Highly ordered nanostructured organic/inorganic hybrids offer chemical tunability, novel functionalities and enhanced performance over their individual components. Hybrids of complementary p-type organic and n-type inorganic components have attracted interest in optoelectronics, where high-efficiency devices with minimal cost are desired. We demonstrate here self-assembly of a lamellar hybrid containing periodic and alternating 1-nm-thick sheets of polycrystalline ZnO separated by 2-3 nm layers of conjugated molecules, directly onto an electrode. Initially the electrodeposited inorganic is Zn(OH)(2), but pi-pi interactions among conjugated molecules stabilize synergistically the periodic nanostructure as it converts to ZnO at 150 degrees C. As photoconductors, normalized detectivities (D(*)) greater than 2x10(10) Jones, photocurrent gains of 120 at 1.2 V microm(-1) and dynamic ranges greater than 60 dB are observed on selective excitation of the organic. These are among the highest values measured for organic, hybrid and amorphous silicon, making them technologically competitive as low-power, wavelength-tunable, flexible and environmentally benign photoconductors.
We studied the effects of postfabrication annealing on heterojunction photovoltaic cells made from vacuum deposited pentacene and C60. The maximum power conversion efficiency under 115mW∕cm2 illumination increases from 0.45% to 1.07% after annealing the cells at 200°C. The increased performance is a result of better molecular ordering, which leads to an increased shunt resistance and built-in potential.
Forces between negatively charged silica particles in aqueous electrolyte solutions were measured with the colloidal probe technique based on the atomic force microscope (AFM). The present study focuses on the comparison of monovalent and multivalent counterions, namely K(+), Mg(2+), and La(3+). The force profiles can be well described with the theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO) down to distances of about 4 nm. At smaller distances, the forces become strongly repulsive due to additional non-DLVO repulsion. In the presence of La(3+), one observes an additional attractive force with a range of about 1 nm at intermediate salt concentrations. This force is probably related to ion-ion correlations, but could also be influenced by surface charge heterogeneities or charge fluctuation forces.
One of the challenges in organic systems with semiconducting function is the achievement of molecular orientation over large scales. We report here on the use of self-assembly kinetics to control long-range orientation of a quarterthiophene derivative designed to combine intermolecular π-π stacking and hydrogen bonding among amide groups. Assembly of these molecules in the solution phase is prevented by the hydrogen-bond-accepting solvent tetrahydrofuran, whereas formation of H-aggregates is facilitated in toluene. Rapid evaporation of solvent in a solution of the quarterthiophene in a 2:1:1 mixture of 1,4-dioxane/tetrahydrofuran/toluene leads to self-assembly of kinetically trapped mats of bundled fibers. In great contrast, slow drying in a toluene atmosphere leads to the homogeneous nucleation and growth of ordered structures shaped as rhombohedra or hexagonal prisms depending on concentration. Furthermore, exceedingly slow delivery of toluene from a high molecular weight polymer solution into the system through a porous aluminum oxide membrane results in the growth of highly oriented hexagonal prisms perpendicular to the interface. The amide groups of the compound likely adsorb onto the polar aluminum oxide surface and direct the self-assembly pathway toward heterogeneous nucleation and growth to form hexagonal prisms. We propose that the oriented prismatic polymorph results from the synergy of surface interactions rooted in hydrogen bonding on the solid membrane and the slow kinetics of self-assembly. These observations demonstrate how self-assembly conditions can be used to guide the supramolecular energy landscape to generate vastly different structures. These fundamental principles allowed us to grow oriented prismatic assemblies on transparent indium-doped tin oxide electrodes, which are of interest in organic electronics.
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