Electrochemical fabrication of highly stable redox-active nanojunctions

Redox-gated molecular junctions were obtained starting with a relatively large gap between two electrodes, in the micrometer range, followed by electrochemical polymerization of aniline. Polyaniline (PANI) grows from the tip side until it bridges the two electrodes. The resulting junctions were characterized electrochemically by following the variation of the tip-substrate current as a function of the electrochemical gate potential for various bias voltages and by recording their I(V) characteristics. The two electrodes make contact through PANI wires, and microjunctions with conductances around 10(-3) S were obtained. On the basis of a similar setup, PANI nanojunctions with conductances between 10(-7) and 10(-8) S were made, where the current appears to be controlled by fewer than 10 oligoaniline strands. Despite the small number of strands connecting the two electrodes, the junctions are highly stable even when several successive potential sweeps are performed. Comparison of the conductance measured in the oxidized and reduced states leads to an on/off ratio of about 70-100, which is higher than that reported for a single aniline heptamer bridging two electrodes, highlighting the interest of connecting a few tens of molecules using the scanning electrochemical microscopy (SECM) configuration. In some cases, the switching of the PANI takes place in several individual conductance steps close to that obtained for a single oligoaniline. Finally, starting with a microjunction and mechanically withdrawing the tip shrinks it down to the nanometer scale and makes it possible to reach the regime where the conductance is controlled by a limited number of strands. This work presents an easy method for making redox-gated nanojunctions and for probing the conductance of a few oligoanilines despite an initially large tip-substrate gap.     

Fast Transient Current Response to Switching Events in Short Chains of Molecular Islands

We consider current flow between two metallic leads joined by tunneling junctions to a molecular island. The junctions are assumed to be “wiggly,” that is, switching on and off intermittently. The resulting sequence of current transients overlaps in dependence on the interplay between the switching times and the decay time of “initial” correlations induced by each switching event. The process is described in terms of nonequilibrium Green’s functions.     

The effect of alternating current on the thermal activation threshold of the tunnel Josephson junctions

The process of thermal activation in the tunnel Josephson junctions simultaneously carrying both constant (dc) and alternating (ac) currents has been studied. The presence of the ac component leads to a decrease in the potential barrier for a metastable state of the Josephson junction. The thermal activation threshold is expressed as a function of the ac current amplitude. The results agree with the data of recent experiments on the statistics of switching from a superconducting to resistive state in the Josephson tunneling junctions.     

Molecular Signatures in the Transport Properties of Molecular Wire Junctions: What Makes a Junction “Molecular”?

The simplest component of molecular electronics consists of a single-molecule transport junction: a molecule sandwiched between source and drain electrodes, with or without a third gate electrode. In this Concept article, we focus on how molecules control transport in metal-electrode molecular junctions, and where the molecular signatures are to be found. In the situation where the molecule is relatively short and the gap between injection energy and molecular eigenstates is large, transport occurs largely by elastic tunneling, stochastic switching is common, and the vibronic signature can be found using inelastic electron tunneling spectroscopy (IETS). As the energy gaps for injection become smaller, one begins to see stronger molecular signatures - these include Franck-Condon-like structures in the current/voltage characteristic and strong vibronic interactions, which can lead to hopping behavior at the polaron limit. Conformational changes induced by the strong electric field lead to another strong manifestation of the molecular nature of the junction. We overview some of this mechanistic landscape, focusing on significant effects of switching (both stochastic and controlled by the electric field) and of molecular vibronic coupling.     

Quasiparticle tunneling through rare earth trihydroxide barriers

Symmetric tunneling junctions with 4000-Å-thick Pb electrodes and polycrystalline insulating barriers of Lu(OH)₃, Er(OH)₃, and Ho(OH)₃ have been fabricated. In bulk, these three rare earth trihydroxides are nonmagnetic, antiferromagnetic (T _N<1.1 K), and ferromagnetic (T_c=2.54 K), respectively. Tunneling resistances ranged from 600 to greater than 40,000 with a junction area of 6.25×10^–2 cm². Single-particle tunneling characteristics of these junctions were always broadened relative to the characteristics of Pb-PbO-Pb junctions, although the ratio of the zero-bias tunneling resistance to the normal tunneling resistance in some instances was of the order of 1000. A threefold splitting of the conductance peak at the gap was observed only in junctions with Ho(OH)₃ barriers. The gap peak of junctions with Er(OH)₃ barriers was broadened significantly relative to that of junctions with Lu(OH)₃ barriers. From measurements of the temperature and magnetic field dependences of the tunneling conductance it is argued that the splitting in junctions with Ho(OH)₃ barriers is consistent with the existence of a peak in the electronic density of states at an energy below that of the gap of each of the electrodes. This peak is believed to be the signature of a bound state near the barrier where the pair potential is depressed by virtue of the exchange coupling between the spins of the superconducting electrons and the localized spins of the barrier. Qualitative interpretations of the data support the view that the observed structure in Ho(OH)₃ barrier junctions is neither a consequence of intrinsic gap anisotropy in Pb nor of inelastic magnon-assisted tunnelling.     

Organic memory using [6,6]-phenyl-C(61) butyric acid methyl ester: morphology, thickness and concentration dependence studies

We report a simple memory device in which the fullerene-derivative [6,6]-phenyl-C(61) butyric acid methyl ester (PCBM) mixed with inert polystyrene (PS) matrix is sandwiched between two aluminum (Al) electrodes. Transmission electron microscopy (TEM) images of PCBM:PS films showed well controlled morphology without forming any aggregates at low weight percentages (<10?wt%) of PCBM in PS. Energy dispersive x-ray spectroscopy (EDX) analysis of the device cross-sections indicated that the thermal evaporation of the Al electrodes did not lead to the inclusion of Al metal nanoparticles into the active PCBM:PS film. Above a threshold voltage of <3?V, independent of thickness, a consistent negative differential resistance (NDR) is observed in devices in the thickness range from 200 to 350?nm made from solutions with 4-10?wt% of PCBM in PS. We found that the threshold voltage (V(th)) for switching from the high-impedance state to the low-impedance state, the voltage at maximum current density (V(max)) and the voltage at minimum current density (V(min)) in the NDR regime are constant within this thickness range. The current density ratio at V(max) and V(min) is more than or equal to 10, increasing with thickness. Furthermore, the current density is exponentially dependent on the longest tunneling jump between two PCBM molecules, suggesting a tunneling mechanism between individual PCBM molecules. This is further supported with temperature independent NDR down to 240?K.     

Nanoelectromechanical switch operating by tunneling of an entire C60 molecule

We present a solid state single molecule electronic device where switching between two states with different conductance happens predominantly by tunneling of an entire C60 molecule. This conclusion is based on a novel statistical analysis of approximately 10(5) switching events. The analysis yields (i) the relative contribution of tunneling, current induced heating and thermal fluctuations to the switching mechanism, (ii) the voltage dependent energy barrier (approximately 100-200 meV) separating the two states of the switch and (iii) the switching attempt frequency, omega0, corresponding to a 2.8 meV mode, which is most likely rotational.     

Possible Spin Pumping Effects on Spin Torque Induced Magnetization Switching in Magnetic Tunneling Junctions

Dependence of spin torque induced magnetization switching upon interfacial insulating layers properties of magnetic tunneling junctions (MTJ) are studied. For the same magnetic properties and patterning geometric dimensions, changes in MTJ interfacial insulating layers properties reveal interesting magnetization switching behaviors. These behaviors cannot be explained by conventional Landau-Lifshitz-Gilbert equation with a spin torque term and an intrinsic ferromagnetic relaxation damping. However the magnetization switching dynamics can be understood through assumption of spin pumping effects in magnetic tunneling junctions. This is not only important for fundamental understanding of spin and electronic transport in MTJ but also important for practical trade-offs between critical switching current and MTJ resistance for spin torque random access memory.     

Macroscopic Quantum Phenomena in High Critical Temperature Superconducting Josephson Junctions

YBa₂Cu₃O_7?δ grain boundary bi-epitaxial Josepshon junctions (JJs) allow a very clear demonstration of Josephson current variation with the misorientation angle, consistent with the d-wave symmetry of the superconducting order parameter in cuprate, high temperature superconductors. Our bi-epitaxial junctions show a strong suppression of the first harmonic, I ₁ sin ø, of the current phase relation when tunneling from a lobe into a node of the superconducting gap function. In these configurations, the contribution of the second harmonic, I ₂ sin 2ø, becomes of the same magnitude as the first one, giving rise to a characteristic two-well Josephson potential as a function of phase ø instead of the usual single well. This characteristic intrinsic property has suggested proposals of a new class of qu-bit named “quiet” because of the existence a spontaneously degenerate fundamental state without the need of applying an external field. Our experiments probe the macroscopic quantum properties in a d-wave Josephson junction by measuring macroscopic quantum tunneling and energy level quantization. The switching current out of the zero voltage state is measured as a function of temperature down to 20 mK. The temperature variation of the width of an ensemble of switching events goes over from one, which is characteristic of a thermal activation of phase fluctuations to a temperature independent width which is a token of quantum tunneling of the phase. The transition regime is affected by the two-well potential in a 45^° misorientation junction as the second harmonic term gives rise to additional thermal transitions. The difference between quantized energy levels in the harmonic potential was determined by microwave spectroscopy. From the broadening of energy levels, it was possible to extract a Q-value of about 40 for the phase oscillations. The relatively high Q indicates quantum coherence over a sizeable time in d-wave junctions and gives hopes for a realization of a “quiet” high-T _c qu-bit. The contributions of V. L. Ginzburg to several different fields of physics are impressive and long standing. In superconductivity the Ginzburg–Landau theory, for instance, still represents a very powerful approach to model a huge number of different physical systems. High Temperature Superconductors (HTS) have strongly influenced research of the last 20 years and their d-wave order parameter symmetry represents one of the most intriguing features from both the fundamental point of view and some types of innovative long-term applications.     

Simultaneous determination of conductance and thermopower of single molecule junctions

We report the first concurrent determination of conductance (G) and thermopower (S) of single-molecule junctions via direct measurement of electrical and thermoelectric currents using a scanning tunneling microscope-based break-junction technique. We explore several amine-Au and pyridine-Au linked molecules that are predicted to conduct through either the highest occupied molecular orbital (HOMO) or the lowest unoccupied molecular orbital (LUMO), respectively. We find that the Seebeck coefficient is negative for pyridine-Au linked LUMO-conducting junctions and positive for amine-Au linked HOMO-conducting junctions. Within the accessible temperature gradients (<30 K), we do not observe a strong dependence of the junction Seebeck coefficient on temperature. From histograms of thousands of junctions, we use the most probable Seebeck coefficient to determine a power factor, GS(2), for each junction studied, and find that GS(2) increases with G. Finally, we find that conductance and Seebeck coefficient values are in good quantitative agreement with our self-energy corrected density functional theory calculations.     

Multi‐Nonvolatile State Resistive Switching Arising from Ferroelectricity and Oxygen Vacancy Migration

Resistive switching phenomena form the basis of competing memory technologies. Among them, resistive switching, originating from oxygen vacancy migration (OVM), and ferroelectric switching offer two promising approaches. OVM in oxide films/heterostructures can exhibit high/low resistive state via conducting filament forming/deforming, while the resistive switching of ferroelectric tunnel junctions (FTJs) arises from barrier height or width variation while ferroelectric polarization reverses between asymmetric electrodes. Here the authors demonstrate a coexistence of OVM and ferroelectric induced resistive switching in a BaTiO₃ FTJ by comparing BaTiO₃ with SrTiO₃ based tunnel junctions. This coexistence results in two distinguishable loops with multi‐nonvolatile resistive states. The primary loop originates from the ferroelectric switching. The second loop emerges at a voltage close to the SrTiO₃ switching voltage, showing OVM being its origin. BaTiO₃ based devices with controlled oxygen vacancies enable us to combine the benefits of both OVM and ferroelectric tunneling to produce multistate nonvolatile memory devices.     

Reversible Chiral Switching of Bis(phthalocyaninato) Terbium(III) on a Metal Surface

We demonstrate a reversible chiral switching of bis(phthalocyaninato) terbium(III) molecules on an Ir(111) surface by low temperature scanning tunneling microscopy. With an azimuthal rotation of its upper phthalocyanine ligand, the molecule can be switched between a chiral and an achiral configuration actuated by respective inelastic electron tunneling and local current heating. Moreover, the molecular chiral configuration can be interchanged between left and right handedness during the switching manipulations, thereby opening up potential nanotechnological applications.     

Experimental Studies to Realize Josephson Junctions and Qubits in Cuprate and Fe-based Superconductors

Cuprate superconductors are very promising in terms of Josephson junction device because of the large energy scale of high-T _c superconductivity. In particular, fabrication of qubits attracts lots of attention because of its primary importance for future computer technology. We will present some of our recent activities pointing to this purpose. (1) We succeeded in fabricating Josephson junction of cuprate without making any extra oxide barrier layer, rather putting Fe islands on the small strip of cuprate superconductors. This is very promising, since the fabrication of good Josephson junction was unsuccessful so far. Together with the introduction of the data, we discuss the possible mechanism of the weak-link fabrication in this structure. (2) We investigated the switching events in the I–V characteristics of the intrinsic Josephson junctions of Bi-cuprate superconductor, where macroscopic quantum tunneling (MQT) observation is well established recently. In addition to confirm the MQT for the first switching at 1 K in the multiple-branched current–voltage characteristics, we found that the temperature independence of the switching distribution for the second switching up to higher temperatures (10 K) is not due to the trivial Joule heating. We discuss the mechanism of the phenomena, including the possibility of MQT. (3) New Fe-based superconductors are also promising in terms of the application of superconductivity, since the anisotropy looks rather weak, in contrast to cuprates. We will introduce our trial to fabricate epitaxial thin films as the initial step to fabricate Josephson junction of this material.     

Room-temperature gating of molecular junctions using few-layer graphene nanogap electrodes

We report on a method to fabricate and measure gateable molecular junctions that are stable at room temperature. The devices are made by depositing molecules inside a few-layer graphene nanogap, formed by feedback controlled electroburning. The gaps have separations on the order of 1-2 nm as estimated from a Simmons model for tunneling. The molecular junctions display gateable I-V-characteristics at room temperature.     

Fabrication of Reproducible,Integration‐Compatible Hybrid Molecular/Si Electronics

Reproducible molecular junctions can be integrated within standard CMOS technology. Metal–molecule–semiconductor junctions are fabricated by direct Si–C binding of hexadecane or methyl‐styrene onto oxide‐free H‐Si(111) surfaces, with the lateral size of the junctions defined by an etched SiO₂ well and with evaporated Pb as the top contact. The current density, J, is highly reproducible with a standard deviation in log(J) of 0.2 over a junction diameter change from 3 to 100 μm. Reproducibility over such a large range indicates that transport is truly across the molecules and does not result from artifacts like edge effects or defects in the molecular monolayer. Device fabrication is tested for two n‐Si doping levels. With highly doped Si, transport is dominated by tunneling and reveals sharp conductance onsets at room temperature. Using the temperature dependence of current across medium‐doped n‐Si, the molecular tunneling barrier can be separated from the Si‐Schottky one, which is a 0.47 eV, in agreement with the molecular‐modified surface dipole and quite different from the bare Si–H junction. This indicates that Pb evaporation does not cause significant chemical changes to the molecules. The ability to manufacture reliable devices constitutes important progress toward possible future hybrid Si‐based molecular electronics.     

NbN/MgO/NbN superconducting tunnel junctions as x-ray detectors

We report on our work using NbN/MgO/NbN junctions for the detection of x-rays. Detectors based on superconducting tunneling junctions offer the prospect of energy resolution over an order of magnitude higher than is obtainable with the current generation of semiconductor-based detectors. NbN is interesting due to the possibility of its use in trapping layer devices. The junctions were fabricated at the NASA Jet Propulsion Laboratory (JPL) with an area of 4 µm by 4 µm. They were tested at the Naval Research Laboratory (NRL) in an applied magnetic field of approximately 250 gauss, a current bias of several hundred nanoamps and an operating temperature of 1.7 K.     

Electric-field-assisted switching in magnetic tunnel junctions

The advent of spin transfer torque effect accommodates site-specific switching of magnetic nanostructures by current alone without magnetic field. However, the critical current density required for usual spin torque switching remains stubbornly high around 10(6)-10(7) A cm(-2). It would be fundamentally transformative if an electric field through a voltage could assist or accomplish the switching of ferromagnets. Here we report electric-field-assisted reversible switching in CoFeB/MgO/CoFeB magnetic tunnel junctions with interfacial perpendicular magnetic anisotropy, where the coercivity, the magnetic configuration and the tunnelling magnetoresistance can be manipulated by voltage pulses associated with much smaller current densities. These results represent a crucial step towards ultralow energy switching in magnetic tunnel junctions, and open a new avenue for exploring other voltage-controlled spintronic devices.     

Observation of negative differential resistance and single-electron tunneling in electromigrated break junctions

We observed a negative differential resistance (NDR) along with single-electron tunneling (SET) in the electron transport of electromigrated break junctions with metal-free tetraphenylporphyrin (H₂BSTBPP) at a temperature of 11 K. The NDR strongly depended on the applied gate voltages, and appeared only in the electron tunneling region of the Coulomb diamond. We could explain the mechanism of this new type of electron transport by a model assuming a molecular Coulomb island and local density of states of the source and the drain electrodes.     

Investigations onNb/Al-AlO x -Al/Nb proximity tunneling junctions for X-ray detection

A new Nb/Al-AlO_x-Al/Nb trilayer process using a movable mechanical slit for junction-detector applications is described. Best junctions have a quality factor of 42 mV with a Josephson current density of 1200 A/cm ² at 4.2 K. The temperature dependence of the sub-gap current in the range of 0.45 to 4.2 K has been measured. Deviations from the thermally activated behavior due to imperfections in the tunneling barrier are observed. We compare our simple method with the usual whole wafer processes and we discuss the influence of proximity effects in these junctions in terms of the models proposed by Golubov et al. and by McMillan.