Nanoscale Characterization of the Electrical Properties of Oxide Electrodes at the Organic Semiconductor-Oxide Electrode Interface in Organic Solar Cells

This dissertation focuses on characterizing the nanoscale and surface averaged electrical properties of transparent conducting oxide (TCO) electrodes such as indium tin oxide (ITO) and transparent metal-oxide (MO) electron selective interlayers (ESLs), such as zinc oxide (ZnO), the ability of these materials to rapidly extract photogenerated charges from organic semiconductors (OSCs) used in organic photovoltaic (OPV) cells, and evaluating their impact on the power conversion efficiency (PCE) of OPV devices. In Chapter 1, we will introduce the fundamental principles regarding the need for low cost power generation, the benefits of OPV technologies, as well as the key principles that govern the operation of OPV devices and the key innovations that have advanced this technology. In Chapter 2 of this dissertation, we demonstrate an innovative application of conductive probe atomic force microscopy (CAFM) to map the nanoscale electrical heterogeneity at the interface between an electrode, such as ITO, and an OSC such as the p-type OSC copper phthalocyanine (CuPc).(MacDonald et al. (2012) ACS Nano, 6, p. 9623) In this work we collected arrays of J-V curves, using a CAFM probe as the top contact of CuPc/ITO systems, to map the local J-V responses. By comparing J-V responses to known models for charge transport, we were able to determine if the local rate-limiting step for charge transport is through the OSC (ohmic) or the CuPc/ITO interface (nonohmic). These results strongly correlate with device PCE, as demonstrated through the controlled addition of insulating alkylphosphonic acid self-assembled monolayers (SAMs) at the ITO/CuPc interface. Subsequent chapters focus on the electrical property characterization of RF-magnetron sputtered ZnO (sp-ZnO) ESL films on ITO substrates. We have shown that the energetic alignment of ESLs and the organic semiconducting (OSC) active materials plays a critical role in determining the PCE of OPV devices and the appearance of, or lack thereof, UV light soaking sensitivity. For ZnO and fullerene interfaces, we have shown that either minimizing the oxygen partial pressure during ZnO deposition or exposure of ZnO to UV light minimizes the energetic offset at this interface and maximizes device PCE. We have used a combination of device testing, device modeling, and impedance spectroscopy to fully characterize the effects that energetic alignment has on the charge carrier transport and charge carrier distribution within the OPV device. This work can be found in Chapter 3 of this dissertation and is in preparation for publication. We have also shown that the local properties of sp-ZnO films varies as a function of the underlying ITO crystal face. We show that the local ITO crystal face determines the local nucleation and growth of the sp-ZnO films. We demonstrate that this effects the morphology, the chemical resistance to etching as well as the surface electrical properties of the sp-ZnO films. This is likely due to differences in the surface mobility of sputtered Zn and O atoms on these crystal faces during film nucleation. This affects the nanoscale distribution of electrical and chemical properties. As a result we demonstrate that the PCE, and UV sensitivity of the J-V response of OPVs using sp-ZnO ESLs are strongly impacted by the distribution of ITO crystal faces at the surface of the substrate. This work can be found in Chapter 4 of this dissertation and is in preparation for publication. These studies have contributed to a detailed understanding of the role that electrical heterogeneity, insulating barriers and energetic alignment at the MO/OSC interface play in OPV PCE