低强度飞秒激光激发下CdTe和CdTe/CdS核壳量子点的荧光上转换研究

利用400 nm和800 nm不同波长的低强度飞秒激光,对CdTe和CdTe/CdS核壳量子点溶胶进行激发,研究其稳态和时间分辨荧光性质.800 nm飞秒激光激发下,CdTe和CdTe/CdS核壳量子点产生上转换发光现象,上转换荧光峰与400 nm激发下的荧光峰相比蓝移最多达15 nm,而且蓝移值与荧光量子产率有关.变功率激发确认激发光功率与上转换荧光强度间满足二次方关系,时间分辨荧光的研究表明荧光动力学曲线服从双e指数衰减.提出表面态辅助的双光子吸收模型是低激发强度上转换发光的主要机理.CdTe和CdT 关键词： CdTe量子点 CdTe/CdS核壳量子点 时间分辨荧光 上转换荧光     

CdTe量子点的超快过程研究

使用pumpprobe技术研究了CdTe量子点的瞬态吸收光谱,通过双指数拟合,得到两个弛豫过程,将得到快过程归结为表面俘获载流子跟价带底空穴的直接复合,即表面态辐射过程;慢过程被归结为电子被深表面态俘获,然后以发射荧光或无辐射跃迁的形式与空穴进行复合,即深表面俘获态辐射过程. 并细致的研究了量子点的尺寸对单纯核的弛豫过程的影响.     

CdSe/CdS/ZnS 量子点体系中的超快载流子动力学

利用飞秒泵浦探测技术对CdSe/CdS/ZnS量子点体系中的超快载流子动力学过程进行了研究. 通过选择不同波长的泵浦光分别激发样品壳层和核层,研究了载流子在壳层和核层中的超快动力学过程. 实验结果表明,载流子在CdS壳层导带中弛豫过程非常迅速(约130 fs),时间明显短于载流子在CdSe核层导带中的弛豫时间(约400 fs). 实验中也发现在CdS壳层和CdSe核层的分界面存在一定量的缺陷态.     

水溶性CdTe/CdS纳米晶表面SiO2壳层的反相胶束法包覆

"提出了一种水相中制备CdTe/CdS核壳结构纳米粒子的方法.用Te粉作为碲源,用Na2S作为硫源,在50 ℃下制备了CdTe/CdS核壳结构纳米粒子. 用紫外可见吸收光谱和荧光光谱分析了CdS壳层对CdTe核的影响. 随CdS壳层厚度的增加,紫外可见吸收光谱和荧光光谱均发生了红移. CdS壳层厚度较薄时,CdTe/CdS纳米晶的荧光强度较CdTe纳米粒子有显著提高;而CdS壳层厚度较厚时,CdTe/CdS纳米晶的荧光强度会逐渐降低. 用反相胶束法在CdTe/CdS核壳结构纳米粒子的表面包被一层SiO2,     

CdTe量子点的室温激子自旋弛豫动力学

利用交叉偏振三阶非线性瞬态光栅技术,研究了室温下CdTe胶体量子点激子自旋弛豫动力学的尺寸效应.在抽运-探测光子能量与CdTe量子点的最低激子吸收(1Se—1Sh)跃迁相共振时,量子点激子自旋弛豫显示了时间常数为0.1—0.5 ps的单指数衰减行为.CdTe量子点激子自旋的快速弛豫源于亮暗激子精细结构态跃迁,即J=±1←→■2跃迁.激子自旋弛豫主要由空穴的自旋翻转过程决定.研究结果表明:CdTe量子点激子自旋弛豫速率与量子点尺寸的4次方成反比.     

CdTe,核 壳型CdTe/CdS及CdTe/ZnS量子点的合成及表征

在水相中制备了半导体CdTe纳米晶,核 壳型CdTe/CdS和CdTe/ZnS纳米晶（即量子点;QDs）.利用扫描隧道显微镜（STM）和荧光光谱(FS)对合成的纳米晶量子点进行了研究,并且根据FS的数据进行了量子效率的计算.STM的结果表明合成的量子点直径约为3 nm并且分布良好.为了提高量子效率,对Cd2+浓度和Cd2+∶S2－比例等反应条件进行了研究,结果表明随着回流时间的增加,核 壳型量子点CdTe/CdS的量子效率总体上呈下降趋势.CdTe/CdS在pH8.5,Cd2+∶S2－=10∶1（摩尔比）时可获得80.0%的最大量子效率.同时制备了核 壳型量子点CdTe/ZnS,其最大发射波长由551 nm（CdTe）红移到635 nm（CdTe/ZnS）表明量子点的尺寸在增长,但是量子效率下降到14.4%. 当前研究的量子点可适用于生物标记,生物成像,以及基于共振能量转移的生物传感研究.     

ZnSe:Cu/CdS核壳量子点的合成及光学性能研究

以CdS为壳层材料对核水溶性ZnSe:Cu量子点进行包覆,得到ZnSe:Cu/CdS核壳结构的量子点。研究了壳层厚度对ZnSe:Cu量子点光学性能的影响,采用TEM、XRD、PL和UV-Vis手段对所得样品进行表征。实验结果表明:量子点为立方闪锌矿结构,分散性好,形状为球形,经壳层修饰后量子点的粒径由2.7 nm增大到4.0 nm。随着包覆CdS壳层数的增加,量子点的发射和紫外吸收谱红移,说明量子点在长大,证明CdS壳层生长在ZnSe:Cu量子点的表面,形成了核壳结构的ZnSe:Cu/CdS量子点。包覆CdS壳层后ZnSe:Cu量子点的发光强度减弱,但稳定性得到了提高。     

圆柱状量子点量子导线复合系统的激子能量和电子概率分布

建立了圆柱状量子点量子导线复合系统中激子满足的方程，用微扰论求出激子能量.以CdS/HgS/CdS/HgS/CdS圆柱状量子点量子导线复合系统为例，研究了系统中电子的概率分布和系统线度对激子能量的影响.结果表明：系统中电子、空穴以及激子的能量均随量子点高度h₀的增大而减小，电子-空穴相互作用对基态激子能量的影响要大于激发态；电子沿径向方向的概率分布呈起伏状，在轴线和表面附近的概率趋于零，而在R/2附近概率最大；在量子点附近电子沿轴向方向的概率分布呈振荡特征 关键词： 量子点 量子导线 激子 能量     

空穴传输材料对CdSe核壳量子点的荧光影响

用稳态光谱和时间分辨光谱技术研究了空穴传输材料对CdSe/ZnSe 与CdSe/ZnS核壳量子点的荧光影响。结果表明,空穴传输材料对量子点有较强的猝灭作用,随空穴传输材料分子浓度的增加,量子点的荧光强度明显地被猝灭,同时量子点的荧光寿命也被减短。两种不同空穴传输分子对CdSe/ZnSe量子点的荧光猝灭明显不同。在与相同空穴传输分子相互作用时,包覆ZnS壳层的CdSe核壳量子点荧光猝灭效率明显低于包覆ZnSe壳层的CdSe核壳量子点。量子点的荧光猝灭过程可以解释为静态猝灭和动态猝灭过程,其中静态猝灭来源于量子点表面与空穴传输材料间相互作用,而动态猝灭则主要来源于量子点到空穴传输材料的空穴转移过程。实验结果表明空穴传输材料的种类以及核壳量子点的壳层结构都对其荧光猝灭效应起关键作用。     

ZnS/CdS复合窗口层对CdTe太阳能电池短波光谱响应的影响

采用磁控溅射法制备了ZnS/CdS复合窗口层,并将其应用于CdTe太阳能电池。对所制备薄膜的形貌和结构等进行了研究。测试了具有不同窗口层的CdTe太阳电池的量子效率和光Ⅰ-Ⅴ特性,分析了ZnS薄膜制备条件对CdTe电池器件性能影响;研究了CdS薄膜厚度和ZnS/CdS复合窗口层对短波区透过率以及CdTe太阳电池的光谱响应的影响。着重研究了具有ZnS/CdS复合窗口层的CdTe太阳电池的短波光谱响应。结果表明,CdS窗口层厚度从100 nm减至50 nm后,其对短波区光子透过率平均提高了18.3%,CdTe太阳电池短波区光谱响应平均提高了27.6%。衬底温度250 ℃条件下制备的ZnS晶粒尺寸小于室温下制备的ZnS。具有ZnS/CdS复合窗口层的CdTe电池中,采用衬底温度250 ℃沉积ZnS薄膜来制备窗口层的电池器件,其性能要优于室温下沉积ZnS制备窗口层的电池器件。这说明晶粒尺寸的大小对电子输运有一定影响。在相同厚度CdS的前提下,具有ZnS/CdS复合窗口层的CdTe电池比具有CdS窗口层在短波的光谱响应提高了约2%。这说明ZnS/CdS复合窗口层能够做到减少对短波光子的吸收,从而使更多的光子被CdTe电池的吸收层吸收。     

Preparation of water-soluble CdTe/CdS core/shell quantum dots with enhanced photostability

CdTe/CdS core/shell quantum dots (QDs) have been synthesized in an aqueous phase using thioacetamide as a sulfur source. The quantum yield was greatly enhanced by the epitaxial growth of a CdS shell, which was confirmed by X-ray photoelectron spectroscopy (XPS) results. The quantum yield of as-prepared CdTe/CdS core/shell QDs without any post-preparative processing reached 58%. The experimental results illustrate that the QDs with core/shell structure show better photostability than thioglycolic acid (TGA)-capped CdTe QDs. The cyclic voltammograms reveal higher oxidation potentials for CdTe/CdS core/shell QDs than for TGA-capped CdTe QDs, which explains the superior photostability of QDs with a core/shell structure. This enhanced photostability makes these QDs with core/shell structure more suitable for bio-labeling and imaging.     

Cell labeling and cytotoxicity of aqueously synthesized CdTe/CdS/ZnS core–shell–shell quantum dots by a water bath-hydrothermal method

CdTe/CdS/ZnS core–shell–shell quantum dots (QDs) were synthesized in aqueous solution via water-bathing combined hydrothermal method using L-cysteine as a stabilizer. The present method features markedly reduced synthesis time, higher fluorescent intensity and lower cytotoxicity of the QDs. Structural and spectroscopic properties of core–shell–shell QDs are well characterized by absorption and fluorescence spectroscopy, X-ray diffraction, transmission electron microscopy, and fourier transform infrared spectroscopy. Both CdS and ZnS shells were capped on the CdTe core and the fluorescence was greatly enhanced by the ZnS coating. The ternary QDs conjugated with transferrins were successfully employed for the biolabeling and fluorescent imaging of HeLa cells. Cytotoxicity evaluation shows that CdTe/CdS/ZnS was less toxic for cells than CdTe and CdTe/CdS due to the presence of a ZnS coating on surface, which inhibited the release of cadmium ions.     

Facile synthesis of mercaptosuccinic acid-capped CdTe/CdS/ZnS core/double shell quantum dots with improved cell viability on different cancer cells and normal cells

Water-soluble, mercaptosuccinic acid (MSA)-capped CdTe/CdS/ZnS core/double shell quantum dots (QDs) were prepared by successive growth of CdS and ZnS shells on the as-synthesized CdTe/CdS_thin core/shell quantum dots. The formation of core/double shell structured QDs was investigated by ultraviolet-visible (UV–Vis) absorption and photoluminescence (PL) spectroscopy, PL decay studies, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The core/double shell QDs exhibited good photoluminescence quantum yield (PLQY) which is 70% higher than that of the parent core/shell QDs, and they are stable for months. The average particle size of the core/double shell QDs was ～3 nm as calculated from the transmission electron microscope (TEM) images. The cytotoxicity of the QDs was evaluated on a variety of cancer cells such as HeLa, MCF-7, A549, and normal Vero cells by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) cell viability assay. The results showed that core/double shell QDs were less toxic to the cells when compared to the parent core/shell QDs. MCF-7 cells showed proliferation on incubation with QDs, and this is attributed to the metalloestrogenic activity of cadmium ions released from QDs. The core/double shell CdTe/CdS/ZnS (CSS) QDs were conjugated with transferrin and successfully employed for the biolabeling and fluorescent imaging of HeLa cells. These core/double shell QDs are highly promising fluorescent probe for cancer cell labeling and imaging applications.     

Size-dependent carrier dynamics in self-assembled CdTe/ZnTe quantum dots

We investigate size-dependent carrier dynamics in self-assembled CdTe/ZnTe quantum dots (QDs) grown using molecular beam epitaxy and atomic layer epitaxy. Photoluminescence (PL) spectra show that the excitonic peak corresponding to transitions from the ground electronic subband to ground heavy-hole band in CdTe/ZnTe QDs shifts to a lower energy with increasing ZnTe buffer thicknesses. This shift of the PL peak can be attributed to size variation of the CdTe QDs. In particular, carrier dynamics in CdTe QDs grown on various ZnTe buffer layer thicknesses is studied using time-resolved PL measurements. As a result, the decay time of CdTe QDs is shown to increase with increasing ZnTe buffer layer thicknesses due to the reduction of the exciton oscillator strength in the larger QDs.     

Photoluminescence quenching of CdTe/CdS core-shell quantum dots in aqueous solution by ZnO nanocrystals

Photoluminescence (PL) properties of 3-mercaptopropionic acid (MPA) coated CdTe/CdS core-shell quantum dots (QDs) in aqueous solution in the presence of ZnO colloidal nanocrystals were studied by steady-state and time-resolved PL spectroscopy. The PL quenching of CdTe/CdS core-shell QDs with addition of purified ZnO nanocrystals resulted in a decrease in PL lifetime and a small red shift of the PL band. It was found that CdTe(1.5 nm)/CdS type II core-shell QDs exhibited higher efficiency of PL quenching than the CdTe(3.0 nm)/CdS type I core-shell QDs, indicating an electron transfer process from CdTe/CdS core-shell QDs to ZnO nanocrystals. The experimental results indicated that the efficient electron transfer process from CdTe/CdS core-shell QDs to ZnO nanocrystals could be controlled by changing the CdTe core size on the basis of the quantum confinement effect.     

Enhanced Oxidation Stability of Quasi Core-Shell Alloyed CdSeS Quantum Dots Prepared Through Aqueous Microwave Synthesis Technique

Quasi core shell alloyed CdSeS quantum dots (QDs) have been prepared through a facile aqueous-phase route employing microwave irradiation technique. The optical spectroscopy and structure characterization evidenced the quasi core shell alloyed structures of CdSeS QDs. The X-ray diffraction patterns of the obtained CdSeS QDs displayed peak positions very close to those of bulk cubic CdS crystal structures and the result of X-ray photoelectron spectroscopy data re-confirmed the thick CdS shell on the CdSe core. The TEM images and HRTEM images of the CdSeS QDs ascertained the well-defined spherical particles and a relatively narrow size distribution. On the basis, the stability of the obtained QDs in an oxidative environment was also discussed using etching reaction by H₂O₂. The experiments result showed the as-prepared QDs present high tolerance towards H₂O₂, obviously superior to the commonly used CdTe QDs and core-shell CdTe/CdS QDs, which was attributed to the unique quasi core-shell CdSeS crystal structure and the small lattice mismatch between CdSe and CdS semiconductor materials. This assay provided insight to obtain high stable crystal structured semiconductor nanocrystals in the design and synthesis process.     

Microwave-Assisted Aqueous Synthesis of Highly Luminescent Carboxymethyl Chitosan-Coated CdTe/CdS Quantum Dots as Fluorescent Probe for Live Cell Imaging

This paper describes the development of a simplified and rapid method for the aqueous synthesis of quantum dots (QDs) with CdTe cores and gradient CdS external shells (CdTe/CdS QDs) aided by microwave irradiation. Several synthesis parameters, such as molar ratio of reagents, pH, reaction temperature, and reaction time, were studied in details. Under the optimized conditions, highly effective CdTe/CdS QDs could be synthesized in aqueous phase in only 15 min. In order to improve the biocompatibility of the CdTe/CdS QDs, these QDs were then interacted with carboxymethyl chitosan (CMC) so as they could be used as fluorescent probes in the aqueous phase. With the incorporation of CMC, the stability of modified QDs was found to have improved significantly (from 4 months to more than 10 months at room temperature). The photoluminescence quantum yield (PLQY) of the modified QDs could reach 75%, other parameters include a full width at half maximum of the emission (FWHM) spectrum as 40 ~ 60 nm, and an average size, estimated from electron microscopic images, as 3.5 nm. As fluorescent probes, these modified QDs were successfully used for imaging live Madin–Darby canine kidney (MDCK) cells, in which the preliminary results indicated that these modified QDs demonstrated good biocompatibility and showed promising applications for bio-labeling and imaging.     

Surface-Modified Colloid CdTe/CdS Quantum Dots by a Biocompatible Thiazolidine Derivative as Promising Platform for Immobilization of Glucose Oxidase: Application to Fluorescence Sensing of Glucose

Journal of Fluorescence - This work focuses on the synthesis of novel modified core–shell CdTe/CdS quantum dots (QDs) and develops as a fluorescence sensor for glucose determination. The...