Ultrathin films of TiO2, ZrO2, and Al2O3 were conformally created on SnO2 and TiO2 photoelectrodes via atomic layer deposition (ALD) to examine their influence upon electron transfer (ET) from the electrodes to a representative molecular receptor, I3(-). Films thicker than 2 Å engender an exponential decrease in ET time with increasing film thickness, consistent with tunneling theory. Increasing the height of the barrier, as measured by the energy difference between the transferring electron and the bottom of the conduction band of the barrier material, results in steeper exponential drops in tunneling rate or probability. The variations are quantitatively consistent with a simple model of quantum tunneling of electrons through square barriers (i.e., barriers of individually uniform energy height) that are characterized by individually uniform physical thickness. The findings demonstrate that ALD is a remarkably uniform and precise method for modifying electrode surfaces and imply that standard tunneling theory can be used as a quantitative guide to intentionally and predictively modulating rates of ET between molecules and electrodes.

Through in situ quartz crystal microbalance (QCM) monitoring, we resolve the growth of a self-assembled monolayer (SAM) and subsequent metal oxide deposition with high resolution. We introduce the fitting of mass deposited during each atomic layer deposition (ALD) cycle to an analytical island-growth model that enables quantification of growth inhibition, nucleation density, and the uninhibited ALD growth rate. A long-chain alkanethiol was self-assembled as a monolayer on gold-coated quartz crystals in order to investigate its effectiveness as a barrier to ALD. Compared to solution-loading, vapor-loading is observed to produce a SAM with equal or greater inhibition ability in minutes vs days. The metal oxide growth temperature and the choice of precursor also significantly affect the nucleation density, which ranges from 0.001 to 1 sites/nm(2). Finally, we observe a minimum 100 cycle inhibition of an oxide ALD process, ZnO, under moderately optimized conditions.

Optical limiting is desirable or necessary in a variety of applications that employ high-power light sources or sensitive photodetectors. However, the most prevalent methods compromise between on-state transmission and turndown ratio or rely on narrow transmission windows. We demonstrate that a metasurface-based architecture incorporating phase-change materials enables both high and broadband on-state transmission (−4.8 dB) while also providing a large turndown ratio (25.2 dB). Additionally, this design can be extended for broadband multiwavelength limiting due to the high off-resonance transmittance and readily scalable resonant wavelength. Furthermore, our choice of active material allows for protection in ultrafast laser environments due to the speed of the phase transition. These benefits offer a strong alternative to state-of-the-art optical limiters in technologies ranging from sensor protection to protective eyewear.

Transition metal sulfides show great promise for applications ranging from catalysis to electrocatalysis to photovoltaics due to their high stability and conductivity. Nickel sulfide, particularly known for its ability to electrochemically reduce protons to hydrogen gas nearly as efficiently as expensive noble metals, can be challenging to produce with certain surface site compositions or morphologies, e.g., conformal thin films. To this end, we employed atomic layer deposition (ALD), a preeminent method to fabricate uniform and conformal films, to construct thin films of nickel sulfide (NiS x ) using bis­(N,N′-di-tert-butyl­acetamidinato)­nickel­(II) (Ni­(amd)2) vapor and hydrogen sulfide gas. Effects of experimental conditions such as pulse and purge times and temperature on the growth of NiS x were investigated. These revealed a wide temperature range, 125–225 °C, over which self-limiting NiS x growth can be observed. In situ quartz crystal microbalance (QCM) studies revealed conventional linear growth behavior for NiS x films, with a growth rate of 9.3 ng/cm2 per cycle being obtained. The ALD-synthesized films were characterized using X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) methods. To assess the electrocatalyitic activity of NiS x for evolution of molecular hydrogen, films were grown on conductive-glass supports. Overpotentials at a current density of 10 mA/cm2 were recorded in both acidic and pH 7 phosphate buffer aqueous reaction media and found to be 440 and 576 mV, respectively, with very low NiS x loading. These results hint at the promise of ALD-grown NiS x materials as water-compatible electrocatalysts.

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