To demonstrate area selective atomic layer deposition (ALD) using UV-nanoimprinted resin patterns as physical passivation masks, we investigated the removal of UV-cured resin films subjected to sequential mutual doses of trimethylaluminum (TMA) and H2O by using dry etching procedures. On the basis of the removal of a residual layer characteristic from imprint resin patterns by anisotropic oxygen reactive ion etching (O2 RIE), oxidatively etched UV-cured films were modified with TMA and H2O in an ALD-like cyclic manner. Atomic force microscopy and time-of-flight secondary ion mass spectrometry [time-of-flight secondary ion mass spectrometry (TOF-SIMS)] analysis suggested that the combination of physical Ar ion milling and subsequent chemical O2 RIE enabled the elimination of oxidized UV-cured resin masks modified with 5-cycle TMA doses. By contrast, Ar ion milling or O2 RIE left organic or inorganic residues on silicon surfaces, respectively. A TMA-modified hybridized resin layer was etched by physical Ar ion milling; subsequently, the organic residual resin layer was removed by chemical O2 RIE in the case of 5-cycle modification with TMA. The mapping image of Al+ visualized by TOF-SIMS suggested that line patterns of aluminum oxide were left selectively on unmasked silicon substrate surfaces by site-selective dry etching of TMA-modified imprint resin passivation masks with 500 nm linewidth.

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The fabrication of resist patterns using UV nanoimprinting is required on consideration of the reduction of the use of hydrocarbons along recent amendments for environmental sustainability. In this study, we investigated the generation of resist pattern defects through UV nanoimprinting in a readily condensable trans-1,3,3,3-tetrafluoropropene (TFP) gas with a low global warming potential for elimination of nonfill defects arising from a bubble trap and subsequent sequential infiltration synthesis (SIS) to result in a vapor phase organic-inorganic hybridization for dry etching durability. A bisphenol A-based UV-curable imprint resin enabled the nanostructure fabrication of resist patterns without any nonfill defects in TFP; however, SIS consisting of subsequent mutual doses of trimethylaluminum and water caused a resist pattern collapse of 100-nm-height patterns with linewidths of <60 nm. A crosslinker with six acrylate moieties was selected based on its low TFP absorption. The crosslinker-containing imprint resin decreased the resist pattern collapse during SIS. Nanoindentation measurements suggest that the resist patterns made using the crosslinker-containing imprint resin were strengthened at 100 °C to carry out an SIS.