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    Optically Reconfigurable Monolayer of Azobenzene Donor Molecules on Oxide Surfaces

    Year: 2017

    Journal: Langmuir, Volume 33, nov-07, page 2157–2168

    Authors: McElhinny, Kyle M.; Huang, Peishen; Joo, Yongho; Kanimozhi, Catherine; Lakkham, Arunee; Sakurai, Kenji; Evans, Paul G.; Gopalan, Padma

    Organizations: Division of Materials Science and Engineering, Office of Basic Energy Science, U.S. Department of Energy [ER46590]; National Science Foundation through the University of Wisconsin Materials Research Science and Engineering Center (MRSEC) (NSF) [DMR-1121288]; 3M Corporation through 3M Science and Technology Fellowship Program; Japanese Society for the Promotion of Science; National Science Foundation [OISE-1515273]

    The structural configuration of molecules assembled at organic-inorganic interfaces within electronic materials strongly influences the functional electronic and vibrational properties relevant to applications ranging from energy storage to photovoltaics. Controlling and characterizing the structural state of an interface and its evolution under external stimuli is crucial both for the fundamental understanding of the factors influenced by molecular structure and for the development of methods for material synthesis. It has been challenging to create complete molecular monolayers that exhibit external reversible control of the structure and electronic configuration. We report a monolayer/inorganic interface consisting of an organic monolayer assembled on an oxide surface, exhibiting structural and electronic reconfiguration under ultraviolet illumination. The molecular monolayer is linked to the surface through a carboxylate link, with the backbone bearing an azobenzene functional group and the head group consisting bipyridine group. Optical spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and X-ray reflectivity show that closely packed monolayers are formed from these molecules via the Langmuir-Blodgett technique. Reversible photoisomerization is observed in solution and in monolayers assembled on Si and quartz substrates. The reconfiguration of these monolayers provides additional means to control excitation and charge transfer processes that are important in applications in catalysis, molecular electronics, and solar energy conversion.
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