Effect of surface ligands on the photoinduced electron transfer rate and efficiency in ZnO quantum dots and graphene oxide assemblies.

Apart from biocompatibility, ZnO quantum dots (QDs) are considered to be an efficient luminescence material due to their low cost and high redox potential. Here, we report the synthesis of ZnO QDs by using five different functionalizing ligands like mercaptoacetic acid (MAA), 3-mercaptopropionic acid (MPA), octadecene (ODE), ethylene glycol (EG), and oleyl amine (OLA) and fabricate their assemblies with graphene oxide (GO). We investigate the role of functionalizing ligands as a surface modifier of ZnO QDs for their attachment to GO. The steady-state photoluminescence (SSPL) and time-resolved photoluminescence (TRPL) analyses demonstrate the photoluminescence (PL) quenching of ZnO QDs in ZnO QDs-GO assembly. The highest reduction in PL intensity is observed with ZnO QDs-GO assembly with EG as a surface functionalizing ligand. Cyclic voltammetry (CV) analysis confirms the feasibility of charge transfer from ZnO QDs to the GO. The maximum (79.43%) charge transfer efficiency (ECT ) is observed in the case of ZnO-MAA-GO as compared to other assemblies. This means the thiol group-containing ligands facilitate charge transfer as compared to hydroxyl and amine group ligands. This leads to the conclusion that charge transfer in ZnO QDs-GO assemblies depends strongly on the nature of surface ligands.

Probing the Förster Resonance Energy Transfer Dynamics in Colloidal Donor-Acceptor Quantum Dots Assemblies.

In this article, we report the synthesis of graphene quantum dots (GQDs) by hydrothermal method and surface modified CdS quantum dots (QDs) via the colloidal method and the fabrication of their dyad. The CdS QDs functionalized by mercaptoacetic acid (MAA) attach to the GQDs via electrostatic interactions. Spectral overlapping between the emission spectrum of GQDs and the absorption spectrum of CdS QDs allows efficient Förster resonance energy transfer (FRET) from GQDs to the CdS QDs in the GQDs-CdS QDs dyads. The magnitude of FRET efficiency (E) and the rate of energy transfer (kE) assessed by the photoluminescence (PL) decay kinetics are ~61.84% and ⁓3.8 × 108 s- 1, respectively. These high values of FRET efficiency and energy transfer rate can be assigned to the existence of strong electrostatic interactions between GQDs and CdS QDs, which arise due to the presence of polar functionalities on the surface of both GQDs and CdS QDs. The understanding of energy transfer in the luminescent donor-acceptor FRET system is of significant importance and the practical implications of such FRET systems could overall improve the efficiency of photovoltaics, sensing, imaging and optoelectronic devices.

Aspect ratio dependent air stability of PbSe nanorods and photovoltaic applications.

Development of unique strategies to overcome Shockley-Queisser (SQ) limit in solar cells has gained a great deal of interest. Multiple exciton generation (MEG) process has been considered as one of the best approaches to the SQ limitation. In this respect, PbSe quantum dots (QDs) and nanorods (NRs) have been regarded as promising solar energy harvesting materials owing to their noticeable MEG yields. Although air stability has been regarded as one of the main disadvantage of PbSe QDs, no study has pointed out to the air sensitivity of PbSe NRs yet. Here, we reveal the effect of aspect ratio on air sensitivity and optical properties of PbSe NRs and discover that NRs with higher aspect ratios are more air stable, attributed to the reduced density of NR ends with air sensitive {100} facets. Furthermore, a band offset was created by utilization of tetrabutylammonium iodide and 1,2-ethanedithiol ligands in cell designs. We found that solar cells based on pristine PbSe NRs are limited by low open circuit voltages due to leakage current pathways. On the other hand, modified cells comprising light absorbing layers prepared by blending NRs and QDs and hole transporting QD layer exhibit a 10-fold improvement in solar cell efficiency.

Temperature- and voltage-induced ligand rearrangement of a dynamic electroluminescent metallopolymer.

A dynamic-covalent metal-containing polymer was synthesized by the condensation of linear diamine and dialdehyde subcomponents around copper(I) templates in the presence of bidentate phosphine ligands. In solution, the red polymers undergo a sol-gel transition upon heating to form a yellow gel, a process that can be either reversible or irreversible depending on the solvent used. When fabricated into a light-emitting electrochemical cell (LEC), the polymer emits infrared light at low voltage. As the voltage is increased, a blue shift in the emission wavelength is observed until yellow light is emitted, a process which is gradually reversed over time upon lowering the voltage. The mechanism underlying these apparently disparate responses is deduced to be due to loss of the copper phosphine complex from the polymer.

Aqueous self-assembly of an electroluminescent double-helical metallopolymer.

A new type of water-soluble copper-containing polymer has been synthesized using the technique of subcomponent self-assembly. Copper(I)-directed imine bond formation between triethylene glycol functionalized 1,2-phenylenediamine and 2,9-diformylphenanthroline subcomponents resulted in the formation of a chain in which two conjugated helical ligand strands wrap around a linear array of metal ions. Characterization data from a variety of analytical methods are consistent with our formulation of this material. After purification by dialysis, the polymer was shown to possess several properties of conceptual and practical interest. (1) Individual double-helical strands appear to further aggregate through entanglement of their side chains to form well-defined superstructures such as nanoscale bow ties and macrocycles, which can be imaged on a surface. (2) The material's copper(I) ions underwent reversible electrochemical oxidation in solution, whereas analogous model compounds were observed to decompose upon oxidation: the polymer's greater length appeared to stabilize oxidized states through delocalization or entrapment. (3) Photophysical measurements reveal this material to be photo- and electroluminescent. It has been successfully used for the fabrication of electroluminescent devices and shows a weak emission of white-blue light with CIE coordinates of (0.337, 0.359). This study further demonstrates the utility of the technique of subcomponent self-assembly for the straightforward generation of materials with useful properties.

A glow in the dark: synthesis and electropolymerization of a novel chemiluminescent terthienyl system.

The synthesis and characterization of a unique (electro)chemiluminescent monomer based on a terthienyl system, and its corresponding polymer which is the first example of an electro-active chemiluminescent polymer bearing a pyridazine appendage, are described.