Physical and Optical Properties of Calcium Zinc Borophosphate Glasses Doped with Manganese Ions

This article reports on the physical and optical properties, absorption, and luminescence spectra in the visible region, of calcium zinc borophosphate glasses doped with manganese ions. The manganese composition was varied up to 10 mol%. The aim of this work was to investigate the effect of the luminescence properties when the glasses were doped with different compositions of manganese ions. X-ray diffraction profiles confirmed their glassy nature. The optical absorption spectrum showed bands characteristic of manganese ions in octahedral symmetry. Both excitation and emission spectra were recorded for these glasses to understand their optical performances. The emission spectrum showed a single broad band (green region) in octahedral symmetry at 582 nm as a result of transition from the upper ⁴T_1g state to the ⁶A_1g ground state of manganese ions. As the concentration of manganese ions increased, the emission band increased from 582 nm (green-light emission) to 650 nm (red-light emission). Apart from the spectral analysis, different physical properties of these glasses were also analyzed. Based on the physical and optical properties, we found the samples to be more promising for their use as novel luminescent optical materials.     

Investigation of the luminescence properties and thermal stability of dysprosium,terbium, and europium ions singly- and co-doped strontium yttrium borate phosphors

A series of trivalent rare-earth element ions (europium, terbium, dysprosium) singly- and co-doped strontium yttrium borate phosphors was synthesized via the sol–gel method. The phase formation, luminescence properties, decay times, and energy transfer behaviors from terbium ions to europium ions, the thermal stability, and the Commission Internationale de L’Eclairage coordinates were investigated. Under the excitation of ultraviolet light, the singly doped phosphors exhibited green emission of terbium ions, white emission of dysprosium ions, and red emission of europium ions, respectively. For the terbium and europium ions co-doped strontium yttrium borate samples, a white emission can be realized by blending the doping concentration of terbium and europium ions. The critical distance between terbium and europium ions has been calculated to be about 14.52?Å and the energy transfer from terbium to europium occurred through the dipole–quadrupole interaction. At 150°C, the emission intensity of terbium and europium in the 12?mol% terbium and 14?mol% europium co-doped strontium yttrium borate sample was maintained at about 74% and 87% of their corresponding initial values, respectively, and the dysprosium ions singly doped strontium yttrium borate sample showed about 70% of its initial emission intensity at room temperature. The above results suggested that europium, terbium, dysprosium ions singly- and co-doped strontium yttrium borate phosphors have potential applications as ultraviolet-convertible phosphors.     

α-噻吩羧酸锌铕复合物的光谱性质

本文采用流变相反应法合成了具有很强红色发光的α－噻吩羧酸锌铕复合物,测定了样品的粉末Ｘ－射线衍射数据,热重曲线,紫外、红外光谱、激发和发射光谱,讨论了硫杂环和锌对铕离子特征发射的影响。α－噻吩羧酸锌铕复合物中锌能增加铕离子的特征发射强度,硫杂环能增强铕离子发光的效率。     

Terbium single-doped or terbium and sodium codoped barium zinc phosphate: A novel green phosphor for near ultraviolet-pumped white light-emitting diodes

The novel green terbium single-doped or terbium and sodium codoped barium zinc phosphate phosphors were successfully synthesized by a high temperature solid-state reaction. Terbium single-doped and terbium and sodium codoped barium zinc phosphate phosphors can be efficiently excited by near ultraviolet (n-UV) light, and the emission spectrum consists of four main emission peaks at 495, 545, 589, and 622?nm. By increasing the terbium concentration, the emission signal of the phosphor can reach the maximum at 0.09 molar terbium, then the content quenching occurs. By introducing the charge compensator sodium ions into the terbium-doped barium zinc phosphate phosphors, its emission signal can be obviously enhanced. The Commission International de l’Eclairage chromaticity coordinates of the two typical samples are (0.30, 0.47) and (0.31, 0.48), which are both in the green region. The decay time and quantum yield of the typical sample are 365.84 µs and 0.49, respectively. All the results indicate that terbium single-doped and terbium and sodium codoped barium zinc phosphate are promising green phosphors for near ultraviolet pumped white light-emitting diodes.     

Ca8Mg(SiO4)4Cl2中Ce3+和Eu2+的光谱性质和能量传递

首次合成了Ｃｅ＾３＋和Ｅｕ＾２＋共激活氯硅酸镁钙Ｃａ８Ｍｇ（ＳｉＯ４）４Ｃｌ２：Ｃｅ＾３＋，Ｅｕ＾２＋高效绿色荧光粉，报道了它们的漫反射光谱、激发和发射光，观察到氯硅酸镁钙中Ｃｅ＾３＋ Ｅｕ＾２＋     

铈铕掺杂氯硅酸镁钙体系的相对光谱功率分布与色坐标定位

采用高温固相反应法合成铈铕掺杂氯硅酸镁钙系列粉体,利用X射线衍射(XRD)对晶体结构加以鉴定,并对其荧光光谱进行了测试和分析.通过光谱功率校准曲线,推演出样品的相对光谱功率分布,进而对粉体发光色坐标进行计算和表征.实验结果表明,合成粉体为面心立方晶体Ca8Mg(SiO4)4Cl2,铈铕单掺氯硅酸镁钙样品在紫外光激发下分...     

Ce~(3+)和Tb~(3+)掺杂钆-钡-硅酸盐闪烁玻璃的发光性能

采用高温熔融法制备Ce~(3+)或Tb~(3+)单掺和Ce~(3+)/Tb~(3+)共掺钆-钡-硅酸盐闪烁玻璃。通过透射光谱、光致激发和发射光谱、X射线激发发射光谱及荧光衰减曲线等手段对其发光性能进行研究。实验结果表明:在紫外光的激发下,Tb~(3+)掺杂闪烁玻璃发出明亮的绿光(544 nm),而Ce~(3+)掺杂闪烁玻璃发出蓝紫光。对于Ce~(3+)/Tb~(3+)共掺闪烁玻璃,在紫外光和X射线激发下均观察到Ce~(3+)离子敏化Tb~(3+)离子发光的现象,这是由于存在Ce~(3+)→Tb~(3+)的能量转移。Ce~(3+)/Tb~(3+)共掺闪烁玻璃的最佳Ce2O3掺杂摩尔分数为0.2%,此时Ce~(3+)离子向Tb~(3+)离子的能量传递效率为45.7%。在X射线激发下,Ce_2O_3摩尔分数为0.2%的Ce~(3+)/Tb~(3+)共掺闪烁玻璃在544 nm处的发光强度是Bi_4Ge_3O_(12)(BGO)闪烁晶体在500 nm处发光强度的4.2倍,积分闪烁效率达到BGO晶体的55.6%,这有利于在高分辨率医学成像中降低辐射剂量。     

Photon conversion in Bi(3+)/Pr(3+)-codoped CaTiO(3)

The luminescence properties of CaTiO(3) both singly and doubly doped with Bi(3+) and Pr(3+) have been measured in different experimental conditions in order to investigate the de-excitation processes active in these materials and in particular to understand the mechanism responsible for the significant increment of the red emission observed in the codoped system upon near-ultraviolet (NUV) excitation. The steady state spectra and the decay profiles have been analyzed in the light of the possible interactions between active ions and host lattice. The general model applied to the analysis of the temporal profiles of the emission allows us to assess which are the main mechanisms involved in the Bi(3+) → Pr(3+) sensitization process.     

钡钇氟化物中Eu2+离子的激发光谱和发射光谱

在298和77K下分别研究BaYF5(BaF2·YF3)中Eu2+的激发和发射光谱。Eu2+的发射光谱中,除了一个属5d-4f跃迁的宽发射带外,还有一组6PJ→8S7/2的4f-4f跃迁窄谱线发射。它们的发射强度与Eu2+的浓度和温度有关。由於Eu2+从4f7基态跃迁到4f65d1态产生两个宽的激发带,4f65d(eg)和4f65d(t2g)。实验证实,Eu2+的6PJ→8S7/2的窄谱线发射主要来自高能级的t2g激发能弛豫的结果。     

聚乙烯吡咯烷酮与苯磺酸铕相互作用研究

用变温红外光谱法和荧光光谱法研究了聚乙烯吡咯烷酮与苯磺酸铕的相互作用。聚乙烯吡咯烷酮的酰胺基团可与苯磺酸铕中的铕离子发生络合配位作用,导致聚乙烯吡咯烷酮的酰胺Ⅰ带发生红移。这种络合配位作用,使原本不溶于氯仿的苯磺酸铕可溶于含聚乙烯吡咯烷酮的氯仿溶液。在苯磺酸铕固体的发射光谱中,只能观察到铕离子的f—f跃迁特征发射峰,而在苯磺酸铕浓水溶液的荧光光谱中,亦可观测到苯磺酸根的π*→π跃迁峰,说明苯磺酸铕在水溶液中存在解络合现象。苯磺酸铕在溶液中的解络合行为使铕离子周围的可配位空间增大,这为PVP的酰胺基团与铕离子发生络合配位作用创造了条件。     

Luminescence properties of Tb doped and Tm/Tb/Sm co-doped glasses for LED applications

Tb³⁺ ions doped and Tm/Tb/Sm co-doped glasses for light-emitting-diodes (LED) applications have been synthesized by melt quenching method. Their photoluminescence properties were studied by emission and excitation spectra. The ⁵D₃ and ⁵D₄ emission of Tb³⁺ can be varied by adjusting Tb³⁺ concentrations and the compositions of glass matrix. Blue, green and reddish orange emission bands were observed in the emission spectra of Tm/Tb/Sm co-doped glasses. The combination of these emission bands allows the realization of white light when the glasses are excited by near ultraviolet light. In addition, the relative intensity ratios of respective emission lines are dependent on the composition of glasses and the excitation wavelength.     

Features of Emission and Absorption of Indotricarbocyanine Dyes on Excitation to Higher Electronic States

The manifestation of ion pairs in the absorption and emission of fluorescence by symmetric indotricarbocyanine dyes with the same cation and anions Br, I, and BF₄ in ethanol, methylene chloride, and dichlorobenzene has been investigated. It is shown that the formation of ion pairs on passing to low-polarity solvents, along with the changes in the electronic absorption and emission spectra, manifests itself in the polarization and fluorescence excitation spectra. We were the first to establish that the presence of an equilibrium mixture of contact ion pairs and free ions in solutions has an effect on the position and probabilities of transitions not only for the first but also for higher excited singlet states of the molecules of polymethine dyes. The formation of ion pairs manifests itself more clearly when the spectral-luminescence properties of compounds in the shortwave spectral region are analyzed. It has been established that marked changes arise in the absorption, excitation, emission, and polarization fluorescence spectra, as well as in the lifetime and quantum yield of fluorescence in this spectral region when the solvent is changed.     

铕与苯乙酮酸、1,10-罗啉及三苯基氧膦配合物的合成、结构表征及荧光性能的研究

以硝酸铕、苯乙酮酸（HE）、1,10-罗啉（phen）和三苯基氧膦（TPPO）合成了Eu—L,EuL3phen和EuL2（TPPO）2NO3三种新型固态配合物。用元素分析、电导率、红外光谱、核磁共振谱对配合物进行了表征,确定了三元配合物的组成。IR表明,苯乙酮酸与Eu^3＋离子形成配合物后△v（vas（CO2^-）-vs（CO2））（△v（Eu—L）=391cm^-1;△v（EuL3phen）=389cm^-1;△v（EuL2（TPPO）2NO3）=402cm^-1）值均大于钠盐的△v（379cm^-1）值,配合物中羧酸根以单齿方式配位;配合物中苯乙酮酸的α-酮基参与配位,其红外吸收峰移向低波数。在^1H NMR中,苯乙酮酸苯环上5个氢原子的化学位移在形成配合物后移向高场。室温下测定了配合物的荧光激发光谱和发射光谱。激发光谱表明配合物Eu—L,EuL3phen和EuL2（TPPO）2NO3最佳激发波长分别为374．0,358．2和383．4nm。发射光谱显示Eu^3＋离子的特征发射光谱。分别是^5D0-^7F0,^5D0-^7F1,^5D0-^7F2,^5D0-^7F3,^5D0-^7F4跃迁（Eu—L：577．8,590．2,614．0,648．4,695．4nm;EuL3phen：578．0,588．4,591．6,611．2,617．0,649．4,687．6,698．6nm;EuL2（TPPO）2NO3：577．8,590．4,614．6,649．2,697．6nm）。荧光光谱表明TPPO对Eu^3＋离子的荧光发射有明显增强作用。     

掺杂铽的对甲基苯甲酸锌发光材料的合成与荧光性能研究

采用流变相法合成了掺杂三价铽离子的对甲基苯甲酸锌发光材料。在紫外灯的照射下,观察比较了对甲基苯甲酸、对甲基苯甲酸锌以及掺杂Tb（Ⅲ）的对甲基苯甲酸锌盐的荧光现象,利用荧光分光光度计测定了三者的激发光谱和发射光谱,并讨论三者的发光特性和机理。结果表明：对甲基苯甲酸作为有机配体可以改善Tb^3＋离子的发光性能。     

Efficient near-infrared emission from neodymium by broadband sensitization of bismuth in zeolites

Nd-Bi codoped zeolites were prepared by an ion-exchange process, and the optical properties were investigated by photoluminescence (PL) and PL excitation spectra, and decay time measurements. The results show that the NIR emission of Nd(3+) ions is significantly enhanced by the introduction of bismuth in codoped samples, and the lifetime reaches 246?μs. It is also observed that NIR-active Bi acts as a sensitizer of Nd(3+) ions. The energy transfer efficiency is also estimated. The peculiar optical properties make Nd-Bi codoped zeolites promising for potential application in biological probes.     

LED红色发光粉的制备及封装性能(英文)

实验采用碳酸锂、氧化钨、氧化铕制备了LiEuW2O8发光粉,通过扫描电镜和光谱仪分别研究了它的形貌与光谱特征。结果显示:LiEuW2O8发光粉的激发光谱较宽,非常适合于近紫外、蓝光及绿光芯片,发射光谱峰值位于615nm,色坐标为(x=0.666,y=0.331);球磨对它的形貌影响非常明显。为了比较硫化物发光粉和LiEuW2O8发光粉的性能,分别对他们进行了封装实验,结果显示:LiEuW2O8发光粉能够有效降低色温,更重要的是,它对光效影响较小,4000K时,光效可以保持在60lm/W以上。     

SrB4O7：Pr3+,Mn2+中的Pr→Mn能量传递

从能量传递的角度出发,利用同步辐射光源(德国HASYLAB实验室的SUPERLUMI实验站)对Pr³⁺和Mn²⁺掺杂的SrB₄O₇粉末样品进行了光谱研究.206nm激发下,在SrB₄O₇:Pr³⁺(0.1%,摩尔分数)样品中观察到了来自Pr³⁺离子1S0能级的光子级联发射.SrB₄O₇:Pr³⁺样品的发射谱与SrB₄O₇:Mn²⁺样品监测Mn²⁺离子640nm发射的激发谱在330~430nm的波长范围里存在显著的光谱重叠.这个光谱重叠有利于Pr³⁺→Mn²⁺的能量传递发生,从而将Pr³⁺离子级联发射中第一步不实用的紫外或近紫外光子转换为Mn²⁺的红光发射.双掺杂样品SrB₄O₇:Pr³⁺,Mn²⁺与单掺杂样品SrB₄O₇:Pr³⁺的发射谱比较揭示出Pr³⁺→Mn²⁺的能量传递的确存在,并且提供了一种传递效率的估算方法,表明通过“Pr³⁺-Mn²⁺”组合有可能获得量子效率大于1的高效真空紫外激发发光材料.     

Electron–hole liquid formation by exciton and biexciton resonant excitation in CuCl

The dynamics of a cold photoexcited electron–hole system created by resonant excitation with picosecond optical pulses are studied by time-resolved emission and pump–probe measurements. A rapid build-up of strong metallic reflection in the mid-infrared region was observed, which indicates the creation of electron–hole plasma via the exciton or biexciton Mott transition. Transient reflection spectra clearly show the transformation of high-density electron–hole plasma into a metallic colloid-like state within 10 ps. In the meantime, broad plasma emission turns to a narrow emission band, in which the spectral profile does not change within several tens of picoseconds. These features in the emission spectra disappear when switched to the band-to-band excitation. An analysis of the reflection and emission spectra reveals that the density of metastable electron–hole liquid is as high as 10²⁰ cm⁻³. This indicates that the plasma formation via the Mott transition is crucial to eliminate excess heating for reaching the low-temperature states of an electron–hole ensemble.     

Deep level emission of ZnO nanoparticles deposited inside UV opal

The temperature-dependent photoluminescence spectra of zinc oxide (ZnO) nanocrystals deposited inside the ultraviolet (UV) opal were studied. ZnO was grown in the voids between FCC packed SiO₂ spheres using spray pyrolysis under ultrasonic vibration in the solution containing a zinc nitrate precursor. The ZnO nanoparticles inside opal matrix with UV photonic band-gap exhibit suppression of the excitonic emission and enhancement of the deep level emission. Suppression of the excitonic lines is due to the inhibition of spontaneous emission, while enhancement and broadening of the DL emission in the green spectral region is due to Purcell effect. The infiltration of ZnO nanoparticles inside the photonic crystal may be a useful technique to increase its emission efficiency in the selected spectral region.     

Structural and photoluminescence studies on europium-doped lithium tetraborate(Eu:Li_2B_4O_7) single crystal grown by microtube Czochralski(μT-Cz) technique

Rare earth europium(Eu(3+))-doped lithium tetraborate(Eu:Li_2B_4O_7) crystal is grown from its stoichiometric melt by microtube Czochralski pulling technique(μT-Cz) for the first time. The grown crystals are subjected to powder x-ray diffraction(PXRD) analysis which reveals the tetragonal crystal structure of the crystals. UV–vis–NIR spectral analysis is carried out to study the optical characteristics of the grown crystals. The crystal is transparent in the entire visible region, and the lower cutoff is observed to be at 304 nm. The existence of BO_3 and BO_4 bonding structure and the molecular associations are analyzed by Fourier transform infrared(FTIR) spectroscopy. The results of excitation and emission-photoluminescence spectra of europium ion incorporated in lithium tetraborate(LTB) single crystal reveal that the observations of peaks at 258,297, and 318 nm in the excitation spectra and peaks at 579, 591, 597, 613, and 651 nm are observed in the emission spectra.The chromaticity coordinates are calculated from the emission spectra, and the emission intensity of the grown crystal is characterized through a CIE 1931(Commission International d'Eclairage) color chromaticity diagram.