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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH FRONT

Characterization of the Non-uniform Reaction in Chemically Amplified Calix[4]resorcinarene Molecular Resist Thin Films1

Vivek M. Prabhu A F , Shuhui Kang A , R. Joseph Kline A , Dean M. DeLongchamp A , Daniel A. Fischer B , Wen-li Wu A , Sushil K. Satija C , Peter V. Bonnesen D , Jing Sha E and Christopher K. Ober E

A Polymers Division, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA.

B Ceramics Division, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA.

C Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA.

D Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA.

E Cornell University, Materials Science and Engineering, Ithaca, NY 14853, USA.

F Corresponding author. Email: vprabhu@nist.gov

Australian Journal of Chemistry 64(8) 1065-1073 http://dx.doi.org/10.1071/CH11242
Submitted: 15 June 2011  Accepted: 19 July 2011   Published: 19 August 2011

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 ± 1.8 nm 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.

Graphical Abstract Image


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