Luminescent CdSe and CdSe/CdS core-shell nanocrystals synthesized via a combination of solvothermal and two-phase thermal routes

A new solvothermal route has been developed for synthesizing the size-controlled CdSe nanocrystals with relatively narrow size distribution, and the photoluminescence (PL) quantum yields (QYs) of the nanocrystals can reach 5-10%. Then the obtained CdSe nanocrystals served as cores to prepare the core/shell CdSe/CdS nanocrystals via a two-phase thermal approach, which exhibited much higher PL QYs (up to 18-40%) than the CdSe core nanocrystals. The nanocrystal samples were characterized by ultraviolet-visible (UV-vis) absorption spectra, PL spectra, wide-angle X-ray diffraction (WAXD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM).     

The temporal evolution of the structure and luminescence properties of CdSe semiconductor quantum dots grown at low temperatures

Mono-dispersed CdSe quantum dots have been prepared by water based route using 2-mercaptoethanol at low temperatures. The structures of the CdSe nanocrystals were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The XRD pattern showed that the prepared CdSe has a cubic phase with zinc blende structure. The temporal evolution of the absorption and photoluminescence spectra was used to follow the reaction process and to characterize the optical properties of the prepared CdSe quantum dots. The results exhibited clear exciton peaks in the absorption spectra. The influence of the temperature and/or time of reaction on the properties of the CdSe nanocrystals were investigated. It is found that the size of CdSe nanoparticles increases, as the reaction temperature and/or time are increased. The results showed that the Stokes shift between photoluminescence emission peak and absorption peaks is increased with the increase of the reaction temperature.     

CdSe/ZnSe核-壳结构纳米粒子合成新方法

报道用“一步”合成新方法制备了CdSe/ZnSe核-壳结构的发光纳米粒子.该方法是将锌的前驱体注入表面Se富集的CdSe发光纳米粒子溶液中,通过Zn²⁺与Se共价键结合,从而在CdSe发光纳米粒子的表面形成ZnSe壳.分别通过X射线粉末衍射、光电子能谱、透射电镜、紫外-可见吸收光谱和光致发光光谱,对核-壳结构的发光纳米粒子的结构及光学性质进行了表征.结果表明,以较宽带隙的ZnSe在较窄带隙的CdSe纳米粒子表面形成的壳层有效地钝化了CdSe纳米粒子的表面缺陷,明显地提高了室温下CdSe纳米粒子的光致发光效率.X射线粉末衍射表明随着Zn²⁺的不断注入,CdSe/ZnSe的衍射峰逐渐移向ZnSe衍射峰.光电子能谱数据显示,Zn2p的双峰分别位于1020,1040eV附近,通过与体材料ZnO相比,确定为Zn²⁺的光电子发射,说明Zn是以共价键形式存在于CdSe纳米粒子的表面.透射电镜照片显示纳米粒子具有良好的单分散性,核-壳结构的发光纳米粒子直径较CdSe核的直径明显增加.     

CdSe/CdS核壳纳米晶微波水热法一步合成与发光光谱分析

采用微波水热法一步合成了核壳结构的CdSe/CdS纳米晶,讨论了巯基丙酸中S^2-的释放过程对纳米晶生长的影响。XRD和Raman光谱结果表明,140℃合成温度下获得了CdSe/CdS核壳结构的纳米晶。FTIR光谱结果表明,巯基丙酸随时间的分解有助于CdS壳层的形成。PL光谱呈现出CdSe纳米晶的带间发射和缺陷发射,随着核壳结构的形成,CdSe纳米晶的表面缺陷被抑制,相关的荧光发射减弱。     

单核/双壳结构CdSe/CdS/ZnS纳米晶的合成与发光性质

以巯基乙酸为稳定剂,在水溶液中合成了单核/双壳结构的CdSe/CdS/ZnS纳米晶。在内核CdSe和外壳ZnS之间的内壳CdS作为晶格匹配调节层,能够很好的改善核/壳界面处的性能,而且,最外层ZnS能够最大程度地使激子受限。用TEM和XPS对纳米晶进行了表征,并且用光致发光光谱和吸收光谱对不同核壳结构的纳米晶的发光性能进行了比较,结果表明单核/双壳结构的纳米晶具有更加优异的发光特性。     

The optical properties of the blends of CdSe nanocrystals and poly(N-vinylcarbazole)

The CdSe nanocrystals with different sizes were synthesized in aqueous solution through water-sol method using l-cysteine hydrochloride as the stabilizer. The pH-dependent optical properties of the CdSe nanocrystals were investigated. Furthermore, the CdSe nanocrystals were dispersed into chloroform by using a cationic surfactant, and mixed with poly(N-vinylcarbazole) (PVK) in different mass ratios. The investigation of the photoluminescence (PL) and absorption spectra of the CdSe:PVK blends suggested that energy transfer from the PVK excited states to the CdSe nanocrystals, and it is more efficient for the smaller size nanocrystals. In the meantime, it was found that the relative emission intensity of the CdSe nanocrystals to PVK in the blends depended on the mass ratios, and the emission from the CdSe nanocrystals was the strongest as the mass ratio of CdSe to PVK was 2:1.     

Nanocrystals of CdSe Formed by the Pressure Cycle Method

CdSe nanocrystals were prepared by the pressure cycle method using the Paris-Edinburgh cell up to 7 GPa. The recovered samples are nanocrystals in the cubic phase (zinc-blende structure) and were characterized using transmission electron microscopy (TEM), electron diffraction and Raman scattering. Transmission electron micrographs shows that these nanocrystals are nearly spherical with diameters ranging from 20 to 50 nm. The Raman scattering measurement confirm the existence of CdSe nanocrystals in the cubic phase (ZB).     

用巯基乙酸作稳定剂制备CdSe纳米晶的光学性质

以巯基乙酸为稳定剂制备了CdSe纳米晶，通过尺寸选择沉淀得到2nm到3nm之间不同尺寸的纳米晶，利用室温光吸收，光致发光（PL）和光致发光激发（PLE）谱来研究了CdSe纳米团簇的光学性质。紫外－可见吸收谱给了具有清晰激光特征的尖锐吸收边，这表明样品的尺寸分布很窄。光致发光研究表明，样品有两个发射带，一个具有较高能量位于吸收边，来自电子－空穴对从最低激发态能级弛豫后的辐射复合，另一个低能发射带归属于基质与纳米晶界面存在的俘获中心。PLE谱中有2个吸收带，分别是S－S和P－P跃迁。最后还给出了不同激发能量下的发光特性。     

Synthesis and properties of CdSe Quantum Dot sensitized ZnO nanocomposites

In this work, zinc oxide nanocrystals with an average particle size of 13–22 nm are readily synthesized in aqueous medium by the wet synthesis method. Different sized nanocrystals obtained with change in calcination temperature are characterized by PL photoluminescence (PL) and UV–vis absorption spectroscopies, X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The average crystal size of the as prepared ZnO nanopowder is determined by XRD and was found to be in good agreement with the UV–vis absorption analysis. The quality of different ZnO nanopowders is confirmed by XRD spectra. On the basis of different characterizations, ZnO calcined for 1 h (due to its large size and less agglomeration) is chosen for synthesis of ZnO–CdSe nanocomposites with variable sized CdSe QD's (Quantum Dots). Nano-composites are synthesized using bifunctional linker molecule Mercaptopropionic Acid (MPA), and by directly adsorbing CdSe QD's over the surface of ZnO nanocrystals. The difference in charge transfer mechanism in ZnO–CdSe nanocomposites due to different crystallite size of CdSe QD's is studied. Higher crystallinity of ZnO–CdSe nanocomposites can be determined from XRD characterization. Size and mode of attachment in various ZnO–CdSe nanocomposites are determined by SEM studies.     

氨基酸稳定的CdSe纳米晶对溶菌酶进行荧光标记

利用氨基酸中惟一带有巯基的L-半胱氨酸盐酸盐(L-Cys)作为稳定剂在水相体系中合成CdSe纳米晶,通过表面包覆的L-Cys与生物试剂溶菌酶进行结合,实现CdSe纳米晶对溶菌酶的荧光标记.利用TEM、荧光光谱仪及荧光显微镜等多种手段对样品的结构、形貌及光学性能进行表征.试验结果表明,利用L-Cys为稳定剂合成的CdSe纳米晶具有较强的生物活性,L-Cys本身所带的氨基和羧基可以和多种生物试剂通过不同途径进行结合.对溶菌酶(Lys)标记前后,CdSe纳米晶的发射光谱的峰位发生微小红移,大约为2nm,半峰全宽基本保持不变,在40~50nm之间,荧光强度随所标记的Lys浓度的不同均发生明显增强.所有特性均表明实验所合成的CdSe纳米晶在生物标记方面具有很好的实用价值.     

基于CdSe纳米晶发光器件的电致发光特性的研究

以巯基乙酸为稳定剂,在水溶液中制备了硒化镉(CdSe)纳米晶。用X射线光电子能谱(XPS)及其在水溶液中的紫外可见吸收光谱对其进行了表征。又以CdSe为发光材料制备了两种结构的电致发光器件,并对它们的光致发光和电致发光特性进行了研究。在两个器件的电致发光中都得到了CdSe纳米晶的发光,说明CdSe纳米晶是主要的发光中心而聚乙烯咔唑(PVK)只是空穴注入和传输的媒介。在电致发光光谱中还出现了一个不同于CdSe纳米晶和PVK的发光峰值,它是CdSe/BCP(2,9-二甲基-4,7-二苯基-1,10-菲咯啉)界面处的电致发光激基复合物的发光。     

Core-shell structure and quantum effect of CdSe/HgSe/CdSe quantum dot quantum well

Core-shell structure CdSe/HgSe/CdSe quantum dot quantum well (QDQW) nanocrystals were firstly synthesized and well controlled by colloidal chemical methods. High-resolution transmission electron microscope (HRTEM) photographs show that the CdSe core has a wurtzite crystal structure and the shell of HgSe has a hexagonal structure. The enhancement and blue shift of photoluminescence (PL) peak was observed which was attributed to the quantum confinement effect of carriers in the HgSe well.     

Surface control of CdSe nanocrystals by UV-exposure in air and successive thermal treatment under ultra high vacuum

Colloidal CdSe nanocrystals were synthesized through a solution process. The CdSe nanocrystals coated on Si(1 0 0) wafers were UV-exposed in either an air or argon atmosphere to distinguish the effect of generated ozone from UV-radiation at 365 nm on the removal of surface capping pyridine molecules. The pyridine on the CdSe nanocrystal's surface could be effectively removed by the ozone generated during UV-exposure with an accompanying highly oxidized surface state of the CdSe nanocrystals. For the removal of surface oxides of CdSe nanocrystals, a successive thermal treatment under ultra high vacuum (UHV) was adopted. The optical energy bandgap measured by using UV-vis absorption spectroscopy showed a red shift with treatment with an increase of annealing temperature. The electronic energy structure of UHV-annealed CdSe nanocrystals film was analyzed in situ using X-ray absorption and photoelectron spectroscopy. A great resemblance was found between the values of the optical and electron energy bandgaps of effectively surface-treated CdSe nanocrystals film after UHV-annealing at 400 °C.     

CdSe纳米晶的制备条件对发光特性的影响

以巯基乙酸为稳定剂,在水相中制备了CdSe纳米晶水溶胶,并用X射线光电子能谱和透射电子显微镜对其进行了表征,证明了CdSe纳米晶的形成。研究了在不同反应时间所制备的CdSe纳米晶的XRD谱以及吸收光谱和发射光谱的变化情况,并且还研究了不同反应物配比情况下的发射光谱的变化,结果表明改变CdSe纳米晶的制备条件,将会对CdSe纳米晶的发光特性有显著的影响。     

Influences of capping molecules on optical properties of nanocrystalline ZnS:Cu

ZnS:Cu nanocrystals capped with different capping molecules have been successfully synthesized by a simple aqueous method. The prepared nanocrystals were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive analysis by X-rays (EDAX). The surface characterization of the nanocrystals was done by FTIR spectroscopy. The effect of capping agents on absorption and photoluminescence (PL) spectra of the ZnS:Cu nanocrystals was studied. A blue shift of the absorption peaks was observed and attributed to a quantum confinement effect, which increases the band gap energy. The photoluminescence spectra of the capped ZnS:Cu nanocrystals showed a broad peak in the range of 460–480 nm. The intensity of the PL spectra strongly depended on the capping agents.     

MEH-PPV/CdSe纳米复合器件的光电导特性的研究

以CdO和Se粉作为前驱物,在TOPO/TOP有机体系中制备了CdSe纳米晶,将其与聚合物MEH-PPV复合制备了复合光电导器件,研究了它的光电导特性,并将其与单层MEH-PPV光电导器件的特性进行了比较。结果发现纳米复合光电导器件的光电流响应光谱的2个峰的位置基本上与MEH-PPV和CdSe纳米晶的吸收峰的位置相对应,这说明CdSe纳米晶和聚合物MEH-PPV的吸收对光电流都有贡献,主要是由于CdSe纳米晶和MEH-PPV界面处的激子离化和电荷转移造成的。而且复合器件的光电流较单层有所增强,且MEH-PPV器件光谱的响应范围更宽。     

Photoluminescence of colloidal CdSe nano-tetrapods and quantum dots in oxygenic and oxygen-free environments

The effects of oxygenic versus oxygen-free environments on colloidal CdSe nano-tetrapods and quantum dots (QDs) were studied using both continuous and time-resolved photoluminescence (PL) measurements. The decays of PL intensities for tetrapods and QDs in oxygen-free solution (chloroform) and in air (on silicon) can be well fitted by a bi-exponential function. Based on the emission-energy dependence of carrier lifetimes and the amplitude ratio of the fast-decay component to the slow-decay component, the fast and slow PL decays of CdSe nanocrystals are attributed to the recombination of delocalized carriers in the core states and localized carriers in the surface states, respectively. The PL intensities of CdSe nano-tetrapods and QDs were found to be five times and an order of magnitude higher in air than in vacuum, respectively, which is explained by the passivation of surface defects by the polar gas (oxygen) absorption. The lower enhancement in PL intensities of CdSe nano-tetrapods is explained by the special morphology of the tetrapods.     

Using two-dimensional photon echo spectroscopy to probe the fine structure of the ground state biexciton of CdSe nanocrystals

The origin of the fine structure of the ground state single- and biexciton of CdSe nanocrystals is reviewed, along with the theoretical framework used to describe these states. Calculations were performed to determine the transition dipole moments of optically allowed transitions from the single- to biexciton fine structure states. Two-dimensional photon echo spectroscopy measurements for a sample of CdSe nanocrystals are reported. The two-dimensional electronic spectrum at a population time of 0 fs is analyzed using a simulation based on k.p theory predictions of the exciton and biexciton manifolds of states. The analysis suggests that a particular excited state absorption transition from the single- to biexciton fine structure dominates the 2D spectra. These excited state absorptions are clearly resolved in 2D spectra and the method therefore has promise for gaining clearer insights into quantum dot spectroscopy.     

CdSe/CdS核/壳型纳米晶的光谱特性

以巯基乙酸为稳定剂制备了CdSe/CdS核／壳型纳米晶。用光吸收谱（Abs)、光致发光谱（PL）及光致发光激发谱（PLE）研究了CdS壳层对CdSe纳米晶电子结构，从而对其吸收和发光性能的影响。根据PL和PLE的结果以及带边激子精细结构的计算结果，我们用尺寸很小的纳米晶中所形成的基激缔合物解释了PL光谱与吸收边之间较大的Stokes位移。     

Self-assembly and photoluminescence of CdS-mercaptoacetic clusters with internal structures

CdS-mercaptoacetic (CdS/M) clusters were synthesized by using mercaptoacetic acid as the stabilizing agent in the aqueous solution. From the transmission electron microscopy (TEM) image and the electron diffraction (ED) pattern, a two-dimensional nearly ordered CdS/M cluster array is observed and the CdS/M cluster is found to be constructed of small CdS/M nanocrystals. The model of self-assembly of the CdS/M clusters with internal structure is presented. The absorption spectrum of the CdS/M nanocrystal solution reveals a maximum at 372 nm and the corresponding photoluminescence (PL) spectrum shows a strong peak at 556 nm at room temperature. The PL spectra of various concentrations of CdS/M reveal the passivation effect of mercaptoacetic acid.