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Molecular junctions are building blocks for constructing future nanoelectronic devices that enable the investigation of a broad range of electronic transport properties within nanoscale regions. Crossing both the nanoscopic and mesoscopic length scales, plasmonics lies at the intersection of the macroscopic photonics and nanoelectronics, owing to their capability of confining light to dimensions far below the diffraction limit. Research activities on plasmonic phenomena in molecular electronics started around 2010, and feedback between plasmons and molecular junctions has increased over the past years. These efforts can provide new insights into the near-field interaction and the corresponding tunability in properties, as well as resultant plasmon-based molecular devices. This Review presents the latest advancements of plasmonic resonances in molecular junctions and details the progress in plasmon excitation and plasmon coupling. We also highlight emerging experimental approaches to unravel the mechanisms behind the various types of light–matter interactions at molecular length scales, where quantum effects come into play. Finally, we discuss the potential of these plasmonic–electronic hybrid systems across various future applications, including sensing, photocatalysis, molecular trapping and active control of molecular switches. [Figure not available: see fulltext.].

The coexistence of different properties in the same material often results in exciting physical effects. At low temperatures, the pyrite transition-metal disulphide NiS2 hosts both antiferromagnetic and weak ferromagnetic orders, along with surface metallicity dominating its electronic transport. The interplay between such a complex magnetic structure and surface-dominated conduction in NiS2, however, is still not understood. A possible reason for this limited understanding is that NiS2 has been available primarily in bulk single-crystal form, which makes it difficult to perform studies combining magnetometry and transport measurements with high spatial resolution. Here, NiS2 nanoflakes are produced via mechanical cleaving and exfoliation of NiS2 single crystals and their properties are studied on a local (micron-size) scale. Strongly field-asymmetric magnetotransport features are found at low temperatures, which resemble those of more complex magnetic thin film heterostructures. Using nitrogen vacancy magnetometry, these magnetotransport features are related to exchange-bias-type effects between ferromagnetic and antiferromagnetic regions forming near step edges at the nanoflake surface. Nanoflakes with bigger steps exhibit giant magnetoresistance, which suggests a strong influence of magnetic spin textures at the NiS2 surface on its electronic transport. These findings pave the way for the application of NiS2 nanoflakes in van der Waals heterostructures for low-temperature spintronics and superconducting spintronics.

We report transport measurements on tunable single-molecule junctions of the organic perchlorotrityl radical molecule, contacted with gold electrodes at low temperature. The current-voltage characteristics of a subset of junctions shows zero-bias anomalies due to the Kondo effect and in addition elevated magnetoresistance (MR). Junctions without Kondo resonance reveal a much stronger MR. Furthermore, we show that the amplitude of the MR can be tuned by mechanically stretching the junction. On the basis of these findings, we attribute the high MR to an interference effect involving spin-dependent scattering at the metal-molecule interface and assign the Kondo effect to the unpaired spin located in the center of the molecule in asymmetric junctions.

Developing optoelectronic devices, biological or chemical sensors, displays, and other devices based on nanoparticles (NP) requires designing tailored NP assemblies on solid substrates, and often w...

We study voltage-induced conductance changes of Pb, Au, Al, and Cu atomic contacts. The experiments are performed in vacuum at low temperature using mechanically controllable break junctions. We determine switching histograms, i.e., distribution functions of switching voltages and switching currents, as a function of the conductance. We observe a clear material dependence: Au reveals the highest and almost conductance-independent switching voltage, while Al has the lowest with a pronounced dependence on the conductance. The theoretical study uses density functional theory and a generalized Langevin equation considering the pumping of particular phonon modes. We identify a runaway voltage as the threshold at which the pumping destabilizes the atomic arrangement. We find qualitative agreement between the average switching voltage and the runaway voltage regarding the material and conductance dependence and contact-to-contact variation of the average characteristic voltages, suggesting that the phonon pumping is a relevant mechanism driving the rearrangements in the experimental contacts.

In a Josephson junction, which is the central element in superconducting quantum technology, irreversibility arises from abrupt slips of the gauge-invariant quantum phase difference across the contact. A quantum phase slip (QPS) is often visualized as the tunneling of a flux quantum in the transverse direction to the superconducting weak link, which produces dissipation. Here, we detect the instantaneous heat release caused by a QPS in a Josephson junction using time-resolved electron thermometry on a nanocalorimeter, signaled by an abrupt increase of the local electronic temperature in the weak link and subsequent relaxation back to equilibrium. Beyond providing a cornerstone in experimental quantum thermodynamics in form of observation of heat in an elementary quantum process, this result sets the ground for experimentally addressing the ubiquity of dissipation, including that in superconducting quantum sensors and qubits.

International audience; We report on the first systematic transport study of alkynyl-ended oligophenyl-diethynyl (OPA) single-molecule junctions with direct Au-C anchoring scheme at low temperature using the mechanically controlled break junction technique. Through quantitative statistical analysis of opening traces, conductance histograms and density functional theory studies, we identified different types of junctions, classified by their conductance and stretching behavior, for OPA molecules between Au electrodes with two to four phenyl rings. We performed inelastic electron tunneling spectroscopy and observed the excitation of Au-C vibrational modes confirming the existence of Au-C bonds at low temperature and compared the stability of molecule junctions upon mechanical stretching. Our findings reveal the huge potential for future functional molecule transport studies at low temperature using alkynyl endgroups.

Two-dimensional (2D) materials prepared by a wet-chemical precipitation route exhibit many unique properties and high potential in various fields. Still, simple, rational and green fabrication of target materials remains challenging due to the lack of a guiding principle. Here, we propose a universal qualitative model for 2D materials grown for layered and non-layered crystal structures by wet-chemical precipitation, which is confirmed by both theoretical simulation and experimental results. It demonstrates that 2D growth can be obtained by only tuning reaction concentration and temperature. This model not only has been applied to fabricate more than 30 different 2D nanomaterials in water at room temperature in the absence of additives, but also is promising in optimizing the experimental design of numerous other 2D nanomaterials.

Materials with strongly correlated electrons often exhibit interesting physical properties. An example of these materials is the layered oxide perovskite Sr2RuO4, which has been intensively investigated due to its unusual properties. Whilst the debate on the symmetry of the superconducting state in Sr2RuO4 is still ongoing, a deeper understanding of the Sr2RuO4 normal state appears crucial as this is the background in which electron pairing occurs. Here, by using low-energy muon spin spectroscopy we discover the existence of surface magnetism in Sr2RuO4 in its normal state. We detect static weak dipolar fields yet manifesting at an onset temperature higher than 50 K. We ascribe this unconventional magnetism to orbital loop currents forming at the reconstructed Sr2RuO4 surface. Our observations set a reference for the discovery of the same magnetic phase in other materials and unveil an electronic ordering mechanism that can influence electron pairing with broken time reversal symmetry. Strontium Ruthenate, Sr2RuO4, displays a remarkable number of intriguing physical phenomena, from superconductivity, to strain-induced ferromagnetism. Here, using low-energy muon spectroscopy, Fittipaldi et al. demonstrate the existence of unconventional magnetism at the surface of Sr2RuO4 in its normal state and without any applied strain.

We report measurements of the shot noise of atomic contacts of the ferromagnets cobalt and gadolinium and the strong paramagnets palladium, platinum, and iridium. The contacts are fabricated using the mechanically controlled break-junction technique at 4 K. Single-atom contacts of Co and Gd with conductance smaller than the conductance quantum show reduced noise compared to the expectation for the spin-degenerate single-channel case. We discuss by how far this observation gives evidence for spin-polarized transport. Pd, Pt, and Ir reveal noise levels which are above, but close to the threshold to the spin-degenerate single-channel situation. Since for such multivalent metals more than one channel is expected to contribute to the transport, our findings do not exclude spin-polarized transport for these elements. We observe an anticorrelation between the minimum noise and the bulk Stoner parameter of these elements, supporting that spin polarization might be reflected in the shot-noise signal in strong paramagnets.

We fabricate and characterize vertical molecular junctions consisting of self-assembled monolayers of diarylethene (DAE) contacted by a multilayer graphene (MLG) electrode on the top and gold on the bottom. The DAE molecular junctions show two stable electrical states, a closed state (high conductance) or an open state (low conductance), which are created upon illumination with UV or visible light, respectively. For the Au-DAE-MLG junction structure, we observe that the current levels between the two conductance states are separated by 2 orders of magnitude. However, in a real-time measurement, we observe only unidirectional switching behavior from the open to the closed state.

Chemical coupling of functional molecules on top of the so-called platform molecules allows the formation of functional self-assembled monolayers (SAMs). An often-used example of such a platform is triazatriangulenium (TATA), which features an extended aromatic core providing good electronic contact to the underlying metal surface. Here, we present a study of the SAM formation of a TATA platform on Au(111) employing scanning tunneling microscopy (STM) under ambient atmospheric conditions. In solution, the TATA platform is stabilized by BF4 counterions, while after deposition on a gold substrate, the localization of the BF4 counterions remains unknown. We used 1,2,4-trichlorobenzene as a solvent of TATA–BF4 to induce SAM formation on a heated (∼50 °C) Au substrate. We show by STM how to detect and distinguish TATA–BF4 from TATA platforms, which lost their BF4 counterions. Finally, we observe a change of the counterion position on the SAM during the STM scanning, which we explain by an electric-field-induced decrease of the electrostatic interaction in TATA–BF4 on the surface. We applied DFT calculations to reveal the influence of the gold lattice and the electric field of the STM tip on the stability of TATA–BF4 physisorbed on the surface. published

We examined the modified electronic structure and single-carrier transport of individual hybrid core–shell metal–semiconductor Au-ZnS quantum dots (QDs) using a scanning tunnelling microscope. Nearly monodisperse ultra-small QDs are achieved by a facile wet chemical route. The exact energy structures are evaluated by scanning tunnelling spectroscopy (STS) measurements at 300 mK for the individual nanoobjects starting from the main building block Au nanocrystals (NCs) to the final Au-ZnS QDs. The study divulges the evolution of the energy structure and the charge transport from the single metallic building block core to the core–shell metal–semiconductor QDs. Furthermore, we successfully determined the contributions related to the quantum-confinement-induced excitonic band structure of the ZnS nano-shell and the charging energy of the system by applying a semi-empirical approach considering a double barrier tunnel junction (DBTJ) arrangement. We detect strong conductance peaks in Au-ZnS QDs due to the overlapping of the energy structure of the Au nano-core and the discrete energy states of the semiconductor ZnS nano-shell. Our findings will help in understanding the electronic properties of metal–semiconductor QDs. The outcomes therefore have the potential to fabricate tailored metal–semiconductor QDs for single-electron devices.

The coupling of a superconductor to a different material often results in a system with unconventional superconducting properties. A conventional superconductor is a perfect diamagnet expelling magnetic fields out of its volume, a phenomenon known as Meissner effect. Here, we show that the simple adsorption of a monolayer of chiral molecules, which are non-magnetic in solution, onto the surface of a conventional superconductor can markedly change its diamagnetic Meissner response. By measuring the internal magnetic field profile in superconducting Nb thin films under an applied transverse field by low-energy muon spin rotation spectroscopy, we demonstrate that the local field profile inside Nb is considerably modified upon molecular adsorption in a way that also depends on the applied field direction. The modification is not limited to the chiral molecules/Nb interface, but it is long ranged and occurs over a length scale comparable to the superconducting coherence length. Zero-field muon spin spectroscopy measurements in combination with our theoretical analysis show that odd-frequency spin-triplet states induced by the chiral molecules are responsible for the modification of the Meissner response observed inside Nb. These results indicate that a chiral molecules/superconductor system supports odd-frequency spin-triplet pairs due to the molecules acting as a spin active layer and therefore they imply that such system can be used as a simpler alternative to superconductor/ferromagnet or superconductor/topological insulator hybrids for the generation and manipulation of unconventional spin-triplet superconducting states., 13 pages and 5 figures plus Appendixes

We investigate the sideband spectra of a driven nonlinear mode with its eigenfrequency being modulated at a low frequency (

We have studied the spatial distribution of charges trapped at the surface of superfluid helium in the inhomogeneous electric field of a metallic tip close to the liquid surface. The electrostatic pressure of the charges generates a deformation of the liquid surface, leading to a “hillock” (called “Taylor cone”) or “dimple”, depending on whether the tip is placed above or below the surface. We use finite element simulations for calculating the surface profile and the corresponding charge density in the vicinity of the tip. Typical electric fields E are in the range of a few kV/cm, the maximum equilibrium surface deformations have a height on the order of (but somewhat smaller than) the capillary length of liquid 4He (0.5 mm), and the maximum number density of elementary charges in a hillock or dimple, limited by an electrohydrodynamic instability, is some 1013 m−2. These results can be used to determine the charge density at a liquid helium surface from the measured surface profile. They also imply that inhomogeneous electric fields at a bulk helium surface do not allow one to increase the electron density substantially beyond the limit for a homogeneous field, and are therefore not feasible for reaching a density regime where surface state electrons are expected to show deviations from the classical behavior. Some alternative solutions are discussed.

Fitting the I/V curves of molecular junctions by simple analytical models is often done to extract relevant molecular parameters such as energy level alignment or interfacial electronic coupling to build up useful property-relationships. However, such models can suffer from severe limitations and hence provide unreliable molecular parameters. This is illustrated here by extracting key molecular parameters by fitting computed voltage-dependent transmission spectra and by comparing them to the values obtained by fitting the calculated I/V curves with a typical Lorentzian model used in the literature. Doing so, we observe a large discrepancy between the two sets of values which warns us about the risks of using simple fitting expressions. Interestingly, we demonstrate that the quality of the fit can be improved by imposing the low bias conductance and Seebeck coefficient of the junction to be recovered in the fitting procedure.

International audience; Fitting the I/V curves of molecular junctions by simple analytical models is often done to extract relevant molecular parameters such as energy level alignment or interfacial electronic coupling to build up useful property-relationships. However, such models can suffer from severe limitations and hence provide unreliable molecular parameters. This is illustrated here by extracting key molecular parameters by fitting computed voltage-dependent transmission spectra and by comparing them to the values obtained by fitting the calculated I/V curves with a typical Lorentzian model used in the literature. Doing so, we observe a large discrepancy between the two sets of values which warns us about the risks of using simple fitting expressions. Interestingly, we demonstrate that the quality of the fit can be improved by imposing the low bias conductance and Seebeck coefficient of the junction to be recovered in the fitting procedure.

Diarylethene molecules are discussed as possible optical switches, which can reversibly transition between completely conjugated (closed) and nonconjugated (open) forms with different electrical conductance and optical absorbance, by exposure to UV and visible light. However, in general the opening reaction exhibits much lower quantum yield than the closing process, hindering their usage in optoelectronic devices. To enhance the opening process, which is supported by visible light, we employ the plasmonic field enhancement of gold films perforated with nanoholes. We show that gold nanohole arrays reveal strong optical transmission in the visible range (∼60%) and pronounced enhancement of field intensities, resulting in around 50% faster switching kinetics of the molecular species in comparison with quartz substrates. The experimental UV-vis measurements are verified with finite-difference time-domain simulation that confirm the obtained results. Thus, we propose gold nanohole arrays as transparent and conductive plasmonic material that accelerates visible-light-triggered chemical reactions including molecular switching.

We have fabricated organically capped stable luminescent silicon nanocrystals with narrow size distribution by a novel, high yield and easy to implement technique. We demonstrate transport measurements of individual silicon nanocrystals by scanning tunnelling microscopy at a low temperature in a double-barrier tunnel junction arrangement in which we observed pronounced single electron tunnelling effects. The tunnelling spectroscopy of these nanocrystals with different diameters reveals quantum confinement induced bandgap modifications. Furthermore, from the features in the tunnelling spectra, we differentiate several energy contributions arising from electronic interactions inside the nanocrystal. By applying a magnetic field, we have detected a variation in the differential conductance profile that we attribute to arising from higher order tunnelling processes. We have also systematically simulated our experimental data with the Orthodox theory, and the results show good agreement with the experiment. The study establishes a correlation between the nanocrystal size and quantum confinement induced band-structure modifications which will pave the way to devise tailored nanocrystals. published

We study experimentally and theoretically the phenomenon of persistent response in ultra-strongly driven membrane resonators. This term denotes the development of a vibrating state with nearly constant amplitude over an extreme wide frequency range. We reveal the underlying mechanism of the persistent response state by directly imaging the vibrational state using advanced optical interferometry. We argue that the persistent state is related to the nonlinear interaction between higher order flexural modes and higher-order overtones of the driven mode. Finally, we propose a stability diagram for the different vibrational states that the membrane can adopt.

Single-molecule devices with low variability can be made by decoupling electronic transport and chemical attachment to the electrode.

The knowledge of the electronic structure and dynamics of nanoparticles is a prerequisite to develop miniaturized single-electron devices based on nanoparticles. Low-temperature transport measurements of individual stable metallic nanoparticles enable unravelling the system specific electronic structure while ultrafast optical spectroscopy gives access to the electron dynamics. In this work, we investigate bare and thiol-functionalized gold nanoparticles. For the latter, we employ a fast and low-cost fabrication technique which yields nanoparticles with narrow size distribution. Using relatively long thiol-ended alkane chains for the functionalization modifies the electronic density of states of the nanoparticles. The study of decay dynamics of surface-plasmon-related hot electrons reveals the presence of electronic states at the interface which serve as a fast decay channel for electronic relaxation. By low-temperature scanning tunnelling microscopy we precisely investigate the energy scales and electronic interactions relevant for the tunnel charge transport through this system. We observe that the interaction between the functional ligand and the substrate on which the nanoparticles reside also influences the electronic transport. The procedure that we employ can be easily adapted to other metallic nanoparticles. Our findings are therefore important for incorporating them into single-electron devices.

We study the vibrational motion of mechanical resonators under strong drive in the strongly nonlinear regime. By imaging the vibrational state of rectangular silicon nitride membrane resonators and by analyzing the frequency response using optical interferometry, we show that, upon increasing the driving strength, the membrane adopts a peculiar deflection pattern formed by concentric rings superimposed onto the drum head shape of the fundamental mode. Such a circular symmetry cannot be described as a superposition of a small number of excited linear eigenmodes. Furthermore, different parts of the membrane vibrate at different multiples of the drive frequency, an observation that we denominate as "localization of overtones." We introduce a phenomenological model that is based on the coupling of a small number of effective nonlinear resonators, representing the different parts of the membrane, and that describes the experimental observations correctly. published

Pairs of electrodes with nanometer gap, termed as nano-gapped electrodes, are fundamental building blocks for the fabrication of nanometer-sized devices and are essential for the examination of molecular properties and extreme nano-optics. Although modern fabrication techniques make it feasible to fabricate nanometer gaps, it is still a formidable challenge to fabricate adjustable gaps arrays with angstrom precision. Here, we demonstrate that in-situ adjustable nanogaps (arrays) with sub-angstrom precision can be fabricated via laser irradiation on the substrate which supports the electrode pairs. We further demonstrate that atomic-level metal contacts can be switched and the direction of the switching can be selectively controlled by the laser irradiation position. By varying the laser power gradually, the nanogap’s size can be continuously changed, providing a reliable break junction technique to address the properties of single-molecule junctions. The small spatial focus size of the laser beam makes it feasible to realize addressable on-chip molecular junction arrays.

We report the development of a novel method to determine the thermopower of atomic-sized gold contacts at low temperature. For these measurements a mechanically controllable break junction (MCBJ) system is used and a laser source generates a temperature difference of a few kelvins across the junction to create a thermo-voltage. Since the temperature difference enters directly into the Seebeck coefficient S = −ΔV/ΔT, the determination of the temperature plays an important role. We present a method for the determination of the temperature difference using a combination of a finite element simulation, which reveals the temperature distribution of the sample, and the measurement of the resistance change due to laser heating of sensor leads on both sides next to the junction. Our results for the measured thermopower are in agreement with recent reports in the literature.

In this article we present the fabrication of freestanding thin-film nanobridges of Ir. We perform magnetoconductance (MC) measurements of atomic contacts and monoatomic chains of Ir, realized by the mechanically controlled break-junction method. We observe continuous changes of the MC on the field scale of several tesla, as observed earlier for atomic-size contacts of two other strong paramagnets, Pd and Pt. The amplitude and the shape of the MC depend on the orientation of the magnetic field as well as on subtle details of the atomic arrangement, as confirmed by stretching studies of the contacts. Both positive dominant MC and negative dominant MC occur and are attributed to collinear or noncollinear alignment of the magnetic moments of the electrodes, respectively. By careful manipulation of the chain geometry we are able to study the transition between these two cases, which is hallmarked by a complex MC behavior. For special arrangements the MC almost vanishes. Our findings are in agreement with recent calculations of the geometry dependence of the magnetic anisotropy energy and open a route to tailor the MC behavior as required for particular applications.

Computer, Tablets, Mobiltelefone werden immer leistungsfahiger, weil immer mehr und immer kleinere elektronische Bauteile, uberwiegend Kondensatoren und Transistoren, darin enthalten sind. Dabei dienen die Kondensatoren zum Speichern der Information und Transistoren als Schalter. Beides wird ublicherweise aus dem Halbleitermaterial Silizium hergestellt. Wenn die Miniaturisierung so weitergeht, konnten demnachst einzelne Molekule oder Atome Schaltfunktionen ubernehmen, die bisher von Transistoren ausgefuhrt werden. In diesem Kapitel wird erklart, wie man die Funktion solch kleiner Schalter erforschen kann. Auserdem wird ein Beispiel gezeigt fur ein Speicher- und Schaltelement, das durch Umlagerung eines einzelnen Atoms betrieben wird.

Heat management at the nanoscale is an issue of increasing importance. In optoelectronic devices the transport and decay of plasmons contribute to the dissipation of heat. By comparison of experimental data and simulations we demonstrate that it is possible to gain quantitative information about excitation, propagation and decay of surface plasmon polaritons (SPPs) in a thin gold stripe supported by a silicon membrane. The temperature-dependent optical transmissivity of the membrane is used to determine the temperature distribution around the metal stripe with high spatial and temporal resolution. This method is complementary to techniques where the propagation of SPPs is monitored optically, and provides additional information which is not readily accessible by other means. In particular, we demonstrate that the thermal conductivity of the membrane can also be derived from our analysis. The results presented here show the high potential of this tool for heat management studies in nanoscale devices. published

We study the magnetoresistance of aluminium 'double-networks' formed by connecting the vertexes of nano-loops with relatively long wires, creating two interlaced subnetworks of small and large loops (SL and LL, respectively). Far below the critical temperature, Aharonov-Bohm like quantum interference effects are observed for both the LL and the SL subnetworks. When approaching T c, both exhibit the usual Little-Parks oscillations, with periodicity of the superconducting flux quantum Φ 0 =h/2e. For one sample, with a relatively large coherence length, ξ, at temperatures very close to T c, the Φ 0 periodicity of the SL disappears, and the waveform of the first period is consistent with that predicted recently for loops with a size a < ξ, indicating a crossover to 2Φ 0 periodicity. published

We report measurements of the shot noise on single-molecule Au-1,4-benzenedithiol-Au junctions, fabricated with the mechanically controllable break junction (MCBJ) technique at 4.2 K in a wide range of conductance values from 10(-2) to 0.24 conductance quanta. We introduce a simple measurement scheme using a current amplifier and a spectrum analyzer and that does not imply special requirements regarding the electrical leads. The experimental findings provide evidence that the current is carried by a single conduction channel throughout the whole conductance range. This observation suggests that the number of channels is limited by the Au-thiol bonds and that contributions due to direct tunneling from the Au to the π-system of the aromatic ring are negligible also for high conductance. The results are supported by quantum transport calculations using density functional theory.