Understanding interfacial charge injection processes is one of the key factors needed for development of efficient organic electronic devices, such as biosensors and energy conversion systems, since these processes control the electrical characteristics of these devices. Spectroelectrochemical characterization of electron transfer processes occurring at the electrode - electroactive thin film interface has been evaluated to improve our understanding of charge transfer kinetics using a novel form of electroreflectance spectroscopy, potential-modulated attenuated total reflectance (PM-ATR), which makes it possible to sensitively monitor spectroscopic changes in thin films as a function of applied potential.PM-ATR was used to evaluate three different redox-active films deposited on indium tin oxide (ITO) electrodes to investigate: i) the orientation dependence of charge transfer rates of thin films of biomolecules, ii) surface treatment and modification effects on charge transfer kinetics of conducting polymers and, iii) estimation of rates of electron injection and conduction band edge of semiconductor nanocrystalline materials.First, Prussian blue film as a model system was used successfully to examine the PM-ATR technique for determination of the charge transfer rate constant between ITO and a molecular film.Second, an anisotropic and redox active protein film, cytochrome c, was used to probe charge transfer rates with respect to molecular orientation. The electron transfer rate measured using TM polarized light was four-fold greater than that measured using TE polarized light. These data are the first to correlate a distribution of molecular orientations with a distribution of electron transfer rates in a redox-active molecular film.Third, the effects of ITO surface treatment and modification on charge transfer kinetics on a conducting polymer, poly(3,4-ethylenedioxythiophene/)/poly(styrenesulfonate) (PEDOT/PSS), were studied. The apparent interfacial charge transfer rate constant for PEDOT/PSS on ITO has been reported for the first time which cannot be measured otherwise with conventional electrochemistry due to high non-Faradaic background of PEDOT/PSS films.Fourth, PM-ATR enabled characterization of reversible redox processes between submonolayer coverages of surface-tethered, CdSe nanocrystals and ITO for the first time. Optically determined onset potentials for electron injection were used for estimation for the conduction band and valance band energies (ECB and EVB, respectively).

Chemisorption of an organic monolayer to tune the surface properties of a transparent conductive oxide (TCO) electrode can improve the performance of organic electronic devices that rely on efficient charge transfer between an organic active layer and a TCO contact. Here, a series of perylene diimides (PDIs) was synthesized and used to study relationships between monolayer structure/properties and electron transfer kinetics at PDI-modified indium-tin oxide (ITO) electrodes. In these PDI molecules, one of the imide substituents is a benzene ring bearing a phosphonic acid (PA) and the other is a bulky aryl group that is twisted out of the plane of the PDI core. The size of the bulky aryl group and the substitution of the benzene ring bearing the PA were both varied, which altered the extent of aggregation when these molecules were absorbed as monolayer films (MLs) on ITO, as revealed by both attenuated total reflectance (ATR) and total internal reflection fluorescence spectra. Polarized ATR measurements indicate that, in these MLs, the long axis of the PDI core is tilted at an angle of 33-42 degrees relative to the surface normal; the tilt angle increased as the degree of bulky substitution increased. Rate constants for electron transfer (k(s,opt)) between these redox-active modifiers and ITO were determined by potential-modulated ATR spectroscopy. As the degree of PDI aggregation was reduced, k(s,opt) declined, which is attributed to a reduction in the lateral electron self-exchange rate between adsorbed PDI molecules, as well as the heterogeneous conductivity of the ITO electrode surface. Photoelectrochemical measurements using a dissolved aluminum phthalocyanine as an electron donor showed that ITO modified with any of these PDIs is a more effective electron-collecting electrode than bare ITO.