Nanopores
are promising for many applications including DNA sequencing
and molecular filtration. Solid-state nanopores are preferable over
their biological counterparts for applications requiring durability
and operation under a wider range of external parameters, yet few
studies have focused on optimizing their robustness. We report the
lifetime and durability of pores and porous arrays in 10 to 100 nm-thick,
low-stress silicon nitride (SiN
x
) membranes.
Pores are fabricated using a transmission electron microscope (TEM)
and/or electron beam lithography (EBL) and reactive ion etching (RIE),
with diameters from 2 to 80 nm. We store them in various electrolyte
solutions (KCl, LiCl, MgCl2) and record open pore conductance
over months to quantify pore stability. Pore diameters increase with
time, and diameter etch rate increases with electrolyte concentration
from Δd/Δt ∼
0.2 to ∼ 3 nm/day for 0.01 to 3 M KCl, respectively. TEM confirms
the range of diameter etch rates from ionic measurements. Using electron
energy loss spectroscopy (EELS), we observe a N-deficient region around
the edges of TEM-drilled pores. Pore expansion is caused by etching
of the Si/SiO2 pore walls, which resembles the dissolution
of silicon found in minerals such as silica (SiO2) in salty
ocean water. The etching process occurs where the membrane was exposed
to the electron beam and can result in pore formation. However, coating
pores with a conformal 1 nm-thick hafnium oxide layer prevents expansion
in 1 M KCl, in stark contrast to bare SiN
x
pores (∼ 1.7 nm/day). EELS data reveal the atomic composition
of bare and HfO2-coated pores.