The thermal expansion behavior for various aromatic polymides was investigated. Usally polymers, including polyimides, have high thermal expansion coefficients (3–6 × 10−5 K−1), compared with metals and ceramics. However, there are some polyimides which have very low thermal expansion coefficients below 1 × 10−5 K−1. This property was observed for the polymides obtained from pyromellitic dianhydride or 3,3′ 4,4′‐biphenyltetracarboxylic dianhydride and aromatic diamines which were constituted of only benzene rings fused at para positions. It was proposed that their low thermal expansion coefficient related to the linearity in their polymer molecular skeltons.
To improve the spatial resolution of solid-state nanopores, thinning the membrane is a very important issue. The most commonly used membrane material for solid-state nanopores is silicon nitride (Si3N4). However, until now, stable wafer-scale fabrication of Si3N4 membranes with a thickness of less than 5 nm has not been reported, although a further reduction in thickness is desired to improve spatial resolution. In the present study, to fabricate thinner Si3N4 membranes with a thickness of less than 5 nm in a wafer, a new fabrication process that employs a polycrystalline-Si (poly-Si) sacrificial layer was developed. This process enables the stable fabrication of Si3N4 membranes with thicknesses of 3 nm. Nanopores were fabricated in the membrane using a transmission electron microscope (TEM) beam. Based on the relationship between the ionic current through the nanopores and their diameter, the effective thickness of the nanopores was estimated to range from 0.6 to 2.2 nm. Moreover, DNA translocation through the nanopores was observed.
Recently, dielectric breakdown of solid-state membranes in solution has come to be known as a powerful method for fabricating nanopore sensors. This method has enabled a stable fabrication of nanopores down to sub-2 nm in diameter, which can be used to detect the sizes and structures of small molecules. Until now, the behavior of dielectric breakdown for nanopore creation in SiN membranes with thicknesses of less than 10 nm has not been studied, while the thinner nanopore membranes are preferable for nanopore sensors in terms of spatial resolution. In the present study, the thickness dependence of the dielectric breakdown of sub-10-nm-thick SiN membranes in solution was investigated using gradually increased voltage pulses. The increment in leakage current through the membrane at the breakdown was found to become smaller with a decrease in the thickness of the membrane, which resulted in the creation of smaller nanopores. In addition, the electric field for dielectric breakdown drastically decreased when the thickness of the membrane was less than 5 nm. These breakdown behaviors are quite similar to those observed in gate insulators of metal-oxide-semiconductor devices. Finally, stable ionic-current blockades were observed when single-stranded DNA passed through the nanopores created on the membranes with thicknesses of 3–7 nm.
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