Design and fabrication of asymmetric nanopores using pulsed PECVD

Abstract

Manipulating matter at nanometric length scales is important for many electronic, chemical and biological applications. Structures such as nanopores demonstrate a phenomenon known as hindered transport which can be exploited in analytical applications such as DNA sequencing, ionic transistors, and molecular sieving. Precisely controlling the size, geometry and surface characteristics of the nanopores is important for realizing these applications. In this work, we employ relatively large template structures (~ 100 nm) produced by track-etching or electron beam lithography. The pore size is then reduced to the desired level by deposition of material using pulsed plasma enhanced chemical vapor deposition (PECVD). Pulsed PECVD has been developed as a high throughput alternative to atomic layer deposition (ALD) to deliver self-limiting growth of thin films. The goal of this thesis is to extend the application of pulsed PECVD to fabricate asymmetric nanopores. In contrast to ALD, pulsed PECVD does not result in perfectly conformal deposition profiles, and predicting the final nanostructure is more complicated. A two dimensional feature scale model was developed to predict film profile evolution. The model was built in COMSOL, and is based on a diffusion reaction framework with a spatially varying Knudsen diffusion coefficient to account for the molecular transport inside the features. A scaling analysis was used to account for ALD exposure limitations that commonly occur when coating these extremely high aspect ratio features. The model was verified by cross-section microscopy of deposition profiles on patterned cylinders and trenches. The model shows that it is possible to obtain unique nanopore morphologies in pulsed PECVD that are distinct from either steady state deposition processes such as physical vapor deposition (PVD) or conventional ALD. Polymeric track etched (TE) membrane supports with a nominal size of 100 nm were employed as model template structures to demonstrate the capability of pulsed PECVD for precise pore size reduction of model supports. The efficacy of pulsed PECVD for nanopore fabrication was compared to both ALD and PVD. Flux and solute rejection measurements demonstrate that the pulsed PECVD-modified TE membranes exhibit higher selectivity without compromising on the flux due to their asymmetric structure. For example, the TiO2 modified supports were demonstrated to deliver high retention (~ 75%) of bovine serum albumin (BSA) protein while maintaining 70% of their initial pure water flux. PVD also forms asymmetric membranes that enable high flux. But due to morphological instabilities, reproducibility and control were poor in the PVD-modified membranes, and it was not possible to optimize the flux and the selectivity of the membranes simultaneously. Excellent agreement between measured flux and model predictions based on feature scale simulations provided further validation of the tool’s fidelity. Since surface energetics can often dominate hindered transport, the kinetics and thermodynamics of the octadecyltrichlorosilane (OTS) attachment was investigated in-depth as an approach to convert hydrophilic metal oxides into hydrophobic surfaces. It was shown that a simple ozone treatment was a satisfactory alternative to hazardous acids to create the highly hydroxylated surface required for OTS attachment, and that using heptane as the solvent enabled the process to be conducted under ambient conditions without the need of a glovebox. The kinetics of OTS self-assembled monolayer (SAM) formation and the saturation contact angle (∼100◦) on alumina are comparable to what has been observed for OTS attachment on silicon. The OTS SAMs also demonstrated excellent thermal stability, and the modified surface showed a critical surface tension of 21.4 dyne/cm.