The influence of extra free volume content, generated during spin-coating, on the lithographic performance of DUV chemically amplified positive resists has been reported in several papers. During exposure and PEB, the deprotection reaction, together with the evolution of the protecting group, constitute a new source of free volume. As investigated in this study, in addition to the chemical modifications resulting from the deprotection reaction, the free volume content, and its variations during PEB, may affect the dissolution properties of the exposed areas.