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A systematic study of "coffee-ring" formation dynamics was carried out using chemically and physically well-controlled substrates and colloids.1 Clean silicon wafers were reacted with tris(trimethylsiloxyl)chlorosilane in the vapor phase to yield molecularly smooth substrates with advancing and receding contact angles up to 84°/74° (θA/θR) and a constant hysteresis of 12 ± 2°.