This study focused on how the formation of phosphosilicate glass (PSG) film affects the solar cell emitter profile when using an inline ultrasonic mist phosphoric acid source and an inline diffusion furnace. This investigation used a novel approach, whereby the samples were extracted from the inline furnace mid-process that allowed for the investigation of incompletely formed PSGs. All experimentation was conducted at BP Solar Australia. Total Gravimetric Analysis found that the dilute phosphoric acid dehydrates to form a high concentration phosphoric acid layer on the top surface. X-ray photoelectron spectroscopy then showed this top surface reacts with the silicon and is reduced to form silicon phosphide. ECV results then demonstrated that the sheet resistance and emitter surface concentration of phosphorus is dependent upon the ratio of phosphide to total phosphorus in the PSG film. Copyright © 2010 John Wiley & Sons, Ltd.