Synthesis and photoluminescence properties of a novel Sr2CeO4:Dy3+ nanophosphor with enhanced brightness by Li+ co-doping

A series of Dy3+ (0.5-9 mol%) and Li+ (0.5-3 mol%) co-doped strontium cerate (Sr2CeO4) nanopowders are synthesized by low temperature solution combustion synthesis. The effects of Li+ doping on the crystal structure, chemical composition, surface morphology and photoluminescence properties are investigated. The X-ray diffraction results confirm that all the samples calcined at 900 degrees C show the pure orthorhombic (Pbam) phase. Scanning electron microscopy analysis reveals that the particles adopt irregular morphology and the porous nature of the product. Room temperature photoluminescence results indicate that the phosphor can be effectively excited by near UV radiation (290 to 390 nm) which results in the blue (484 nm) and yellow (575 nm) emission. Furthermore, PL emission intensity and wavelength are highly dependent on the concentration of Li+ doping. The emission intensity is enhanced by similar to 3 fold with Li+ doping. White light is achieved by merely varying dopant concentration. The colour purity of the phosphor is confirmed by CIE co-ordinates (x = 0.298, y = 0.360). The study demonstrates a simple and efficient method for the synthesis of novel nanophosphors with enhanced white emission.

One pot auto-ignition based synthesis of novel Sr2CeO4: Ho3+ nanophosphor for photoluminescent applications

Ho3+ (0.25-7 mol%) doped Sr2CeO4 nanophosphors were synthesized by solution combustion method using urea as fuel. The structural properties of the nanophosphors were investigated by powder X-ray diffraction studies (PXRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. UV-Visible and photoluminescence (PL) spectroscopic techniques were used for analysing the optical properties of the nanoparticles. PXRD and TEM results revealed the formation of Sr2CeO4: Ho3+ nanocrystalline particles with orthorhombic crystal structure. From the UV-Vis studies the optical band gap energy found to decrease from 5.9 to 5.74 eV with increase in dopant concentration. The PL spectra exhibit the broad excitation band from 200 to 400 nm which concurs well with the commercial near UV LED. The PL spectra vary with the dopant content due to energy transfer from the host to the activator. In this present work we demonstrate that color tuning of phosphor can be achieved by merely varying the Ho3+ ions concentration. The CIE and CCT chromaticity coordinates suggests Sr2CeO4: Ho3+ nanophosphors may be potentially applicable as promising single - phased phosphors for lighting applications. (C) 2015 Elsevier B.V. All rights reserved.

Investigation on charge transfer bands of Ce4+ in Sr2CeO4 blue phosphor

Bulk and nano-materials Sr2CeO4 were prepared by solid-state reaction and sol-gel technique, respectively. Photoluminescence shows that luminescence has the characteristic of a ligand-to-metal charge transfer (CT) emission. Compared with bulk Sr2CeO4, the nano-material exhibits stronger emission intensity, longer decay time, and higher CT excitation energy. Three CT excitation peaks were observed in both bulk and nano samples.

Synthesis and characterization of spherical Sr2CeO4 phosphors by spray pyrolysis for field emission displays

A blue emitting Sr2CeO4 phosphor with a one-dimensional structure has been prepared by a two-step spray pyrolysis (SP) method, starting from the aqueous solutions of metal nitrates with citric acid and polyethylene glycol (PEG) as additives. The material is ultimately designed for field emission displays (FEDs). X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG-DTA), field emission scanning electron microscope pictures (FE-SEM) as well as photoluminescence (PL) and cathodoluminescence (CL) spectroscopy and lifetime measurements have been employed to characterize the samples. The morphology, PL and low voltage CL properties of Sr2CeO4 phosphors as-prepared using the SP method have been investigated by changing the concentration of the precursor solution, concentration of PEG, annealing temperature, acceleration voltage and filament current. The obtained Sr2CeO4 phosphor particles are spherical and of submicron size, 0.5-2 mu m. The emission spectrum of the phosphors shows a broad band with maximum at 467 nm (lifetime = 37.4 mu s; CIE chromaticity coordinates: x = 0.15 and y = 0.21), presumably due to a ligand-to-metal charge-transfer transition.

Synthesis of Sr2CeO4: Eu-3 by citrate-gel method and its luminescence properties

A novel phosphor Sr2CeO4 was synthesized by the citrate-gel method. The results of XRD show that the temperature at which the crystallization starting is lowered and the soak time for complete crystallization is decreased. The values of pH of the precursor and the ratio( R) between the citrate and cation ions have an effect on the crystallization process. The host can transfer its exciting energy to rare earth ion Eu3+. The doped compound emits strong white light when the concentration of the doped Eu3+ is low. When that of Eu3+ is increased, it emits strong red light. The fluorescence from the higher excited states can be observed because the multiphonon relaxation probability between Eu3+ ions is low.

Luminescent and morphological study of Sr2CeO4 blue phosphor prepared from oxalate precursors

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Sr2CeO4: Electronic and structural properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Photoluminescence of Sr(2-x)Ln(x)CeO(4+x/2) (Ln = Eu, Sm or Yb) prepared by a wet chemical method

A wet chemical route is developed for the preparation of Sr2CeO4 denoted the carbonate-gel composite technique. This involves the coprecipitation of strontium as fine particles of carbonates within hydrated gels of ceria (CeO2.xH(2)O, 40Sr2CeO4 with complete phase purity. Doping of other rare-earths is carried out at the co-precipitation stage. The photoluminescence (PL) observed for Sr2CeO4 originates from the Ce4+-O2- charge-transfer (CT) transition resulting from the interaction of Ce4+ ion with the neighboring oxide ions. The effect of next-nearest-neighbor (NNN) environment on the Ce4+-O2- CT emission is studied by doping with Eu3+, Sm3+ or Yb3+ which in turn, have unique charge-transfer associated energy levels in the excited states in oxides. Efficient energy transfer occurs from Ce4+-O2- CT state to trivalent lanthanide ions (Ln(3+)) if the latter has CT excited states, leading to sensitizer-activator relation, through non-resonance process involving exchange interaction. Yb3+-substituted Sr2CeO4 does not show any line emission because the energy of Yb3+-O2- CT level is higher than that of the Ce4+-O2- CT level. Sr2-xEuxCeO4+x/2 shows white emission at xless than or equal to0.02 because of the dominant intensities of D-5(2)-F-7(0-3) transitions in blue-green region whereas the intensities of D-5(0)-F-7(0-3) transitions in orange-red regions dominate at concentrations xgreater than or equal to0.03 and give red emission. The appearance of all the emissions from D-5(2), D-5(1) and D-5(0) excited states to the F-7(0-3) ground multiplets of Eu3+ is explained on the basis of the shift from the hypersensitive electric-dipole to magnetic-dipole related transitions with the variation in site symmetry with increasing concentration of Eu3+. White emission of Sr2-x SmxCeO4+x/2 at xless than or equal to0.02 is due the co-existence of Ce4+-O2- CT emission and (4)G(4)(5/2)-H-6(J) Sm3+ transitions whereas only the Sm3+ red emission prevails for xgreater than or equal to0.03. The above unique changes in PL emission features are explained in terms of the changes in NNN environments of Ce4+. Quenching of Ce4+-O2- CT emission by other Ln(3+) is due to the ground state crossover arising out of the NNN interactions.

稀土离子的电荷迁移带与化学键性质研究

本论文主要研究的是掺杂在无机材料中的稀土离子的电荷迁移带，利用复杂晶体化学键的介电理论对晶体的化学键性质进行计算和分析，阐明了稀土离子的电荷迁移带与基质的化学键性质之间的规律，揭示了宏观电荷迁移带的微观机制，进而丰富和发展了稀土发光材料的理论知识。 根据大量掺杂稀土离子的化合物的电荷迁移带数据，利用复杂晶体的介电理论计算和分析出化合物的共价性、键体积极化率、配体在晶体中所呈现的电荷及配位数，进而得到由这四个参数定义的环境因子he。发现环境因子he能够有效地描述电荷迁移带的变化趋势,可以揭示电荷迁移的微观机制。具体获得了Eu3+、Sm3+和Yb3+在不同基质中的电荷迁移能与环境因子之间的定量关系。通过这些定量关系式，我们能够利用复杂晶体的介电理论来估算各种复杂晶体中稀土离子的电荷迁移带位置，为电荷迁移带方面的研究工作提供了理论依据。反过来，利用这一关系我们也可以从实验上测得的电荷迁移能数据来判断晶体结构的正确性。在此基础上，我们从化学键和YBO3：Eu的电荷迁移带的角度出发，研究了YBO3的结构，从而确定它的空间群为C2/c，排除了其他的可能性。 考虑到Eu3+的电荷迁移能随着基质平均能隙的增大而增大，而且利用复杂晶体化学键的介电理论可以估算化学键的平均能隙，我们研究了Eu3+在不同基质中的电荷迁移能与相应的化学键的平均能隙之间的关系，发现它们之间符合定量的线性关系。通过这一线性关系估算出的电荷迁移能与实验值一致，说明利用化学键的平均能隙来估算电荷迁移能的可靠性。在此基础上，我们预测了发光材料Gd4GdO(BO3)3:Eu的电荷迁移带位置，计算的结果与实验值相吻合；探索复杂化合物Li2Lu5O4(BO3)3:Eu中Eu3+取代的阳离子的格位，计算结果表明能量最低的电荷迁移带来源于Eu3+取代五种Lu中的Lu1格位，电荷迁移能的计算值与实验值一致。块状和纳米的Sr2CeO4分别通过高温固相法和溶胶凝胶法获得，根据电荷迁移能随平均能隙的增大而增大的规律，可以将激发光谱中出现的三个峰分别归属为：能量最高的激发峰来源于从O1到Ce的电荷迁移，能量最低的激发峰来源于从O2到Ce的电荷迁移，中间的峰是前面两种峰的叠加。

场发射(FED)用荧光粉的研制与改性

场发射平板显示器（Field Emission Displays, FED）是一种新发展起来的平板显示器，由于其在亮度、视角、响应时间、工作温度范围、能耗等方面具有优良的特性，成为近年新型显示器研究的热点之一。为实现高效的FED红、绿、蓝全色显示，荧光粉在其中起着十分重要的作用。制备性能优良的场发射用彩色荧光粉是决定将来FED技术成功与否的关键因素之一。 本论文研究的内容包括场发射(FED)用荧光粉的研制和改性工作。在场发射(FED)用荧光粉研制方面，采用溶胶-凝胶方法，制备了一系列新型场发射(FED)用荧光粉，包括稀土离子激活的镓酸镧 [(LaGaO3: Re3+ (Re = Eu, Tb, Dy, Tm, Sm)]体系、铟酸钙[(CaIn2O4: Re3+ (Re = Eu, Pr, Tb, Dy,)]体系、铟酸锶[(SrIn2O4: Re3+ (Re = Pr, Tb, Dy)]体系、镓酸镥[Lu3Ga5O12:Re3+ (Re = Eu, Tb，Pr)]体系，并研究了Pr, Sm, Eu, Tb, Dy, Tm等稀土离子在这些基质中的光致发光、低压阴极射线发光性质和能量传递等性质。在荧光粉的改性方面，采用喷雾热解法制备了Sr2CeO4球形场发射用荧光粉，研究了喷雾前驱体溶液中，聚乙二醇浓度、金属离子浓度、烧结温度对形貌及发光性能的影响；采用溶胶－凝胶方法成功将SiO2表明包覆一层CaTiO3:Pr3+, Y3Al5O12:Ce3+/Tb3+荧光粉，得到单分散，球形形貌，分布均匀，具有核/壳结构的球形荧光粉；另外研究了不同的制备方法对Ga2O3:Dy3+荧光粉的发光性能的影响。所得样品用XRD、FTIR、SEM、TEM、漫反射光谱、光致发光(PL)光谱、荧光寿命曲线、低压阴极射线(CL)光谱等进行表征。 在紫外光激发下，稀土离子激活的镓酸镧彩色荧光粉有基质(LaGaO3)的发射和稀土离子(Eu3+, Tb3+, Dy3+, Tm3+, Sm3+)的特征发射，研究表明在基质和稀土离子之间存在能量传递，其能量传递效率因离子而异。在阴极射线激发下，样品仅有稀土离子(Eu3+, Tb3+, Dy3+, Tm3+, Sm3+)的特征发射。如：LaGaO3: Eu3+发红光，LaGaO3: Dy3+发白光，LaGaO3: Tm3+发蓝光，LaGaO3: Sm3+发黄光，LaGaO3: Sm3+,Tb3+发白光。LaGaO3: Tb3+的发光颜色可通过不同Tb3+的掺杂浓度从蓝光到绿光进行调控。在相同的激发条件下，所制备的蓝光发射的LaGaO3: Tb3+和LaGaO3: Tm3+荧光粉与商业FED用蓝粉(Y2SiO5: Ce3+，日亚化学工业株式会社，NP-1047)相比具有更好的色纯度和更高的发光效率；所制备的黄光发射的LaGaO3: Sm3+荧光粉与商业低压黄色荧光粉((Zn,Cd)S: Ag，日亚化学工业株式会社，NP-1020)相比，色纯度接近，但具有更高的发光效率。并首次实现了单一基质中白光发射(LaGaO3: Sm3+,Tb3+), 所制备的稀土离子激活的镓酸镧彩色荧光粉[(LaGaO3: Re3+ (Re = Eu, Tb, Dy, Tm, Sm )]在场发射器件有潜在的应用。 在稀土离子掺杂的Sr/CaIn2O4荧光粉体系中，在基质Sr/CaIn2O4和掺杂离子Pr3+/Tb3+/Dy3+存在高效能量传递。基质Sr/CaIn2O4吸收能量向激活离子Pr3+/ Tb3+/Dy3+传递，发射为稀土离子Pr3+/Tb3+/Dy3+的特征发射，发光强度、荧光寿命等符合应用要求，在低压电子束激发下，Sr/CaIn2O4: Pr3+/Tb3+/Dy3+荧光粉为稀土离子的特征发射，其低压阴极射线发光(CL)光谱与光致发光(PL)发射光谱一致，CL强度随激发电压，电流密度增加而增强。 对于CaIn2O4:Eu3+荧光粉，进一步研究表明CaIn2O4:Eu3+荧光粉的光致发光和阴极射线发光颜色可以通过掺杂不同浓度的Eu3+从白光，黄光，到红光进行调控。低浓度掺杂发白光，高浓度掺杂发红光，适当的浓度发黄光。 在Lu3Ga5O12:Re3+ (Re = Eu, Tb，Pr)荧光粉体系中，在紫外（UV）和低压阴极射线激发下，所制备的荧光粉Lu3Ga5O12: Eu3+, Lu3Ga5O12: Pr3+为稀土离子Eu3+, Pr3+的特征发射，分别发黄光和绿光。Lu3Ga5O12:Tb3+的发光颜色因Tb3+掺杂浓度不同而不同，低浓度掺杂发蓝光，高浓度发绿光。 Sr2CeO4荧光粉在UV及低压阴极射线激发下发出强烈蓝光，源于配体到金属离子电荷迁移带跃迁(Ce4+-O2-)。其阴极射线发光强度与电压及灯丝电流呈良好的线性关系。 采用溶胶－凝胶方法的核壳结构的SiO2@CaTiO3:Pr3+和SiO2@Y3Al5O12: Ce3+/Tb3+荧光粉, FESEM和TEM结果表明这种核壳结构的发光材料表面致密，厚度均匀，保持了单分散SiO2微球的形貌特征。在UV及低压阴极射线激发下，SiO2@CaTiO3:Pr3+呈强红色发射，源于Pr3+ 的1D2—3H4 (612 nm)跃迁；SiO2@Y3Al5O12:Ce3+和SiO2@Y3Al5O12:Tb3+ 分别发黄绿光和绿光，源于Ce3+的5d-4f和Tb3+的5D4-7FJ (J = 6, 5, 4, 3)跃迁。PL强度可以通过包覆次数调控，CL强度随激发电压及灯丝电流增加而增强。 在Ga2O3:Dy3+荧光粉体系中，采用了溶胶-凝胶，氨水共沉淀，和高温固相法制备了Ga2O3:Dy3+荧光粉并比较了他们的结晶行为，形貌，光致发光和低压阴极射线发光性能。溶胶-凝胶法制备由于原料在分子层次上混合，可以得到纯相，氨水共沉淀和高温固相法原料不如溶胶凝胶法混合均匀，很难得到纯相。溶胶-凝胶和氨水共沉淀所得荧光粉为纳米级别大小，分别呈球形和玉米棒形状；高温固相法微米级别且呈不规则形状。Ga2O3向Dy3+传递能量效率依次按溶胶-凝胶，氨水共沉淀，和高温固相法逐渐降低。在紫外光激发下，分别发白光，蓝白光，蓝光。其低压阴极射线发光与光致发光类似。相比之下，溶胶-凝胶法制备Ga2O3:Dy3+荧光粉比氨水共沉淀和高温固相法制备要好。

溶胶-凝胶法合成Sr_2CeO_4及其发光性能的研究

采用Pechini溶胶 凝胶法合成了Sr2 CeO4 粉末。利用X射线衍射 (XRD)、扫描电镜 (SEM)、热重及差热分析 (TG DTA)以及发光光谱等测试手段对Sr2 CeO4 的结晶过程、发光性质进行了研究。XRD结果表明,用Pe chini溶胶 凝胶法合成的样品800℃时已开始结晶,900℃时可得到三斜晶系的Sr2 CeO4 多晶粉末。扫描电镜照片可以看出颗粒大小不均匀,粒径约为1～5μm。发光光谱测试表明Sr2 CeO4 粉末的激发光谱是一个宽带双峰结构,分别位于310nm和340nm。这个宽带属于Ce4 + 的电荷迁移带。用340nm激发样品,其发射光谱也是一个宽带,最大峰位于475nm ,这个峰属于Ce4 + 的f→t1g跃迁。用310nm激发得到的发射光谱与用340nm激发得到的发射光谱相同。

M_2CeO_4(M=Ca,Sr,Ba)的结构与发光特性

Sr_2CeO_4是一种新型的一维结构发光材料,其特殊的结构对其发光特性有决定性的作用。Sr2CeO4体系中可以顺利地进行能量传递,产生较强电荷迁移发光。合成了M2CeO4（M=Ca,Sr,Ba）,发现与Sr2CeO4具有类似结构的Ba2CeO4也可以发光,而结构完全发生了变化的Ca2CeO4则不发光。

Estudo da decomposição térmica de oxalato de estrôncio dopado com cério(III) como precursor de materiais luminescentes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)