Thermal degradation behavior of self-assembled monolayer surfactant on silicon substrate

Abstract

In nanoimprint lithography, a release agent on the mold surface is usually necessary for easy demolding between the mold and the imprinted (thermal) resist. In this work, the thermal stability of 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS) monolayers is studied using x-ray photoelectron spectroscopy. The FDTS monolayers are deposited on Si (100) substrates via vapor phase reactions. Significant fluorine desorption of the monolayers is observed for samples annealed at 250 and 300 °C in air. The fluorine coverage decreases as a function of annealing time at a given annealing temperature. The desorption is proposed to be dependent on the monolayer packing details and may be influenced by the intermolecular heat transfer. Removal of the CF3 groups is found to be faster than that of the CF2 group as evidenced by the CF2/CF3 peak area ratios that increase with the annealing time. Sessile drop water contact angle and fluorine coverage evolution results show that the estimated useful coating lifetime is 180 min when the samples are annealed at 300 °C and ∼560 min when annealed at 250 °C. The peak position of the binding energy of the F 1s spectral line is related to the monolayer fluorine coverage and it may be a result of the interactions between the molecular chain and the negatively charged silicon substrate. Furthermore, nearly no chain desorption is detected for samples annealed in an inert environment, which may be attributed to the elimination of reactive oxygen and moisture molecules. The thermal degradation behaviors in ambient and inert atmosphere provide useful information for designing a nanoimprint process for the commercial manufacturing of polymeric microstructure and nanostructure.