Block copolymers (BCPs), especially in the form of chemically modifiable thin films, are of tremendous academic and industrial interest, as they exhibit myriad tunable properties useful across a broad range of applications. While electron and scanning probe microscopies are conventional choices for characterizing nanostructured BCP film surfaces, optical super-resolution microscopy (SRM) in the far field has recently provided opportunities for alternative approaches. We report the optical SRM of BCP thin film surface nanostructures through stochastic optical reconstruction microscopy (STORM). We show that ultrabright silica nanoparticles (SNPs) can undergo selective surface attachment to hydrophilic BCP domains using reliable “click” chemistries, thereby enabling the use of STORM. To that end, we compare a set of surface-functionalized fluorescent core–shell silica nanoparticles (SNPs) encapsulating organic dyes with their free-dye counterparts in STORM. Using various click-type chemistries, these probes are covalently attached to the surface of specific blocks of BCP thin films, enabling selective block staining and optical visualization. We demonstrate that the enhanced brightness of our SNP probes offers distinct advantages over conventional dye labeling. The facile imaging of features on the near-molecular scale provides a versatile method for materials surface morphology assessments using optical imaging. Finally, we show efforts to expand the versatility of our method beyond surface attachment. Combining surface with such volume imaging approaches will ultimately enable full characterization of BCP-SNP nanocomposite thin films.

Novel nanoprobes for optical super-resolution microscopy of model block copolymer thin film surfaces

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.