Inelastic Electron Tunneling Spectra Research Articles

Graphene-molecule-graphene single-molecule junctions to detect electronic reactions at the molecular scale.

The ability to measure the behavior of a single molecule during a reaction implies the detection of inherent dynamic and static disordered states, which may not be represented when measuring ensemble averages. Here, we describe the building of devices with graphene-molecule-graphene single-molecule junctions integrated into an electrical circuit. These devices are simple to build and are stable, showing tolerance to mechanical changes, solution environment and voltage stimulation. The design of a conductive channel based on a single molecule enables single-molecule detection and is sensitive to variations in physical properties and chemical structures of the detected molecules. The on-chip setup of single-molecule junctions further offers complementary metal-oxide-semiconductor (CMOS) compatibility, enabling logic functions in circuit elements, as well as deciphering of reaction intermediates. We detail the experimental procedure to prepare graphene transistor arrays as a basis for single-molecule junctions and the preparation of nanogapped carboxyl-terminal graphene electrodes by using electron-beam lithography and oxygen plasma etching. We describe the basic design of a molecular bridge with desired functions and terminals to form covalent bonds with electrode arrays, via a chemical reaction, to construct stably integrated single-molecule devices with a yield of 30-50% per chip. The immobilization of the single molecules is then characterized by using inelastic electron tunneling spectra, single-molecule imaging and fluorescent spectra. The whole protocol can be implemented within 2 weeks and requires users trained in using ultra-clean laboratory facilities and the aforementioned instrumentation.

Inelastic Tunnel Transport and Nanoscale Junction Thermoelectricity with Varying Electrode Topology

AbstractIntricacies in the charge transport behavior of single‐molecule junctions often revolve around the complex nature of orbital hybridization stemming from diversified metal‐molecule coupling at interfaces. It will hence be pertinent to fathom the myriad aspect of inelastic charge transport and nanoscale thermoelectricity in single‐molecule junctions. It is examined from first‐principles, achiral and chiral quasi‐1D electrodes to understand the role of junction heterogeneity in overall thermoelectric behavior during charge transport. This calculated inelastic electron tunneling spectra exhibit intense peaks in the low‐frequency regime (< 25 meV) with characteristic bending and rocking modes, which auger well with the available measured data. It is subsequently found that the thermopower can be as high as 212 µV K−1 for σ‐saturated molecular moieties, depending strongly on the configuration of electrodes. Besides, a majority of such single‐molecule junctions turn out to deviate from the Wiedemann–Franz law, leading to anomalies in the electronic thermal conductance. The authors' analysis suggests that as nanoscale electrodes, Au(111) nanowires are likely to render a relatively high thermoelectric figure of merit (ZT > 1) for a small molecular junction at room temperature. Discerning the diversity as driven exigently by the electrode topology may thus augment the device performance in terms of thermal stability at molecular scale.

Protein Binding and Orientation Matter: Bias-Induced Conductance Switching in a Mutated Azurin Junction.

We observe reversible, bias-induced switching of conductance via a blue copper protein azurin mutant, N42C Az, with a nearly 10-fold increase at |V| > 0.8 V than at lower bias. No such switching is found for wild-type azurin, WT Az, up to |1.2 V|, beyond which irreversible changes occur. The N42C Az mutant will, when positioned between electrodes in a solid-state Au–protein–Au junction, have an orientation opposite that of WT Az with respect to the electrodes. Current(s) via both proteins are temperature-independent, consistent with quantum mechanical tunneling as dominant transport mechanism. No noticeable difference is resolved between the two proteins in conductance and inelastic electron tunneling spectra at <|0.5 V| bias voltages. Switching behavior persists from 15 K up to room temperature. The conductance peak is consistent with the system switching in and out of resonance with the changing bias. With further input from UV photoemission measurements on Au–protein systems, these striking differences in conductance are rationalized by having the location of the Cu(II) coordination sphere in the N42C Az mutant, proximal to the (larger) substrate-electrode, to which the protein is chemically bound, while for the WT Az that coordination sphere is closest to the other Au electrode, with which only physical contact is made. Our results establish the key roles that a protein’s orientation and binding nature to the electrodes play in determining the electron transport tunnel barrier.

Tunneling spectroscopy as a probe of fractionalization in two-dimensional magnetic heterostructures

In this paper we develop the theory for 2D-to-2D tunneling spectroscopy aided by magnetic or quantum-order excitations, and apply it to the description of van-der-Waals heterostructures of graphene/ultrathin $\alpha-{\rm RuCl}_3$. We study the behavior of both the differential conductance and the inelastic electron tunneling spectrum (IETS) of these heterostructures. The IETS in particular exhibits features, such as the gap of continuum spinon excitations and Majorana bound states, whose energies scale {\it cubicly} with the applied magnetic field. Such scaling, which exists for a relatively wide range of fields, is at odds with the linear one exhibited by conventional magnons and can be used to prove the existence of Kitaev quantum spin liquids.

Crossover in the inelastic electron tunneling spectra of conjugated molecules with direct Au-C links.

We use inelastic electron tunneling spectroscopy (IETS) first-principles simulations to identify and characterize the different vibrational modes of single conjugated molecules bonded to Au metal electrodes. The molecules are polyphenyls (with 1 to 4 benzene units) bonded to Au via highly conducting direct Au-C bonds. The short molecule shows near resonant elastic transmission, with a crossover to tunneling for the longer backbones. The calculated inelastic spectra exhibit dips in the IETS signal of the short molecule and peaks for the longer molecules. We characterize the symmetry of vibrational modes and scattering states and discuss the changes with increasing length, where the inelastic signal of different modes can be amplified, quenched or present a crossover as more benzene units are added to the molecular backbone. This analysis rationalizes the observed trends as a function of molecular length and illustrates the role of electronic and vibrational properties on Au-C bonded molecular junctions.

Inelastic electron tunneling spectroscopy of difurylethene-based photochromic single-molecule junctions.

Diarylethene-derived molecules alter their electronic structure upon transformation between the open and closed forms of the diarylethene core, when exposed to ultraviolet (UV) or visible light. This transformation results in a significant variation of electrical conductance and vibrational properties of corresponding molecular junctions. We report here a combined experimental and theoretical analysis of charge transport through diarylethene-derived single-molecule devices, which are created using the mechanically controlled break-junction technique. Inelastic electron tunneling (IET) spectroscopy measurements performed at 4.2 K are compared with first-principles calculations in the two distinct forms of diarylethenes connected to gold electrodes. The combined approach clearly demonstrates that the IET spectra of single-molecule junctions show specific vibrational features that can be used to identify different isomeric molecular states by transport experiments.

Electrical characterization of benzenedithiolate molecular electronic devices with graphene electrodes on rigid and flexible substrates

We investigated the electrical characteristics of molecular electronic devices consisting of benzenedithiolate self-assembled monolayers and a graphene electrode. We used the multilayer graphene electrode as a protective interlayer to prevent filamentary path formation during the evaporation of the top electrode in the vertical metal–molecule–metal junction structure. The devices were fabricated both on a rigid SiO2/Si substrate and on a flexible poly(ethylene terephthalate) substrate. Using these devices, we investigated the basic charge transport characteristics of benzenedithiolate molecular junctions in length- and temperature-dependent analyses. Additionally, the reliability of the electrical characteristics of the flexible benzenedithiolate molecular devices was investigated under various mechanical bending conditions, such as different bending radii, repeated bending cycles, and a retention test under bending. We also observed the inelastic electron tunneling spectra of our fabricated graphene–electrode molecular devices. Based on the results, we verified that benzenedithiolate molecules participate in charge transport, serving as an active tunneling barrier in solid-state graphene–electrode molecular junctions.

The origin of the transition voltage of gold–alkanedithiol–gold molecular junctions

We studied the origin of the transition voltage of octanedithiol (C8DT) molecules sandwiched between two gold electrodes. Au–C8DT–Au molecular junctions were fabricated using the feedback controlled electromigration technique. The conductance measurement and the inelastic electron tunneling spectrum validate that the observed current–voltage characteristics indeed originate from the C8DT molecule in the junction. The transition voltage of Au–C8DT–Au junctions is determined to be about 0.95V, which cannot be interpreted using the energy difference between the highest occupied molecular orbital or lowest unoccupied molecular orbital of the alkyl chain and the Fermi level of electrodes. Instead, we relate the measured transition voltage to the Au–S bonds, which are about 1.4eV below the gold Fermi level. Our interpretation is supported by the ultraviolet photoelectron spectroscopy measurements and first-principles quantum transport simulations. These findings provide convincing evidence that the Au–S occupied states play a significant role in the charge transport of Au–alkanedithiol–Au molecular devices.

Effects of electron-phonon interactions on the electron tunneling spectrum of PbS quantum dots

We present a tunnel spectroscopy study of single PbS quantum dots (QDs) as a function of temperature and gate voltage. Three distinct signatures of strong electron-phonon coupling are observed in the electron tunneling spectrum (ETS) of these QDs. In the shell-filling regime, the $8\ifmmode\times\else\texttimes\fi{}$ degeneracy of the electronic levels is lifted by the Coulomb interactions and allows the observation of phonon subbands that result from the emission of optical phonons. At low bias, a gap is observed in the ETS that cannot be closed with the gate voltage, which is a distinguishing feature of the Franck-Condon blockade. From the data, a Huang-Rhys factor in the range $S\ensuremath{\sim}1.7\text{--}2.5$ is obtained. Finally, in the shell-tunneling regime, the optical phonons appear in the inelastic ETS ${d}^{2}I/d{V}^{2}$.

Investigation of inelastic electron tunneling spectra of metal-molecule-metal junctions fabricated using direct metal transfer method

We measured the inelastic electron tunneling spectroscopy (IETS) characteristics of metal-molecule-metal junctions made with alkanethiolate self-assembled monolayers. The molecular junctions were fabricated using a direct metal transfer method, which we previously reported for high-yield metal-molecule-metal junctions. The measured IETS data could be assigned to molecular vibration modes that were determined by the chemical structure of the molecules. We also observed discrepancies and device-to-device variations in the IETS data that possibly originate from defects in the molecular junctions and insulating walls introduced during the fabrication process and from the junction structure.

Role ofk-point sampling in the supercell approach to inelastic electron tunneling spectroscopy simulations of molecular monolayers

While the role of sampling of the electron momentum $k$ in supercell calculations of the elastic electron transmission is well understood, its influence in the case of inelastic electron tunneling (IET) has not yet been systematically explored. Here we compare ab initio IET spectra of molecular monolayers in the commonly used $\ensuremath{\Gamma}$-point approximation to rigorously $k$-converged results. We study four idealized molecular junctions with either alkanedithiolates or benzenedithiolates, and explore variations due to varying molecular tilt angle, density, as well as chemical identity of the monolayer. We show that the $\ensuremath{\Gamma}$-point approximation is reasonable for a range of systems, but that a rigorous convergence is needed for accurate signal amplitudes. We also describe an approximative scheme which reduces the computational cost of the $k$-averaged calculation in our implementation.

Electronic transport in benzodifuran single-molecule transistors.

Benzodifuran (BDF) single-molecule transistors have been fabricated in electromigration break junctions for electronic measurements. The inelastic electron tunneling spectrum validates that the BDF molecule is the pathway of charge transport. The gating effect is analyzed in the framework of a single-level tunneling model combined with transition voltage spectroscopy (TVS). The analysis reveals that the highest occupied molecular orbital (HOMO) of the thiol-terminated BDF molecule dominates the charge transport through Au-BDF-Au junctions. Moreover, the energy shift of the HOMO caused by the gate voltage is the main reason for conductance modulation. In contrast, the electronic coupling between the BDF molecule and the gold electrodes, which significantly affects the low-bias junction conductance, is only influenced slightly by the applied gate voltage. These findings will help in the design of future molecular electronic devices.

Effect of electron trap states on spin-dependent transport characteristics in CoFe/MgO/n+-Si junctions investigated by Hanle effect measurements and inelastic electron tunneling spectroscopy

Spin-dependent transport properties in CoFe/MgO/n+-Si junctions were investigated by Hanle effect measurements and inelastic electron tunneling (IET) spectroscopy. The CoFe/MgO/n+-Si junctions examined in this study exhibited two different Hanle curves. In the low bias region, broad Hanle signals were mainly observed; in the high bias region, narrow Hanle signals were mainly observed. The d2I/dV2-V curves (which correspond to IET spectra) contain several peaks originating from phonon modes and other peaks originating from electron trap states. At the bias voltage where electron trap states are observed, Δd2I/dV2 depends on the magnetic field and the full width at half-maximum of the Δd2I/dV2–H curves corresponds to that of the broad Hanle signals. These results indicate that electron trap states are located in the low energy region and cause a decrease in spin lifetime.

Conductance enhancement due to interface magnons in electron-beam evaporated MgO magnetic tunnel junctions with CoFeB free layer deposited at different pressure

Electron-beam evaporated MgO-based magnetic tunnel junctions have been fabricated with the CoFeB free layer deposited at Ar pressure from 1 to 4 mTorr, and their tunneling process has been studied as a function of temperature and bias voltage. By changing the growth pressure, the junction dynamic conductance dI/dV, inelastic electron tunneling spectrum d2I/dV2, and tunneling magnetoresistance vary with temperature. Moreover, the low-energy magnon cutoff energy EC derived from the conductance versus temperature curve agrees with interface magnon energy obtained directly from the inelastic electron tunneling spectrum, which demonstrates that interface magnons are involved in the electron tunneling process, opening an additional conductance channel and thus enhancing the total conductance.

Excitation of bond-alternating spin-1/2 Heisenberg chains by tunnelling electrons

Inelastic electron tunneling spectra (IETS) are evaluated for spin-1/2 Heisenberg chains showing different phases of their spin ordering. The spin ordering is controlled by the value of the two different Heisenberg couplings on the two sides of each of the chain's atoms (bond-alternating chains). The perfect anti-ferromagnetic phase, i.e. a unique exchange coupling, marks a topological quantum phase transition (TQPT) of the bond-alternating chain. Our calculations show that the TQPT is recognizable in the excited states of the chain and hence that IETS is in principle capable of discriminating the phases. We show that perfectly symmetric chains, such as closed rings mimicking infinite chains, yield the same spectra on both sides of the TQPT and IETS cannot reveal the nature of the spin phase. However, for finite size open chains, both sides of the TQPT are associated with different IETS spectra, especially on the edge atoms, thus outlining the transition.

Signatures of electron-magnon interaction in charge and spin currents through magnetic tunnel junctions: A nonequilibrium many-body perturbation theory approach

We develop a numerically exact scheme for resumming certain classes of Feynman diagrams in the self-consistent perturbative expansion for the electron and magnon self-energies in the nonequilibrium Green function formalism applied to a coupled electron-magnon (e-m) system driven out of equilibrium by the applied finite bias voltage. Our scheme operates with the electronic and magnonic GFs and the corresponding self-energies viewed as matrices in the Keldysh space, rather than conventionally extracting their retarded and lesser components, which greatly simplifies translation of diagrams into compact mathematical expressions and their computational implementation. This is employed to understand the effect of inelastic e-m scattering on charge and spin current vs bias voltage ${V}_{b}$ in F/I/F (F-ferromagnet; I-insulating barrier) magnetic tunnel junctions (MTJs), which are modeled on a quasi-one-dimensional (quasi-1D) tight-binding lattice for the electronic subsystem and quasi-1D Heisenberg model for the magnonic subsystem. For this purpose, we evaluate the Fock diagram for the electronic self-energy and the electron-hole polarization bubble diagram for the magnonic self-energy. The respective electronic and magnonic GF lines within these diagrams are the fully interacting ones, thereby requiring to solve the ensuing coupled system of nonlinear integral equations self-consistently. Despite using the quasi-1D model and treating e-m interaction in many-body fashion only within a small active region consisting of few lattice sites around the F/I interface, our analysis captures essential features of the so-called zero-bias anomaly observed [V. Drewello, J. Schmalhorst, A. Thomas, and G. Reiss, Phys. Rev. B 77, 014440 (2008)] in both MgO- and ${\mathrm{AlO}}_{x}\ensuremath{-}$based realistic 3D MTJs where the second derivative ${d}^{2}I/d{V}_{b}^{2}$ (i.e., inelastic electron tunneling spectrum) of charge current exhibits sharp peaks of opposite sign on either side ${V}_{b}=0$. We show that this is closely related to a substantially modified magnonic density of states (DOS) after the e-m interaction is turned on---the magnonic bandwidth over which DOS is nonzero becomes broadened, thereby making e-m scattering at arbitrary small bias voltage possible, while DOS also acquires peaks (on the top of a continuous background) signifying the formation of quasibound states of magnons dressed by the cloud of electron-hole pair excitations. We also demonstrate that the sum of electronic spin currents in all of the semi-infinite leads attached to the active region quantifies the loss of spin angular momentum carried away from the active region by the magnonic spin current.

Theoretical Insight into the Inelastic Electron Tunneling Spectra of an Anil Derivative

First-principles simulations have been employed to simulate the inelastic electron tunneling (IET) spectra of the enol and keto forms of an anil molecular switch and to analyze them with respect to the character of the vibrational normal modes. When the molecules are sandwiched between Au plates, the dominant IET signatures appear at very similar voltages for both forms, but their intensities are clearly different, which makes IET an efficient technique to probe the molecular state of the switch. The IET-active modes are also similar for both anil forms and consist of in-plane molecular motions, CC and ring stretching, and C-H bending motions. Moreover, the IET activity of the vibrational modes specific to the enol and keto forms, i.e., those involving bending motions of the C-O-H and C-N-H groups, respectively, demonstrates that IET spectroscopy is an efficient technique to distinguish unambiguously between the two states of the keto/enol switch.

Influence of vibrations on electron transport through nanoscale contacts

In this paper, we present a novel semi‐analytical approach to calculate first‐order electron–vibration (EV) coupling constants within the framework of density functional theory. It combines analytical expressions for the first‐order derivative of the Kohn–Sham operator with respect to nuclear displacements with coupled‐perturbed Kohn–Sham theory to determine the derivative of the electronic density matrix. This allows us to efficiently compute accurate EV coupling constants.We apply our approach to describe inelastic electron tunneling (IET) spectra of metallic and molecular junctions. A gold junction bridged by an atomic chain is used to validate the developed method, reproducing established experimental and theoretical results. For octanedithiol and octanediamine single‐molecule junctions, we discuss the influence of the anchoring group and mechanical stretching on the IET spectra.

Spin-pumping and inelastic electron tunneling spectroscopy in topological insulators

We demonstrate that a quantum spin Hall current, spontaneously generated at the edge of a two-dimensional topological insulator, acts as a source of spin-pumping for a magnetic impurity with uniaxial anisotropy. One can then manipulate the impurity spin direction by means of an electrical current without using either magnetic electrodes or an external magnetic field. Furthermore we show that the unique properties of the quantum spin Hall topological state have profound effects on the inelastic electron tunneling spectrum of the impurity. For low current densities inelastic spin-flip events do not contribute to the conductance. As a consequence the conductance steps, normally appearing at voltages corresponding to the spin excitations, are completely suppressed. In contrast an intense current leads to spin pumping and generates a transverse component of the impurity spin. This breaks the topological phase yielding to the conductance steps.

Effects of the basis set and of the exchange–correlation functional on the Inelastic Electron Tunneling signatures of 1,4-benzenedithiol

The effects of the atomic basis set and of the exchange–correlation (XC) functional on the Inelastic Electron Tunneling (IET) spectra have been investigated by considering the prototypical 1,4-benzenedithiol molecule. These studies have been completed by tackling the reliability of the same methods for predicting the IR absorption spectrum of the same molecule. The main conclusions are (i) the B3LYP XC functional is suitable to predict the relative vibrational frequencies, (ii) provided a scaling factor is used, the root mean square error on the vibrational frequencies goes down to 18cm−1, (iii) triple-ζ basis sets and in particular the cc-pVTZ basis set is a good compromise between accuracy and computational needs, (iv) basis set effects on the IET intensities are larger than those of the XC functional, and (v) the cc-pVTZ, cc-pVQZ, and aug-cc-pVDZ basis sets provide consistent IET intensities.