Exploiting Chemical Switching in a Diels–Alder Polymer for Nanoscale Probe Lithography and Data Storage

Abstract Reversibly crosslinked polymer films have properties that are beneficial to scanned‐probe data storage and lithographic applications that use thermomechanical nanoindentation as a write or expose mechanism. The novel polymer under study contains linkages based on thermally reversible Diels–Alder crosslinking. Thermomechanical properties on the nanometer scale are analyzed by indentation experiments on polymer thin films using heated tips. The underlying indentation mechanism is studied at varying tip temperatures and indentation times, revealing Arrhenius kinetics. This is in contrast to the Williams–Landau–Ferry kinetics usually observed for polymer systems. The discrepancy is explained by the reversible crosslinking incorporated into the structure of the polymer that allows switching between two different states: a rigid, highly crosslinked, low‐temperature state, and a deformable, fragmented, high‐temperature state. An individual indentation volume of less than 10^–20 L (10 000 molecule pairs) is estimated. These kinetics experiments demonstrate that a chemical reaction of only a few thousand molecules can be transduced into a mechanically measurable action. The ability to cycle between two sets of properties in these materials opens up new perspectives in lithography and data storage. Examples of data storage with densities up to 1 Tb in.^–2 and maskless lithography with resolution below 20 nm are demonstrated at writing times of 10 μs per bit/pixel.