Three-dimensional (3D) polymer structures are very attractive because the extra structural dimension can provide denser integration and superior performance to accomplish complex tasks. Successful fabrication of 3D multilayer microstructures in thermoplastic polymers using optimized nanoimprint lithography techniques such as layer-transfer and transfer-bonding methods are developed in this dissertation work. The capability and flexibility of the techniques developed here are expected to have deep impact on the applications of soft materials such as polymers including functional polymers in micro- and nanofabricated devices and systems. Although NIL technique is developing rapidly in recent years, there are still issues that need to be addressed for broader adoption of the nanoimprint technique. One of the problems is the residual layer that remains in the polymer pattern after nanoimprint. The conventional approach, oxygen reactive-ion-etching (RIE) process, to remove the residual layers, increases the cost and lowers the overall throughput of the nanoimprint process. More severely, it can degrade or even damage the functional polymers. In order to overcome these problems, new residual layer removal techniques need to be developed. In this dissertation, two methods are newly developed, which do not negatively affect the chemistry of the polymer materials. The techniques are suitable for all thermoplastic polymers, particularly functional polymers. Another advantage of nanoimprint is its ability to directly create functional polymers structures. This is because thermal nanoimprint only needs temperature and pressure for pattern replication, which both are benign to functional polymers. This feature combined with newly developed techniques such as transfer-bonding and residue removal techniques opens up the possibilities in nondestructive functional polymers patterning at the micro- and nanoscale for novel applications in electronics, optoelectronics, photonics and bioengineering. Finally, several applications of 3D multilayer structures fabricated by the techniques developed in this dissertation are demonstrated. The first application is a multilayer metal-dielectric-metal structure with embedded microfluidic channels. This structure can be used as an on-chip tunable filter for integrated microfluidic applications. The second application is a multilayer microfluidic channels in which each layer has a different channel size. This device can be used for particle separation and filtration based on lateral fluid flow.

A novel strategy to investigate interfaces relevant to chromatographic separations is presented. The strategy in this dissertation relies on three key ideas: 1) design and fabrication of appropriate model of chromatographic interface, 2) use of forced dewetting to separate interfacial constituent of mobile phase from its bulk component yet preserves the interface, and 3) use of IR spectroscopy and ellipsometry to investigate the structure and thickness of isolated interface.Stratified structures of ultrathin (< 10 nm thick) silica films on gold using gold oxide as adhesive layer and wetting control agent are used as model solid phase. Such design provides chemical environment of bulk silica surface, does not introduce significant spectral background, is suitable for reflection-based spectroscopies, and allow for easy modification to mimic wide range of silica - solvent interfaces. Bare silica-water models capillary electrophoresis interfaces; water-methanol mixture at octadecylsilane-modified silica represents reversed phase liquid chromatography interfaces.Forced dewetting is used to decouple interfacial constituent of mobile phase from its bulk component; yet, the integrity of interface is preserved. This approach, combined with the use of IR spectroscopy and ellipsometry, allowed for ambient atmosphere characterization of these interfacial layers in terms of their structure, composition, and thickness for water at bare silica. Hydrogen bonding was probed in case of complex water-methanol binary mixture at octadecylsilane-modified silica surface.The analysis of residual water layers formed by forced dewetting at bare silica as a function of bulk solution pH shows that the structure of the interfacial layer is highly ordered compared to bulk, and is also pH dependent. Further, thicknesses of interfacial layers were found to be pH dependent and vary from ~6 (pH 1) to ~9 nm (pH 9). Gouy-Chapman-Stern double layer was found to be inadequate to satisfactorily describe observed trends. In addition, surface enhanced infrared absorbance phenomenon was also observed that aided increased quality of resulting IR spectra.The analysis of residual water-methanol layers formed by forced dewetting at octadecylsilane-modified silica surface as a function of gas phase atmosphere shows that the structure of the interfacial layer is highly dependent on the composition of gas phase. The observed changes indicate that condensation of methanol from gas phase into residual layer and/or evaporation of water from residual layer into gas phase may occur in used experimental setup used in this dissertation. For that reason, more precise quantification of relative amounts of water and methanol in residual layers was precluded. Yet, regardless of investigational conditions, two different hydrogen bonding environments for methanol were distinctively observed.