Here we show direct polymer growth on hydrogen‐terminated silicon (SiH) as a one‐step process. SiH is immersed in a heated solution of an initiator, a monomer, and a crosslinker. The resulting polymer films are 2–15 nm thick, the thickness can be tuned by varying reaction conditions, and the polymer films are robust. Thinner films are obtained in polymer growth without crosslinker. Radicals produced by the initiator and in growing polymer chains may pluck H atoms from SiH to make reactive dangling bonds. These in turn appear to react with monomers and crosslinkers. Crosslinkers tethered through one double bond may be grafted into polymer chains growing in solution. Surface reactivity is demonstrated by optical ellipsometry, X‐ray photoelectron spectroscopy, atomic force microscopy, and wetting.
Cover: During the past ten years, a number of researchers have described multistep methods for preparing thin polymer films on hydrogen-terminated silicon. To the best of our knowledge we now show the first one-step method (shown on the cover) for polymer thin film growth on this important substrate. This procedure involves the thermal decomposition of a radical initiator, which is believed to abstract hydrogen from the silicon surface. The resulting silicon radicals then appear to react with monomers in solution. Thicker polymer films are obtained by addition of a bifunctional monomer.
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