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Application of Thioether-Modified Calix[4]arenes as Resistors in Microcontact Printing

M. Liebau*, J. Huskens, and D.N. Reinhoudt

Laboratory of Supramolecular Chemistry and Technology, MESA+ Research Institute, University of Twente,
P.O. Box 217, 7500 AE Enschede, The Netherlands

This is an abstract for a presentation given at the
Seventh Foresight Conference on Molecular Nanotechnology.
There will be a link from here to the full article when it is available on the web.


Microcontact printing is a well-known tool for the replication of small features. The state of the art is the development of structures in dimensions of some hundreds of nanometers. A variety of problems are encountered upon approaching the 100 nm scale. Diffusion processes appear to be responsible for the unsharpness of the replicated structures. We try to overcome this problem by the application less volatile sulfur compounds which still provide monolayers, such as thioether-modified calix[4]arenes.

The presented results give a comparison of the resistance of monolayers of decanethiol, didecylsulfide, and a thioether-modified calix[4]arene to a cyanide etchant. It is shown that the thiol and the calix[4]arene monolayers are stable against the etchant, whereas self-assembled monolayer (SAMs), made of didecylsulfide, showed significant changes in their electrochemical behavior. Using SAMs of decanethiol, the electrochemical resistivity dropped from 63.48 kOhm to 8.70 kOhm after 30 min etching. Similar results were obtained for the thioether-modified calix[4]arene. In contrast, the influence of the etchant on didecylsulfide monolayers is more significant (resistance of etched layers: 0.248 kOhm). We found that SAMs, made of calix[4]arenes, are as resistant as decanethiol SAMs to the cyanide etchant. These results are confirmed by measuring the capacitance, the heterogeneous electron transfer, and by contact angle measurements.

*Corresponding Address:
Maik Liebau
Laboratory of Supramolecular Chemistry and Technology, MESA+ Research Institute, University of Twente
P.O. Box 217, 7500 AE Enschede, The Netherlands
Phone: +31-53-4892933; Fax: +31-53-4894645
Email:; Web:


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