Relaxation times in single event electrospraying controlled by nozzle front surface modification

Single event electrospraying (SEE) is a method for on-demand deposition of femtoliter to picoliter volumes of fluids. To determine the influence of the size of the meniscus on the characteristics of the single event electrospraying process, glass capillaries were used with and without an antiwetting coating comprising a self-assembled 1H,1H,2H,2H-perfluorodecyltrichlorosilane-based monolayer to control the meniscus size. A large difference was found in driving single event electrospraying from a small meniscus compared to what is needed to generate a single event electrospraying from a large meniscus. Furthermore, after studying the different time constants related to the electrical and the hydrodynamic phenomena, we are able to explain the timing limitations of the deposition process from both a small and a large meniscus. The hydrodynamic relaxation time is significantly reduced in the case of the modified capillary, and the timing of SEE, which determines the deposition time, is limited by the resistor-capacitor RC time of the electrical circuit needed to drive the SEE. We have built a model that describes the almost one-dimensional motion of the liquid in the capillary during pulsing. The model has been used to estimate the hydrodynamic relaxation times related to the meniscus-to-cone and cone-to-meniscus transitions during SEE. By confining the meniscus to the inner diameter of the nozzle, we are able to deposit a volume smaller than 5 pL per SEE.