Comparative behavior of CdS and CdSe quantum dots in poly(3-hexylthiophene) based nanocomposites

CdS and CdSe nanoparticles have been prepared using conducting poly(3-hexylthiophene) (P3HT) matrix with an objective to understand the effect of nanoparticles on the polymer matrix using electrochemical and spectroscopic techniques. The spectroscopic results reveal that the electronic structure of polymer is strongly influenced by the characteristics of embedded semiconducting nanoparticles. SEM and TEM images show the ordered morphology of the CdS and CdSe nanoparticles in presence of the polymer matrix. Cyclic voltammetry performed both in the presence and absence of light enables us to understand the redox changes in P3HT due to CdS and CdSe quantum dots such as the generation of free radical in the excited state and their electrochemical band gaps.

Enhanced electron lifetime of CdSe/CdS quantum dot (QD) sensitized solar cells using ZnSe core–shell structure with efficient regeneration of quantum Ddots

Research on development of efficient passivation materials for high performance and stable quantum dot sensitized solar cells (QDSCs) is highly important. While ZnS is one of the most widely used passivation material in QDSCs, an alternative material based on ZnSe which was deposited on CdS/CdSe/TiO2 photoanode to form a semi-core/shell structure has been found to be more efficient in terms of reducing electron recombination in QDSCs in this work. It has been found that the solar cell efficiency was improved from 1.86% for ZnSe0 (without coating) to 3.99% using 2 layers of ZnSe coating (ZnSe2) deposited by successive ionic layer adsorption and reaction (SILAR) method. The short circuit current density (Jsc) increased nearly 1-fold (from 7.25 mA/cm2 to13.4 mA/cm2), and the open circuit voltage (Voc) was enhanced by 100 mV using ZnSe2 passivation layer compared to ZnSe0. Studies on the light harvesting efficiency (ηLHE) and the absorbed photon-to-current conversion efficiency (APCE) have revealed that the ZnSe coating layer caused the enhanced ηLHE at wavelength beyond 500 nm and a significant increase of the APCE over the spectrum 400−550 nm. A nearly 100% APCE was obtained with ZnSe2, indicating the excellent charge injection and collection process in the device. The investigation on charge transport and recombination of the device has indicated that the enhanced electron collection efficiency and reduced electron recombination should be responsible for the improved Jsc and Voc of the QDSCs. The effective electron lifetime of the device with ZnSe2 was nearly 6 times higher than ZnSe0 while the electron diffusion coefficient was largely unaffected by the coating. Study on the regeneration of QDs after photoinduced excitation has indicated that the hole transport from QDs to the reduced species (S2−) in electrolyte was very efficient even when the QDs were coated with a thick ZnSe shell (three layers). For comparison, ZnS coated CdS/CdSe sensitized solar cell with optimum shell thickness was also fabricated, which generated a lower energy conversion efficiency (η = 3.43%) than the ZnSe based QDSC counterpart due to a lower Voc and FF. This study suggests that ZnSe may be a more efficient passivation layer than ZnS, which is attributed to the type II energy band alignment of the core (CdS/CdSe quantum dots) and passivation shell (ZnSe) structure, leading to more efficient electron−hole separation and slower electron recombination.

Structural and optical investigation of semiconductor CdSe/CdS core-shell quantum dot thin films

Highly luminescent CdSe/CdS core-shell nanocrystals have been assembled on indium tin oxide (ITO) coated glass substrates using a wet synthesis route. The physical properties of the quantum dots (QD) have been investigated using X-ray diffraction, transmission electron microscopy and optical absorption spectroscopy techniques. These quantum dots showed a strong enhancement in the near band edge absorption. The in situ luminescence behavior has been interpreted in the light of the quantum confinement effect and induced strain in the core-shell structure.

Biphenyl ethers conjugated CdSe/ZnS core/shell quantum dots and interpretation of the mechanism of amyloid fibril disruption

The biphenyl ethers (BPEs) are the potent inhibitors of TTR fibril formation and are efficient fibril disrupter. However, the mechanism by which the fibril disruption occurs is yet to be fully elucidated. To gain insight into the mechanism, we synthesized and used a new QD labeled BPE to track the process of fibril disruption. Our studies showed that the new BPE-QDs bind to the fiber uniformly and has affinity and specificity for TTR fiber and disrupted the pre-formed fiber at a relatively slow rate. Based on these studies we put forth the probable mechanism of fiber disruption by BPEs. Also, we show here that the BPE-QDs interact with high affinity to the amyloids of A beta(42), lysozyme and insulin. The potential of BPE-QDs in the detection of senile plaque in the brain of transgenic Alzheimer's mice has also been explored. (C) 2010 Elsevier Ltd. All rights reserved.

Brush plated CdSe films and their photoelectrochemical characteristics

The brush plating technique has been employed for the first time to obtain CdSe films on Ti and conducting glass substrates. These films have been annealed in an argon atmosphere and their structural, optical and photoelectrochemical properties are discussed. The power conversion efficiency has been found to be 7.43% under an illumination of 80 mW cm-2. A peak quantum efficiency of 0.64 is obtained for an incident wavelength of 720 nm. Donor concentration of 3.42 x 10(17) cm-3, electron mobility of 3 cm2 V-1 s-1 and minority carrier diffusion length of 0.013 mum have been obtained.

A Raman study of CdSe and ZnSe nanostructures

Raman studies have been carried out on CdSe nanotubes and ZnSe nanorods produced by surfactant-assisted synthesis. The Raman spectrum of CdSe nanotubes shows modes at 207.5 and 198 cm(-1); the former arises from the longitudinal optic phonon mode red-shifted with respect to the bulk mode because of phonon confinement, and the latter is the I = 1 surface phonon. Analysis based on the phonon confinement model demonstrates that the size of the nanoparticle responsible for the red-shift is about 4 nm, close to the estimate from the blue-shift of the photoluminescence. The Raman spectrum of ZnSe,nanorods shows modes at 257 and 213 cm(-1), assigned to longitudinal and transverse optic phonons, blue-shifted with respect to the bulk ZnSe modes because of compressive strain. The mode at 237 cm(-1) is the surface phonon.

Coalescence of magic sized CdSe into rods and wires and subsequent energy transfer

We report on the synthesis of CdSe magic-sized clusters (MSCs) and their evolution into 1D rod and wires retaining the diameter of the order of MSCs. At the beginning of the reaction, different classes of stable MSCs with band gaps of 3.02 eV and 2.57 eV are formed, which exhibit sharp band edge photoluminescence features with FWHM in the order of similar to 13 nm. Reaction annealing time was carried out in order to monitor the shape evolution of the MSCs. We find that magic sized CdSe evolve into 1D rod and wires retaining the same diameter upon increasing annealing time. We observed the gradual emergence of new red shifted emission peaks during this shape evolution process, which emerge as a result of one dimensional energy transfer within the magic sized clusters during their subsequent transformation into rods and wires. The smallest, the second smallest sized MSC and the wires sequentially act as donors and acceptors during the size evolution from small MSCs to larger ones, and then eventually to wires. Steady-state and time-resolved luminescent spectroscopy revealed Forster resonance energy transfer (FRET) between the MSCs to the rods and wires.

Synthesis, characterization and spectroscopy of composites of graphene with CdSe and CdS nanoparticles

Nanocomposites of few-layer graphene with nanoparticles of CdSe and CdS have been synthesized by two different methods, one involving ultrasonication of a mixture of graphene and the chalcogenide nanoparticles, and another involving assembly at the organic-aqueous interface. The nanocomposites have been examined by electron microscopy, electronic absorption and photoluminescence spectroscopies as well as Raman spectroscopy. Electron microscopy reveals that the nanoparticles are dispersed on the graphene surface. Raman spectra show the presence of definitive electronic interaction between the nanoparticles and graphene depending on the capping agent. Photoluminescence spectra are markedly influenced by the interaction of the nanoparticles with the graphene surface, depending on the capping agent.

The effect of potential on electrodeposited CdSe thin films

Cadmium selenide (CdSe) thin films have been successfully prepared by the electrodeposition technique on indium doped tin oxide (ITO) substrates with aqueous solutions of cadmium sulphate and selenium dioxide. The deposited films were characterized with X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive analysis by X-rays (EDAX), photoluminescence (PL), UV spectrometry and electrical resistivity measurements. XRD analysis shows that the films are polycrystalline in nature with hexagonal crystalline structure. The various parameters such as crystallite size, micro strain, dislocation density and texture coefficients were evaluated. SEM study shows that the total substrate surface is well covered with uniformly distributed spherical shaped grains. Photoluminescence spectra of films were recorded to understand the emission properties of the films. The presence of direct transition with band gap energy 1.75 eV is established from optical studies. The electrical resistivity of the thin films is found to be 10(6) Omega cm and the results are discussed. (c) 2011 Elsevier Ltd. All rights reserved.

Strain induced phase transition in CdSe nanowires: Effect of size and temperature

Using all-atom molecular dynamics simulation, we have studied the effect of size and temperature on the strain induced phase transition of wurtzite CdSe nanowires. The wurtzite structure transforms into a five-fold coordinated structure under uniaxial strain along the c axis. Our results show that lower temperature and smaller size of the nanowires stabilize the five-fold coordinated phase which is not a stable structure in bulk CdSe. High reversibility of this transformation with a very small heat loss will make these nanowires suitable for building efficient nanodevices. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4734990]

Interaction of CdSe and ZnO nanocrystals with electron-donor and -acceptor molecules

Interaction of CdSe and ZnO nanocrystals with electron-donating tetrathiafulvalene (TTF) and electron-withdrawing tetracyanoethylene (TCNE) has been investigated. Isothermal calorimetry shows CdSe nanocrystals interact more strongly with TCNE than TTF. Interaction of larger CdSe nanocrystals with TCNE causes a red-shift in the band-edge emission because of agglomeration, while the smaller CdSe nanocrystals, exhibiting stronger interaction with TCNE modify the optical gap of the nanocrystal. Luminescence of CdSe gets quenched sharply after addition of both TTF and TCNE. ZnO nanocrystals also exhibit luminescence quenching to lesser extent. Defect-emission of ZnO nanocrystals gets red or blue-shifted after interaction with TTF or TCNE respectively. (C) 2012 Elsevier B. V. All rights reserved.

Cadmium deoxycholate: a new and efficient precursor for highly luminescent CdSe nanocrystals

We have demonstrated that cadmium deoxycholate (1), a Cd-salt, provides a convenient and inexpensive route to high quality CdSe nanocrystals with photoluminescence (PL) in the blue to red region of the visible spectrum, with reproducible quantum yields as high as similar to 47%. Owing to the high thermal stability of the bile acid based cadmium precursor (decomposition point: 332 degrees C), it was possible to achieve high injection and growth temperatures (similar to 300 degrees C) for the nanocrystals, which was essential for obtaining larger CdSe nanocrystals emitting in the red region (625-650 nm) with a sharp full width at half maximum (FWHM) (23 nm) and multiple (6-7) excitonic absorption features. The as-prepared CdSe nanocrystals synthesized from cadmium deoxycholate represent a series of highly efficient emitters with pure colours and controllable sizes, shapes and structures.

Photoluminescence decay rate engineering of CdSe quantum dots in ensemble arrays embedded with gold nano-antennae

We discuss experimental results on the ability to significantly tune the photoluminescence decay rates of CdSe quantum dots embedded in an ordered template, using lightly doped small gold nanoparticles (nano-antennae), of relatively low optical efficiency. We observe both enhancement and quenching of photoluminescence intensity of the quantum dots varying monotonically with increasing volume fraction of added gold nanoparticles, with respect to undoped quantum dot arrays. However, the corresponding variation in lifetime of photoluminescence spectra decay shows a hitherto unobserved, non-monotonic variation with gold nanoparticle doping. We also demonstrate that Purcell effect is quite effective for the larger (5 nm) gold nano-antenna leading to more than four times enhanced radiative rate at spectral resonance, for largest doping and about 1.75 times enhancement for off-resonance. Significantly for spectral off-resonance samples, we could simultaneously engineer reduction of non-radiative decay rate along with increase of radiative decay rate. Non-radiative decay dominates the system for the smaller (2 nm) gold nano-antenna setting the limit on how small these plasmonic nano-antennae could be to be effective in engineering significant enhancement in radiative decay rate and, hence, the overall quantum efficiency of quantum dot based hybrid photonic assemblies.

Tuning the parameters to establish Quenching and enhancement regimes in hybrid Gold nanoparticles and CdSe Quantum dots monolayer

The multi-component nanomaterials combine the individual properties and give rise to emergent phenomenon. Optical excitations in such hybrid nonmaterial's ( for example Exciton in semiconductor quantum dots and Plasmon in Metal nanomaterials) undergo strong weak electromagnetic coupling. Such exciton-plasmon interactions allow design of absorption and emission properties, control of nanoscale energy-transfer processes, and creation of new excitations in the strong coupling regime.This Exciton plasmon interaction in hybrid nanomaterial can lead to both enhancement in the emission as well as quenching. In this work we prepared close-packed hybrid monolayer of thiol capped CdSe and gold nanoparticles. They exhibit both the Quenching and enhancements the in PL emission.The systematic variance of PL from such hybrid nanomaterials monolayer is studied by tuning the Number ratio of Gold per Quantum dots, the surface density of QDs and the spectral overlap of emission spectrum of QD and absorption spectrum of Gold nanoparticles. Role of Localized surface Plasmon which not only leads to quenching but strong enhancements as well, is explored.