Constructive Microlithography: Electrochemical Printing of Monolayer Template Patterns Extends Constructive Nanolithography to the Micrometer−Millimeter Dimension Range

Micrometer-scale patterns consisting of water-wetted hydrophilic features on the surface of a rigid metallic object (stamp) are successfully transferred to the hydrophobic surface of a highly ordered organosilane monolayer self-assembled on silicon upon the application of an appropriate voltage bias between the stamp and the silicon wafer substrate while the two are pressed against one another. The monolayer imprint is the result of a water bridge-mediated electrochemical oxidation process selectively converting surface exposed −CH 3 groups of the monolayer to −COOH. This novel electrochemical printing process, analogous to the monolayer pattern inscription with a conductive scanning probe tip underlying constructive nanolithography (Maoz, R.; Cohen, S. R.; Sagiv, J. Adv. Mater. 1999, 11, 55−61. Maoz, R.; Frydman, E.; Cohen, S. R.; Sagiv, J. Adv. Mater. 2000, 12, 424−429. Maoz, R.; Frydman, E.; Cohen, S. R.; Sagiv, J. Adv. Mater. 2000, 12, 725−731.), paves the way to the possible advancement of a “bottom-up” nano−micro fabrication methodology applicable within the entire nanometer−millimeter dimension range.