Polyelectrolyte complex (PEC) membranes prepared from poly(styrene sulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC) were modified by crossflow polymerization of aniline (ANI). The PEC membranes were used as separators in a two-compartment setup where ANI monomer and ammonium persulfate (APS) oxidant diffused through the membranes to form polyaniline (PANI). APS and ANI having different distributions throughout the membranes, the reaction led to the asymmetric polymerization of PANI on one face of each PEC membrane thus producing Janus membranes. Due to the excess PANI content, the membrane displayed distinct asymmetric electrical conductivities on each face. Interestingly, very different ANI polymerizations were obtained when nonstoichiometric PEC membranes having different molar ratio of cationic and anionic polyelectrolytes (P + :P − represents PDADMAC:PSS) were used and transport of APS was fastest through the 2:1 PEC when compared to the 1:2 PEC. In all experiments, the polymerization was most intense on the ANI side of the membranes. Also, the influence of NaCl both during PEC fabrication and during polymerization was studied and found to have some effect on the solute permeability. Results showed that a higher content of PANI was formed on PEC membranes having excess P + and with no NaCl added during PEC fabrication. Although X-ray diffraction confirmed the presence of PANI on both sides of each membrane, scanning electron microscopy images demonstrated that both sides of each membrane had different PANI content deposited. Electrical conductivity measurements using a four-point probe setup also showed that the PEC-PANI exhibits asymmetric electrical property on different sides.

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Large scale and low-cost nanopatterning of materials is of tremendous interest for optoelectronic devices. Nanoimprint lithography has emerged in recent years as a nanofabrication strategy that is high-throughput and has a resolution comparable to that of electron-beam lithography (EBL). It is enabled by pattern replication of an EBL master into polydimethylsiloxane (PDMS), that is then used to pattern a resist for further processing, or a sol−gel that could be calcinated into a solid material. Although the sol−gel chemistry offers a wide spectrum of material compositions, metals are still difficult to achieve. This gap could be bridged by using colloidal nanoparticles as resist, but deep understanding of the key parameters is still lacking. Here, we use supported metallic nanocubes as a model resist to gain fundamental insights into nanoparticle imprinting. We uncover the major role played by the surfactant layer trapped between nanocubes and substrate, and measure its thickness with subnanometer resolution by using gap plasmon spectroscopy as a metrology platform. This enables us to quantify the van der Waals (VDW) interactions responsible for the friction opposing the nanocube motion, and we find that these are almost in quantitative agreement with the Stokes drag acting on the nanocubes during nanoimprint, that is estimated with a simplified fluid mechanics model. These results reveal that a minimum thickness of surfactant is required, acting as a spacer layer mitigating van der Waals forces between nanocubes and the substrate. In the light of these findings we propose a general method for resist preparation to achieve optimal nanoparticle mobility and show the assembly of printable Ag and Au nanocube grids, that could enable the fabrication of lowcost transparent electrodes of high material quality upon nanocube epitaxy.