Henning Vieker

Layer-by-Layer Assembled Heteroatom-Doped Graphene Films with Ultrahigh Volumetric Capacitance and Rate Capability for Micro-Supercapacitors

Highly uniform, ultrathin, layer-by-layer heteroatom (N, B) co-doped graphene films are fabricated for high-performance on-chip planar micro-supercapacitors with an ultrahigh volumetric capacitance of ∼488 F cm(-3) and excellent rate capability due to the synergistic effect of nitrogen and boron co-doping.

Toward Plasmonics with Nanometer Precision: Nonlinear Optics of Helium-Ion Milled Gold Nanoantennas

Plasmonic nanoantennas are versatile tools for coherently controlling and directing light on the nanoscale. For these antennas, current fabrication techniques such as electron beam lithography (EBL) or focused ion beam (FIB) milling with Ga(+)-ions routinely achieve feature sizes in the 10 nm range. However, they suffer increasingly from inherent limitations when a precision of single nanometers down to atomic length scales is required, where exciting quantum mechanical effects are expected to affect the nanoantenna optics. Here, we demonstrate that a combined approach of Ga(+)-FIB and milling-based He(+)-ion lithography (HIL) for the fabrication of nanoantennas offers to readily overcome some of these limitations. Gold bowtie antennas with 6 nm gap size were fabricated with single-nanometer accuracy and high reproducibility. Using third harmonic (TH) spectroscopy, we find a substantial enhancement of the nonlinear emission intensity of single HIL-antennas compared to those produced by state-of-the-art gallium-based milling. Moreover, HIL-antennas show a vastly improved polarization contrast. This superior nonlinear performance of HIL-derived plasmonic structures is an excellent testimonial to the application of He(+)-ion beam milling for ultrahigh precision nanofabrication, which in turn can be viewed as a stepping stone to mastering quantum optical investigations in the near-field.

A Universal Scheme to Convert Aromatic Molecular Monolayers into Functional Carbon Nanomembranes

Free-standing nanomembranes with molecular or atomic thickness are currently explored for separation technologies, electronics, and sensing. Their engineering with well-defined structural and functional properties is a challenge for materials research. Here we present a broadly applicable scheme to create mechanically stable carbon nanomembranes (CNMs) with a thickness of ~0.5 to ~3 nm. Monolayers of polyaromatic molecules (oligophenyls, hexaphenylbenzene, and polycyclic aromatic hydrocarbons) were assembled and exposed to electrons that cross-link them into CNMs; subsequent pyrolysis converts the CNMs into graphene sheets. In this transformation the thickness, porosity, and surface functionality of the nanomembranes are determined by the monolayers, and structural and functional features are passed on from the molecules through their monolayers to the CNMs and finally on to the graphene. Our procedure is scalable to large areas and allows the engineering of ultrathin nanomembranes by controlling the composition and structure of precursor molecules and their monolayers.

Cooperative self-assembly of discoid dimers: hierarchical formation of nanostructures with a pH switch.

Derivatives of the self-complementary 2-guanidiniocarbonyl pyrrole 5-carboxylate zwitterion (1) (previously reported by us to dimerize to 1•1 with an aggregation constant of ca. >10(10) M(-l) in DMSO) aggregate in a diverse manner depending on, e.g., variation of concentration or its protonation state. The mode of aggregation was analyzed by spectroscopic (NMR, UV) and microscopic (AFM, SEM, HIM, and TEM) methods. Aggregation of dimers of these zwitterions to higher supramolecular structures was achieved by introduction of sec-amide substituents at the 3-position, i.e., at the rearward periphery of the parent binding motif. A butyl amide substituent as in 2b enables the discoid dimers to further aggregate into one-dimensional (rod-like) stacks. Quantitative UV dilution studies showed that this aggregation is strongly cooperative following a nucleation elongation mechanism. The amide hydrogen seems to be essential for this rod-like aggregation, as neither 1 nor a corresponding tert-amide congener 2a form comparable structures. Therefore, a hydrogen bond-assisted π-π-interaction of the dimeric zwitterions is suggested to promote this aggregation mode, which is further affected by the nature of the amide substituent (e.g., steric demand), enabling the formation of bundles of strands or even two-dimensional sheets. By exploiting the zwitterionic nature of the aggregating discoid dimers, a reversible pH switch was realized: dimerization of all compounds is suppressed by protonation of the carboxylate moiety, converting the zwitterions into typical cationic amphiphiles. Accordingly, typical nanostructures like vesicles, tubes, and flat sheets are formed reversibly under acidic conditions, which reassemble into the original rod-like aggregates upon readjustment to neutral pH.

Imaging nanocarbon materials: soot particles in flames are not structurally homogeneous.

For the first time, nascent soot particles are probed by using helium-ion microscopy (HIM). HIM is a technique that is similar to scanning electron microscopy (SEM) but it can achieve higher contrast and improved surface sensitivity, especially for carbonaceous materials. The HIM microscope yields images with a high contrast, which allows for the unambiguous recognition of smaller nascent soot particles than those observed in previous transmission electron microscopy studies. The results indicate that HIM is ideal for rapid and reliable probing of the morphology of nascent soot, with surface details visible down to approximately 5 nm, and particles as small as 2 nm are detectable. The results also show that nascent soot is structurally and chemically inhomogeneous, and even the smallest particles can have shapes that deviate from a perfect sphere.

Structure–activity relation of spinel-type Co–Fe oxides for low-temperature CO oxidation

A series of cobalt ferrite thin films was prepared via pulsed spray evaporation chemical vapour deposition (PSE-CVD). The samples were comprehensively characterised in terms of structure, surface, morphology, and optical and redox properties. Both X-ray diffraction (XRD) and Raman analysis show that all samples exhibited an inverse spinel structure. X-ray photoelectron spectroscopy (XPS) results indicate that the films were mainly composed of Co, Fe and O species, and an increase in the Co : Fe ratio with Fe substitution by Co was observed. Helium ion microscopy (HIM) images show the film morphology to be dependent on the Co : Fe ratio. The investigation of the optical property using ultraviolet-visible spectroscopy reveals that the increase in the Co content results in an increase in the band gap energy. In situ emission FTIR spectroscopy was used to evaluate the redox properties of the samples, and a shift of the redox temperature to higher values was observed upon increase in the Co content. The effect of Fe substitution by Co in the mixed oxide systems on their catalytic performance for CO oxidation was investigated. Co–Fe oxides exhibit substantially better catalytic performance than the single α-Fe2O3. The catalytic performance of the Co–Fe oxides towards CO oxidation was discussed with respect to the participation of surface and lattice oxygen in the oxidation process. According to XPS and temperature-programmed reduction/oxidation (TPR/TPO) results, a suprafacial mechanism where CO molecules react with surface-adsorbed oxygen functions to form CO2 was proposed as the dominant mechanism.

Selective synthesis of α-Fe2O3 thin films and effect of the deposition temperature and lattice oxygen on the catalytic combustion of propene

Pulsed spray evaporation chemical vapour deposition (PSE-CVD), an elaborate CVD process, was employed to synthesize thin films of α-Fe2O3 for the catalytic combustion of propene. According to X-ray diffraction and Raman spectroscopy, the alpha structure type was presented as the unique phase. α-Fe2O3 with fine crystalline structure was revealed by scanning electron microscopy, and probed in depth for the first time by helium ion microscopy. Energy dispersive X-ray microscopy and X-ray photoelectron spectroscopy displayed an overview of the chemical composition of the samples. In situ emission FTIR spectroscopy was used for the accurate determination of the thermal stability of the samples at around 500 °C, and temperature-programmed reduction was performed to correlate the catalytic performance and reduction properties of the obtained α-Fe2O3 thin films. The results showed that the increase of the deposition temperature leads to significant changes of film morphology, chemical composition and reduction properties, with a direct consequence on the catalytic performance. α-Fe2O3 prepared at a low temperature (350 °C) exhibited high activity towards the deep oxidation of propene, which was attributed to its good reducibility and the plate-like structures. The alternate reduction and oxidation of the oxide surface (favored by the bulk oxygen migration towards the surface) and replenishment of bulk oxygen by gas-phase oxygen suggest that the oxidation of propene may proceed according to the Mars van Krevelen mechanism. The morphology and surface composition of the prepared samples remain the same before and after the catalytic test, demonstrating very good stability and reproducibility. We thus conclude that α-Fe2O3 effective in propene conversion can be selectively synthesized with PSE-CVD.

Fabrication of carbon nanotube nanogap electrodes by helium ion sputtering for molecular contacts

Carbon nanotube nanogaps have been used to contact individual organic molecules. However, the reliable fabrication of a truly nanometer-sized gap remains a challenge. We use helium ion beam lithography to sputter nanogaps of only (2.8 ± 0.6) nm size into single metallic carbon nanotubes embedded in a device geometry. The high reproducibility of the gap size formation provides a reliable nanogap electrode testbed for contacting small organic molecules. To demonstrate the functionality of these nanogap electrodes, we integrate oligo(phenylene ethynylene) molecular rods, and measure resistance before and after gap formation and with and without contacted molecules.

Carbon Nanomembranes (CNMs) Supported by Polymer: Mechanics and Gas Permeation

Gas permeation characteristics of carbon nanomembranes (CNMs) from self-assembled monolayers are reported for the first time. The assembly of CNMs onto polydimethylsiloxane (PDMS) support membranes allows mechanical measurements under compression as well as determination of gas permeation characteristics. The results suggest that molecular-sized channels in CNMs dominate the permeation properties of the 1 nm thin CNMs.

Fabrication of nanopores in 1 nm thick carbon nanomembranes with slow highly charged ions

We describe the use of slow highly charged ions as a simple tool for the fabrication of nanopores with well-defined diameters typically between 10 and 20 nm in freestanding, 1 nm thick carbon nanomembranes (CNMs). When CNMs are exposed to a flux of highly charged ions, for example Xe40+, each individual ion creates a circular nanopore, the size of which depends on the kinetic and potential energy of the impinging ion. The controlled fabrication of nanopores with a uniform size opens a path for the application of CNM based filters in nanobiotechnology.