Size-dependent photocurrent switching in chemical bath deposited CdSe quantum dot films

Journal of Solid State Electrochemistry - Size-dependent photocurrent switching has been investigated in chemical bath deposited CdSe quantum dot (QD) films with band gaps 2.26, 2.09, and...     

Langmuir-Blodgett thin films of quantum dots: synthesis, surface modification, and fluorescence resonance energy transfer (FRET) studies

We describe herein studies on as-prepared hydrophobic ZnS-CdSe quantum dots (QDs) at the air-water interface. Surface pressure-area (pi-A) isotherms have been used to study the monolayer behavior. Uniform, lamellar multilayer thin films of QDs were deposited by the Langmuir-Blodgett (LB) technique. The role of two different surfactant systems commonly employed in the synthesis of these QDs (trioctylphosphine oxide-octadecylamine (TOPO-ODA) system and trioctylphosphine oxide-tetradecylphosphonic acid (TOPO-TDPA) system) on the monolayer behavior and the quality of thin films produced has been investigated. The thin films were characterized by quartz crystal microgravimetry (QCM), contact angle measurements, fluorescence spectroscopy, and transmission electron microscopy (TEM). These QD films were further modified by an amphiphilic polymer, poly(maleic anhydride-alt-1-tetradecene) (PMA). The hydrophobic interaction between the polymers and the surfactants attached to the QDs drove the self-assembly process. The carboxylic acid functional groups in the polymer were also used to immobilize avidin. We have demonstrated a proof of concept for the biosensing strategy wherein the avidin-coated QD films attracted biotinylated gold nanoparticles, resulting in fluorescence resonance energy transfer (FRET) quenching of the thin films.     

溶液法制备图案化量子点薄膜的研究进展

量子点发光二极管(QLED)由于具有显色性好、 色纯度高和性能稳定等特点而受到广泛关注, 可用于制备具有超薄结构和柔性结构的显示器件. 量子点(QDs)层是QLED器件的核心发光层, 制备高质量的图案化QD薄膜对于提高QLED器件性能至关重要. 本文综述了近年来溶液法制备QD薄膜的研究进展, 探讨了目前主要使用的各种溶液法的优势和前景, 并对最近新发展的纤维辅助的溶液可控转移制备QD薄膜方法的优势和发展前景进行了评述.     

Photoinduced fluorescence enhancement in mono- and multilayer films of CdSe/ZnS quantum dots: dependence on intensity and wavelength of excitation light

Photoinduced fluorescence enhancement (PFE) behavior in mono- and multilayer films of CdSe/ZnS core/shell quantum dots (QDs) on glass substrates was investigated using various intensities and wavelengths of excitation light. CdSe/ZnS QDs capped with tri-n-octylphosphine oxide (TOPO) were produced using colloidal chemical synthesis, and mono- and multilayer QD films were fabricated on glass substrates by spin coating. The fluorescence quantum yield (QY) of the QD monolayer was greatly enhanced by continuous irradiation in a dry nitrogen atmosphere, whereas the QD multilayer showed a small enhancement of the QY or fluorescence intensity decay. In addition, the shorter the excitation wavelength, the more pronounced the PFE. The rate of increase of the QY increased with decreasing excitation intensities at any wavelength. These dependences were observed in both mono- and multilayer films. Our results suggest that the photoejection of electrons to the substrate is the origin of PFE. Assuming the charging effect of electrons trapped in the substrate, a phenomenological model is proposed to explain all of the experimental results, that is, the dependence on the intensity and wavelength of excitation light and the qualitative difference in PFE behavior between mono- and multilayer films.     

Quantum Dot Photoluminescence Quenching by Cr(III) Complexes. Photosensitized Reactions and Evidence for a FRET Mechanism

Reported are quantitative studies of the energy transfer from water-soluble CdSe/ZnS and CdSeS/ZnS core/shell quantum dots (QDs) to the Cr(III) complexes trans-Cr(N(4))(X)(2)(+) (N(4) is a tetraazamacrocycle ligand, X(-) is CN(-), Cl(-), or ONO(-)) in aqueous solution. Variation of N(4), of X(-), and of the QD size and composition allows one to probe the relationship between the emission/absorption overlap integral parameter and the efficiency of the quenching of the QD photoluminescence (PL) by the chromium(III) complexes. Steady-state studies of the QD PL in the presence of different concentrations of trans-Cr(N(4))(X)(2)(+) indicate a clear correlation between quenching efficiency and the overlap integral largely consistent with the predicted behavior of a F?rster resonance energy transfer (FRET)-type mechanism. PL lifetimes show analogous correlations, and these results demonstrate that spectral overlap is an important consideration when designing supramolecular systems that incorporate QDs as photosensitizers. In the latter context, we extend earlier studies demonstrating that the water-soluble CdSe/ZnS and CdSeS/ZnS QDs photosensitize nitric oxide release from the trans-Cr(cyclam)(ONO)(2)(+) cation (cyclam = 1,4,8,11-tetraazacyclotetradecane) and report the efficiency (quantum yield) for this process. An improved synthesis of ternary CdSeS core/shell QDs is also described.     

Fortification of CdSe quantum dots with graphene oxide. Excited state interactions and light energy conversion

Graphene based 2-D carbon nanostructures provide new opportunities to fortify semiconductor based light harvesting assemblies. Electron and energy transfer rates from photoexcited CdSe colloidal quantum dots (QDs) to graphene oxide (GO) and reduced graphene oxide (RGO) were isolated by analysis of excited state deactivation lifetimes as a function of degree of oxidation and charging in (R)GO. Apparent rate constants for energy and electron transfer determined for CdSe-GO composites were 5.5 × 10(8) and 6.7 × 10(8) s(-1), respectively. Additionally, incorporation of GO in colloidal CdSe QD films deposited on conducting glass electrodes was found to enhance the charge separation and electron conduction through the QD film, thus allowing three-dimensional sensitization. Photoanodes assembled from CdSe-graphene composites in quantum dot sensitized solar cells display improved photocurrent response (~150%) over those prepared without GO.     

Confinement-dependent below-gap state in PbS quantum dot films probed by continuous-wave photoinduced absorption

We have measured continuous-wave (cw) photoinduced absorption (PA) spectra of PbS quantum dot (QD) films with four different sizes over a spectral range of 0.25-0.5 eV at T=10 K. The PA spectrum shows a strong asymmetric IR absorption peak (IR-PA). Both the peak position and shape of this IR-PA indicate distinct confinement dependence. Combining with results of interband transitions and Stokes shift, we assign this IR-PA to a transition from a well-defined below-gap state to the second excitonic level (1P). By measuring the frequency dependence of this IR-PA, we estimate the lifetime of this below-gap state to be around several microseconds. Possible interpretations of the origin of this below-gap state are given. This transition could potentially be used to monitor photogenerated charge transfer in such QD systems.     

Triggered aggregation of PbS nanocrystal dispersions; towards directing the morphology of hybrid polymer films using a removable bilinker ligand

Hybrid polymer films consist of quantum dots (QDs) dispersed in a polymer matrix. A key fundamental challenge that is hindering their optimisation in optoelectronic devices such as hybrid solar cells is overcoming uncontrolled aggregation of the QDs. In an effort to direct aggregation, and trigger self-assembly, we added a bilinker ligand (1,2-ethanedithiol) to dispersed PbS QDs in polymer solutions prior to film deposition by spin casting. Turbidity studies of the PbS QD/1,2-ethanedithiol dispersions enabled a relationship to be established between the extent of 1,2-ethanedithiol-triggered QD aggregation and the nominal fractional coverage of the QDs by 1,2-ethanedithiol. The extent of aggregation (and self-assembly) increased with nominal fraction coverage. Above a value of about 1.0 QD aggregation increased substantially. TEM images showed that at low 1,2-ethanedithiol concentrations triggered assembly of network-like QD structures occurred. At high 1,2-ethanedithiol concentrations the QDs self-assembled into more-ordered micrometre-sized crystals. The results suggest that 1,2-ethanedithiol decreases the inter-QD separation in dispersion as a result of rapid ligand exchange and this process results in QD aggregation as well as self-assembly. The assembled QD structures were successfully trapped within polymer films by spin casting of PbS QD/1,2-ethanedithiol dispersions containing added polystyrene or polytriarylamine.     

水相合成CdX (X＝Te, Te/CdS, Te/ZnS)红色量子点及毒性效应

分别以巯基乙酸(Mercaptoacetic Acid, MA)、还原型谷胱甘肽(Glutathione, GSH)为稳定剂在水相中直接合成了巯基乙酸CdTe (CdTe-MA)、红色巯基乙酸CdTe/CdS (CdTe/CdS-MA)、巯基乙酸CdTe/ZnS (CdTe/ZnS-MA)及谷胱甘肽CdTe (CdTe-GSH)量子点. 其中, CdTe-GSH量子点的量子产率可达47.3%. 体外溶血实验证实CdTe/ZnS-MA和CdTe-GSH量子点的溶血率较CdTe-MA和CdTe/CdS-MA低, 浓度为0.05 mmol/L的量子点溶血率＜5%, 达到了生物医用材料的要求. 活体实验证实: 通过尾静脉方式把量子点注入小鼠体内后, 荧光显微镜观察发现高剂量的量子点(0.4 mmol/10 g)在体内主要在心、肝、脾、肾组织中分布较多, 且引起不同程度的组织病变.     

Quantum dot fluorescence quenching pathways with Cr(III) complexes. photosensitized NO production from trans-Cr(cyclam)(ONO)2+

Described is the photoluminescence (PL) of water-soluble CdSe/ZnS core/shell quantum dots (QDs) as perturbed by salts of the chromium(III) complexes trans-Cr(cyclam)Cl2+ (1), trans-Cr(cyclam)(ONO)2+ (2), and trans-Cr(cyclam)(CN)2+ (3) (cyclam = 1,4,8,11-tetraazacyclo-tetradecane). The purpose is to probe the characteristics of such QDs as antennae for photosensitized release of bioactive agents (in the present case, the bioregulatory molecule NO) from transition metal centers. Addition of 1 or 2 to a QD solution results in concentration-dependent quenching of the band edge emission, but 3 has a minimal effect. Added KCl strongly attenuates the quenching by 1, and this suggests that the Cr(III) cations and the QDs form electrostatic assemblies via ion pairing on the negatively charged QD surfaces. Quenching by 2, a known photochemical NO precursor, was accompanied by photosensitized NO release. All three, however, do quench the broad red emission ( approximately 650-850 nm) attributed to radiative decay of surface trapped carriers. The effect of various concentrations of 1 on time-resolved PL and absorbance were explored using ultrafast spectroscopic methods. These observations are interpreted in terms of the F?rster resonance energy-transfer mechanism for quenching of the band edge PL by multiple units of 1 or 2 at the QD surface, whereas quenching of the low-energy trap emission occurs via a charge-transfer pathway.     

CuInS_2量子点敏化太阳能电池中尺寸依赖的电子注入和光电性质

研究了CuInS2(CIS)量子点敏化太阳能电池(QDSSCs)的电子注入和器件性能与粒子尺寸之间的依赖关系.首先合成了不同尺寸的CuInS2量子点(QDs),制备了CuInS2量子点敏化的TiO2薄膜,并组装了量子点敏化太阳能电池.通过循环伏安法确定了CuInS2量子点的能级位置.采用时间分辨荧光光谱分析测量了CuInS2量子点到TiO2薄膜的电子转移速率和效率.结果发现,随着粒子尺寸从4.0 nm减小到2.5 nm,电子注入速率略微增加而电子注入效率减小,同时量子点敏化太阳能电池的开路电压基本不变,而光电转换效率、短路电流和填充因子(FF)均减小.上述研究结果表明量子点敏化太阳能电池性能的优化可以通过改变量子点的尺寸来实现.     

Use of surface-modified CdTe quantum dots as fluorescent probes in sensing mercury (II)

Thioglycolic acid (TGA)-capped CdTe quantum dots (QDs) were synthesized in aqueous medium, and their interaction with metal cations was studied with UV-vis absorption, steady-state and time-resolved fluorescence spectra. The results demonstrated that Hg(II), Cu(II) and Ag(I) could effectively quench the QD emission based on different action mechanisms: Cu(II) and Ag(I) quenched CdTe QDs because they bound onto particle surface and facilitated non-radiative electron/hole recombination annihilation of QDs; electron transfer process between the capping ligands and Hg(II) was mainly responsible for the remarkable quenching effect of Hg(II). To prevent the approach of metal cations to QD core, the original TGA-capped CdTe QDs were further coated by denatured bovine serum albumin (dBSA). It was found that the dBSA-coated CdTe QDs could be quenched effectively by Hg(II), but Cu(II) and Ag(I) could hardly quench the QDs even at fairly higher concentration levels because the dBSA shell layer effectively prevented the binding of metal cations onto the QD core. On the basis of this fact, a simple, rapid and specific method for Hg(II) determination was proposed. Under optimal conditions, the quenched fluorescence intensity increased linearly with the concentration of Hg(II) ranging from 0.012 x 10(-6) to 1.5 x 10(-6) mol L(-1). The limit of detection for Hg(II) was 4.0 x 10(-9) mol L(-1). The developed method was successfully applied to the detection of trace Hg(II) in real samples.     

CuInS2量子点敏化太阳能电池中尺寸依赖的电子注入和光电性质

研究了CuInS₂（CIS）量子点敏化太阳能电池（QDSSCs）的电子注入和器件性能与粒子尺寸之间的依赖关系. 首先合成了不同尺寸的CuInS₂量子点（QDs）,制备了CuInS₂量子点敏化的TiO₂薄膜,并组装了量子点敏化太阳能电池. 通过循环伏安法确定了CuInS₂量子点的能级位置. 采用时间分辨荧光光谱分析测量了CuInS₂量子点到TiO₂薄膜的电子转移速率和效率. 结果发现,随着粒子尺寸从4.0 nm减小到2.5 nm,电子注入速率略微增加而电子注入效率减小,同时量子点敏化太阳能电池的开路电压基本不变,而光电转换效率、短路电流和填充因子（FF）均减小. 上述研究结果表明量子点敏化太阳能电池性能的优化可以通过改变量子点的尺寸来实现.     

Potential energy surface and quantum dynamics study of rovibrational states for HO(3) (X (2)A')

An analytic potential energy surface has been constructed by fitting to about 28 thousand energy points for the electronic ground-state (X (2)A') of HO(3). The energy points are calculated using a hybrid density functional HCTH and a large basis set aug-cc-pVTZ, i.e., a HCTH/aug-cc-pVTZ density functional theory (DFT) method. The DFT calculations show that the trans-HO(3) isomer is the global minimum with a potential well depth of 9.94 kcal mol(-1) with respect to the OH + O(2) asymptote. The equilibrium geometry of the cis-HO(3) conformer is located 1.08 kcal mol(-1) above that of the trans-HO(3) one with an isomerization barrier of 2.41 kcal mol(-1) from trans- to cis-HO(3). By using this surface, a rigorous quantum dynamics (QD) study has been carried out for computing the rovibrational energy levels of HO(3). The calculated results determine a dissociation energy of 6.15 kcal mol(-1), which is in excellent agreement with the experimental value of Lester et al. [J. Phys. Chem. A, 2007, 111, 4727.].     

Hybrid fluorescent nanoparticles from quantum dots coupled to cellulose nanocrystals

Carboxylated cellulose nanocrystals (CNCs) were decorated with CdSe/ZnS quantum dots (QDs) using a carbodiimide chemistry coupling approach. The one-step covalent modification was supported by nanoscale imaging, which showed QDs clustered on and around the CNCs after coupling. The QD–CNC hybrid nanoparticles remained colloidally stable in aqueous suspension and were fluorescent, exhibiting the broad excitation and narrow emission profile characteristic of the QDs. QD–CNCs in nanocomposite films imparted strong fluorescence within CNC-compatible matrices at relatively low loadings (0.15 nmol QDs/g of dry film), without altering the overall physical properties or self-assembly of the CNCs. The hybrid QD–CNCs may find applications in nanoparticle tracking, bio-imaging, optical/sensing devices, and anti-counterfeit technologies.     

Highly photoluminescent multilayer QD-glass films prepared by LbL self-assembly

A novel and facile preparation method for layer-by-layer (LbL) self-assembled films incorporating quantum dots (QDs) and having intense photoluminescence (PL) from blue to red is presented. Functional sol-gel-derived glass layers prepared by the hydrolysis of 3-aminopropyltrimethoxysilane (APS) or 3-mercaptopropyltrimethoxysilane (MPS) have been used as a linkage between QD layers. Absorption, PL spectroscopy, transmission electron microscopy, and atomic force microscopy were employed for characterization, which revealed that the QDs in the prepared films had a nearly close-packed coverage and were not aggregated. The PL efficiencies of the QDs (CdTe or ZnSe, both are thioglycolic acid-stabilized) dispersed in the films were roughly half that of the initial colloidal solutions but reached 24% before a refractive index correction. The thickness of the red-emitting film with 10 CdTe QD layers was approximately 50 nm. The concentration of QDs in the film derived from the first absorption peak was approximately 0.01 M. Because the PL starts to show a red shift, the obtained concentration is practically the ultimate one in the glass matrix. The mercapto, amino, and carboxyl groups play important roles in LbL self-assembling processes.     

Current density enhancement for quantum dot-sensitized solar cells by modulation on the quantum dot loading amount of anatase nanowire array photoelectrodes

Journal of Solid State Electrochemistry - A second spin-coating process was employed for CuInS2 quantum dot (QD)-sensitized TiO2 nanowire-based solar cells, which is anticipated to increase the QD...     

Synergistic effect of ZnS outer layers and electrolyte methanol content on efficiency in TiO(2)/CdS/CdSe sensitized solar cells

The effect of methanol content in water based polysulfide electrolytes in TiO(2)/CdS/CdSe quantum dot sensitized solar cells (QDSSCs) prepared by the SILAR method was studied. In addition, the effect of coating the mesoporous QD sensitized films with ZnS outer layers was investigated. Charge recombination reactions were measured using time resolved spectroscopic measurements. These studies reveal a synergistically beneficial effect from using ZnS layers and methanol in the polysulfide electrolyte on the control of charge transfer processes within these devices and ultimately on overall cell performance.     

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     

Modulation of surface reactivity via electron confinement in metal quantum well films: O2 adsorption on PbSi(111)

Pb quantum well films with atomic-scale uniformity in thickness over macroscopic areas were prepared on Si(111)-7x7 surfaces. As a probe molecule, O(2) was used to explore the effect of electron confinement in the metal films on the surface reactivity. X-ray photoelectron spectroscopy results showed clear oscillations of oxygen adsorption and Pb oxidation with the thickness of the Pb films. The higher reactivity to O(2) on the films with 23 and 25 ML Pb has been attributed to their highest occupied quantum well states being close to the Fermi level (E(F)) and the high density of the electron states at E(F) (DOS-E(F)), as evidenced by the corresponding ultraviolet photoelectron spectroscopy. A dominant role of DOS-E(F) was suggested to explain the quantum modulation of surface reactivity in metal quantum well films.