RESUMO
In this work, we show that in order to fabricate coherent titania (TiO2) films with precise thickness control, it is critical to generate a complete polymer brush monolayer. To date, demonstrations of such dense polymer monolayer formation that can be utilized for inorganic infiltration have been elusive. We describe a versatile bottom-up approach to covalently and rapidly (60 s processing) graft hydroxyl-terminated poly(2-vinyl pyridine) (P2VP-OH) polymers on silicon substrates. P2VP-OH monolayer films of varying thicknesses can subsequently be used to fabricate high-quality TiO2 films. Our innovative strategy is based upon room-temperature titanium vapor-phase infiltration of the grafted P2VP-OH polymer brushes that can produce TiO2 nanofilms of 2-4 nm thicknesses. Crucial parameters are explored, including molecular weight and solution concentration for grafting dense P2VP-OH monolayers from the liquid phase with high coverage and uniformity across wafer-scale areas (>2 cm2). Additionally, we compare the P2VP-OH polymer systems with another reactive polymer, poly(methyl methacrylate)-OH, and a relatively nonreactive polymer, poly(styrene)-OH. Furthermore, we prove the latter to be effective for surface blocking and deactivation. We show a simple process to graft monolayers for polymers that are weakly interacting with one another but more challenging for reactive systems. Our methodology provides new insight into the rapid grafting of polymer brushes and their ability to form TiO2 films. We believe that the results described herein are important for further expanding the use of reactive and unreactive polymers for fields including area-selective deposition, solar cell absorber layers, and antimicrobial surface coatings.
RESUMO
The turn of the 21st century heralded in the semiconductor age alongside the Anthropocene epoch, characterised by the ever-increasing human impact on the environment. The ecological consequences of semiconductor chip manufacturing are the most predominant within the electronics industry. This is due to current reliance upon large amounts of solvents, acids and gases that have numerous toxicological impacts. Management and assessment of hazardous chemicals is complicated by trade secrets and continual rapid change in the electronic manufacturing process. Of the many subprocesses involved in chip manufacturing, lithographic processes are of particular concern. Current developments in bottom-up lithography, such as directed self-assembly (DSA) of block copolymers (BCPs), are being considered as a next-generation technology for semiconductor chip production. These nanofabrication techniques present a novel opportunity for improving the sustainability of lithography by reducing the number of processing steps, energy and chemical waste products involved. At present, to the extent of our knowledge, there is no published life cycle assessment (LCA) evaluating the environmental impact of new bottom-up lithography versus conventional lithographic techniques. Quantification of this impact is central to verifying whether these new nanofabrication routes can replace conventional deposition techniques in industry as a more environmentally friendly option.
RESUMO
Percutaneous cryoablation of pulmonary tumors at the posterior lung base is challenging due to diaphragmatic motion and the requirement for prone positioning. High-frequency jet ventilation allows oxygenation and ventilation with minimal diaphragmatic movement. In this case report, we describe the use of high-frequency jet ventilation in the prone position to facilitate the cryoablation of a peridiaphragmatic pulmonary neoplasm.