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We investigate gold-4,4'-bipyridine-gold single-molecule junctions with the mechanically controllable break junction technique at cryogenic temperature ($T=4.2\,\text{K}$). We observe bistable probabilistic conductance switching between the two molecular binding configurations, influenced both by the mechanical actuation, and the applied voltage. We demonstrate that the relative dominance of the two conductance states is tunable by the electrode displacement, whereas the voltage manipulation induces an exponential speedup of both switching times. The detailed investigation of the voltage-tunable switching rates provides an insight into the possible switching mechanisms.

Graphene nanogaps are considered as essential building blocks of two-dimensional electronic circuits, as they offer the possibility to interconnect a broad range of atomic-scale objects. Here we provide an insight into the microscopic processes taking place during the formation of graphene nanogaps through the detailed analysis of their low-frequency noise properties. Following the evolution of the noise level, we identify the fundamentally different regimes throughout the nanogap formation. By modeling the resistance and bias dependence of the noise, we resolve the major noise-generating processes: atomic-scale junction-width fluctuations in the nanojunction regime and sub-atomic gap-size fluctuations in the nanogap regime. As a milestone toward graphene-based atomic electronics, our results facilitate the automation of an optimized electrical breakdown protocol for high yield graphene nanogap fabrication., npj 2D Materials and Applications, 5 (1), ISSN:2397-7132

In this study, the possibilities of noise tailoring in filamentary resistive switching memory devices are investigated. To this end, the resistance and frequency scaling of the low-frequency 1/f-type noise properties are studied in representative mainstream material systems. It is shown that the overall noise floor is tailorable by the proper material choice, as demonstrated by the order-of-magnitude smaller noise levels in Ta2O5 and Nb2O5 transition-metal oxide memristors compared to Ag-based devices. Furthermore, the variation of the resistance states allows orders-of-magnitude tuning of the relative noise level in all of these material systems. This behavior is analyzed in the framework of a point-contact noise model highlighting the possibility for the disorder-induced suppression of the noise contribution arising from remote fluctuators. These findings promote the design of multipurpose resistive switching units, which can simultaneously serve as analog-tunable memory elements and tunable noise sources in probabilistic computing machines., ACS Applied Materials & Interfaces, 13 (6), ISSN:1944-8244, ISSN:1944-8252

We study the vulnerability of single-molecule nanowires against a temporary disconnection of the junction. To this end, we compare the room and low-temperature junction formation trajectories along the opening and closing of gold-4,4'-bipyridine-gold single-molecule nanowires. In the low-temperature measurements, the cross-correlations between the opening and subsequent closing conductance traces demonstrate a strong structural memory effect: around half of the molecular opening traces exhibit similar, statistically dependent molecular features as the junction is closed again. This means that the junction stays rigid and the molecule remains protruding from one electrode even after the rupture of the junction, and therefore, the same single-molecule junction can be reestablished if the electrodes are closed again. In the room-temperature measurements, however, weak opening-closing correlations are found, indicating a significant rearrangement of the junction after the rupture and the related loss of structural memory effects.

Nanometer-scale resistive switching devices operated in the metallic conductance regime offer ultimately scalable and widely reconfigurable hardware elements for novel in-memory and neuromorphic computing architectures. Moreover, they exhibit high operation speed at low power arising from the ease of the electric-field-driven redistribution of only a small amount of highly mobile ionic species upon resistive switching. We investigate the memristive behavior of a so-far less explored representative of this class, the Ag/AgI material system in a point contact arrangement established by the conducting PtIr tip of a scanning probe microscope. We demonstrate stable resistive switching duty cycles and investigate the dynamical aspects of non-volatile operation in detail. The high-speed switching capabilities are explored by a custom-designed microwave setup that enables time-resolved studies of subsequent set and reset transitions upon biasing the Ag/AgI/PtIr nanojunctions with sub-nanosecond voltage pulses. Our results demonstrate the potential of Ag-based filamentary memristive nanodevices to serve as the hardware elements in high-speed neuromorphic circuits., Beilstein Journal of Nanotechnology, 11, ISSN:2190-4286

Atomic synapses represent a special class of memristors whose operation relies on the formation of metallic nanofilaments bridging two electrodes across an insulator. Due to the magnifying effect of this narrowest cross section on the device conductance, a nanometer-scale displacement of a few atoms grants access to various resistive states at ultimately low energy costs, satisfying the fundamental requirements of neuromorphic computing hardware. However, device engineering lacks the complete quantum characterization of such filamentary conductance. Here we analyze multiple Andreev reflection processes emerging at the filament terminals when superconducting electrodes are utilized. Thereby, the quantum PIN code, i.e., the transmission probabilities of each individual conduction channel contributing to the conductance of the nanojunctions, is revealed. Our measurements on Nb2O5 resistive switching junctions provide profound experimental evidence that the onset of the high conductance ON state is manifested via the formation of truly atomic-sized metallic filaments., Nano Letters, 20 (2), ISSN:1530-6984, ISSN:1530-6992

Break-junction measurements are typically aimed at characterizing electronic properties of single molecules bound between two metal electrodes. Although these measurements have provided structure-function relationships for such devices, there is little work that studies the impact of molecule-molecule interactions on junction characteristics. Here, we use a scanning tunneling microscope based break-junction technique to study pi-stacked dimer junctions formed with two amine-terminated conjugated molecules. We show that the conductance, force and flicker noise of such dimers differ dramatically when compared with the corresponding monomer junctions and discuss the implications of these results on intra- and inter-molecular charge transport.

The resistive switching behavior in SiOx-based phase change memory devices confined by few nanometer wide graphene nanogaps is investigated. Our experiments and analysis reveal that the switching dynamics is not only determined by the commonly observed bias voltage dependent set and reset times. We demonstrate that an internal time scale, the dead time, plays a fundamental role in the system’s response to various driving signals. We associate the switching behavior with the formation of microscopically distinct SiOx amorphous and crystalline phases between the graphene electrodes. The reset transition is attributed to an amorphization process due to a voltage driven self-heating; it can be triggered at any time by appropriate voltage levels. In contrast, the formation of the crystalline ON state is conditional and only occurs after the completion of a thermally assisted structural rearrangement of the as-quenched OFF state which takes place within the dead time after a reset operation. Our results demonst...

The microscopic origins and technological impact of 1/f type current fluctuations in Ag based, filamentary type resistive switching devices have been investigated upon downscaling toward the ultimate single atomic limit. The analysis of the low-frequency current noise spectra revealed that the main electronic noise contribution arises from the resistance fluctuations due to internal dynamical defects of Ag nanofilaments. The resulting 0.01-1% current noise ratio, i.e. the total noise level with respect to the mean value of the current, is found to be universal: its magnitude only depends on the total resistance of the device, irrespective of the materials aspects of the surrounding solid electrolyte and of the specific filament formation procedure. Moreover, the resistance dependence of the current noise ratio also displays the diffusive to ballistic crossover, confirming that stable resistive switching operation utilizing Ag nanofilaments is not compromised even in truly atomic scale junctions by technologically impeding noise levels.

We present a new automated method for structural classification of the traces obtained in break junction experiments. Using recurrent neural networks trained on the traces of minimal cross-sectional area in molecular dynamics simulations, we successfully separate the traces into two classes: point contact or nanowire. This is done without any assumptions about the expected features of each class. The trained neural network is applied to experimental break junction conductance traces, and it separates the classes as well as the previously used experimental methods. The effect of using partial conductance traces is explored, and we show that the method performs equally well using full or partial traces (as long as the trace just prior to breaking is included). When only the initial part of the trace is included, the results are still better than random chance. Finally, we show that the neural network classification method can be used to classify experimental conductance traces without using simulated results for training, but instead training the network on a few representative experimental traces. This offers a tool to recognize some characteristic motifs of the traces, which can be hard to find by simple data selection algorithms.

The dynamical aspects of bipolar resistive switchings have been investigated in Nb/Nb2O5/PtIr nanojunctions. We found that the widely tuneable ON and OFF state resistances are well separated at low bias. On the other hand, the high-bias regime of the resistive switchings coincides with the onset of a high nonlinearity in the current–voltage characteristics, where the impedance of both states rapidly decreases and becomes equivalent around 50 Ω. This phenomenon enables the overriding of the RC limitations of fast switchings between higher resistance ON and OFF states. Consequently, nanosecond switching times between multiple resistance states due to subnanosecond voltage pulses are demonstrated. Moreover, this finding provides the possibility of impedance engineering by the appropriate choice of voltage signals, which facilitates that both the set and reset transitions take place in an impedance matched manner to the surrounding circuit, demonstrating the merits of ultra-fast operation of Nb2O5 based neuromorphic networks., Nanoscale, 10 (41), ISSN:2040-3364, ISSN:2040-3372

We report on the characterization of the electrical breakdown (EB) process for the formation of tunneling nanogaps in single-layer graphene. In particular, we investigated the role of oxygen in the breakdown process by varying the environmental conditions (vacuum and ambient conditions). We show that the density of oxygen molecules in the chamber is a crucial parameter that defines the physical breakdown process: at low density, the graphene lattice is sublimating, whereas at high density, the process involved is oxidation, independent of the substrate material. To estimate the activation energies of the two processes, we use a scheme which consists of applying voltage pulses across the junction during the breakdown. By systematically varying the voltage pulse length, and estimating the junction temperature from a 1D thermal model, we extract activation energies which are consistent with the sublimation of graphene under high vacuum and the electroburning process under air. Our study demonstrates that, in our system, a better control of the gap formation is achieved in the sublimation regime.

The interaction of carbon monoxide molecules with atomic-scale platinum nanojunctions is investigated by low temperature mechanically controllable break junction experiments. Combining plateaus' length analysis, two dimensional conductance-displacement histograms and conditional correlation analysis a comprehensive microscopic picture is proposed about the formation and evolution of Pt-CO-Pt single-molecule configurations. Our analysis implies that before pure Pt monoatomic chains would be formed a CO molecule infiltrates the junction, first in a configuration being perpendicular to the contact axis. This molecular junction is strong enough to pull a monoatomic platinum chain with the molecule being incorporated in the chain. Along the chain formation the molecule can either stay in the perpendicular configuration, or rotate to a parallel configuration. The evolution of the single-molecule configurations along the junction displacement shows quantitative agreement with theoretical predictions, justifying the interpretation in terms of perpendicular and parallel molecular alignment. Our analysis demonstrates that the combination of two dimensional conductance-displacement histograms with conditional correlation analysis is a useful tool to separately analyze fundamentally different types of junction trajectories in single molecule break junction experiments.

Prevailing models of resistive switching arising from electrochemical formation of conducting filaments across solid state ionic conductors commonly attribute the observed polarity of the voltage-biased switching to the sequence of the active and inert electrodes confining the resistive switching memory cell. Here we demonstrate stable switching behaviour in metallic Ag-Ag2S-Ag nanojunctions at room temperature exhibiting similar characteristics. Our experimental results and numerical simulations reveal that the polarity of the switchings is solely determined by the geometrical asymmetry of the electrode surfaces. By the lithographical design of a proof of principle device we demonstrate the merits of simplified fabrication of atomic-scale, robust planar Ag2S memory cells., Scientific Reports, 6, ISSN:2045-2322

We review data analysis techniques that can be used to study temporal correlations among conductance traces in break junction measurements. We show that temporal histograms are a simple but efficient tool to check the temporal homogeneity of the conductance traces, or to follow spontaneous or triggered temporal variations, like structural modifications in trained contacts, or the emergence of single-molecule signatures after molecule dosing. To statistically analyze the presence and the decay time of temporal correlations, we introduce shifted correlation plots. Finally, we demonstrate that correlations between opening and subsequent closing traces may indicate structural memory effects in atomic-sized metallic and molecular junctions. Applying these methods on measured and simulated gold metallic contacts as a test system, we show that the surface diffusion induced flattening of the broken junctions helps to produce statistically independent conductance traces at room temperature, whereas at low temperature repeating tendencies are observed as long as the contacts are not closed to sufficiently high conductance setpoints. Applying opening-closing correlation analysis on Pt-CO-Pt single-molecule junctions, we demonstrate pronounced contact memory effects and recovery of the molecule for junctions breaking before atomic chains are formed. However, if chains are pulled the random relaxation of the chain and molecule after rupture prevents opening-closing correlations.

The nonlinear transport properties of nanometer-scale junctions formed between an inert metallic tip and an Ag film covered by a thin Ag2S layer are investigated. Suitably prepared samples exhibit memristive behavior with technologically optimal ON and OFF state resistances yielding to resistive switching on the nanosecond time scale. Utilizing point contact Andreev reflection spectroscopy, we studied the nature of electron transport in the active volume of memristive junctions showing that both the ON and OFF states correspond to truly nanometer-scale, highly transparent metallic channels. Our results demonstrate the merits of Ag2S nanojunctions as nanometer-scale memory cells which can be switched by nanosecond voltage pulses., Nanoscale, 6 (5), ISSN:2040-3364, ISSN:2040-3372

Results of point contact Andreev reflection (PCAR) experiments on (In,Mn)Sb are presented and analyzed in terms of current models of charge conversion at a superconductor-ferromagnet interface. We investigate the influence of surface transparency, and study the crossover from ballistic to diffusive transport regime as contact size is varied. Application of a Nb tip to a (In,Mn)Sb sample with Curie temperature Tc of 5.4 K allowed the determination of spin-polarization when the ferromagnetic phase transition temperature is crossed. We find a striking difference between the temperature dependence of the local spin polarization and of the macroscopic magnetization, and demonstrate that nanoscale clusters with magnetization close to the saturated value are present even well above the magnetic phase transition temperature., 4 pages