When etching high-aspect-ratio silicon features using deep reactive ion etching (DRIE), researchers find that there is a maximum achievable aspect ratio, which we define as the critical aspect ratio, of an etched silicon trench using a DRIE process. At this critical aspect ratio, the apparent etch rate (defined as the total depth etched divided by the total elapsed time) no longer monotonically decreases as the aspect ratio increases, but abruptly drops to zero. In this paper, we propose a theoretical model to predict the critical aspect ratio and reveal its causal mechanism. The model considers aspect ratio dependent transport mechanisms specific to each of the reactant species in the three subprocesses of a time-multiplexed etch cycle: deposition of a fluorocarbon passivation layer, etching of the fluorocarbon polymer at the bottom of the trench, and the subsequent etching of the underlying silicon. The model predicts that the critical aspect ratio is defined by the aspect ratio at which the polymer etch rate equals the product of the deposition rate and the set time ratio between the deposition and etching phases for the time-multiplexed process. Several DRIE experiments were performed to qualitatively validate the model. Both model simulations and experimental results demonstrate that the magnitude of the critical aspect ratio primarily depends on (i) the relative flux of neutral species at the trench opening, i.e., the microloading effect, and (ii) aspect ratio dependent transport of ions during the polymer etching subprocess of a DRIE cycle.

Increasing concentrations of anthropogenic antibiotics and their metabolites in aqueous environments has caused growing concerns over the proliferation of antibiotic resistance and potential adverse impacts to agro-environmental quality and human health. Photocatalysis using novel engineered nanomaterials such as ZnO nanowires may be promising for removing antibiotics from waters. However, much remains to be learned about efficiency and mechanism for photocatalytic degradation of antibiotics by ZnO nanowires. This study systematically investigated photodegradation of cephalexin using ZnO nanowires under simulated sunlight. The degradation efficiency of cephalexin was substantially increased in the presence of ZnO nanowires especially at circumneutral and alkaline condition (solution pH of 7.2-9.2). The photodegradation followed the first-order kinetics with degradation rate constants (k) ranging between 1.19 × 10-1 and 2.52 × 10-1 min-1 at 20-80 mg L-1 ZnO nanowires. Radical trapping experiments demonstrated that hydroxyl radicals (OH) and superoxide radicals (O2-) predominantly contributed to the removal of cephalexin. With the addition of HCO3- (1-5 mM) or Suwannee River natural organic matter (SRNOM, 2-10 mg L-1), the k values were substantially decreased by a factor of 1.8-70 to 1.69 × 10-3-6.67 × 10-2 min-1, probably due to screening effect of HCO3- or SRNOM sorbed on ZnO nanowires and scavenging of free radicals by free HCO3- or SRNOM in solution. Combining product identification by mass spectrometry and molecular computation, cephalexin photodegradation pathways were identified, including hydroxylation, demethylation, decarboxylation, and dealkylation. Overall, the novel ZnO nanowires have the potential to be used for removing antibiotics from contaminated waters.

Highlights ZnO nanowires were securely immobilized onto a floatable photocatalytic platform, which had a uniform diameter (55 ± 5 nm) and length (1.5 ± 0.3 μm). An additional 20% of the probe pollutant (methylene blue) was degraded by piezocatalysis-assisted photocatalytic degradation. The crude oil pollutant was decomposed up to 20% within 6 h. Abstract Photocatalytic degradation attracts considerable attention because it is a promising strategy to treat pollutants from industrial and agricultural wastes. In recent years, other than the development of efficient photocatalysts, much effort has been devoted to the design of reliable and inexpensive photocatalytic platforms that work in various environment conditions. Here, we describe a novel photocatalytic platform that is able to float and freely move atop water while performing photodegradation. Compared to common platforms, such as slurry reactors and immobilized photoreactors, the proposed platform is advantageous in terms of easy recycling and energy saving. Furthermore, the special configuration resulting from a two-step synthesis route, semi-embedded photocatalysts, addresses some of the remaining challenges, for instance, the contamination from the loose photocatalysts themselves. For the probe pollutant, methylene blue (MB), a reproducible and remarkable degradation activity of the platform, is observed and the effect of two primary factors, including surface area of the catalyst and mass transfer rate, is investigated. Besides, the piezo-photocatalysis effect, serving as an additional functionality, is confirmed to further improve the degradability of the platform, which offers an additional 20% of degraded MB. At last, the promising result of the degradation toward crude oil reveals the possibility of the platform to be used in gasoline pollution treatment.