Nanoporous block copolymer films using highly selective solvents and non-solvent extraction

Nanoporous block copolymer thin films are fabricated by selective solvent swelling of the majority phase and subsequent rapid extraction with a miscible non-solvent (water). Selection of the initial solvent provides a facile route to tune the porosity of the films. Poly(butylnorbornene)-block-poly(hydroxyhexafluoroisopropyl norbornene) (BuHFA) is used to generate these porous thin films due to its high T-g (>300 degrees C) and the selectivity of primary alcohols towards poly(hydroxyhexafluoroisopropyl norbornene) (pHFANB) to enable a relatively environmentally benign process. As the solvent quality for the HFA increases from ethanol to isopropanol to n-butanol, the porosity of the film developed by water extraction increases up to 69%. Aqueous mixtures of ethanol provide an addition handle to tune the porosity between 10 and 54%. These nanoporous films are robust with the porosity nearly unchanged after extended heating at 160 degrees C. Their elastic moduli are investigated using surface wrinkling and the modulus, E, scales with the film density, rho, as E similar to rho(2.2), which is similar to cellular solids. The nanopores are templated by the self-assembled structure of the block copolymer, so these coatings are transparent despite the high porosity. These thin films act as anti-reflective coatings for glass slides. Spin coating provides a coating on both sides and processing to generate 55% porosity leads to an increase in transmittance from approximately 92% to 99.1% (average for the full range of visible light). A maximum transmittance of 99.8% is found at 523 nm. This methodology is simple and highly tunable; extension to other block copolymer systems is likely possible if sufficient solubility contrast between segments exists.