Molecular layer deposited alucone thin films from long-chain organic precursors: from brittle to ductile mechanical characteristics

Abstract

Molecular layer deposition (MLD) is a strongly emerging thin-film technique for deposition of ultra-thin inorganic–organic hybrid (“metalcone”) coatings directly from the gas phase, even on complex three-dimensional surfaces. In particular alucones (Al-based hybrids) have been found interesting e.g. for Li-ion battery and gas-barrier applications owing to the promise for enhanced mechanical performance provided by the organic fragments in the materials’ structure. However, the metalcones based on short/small organic fragments are relatively brittle from the mechanical perspective. Here, we demonstrate an efficient approach for tailoring mechanical properties of MLD-fabricated hybrid inorganic–organic thin films through control over the organic precursor chain length. The proof-of-concept data is presented for alucones prepared using trimethyl aluminum together with 1,6-hexanediol or 1,10-decanediol as the precursors. Tensile testing coupled with in situ optical microscopy reveals a gradual increase in stretchability with the increasing chain length, such that the crack onset strain value of 9.9 ± 0.2% is obtained for the 1,10-decanediol-based 100 nm-thick film. Through the demonstration of substantially suppressed crack propagation—as a sign of brittle-to-ductile transition—and the decrease in the elastic modulus value down to 4.6 ± 2.1 GPa, the mechanical performance of the alucone family is extended to the polymeric regime. The substantial increase in the mechanical performance within the metalcone material family makes the results particularly interesting for high-capacity high-volume-change battery electrodes requiring mechanically highly robust coatings.