Electron counting of a single porphyrin molecule between two electrodes shows a crossover from sub- to super-Poissonian statistics as the bias voltage is scanned. This is attributed to the simultaneous activation of states with electron transfer rates spanning several orders of magnitude. Time-series analysis of consecutive single electron transfer events reveals fast and slow transport channels, which are not resolved by the average current alone.
Porphyrin molecules can form stable single molecule junctions without anchoring groups. Adding thiol end groups and pyridine axial groups yields more stable junctions with an increased spread in low-bias conductance. This is a result of different bridging geometries during breaking, the stability of which is demonstrated in time-dependent conductance measurements. This is in strong contrast with rod like molecules which show one preferential binding geometry.
We have investigated charge transport in ZnTPPdT-Pyr molecular junctions using the lithographic MCBJ technique at room temperature and cryogenic temperature (6K). We combined low-bias statistical measurements with spectroscopy of the molecular levels using I(V) characteristics. This combination allows us to characterize the transport in a molecular junction in detail. This complex molecule can form different junction configurations, which is observed in trace histograms and in current-voltage (I(V)) measurements. Both methods show that multiple stable single-molecule junction configurations ca…
The oxidation and spin state of a metal-organic molecule determine its chemical reactivity and magnetic properties. Here, we demonstrate the reversible control of the oxidation and spin state in a single Fe-porphyrin molecule in the force field of the tip of a scanning tunneling microscope. Within the regimes of half-integer and integer spin state, we can further track the evolution of the magnetocrystalline anisotropy. Our experimental results are corroborated by density functional theory and wave function theory. This combined analysis allows us to draw a complete picture of the molecular st…
We present measurements of the time-dependent fluctuations in electrical current in a voltage-biased tunnel junction. We were able to simultaneously extract the first three moments of the tunnel current counting statistics. Detailed comparison of the second and the third moment reveals that counting statistics is accurately described by the Poissonian distribution expected for spontaneous current fluctuations due to electron charge discreteness, realized in tunneling transport at negligible coupling to environment.
We discuss how threshold detectors can be used for a direct measurement of the full counting statistics (FCS) of current fluctuations and how to implement Jose phson junctions in this respect. We propose a scheme to characterize the full co unting statistics from the current dependence of the escape rate measured. We il lustrate the scheme with explicit results for tunnel, diffusive and quasi-ballis tic mesoscopic conductors.
We present a theory for the full distribution of current fluctuations in incoherent diffusive superconducting junctions, subjected to a voltage bias. This theory of full counting statistics of incoherent multiple Andreev reflections is valid for arbitrary applied voltage. We present a detailed discussion of the properties of the first four cumulants as well as the low and high voltage regimes of the full counting statistics. The work is an extension of the results of Pilgram and the author, Phys. Rev. Lett. 94, 086806 (2005).
The full counting statistics of a molecular level weakly interacting with a local phonon mode is derived. We find an analytic formula that gives the behavior of arbitrary irreducible moments of the distribution upon phonon excitation. The underlying competition between quasi-elastic and inelastic processes results in the formation of domains in parameter space characterized by a given sign in the jump of the irreducible moments. In the limit of perfect transmission, the corresponding distribution is distorted from Gaussian statistics for electrons to Poissonian transfer of holes above the inel…
Economical solar energy conversion to electricity can be boosted by the discovery of fundamentally new photovoltaic mechanism, and a suitable system to realize it with commonly available materials like iron (Fe) and nickel (Ni). This paper reports the observation of photovoltaic effect on a molecular spintronics device, composed of magnetic tunnel junction (MTJ) and organometallic molecular clusters (OMCs). A prefabricated MTJ with exposed side edges, after enabling the bridging of OMC channels between its two ferromagnetic films, exhibited following phenomenon (i) dramatic increase in exchang…
The characteristics of molecular electronic devices are critically determined by metal-organic interfaces, which influence the arrangement of the orbital levels that participate in charge transport. Studies on self-assembled monolayers (SAMs) show (molecule-dependent) level shifts as well as transport-gap renormalization, suggesting that polarization effects in the metal substrate play a key role in the level alignment with respect to the metal's Fermi energy. Here, we provide direct evidence for an electrode-induced gap renormalization in single-molecule junctions. We study charge transport i…
We present first-principles calculations for moments of the current up to the third order in atomic-scale junctions. The quantum correlations of the current are calculated using the current operator in terms of the wave functions obtained self-consistently within the static density-functional theory. We investigate the relationships of the conductance, the second, and the third moment of the current for carbon atom chains of various lengths bridging two metal electrodes in the linear and nonlinear regimes. The conductance, the second-, and the third-order Fano factors exhibit odd-even oscillat…
We consider a quantum wire double junction system with each wire segment described by a spinless Luttinger model, and study theoretically shot noise in this system in the sequential tunneling regime. We find that the non-equilibrium plasmonic excitations in the central wire segment give rise to qualitatively different behavior compared to the case with equilibrium plasmons. In particular, shot noise is greatly enhanced by them, and exceeds the Poisson limit. We show that the enhancement can be explained by the emergence of several current-carrying processes, and that the effect disappears if t…
The coupling of the charge carriers passing through a molecule bridging two bulky conductors with local vibrational modes of the molecule, gives rise to distinct features in the electronic transport properties on one hand, and to nonequilibrium features in the vibrations' properties, e.g., their population, on the other. Here we explore theoretically a generic model for a molecular junction biased by an arbitrary dc voltage in the weak-coupling regime. We analyze the signature of the electron-vibration interaction on the full-counting statistics of the current fluctuations (i.e., the cumulant …
We propose a general framework that unifies the point of view of counting statistics of transmitted (fermionic) charges as it is commonly used in the quantum transport community to the point of view of counting statics of phonons (bosons) as it is known from the field of quantum optics. As a particular example, we study on the same footing the counting statistics of electrons transfered through a molecular junction and the corresponding population dynamics of the associated molecular vibrational mode. In the tunnel limit, non-perturbative results in the electron-phonon interaction are derived …
The interplay between nuclear and electronic degrees of freedom strongly influences molecular charge transport. Herein, we report on transport through a porphyrin dimer molecule, weakly coupled to graphene electrodes, that displays sequential tunneling within the Coulomb-blockade regime. The sequential transport is initiated by current-induced phonon absorption and proceeds by rapid sequential transport via a non-equilibrium vibrational distribution. We demonstrate this is possible only when the vibrational dissipation is slow relative to sequential tunneling rates, and obtain a lower bound fo…
We investigate the full-counting statistics (FCS) of energy transport carried by electrons in molecular junctions for the Anderson-Holstein model in the polaronic regime. Using two-time quantum measurement scheme, generating function (GF) for the energy transport is derived and expressed as a Fredholm determinant in terms of Keldysh nonequilibrium Green's function in the time domain. Dressed tunneling approximation is used in decoupling the phonon cloud operator in the polaronic regime. This formalism enables us to analyze the time evolution of energy transport dynamics after a sudden switch-o…
We study the full-counting statistics of charges transmitted through a single-level quantum dot weakly coupled to a local Einstein phonon which causes fluctuations in the dot energy. An analytic expression for the cumulant generating function, accurate up to second order in the electron-phonon coupling and valid for finite voltages and temperatures, is obtained in the extended wide-band limit. The result accounts for nonequilibrium phonon distributions induced by the source-drain bias voltage, and concomitantly satisfies the fluctuation theorem. Extending the counting field to the complex plan…
We present an investigation of the energy dependence of the full charge counting statistics in diffusive normal-insulating-normal-insulating-superconducting junctions. It is found that the current in general is transported via a correlated transfer of pairs of electrons. Only in the case of strongly asymmetric tunnel barriers or energies much larger than the Thouless energy is the pair transfer uncorrelated. The second cumulant, the noise, is found to depend strongly on the applied voltage and temperature. For a junction resistance dominated by the tunnel barrier to the normal reservoir, the d…
The Electron Counting Capacitance Standard currently pursued at PTB aims to close the Quantum Metrological Triangle with a final precision of a few parts in 10^7. This paper reports the considerable progress recently achieved with a new generation of single-electron tunnelling devices. A five-junction R-pump was operated with a relative charge transfer error of five electrons in 10^7, and was used to successfully perform single-electron charging of a cryogenic capacitor. The preliminary result for the single-electron charge quantum has an uncertainty of less than two parts in 10^6 and is consi…
We demonstrate that the probability distribution of the net number of electrons passing through a quantum system in a junction obeys a steady-state fluctuation theorem (FT) which can be tested experimentally by the full counting statistics (FCS) of electrons crossing the lead-system interface. The FCS is calculated using a many-body quantum master equation (QME) combined with a Liouville space generating function (GF) formalism. For a model of two coupled quantum dots, we show that the FT becomes valid for long binning times and provide an estimate for the finite-time deviations. We also demon…
We study theoretically the full distribution of transferred charge in a tunnel junction (or quantum point contact) coupled to a nanomechanical oscillator, as well as the conditional evolution of the oscillator. Even if the oscillator is very weakly coupled to the tunnel junction, it can strongly affect the tunneling statistics and lead to a highly non-Gaussian distribution. Conversely, given a particular measurement history of the current, the oscillator energy distribution may be localized and highly non-thermal. We also discuss non-Gaussian correlations between the oscillator motion and tunn…
Statistics of electron tunneling in normal tunnel junctions is studied analytically and numerically taking into account circuit (environment) effects. Full counting statistics, as well as full statistics of voltage and phase have been found for arbitrary times of observation. The theoretical analysis was based on the classical master equation, whereas the numerical simulations employed standard Monte-Carlo methods.
Off-resonant charge transport through molecular junctions has been extensively studied since the advent of single-molecule electronics and it is now well understood within the framework of the non-interacting Landauer approach. Conversely, gaining a qualitative and quantitative understanding of the resonant transport regime has proven more elusive. Here, we study resonant charge transport through graphene-based zinc-porphyrin junctions. We experimentally demonstrate an inadequacy of the non-interacting Landauer theory as well as the conventional single-mode Franck-Condon model. Instead, we mod…
We study current-induced vibrational cooling, heating, and instability in a donor-acceptor rectifying molecular junction using a full counting statistics approach. In our model, electron-hole pair excitations are coupled to a given molecular vibrational mode which is either harmonic or highly anharmonic. This mode may be further coupled to a dissipative thermal environment. Adopting a master equation approach, we confirm the charge and heat exchange fluctuation theorem in the steady-state limit, for both harmonic and anharmonic models. Using simple analytical expressions, we calculate the char…
Similarly to the recently obtained result for two-terminal systems, we show that there are constraints on the full counting statistics for non-interacting fermions in multi-terminal contacts. In contrast to the two-terminal result, however, there is no factorization property in the multi-terminal case.
We analyze the effect of electron-phonon coupling on the full counting statistics of a molecular junction beyond the lowest order perturbation theory. Our approach allows to take into account analytically the feedback between the non-equilibrium phonon and electronic distributions in the quantum regime. We show that even for junctions with high transmission and relatively weak electron-phonon coupling this feedback gives rise to increasingly higher nonlinearities in the voltage dependence of the cumulants of the transmitted charges distribution.
I study the dynamics of a Josephson junction serving as a threshold detector of fluctuations which is subjected to a general non-equilibrium electronic noise source whose characteristics is to be determined by the junction. This experimental setup has been proposed several years ago as a prospective scheme for determining the Full Counting Statistics of the electronic noise source. Despite of intensive theoretical as well as experimental research in this direction the promise has not been quite fulfilled yet and I will discuss what are the unsolved issues. First, I review a general theory for …
We investigate the effects of phonon scattering on the electronic current noise through nanojunctions using the non-equilibrium Green's functions formalism extended to include the counting field. In the case of weak electron-phonon coupling and a single broad electronic level we derive an analytic expression for the current noise at arbitrary temperature and identify physically distinct contributions based on their voltage dependence. We apply our theory to the experimentally relevant case of a deuterium molecule placed in a break-junction and predict a significant inelastic contribution to th…
We analyse the full counting statistics (FCS) of a superconducting junction in non-equilibrium in the limit of small interface transparency. In this limit we treat both supercurrent and multiple Andreev reflections on equal footing and show how to generalise previous results for both phenomena. Furthermore, we also allow for different gaps of both superconductors and investigate the intermediate regime which allows to make contact with previous results on normal-superconductor heterostructures. We also compare our predictions in this regime to experimental data.
The time dependent full counting statistics of charge transport through an interacting quantum junction is evaluated from its generating function, controllably computed with the inchworm Monte Carlo method. Exact noninteracting results are reproduced; then, we continue to explore the effect of electron--electron interactions on the time-dependent charge cumulants, first-passage time distributions and $n$-electron transfer distributions. We observe a crossover in the noise from Coulomb blockade- to Kondo-dominated physics as the temperature is decreased. In addition, we uncover long-tailed spin…
Time-dependent driving influences the quantum and thermodynamic fluctuations of a system, changing the familiar physical picture of electronic noise which is an important source of information the about microscopic mechanism of quantum transport. Giving access to all cumulants of the current, the full counting statistics (FCS) is the powerful theoretical method to study fluctuations in nonequilibrium quantum systems. In this paper, we propose the application of FCS to consider periodic driven junctions. The combination of Floquet theory for time dynamics and nonequilibrium counting-field Green…
We present a comprehensive theoretical analysis of the dc transport properties of superconducting point contacts. We determine the full counting statistics for these junctions, which allows us to calculate not only the current or the noise, but all the cumulants of the current distribution. We show how the knowledge of the statistics of charge transfer provides an unprecedented level of understanding of the different transport properties for a great variety of situations. We illustrate our results with the analysis of junctions between BCS superconductors, contacts between superconductors with…
We study theoretically the current-voltage characteristics, shot noise, and full counting statistics of a quantum wire double barrier structure. We model each wire segment by a spinless Luttinger liquid. Within the sequential tunneling approach, we describe the system's dynamics using a master equation. We show that at finite bias the non-equilibrium distribution of plasmons in the central wire segment leads to increased average current, enhanced shot noise, and full counting statistics corresponding to a super-Poissonian process. These effects are particularly pronounced in the strong interac…
We analyse the zero temperature Full Counting Statistics (FCS) for the charge transfer across a biased tunnel junction. We find the FCS from the eigenvalues of the density matrix of outgoing states of one lead. In the general case of a general time-dependent bias and time-dependent transparency we solve for these eigenvalues numerically. We report the FCS for the case of a step pulse applied between the leads and a constant barrier transparency (this case is equivalent to Fermi edge singularity problem). We have also studied combinations of a time-dependent barrier transparency and biases betw…
We derive the full counting statistics of charge transfer through a voltage biased superconducting junction. We find that for measurement times much longer than the inverse Josephson frequency, the counting statistics describes a correlated transfer of quanta of multiple electron charges, each quantum associated with the transfer of a single quasiparticle. An expression for the the counting statistics in terms of the quasiparticle scattering amplitudes is derived.
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-char…
A very recent article [(1) E. Zakka-Bajjani et al., PRL104, 206802 (2010)] has addressed the problem of how the statistics of electrons crossing a quantum conductor influences that of the photons they emit. It is however not clear that the detection used in [1] is sensitive to emitted photons and not to the overall electromagnetic fluctuations, which include vacuum fluctuations. We show that the proof in [1] that non-symmetrized noise is detected is erroneous: supposing that the detection simply takes the square of the voltage, i.e. is sensitive to vacuum fluctuations, leads to identical resul…
We study inelastic effects on the electronic current noise in molecular junctions, due to the coupling between transport electrons and vibrational degrees of freedom. Using a full counting statistics approach based on the generalized Keldysh Green's function technique, we calculate in an unified manner both the mean current and the zero-frequency current noise. For multilevel junctions with weak electron-phonon coupling, we give analytical formulas for the lowest order inelastic corrections to the noise in terms of universal temperature- and voltage-dependent functions and junction-dependent p…
In this work, we study the short time dynamics of a molecular junction described by Anderson-Holstein model using full-counting statistics after projective measurement. The coupling between the central quantum dot (QD) and two leads was turned on at remote past and the system is evolved to steady state at time $t=0$, when we perform the projective measurement in one of the lead. Generating function for the charge transfer is expressed as a Fredholm determinant in terms of Keldysh nonequilibrium Green's function in the time domain. It is found that the current is not constant at short times ind…
A capacitance standard based on the definition of capacitance C = Ne/U is realized when a capacitor is charged with a known number N of electrons (e is the elementary charge) and the voltage U across the capacitor is measured. If U is measured by means of a Josephson voltage standard, C is solely determined by quantum numbers and fundamental constants. Presently, PTB is setting up this experiment using a special type of single-electron pump, the so-called r-pump, for transferring electrons one by one onto a cryogenic vacuum capacitor with the decadic capacitance C = 1 pF. We report on the prog…
The fact that electrical current is carried by individual charges has been known for over 100 years, yet this discreteness has not been directly observed so far. Almost all current measurements involve measuring the voltage drop across a resistor, using Ohm's law, in which the discrete nature of charge does not come into play. However, by sending a direct current through a microelectronic circuit with a chain of islands connected by small tunnel junctions, the individual electrons can be observed one by one. The quantum mechanical tunnelling of single charges in this one-dimensional array is t…
In quantum transport through nanoscale devices, fluctuations arise from various sources: the discreteness of charge carriers, the statistical non-equilibrium that is required for device operation, and unavoidable quantum uncertainty. As experimental techniques have improved over the last decade, measurements of these fluctuations have become available.} They have been accompanied by a plethora of theoretical literature using many different fluctuation statistics to describe the quantum transport. In this paper, we overview three prominent fluctuation statistics: full counting, waiting time, an…
We perform in-situ detection of individual electrons pumped through a single-electron turnstile based on ultrasmall normal metal - insulator - superconductor tunnel junctions. In our setup, limited by the detector bandwidth, at low repetition rates we observe errorless sequential transfer of up to several hundred electrons through the system. At faster pumping speeds up to 100 kHz, we show relative error rates down to 10^-3, comparable to typical values obtained from measurements of average pumped current in non-optimized individual turnstiles. The work constitutes an initial step towards a se…
Using a simple quantum master equation approach, we calculate the Full Counting Statistics of a single electron transistor strongly coupled to vibrations. The Full Counting Statistics contains both the statistics of integrated particle and energy currents associated to the transferred electrons and phonons. A universal as well as an effective fluctuation theorem are derived for the general case where the various reservoir temperatures and chemical potentials are different. The first relates to the entropy production generated in the junction while the second reveals internal information of the…
Charge transfer statistics of quantum particles is obtained by analysing the time evolution of the many-body wave function. Exploiting properly chosen gauge transformations, we construct the probabilities for transfers of a discrete number of particles. Generally, the derived formula for counting statistics differs from the one previously obtained by Levitov {\it et al.} (J. of Math. Phys. {\bf 37}, 4845 (1996)). The two formulae agree only if the initial state is prohibited from being a superposition of different charge states. Their difference is illustrated for cases of a single particle an…
We study the charge transport statistics in coherent two-terminal double junctions within the framework of the circuit theory of mesoscopic transport. We obtain the general solution of the circuit-theory matrix equations for the Green's function of a chaotic cavity between arbitrary contacts. As an example we discuss the full counting statistics and the first three cumulants for an open asymmetric cavity between a superconductor and a normal-metal lead at temperatures and voltages below the superconducting gap. The third cumulant shows a characteristic sign change as a function of the asymmetr…
We study the statistical properties of charge and energy transport in electron conducting junctions with electron-phonon interactions, specifically, the thermoelectric efficiency and its fluctuations. The system comprises donor and acceptor electronic states, representing a two-site molecule or a double quantum dot system. Electron transfer between metals through the two molecular sites is coupled to a particular vibrational mode which is taken to be either harmonic or anharmonic- a truncated (two-state) spectrum. Considering these models we derive the cumulant generating function in steady st…
Nonequilibrium Green's functions provide a powerful tool for computing the dynamical response and particle exchange statistics of coupled quantum systems. We formulate the theory in terms of the density matrix in Liouville space and introduce superoperator algebra that greatly simplifies the derivation and the physical interpretation of all quantities. Expressions for various observables are derived directly in real time in terms of superoperator nonequilibrium Green's functions (SNGF), rather than the artificial time-loop required in Schwinger's Hilbert-space formulation. Applications for com…
We present an extension of the Keldysh-Green's function method, which allows to calculate the full distribution of transmitted particles through a mesoscopic superconductor. The method is applied to the statistics of supercurrent in short contacts. If the current is carried by Andreev bound states the distribution corresponds to switching between long trains of electrons going in opposite directions. For weak (gapless) superconductors or tunnel junctions we find that at low temperatures the distribution has negative `probabilities'. Accounting for the quantum mechanical nature of the measuring…
We analyze shot noise in a magnetic tunnel junction with a two-level quantum dot attached to the magnetic electrodes. The considerations are limited to the case when some transport channels are suppressed at low temperatures. Coupling of the two dot's levels to the electrodes are assumed to be generally different and also spin-dependent. To calculate the shot noise we apply the approach based on the full counting statistics. The approach is used to account for experimental data obtained in magnetic tunnel junctions with organic barriers. The experimentally observed Fano factors correspond to t…
We report a direct detection of time correlated single-electron tunneling oscillations in a series array of small tunnel junctions. Here the current, I, is made up of a lattice of charge solitons moving throughout the array by time correlated tunneling with the frequency f=I/e, where e is the electron charge. To detect the single charges, we have integrated the array with a radio-frequency single-electron transistor (RF-SET) and employed two different methods to couple the array to the SET input: by direct injection through a tunnel junction, and by capacitive coupling. In this paper we report…
When a mesoscopic conductor is coupled to a high-quality electromagnetic cavity the flow of charges and the flux of photons leaking out of the cavity can both depend strongly on the coupled quantum dynamics of the system. Using a voltage-biased Josephson junction as a model system, we demonstrate that there is a simple connection between the full counting statistics of the charges and the photons in the long time limit. We then reveal the intimate relation between the counting statistics and the nonlinear dynamics of the system, uncovering novel regimes of coherent charge and photon transport …
We calculate the spin current distribution function for a Kondo dot in two different regimes. In the exactly solvable Toulouse limit the linear response, zero temperature statistics of the spin transfer is trinomial, such that all the odd moments vanish and the even moments follow a binomial distribution. On the contrary, the corresponding spin-resolved distribution turns out to be binomial. The combined spin and charge statistics is also determined. In particular, we find that in the case of a finite magnetic field or an asymmetric junction the spin and charge measurements become statisticall…
Many molecular junctions display stochastic telegraphic switching between two distinct current values, which is therefore an important source of fluctuations in nanoscale quantum transport. We investigate electronic fluctuations arising via Markovian master equations; identifying regions of non-renewal behavior due to telegraphic switching. Non-renewal behavior is characterized by the emergence of correlations between successive first-passage times of detection in one of the leads. Our method of including telegraphic switching is general for any source-molecule-drain setup, but we consider thr…
We investigate electron transport through multiterminal networks hosting Majorana bound states (MBS) in the framework of full counting statistics (FCS). In particular, we apply our general results to T-shaped junctions of two Majorana nanowires. When the wires are in the topologically nontrivial regime, three MBS are localized near the outer ends of the wires, while one MBS is localized near the crossing point, and when the lengths of the wires are finite adjacent MBS can overlap. We propose a combination of current and cross-correlation measurements to reveal the predicted coupling of four Ma…
We show theoretically that hot-electron nanobolometers consisting of a small piece of normal metal, capacitively coupled to a superconducting antenna through a pair of normal metal--insulator--superconductor (NIS) tunnel junctions may be used as far-infrared photon counters. To make the device most effective at high counting rates, we suggest the use of the bolometer in the simplest configuration, when the NIS tunnel junctions are used as both an electron cooler and thermometer. The absorption of the photon in the normal metal produces a pulse in the electron temperature, which is measured by …
The transport properties of a conduction junction model characterized by two mutually coupled channels that strongly differ in their couplings to the leads are investigated. Models of this type describe molecular redox junctions (where a level that is weakly coupled to the leads controls the molecular charge, while a strongly coupled one dominates the molecular conduction), and electron counting devices in which the current in a point contact is sensitive to the charging state of a nearby quantum dot. Here we consider the case where transport in the strongly coupled channel has to be described…
