Anodic electrochemiluminescence of CdTe quantum dots and its energy transfer for detection of catechol derivatives

This work reported for the first time the anodic electrochemiluminescence (ECL) of CdTe quantum dots (QDs) in aqueous system and its analytical application based on the ECL energy transfer to analytes. The CdTe QDs were modified with mercaptopropionic acid to obtain water-soluble QDs and stable and intensive anodic ECL emission with a peak value at +1.17 V (vs Ag/AgCl) in pH 9.3 PBS at an indium tin oxide (ITO) electrode. The ECL emission was demonstrated to involve the participation of superoxide ion produced at the ITO surface, which could inject an electron into the 1Se quantum-confined orbital of CdTe to form QDs anions. The collision between these anions and the oxidation products of QDs led to the formation of the excited state of QDs and ECL emission. The ECL energy transfer from the excited CdTe QDs to quencher produced a novel methodology for detection of catechol derivatives. Using dopamine and L-adrenalin as model analytes, this ECL method showed wide linear ranges from 50 nM to 5 microM and 80 nM to 30 microM for these species. Both ascorbic acid and uric acid, which are common interferences, did not interfere with the detection of catechol derivatives in practical biological samples.     

Large-Area (over 50 cm × 50 cm) Freestanding Films of Colloidal InP/ZnS Quantum Dots

We propose and demonstrate the fabrication of flexible, freestanding films of InP/ZnS quantum dots (QDs) using fatty acid ligands across very large areas (greater than 50 cm × 50 cm), which have been developed for remote phosphor applications in solid-state lighting. Embedded in a poly(methyl methacrylate) matrix, although the formation of stand-alone films using other QDs commonly capped with trioctylphosphine oxide (TOPO) and oleic acid is not efficient, employing myristic acid as ligand in the synthesis of these QDs, which imparts a strongly hydrophobic character to the thin film, enables film formation and ease of removal even on surprisingly large areas, thereby avoiding the need for ligand exchange. When pumped by a blue LED, these Cd-free QD films allow for high color rendering, warm white light generation with a color rendering index of 89.30 and a correlated color temperature of 2298 K. In the composite film, the temperature-dependent emission kinetics and energy transfer dynamics among different-sized InP/ZnS QDs are investigated and a model is proposed. High levels of energy transfer efficiency (up to 80%) and strong donor lifetime modification (from 18 to 4 ns) are achieved. The suppression of the nonradiative channels is observed when the hybrid film is cooled to cryogenic temperatures. The lifetime changes of the donor and acceptor InP/ZnS QDs in the film as a result of the energy transfer are explained well by our theoretical model based on the exciton-exciton interactions among the dots and are in excellent agreement with the experimental results. The understanding of these excitonic interactions is essential to facilitate improvements in the fabrication of photometrically high quality nanophosphors. The ability to make such large-area, flexible, freestanding Cd-free QD films pave the way for environmentally friendly phosphor applications including flexible, surface-emitting light engines.     

Morphology and energy transfer in PbS quantum dot arrays formed with supercritical fluid deposition

Lead sulfide (PbS) quantum dots (QDs) were synthesized in our lab with controllable and tunable sizes. Supercritical fluid CO₂ (sc-CO₂) provides a useful tool to deposit PbS QDs on substrate surfaces with lateral uniformity. Either in the PbS/toluene solution or in the sc-CO₂ fabricated film, the absorbance maxima of the PbS QDs do not show an obvious dependence on the PbS QD concentrations. Fluorescence spectra of PbS QDs obtained from the films prepared by the sc-CO₂ method indicate energy transfer between PbS QDs with different sizes, the small QDs serving as energy donors and large ones as acceptors. Samples formed with sc-CO₂ method measured by photoluminescence (PL) show a red-shift and an enhanced emission intensity with respect to samples formed with solution deposition method (SDM), specifically at cryogenic temperatures.     

Aspects of emission variation in CdSeTe/ZnS quantum dots conjugated to antibodies

CdSeTe/ZnS quantum dots (QDs) with the emission peak at 705 nm have been studied comparatively in the non-conjugated state and after bioconjugation to anti-pseudo rabies virus antibodies (ABs) by means of photoluminescence (PL) and Raman scattering methods. It is revealed that PL spectra of QDs vary significantly after conjugating to ABs. In PL spectra of non-conjugated QDs only one PL band of Gaussian shape peaked at 1.76–1.78 eV and related to exciton emission in the CdSeTe core has been detected. The PL spectra of bio-conjugated QDs demonstrate the high energy spectral shift and asymmetric shape of PL bands. The study of Raman scattering spectra permits to estimate the CdSeTe alloy composition and to detect the surface enhanced Raman scattering (SERS) effect for bioconjugated QDs. The last fact testifies on the interaction of excitation light electromagnetic field with the electric dipoles excited in ABs. The optical band gap in CdSeTe core has been calculated numerically versus core radius on the base of the effective mass approximation model. Then the energy band diagrams for non-conjugated and bio-conjugated states of CdSeTe/ZnS QDs have been designed. It is revealed the type II quantum well in CdSeTe core that explains the optical transition at 705 nm in the wide band gap CdSeTe alloy. The analysis has shown that AB dipoles excited in bio-conjugated QDs stimulate changing the profile of QD energy band diagram that manifests itself in the mentioned PL spectrum transformations. Actually, the study of PL spectrum varying in CdSeTe/ZnS QDs conjugated to specific antibodies can be an informative tool in biology and medicine for early medical diagnostics.     

Preparation of water soluble l-arginine capped CdSe/ZnS QDs and their interaction with synthetic DNA: Picosecond-resolved FRET study

We have exchanged TOPO (trioctylphosphine oxide) ligand of CdSe/ZnS core/shell quantum dots (QDs) with an amino acid l-arginine (Arg) at the toluene/water interface and eventually rendered the QDs from toluene to aqueous phase. We have studied the interaction of the water soluble Arg-capped QDs (energy donor) with ethidium (EB) labeled synthetic dodecamer DNA (energy acceptor) using picoseconds resolved Förster resonance energy transfer (FRET) technique. Furthermore, we have applied a model developed by M. Tachiya to understand the kinetics of energy transfer and the distribution of acceptor (EB-DNA) molecules around the donor QDs. Circular dichroism (CD) studies revealed a negligible perturbation in the native B-form structure of the DNA upon interaction with Arg-capped QDs. The melting and the rehybridization pathways of the DNA attached to the QDs have been monitored by the CD which reveals hydrogen bonding is the associative mechanism for interaction between Arg-capped QDs and DNA.     

Enhanced electron transfer rate for quantum dot sensitized solar cell based on CNT-TiO2 film

In this paper, we have fabricated a quantum dot sensitized solar cell (QDSSC) based on carbon nanotube (CNT) doped TiO2 mesopores film. As revealed by field emission scanning electron microscopy and absorption spectra, the CdSe QDs were adsorbed onto CNT-TiO2 nanocomposite. An improved efficiency is achieved for the CNT-TiO2/CdSe devices compared to that of TiO2/CdSe, which is due to the increased surface area and reduced charge recombination in TiO2 film by the presence of CNTs. A power conversion efficiency of the as-prepared QDSSC of 0.98% was obtained under 100 mW/cm2 solar irradiation. The emission decay profile demonstrates that the electrons transfer from CdSe QDs to CNT-TiO2 is faster than that from CdSe QDs to TiO2, resulting in the reduction of the charge recombination, leading to a higher FF value in QDSSC. The average lifetime of CdSe QDs adsorbed on TiO2 doped with CNT is 6.2 ns and the electron transfer rate constant of 1.1 x 10(8) s(-1) can be calculated.     

Evolution of luminescence properties of CdTe quantum dots in liquid/solid environment

We studied the luminescence behavior of different sized CdTe quantum dots (QDs) dispersed in liquid solution, close-packed films and layer-by-layer assembled films respectively. The changes of emission color from CdTe QDs in water droplets during the evaporation of solvent have been observed. The quenching of the emission from small dots accompanied by the enhancement of the emission from large dots indicate that Forster resonance energy transfer processes occur from donors (small dots) to acceptors (large dot) for CdTe QDs system. Excitation (PLE) spectra confirm that the changes of the luminescence were attributed to the resonance energy transfer between small and larger dots in a mixed QD system.     

Coreactant enhanced anodic electrochemiluminescence of CdTe quantum dots at low potential for sensitive biosensing amplified by enzymatic cycle

This work used sulfite as a coreactant to enhance the anodic electrochemiluminescence (ECL) of mercaptopropionic acid modified CdTe quantum dots (QDs). This strategy proposed the first coreactant anodic ECL of QDs and led to a sensitive ECL emission of QDs in aqueous solution at relatively low potential. In the presence of dissolved oxygen, the stable ECL emission resulted from the excited QDs. Thus, an ECL detection method was proposed at +0.90 V (vs Ag/AgCl) based on the quenching of excited QDs by the analyte. Using tyrosine as a model compound, whose electrooxidized product could quench the excited QDs and thus the ECL emission, an analytical method for detection of tyrosine in a wide concentration range was developed. Furthermore, by combining an enzymatic cycle of trace tyrosinase to produce the oxidized product with an energy-transfer process, an extremely sensitive method for ECL detection of tyrosine with a subpicomolar limit of detection was developed. The sulfite-enhanced anodic ECL emission provided an alternative for traditional ECL light emitters and a new methodology for extremely sensitive ECL detection of mono- and dihydroxybenzenes at relatively low anodic potential. This strategy could be easily realized and opened new avenues for the applications of QDs in ECL biosensing.     

Carrier Multiplication in PbS Quantum Dots Anchored on a Au Tip using Conductive Atomic Force Microscopy

Carrier multiplication (CM) is the amplification of the excited carrier density by two times or more when the incident photon energy is larger than twice the bandgap of semiconductors. A practical approach to demonstrate the CM involves the direct measurement of photocurrent in the device. Specifically, photocurrent measurement in quantum dots (QDs) is typically limited by high contact resistance and long carrier-transfer length, which yields a low CM conversion efficiency and high CM threshold energy. Here, the local photocurrent is measured to evaluate the CM quantum efficiency from a QD-attached Au tip of a conductive atomic force microscope (CAFM) system. The photocurrent is efficiently measured between the PbS QDs anchored on a Au tip and a graphene layer on a SiO₂/Si substrate as a counter electrode, yielding an extremely short channel length that reduces the contact resistance. The quantum efficiency extracted from the local photocurrent data with an incident photon energy exhibits a step-like behavior. More importantly, the CM threshold energy is as low as twice the bandgap, which is the lowest threshold energy of optically observed QDs to date. This enables the CAFM-based photocurrent technique to directly evaluate the CM conversion efficiency in low-dimensional materials.     

Ordered systems of site-controlled pyramidal quantum dots incorporated in photonic crystal cavities

The coupling of a prescribed number of site-controlled pyramidal quantum dots (QDs) with photonic crystal (PhC) cavities was studied by polarization and power-dependent photoluminescence measurements. The energy of the cavity mode could be readily tuned, making use of the high spectral uniformity of the QDs and designing PhC cavities with different hole radii. Efficient coupling of the PhC cavity modes both to the ground state and to the excited state transitions of the QDs was observed, whereas no evidence for far off-resonant coupling was found.     

Magneto-Optical Study of Multiple Layers of Self-Assembled Quantum Dots Involving Diluted Magnetic Semiconductors

Magneto-optical experiments were carried out on structures comprised of multiple layers of self-assembled quantum dots (QDs) involving diluted magnetic semiconductors (DMSs). Photoluminescence (PL) from interband ground state transitions was clearly observed in these DMS-based QD systems. The PL energy from QD multilayers appears at a lower energy than that emitted by a single QD layer, suggesting that there exists electronic coupling between the QD layers. When an external magnetic field is applied, the PL peaks from QDs both in single-layer and in multilayer form exhibit large Zeeman shifts and a significant enhancement of intensity, a behavior that is typical for many low dimensional systems involving DMSs. In contrast to this behavior, however, we have observed a decrease of the PL intensity as a function of magnetic field in multilayer structures where alternating QW layers contain DMS and non-DMS QDs. We will show evidence that this effect arises from carrier transfer between pairs of QDs from adjacent layers (double QDs) due to the large Zeeman shifts of the conduction and valence bands characteristic of DMS QDs.     

Fluorescent resonance energy transfer based detection of biological contaminants through hybrid quantum dot-quencher interactions

A nanoscale sensor employing fluorescent resonance energy transfer interactions between fluorescent quantum dots (QDs) and organic quencher molecules can be used for the multiplexed detection of biological antigens in solution. Detection occurs when the antigens to be detected displace quencher-labelled inactivated (or dead) antigens of the same type attached to QD-antibody complexes through equilibrium reactions. This unquenches the QDs, allowing detection to take place through the observation of photoluminescence in solution or through the fluorescence imaging of unquenched QD complexes trapped on filter surfaces. Multiplexing can be accomplished by using several different sizes of QDs, with each size QD labelled with an antibody for a different antigen, providing the ability to detect several types of antigens or biological contaminants simultaneously in near real-time with high specificity and sensitivity.     

Protein‐Directed Synthesis of NIR‐Emitting,Tunable HgS Quantum Dots and their Applications in Metal‐Ion Sensing

The development of luminescent mercury sulfide quantum dots (HgS QDs) through the bio‐mineralization process has remained unexplored. Herein, a simple, two‐step route for the synthesis of HgS quantum dots in bovine serum albumin (BSA) is reported. The QDs are characterized by UV–vis spectroscopy, Fourier transform infrared (FT‐IR) spectroscopy, luminescence, Raman spectroscopy, transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), circular dichroism (CD), energy dispersive X‐ray analysis (EDX), and picosecond‐resolved optical spectroscopy. Formation of various sizes of QDs is observed by modifying the conditions suitably. The QDs also show tunable luminescence over the 680–800 nm spectral regions, with a quantum yield of 4–5%. The as‐prepared QDs can serve as selective sensor materials for Hg(II) and Cu(II), based on selective luminescence quenching. The quenching mechanism is found to be based on Dexter energy transfer and photoinduced electron transfer for Hg(II) and Cu(II), respectively. The simple synthesis route of protein‐capped HgS QDs would provide additional impetus to explore applications for these materials.     

On the quenching of semiconductor quantum dot photoluminescence by proximal gold nanoparticles

Luminescent quantum dots (QDs) were proven to be very effective fluorescence resonance energy transfer donors with an array of organic dye acceptors, and several fluorescence resonance energy transfer based biosensing assemblies utilizing QDs have been demonstrated in the past few years. Conversely, gold nanoparticles (Au-NPs) are known for their capacity to induce strong fluorescence quenching of conventional dye donors. Using a rigid variable-length polypeptide as a bifunctional biological linker, we monitor the photoluminescence quenching of CdSe-ZnS QDs by Au-NP acceptors arrayed around the QD surface, where the center-to-center separation distance was varied over a broad range of values (approximately 50-200 Angstrom). We measure the Au-NP-induced quenching rates for such QD conjugates using steady-state and time-resolved fluorescence measurements and examine the results within the context of theoretical treatments based on the F?rster dipole-dipole resonance energy transfer, dipole-metal particle energy transfer, and nanosurface energy transfer. Our results indicate that nonradiative quenching of the QD emission by proximal Au-NPs is due to long-distance dipole-metal interactions that extend significantly beyond the classical F?rster range, in agreement with previous studies using organic dye-Au-NP donor-acceptor pairs.     

High resolution imaging analysis of CdSe/ZnS core–shell quantum dots (QDs) using Cs-corrected HR-TEM/STEM

CdSe/ZnS core–shell structured nano-crystal quantum dots (QDs) are ideal candidates for light-emission applications due to their high quantum efficiency, narrow-band, and particle-size-tunable photoluminescence. In particular, their small size results in the quantum confinement of semiconductor nano-crystals, which widens their energy gaps. In general, high resolution imaging analyses of QDs using a transmission electron microscope are very difficult due to their significantly small size. Successful imaging depends on the capabilities of TEM equipment and the contrast of the QDs sample relative to the supporting film. In this work, all imaging analyses were performed on a TEM equipped with a probe Cs corrector. The samples for observing QDs were prepared by drying each QDs solution on a lacey carbon Cu (300 mesh) grid previously coated with an ultra-thin graphene monolayer (thickness = 0.3 nm), due to the need to minimize the effect of the supported film.     

Giant Zeeman Effects and Spin Dynamics of Excitons in Dense Self-Organized Quantum Dots of CdSe and Cd1?xMnxSe

Giant Zeeman effects and spin dynamics of excitons are studied in dense self-organized quantum dots (QDs) of CdSe and Cd_1–xMn_xSe. Microphotoluminescence (PL) measurements for each individual dot reveal the typical dot diameter of 3.5 ± 0.2 nm and the density of 5000 m^–2 in the CdSe QDs. The exciton lifetime is shorter in smaller dots with higher energies, indicating energy transfer and tunneling processes among the dots. Circular polarization of excitonic PL is observed at 0 T with an opposite sign to that of the excited light and with the rise time of 50 ps. The CdSe QDs coupled with a Zn_1–xMn_xSe layer show the giant Zeeman shift of exciton, arising from overlapping of exciton wavefunctions in the dots with Mn ions. Spin polarization dynamics in the coupled QDs is also studied.     

Giant Zeeman Effects and Spin Dynamics of Excitons in Dense Self-Organized Quantum Dots of CdSe and Cd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se

Giant Zeeman effects and spin dynamics of excitons are studied in dense self-organized quantum dots (QDs) of CdSe and Cd_1–xMn_xSe. Microphotoluminescence (PL) measurements for each individual dot reveal the typical dot diameter of 3.5 ± 0.2 nm and the density of 5000 m^–2 in the CdSe QDs. The exciton lifetime is shorter in smaller dots with higher energies, indicating energy transfer and tunneling processes among the dots. Circular polarization of excitonic PL is observed at 0 T with an opposite sign to that of the excited light and with the rise time of 50 ps. The CdSe QDs coupled with a Zn_1–xMn_xSe layer show the giant Zeeman shift of exciton, arising from overlapping of exciton wavefunctions in the dots with Mn ions. Spin polarization dynamics in the coupled QDs is also studied.     

Plasmonic waveguides mediated energy transfer between two distant quantum dots

We investigate theoretically the radiative energy transfer between two distant quantum dots (QDs) mediated by the guided modes of Ag nanowire. The cross decay rate between the two quantum dots is derived with Markov approximation and the decay behaviors of the superradiant state and the subradiant state of quantum dots are exhibited. Due to the interference of the radiation emitted by the two QDs, the cross decay rate, the decay rates of the superradiant state, and the subradiant state show oscillation behaviors. This reveals that energy transfer from one QD to a distant QD can be controlled by adjusting the distance between the two QDs due to the periodicity of the cross decay rate.     

ZnO-CdS core-shell quantum dots sensitized solar cell: influence of crystalline and amorphous CdS structures in photovoltaic performance

ZnO nanoparticles (NPs) coated with amorphous and crystalline CdS quantum dots (QDs) were successfully synthesized through chemical bath deposition (CBD) process. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) have been utilized to characterize the samples morphology and structural properties. The conduction band of CdS QDs is much higher than the ZnO conduction band facilitates electron transfer process through cascade system. The thickness and crystallinity of the CdS QDs coated on ZnO NPs critically controls the electron diffusion length and photovoltaic performance of the solar cell. The red shift from 506 to 524 nm, increased optical absorption in the UV-visible range and electron diffusion length limited by the thickness of the amorphous/crystalline CdS QDs coated on ZnO NPs film, influences the performance of the QDs sensitized solar cell (QDSSCs) under one sun illumination intensity (AM 1.5, 100 mW/cm2). The results discuss the CBD process controlled growth of CdS QDs on ZnO NPs and its influence on the photovoltaic performance of QDSSCs.     

Assembly of CdS quantum dots onto mesoscopic TiO(2) films for quantum dot-sensitized solar cell applications

Colloidal cadmium sulfide (CdS) quantum dots (QDs) were prepared and surface modified by mercaptosuccinic acid (MSA) to render a surface with carboxylic acid groups (MSA-CdS). The MSA-CdS QDs were then assembled onto bare TiO(2) mesoporous films using the carboxylic groups/TiO(2) interaction. The TiO(2) film was also surface modified by 3-mercaptopropyl trimethoxysilane (MPTMS) or 3-aminopropyl-methyl diethoxysilane (APMDS) to prepare, respectively, a thiol (-SH) or amino (-NH(2)) terminated surface for binding with the CdS QDs. The experimental results showed that the MPTMS-modified film has the highest adsorption rate and adsorption amount to the CdS QDs, attributable to the strong thiol/CdS interaction. In contrast, the adsorption rate and incorporated amount of the QDs on the bare TiO(2) film are much lower than for the silane-modified films. The incident photon-to-current conversion efficiency (IPCE) obtained for the CdS-sensitized TiO(2) electrode was about 20% (at 400?nm) for the bare TiO(2), 13% for the MPTMS-TiO(2), and 6% for APMDS-TiO(2). The current-voltage measurement under dark conditions reveals a higher dark current on the MPTMS-?and APMDS-modified electrodes, indicating a lower coverage ratio of CdS on these TiO(2) films. This result is attributed to the fast adsorption rate of CdS QDs on the bottleneck of a mesopore which inhibits the transport of the QDs deep into the inner region of a pore. For the bare TiO(2) film, the lower incorporated amount of CdS but higher energy conversion efficiency indicates the formation of a better-covered CdS QDs monolayer. The moderate adsorption rate of MSA-CdS QDs using the carboxylic acid/TiO(2) interaction is responsible for the efficient assembly of QDs onto the mesoporous TiO(2) films.