A new synthetic pathway of Sr2CeO4 phosphor and its characterization

A blue-white emitting Sr₂CeO₄ phosphor was synthesized via a simple sol-gel poly vinyl alcohol (PVA)-complexing process using strontium nitrate and cerium nitrate as raw materials. The samples were characterized by TG/DTA, XRD, FTIR, SEM and photoluminescence spectroscopy. The X-ray diffraction study confirms the structure of the system to be orthorhombic. The emission spectra when excited at 267 nm peaks at ∼470 nm. The emission band is assigned to the energy transfer between the molecular orbital of the ligand and charge transfer state of the Ce⁴⁺ ion. The Commission International de l'Eclairage (CIE) co-ordinates for the Sr₂CeO₄ sample were also calculated.     

Ion beam mixing induced by electronic energy deposition in Fe-Si multilayers

Abstract

Spectroscopic properties of Ce³⁺ ions in GdAlO₃ crystal are presented. At least three Ce³⁺ nonequivalent centres (multisites) are present in this crystal. Energy transfer from the Ce³⁺ main in the UV emitting centres to the Ce³⁺ green emitting centres is observed. Ce³⁺ fluorescence decays are either fast (1.5–20 ns) or slower due to complicated processes of energy transfer and migration (Ce³⁺)_i → (Gd³⁺)_n-steps → (Ce³⁺)_j (energy transfer through Gd³⁺ sublattice).     

TADF激基复合物主体材料提升溶液法制备蓝色荧光有机发光二极管的效率

为了提升溶液法制备的蓝色荧光有机发光二极管(OLEDs)的效率,采用了基于热激活延迟发光(TADF)的激基复合物作为主体材料。TADF激基复合物主体可以利用反向系间窜跃上转换形成单线态激子并将能量传递到客体,从而可以同时利用发光层中的三线态激子和单线态激子,以提升蓝色荧光器件的效率。选择蓝色荧光材料1-4-Di-[4-(N,N-diphenyl)amino]styryl-benzene(DSA-ph)作为客体发光材料,4,4′,4″-T-ris(carbazol-9-yl)triphenylamine(TCTA)掺杂1,3,5-Tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)(TPBi)作为热激活延迟荧光激基复合物主体,通过溶液法制备了蓝色荧光OLEDs。通过测试TCTA,TPBi以及TCTA掺杂TPBi的光致发光光谱发现,与TCTA和TPBi相比,TCTA掺杂TPBi的光致发光谱(PL)发生了明显的红移(峰值波长变为437 nm),而且光谱变宽,证明了TCTA∶TPBi激基复合物的形成。通过对于DSA-ph掺杂激基复合物主体的薄膜与DSA-ph掺杂poly(methyl methacrylate)(PMMA)的薄膜进行PL测试发现,两者发光峰相同,都是来自DSA-ph的发光,说明激基复合物主体将能量传递到了DSA-ph;DSA-ph的吸收光谱与激基复合物主体的PL光谱存在很大重叠,说明激基复合物主体与DSA-ph的能量传递非常有效;通过对激基复合物主体掺杂不同浓度客体的薄膜进行瞬态PL衰减测试发现,与纯DSA-ph的寿命相比,DSA-ph掺杂激基复合物主体之后其寿命会延长,纯DSA-ph的寿命只有1.19 ns,DSA-ph掺杂激基复合物主体的荧光衰减曲线与激基复合物主体的荧光衰减曲线相似,这进一步证明了激基复合物主体将能量传递到了DSA-ph。研究了主体引入以及DSA-ph掺杂浓度对器件性能的影响。对于器件的亮度、电流密度、电压、电流效率、电致发光光谱等参数进行了测试,与不采用激基复合物主体的器件相比,采用激基复合物主体的器件性能明显改善,在DSA-ph掺杂浓度为10%时,器件亮度从2133.6 cd·m^-2提升到了3597.6 cd·m^-2,器件效率从1.44 cd·A-1提升到了3.15 cd·A-1,发光峰只有来自DSA-ph的发光。采用TADF激基复合物主体的方法有潜力实现溶液法制备的高效蓝色荧光OLEDs。     

Temperature-dependent Time-resolved Fluorescence Study of Cinchonine Alkaloid Dication

Photo induced excited state dynamical processes of cinchonine alkaloid dication (C⁺⁺) have been studied over a wide range of temperature using steady state and nanosecond time-resolved fluorescence spectroscopic techniques. The temperature-dependent fluorescence studies of C⁺⁺ clearly indicate the existence of two distinct emitting species having their own characteristic decay rates. The shorter-lived species shows a usual temperature dependence with increasing non-radiative deactivation at higher temperatures, while the longer-lived species show features resembling to the excited state solvent relaxation process with a large solvent relaxation time (τ _r ∼ 6 ns). The species emitting in the lower energy side, having longer decay time is found to be more sensitive towards chloride ion quenching and has a charge transfer character. Further, concentration quenching with decrease in τ _r of long lived species shows the possibility of energy migration along with solvent relaxation in C⁺⁺.     

Effect of RE as a co-dopant in long-lasting phosphorescence CdSiO3:Mn (RE=Y, La, Gd, Lu)

Effect of RE³⁺ as a co-dopant in long-lasting phosphorescence CdSiO₃:Mn²⁺ (RE=Y, La, Gd, Lu) has been investigated. A longer orange emitting phosphorescence phenomenon was observed in the co-doped CdSiO₃:Mn²⁺,RE³⁺ phosphors after exciting with ultraviolet (UV) light. The luminescence properties, including photoluminescence (PL) spectra and thermoluminescence (TL) spectra, as well as the afterglow decay curves, were studied. The results revealed that one of the origins of the improvement is due to nonequivalent substitution to produce more e-traps, and energy transfer from Gd³⁺ to Mn²⁺ to boost the performance of CdSiO₃:Mn²⁺,Gd³⁺. Role of RE³⁺ co-doped into CdSiO₃:Mn²⁺ matrix and the possible long-lasting phosphorescence process are discussed in this paper.     

Design, Synthesis and Photostability of Novel 1,8-naphthalimide PAMAM Light-harvesting Dendrons

This paper reports on the divergent synthesis, photophysical properties and photodegradation of novel PAMAM dendrons, core and peripherally functionalized with 1,8-naphthalimide fluorophores. The novel compounds were configured as light-harvesting antennae where the system surface is labeled with blue emitting 4-allyloxy-1,8-naphthalimide ??donor?? fluorophores capable of absorbing light and efficiently transferring the energy to a single yellow-green emitting 4-alkylamino-1,8-naphthalimide ??acceptor?? dye. The focal 1,8-naphthalimide fluorophores in the antennae were modified with a HALS fragment (2,2,6,6-tetramethylpiperidine or 1,2,2,6,6-pentamethylpiperidine) with a view to improve their photostability. Novel light-harvesting systems showed highly efficient energy transfer, depending on the volume of the core substituent. Due to the HALS fragments the chromophoric system of the novel antennae showed higher photostability, while the photostability of the PAMAM scaffold was found to be lower.     

Synthesis,Photoluminescence Behavior of Green Light Emitting Tb(III) Complexes and Mechanistic Investigation of Energy Transfer Process

A series of five new terbium(III) ion complexes with 4,4-difluoro-1-phenylbutane-1,3-dione (HDPBD) and anciliary ligands was synthesized. The composition and properties of complexes were analyzed by elemental analysis, IR, NMR, powder X-ray diffaraction, TG-DTG and photoluminescence spectroscopy. These complexes exhibited ligand sensitized green emission at 546 nm associated with ⁵D₄?→?⁷F₅ transitions of terbium ion in the emission spectra. The photoluminescence study manifested that the organic ligands act as antenna and facilitate the absorbed energy to emitting levels of Tb(III) ion efficiently. The enhanced luminescence intensity and decay time of ternary C2-C5 complexes observed due to synergistic effect of anciliary ligands. The CIE color coordinates of complexes came under the green region of chromaticity diagram. The mechanistic investigation of intramolecular energy transfer in the complexes was discussed in detail. These terbium(III) complexes can be thrivingly used as one of the green component in light emitting material and in display devices.

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Graphical Abstract Illustrate the sensitization process of the Tb ion and intramolecular energy transfer process in the Tb³⁺ complex.

     

共轭聚合物单分子构象和能量转移特性研究

利用基于宽场显微光学系统的单分子散焦成像技术测量了不同构象poly[2,7-(9,9-dioctylfluorene)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole](PFO-DBT)共轭聚合物单分子的光物理与动力学特性.通过分析共轭聚合物单分子的荧光轨迹和对应的发射偶极取向变化识别共轭聚合物单分子发光单元,发现延伸构象下的单分子呈现多发色团发光特性,而折叠构象下的单分子保持高效链间能量转移,呈现单个发色团发光特性.共轭聚合物单分子构象对能量转移效率的影响可用于研究基于共轭聚合物的光电器件和分子器件.     

Radiative transfer in absorbing, emitting and linearly anisotropic-scattering inhomogeneous cylindrical medium

Radiative integral transfer equations for one-dimensional solid cylinder with absorbing, emitting and linearly anisotropic-scattering inhomogeneous medium were derived by Abulwafa et al. (JQSRT 62 (1999) 755). The anisotropic terms in the integral equations and their results for anisotropic benchmark problems (JQSRT 66 (2000) 487) are inaccurate. In this study, the integral equations for absorbing, emitting and linearly anisotropic-scattering medium are rederived, and the integral equations for one-dimensional solid cylindrical medium are solved. The results are compared with selected cases using the discrete ordinates S₁₆ and the exact solutions available in the literature.     

Energy transfer in a thin film of TPD fluorescent molecules doped with PtOEP and Ir(ppy)3 phosphorescent molecules

A thin film of triphenylamine dimer, N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)-benzidine (TPD), doped with fac tris(2-phenylpyridine) iridium (Ir(ppy)₃) and platinum octaethyl porphine (PtOEP) is characterized by photoluminescence emission measurements at several excitation wavelengths and photoluminescence excitation measurements at relevant emission wavelengths in the temperature range from 10 K to room temperature. The investigated film is a phosphorescent OLED material with singlet absorbing host (TPD) and triplet emitting guests [Ir(ppy)₃ and PtOEP]. At short wavelength excitation simultaneous triple band emission from singlet TPD, triplet Ir(ppy)₃ and TPD, and from triplet PtOEP is observed. Förster-type singlet-singlet state energy transfer from TPD to Ir(ppy)₃ and PtOEP, intra-component intersystem crossing, and Dexter-type triplet-triplet energy transfer between the substituents are studied.     

Cooperative emission study in ytterbium doped NdVO4

The infrared and visible cooperative emissions of ytterbium ions are studied in Yb-doped NdVO₄ single crystals. The absorption of optical phonons allows the emissions at room temperature when a Nd:YAG laser is used. Low temperature emissions are observed due to the Nd³⁺→Yb³⁺ energy transfer following an argon ion laser excitation of the Nd³⁺ ions. Analysis of the cooperative emission at low doping concentration (1%) indicates that it is generated by distant pair forming Yb³⁺ ions while at high doping concentration (≥ 5%) close ions magnetically coupled and superexchange mechanisms prevail in the emitting process.     

Improved performances of red organic light-emitting devices by co-doping a rubrene derivative and DCJTB into tris-(8-hydroxyquinoline) aluminum host

Performances of red organic light-emitting device were improved by co-doping 2-formyl-5,6,11,12-tetraphenylnaphthacene (2FRb) and 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetra-methyljulolidyl-9-enyl)-4H-pyran (DCJTB) in tris-(8-hydroxyquinoline) aluminum (Alq₃) host as the emitting layer. The device with 1 wt% DCJTB and 2.4 w% 2FRb in Alq₃ host gave a saturated red emission with CIE chromaticity coordinates of (0.65, 0.35) and a maximum current efficiency as high as 6.45 cd/A, which are 2 and 2.4 fold larger than that of the device with 1 wt% DCJTB (3.28 cd/A) in Alq₃ host and the device with 2.4 wt% 2FRb (2.72 cd/A) in Alq₃ host at the current density of 20 mA/cm², respectively. The improvement could be attributed to the effective utilization of host energy by both energy transfer and trapping in the electroluminescence process and the depression of concentration quenching between the dopants molecules.     

Sr3Gd0.5-xTb0.5(BO3)3∶xEu3+的发光性质及能量传递

采用高温固相法制备了Sr₃Gd_0.5-xTb_0.5(BO₃)₃∶xEu³⁺系列荧光粉,并研究了其发光性质与能量传递过程。Sr₃Gd_0.5-xTb_0.5(BO₃)₃∶xEu³⁺系列荧光粉在300~400 nm的近紫外光有效激发下产生489,544,594,614,624 nm的发射谱线,分别对应于Tb³⁺和Eu³⁺的特征跃迁。荧光寿命测试表明,随着Eu³⁺掺杂浓度的增大,Tb³⁺寿命逐渐缩短,证实该体系中存在Tb³⁺→Eu³⁺的能量传递过程,能量传递效率最大值为20.53%。在对Tb³⁺和Eu³⁺的能级结构进行分析的基础上,进一步探讨了Tb³⁺→Eu³⁺能量传递过程。Sr₃Gd_0.5-xTb_0.5-(BO₃)₃∶xEu³⁺系列荧光粉具有良好的红色发光性质,是潜在的可以应用于白光LED的光转换材料。     

Luminescence properties of Ce and Tb co-activated ZnAl2O4 phosphor

In this study, a solution combustion method was used to prepare green emitting Ce³⁺–Tb³⁺ co-activated ZnAl₂O₄ phosphor. The samples were annealed at 700 °C in air or hydrogen atmosphere to improve their crystallinity and optical properties. X-ray diffraction study confirmed that both as-prepared and post-preparation annealed samples crystallized in the well known cubic spinel structure of ZnAl₂O₄. An agglomeration of irregular platelet-like particles whose surfaces were encrusted with smaller spheroidal particles was confirmed by scanning electron microscopy (SEM). The fluorescence data collected from the annealed samples with different concentrations of Ce³⁺ and Tb³⁺ show the enhanced green emission at 543 nm associated with ⁵D₄→⁷F₅ transitions of Tb³⁺. The enhancement was attributed to energy transfer from Ce³⁺ to Tb³⁺. Possible mechanism of energy transfer via a down conversion process is discussed. Furthermore, cathodoluminescence (CL) intensity degradation of this phosphor was also investigated and the degradation data suggest that the material was chemically stable and the CL intensity was also stable after 10 h of irradiation by a beam of high energy electrons.     

Swift heavy ion irradiation-induced modifications of tris-(8-hydroxyquinoline)aluminum thin films

Tris-(8-hydroxyquinoline)aluminum (Alq₃), one of the most widely used light emitting and electron transport materials in organic luminescent devices, has been synthesized. Alq₃ thin films have been deposited by a thermal evaporation process on glass substrates. The effect of swift heavy ion (SHI) irradiation using 40 MeV Li³⁺ on the Alq₃ thin films has been studied by UV-visible, infrared, photoluminescence (PL) and time-resolved photoluminescence (TRPL) spectroscopy. From TRPL studies, it is found that the PL of Alq₃ thin films arises from two species corresponding to its two geometrical isomers, namely facial and meridional having two different life times. It is also confirmed that the PL and lifetimes of excitons decrease with the increase of ion fluences of SHI of 40 MeV Li³⁺, indicating a transfer of exciton energy to unstable cationic Alq₃ species generated by SHI irradiation.     

一种改善红光顶发射OLED色纯度及角度依赖特性的方法研究

在Si/SiO₂衬底上生长金属银作为阳极,4,4,4-tris(3-methylphenylpheny-lamino)-triphenylamine(m-MTDATA):MoOx/m-MTDATA/N,N-bis-(1-naphthyl)-N,N-diphenyl-1,1-biphenyl-4,4-diamine(NPB)作为空穴注入及传输层,发光层采用4,4-N,N-dicarbazole-biphenyl(CBP)掺杂磷光染料(1-(phenyl)isoquinoline)iridium(III) acetylanetonate(Ir(piq)₂(acac))的结构,4,7-di-phenyl-1,10-phenanthroline(BPhen)作为空穴阻挡层及电子传输层,阴极为LiF(1 nm)/Al(2 nm)/Ag(20 nm)复合阴极结构.通过在光取出的复合阴极上方生长一层CBP光学覆盖层,有效地改善了复合阴极膜系的透射率,从而改善了顶发射结构的光学耦合输出特性,在提高器件的正向发光效率的同时还使色坐标往深红光区移动.并且生长光学覆盖层结构的器件角度依赖特性明显得到改善,这对于制作高显示质量的显示器件具有重要意义.在原有结构的基础上增加20 nm的NPB掺杂磷光染料Ir(piq)₂(acac)作发光层,从而得到双发光层结构为NPB:Ir(piq)₂(acac)(1%,20 nm)/CBP:Ir(piq)₂(acac)(1%, 20 nm).由于NPB具有较高的空穴迁移率,避免了由于光学厚度的增加而引起器件工作电压的大幅升高,而双发光层的结构有利于增大激子复合区域,提高辐射复合几率,减少非辐射损耗,实现主客体之间高效的三线态能量传递,相对单发光层顶发射结构,双发光层结构不仅提高了器件的发光效率,而且改善了器件的色坐标.     

Non-equilibrium effects and self-heating in single-electron Coulomb blockade devices

We present a comprehensive investigation of non-equilibrium effects and self-heating in single electron transfer devices based primarily on the Coulomb blockade effect. During an electron trapping process, a hot electron maybe deposited in a quantum dot or metal island, with an extra energy usually of the order of the Coulomb charging energy, which is much higher than the temperature in typical experiments. The hot electron may relax through three channels: tunneling back and forth to the feeding lead (or island), emitting phonons, and exciting background electrons. Depending on the magnitudes of the rates in the latter two channels relative to the device operation frequency and to each other, the system may be in one of three different regimes: equilibrium, non-equilibrium, and self-heating (partial equilibrium). In the equilibrium regime, a hot electron fully gives up its energy to phonons within a pump cycle. In the non-equilibrium regime, the relaxation is via tunneling with a distribution of characteristic rates; the approach to equilibrium goes like a power law of time (frequency) instead of an exponential. This channel is plagued completely in the continuum limit of the single-electron levels. In the self-heating regime, the hot electron thermalizes quickly with background electrons, whose temperature T_e is elevated above the lattice temperature T_ol. We have calculated the coefficient in the well-known T⁵ law of energy dissipation rate, and compared the results to experimental values for aluminum and copper islands and for a two-dimensional semiconductor quantum dot. Moreover, we have obtained different scaling relations between the electron temperature, the operation frequency and device size for various types of devices.     

Synthesis and Fluorescence Properties of Eu<Superscript>3+</Superscript>, Tb<Superscript>3+</Superscript> Complexes with Schiff Base Derivatives

Novel Schiff base ligands derived from N′-benzylidene-benzohydrazide (substituted by –H, ?CH₃, ?OCH₃, ?Cl) and 2-chloro-N-phenylacetamide were synthesized. The solid complexes of rare earth (Eu, Tb) nitrate with these Schiff base ligands were synthesized and characterized by elemental analysis, EDTA titrimetric analysis, thermal analysis, infrared spectra and UV–Vis spectra analysis. The fluorescence properties of rare earth (Eu, Tb) complexes in solid were studied. Under the excitation of ultraviolet light, these complexes exhibited characteristic emission of europium and terbium ions. The results showed that the ligand favored energy transfer to the emitting energy of Eu and Tb ions. Effects of different ligands on the fluorescence intensity of rare earth (Eu, Tb) complexes had been discussed. The electrochemical properties of rare earth (Eu, Tb) complexes were also investigated.     

掺杂型红色有机电致发光显示器件

全色显示是有机电致发光显示(OLED)器件发展的目标,而高性能红色发光器件一直是制约全彩色OLED器件实用化的瓶颈,也是目前有机电致发光显示研究的热点。制作了掺杂DCJTB和不同浓度的rubrene两种荧光染料的红色有机电致发光显示器件,以NPB和Alq₃分别作为空穴传输层和电子传输层,发现器件性能与只掺杂DCJTB的器件相比有明显提高,发光效率提高到2～3倍。通过Frster理论和能带理论分析了器件的能量转移机理,研究发现Frster能量转移不是掺杂器件能量转移的主要形式,载流子俘获机制才是器件效率提高的主要原因;rubrene的引入使得能量能够更有效地从Alq₃转移到DCJTB,从而显著地提高了器件的发光效率和性能。     

共掺杂稀土配合物Tb0.5Eu0.5(TTA)3Dipy发光性质的研究

以TTA为TTA配体合成了新的共掺杂稀土配合物Tb0.5 s Eu0.5(TTA)3 Dipy,通过与PVK的掺杂,分析了PVK 和Tb0.5Eu0.5(TTA)3Dipy之间的能量传递过程,并且制备了以PVK:Tb0.5Eu0.5(TTA)3Dipy为发光层的结构为ITO/PVK:Tb0.5 Eu0.5(TTA)3 Dipy/PBD/Al的发光器件,通过改变两者之间的质量比,得到了较纯的Eu3 的红色发光.通过与PVK:Eu(TTA)3混合体系的比较,发现Tb3 的引入,起到了能量传递桥梁的作用,提高了PVK 到Eu3 的能量传递,从而抑制了PVK 的发光.因此,通过引人适当的第二种金属离子,会增强另一稀土离子的发光,是作者提高稀土离子发光效率的一种有效的手段.