Ballistic electron emission microscopy studies of Au/molecule/n-GaAs diodes

We present nanometer-scale resolution, ballistic electron emission microscopy (BEEM) studies of Au/octanedithiol/n-GaAs (001) diodes. The presence of the molecule dramatically increases the BEEM threshold voltage and displays an unusual transport signature as compared to reference Au/GaAs diodes. Furthermore, BEEM images indicate laterally inhomogeneous interfacial structure. We present calculations that address the role of the molecular layer at the interface. Our results indicate that spatially resolved measurements add new insight to studies using conventional spatial-averaging techniques.     

Electron flow generated by gas phase exothermic catalytic reactions using a platinum-gallium nitride nanodiode

We report steady-state conversion of chemical reaction energy into hot electrons by ballistic injection into a platinum-gallium nitride (Pt/GaN) nanodiode during the platinum-catalyzed oxidation of carbon monoxide. Surface catalytic reactions of molecules from the gas phase generated continuous steady-state hot electron currents with energies at least that of Schottky barrier energy ( approximately 1 eV). These hot electron currents were observed on two different nanodiodes (Pt/TiO2 and Pt/GaN) and represent a new method of chemical energy conversion.     

Absorption spectroscopic and ESR studies on one-electron reduction products of copper(II) and oxovanadium(IV) tetraphenylporphyrins produced by γ-radiolysis in 2-methyltetrahydrofuran solutions at 77 K

Optical absorption spectra of one-electron reduced species of copper(II) and oxovanadium(IV) tetraphenylporphyrins. Cu(II)TPP and V(IV)OTPP, in 2-methyltetrahydrofuran at 77 K reveal that not the central metal but the porphyrin ligand is reduced by an excess electron. The triplet ESR spectrum resulting from the spin-spin interaction between two odd electrons located on the porphyrin ligand and the central metal is observed for the one-electron reduced species of V(IV)OTPP while not for that of Cu(II)TPP.     

Hot adsorbate-induced retardation of the internal thermalization of nonequilibrium electrons in adsorbate-covered metal nanoparticles

Femtosecond transient absorption spectroscopy has been used to investigate the electron-electron scattering dynamics in sulfate-covered gold nanoparticles of 2.5 and 9.2 nm in diameter. We observe an unexpected retardation of the absolute internal thermalization time compared to bulk gold, which is attributed to a negative feedback by the vibrationally excited sulfate molecules. These hot adsorbates, acting as a transient energy reservoir, result from the back and forth inelastic scattering of metal nonequilibrium electrons into the pi orbital of the sulfate. The vibrationally excited adsorbates temporarily govern the dynamical behavior of nonequilibrium electrons in the metal by re-emitting hot electrons. In other terms, metal electrons reabsorb the energy deposited in the hot sulfates by a mechanism involving the charge resonance between the sulfate molecules and the gold NPs. The higher surface-to-volume ratio of sulfate-covered gold nanoparticles of 2.5 nm leads to a stronger inhibition of the internal thermalization. Interestingly, we also note an analogy between the mechanism described here for the slow-down of electron-electron scattering in metal nanoparticles by the hot adsorbates and the hot phonon-induced retardation of hot charge carriers cooling in semiconductors.     

Storage modulus’ variation in aging and its application in assessing the stability of emulsion explosive matrix

An investigation was performed into the stability of bulk emulsion explosive matrix (BEEM) via studying on the variation of storage modulus in aging. The experimental results show that there is a tight relationship between storage modulus (G′) and the stability of BEEM. The increase of the amount of ammonium nitrate (AN) crystals in aging leads to the increase of G′. When the amount of AN crystals reaches a certain extent, the vastly destroyed microstructure results in the disappear of viscoelastic property of BEEM. The results demonstrated that the less growth ratio of G′ causes a better stability of BEEM. The G′ was used to investigate the effect of the nature of emulsifier and continuous phase on the stability of BEEM. It is found that the chemical structure of head group, the length of hydrophobic chain and the content of emulsifier affect the stability of BEEM. Besides that, the viscosity and polarity of continuous phase also have important effect on the stability of BEEM.     

Radiation-Induced Injection Conductivity of Polymers

Steady-state currents flowing through planar polymer layers under irradiation with 15–50 keV electrons were studied experimentally and theoretically. The ultimate range of electrons was somewhat below the layer thickness. The Monte Carlo method was used to determine the basic transport characteristics of fast electrons in polymers (maximum range, depth distribution of absorbed dose and forward current). It was shown that significant steady-state currents (1 to 10% of the electron beam current) were observed only if the thickness of blocking (unirradiated) layer did not exceed 5 m. The magnitude of these currents was almost unaffected by the polymer type (polymers with minimum radiation-induced conductivity and polymers with electron or hole conductivity were examined). It was found that conventional theories of conductivity of dielectrics failed to explain the observed experimental data. Additional arguments in favor of the hypothesis of streamer mechanism of injection currents through an unirradiated polymer layer were obtained. It is emphasized that the radiation-induced heating of polymer samples can play an important role in the phenomenon under study, acting as an undesirable technical factor, that strongly distorts obtainable experimental data.     

Electrical properties of single-crystalline CaAl2Si2

Electrical resistivity and Hall coefficient measurements of single-crystalline CaAl(2)Si(2) revealed that CaAl(2)Si(2) is a metal in which both electrons and holes contribute to the transport properties; its dominant carriers are holes at temperature below 150 K but electrons above that temperature.     

An endogenous multiple scattering method for the calculation of the elastic scattering cross sections of electron shape resonances in polyatomic molecu

A procedure is described for obtaining the scattering potential for elastic electron—molecule scattering within the one-electron overlapping sphere multiple scattering Xα method. The method has been used to calculate the total elastic electron scattering cross sections for the nitrogen, ethylene and 1,3,5-trifluorobenzene molecules, which compare well with experimental data.     

Galvanomagnetic size studies of metallic surface processes

This review gives an account of basic ideas concerning scattering of current carriers at metallic surfaces. It deals with the physical picture and theory of surface-sensitive galvanomagnetic size effects, i.e., transverse magnetic resistance, static skin effect, Sondheimer oscillations, and conduction electron focusing. These processes are employed to study the peculiarities of current carrier surface scattering with regard to the electron–hole transfers. Diffraction of conduction electrons at adsorbed submonolayer lattices is considered. An outlook is given of the application of these phenomena to the study of adsorption and ordering of adsorbed submonolayer films of various symmetries and chemical content, involving, in particular, precursor states. Influence of the diffusion of adsorbed atoms into the substrate on the kinetic size effects is considered in detail.     

Half metallic properties of LaSrVMoO6

The recent synthesized LaSrVMoO₆ was speculated to be compensated half metal, i.e., half metal with zero magnetic moment. Based on the experimental structure, our first principles study indicates that it is ferrimagnetic and half metallic with the magnetic moment 2.0 μ_B when the electron correlation of Mo 4d electrons is larger than 2.72 eV. This indicates the strong electron correlation effect of Mo 4d electrons. Nonetheless, the obtained large magnetic moment (2.0 μ_B) contradicts with the experimental observed nearly zero magnetic moment. Although the large antisite defects of the experimental sample might be the reason to reduce the saturated magnetic moment, further physical insights need to be investigated. The spin‐orbit coupling effect has minor effect on the studied properties. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

Secondary Electron Emission from an Organic Layer with a Surface Charge

Using secondary electron emission (SEE) techniques, conditions for the traveling of electrons near a charged surface were studied. A simple analytical expression was found to relate the effective coefficient of secondary electron emission from the charged surface of an organic liquid layer with the primary-electron current. At low currents, the relationship is close to a root law, the pattern of the dependence does not change with the varying conductivity of the liquid, its thickness, and the charge spot area. This finding suggests that the effective secondary electron emission coefficient and, hence, the conditions of electron motion near a surface charge depend on the only parameter, the current density of incident electrons. According to the estimates of the dielectric permittivity of a liquid, its resistivity, and ion mobility, the effective SEE coefficient at low charging currents is formed in the ohmic mode of current flow through the liquid.     

A local one-electron operator for the generalized-overlap amplitudes

An approach to the N-electron behavior is presented which emphasizes the dynamics of an individual electron. The generalized overlap amplitudes (GOAS ), although formally defined by an integration over the coordinates of N ? 1 electrons, are, instead, resolved as a column vector, eigenfunction to a local one-electron differential operator. These amplitudes have no restrictions of linear independence between them, but each satisfies the one-electron boundary conditions at the nuclei and at large distances. The one-electron (or charge) density is the sum of the squares of the elements of the column. The energy density, a constant times the one-electron density, maintains this one-to-one relationship throughout modifications in total number of electrons or external potential, although the constant of proportionality, the total energy of the system, may change in the process. Indistinguishability of electrons and antisymmetry is always observed by the dynamics of each electron. A numerical example, the ground state of helium, is presented. © 1995 John Wiley & Sons, Inc.     

Monte Carlo simulation of full energy spectrum of electrons emitted from silicon in Auger electron spectroscopy

A Monte Carlo simulation including surface excitation, Auger electron‐ and secondary electron production has been performed to calculate the energy spectrum of electrons emitted from silicon in Auger electron spectroscopy (AES), covering the full energy range from the elastic peak down to the true‐secondary‐electron peak. The work aims to provide a more comprehensive understanding of the experimental AES spectrum by integrating the up‐to‐date knowledge of electron scattering and electronic excitation near the solid surface region. The Monte Carlo simulation model of beam–sample interaction includes the atomic ionization and relaxation for Auger electron production with Casnati's ionization cross section, surface plasmon excitation and bulk plasmon excitation as well as other bulk electronic excitation for inelastic scattering of electrons (including primary electrons, Auger electrons and secondary electrons) through a dielectric functional approach, cascade secondary electron production in electron inelastic scattering events, and electron elastic scattering with use of Mott's cross section. The simulated energy spectrum for Si sample describes very well the experimental AES EN(E) spectrum measured with a cylindrical mirror analyzer for primary energies ranging from 500 eV to 3000 eV. Surface excitation is found to affect strongly the loss peak shape and the intensities of the elastic peak and Auger peak, and weakly the low energy backscattering background, but it has less effect to high energy backscattering background and the Auger electron peak shape. Copyright © 2014 John Wiley & Sons, Ltd.     

Switching from Metal- to Ligand-Based Oxidation in Cobalt Complexes with Redox-Active Bisguanidine Ligands

The control of the redox reactivity, magnetic and optical properties of the different redox states of complexes with redox-active ligands permits their rational use in catalysis and materials science. The redox-chemistry of octahedrally coordinated high-spin Co^II complexes (three unpaired electrons) with one redox-active bisguanidine ligand and two acetylacetonato (acac) co-ligands is completely changed by replacing the acac by hexafluoro-acetylacetonato (hfacac) co-ligands. The first one-electron oxidation is metal-centered in the case of the complexes with acac co-ligands, giving diamagnetic Co^III complexes. By contrast, in the case of the less Lewis-basic hfacac co-ligands, the first one-electron oxidation becomes ligand-centered, leading to high-spin Co^II complexes with a radical monocationic guanidine ligand unit (four unpaired electrons). Ferromagnetic coupling between the spins on the metal and the organic radical in solution is evidenced by temperature-dependent paramagnetic NMR studies, allowing to estimate the isotropic exchange coupling constant in solution. Second one-electron oxidation leads to high-spin Co^II complexes with dicationic guanidine ligand units (three unpaired electrons) in the presence of hfacac co-ligands, but to low-spin Co^III complexes with radical monocationic, peralkylated guanidine ligand (one unpaired electron) in the presence of acac co-ligands. The analysis of the electronic structures is complemented by quantum-chemical calculations on the spin density distributions and relative energies of the possible redox isomers.     

Recent progress in the understanding of light particle tunneling in metals

Light positive particles can be introduced in metallic lattices where they take up interstitial positions. The motion of particles between these sites is usually described as a phonon-assisted tunneling process, which at high temperatures approaches a classical over-barrier jump motion. The present paper reviews briefly the study of such phenomena at very low temperatures where phonon assistance is no longer effective. Experiments on proton transfer between certain sites in niobium metal and on positive muons which diffuse in copper or aluminium lattices show unusual temperature dependencies, which have been explained quantitatively with recent tunneling theories. These approaches take into account the simultaneous dissipation of energy to the electron bath, a phenomenon which was shown by J. Kondo to be determined by the screening electrons following the particle. The temperature dependence is essentially an effect of the Fermi distribution of the conduction electrons. The interaction of the particle with the itinerant electrons will also determine whether the particle wavefunction will be localized or form an extended (Bloch-like) state.     

Ultrafast chemical interface scattering as an additional decay channel for nascent nonthermal electrons in small metal nanoparticles

The use of 4.2 nm gold nanoparticles wrapped in an adsorbates shell and embedded in a TiO2 metal oxide matrix gives the opportunity to investigate ultrafast electron-electron scattering dynamics in combination with electronic surface phenomena via the surface plasmon lifetimes. These gold nanoparticles (NPs) exhibit a large nonclassical broadening of the surface plasmon band, which is attributed to a chemical interface damping. The acceleration of the loss of surface plasmon phase coherence indicates that the energy and the momentum of the collective electrons can be dissipated into electronic affinity levels of adsorbates. As a result of the preparation process, gold NPs are wrapped in a shell of sulfate compounds that gives rise to a large density of interfacial molecules confined between Au and TiO2, as revealed by Fourier-transform-infrared spectroscopy. A detailed analysis of the transient absorption spectra obtained by broadband femtosecond transient absorption spectroscopy allows separating electron-electron and electron-phonon interaction. Internal thermalization times (electron-electron scattering) are determined by probing the decay of nascent nonthermal electrons (NNEs) and the build-up of the Fermi-Dirac electron distribution, giving time constants of 540 to 760 fs at 0.42 and 0.34 eV from the Fermi level, respectively. Comparison with literature data reveals that lifetimes of NNEs measured for these small gold NPs are more than four times longer than for silver NPs with similar sizes. The surprisingly long internal thermalization time is attributed to an additional decay mechanism (besides the classical e-e scattering) for the energy loss of NNEs, identified as the ultrafast chemical interface scattering process. NNEs experience an inelastic resonant scattering process into unoccupied electronic states of adsorbates, that directly act as an efficient heat bath, via the excitation of molecular vibrational modes. The two-temperature model is no longer valid for this system because of (i) the temporal overlap between the internal and external thermalization process is very important; (ii) a part of the photonic energy is directly transferred toward the adsorbates (not among "cold" conduction band electrons). These findings have important consequence for femtochemistry on metal surfaces since they show that reactions can be initiated by nascent nonthermal electrons (as photoexcited, out of a Fermi-Dirac distribution) besides of the hot electron gas.     

DEPTH RESOLUTION IN PHOTOELECTRON MICROSCOPY OF ORGANIC SURFACES. THE PHOTOELECTRIC EFFECT OF PHTHALOCYANINE THIN FILMS

Abstract— The application of photoelectron microscopy as a general method of imaging organic and biological surfaces requires a knowledge of the photoelectric effect of very thin organic films. In this study, low magnification images of a 7 Å thick pattern of copper phthalocyanine were obtained, demonstrating that it is possible to visualize a monolayer of organic compound in photoelectron microscopy. Relative photoelectron currents were measured for a series of copper phthalocyanine films ranging in thickness up to 1900 Å. The relative photoelectron currents were independent of temperature (90–298°K), suggesting that electron-electron and not electron-phonon scattering is the dominant mechanism. The photoelectric properties measured are determined primarily by the large organic ring structure and not the central metal atom, as evidenced by the fact that substitution of metal-free phthalocyanine for copper phthalocyanine did not substantially alter the values of observed photoelectron currents. An analysis of the data indicates the depth resolution is 15 ű 5 Å, and equals the electron mean free path. This very good depth resolution is a result of the low kinetic energy associated with electrons released by irradiation near the photoemission threshold.     

The catalytic nanodiode: detecting continuous electron flow at oxide-metal interfaces generated by a gas-phase exothermic reaction.

Continuous flow of ballistic charge carriers is generated by an exothermic chemical reaction and detected using the catalytic metal-semiconductor Schottky diode. We obtained a hot electron current for several hours using two types of catalytic nanodiodes, Pt/TiO2 or Pt/GaN, during carbon monoxide oxidation at pressures of 100 Torr of O2 and 40 Torr of CO at 413-573 K. This result reveals that the chemical energy of an exothermic catalytic reaction is directly converted into hot electrons flux in the catalytic nanodiode. By heating the nanodiodes in He, we could measure the thermoelectric current which is in the opposite direction to the flow of the hot electron current. The chemicurrent is well correlated with the turnover rate of CO oxidation, which is separately measured with gas chromatography. The influence of the flow of hot charge carriers on the chemistry at the oxide-metal interface, and the turnover rate in the chemical reaction are discussed.     

Measurement of exchange and spin-orbit effects and their interference in elastic e-Cs scattering at 7 eV

Twenty years ago a theoretical analysis showed that electron scattering by high-Z one-electron atoms might lead to interference of exchange and spin-orbit interactions at low electron energies, observable as a cross-section asymmetry if unpolarized electrons are scattered by polarized cesium atoms. By using a highly polarized cesium atomic beam, we studied exchange and spin-orbit effects at different electron energies, starting at 20 eV and going down. We observed the first distinctly non-zero interference asymmetry at 7 eV: Over the angular range of 35 to 145°, it varies between +0.02 and ?0.02 and goes through zero near 110° being negative at larger angles.