Hyperthermal ion beam system optimized for studying the effects of kinetic energy on thin-film growth
25 Oct 2002-Review of Scientific Instruments (American Institute of Physics)-Vol. 73, Iss: 11, pp 3846-3852
TL;DR: In this article, a hyperthermal and low-energy ion beam optimized for studying morphological trends in epitaxial metal thin films as a function of atomic kinetic energy has been built and characterized.
Abstract: A hyperthermal and low-energy ion beam (10–1000 eV) optimized for studying morphological trends in epitaxial metal thin films as a function of atomic kinetic energy has been built and characterized. The ion beam line produces metal and inert gas ions and is specially designed to produce up to 2.9 μA of highly collimated ions with single amu mass resolution while precisely controlling the ion’s energy, achieving a ΔE/E∼0.1. Energy resolution can be enhanced further at the expense of flux. Varying the focal length of the final electrostatic lens allows the flux density to be adjusted from 10 to 500 nA/mm2. The beam line has been coupled to an ultra-high-vacuum deposition chamber with a versatile sample manipulator, an electron beam deposition source, residual gas analysis, and real-time reflection high-energy electron diffraction (RHEED). Once prepared, the sample can be moved in situ to perform Auger electron spectroscopy (AES), and scanning tunneling microscopy (STM). The high fluxes with narrow energy di...
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TL;DR: Detailed aspects of Cs reactive scattering and its application for surface analysis have been reviewed and the mechanism for abstraction reaction is described.
Abstract: ion mechanism, discussed in section 1.1.2. Figure 27 illustrates the reactive scattering mechanism with four representative snapshots of a Cs scattering trajectory in a classical MD simulation. The abstraction reaction is driven by the ion−dipole attraction force between the Cs ion and an adsorbate molecule. The impinging projectile first releases part of its initial energy to the surface (Figure 27b) even without direct collision with the adsorbate. Subsequently, the projectile pulls the adsorbate gently away from the surface in its outgoing trajectory (parts c and d of Figures 27 in sequence), leading to the formation of a Cs−molecule complex. The velocity of the outgoing Cs must be slow enough to accommodate the inertia of the adsorbate. As a result, adsorbates of low mass and small binding energy are efficiently abstracted. A heavier projectile like Cs transfers more energy to the target surface, and its lower velocity in the outgoing trajectory enhances the efficiency of reactive scattering events. Detailed aspects of Cs reactive scattering and its application for surface analysis have been reviewed. Table 9. Hyperthermal Energy Collisions at Condensed Molecular Solids method (projectile ion) system aim/observations refs reactive scattering and LES (Cs) H2O−D2O rate and activation energy of self-diffusion and H/D exchange of water 462, 476, 479, 496 H3O −water ice affinity of protons for the ice surface and proton transfer mechanism 478−480 H3O −H2O−D2O hydronium ion-mediated proton transfer at the ice surface 495 OH−H2O−D2O hydroxide ion-mediated proton transfer at the ice surface 497 HCl−water ice molecular and ionized states of HCl on ice 457, 477 Na−water ice hydrolysis of Na 484 H3O −NH3−water ice incomplete proton transfer from H3O to NH3 on the ice surface 454, 458 H3O −amine−water ice proton transfer efficiency on ice is reversed from the order of amine basicity 502 CO2−Na−water ice CO2 hydrolysis is not facilitated by a hydroxide ion 463 NO2−water ice NO2 hydrolysis produces nitrous acid 465 SO2−water ice SO2 hydrolysis occurs through various intermediates 511 C2H4−HCl−water ice electrophilic addition reaction mechanism at the condensed molecular surface 466 ethanol/2-methylpropan-2-ol−water ice SN1 and SN2 mechanisms at the condensed molecular surface 505 NH3−water ice and UV irradiation ammonium ion formation 608 CH3NH2−water ice and UV irradiation protonated methylamine formation 483 CH3NH2−CO2−water ice and UV irradiation glycine and carbamic acid formation 464 NaX−water ice (X = F, Cl, Br) surface/bulk segregation and transport properties of electrolyte ions 472−474 reactive scattering (Cs) CO and CO2 on Pt(111) mechanism of Cs + reactive ion scattering 89 Ar, Kr, Xe, and N2 on Pt(111) adsorbate mass effect on the reactive ion scattering cross-section 609 C2H4 on Pt(111) dehydrogenation mechanism of ethylene to ethylidyne 459, 610 C2D4 and H on Pt(111) ethylidene intermediate in H/D exchange reaction with ethylene 80, 610 reactive scattering (H) water ice and alcohol H2 + formation 469 CS (Ar) water ice−chloromethanes (CCl4, CHCl3, CH2Cl2) except CCl4, others undergo diffusive mixing 174 water ice−simple carboxylic acids structural reorganization on the ice film 175 water ice micropore collapse in the top layers of the ice film 176 water ice−butanol 494 Figure 27. Illustration of the reactive scattering mechanism of a Cs ion in four snapshots of a scattering trajectory from a Pt(111) surface: (a) initial positions before impact, (b) impact of the Cs and energy release to the surface, (c) Cs pulling the adsorbate away in its outgoing trajectory, (d) slow outgoing Cs dragging the adsorbate along and forming a Cs−molecule association product. Reprinted with permission from ref 88. Copyright 2004 John Wiley and Sons, Inc. Chemical Reviews Review dx.doi.org/10.1021/cr200384k | Chem. Rev. 2012, 112, 5356−5411 5388 Figure 28 shows an example of reactive collision mass spectra, which were obtained on a D2O ice film exposed first to 0.5 L of HCl gas and then to varying amounts of NH3 gas at 140 K. The spectra show peaks at higher masses than Cs (m/z 133), viz., CsNH3 + at m/z 150, Cs(D2O)n + (n = 1, 2) at m/z 153 and 173, and CsHCl at m/z 168, indicating the presence of the corresponding molecules on the surface. The intensities of H/D-exchanged species represent their original concentrations on the surface, because H/D isotopic scrambling does not occur during the ion/surface collision time (<1 × 10−12 s). The conversion efficiency of a neutral adsorbate (X) into a gaseous ion (CsX) ranges from ∼10−4 for chemisorbed species to ∼0.1 for physisorbed small molecules. Typical product ion signal intensities for ice film surfaces are much stronger than those for chemisorbed species. Also, it is worthwhile to point out that reactive collisions of Cs are ineffective for detecting large molecules such as polymers or long-chain SAM molecules. The mass spectra in Figure 28 also show LES signals corresponding to pre-existing ions on the surface. The hydronium ions seen are produced by the spontaneous ionization of HCl on the ice surface, and they undergo proton transfer reactions with NH3 to generate ammonium ions. The spectra show characteristic H/D isotopomers of each species produced by H/D exchange reactions with D2O molecules. The LES signals due to preformed hydronium and ammonium ions exhibited sputtering thresholds at Cs impact energies of 17 and 19 eV, respectively. On the other hand, on pure H2O and NH3 surfaces, these ions were emitted only above ∼60 eV due to their formation during secondary ion emission. It was also found that ultra-low-energy (a few electronvolts) collision of H with the ice surface can produce H2 +. The reaction proceeds more efficiently on amorphous solid water than crystalline water, reflecting differences in the surface concentration of dangling O−H bonds. Simple alkanols also behave in the same manner. The combined occurrence of reactive scattering and LES provides a powerful means to probe both neutral molecules and ions on surfaces and, therefore, to follow reactions on ice surfaces such as the ionization of electrolytes and acid−base reactions, which are described below. 7.2. Surface Composition and Structure Impurities in ice become concentrated in the quasi-liquid layers in the surface and at grain boundary regions due to the “freeze concentration effect”, and this has important consequences for atmospheric reactions on ice surfaces. However, there appear to be numerous exceptions to this general trend, where the surface segregation behavior of the dissolving species and their bulk solubility are determined by thermodynamic factors specific to individual chemical species. A good example is the formation of stable bulk phases of clathrate hydrates. Chemical specificity in the segregation phenomena can be studied by monitoring the surface populations of the dissolving species during the slow annealing of ice samples. Kang and coworkers examined these propensities in Na and halide ions at the surface and in the interior of ice films. They ionized NaF, NaCl, and NaBr molecules on ice films by the vapor deposition of the salts, and the variation in the surface population of the ions was monitored as a function of the ice temperature for 100−140 K by using LES. As shown in Figure 29, the LES intensities of Na and F− ions decrease with an increase in temperature above ∼120 K, whereas the Cl− and Br− intensities remain unchanged. The results indicate that Na and F− ions migrate from the ice surface to the interior at the elevated temperatures. The migration process is driven Figure 28. Cs reactive scattering and LES spectra monitoring the H3O −NH3 reaction on ice. The D2O film [3−4 bilayers (BLs), 1 BL = 1.1 × 10 water molecules cm−2] was exposed first to 0.5 L of HCl to generate hydronium ions and then to NH3 at varying exposures: (a) 0.02 L, (b) 0.3 L, (c) 0.7 L. The sample temperature was 100 K. The Cs collision energy was 30 eV. Reprinted with permission from ref 454. Copyright 2001 John Wiley and Sons, Inc. Figure 29. Surface populations of Na (□), F− (▲), Cl− (◇), and Br− (●) ions as a function of the ice film temperature measured from LES intensities of the ions. NaF, NaCl, and NaBr were deposited for a coverage of 0.8 ML for each salt on a D2O ice film grown at 130 K. The LES signals were measured at the indicated temperatures of salt adsorption. The LES intensities are shown on the normalized scale with the intensity at 100−105 K as a reference. The Cs beam energy was 35 eV. The figure is drawn on the basis of the data in refs 473 and 474. Chemical Reviews Review dx.doi.org/10.1021/cr200384k | Chem. Rev. 2012, 112, 5356−5411 5389 by the ion solvation energy, and it requires that surface water molecules have enough mobility to facilitate ion passage at temperatures above 120 K. It is worth noting that such a segregation behavior for ice agrees with the negative adsorption energy of these ions at water surfaces predicted by the Gibbs surface tension equation and MD simulations. An interesting property of hydronium ions observed in recent studies is that they preferentially reside at the surface of ice rather than in its interior. Evidence of this property has come from a variety of experimental observations over the past decade. The adsorption and ionization of HCl on an ice film promotes H/D exchange on the surface. However, vertical proton transfer to the film interior is inefficient. Continuous exposure of HCl gas on the ice film led to saturation in the hydronium ion population at the surface, and the amount of HCl uptake required for this saturation was independent of the thickness of the ice film. These observations suggest that protons stay at the ice surface and hardly migrate to the interior. This behavior can be attributed either to the active trapping of protons at the surface or to the lack of proton mobility to the ice interior. The observation of asymmetric
99 citations
TL;DR: This review of soft landing in the hyperthermal and thermal kinetic energy regimes is organized according to instrumental considerations and molecular families, with a discussion of theoretical work at the end.
Abstract: Preparative mass spectrometry has become a diverse field that covers the spectrum of kinetic energy deposition. Of these methods, soft-landing mass spectrometry has many fundamental properties, which make it an advantageous technique for ion isolation and deposition. Its definition implies the preservation of ionic structural integrity after landing, which ensures the structure–function relationship of a molecule remains intact. Here the focus is on the instruments and applications of studying ion–surface landing in the hyperthermal and thermal kinetic energy regimes. Soft-landing preparative mass spectrometry covers the breadth of mass spectrometric ionization sources, instrumental configurations, and molecular families. Due to the diverse nature of soft landing, and to maximize readability, this review has been organized according to instrumental considerations and molecular families, with a discussion of theoretical work at the end.
58 citations
TL;DR: Using a laboratory-scale apparatus, they enrich 28Si and produce material with 40 times less residual 29Si than previously reported as discussed by the authors, which is an alternative to industrial gas centrifuges for providing materials critical for long spin coherence times in quantum information devices.
Abstract: Using a laboratory-scale apparatus, we enrich 28Si and produce material with 40 times less residual 29Si than previously reported. Starting from natural abundance silane gas, we offer an alternative to industrial gas centrifuges for providing materials critical for long spin coherence times in quantum information devices. Using a mass spectrometry approach, silicon ions are produced from commercial silane gas and the isotopes are separated in a magnetic sector analyzer before deposition onto a Si(1 0 0) substrate. Isotope fractions for 29Si and 30Si of <1 × 10−6 are found in the deposited films using secondary ion mass spectrometry. Additional assessments of the deposited films are also presented as we work to develop substrates and source material to support the growing silicon quantum computing community. Finally, we demonstrate modulation of the 29Si concentration in a deposited film as a precursor to dual enrichment of heterostructures and compound materials such as 28Si74Ge.
21 citations
09 Mar 2020
TL;DR: This work uses hyperthermal energy ion beam deposition with silane gas to deposit epitaxial 28Si and develops a model to predict the residual 29Si isotope fraction based on deposition parameters, which is measured using secondary ion mass spectrometry (SIMS).
Abstract: We report on the growth of isotopically enriched 28Si epitaxial films with precisely controlled enrichment levels, ranging from natural abundance ratio of 92.2% all the way to 99.99987% (0.83 × 10-6 mol mol-1 29Si). Isotopically enriched 28Si is regarded as an ideal host material for semiconducting quantum computing due to the lack of 29Si nuclear spins. However, the detailed mechanisms for quantum decoherence and the exact level of enrichment needed for quantum computing remain unknown. Here we use hyperthermal energy ion beam deposition with silane gas to deposit epitaxial 28Si. We switch the mass selective magnetic field periodically to control the 29Si concentration. We develop a model to predict the residual 29Si isotope fraction based on deposition parameters and measure the deposited film using secondary ion mass spectrometry (SIMS). The measured 29Si concentrations show excellent agreement with the prediction, deviating on average by only 10%.
7 citations
TL;DR: In this article, an experimental exploration of island nucleation dynamics during epitaxial film growth on the $\mathrm{Cu}(100)$ surface is presented that connects previous results from other groups at low temperatures with the room temperature regime.
Abstract: An experimental exploration of island nucleation dynamics during epitaxial film growth on the $\mathrm{Cu}(100)$ surface is presented that connects previous results from other groups at low temperatures with the room temperature regime. The steady-state balance of various atomistic processes during island nucleation has direct impact on the physical properties of epitaxial films, e.g., larger nuclei densities allow layer-by-layer growth to be achieved at lower temperatures. Within many theoretical frameworks, the critical nuclei size $i$ (the largest assembly of atoms with a higher probability for decay than growth) plays a major role in determining island nuclei densities, and, by extension, the physics of film growth. This paper presents island density and island size distributions from recent STM studies and analysis that allows for accurate determination of the critical nuclei size at various deposition rates and temperatures near room temperature and the $i=1$ to $i=3$ boundary (dimer to tetramer stable island). This is accomplished by using the scaling behavior of coarsening to develop statistical weight by rescaling individual distributions and summing them. The rescaled island size distributions are then compared with analytical models that allow unambiguous assignment of the critical island size. The results of this study are then combined with previously published results from other researchers to determine empirically the structure of the phase boundary from $i=1$ to $i=3$ as a function of temperature and deposition rate. At low temperatures and fluxes, the observed position of the phase boundary agrees with predictions when only adatom mobility is considered. Deviations at higher temperatures suggest that the mobility of dimers and other small islands may be important in determining the effective critical nucleus near room temperature.
6 citations
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TL;DR: In this paper, the authors present a comprehensive overview of electrode processes and their application in the field of chemical simulation, including potential sweep and potential sweep methods, coupled homogeneous chemical reactions, double-layer structure and adsorption.
Abstract: Major Symbols. Standard Abbreviations. Introduction and Overview of Electrode Processes. Potentials and Thermodynamics of Cells. Kinetics of Electrode Reactions. Mass Transfer by Migration and Diffusion. Basic Potential Step Methods. Potential Sweep Methods. Polarography and Pulse Voltammetry. Controlled--Current Techniques. Method Involving Forced Convention--Hydrodynamic Methods. Techniques Based on Concepts of Impedance. Bulk Electrolysis Methods. Electrode Reactions with Coupled Homogeneous Chemical Reactions. Double--Layer Structure and Adsorption. Electroactive Layers and Modified Electrodes. Electrochemical Instrumentation. Scanning Probe Techniques. Spectroelectrochemistry and Other Coupled Characterization Methods. Photoelectrochemistry and Electrogenerated Chemiluminescence. Appendix A: Mathematical Methods. Appendix B: Digital Simulations of Electrochemical Problems. Appendix C: Reference Tables. Index.
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TL;DR: In this paper, the basic physical processes involved in the nucleation and growth of thin films of materials on solid surfaces are described, and the relationships between the thermodynamics of adsorption and the kinetics of crystal growth are explored in general terms.
Abstract: The purpose of this article is to describe the basic physical processes involved in the nucleation and growth of thin films of materials on solid surfaces. In this introduction the three modes of crystal growth which are thought to occur on surfaces in the absence of interdiffusion are described, and the relationships between the thermodynamics of adsorption and the kinetics of crystal growth are explored in general terms. This is followed by a brief review of atomistic nucleation theory, explaining the relations of such theories to experimental observables. In the next three sections, recent experimental examples of these three growth modes are given, which are interpreted where possible in terms of nucleation and growth theory. The last section discusses observations on the shapes of growing crystallites and the relation of such observations to nucleation and surface diffusion processes.
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TL;DR: Electron Beam Systems MEBS is run jointly by Eric Munro John Rouse and Haoning Liu who jointly have over 80 years of experience in the design of charged particle optics devices and systems.
Abstract: Design Software for Electron Beam Systems mebs co uk April 23rd, 2019 Specialised software for the computer aided design of electron and ion optical systems • Expert consultancy services in the design of electron and ion beam devices and systems • Training courses in theory and design methods in charged particle optics MEBS is run jointly by Eric Munro John Rouse and Haoning Liu who jointly have over 80
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TL;DR: In this article, a review of microstructuring techniques for silicon micromachining is presented, where the basic principles are described, the technological realization is discussed and examples for applications in the field of microsensors are given.
Abstract: Sensors, actuators and microsystems can be realized by silicon micromachining. The structures are typically three-dimensional. To realize them, the methods known from microelectronics are not suffucient but new structuring methods which allow deep etching are applied. For that reason, the microstructing of silicon is one of the characteristic and essential tasks of the technology of microelectromechanical systems (MEMS). In this review four important microstructing techniques are described: bulk micromachining by anistropic etching, reactive ion etching, surface micromachining and porous silicon technology. The basic principles are described, the technological realization is discussed and examples for applications in the field of microsensors are given.
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