One of the most exciting and debated aspects of polariton chemistry is the possibility that chemical reactions can be catalyzed by vibrational strong coupling (VSC) with confined optical modes in the absence of external illumination. Here, we report an attempt to reproduce the enhanced rate of cyanate ion hydrolysis reported by Hiura et al. [chemRxiv:7234721 (2019)] when the collective OH stretching vibrations of water (which is both the solvent and a reactant) are strongly coupled to a Fabry–Pérot cavity mode. Using a piezo-tunable microcavity, we reproduce the reported vacuum Rabi splitting but fail to observe any change in the reaction rate as the cavity thickness is tuned in and out of the strong coupling regime during a given experiment. These findings suggest that there are subtleties involved in successfully realizing VSC-catalyzed reaction kinetics and therefore motivate a broader effort within the community to validate the claims of polariton chemistry in the dark.
We demonstrate ferroelectricity in Mg-substituted ZnO thin films with the wurtzite structure. Zn 1−x Mg x O films are grown by dual-cathode reactive magnetron sputtering on (111)-Pt // (0001)-Al 2 O 3 substrates at temperatures ranging from 26 to 200 °C for compositions spanning from x = 0 to x = 0.37. X-ray diffraction indicates a decrease in the c-lattice parameter and an increase in the a-lattice parameter with increasing Mg content, resulting in a nearly constant c/a axial ratio of 1.595 over this composition range. Transmission electron microscopy studies show abrupt interfaces between Zn 1−x Mg x O films and the Pt electrode. When prepared at pO 2 = 0.025, film surfaces are populated by abnormally oriented grains as measured by atomic force microscopy for Mg concentrations >29%. Raising pO 2 to 0.25 eliminates the misoriented grains. Optical measurements show increasing bandgap values with increasing Mg content. When prepared on a 200 °C substrate, films display ferroelectric switching with remanent polarizations exceeding 100 μC cm −2 and coercive fields below 3 MV cm −1 when the Mg content is between ∼30% and ∼37%. Substrate temperature can be lowered to ambient conditions, and when doing so, capacitor stacks show only minor sacrifices to crystal orientation and nearly identical remanent polarization values; however, coercive fields drop below 2 MV/cm. Using ambient temperature deposition, we demonstrate ferroelectric capacitor stacks integrated directly with polymer substrate surfaces.
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