Anchoring Atomically Precise Chiral Bismuth Oxido Nanoclusters on Gold: The Role of Amino Acid Linkers.

The adsorption of chiral molecules onto metallic surfaces triggers electron spin polarization at the interface, paving the way for applications in chiral opto-spintronics. However, the spin effects sensitively depend on the binding and ordering of the chiral species on surfaces. This study explores the adsorption of chiral thioether-functionalized atomically precise bismuth oxido nanoclusters (BiO-NCs) on gold (Au) surfaces, extending the conventional approach of using thiol-containing molecules and complexes to nanoclusters. Starting from the precursor [Bi38O45(NO3)20(dmso)28](NO3)4·4dmso (A), chiral BiO-NCs were synthesized by substituting the nitrates with N-(tert-butoxycarbonyl)-l-methionine (Boc-l-Met-O-) ligands to obtain [Bi38O45(Boc-l-Met-O)24] (2). The full exchange of nitrate by the Boc-l-methionine ligand was demonstrated by powder X-ray diffractograms, dynamic light scattering, electrospray ionization mass spectrometry, nuclear magnetic resonance, infrared, circular dichroism, and X-ray photoelectron spectroscopy. Compared to previously reported [Bi38O45(Boc-l-Phe-O)24(dmso)9] (1), BiO-NC 2 shows differences in the growth mode on a Au surface as revealed by scanning electron microscopy, wherefore a stronger binding of BiO-NC 2 is assumed. Anchoring of BiO-NC 2 to the Au surface through thioether groups induced a discernible change in the optical response of the Au surface analyzed by spectroscopic ellipsometry (SE). From the numerical modeling of the SE parameters, a layer thickness of ∼2 nm, corresponding to a monolayer of BiO-NC 2, was estimated for the samples prepared by dip coating. Thus, strong adsorption of BiO-NC 2 to the Au surface is concluded, which is an essential prerequisite for chiral-induced interface spin polarization.

Towards Embedded Electrochemical Sensors for On-Site Nitrite Detection by Gold Nanoparticles Modified Screen Printed Carbon Electrodes.

The transition of electrochemical sensors from lab-based measurements to real-time analysis requires special attention to different aspects in addition to the classical development of new sensing materials. Several critical challenges need to be addressed including a reproducible fabrication procedure, stability, lifetime, and development of cost-effective sensor electronics. In this paper, we address these aspects exemplarily for a nitrite sensor. An electrochemical sensor has been developed using one-step electrodeposited (Ed) gold nanoparticles (EdAu) for the detection of nitrite in water, which shows a low limit of detection of 0.38 µM and excellent analytical capabilities in groundwater. Experimental investigations with 10 realized sensors show a very high reproducibility enabling mass production. A comprehensive investigation of the sensor drift by calendar and cyclic aging was carried out for 160 cycles to assess the stability of the electrodes. Electrochemical impedance spectroscopy (EIS) shows significant changes with increasing aging inferring the deterioration of the electrode surface. To enable on-site measurements outside the laboratory, a compact and cost-effective wireless potentiostat combining cyclic and square wave voltammetry, and EIS capabilities has been designed and validated. The implemented methodology in this study builds a basis for the development of further on-site distributed electrochemical sensor networks.

Proximity-Induced Gap Opening by Twisted Plumbene in Epitaxial Graphene.

Besides graphene, further honeycomb 2D structures were successfully synthesized on various surfaces. However, almost flat plumbene hosting topologically protected edge states could not yet be realized. In this Letter, we investigated the intercalation of Pb on buffer layers on SiC(0001). Thereby, suspended and charge neutral graphene emerged, and the intercalated Pb formed plumbene honeycomb lattices, which are rotated by ±7.5° with respect to graphene. Along with this twist, a proximity-induced modulation of the hopping parameter in graphene opens a band gap of around 30 meV at the Fermi energy, giving rise to a metal-insulator transition. Moreover, the edges of the intercalated plumbene layers revealed edge states within the gap of the conduction bands at around 1 eV as expected for charge neutral plumbene.

Topological Surface State in Epitaxial Zigzag Graphene Nanoribbons.

Protected and spin-polarized transport channels are the hallmark of topological insulators, coming along with an intrinsic strong spin-orbit coupling. Here we identified such corresponding chiral states in epitaxially grown zigzag graphene nanoribbons (zz-GNRs), albeit with an extremely weak spin-orbit interaction. While the bulk of the monolayer zz-GNR is fully suspended across a SiC facet, the lower edge merges into the SiC(0001) substrate and reveals a surface state at the Fermi energy, which is extended along the edge and splits in energy toward the bulk. All of the spectroscopic details are precisely described within a tight binding model incorporating a Haldane term and strain effects. The concomitant breaking of time-reversal symmetry without the application of external magnetic fields is supported by ballistic transport revealing a conduction of G = e2/h.

Hierarchically Structured Microsieves Produced via Float-Casting.

This article shows a new way to produce hierarchical microsieves by layering three types of float-cast microsieves, differing from each other in their pore diameters (approximately 68 µm, 7 µm, and 0.24 µm) on top of each other. The unsupported microsieves with 7 and 0.24 µm pore sizes are mechanically fragile. The complete hierarchical sieve composed of all three layers, however, can be handled manually without special precaution. This article further investigates the flow through the hierarchical sieve and filtration via experiment, theory (Hagen-Poiseuille's and Sampson-Roscoe's law), and simulation (numerically solving the Navier-Stokes equations for a predefined set of discrete volumetric elements). The experimental, theoretical, and simulated permeances of the microsieves and the hierarchical sieves are in reasonable agreement with each other and are significantly higher than the permeances of conventional filtration media. In filtration experiments, the hierarchical sieves show the expected sharp size cut-off, retaining particles of diameters exceeding the pore diameter.

The Weak 3D Topological Insulator Bi12 Rh3 Sn3 I9.

Topological insulators (TIs) gained high interest due to their protected electronic surface states that allow dissipation-free electron and information transport. In consequence, TIs are recommended as materials for spintronics and quantum computing. Yet, the number of well-characterized TIs is rather limited. To contribute to this field of research, we focused on new bismuth-based subiodides and recently succeeded in synthesizing a new compound Bi12 Rh3 Sn3 I9 , which is structurally closely related to Bi14 Rh3 I9 - a stable, layered material. In fact, Bi14 Rh3 I9 is the first experimentally supported weak 3D TI. Both structures are composed of well-defined intermetallic layers of ∞ 2 [(Bi4 Rh)3 I]2+ with topologically protected electronic edge-states. The fundamental difference between Bi14 Rh3 I9 and Bi12 Rh3 Sn3 I9 lies in the composition and the arrangement of the anionic spacer. While the intermetallic 2D TI layers in Bi14 Rh3 I9 are isolated by ∞ 1 [Bi2 I8 ]2- chains, the isoelectronic substitution of bismuth(III) with tin(II) leads to ∞ 2 [Sn3 I8 ]2- layers as anionic spacers. First transport experiments support the 2D character of this material class and revealed metallic conductivity.

Exceptional ballistic transport in epitaxial graphene nanoribbons.

Graphene nanoribbons will be essential components in future graphene nanoelectronics. However, in typical nanoribbons produced from lithographically patterned exfoliated graphene, the charge carriers travel only about ten nanometres between scattering events, resulting in minimum sheet resistances of about one kilohm per square. Here we show that 40-nanometre-wide graphene nanoribbons epitaxially grown on silicon carbide are single-channel room-temperature ballistic conductors on a length scale greater than ten micrometres, which is similar to the performance of metallic carbon nanotubes. This is equivalent to sheet resistances below 1 ohm per square, surpassing theoretical predictions for perfect graphene by at least an order of magnitude. In neutral graphene ribbons, we show that transport is dominated by two modes. One is ballistic and temperature independent; the other is thermally activated. Transport is protected from back-scattering, possibly reflecting ground-state properties of neutral graphene. At room temperature, the resistance of both modes is found to increase abruptly at a particular length--the ballistic mode at 16 micrometres and the other at 160 nanometres. Our epitaxial graphene nanoribbons will be important not only in fundamental science, but also--because they can be readily produced in thousands--in advanced nanoelectronics, which can make use of their room-temperature ballistic transport properties.

Charge Transport through Ferrocene 1,1'-Diamine Single-Molecule Junctions.

The charge transport through ferrocene 1,1'-diamine (FDA) molecules between gold electrodes is investigated using the mechanically controllable break junction technique combined with a theoretical framework of density functional theory simulations to understand the physics of these molecular junctions. The characteristic conductances of the molecule are measured at low bias as well as current-voltage (IV) characteristics. By fitting the IV characteristics to the single-level model, the values for the position of the molecular level, mainly responsible for the transport, and its coupling to the leads, are obtained. The influence of the binding sites, molecular conformation, and electrode distance are systematically studied from a theoretical perspective. While a strong dependence of conductance on the adsorption geometry is found, the decrease of conductance as a function of electrode distance arises mainly from a decrease of coupling strength of the molecular electronic orbitals through a reduced overlap and, to a lesser extent, from a shift of their alignment with respect to the Fermi energy.

Electron Interference in Ballistic Graphene Nanoconstrictions.

We realize nanometer size constrictions in ballistic graphene nanoribbons grown on sidewalls of SiC mesa structures. The high quality of our devices allows the observation of a number of electronic quantum interference phenomena. The transmissions of Fabry-Perot-like resonances are probed by in situ transport measurements at various temperatures. The energies of the resonances are determined by the size of the constrictions, which can be controlled precisely using STM lithography. The temperature and size dependence of the measured conductances are in quantitative agreement with tight-binding calculations. The fact that these interference effects are visible even at room temperature makes the reported devices attractive as building blocks for future carbon based electronics.

Surface-dominated transport on a bulk topological insulator.

Topological insulators are guaranteed to support metallic surface states on an insulating bulk, and one should thus expect that the electronic transport in these materials is dominated by the surfaces states. Alas, due to the high remaining bulk conductivity, it is challenging to achieve surface-dominated transport. Here we use nanoscale four-point setups with a variable contact distance on an atomically clean surface of bulk-insulating Bi2Te2Se. We show that the transport at 30 K is two-dimensional rather than three-dimensional, that is, surface-dominated, and we find a surface state mobility of 390(30) cm(2) V(-1) s(-1) at 30 K at a carrier concentration of 8.71(7) × 10(12) cm(-2).

Hybrid Organosulfur Network/MWCNT Composite Cathodes for Li-S Batteries.

Lithium-sulfur (Li-S) batteries hold a promising position as candidates for next-generation high-energy storage systems. Here, we combine inverse vulcanization of sulfur with multiwalled carbon nanotubes (MWCNTs) to increase the conductivity of cathode materials for Li-S batteries. The mixing process of inversely vulcanized sulfur copolymer networks with MWCNTs is aided by shear in a two-roll mill to take advantage of the soft nature of the copolymer. The high-throughput mixing method demands a source of conductive carbon that can be intimately mixed with the S copolymer, rendering MWCNTs an excellent choice for this purpose. The resulting sulfur copolymer network-MWCNTs composites were thoroughly characterized in terms of structure, chemical composition, thermal, and electronic transport properties, and finally evaluated by electrochemical benchmarking. These promising hybrids yielded electrodes with high sulfur content and demonstrate stable electrochemical performance exhibiting a specific capacity of ca. 550 mAh·gsulfur-1 (380 mAh·gelectrode-1) even after 500 charge-discharge cycles at specific current of 167 mA·g-1 (corresponds to 0.1C discharge rate), and thus are superior to melt-infiltrated reference samples.

Toward Humidity-Independent Sensitive and Fast Response Temperature Sensors Based on Reduced Graphene Oxide/Poly(vinyl alcohol) Nanocomposites.

Flexible temperature sensors are becoming increasingly important these days. In this work, we explore graphene oxide (GO)/poly(vinyl alcohol) (PVA) nanocomposites for potential application in temperature sensors. The influence of the mixing ratio of both materials, the reduction temperature, and passivation on the sensing performance has been investigated. Various spectroscopic techniques revealed the composite structure and atomic composition. These were complemented by semiempirical quantum chemical calculations to investigate rGO and PVA interaction. Scanning electron and atomic force microscopy measurements were carried out to evaluate dispersion and coated film quality. The temperature sensitivity has been evaluated for several composite materials with different compositions in the range from 10 to 80 °C. The results show that a linear temperature behavior can be realized based on rGO/PVA composites with temperature coefficients of resistance (TCR) larger than 1.8% K-1 and a fast response time of 0.3 s with minimal hysteresis. Furthermore, humidity influence has been investigated in the range from 10% to 80%, and a minor effect is shown. Therefore, we can conclude that rGO/PVA composites have a high potential for excellent passivation-free, humidity-independent, sensitive, and fast response temperature sensors for various applications. The GO reduction is tunable, and PVA improves the rGO/PVA sensor performance by increasing the tunneling effect and band gap energy, consequently improving temperature sensitivity. Additionally, PVA exhibits minimal water absorption, reducing the humidity sensitivity. rGO/PVA maintains its temperature sensitivity during and after several mechanical deformations.

Morphology of Bi(110) quantum islands on epitaxial graphene.

Proximitized 2D materials present exciting prospects for exploring new quantum properties, enabled by precise control of structures and interfaces through epitaxial methods. In this study, we investigated the structure of ultrathin coverages formed by depositing high-Z element bismuth (Bi) on monolayer graphene (MLG)/SiC(0001). By utilizing electron diffraction and scanning tunneling microscopy, ultrathin Bi nanostructures epitaxially grown on MLG were studied. Deposition at 300 K resulted in formation of needle-like Bi(110)-terminated islands elongated in the zig-zag direction and aligned at an angle of approximately 1.75∘with respect to the MLG armchair direction. By both strain and quantum size effects, the shape, the orientation and the thickness of the Bi(110) islands can be rationalized. Additionally, a minority phase of Bi(110) islands orthogonally aligned to the former ones were seen. The four sub-domains of this minority structure are attributed to the formation of mirror twin boundaries, resulting in two potential alignments of Bi(110) majority and minority domains with respect to each other, in addition to two possible alignments of the majority domain with respect to graphene. Notably, an annealing step at 410 K or lowering the deposition temperature, significantly increases the concentration of the Bi(110) minority domain. Our findings shed light on the structural control of proximitized 2D materials, showcasing the potential for manipulating 2D interfaces.

Spin Polarization of Polyalanine Molecules in 2D and Dimer-Row Assemblies Adsorbed on Magnetic Substrates: The Role of Coupling, Chirality, and Coordination.

Propagation of electrons along helical molecules adsorbed on surfaces comes along with a robust spin polarization effect called chirality induced spin selectivity CISS. However, experiments on the molecular scale that allow a true correlation of spin effects with the molecular structure are quite rare. Here we have studied the structure of self-assembled chiral molecules and the electronic transmission and spin polarization of the current through the system by means of ambient scanning tunneling microscopy and spectroscopy in heterostructures of various α-helix polyalanine-based molecules (PA) adsorbed on Al2O3/Pt/Au/Co/Au substrates with perpendicular magnetic anisotropy. We have found a phase separation of the molecules into well-ordered enantiopure 2D hexagonal phases and quasi-1D heterochiral-dimer structures, which allows for the analysis of the spin polarization with almost atomic precision of PA in different phases. The spin polarization reaches up to 75% for chemisorbed molecules arranged in a hexagonal phase. On the contrary, for weakly coupled PA molecules without cysteine anchoring groups in a quasi-1D phase, a spin polarization of around 50% was found. Our results show that both the intermolecular interaction as well as the coupling to the substrate are important and point out that collective effects within the molecules and at the interfaces are required to achieve a high chiral induced spin selectivity.

Quantum Confinement in Epitaxial Armchair Graphene Nanoribbons on SiC Sidewalls.

The integration of graphene into devices necessitates large-scale growth and precise nanostructuring. Epitaxial growth of graphene on SiC surfaces offers a solution by enabling both simultaneous and targeted realization of quantum structures. We investigated the impact of local variations in the width and edge termination of armchair graphene nanoribbons (AGNRs) on quantum confinement effects using scanning tunneling microscopy and spectroscopy (STM, STS), along with density-functional tight-binding (DFTB) calculations. AGNRs were grown as an ensemble on refaceted sidewalls of SiC mesas with adjacent AGNRs separated by SiC(0001) terraces hosting a buffer layer seamlessly connected to the AGNRs. Energy band gaps measured by STS at the centers of ribbons of different widths align with theoretical expectations, indicating that hybridization of π-electrons with the SiC substrate mimics sharp electronic edges. However, regardless of the ribbon width, band gaps near the edges of AGNRs are significantly reduced. DFTB calculations successfully replicate this effect by considering the role of edge passivation, while strain or electric fields do not account for the observed effect. Unlike idealized nanoribbons with uniform hydrogen passivation, AGNRs on SiC sidewalls generate additional energy bands with non-pz character and nonuniform distribution across the nanoribbon. In AGNRs terminated with Si, these additional states occur at the conduction band edge and rapidly decay into the bulk of the ribbon. This agrees with our experimental findings, demonstrating that edge passivation is crucial in determining the local electronic properties of epitaxial nanoribbons.

All-Carbon Monolithic Composites from Carbon Foam and Hierarchical Porous Carbon for Energy Storage.

We designed high-volumetric-energy-density supercapacitors from monolithic composites composed of self-standing carbon foam (CF) as the conducting matrix and embedded hierarchically organized porous carbon (PICK) as the active material. Using multiprobe scanning tunneling microscopy at selected areas, we were able to disentangle morphology-dependent contributions of the heterogeneous composite to the overall conductivity. Adding PICK is found to enhance the conductivity of the monoliths by providing additional links for the CF network, enabling high and stable performance. The resulting all-carbon CF-PICK composites were used as self-standing electrodes for symmetric supercapacitors without the need for a binder, additional conducting additive, metals as a current collector, or casting/drying steps. Supercapacitors achieved a capacitance of 181 F g-1 based on the entire mass of the monolithic electrode as well as an outstanding rate capability. Our symmetrical supercapacitors also delivered a record volumetric energy density of 19.4 mW h cm-3 when using aqueous electrolytes. Excellent cycling stability with almost quantitative retention of capacitance was found after 10,000 cycles in 6.0 M KOH as the electrolyte. Furthermore, charge-discharge testing at different currents demonstrated the fast charge-discharge capability of this material system that meets the requirements for practical applications.

Cooperative Effect of Electron Spin Polarization in Chiral Molecules Studied with Non-Spin-Polarized Scanning Tunneling Microscopy.

Polyalanine molecules (PA) with an α-helix conformation have recently attracted a great deal of interest, as the propagation of electrons through the chiral backbone structure comes along with spin polarization of the transmitted electrons. By means of scanning tunneling microscopy and spectroscopy under ambient conditions, PA molecules adsorbed on surfaces of epitaxial magnetic Al2O3/Pt/Au/Co/Au nanostructures with perpendicular anisotropy were studied. Thereby, a correlation between the PA molecules ordering at the surface with the electron tunneling across this hybrid system as a function of the substrate magnetization orientation as well as the coverage density and helicity of the PA molecules was observed. The highest spin polarization values, P, were found for well-ordered self-assembled monolayers and with a defined chemical coupling of the molecules to the magnetic substrate surface, showing that the current-induced spin selectivity is a cooperative effect. Thereby, P deduced from the electron transmission along unoccupied molecular orbitals of the chiral molecules is larger as compared to values derived from the occupied molecular orbitals. Apparently, the larger orbital overlap results in a higher electron mobility, yielding a higher P value. By switching the magnetization direction of the Co layer, it was demonstrated that the non-spin-polarized STM can be used to study chiral molecules with a submolecular resolution, to detect properties of buried magnetic layers and to detect the spin polarization of the molecules from the change in the magnetoresistance of such hybrid structures.

Deposition of Nanosized Amino Acid Functionalized Bismuth Oxido Clusters on Gold Surfaces.

Bismuth compounds are of growing interest with regard to potential applications in catalysis, medicine, and electronics, for which their environmentally benign nature is one of the key factors. One thing that currently hampers the further development of bismuth oxido-based materials, however, is the often low solubility of the precursors, which makes targeted immobilisation on substrates challenging. We present an approach towards the solubilisation of bismuth oxido clusters by introducing an amino carboxylate as a functional group. For this purpose, the bismuth oxido cluster [Bi38O45(NO3)20(dmso)28](NO3)4·4dmso (dmso = dimethyl sulfoxide) was reacted with the sodium salt of tert-butyloxycabonyl (Boc)-protected phenylalanine (L-Phe) to obtain the soluble and chiral nanocluster [Bi38O45(Boc-Phe-O)24(dmso)9]. The exchange of the nitrates by the amino carboxylates was proven by nuclear magnetic resonance, Fourier-transform infrared spectroscopy, as well as elemental analysis and X-ray photoemission spectroscopy. The solubility of the bismuth oxido cluster in a protic as well as an aprotic polar organic solvent and the growth mode of the clusters upon spin, dip, and drop coating on gold surfaces were studied by a variety of microscopy, as well as spectroscopic techniques. In all cases, the bismuth oxido clusters form crystalline agglomerations with size, height, and distribution on the substrate that can be controlled by the choice of the solvent and of the deposition method.

Surface Transport Properties of Pb-Intercalated Graphene.

Intercalation experiments on epitaxial graphene are attracting a lot of attention at present as a tool to further boost the electronic properties of 2D graphene. In this work, we studied the intercalation of Pb using buffer layers on 6H-SiC(0001) by means of electron diffraction, scanning tunneling microscopy, photoelectron spectroscopy and in situ surface transport. Large-area intercalation of a few Pb monolayers succeeded via surface defects. The intercalated Pb forms a characteristic striped phase and leads to formation of almost charge neutral graphene in proximity to a Pb layer. The Pb intercalated layer consists of 2 ML and shows a strong structural corrugation. The epitaxial heterostructure provides an extremely high conductivity of σ=100 mS/□. However, at low temperatures (70 K), we found a metal-insulator transition that we assign to the formation of minigaps in epitaxial graphene, possibly induced by a static distortion of graphene following the corrugation of the interface layer.

High Mass Loading Asymmetric Micro-supercapacitors with Ultrahigh Areal Energy and Power Density.

High mass loading asymmetric micro-supercapacitors (MSCs) are key components for the development of high-performance energy and power supply systems. Here, a concept for achieving high mass loading electrodes is presented and applied to high mass loading micro-supercapacitors with ultrahigh areal energy and power density. The positive electrode is made from porous carbon with birnessite coverage and multiwalled carbon nanotubes (CNTs) as conducting additives (PIC-CNTs-MnO2). The negative electrode is prepared from hierarchically porous active carbon mixed with CNTs (PICK-CNTs). Both positive and negative electrode materials are tailored to ensure a high content of macro- and mesopores. MSCs with an optimized mass loading of 13.9 mg·cm-2 (maximum: 23.6 mg·cm-2) provide an ultrahigh areal capacitance of 1.13 F·cm-2 (volumetric capacitance: 22.6 F·cm-3), an outstanding energy of 627.8 µWh·cm-2, and a maximum power density of 64 mW·cm-2. About 85% of the initial capacitance remained after 5000 cycles. Moreover, shunt and tandem device testing confirmed a high uniformity of these MSCs, meeting the requirements of adjustable output currents and voltages in microchips.