Langmuir monolayers floating on supersaturated aqueous subphases can act as templates for the growth of oriented inorganic films—a “bioinspired” nucleation process. We have performed in situ grazing incidence x-ray diffraction studies of the selective nucleation of BaClF and BaF2 under fatty acid monolayers. The arrangement of the fatty acid headgroups, the monolayer charge, and ion-specific effects all play important roles in selecting the inorganic species. When the monolayer is in a neutral state, both BaClF and BaF2 nucleate at the interface and are well aligned, but when the monolayer headgroup is deprotonated, only oriented BaF2 grows at the interface. We also observe an enhanced alignment of BaF2 crystals during growth from highly supersaturated solutions, presumably due to reorganization of preformed crystals at the organic template. These results show that a delicate interplay between multiple factors governs the oriented growth of inorganic films at organic templates.
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This work was supported by the United States Department of Energy under Grant No. DE-FG02-ER45125. It was performed at Sector 33 (bending magnet beamline-Station C) of the Advanced Photon Source and at beamline X14-A of the National Synchrotron Light Source, both of which are also supported by the United States Department of Energy.
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Kewalramani, S., Kim, K., Evmenenko, G. et al. Mechanisms for species-selective oriented crystal growth at organic templates. Journal of Materials Research 22, 2785–2790 (2007). https://doi.org/10.1557/JMR.2007.0347