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Helical molecules have been proposed as candidates for producing spin-polarized currents, even at room conditions, due to their chiral asymmetry. However, describing their transport mechanism in single molecular junctions is not straightforward. In this work, we show the synthesis of two novel kinds of dithia[11]helicenes to study their electronic transport in break junctions among a series of three helical molecules: dithia[ n ]helicenes, with n = 7, 9, and 11 molecular units. Our experimental measurements and clustering-based analysis demonstrate low conductance values that remain similar across different applied voltages and molecules. Additionally, we assess the length dependence of the conductance for each helicene, revealing an exponential decay characteristic of off-resonant transport. This behavior is primarily attributed to the misalignment between the energy levels of the molecule-electrodes system. The length dependence trend described above is supported by ab initio calculations, further confirming an off-resonant transport mechanism.

We present the electrical characterization of wafer-scale graphene devices fabricated with an industrially-relevant, contact-first integration scheme combined with Al 2 O 3 encapsulation via atomic layer deposition. All the devices show a statistically significant reduction in the Dirac point position,Vcnp, from around +47 V to between -5 and 5 V (on 285 nm SiO 2 ), while maintaining the mobility values. The data and methods presented are relevant for further integration of graphene devices, specifically sensors, at the back-end-of-line of a standard CMOS flow., (© 2024 IOP Publishing Ltd.)

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.

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.

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, CH 3 , Br or NH 2 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.

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 MoS 2 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.

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 cm 2 /(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.

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.

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.

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.

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.

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.

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.

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.

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., (Copyright © 2014, American Association for the Advancement of Science.)

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.

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.

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.

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., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Single-layer MoS(2) is an attractive semiconducting analogue of graphene that combines high mechanical flexibility with a large direct bandgap of 1.8 eV. On the other hand, bulk MoS(2) is an indirect bandgap semiconductor similar to silicon, with a gap of 1.2 eV, and therefore deterministic preparation of single MoS(2) layers is a crucial step toward exploiting the large direct bandgap of monolayer MoS(2) in electronic, optoelectronic, and photovoltaic applications. Although mechanical and chemical exfoliation methods can be used to obtain high quality MoS(2) single layers, the lack of control in the thickness, shape, size, and position of the flakes limits their usefulness. Here we present a technique for controllably thinning multilayered MoS(2) down to a single-layer two-dimensional crystal using a laser. We generate single layers in arbitrary shapes and patterns with feature sizes down to 200 nm and show that the resulting two-dimensional crystals have optical and electronic properties comparable to that of pristine exfoliated MoS(2) single layers.

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.

We report an in situ transmission electron microscopy (TEM) imaging of grain growth in a Pt nanobridge induced by a high electric current density. The change in morphology at the nanoscale was recorded in real time together with the electrical characterization of the Pt nanobridge. We find a drop in the differential resistance as the voltage across the bridge is increased; TEM inspection shows that this coincides with thermally induced grain growth, indicating that a reduction of grain boundary scattering is the cause of the resistance decrease.

We have measured the backaction of a dc superconducting quantum interference device (SQUID) position detector on an integrated 1 MHz flexural resonator. The frequency and quality factor of the micromechanical resonator can be tuned with bias current and applied magnetic flux. The backaction is caused by the Lorentz force due to the change in circulating current when the resonator displaces. The experimental features are reproduced by numerical calculations using the resistively and capacitively shunted junction model.

A theoretical and experimental investigation is presented on the intermodal coupling between the flexural vibration modes of a single clamped-clamped beam. Nonlinear coupling allows an arbitrary flexural mode to be used as a self-detector for the amplitude of another mode, presenting a method to measure the energy stored in a specific resonance mode. The observed complex nonlinear dynamics are quantitatively captured by a model based on coupling of the modes via the beam extension; the same mechanism is responsible for the well-known Duffing nonlinearity in clamped-clamped beams.

We have fabricated nanometer-spaced electrodes on electron-transparent silicon nitride membranes. A thin Cr/Au layer is evaporated on the backside of the membrane which serves as a gate electrode. Using these devices, we have performed three-terminal electron transport measurements on gold nano-particles at liquid helium temperature. Coulomb Blockade features have been observed and the capacitance to the gate has been extracted. After transport measurements, the Cr/Au back gate is removed and the devices are inspected with a transmission-electron microscope (TEM). TEM inspection reveals the presence of a few nano-particles in the nanogap, which is in agreement with the transport measurements. In addition, the nano-particle size as observed by TEM coincides with the one estimated from the gate capacitance value.

Nanoscale resonators that oscillate at high frequencies are useful in many measurement applications. We studied a high-quality mechanical resonator made from a suspended carbon nanotube driven into motion by applying a periodic radio frequency potential using a nearby antenna. Single-electron charge fluctuations created periodic modulations of the mechanical resonance frequency. A quality factor exceeding 10(5) allows the detection of a shift in resonance frequency caused by the addition of a single-electron charge on the nanotube. Additional evidence for the strong coupling of mechanical motion and electron tunneling is provided by an energy transfer to the electrons causing mechanical damping and unusual nonlinear behavior. We also discovered that a direct current through the nanotube spontaneously drives the mechanical resonator, exerting a force that is coherent with the high-frequency resonant mechanical motion.

Low-temperature transport spectroscopy measurements on a suspended few-hole carbon nanotube quantum dot are presented, showing a gate-dependent harmonic excitation spectrum which, strikingly, occurs in the Coulomb-blockade regime. The quantized excitation energy corresponds to the scale expected for longitudinal vibrations of the nanotube. The electronic transport processes are identified as cotunnel-assisted sequential tunneling, resulting from nonequilibrium occupation of the mechanical mode. They appear only above a high-bias threshold at the scale of electronic nanotube excitations. We discuss models for the pumping process that explain the enhancement of the nonequilibrium occupation and show that it is connected to a subtle interplay between electronic and vibrational degrees of freedom.

Transport through single molecules has been studied using different test beds. In this paper we focus on three-terminal devices in which a molecule bridges the gap between two gold electrodes and a third electrode-the gate-is able to modulate the conduction properties of the junction. Depending on the electronic coupling, Γ, between the molecule and the gold electrodes, different transport regimes can be distinguished. We show measurements on junctions incorporating different single-molecule systems which demonstrate the distinction between these regimes, as well as the experimental limitations in controlling the exact value of Γ.

We report transport measurements through a single-molecule magnet, the Mn12 derivative [Mn12O12(O2C-C6H4-SAc)16(H2O)4], in a single-molecule transistor geometry. Thiol groups connect the molecule to gold electrodes that are fabricated by electromigration. Striking observations are regions of complete current suppression and excitations of negative differential conductance on the energy scale of the anisotropy barrier of the molecule. Transport calculations, taking into account the high-spin ground state and magnetic excitations of the molecule, reveal a blocking mechanism of the current involving nondegenerate spin multiplets.

We have fabricated longitudinal nanoconstrictions in the charge-density wave conductor (CDW) NbSe3 using a focused ion beam and using a mechanically controlled break-junction technique. Conductance peaks are observed below the TP1=145 K and TP2=59 K CDW transitions, which correspond closely with previous values of the full CDW gaps 2Delta1 and 2Delta2 obtained from photoemission. These results can be explained by assuming CDW-CDW tunneling in the presence of an energy gap corrugation epsilon2 comparable to Delta2, which eliminates expected peaks at +/-|Delta1+Delta2|. The nanometer length scales our experiments imply indicate that an alternative explanation based on tunneling through back-to-back CDW-normal-conductor junctions is unlikely.

Current-voltage characteristics of suspended single-wall carbon nanotube quantum dots show a series of steps equally spaced in voltage. The energy scale of this harmonic, low-energy excitation spectrum is consistent with that of the longitudinal low-k phonon mode (stretching mode) in the nanotube. Agreement is found with a Franck-Condon-based model in which the phonon-assisted tunneling process is modeled as a coupling of electronic levels to underdamped quantum harmonic oscillators. A comparison with this model indicates a rather strong electron-phonon coupling factor of order unity.

We measure transport through gold grain quantum dots fabricated using electromigration, with magnetic impurities in the leads. A Kondo interaction is observed between dot and leads, but the presence of magnetic impurities results in a gate-dependent zero-bias conductance peak that is split due to a RKKY interaction between the spin of the dot and the static spins of the impurities. A magnetic field restores the single Kondo peak in the case of an antiferromagnetic RKKY interaction. This system provides a new platform to study Kondo and RKKY interactions in metals at the level of a single spin.

We report magnetic field spectroscopy measurements in carbon nanotube quantum dots exhibiting fourfold shell structure in the energy level spectrum. The magnetic field induces a large splitting between the two orbital states of each shell, demonstrating their opposite magnetic moment and determining transitions in the spin and orbital configuration of the quantum dot ground state. We use inelastic cotunneling spectroscopy to accurately resolve the spin and orbital contributions to the magnetic moment. A small coupling is found between orbitals with opposite magnetic moment leading to anticrossing behavior at zero field.

We report a systematic study of the transport properties of coupled one-dimensional metallic chains as a function of the number of parallel chains. When the number of parallel chains is less than 2000, the transport properties show power-law behavior on temperature and voltage, characteristic for one-dimensional systems.