Polymers with their tunable functionalities offer the ability to rationally design micro- and nano-engineered materials. Their synthesis as thin films have significant advantages due to the reduced amounts of materials used, faster processing times and the ability to modify the surface while preserving the structural properties of the bulk. Furthermore, their low cost, ease of fabrication and the ability to be easily integrated into processing lines, make them attractive alternatives to their inorganic thin film counterparts. Chemical vapor deposition (CVD) as a polymer thin-film deposition technique offers a versatile platform for fabrication of a wide range of polymer thin films preserving all the functionalities. Solventless, vapor-phase deposition enable the integration of polymer thin films or nanostructures into micro- and nanodevices for improved performance. In this review, CVD of functional polymer thin films and the polymerization mechanisms are introduced. The properties of the polymer thin films that determine their behavior are discussed and their technological advances and applications are reviewed.

The formation of self-organized Si nanostructures induced by Mo seeding during normal incidence Ar+ ion bombardment at room temperature is reported. Silicon surfaces without Mo seeding develop only power-law roughness during 1000eV ion bombardment at normal incidence, in agreement with scaling theory expectations of surface roughening. However, supplying Mo atoms to the surface during ion bombardment seeds the development of highly correlated, nanoscale structures (“dots”) that are typically 3nm high with a spatial wavelength of approximately 30nm. With time, these saturate and further surface roughening is dominated by the growth of long-wavelength corrugations.

In this work, initiated chemical vapor deposition (iCVD) of the poly(ethylene glycol diacrylate) is reported and the effects of process parameters on the deposition rates are investigated. The systematic studies of depositions performed at different filament temperatures showed that the deposition rates increased with the temperature due to the increase in the radical concentration which was monitored with a gas-phase Fourier transform infrared spectroscopy. For temperatures below 242±3 and 224±2°C for 2 and 1SCCM (SCCM denotes cubic centimeter per minute at STP) of monomer flowrates, respectively, a reaction-kinetics limited regime was observed, where the deposition kinetics was limited by the decomposition of the radicals. In this regime, the deposition rates were highly dependent on the filament temperature and the apparent activation energy was found to be 166±5kJ∕mol, consistent with the cleavage of the O–O bond in the tert-butyl peroxide initiator as the rate limiting reaction in the deposition mechanism. Above these temperatures, transition to a mass transfer limited regime was observed where the deposition rates were less dependent on the filament temperature. In the studies performed at different substrate temperatures, on the other hand, an inverse relation between the deposition rate and the substrate temperature was observed which indicated an adsorption limited regime. The studies presented in this work demonstrate the dependence of the deposition kinetics on the process temperatures, which can also be applied to other iCVD systems to achieve higher deposition rates and better conformality.

Seventy percent of global electricity is generated by steam-cycle power plants. A hydrophobic condenser surface within these plants could boost overall cycle efficiency by 2%. In 2022, this enhancement equates to an additional electrical power generation of 1000 TWh annually, or 83% of the global solar electricity production. Furthermore, this efficiency increase reduces CO₂ emissions by 460 million tons /year with a decreased use of 2 trillion gallons of cooling water per year. However, the main challenge with hydrophobic surfaces is their poor durability. Here, we show that solid microscale-thick fluorinated diamond-like carbon (F-DLC) possesses mechanical and thermal properties that ensure durability in moist, abrasive, and thermally harsh conditions. The F-DLC coating achieves this without relying on atmospheric interactions, infused lubricants, self-healing strategies, or sacrificial surface designs. Through tailored substrate adhesion and multilayer deposition, we develop a pinhole-free F-DLC coating with low surface energy and comparable Young’s modulus to metals. In a three-year steam condensation experiment, the F-DLC coating maintains hydrophobicity, resulting in sustained and improved dropwise condensation on multiple metallic substrates. Our findings provide a promising solution to hydrophobic material fragility and can enhance the sustainability of renewable and non-renewable energy sources.