Fabricating vertically ordered and etchable high aspect
ratio nanodomains
of block copolymer (BCP) thin films on diverse substrates via continuous
processing dynamic cold zone annealing (CZA) is particularly attractive
for nanomanufacturing of next-generation electronics. Previously,
we reported dynamic CZA studies with a shallow thermal gradient (maximum
∇T ∼ 14 °C/mm) that produced only
BCP cylinders oriented parallel to substrate. Here, we report a CZA
utilizing a dynamic sharp thermal gradient (∇T ∼ 45 °C/mm) (i.e., CZA-S). This method allows for production
of etchable and vertically oriented cylindrical domains of poly(styrene-b-methyl methacrylate) in 100–1000 nm thick films
on low thermal conductivity rigid (quartz) and flexible (PDMS, Kapton)
substrates. Competing substrate wetting interactions dominate BCP
orientation in films below 100 nm while broadening of the thermal
gradient profile in films thicker than 1000 nm leads to loss of vertical
orientation. An optimal dynamic sweep rate (∼5 μm/s)
produces the best vertical order. At too fast a sweep rate (>10
μm/s)
the BCP film ordering is kinetically hindered, while at too slow a
sweep rate (<1 μm/s), polymer relaxation and preferential
surface wetting dynamics favor parallel BCP orientation. Equivalent
static gradient conditions produce vertically aligned BCP cylinders
only at the maximum ∇T. CZA-S mechanism involves
propagating this vertically oriented BCP zone across the sample.
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