Topographic nanomanufacturing with a depth precision down to atomic dimension is of importance for advancement of nanoelectronics with new functionalities. Here we demonstrate a mask-less and chemical-free nanolithography process for regio-specific removal of atomic layers on a single crystalline silicon surface via shear-induced mechanochemical reactions. Since chemical reactions involve only the topmost atomic layer exposed at the interface, the removal of a single atomic layer is possible and the crystalline lattice beneath the processed area remains intact without subsurface structural damages. Molecular dynamics simulations depict the atom-by-atom removal process, where the first atomic layer is removed preferentially through the formation and dissociation of interfacial bridge bonds. Based on the parametric thresholds needed for single atomic layer removal, the critical energy barrier for water-assisted mechanochemical dissociation of Si–Si bonds was determined. The mechanochemical nanolithography method demonstrated here could be extended to nanofabrication of other crystalline materials.
Most inorganic material surfaces exposed to ambient air can adsorb water, and hydrogen bonding interactions among adsorbed water molecules vary depending on, not only intrinsic properties of material surfaces, but also extrinsic working conditions. When dimensions of solid objects shrink to micro- and nano-scales, the ratio of surface area to volume increases greatly and the contribution of water condensation on interfacial forces, such as adhesion (Fa) and friction (Ft), becomes significant. This paper reviews the structural evolution of the adsorbed water layer on solid surfaces and its effect on Fa and Ft at nanoasperity contact for sphere-on-flat geometry. The details of the underlying mechanisms governing water adsorption behaviors vary depending on the atomic structure of the substrate, surface hydrophilicity and atmospheric conditions. The solid surfaces reviewed in this paper include metal/metallic oxides, silicon/silicon oxides, fluorides, and two-dimensional materials. The mechanism by which water condensation influences Fa is discussed based on the competition among capillary force, van der Waals force and the rupture force of solid-like water bridge. The condensed meniscus and the molecular configuration of the water bridge are influenced by surface roughness, surface hydrophilicity, temperature, sliding velocity, which in turn affect the kinetics of water condensation and interfacial Ft. Taking the effects of the thickness and structure of adsorbed water into account is important to obtain a full understanding of the interfacial forces at nanoasperity contact under ambient conditions.
Harvesting the energy from the interaction between hygroscopic materials and atmospheric water can generate green and clean energy. However, the ion diffusion process of moisture-induced dissociation leads to the disappearance of the ion concentration gradient gradually, and there is still a lack of moisture-based power generation devices with truly continuous operation, especially the duration of the current output still needs to be extended. Here, we propose a design for reconstructing the ion concentration gradient by coupling photocatalytic hydrogen evolution reaction with hydrovoltaic effect, to report a moisture-enabled electric generator (MEG) with continuous current output. We show that the introduction of the photocatalytic layer not only absorbs light energy to greatly increase the power generation of the MEG (500% power density enhancement), but more importantly, the photocatalytic hydrogen evolution process consumes the pre-stacked ions to restore the ion concentration gradient, allowing the MEG to continuously output current for more than 600 hours, which is 1 to 2 orders of magnitude higher than the great majority of existed MEGs in terms of the current output duration.
Mechanochemical reactions of the GaN-Al2O3 interface offer a novel principle for scientific and technological merits in the micro-/nano-scale ultra-precision surface machining. In this work, the mechanochemical reactions on Ga- and N-faced GaN surfaces rubbed by the Al2O3 nanoasperity as a function of the environmental humidity were investigated. Experimental results indicate that the N-face exhibits much stronger mechanochemical removal over the relative humidity range of 20%–80% than the Ga-face. Increasing water molecules in environmental conditions significantly promotes the interfacial mechanochemical reactions and hence accelerates the atomic attrition on N-face. The hypothesized mechanism of the selective water-involved mechanochemical removal is associated with the dangling bond configuration, which affects the mechanically-stimulated chemical reactions via altering the activation energy barrier to form the bonding bridge across the sliding interface. These findings can enrich the understanding of the underlying mechanism of mechanochemical reactions at GaN-Al2O3 interface and a broad cognition for regulating the mechanochemical reactions widely existing in scientific and engineering applications.
The friction of hydrogenated diamond-like carbon (H-DLC) films was evaluated under the controlled environments of humid air and vacuum by varying the applied load. In humid air, there is a threshold applied load below which no obvious friction drop occurs and above which the friction decreases to a relatively low level following the running-in process. By contrast, superlubricity can be realized at low applied loads but easily fails at high applied loads under vacuum conditions. Further analysis indicates that the graphitization of the sliding H-DLC surface has a negligible contribution to the sharp drop of friction during the running-in process under both humid air and vacuum conditions. The low friction in humid air and the superlow friction in vacuum are mainly attributed to the formation and stability of the transfer layer on the counterface, which depend on the load and surrounding environment. These results can help us understand the low-friction mechanism of H-DLC film and define optimized working conditions in practical applications, in which the transfer layer can be maintained for a long time under low applied load conditions in vacuum, whereas a high load can benefit the formation of the transfer layer in humid air.