La、Ce掺杂ZnO纳米晶的发光特性

共沉淀法制备了稀土镧、铈掺杂的ZnO半导体纳米晶。X射线衍射(XRD)结果表明:掺杂的ZnO纳米晶为六方纤锌矿结构,随掺杂浓度增加ZnO粒径减小。对铈掺杂纳米ZnO,以波长380nm激发,在443nm处出现了半峰宽较窄的强的蓝光发射峰;镧掺杂ZnO纳米晶则为从418~610nm的多峰宽带发射。     

铜掺杂氧化锌纳米棒的非线性光学响应竞争特性

利用飞秒脉冲激光激发Cu掺杂ZnO纳米棒,研究其特有的非线性光学性质和激发机制。在激发波长为750 nm的荧光光谱中,二次谐波峰非常弱,几乎可以忽略,存在非常强的激子发光峰和Cu掺杂导致缺陷发光峰。激发强度的增大会导致这两个发光峰强度呈非线性增大,激子发光峰位产生明显红移,而缺陷发光峰位没有变化。进一步增大激发强度,缺陷发光峰强度会出现饱和甚至有所下降,而激子发光峰强度持续增大。当激发波长增加到760 nm时,从样品的荧光光谱可以清楚地识别到二次谐波峰和激子发光峰以及缺陷发光峰并存。随着激发波长的进一步增加,二次谐波强度不断增大,而激子发光峰和缺陷发光峰的强度却随之下降。当激发波长为790 nm和800 nm时,未发现激子发光峰和缺陷发光峰,非线性光谱以二次谐波为主导。研究结果表明,通过选择合适的激发波长和激发强度,可以实现发光颜色的转变,使得Cu掺杂ZnO纳米棒在全光显示方面具有潜在的发展前景。     

ZnO亚微米和微米棒的晶体生长及发光性质

用硝酸锌Zn(NO3 )2·4H2O和六亚甲基四胺 (CH2 )6N4,通过化学溶液法在玻璃衬底上生长出ZnO六角形亚微米和微米棒(长 5~6μm,直径 0. 8 ~5μm)。生长时间达两天后,ZnO棒呈中空六角形微米管。测量了样品的X射线衍射(XRD)谱,扫描电镜像和喇曼光谱。ZnO微米棒的光致发光为橙红色宽谱带发射(峰值 630nm, 半峰全宽 250nm), 其激发光谱除带间本征激发(短于 370nm)外,还有很强的在导带底附近的室温激子激发峰(峰值 387nm,半峰全宽 30nm)。而阴极射线发光有两个发射峰,橙色宽谱带强峰 (峰值580nm,半峰全宽约为140nm)是缺陷发光峰,近紫外窄谱带弱峰(峰值 395nm,半峰全宽约为 20nm)是激子发光峰。     

In掺杂的ZnO纳米棒的共振Raman光谱研究

本文报道In掺杂ZnO纳米棒的成功制备和对其结构以及光荧光性能的详尽研究。在室温条件下ZnO的共振拉曼谱线容易受到很强的荧光干扰, 甚至导致共振拉曼谱线完全被湮没。微量In掺杂入ZnO纳米棒中, 调控紫外发光峰由378 nm(纯ZnO)红移至397 nm; 另外, 在制备过程中引入过量的氧, 在样品中产生大量缺陷, 降低了ZnO的紫外近带边发光峰强度。这两方面导致在室温下可清楚的观察到In掺杂ZnO纳米棒的6阶LO拉曼峰。     

Cl-离子修饰Ce3+掺杂SiO2材料发光峰的蓝移

采用溶胶凝胶技术通过添加Ce(NO3)3制备了掺杂Ce3 离子的纳米SiO2材料,进行了不同温度的氯化处理。采用电子能谱、吸收光谱以及荧光光谱对Cl-离子修饰Ce3 掺杂SiO2材料的成分及光学性能进行分析、测试,研究Cl-离子修饰对掺杂SiO2材料中Ce3 离子光学性能的影响。测试结果表明,经过氯化处理不仅可以明显提高Ce3 离子掺杂SiO2材料的发光强度,还可以使发光和激发波长产生明显的变化,发光波长由445 nm蓝移至390 nm,激发波长由326 nm蓝移至290 nm左右。这种转化具有可逆性,将经氯化处理的样品重新在空气中处理后,发光强度减弱,发光和激发波长也恢复到氯化处理前的位置。     

Mg掺杂ZnO纳米晶的低温共沉淀法制备及光学性质

采用共沉淀(co-precipitation)法制备了Mg掺杂ZnO纳米晶,分别用X射线衍射(XRD)、傅立叶变换红外光谱(FTIR)、紫外可见吸收(UV-Vis)光谱、光致发光(PL)光谱、透射电镜(TEM)、电子顺磁共振(EPR)等分析手段对样品进行了表征。探究了Mg离子在ZnO纳米晶中的存在状态,ZnO纳米晶颗粒尺寸和发射光谱随Mg掺杂浓度的变化,并对其发光机理进行了分析。结果表明:Mg离子在ZnO晶格中以部分晶格位,部分间隙位的方式存在,没有形成MgO表面壳层结构;随Mg掺杂浓度的增大,ZnO纳米晶的颗粒尺寸变小,发射光的光强增大。发射光的最佳激发波长为342nm,中心波长为500nm,荧光量子产率为22.8%。实验分析表明:Mg离子的掺杂在ZnO纳米晶中引入了锌空位(VZn),间隙位的镁离子(IMg),提供了新的复合中心,从而增强了ZnO纳米晶的光致发光。     

紫外光激发下氧化锌纳米线的发光特性研究

室温条件下,用355 nm的激光激发氧化锌纳米线,测量了其发光光谱.观察到半宽度较小、峰值波长约382 nm的紫光峰和半宽度较宽、峰值波长约507 nm的绿光峰;两峰的发光强度随激发光功率密度的变化而变化,且均存在饱和效应,但各自的变化规律及饱和值的大小不同;紫光峰的中心波长随激发光功率密度的增加而发生了明显的红移.对两峰产生的机理、强度饱和值存在的原由、强度随激发光功率密度变化及紫光峰红移的起因进行了分析.     

气相沉积法生长不同结构ZnO纳米线及其发光

用Zn粉、Zn／In2O3／C粉作为不同锌源,通过气相沉积法在空气或N2／O2混合气氛下生长出多种形貌的ZnO纳米线（如：四脚状、多脚状、梳子状、绒棒状,以及纳米棒、纳米丝、纳米带等多种形貌）,直径约为50-1000nm,长度约为1—20μm。测量了样品的XRD谱、扫描电镜、透射电镜和选区电子衍射像,证明这些样品都是六方纤锌矿结构的ZnO单晶。四脚状样品的PL光谱显示样品存在近紫外峰（380nm）和绿峰（500nm）两个发射带,半峰全宽分别约为15,90nm,其峰值强度比其他方法（如溶液法）制得样品的峰值强。样品的尺寸对光谱强度有一定影响,但对谱峰位置并无影响。用He-Cd激光器的325nm激光对四脚状样品进行发射光谱分析,发现其近紫外激子发光大大增强而绿色缺陷发光相对较弱,近紫外的峰值位于383nm,半峰全宽约为16nm;绿峰峰值位于515nm,半峰全宽约为76nm。     

Sn掺杂ZnO纳米晶的水热法制备及光学性能

以ZnCl2和NaOH为原料,用SnCl4·4H2O作掺杂剂,通过水热法合成了Sn掺杂ZnO纳米颗粒。利用X射线衍射(XRD)、场发射扫描电镜(FE-SEM)、紫外-可见吸收光谱(UV-Vis)及光致发光(PL)光谱等测试技术对样品的物相、形貌及光学性能进行了表征。结果表明:制得的Sn掺杂ZnO纳米粒子具有六角纤锌矿结构。随着锡掺杂浓度的增大,纳米晶的平均粒度增加,晶体形貌由短棒状向单锥和双锥状转变;提高前驱液的pH值,所得样品的形貌由长柱状向短柱状转变。室温下,观测到三个光致发光带,一个峰值在433nm处的强紫光发射峰,一个约在401nm处的近紫外发光峰及一个在466nm处的弱蓝光发光峰。在实验掺杂浓度范围内,Sn的掺杂只是改变纳米ZnO的发光强度,对发光峰位置影响不大。     

稀土Tb3+掺杂纳米ZnO的发光性质

ZnO是一种优良的直接宽带隙半导体发光材料(Eg=3.4 eV),具有优异的晶格、光学和电学性质,稀土离子掺杂浓度和热处理温度对ZnO∶Re3 纳米晶发光强度、峰位变化等光学性质具有重要影响.利用溶胶-凝胶法(Sol-Gel),在不同退火温度下,制备了不同浓度的ZnO∶Tb3 纳米晶.室温下,测量了样品的X射线衍射谱(XRD)、光致发光谱(PL)和激发谱(PLE).观察到纳米ZnO基质在520 nm附近宽的绿光可见发射和稀土Tb3 在485,544,584和620 nm附近的特征发射.通过ZnO基质可见发射强度和稀土Tb3 特征发射强度随Tb3 掺杂浓度、退火温度的变化关系,获得了5D4→7F5跃迁的绿色主发射峰最强的样品制备工艺参数,其退火温度为600℃、掺杂浓度为4 at%;给出了稀土Tb3 的激发态5D4→7F6(485 nm),5D4→7F5(544 nm)和5D4→7F4(584 nm)的发射机制;证实了稀土Tb3 与纳米ZnO基质之间存在双向能量传递.     

钨酸锌晶体的受激拉曼散射和光致发光研究

采用皮秒532nm 激光激发，研究了ZnWO₄晶体的受激拉曼散射和本征荧光发射.在SRS光谱中观察到一级(558.7nm)和二级(588.6nm)斯托克斯光，线宽分别为130和77cm^－1, 一级斯托克斯光的抽运阈值为6.8mJ.在532nm激光抽运下ZnWO₄晶体的荧光光谱呈现出由能量为2.30，2.45和2.83eV的3个高斯分量组成的独特结构.光致发光表明晶体具有从400nm到650nm的宽带本征发光，其峰值波长为472.0nm，相应于钨氧之间的辐射跃迁. 关键词： 晶体 钨酸锌 受激拉曼散射 闪烁体     

水溶性CdTe量子点的稳态和纳秒时间分辨光致发光光谱

报道了以飞秒脉冲激光为激发光源的水溶性CdTe量子点(QDs)的稳态荧光光谱和纳秒时间分辨荧光光谱.实验发现CdTe量子点的荧光光谱峰值位置随激发波长变化发生明显移动，激发脉冲波长越长，荧光峰位红移越大.荧光动力学实验数据显示，在400nm和800nm脉冲激光激发下，水溶性CdTe量子点的荧光光谱中均含有激子态和诱捕态两个衰减成分，两者的发射峰相距很近，诱捕态的发射峰波长较长.在800nm脉冲激光激发下的诱捕态成分占总荧光强度的比重比400nm激发下的约高3倍，其相对强度的这种变化导致了稳态荧光发射峰位的红移. 关键词： CdTe 量子点 时间分辨 荧光光谱 上转换荧光     

Photochemical Characterization of Up-Converting Inorganic Lanthanide Phosphors as Potential Labels

We have characterized commercially available up-converting inorganic lanthanide phosphors for their rare earth composition and photoluminescence properties under infrared laser diode excitation. These up-converting phosphors, in contrast to proprietary materials reported earlier, are readily available to be utilized as particulate reporters in various ligand binding assays after grinding to submicron particle size. The laser power density required at 980 nm to generate anti-Stokes photoluminescence from these particulate reporters is significantly lower than required for two-photon excitation. The narrow photoluminescence emission bands at 520–550 nm and at 650–670 nm are at shorter wavelengths and thus totally discriminated from autofluorescence and scattered excitation light even without temporal resolution. Transparent solution of colloidal bead-milled up-converting phosphor nanoparticles provides intense green emission visible to the human eye under illumination by an infrared laser pointer. In this article, we show that the unique photoluminescence properties of the up-converting phosphors and the inexpensive measurement configuration, which is adequate for their sensitive detection, render the up-conversion an attractive alternative to the ultraviolet-excited time-resolved fluorescence of down-converting lanthanide compounds widely employed in biomedical research and diagnostics.     

Strong violet luminescence from ZnO nanocrystals grown by the low-temperature chemical solution deposition

The luminescence properties of zinc oxide (ZnO) nanocrystals grown from solution are reported. The ZnO nanocrystals were characterized by scanning electron microscopy, X-ray diffraction, cathodo- and photoluminescence (PL) spectroscopy. The ZnO nanocrystals have the same regular cone form with the average sizes of 100-500 nm. Apart from the near-band-edge emission around 381 nm and a weak yellow-orange band around 560-580 nm at 300 K, the PL spectra of the as-prepared ZnO nanocrystals under high-power laser excitation also showed a strong defect-induced violet emission peak in the range of 400 nm. The violet band intensity exhibits superlinear excitation power dependence while the UV emission intensity is saturated at high excitation laser power. With temperature raising the violet peak redshifts and its intensity increases displaying unconventional negative thermal quenching behavior, whereas intensity of the UV and yellow-orange bands decreases. The origin of the observed emission bands is discussed.     

一维氧化锌柱阵列空间取向激发的荧光光谱研究

用两步气相沉积-氧化法制备了具有高度一致指向性的一维纤锌矿六方结构的氧化锌单晶柱阵列,探测它的不同空间取向激发条件下的荧光光谱。结果表明,一维阵列样品在不同空间取向的激发光照射下,其荧光光谱有明显变化。当低功率355 nm激光对一维方向进行横向激发时,激子发光的相对强度较大;当用1 064 nm 激光取向激发时,发射光谱的差异更明显。除了荧光光谱的发射峰强弱发生变化外,在一维横向激发时上转换发射光谱产生了新的发射峰,表明在不同的取向激发下一维阵列样品对激发光的吸收有明显变化。由此产生的荧光发射的差异非常明显,表明一维氧化锌柱阵列对能量吸收、能量传递等有很强的方向性。上转换偏振光谱表明,当偏振光的振动方向与阵列的一维方向平行时,发射光谱中400 nm的发光峰强度比偏振方向与一维方向垂直时要大,表明偏振方向对一维阵列的空间取向激发荧光光谱是有影响的。在讨论阵列发光性质如发光光谱,发射强度的时候,必须明确激发光的强度、取向以及激发光的偏振方向。     

低能量光子激发下纳米ZnO的超快时间分辨光谱特性

室温下获得了均匀沉积法制备的纳米ZnO颗粒在低能量2.33 eV光子(532 mm)的准连续皮秒脉冲激发下的频谱范围从550～1 000 mm的时间分辨光谱和时间积分光谱.随着样品粒径的增加,发光带谱带峰值出现规律性的红移.通过高斯拟合对光谱结构解迭发现,这种规律性的红移是由于低能端区域的高斯组分的相对比例增加所致.时间分辨光谱中超快发射的荧光衰减寿命(皮秒量级)也出现随着样品粒径的增大而相应变长.源于材料尺寸、纳米颗粒大的比表面积所引起的表面能级可以较好的解释此范围的超快发射特性.     

制备水溶性CdS量子点的一种物理方法：飞秒激光烧蚀法

用Ti/sapphire飞秒激光系统产生的100fs、800nm激光对置于水中的CdS体相材料进行烧蚀,得到了水溶性CdS纳米粒子。这种纯物理过程保证了无污染的制备环境,从而保证了所合成材料的纯洁性。通过透射电子显微镜、紫外/可见/近红外吸收光谱、室温光致发光谱的方法对CdS量子点的形貌及其光学性质进行了表征。结果表明:利用飞秒激光烧蚀法所制备的CdS量子点可直接分散在水中而且具有粒径小、分布均匀的特点;同时具有较好的胶体稳定性,可在空气中稳定存放6个月以上。飞秒激光烧蚀法所制备的CdS量子点所具有的这些性质使其在生物标记领域引起极大的兴趣,而且也为纳米材料的制备提供了新的思路。     

Photoluminescence Response from the Chromian Clinochlore (Kammererite)

The three-dimensional photoluminescence emissions between 450 and 800 nm of kammererite from Turkey were obtained at the temperatures between 230 and 350 K under 366 nm excitation. The most advantage of three-dimensional photoluminescence is to demonstrate clearly all vibronic structures through temperature increasing on the spectra. Hence, photoluminescence response from the unique gem material was discussed in relation to chemical impurities. In the photoluminescence spectra, two strong and three weaker emission bands became clear at the lower temperature conditions. First strong green band with the highest emission peak at 545 nm, and second strong yellowish-orange band with the highest emission peak at 610 nm were observed at 230 K. The half-width of the main bands is approximately 10–12 nm and such band's combination is typical for trivalent rare-earth elements. These two strong emission bands are due to europium and gadolinium ions, respectively. In addition, the weaker emission bands at 485, 585, and 615 nm were detected at mainly 230 K. The bands peaked at 485 was attributed to lanthanum, lutetium, promethium, scandium, and yttrium centers, and 585 nm was attributed to dysprosium center. Since, the abundances of these rare-earth elements produced relatively strong luminescence bands in the spectra. Finally, the weakest band peaked at 615 nm was attributed to neodymium. As a result, the intensities of these bands gradually decreased forming a sequence until the temperature of 280 K. The lanthanum is the main responsible ion that extinguishes the photoluminescence at the relatively higher temperature conditions in the minerals. Therefore, the photoluminescence of kammererite exists at low temperatures only, because of mainly high lanthanum (90 ppm) abundance.     

CaLuBO4∶Tb^3+荧光粉的制备及发光性质

采用高温固相反应法合成了不同Tb^3+掺杂浓度的CaLuBO4∶xTb^3+荧光粉,研究了样品的晶体结构和发光性质。在紫外光激发下,样品的发射光谱由Tb3+离子的5D3→7FJ(J=6,5,4)和5D4→7FJ′(J′=6,5,4,3)特征发射组成,其中位于545 nm和554 nm附近的5D4→7F5跃迁发射强度最大。荧光粉的激发光谱是由位于紫外区的Tb3+的4f-5d和f-f跃迁构成的。研究了Tb3+浓度对样品发光性质的影响。测量并分析了CaLuBO4∶xTb^3+荧光粉的5D3能级和5D4能级荧光寿命。结果表明,CaLuBO4∶xTb^3+是一种适于紫外激发的新型黄绿光荧光粉。     

Three-photon-induced fluorescence of diphenylhexatriene in solvents and lipid bilayers

We observed the emission of l,6-diphenyl-l,3,5-hexatriene (DPH) when excited with the fundamental output of a fs Ti:sapphire laser at 860 nm. The emission spectra of DPH were identical to that observed for one-photon excitation at 287 nm. The dependence of the DPH emission intensity on laser power was cubic, indicating three-photon excitation of DPH at 860 nm. At a shorter wavelength of 810 nm, the dependence on laser power was quadratic, indicating a two-photon process. At an intermediate wavelength of 830 nm the mode of excitation was a mixture of two- and three-photon excitation. At 830 nm the anisotropy is no longer a molecular parameter, and the mode of excitation and anisotropy of DPH depends on laser power. Frequency-domain anisotropy decays of DPH in triacetin revealed the same rotational correlation times for two- and three-photon excitation. However, the time 0 anisotropy of DPH was larger for three-photon excitation than for two-photon excitation. Steady-state anisotropy data for DPH-labeled membranes revealed the same transition temperature for one- and three-photon excitation. These anisotropy data indicate that membrane heating was not significant with three-photon excitation and that three-photon excitation may thus be of practical usefulness in fluorescence spectroscopy and microscopy of membranes.