The electronic structure and photoluminescence properties of Ca2GeO4:Eu in ultraviolet and vacuum ultraviolet region

Ca₂GeO₄:Eu³⁺ phosphors were synthesized by the solid state method. The ultraviolet and vacuum ultraviolet excited photoluminescence properties were investigated in detail. It revealed that the emission of Ca₂GeO₄:Eu³⁺ comprised two parts: the red emission of Eu³⁺ and host defect emission in 330-550 nm. Ca₂GeO₄:Eu³⁺ presented intense excitation intensity at 163-200 and 466 nm, which suggested the potential applications in plasma display panels and light emitting diodes. The excitation spectra were studied to identify the photoluminescence mechanisms of Ca₂GeO₄:Eu³⁺. First principles calculation within the local density approximation of the density functional theory was applied to calculate the electronic structure and linear optical properties of Ca₂GeO₄.     

Excited state absorption and stimulated emission of Nd3+ in crystals. Part 2: YVO4, GdVO4, and Sr5(PO4)3F

3+ ion in the crystals YVO₄, GdVO₄, and Sr₅(PO₄)₃F. The measurements were performed in the spectral region of the main laser transitions ⁴F_3/2→⁴I_9/2, ⁴F_3/2→⁴I_11/2, and ⁴F_3/2→⁴I_13/2by a continuous wave pump and probe technique. The calibrated gain and ESA spectra are presented and possible implications of ESA on the laser performance are estimated. It is shown that ESA can be a small loss factor to the laser emission near 1060 nm but does considerably diminish the effective emission cross sections near 1340 nm especially in Nd:YVO₄ and Nd:GdVO₄. Received: 29 January 1998/Revised version: 8 May 1998     

Emission spectra of MgSO4:Dy,MgSO4:Tm and MgSO4:Dy,Mn phosphors

MgSO₄:Dy, MgSO₄:Tm and MgSO₄:Dy,Mn thermoluminescence (TL) phosphors have been prepared and their emission spectra were measured using a linear heater and optical multichannel analyzer. Emission bands at about 480, 580 and 660 nm of MgSO₄ doped with Dy were observed in three dimension (3D) glow curve. Emission bands about 360, 460, and 660 nm were observed in a 3D glow curve of MgSO₄ doped with Tm. The emission spectra of MgSO₄:Dy and MgSO₄:Tm are attributed to the characteristic emission wavelengths from transitions of Dy³⁺ and Tm³⁺ respectively. The results show that the structures of traps in matrix materials determine the activation energy distribution and dopant energy levels of rare earth ions are related with the emission spectrum wavelengths of sulfate phosphors. The intensities of the glow peaks in both bands at about 480 and 580 nm in MgSO₄ doped Dy and Mn were dramatically reduced in comparison with that of MgSO₄ doped Dy except above 300°C. It means that the trapping structures of MgSO₄ :Dy phosphor has greatly been altered by the co-dopant Mn but no change is observed in wavelengths of the emission spectra.     

Spectroscopic Properties of Er3+/Yb3+-codoped PbO–Bi2O3–Ga2O3–GeO2 Glasses

We investigate the spectroscopic properties of the 1.5-μm emission from the ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺ ions in PbO–Bi₂O₃–Ga₂O₃–GeO₂ glasses for applications in broadband fiber amplifiers. The measured emission peak locates at 1,532 nm with a full width at half-maximum of ∼45 nm. The glasses exhibit a large stimulated emission cross-section of 0.89 × 10⁻²⁰ cm² and a large product of 40.0. Infrared-to-green upconversion occurs simultaneously upon excitation of the 1.5-μm emission with a commercially available 980 nm laser diode. The green-upconversion intensity has a quadratic dependence on incident pump laser power, indicating a two-photon process. Energy transfer processes and nonradiative phonon-assisted decays could account for the population of the ²H_11/2 of Er³⁺. The results indicate the possibility towards the development of lead–bismuth–gallate–germanate based glasses as photonics devices.     

Photoluminescence characteristics of ZnS nanocrystallites doped with Ti3+and Ti4+

Direct synthesis of ZnS nanocrystallites doped with Ti³⁺ or Ti⁴⁺ by precipitation has led to novel photoluminescence properties. Detailed X-ray diffraction (XRD), fluorescence spectrophotometry, UV–vis spectrophotometry and X-ray photoelectron spectroscopy (XPS) analysis reveal the crystal lattice structure, average size, emission spectra, absorption spectra and composition. The average crystallite size doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2.6±0.2 nm. The nanoparticles can be doped with Ti³⁺ and Ti⁴⁺ during the synthesis without the X-ray diffraction pattern being altered. The strong and stable visible-light emission has been observed from ZnS nanocrystallites doped with Ti³⁺ (its maximum fluorescence intensity is about twice that of undoped ZnS nanoparticles). However, the fluorescence intensity of the ZnS nanocrystallites doped with Ti⁴⁺ is almost the same as that of the undoped ZnS nanoparticles. The emission peak of the undoped sample is at 440–450 nm. The emission spectrum of the doped sample consists of two emission peaks, one at 420–430 nm and the other at 510 nm. Received: 27 April 2001 / Accepted: 16 August 2001 / Published online: 17 October 2001     

Characterization and photoluminescence studies of Eu<Superscript>2+</Superscript>-doped BaSO<Subscript>4</Subscript> phosphor prepared by the recrystallization method

Eu doped BaSO₄ was prepared by the recrystallization method and characterization of the material was done by using X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR) techniques. From the XRD pattern of Eu doped BaSO₄ compound, it was found that the prominent phase formed was BaSO₄ and traces of other phases were very weak and the result of FTIR spectrum of BaSO₄:Eu shows that the sulfur-oxygen stretch was found at around 1100 cm⁻¹. The room-temperature PL spectra of the Eu doped BaSO₄ sample showed one peak centered at 374 nm, which is the characteristic emission of Eu²⁺ ion. This emission band at 374 nm corresponds to the 4f⁶ 5d→4f⁷ (⁸S_7/2) transitions of Eu²⁺ ions. The excitation spectrum taken at the wavelength 374 nm extends over a wide range of wavelengths from 220–350 nm with a strong peak at around 260 nm. Furthermore, the present sample shows good crystal quality and high photoluminescence sensitivity. Hence our results suggest possible potential applications of Eu doped BaSO₄ phosphor in optoelectronic devices.     

Spectroscopic study of chromium-doped transparent calcium germanate glass-ceramics

The optical properties of transparent chromium-doped glass-ceramics with the chemical composition similar to that of cunyite (Cr⁴⁺:Ca₂GeO₄) laser crystal were investigated. Room and low temperature absorption, excitation, fluorescence and Raman spectroscopy, as well as lifetime measurements were used to develop a model for the optical centers in the glass and nanocrystals. Parent (as quenched) glass does not exhibit any fluorescence; after the heat treatment Cr⁴⁺ fluorescence band appears at ∼1280 nm. Optical properties of nanocrystals formed in the glass-ceramics differ from those in the bulk single crystal Ca₂GeO₄. By comparison of Ca₂GeO₄ - like glass-ceramics with the Ca₂GeO₄ bulk single crystals and Mg₂SiO₄ - glass-ceramics we concluded that the nanocrystal phase is a modified Ca₂GeO₄ structure. Broadband fluorescence and a high quantum efficiency of new glass-ceramics make the new Cr-doped glass-ceramics promising medium for fiber lasers and amplifiers.     

Quantum Effect on the Energy Levels of Eu2+ Doped K2Ca2(SO4)3 Nanoparticles

Quantum confinement effect on the energy levels of Eu²⁺ doped K₂Ca₂(SO₄)₃ nanoparticles has been observed. The broad photoluminescence (PL) emission band of Eu²⁺ doped K₂Ca₂(SO₄)₃ microcrystalline sample observed at ～436 nm is found to split into two narrow well resolved bands, located at 422 and 445 nm in the nanostructure form of this material. This has been attributed to the reduction in the crystal field strength of the nanomaterials, which results in widening the energy band gap and splitting the broad 4f⁶5d energy level of Eu²⁺. Energy band gap values of the micro and nanocrystalline K₂Ca₂(SO₄)₃ samples were also determined by measuring the UV–visible absorption spectra. These values are 3.34 and 3.44 eV for the micro and nanocrystalline samples, respectively. These remarkable results suggest that activators having wide emission bands might be subjected to weak crystal strength via nanostructure materials to modify their electronic transitions. This might prove a powerful technique for producing new-advanced materials for use in the fields of solid state lasers and optoelectronic devises.     

Photoluminescence from germanate glasses containing silicon nanocrystals and erbium ions

We report the first observation of photoluminescence enhancement in Er³⁺ doped GeO₂–Bi₂O₃ glasses containing silicon nanocrystals (Si-NCs) excited by a laser operating at 980 nm. The growth of ≈200% in the intensity of the Er³⁺ transition ⁴S_3/2→⁴I_15/2 (545 nm) and of ≈100% for transitions ²H_11/2→⁴I_15/2 (525 nm), ⁴F_9/2→⁴I_15/2 (660 nm), and ⁴I_5/2→⁴I_13/2 (1530 nm) was observed in comparison with a reference sample that does not contain Si-NCs. The results open a new road for obtaining efficient Stokes and anti-Stokes emissions in germanate composites doped with rare-earth ions.     

Vacuum ultraviolet 5d14f9-4f10 emission of Ho3+ ions in alkaline-earth fluorides

Time-resolved emission and excitation spectra as well as emission decay kinetics of CaF₂, SrF₂, BaF₂ doped with HoF₃ were investigated. Intensive emission bands near 168 nm, having long decay time, are caused by the spin-forbidden transitions from the 5d¹4f⁹ high-spin states to the ground ⁵I₈ states of Ho³⁺ ions. Weak spin allowed 5d¹4f⁹(low-spin)-4f¹⁰ emission band at 158 nm was observed only in CaF₂–Ho crystals. Spin allowed and spin-forbidden excitation bands were observed near 166 and 155 nm, respectively, in all studied crystals. Fast component of spin-forbidden emissions due to multiphonon relaxation to low-lying 4f¹⁰ Ho³⁺ level also was observed for all crystals.     

Visible upconversion and infrared luminescence investigations of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powders doped with Er<Superscript>3+</Superscript>, Yb<Superscript>3+</Superscript> and Zn<Superscript>2+</Superscript> ions

Alumina (Al₂O₃) powders doped with Er³⁺, Yb³⁺ and Zn²⁺ ions have been prepared by a low-temperature combustion synthesis technique. The phase purity and crystalline structure of the combustion products are confirmed by powder X-ray diffraction. An efficient frequency upconversion in the visible region and the emission in the infrared (IR) region respectively corresponding to the ²H_11/2, ⁴S_3/2→⁴I_15/2, ⁴F_9/2→⁴I_15/2 and ⁴I_13/2→⁴I_15/2 transitions upon direct excitation with a CW laser lasing at ∼980 nm are discussed. The enhancement observed in the intensity of the upconversion emission bands in the visible region and the emission band in the IR region due to the presence of Yb³⁺ and Zn²⁺ in Er³⁺:Al₂O₃ powders is reported and explained in detail.     

Luminescence characteristics of Eu2+ activated Ca2SiO4 Sr2SiO4 and Ba2SiO4 phosphorsfor white LEDs

<正>This paper investigates the luminescence characteristics of Eu²⁺ activated Ca₂SiO₄,Sr₂SiO₄ and Ba₂SiO₄ phosphors. Two emission bands are assigned to the f-d transitions of Eu²⁺ ions doped into two different cation sites in host lattices,and show different emission colour variation caused by substituting M²⁺ cations for smaller cations.This behaviour is discussed in terms of two competing factors of the crystal field strength and covalence.These phosphors with maximum excitation of around 370 nm can be applied as a colour-tunable phosphor for light-emitting diodes（LEDs） based on ultraviolet chip/phosphor technology.     

Upconverted VUV luminescence of Nd and Er doped into LiYF4 crystals under XeF-laser excitation

The upconverted VUV (185 nm) and UV (230 and 260 nm) luminescence due to 5d-4f radiative transitions in Nd³⁺ ions doped into a LiYF₄ crystal has been obtained under excitation by 351/353 nm radiation from a XeF excimer laser. The maximum upconversion efficiency, defined as the ratio of intensity for 5d-4f luminescence to overall intensity for 5d-4f and 4f-4f luminescence from the ⁴D_3/2 Nd³⁺ level, has been estimated to be about 70% under optimal focusing conditions for XeF laser radiation. A redistribution of intensity between three main components of 5d-4f Nd³⁺ luminescence is observed under changing the excitation power density, which favors the most long-wavelength band (260 nm) at higher excitation density level. The effect is interpreted as being due to excited state absorption of radiation emitted. The upconverted VUV and UV luminescence from the high-lying ²F(2)_7/2 4f level of Er³⁺ doped into a LiYF₄ crystal has also been obtained under XeF-laser excitation the most intense line being at 280 nm from the spin-allowed transition to the ²H(2)_11/2 4f level of Er³⁺, but the efficiency of upconversion for Er³⁺ emission is low, less than 5%.     

Ca2GeO4 ∶Eu3+ 的电子结构和紫外-真空紫外发光特性的研究

采用高温固相法合成了发光材料Ca₂GeO₄ ∶Eu³⁺ ,并详细研究了其紫外-真空紫外发光特性. 发现并解释了Eu³⁺ 离子在空气中的自还原以及在不同波长激发下的颜色转换现象. Ca₂GeO₄ ∶Eu³⁺ 在163—230和301,466 nm处具有强激发带,表明Ca₂GeO₄ ∶Eu³⁺ 关键词： 2GeO₄ ∶Eu³⁺')" href="#">Ca₂GeO₄ ∶Eu³⁺ 光致发光机理 空气中自还原 颜色转换     

Nonlinear absorption properties of Co2+:MgAl2O4 crystal

The differential absorption spectra of Co²⁺: MgAl₂O₄ (MALO) crystal were studied with a picosecond pump-probe technique under excitation of the ⁴A₂→⁴T₁(⁴P) and ⁴A₂→⁴T₁(⁴F) transitions of the tetrahedral Co²⁺ ion. The difference spectra of stimulated emission (SE) and excited state absorption (ESA) were derived from the measured differential absorption spectra. The ⁴T₁(⁴P)→⁴A₂ SE band around 660 nm was observed. The ESA bands were assigned to the ⁴T₂→⁴T₁(⁴P) transition and to transitions from the thermally populated ²E(²G) excited state to doublet levels arising from the ²F free-ion level of the tetrahedrally coordinated Co²⁺ ion. Absorption saturation measurements were performed at 1.34 μm and 1.54 μm. Passive Q-switching of 1.34-μm Nd³⁺:YAlO₃ and 1.54-μm Er³⁺:glass lasers was realized using the Co²⁺:MALO crystal as saturable absorber. The Q-switched laser pulses of 38 ns (110 ns) in duration and up to 2.7 mJ (10 mJ) in energy at 1.54 μm (1.34 μm) were obtained. Received: 3 March 1999 / Revised version: 30 June 1999 / Published online: 30 November 1999     

Excited-state absorption in Er: BaY2F8 and Cs3Er2Br9 and comparison with Er: LiYF4

The influence of Excited-State Absorption (ESA) on the green laser transition and the overlap of Ground-State Absorption (GSA) and ESA for 970 nm upconversion pumping in erbium is investigated in Er³⁺ : BaY₂F₈ and Cs₃Er₂Br₉. Results are compared to Er³⁺ : LiYF₄. In Er³⁺: BaY₂F₈, a good overlap between GSA and ESA is found at 969 nm in one polarization direction. The emission cross section at 550 nm is a factor of two smaller than in LiYF₄. In Cs₃Er₂Br₉, the smaller Stark splitting of the levels shifts the wavelengths of the green emission and ESA from⁴ I _{1 3/2} off resonance. It enhances, however, ground-state reabsorption. The emission cross section at 550 nm is comparable to LiYF₄. Upconversion leads to significant green fluorescence from² H _9/2. A significant population of the⁴ I _11/2 level and ESA at 970 nm are not present under 800 nm pumping.     

KBaPO4:Ln (Ln=Eu, Tb, Sm) phosphors for UV excitable white light-emitting diodes

This letter reports the novel three emission bands based on phosphate host matrix, KBaPO₄ doped with Eu²⁺, Tb³⁺, and Sm³⁺ for white light-emitting diodes (LEDs). The phosphors were synthesized by solid-state reaction and thermal stability was elucidated by measuring photoluminescence at higher temperatures. Eu²⁺-doped KBaPO₄ phosphor emits blue luminescence with a peak wavelength at 420 nm under maximum near-ultraviolet excitation of 360 nm. Tb³⁺-doped KBaPO₄ phosphor emits green luminescence with a peak wavelength at 540 nm under maximum near-ultraviolet excitation of 370 nm. Sm³⁺-doped KBaPO₄ phosphor emits orange-red luminescence with a peak wavelength at 594 nm under maximum near-ultraviolet excitation of 400 nm. The thermal stabilities of KBaPO₄:Ln (Ln=Eu²⁺, Tb³⁺, Sm³⁺), in comparison to commercially available YAG:Ce³⁺ phosphor were found to be higher in a wide temperature range of 25-300 °C.     

Strong green luminescence of Ni2+-doped ZnS nanocrystals

ZnS nanoparticles doped with Ni²⁺ have been obtained by chemical co-precipitation from homogeneous solutions of zinc and nickel salt compounds, with S^2- as precipitating anion, formed by decomposition of thioacetamide (TAA). The average size of particles doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2–2.5 nm. The nanoparticles could be doped with nickel during synthesis without altering the X-ray diffraction pattern. A Hitachi M-850 fluorescence spectrophotometer reveals the emission spectra of samples. The absorption spectra show that the excitation spectra of Ni-doped ZnS nanocrystallites are almost the same as those of pure ZnS nanocrystallites (λ_ex=308–310 nm). Because a Ni²⁺ luminescent center is formed in ZnS nanocrystallites, the photoluminescence intensity increases with the amount of ZnS nanoparticles doped with Ni²⁺. Stronger and stable green-light emission (520 nm) (its intensity is about two times that of pure ZnS nanoparticles) has been observed from ZnS nanoparticles doped with Ni²⁺. Received: 18 December 2000 / Accepted: 17 March 2001 / Published online: 20 June 2001     

Growth,spectroscopic and laser properties of Yb<Superscript>3<Emphasis Type="Bold">+</Emphasis></Superscript>-doped GdAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal: a candidate for infrared laser crystal

Yb³⁺:GdAl₃(BO₃)₄ (hereafter Yb³⁺:GAB) crystals with large sizes and good optical quality have been grown by the top-seed solution growth (TSSG) method. The polarized absorption and emission spectra have been investigated at room temperature. For the σ-polarization, the intensities of both absorption and emission spectra are stronger than those for the π-polarization, the σ-absorption cross section of Yb³⁺ in GAB being 3.43×10^-20 cm² at 977 nm, and the σ-emission cross section being 0.98×10^-20 cm² at 1045 nm. The fluorescence lifetime of the ² F _5/2→² F _7/2 transition was measured to be 800 μs in the 5% doped sample used for our laser experiments, 993 μs in a 10% doped sample and 569 μs in a 0.5% doped sample. The laser parameters were estimated as: β_min=0.022, I_sat=10.4 kW/cm² and I_min=0.23 kW/cm². About 0.4 W laseroutput at the wavelength of 1043 nm was achieved when the Yb³⁺:GAB crystal was pumped by a 974 nm laser diode, with 27.4% slope efficiency. PACS 42.55.-f; 42.70.Hj; 78.20.-e; 81.10.Dn     

Ca2SiO4:Dy3+材料的制备及其发光特性

采用高温固相法制备了Ca₂SiO₄:Dy³⁺发光材料.在365nm紫外光激发下,测得Ca₂SiO₄:Dy³⁺材料的发射光谱为一多峰宽谱,主峰分别位于486nm,575nm和665nm处;监测575nm发射峰,测得材料的激发光谱为一多峰宽谱,主峰分别位于331nm,361nm,371nm,397nm,435nm,461nm和478nm处.研究了Dy³⁺掺杂浓度对Ca₂SiO₄:Dy³⁺材料发射光谱及发光强度的影响,结果显示,随Dy³⁺浓度的增大,黄、蓝发射峰强度比(Y/B)逐渐增大,利用Judd-Ofelt理论解释了其原因;随Dy³⁺浓度的增大,Ca₂SiO₄:Dy³⁺材料发光强度先增大,在Dy³⁺浓度为4 mol%时到达峰值,而后减小,根据Dexter理论其浓度猝灭机理为电偶极-电偶极相互作用.研究了电荷补偿剂Li⁺,Na⁺和K⁺对Ca₂SiO₄:Dy³⁺材料发射光谱的影响,结果显示,不同电荷补偿剂下,随电荷补偿剂掺杂浓度的增大,Ca₂SiO₄:Dy³⁺材料发射光谱强度的演化趋势相同,即Ca₂SiO₄:Dy³⁺材料发射峰强度先增大后减小,但不同电荷补偿剂下,材料发射峰强度最大处对应的补偿剂浓度不同,对应Li⁺,Na⁺和K⁺时,浓度分别为4mol%,4mol%和3mol%. 关键词： 白光LED 2SiO₄:Dy³⁺')" href="#">Ca₂SiO₄:Dy³⁺ 发光特性 电荷补偿