Direct correlation between work function of indium-tin-oxide electrodes and solar cell performance influenced by ultraviolet irradiation and air exposure

We report on reversible changes of the work function (WF) values of indium-tin-oxide (ITO) under prolonged ultraviolet (UV) and air exposure. The WF of ITO is reduced from 4.7 eV to 4.2 eV by photon absorption in ITO under UV illumination or an air mass 1.5 solar simulator (100 mW cm(-2)). Air or oxygen exposure is found to increase the WF of ITO (UV-exposed) to a value of 4.6 eV. These changes of ITO's WF lead to reversible variations of the performance of organic photovoltaic devices where ITO acts primarily as the electron collecting or hole collecting electrode. These variations can be reflected in the disappearance (or appearance) of an S-shaped kink in the J-V characteristics upon continuous UV or solar simulator illumination (or air exposure). This reversible phenomenon is ascribed to the adsorption and desorption of oxygen on the surface and grain boundaries of ITO. The use of surface modifiers to either decrease or increase the WF of ITO in organic photovoltaic devices with inverted and conventional geometries is also shown to be an effective route to stabilize the device performance under UV illumination.