The high toughness of natural spider-silk is attributed to their unique β-sheet secondary structures. However, the preparation of mechanically strong β-sheet rich materials remains a significant challenge due to challenges involved in processing the polymers/proteins, and managing the assembly of the hydrophobic residues. Inspired by spider-silk, our approach effectively utilizes the superior mechanical toughness and stability afforded by localised βsheet domains within an amorphous network. Using a grafting-from polymerisation approach within an amorphous hydrophilic network allows for spatially controlled growth of poly (valine) and poly(valine-r-glycine) as β-sheet forming polypeptides via N-carboxyanhydride ring opening polymerisation. The resulting continuous β-sheet nanocrystal network exhibits improved compressive strength and stiffness over the initial network lacking β-sheets of up to 30 MPa (300 times greater than the initial network) and 6 MPa (100 times greater than the initial network) respectively. The network demonstrates improved resistance to strong acid, base and protein denaturants over 28 days.

The area selective growth of polymers and their use as inhibiting layers for inorganic film depositions may provide a valuable self-aligned process for fabrication. Polynorbornene (PNB) thin films were grown from surface-bound initiators and show inhibitory properties against the atomic layer deposition (ALD) of ZnO and TiO2. Area selective control of the polymerization was achieved through the synthesis of initiators that incorporate surface-binding ligands, enabling their selective attachment to metal oxide features versus silicon dielectrics, which were then used to initiate surface polymerizations. The subsequent use of these films in an ALD process enabled the area selective deposition (ASD) of up to 39 nm of ZnO. In addition, polymer thickness was found to play a key role, where films that underwent longer polymerization times were more effective at inhibiting higher numbers of ALD cycles. Finally, while the ASD of a TiO2 film was not achieved despite blanket studies showing inhibition, the ALD deposition on polymer regions of a patterned film produced a different quality metal oxide and therefore altered its etch resistance. This property was exploited in the area selective etch of a metal feature. This demonstration of an area selective surface-grown polymer to enable ASD and selective etch has implications for the fabrication of both micro- and nanoscale features and surfaces.

The ability to modify substrates with thin polymer films allows for the tailoring of surface properties, and through combination of patterning finds use in a large variety of applications such as electronics and lab-on-chip devices. Although many techniques can be used to afford polymer-modified surfaces such as surface-initiated polymerization or layer-by-layer methodologies, their stability in a wide range of environments as well as their ability to target specific chemistry are critical factors to enable their successful application. In this paper, we report a facile technique in creating nanoscale polymer thin films using solid-state continuous assembly of polymers via ring-opening metathesis polymerization (ssCAP ROMP ) directly from surfaces functionalized through silanization. Using a polymeric precursor that includes norbornene moieties, a highly dense cross-linked network of polymer can be grown in a bottom-up fashion to afford thin films from an olefin-terminated silanized planar surface. Such nanotechnology affords films retaining the desirable qualities of previously reported methods while, at the same time, being covalently bound to the substrate: they are virtually pinhole free and can be reinitiated multiple times. By combining this process with microcontact printing, patterned films can be created by either the patterned deposition of a catalyst or by controlling the surface silanization chemistry and placement of olefin-terminated and nonreactive silanes. Additionally, patterned ssCAP ROMP films were grown from SU-8 by selectively functionalizing the surface through masking and lift-off processes after the silanization step, thereby spatially controlling the surface-initiation, and subsequent polymer film formation. These patterned films expand the capabilities of the CAP ROMP process and offer advantages over other film formation techniques in processes where patterned substrates and modified but robust surface chemistries are utilized.