Electron-surface Interactions Research Articles

Nonlocal dynamics of secondary electrons in capacitively coupled radio frequency discharges

In capacitively coupled radio frequency discharges, the interaction of the plasma and the surface boundaries is linked to a variety of highly relevant phenomena for technological processes. One possible plasma-surface interaction is the generation of secondary electrons (SEs), which significantly influence the discharge when accelerated in the sheath electric field. However, SEs, in particular electron-induced SEs (δ-electrons), are frequently neglected in theory and simulations. Due to the relatively high threshold energy for the effective generation of δ-electrons at surfaces, their dynamics are closely connected and entangled with the dynamics of the ion-induced SEs (γ-electrons). Thus, a fundamental understanding of the electron dynamics has to be achieved on a nanosecond timescale, and the effects of the different electron groups have to be segregated. This work utilizes particle-in-cell/Monte Carlo collisions simulations of a symmetric discharge in the low-pressure regime (p = 1 Pa) with the inclusion of realistic electron-surface interactions for silicon dioxide. A diagnostic framework is introduced that segregates the electrons into three groups (‘bulk-electrons’, ‘γ-electrons’, and ‘δ-electrons’) in order to analyze and discuss their dynamics. A variation of the electrode gap size is then presented as a control tool to alter the dynamics of the discharge significantly. It is demonstrated that this control results in two different regimes of low and high plasma density, respectively. The fundamental electron dynamics of both regimes are explained, which requires a complete analysis starting at global parameters (e.g. densities) down to single electron trajectories.

The effects of electron surface interactions in geometrically symmetric capacitive RF plasmas in the presence of different electrode surface materials

Particle-in-cell/Monte Carlo collision (PIC/MCC) simulations are performed to investigate the asymmetric secondary electron emission (SEE) effects when electrons strike two different material electrodes in low pressure capacitively coupled plasmas (CCPs). To describe the electron-surface interactions, a realistic model, considering the primary electron impact energy and angle, as well as the corresponding surface property-dependent secondary electron yields, is employed in PIC/MCC simulations. In this model, three kinds of electrons emitted from the surface are considered: (i) elastically reflected electrons, (ii) inelastically backscattered electrons, and (iii) electron induced secondary electrons (SEs, i.e., δ-electrons). Here, we examined the effects of electron-surface interactions on the ionization dynamics and plasma characteristics of an argon discharge. The discharge is driven by a voltage source of 13.56 MHz with amplitudes in the range of 200–2000 V. The grounded electrode material is copper (Cu) for all cases, while the powered electrode material is either Cu or silicon dioxide (SiO2). The simulations reveal that the electron impact-induced SEE is an essential process at low pressures, especially at high voltages. Different electrode materials result in an asymmetric response of SEE. Depending on the instantaneous local sheath potential and the phase of the SEE, these SEs either are reflected by the opposite sheath or strike the electrode surface, where they can induce δ-electrons upon their residual energies. It is shown that highly energetic δ-electrons contribute significantly to the ionization rate and a self-bias forms when the powered electrode material is assumed to be made of SiO2. Complex dynamics is observed due to the multiple electron-surface interaction processes and asymmetric yields of SEs in CCPs.

Deterministic Nanopatterning of Diamond Using Electron Beams.

Diamond is an ideal material for a broad range of current and emerging applications in tribology, quantum photonics, high-power electronics, and sensing. However, top-down processing is very challenging due to its extreme chemical and physical properties. Gas-mediated electron beam-induced etching (EBIE) has recently emerged as a minimally invasive, facile means to dry etch and pattern diamond at the nanoscale using oxidizing precursor gases such as O2 and H2O. Here we explain the roles of oxygen and hydrogen in the etch process and show that oxygen gives rise to rapid, isotropic etching, while the addition of hydrogen gives rise to anisotropic etching and the formation of topographic surface patterns. We identify the etch reaction pathways and show that the anisotropy is caused by preferential passivation of specific crystal planes. The anisotropy can be controlled by the partial pressure of hydrogen and by using a remote RF plasma source to radicalize the precursor gas. It can be used to manipulate the geometries of topographic surface patterns as well as nano- and microstructures fabricated by EBIE. Our findings constitute a comprehensive explanation of the anisotropic etch process and advance present understanding of electron-surface interactions.

The role of electron induced secondary electron emission from SiO2 surfaces in capacitively coupled radio frequency plasmas operated at low pressures

The effects of electron induced secondary electron (SE) emission from SiO2 electrodes in single-frequency capacitively coupled plasmas (CCPs) are studied by particle-in-cell/Monte Carlo collisions (PIC/MCC) simulations in argon gas at 0.5 Pa for different voltage amplitudes. Unlike conventional simulations, we use a realistic model for the description of electron-surface interactions, which takes into account the elastic reflection and the inelastic backscattering of electrons, as well as the emission of electron induced SEs (δ-electrons). The emission coefficients corresponding to these elementary processes are determined as a function of the electron energy and angle of incidence, taking the properties of the surface into account. Compared to the results obtained by using a simplified model for the electron-surface interaction, widely used in PIC/MCC simulations of CCPs, which includes only elastic electron reflection at a constant probability of 0.2, strongly different electron power absorption and ionization dynamics are observed. We find that ion induced SEs (γ-electrons) emitted at one electrode and accelerated to high energies by the local sheath electric field propagate through the plasma almost collisionlessly and impinge on the opposing sheath within a few nanoseconds. Depending on the instantaneous local sheath voltage these energetic electrons are either reflected by the sheath electric field or they hit the electrode surface, where each γ-electron can generate multiple δ-electrons upon impact. These electron induced SEs are accelerated back into the plasma by the momentary sheath electric field and can again generate δ-electrons at the opposite electrode after propagating through the plasma bulk. Overall, a complex dynamics of γ- and δ-electrons is observed including multiple reflections between the boundary sheaths. At high voltages, the electron induced SE emission is found to strongly affect the plasma density and the ionization dynamics and, thus, it represents an important plasma-surface interaction that should be included in PIC/MCC simulations of CCPs under such conditions.

Graphene oxide electrochemistry: the electrochemistry of graphene oxide modified electrodes reveals coverage dependent beneficial electrocatalysis.

The modification of electrode surfaces is widely implemented in order to try and improve electron transfer kinetics and surface interactions, most recently using graphene related materials. Currently, the use of ‘as is’ graphene oxide (GO) has been largely overlooked, with the vast majority of researchers choosing to reduce GO to graphene or use it as part of a composite electrode. In this paper, ‘as is’ GO is explored and electrochemically characterized using a range of electrochemical redox probes, namely potassium ferrocyanide(II), N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD), dopamine hydrochloride and epinephrine. Furthermore, the electroanalytical efficacy of GO is explored towards the sensing of dopamine hydrochloride and epinephrine via cyclic voltammetry. The electrochemical response of GO is benchmarked against pristine graphene and edge plane-/basal plane pyrolytic graphite (EPPG and BPPG respectively) alternatives, where the GO shows an enhanced electrochemical/electroanalytical response. When using GO as an electrode material, the electrochemical response of the analytes studied herein deviate from that expected and exhibit altered electrochemical responses. The oxygenated species encompassing GO strongly influence and dominate the observed voltammetry, which is crucially coverage dependent. GO electrocatalysis is observed, which is attributed to the presence of beneficial oxygenated species dictating the response in specific cases, demonstrating potential for advantageous electroanalysis to be realized. Note however, that crucial coverage based regions are observed at GO modified electrodes, owing to the synergy of edge plane sites and oxygenated species. We report the true beneficial electrochemistry of GO, which has enormous potential to be beneficially used in various electrochemical applications ‘as is’ rather than be simply used as a precursor to making graphene and is truly a fascinating member of the graphene family.

Size-dependence of the effective electron-phonon energy relaxation in hollow gold nanospheres

AbstractIn this paper the size-dependence of energy relaxation, which is induced by the electron-phonon (e-ph) interactions and the electron-surface (e-s) interactions in noble metal nanoparticles, is investigated. Then based on the analysis and the derivation of the e-s coupling constant in metal nanospheres, the formula of the effective electron-phonon coupling constant Geff of hollow gold nanospheres (HGNs) is deduced. Moreover, the correctness of the formulae gets proved by contrast analyses of the calculated Geff values and experimental values obtained from literature.

A Modified Formal Theory on Semi-Relativistic Effects during Electron Emission from Metallic Surfaces upon the Impact of High Energy Particles

In this paper we introduce a formal theory on unveiling relativistic effects during electron emission from clean metallic surfaces upon high charged particle impact using a Jellium-type wave function including suitable spinors. In addition image charge final state electron surface interactions have been initiated in the relativistic region as well as the scattering of the projectile from the multi-center bulk potential. Finally, a semi-relativistic condition is considered in place of the ionization mechanism of scattering from an aluminium semi-infinite solid target by non-relativistic electrons to determine multiple differential cross-section.

Quantitative secondary ion mass spectrometry imaging of self-assembled monolayer films for electron beam dose mapping in the environmental scanning electron microscope

Fluorinated alkanethiol self-assembled monolayers (SAM) films immobilized on gold substrates have been used as electron-sensitive resists to map quantitatively the spatial distribution of the primary electronbeam scattering in an environmental scanning electron microscope (ESEM). In this procedure, a series of electron dose standards are prepared by exposing a SAM film to electron bombardment in well-defined regions at different levels of electron dose. Microbeam secondary ion mass spectrometry (SIMS) using Cs+ bombardment is then used to image the F- secondary ion signal from these areas. From the reduction in F- intensity as a function of increasing electron dose, a calibration curve is generated that allows conversion of secondary ion signal to electron dose on a pixel-by-pixel basis. Using this calibration, electron dose images can be prepared that quantitatively map the electron scattering distribution in the ESEM with micrometer spatial resolution. The SIMS imaging technique may also be used to explore other aspects of electron-surface interactions in the ESEM.

Electron ejection from clean metallic surfaces upon charged particle impact

In this work we present a theoretical treatment of electron ejection from a clean metallic semi-infinite solid with an ideal orthorhombic Bravais lattice following the impact of moderately fast charged particles with respect to the Fermi momentum of the initially bound electron. For an aluminum semi-infinite solid target multiple differential cross sections have been evaluated using a jellium-type wave function of the undisturbed surface in the initial state. Image-charge final-state electron-surface interactions have been included as well as the scattering of the projectile from the multicenter bulk potential. From a kinematic analysis of the process various ionization mechanisms are inferred and confirmed by the present dynamical model.

Self Organized Growth and Ultrafast Electron Dynamics in Metallic Nanoparticles

ABSTRACTWe present ultrafast transient reflectivity measurements performed on metallic tin nanoparticles with an average radius between 20 and 60 Å in amorphous matrix. The samples, grown using an evaporation-condensation technique, were characterized by a relatively low nanocrystals size dispersion and a negligible clusters-matrix interaction. The excitation decays exhibited a size-dependent behaviour, which is interpreted in terms of the important role played by the electron-surface interactions.

Ripplonic Polarons in a Wigner Crystal

By the use of the path-integral method, general formula of the free energy and the conductivity of electrons in a two-dimensional Wigner crystal are obtained when both of the electron-electron and the electron-surface interactions are present. The dc conductivity is calculated explicitly for electrons bound on the surface of liquid He in the case of the weak electron-ripplon coupling. Good agreement is obtained between theory and experiment about the density dependence of the collision time.

Intraband optical conductivityσ(ω,T)of Cu, Ag, and Au: Contribution from electron-electron scattering

The frequency and temperature dependence of the intraband optical conductivity of the noble metals Cu, Ag and Au is measured and contributions of electron-electron scattering are assessed. Optical measurements were performed at temperatures of 77, 295 and 425 K to obtain values of the Drude electron scattering rate with a linear dependence on temperature which may be attributed to electron-phonon scattering, and a quadratic dependence on photon energy, which is suggestive of electron-electron scattering but is a factor of two to three times greater than would be expected. Comparison of the optical data with dc electrical and thermal resistivity data which also show behavior attributed to electron-electron scattering reveals discrepancies of up to an order of magnitude. Other possible mechanisms for the frequency dependence, including absorptance, electron-surface plasmon interactions, a two-carrier model, and a structure dependence are considered, and it is concluded that the frequency dependence in the Drude scattering rates of the noble metals is not yet quantitatively understood

Photoemission of electrons from many-body systems

The energy distribution of photoelectrons emitted from a solid is expressed exactly in terms of time-ordered correlation functions. The expression is valid for arbitrary electron-electron, electron-lattice and electron-surface interactions.