Metal assisted chemical etching (MACE) of Si has been used to fabricate both simple and complex Si nanostructures, through the relatively straightforward process of noble metal deposition and patterning followed by immersion in a suitable etching solution. Under appropriate conditions, etching is catalyzed by the metal and occurs only at the metal−silicon interface. MACE therefore requires that a force be present that keeps the metal and silicon in close proximity during etching. The geometrical characteristics of the etched nanostructures therefore depend not only on the solution chemistry, but also on the mechanical properties and constraints of the noble metal catalysts. Here we report experimental studies of etching with nanoscale Au catalyst strips that are mechanically constrained at both ends. The mechanical constraint of these strips leads to termination of etching when a mechanical force balance is achieved. Through experimental characterization of the etching end-state and through modeling, we determine the force between the catalyst and the silicon during etching, and determine how this force depends on the chemistry of the solution.

ABSTRACT:The capillary rise of liquid on a surface, or "wicking", has potential applications in biological and industrial processes such as drug delivery, oil recovery, and integrated circuit chip cooling. This paper presents a theoretical study on the dynamics of wicking on silicon nanopillars based on a balance between the driving capillary forces and viscous dissipation forces. Our model predicts that the invasion of the liquid front follows a diffusion process and strongly depends on the structural geometry. The model is validated against experimental observations of wicking in silicon nanopillars with different heights synthesized by interference lithography and metalassisted chemical etching techniques. Excellent agreement between theoretical and experimental results, from both our samples and data published in the literature, was achieved.

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Metal assisted anodic etching (MAAE) of Si in HF, without H2O2, is demonstrated. Si wafers were coated with Au films, and the Au films were patterned with an array of holes. A Pt mesh was used as the cathode while the anodic contact was made through either the patterned Au film or the back side of the Si wafer. Experiments were carried out on P-type, N-type, P(+)-type and N(+)-type Si wafers and a wide range of nanostructure morphologies were observed, including solid Si nanowires, porous Si nanowires, a porous Si layer without Si nanowires, and porous Si nanowires on a thick porous Si layer. Formation of wires was the result of selective etching at the Au-Si interface. It was found that when the anodic contact was made through P-type or P(+)-type Si, regular anodic etching due to electronic hole injection leads to formation of porous silicon simultaneously with metal assisted anodic etching. When the anodic contact was made through N-type or N(+)-type Si, generation of electronic holes through processes such as impact ionization and tunnelling-assisted surface generation were required for etching. In addition, it was found that metal assisted anodic etching of Si with the anodic contact made through the patterned Au film essentially reproduces the phenomenology of metal assisted chemical etching (MACE), in which holes are generated through metal assisted reduction of H2O2 rather than current flow. These results clarify the linked roles of electrical and chemical processes that occur during electrochemical etching of Si.

Wetting is a pervasive phenomenon that governs many natural and artificial processes. Asymmetric wetting along a single axis, in particular, has generated considerable interest but has thus far been achieved only by the creation of structural anisotropy. In this paper, we report that such directional wetting can also be achieved by anisotropically coating nanostructure surfaces with materials that modify the nanostructure surface energy, a phenomenon that has not been observed in natural or artificial systems thus far. Moreover, by combining this newfound chemical influence on wetting with topographic features, we are able to restrict wetting in one, two and three directions. A model that explains these findings in terms of anisotropy of the pinning forces at the triple phase contact line is presented. Through the resulting insights, a flexible method for precise control of wetting is created.

Recent investigations on the interactions of bacteria with micro/nanostructures have revealed a wide range of prokaryotic responses that were previously unknown. Despite these advances, however, it remains unclear how collective bacterial behavior on a surface would be influenced by the presence of anisotropic nanostructures with subcellular dimensions. To clarify this, the attachment, aggregation, and alignment of Pseudomonas aeruginosa on orderly subcellular nanogratings with systematically varied geometries were investigated. Compared with a flat surface, attachment and aggregation of bacteria on the nanogratings were reduced by up to 83 and 84% respectively, whereas alignment increased by a maximum of 850%. Using a semiempirical quantitative model, these results were shown to be caused by a lowering of physicochemical attraction between the substrate and bacteria, possible disruption to cell communication, and physical isolation of bacteria that were entrenched in the nanogratings by capillary action. Furthermore, the bacterial attachment level was generally found to be exponentially related to the contact area between the substrate and bacterial cells, except when there were significant deficits in the available contact area, which prompted the bacterial cells to employ their appendages to maintain a minimum attachment rate. Because the contact area for adhesion is strongly dependent on the geometry of the surface features and orientation of the bacterial cells, these results indicate that the conventional practice of using roughness parameters to draw quantitative relationships between surface topographies and bacterial attachment could suffer from inaccuracies due to the lack of shape and orientation information provided by these parameters. On the basis of these insights, design principles for generating maximal and minimal bacterial attachment on a surface were also proposed and verified with results reported in the literature.

The dynamics of droplet spreading on two-dimensional wicking surfaces were studied using square arrays of Si nanopillars. It was observed that the wicking film always precedes the droplet edge during the spreading process causing the droplet to effectively spread on a Cassie-Baxter surface composed of solid and liquid phases. Unlike the continual spreading of the wicking film, however, the droplet will eventually reach a shape where further spreading becomes energetically unfavorable. In addition, we found that the displacement-time relationship for droplet spreading follows a power law that is different from that of the wicking film. A quantitative model was put forth to derive this displacement-time relationship and predict the contact angle at which the droplet will stop spreading. The predictions of our model were validated with experimental data and results published in the literature.

The mechanics of intracardiac blood flow and the epigenetic influence it exerts over the heart function have been the subjects of intense research lately. Fetal intracardiac flows are especially useful for gaining insights into the development of congenital heart diseases, but have not received due attention thus far, most likely because of technical difficulties in collecting sufficient intracardiac flow data in a safe manner. Here, we circumvent such obstacles by employing 4D STIC ultrasound scans to quantify the fetal heart motion in three normal 20-week fetuses, subsequently performing 3D computational fluid dynamics simulations on the left ventricles based on these patient-specific heart movements. Analysis of the simulation results shows that there are significant differences between fetal and adult ventricular blood flows which arise because of dissimilar heart morphology, E/A ratio, diastolic-systolic duration ratio, and heart rate. The formations of ventricular vortex rings were observed for both E- and A-wave in the flow simulations. These vortices had sufficient momentum to last until the end of diastole and were responsible for generating significant wall shear stresses on the myocardial endothelium, as well as helicity in systolic outflow. Based on findings from previous studies, we hypothesized that these vortex-induced flow properties play an important role in sustaining the efficiency of diastolic filling, systolic pumping, and cardiovascular flow in normal fetal hearts.