XiuMei Xu

Capturing Wetting States in Nanopatterned Silicon

Spectacular progress in developing advanced Si circuits with reduced size, along the track of Moores law, has been relying on necessary developments in wet cleaning of nanopatterned Si wafers to provide contaminant free surfaces. The most efficient cleaning is achieved when complete wetting can be realized. In this work, ordered arrays of silicon nanopillars on a hitherto unexplored small scale have been used to study the wetting behavior on nanomodulated surfaces in a substantial range of surface treatments and geometrical parameters. With the use of optical reflectance measurements, the nanoscale water imbibition depths have been measured and the transition to the superhydrophobic Cassie-Baxter state has been accurately determined. For pillars of high aspect ratio (about 15), the transition occurs even when the surface is grafted with a hydrophilic functional group. We have found a striking consistent deviation between the contact angle measurements and the straightforward application of the classical wetting models. Molecular dynamics simulations show that these deviations can be attributed to the long overlooked atomic-scale surface perturbations that are introduced during the nanofabrication process. When the transition condition is approached, transient states of partial imbibition that characterize intermediate states between the Wenzel and Cassie-Baxter states are revealed in our experiments.

High-frequency acoustic for nanostructure wetting characterization.

Nanostructure wetting is a key problem when developing superhydrophobic surfaces. Conventional methods do not allow us to draw conclusions about the partial or complete wetting of structures on the nanoscale. Moreover, advanced techniques are not always compatible with an in situ, real time, multiscale (from macro to nanoscale) characterization. A high-frequency (1 GHz) acoustic method is used for the first time to characterize locally partial wetting and the wetting transition between nanostructures according to the surface tension of liquids (the variation is obtained by ethanol concentration modification). We can see that this method is extremely sensitive both to the level of liquid imbibition and to the impalement dynamic. We thus demonstrate the possibility to evaluate the critical surface tension of a liquid for which total wetting occurs according to the aspect ratio of the nanostructures. We also manage to identify intermediate states according to the height of the nanotexturation. Finally, our measurements revealed that the drop impalement depending on the surface tension of the liquid also depends on the aspect ratio of the nanostructures. We do believe that our method may lead to new insights into nanoscale wetting characterization by accessing the dynamic mapping of the liquid imbibition under the droplet.

Superhydrophobic Breakdown of Nanostructured Surfaces Characterized in Situ Using ATR–FTIR

In situ characterization of the underwater stability of superhydrophobic micro- and nanostructured surfaces is important for the development of self-cleaning and antifouling materials. In this work, we demonstrate a novel attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy-based method for large-area wetting characterization of silicon nanopillars. When air is present in between the structures, as is characteristic of the Cassie-Baxter state, the relative intensities of the water bands in the absorption spectrum change because of the wavelength-dependent attenuation of the evanescent wave. This phenomenon enables unambiguous identification of the wetting state and assessment of liquid impalement. Using mixtures of isopropanol and water with different concentrations, the breakdown of superhydrophobic states and the wetting hysteresis effects are systematically studied on uniform arrays of silicon nanopillars. A transition from the Cassie-Baxter to Wenzel state is observed when the isopropanol concentration exceeds 2.8 mol %, corresponding to a critical surface tension of 39 mN/m. Spontaneous dewetting does not occur upon decreasing the isopropanol concentration, and pure water can be obtained in a stable Wenzel state on the originally superhydrophobic substrates. The developed ATR-FTIR method can be promising for real-time monitoring of the wetting kinetics on nanostructured surfaces.

Influence of wetting state on optical reflectance spectra of Si nanopillar arrays

Finite-difference time-domain (FDTD) simulations showed that the reflectance spectra of crystalline Si nanopillar (NP) arrays with diameters of 40, 70, 100, and 130 nm differed depending on wetting state. The observed reflectance dips of the 40-nm-diameter NP array were in good agreement with those estimated from destructive interference conditions at the top and bottom of the NPs: the NP arrays were treated as a homogeneous medium with an effective permittivity according to the effective medium approximation model. In contrast, the dip positions of the FDTD-simulated spectra for 70-, 100-, and 130-nm-diameter NP arrays deviated from the results of interference calculations, particularly for short wavelengths. This suggested that Mie resonances in individual NPs significantly increased the absorption cross-section at the resonant wavelengths, which was sensitive to the refractive index of the surrounding medium (i.e., the wetting state). Optical reflectance measurements provide an easy and efficient means...

In-situ ATR-FTIR for dynamic analysis of superhydrophobic breakdown on nanostructured silicon surfaces

Superhydrophobic surfaces are highly promising for self-cleaning, anti-fouling and anti-corrosion applications. However, accurate assessment of the lifetime and sustainability of super-hydrophobic materials is hindered by the lack of large area characterization of superhydrophobic breakdown. In this work, attenuated total reflectance−Fourier transform infrared spectroscopy (ATR-FTIR) is explored for a dynamic study of wetting transitions on immersed superhydrophobic arrays of silicon nanopillars. Spontaneous breakdown of the superhydrophobic state is triggered by in-situ modulation of the liquid surface tension. The high surface sensitivity of ATR-FTIR allows for accurate detection of local liquid infiltration. Experimentally determined wetting transition criteria show significant deviations from predictions by classical wetting models. Breakdown kinetics is found to slow down dramatically when the liquid surface tension approaches the transition criterion, which clearly underlines the importance of more accurate wetting analysis on large-area surfaces. Precise actuation of the superhydrophobic breakdown process is demonstrated for the first time through careful modulation of the liquid surface tension around the transition criterion. The developed ATR-FTIR method can be a promising technique to study wetting transitions and associated dynamics on various types of superhydrophobic surfaces.

Imaging the air-water interface: Characterising biomimetic and natural hydrophobic surfaces using in situ atomic force microscopy

The interface between water and a textured hydrophobic surface can exist in two regimes; either the Wenzel (surface-engulfed) or Cassie-Baxter (water-suspended) state. Better understanding of the influence of pattern geometry and spacing is crucial for the design of functional (super)hydrophobic surfaces, as inspired by numerous examples in nature. In this work, we have employed amplitude modulated - atomic force microscopy to visualize the air-water interface with an unprecedented degree of clarity on a superhydrophobic and a highly hydrophobic nanostructured surface. The images obtained provide the first real-time experimental visualization of the Cassie-Baxter wetting on the surface of biomimetic silicon nanopillars and a naturally superhydrophobic cicada wing. For both surfaces, the air-water interface was found to be remarkably well-defined, revealing a distinctly nanostructured air-water interface in the interstitial spacing. The degree of interfacial texture differed as a function of surface geometry. These results reveal that the air-water interface is heterogeneous in its structure and confirmed the presence of short-range interfacial ordering. Additionally, the overpressure values for each point on the interface were calculated, quantifying the difference in wetting behavior for the biomimetic and natural surface. Results suggest that highly-ordered, closely spaced nanofeatures facilitate robust Cassie-Baxter wetting states and therefore, can enhance the stability of (super)hydrophobic surfaces.