Abstract
The ccc stereoisomer-purified tert-butoxycarbonyloxy-protected calix[4]resorcinarene molecular resists blended with photoacid generator exhibit a non-uniform photoacid-catalyzed reaction in thin films. The surface displays a reduced reaction extent, compared with the bulk, with average surface-layer thickness 7.0±1.8nm determined by neutron reflectivity with deuterium-labelled tert-butoxycarbonyloxy groups. Ambient impurities (amines and organic bases) are known to quench surface reactions and contribute, but grazing-incidence X-ray diffraction shows an additional effect that the protected molecular resists are preferentially oriented at the surface, whereas the bulk of the film displays diffuse scattering representative of amorphous packing. The surface deprotection reaction and presence of photoacid were quantified by near-edge X-ray absorption fine-structure measurements.
| Original language | English |
|---|---|
| Pages (from-to) | 1065-1073 |
| Number of pages | 9 |
| Journal | Australian Journal of Chemistry |
| Volume | 64 |
| Issue number | 8 |
| DOIs | |
| State | Published - 2011 |
Funding
We acknowledge Michael Toney (SSRL) for assistance in GIXD experimentation. This work was supported by a cooperative research and development agreement (CRADA 1893) between Intel Corporation and NIST. A portion of this research was carried out at Oak Ridge National Laboratory’s Center for Nanophase Materials Sciences under User Proposal 2008–286, and was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, US Department of Energy. Cornell Nanoscale Science and Technology Facility (CNF), Cornell Center for Materials Research (CCMR) and a grant from the National Science Foundation (DMR-0518785) are acknowledged for partial support of this work.