Quantitative Element-Sensitive Analysis of Individual Nanoobjects.

A reliable and quantitative material analysis is crucial for assessing new technological processes, especially to facilitate a quantitative understanding of advanced material properties at the nanoscale. To this end, X-ray fluorescence microscopy techniques can offer an element-sensitive and non-destructive tool for the investigation of a wide range of nanotechnological materials. Since X-ray radiation provides information depths of up to the microscale, even stratified or buried arrangements are easily accessible without invasive sample preparation. However, in terms of the quantification capabilities, these approaches are usually restricted to a qualitative or semi-quantitative analysis at the nanoscale. Relying on comparable reference nanomaterials is often not straightforward or impossible because the development of innovative nanomaterials has proven to be more fast-paced than any development process for appropriate reference materials. The present work corroborates that a traceable quantification of individual nanoobjects can be realized by means of an X-ray fluorescence microscope when utilizing rather conventional but well-calibrated instrumentation instead of reference materials. As a proof of concept, the total number of atoms forming a germanium nanoobject is quantified using soft X-ray radiation. Furthermore, complementary dimensional parameters of such objects are reconstructed.

Two-Dimensional Photosensitizer Nanosheets via Low-Energy Electron Beam Induced Cross-Linking of Self-Assembled RuII Polypyridine Monolayers.

Artificial photosynthesis for hydrogen production is an important element in the search for green energy sources. The incorporation of photoactive units into mechanically stable 2D materials paves the way toward the realization of ultrathin membranes as mimics for leaves. Here we present and compare two concepts to introduce a photoactive RuII polypyridine complex into ≈1 nm thick carbon nanomembranes (CNMs) generated by low-energy electron irradiation induced cross-linking of aromatic self-assembled monolayers. The photoactive units are either directly incorporated into the CNM scaffold or covalently grafted to its surface. We characterize RuII CNMs using X-ray photoelectron, surface-enhanced Raman, photothermal deflection spectroscopy, atomic force, scanning electron microscopy, and study their photoactivity in graphene field-effect devices. Therewith, we explore the applicability of low-energy electron irradiation of metal complexes for photosensitizer nanosheet formation.

Trapping and Counting Ballistic Nonequilibrium Electrons.

We demonstrate the trapping of electrons propagating ballistically at far-above-equilibrium energies in GaAs/AlGaAs heterostructures in high magnetic field. We find low-loss transport along a gate-modified mesa edge in contrast to an effective decay of excess energy for the loop around a neighboring, mesa-confined node, enabling high-fidelity trapping. Measuring the full counting statistics via single-charge detection yields the trapping (and escape) probabilities of electrons scattered (and excited) within the node. Energetic and arrival-time distributions of captured electron wave packets are characterized by modulating tunnel barrier transmission.

Optically Triggered Control of the Charge Carrier Density in Chemically Functionalized Graphene Field Effect Transistors.

Field effect transistors (FETs) based on 2D materials are of great interest for applications in ultrathin electronic and sensing devices. Here we demonstrate the possibility to add optical switchability to graphene FETs (GFET) by functionalizing the graphene channel with optically switchable azobenzene molecules. The azobenzene molecules were incorporated to the GFET channel by building a van der Waals heterostructure with a carbon nanomembrane (CNM), which is used as a molecular interposer to attach the azobenzene molecules. Under exposure with 365 nm and 455 nm light, azobenzene molecules transition between cis and trans molecular conformations, respectively, resulting in a switching of the molecular dipole moment. Thus, the effective electric field acting on the GFET channel is tuned by optical stimulation and the carrier density is modulated.

Grazing incidence-x-ray fluorescence for a dimensional and compositional characterization of well-ordered 2D and 3D nanostructures.

The increasing importance of well-controlled ordered nanostructures on surfaces represents a challenge for existing metrology techniques. To develop such nanostructures and monitor complex processing constraints fabrication, both a dimensional reconstruction of nanostructures and a characterization (ideally a quantitative characterization) of their composition is required. In this work, we present a soft x-ray fluorescence-based methodology that allows both of these requirements to be addressed at the same time. By applying the grazing-incidence x-ray fluorescence technique and thus utilizing the x-ray standing wave field effect, nanostructures can be investigated with a high sensitivity with respect to their dimensional and compositional characteristics. By varying the incident angles of the exciting radiation, element-sensitive fluorescence radiation is emitted from different regions inside the nanoobjects. By applying an adequate modeling scheme, these datasets can be used to determine the nanostructure characteristics. We demonstrate these capabilities by performing an element-sensitive reconstruction of a lamellar grating made of Si3N4, where GIXRF data for the O-Kα and N-Kα fluorescence emission allows a thin oxide layer to be reconstructed on the surface of the grating structure. In addition, we employ the technique also to three dimensional nanostructures and derive both dimensional and compositional parameters in a quantitative manner.

Self-referenced single-electron quantized current source.

The future redefinition of the international system of units in terms of natural constants requires a robust, high-precision quantum standard for the electrical base unit ampere. However, the reliability of any single-electron current source generating a nominally quantized output current I=ef by delivering single electrons with charge e at a frequency f is eventually limited by the stochastic nature of the underlying quantum mechanical tunneling process. We experimentally explore a path to overcome this fundamental limitation by serially connecting clocked single-electron emitters with multiple in situ single-electron detectors. Correlation analysis of the detector signatures during current generation reveals erroneous pumping events and enables us to determine the deviation of the output current from the nominal quantized value ef. This demonstrates the concept of a self-referenced single-electron source for electrical quantum metrology.

Counting statistics for electron capture in a dynamic quantum dot.

We report noninvasive single-charge detection of the full probability distribution P(n) of the initialization of a quantum dot with n electrons for rapid decoupling from an electron reservoir. We analyze the data in the context of a model for sequential tunneling pinch-off, which has generic solutions corresponding to two opposing mechanisms. One limit considers sequential "freeze-out" of an adiabatically evolving grand canonical distribution, the other one is an athermal limit equivalent to the solution of a generalized decay cascade model. We identify the athermal capturing mechanism in our sample, testifying to the high precision of our combined theoretical and experimental methods. The distinction between the capturing mechanisms allows us to derive efficient experimental strategies for improving the initialization.

Critical Point Drying of Graphene Field-Effect Transistors Improves Their Electric Transport Characteristics.

A critical point drying (CPD) technique is reported with supercritical CO2 as a cleaning step for graphene field-effect transistors (GFETs) microfabricated on oxidized Si wafers, which results in an increase of the field-effect mobility and a decrease of the impurity doping. It is shown that the polymeric residues remaining on graphene after the transfer process and device microfabrication are significantly reduced after the CPD treatment. Moreover, the CPD effectively removes ambient adsorbates such as water therewith reducing the undesirable p-type doping of the GFETs. It is proposed that CPD of electronic, optoelectronic, and photonic devices based on 2D materials as a promising technique to recover their intrinsic properties after the microfabrication in a cleanroom and after storage at ambient conditions.

Two electrons interacting at a mesoscopic beam splitter.

The nonlinear response of a beam splitter to the coincident arrival of interacting particles enables numerous applications in quantum engineering and metrology. Yet, it poses considerable challenges to control interactions on the individual particle level. Here, we probe the coincidence correlations at a mesoscopic constriction between individual ballistic electrons in a system with unscreened Coulomb interactions and introduce concepts to quantify the associated parametric nonlinearity. The full counting statistics of joint detection allows us to explore the interaction-mediated energy exchange. We observe an increase from 50% up to 70% in coincidence counts between statistically indistinguishable on-demand sources and a correlation signature consistent with the independent tomography of the electron emission. Analytical modelling and numerical simulations underpin the consistency of the experimental results with Coulomb interactions between two electrons counterpropagating in a quadratic saddle potential. Coulomb repulsion energy and beam splitter dispersion define a figure of merit, which in this experiment is demonstrated to be sufficiently large to enable future applications, such as single-shot in-flight detection and quantum logic gates.

Standardization of egg collection from aquatic birds for biomonitoring--a critical review.

Collecting bird eggs is an established method of biomonitoring for specific pollution hazards. One of the most critical problems with this method is the extreme biological variability in bird eggs, but standardizing the collection and preservation of eggs can reduce these problems. Furthermore, standard practices are required so that the results can be compared among studies because mistakes cannot be corrected by laboratory analysis. Therefore, a standard procedure for collecting and preserving bird eggs may be necessary. The objective of this review is to investigate the current standard of quality assurance in the field by analyzing 86 peer-reviewed papers describing egg collection and use for aquatic birds. We show that little attention has been paid to standardizing how eggs are collected and stored in the field. Important information is often absent, including crucial aspects of sample collection and preservation, such as the freshness of the eggs, the position of the eggs in the laying sequence, the selection criteria, random sampling, and the duration and temperature of transport. Potential standards are suggested and discussed as a foundation for the development of quality assurance standards in the field.

Versatile sputtering technology for Al2O3 gate insulators on graphene.

We report a novel, sputtering-based fabrication method of Al2O3 gate insulators on graphene. Electrical performance of dual-gated mono- and bilayer exfoliated graphene devices is presented. Sputtered Al2O3 layers possess comparable quality to oxides obtained by atomic layer deposition with respect to a high relative dielectric constant of about 8, as well as low-hysteresis performance and high breakdown voltage. We observe a moderate carrier mobility of about 1000 cm2 V-1 s-1 in monolayer graphene and 350 cm2 V-1 s-1 in bilayer graphene, respectively. The mobility decrease can be attributed to the resonant scattering on atomic-scale defects, likely originating from the Al precursor layer evaporated prior to sputtering.

Rational design of functional oxide thin films with embedded magnetic or plasmonic metallic nanoparticles.

Getting into films: semiconductor thin films containing magnetic or plasmonic metal nanoparticles are key materials for the development of high-efficiency solar cells, bright light-emitting diodes, and new magnetoelectric devices. The catalytically driven chemical vapor deposition offers a unique way to combine deposition of the metallic nanoparticles with that of functional oxides to produce such films.

Fabrication Process for Deep Submicron SQUID Circuits with Three Independent Niobium Layers.

We present a fabrication technology for nanoscale superconducting quantum interference devices (SQUIDs) with overdamped superconductor-normal metal-superconductor (SNS) trilayer Nb/HfTi/Nb Josephson junctions. A combination of electron-beam lithography with chemical-mechanical polishing and magnetron sputtering on thermally oxidized Si wafers is used to produce direct current SQUIDs with 100-nm-lateral dimensions for Nb lines and junctions. We extended the process from originally two to three independent Nb layers. This extension offers the possibility to realize superconducting vias to all Nb layers without the HfTi barrier, and hence to increase the density and complexity of circuit structures. We present results on the yield of this process and measurements of SQUID characteristics.

Directly addressable GaN-based nano-LED arrays: fabrication and electro-optical characterization.

The rapid development of display technologies has raised interest in arrays of self-emitting, individually controlled light sources atthe microscale. Gallium nitride (GaN) micro-light-emitting diode (LED) technology meets this demand. However, the current technology is not suitable for the fabrication of arrays of submicron light sources that can be controlled individually. Our approach is based on nanoLED arrays that can directly address each array element and a self-pitch with dimensions below the wavelength of light. The design and fabrication processes are explained in detail and possess two geometries: a 6 × 6 array with 400 nm LEDs and a 2 × 32 line array with 200 nm LEDs. These nanoLEDs are developed as core elements of a novel on-chip super-resolution microscope. GaN technology, based on its physical properties, is an ideal platform for such nanoLEDs.

Bottom-Up Synthesis of Graphene Monolayers with Tunable Crystallinity and Porosity.

We present a method for a bottom-up synthesis of atomically thin graphene sheets with tunable crystallinity and porosity using aromatic self-assembled monolayers (SAMs) as molecular precursors. To this end, we employ SAMs with pyridine and pyrrole constituents on polycrystalline copper foils and convert them initially into molecular nanosheets-carbon nanomembranes (CNMs)- via low-energy electron irradiation induced cross-linking and then into graphene monolayers via pyrolysis. As the nitrogen atoms are leaving the nanosheets during pyrolysis, nanopores are generated in the formed single-layer graphene. We elucidate the structural changes upon the cross-linking and pyrolysis down to the atomic scale by complementary spectroscopy and microscopy techniques including X-ray photoelectron and Raman spectroscopy, low energy electron diffraction, atomic force, helium ion, and high-resolution transmission electron microscopy, and electrical transport measurements. We demonstrate that the crystallinity and porosity of the formed graphene can be adjusted via the choice of molecular precursors and pyrolysis temperature, and we present a kinetic growth model quantitatively describing the conversion of molecular CNMs into graphene. The synthesized nanoporous graphene monolayers resemble a percolated network of graphene nanoribbons with a high charge carrier mobility (∼600 cm2/(V s)), making them attractive for implementations in electronic field-effect devices.

Large-Area All-Carbon Nanocapacitors from Graphene and Carbon Nanomembranes.

We report on the fabrication of large-area all-carbon capacitors (ACCs) composed of multilayer stacks of carbon nanomembranes as dielectrics sandwiched between two carbon-based conducting electrodes. Carbon nanomembranes (CNMs) are prepared from aromatic self-assembled monolayers of phenylthiol homologues via electron irradiation. Two types of carbon-based electrode materials, (1) trilayer graphene made by chemical vapor deposition and mechanical stacking and (2) pyrolyzed graphitic carbon made by pyrolysis of cross-linked aromatic molecules, have been employed for this study. The capacitor area is defined by the width of electrode ribbons, and the separation between two electrodes is tuned by the number of CNM layers. Working ACCs with an area of up to 1200 µm2 were successfully fabricated by a combination of bottom-up molecular self-assembly and top-down lithographic approaches. Then ACCs were characterized by Raman spectroscopy, helium ion microscopy, and impedance spectroscopy. A dielectric constant of 3.5 and an average capacitance density of 0.3 µF/cm2 were derived from the obtained capacitances. A dielectric strength of 3.2 MV/cm was determined for CNMs embedded in graphene electrodes with the interfacial capacitance being taken into account. These results show the potential of carbon nanomembranes to be used as dielectric components in next-generation environment-friendly carbon-based energy storage devices.

All-carbon vertical van der Waals heterostructures: non-destructive functionalization of graphene for electronic applications.

Non-destructive chemical functionalization of graphene for applications in electronic devices (e.g., sensors or transducers) is achieved via assembly of carbon nanomembrane (CNM)/single-layer graphene (SLG) van der Waals heterostructures. The CNMs are 1 nm-thick, dielectric molecular sheets terminated with functional amino groups. The structure and performance of heterostructured field-effect transistors (FETs) are characterized by photoelectron/Raman spectroscopy and by electric transport measurements in vacuum, ambient conditions and water.

Functional single-layer graphene sheets from aromatic monolayers.

Self-assembled monolayers of aromatic molecules on copper substrates can be converted into high-quality single-layer graphene using low-energy electron irradiation and subsequent annealing. This two-dimensional solid state transformation is characterized on the atomic scale and the physical and chemical properties of the formed graphene sheets are studied by complementary microscopic and spectroscopic techniques and by electrical transport measurements. As substrates, Cu(111) single crystals and the technologically relevant polycrystalline copper foils are successfully used.

Conductance enhancement of InAs/InP heterostructure nanowires by surface functionalization with oligo(phenylene vinylene)s.

We have investigated the electronic transport through 3 µm long, 45 nm diameter InAs nanowires comprising a 5 nm long InP segment as electronic barrier. After assembly of 12 nm long oligo(phenylene vinylene) derivative molecules onto these InAs/InP nanowires, we observed a pronounced, nonlinear I-V characteristic with significantly increased currents of up to 1 µA at 1 V bias, for a back-gate voltage of 3 V. As supported by our model calculations based on a nonequilibrium Green Function approach, we attribute this effect to charge transport through those surface-bound molecules, which electrically bridge both InAs regions across the embedded InP barrier.