-doped metal oxide polycrystalline transparent ceramics are highly desirable for photothermal window systems served in extreme environments;however,obtaining efficient photoluminescence(PL)together with high transparency in these ceramics is still posing serious challenges,which undoubtedly limits their applications.Here,Pr-doped Y_(2)Zr_(2)O_(7)(YZO)transparent ceramics,as an illustrative example,are prepared by a solid-state reaction and vacuum sintering method.Owing to the elimination of defect clusters[Pr_(Y)^(4+)-O^(2-)Pr_(Y)^(4+)]and[Pr_(Y)^(4+)-e′]without the introduction of impurities and additional defects,the fabricated YZO:Pr ceramics exhibit high transparency(74%)and efficient PL(39-fold enhanced)after air annealing plus vacuum re-annealing treatment.Moreover,upon 295/450 nm excitation,the emission bands(blue,green,red,and dark red)from YZO:Pr ceramics present different temperature-dependent properties due to the thermalquenching channel generated by the intervalence charge transfer(IVCT)state between Pr_(Y)^(4+)and Zr^(4+)ions.Furthermore,a self-calibrated temperature feedback window with the same fluorescence intensity ratio(FIR)model(I_(613)/I_(503),where I represents the intensity)under different excitation light sources(295 and 450 nm)is designed.The developed photothermal window operated in a wide temperature range(303-663 K)shows relatively high sensitivities(absolute sensitivity(Sa)and relative sensitivity(S)reach 0.008 K^(-1)at 663 K and 0.47%K^(-1)at 363 K,respectively),high repeatability(>98%),and low temperature uncertainty(T<3.2 K).This work presents a paradigm for achieving enhanced PL along with elevated transparency of lanthanide(Ln)-doped ceramics through vacuum re-annealing treatment engineering and demonstrates their promising potential for photothermal window systems.

Tunable multicolor luminescence in vanadates from yttrium to indium with enhanced luminous efficiency and stability for its application in WLEDs and indoor photovoltaics

The preparation of high-efficiency phosphor is the key to the construction of white light-emitting diode(WLED)devices and their application in indoor photovoltaics.Compared with YVO_(4),InVO_(4)is not suitable as the host material of lanthanide ions because of its strong self-luminescence.Here,the work focused on combining the broadband emission from InVO_(4)and the red luminescence from YVO_(4):Eu^(3+)to obtain enhanced and stable multicolor luminescence.The band structure,density of state,and optical properties were studied by density functional theory.The spectral configuration of YVO_(4):In^(3+)/Eu^(3+)with(112)surface appears to be broadening and redshifts with increasing layer number.When the In^(3+)concentration is 3.5 mol%,the YVO_(4):30%Eu^(3+)/In^(3+)emits the strongest light.The Judd-Ofelt parameterΩ2 of YVO_(4):In^(3+)/Eu^(3+)increases with increaing In^(3+)concentration,indicating that the symmetry decreases.By adjusting In^(3+)/Eu^(3+)contents,the YVO_(4):In^(3+)/Eu^(3+)not only can emit white light with a color rendering index of 95,but also can be used as high-efficiency red phosphor to build WLED devices with blue emitting N/Tb codoped carbon quantum dots(CQDs-N:Tb^(3+))and green emitting MOF:Tb^(3+)(MOF=metal organic framework),for which the color rendering index can also reach 95 and the color temperature is 5549 K.The manufactured WLED devices were further used to excite the silicon solar cell and make it show good photoelectric characteristics.

Unexpected luminescence enhancement of upconverting nanocrystals by cation exchange with well retained small particle size

有小尺寸的高度光的 upconversion nanoparticles (UCNP ) 为 bioapplications 是高度合乎需要的。在 situ 阳离子交换策略灵巧的 A 被开发了极大地提高六角形的阶段 NaYF 的 UC 光 < 潜水艇 class= “ a-plus-plus ” > 4 NP 当维持他们的小粒子尺寸和形状时。经由由热注射的 Gd 的一个阳离子交换处理 < 啜 class= “ a-plus-plus ” >3+ 位 先锋进没有分离前的同样准备的 NP 答案， NP 的裸体眼睛的可见 UC 排放在 980 nm 下面被提高大约 29 次近红外线(NIR ) 有未改变的粒子尺寸的刺激。阳离子交换过程进一步为 NaYF 的盒子被表明 < 潜水艇 class= “ a-plus-plus ” > 4 nanorods (NR ) 。在阳离子交换以后， nanorod 与更强壮的排放被分解为二 NP。阳离子交换了恐水病的 UCNP 进一步被包含与 poly (氨基酸) 并且成功地申请了指向的癌症房间 UC 光成像。

Enhancement of the up-conversion luminescence of ZnO:Yb3+/Er3+ by photonic crystals

The opal photonic crystals(PCs) were assembled by vertical deposition of polystyrene microspheres(PS), in which Yb3+, Er3+ co-doped ZnO powders were deposited on the surface of PC films. The phase, structure and morphology of the obtained samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and transmission electron microscope(TEM). The performance of up-conversion photoluminescence(UCPL) was investigated by fluorescence spectrophotometer. The up-conversion(UC) emission of Zn O:Yb3+/Er3+ on the PC surface is notably enhanced when the UC emission wavelength is overlapped with the photonic bandgaps of opals, which is attributed to Bragg reflection of photonic bandgap. The results show that PCs may have potential applications in the enhancement of UCPL and optoelectronic devices.

Luminescence enhancement of CaMoO_(4):Eu^(3+) phosphor by charge compensation using microwave sintering method

CaMoO_(4):Eu^(3+)and CaMoO_(4):Eu^(3+),A+(A=Li,Na,K)phosphors for light-emitting diode(LED)applications have been prepared by microwave sintering method(MSM),and their structure and luminescence properties are investigated.The influences of microwave reaction time and concentration of different kinds of charge compensation A+and Eu^(3+)on luminescence have also been discussed.The samples emit a red luminescence at 615 nm attributed to the^(5)D0→^(7)F2 transition of Eu^(3+)under 464 nm excitation.It is observed that adding charge compensation A+in the sample synthesis increases luminescence intensity.The optimized sample made with 32 mol%Li+and 32 mol%Eu^(3+)has an enhancement factor of 4 in photoluminescence compared to the sample made without charge compensation.The CIE(Commission Internationale de l'Eclairage)coordinates of Ca0.36MoO_(4):0.32Eu^(3+),0.32Li+are x=0.661 and y=0.339,which indicate that the obtained phosphor can be a promising red color candidate for white LED fabrications.

A luminescence enhancement approach through Si/O nanostructure

An Si/O patterned shell array was fabricated by a technique utilizing nanosphere self assembly and reactive pressure pulsed laser deposition.The nanostructure produced by this technique enhanced the luminescence intensity by a factor of three compared with that of a flat film.The amount of enhance-ment observed coincided well with the expected enhancement by simulation.The technique in this paper provided a flexible,designable and compatible approach to luminescence enhancement.

Effects of Doping Trace Sm^(3+) and Gd^(3+) on Luminescent Character of Y_2O_2S∶Eu^(3+)

After trace Sm^3＋ ions and Gd^3＋ ions doping, the emission intensity of red phosphors Y2O2S： Eu^3 ＋ was enhanced and the voltage character （relation between emission intensity and excitation voltage） was improved while the other properties of physics and chemistry were not changed. The origins of enhancement and improvement are discussed. Probably the distortion and the defect of crystals are decreased by the substitution of Gd^3＋ for Y^3＋ instead of Eu^3＋ for Y^3＋ , and thus the Eu^3＋ crystal field is improved, and radiationless process and energy loss resulted from crystal defect are weakened, which leads to increased luminescence intensity and voltage character improvement. The overlapping fluorescent spectra of Y2O2S： Sm^3＋ emission and Y2O2S：Eu^3＋ excitation as well as Eu^3 ＋ excitation spectra transitions spectra lead to energy transfer from Sm^3 ＋ sensitization of Sm^3＋ ions fectively. containing Sm^3＋ excitation the possibility of resonance ions to Eu^3＋ ions, and the to Eu^3＋ ions is achieved effectively.

Enhancement of up-conversion luminescence properties in Yb^(3+)/Tm^(3+)/Er^(3+) tri-doped transparent oxyfluoride tellurite glass ceramics

Optically transparent Er3＋/Tm3＋/Yb3＋ tri-doped oxyfluoride tellurite based nano-crystallized glass ceramics with the batching composition of 73TeO2-15ZnO-7ZnF2-3YF3-1.5YbF3-0.3ErF3-0.2TmF3 （mol%） is prepared by a conventional melting quenching and the subsequent heat treatment processes. The sizes of grown nano-crystals in glass matrix appear to be smaller than 100 nm from the scanning electron mi- croscope measurement. Visible up-conversion luminescence of the as melted glass and glass ceramics is investigated. The three-color up-conversion luminescence intensities by 980-nm pumping are increased significantly due to the heat treatment, and the blue intensity increases with a higher magnitude than other wavelengths after heat treatment.

Enhancement of the upconversion luminescence in Y_2O_3:Er^(3+) powders by codoping with La^(3+) ions

Infrared-to-visible upconverted luminescent spectra of Er3 t and La3 t codoped Y2O3 powders are investigated.By introducing La3 t ions, the upconversion green radiation is found to be greatly enhanced when compared with the powders with La3 t absent. Such enhancement can be attributed to the modification of the local symmetry surrounding the Er3 t ion, which benefits the intra-4f transitions of Er3 t ion, and the decreasing interaction between Er3 t ions, which suppresses the energy transfer process4F7∕2t 4I11∕2→ 4F9∕2t 4F9∕2.

金纳米核-壳结构(Au@SiO_(2))对铕元素的发光增强机制研究

为了增强稀土有机薄膜的发光效果,在制备稀土发光薄膜过程中引入了金纳米核-壳结构(Au@SiO_(2)).利用滴铸法将不同浓度的Au@SiO_(2)滴在石英片上;利用旋涂法将Eu(dbm)_(3)phen.聚甲基丙烯酸甲酯(PMMA):CH_(2)Cl_(2)混合溶液旋涂在石英片上,制备成薄膜样品.通过对薄膜样品的性能表征后发现:引入Au@SiO_(2)后可增强薄膜的发光强度;激发和发光增强因子最大分别为279.1%和222.9%,同时延长了薄膜样品的荧光寿命.将Au@SiO_(2)引入稀土发光薄膜的制备过程中,能够有效地提升薄膜的发光性能,应用潜力较好.

两种离子型铱配合物的合成、光物理性质及对OH^(-)的检测

以两种2,2’-联吡啶衍生物为中性配体,2-(3-氟苯基)吡啶为环金属配体,合成了两种新型的离子型Ir(Ⅲ)配合物Ir1和Ir2。利用核磁、质谱和晶体结构分析确认了配合物Ir1和Ir2的结构。配合物Ir1和Ir2在CH_(2)Cl_(2)溶液中的最大发射波长分别为570和528 nm,为橙红光和黄光。两种配合物在无氧CH_(2)Cl_(2)溶液中的量子产率分别为0.88和0.57,磷光寿命分别为2.43和2.40μs。通过理论计算详细讨论了中性配体的取代基种类对其光谱性质的影响。在配合物Ir1的DMSO/H_(2)O溶液中加入OH^(-)后,其发射峰强度提高了近100倍,溶液的发光颜色由红色变为明亮的绿色,检出限为8.47×10^(-6)mol/L。机理研究表明,OH^(-)取代了Ir1的中性配体上的溴取代基,形成了新的含有羟基的配合物,从而改变了Ir1的光谱特性,实现对OH^(-)的高选择性和高灵敏度检测。

GaN基LED表面三维凹球结构的制备及其发光增强

以紫外曝光技术为基础,得到了欠曝光条件下的三维凹球结构,结合菲涅尔衍射效应和邻近效应开发了一种制备密排三维周期性凹球结构的方法,并重点研究了掩膜版类型和光刻胶厚度对曝光图形的影响。实验结果表明,采用六方密排结构的明场掩膜图案,当光刻胶厚度为1.3~1.5μm时,可以得到周期为3~5μm、占空比接近100%的三维凹球结构阵列。该三维凹球结构阵列在LED发光增强及微透镜阵列等方面有广阔的应用前景,并在实验中实现了GaN基LED发光增强163.4%,通过角分辨分析得到LED发光在法线方向的30°~65°和115°~150°增强最为明显,扩大了LED光出射的角度,对LED作为显示器件增大可视角度具有重要意义。