High-frequency gas effusion through nanopores in suspended graphene.

Porous, atomically thin graphene membranes have interesting properties for filtration and sieving applications. Here, graphene membranes are used to pump gases through nanopores using optothermal forces, enabling the study of gas flow through nanopores at frequencies above 100 kHz. At these frequencies, the motion of graphene is closely linked to the dynamic gas flow through the nanopore and can thus be used to study gas permeation at the nanoscale. By monitoring the time delay between the actuation force and the membrane mechanical motion, the permeation time-constants of various gases through pores with diameters from 10-400 nm are shown to be significantly different. Thus, a method is presented for differentiating gases based on their molecular mass and for studying gas flow mechanisms. The presented microscopic effusion-based gas sensing methodology provides a nanomechanical alternative for large-scale mass-spectrometry and optical spectrometry based gas characterisation methods.

Ground-State Spin Blockade in a Single-Molecule Junction.

It is known that the quantum mechanical ground state of a nanoscale junction has a significant impact on its electrical transport properties. This becomes particularly important in transistors consisting of a single molecule. Because of strong electron-electron interactions and the possibility of accessing ground states with high spins, these systems are eligible hosts of a current-blockade phenomenon called a ground-state spin blockade. This effect arises from the inability of a charge carrier to account for the spin difference required to enter the junction, as that process would violate the spin selection rules. Here, we present a direct experimental demonstration of a ground-state spin blockade in a high-spin single-molecule transistor. The measured transport characteristics of this device exhibit a complete suppression of resonant transport due to a ground-state spin difference of 3/2 between subsequent charge states. Strikingly, the blockade can be reversibly lifted by driving the system through a magnetic ground-state transition in one charge state, using the tunability offered by both magnetic and electric fields.

Isoreticular two-dimensional magnetic coordination polymers prepared through pre-synthetic ligand functionalization.

Chemical functionalization is a powerful approach to tailor the physical and chemical properties of two-dimensional (2D) materials, increase their processability and stability, tune their functionalities and, even, create new 2D materials. This is typically achieved through post-synthetic functionalization by anchoring molecules on the surface of an exfoliated 2D crystal, but it inevitably alters the long-range structural order of the material. Here we present a pre-synthetic approach that allows the isolation of crystalline, robust and magnetic functionalized monolayers of coordination polymers. A series of five isostructural layered magnetic coordination polymers based on Fe(II) centres and different benzimidazole derivatives (bearing a Cl, H, CH3, Br or NH2 side group) were first prepared. On mechanical exfoliation, 2D materials are obtained that retain their long-range structural order and exhibit good mechanical and magnetic properties. This combination, together with the possibility to functionalize their surface at will, makes them good candidates to explore magnetism in the 2D limit and to fabricate mechanical resonators for selective gas sensing.

Nonlinear dynamic characterization of two-dimensional materials.

Owing to their atomic-scale thickness, the resonances of two-dimensional (2D) material membranes show signatures of nonlinearities at forces of only a few picoNewtons. Although the linear dynamics of membranes is well understood, the exact relation between the nonlinear response and the resonator's material properties has remained elusive. Here we show a method for determining the Young's modulus of suspended 2D material membranes from their nonlinear dynamic response. To demonstrate the method, we perform measurements on graphene and MoS2 nanodrums electrostatically driven into the nonlinear regime at multiple driving forces. We show that a set of frequency response curves can be fitted using only the cubic spring constant as a fit parameter, which we then relate to the Young's modulus of the material using membrane theory. The presented method is fast, contactless, and provides a platform for high-frequency characterization of the mechanical properties of 2D materials.

Transport Properties of a Two-Dimensional PbSe Square Superstructure in an Electrolyte-Gated Transistor.

Self-assembled nanocrystal solids show promise as a versatile platform for novel optoelectronic materials. Superlattices composed of a single layer of lead-chalcogenide and cadmium-chalcogenide nanocrystals with epitaxial connections between the nanocrystals, present outstanding questions to the community regarding their predicted band structure and electronic transport properties. However, the as-prepared materials are intrinsic semiconductors; to occupy the bands in a controlled way, chemical doping or external gating is required. Here, we show that square superlattices of PbSe nanocrystals can be incorporated as a nanocrystal monolayer in a transistor setup with an electrolyte gate. The electron (and hole) density can be controlled by the gate potential, up to 8 electrons per nanocrystal site. The electron mobility at room temperature is 18 cm2/(V s). Our work forms a first step in the investigation of the band structure and electronic transport properties of two-dimensional nanocrystal superlattices with controlled geometry, chemical composition, and carrier density.

Phase Transitions in Spin-Crossover Thin Films Probed by Graphene Transport Measurements.

Future multifunctional hybrid devices might combine switchable molecules and 2D material-based devices. Spin-crossover compounds are of particular interest in this context since they exhibit bistability and memory effects at room temperature while responding to numerous external stimuli. Atomically thin 2D materials such as graphene attract a lot of attention for their fascinating electrical, optical, and mechanical properties, but also for their reliability for room-temperature operations. Here, we demonstrate that thermally induced spin-state switching of spin-crossover nanoparticle thin films can be monitored through the electrical transport properties of graphene lying underneath the films. Model calculations indicate that the charge carrier scattering mechanism in graphene is sensitive to the spin-state dependence of the relative dielectric constants of the spin-crossover nanoparticles. This graphene sensor approach can be applied to a wide class of (molecular) systems with tunable electronic polarizabilities.

Transition from Strong to Weak Electronic Coupling in a Single-Molecule Junction.

We have investigated charge transport in single-molecule junctions using gold nanoelectrodes at room and cryogenic (10 K) temperatures. A statistical analysis of the low-bias conductance, measured during the stretching of the molecular junctions, shows that the most probable single-molecule conductance is insensitive to the temperature as expected for off-resonant coherent transport. Low-temperature current-voltage measurements show that these junction conformations have a smooth tunnelinglike shape. While separating the electrodes further we find that, in about one-fourth of the cases, the junction switches in an abrupt way to a configuration with I-V characteristics exhibiting a gap around zero bias and resonances at finite bias. The analysis of the I-V shape and of the conductance distance dependence suggests a stretching-induced transition from the strong to the weak electronic coupling regime. The transition involves a large renormalization of the injection barrier and of the electronic coupling between the molecule and the electrodes.

Exchange Coupling Inversion in a High-Spin Organic Triradical Molecule.

The magnetic properties of a nanoscale system are inextricably linked to its local environment. In adatoms on surfaces and inorganic layered structures, the exchange interactions result from the relative lattice positions, layer thicknesses, and other environmental parameters. Here, we report on a sample-dependent sign inversion of the magnetic exchange coupling between the three unpaired spins of an organic triradical molecule embedded in a three-terminal device. This ferro-to-antiferromagnetic transition is due to structural distortions and results in a high-to-low spin ground-state change in a molecule traditionally considered to be a robust high-spin quartet. Moreover, the flexibility of the molecule yields an in situ electric tunability of the exchange coupling via the gate electrode. These findings open a route to the controlled reversal of the magnetic states in organic molecule-based nanodevices by mechanical means, electrical gating, or chemical tailoring.

Gate Controlled Photocurrent Generation Mechanisms in High-Gain In2Se3 Phototransistors.

Photocurrent in photodetectors incorporating van der Waals materials is typically produced by a combination of photocurrent generation mechanisms that occur simultaneously during operation. Because of this, response times in these devices often yield to slower, high gain processes, which cannot be turned off. Here we report on photodetectors incorporating the layered material In2Se3, which allow complete modulation of a high gain, photogating mechanism in the ON state in favor of fast photoconduction in the OFF state. While photoconduction is largely gate independent, photocurrent from the photogating effect is strongly modulated through application of a back gate voltage. By varying the back gate, we demonstrate control over the dominant mechanism responsible for photocurrent generation. Furthermore, because of the strong photogating effect, these direct-band gap, multilayer phototransistors produce ultrahigh gains of (9.8 ± 2.5) × 10(4) A/W and inferred detectivities of (3.3 ± 0.8) × 10(13) Jones, putting In2Se3 among the most sensitive 2D materials for photodetection studied to date.

Image effects in transport at metal-molecule interfaces.

We present a method for incorporating image-charge effects into the description of charge transport through molecular devices. A simple model allows us to calculate the adjustment of the transport levels, due to the polarization of the electrodes as charge is added to and removed from the molecule. For this, we use the charge distributions of the molecule between two metal electrodes in several charge states, rather than in gas phase, as obtained from a density-functional theory-based transport code. This enables us to efficiently model level shifts and gap renormalization caused by image-charge effects, which are essential for understanding molecular transport experiments. We apply the method to benzene di-amine molecules and compare our results with the standard approach based on gas phase charges. Finally, we give a detailed account of the application of our approach to porphyrin-derivative devices recently studied experimentally by Perrin et al. [Nat. Nanotechnol. 8, 282 (2013)], which demonstrates the importance of accounting for image-charge effects when modeling transport through molecular junctions.

Pick-up and drop transfer of diamond nanosheets.

Nanocrystalline diamond (NCD) is a promising material for electronic and mechanical micro- and nanodevices. Here we introduce a versatile pick-up and drop technique that makes it possible to investigate the electrical, optical and mechanical properties of as-grown NCD films. Using this technique, NCD nanosheets, as thin as 55 nm, can be picked-up from a growth substrate and positioned on another substrate. As a proof of concept, electronic devices and mechanical resonators are fabricated and their properties are characterized. In addition, the versatility of the method is further explored by transferring NCD nanosheets onto an optical fiber, which allows measuring its optical absorption. Finally, we show that NCD nanosheets can also be transferred onto two-dimensional crystals, such as MoS2, to fabricate heterostructures. Pick-up and drop transfer enables the fabrication of a variety of NCD-based devices without requiring lithography or wet processing.

Observing magnetic anisotropy in electronic transport through individual single-molecule magnets.

We review different electron transport methods to probe the magnetic properties, such as the magnetic anisotropy, of an individual Fe4 SMM. The different approaches comprise first and higher order transport through the molecule. Gate spectroscopy, focusing on the charge degeneracy-point, is presented as a robust technique to quantify the longitudinal magnetic anisotropy of the SMM in different redox states. We provide statistics showing the robustness and reproducibility of the different methods. In addition, conductance measurements typically show high-energy excited states well beyond the ground spin multiplet of SMM. Some of these excitations have their origin in excited spin multiplets, others in vibrational modes of the molecule. The interplay between vibrations, charge and spin may yield a new approach for spin control.

Fabrication of hybrid molecular devices using multi-layer graphene break junctions.

We report on the fabrication of hybrid molecular devices employing multi-layer graphene (MLG) flakes which are patterned with a constriction using a helium ion microscope or an oxygen plasma etch. The patterning step allows for the localization of a few-nanometer gap, created by electroburning, that can host single molecules or molecular ensembles. By controlling the width of the sculpted constriction, we regulate the critical power at which the electroburning process begins. We estimate the flake temperature given the critical power and find that at low powers it is possible to electroburn MLG with superconducting contacts in close proximity. Finally, we demonstrate the fabrication of hybrid devices with superconducting contacts and anthracene-functionalized copper curcuminoid molecules. This method is extendable to spintronic devices with ferromagnetic contacts and a first step towards molecular integrated circuits.

Long-range orientation and atomic attachment of nanocrystals in 2D honeycomb superlattices.

Oriented attachment of synthetic semiconductor nanocrystals is emerging as a route for obtaining new semiconductors that can have Dirac-type electronic bands such as graphene, but also strong spin-orbit coupling. The two-dimensional (2D) assembly geometry will require both atomic coherence and long-range periodicity of the superlattices. We show how the interfacial self-assembly and oriented attachment of nanocrystals results in 2D metal chalcogenide semiconductors with a honeycomb superlattice. We present an extensive atomic and nanoscale characterization of these systems using direct imaging and wave scattering methods. The honeycomb superlattices are atomically coherent and have an octahedral symmetry that is buckled; the nanocrystals occupy two parallel planes. Considerable necking and large-scale atomic motion occurred during the attachment process.

Hydrogen termination of CVD diamond films by high-temperature annealing at atmospheric pressure.

A high-temperature procedure to hydrogenate diamond films using molecular hydrogen at atmospheric pressure was explored. Undoped and doped chemical vapour deposited (CVD) polycrystalline diamond films were treated according to our annealing method using a H2 gas flow down to ~50 ml∕min (STP) at ~850 °C. The films were extensively evaluated by surface wettability, electron affinity, elemental composition, photoconductivity, and redox studies. In addition, electrografting experiments were performed. The surface characteristics as well as the optoelectronic and redox properties of the annealed films were found to be very similar to hydrogen plasma-treated films. Moreover, the presented method is compatible with atmospheric pressure and provides a low-cost solution to hydrogenate CVD diamond, which makes it interesting for industrial applications. The plausible mechanism for the hydrogen termination of CVD diamond films is based on the formation of surface carbon dangling bonds and carbon-carbon unsaturated bonds at the applied tempera-ture, which react with molecular hydrogen to produce a hydrogen-terminated surface.

Self-sustained oscillations of a torsional SQUID resonator induced by Lorentz-force back-action.

For the study of nanomechanical resonators, ultra-sensitive measurement techniques are crucial. However, if the measurement sensitivity approaches quantum-mechanical limits, the back-action of the detector on the resonator cannot be neglected. If the back-action is strong enough, the corresponding instability can create self-sustained oscillators in the resonator. Here we demonstrate that a torsional mechanical resonator, which contains a direct current SQUID displacement detector, leads to this effect. We find that the Lorentz-force back-action can be so large that, in combination with complex nonlinear Josephson dynamics, it generates intrinsic self-sustained oscillations. The flux quantization limit of the maximum oscillation amplitude is exploited to calibrate the displacement resolution, which is shown to be below the standard quantum limit. The suspended torsional SQUID provides an interesting platform to study on-chip laser-like physics in an electromechanical system that can be controlled by both a flux and current bias.

Direct observation of magnetic anisotropy in an individual Fe4 single-molecule magnet.

We study three-terminal charge transport through individual Fe4 single-molecule magnets. Magnetic anisotropy of the single molecule is directly observed by introducing a spectroscopic technique based on measuring the position of the degeneracy point as a function of gate voltage and applied magnetic field. A nonlinear field-dependence is observed which changes by rotating the sample and is, thus, a direct proof of magnetic anisotropy. The sensitivity of this method allows us to observe small changes in the orientation and magnitude of the anisotropy in different charge states. We find that the easy axes in adjacent states are (almost) collinear.

Coupling carbon nanotube mechanics to a superconducting circuit.

The quantum behaviour of mechanical resonators is a new and emerging field driven by recent experiments reaching the quantum ground state. The high frequency, small mass, and large quality-factor of carbon nanotube resonators make them attractive for quantum nanomechanical applications. A common element in experiments achieving the resonator ground state is a second quantum system, such as coherent photons or a superconducting device, coupled to the resonators motion. For nanotubes, however, this is a challenge due to their small size. Here, we couple a carbon nanoelectromechanical (NEMS) device to a superconducting circuit. Suspended carbon nanotubes act as both superconducting junctions and moving elements in a Superconducting Quantum Interference Device (SQUID). We observe a strong modulation of the flux through the SQUID from displacements of the nanotube. Incorporating this SQUID into superconducting resonators and qubits should enable the detection and manipulation of nanotube mechanical quantum states at the single-phonon level.

Modal interactions of flexural and torsional vibrations in a microcantilever.

The nonlinear interactions between flexural and torsional modes of a microcantilever are experimentally studied. The coupling is demonstrated by measuring the frequency response of one mode, which is sensitive to the motion of another resonance mode. The flexural-flexural, torsional-torsional and flexural-torsional modes are coupled due to nonlinearities, which affect the dynamics at high vibration amplitudes and cause the resonance frequency of one mode to depend on the amplitude of the other modes. We also investigate the nonlinear dynamics of torsional modes, which cause a frequency stiffening of the response. By simultaneously driving another torsional mode in the nonlinear regime, the nonlinear response is tuned from stiffening to weakening. By balancing the positive and negative cubic nonlinearities a linear response is obtained for the strongly driven system. The nonlinear modal interactions play an important role in the dynamics of multi-mode scanning probe microscopes.