Additive Lithography-Organic Monolayer Patterning Coupled with an Area-Selective Deposition.

The combination of area-selective deposition (ASD) with a patternable organic monolayer provides a versatile additive lithography platform, enabling the generation of a variety of nanoscale feature geometries. Stearate hydroxamic acid self-assembled monolayers (SAMs) were patterned with extreme ultraviolet (λ = 13.5 nm) or electron beam irradiation and developed with ASD to achieve line space patterns as small as 50 nm. Density functional theory was employed to aid in the synthesis of hydroxamic acid derivatives with optimized packing density to enhance the imaging contrast and improve dose sensitivity. Near-edge X-ray absorption fine structure spectroscopy and infrared spectroscopy reveal that the imaging mechanism is based on improved deposition inhibition provided by the cross-linking of the SAM to produce a more effective barrier during a subsequent deposition step. With patterned substrates composed of coplanar copper lines and silicon spacers, hydroxamic acids selectively formed monolayers on the metal portions and could undergo a pattern-wise exposure followed by ASD in the first combination of a patternable monolayer with ASD. This material system presents an additional capability compared to traditional ASD approaches that generally reflect a starting patterned surface. Furthermore, this bottoms-up additive approach to lithography may be a viable alternative to subtractive nanoscale feature generation.

Surface Initiated Polymer Thin Films for the Area Selective Deposition and Etching of Metal Oxides.

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.

Chelated charge assisted halogen bonding enhanced halide recognition by a pyridinium-iodotriazolium axle containing [2]rotaxane.

Four halogen and hydrogen bonding rotaxane host systems featuring pyridinium bis-amide-iodotriazole/prototriazole and pyridinium bis-amide-iodotriazolium/prototriazolium axle components have been synthesized by CuAAC-mediated mono-stoppering chloride anion templation and post-rotaxanation methylation reactions. In competitive 45 : 45 : 10 CDCl3-CD3OD-D2O aqueous solvent media, the dicationic halogen bonding rotaxane displayed a notable enhanced binding affinity and marked selectivity for Br- over other halides and nitrate and dihydrogen phosphate oxoanions in contrast to an all hydrogen bonding counterpart which is attributed to chelated charge assisted halogen bonding interactions.