The controlled patterning of polymeric surfaces at the micro- and nanoscale offers potential in the technological development of small-scale devices, particularly within the fields of photovoltaics, micro-optics and lab- and organ-on-chip, where the topological arrangement of the surface can influence a system's power generation, optical properties or biological function - such as, in the latter case, biomimicking surfaces or topological control of cellular differentiation. One of the most promising approaches in reducing manufacturing costs and complexity is by exploitation of the self-assembling properties of colloidal particles. Self-assembly techniques can be used to produce colloidal crystals onto surfaces, which can act as replicative masks, as has previously been demonstrated with colloidal lithography, or templates in mold-replication methods with resolutions dependent on particle size. Within this context, a particular emerging interest is focused on the use of self-assembled colloidal crystal surfaces in polymer replication methods such as soft lithography, hot and soft embossing and nano-imprint lithography, offering low-cost and high-resolution alternatives to conventional lithographic techniques. However, there are still challenges to overcome for this surface patterning approach to reach a manufacturing reliability and process robustness comparable to competitive technologies already available in the market, as self-assembly processes are not always 100% effective in organizing colloids within a structural pattern onto the surface. Defects often occur during template fabrication. Furthermore, issues often arise mainly at the interface between colloidal crystals and other surfaces and substrates. Particularly when utilized in high-temperature pattern replication processes, poor adhesion of colloidal particles onto the substrate results in degradation of the patterning template. These effects can render difficulties in creating stable structures with little defect that are well controlled such that a large variety of shapes can be reproduced reliably. This review presents an overview of available self-assembly methods for the creation of colloidal crystals, organized by the type of forces governing the self-assembly process: fluidic, physical, external fields, and chemical. The main focus lies on the use of spherical particles, which are favorable due to their high commercial availability and ease of synthesis. However, also shape-anisotropic particle self-assembly will be introduced, since it has recently been gaining research momentum, offering a greater flexibility in terms of patterning. Finally, an overview is provided of recent research on the fabrication of polymer nano- and microstructures by making use of colloidal self-assembled templates.

We present here an electrochemical sensor microsystem for the monitoring of pH. The all-polymeric device is comprised of a cyclic olefin copolymer substrate, a 200 nm-thin patterned layer of conductive polymer (PEDOT), and a 70 nm electropolymerized layer of a pH sensitive conductive polymer (polyaniline). The patterning of the fluidic (microfluidic channels) and conductive (wiring and electrodes) functional elements was achieved with a single soft PDMS mold via a single embossing step process. A post-processing treatment with ethylene glycol assured the functional enhancement of the electrodes, as demonstrated via an electrical and electrochemical characterization. A surface modification of the electrodes was carried out, based on voltammetric electropolymerization, to obtain a thin layer of polyaniline. The mechanism for pH sensing is based on the redox reactions of the polyaniline layer caused by protonation. The sensing performance of the microsystem was finally validated by monitoring its potentiometric response upon exposure to a relevant range of pH.