Bulk chemical composition contrast from attractive forces in AFM force spectroscopy

Abstract

A key application of atomic force microscopy (AFM) is the measurement of physical properties at sub-micrometer resolution. Methods such as force–distance curves (FDCs) or dynamic variants (such as intermodulation AFM (ImAFM)) are able to measure mechanical properties (such as the local stiffness, k r) of nanoscopic heterogeneous materials. For a complete structure–property correlation, these mechanical measurements are considered to lack the ability to identify the chemical structure of the materials. In this study, the measured attractive force, F attr, acting between the AFM tip and the sample is shown to be an independent measurement for the local chemical composition and hence a complete structure–property correlation can be obtained. A proof of concept is provided by two model samples comprised of (1) epoxy/polycarbonate and (2) epoxy/boehmite. The preparation of the model samples allowed for the assignment of material phases based on AFM topography. Additional chemical characterization on the nanoscale is performed by an AFM/infrared-spectroscopy hybrid method. Mechanical properties (k r) and attractive forces (F attr) are calculated and a structure–property correlation is obtained by a manual principle component analysis (mPCA) from a k r/F attr diagram. A third sample comprised of (3) epoxy/polycarbonate/boehmite is measured by ImAFM. The measurement of a 2 × 2 µm cross section yields 128 × 128 force curves which are successfully evaluated by a k r/F attr diagram and the nanoscopic heterogeneity of the sample is determined.