Nanometer-scale design and fabrication of polymer interfaces using polydiacetylene monolayers

The incorporation of photopolymerizable diacetylene structures within spont aneously organized monolayers has facilitated the fabrication of robust int erfacial assemblies with covalent molecular scaffolding. Through selective ultraviolet-induced polymerization, the resulting polydiacetylene monolayer s permit precise structural control in the lateral domain through phototemp lating. Results: presented in this article demonstrate that these unique mo nolayer polymers also allow control of the vertical domain within the monol ayer through variation of the conjugated polymer backbone position along th e-length of the alkyl chains. Small variations in the vertical position of the diacetylene groups of less than a nanometer are found to have a profoun d. impact on both polymerization;efficiency and the resulting conjugation l ength of the Polymer interface. Furthermore, the relative position of this polymer backbone within the alkyl chains can be utilized to manipulate the overall properties of the assembly such as the long- and shea-range, order. In this article, spectroscopic and electrochemical techniques are utilized to demonstrate the range of interfacial environments obtainable with these unique polymer monolayers. These advances are currently being utilized to create robust assemblies with three-dimensional control of the physical and chemical properties on a micro- to nanometer scale. (C) 1999 American Vacu um Society. [S0734-2101(99)00804-0].