CdSe/ZnS量子点在倏逝波光纤pH传感中的应用

将新型量子点荧光传感技术与光纤倏逝波传感技术相结合,发展了一种基于量子点荧光效应并结合倏逝波传导进行溶液酸碱度检测的新型传感技术,具有灵敏度高、检测速度快、便于微环境检测、可实现远程探测、实时监测和原位分析等特点。详细介绍了用于倏逝波传感的锥柱组合型光纤荧光探头的制备方法,量子点在光纤探头表面的修饰流程,光谱与强度两种光纤pH传感平台的建立,并分别从响应范围、线性度、重复性和稳定性等方面对CdSe/ZnS量子点应用于光纤pH传感进行了评价。结果表明,在pH值为2~12的范围内,CdSe/ZnS量子点的荧光光谱信号的峰位在强酸和强碱的情况下都会产生红移,且红移量随pH值的变化呈线性关系,其量子点荧光强度信号随pH值的减小呈线性降低关系,通过在强酸和强碱下交替测试的实验表明其具有较好的重复性,利用荧光强度传感平台进行实时监测的实验表明其具有较好的稳定性。因此,将CdSe/ZnS量子点用于倏逝波光纤pH传感具有可行性,在生物化学、环境监测、医学临床、食品安全等领域的pH值测量方面有着广泛的应用前景。     

巯基丙酸分子对CdSe核壳量子点和 ZnO纳米粒子薄膜之间电荷转移的影响

通过稳态光谱和时间分辨荧光光谱研究了巯基丙酸(MPA)分子对由量子点到ZnO纳米粒子薄膜的电荷转移过程的影响。研究发现,相对于CdSe纳米粒子薄膜样品,没有MPA分子参与作用的CdSe/ZnO薄膜样品和有MPA分子连接的CdSe/MPA/ZnO薄膜样品中都存在从CdSe量子点到ZnO纳米粒子薄膜的有效电荷分离过程,但是相对于CdSe/ZnO样品, CdSe/MPA/ZnO样品中电荷转移速率明显变小。这表明MPA分子本身它并不能促进CdSe到ZnO电荷分离过程,因此可以认为用金属氧化物薄膜直接吸附量子点吸收材料,将能获得高功率转换效率的量子点敏化太阳能电池。     

Effect of the Semiconductor Quantum Dot Shell Structure on Fluorescence Quenching by Acridine Ligand

The main line of research in cancer treatment is the development of methods for early diagnosis and targeted drug delivery to cancer cells. Fluorescent semiconductor core/shell nanocrystals of quantum dots (e.g., CdSe/ZnS) conjugated with an anticancer drug, e.g., an acridine derivative, allow real-time tracking and control of the process of the drug delivery to tumors. However, linking of acridine derivatives to a quantum dot can be accompanied by quantum dot fluorescence quenching caused by electron transfer from the quantum dot to the organic molecule. In this work, it has been shown that the structure of the shell of the quantum dot plays the decisive role in the process of photoinduced charge transfer from the quantum dot to the acridine ligand, which is responsible for fluorescence quenching. It has been shown that multicomponent ZnS/CdS/ZnS shells of CdSe cores of quantum dots, which have a relatively small thickness, make it possible to significantly suppress a decrease in the quantum yield of fluorescence of quantum dots as compared to both the classical ZnS thin shell and superthick shells of the same composition. Thus, core/multicomponent shell CdSe/ZnS/CdS/ZnS quantum dots can be used as optimal fluorescent probes for the development of systems for diagnosis and treatment of cancer with the use of anticancer compounds based on acridine derivatives.     

Enhanced lateral photovoltaic effect observed in CdSe quantum dots embedded structure of Zn/CdSe/Si

The quantum dots (QDs) system has been intensively studied for decades owing to its huge potential for applications. In this Letter, we report a lateral photovoltaic effect (LPE) with a large sensitivity observed in CdSe QDs embedded structure of Zn/CdSe/Si. This result not only enriches applications of the QDs system but also opens a new window to study the carrier dynamics of the QDs system.     

Chemical role of amines in the colloidal synthesis of CdSe quantum dots and their luminescence properties

The role of organic amines in the colloidal synthesis of CdSe quantum dots (QDs) has been studied. CdSe QDs were synthesized from the source solutions containing 5 vol% of amines having various alkyl chain lengths, stereochemical sizes and electron donation abilities. The role of the additional amines was evaluated on the basis of the photoluminescence (PL) properties such as PL wavelength and intensity of the obtained CdSe QDs. The observed PL spectra were explained by the fact that the amines behaved as capping ligands on the surface of the QDs in the product colloidal solution and complex ligands for cadmium in the source solutions. It was shown that the particle size was controlled by the diffusion process depending on the mass and stereochemical shape of the amines, and the luminescence intensity increased with the increasing electron donation ability and capping density of the amines.     

The Influence of Surface Trapping and Dark States on the Fluorescence Emission Efficiency and Lifetime of CdSe and CdSe/ZnS Quantum Dots

To investigate the influence of surface trapping and dark states on CdSe and CdSe/ZnS quantum dots (QDs), we studied the absorption, fluorescence intensity and lifetime by using one-and two-photon excitation, respectively. Experimental results show that both one- and two-photon fluorescence emission efficiencies of the QDs enhance greatly and the lifetime increase after capping CdSe with ZnS due to the effective surface passivation. The lifetime of one-photon fluorescence of CdSe and CdSe/ZnS QDs increase with increasing emission wavelength in a supralinear way, which is attributed to the energy transfer of dark excitons. On the contrary, the lifetime of two-photon fluorescence of bare and core-shell QDs decrease with increasing emission wavelength, and this indicates that the surface trapping is the dominant decay mechanism in this case.     

Creation and Investigation of Organic Light-Emitting Structures Containing Arrays of Colloidal Quantum Dots

We have created organic electroluminescent structures—ITO/TPD/Alq3/Al and ITO/PEDOT:PSS/TPD/Alq3/Al—which are organic light-emitting diodes (OLEDs). Experiments on the incorporation of CdSe/ZnS colloidal quantum dots into the active layer of the structure have been performed. The parameters of the created structures have been determined using optical-spectroscopy methods. The appropriateness of using the method of high-speed vacuum thermal deposition as a main method for the deposition of structural layers has been demonstrated, and the possibility of accelerated formation of layers of the material without disturbing its chemical structure has been shown. By measuring the photoluminescence spectra at different points in samples, we have determined the quality of the obtained structures and plotted maps of the radiation power distribution of the material and of its thickness. Recommendations for the creation of upper contacts and other regions of light-emitting structures have been formulated. We have created organic structures with ITO/PEDOT:PSS/TPD/TPD + CQD’s CdSe/Alq3/Al colloidal quantum dots, in which electroluminescence of CdSe/ZnS quantum dots has been obtained for a wide range of applied voltages. It has been shown that the introduction of colloidal quantum dots into the structure leads to a significant modification of its electroluminescence spectrum.     

Effects of increasing number of rings on the ion sensing ability of CdSe quantum dots: a theoretical study

A computational study on the structural and electronic properties of a special class of artificial atoms, known as quantum dots, has been carried out. These are semiconductors with unique optical and electronic properties and have been widely used in various applications, such as bio-sensing, bio-imaging, and so on. We have considered quantum dots belonging to II–VI types of semiconductors, due to their wide band gap, possession of large exciton binding energies and unique optical and electronic properties. We have studied their applications as chemical ion sensors by beginning with the study of the ion sensing ability of (CdSe) _n (n?=?3, 6, 9 which are in the size range of ~?0.24, 0.49, 0.74 nm, respectively) quantum dots for cations of the zinc triad, namely Zn²⁺, Cd²⁺, Hg²⁺, and various anions of biological and environmental importance, and studied the effect of increasing number of rings on their ion sensing ability. The various structural, electronic, and optical properties, their interaction energies, and charge transfer on interaction with metal ions and anions have been calculated and reported. Our studies indicate that the CdSe quantum dots can be employed as sensors for both divalent cations and anions, but they can sense cations better than anions.     

Luminescent properties of cadmium selenide quantum dots in fluorophosphate glasses

The optical properties of fluorophosphate glasses with CdSe quantum dots are studied. Secondary heat treatment at a temperature exceeding the glass transition temperature resulted in the formation of quantum dots with sizes of 3.7–6.2 nm. The influence of the semiconductor component concentration on the spectral-luminescent characteristics of glasses is shown. It is experimentally demonstrated that glasses with a lower CdSe concentration have a higher absolute luminescence quantum yield.     

Polarization selective magneto-optical study on the coupled quantum dots using resonant excitation

We have studied a double-layer self-assembled quantum dot (QD) structures consisting of non-magnetic CdSe and magnetic CdMnSe. Transmission electron microscopy image shows that QDs are formed within the CdSe and CdMnSe layers, and they are vertically correlated in the system. The strong interband ground state transition was observed in magneto-photoluminescence (PL) experiments. In contrast to a typical behavior for many low-dimensional systems involving diluted magnetic semiconductors (DMSs), where PL signal dramatically increases when an external magnetic field is applied, we have observed a significant decrease of the PL intensity as a function of magnetic field in the double-layer structures where the alternating QD layers contain the DMS and non-DMS QDs. We attribute such effect to carrier transfer from non-magnetic CdSe dots to magnetic CdMnSe dots due to the large Zeeman shift of the band edges of DMS QDs in magnetic field. Since the band alignment of QD structure strongly depends on the spin states of system, we performed polarization-selective PL measurement to identify spin-dependent carrier tunneling in this coupled system.     

CdSe量子点的光物理性质研究与荧光杂化纤维的制备

半导体纳米晶体(NCs)具有良好的光稳定性,广泛的发射持久性和高消光系数,在过去几年被广泛研究报道,其中,硒化镉半导体纳米晶体(CdSe NCs)被广泛用于电子照明、太阳能发电、光电传感等领域.然而CdSe NCs的电学、热力学和光物理性质具有较强的尺寸依赖性,在传统的制备方法及应用中容易出现晶体表面缺陷和悬空键以及较...     

Speedy photoelectric exchange of CdSe quantum dots/mesoporous titania composite system

Two classes of important nano-materials, mesoporous titania (MT) and CdSe quantum dots, are prepared via chemical methods. Rapid immobilization of CdSe quantum dots into mesoporous titania has been achieved and the composite system is characterized by high-resolution transmission electron microscopy and photoluminescence. The band-to-band photoluminescence emission of CdSe quantum dots is blue-shifted for 20 nm after the dots are immobilized into mesoporous titania. Loading CdSe quantum dots into mesoporous titania leads to speedy photoelectric exchange process of the system and a significant rise in photoconductivity (for a factor of 8), which would attract great deal of attention in quantum dots solar cell.     

近红外量子点的发光机理研究

近红外量子点具有独特的光学性质,如荧光量子产率高,荧光寿命长,荧光发射波长可调,半峰宽窄且斯托克斯位移较大,耐光漂白能力强等, 及“近红外生物窗口”的优势,使它们在生物荧光标记、太阳能电池、量子化计算、光催化、化学分析、食品检测及活体成像等领域具有巨大的潜在应用价值。目前对近红外量子点的发光机理研究还不够完善,针对国内外的研究现状,重点对核/壳结构的量子点(CdTe/CdSe,CdSe/CdTe/ZnSe等)、三元量子点(Cu-In-Se,CuInS₂等)和掺杂型量子点(Cu∶InP等)三种不同类型近红外量子点的发光机理进行了综述。其中,Type-Ⅱ型核/壳结构量子点的发光机理多为带间复合发光,三元量子点以本征缺陷型发光为主,掺杂型量子点多为杂质缺陷型发光。探讨了近红外量子点发光原理存在的问题及发展的方向。对近红外量子点的发光机理进行系统地研究不仅有助于我们理解近红外量子点的发光性质,而且对完善相似高品质量子点的合成方法具有重要意义。     

Encapsulation of highly confined CdSe quantum dots for defect free luminescence and improved stability

This is the first report on the generation of trap states and their effective elimination in highly confined CdSe quantum dots in order to obtain enhanced and stable optical properties prepared by aqueous route. Surface plays an important role in optical properties of quantum dots (QDs) and surface modification of quantum dots can improve optical properties. In present work luminescent CdSe QDs were prepared using 2-Mercaptoethanol (2-ME) as stabilizing agent and encapsulated by polymer. Different concentrations of 2-ME were used to tune the emission spectra with respect to their reduced size. Addition of 2-ME to CdSe QDs enhances the trap emission and quenching band edge emission due to (i) increased surface to volume ratio and; (ii) presence of high concentration of sulfide ions as confirmed from EDX analysis as sulfide ions possesses the hole scavenging characteristics. Polymer encapsulation of QDs was carried out to make them stable and to improve their optical properties. Even though there are previous reports addressing the improved optical properties by polymer encapsulation and silica encapsulation but experimentally it has not been reported yet experimentally. In this work we have synthesized and characterized water soluble polymer encapsulated QDs and proved the facts experimentally. Photoluminescence spectroscopy clearly reveals the role of polymer encapsulation in boosting the optical properties of CdSe QDs. FTIR spectra validate the presence of biocompatible functional groups on CdSe4/PEG (Polymer encapsulated QDs).     

CdSe量子点滤光片尺寸、温度依赖的光学特性

为了缩小光谱仪体积使之适用于军事卫星等领域,本文将胶体量子点作为滤光材料,研究了CdSe胶体量子点滤光片的光学特性.本文采用热注入法合成出了高质量的CdSe胶体量子点,经过对苯二胺消光处理制备成CdSe胶体量子点滤光片.利用透射电子显微镜(TEM)进行样品形貌结构的表征及粒径尺寸的测量,并分别在不同温度下进行了紫外.可...     

CdSe量子点“开关”的构建及其在药物分析中的应用

以CdCl₂·2.5H₂O,Na₂SeO₃和NaBH₄为反应物,制备巯基丁二酸稳定的CdSe量子点。在合成的量子点中加入一定浓度的铜离子,铜离子结合于量子点表面而使其荧光猝灭。在猝灭后的体系中加入青霉胺,由于青霉胺能使结合于量子点表面的铜离子释放出来而使量子点的荧光恢复。据此,建立了一种CdSe量子点"开关"测定青霉胺的新方法。在选定的实验条件下,方法的线性范围为1~72 μg/mL,检出限为0.031 μg/mL。应用于实际样品中青霉胺的测定,结果令人满意。     

Direct observation of electron-to-hole energy transfer in CdSe quantum dots

We independently determine the subpicosecond cooling rates for holes and electrons in CdSe quantum dots. Time-resolved luminescence and terahertz spectroscopy reveal that the rate of hole cooling, following photoexcitation of the quantum dots, depends critically on the electron excess energy. This constitutes the first direct, quantitative measurement of electron-to-hole energy transfer, the hypothesis behind the Auger cooling mechanism proposed in quantum dots, which is found to occur on a 1 +/- 0.15 ps time scale.     

复合荧光CdSe量子点-脂质体的制备与表征

通过脂质体方法成功地将三辛基氧化膦(TOPO)包覆的CdSe发光量子点从非极性有机溶剂转移到生物相容性的水溶液中.分别通过透射电镜(TEM)、荧光Mapping图像,以及光致发光(PL)光谱进行表征.TEM照片显示制备的CdSe核量子点为球形,具有良好的单分散特性,平均粒径约为3nm.CdSe-脂质体复合体的平均尺寸大约20nm,TEM清楚地显示了CdSe量子点被诱捕在脂质体中.荧光Mapping显示了CdSe-脂质体复合体的发光强度分布.脂质体方法转移TOPO包覆的CdSe量子点,借助了磷脂的双分子链与CdSe表面的TOPO配体之间的疏水相互作用,在CdSe的第一配体层外部形成第二配体层,保留了CdSe的存在环境,光致发光光谱表明,量子点-脂质复合体基本保持了CdSe核量子点的发射效率.     

Hole mobility and trapping in PVK films doped with CdSe/CdS and CdSe quantum dots

Experimental study of the hole mobility in polyvinylcarbazole (PVK) films doped with two kinds of nanocrystals, on bare core CdSe and core-shell CdSe/CdS quantum dots, with concentrations ranging from 3 · 10¹⁰ to 3 · 10¹⁵ cm⁻³, is presented. The quantum dots investigated were made using colloidal chemistry. The hole mobility was measured using the time-of-flight technique as a function of the applied electrical field in the range 10⁵–10⁶ V/cm and for temperatures from 20°C to 50°C. The transient curves, being featureless on a linear plot, show on a double logarithmic scale a sharp inflection point indicating a dispersive carrier drift process. The recovered values of the mobility are in the range 3 · 10⁻⁸–10⁻⁶ cm²·V⁻¹·s⁻¹ and their field and temperature dependences can be analyzed formally within the framework of the Gaussian disorder model proposed by B?ssler. The energetic disorder is, within the experimental accuracy, independent of the concentration and type of quantum dots for the CdSe quantum dots at all concentrations and for the CdS/CdSe quantum dots up to 10¹⁴ cm⁻³. The spatial disorder factors are very large (from 5.3 to 8.7) and do not depend in a systematic way upon the type and concentration of quantum dots (QDs). The experiments show that the apparent mobility does not change considerably with concentration, but it was found that the samples with CdSe/CdS quantum dots at concentrations from 10¹⁵ to 3 · 10¹⁵ cm⁻³ show a decreased photocurrent response. The dependence of the time-integrated transients (corresponding to the full charge value) upon the quantum-dot concentration has been determined. Differences in total photogenerated charge for pure and doped polymer films imply that the quantum dots of that type are the hole traps with capture times much more smaller than the transit time and with emission times a few orders longer than the transit time. CdSe quantum dots without a shell do not seem to exhibit the same properties as core shells and do not produce considerable changes in the charge transfer, even at a density of 10¹⁵ cm⁻³.     

Structural dependency of optical excitation transfer via optical near-field interactions between semiconductor quantum dots

The distribution dependency of quantum dots was theoretically and experimentally investigated with respect to the basic properties optical excitation transfer via optical near-field interactions between quantum dots. The effects of three-dimensional structure and arraying precision of quantum dots on the signal transfer performance were analyzed. In addition, the quantum dot distribution dependency of the signal transfer performance was experimentally evaluated by using stacked CdSe quantum dots and an optical near-field fiber probe tip laminated with quantum dots serving as an output terminal, showing good agreement with theory. These results demonstrate the basic properties of signal transfer via optical near-field interactions and serve as guidelines for a nanostructure design optimized to attain the desired signal transfer performances.