Rasmus H. Pedersen

Design and fabrication of memory devices based on nanoscale polyoxometalate clusters

Flash memory devices—that is, non-volatile computer storage media that can be electrically erased and reprogrammed—are vital for portable electronics, but the scaling down of metal–oxide–semiconductor (MOS) flash memory to sizes of below ten nanometres per data cell presents challenges. Molecules have been proposed to replace MOS flash memory, but they suffer from low electrical conductivity, high resistance, low device yield, and finite thermal stability, limiting their integration into current MOS technologies. Although great advances have been made in the pursuit of molecule-based flash memory, there are a number of significant barriers to the realization of devices using conventional MOS technologies. Here we show that core–shell polyoxometalate (POM) molecules can act as candidate storage nodes for MOS flash memory. Realistic, industry-standard device simulations validate our approach at the nanometre scale, where the device performance is determined mainly by the number of molecules in the storage media and not by their position. To exploit the nature of the core–shell POM clusters, we show, at both the molecular and device level, that embedding [(Se(iv)O3)2]4− as an oxidizable dopant in the cluster core allows the oxidation of the molecule to a [Se(v)2O6]2− moiety containing a {Se(v)–Se(v)} bond (where curly brackets indicate a moiety, not a molecule) and reveals a new 5+ oxidation state for selenium. This new oxidation state can be observed at the device level, resulting in a new type of memory, which we call ‘write-once-erase’. Taken together, these results show that POMs have the potential to be used as a realistic nanoscale flash memory. Also, the configuration of the doped POM core may lead to new types of electrical behaviour. This work suggests a route to the practical integration of configurable molecules in MOS technologies as the lithographic scales approach the molecular limit.

Injection moulding of ultra high aspect ratio nanostructures using coated polymer tooling

Replication-based nanofabrication techniques offer rapid, cost effective ways to produce nanostructured devices for a host of applications in engineering, biological research and beyond. In this work we developed a method to replicate ultra high aspect ratio (UHAR) nanopillars by injection molding with failure rates lower than one pillar in a thousand. We provide a review of the literature in which replication of difficult micro- and nanostructures is facilitated through the use of different tooling materials and surface coatings, before describing the non-adhesive surface coatings which we used to translate a previously developed technique from low to high aspect ratios. This development involved a systematic study of nine different surface coatings on polymer tooling initially patterned by nanoimprint lithography. Using this method we were able to produce injection moulded pillar-like nanostructures with aspect ratios of up to 20:1, more than 6 times that reported elsewhere in the literature for this type of feature.

Label-free segmentation of Co-cultured cells on a nanotopographical gradient.

The function and fate of cells is influenced by many different factors, one of which is surface topography of the support culture substrate. Systematic studies of nanotopography and cell response have typically been limited to single cell types and a small set of topographical variations. Here, we show a radical expansion of experimental throughput using automated detection, measurement, and classification of co-cultured cells on a nanopillar array where feature height changes continuously from planar to 250 nm over 9 mm. Individual cells are identified and characterized by more than 200 descriptors, which are used to construct a set of rules for label-free segmentation into individual cell types. Using this approach we can achieve label-free segmentation with 84% confidence across large image data sets and suggest optimized surface parameters for nanostructuring of implant devices such as vascular stents.

A Dual Gradient Assay for the Parametric Analysis of Cell-Surface Interactions

Cellular response to microgrooves is addressed using a new assay format, comprising orthogonal gradients of continuously varied groove pitch and depth. Dual layer etch masks are created using a combination of micropatterning and plasma polymer deposition. A silicon substrate with a constant groove width of 8 μm and with ridge width increasing from 8 μm in 0.5 μm steps across 10 mm is fabricated by photolithography. A plasma-polymerized hexane film which is 120 nm thick at one end of these grooves, and 10 nm at the other, is deposited under a diffusion mask. Reactive etching of the patterned sample transfers a gradient of groove pitch and groove depth into the silicon substrate. A silicon master with a gradient of groove depth spanning more than two orders of magnitude (less than 10 nm to over 1000 nm) is used to create an injection molding inlay for mass replication of the screening topography. Polycarbonate replicas are molded for use in cell culture studies, and the functionality of the topography as a high-throughput screening platform is investigated. The response of MDCK, h-TERT fibroblasts, and LE2 endothelial cells is examined, in terms of attachment and morphological response to the variation in topographical cues, with the aim of pinpointing the optimal combination of groove pitch and depth to elicit a tailored response from each cell type. When the range of topographical features screened on a single substrate is considered, this new assay represents a significant step forward in the parametric design and analysis of topographical cues at the biomaterial interface.

Electrical properties of in-situ grown and transferred organic nanofibers

Para-hexaphenylene (p6P) molecules have the ability to self-assemble into organic nanofibers, which exhibit a range of interesting optical and optoelectronic properties such as intense, polarized luminescence, waveguiding and lasing. The nanofibers are typically grown on specific single-crystalline templates, such as muscovite mica, on which mutually parallel nanofibers are self-assembled upon vapor deposition of the organic material under high vacuum conditions. Besides such single-crystalline templates, the nanofibers can also be grown on non-crystalline gold surfaces, on which the orientation of the nanofibers can be manipulated by structuring the gold surface prior to parahexaphenylene (p6P) deposition. In this work it is demonstrated, how such organic nanofiber growth can be controlled by modifying the design of the underlying gold structures prior to growth. Here, the investigated designs include pinning lines and gratings. We demonstrate how gold gratings fabricated on an insulating substrate can enable electrical contact to in-situ grown p6P nanofibers. Furthermore, the electrical characteristics of in-situ grown fibers are compared to that of transferred p6P nanofibers. The transferred nanofibers are initially grown on muscovite mica, and subsequently transferred onto a target substrate by drop casting, and electrodes are applied on top by a special shadow mask technique.

Polymer Replication Techniques

Direct nanopatterning of surfaces using lithographic methods, such as electron beam lithography (EBL) or photolithography, allows unique structures to be defined in a methodical, step-by-step manner that delivers fantastically high-quality results that cannot be obtained by any other means, but is generally unsuitable for mass production or requires substantial infrastructure and financial investment to make it suitable as is the case with optical lithography in the microelectronics industry. A more economical route to create large number of nanostructured devices lies in replication-based technology where a single master may give birth to many clones of itself, eliminating the need to repeat an entire fabrication process. These methods are gaining increasing interest where the resolution limit of optical lithography makes it harder to form the ever smaller structures that are desired and in other emerging application areas that also require nanoscale patterns, but do not have the volume required for the investment in advanced conventional systems. Examples of such applications include substrates for biochemical research such as cell growth, advanced lab-on-a-chip devices, integrated nanophotonic devices and hard disk storage devices. Developments in polymer-based replication technology have also been extensive for applications where conventional fabrication techniques are not well suited such as flexible display systems.