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Advancing open atmosphere printing technologies to produce features in thenanoscale range has important and broad applications ranging from electronics,to photonics, plasmonics and biology. Recently an electrohydrodynamic printingregime has been demonstrated in a rapid dripping mode (termed NanoDrip), wherethe ejected colloidal droplets from nozzles of diameters of O(1 {\mu}m) cancontrollably reach sizes an order of magnitude smaller than the nozzle and cangenerate planar and out-of-plane structures of similar sizes. Despitedemonstrated capabilities, our fundamental understanding of important aspectsof the physics of NanoDrip printing needs further improvement. Here we addressthe topics of charge content and transport in NanoDrip printing. We employquantum dot and gold nanoparticle dispersions in combination with a speciallydesigned, auxiliary, asymmetric electric field, targeting the understanding ofcharge locality (particles vs. solvent) and particle distribution in thedeposits as indicated by the dried nanoparticle patterns (footprints) on thesubstrate. We show that droplets of alternating charge can be spatiallyseparated when applying an ac field to the nozzle. The nanoparticles within adroplet are distributed asymmetrically under the influence of the auxiliarylateral electric field, indicating that they are the main carriers. We alsoshow that the ligand length of the nanoparticles in the colloid affects theirmobility after deposition (in the sessile droplet state).

Charge Effects and Nanoparticle Pattern Formation in Electrohydrodynamic NanoDrip Printing of Colloids