The fundamental challenge of nanomanufacturing is to create, control, and assemble enormous quantities of nanoscale objects and distribute them over large surface areas. Electrospray ionization (ESI) has the potential to address this challenge due to its simplicity, applicability to a broad range of materials, and intrinsic scalability. ESI uses high voltages to electrically charge and disperse materials ranging in size from sub-nanometers to micrometers in diameter, which can then be guided and deposited on a substrate. However, the interactions between initial spray parameters and final deposited morphology are not well understood. In this study, we show that when electrospraying polymers, deposited particle size and morphology can be modified through the initial polymer concentration and nozzle-substrate distance. We report the results of electrospraying 0.1% and 0.5% concentrations of poly(acrylic acid) (PAA) onto substrates with 1, 3, and 5 cm nozzle-substrate distances. Scanning electron microscopy showed that deposited particles ranged from less than 10 nm to nearly 200 nm in diameter with tight, multi-modal size distributions. Particle shape and spread on the substrate were also examined. We use physics-based models to show that the size distributions are a function of the evaporation and drop fission during the spray along with the effect of solute concentration gradients within an evaporating drop. This work validates our previously developed models and will lead to future process guidelines.

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