Thin air-plasma-treated alkali fluoride layers for improved hole extraction in copper phthalocyanine/C70-based solar cells

Alkali fluorides, mostly LiF and CsF, are well-known to improve electron injection/extraction in organic light-emitting diodes (OLEDs) and organic solar cells (OSCs). They are also utilized, though to a lesser extent, for hole injection in OLEDs. Here we demonstrate a new role for such fluorides in enhancing OSCs' hole extraction. We show that an ultrathin air-plasma-treated alkali fluoride layer between the indium tin oxide (ITO) anode and the active layer in copper phthalocyanine (CuPc)/C70-based OSCs increases the short circuit current by up to ∼ 17% for cells with LiF and ∼ 7% for cells with NaF or CsF. The effects of the fluoride layer thickness and treatment duration were evaluated, as were OSCs with oxidized and plasma-treated Li and UV-ozone treated LiF. Measurements included current voltage, absorption, external quantum efficiency (EQE), atomic force microscopy, and x-ray photoelectron spectroscopy, which showed the presence of alkali atoms F and O at the treated ITO/fluoride surface. The EQE of optimized devices with LiF increased at wavelengths >560  nm, exceeding the absorption increase. Overall, the results indicate that the improved performance is due largely to enhanced hole extraction, possibly related to improved energy-level alignment at the fluorinated ITO/CuPc interface, reduced OSC series resistance, and in the case of LiF, improved absorption.