Electron Tunneling Spectroscopy Research Articles

Strong Electron-Vibration Signals in Weakly Coupled Molecular Junctions: Activation of Spin-Crossover.

Manipulating individual molecular spin states with electronic current has the potential to revolutionize quantum information devices. However, it is still unclear how a current can cause a spin transition in single-molecule devices. Here, we propose a spin-crossover (SCO) mechanism induced by electron-phonon coupling in an iron(II) phthalocyanine molecule situated on a graphene-decoupled Ir(111) substrate. We performed simulations of both elastic and inelastic electron tunneling spectroscopy (IETS), which reveal current-induced Fe-N vibrations and an underestimation of established electron-vibration signals. Going beyond standard perturbation theory, we examined molecules in various charge and spin states using the Franck-Condon framework. The increased probability of spin switching suggests that notable IETS signals indicate SCO triggered by the inelastic vibrational excitation associated with Fe-N stretching.

Impact of Single-Melamine Tautomerization on the Excitation of Molecular Vibrations in Inelastic Electron Tunneling Spectroscopy.

Vibrational quanta of melamine and its tautomer are analyzed at the single-molecule level on Cu(100) with inelastic electron tunneling spectroscopy. The on-surface tautomerization gives rise to markedly different low-energy vibrational spectra of the isomers, as evidenced by a shift in mode energies and a variation in inelastic cross sections. Spatially resolved spectroscopy reveals the maximum signal strength on an orbital nodal plane, excluding resonant inelastic tunneling as the mechanism underlying the quantum excitations. Decreasing the probe-molecule separation down to the formation of a chemical bond between the melamine amino group and the Cu apex atom of the tip leads to a quenched vibrational spectrum with different excitation energies. Density functional and electron transport calculations reproduce the experimental findings and show that the shift in the quantum energies applies to internal molecular bending modes. The simulations moreover suggest that the bond formation represents an efficient manner of tautomerizing the molecule.

Enantioselectivity from inelastic electron tunnelling through a chiral sensor

The vibration theory of olfaction, which explains it as the sensing of odorant molecules by their vibrational energies through inelastic electron tunnelling spectroscopy (IETS) has inspired olfactory sensor ideas. However, this theory has been presumed inadequate to explain the difference in smell between enantiomers (chiral molecules, which are mirror images of each other), since these have identical vibrational spectra. Going beyond phenomenological assumptions of enantioselective tunnelling, we show on the basis of ab initio modelling of real chiral molecules, that this drawback is indeed obviated for IETS-based olfactory sensors if they are chiral. Our treatment unifies IETS with chirality induced spin selectivity, which explains that charge polarization in chiral molecules by accompanied by spin polarization. First, we apply ab initio symmetry adapted perturbation theory to explain and illustrate enantioselective coupling of chiral odorant molecules and chiral olfactory sensors. This naturally leads to enantioselective coupling of the vibrational mode of an odorant to electron transport (electron-vibron coupling) in an IETS-based sensor when both odorant and sensor are chiral. Finally, we show, from phenomenological quantum transport calculations, that that in turn results in enantioselective IET spectra. Thus, we have demonstrated the feasibility of enantioselective sensing within a vibration framework. Our work also limns the possibility of quantum biomimetic electronic nose sensors that are enantioselective, a feature which could open up new sensing applications.

Molecular-Scale Visualization of Steric Effects of Ligand Binding to Reconstructed Au(111) Surfaces.

Direct imaging of single molecules at nanostructured interfaces is a grand challenge with potential to enable new, precise material architectures and technologies. Of particular interest are the structural morphology and spectroscopic signatures of the adsorbed molecule, where modern probes are only now being developed with the necessary spatial and energetic resolution to provide detailed information at the molecule-surface interface. Here, we directly characterize the adsorption of individual m-terphenyl isocyanide ligands on a reconstructed Au(111) surface through scanning tunneling microscopy and inelastic electron tunneling spectroscopy. The site-dependent steric pressure of the various surface features alters the vibrational fingerprints of the m-terphenyl isocyanides, which are characterized with single-molecule precision through joint experimental and theoretical approaches. This study provides molecular-level insights into the steric-pressure-enabled surface binding selectivity as well as its effect on the chemical properties of individual surface-binding ligands.

Temperature and bias voltage dependences of magnetic tunnel junction with FeAlSi electrode

We fabricated magnetic tunnel junctions (MTJs) with FeAlSi free layers and investigated the tunnel magnetoresistance (TMR) properties. We found that the temperature and bias voltage dependences of the TMR effect in FeAlSi-MTJs were almost the same as MTJs with Fe free layers despite the low Curie temperature of FeAlSi. In the inelastic electron tunneling spectroscopy measured at low temperatures, the relatively large cutoff energy of magnon excitation at the FeAlSi and MgO interface was confirmed. In addition, we studied for the first time the exchange stiffness constant of FeAlSi films by Brillouin light scattering. The determined value of the stiffness constant of FeAlSi was 14.3 (pJ/m), which was similar to that of Fe. Both the large magnon cutoff at the interface and the stiffness constant of FeAlSi are considered to be the reason for the good temperature and voltage dependences of FeAlSi-MTJs.

Large negative differential conductance and its transformation in a single radical molecule.

The discovery of negative differential conductance (NDC) in a single molecule and mechanism controlling this phenomenon are important for molecular electronics. We investigated the electronic properties of a typical radical molecule 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-yloxy (CTPO) on an Au(111) surface using low-temperature scanning tunneling microscopy (STM) and inelastic electron tunneling spectroscopy. Large NDC was observed in single CTPO molecules at the boundary of the crystal monolayer. The origin of observed NDC is revealed as the inelastic electron-phonon scattering during tunneling, and the strong spatial variation of the NDC over the single molecule illustrates the nature of the localized radical group. In addition, the NDC can be transformed into a positive differential conductance peak by tuning coupling strengths between different tunneling channels. An empirical multi-channel model has been developed to describe the competition between the valley-shaped NDC and peak-shaped positive differential conductance. The unique electronic property and giant conductance change observed in this radical molecule is valuable for designing novel molecular devices in the future.

Exchange Interactions and Intermolecular Hybridization in a Spin-1/2 Nanographene Dimer.

Phenalenyl is a radical nanographene with a triangular shape hosting an unpaired electron with spin S = 1/2. The open-shell nature of the phenalenyl is expected to be retained in covalently bonded networks. As a first step, we report synthesis of the phenalenyl dimer by combining in-solution synthesis and on-surface activation and its characterization on Au(111) and on a NaCl decoupling layer by means of inelastic electron tunneling spectroscopy (IETS). IETS shows inelastic steps that are identified as singlet-triplet excitation arising from interphenalenyl exchange. Spin excitation energies with and without the NaCl decoupling layer are 48 and 41 meV, respectively, indicating significant renormalization due to exchange with Au(111) electrons. Furthermore, third-neighbor hopping-induced interphenalenyl hybridization is fundamental to explaining the position-dependent bias asymmetry of the inelastic steps and activation of kinetic interphenalenyl exchange. Our results pave the way for bottom-up synthesis of S = 1/2 spin-lattices with large exchange interactions.

Single-Molecule Continuous-Wave Terahertz Rectification Spectroscopy and Microscopy

We report rectification spectroscopy (RS) for single molecules performed with continuous-wave terahertz (CW THz) radiation at the tunneling junction of a scanning tunneling microscope (STM) at 8 K. CW THz-RS serves as a new technique in single-molecule vibrational and magnetic excitation spectroscopy besides inelastic electron tunneling spectroscopy (IETS). By quantitatively studying IETS and THz RS, we show that CW THz induces a sinusoidal bias modulation with amplitude linearly dependent on the THz far-field amplitude. Such THz-induced bias modulation amplitude appears to be sensitive to the THz beam alignment but insensitive to variation in the tunneling gap far smaller than the THz wavelength.

Detecting Majorana zero modes with transport measurements

Topological superconductors have attracted much research interest, because they were proposed to host non-abelian Ising Anyon Majorana zero modes and thus can be used to construct fault-tolerant topological quantum computers. This paper mainly reviews the electrical transport methods for detecting the presence of Majorana zero modes. First, the basic concepts of topological superconductivity, Majorana zero modes and non-Abelian statistics are introduced, followed by a summary of various schemes for implementing topological superconductivity. Then, the experimental methods for detecting topological superconductivity or Majorana zero modes by using low-temperature transport methods, including electron tunneling spectroscopy, Coulomb blockade spectroscopy and non-local conductance detection, which are widely used in superconductor/nanowire hybrid systems, are discussed. On the other hand, the measurements of the (inverse) AC Josephson effect and current (energy) phase relationships are also reviewed to identify Majorana zero modes in Josephson devices. Meanwhile, to deepen our understanding of Majorana zero modes, some mechanisms for explaining the experimental data observed in the above experiments are provided. Finally, a brief summary and outlook of the electrical transport methods of Majorana zero modes are presented.

Simplified inelastic electron tunneling spectroscopy based on low-noise derivatives

A standard experimental setup for Inelastic Electron Tunneling Spectroscopy (IETS) performs the measurement of the second derivative of the current with respect to the voltage (d^2I/dV^2) using a small AC signal and a lock-in based second harmonic detection. This avoids noise arising from direct differentiation of the current-voltage characteristics (I–V) by standard numerical methods. Here we demonstrate a noise-filtering algorithm based on Tikhonov Regularization to obtain IET spectra (i.e. d^2I/dV^2 vs. V) from measured DC I–V curves. This leads to a simple and effective numerical method for IETS extraction. We apply the algorithm to I–V data from a molecular junction and a metal-insulator-semiconductor tunneling device, demonstrating that the computed first/second derivatives have a workable match with those obtained from our lock-in measurements; the computed IET spectral peaks also correlate well with reported experimental ones. Finally, we present a scheme for automated tuning of the algorithm parameters well-suited for the use of this numerical protocol in real applications.

Magnetic Fingerprints in an All-Organic Radical Molecular Break Junction.

Polycyclic aromatic hydrocarbons radicals are organic molecules with a nonzero total magnetic moment. Here, we report on charge-transport experiments with bianthracene-based radicals using a mechanically controlled break junction technique at low temperatures (6 K). The conductance spectra demonstrate that the magnetism of the diradical is preserved in solid-state devices and that it manifests itself either in the form of a Kondo resonance or inelastic electron tunneling spectroscopy signature caused by spin-flip processes. The magnetic fingerprints depend on the exact configuration of the molecule in the junction; this picture is supported by reference measurements on a radical molecule with the same backbone but with one free spin, in which only Kondo anomalies are observed. The results show that the open-shell structures based on the bianthracene core are interesting systems to study spin–spin interactions in solid-state devices, and this may open the way to control them either electrically or by mechanical strain.

Role of the Magnetic Anisotropy in Atomic-Spin Sensing of 1D Molecular Chains.

One-dimensional metal-organic chains often possess a complex magnetic structure susceptible to modification by alteration of their chemical composition. The possibility to tune their magnetic properties provides an interesting playground to explore quasi-particle interactions in low-dimensional systems. Despite the great effort invested so far, a detailed understanding of the interactions governing the electronic and magnetic properties of the low-dimensional systems is still incomplete. One of the reasons is the limited ability to characterize their magnetic properties at the atomic scale. Here, we provide a comprehensive study of the magnetic properties of metal-organic one-dimensional (1D) coordination polymers consisting of 2,5-diamino-1,4-benzoquinonediimine ligands coordinated with Co or Cr atoms synthesized under ultrahigh-vacuum conditions on a Au(111) surface. A combination of integral X-ray spectroscopy with local-probe inelastic electron tunneling spectroscopy corroborated by multiplet analysis, density functional theory, and inelastic electron tunneling simulations enables us to obtain essential information about their magnetic structures, including the spin magnitude and orientation at the magnetic atoms, as well as the magnetic anisotropy.

Spin excitations of individual magnetic dopants in an ionic thin film

Individual magnetic transition metal dopants in a solid host usually exhibit relatively small spin excitation energies of a few meV. Using scanning tunneling microscopy and inelastic electron tunneling spectroscopy (IETS) techniques, we have observed a high spin excitation energy around 36 meV for an individual Co substitutional dopant in ultrathin NaCl films. In contrast, the Cr dopant in the NaCl film shows much lower spin excitation energy around 2.5 meV. Electronic multiplet calculations combined with first-principles calculations confirm the spin excitation induced IETS, and quantitatively reveal the out-of-plane magnetic anisotropies for both Co and Cr. They also allow reproducing the experimentally observed redshift in the spin excitations of Co dimers and ascribe it to a charge and geometry redistribution.

Atomic-Scale Rectification and Inelastic Electron Tunneling Spectromicroscopy.

The phenomenon of rectification describes the emergence of a DC current from the application of an oscillating voltage. Although the origin of this effect has been associated with the nonlinearity in the current-voltage I(V) relation, a rigorous understanding of the microscopic mechanisms for this phenomenon remains challenging. Here, we show the close connection between rectification and inelastic electron tunneling spectroscopy and microscopy for single molecules with a scanning tunneling microscope. While both techniques are based on nonlinear features in the I(V) curve, comprehensive line shape analyses reveal notable differences that highlight the two complementary techniques of nonlinear conductivity spectromicroscopy for probing nanoscale systems.

The Limits of Inelastic Tunneling Spectroscopy for Identifying Transport Pathways

Inelastic electron tunneling spectroscopy (IETS) is a powerful tool to study the properties of molecular junctions. In particular, it is considered useful for extracting information on electron transport pathways. We explore the limits of this approach by comparing computed interatomic transmission pathways with IETS intensities for different molecular junctions, employing a new efficient implementation for evaluating IETS intensities via the mode-tracking algorithm. While we indeed find a correlation between pathways and IETS intensities when vibrations are clearly localized on atoms off the transport pathway, we do not see such a correlation for molecules with less localized vibrations, even if transport pathways only a sample part of the molecule and even if a statistical analysis over the vibrational modes is made. This could indicate that the significance of IETS signals for transport pathways is limited to molecules with localized vibrational modes.

Electron tunneling spectroscopy of an anisotropic Kitaev quantum spin liquid sandwiched between superconductors

We present the electron tunneling transport and spectroscopic characters of a superconducting (SC) Josephson junction with a barrier of a single anisotropic Kitaev quantum spin liquid (QSL) layer. We find that the dynamical spin-correlation features are well reflected in the direct-current differential conductance $d{I}^{c}/dV$ of single-particle tunneling, including the unique spin gap and dressed itinerant Majorana dispersive band, in addition to an energy shift $2\mathrm{\ensuremath{\Delta}}$ from the two-SC-lead gap. From the spectral characters, we identify different topological quantum phases of the anisotropic Kitaev QSL. We also present the zero-voltage Josephson current ${I}^{s}$, which displays residual features of the anisotropic Kitaev QSL. These results pave a new path to measurement of dynamical spinon or Majorana fermion spectroscopy of Kitaev and other spin-liquid materials.

Charge-Trapping-Induced Hysteresis Effects in Highly Doped Silicon Metal-Oxide-Semiconductor Structures.

It is shown that a simple metal–oxide–semiconductor (MOS) structure with highly doped silicon substrate can exhibit current–voltage hysteresis effects related to sudden rises and drops in the flowing electric current. Experimental current–voltage characteristics of Al-SiO2-(n++Si) structures are presented and discussed. Their analysis shows that the ohmic and shallow traps assisted space-charge limited conduction (SCLC) are the dominating transport mechanisms. Sudden rises and drops in the flowing current, leading to the current–voltage hysteresis effects, are attributed to tunneling through deep traps in the oxide. Based on inelastic electron tunneling spectroscopy (IETS), the energy levels of the deep traps and their position in the oxide are evaluated.

A qPlus-based scanning probe microscope compatible with optical measurements.

We design and develop a scanning probe microscope (SPM) system based on the qPlus sensor for atomic-scale optical experiments. The microscope operates under ultrahigh vacuum and low temperature (6.2K). In order to obtain high efficiency of light excitation and collection, two front lenses with high numerical apertures (N.A. = 0.38) driven by compact nano-positioners are directly integrated on the scanner head without degrading its mechanical and thermal stability. The electric noise floor of the background current is 5 fA/Hz1/2, and the maximum vibrational noise of the tip height is below 200 fm/Hz1/2. The drift of the tip-sample spacing is smaller than 0.1 pm/min. Such a rigid scanner head yields small background noise (oscillation amplitude of ∼2pm without excitation) and high quality factor (Q factor up to 140 000) for the qPlus sensor. Atomic-resolution imaging and inelastic electron tunneling spectroscopy are obtained under the scanning tunneling microscope mode on the Au(111) surface. The hydrogen-bonding structure of two-dimensional (2D) ice on the Au(111) surface is clearly resolved under the atomic force microscope (AFM) mode with a CO-terminated tip. Finally, the electroluminescence spectrum from a plasmonic AFM tip is demonstrated, which paves the way for future photon-assisted SPM experiments.

Electronic transport through single-molecule oligophenyl-diethynyl junctions with direct gold-carbon bonds formed at low temperature.

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

On‐Surface Synthesis and Collective Spin Excitations of a Triangulene‐Based Nanostar

AbstractTriangulene nanographenes are open‐shell molecules with predicted high spin state due to the frustration of their conjugated network. Their long‐sought synthesis became recently possible over a metal surface. Here, we present a macrocycle formed by six [3]triangulenes, which was obtained by combining the solution synthesis of a dimethylphenyl‐anthracene cyclic hexamer and the on‐surface cyclodehydrogenation of this precursor over a gold substrate. The resulting triangulene nanostar exhibits a collective spin state generated by the interaction of its 12 unpaired π‐electrons along the conjugated lattice, corresponding to the antiferromagnetic ordering of six S=1 sites (one per triangulene unit). Inelastic electron tunneling spectroscopy resolved three spin excitations connecting the singlet ground state with triplet states. The nanostar behaves close to predictions from the Heisenberg model of an S=1 spin ring, representing a unique system to test collective spin modes in cyclic systems.