Luminescence properties of CaS:Ce, Sm nanophosphors

CaS:Ce, Sm nanophosphors were synthesized via solid state diffusion method. X-Ray diffraction confirmed the cubic crystalline phase of CaS:Ce, Sm nanoparticles. The particle size calculated using Debye-Scherrer formula was found to be 52 nm. The morphological investigations of the nanoparticles were made using TEM and found to have nearly spherical morphology with diameter 45-50 nm, which is in close agreement with the XRD result. The PL emission characteristics of CaS:Ce, Sm as a function of cerium and samarium concentrations have been studied and CaS:Ce_0.6Sm_0.4 system has maximum emission intensity, hence it was opted for further studies. The CaS:Ce_0.6Sm_0.4 system showed independent emission of Sm and Ce when excited at 330 and 450 nm, respectively. To study the energy transfer between cerium and samarium, the CaS:Ce_0.6Sm_0.4 was excited at wavelengths other than the excitation wavelengths of Ce (450 nm) and Sm (330 nm). The existence of Ce emission (at an excitation of 390 nm) even in the absence of Ce excitation band and Sm emission at an excitation of 405 nm, which is the excitation band of Ce, indicates the energy transfer at these two wavelengths. Thermoluminescence characteristics of ⁶⁰Co irradiated CaS:Ce_0.6Sm_0.4 have been investigated for different doses of 0.14-125 Gy. All the glow curves show a single peak at 475 K. With increasing dose, the intensity of this peak increases and a shoulder is formed on the lower temperature side at 415 K at 21 Gy of exposure. CaS:Ce_0.6Sm_0.4 shows almost linear dose dependence up to 125 Gy.     

Green Emitting Cerium Doped CaS Whiskers Grown by Solid State Diffusion Method

Undoped and cerium doped Calcium sulfide (CaS) phosphors were synthesized using solid state diffusion method. The X-ray diffraction pattern revealed that both undoped and doped CaS crystallites have cubic structure with average crystallite size varying from 20 to 30 nm. Scanning electron micrographs indicated that Ce doped CaS phosphors were composed of whiskers with different dimensions and orientations. The optical properties of undoped and Ce doped particles were characterized using Photoluminescence (PL) and UV-Vis absorption spectroscopy. The PL emission spectrum of cerium doped CaS phosphors for an excitation wavelength 465 nm showed a main peak at 500 nm and a shoulder peak at 556 nm due to 5d?→?4f transition in Ce³⁺ ions. The variation of PL intensity with cerium concentration was investigated and the maximum PL intensity was obtained for a doping concentration of 3 wt.%. The optical band gap of the samples was estimated from the diffuse reflectance spectrum and was found to increase with increase in cerium concentration. The enhanced optical properties of these phosphors can be exploited in various optoelectronic devices including displays and bioimaging techniques.     

CaS:Ce,Tb中Tb3+到Ce3+的能量传递

本文通过发射光谱、激发光谱和发光的衰减特性,研究了三价稀土离子Ce3+和Tb3+在CaS基质中的相互作用。实验结果表明,在CaS中Tb3+敏化了Ce3+的发光,监测Ce3+的发光(505nm),在激发光谱中出现Tb3+中心特征辐射的激发带。而且在CaS:Ce、Tb中,Ce3+中心的发光衰减变慢,衰减后期的慢成份正是反映了能量施主Tb3+的衰减特性,证明在CaS:Ce、Tb中存在着Tb3+到Ce3+的能量传递。     

Energy transfer and sensitised luminescence in single crystals of CaF2:(Ce+Mn) system

The measurement of absorption, luminescence, and relative intensity of cerium and manganese emission during fluorescence, on single crystals of CaF₂:(Ce+Mn), have been reported in this paper. The occurence of the absorption bands have been explained in the following manner: (i) 250 mu band due to the transfer transition from F^? to²D, the excited state of Ce³⁺, (ii) 305 mμ band due to the characteristic transition of Ce³⁺ and (iii) 335 mμ band due to the perturbed level of the lattice. The emission bands have been explained like this, (i) 320 and 340 mμ bands due to the transitions of²D to²F_5/2,7/2 levels of Ce³⁺ (ii) 380 and 440 mμ bands corresponding to the perturbed levels and (iii) 520 mμ band due to transfer of energy from cerium centres to manganese centres. The results of the present investigation indicate that energy transfer in this system occures not only from cerium to manganese centres but also from cerium to cerium and cerium to perturbed levels of the lattice. It has also been observed that energy transfer process is temperature dependent in this case. An energy level scheme is proposed to explain the transfer mechanism.     

Effect of Fe,Co, Ni and Cd CO‒activation on luminescence emission and decay of CaS:Ce phosphors

Cathodoluminescence (CL), photoluminescence (PL), thermoluminescence (TL) spectra, and decay after laser beam excitation of cerium-activated CaS phosphors doped with Fe, Co, Ni or Cd have been investigated. These studies shed some light on the nature of luminescence centres and the association of various groups of traps with the dopants. Effect of concentiation variation of these four elements on emission and decay characteristics of CaS:Ce phosphor has been discussed. In contrast with the earlier publication [W. Lehmann and F. M. Ryan, J. Electrochem. Soc. 119, 275 (1972)] we have found that Ni is an effective killer, Cd ineffective and Co has no clearly observable effect. Fe has also been found to be an effective killer for CaS:Ce phosphors. Ni and Fe appear to be more effective quenchers for shorter wavelength emission band characteristic of Ce in CaS.     

Tailored photoluminescence of YAG:Ce phosphor through various methods

Trivalent cerium Ce³⁺ (Ce) activated yttrium aluminum garnet Y₃Al₅O₁₂ (YAG) phosphor was synthesized by two methods: solid state reaction (SS), and combustion (CB) with urea, respectively. The crystallization and luminescent properties of the phosphors were studied. Factors influencing on the intensity of luminescence and the location of emission band of YAG:Ce, such as the type of flux used in SS, the reaction atmosphere, the concentration of activator, were investigated in detail. We accomplished red or blue shift of Ce emission band by a number of techniques in order to match with the variable emission wavelength of blue light emitting diodes. The change of emission in color coordinates was illustrated by chromaticity. Co-doping other rare earth ions with Ce³⁺ ions into YAG was attempted to increase the color rendering index.     

Studies on luminescence properties and energy transfer in Ce/Dy co-doped CaS nano-phosphors

Luminescence properties of CaS:Ce co-doped with dysprosium has been studied. Ce/Dy co-doped CaS nanophosphors (CaS:Ce_0.25Dy_0.75, CaS:Ce_0.50Dy_0.50, CaS:Ce_0.75Dy_0.25) were synthesized using the solid state diffusion method. The phase purity of the samples was confirmed using XRD data. The particle size was calculated using Debye–Scherrer formula and was found to be varying between 50 and 60 nm for all the three samples (CaS:Ce_0.25Dy_0.75, CaS:Ce_0.50Dy_0.50 and CaS:Ce_0.75Dy_0.25). TEM image analysis of CaS:Ce_0.50Dy_0.50 shows nearly spherical particles with diameter varying between 50 and60 nm. One way energy transfer from Dy³⁺ to Ce³⁺ in CaS host has been investigated using photoluminescence studies. Thermoluminescence of these nanophosphors has been studied for 0.5 Gy–21 kGy dose of gamma rays and the dose linearity of CaS:Ce_0.50Dy_0.50 has been compared with CaSO₄:Dy (standard TL dosimeter). Linear behavior over a large dose range between 0.5 Gy and 21 kGy was found for CaS:Ce_0.50Dy_0.50 as compared to CaSO₄:Dy (nanocrystalline and microcrystalline) but it is found to be less sensitive than microcrystalline CaSO₄:Dy. To identify the peaks of Ce³⁺ and Dy³⁺ in CaS, the TL spectra of CaS, CaS:Ce, CaS:Dy and CaS:Ce_0.50Dy_0.50 were recorded. The addition of dopants does not add new peaks in CaS but aid to enhance the TL emission. The peaks in CaS may be associated to intrinsic traps in the host lattice.     

铈掺杂氧化铝薄膜的蓝紫色发光特性

应用中频反应磁控溅射技术制备了Al₂O₃:Ce³⁺的非晶薄膜.X射线光电子谱(XPS)检测显示薄膜中有Ce³⁺生成.这些薄膜的光致发光峰是在374nm附近,它来自于Ce³⁺离子的5d¹激发态向基态4f¹的两个劈裂能级的跃迁.发光强度强烈地依赖于薄膜的掺杂浓度,但发光峰位置不随掺杂浓度而变化.Ce³⁺含量和薄膜的化学成分是通过X射线散 关键词： 光致发光 2O₃')" href="#">Al₂O₃ 薄膜 稀土元素     

Structural, optical and scintillation properties of cerium cyclotriphosphates and polyphosphates

The cerium cyclotriphosphate CeP₃O₉·3H₂O and polyphosphate Ce(PO₃)₃ have been optically investigated for the first time. In both materials, excitation and emission spectra under UV and X-ray excitations as well as emission decays of Ce³⁺ were measured at room temperature. The spectroscopic results of anhydrous Ce(PO₃)₃, prepared by progressively heating the corresponding CeP₃O₉. 3H₂O, are discussed and correlated with the structural data.For the Ce(PO₃)₃ polyphosphate material, the Stokes shift of the d-f emission is very small (760 cm⁻¹), inducing an efficient ultraviolet luminescence and a new application as scintillator.     

硼酸对亚微米级Ca3Sc2Si3O12:Ce绿色荧光粉的制备及发光性能的影响

采用凝胶-燃烧法合成了Ca₃Sc₂Si₃O₁₂ ∶Ce绿色LED用荧光粉,用X射线粉末衍射(XRD)、扫描电镜(SEM)、荧光光谱仪等对合成产物进行了分析和表征.结果表明:通过添加H₃BO₃做助熔剂,制得的荧光粉晶相纯正,颗粒形貌均呈现为较规则的类球形,而且所得荧光粉的粒径均小于1 μm.发射光谱呈现为一宽带,发射主峰位于505 nm,该宽峰对应于Ce³⁺关键词： 白光LED 荧光粉 3Sc₂Si₃O₁₂ ∶Ce')" href="#">Ca₃Sc₂Si₃O₁₂ ∶Ce 发光     

A resonant photoemission study of the Ce and Ce-oxide/Pd(1 1 1) interfaces

We have investigated the Ce 4f electronic states in the Ce/Pd(1 1 1) and Ce-oxide/Pd(1 1 1) systems, using resonant photoemission (Ce 4d → 4f transitions), and XPS to understand Pd-Ce interactions in ultra thin layers of cerium and ceria deposited on Pd(1 1 1). Cerium deposited on Pd(1 1 1) at room temperature forms surface Ce-Pd alloys with Ce rich character, while a Pd rich Ce-Pd alloy is formed by heating to 700 °C. A modification of the chemical state of Ce can also be seen after oxygen exposure. RPES provides evidence that Ce-oxide layers deposited on Pd(1 1 1) have a CeO₂ (Ce⁴⁺) character, however a net contribution of the Ce³⁺ states is also revealed. The Ce³⁺ states have surface character and are accompanied by oxygen vacancies. Heating to 600 °C causes Ce-oxide reduction. A significant shift of Pd 4d-derived states, induced by Pd 4d and Ce 4f hybridization, was observed. The resonant features in the valence band corresponding to Ce⁴⁺, Ce³⁺ and Ce⁰ states have been investigated for various Pd−Ce(CeO_x) coverages.     

Photoluminescence Spectra of CaS:Er and CaS:Tb Powder Phosphors

This paper reports the method of preparation and the emission level assignments for the light emitting powder phosphors of CaS:Er³⁺ and CaS:Tb³⁺. The recorded photoluminescence spectra of these powder phosphors have shown that the light emission would be better at lower dopant concentrations.     

Ce掺杂SrMnO3的电子结构和磁性的第一性原理研究

用含超软赝势平面波方法的广义梯度近似第一性原理对Ce掺杂SrMnO₃的电子结构和磁性进行了相关研究. 不同的Mn-O键长说明MnO₆八面体发生了强的Jahn-Teller扭曲, 并伴随着晶体构型由立方体(Pm3m)转变为四方晶系(I4/mcm), 同时,Jahn-Teller扭曲也稳定了C型反铁磁基态构型. 电子结构结果表明SrMnO₃和Sr_1-xCe_xMnO₃(x=0.12     

Two-step photoconductivity in LiY<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript>Lu<Subscript>1 – <Emphasis Type="Italic">x</Emphasis> </Subscript>F<Subscript>4</Subscript>:Ce,Yb crystals

Photoconductivity of LiY_xLu_1–xF₄:Ce,Yb (x = 0–1) crystals is measured under one- and two-step excitation. It is established that the photoconductivity is due to intra-center transitions from excited states of Ce³⁺ ions. The position of the ground 4 f-state of Ce³⁺ ion relative to the bottom of the conduction band is determined. The choice of pumping conditions to obtain the lasing on the 5d–4f transitions of trivalent cerium in these active media is substantiated.     

Luminescence and Scintillation Characterization of Cs2NaGdBr6: Ce3+ Single Crystal

Luminescence and scintillation properties of newly discovered bromo-elpasolites Cs₂NaGdBr₆: Ce³⁺ (CNGB: Ce³⁺) are presented. Single crystals of CNGB: Ce³⁺ with dimensions up to Ø7×10 mm³ are successfully grown by the Bridgman technique. X-ray excited luminescence measurements of the grown samples showed a broad emission band in the wavelength range from 365 to 470 nm. It offered an energy resolution of 5.1% (FWHM) at 662 keV for 10% Ce sample. The light output of the investigated samples increases along with cerium concentration. A maximum light yield of ～36,800 ph/MeV is measured for the 10% Ce sample crystal. Under γ-ray excitation, CNGB: Ce³⁺ crystals showed three exponential decay time components. The scintillation mechanism in the sample crystal is presented.     

Anomalous thermally stimulated currents in CaS

Information on the nature of traps in CaS has been sought by studying the TSC behaviour in a range of samples. Results are in agreement with those reported previously and suggest that the TSC peak at 308 ± 3K is independent of the nature and concentration of dopant. Evidence is presented which indicates that surface states are responsible for the currents rather than the release of trapped charge from states within the band gap; the source of the charge carriers is uncertain. Simultaneous TSC and TL measurements on CaS:Ce, Cu indicate that the TL peak at 300K and the TSC peak at 308K are mutually independent.     

Specific features of the electronic structure of the CeCu<Subscript>6</Subscript>, CePd<Subscript>3</Subscript>, CeSi<Subscript>2</Subscript>, and CeF<Subscript>3</Subscript> systems

The electronic structure of cerium systems, the hybridization of 4 f and outer-shell electrons, and the influence of the position of the localized 4 f level with respect to the Fermi level E _F in the conduction band have been investigated. The CeCu₆, CePd₃, CeSi₂, and CeF₃ systems have been studied using X-ray photoelectron spectroscopy. The densities of states have been calculated by the tight-binding linearized muffin-tin orbital method within the atomic sphere approximation, which takes into account the covalent character of bonds and the nonspherical distribution of the electron density. The results obtained from the calculations of the total density of states are in good agreement with the valence band X-ray photoelectron data for the systems under investigation. It has been shown that the differences in the properties of the cerium systems are determined by the specific features of their electronic structure. A strong interatomic interaction is characteristic of heavy-fermion systems.     

Effect of hyperfine interaction on the luminiscence of Pb2+ and Bi3+ centers in alkaline-earth chalcogenides

Emission spectra of MgS, CaO, CaS, CaSe and SrS phosphors activated with a Pb²⁺ or a Bi³⁺ ion are measured at 4.2 K. By the analysis of the phonon structure of the ³A_1u → ¹A₁g emission band, it is found that the hyperfine interaction provokes the zero-phonon line on the emission band for the alkaline-earth chalcogenide phosphors activated with a Pb²⁺ or a Bi³⁺ ion.     

铈激活磷光体的发光特性

Ce3+的发光属于f-d跃迁,它的荧光寿命非常短,发射光谱呈现带状,并随着基质的不同,发射峰位置发生显著的变化,能从紫外一直到可见区.Ce3+发射峰位置的变化与基质中直接配位的阴离子、阳离子以及阴离予基团等的变化有关,也受晶场劈裂、Stokes位移的影响.Ce3+发射峰位置的变化与化台物的共价程度有关,并得到一些规律性的结果,这将为材料设讨提供依据.文中对一些典型的Ce3+的能量传递和敏化作用作了介绍.     

铈离子掺杂浓度对氯化镧(LaCl_3:Ce)闪烁晶体发光性能的影响

本文采用垂直Bridgman法,分别生长了未掺杂LaCl3和掺有不同浓度CeCl3的LaCl3闪烁晶体,并对它们的透光性质、发光性质和光衰减特性进行了测试和对比分析.发现未掺杂LaCl3晶体的吸收边位于215 nm附近,本征发射峰为405 nm,衰减时间在1μs以上.该发光属于纯氯化镧晶体的自陷激子发射,但随着CeCl3掺杂浓度的提高,源于自陷激子(STE)的本征发射强度逐渐降低,LaCl3:Ce晶体中的吸收边逐渐红移至300nm,由Ce3+中心所产生的5d→4f发射逐渐增强,其衰减时间加快至～20 ns.这种现象被解释为LaCl3晶格中的自陷激子向Ce3+离子发光中心的能量传递作用所致.