Nanolithographic Fabrication Technologies for Network-Based Biocomputation Devices.

Network-based biocomputation (NBC) relies on accurate guiding of biological agents through nanofabricated channels produced by lithographic patterning techniques. Here, we report on the large-scale, wafer-level fabrication of optimized microfluidic channel networks (NBC networks) using electron-beam lithography as the central method. To confirm the functionality of these NBC networks, we solve an instance of a classical non-deterministic-polynomial-time complete ("NP-complete") problem, the subset-sum problem. The propagation of cytoskeletal filaments, e.g., molecular motor-propelled microtubules or actin filaments, relies on a combination of physical and chemical guiding along the channels of an NBC network. Therefore, the nanofabricated channels have to fulfill specific requirements with respect to the biochemical treatment as well as the geometrical confienement, with walls surrounding the floors where functional molecular motors attach. We show how the material stack used for the NBC network can be optimized so that the motor-proteins attach themselves in functional form only to the floor of the channels. Further optimizations in the nanolithographic fabrication processes greatly improve the smoothness of the channel walls and floors, while optimizations in motor-protein expression and purification improve the activity of the motor proteins, and therefore, the motility of the filaments. Together, these optimizations provide us with the opportunity to increase the reliability of our NBC devices. In the future, we expect that these nanolithographic fabrication technologies will enable production of large-scale NBC networks intended to solve substantially larger combinatorial problems that are currently outside the capabilities of conventional software-based solvers.

Exciton tuning in monolayer WSe2 via substrate induced electron doping.

We report large exciton tuning in WSe2 monolayers via substrate induced non-degenerate doping. We observe a redshift of ∼62 meV for the A exciton together with a 1-2 orders of magnitude photoluminescence (PL) quenching when the monolayer WSe2 is brought in contact with highly oriented pyrolytic graphite (HOPG) compared to dielectric substrates such as hBN and SiO2. As the evidence of doping from HOPG to WSe2, a drastic increase of the intensity ratio of trions to neutral excitons was observed. Using a systematic PL and Kelvin probe force microscopy (KPFM) investigation on WSe2/HOPG, WSe2/hBN, and WSe2/graphene, we conclude that this unique excitonic behavior is induced by electron doping from the substrate. Our results propose a simple yet efficient way for exciton tuning in monolayer WSe2, which plays a central role in the fundamental understanding and further device development.

Ferrocenyl-Pyrenes, Ferrocenyl-9,10-Phenanthrenediones, and Ferrocenyl-9,10-Dimethoxyphenanthrenes: Charge-Transfer Studies and SWCNT Functionalization.

The synthesis of 1-Fc- (3), 1-Br-6-Fc- (5 a), 2-Br-7-Fc- (7 a), 1,6-Fc2 - (5 b), 2,7-Fc2 -pyrene (7 b), 3,6-Fc2 -9,10-phenanthrenedione (10), and 3,6-Fc2 -9,10-dimethoxyphenanthrene (12; Fc=Fe(η5 -C5 H4 )(η5 -C5 H5 )) is discussed. Of these compounds, 10 and 12 form 1D or 2D coordination polymers in the solid state. (Spectro)Electrochemical studies confirmed reversible Fc/Fc+ redox events between -130 and 160 mV. 1,6- and 2,7-Substitution in 5 a (E°'=-130 mV) and 7 a (E°'=50 mV) influences the redox potentials, whereas the ones of 5 b and 7 b (E°'=20 mV) are independent. Compounds 5 b, 7 b, 10, and 12 show single Fc oxidation processes with redox splittings between 70 and 100 mV. UV/Vis/NIR spectroelectrochemistry confirmed a weak electron transfer between FeII /FeIII in mixed-valent [5 b]+ and [12]+ . DFT calculations showed that 5 b non-covalently interacts with the single-walled carbon nanotube (SWCNT) sidewalls as proven by, for example, disentangling experiments. In addition, CV studies of the as-obtained dispersions confirmed exohedral attachment of 5 b at the SWCNTs.

The nature of non-FRET photoluminescence quenching in nanoassemblies from semiconductor quantum dots and dye molecules.

Nanoassemblies formed via self-assembly based on colloidal CdSe quantum dots (QDs) and porphyrin (H2P) dye molecules show Fluorescence Resonant Energy Transfer (FRET) and non-FRET quenching of QD photoluminescence (PL). We present a procedure to unravel and quantify these two relaxation pathways via dynamic and static PL quenching experiments. Accordingly, FRET amounts at maximum to 10% of the total quenching efficiency. Since the degree of ligand coverage is inhomogeneously distributed across the QD ensemble PL quantum yields vary broadly. The attachment of H2P molecules occurs preferentially to those QDs with low ligand coverage. Along with that, nanoassembly formation deviates strongly from Poisson statistics. Like FRET, non-FRET depends on the QD size. We assign non-FRET quenching to the formation of specific new Cd2+ trap states following depletion of several ligands by the spacious dye molecules. While FRET follows quantitatively the Förster model, non-FRET appears on time scales of 1-3 ns in new and enhanced non-radiative near-band-edge QD PL decay channels caused by a trapping of the electrons in long-lived intra-gap states which then manifests itself in a subsequent weak PL emission. We assign the related intra-band emission to a recombination of deep-trap electrons and shallow-trap holes.

Inkjet Printing of Colloidal Nanospheres: Engineering the Evaporation-Driven Self-Assembly Process to Form Defined Layer Morphologies.

We report on inkjet printing of aqueous colloidal suspensions containing monodisperse silica and/or polystyrene nanosphere particles and a systematic study of the morphology of the deposits as a function of different parameters during inkjet printing and solvent evaporation. The colloidal suspensions act as a model ink for an understanding of layer formation processes and resulting morphologies in inkjet printing in general. We investigated the influence of the surface energy and the temperature of the substrate, the formulation of the suspensions, and the multi-pass printing aiming for layer stacks on the morphology of the deposits. We explain our findings with models of evaporation-driven self-assembly of the nanosphere particles in a liquid droplet and derive methods to direct the self-assembly processes into distinct one- and two-dimensional deposit morphologies.

Inkjet printing as a tool for the patterned deposition of octadecylsiloxane monolayers on silicon oxide surfaces.

We present a case study about inkjet printing as a tool for molecular patterning of silicon oxide surfaces with hydrophobic functionality, mediated by n-octadecyltrichlorosilane (OTS) molecules. In contrast to state-of-the-art techniques such as micro contact printing or chemical immersion with subsequent lithography processes, piezo drop-on-demand inkjet printing does not depend on physical masters, which allows an effective direct-write patterning of rigid or flexible substrates and enables short run-lengths of the individual pattern. In this paper, we used mesithylene-based OTS inks, jetted them in droplets of 10 pL on a silicon oxide surface, evaluated the water contact angle of the patterned areas and fitted the results with Cassie's law. For inks of 2.0 mM OTS concentration, we found that effective area coverages of 38% can be obtained. Our results hence show that contact times of the order of hundred milliseconds are sufficient to form a pattern of regions with OTS molecules adsorbed to the surface, representing at least a fragmented, inhomogeneous self-assembled OTS monolayer (OTS-SAM).

Formation principles and ligand dynamics of nanoassemblies of CdSe quantum dots and functionalised dye molecules.

Functional dye molecules, such as porphyrins, attached to CdSe quantum dots (QDs) through anchoring meso-pyridyl substituents, form quasi-stable nanoassemblies. This fact results in photoluminescence (PL) quenching of the QDs both due to Förster resonance energy transfer (FRET) and the formation of non-radiative surface states under conditions of quantum confinement (non-FRET). The formation process is in competition with the ligand dynamics. At least two timescales are found for the formation of the assemblies: 1) one faster than 60 s attributed to saturation of empty attachment sites and 2) one slower than 600 s, which is attributed to a reorganisation of the tri-n-octylphosphine oxide (TOPO) ligand shell. Finally, this process results in almost complete exchange of the TOPO shell by porphyrin dye molecules. Following a Stern-Volmer analysis, we established a microscopic description of PL quenching and assembly formation. Based on this formalism, we determined the equilibrium constant for assembly formation between QDs and the pyridyl-functionalised dye molecules to be K ≈ 10(5) - 10(7) M(-1), which is several orders of magnitude larger than that of the TOPO ligands. Our results give additional insights into the non-FRET PL quenching processes involved and show that the QD surface is inhomogeneous with respect to the involved attachment and detachment processes. In comparison with other methods, such as NMR spectroscopy, the advantage of our approach is that ligand dynamics can be investigated at extremely low ratios of dye molecules to QDs.