Inelastic electron tunneling spectroscopy evidence for a surface chemical reaction

The inelastic electron tunnel effect has been used to show the occurence of a surface chemical reaction between an organic molecule (benzoyl chloride) dopant and the tunnel barrier of a junction (Al-oxide-Pb).     

Inelastic electron tunneling

Inelastic Electron Tunneling Spectroscopy (IETS) is a new technique for measuring the vibrational spectrum of minute quantities of organic compounds. Sensitivity is its key advantage over the conventional techniques of infrared and Raman spectroscopy. This article will first discuss the technique itself: its theoretical basis, selection rules, sensitivity, vibrational mode shifts due to surface interactions and superconductivity, and sample preparation. Then it will discuss applications of the technique to problems in biology, radiation physics, surface physics, and catalysis.     

Inelastic electron tunneling spectroscopy: Intensity as a function of surface coverage

Inelastic election tunneling spectroscopy (IETS) is a sensitive technique for obtaining vibrational spectra of molecules adsorbed on an oxide surface and incorporated into a metal-oxide-metal tunnel junction. IETS energy data are used routinely. However, IETS intensities contain additional information which, for theoretical and experimental reasons, has not been used systematically. This paper examines the variation of IETS intensity with surface coverage of dopant molecules in the junction, a relationship of practical and theoretical importance. IET spectra are taken using standard experimental techniques and a liquid doping technique which allows the surface coverage to be determined independently. From an analysis of a large number of modes of benzoic acid on alumina, it is found that IETS intensity, defined in the usual way as the normalized change in conductance, $\text{Δ σ}\text{σ}$, is a nonlinear function of surface coverage. A physical model is presented which attributes this behavior to a difference in elastic tunneling conductances through empty or filled regions of the dopant layer in a junction with a fraction of a monolayer coverage. In addition, the liquid and vapor doping techniques in common use in IETS are discussed in terms of statistical mechanics and are shown to be manifestations of the same basic phenomenon.     

Inelastic electron tunneling spectroscopy of an alkanethiol self-assembled monolayer using scanning tunneling microscopy

We report inelastic electron tunneling spectroscopy (IETS) of a C8 alkanethiol self-assembled monolayer using a scanning tunneling microscope (STM). High-resolution STM IETS spectra show clear features of the C-H bending and C-C stretching modes in addition to the C-H stretching mode, which enables a precise comparison with previously reported vibrational spectroscopy, especially electron energy loss spectroscopy data. Intensity variation of vibrational peaks with tip position is discussed with the STM IETS detection mechanism.     

Inelastic electron tunneling spectroscopy on ultrahigh vacuum prepared tunnel junctions

Inelastic electron tunneling (IET) spectra of clean ultrahigh vacuum (UHV) prepared (Al/Al oxide/Pb) tunnel junctions are discussed. Microcrystalline Al oxide is shown to grow on these Al films. This is in contrast to the formation of amorphous Al oxide in the common high vacuum (HV) preparation process. The IET-spectra of UHV prepared tunnel junctions are free of peaks due to contaminations. Conclusions concerning the growth of oxides on Al films are drawn.     

Inelastic electron tunneling spectroscopy of carboxylic acids on alumina at low coverage

The difficulties in assigning certain modes of carboxylic acids adsorbed on alumina are discussed. The study of the spectra of marked acetic acid CH₃C¹⁸O¹⁸OH adsorbed on alumina has allowed us to clarify the assignments of the acetate ion formed. Then an examination of the spectra at very low coverages has enabled us to propose a model for the adsorption, which occurs on (at least) two different sites.     

Inelastic electron tunneling spectroscopy on MOS structures with very thin oxide films

Inelastic electron tunneling spectroscopy at 4.2 K was used to investigate the defect structure of MOS capacitors with very thin SiO₂ films. Samples were degeneratelyP-andB-doped Si substrates, oxidized in O₂ at 600°C and provided with evaporated Pb, Au, In, Al or Mg electrodes. The observed peaks in the second derivative of theI-U characteristic were assigned to the excitation of phonons and of vibrational modes of the dopants and impurities. The results were found to correlate with infrared data. In addition, a distinct effect of Si/SiO₂ interface states on the characteristic was found.     

Inelastic electron tunneling spectroscopy of a model catalyst: CO on Rh/Al2O3

Using tunneling spectroscopy we have studied the preparation and behavior of dispersed rhodium model catalysts supported on alumina. Samples were prepared by vacuum evaporation from Rh metal or Rh₂O₃ sources onto an oxidized Al film and CO was adsorbed in-situ. The tunnel junctions were formed by adding a Pb top electrode and the vibrational spectra of the adsorbed species were measured. We observed qualitatively different spectra when the preparation procedure was varied. Special care was taken to monitor and control background gases. We obtained different results from Rh of Rh₂O₃ sources and the presence of oxygen or water affects the vibrational spectra of the adsorbed CO. We also study the effect of the Rh thickness on the spectral intensity. Other experiments were measurement of the superconducting tunneling spectra of the Pb and a TEM study of Rh particle size. Previously reported data from tunneling and IR measurements are compared with the present work. Based on these results, we conclude that there are two species present, either a linear Rh-CO or doubly (geminal) adsorbed Rh(CO)₂ depending upon the degree of dispersion and oxidation of the Rh. The evidence also indicates that in both instances a dispersed form of Rh, rather than relatively large Rh metal particles, is responsible for the observed spectra.     

Dynamics of quantum dot nuclear spin polarization controlled by a single electron

We present measurements of the buildup and decay of nuclear spin polarization in a single semiconductor quantum dot. Our experiment shows that we polarize the nuclei in a few milliseconds, while their decay dynamics depends drastically on external parameters. We show that a single electron can very efficiently depolarize nuclear spins in milliseconds whereas in the absence of the electron the nuclear spin lifetime is on the scale of seconds. This lifetime is further enhanced by 1-2 orders of magnitude by quenching the nonsecular nuclear dipole-dipole interactions with a magnetic field of 1 mT.     

Hyperfine switching triggered by resonant tunneling for the detection of a single nuclear spin qubit

A novel detection mechanism and a robust control of a single nuclear spin-flip by hyperfine interactions between the nuclear spin and tunneling electron spin are proposed on the basis of ab initio non-equilibrium Green's function calculations. The calculated relaxation times of the nuclear spin of proton in a nano-contact system, Pd(electrode)-H₂-Pd(electrode), show that ON/OFF switching of hyperfine interactions is effectively triggered by resonant tunneling mediated through the d-orbitals of Pd. The relaxation times at ON-resonance are ∼¹⁰³ times faster than those at OFF-resonance, indicating that ON-resonance is suitable for the detection (read-out) of nuclear spin states. In addition, the effectiveness of bias voltage applications at OFF-resonance for selective operations on the proton qubit is demonstrated in the calculations of the resonant frequencies of proton using the gauge-invariant atomic orbital method.     

Inelastic electron scattering from nuclear matter

The response function, which is directly related to the cross section for inelastic scattering of electrons from nuclear matter, is calculated with the help of a time-dependent perturbation theory using a separable potential. All diagrams through second order in the interaction are computed and their contributions compared. The self-energy problem is examined, and it is concluded that a Hartree-Fock approximation is preferable to one which attempts to takeK-matrix insertions into account. Results for the response function are compared with those of previous workers.     

Resonant tunneling single electron transistors

We use a modulation-doped double barrier heterostructure to fabricate a resonant tunneling single electron transistor. Irregular Coulomb blockade oscillations are observed when the gate voltage is swept to vary one-by-one the number of electrons in the dot close to 'pinch-off'. The oscillation period is not regular, and generally becomes longer as the electron number is decreased down to zero, reflecting the growing importance of electron-electron interactions and size quantization. Negative differential resistance associated with resonant tunneling through zero-dimensional states is pronounced for a dot holding just a few electrons. The temperature dependence of the Coulomb blockade oscillations and that for the negative differential resistance are not the same. This highlights the different effects of charging and resonant tunneling on the transport characteristics.     

Inelastic resonant tunneling

A general expression for the resonant contribution to a tunneling current has been obtained and analyzed in the tunneling Hamiltonian approximation. Two types of resonant tunneling structures are considered: structures with a random impurity distribution and double-barrier structures, where the resonant level results from size quantization. The effect of temperature on the current-voltage curves of tunneling structures is discussed. The study of the effect of potential barrier profile on the d ² I/dV ² line shape is of interest for experiments in inelastic tunneling spectroscopy. Various experimental situations where the inelastic component of the tunneling current can become comparable to the elastic one are discussed. Fiz. Tverd. Tela (St. Petersburg) 40, 1151–1155 (June 1998)     

Nature of tunneling electron spin resonance of an isolated surface spin

A phenomenological model has been proposed for tunneling electron spin resonance (ESR) of an isolated surface spin situated in a scanning tunneling microscope (STM), which explains the dependence of features (local maxima) of the tunneling current on the radio-frequency (RF) electric field and on the position of the tip with respect to the spin. A crossover of the line shape of the resonance signals, whose nature in weak and strong pumping fields corresponds to Lorentzian and Fano resonances, respectively, has been interpreted. New ESR–STM effects that are linear and nonlinear in the RF field and are promising for developing the methods of controlling spin qubits have been predicted.     

Effects of spin relaxation on electron tunneling through single discrete levels in magnetic tunnel junctions

Electron tunneling through a single discrete level of a quantum dot, coupled to two ferromagnetic leads, is studied theoretically in the sequential tunneling regime. Electron correlations and spin relaxation processes on the dot are taken into account. It is shown that strong Coulomb correlations can enhance tunnel magnetoresistance in a certain bias range. The effect, however, is suppressed by spin-flip processes.     

Inelastic tunneling of electrons through a quantum dot with an embedded single molecular magnet

We report a theoretical analysis of electron transport through a quantum dot with an embedded biaxial single-molecule magnet (SMM) based on mapping of the many-body interaction-system onto a one-body problem by means of the non-equilibrium Green function technique. It is found that the conducting current exhibits a stepwise behavior and the nonlinear differential conductance displays additional peaks with variation of the sweeping speed and the magnitude of magnetic field. This observation can be interpreted by the interaction of electron-spin with the SMM and the quantum tunneling of magnetization. The inelastic conductance and the corresponding tunneling processes are investigated with normal as well as ferromagnetic electrodes. In the case of ferromagnetic configuration, the coupling to the SMM leads to an asymmetric tunneling magnetoresistance (TMR), which can be enhanced or suppressed greatly in certain regions. Moreover, a sudden TMR-switch with the variation of magnetic field is observed, which is seen to be caused by the inelastic tunneling.     

Observation of coherent oscillations in a single electron spin

Rabi nutations and Hahn echo modulation of a single electron spin in a single defect center have been observed. The coherent evolution of the spin quantum state is followed via optical detection of the spin state. Coherence times up to several microseconds at room temperature have been measured. Optical excitation of the spin states leads to decoherence. Quantum beats between electron spin transitions in a single spin Hahn echo experiment are observed. A closer analysis reveals that beats also result from the hyperfine coupling of the electron spin to a single 14N nuclear spin. The results are analyzed in terms of a density matrix approach of an electron spin interacting with two oscillating fields.