Alexander Alekseev

Determining the optimum morphology in high-performance polymer-fullerene organic photovoltaic cells

The morphology of bulk heterojunction organic photovoltaic cells controls many of the performance characteristics of devices. However, measuring this morphology is challenging because of the small length-scales and low contrast between organic materials. Here we use nanoscale photocurrent mapping, ultrafast fluorescence and exciton diffusion to observe the detailed morphology of a high-performance blend of PTB7:PC71BM. We show that optimized blends consist of elongated fullerene-rich and polymer-rich fibre-like domains, which are 10–50 nm wide and 200–400 nm long. These elongated domains provide a concentration gradient for directional charge diffusion that helps in the extraction of charge pairs with 80% efficiency. In contrast, blends with agglomerated fullerene domains show a much lower efficiency of charge extraction of ~45%, which is attributed to poor electron and hole transport. Our results show that the formation of narrow and elongated domains is desirable for efficient bulk heterojunction solar cells.

Three-dimensional Electrical Property Mapping with Nanometer Resolution

The conductivity behavior of MWCNT networks within the volume of polymer nanocomposite samples is analyzed with nanometer resolution in all three dimensions. It is demonstrated that close to but above the percolation threshold for electrical conduction most of the MWCNTs do not contribute to the conductive network within the nanocomposite.

Experimental and theoretical study of the influence of the state of dispersion of graphene on the percolation threshold of conductive graphene/polystyrene nanocomposites

The effect of the dispersed state of graphene is studied as a factor influencing the electrical percolation threshold of graphene/polystyrene nanocomposites. We find the percolation threshold of our nanocomposites, prepared with graphene dispersions with different thermodynamic stabilities, degrees of exfoliation, and size polydispersities, to range from 2 to 4.5 wt %. Connectedness percolation theory is applied to calculate percolation thresholds of the corresponding nanocomposites, based on the premise that size polydispersity of graphene platelets in the corresponding solutions must have a strong influence on it. Theory and experimental results agree qualitatively.

Significance of the Amide Functionality on DOPA-Based Monolayers on Gold

The adhesive proteins secreted by marine mussels contain an unusual amino acid, 3,4-dihydroxyphenylalanine (DOPA), that is responsible for the cohesive and adhesive strength of this natural glue and gives mussels the ability to attach themselves to rocks, metals, and plastics. Here we report a detailed structural and spectroscopic investigation of the interface between N-stearoyldopamine and a single-crystalline Au(111) model surface and an amide-absent molecule, 4-stearylcatechol, also on Au(111), with the aim of understanding the role of the amide functionality in the packing, orientation, and fundamental interaction between the substrate and the monolayer formed from an aqueous environment by the Langmuir-Blodgett technique. The organization of monolayers on gold was observed directly and studied in detail by X-ray photoelectron spectroscopy (XPS), contact angle measurements (CA), surface-enhanced Raman spectroscopy (SERS), infrared reflection-absorption spectroscopy (IRRAS), and atomic force microscopy (AFM). Our study shows that within the monolayer the catecholic oxygen atoms are coordinated to the gold surface, having a more perpendicular orientation with respect to the aromatic ring and the apparently tilted alkyl chains, whereas the amide functionality stabilizes the monolayer that is formed.

Morphology and local electrical properties of PTB7:PC71BM blends

The power conversion efficiency of single layer organic solar cells can approach 10% with blends such as the polymer PTB7 and the fullerene derivative PC71BM. Here the detailed structure of PTB7:PC71BM blends deposited with and without addition of diiodooctane is studied by transmission electron microscopy and scanning probe microscopy. The details of bulk structure, such as the thickness of the layer covering fullerene domains and the grain structure of the film are examined. We find that fullerene-rich domains can be near the surface of the film or buried deeper, near the substrate. The local electrical properties of these blends are studied by conductive atomic force microscopy for different configurations of electrodes. Different power conversion efficiencies of blends with and without diiodooctane are explained in terms of local photoconductive properties.

Vectorial photoinduced electron transfer of phytochlorin- fullerene systems in Langmuir-Blodgett films

Molecular systems capable of photoinduced vectorial electron transfer (ET) were assembled using the Langmuir-Blodgett technique. The active part of the systems consisted of phytochlorin-fullerene donor-acceptor layers and polythiophene secondary donor layers. Such structures can promote multi-step inter-layer ET in a direction determined by the film architecture. Transient photovoltage and photocurrent were studied and ET rates and efficiencies were determined. The primary intramolecular charge separated state was formed upon photoexcitation in less than 1 ns and it recombined in approximately 50 ns. Addition of the polythiophene layer at the side of the phytochlorin moieties increased the distance of charge transfer and the lifetime of the charge separated state by promoting spontaneous interlayer electron transfer from the polymer to the phytochlorin cation.

Etchant-based design of gold tip apexes for plasmon-enhanced Raman spectromicroscopy

In this paper, we gain insight into the design and optimization of plasmonic (metallic) tips prepared with dc-pulsed voltage electrochemical etching gold wires, provided that, a duty cycle is self-tuned. Physically, it means that etching electrolyte attacks the gold wire equally for all pulse lengths, regardless of its surface shape. Etchant effect on the reproducibility of a curvature radius of the tip apex is demonstrated. It means that the gold conical tips can be designed chemically with a choice of proper etchant electrolyte. It is suggested to use a microtomed binary polymer blend consisting of polyamide and low density polyethylene, as a calibration grating, for optimizing and standardizing tip-enhanced Raman scattering performance.

Effect of horizontal magnetization reversal of the tips on magnetic force microscopy images

The effect of magnetization reversal of magnetic force microscope (MFM) tips based on low coercive thin-films on MFM images has been studied both experimentally and theoretically. By analyzing the MFM images obtained on structures with high magnetic stray fields we show that during the imaging process the magnetic state of the probe is modified anisotropically: the horizontal component of the magnetization follows the external field, whereas the vertical component of the magnetization stays almost constant. The observed complex magnetic behavior of the tip is explained theoretically based on the shape anisotropy of the tip. The obtained results are important for interpretation of MFM images of structures with high magnetic moment. Moreover, these results can be used for characterization of both laboratory-made and commercially available MFM tips.