微波法合成红色长余辉发光材料Gd_2O_2S∶Eu,Mg,Ti及其发光特性

用微波辐射法首次合成了Gd2O2S∶Eu,Mg,Ti红色磷光化合物,用X射线粉末衍射（XRD）、扫描电镜（SEM）、荧光分光光度计等对合成产物进行了分析和表征。结果表明：材料的晶体结构为六方晶系,与Gd2O2S的相同。颗粒的形貌为类球形,分散性较好,尺寸在1-2μm之间。Gd2O2S∶Eu,Mg,Ti的激发光谱呈带状,激发光谱主峰位于360nm,另外在400,422,472nm等处也有激发峰存在;发射光谱为线状光谱,归属于Eu^3＋的5^DJ（J=0,1,2）到7^FJ（J=0,1,2,3,4）的跃迁。随着Eu浓度的增加,位于蓝绿区的586,557,541,513,498,471,468nm处的发射峰逐渐减弱,而主峰位于627nm处的红光发射明显增强。当Eu浓度为6mol%时,红光发射最强。Mg,Ti共掺杂可显著改善其余辉性质。

微波法合成新型红色长余辉材料Gd_2O_2S:Eu,Mg,Ti中助熔剂的影响

用微波辐射法合成了红色长余辉材料Gd2O2S:Eu,Mg,Ti,用X射线粉末衍射(XRD)、扫描电镜(SEM)、荧光分光光度计等手段对合成产物进行了分析和表征,并研究了不同助熔剂L i2CO3,Na2CO3,K2CO3,Na3PO4,KH2PO4以及L i2CO3和Na2CO3共同作用对材料的微观形貌及发光性能的影响。结果表明:不同的助熔剂的加入均可得到单相晶体,材料的晶体结构为六方晶系,与Gd2O2S的相同。颗粒分散性较好,晶粒尺寸以及形貌因助熔剂的不同而有所差别。发光性质研究表明:不同助熔剂的加入并没有改变样品发射谱主峰位置(627nm),但对其峰强度产生明显影响,激发光谱中的情况与此相似。研究发现L i2CO3和Na2CO3共同作用可有效延长余辉时间。

Y_2O_2S∶Eu,Ti,Mg红色长余辉的温度依赖

实际应用中在低温下一些长余辉材料不能正带工作，因此需要研究长余辉材料的温度依赖特性。用固相反应法合成了Y2O2S：Eu，Ti，Mg，测量了其余辉发射谱和热释光曲线，研究Y2O2S：Eu，Ti，Mg在140～300K和290～350K温区的长余辉发光的发射光谱和衰减曲线的温度依赖。当温度低于其热释光曲线起始点230K时，其余辉的发射光谱强度较弱。随温度增加，其余辉的发射光谱强度随温度增强。300K后，其余辉衰减时间随温度变快。Y2O2S：Eu，Ti，Mg长余辉的温度依赖行为与其热释光曲线密切相关，并通过长余辉机制对其进行了分析和讨论。

EDTA络合溶胶-凝胶法制备Y_2O_2S:Eu^(3+),Mg^(2+),Ti^(4+)红色长余辉材料

采用EDTA(乙二胺四乙酸)络合溶胶-凝胶法制备了Y2O2S:Eu3+,Mg2+,Ti4+粉体。采用X射线衍射仪、扫描电子显微镜和荧光分光光度计对不同温度合成的样品性能进行测试与表征。结果表明:当硫化温度低于1 000℃时,样品为Y2O3与Y2O2S的混合相;当温度在1 050～1 100℃时,样品为纯相的Y2O2S;当温度升高到1 150℃时,再次出现Y2O3的相。硫化温度在950～1 100℃时,产物的粒径为50～300 nm。用波长为330 nm的紫外光激发样品时,626 nm处的发射对应于Eu3+的5D0-7F2跃迁。硫化温度为1 100℃时,样品的余辉时间最佳,为95 min(≥1 mcd/m2)。相比于以乙酰丙酮为络合剂的溶胶-凝胶法,EDTA络合溶胶-凝胶法制备的样品的发光性能具有较大提高。

Characterization of Y_2O_2S∶Eu ^(3+), Mg^(2+), Ti^(4+) Long-Lasting Phosphor Synthesized by Flux Method

Long-lasting phosphor Y2O2S ： Eu^3＋ , Mg^2＋ , Ti^4＋ was synthesized by a flux method and their luminescence properties were investigated. The result indicates that the unit cell parameter c is linearly increased with the increase of Eu2O3 content in Y2O2S： Eu^3＋ （0.01 ≤ x ≤0.10）. On the other hand, the change of unit cell parameter a is not linear dependence. In the Y2O2S： Eu^3 ＋ crystal structure, Eu^3＋ ions only replaced Y^3 ＋ ions＇ places in which it posited center position of c axis. With the increase of Eu2O3 content, the position of the strongest emission peak changed from 540 nm （5D1→^ 7F2 transition） to 626 nm （^5Do→^7TF2 transition）, and the maximum intensity was obtained when x = 0.09 in Y2O2S： Eu^3＋ （0.01 ≤x ≤0.10）. This is due to the environment of trivalent europium in the crystal structure of Y2O2S. Doping with Mg^2＋ or Ti^4＋. ions alone cannot get the good long-lasting afterglow effect, whereas co-doping with Mg^2 ＋ and Ti^4 ＋ ions and excited with 365 nm ultraviolet light, a strong thermoluminesence peak appeared, red and orange long-lasting phosphorescence （LLP） was also observed and the phosphorescence lasted nearly 3 h in the light perception of the dark-adapted human eye （0.32 mcd·m^-2）. Thus the LLP mechanism was analyzed.

碱土金属离子对红色长余辉材料Y2O2S∶Eu3+,M2+ (M=Mg,Ca,Sr,Ba),Ti4+纳米阵列发光性能的影响

采用溶胶凝胶模板法制备红色长余辉发光材料Y2O2S∶Eu3+,M2+(M=Mg,Ca,Sr,Ba),Ti4+纳米阵列,利用X射线衍射、扫描电子显微镜和荧光分光光度计、照度计分别研究了不同二价离子掺杂下所合成样品的物相、形貌及发光性能。结果表明:样品排列整齐有序,管径大小统一;不同的二价离子种类没有改变晶体结构和发射峰的位置,但对余辉性能有较大的影响。用324 nm波长光激发样品,由于Eu3+的5D0→7F2跃迁,最强的红色发射峰位于626 nm处;不同离子掺杂样品的余辉性能按Ba2+、Ca2+、Sr2+、Mg2+的顺序递加,其中二价离子为Mg2+时,余辉时间长达287 s(≥1 mcd/m2),表现出最佳的余辉性能。

Temperature Dependence of Red Long Afterglow from Y_2O_2S∶Eu, Ti, Mg

At low temperature, some long-lasting phosphors could not work well in practical applications. So it is necessary to investigate the temperature dependence of the phosphors. The Y2O2S.Eu, Ti, Mg microcrystalline samples were prepared by solid state reaction method. Phosphors were sintered at 1150 ℃ for 20 min in air, putting in and taking out both at high temperature. The emission spectra and the afterglow spectra as well as the thermoluminescence curve were measured for Y2O2S：Eu,

Y_2O_2S:Eu^(3+),Mg^(2+),Ti^(4+)红色材料的制备和长余辉性能

用高温固相法制备了Y_2O_2S:Eu^(3+),Mg^(2+),Ti^(4+)红色长余辉材料,余辉时间达到1h以上,X射线衍射测量表明材料的晶体结构为Y_2O_2S。发射光谱对应了Eu^(3+)离子~5D_J(J=0,1,2,3)→~7F_J(J=0,1,2,3,4)的特征发射;激发光谱主峰位于345 um,另外在260,396,468,540 um等处也存在激发峰。对比测量了Y_2O_2S:Eu^(3+),Mg^(2+),Ti_(4+)和Y_2O_2S:Eu^(3+)的热释发光曲线,Y_2O_2S:Eu^(3+)的热释发光曲线可以拟合成3个热释发光峰的叠加:237,226,301K;而Y_2O_2S:Eu^(3+),Mg^(2+),Ti^(4+)的热释发光曲线可以拟合成5个热释发光峰的叠加:149,215,262,287,334 K,并计算了相应的陷阱能级。Ti^(4+)是引起较深陷阱能级的主要原因,Mg^(2+)起电荷补偿的作用。

Optical performance study of Sr_2ZnSi_2O_7:Eu^(2+),Dy^(3+), SrAl_2O_4:Eu^(2+),Dy^(3+) and Y_2O_2S:Eu^(3+),Mg^(2+),Ti^(4+) ternary luminous fiber

In this study, down-conversion fluorescent powder of Sr2ZnSi2O7：Eu-（2＋）,Dy-（3＋）, SrAl2O4：Eu-（2＋）,Dy-（3＋） and Y2O2S：Eu-（3＋）,Mg-（2＋）,Ti-（4＋）, which were the common three primary colors materials with long afterglow, were synthesized by high temperature solid state method. The blends of rare earth（RE） luminescent materials have been of interest to reinvest the luminescent characteristics of polyethylene terephtahalate（PET） luminous fiber. The scanning electron microscopy（SEM） and an inversion fluorescence microscope were used to characterize the surface morphology and the dispersion of inclusion. Through analysis of microcosmic morphology, three typical dispersions of luminescent particles were summarized. The X-ray diffraction indicated that the phase structure of fiber samples and crystal structure of luminescence materials kept complete after prilling and spinning. From the fluorescence spectra and CIE 1931 coordinates, it could be found that different combinations of luminous fibers were desired to obtain divers colors emission luminous fiber. And the fiber samples were a light sensation which could induct different excitation wavelengths and convert it down to different colors. The afterglow decay curve and its differential curve were summarized indicating the three decay stages. The decay curve and decay rate curve showed that the contents of Sr2ZnSi2O7：Eu-（2＋）,Dy-（3＋）, SrAl2O4：Eu-（2＋）,Dy-（3＋） and Y2O2S：Eu-（3＋）,Mg-（2＋）,Ti-（4＋） had obvious influence on the afterglow of fiber samples.

塔里木盆地东南缘安南坝地区镁铁质麻粒岩的成因--来自地球化学及Sr-Nd-Pb同位素的制约

甘肃阿克塞县安南坝地区镁铁质麻粒岩呈脉状、透镜状赋存于新太古代米兰岩群和TTG片麻岩中。岩石主要由斜长石(Pl)+斜方辉石(Opx)+单斜辉石(Cpx)+角闪石(Amp)+磁铁矿(Mt)等组成。安南坝镁铁质麻粒岩中Ti、P、Nb、Ta、Th、Hf、Sr及REE等元素与Zr相关性较好,表明其在变质作用过程中保持基本稳定。地球化学数据显示其原岩属于拉斑玄武质岩系列,Si O_2、Ti O_2、Al_2O_3、P_2O_5含量相对较低,Ca O、Mg O含量相对较高。Mg~#值为41.52~43.09,低于原生玄武质岩石的Mg~#值,Fe_2O_3~T、Mg O、Ca O与Si O_2含量呈负相关性,指示原岩岩浆演化过程中可能发生了辉石、角闪石等镁铁质矿物的分异结晶作用。镁铁质麻粒岩∑REE较低,稀土元素配分模式为轻稀土元素弱富集、重稀土元素相对平坦的右倾型,Eu异常不明显(Eu/Eu~*=0.91~1.01)。岩石富集Rb、Ba、Sr等大离子亲石元素,亏损Nb、Ta、Zr、Ti等高场强元素,具有显生宙典型岛弧玄武质岩石的地球化学特征。Sr、Nd、Pb同位素组成显示镁铁质麻粒岩原岩源自富集地幔,并受到一定程度的地壳物质混染。构造环境分析表明安南坝镁铁质麻粒岩原岩形成于与俯冲有关的岛弧环境。在俯冲作用机制下,俯冲板片流体交代使地幔楔发生富集,形成富集地幔,随着(弧后)伸展作用的加强,进一步诱发富集地幔的部分熔融形成镁铁质岩浆,最终岩浆就位形成辉长岩或辉绿岩脉,后期在麻粒岩相变质作用条件下变质为镁铁质麻粒岩。