The polymer light-emitting electrochemical cell (LEC) is an alternative method for producing electroluminescence (EL) from conjugated luminescent polymers. The in situ electrochemical doping process that leads to a dynamic p-n junction makes the devices highly insensitive to device thickness and relatively insensitive to electrode materials. These characteristics make an extremely large planar configuration accessible for observing the cross-section of the device and watching it turn on dynamically. By cooling the device to freeze ionic motion, the junction can be stabilized and photovoltaic (PV) characteristics investigated. In the planar configuration, the p-n junction was found to make up a small fraction of the inter-electrode spacing. Enabled by the insensitivity to electrode materials, small metallic particles embedded in the LEC film led to a large number of p-n junctions that could be turned on in series and parallel. This alleviates the issue of low specific emitting area suffered by planar devices and leads to improved EL effciency as well as a high open circuit voltage (Voc) when operated as a PV cell. The bulk homojunction fabrication process has been optimized by segregating the metallic particles to eliminate large aggregates. A new technique to achieve highly uniform EL from large planar LECs is also presented here. By the evaporation of a thin gold or silver film on top of an LEC, independent islands form that act as doping initiation sites across the device width. A bulk homojunction is turned on in the top layer of the LEC with a high applied bias. Island diameters and spacings are several orders of magnitude smaller than the particles in previously-reported bulk homojunction devices. Both island and particle devices had their interelectrode spacings scaled down by at least a factor of 10. The successful scaling is a promising result for the possibility of a sandwich configuration bulk homojunction device. In the case of silver island devices, cooling a 50-micron wide device after turn-on resulted in a PV cell with an open circuit voltage of 8.3 V, several times the band gap of the luminescent polymer used. / Thesis (Master, Physics, Engineering Physics and Astronomy) -- Queen's University, 2008-09-12 12:21:12.949