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Article Cite This: Chem. Mater. 2018, 30, 4124−4133

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Metal−Organic Framework-Inspired Metal-Containing Clusters for High-Resolution Patterning Hong Xu,† Kazunori Sakai,†,‡ Kazuki Kasahara,†,‡ Vasiliki Kosma,† Kou Yang,† Henry C. Herbol,† Jeremy Odent,† Paulette Clancy,§ Emmanuel P. Giannelis,† and Christopher K. Ober*,† †

Department of Materials Science and Engineering, Cornell University, Ithaca, New York 14853, United States Semiconductor Materials Laboratory, Fine Electronic Research Laboratories, JSR Corporation, 100 Kawajiri-cho, Yokkaichi, Mie 510-8552, Japan § School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, New York 14853, United States Downloaded via NEW MEXICO STATE UNIV on July 1, 2018 at 13:21:17 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.



S Supporting Information *

ABSTRACT: We report the preparation of discrete nanometerscale zinc-based clusters and use them to form sub-15 nm structures by means of extreme ultraviolet lithography. By taking advantage of a metal-containing building unit derived by a metal−organic frameworkMOF-2, we found the 3-methyl-phenyl-modified Zn-mTA cluster that formed is well-defined with controlled size and structure and demonstrates extremely high solubility. Progress in recent years in metal−organic frameworks has created a rich variety of metalcontaining structures that are useful for numerous applications. Substitution of the bridging ligands with monovalent ligands produces a discrete metal−organic cluster that strongly interacts with soft X-rays at a wavelength of 13 nm. Here we describe the design, preparation, computational modeling, and physical characterization of these new materials. Such metal-containing structures may form the basis of photoresists that enable the next generation of microelectronic devices.

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sources,12−14 a more beneficial approach is to design new photoresists, which can absorb EUV light more efficiently. Transition metals demonstrate strong and effective absorption of EUV radiation (unlike the elements C and H),15,16 and recent progress in metal oxide nanoparticles has shown encouraging performance under EUV exposure.16−23 Making metal oxide nanoparticles is not enough to produce a successful photoresist, however. Nanoparticles with a broad size distribution are accompanied by a broad solubility distribution, which results in imperfections during lithography. Furthermore, as the feature size decreases to