Enhancing the device performance of a blue light‐emitting copolymer using CdSe/ZnS quantum dots

An alternating triarylamine‐functionalized fluorene‐based copolymer synthesized using a Suzuki–Miyaura cross‐coupling procedure is used as blue emitting layer in polymer light‐emitting diodes (PLEDs). Subsequently, the effects of CdSe/ZnS quantum dots (QDs) on the optoelectronic properties of the copolymer are investigated. Therefore, CdSe/ZnS QDs are embedded into the copolymer matrix and hybrid PLEDs are fabricated. The devices comprised of CdSe/ZnS QDs reveal enhanced performances, yielding about 3.4 times more luminous efficiency than that of the device without QDs. Further enhancement is achieved by using electron transport layer; the luminous efficiency rose from 0.065 to 1.740 cd A^?1 for the hybrid PLEDs, corresponding to a superb 27‐fold intensification of the efficiency. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 147–156     

Luminescence and stability of aqueous thioalkyl acid capped CdSe/ZnS quantum dots correlated to ligand ionization.

The spectroscopic properties of CdSe/ZnS quantum dots (QDs) were observed to change as a function of thioalkyl acid ligand. Experiments were performed using 2, 3, 6, and 11-carbon linear thioalkyl acids, as well as mercaptosuccinic acid (MSA) and dihydrolipoic acid (DHLA). Bathochromic shifts of up to 14 nm in the emission spectra of QDs capped with these ligands were observed. Similarly, hypsochromic or bathochromic shifts up to 7 nm were observed for a specific ligand in acidic or basic solution, respectively. These shifts could be correlated to the number of ionized ligands and the ability of the ligands to act as hole acceptors. It was also found that differences in quantum yield between the ligands were primarily due to variations in radiative decay rate and not nonradiative decay rate. This indicated that different degrees of QD surface passivation were not responsible for the differences, and that the radiative system must be considered as the sum of the ligands and the QD nanocrystal. The stability of QDs capped with mercaptoacetic acid, MSA, and DHLA towards aggregation at low pH was found to correlate with the pK(a) of the ligands. Spectral shifts were also observed during aggregation. Overall, the luminescence of thioalkyl acid capped QDs appears to be a complex function of dielectric constant, electrostatic or hole-acceptor interactions with ionized ligands, and, to a lesser extent, passivation.     

核-壳结构CdSe/ZnS量子点的制备、硫醇修饰及其光学性能

采用高温有机相包覆技术制备了CdSe/ZnS核壳结构量子点材料,考察了包覆量对量子点材料的光学性能的影响,研究了含脂肪链和芳香基的双硫醇分子1,4-苯二甲硫醇和1,8-辛二硫醇对于具有核-壳结构的CdSe/ZnS量子点材料的修饰作用,考察了修饰作用对于量子点的量子效率和荧光强度等光学性能的影响.实验结果表明:随着硫化锌包覆量的增加,量子点的量子效率及其荧光发射强度明显提高;硫醇的修饰能显著增强量子点的发光强度,随着硫醇浓度的增加,其发光性能增强,但是达到一定程度后,光学性能基本不随硫醇浓度的变化而变化.根据固体核磁共振等实验结果推测:硫醇分子可能部分替代了量子点体系中的正三辛基氧膦配体,稳定了量子点体系,对量子点起修饰保护作用,从而提高了量子点的光学性能.     

Controllable synthesis of novel sandwiched polyaniline/ZnO/polyaniline free‐standing nanocomposite films

Controllable synthesis of novel sandwiched polyaniline (PANI)/ZnO/PANI free‐standing nanocomposite films is reported via spin coating of ZnO quantum‐dot interlayer on PANI base layer and then PANI surface layer on the ZnO interlayer. The thickness of the ZnO interlayer and the PANI surface layer can be easily controlled by adjusting spin time and spin speed, respectively. The effects of the ZnO interlayer thickness and the PANI surface layer thickness are examined in detail on the photoluminescence (PL) property. It is worth noting that coverage of the PANI surface layer on the ZnO interlayer can not only lead to great enhancement in the PL property but also to a maximum PL intensity at a medium PANI surface layer thickness. This maximum PL property is caused by the combined ZnO/PANI carrier transportation and PANI shielding effects. In addition, the nanocomposite films show reasonably good conductivity. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Ionic impurities in nematic liquid crystal doped with quantum dots CdSe/ZnS

We investigated the dielectric losses and the ionic currents in the nematic liquid crystal (NLC) doped with semiconductor quantum dots (QDs) of CdSe/ZnS core – shell type and covered with trioctylphosphine oxide (TOPO) molecules. The dielectric loss tangent of the NLC composites increased with increasing the QDs concentration from 0.1 to 0.3 wt%. The density of mobile ions in the composites increased linearly and the average values of ions mobility in the composites decreased with increasing the QDs concentration. The fast ions with the mobility of about 10^–10 m²/V·s and the slow ions with the mobility of about 10^–11 m²/V·s were detected in the NLC composites. The growth of the content of slow ions took place with increasing the QDs concentrations. Increasing the dielectric loss tangent was observed with increasing the duration of sonication time of the NLC composites to prepare homogeneous suspensions. The fragmentation of the CdS/ZnS shell as a result of the sonication may lead to the appearance of the slow ions in the NLC composites.     

Determination of volume fractions and ligand layer thickness of polymer/CdSe quantum dot blend films by effective medium approximations

We investigate hybrid organic/inorganic films using different polymers and CdSe quantum dots (QD) and nanorods (NR) with hexanoic acid (HA)‐treated hexadecylamine (HDA) or pyridine as the capping ligands. The volume ratios of the polymer:nanoparticle (NP) blends are studied by spectroscopic ellipsometry and transmission intensity data. Effective medium approximation based on the results of the pristine films is applied. With this routine, the polymer/NP volume ratio of the blend can be identified. In combination with the mass ratio of the components, the mass density of the NP including the inorganic crystalline core and the organic ligand layer is obtained. A geometrical model for QD and NR allows for the estimation of the ligand layer thickness. We find pyridine and HDA after HA treatment to be 0.9 and 0.6 nm on the QD surface, respectively. By contrast, the effective thickness of the organic ligand is 3.0 nm on the investigated NR. In both cases, the organic layer is thicker than a monolayer of the expected pyridine due to the presence of extant synthesis ligands as a result of incomplete ligand exchange. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 000: 000–000, 2011     

柠檬酸盐稳定的水溶性CdSe量子点的合成及表征

以柠檬酸三钠为稳定剂在水溶液中合成了水溶性CdSe量子点,用X射线粉末衍射、透射电镜、紫外-可见吸收光谱和荧光发射光谱对CdSe量子点的结构、形貌及其荧光性质进行了表征.结果表明合成的CdSe量子点为立方闪锌矿结构,呈球形,分散性良好,平均尺寸约为2.6nm,具有窄且对称的荧光发射光谱,半峰宽为45nm.     

Characterizing mixed phosphonic acid ligand capping on CdSe/ZnS quantum dots using ligand exchange and NMR spectroscopy

The ligand capping of phosphonic acid functionalized CdSe/ZnS core–shell quantum dots (QDs) was investigated with a combination of solution and solid‐state ³¹P nuclear magnetic resonance (NMR) spectroscopy. Two phosphonic acid ligands were used in the synthesis of the QDs, tetradecylphosphonic acid and ethylphosphonic acid. Both alkyl phosphonic acids showed broad liquid and solid‐state ³¹P NMR resonances for the bound ligands, indicative of heterogeneous binding to the QD surface. In order to quantify the two ligand populations on the surface, ligand exchange facilitated by phenylphosphonic acid resulted in the displacement of the ethylphosphonic acid and tetradecylphosphonic acid and allowed for quantification of the free ligands using ³¹P liquid‐state NMR. After washing away the free ligand, two broad resonances were observed in the liquids' ³¹P NMR corresponding to the alkyl and aromatic phosphonic acids. The washed samples were analyzed via solid‐state ³¹P NMR, which confirmed the ligand populations on the surface following the ligand exchange process. Copyright © 2015 John Wiley & Sons, Ltd.     

Construction of CdSe/ZnS quantum dot microarray in a microfluidic chip

Microarray technology has been proved to be greatly helpful for biomedical and biological diagnosis. And the evaluation of its biological applications lies in the detection sensitivity, which requires high intensity and stability of the signal. Recently, several nanomaterials, especially semiconductor nanomaterials, due to their excellent fluorescence properties, have been widely used to construct microarrays for biosensors. Here, we presented an approach for constructing CdSe/ZnS quantum dot (QD) microarray in microfluidic channels on a glass slide by photolithography. The conditions for immobilizing stable and uniform QD microarray on the glass slide were optimized. Several types of QD microarrays with different emission wavelengths and modified groups were constructed using silanization and lithography technology. Based on the fluorescence quenching effect of Cu2+ on QDs, the microfluidic chip with QD microarray was applied for the determination of Cu2+. 1 nmol/L Cu2+ could be detected by this method.     

La掺杂ZnS量子点的制备及其表征

ZnS量子点的发光强度较弱,用水相合成技术掺杂一定浓度的La3+可以增强其发光性能。本文以实验用N-乙酰-L-半胱氨酸作保护剂,Zn(Ac)2作锌源,Na2S作硫源、La(Ac)3作镧源合成La掺杂的ZnS量子点,并通过透射电镜(TEM)和X-射线粉末衍射(XRD)对其物相进行了表征。紫外-可见(UV-Vis)及荧光(PL)光谱性质亦进行了表征。     

Synthesis and characterization of monodisperse CdSe quantum dots in different organic solvents

Nearly monodisperse CdSe quantum dots (QDs) have been prepared by a soft solution approach using air-stable reagents in different organic solvents. This scheme is a supplement to the conventional thermal decomposition of organometallic compounds at higher temperatures. CdSe nanocrystals of different sizes could be obtained by simply changing the solvent. This method is reproducible and simple and thus can be readily scaled up for industrial production. The reaction process was monitored by the temporal evolution of the UV-Vis absorption and room temperature photoluminensce spectra. The structures of the CdSe quantum dots were determined by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). The phase-transfer of oleic acid-stabilized CdSe nanocrystals into PBS buffer solutions was also studied for their potentials in biological applications. __________ Translated from Journal of Shanghai Jiaotong University, 2005, 39(1) (in Chinese)     

Controllable synthesis of ZnS/PMMA nanocomposite hybrids generated from functionalized ZnS quantum dots nanocrystals

We reported controllable synthesis of ZnS nanocrystal-polymer transparent hybrids by using polymethylmethacrylate (PMMA) as a polymer matrix. In a typical run, the appropriate amounts of zinc chloride (ZnCl₂) and sodium sulfide (Na₂S) in the presence of 2-mercaptoethanol (ME) as the organic ligand were well dispersed in H₂O/dimethylformamide solution without any aggregation. In addition, the Mn-doped ZnS nanocrystals (NCs) were synthesized with similar method. Then, ZnS-PMMA hybrids were obtained via free radical polymerization in situ by using ZnS NCs functionalized with methacryloxypropyltrimethoxysilane (MPS). FT-IR characterization indicates the formation of robust bonding between ZnS NCs and the organic ligand. The TEM images show that ZnS NCs are well dispersed in PMMA matrix, and particle size of as-prepared ZnS NCs is about 2.6 nm, in agreement with the computing results of Brus’s model and Debye–Scherrer formula. The photoluminescence measurements present that ZnS NCs, Mn-doped ZnS NCs, and ZnS/PMMA hybrid show good optical properties.     

Electroluminescence from a conjugated polymer grafted with CdSe/ZnS: High brightness and improved efficiency

A new series of sulfide‐substituted poly(1,4‐phenylene vinylene) derivatives ( S1PPV–S3PPV ) with different composition ratios were successfully synthesized via the Gilch route. The CdSe/ZnS were grafted to the sulfur atoms by ligand exchange reaction. The grafted CdSe/ZnS contents were determined from TGA analysis to be from 4.6 to 37.8%. A new peak at 1151 cm^?1 formed in FT‐IR after ligand exchange, which is attributed to the force formation between sulfur and CdSe. The GPC results show that the molecular weights of final polymers became higher after ligand exchange. Thin films of obtained polymers emitted bright green and yellow light with the max emission peak located from 546 to 556 nm. Double‐layer LEDs with an ITO/PEDOT/polymer/Ca/Al configuration were fabricated to evaluate the potential use of these polymers. The turn‐on voltages of the devices were about 4–5 V. As the CdSe/ZnS content increased in grafted polymers, the device performance was significantly enhanced as compared to pristine polymers. In the case of S3PPV , the double‐layer device showed a maximum luminance of 6073 cd/m² with a current yield of 0.82 cd/A. The maximum luminance and current yield was enhanced to 13,390 cd/m² and 2.25 cd/A by grafting CdSe/ZnS onto polymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5378–5390, 2006     

Use of CdSe/ZnS luminescent quantum dots incorporated within sol-gel matrix for urea detection

In this work, urea detection techniques based on the pH sensitivity of CdSe/ZnS QDs were developed using three types of sol-gel membranes: a QD-entrapped membrane, urease-immobilized membrane and double layer consisting of a QD-entrapped membrane and urease-immobilized membrane. The surface morphology of the sol-gel membranes deposited on the wells in a 24-well microtiter plate was investigated. The linear detection range of urea was in the range of 0-10 mM with the three types of sol-gel membranes. The urea detection technique based on the double layer consisting of the QD-entrapped membrane and urease-immobilized membrane resulted in the highest sensitivity to urea due to the Michaelis-Menten kinetic parameters. That is, the Michaelis-Menten constant (K_m =2.0745 mM) of the free urease in the QD-entrapped membrane was about 4-fold higher than that (K_m =0.549 mM) of the immobilized urease in the urease-immobilized membrane and about 12-fold higher than that (K_m =0.1698 mM) of the immobilized urease in the double layer. The good stability of the three sol-gel membranes for urea sensing over 2 months showed that the use of sol-gel membranes immobilized with QDs or an enzyme is suitable for biomedical and environmental applications.     

CdS和CdSe薄膜的制备及其光电化学性质

本文采用简易的化学水浴沉积法和自牺牲模板法制备CdS、CdSe薄膜,对两种薄膜进行了XRD表征,比较了两种薄膜的紫外吸收光谱并研究了CdS、CdSe薄膜作为太阳能电池中的光阳极时所产生的光电流和光电压,对两种薄膜的电化学性能进行了比较.     

A luminescent nanosensor for Hg(II) based on functionalized CdSe/ZnS quantum dots

Luminescent and stable CdSe/ZnS core/shell quantum dots (QDs) capped with L-carnitine are firstly prepared for optical determination of mercury ions in ethanol. LC capped QDs have desirable dispersibility, uniformity and good fluorescence properties and were characterized by fluorescence spectroscopy, transmission electron microscopy and infrared spectra. The functionalized QDs turned out to exhibit excellent long-term stability. The modified QDs allowed a highly sensitive determination of mercury ions via analyte-induced changes in the photoluminescence of them. A detection limit of 1.8 × 10⁻⁷ M (36.1 μg · L⁻¹) of mercury ions was obtained, while the interfering effect of other ions (including alkali metal ions, alkali earth metal ions, Ni²⁺, Zn²⁺, Fe²⁺, Ag⁺ and anions such as NO₃ ⁻, SO₄ ²⁻, CO₃ ²⁻ and halogen ions) was negligible even at a very high concentration. The possible mechanism is discussed. Correspondence: Haibing Li, Key Laboratory of Pesticide and Chemical Biology (CCNU), Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, P.R. China; Zhinong Gao, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, P.R. China     

Semiconducting thin films of zinc selenide quantum dots

A novel chemical route for deposition of zinc selenide quantum dots in thin film form is developed. The deposited films are characterized with very high purity in crystallographic sense, and behave as typical intrinsic semiconductors. Evolution of the average crystal size, lattice constant, lattice strain and the optical properties of the films upon thermal treatment is followed and discussed. The band gap energy of as-deposited ZnSe films is blue-shifted by ≈0.50 eV with respect to the bulk value, while upon annealing treatment it converges to 2.58 eV. Two discrete electronic states which originate from the bulk valence band are observed in the UV-VIS spectra of ZnSe 3D quantum dots deposited in thin film form via allowed electronic transitions to the 1S electronic state arising from the bulk conduction band—appearing at 3.10 and 3.50 eV. The splitting between these two states is approximately equal to the spin-orbit splitting in the case of bulk ZnSe. The electronic transitions in the case of non-quantized annealed films are discussed in terms of the direct allowed band-to-band transitions with the spin-orbit splitting of the valence band of 0.40 eV. The effective mass approximation model (i.e., the Brus model) with the static relative dielectric constant of bulk ZnSe fails to predict correctly the size dependence of the band gap energy, while only a slight improvement is obtained when the hyperbolic band model is applied. However, when substantially smaller value for ε_r (2.0 instead of 8.1) is used in the Brus model, an excellent agreement with the experimental data is obtained, which supports some earlier indications that the quantum dots ε_r value could be significantly smaller than the bulk material value. The ionization energy of a deep donor impurity level calculated on the basis of the temperature dependence of the film resistivity is 0.82 eV at 0 K.     

Probing cytotoxicity of CdSe and CdSe/CdS quantum dots

Toxicities of CdSe and CdSe/CdS quantum dots(QDs) synthesized by ultrasound-assisted methods were investigated in vitro and in vivo.Five human cell lines were used to assess the cytotoxicity of as-prepared CdSe and CdSe/CdS by assays of MTT viability,red blood cell hemolysis,flow cytometry,and fluorescence imaging.The results show that these QDs may be cytotoxic by their influence in S and G2 phases in cell cycles.The cytotoxicity of QDs depends on both the physicochemical properties and related to target cells.