Influence of OH groups on charge transport across organic-organic interfaces: a systematic approach employing an "ideal" device.
ABSTRACT The charge transport across a pentacene/SAM interface has been studied by scanning tunnelling spectroscopy (STS) as a function of temperature and film thickness in order to obtain information on the transport mechanisms and in particular on the importance of interfacial OH-groups on n-transport in organic semiconductors. The current-voltage (I-V) characteristics of pentacene thin films deposited on a mercaptoundecanol self-assembled monolayer (SAM) on Au(111) reveal an asymmetric behaviour. At positive sample bias the onset currents shift towards higher voltages for decreasing temperatures, whereas such changes are not seen at negative bias. For lower temperatures, the variation of current onset with layer thickness is absent. These observations are explained by OH-groups at the SAM-surface effectively acting as charge traps. When electrons are caught in these traps at the organic-organic interface, charge transport is severely affected. Imaging of the SAM after loading the traps suggests that the attachment of electrons to the OH-groups exposed at the organic surface is a reversible process.
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ABSTRACT: The morphology of pentacene organic thin films deposited on SiO2 and Au(111) surfaces using organic molecular beam deposition (OMBD) has been characterized by a multi-technique approach. Among the techniques applied were X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy (SEM) and thermal desorption spectroscopy (TDS). Our rather detailed studies reveal that on both substrates the growth is strongly influenced by dewetting and islanding phenomena, yielding very rough surfaces. Surprisingly, substantial changes in the morphology were observed also after deposition on room-temperature samples on a time scale of several hours. The rather extensive set of in situ XPS data was analyzed in the framework of a simple model, which allows us to derive rather detailed information on the roughness parameters.Applied Physics A 08/2013; 95(1). · 1.55 Impact Factor
- Chemical Reviews 05/2005; 105(4):1103-69. · 41.30 Impact Factor
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ABSTRACT: Experimental observations are presented on condensed-phase analogues of gas-phase dipole-bound anions and negatively charged clusters of polar molecules. Both monomers and small clusters of such molecules can reversibly trap conduction band electrons in dilute alkane solutions. The dynamics and energetics of this trapping have been studied using pulse radiolysis-transient absorption spectroscopy and time-resolved photoconductivity. Binding energies, thermal detrapping rates, and absorption spectra of excess electrons attached to monomer and multimer solute traps are obtained, and possible structures for these species are discussed. "Dipole coagulation" (stepwise growth of the solute cluster around the cavity electron) predicted by Mozumder in 1972 is observed. The acetonitrile monomer is shown to solvate the electron by its methyl group, just as the alkane solvent does. The electron is dipole-bound to the CN group; the latter points away from the cavity. The resulting negatively charged species has a binding energy of 0.4 eV and absorbs in the infrared. Molecules of straight-chain aliphatic alcohols solvate the excess electron by their OH groups; at equilibrium, the predominant electron trap is a trimer or a tetramer, and the binding energy of this solute trap is ca. 0.8 eV. Trapping by smaller clusters is opposed by the entropy that drives the equilibrium toward the electron in a solvent trap. For alcohol monomers, the trapping does not occur; a slow proton-transfer reaction occurs instead. For the acetonitrile monomer, the trapping is favored energetically, but the thermal detachment is rapid (ca. 1 ns). Our study suggests that a composite cluster anion consisting of a few polar molecules imbedded in an alkane "matrix" might be the closest gas-phase analogue to the core of solvated electron in a neat polar liquid.The Journal of Physical Chemistry A 07/2005; 109(25):5754-69. · 2.77 Impact Factor