Time-resolved luminescence of ZnIn2S4 at low temperature

Summary A detailed study of the time-resolved luminescence of ZnIn₂S₄ after pulsed-laser excitation at 30 K is presented. Results are given on the dependence of the emitted PL intensity at different emission wavelengths on the excitation intensity, on the time-resolved spectra in the range (0÷10⁻¹) s of delay time with respect to excitation and on the time decay of the luminescence intensity for different emission wavelengths. The results are discussed in the framework of a simple model for the recombination processes at low temperatures yielding a good overall agreement with the experimental data. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

Luminescence spectroscopy of Eu3+ and Mn2+ ions in MgGa2O4 spinel

Photoluminescence and excitation spectra of the spinel-type MgGa₂O₄ with 0.5 mol. % Mn²⁺ ions and Eu³⁺ content from 0 to 8 mol. % have been investigated in this work at room temperature. Polycrystalline samples were synthesized via high-temperature solid-state reaction method. Photoluminescence spectra of all samples exhibit host emission presented by a broad “blue” band peaking ∼430 nm, which consists of at least three elementary bands that correspond to different host defects. Excitation of the host luminescence showed the broad band with a maximum at 360 nm. Characteristic bands of d–d transitions of Mn²⁺ ions and f–f transitions of Eu³⁺ ions together with charge-transfer bands (CTB) of these ions were also found on the excitation spectra. Mn²⁺ and Eu³⁺ co-doped samples emit in green and red spectral regions. Mn²⁺ ions are responsible for the green emission band at 505 nm (⁴Т₁→⁶А₁ transition). The studies of photoluminescence spectra of activated samples with different Eu³⁺ ions content show characteristic f–f luminesecence of Eu³⁺ ions. The maximum of Eu³⁺ emission was found at 618 nm (⁵D₀→⁷F₂) and optimal concentration of activator ions was around 4 mol. %.     

稀土掺杂铕(Ⅲ)二苯甲酰甲烷邻菲咯啉三元配合物的合成和荧光性质

合成了 3个系列稀土掺杂铕二苯甲酰甲烷 (Hdbm)邻菲咯啉 (phen)三元配合物 Eux RE1 -x(dbm) 3 phen(RE=La,Y,Gd;x=0 .0 0、0 .1 0、0 .30、0 .5 0、0 .70、0 .80、0 .90、1 .0 0 ) ,通过元素分析、摩尔电导率、红外光谱、X射线粉末衍射对配合物进行了表征。对各配合物系列进行荧光光谱研究 ,发现 L a3 、Y3 和 Gd3 对Eu3 离子均有荧光增敏作用 ,其荧光增敏顺序为 L a3 >Y3 >Gd3 。     

Synthesis, Characterization and Photophysical Properties of Eu3+ Doped in BaMoO4

In this work Ba_0.99Eu_0.01MoO₄ (BEMO) powders were prepared by the first time by the Complex Polymerization Method. The structural and optical properties of the BEMO powders were characterized by Fourier Transform Infra-Red (FTIR), X-ray Diffraction (XRD), Raman Spectra, High-Resolution Scanning Electron Microscopy (HR-SEM) and Photoluminescent Measurements. XRD show a crystalline scheelite-type phase after the heat treatment at temperatures greater than 400 °C. The ionic radius of Eu³⁺ (0.109 nm) is lower than the Ba²⁺ (0.149 nm) one. This difference is responsible for the decrease in the lattice parameters of the BEMO compared to the pure BaMoO₄ matrix. This little difference in the lattice parameters show that Eu³⁺ is expected to occupy the Ba²⁺ site at different temperatures, stayed the tetragonal (S₄) symmetry characteristic of scheelite-type crystalline structures of BaMoO₄. The emission spectra of the samples, when excited at 394 nm, presented the ⁵D₁→⁷F_{0, 1 and 2} and ⁵D₀→⁷F_{0, 1, 2, 3 and 4} Eu³⁺ transitions at 523, 533, 554, 578, 589, 614, 652 and 699 nm, respectively. The emission spectra of the powders heat-treated at 800 and 900 °C showed a marked increase in its intensities compared to the materials heat-treated from 400 to 700 °C. The decay times for the sample were evaluated and all of them presented the average value of 0.61 ms. Eu³⁺ luminescence decay time follows one exponential curve indicating the presence of only one type of Eu³⁺ symmetry site.     

三斜相GdBO3:Eu的溶胶-凝胶法制备及其格位选择激发下的光谱

用溶胶－凝胶法合成了具有三斜结构的低温相GdBO3,并与用常规的固相反应制备球方解石结构的样品作了比较。在高于1000℃时发生了三斜相向常规相的相变。三斜相GdBO3:Eu的荧光光谱表明阳离子在基质晶格中占据了两种格位,用A和B来分别标明。选择激发A、B格位上Eu^3＋,结果揭示了GdBO3结构上的变化和Eu^3+之间的能量传递过程。在较高的Eu^3+掺杂浓度时,两上格位均有较强的发光;在低温和低浓度条件下,得到了可分辨的相应于不同格位的发光,并观察到了两个格位间的不同几率的能量相互传递。     

Tailoring red-green-blue emission from Er3+, Eu3+ and Tb3+ doped Y2O3 nanocrystals produced via PVA-assisted sol-gel route

Y₂O₃ luminescent nanoparticles were synthesized via PVA-assisted sol-gel method and their structural and optical properties were investigated. Effects of rare earth (Er³⁺, Eu³⁺ and Tb³⁺) doping on luminescence properties of the produced nanophosphors have been investigated under NIR (800 nm) and UV (240–300 nm) excitation. Intense infrared to red and green emissions were observed and a weak blue upconverted luminescence was also detected. Moreover, it was observed that changing the doping ions, the color emitted by the samples could be modified and different combinations of UV excitation and doping produced effective white light emissions. The obtained results demonstrate that PVA-assisted sol-gel is an effective methodology for the synthesis of rare-earth doped Y₂O₃ nanophosphors.     

铕掺杂纳米氧化锌晶体结构和荧光光谱的研究

以醋酸锌、氧化铕、氢氧化钠为主要原材料,利用共沉淀法制备ZnO∶Eu3+纳米晶体.在X射线衍射谱中,只观察到氧化锌的峰,没有观察到氧化铕的特征峰.比较了ZnO和ZnO∶Eu3+拉曼光谱,在ZnO∶Eu3+样品拉曼光谱中观察到新的局部振动模.这些现象表明铕离子已经进入氧化锌晶格中.SEM形貌显示Eu3+离子掺入使ZnO晶...     

Structural phase transition and octahedral tilting in the calcium titanate perovskite CaTiO3

Crystal structure of the calcium titanate perovskite CaTiO₃ was refined by the Rietveld analysis of neutron diffraction data collected over the temperature range of 296 to 1720 K. The orthorhombic Pbnm-tetragonal I4/mcm phase transformation reversibly occurred at 1512 ± 13 K and the tetragonal I4/mcm-cubic Pm3?m transition was reversibly observed at 1635 ± 2 K. The structural phase transitions are characterized by the tilt of the TiO₆ octahedron. The tilt systems of the Pbnm, I4/mcm, and Pm3?m CaTiO₃ are ?_x^??_y^??_z⁺ (?_x^? = ?_y^?), ?_x⁰?_y⁰?_z^?, and ?_x⁰?_y⁰?_z⁰, respectively. Here the ?_x^?, ?_z⁺, and ?_x⁰ stand for the out-of-phase tilt angle of TiO₆ octahedron along x axis, the in-phase octahedral tilt angle along z axis, and no octahedral tilting along x axis, respectively. All the tilt angles, ?_x^?, ?_z⁺, and ?_z^? decreased with increasing temperature where the critical exponents were about 0.25. The ?_x^? and ?_y^? of the orthorhombic structure decreased discontinuously to ?_z^? of the tetragonal structure or 0° through the Pbnm-I4/mcm transition. The tilt angle, the unit-cell parameters and unit-cell volume discontinuously changed at the Pbnm-I4/mcm transition temperature, indicating the first-order nature. The increase of the cell volume in the Pbnm-I4/mcm transition was 0.088 vol.%. In contrast, the unit-cell volume continuously increased and the tilt angle ?_z^? continuously decreased with increasing temperature and became 0° at the I4/mcm-Pm3?m transition temperature, indicating a continuous nature of the transformation. The Pbnm-I4/mcm and I4/mcm-Pm3?m phase transitions are induced by the tilting of TiO₆ octahedra, indicating the displacive nature of the transitions. The larger thermal motion of O2 atom in I4/mcm CaTiO₃ indicates the larger positional disorder of O2 atom, which is consistent with the tilt system ?_x⁰?_y⁰?_z^?.     

Upconversion emission in CaTiO3:Er3+ nanocrystals

CaTiO₃:Er³⁺ (5%) nanocrystals were obtained by sol–gel method under acidic conditions. The sizes of nanocrystals were 40 nm. Strong green anti-Stokes emission was observed after excitation of the ⁴I_9/2 and ⁴I_11/2 level. The emission is due to excited state absorption (ESA) and energy transfer upconversion (ETU).     

Novel red perovskite phosphor Ca2AlNbO6:Eu for white light-emitting diode application

Eu³⁺-doped perovskite phosphors of Ca₂AlNbO₆ were synthesized from a solid state reaction. A small amount of the Li₂CO₃ flux was found to greatly shorten calcination time and reduce reaction temperature. The structural and optical properties of the samples were systematically investigated. The excitation spectra of Ca₂AlNbO₆:Eu³⁺ reveal two excitation bands at 398 (⁷F₀→⁵L₆) and 466 nm (⁷F₀→⁵D₂), which match well with the two popular emissions from near-UV and blue LED chips. Under blue light excitation, the red emission of Ca₂AlNbO₆:0.05Eu³⁺ is twice more intense than that of (Y_0.95Eu_0.05)₂O₃. The chromaticity coordinates of (Ca_0.95Eu_0.05)₂AlNbO₆ (x=0.654, y=0.346) are close to the standard values (x=0.670, y=0.330) of National Television Standard Committee (NTSC). The optical properties suggest that Ca₂AlNbO₆:Eu³⁺ is an efficient red-emitting phosphor for light-emitting diode applications.     

Structural,photoluminescent, and dielectric properties of Eu3+-doped Ba0.7Sr0.3TiO3 thin films

Eu³⁺-doped Ba_0.7Sr_0.3TiO₃ thin films were prepared by a chemical solution deposition method and characterized by X-ray diffraction, field emission scanning electron microscopy, photoluminescence and dielectric measurements. The thin films were well crystallized with a pure perovskite structure. A contraction of the unit cell was observed upon incorporation of Eu³⁺ ions below 2 mol%, while an expansion occurred as the Eu³⁺ concentration was further increased above 2 mol%, indicating that Eu³⁺ ions with different concentrations occupied different lattice sites. Photoluminescence spectra showed two prominent transitions of Eu³⁺ ions at 594 nm (⁵D₀ → ⁷F₁) and 618 nm (⁵D₀ → ⁷F₂) upon excitation at 395 nm (⁷F₀ → ⁵L₆). There existed two quenching concentrations at 2 mol% and 4 mol% due to different lattice sites of the Eu³⁺ ions. We also investigated the dielectric properties of the thin films. Our study suggests that Eu³⁺-doped Ba_0.7Sr_0.3TiO₃ thin films have potential applications in multifunctional optoelectronic devices.     

Photoluminescence and radioluminescence study of NaMgF3:Eu nanoparticles

Photoluminescence (PL) and radioluminescence (RL) measurements were made on small (∼25 nm) NaMgF₃ nanoparticles doped with Eu concentrations ranging from 0.1% to 5%. We find that they contained Eu³⁺, Eu²⁺, and an additional unidentified defect with a broad PL emission ∼470 nm. Similar to previous measurements on larger (57 nm–77 nm) NaMgF₃:Eu nanoparticles with 1% Eu and 5% Eu, we find that the PL lifetime decreases with increasing Eu concentration that can be attributed to Eu energy transfer to non-radiative recombination sites. However, there is no change in the fraction of Eu³⁺ distorted sites. The ∼470 nm PL defect peak was also reported for larger nanoparticles, which suggests that this peak arises from similar unidentified point defects. However, the activated non-radiative decay for the small nanoparticles has a significantly lower activation energy. The Eu³⁺ RL decreases by only 2.3% at 10 kGy for low Eu concentrations.     

三维自组装Eu3+-石墨烯复合材料的制备及其磁性研究

采用一锅水热法在180 ℃ 下制备三维Eu³⁺-石墨烯自组装复合材料. 通过X射线衍射、 扫描电子显微镜、透射电子显微镜表征了合成样品的物相及形貌特征. 结果表明: 合成的样品具有多孔性结构, 层与层之间堆叠成三维结构, 并且结果显示产物中没有Eu³⁺的团聚体. 经过拉曼光谱, 傅里叶红外光谱分析表明, Eu³⁺通过含氧官能团与石墨烯复合. 通过振动样品磁强计测定样品的磁滞回线, 对其磁学性能进行研究, 剥离顺磁信号后, 测得相应的矫顽力H_c ≈ 39.61 Oe(1 Oe=79.5775 A/m), 饱和磁化强度M_s ≈ 0.08 emu/g, 发现该产物具有弱的铁磁性, 与石墨烯相比, Eu³⁺的加入使得产物的铁磁性有较大提高. 关键词： 三维石墨烯 3+')" href="#">Eu³⁺ 水热法 磁性     

Er3+、In3+等金属离子对多孔硅光致发光性质的影响

用阳极腐蚀的方法制备了多孔硅样品,用电化学方法在多孔硅中注入Ｅｒ＾３＋、Ｉｎ＾３＋等金属离子,并对注入离子后多孔硅的光致荧光光谱进行了研究,结果表明：注入Ｅｒ＾３＋及Ｉｎ＾３＋后的多孔硅在５８８ｎｍ处的妇光峰强度大大增加,同时发光峰稍有展宽。随着离子注入时间的增长,强度继续增加,但当离子溶液浓度一定时,这种增强对时间具有饱和性。     

Zn2+掺杂对GdTaO4:Eu3+荧光粉结构和发光性能的影响

采用高温固相反应法制备了掺杂不同浓度Zn2 的GdTaO4:Eu0.1荧光粉,研究了Zn2 掺杂对GdTaO4:Eu3 的结晶性能,晶粒形貌和光致发光特性的影响.以X射线衍射(XRD)、扫描电子显微镜(SEM)、激发-发射谱、衰减时间谱等方法对其性能进行了表征.结果表明,Zn2 掺杂可显著提高GdTaO4:Eu3 的光致发光强度,当掺杂浓度x=0.01时,光强被提高至2.7倍,可归因于的Zn2 进入了GdTaO4:Eu3 基质晶格,产生了一定浓度的氧空位以达到电荷平衡,并导致发光中心Eu3 的晶格场发生畸变;当x=0.13时,光强提高至3.2倍,且其衰减时间被缩短至40%,可归因于Zn2 的助熔剂效果;但当x＞0.13时,ZnO和GdTa7O19杂相的出现将导致发光强度减弱和衰减时间延长.另外,初步探索表明,Li2CO3和.KCl的共掺杂能进一步提高G.dTaO4:Eu0.1,Zn0.13的发光强度.     

Eu3+ luminescence and Gd3+-Eu3+ energy transfer in K5Li2GdF10:Eu3+

Polycrystalline samples of europium-doped K₅Li₂GdF₁₀ have been obtained by a slow cooling of melted compound and investigated using spectroscopy methods. Luminescence from the ⁵ D ₂ level of Eu³⁺ is found to be weak. Intense visible emission upon excitation into the ⁵ D ₂ or higher energy levels has been attributed to overlapping transitions from long-lived ⁵ D ₁ and ⁵ D ₀ levels. A strong increase of the ⁵ D ₀ emission at the expense of the ⁵ D ₁ emission occurs between 5 K and 25 K without significant change of the ⁵ D ₁ lifetime. To account for this, it is supposed that both the radiative and the nonradiative transition rates are temperature-dependent. Efficient energy transfer from the ⁶ G _J levels of Gd³⁺ to Eu³⁺ ions has been evidenced by excitation spectra in the VUV region and VUV-excited luminescence. It has been concluded that the cross relaxation contributes to the energy-transfer process. Received: 8 May 2001 / Accepted: 11 May 2001 / Published online: 25 July 2001     

A novel red-emitting phosphor Ca9Bi(PO4)7:Eu3+ for near ultraviolet white light-emitting diodes

Red phosphors Ca₉Bi_1-x(PO₄)₇:xEu³⁺ (x = 0.06, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80 and 1.00) were synthesized by a conventional solid-state reaction (SSR) route. The X-ray diffraction patterns, photoluminescence spectra, ultraviolet–visible reflection spectroscopy, decay time and the International Commission on Illumination (CIE) chromaticity coordinates of these compounds were characterized and analyzed. The Eu-doped Ca₉Bi(PO₄)₇ phosphors exhibited strong red luminescence which peaks located at 615 nm due to the ⁵D₀→⁷F₂ electric dipole transition of Eu³⁺ ions after excitation at 393 nm. Ultraviolet–visible spectra indicated that the band-gap of Ca₉Bi_0.30(PO₄)₇:0.70Eu³⁺ is larger than that of Ca₉Bi(PO₄)₇. The results indicate that the phosphor Ca₉Bi_0.30(PO₄)₇:0.70Eu³⁺ can be a suitable red-emitting phosphor candidate for LEDs.