Strong thermal optical nonlinearity caused by CdSe nanoparticles synthesised in smectic ionic liquid crystal

Spectral and nonlinear optical properties of cadmium octanoate composites containing CdSe nanoparticles (NPs) have been studied by using optical absorption spectroscopy and laser scanning technique (Z-scan). CdSe NPs are chemically synthesised in thermotropic ionic liquid crystal (ILC) phase of cadmium octanoate which is used as nanoreactor. Anisotropic glassy nanocomposites are obtained by the rapid cooling of the ILC phase of nanocomposites to room temperature. The sizes of the CdSe NPs are determined from the absorption spectra. The thermo-optical nonlinearity of the new nanocomposites is characterised by extremely large value of the nonlinear refractive index, n₂, under relatively low-powered CW laser irradiation. This nonlinearity is caused by (1) the efficient light-induced heating due to the CdSe NPs strong exciton absorption, and (2) consequent thermal dissipation, which in turn, produces the photoelastic tensions in the glassy smectic matrix.     

Structural characteristics of different types of nanoparticles synthesised in mesomorphic metal alkanoates

The class of thermotropic ionic liquid crystals (LCs) of the metal alkanoates possesses a number of unique properties, such as intrinsic ionic conductivity, high dissolving ability and ability to form time-stable mesomorphic glasses. These ionic LCs can be used as nanoreactors for the synthesis and stabilisation of different types of nanoparticles (NPs). Thus, some semiconductors, metals and core/shell NPs were chemically synthesised in the thermotropic ionic liquid crystalline phase (smectic A) of the cadmium octanoate (CdC₈) and of the cobalt octanoate (CoC₈). By applying the scanning electron microscopy, the cadmium and cobalt octanoate composites containing CdS, Au, Ag and core/shell Au/CdS NPs have been studied. NPs’ sizes and dispersion distribution of the NPs’ size in the nanocomposites have been obtained.     

Facile synthesis of fluorescent quantum dot‐polymer nanocomposites via frontal polymerization

We report an available approach for quickly fabricating CdS QD‐polymer nanocomposites via frontal polymerization (FP). First, we synthesized (3‐mercaptopropyl)‐1‐trimethoxysilane (MPS)‐capped CdS quantum dots (QDs). With these MPS‐capped CdS QDs containing mercapto groups, MPS‐capped CdS QDs can be easily incorporated into a poly(N‐methylolacrylamide) (PNMA) matrix via FP. A variety of features for preparing QD‐polymer nanocomposites, such as initiator concentration and CdS concentration, were thoroughly investigated. The fluorescence properties of QD‐polymer nanocomposites prepared via FP are comparatively investigated on the basis of ultraviolet–visible (UV–vis) spectra and photoluminescence (PL) spectra. Results show that the PL intensity of QD‐polymer nanocomposites prepared via the FP method is superior to that obtained by the traditional batch polymerization (BP) method. In addition, by measuring the changes of PL intensity of the samples immersed in different concentrations of copper acetate solution, we found the QD‐polymer nanocomposites can be ultrasensitive to copper ions. This FP process can be exploited as a facile and rapid way for synthesis QD‐polymer nanocomposites on a large scale, avoiding the fluorescence quenching of nanocrystals during incorporation nanocrystals into polymer matrices. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2170–2177, 2010     

Fine tuning of the morphology of copper oxide nanostructures and their application in ambient degradation of methylene blue

A low-cost, green, and reproducibly non-injection one-pot synthesis of high-quality CdS quantum dots (QDs) is reported. The synthesis was performed in the open air by mixing precursors cadmium stearate and S powder into a new solvent N-oleoylmorpholine. An overlapped nucleation-growth stage followed by a dominated growth stage was observed. The resulting QDs exhibited well-resolved absorption fine substructure and a dominant band-edge emission with a narrow size distribution (the full width at half maximum (fwhm) was only 22-24nm). The maximum photoluminescence (PL) quantum yield (QY) was as high as 46.5%. Highly monodispersed CdS QDs with tunable sizes and similar PL fwhm and QYs could also be obtained from the CdS QDs in a large-scale synthesis. The high-resolution transmission electron microscopy (HRTEM) images and powder X-ray diffraction (XRD) pattern suggested that the as-prepared QDs with high crystallinity had a cubic structure. A significant PL improvement and a continuous QY increase for the CdS QDs were observed during a long storage time in air and in a glovebox under room temperature. A slow surface reconstruction was proposed to be the cause for the PL enhancement of CdS QDs.     

Direct Anisotropic Growth of CdS Nanocrystals in Thermotropic Liquid Crystal Templates for Heterojunction Optoelectronics

The direct growth of CdS nanocrystals in functional solid‐state thermotropic liquid crystal (LC) small molecules and a conjugated LC polymer by in situ thermal decomposition of a single‐source cadmium xanthate precursor to fabricate LC/CdS hybrid nanocomposites is described. The influence of thermal annealing temperature of the LC/CdS precursors upon the nanomorphology, photophysics, and optoelectronic properties of the LC/CdS nanocomposites is systematically studied. Steady‐state PL and ultrafast emission dynamics studies show that the charge‐transfer rates are strongly dependent on the thermal annealing temperature. Notably, annealing at liquid‐crystal state temperature promotes a more organized nanomorphology of the LC/CdS nanocomposites with improved photophysics and optoelectronic properties. The results confirm that thermotropic LCs can be ideal candidates as organization templates for the control of organic/inorganic hybrid nanocomposites at the nanoscale level. The results also demonstrate that in situ growth of semiconducting nanocrystals in thermotropic LCs is a versatile route to hybrid organic/inorganic nanocomposites and optoelectronic devices.     

Role of surface modification of colloidal CdSe quantum dots on the properties of hybrid organic–inorganic nanocomposites

In this work, tri-octyl phosphine/tri-octyl phosphine oxide (TOPO)-capped cadmium selenide (CdSe) quantum dots (QDs) of varied sizes (5–9 nm), prepared by varying the input Cd:Se precursor ratio using chemical route, were dispersed in conducting polymer matrices viz. poly[2-methoxy, 5-(2-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) and poly(3-hexylthiophene) (P3HT). By using a binary solvent mixture (pyridine–chloroform), homogeneous dispersion of CdSe nanocrystals in polymers (MEH-PPV, P3HT) could be realized. The properties of the resulting dispersions could be tailored by the composition and concentration of QDs in polymer. The emission and structural properties of polymer–CdSe nanocomposites are found to be dependent on the crystallite size and morphology of CdSe nanocrystallites. An effective quenching of photoluminescence emission in the polymer nanocomposite was observed for smaller CdSe quantum dots (size ∼6 nm) as compared to larger CdSe quantum dots (size ∼9 nm), thus ensuring efficient charge transfer process across the polymer–CdSe interface in the former case. The incomplete quenching, particularly for MEH-PPV:CdSe nanocomposites, could be as a result of insufficient coverage of polymers on the surface of CdSe nanocrystallites, mainly due to phase segregation for TOPO-stripped CdSe nanocrystallites. The superior morphology and optical properties of polymer nanocomposite (P3HT:CdSe QDs) could play a pivotal role for the realization of effective charge separation and transport in hybrid solar cells.     

Facile fabrication of fluorescent-superhydrophobic bifunctional ligand-free quantum dots

We present herein a facile strategy for fabrication of fluorescent-ultrahydrophobic bifunctional ligand-free CdS quantum dots (QDs) using cadmium acetate, sodium sulfide as starting materials, and ethanol as the solvent. The as-prepared CdS QDs without ligands exhibit good photochemical stability and photoluminescence (PL) in comparison with the previously reported aqueous CdS QDs. The effects of various experimental variables, including Cd/S molar ratio, reaction time, and reaction temperature on the optical properties of the obtained CdS QDs have been systematically investigated. Subsquently, dodecanethiol was introduced to modify these CdS QDs, further conferring them with superhydrophobic property, along with good compatibility with polymers. The features and structures of the as-prepared QDs and their hybrids on UV–Vis, PL spectroscopy, Fourier transform infrared, transmission electron microscope, X-ray diffraction, and contact angle have been disscussed.     

Role of the Polymer Matrix on the Photoluminescence of Embedded CdSe Quantum Dots

The photoluminescence (PL) of CdSe quantum dots (QDs) that form stable nanocomposites with polymer liquid crystals (LCs) as smectic C hydrogen‐bonded homopolymers from a family of poly[4‐(n‐acryloyloxyalkyloxy)benzoic acids] is reported. The matrix that results from the combination of these units with methoxyphenyl benzoate and cholesterol‐containing units has a cholesteric structure. The exciton PL band of QDs in the smectic matrix is redshifted with respect to QDs in solution, whereas a blueshift is observed with the cholesteric matrix. The PL lifetimes and quantum yield in cholesteric nanocomposites are higher than those in smectic ones. This is interpreted in terms of a higher order of the smectic matrix in comparison to the cholesteric one. CdSe QDs in the ordered smectic matrix demonstrate a splitting of the exciton PL band and an enhancement of the photoinduced differential transmission. These results reveal the effects of the structure of polymer LC matrices on the optical properties of embedded QDs, which offer new possibilities for photonic applications of QD–LC polymer nanocomposites.     

Surface-tunable photoluminescence from block copolymer-stabilized cadmium sulfide quantum dots

The static and time-resolved photoluminescence properties of polystyrene-b-poly(acrylic acid) (PS-b-PAA)-stabilized cadmium sulfide quantum dots (CdS QDs) have been characterized for the first time, demonstrating tunable emission spectra and quantum yields via different chemical treatments of the PAA layer. Samples with the PAA layer in its cadmium carboxylate form showed more-intense band-edge emission and relatively high quantum yields compared with samples in which the PAA layer was in its acid form. This activation effect is explained in terms of passivation of trap sites on the QD surface by specific interactions between the QD and the cadmium-neutralized PAA layer. Lifetimes of band-edge and trap state emission for the various samples ranged from 40 to 61 ns and 244 to 360 ns, respectively. Impressive long-term stability was also shown for a sample of cadmium-neutralized PS-b-PAA-stabilized QDs dispersed in toluene, which maintained 90% of its photoluminescence over 57 days aging under ambient conditions. It is also shown that Cd2+ activation of photoluminescence does not occur when Mg2+ ions are added to similar QD solutions, indicating potential of these block copolymer-stabilized QDs as Cd2+-selective sensors. Irrespective of chemical treatment of the PAA layer, the external PS brush layer effectively stabilized all samples in various organic solvents, resulting in clear CdS colloids with no observed precipitation over several months. Dynamic light scattering and gel permeation chromatography revealed differences in the aggregation numbers and hydrodynamic radii of colloidal QDs for different treatments of the PAA layer, attributed to the lower solubility of the poly(cadmium acrylate) blocks compared to the PAA blocks in the acid form. Finally, it was demonstrated that the PS-b-PAA-stabilized QDs could be well dispersed in PS homopolymer, producing optically transparent photoluminescent films which retained the emission features of the colloidal QDs. Stable and surface-tunable optical properties via the PAA layer and polymer solubility and processability via the PS layer make these PS-b-PAA-stabilized CdS QDs exciting "building blocks" for the bottom-up assembly of functional hierarchical materials for photonics, sensors, and bio-labeling applications.     

低温水相合成巯基化聚乙烯醇/CdS量子点纳米复合物及用于测定环境水样中痕量Cu~(2+)

采用水相合成法,在低温N2气保护条件下,以巯基化聚乙烯醇(PVA)为基体材料合成一种环境友好型PVA/CdS量子点纳米复合物,并通过红外光谱(IR)、X射线粉末衍射(XRD)、透射电子显微镜(TEM)、热重(TG)、荧光光谱(PL)和紫外可见光谱(UV-Vis)等技术手段对复合物进行结构表征和光学性能研究。测试结果表明,复合物中CdS量子点为立方晶型结构,形状为球形,粒径小于5nm,具有很好的稳定性、分散性及发光性质。此外,Cu~(2+)对PVA/CdS水溶液荧光具有良好的猝灭作用,其荧光猝灭程度与Cu~(2+)浓度在1~1000nmol/L范围内呈良好的线性关系,线性相关系数为0.9923,方法检出限为0.12nmol/L。该纳米复合物荧光分析方法简便快速、灵敏度高、检出限低,已应用于实际黄河水样中痕量Cu~(2+)的分析与检测。     

溶剂对聚酰胺-胺树形分子模板法原位制备CdS量子点的影响

为了研究非配位型溶剂对聚酰胺-胺(PAMAM)树形分子的模板法制备CdS量子点的影响, 分别以水、甲醇及二者的混合物( ∶ ＝2∶1)为溶剂, 以4.5代PAMAM树形分子为模板制备了CdS量子点. 结果表明, 相同条件下, 以甲醇为溶剂时制备的CdS量子点为单晶, 平均直径2.7 nm, 尺寸分布窄, 发光强度高; 以水为溶剂制备的CdS量子点为多晶, 平均直径为5.7 nm, 尺寸分布宽, 发光强度低; 在甲醇与水的混合溶剂中制备的CdS量子点为单晶和多晶共存, 平均直径为4.1 nm, 尺寸分布及发光强度都居中. 这主要是由于树形分子的模板作用不同造成的. 树形分子在甲醇中能充分伸展, 起到内模板作用; 树形分子与水之间由双氢键作用而产生交联, 不利于Cd^2＋与树形分子内部基团的配位, 主要起到外模板作用; 在甲醇与水的混合溶剂中, 树形分子则同时起到了内模板和外模板作用.     

Chemical synthesis and optical properties of CdS–poly(lactic acid) nanocomposites and their transparent fluorescent films

This paper describes the first synthesis of cadmium sulfide (CdS)-poly(lactic acid) (PLA) nanocomposites and their transparent fluorescent films by covalently grafting PLA onto the surfaces of CdS nanocrystals (NCs). Synthesis of the nanocomposites involved two steps. Lactic acid (LA)-capped CdS NCs were first prepared by reacting cadmium chloride (CdCl₂) with sodium sulfide (Na₂S) using LA as the organic ligand in H₂O/N,N-dimethylformamide (DMF) solution. CdS–PLA nanocomposites were then formed by in situ ring-opening polymerization of lactide on the surface of modified CdS NCs. We also demonstrated herein the fabrication of the transparent fluorescent films of CdS–PLA nanocomposites by blending as-prepared nanocomposites with high-molecular-weight PLA. The as-prepared CdS NCs and their nanocomposites were studied by transmission electron microscopic imaging, thermogravimetric analyses, and spectroscopic measurements (ultraviolet–visible absorption and photoluminescence). The results revealed that the CdS–polymer nanocomposites exhibited good optical properties in terms of their photoluminescence and transparency.     

Copolymer nanosphere encapsulated CdS quantum dots prepared by RAFT copolymerization: synthesis,characterization and mechanism of formation

Cadmium sulfide (CdS) quantum dots (QDs) encapsulated in block copolymer spheres were synthesized by an aqueous emulsion polymerization process. First, stable dispersions of CdS QDs in water were prepared using a polymer dispersant, either poly(acrylic acid) or a random copolymer having an average of ten acrylic acid and five butyl acrylate units. These polymer dispersants were prepared by reversible addition-fragmentation chain transfer polymerization. Then, the CdS QDs dispersed in water were encapsulated in a polystyrene shell using an emulsion polymerization process. Spectroscopic and microscopic techniques were used to characterize the resulting nanocomposites. Optical properties of QDs in polymer microspheres were investigated by UV-vis and fluorescence spectroscopic studies. Particle sizes of all CdS QD samples were calculated from absorption edges using Henglein's empirical curve. Transmission electron microscopy was used to determine the size and morphology of CdS QD samples. These observations were used to elucidate the mechanism of formation of the resulting well-defined polymer-encapsulated CdS nanoparticles.     

Preparation of cadmium sulfide nanoparticles in self-reproducing reversed micelles

Octyl octanoate (O-OL) underwent hydrolysis in sodium octanoate (NaOA) reversed micelles in 85:15 = isooctane:octanol (OL) (v/v), containing w = [H2O]/[NaOA] = 40. The products of the hydrolysis, octanoic acid (OA) and octanol (OL), lead to the formation of additional (albeit smaller) reversed micelles; hence the process is considered to be self-reproducing. Self-reproduction was found to be catalyzed by lithium hydroxide, solubilized in the water pools, as well as by hydrogen sulfide, added to the solution of the reversed micelles. Addition of hydrogen sulfide to cadmium perchlorate containing self-reproducing reversed micelles resulted in the formation of cadmium sulfide (CdS) nanoparticles. Diameters of the CdS containing nanoparticles could be altered from 5.4 to 1.8 nm by changing the [Cd2+]/[H2S] ratios from 0.25 to 10. The CdS nanoparticles formed were capped by mercaptopropionic acid, isolated as solids, and could be repeatedly redispersed in water without changing their sizes. Additional CdS nanoparticles were generated in the supernatants removed from the precipitated capped CdS nanoparticles.     

Photoassisted synthesis of CdSe and core-shell CdSe/CdS quantum dots

This paper describes the synthesis of core-shell CdSe/CdS quantum dots (QDs) in aqueous solution by a simple photoassisted method. CdSe was prepared from cadmium nitrate and 1,1-dimethylselenourea precursors under illumination for up to 3 h using a pulsed Nd:YAG laser at 532 nm. The effects that the temperature and the laser irradiation process have on the synthesis of CdSe were monitored by a series of experiments using the precursors at a Cd:Se concentration ratio of 4. Upon increasing the temperature (80-140 degrees C), the size of the CdSe QDs increases and the time required for reaching a maximum photoluminescence (PL) is shortened. Although the as-prepared CdSe QDs possess greater quantum yields (up to 0.072%) compared to those obtained by microwave heating (0.016%), they still fluoresce only weakly. After passivation of CdSe (prepared at 80 degrees C) by CdS using thioacetamide as the S source (Se:S concentration ratio of 1) at 80 degrees C for 24 h, the quantum yield of the core-shell CdSe/CdS QDs at 603 nm is 2.4%. Under UV irradiation of CdSe/CdS for 24 h using a 100-W Hg-Xe lamp, the maximum quantum yield of the stable QDs is 60% at 589 nm. A small bandwidth (W1/2 < 35 nm) indicates the narrow size distribution of the as-prepared core-shell CdSe/CdS QDs. This simple photoassisted method also allows the preparation of differently sized (3.7-6.3-nm diameters) core-shell CdSe/CdS QDs that emit in a wide range (from green to red) when excited at 480 nm.     

Liquid-crystalline polymer composites with CdS nanorods: structure and optical properties

We report on the structure, uniaxial orientation, and photoluminescent properties of CdS nanorods that form stable nanocomposites with smectic C hydrogen-bonded polymers from the family of poly(4-(n-acryloyloxyalkoxy)benzoic acids. TEM analysis of microtomed films of nanocomposites reveals that CdS nanorods form small domains that are homogeneously distributed in the LC polymer matrix. They undergo long-range orientation with the formation of one-dimensional aggregates of rods when the composite films are uniaxially deformed. The Stokes photoluminescence was observed from CdS NRs/LC polymer composites with emission peak located almost at the same wavelength as that of NRs solution in heptane. An anti-Stokes photoluminescence (ASPL) in polymer nanocomposites was found under the excitation below the nanoparticles ground state. The mechanism of ASPL was interpreted in terms of thermally populated states that are involved in the excitation process. These nanocomposites represent an unusual material in which the optical properties of anisotropic semiconductor nanostructures can be controlled by mechanical deformation of liquid-crystalline matrix.     

Controlled self-assembly of hydrophobic quantum dots through silanization

We demonstrate the formation of one-, two-, and three-dimensional nanocomposites through the self-assembly of silanized CdSe/ZnS quantum dots (QDs) by using a controlled sol-gel process. The self-assembly behavior of the QDs was created when partially hydrolyzed silicon alkoxide monomers replaced hydrophobic ligands on the QDs. We examined systematically self-assembly conditions such as solvent components and QD sizes in order to elucidate the formation mechanism of various QD nanocomposites. The QD nanocomposites were assembled in water phase or on the interface of water and oil phase in emulsions. The partially hydrolyzed silicon alkoxides act as intermolecules to assemble the QDs. The QD nanocomposites with well-defined solid or hollow spherical, fiber-like, sheet-like, and pearl-like morphologies were prepared by adjusting the experimental conditions. The high photoluminescence efficiency of the prepared QD nanocomposites suggests partially hydrolyzed silicon alkoxides reduced the surface deterioration of QDs during self-assembly. These techniques are applicable to other hydrophobic QDs for fabricating complex QD nanocomposites.     

聚合物/量子点纳米复合材料的制备

量子点具有优异的光电性能,聚合物具有性质稳定、质轻、可加工性好等优点;将聚合物和量子点复合可综合两者的优点,同时还可使量子点的稳定性得以大幅度提高。得到的聚合物/量子点纳米复合材料应用领域广;其制备方法主要有简单易操作的直接分散法、在聚合物中原位生成量子点的原位生成法、在有量子点存在的聚合场所引发有机单体聚合的原位聚合法、层-层组装法以及在量子点表面直接修饰聚合物的表面直接修饰法。本文就这些制备方法进行了概要综述,并对各种方法的特点进行了总结。     

CdS量子点的一步法合成及量子产率

以油酸为配体,十八烯为溶剂,采用一步法合成了CdS量子点,研究了反应温度、反应时间和Cd/S的摩尔比对量子点光谱性能的影响.X射线衍射(XRD)和高分辨透射电镜(HRTEM)测试结果表明,所获得的CdS量子点为立方闪锌矿结构,且尺寸分布均一,结晶度高,其较强的带边发光、尖锐的紫外吸收峰以及狭窄的荧光发射峰进一步表明量子...     

Fragmentation of Magic-Size Cluster Precursor Compounds into Ultrasmall CdS Quantum Dots with Enhanced Particle Yield at Low Temperatures

Colloidal small-size CdS quantum dots (QDs) are produced usually with low particle yield, together with side products such as the particular precursor compounds (PCs) of magic-size clusters (MSC). Here, we report our synthesis of small-size CdS QDs without the coexistence of the PC and thus with enhanced particle yield. For a conventional reaction of cadmium oleate (Cd(OA)₂) and sulfur (S) in 1-octadecene (ODE), we show that after the formation of the PC in the pre-nucleation stage, the addition of tri-n-octylphosphine oxide (TOPO) facilitates the production of small-size QDs. We demonstrate that TOPO fragmentizes the PC that have formed, which enables the nucleation and growth of small-size QDs even at room temperature. Our findings introduce a new approach to making small-size QDs without the coexistence of the PC and with improved particle yield. Providing experimental evidence for the two-pathway model proposed for the pre-nucleation stage of colloidal binary QDs, the present study aids in the advance of non-classical nucleation theory.