The surface morphology of a fatty acid multilayer film has been studied usi
ng atomic force microscopy. Samples were prepared using a range of thermal
treatments that generate intrinsic structural defects in the film. Thermal
contraction of the cooling film gives rise to tensile surface stresses, whi
ch are relieved through the creation and subsequent growth of fractures. Th
e study of these defects elucidates physical properties of the film at the
micron and nanometre scale. Following thermal treatment at low temperatures
, fractures are found to coexist with quasi-circular hole defects that are
localised at the film surface. Fractures and holes result from different nu
cleation mechanisms and propagate via anisotropic and isotropic growth proc
esses, respectively. The two distinct types of defect indicate that the fil
m exhibits both liquid- and solid-like behaviour and suggests that the divi
sion is dependent upon the distance from the graphite substrate. Macroscopi
c fracture resulting from a decrease in volume caused by thermal contractio
n or desiccation occurs widely in nature. The work presented here suggests
the occurrence of a similar physical process for molecular films on the nan
ometre scale. (C) 2000 Elsevier Science B.V. All rights reserved.