Owing to its sensitivity and precise control at the nanoscale, polyelectrolytes have been immensely used to modify surfaces. Polyelectrolyte multilayers are generally water made and are easy to fabricate on any surface by the layer-by-layer (LbL) self-assembly process due to electrostatic interactions. Polyelectrolyte multilayers or PEMs can be assembled to form ultrathin membranes which can have potential applications in water filtration and desalination [1-3]. Hydration in PEMs is a consequence of both the bulk and surface phenomenon [4-7]. Bulk behavior of polymer membranes are well understood. Several techniques including reflectivity and contact angle measurements were used to measure the hydration in the bulk of polymer membranes [4, 8]. On the other hand their internal organization at the molecular level which can have a profound contribution in the transport mechanism, are not understood well. Previously, we engineered a technique, which we refer to as Bright-field Nanoscopy, which allows nanoscale optical imaging using local heterogeneities in a water-soluble germanium (Ge) thin film (~ 25 nm thick) deposited on gold . We use this technique to study the water transport in PEMs. It is understood that the surface charge and outer layers of the PEMs play a significant role in water transport through polymers [9-11]. This well-known ‘odd-even’ effect arising on having different surface termination of the PEMs was optically observed with a spatial resolution unlike any other reported previously . In this communication, we report that on increasing the etchant’s concentration, one can control the lateral etching of the Ge film. This allowed the visualization of the nanoscale internal organization in the PEMs. Knowledge of the internal structure would allow one to engineer polymer membranes specific to applications such as drug delivering capsules, ion transport membranes and barriers etc. We also demonstrate a mathematical model involving a surface permeability term which captures the experimentally observed odd-even effect.
Optical wide-field imaging of sub-diffraction limit nanostructures is of interest in a wide array of applications. In applications where the nanostructures to be visualized are well isolated, a high enough optical contrast is sufficient to detect these. Here we demonstrate a technique to visualize nanoscale features, such as grain boundaries in Chemical Vapor Deposited (CVD) single layer graphene, which are just a few atom length defects, using regular bright field optical microscopy. This remarkably low lateral length scale was imaged using of a special thin film structure consisting of a water-soluble thin film layer deposited on a metal substrate, which produces a strong color change as a function of the film thickness. Small local water transport differences in the graphene layer result in thickness variation of the underlying thin film due to its solubility in water and produces color contrast readily observable under a normal brightfield optical microscope with the naked eye. We demonstrate the use of this technique for direct optical visualization of grain boundaries in graphene as wide as 2-5 nm and sub-100 nm photoresist lines. By using super-resolution image processing algorithms, we may be able to detect structure even smaller in size than currently achieved. We believe that this technique can be extended to single molecule detection.