Redox Control of Particle Deposition from Drying Drops

The coffee-ring effect (CRE), which denotes the accumulation of nonvolatile compounds at the periphery of a pinned sessile drying drop, is a universal and ubiquitous yet complex phenomenon. It is crucial to better understand and control it, either to avoid its various deleterious consequences in many processes requiring homogeneous deposition or to exploit it for applications ranging from controlled particle patterning to low cost diagnostics. Here, we report for the first time the use of a reduction-oxidation (redox) stimulus to cancel the CRE or harness it, leading to a robust and tunable control of particle deposition in drying sessile drops. This is achieved by implementing redox-sensitive ferrocenyl cationic surfactants of different chain lengths in drying drops containing anionic colloids. Varying surfactant hydrophobicity, concentration, and redox state allows us not only to control the overall distribution of deposited particles, including the possibility to fully cancel the CRE, but also to modify the microscopic organization of particles inside the deposit. Notably, with all other parameters being fixed, this method allows the adjustment of the deposited particle patterns, from polycrystalline rings to uniform disks, as a function of the oxidation rate. We show that the redox control can be achieved either chemically by the addition of oxidants or electrochemically by applying a potential for additive-free and reversible actuation in a closed system. This correlation between the redox state and the particle pattern opens a perspective for both redox-programmable particle patterning and original diagnostic applications based on the visual determination of a redox state. It also contributes to clarify the role of surfactant charge and its amphiphilic character in directing particle deposition from drying suspensions.