Chemical self-assembly has garnered tremendous interest as a tool for generating nanometer-scale structures and devices. Organosilane self-assembled monolayers (SAMs) are of particular interest due to their ability to assemble on a wide range of substrates with varied chemical functionalities. Nanoshaving, an atomic force lithographic technique, has been demonstrated as a method to generate nanopatterns of organosilane SAMs. However, this method requires extremely high force setpoints, which rapidly dulls atomic force microscopy tips and degrades the resolution of the resulting nanopattern. In this work, we utilize Cu-ligated mercaptohexadecanoic acid (MHDA) multilayers to circumvent this limitation. Initially, a 10-undecenyltrichlorosilane (UTS) SAM is assembled onto a Si substrate, and the terminal olefin groups of the UTS SAM are oxidized to carboxyl groups. Subsequently, a Cu-ligated MHDA multilayer is assembled via the sequential deposition of Cu2+ ions and MHDA molecules. The interface between the oxidized UTS SAM and Cu-ligated MHDA multilayer serves as a natural low force breakpoint for nanoshaving. We demonstrate that the resulting nanopatterns can function as a chemical resist to fabricate metal nanostructures.
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Expanding the molecular-ruler process through vapor deposition of hexadecanethiol
The development of methods to produce nanoscale features with tailored chemical functionalities is fundamental for applications such as nanoelectronics and sensor fabrication. The molecular-ruler process shows great utility for this purpose as it combines top-down lithography for the creation of complex architectures over large areas in conjunction with molecular self-assembly, which enables precise control over the physical and chemical properties of small local features. The molecular-ruler process, which most commonly uses mercaptoalkanoic acids and metal ions to generate metal-ligated multilayers, can be employed to produce registered nanogaps between metal features. Expansion of this methodology to include molecules with other chemical functionalities could greatly expand the overall versatility, and thus the utility, of this process. Herein, we explore the use of alkanethiol molecules as the terminating layer of metal-ligated multilayers. During this study, it was discovered that the solution deposition of alkanethiol molecules resulted in low overall surface coverage with features that varied in height. Because features with varied heights are not conducive to the production of uniform nanogaps via the molecular-ruler process, the vapor-phase deposition of alkanethiol molecules was explored. Unlike the solution-phase deposition, alkanethiol islands produced by vapor-phase deposition exhibited markedly higher surface coverages of uniform heights. To illustrate the applicability of this method, metal-ligated multilayers, both with and without an alkanethiol capping layer, were utilized to create nanogaps between Au features using the molecular-ruler process.
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- Award ID(s):
- 1536528
- PAR ID:
- 10478911
- Publisher / Repository:
- Beilstein Institute
- Date Published:
- Journal Name:
- Beilstein Journal of Nanotechnology
- Volume:
- 8
- ISSN:
- 2190-4286
- Page Range / eLocation ID:
- 2339 to 2344
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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