Effect of Alkanethiol Chain Length on Gold Nanoparticle Monolayers at the Air–Water Interface

In this study, we report the effects of the alkyl chain length on alkanethiol-capped gold nanoparticle Langmuir films. Gold nanoparticles (2–3 nm) capped with CnH2n+1SH (n = 5–12, 14–16, 18) were prepared via a two-phase synthesis. The films were sampled by Langmuir–Schaefer horizontal transfer at various points in the pressure–area isotherm and monitored with transmission electron microscopy. Changes in surface pressure, temperature, and alkyl chain length did not lead to observable differences in the mesoscale film morphology. Pressure–area isotherms at 22 °C, however, revealed that the work of compression and the collapse pressure are directly dependent on alkyl chain lengths of 14 carbons or greater. Variable temperature isotherms suggest that the work of compression is strongly affected by the phase state (i.e., crystalline vs liquid-like) of the gold–thiolate self-assembled monolayer (SAM) capping the nanoparticles.