Gd~(3+),Tm~(3+)和Yb~(3+)掺杂的Y_2O_3微晶中Gd~(3+)离子的紫外上转换发光及其增强的研究

采用均相沉淀法制备了Y(OH)3微米颗粒,经1 100℃焙烧后制备出具有上转换发光性质的Yb3+-Tm3+-Gd3+共掺的Y2O3微米晶体,讨论了Yb3+-Tm3+-Gd3+在Y2O3中能量传递过程及壳层对发光强度的影响。980 nm近红外光激发下的上转换光谱表明,在Yb3+-Tm3+-Gd3+共掺Y2O3体系中,核-壳结构大幅提高了Gd3+离子和Tm3+离子的上转换发光强度,尤其是样品在紫外发光部分的增强相比于可见和红外光部分更为明显。同时,通过研究Tm3+和Gd3+在不同波段的发光强度与泵浦功率的关系探讨了氧化物中上转换发光的机制。     

纳米Gd2O3:Eu3+中Judd-Ofelt参数的实验确定

报道用Judd-Ofelt理论研究立方相纳米晶Gd2O3:Eu3+材料在77K下的光谱性质.以几乎不受周围晶场环境影响的5D0→7F1跃迁为参考，利用5D0→7F2和5D0→7F4跃迁，从实验上确定强度参数Ωλ(λ＝2，4).发现纳米Gd2O3:Eu3+材料晶场强度参数Ωλ随纳米晶粒径的变化而改变,与体材料相比有显著的不同.随微晶粒径减小，发射能级5D0的寿命变短、量子效率降低.这是因为微晶粒径越小，量子限域效应越强，表体比越大，在无序体调制的表面上表面缺陷作用增强而引起的.对电荷(Eu3+-O2-)迁移态和多声子过程另外两种无辐射通道也进行讨论. 关键词： 纳米Gd2O3:Eu3+ 强度参数 辐射与无辐射弛豫 量子效率     

Small size TiO2 nanoparticles prepared by laser ablation in water

Titanium dioxide nanoparticles in distilled H₂O solvent were prepared by laser ablation. The experiments were performed irradiating a Ti target with a second harmonic (532 nm) output of a Nd:YAG laser varying the operative fluence between 1 and 10 J cm⁻² and for an ablation time ranging from 10 to 30 min. Electron microscopy measurements have evidenced the predominant presence of nanoparticles with diameter smaller than 10 nm together with agglomerations of 100-200 nm whose content increases with the laser fluence. At low laser fluence the particles’ size distribution shows that more than 85% of the nanoparticles have a size smaller than 5 nm while at mid and high fluences the presence of 5-7 nm nanoparticles is predominant. XPS analysis has revealed the presence of different titanium suboxide phases with the prevalence of Ti-O bonds from TiO₂ species. The optical bandgap values, determined by UV-vis absorption measurements, are compatible with the anatase phase.     

Er3+/Yb3+共掺Gd3Sc2Ga3O12晶体的上转换发光

研究了提拉法生长的Er3+/Yb3+:Gd3Sc2Ga3O12和Er3+:Gd3Sc2Ga3O12晶体在室温下320-1700 nm范围的吸收光谱和500-750 nm范围内的上转换荧光谱,同时对其上转换荧光的可能发生机制、途径以及上转换过程可能对Er3+的2.8 μm波段激光振荡产生的影响进行了分析和讨论.结果表明:Yb3+的敏化显著地增强了晶体在966 nm附近的吸收能力,大幅度加宽了晶体在该处的吸收带宽.在940 nm激光的激发下,Er3+/Yb3+:Gd3Sc2Ga3O12中的上转换荧光强度明显强于Er3+:Gd3Sc2Ga3O12中的上转换荧光强度,表明Yb3+与Er3+之间存在高效率的能量传递,其主要上转换机制可能为Yb3+-Er3+,Er3+-Er3+能量传递.     

绿色荧光粉Gd2Ba3B3O12:Tb3+的发光性能研究

采用高温同相法制备了一系列Gd<,2>Ba<,3>B<,3>O<,12>:Tb<'3+>绿色荧光粉,借助X射线粉末衍射仪(XRD)、真空紫外光谱和荧光光谱仪(VUV-UV)对样品的物相、发光性能进行了表征.结果表明,Tb<'3+>作为发光中心全部进入到基质Gd<,2>Ba<,3>B<,3>O<,12>的品格中并占据Gd...     

Er~(3+)及Er~(3+)/Yb~(3+)掺杂ZrO_2-Al_2O_3的制备及发光性质

采用共沉淀法制备了纳米晶ZrO2-Al2O3∶Er3+发光粉体.所制备的粉体室温下具有Er3+离子特征荧光发射,主发射在绿光,其中位于547nm、560nm的绿光最强,并得出稀土离子与基质之间有能量传递.对不同煅烧温度下的样品研究表明:因不同温度下所制得的样品晶相不同.研究了纳米晶ZrO2-Al2O3∶Er3+及ZrO2-Al2O3∶Er3+/Yb3+的上转换发光,并分析了上转换的跃迁机制.发现ZrO2-Al2O3∶Er3+的绿光为双光子过程,而ZrO2-Al2O3∶Er3+、Yb3+的上转换光谱中,红光和绿光也为双光子过程,而极弱的蓝光为三光子过程.讨论了Er3+的浓度猝灭现象.最适宜掺杂浓度的原子分数为2%(Er3+/Zr4+).     

Ce~(3+)掺杂Gd_2O_3基闪烁玻璃的研究

实验用高温熔融法制备了Ce3+掺杂Gd2O3基闪烁玻璃样品,Gd2O3含量高达40mol%,测试了不同Ce3+掺杂浓度与Gd2O3基含量玻璃样品的密度、透过、发射、激发光谱及部分闪烁性能。研究了不同Ce3+掺杂浓度与Gd2O3基含量对玻璃样品密度及光谱性能的影响规律。结果表明:Gd2O3含量的增加不仅提高了玻璃的密度,有利于提高玻璃的辐射性能,还增大了玻璃的光碱度,增大Stokes位移,有利于提高闪烁光的发光效率;Ce3+浓度的提高增大了Ce3+间碰撞的几率,产生能量损失,表现出浓度淬灭效应。在Gd2O3基闪烁玻璃中,随Gd2O3含量增加激发峰的红移较小,高Gd2O3含量的氧化物玻璃中存在Gd3+→Ce3+能量转移机制,Gd3+离子可有效地向Ce3+离子传递能量,敏化Ce3+离子的发光。玻璃样品的衰减时间在17-37ns之间。Ce3+掺杂Gd2O3基闪烁玻璃有望在高能物理等领域中获得应用。     

Er3+单掺及Er3+/Yb3+共掺SiO2-Al2O3-La2O3玻璃光谱性质研究

研究了单掺Er³⁺及Er³⁺/Yb³⁺共掺SiO₂-Al₂O₃-La₂O₃玻璃的光谱性质随稀土离子浓度变化规律,应用McCumber理论计算了玻璃在1.53 μm的发射截面及积分吸收截面.结果表明:在Er³⁺离子掺杂浓度相同时,玻璃在980 nm吸收截面与Yb³⁺掺杂浓度成反比;当样品中Yb³⁺离子掺杂浓度为3.94×10²⁰ cm^-3时,玻璃在1.53 μm的吸收截面和发射截面最大,在1.40～1.60 μm积分吸收截面也最大;Er³⁺/Yb³⁺共掺SiO₂-Al₂O₃-La₂O₃玻璃在1.53 μm的荧光半高宽随Er³⁺掺杂浓度升高而增加,当Er³⁺离子掺杂浓度为2.41×10²⁰ cm^-3时,玻璃的荧光半高宽(FWHM)达到52.5 nm.     

Silver nanoparticles generated by pulsed laser ablation in supercritical CO2 medium

Pulsed laser ablation (PLA) has been widely employed in industrial and biological applications and in other fields. The environmental conditions in which PLA is conducted are important parameters that affect both the solid particle cloud and the deposition produced by the plume. In this work, the generation of nanoparticles (NPs) has been developed by performing PLA of silver (Ag) plates in a supercritical CO₂ medium. Ag NPs were successfully generated by allowing the selective generation of clusters. Laser ablation was performed with an excitation wavelength of 532 nm under various pressures and temperatures of CO₂ medium. On the basis of the experimental result, both surface of the irradiated Ag plate and structure of Ag NPs were significantly affected by the changes in supercritical CO₂ pressure and temperature. With increasing irradiation pressure, plume deposited in the surrounding crater created by the ablation was clearly observed. In Field Emission Scanning Electron Microscopy (FE-SEM) the image of the generated Ag NPs on the silicon wafer and the morphology of Ag particles were basically a sphere-like structure. Ag particles contain NPs with large-varied diameter ranging from 5 nm to 1.2 μm. The bigger Ag NPs melted during the ablation process and then ejected smaller spherical Ag NPs, which formed nanoclusters attached on the molten Ag NPs. The smaller Ag NPs were also formed around the bigger Ag NPs. Based on the results, this new method can also be used to obtain advanced nano-structured materials.     

前驱溶液的PH值对Y2O3: Eu3＋荧光粉发光性质的影响

以甘氨酸为燃料,采用溶液燃烧法制备了Y2O3:Eu3 (3%)纳米粉末,并研究了制备过程中前驱溶液的pH值对Y2O3:Eu3 发光性质的影响.从XRD和SEM分析得到,随着溶液pH值的增大,样品颗粒逐渐变大,并且多孔粉末变得越来越致密.通过对样品发光性质的测量得到,随着pH值的增大,样品发光逐渐增强,但寿命逐渐变短.激发谱显示,基质吸收和电荷迁移带的相对强度比随着pH值的增大逐渐减小.     

Er^3＋：Y2O3透明陶瓷制备及发光性质研究

以Y2O3为基质材料,掺杂不同含量的Er3 ,采用共沉淀法制备出性能良好的Er3 :Y2O3纳米粉,并将粉体在1 700℃和真空度为1×10-3Pa下烧结8 h得到Er3 :Y2O3透明陶瓷.用X射线衍射仪(D/MAX-RB)、透射电子显微镜(EM420)、自动记录分光光度计(DMR-22)、荧光分析仪(F-4500)和发射波长为980 nm的半导体激光器分别对样品的结构、形貌和发光性能进行了研究.结果表明:Er3 完全固溶于Y2O3的立方晶格中,Er3 :Y2O3粉体大小均匀,近似球形,尺寸约40～60 nm左右.Er3 :Y2O3透明陶瓷相对密度为99.8%,在长波长范围内其透光率超过60%,在波长为980 nm的激光下有两个上转换发光带,其中绿色发光中心波长位于562 nm,红色发光中心波长位于660 nm,分别对应4S3/2/2H11/2→4I15/2和4F9/2→4I15/2的跃迁;随着铒浓度的提高颜色从绿色向红色转变,Er3 的掺杂浓度不宜超过2%,超过这个范围,对材料发光强度的增强作用反而很小.     

Synthesis and characterization of TiOx nanoparticles prepared by pulsed-laser ablation of Ti target in water

Nanoparticles (NPs) creation by pulsed-laser ablation of targets in a liquid environment has recently become a promising technique, which has several relative advantages, such as simplicity and low cost. This technique was employed in the present work for preparation of TiO_x NPs suspension by ablation of metal Ti targets into twice-distilled water. A second harmonic generation (SHG) pulsed Nd:YAG laser was used in the experiments. Preferential formation of spherical NPs and their TiO_x nature was established. Aggregation of the created particles during aging was found. Transition of the NPs’ structure from amorphous to crystalline with increasing the laser energy was revealed. A difference was observed in the transmittance of the suspensions obtained depending on the laser intensity.     

火焰原子吸收光谱法测定含钆二氧化铀芯块中微量铯

本文报道了用火焰原子吸收光谱法测定含钆二氧化铀芯块中微量铯的方法。试样经硝酸、氢氟酸分解，其体铀用聚偏氟乙烯－磷酸三丁酯（（TBP）色层术上萃取而分离除去，在氯化钾存在下的1.6mol/L硝酸介质和60％甲基异丙基丁酮－甲醇混合溶剂中，在空气－乙炔火焰下测其铯的原子吸收强度，而得出铯的含量。方法简便、快速、灵敏。测定范围0.2-1.6μg/mL，回收率为96％－102％，精密度优于±10％。     

磁控溅射制备Er~(3+)/Yb~(3+)共掺杂TiO_2薄膜的上转换发光特性

采用射频磁控溅射法制备得到Er~(3+)/Yb~(3+)TiO_2薄膜,980 nm的抽运源作用下上转换可以得到490 nm的绿光和670 nm的红光,上转换红、绿光发光强度受到烧绿石Er_xYb_(2-x)Ti_2O_7晶体的生成以及Er~(3+)/Yb~(3+)掺杂浓度的影响,实验表明,适量共掺杂Er~(3+)/Yb~(3+)可明显增强上转换发光,Er~(3+)在上转换发光中起主要作用,而引入敏化离子Yb~(3+)可以大大提高上转换发光效率,磁控溅射法制备的TiO_2薄膜声子态密度较小,从而抑制了无辐射跃迁过程,导致490nm绿光形成以及红光强度大于绿光强度。     

The effect of liquid environment on size and aggregation of gold nanoparticles prepared by pulsed laser ablation

The effects of liquid environment on nucleation, growth and aggregation of gold nanoparticles were studied. Gold nanoparticles were prepared by pulsed laser ablation in deionised water with various concentrations of ethanol and also in pure ethanol. UV/visible extinction and TEM observations were employed for characterization of optical properties and particle sizes respectively. Preparation in water results in smaller size, shorter wavelength of maximum extinction and stable solution with an average size of 6 nm. Nanoparticles in solution with low concentration ethanol up to 20 vol% are very similar to those prepared in water. In the mixture of deionised water and 40 up to 80 vol% ethanol, wavelength of maximum extinction shows a red shift and mean size of nanoparticles was increased to 8.2 nm. Meanwhile, in this case, nanoparticles cross-linked each other and formed string type structures. In ethanol, TEM experiments show a mean size of 18 nm and strong aggregation of nanoparticles. The data were discussed qualitatively by considering effects of polarity of surrounding molecules on growth mechanism and aggregation. This study provided a technique to control size, cross-linking and aggregation of gold nanoparticles via changing the nature of liquid carrier medium.     

白光LED用红色荧光粉Gd2Mo3O9：Eu3+的制备及表征

利用Na₂CO₃作为助熔剂,采用高温固相反应方法制备了三价铕离子激活的Gd₂Mo₃O₉红色荧光粉。利用XRD和荧光光谱,研究了助熔剂的量、制备时的温度以及激活剂Eu³⁺的浓度对荧光粉的晶体结构和发光性能的影响。测试结果表明,这种新型的荧光粉可以被紫外光280nm,近紫外光395nm和蓝光465nm有效激发,发射主峰位于613nm,并且证明Eu³⁺离子在晶体结构中占据了非反演对称中心的位置。395,465nm的吸收与目前广泛应用的紫外和蓝光LED芯片的输出波长相匹配。因此,这种荧光粉是一种可能应用在白光LED上的红色荧光粉材料。     

980 nm激发下Er3+/Yb3+共掺杂ZrO2-Al2O3粉末的上转换发光特性

通过固相反应法制备了Er3+/Yb3+共掺杂ZrO2-Al2O3粉末的样品,并对样品在980nm激光激发下的上转换发光特性进行了研究.从发射光谱可以发现,在可见光范围内有3个强的发光带,一个位于654nm附近的红光带和两个分别位于545nm、525nm附近的绿光带,分别对应于Er3+离子的以下辐射跃迁:4F9/2→4I15/2、4S3/2→4I15/2、2H11/2→4I15/2.其中又以Er3+离子的4F9/2→4I15/2跃迁产生的红色荧光辐射最强.对其上转换发光机制进行了分析,发现这三个发光过程都是双光子过程.对样品粉末进行了XRD检测,发现ZrO2主要以立方相为主,并且计算得到了这种立方结构的晶格常数.Al2O3固溶于ZrO2中,Al3+嵌入ZrO2后产生氧空位,导致ZrO2晶体的对称性降低,这种结构变化更有利于提高上转换效率,即上转换发光强度增强.     

液相激光烧蚀合成ZnO及Zn/ZnO纳米颗粒及其光致发光性能

利用532 nm脉冲激光对沉浸在去离子水及十二烷基硫酸钠(SDS)水溶液中的金属锌靶进行液相激光烧蚀,合成了ZnO纳米颗粒和Zn/ZnO核壳结构的纳米粒子. 应用X射线衍射仪,透射电子显微镜,紫外可见光分光光度计和荧光光度计表征产物的微观结构和光学性能,并探讨其形成机理. 结果表明:在去离子水中分别烧蚀2 h和4 h生成的ZnO纳米粒子的平均粒径分别为43 nm和19 nm. 激光的长时间作用可以使纳米粒子粒径减小. 在0.005 mol/L的SDS水溶液中合成了Zn/ZnO核壳结构的纳米粒子,这是由于S 关键词： 脉冲激光烧蚀 ZnO纳米粒子 核壳结构 光致发光     

Pulsed laser ablation in liquid of sp-carbon chains: Status and recent advances

This review provides a discussion of the current state of research on sp-carbon chains synthesized by pulsed laser ablation in liquid. In recent years, pulsed laser ablation in liquid (PLAL) has been widely employed for polyynes synthesis thanks to its flexibility with varying laser parameters, solvents, and targets. This allows the control of sp-carbon chains properties as yield, length, termination and stability. Although many reviews related to PLAL have been published, a comprehensive work reporting the current status and advances related to the synthesis of sp-carbon chains by PLAL is still missing. Here we first review the principle of PLAL and the mechanisms of formation of sp-carbon chains. Then we discuss the role of laser fluence (i.e. energy density), solvent, and target for sp-carbon chains synthesis. Lastly, we report the progress related to the prolonged stability of sp-carbon chains by PLAL encapsulated in polymeric matrices. This review will be a helpful guide for researchers interested in synthesizing sp-carbon chains by PLAL.     

热分解法制备MnFe2O4纳米粒子及其超顺磁性

采用热分解法制备了单相的锰铁氧纳米颗粒,X射线衍射以及透射电镜测量显示其颗粒大小约为20 nm.磁滞回线测量显示室温超顺磁性.零场和非零场磁测量显示制备的MnFe2O4纳米粒子平均截止温度为84.3 K,样品中最大颗粒的截止温度为230 K,且平均截止温度与外场H2/3存在线性关系.