核壳结构CdS/ZnS荧光量子点的制备与荧光性能研究

以氧化镉为镉源、硫单质为硫源、油酸为配体、在十八烯体系中合成单分散的CdS纳米颗粒,研究了配体浓度对纳米微粒的生长动力学、颗粒尺寸分布的影响.采用乙基黄原酸锌作为Zn、S源的反应前体,采用逐滴滴加的方法制备了具有核壳结构的CdS/ZnS量子点,吸收光谱和荧光光谱表明CdS/ZnS纳米粒子比单一的CdS纳米粒子具有更优异的发光特性.透射电子显微镜、X射线粉末衍射、X射线光电子能谱、选区电子衍射证明ZnS在CdS表面进行了有效包覆.所制备核壳结构纳米粒子具有较好的尺寸分布,荧光发射峰半高峰宽为18～20nm,荧光量子产率达40%.     

双修饰Fe3O4/CdSe/CdS荧光磁性复合物的制备及其表征

采用共沉淀法制得Fe3O4溶胶,用γ-缩水甘油醚氧丙基三甲氧基硅烷(KH-560)对其表面进行改性,制得有机硅改性的纳米Fe3O4磁性粒子;用L-半胱氨酸盐酸盐(L-Cys)将油相的CdSe/CdS转成水相并带上氨基的CdSe/CdS纳米晶;将其复合制备了Fe3O4/CdSe/CdS荧光磁性双功能纳米复合物颗粒。该Fe3O4/CdSe/CdS复合物颗粒平均尺寸约为40nm,饱和磁化强度为21.287A.m2/kg,该纳米粒子既具有优异的荧光特性,也具有较强的超顺磁性。     

水溶性Cu∶CdTe/CdS核壳量子点的合成、表征及细胞毒性检测

采用水相法合成了Cu掺杂CdTe量子点,并用CdS壳层进行包覆,得到了Cu∶CdTe/CdS核壳结构量子点。采用荧光发射光谱(FL)、紫外可见吸收光谱(UV-Vis)、透射电镜(TEM)以及能谱仪(EDS)等手段对CdTe量子点和Cu∶CdTe/CdS核壳量子点进行了表征。研究了不同Cu掺杂浓度、CdS壳层生长时间以及Cd/硫脲物质的量比对Cu∶CdTe掺杂量子点光学性能的影响,并采用人成骨肉瘤细胞(MG-63细胞)对样品做了细胞毒性分析。研究结果表明:通过掺杂和包壳的步骤,合成的Cu∶CdTe/CdS核壳量子点在CdTe量子点的基础上实现了荧光发射红移,荧光强度提高,以及细胞毒性降低。     

Ⅱ-Ⅵ族量子点掺杂玻璃的光学性质及研究进展

由于量子限域效应,尺寸可调的Ⅱ-Ⅵ族量子点掺杂玻璃在光学滤波片、非线性光学器件上的应用已经被广泛研究。玻璃中量子点的光学性质主要由量子点的尺寸、表面状态和周围基质环境决定,通过提高Se/Cd比可以有效地对量子点的表面缺陷进行钝化,实现CdSe量子点的本征发光;进一步调整热处理制度可以促进Zn离子扩散进入CdSe量子点表面,形成CdSe/Cd_(1-x)Zn_xSe核壳结构,使得缺陷发光几乎完全猝灭,从而提高量子点的荧光量子效率;在玻璃中原位合成的CdS/ZnS核壳结构量子点的荧光量子效率可达到53%。随着基础研究中玻璃中Ⅱ-Ⅵ族量子点荧光效率的不断提高,发光二极管(LED)等小型发光器件的制造成为可能。为了满足实际需要,建立核壳结构中量子点表面钝化机理模型,进一步优化量子点荧光效率是下一步需要解决的问题。     

微波辅助快速合成水溶性CdTe/CdSe核壳量子点

以巯基乙酸(TGA)作为稳定剂,用微波辅助法快速合成了水溶性CdTe/CdSe核壳量子点.比较了传统水热法和微波辅助法制备的量子点性能,研究了加热温度、反应物配比及CdTe量子点浓度对CdTe/CdSe核壳量子点的性能影响.研究结果表明,核壳结构的CdTe/CdSe量子点比单一的CdTe量子点具有更优异的光致发光强度和...     

水相制备CdSe量子点及其ZnS核壳结构量子点

因具有较宽的可调控发光范围,CdSe量子点及其ZnS核壳结构量子点受到了研究者们的普遍关注。采用水相回流法合成了CdSe量子点及其ZnS核壳结构量子点,并结合透射电镜(TEM)、X射线衍射(XRD)、紫外-可见光吸收光谱(UV-Vis)和荧光光谱(PL)对样品进行表征。TEM结果表明,合成的量子点粒径分布较宽且结晶度较高;从XRD分析结果可以看出,CdSe量子点为闪锌矿结构,沿着晶面向外生长ZnS壳层后,谱峰向高角度偏移;从UV-Vis和PL分析结果可以看出,CdSe量子点于500 nm处出现吸收肩峰,于644 nm处出现半高宽较宽的缺陷发光峰;随着反应时间的延长,于577 nm处出现本征发光峰。包覆了ZnS壳层后,量子点不仅发光强度明显增大,而且稳定性显著提高。该合成方法节能环保、生产效率高,具有较大的应用空间。     

在多相体系中制备核壳型CdSe/ZnS量子点

在多相体系中制得了CdSe/ZnS半导体量子点,采用X射线粉末衍射(XRD)、电子透射显微镜(TEM)等测试手段对产物进行了表征,结果表明CaSe/CdS量子点尺寸均一、形貌规则,具有立方晶体结构.初步研究了此体系的反应机理,并通过紫外-可见吸收光谱和荧光光谱对产物的光学性质进行了分析,结果表明在CASe量子点外面包覆一定厚度的ZnS壳层后,其激子发射强度和量子效率显著提高.     

石墨烯量子点/CdS/CdSe共敏化太阳能电池

以三维锐钛矿TiO₂微球为上层光散射层材料, 以商业纳米TiO₂为下层连接材料, 采用刮刀法制备了一种新颖的双层TiO₂薄膜, 并应用于量子点敏化太阳能电池(QDSSC)。其中, 石墨烯量子点(GQDs)采用滴液法引入, CdS/CdSe量子点采用连续离子层吸附法(SILAR)制备。采用场发射扫描电镜、透射电镜、X射线衍射、紫外-可见漫反射光谱及荧光光谱对样品进行表征。实验还制备了CdS/CdSe量子点敏化及石墨烯量子点/CdS/CdSe共敏化太阳能电池, 并研究了石墨烯量子点及CdS不同敏化周期及对电池性能影响。研究结果表明, 石墨烯量子点及CdS不同敏化周期对薄膜的光学性质、电子传输及载流子复合均有较大影响。优选条件下, TiO₂/QGDs/CdS(4)/CdSe电池的光电转换效率为1.24%, 光电流密度为9.47 mA/cm², 显著高于TiO₂/CdS(4)/CdSe电池的这些参数(0.59%与6.22 mA/cm²)。这主要是由于TiO₂表层吸附石墨烯量子点后增强了电子的传输, 减少了载流子的复合。     

CdS/ZnO核壳结构纳米微粒的合成及其发射光谱研究

采用单分子前驱体热分解的方法合成了单分散CdS纳米晶,以CdS纳米晶作为核,在CTAB辅助下,对其表面进行修饰,荧光光谱表明CdS/ZnO核壳结构被成功合成。考查了温度对包覆的影响,结果表明,随着温度的升高晶体结晶越好,包覆越来越完全,ZnO包覆在CdS纳米晶的表面而掩盖了CdS纳米晶的缺陷,使得缺陷发光减弱而带隙发光增强。     

CdSe:X/ZnS掺杂型核壳量子点的化学合成及光谱性质研究

采用绿色合成工艺,通过在核壳量子点中掺杂不同的金属离子,在水溶液中合成了CdSe∶X/ZnS掺杂型核壳量子点。并利用多种分析测试手段对合成产物的结构以及光谱性质进行了详细地研究。XRD分析表明,核壳结构的量子点的衍射峰相对内层CdSe量子点向高角度方向移动,掺杂型核壳量子点的衍射峰较未掺杂量子点有向高角度移动趋势,合成量子点的平均晶粒尺寸约为2.3nm。SEM结果表明,合成的核壳量子点近似为球形。量子点的吸收峰与体材料相比,产生明显的蓝移,表现出明显的量子限域效应。样品具有很好的亲水性,在红外光线照射下出现丁达尔效应,样品的FT-IR结果表明配体MPA成功包覆在量子点的表面。     

Cadmium sulfide and cadmium selenide/cadmium sulfide nanoparticles stabilized in water with poly(cysteine acrylamide)

Cysteine acrylamide (N-acryloyl L-cysteine) stabilizes CdS nanoparticles as the particles form in aqueous dispersions. Cysteine acrylamide also exchanges for citrate on the surfaces of CdSe and core/shell CdSe/CdS nanoparticles to provide greater stability. Heating of the nanoparticle dispersions polymerizes the cysteine acrylamide on the surface to form a more efficient polydentate stabilizer. The polymer-coated nanoparticle dispersions are colloidally stable even after removal of low molecular weight solutes by dialysis. Emission quantum yields of the polymer-coated CdSe and CdSe/CdS samples were 0.9% and 2.6%, respectively, after aging of the samples in light. CdSe/CdS coated with poly(cysteine acrylamide) is colloidally stable for at least two years in the dark at 5 degrees C.     

巯基包覆CdSe和CdSe/CdS核壳纳米晶的水相合成与表征

利用水相合成的方法制备了巯基包覆的具有较高荧光量子产率的CdSe和CdSe／CdS纳米晶．水相合成方法的优点是原料低廉、安全可靠和重复性高，缺点是纳米晶的尺寸分布较宽，发光效率不是很高．采用X-射线粉末衍射、吸收和荧光等光谱手段对纳米晶的平均尺度、粒径分布、晶体结构及发光特性进行了表征。在77K到300K的温度范围内，随着温度降低，CdSe纳米晶的发光峰逐渐蓝移，而CdSe／Cds纳米晶发光峰位基本不随温度变化而变化．此外，在325nm激光辐照下，CdSe／CdS纳米晶的荧光寿命比CdSe纳米晶延长了6倍左右，稳定性大幅度提高．以上结果表明，核壳结构的CdSe／CdS纳米晶具有较高的发光效率和良好的稳定性，具有广阔的应用前景．     

Size tuning of MAA capped CdSe and CdSe/CdS quantum dots and their stability in different pH environments

The present work reports synthesis of mercaptoacetic acid capped CdSe nanoparticles soluble in water at different temperatures and with different precursor ratios. This enabled to tune the particle size of QDs from 2.7 to 5.8 nm. The particles consist of nanocrystals; with mixed phase, hexagonal wurtzite as well as sphalerite cubic and are luminescent with quantum yield 10%. The quantum yield up to 20% has been obtained by growing a shell of CdS over the CdSe. HR-TEM images, XRD patterns and the photoluminescence excitation spectra shows epitaxial growth of CdS shell over CdSe and with average size 3.2 ± 1.2 and 4.7 ± 1.2 nm for CdSe and CdSe/CdS quantum dots respectively. FT-IR spectrum and the negative zeta potential value together confirms the attachment of mercaptoacetic acid to the QD surface, where the carboxylic acid group is facing towards solvent and provides stability due to electrostatic hindrance. Further, the QDs are checked for their stability and the luminescence in environments of different pH (4–11 pH). Both CdSe and CdSe/CdS agglomerate with total elimination of fluorescence for 4 pH medium, and no shift in the fluorescence emission peak observed for the 6–9 pH, therefore QDs can be applicable as the fluorescence tags in this specific range of pH.     

Preparation, characterization, and fluorescence properties of well-dispersed core–shell CdS/carbon nanoparticles

The core–shell CdS-carbon (CdS/C) nanoparticles were synthesized for the first time via a facile pyrolysis approach of bis(β-mercaptoethanol)-cadmium(II) as a single-source precursor. After using acid treatment method, well-dispersed and homogeneous core–shell CdS/C nanoparticles were obtained. The morphology, structure, and properties of CdS/C nanoparticles were investigated by X-ray diffraction (XRD), Raman spectra, transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), and fluorescence spectroscopy. Most of the prepared nanoparticles presented core–shell structures with core diameter of ~10 nm and shell thickness of ~4 nm. The CdS core belonged to hexagonal crystal system. The carbon shell was employed as a good dispersion medium to form well-dispersed small sized CdS particles. XRD and XPS results revealed that there is an interaction between CdS core and carbon shell. Fluorescence measurement showed that the monodispersed CdS-carbon nanoparticles exhibit remarkable fluorescence enhancement effect compared with that of the pristine CdS nanoparticles, which indicates the prepared nanoparticles are a promising photoresponsive material.     

Aqueous synthesis of CdSe and CdSe/CdS quantum dots with controllable introduction of Se and S sources

A new and convenient route is developed to synthesize CdSe and core–shell CdSe/CdS quantum dots (QDs) in aqueous solution. CdSe QDs are prepared by introducing H₂Se gas into the aqueous medium containing Cd²⁺ ions. The synthesized CdSe QDs are further capped with CdS to form core–shell CdSe/CdS QDs by reacting with H₂S gas. The gaseous precursors, H₂Se and H₂S, are generated on-line by reducing SeO₃ ^2? with NaBH₄ and the reaction between Na₂S and H₂SO₄, and introduced sequentially into the solution to form CdSe and CdSe/CdS QDs, respectively. The synthesized water-soluble CdSe and CdSe/CdS QDs possess high quantum yield (3 and 20 %) and narrow full-width-at-half-maximum (43 and 38 nm). The synthesis process is easily reproducible with simple apparatus and low-toxic chemicals. The relatively standard deviation of maxima fluorescence intensity is only 2.1 % (n = 7) for CdSe and 3.6 % (n = 7) for CdSe/CdS QDs. This developed route is simple, environmentally friendly and can be readily extended to the large-scale aqueous synthesis of QDs.     

Optical memory based on photo-activated fluorescence of core/shell CdSe/CdS quantum dots embedded in poly(butylmethacrylate)

This work presents the observation of a photo-activated fluorescence from core/shell quantum dots of CdSe/CdS incorporated in a poly(butylmethacrylate) matrix. Upon illumination with UV-light, the intensity of fluorescence from the quantum dots increases as seen by naked eyes at ambient conditions. This allows its utilization in optical memory media based on thin films of CdSe/CdS polymer nanocomposites suitable for practical application. The quantum dots are synthesized by the hot-injection method and embedded in poly(butylmethacrylate) matrix by radical polymerization with 1,1′-azobis-(cyclohexanecarbonitrile). The fluorescence of quantum dots quenched during the polymerization process, but appeared again after illumination of the nanocomposite material with UV-light. The fluorescence properties of quantum dots are governed by the presence of trioctylphosphine oxide in the matrix, which allows control of the optical memory effect.     

Synthesis of blue fluorescence CdS quantum dots stabilized by L-cysteine in aqueous phase

In this paper we report a novel synthesis method of blue fluorescence CdS quantum dots stabilized by L-cysteine in aqueous phase. When pH value of the core/shell CdTe/CdS colloid solution changed from 11.6 to 1.5, blue fluorescence CdS QDs was obtained. The fluorescence emission wavelength yielded a hypsochromic shift from 540 nm to 438 nm corresponding to the absorption peak position gave a hypsochromic shift from 518 nm to 352 nm. The CdS QDs were characterized by XPS and TEM. And the photostability of CdS QDs solution irradiated with UV lamp under open air condition at room temperature was very stable.     

Charged excitons, Auger recombination and optical gain in CdSe/CdS nanocrystals

CdSe/CdS colloidal nanocrystals are members of a novel class of light-emitting nanoparticles with remarkable optical properties such as suppressed fluorescence blinking and enhanced emission from multiexciton states. These properties have been linked to the suppression of non-radiative Auger recombination. In this work we employ ultrafast spectroscopy techniques to identify optical signatures of neutral and charged excitonic and multiexcitonic states. We show that Auger recombination of biexcitons is not suppressed, while we observe optical gain and amplified spontaneous emission from multiexciton states and from long-lived charged-exciton states.     

Method for determining the elemental composition and distribution in semiconductor core-shell quantum dots

In the biological sciences, the use of core-shell quantum dots (QDs) has gained wide usage but analytical challenges still exist for characterizing the QD structure. The application of energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy (XPS) to bulk materials is relatively straightforward; however, for meaningful applications of surface science techniques to multilayer nanoparticles requires novel modifications and analysis methods. To experimentally characterize the elemental composition and distribution in CdSe/CdS/ZnS QDs, we first develop a XPS signal subtraction technique capable of separating the overlapped selenium 3s (core) and sulfur 2s (shell) peaks (both peaks have binding energies near 230 eV) with higher precision than is typically reported in the nanoparticle literature. This method is valid for any nanoparticle containing selenium and sulfur. Then we apply a correction formula to the XPS data and determine that the 2 nm stoichiometric CdSe core is surrounded by 2 CdS layers and a stoichimetric ZnS monolayer. These findings and the multiapproach methodology represent a significant advancement in the detailed surface science study of multilayer nanoparticles. In agreement with recent surprising findings, the time-of-flight secondary mass spectrometry measurements suggest that the surface sites of the QDs used in this study are primarily covered with a mixture of octadecylphosphonic acid and trioctylphophine oxide.     

Synthesis, morphology, and optical properties of colloidal CdTe/CdSe and CdTe/CdS nanoheterostructures based on CdTe tetrapods

We report the synthesis of colloidal CdTe/CdSe and CdTe/CdS nanoheterostructures based on CdTe tetrapods with a CdSe or CdS shell. The shell growth takes place on the lateral faces of the tetrapod legs, whereas the leg length remains essentially unchanged. Both the CdSe and CdS shell growth shifts the luminescence of the nanoheterostructures to the near-IR range, up to 850 nm, with a quantum yield of up to 20%. Analysis of the kinetics of the shift of the excitonic absorption band during nanoheterostructure growth suggests that the growth rate of CdS exceeds that of CdSe. The variation of the luminescence wavelength with shell thickness is compared to numerical modeling results.