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.     

Incident angle and energy dependences of low‐energy Ar+ ion sputtering of GaAs/AlAs multilayered system

Dependences of the depth resolution in Auger electron spectroscopy sputter‐depth profiling of a GaAs/AlAs superlattice reference material on the incident angle and energy of primary Ar⁺ ions were investigated. The results revealed that the depth resolution is improved for the lower primary energy as a square root of the primary energy of ions at both the incident angles of 50° and 70° , except for 100 eV at 50° , where the significant deterioration of the depth resolution is induced by the preferential sputtering of As in AlAs, and the difference in the etching rate between GaAs and AlAs. The deterioration of the depth resolution, i.e. the difference in the etching rate and the preferential sputtering, observed for 100 eV at 50° was suppressed by changing the incident angle of ions from 50° to 70° , resulting in the high‐depth resolution of ～1.3 nm. The present results revealed that the glancing incidence of primary ions is effective to not only reducing the atomic mixing but also suppressing the difference in the etching rates between GaAs and AlAs and the preferential sputtering in the GaAs/AlAs multilayered system. The results also suggest that careful attention is required for the optimization of conditions of sputter‐depth profiling using GaAs/AlAs superlattice materials under low‐energy ion irradiation. Copyright © 2009 John Wiley & Sons, Ltd.     

Summary of ISO/TC 201 Standard XII. ISO 17973:2002—Surface chemical analysis—Medium‐resolution Auger electron spectrometers—Calibration of energy scales for elemental analysis

This International Standard specifies a method for calibrating the kinetic energy scale of Auger electron spectrometers with an uncertainty of 3 eV for general analytical use for identifying elements at surfaces. It is suitable for instruments used in either the direct mode or the differential mode where the resolution is equal to or less than 0.5% and the modulation amplitude for the differential mode, if used, is 2 eV peak to peak. The spectrometer shall be equipped with an inert gas ion gun or other method for sample cleaning and with an electron gun capable of operating at 4 keV or higher beam energy. This International Standard further specifies a calibration schedule. Crown Copyright © 2003. Published by John Wiley & Sons, Ltd.     

High energy resolution Auger spectroscopy on a CMA instrument

An experimental method that increases the analyzer resolution of cylindrical mirror analyzer CMA‐based Auger spectrometers is described. By means of electrically biasing the sample, the effective energy resolution obtainable from the CMA instrument is improved from the native 0.5 to 0.1% or even better for higher kinetic energy Auger transitions. In addition, the maximum kinetic energy Auger transition observable by the CMA Auger instrument is increased from 3200 to 5700 eV, in the current realization. It is also shown that the sensitivity of the energy scale calibration to sample working distance with respect to the analyzer is simultaneously reduced, making the method suitable for chemical surface analysis. The biasing is accomplished using a special sample holder with electronics and software that can be added to an existing instrument. The overall capability of the Auger instrument for chemical analysis is, therefore, increased, while preserving all the analytical functionality and features of the CMA. Copyright © 2011 John Wiley & Sons, Ltd.     

Topography and field effects in secondary ion mass spectrometry Part II: insulating samples

A study is conducted on the effects of sample topography on the secondary ion mass spectrometry (SIMS) analysis of insulating samples, using poly(ethylene terephthalate) fibres (100 µm diameter) as a model system and simulations of the ion extraction field using finite element analysis. We focus on two significant issues: topographic field effects caused by the penetration of the extraction field into the sample, and the effect of charge compensation on the secondary ion images. Guidance is provided for setting the reflector voltage correctly for insulating fibres in reflectron SIMS instruments. The presence of the topographic sample distorts the extraction field, causing the secondary ions to be deflected laterally. This results in the severe loss of ion signals from the sides of the fibres because of the limited angular acceptance of the analyser. Strategies to reduce topographic field effects, including alternative sample mounting methods, are discussed. We also find that, in general, insulating samples are charged by the flood gun electrons resulting in a negative surface potential. This causes large variations in the SIMS images depending on the electron current, electron energy, raster mode and secondary ion polarity. Recommendations are given for analysts to obtain more reproducible images and reduce the effect of differential electron charging, for example by using a lower electron flood beam energy. © 2011 Crown copyright.     

Summary of ISO/TC 201 Technical Report: ISO/TR 19319: 2003—Surface chemical analysis—Auger electron spectroscopy and x‐ray photoelectron spectroscopy—Determination of lateral resolution,analysis area and sample area viewed by the analyser

ISO Technical Report 19319:2003 contains information on the determination of lateral resolution, analysis area and sample area viewed by the analyser in surface analyses by Auger electron spectroscopy and x‐ray photoelectron spectroscopy. This article provides a brief summary of this information. Copyright © 2004 John Wiley & Sons, Ltd.     

Summary of ISO/TC 201 Technical Report: ISO/TR 19319:2013 – Surface chemical analysis – Fundamental approaches to determination of lateral resolution and sharpness in beam‐based methods

This Technical Report revises ISO/TR 19319:2003 —Surface chemical analysis—Auger electron spectroscopy and X‐ray photoelectron spectroscopy—Determination of lateral resolution, analysis area and sample area viewed by the analyser. The revised Technical Report gives a short introduction to basic models of image formation and introduces functions which characterize the performance of imaging instruments with respect to lateral resolution and sharpness. The determination of lateral resolution by imaging of square‐wave gratings and the determination of sharpness by imaging of narrow stripes and straight edges are described in detail. Finally, physical factors affecting lateral resolution, analysis area and sample area viewed by the analyser are discussed. Copyright © 2013 John Wiley & Sons, Ltd.     

A new high luminosity UHV orange type magnetic spectrometer used for depth selective Mössbauer spectroscopy

A new magnetic spectrometer of the orange type has been built for energies up to 45 keV. Its features are: ·?Transmission: 20% of 4π ·?Relative momentum resolution: 0.1 to 1%, ·?Energy band width: ΔE/E = ± 4% For Auger Electron Spectroscopy (AES) a combination with an electrostatic retardation field around the sample will provide an even higher resolution. For depth selective conversion electron Mössbauer spectroscopy (DCEMS) the exceptional high effective luminosity of the ultrahigh vacuum (UHV) orange spectrometer allows the analysis of non-enriched samples in reasonable time without loss in depth resolution. The UHV was realized by a differentially evacuated double chamber system made of an aluminium alloy using Viton gaskets. The inner part can be heated to 150°?C.     

High-resolution, low-voltage SEM for true surface imaging and analysis

A novel design concept for the electron optical column has been implemented in the realization of a new ultra-high performance SEM. A compound magnetic/ electrostatic objective lens is at the heart of the high-performance column: the imaging aberrations of this new lens type decrease with decreasing beam energy. Any beam cross-over between the electron source (Schottky FE-gun) and the sample has been eliminated in order to avoid broadening of the beam energy spread (Boersch effect). A high beam energy is maintained throughout the column regardless of the electron probe energy selected by the operator. This protects the beam against the effect of stray fields and minimizes any loss of beam brigthness due to stochastic electron-electron interactions. The new SEM achieves outstanding resolution, particularly at the low beam energies (3 nm achievable at E_PE = 1 keV). The secondary electrons emitted by the sample are detected with very high efficiency by an internal annular detector situated above the final lens. Due to the low imaging aberration level, a high current can easily be focused in a very small probe, thus making the new SEM ideally suited for high-resolution, quantitative X-ray analysis.     

Richardson–Lucy deconvolution of reflection electron energy loss spectra

A procedure for deconvolving the energy spread introduced by the primary beam and the analyzer in a reflection electron energy loss spectrum (REELS) has been developed. The procedure is based on the Richardson–Lucy (RL) algorithm. The approach has been successfully tested on experimental spectra by comparison with spectra with an inherent high‐energy resolution. As a typical result, it was found that the effective energy resolution of spectra with a full width half maximum (FWHM) of the elastic peak of ～1.5 eV in the raw experimental data can be reduced to ～0.7 eV in the deconvoluted spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Translational energy distribution of the excited hydrogen atom produced by controlled electron impact on HCl

The translational energy distribution of an atom can be calculated by differentiating the Doppler line shape of its emission line taken at a high optical resolution. The Balmer-β line of the excited hydrogen atom (n = 4) produced by electron impact on HCl has been measured at a high resolution (0.033Å) and at two angles (55° and 90°) with respect to the electron beam. The translation energy distribution depends on the electron energies and has almost two groups of components: ≈ 5 eV (fast) and ≈ eV (slow). Anisotropy is imporant for the slow component. The excitation function shows the corresponding structures. It is concluded that Rydberg states converging to the ²Π state of HCl⁺ produce the fast component and Rydberg states converging to the repulsive HCl⁺ states which cross the ²Σ⁺ state produce the slow component.     

AES depth profiling with a tilted sample in front of a cylindrical mirror analyzer: quantification and profile shape changes according to an extension of the conventional MRI model

The influence of the tilt angle of a sample in front of a cylindrical mirror analyzer (CMA) on AES depth profiles is calculated with the conventional mixing‐roughness‐information (MRI) depth model and an extended MRI model. While the conventional model works with an average electron escape depth value, the extended model takes into account the intensity from different segments along the azimuth angle corresponding to different escape depth values before summing up for the total, measured intensity. The deviation between both approaches is generally less than 4%, even for the worst case at 47.7° tilt angle. The shape of the profile is slightly different for both approaches. Because, for a CMA with coaxial gun, the sample tilt angle varies as the electron beam incidence angle, the influence of the latter has to be additionally taken into account for quantification of AES. In reasonable agreement with experimental results it is shown that above 45° the Auger peak intensity of Cu (914 eV) increases up to about a factor of two for an incidence angle of 85°. Copyright © 2006 John Wiley & Sons, Ltd.     

Capillary array as an effusive molecular beam source for high resolution recoil ion momentum spectrometry

The role of a capillary array as a molecular beam source for use in recoil ion momentum spectrometry in ion-atom collisions is investigated. Numerical simulations show that by using a capillary array it is possible to obtain a half-width of 1 meV at room temperature, while the sensitivity could be in the range as low as 100 µeV. Preliminary measurements with electron impact ionisation showed the effectiveness of this technique by providing an energy resolution of about 2 meV at room temperature, which is superior to the resolution reported using a gas cell cooled to 30° K.     

Temporary negative-ion states in pyridine and diazine molecules

Results of electron scattering experiments using a transmission spectrometer are reported for the N-heterocyclic molecules: pyridine, pyridazine, pyrimidine and pyrazine. A number of resonant states are observed in the energy range 0.05 eV to 10 eV. Substituting an N atom for a CH radical in the benzeene ring is shown to remove the degeneracy of the two lowest empty π-orbitals. The derivative technique is applied to the 127° momentum analyser but none of the vibrational structure observed in an experiment using a trochoidal monochromator is detected. Reasonable agreement is reached for values of the first electron affinity.     

Novel floating‐type low‐energy ion gun for high‐resolution depth profiling in ultrahigh vacuum

A floating‐type low‐energy ion gun (FLIG) has been developed for high‐resolution depth profiling in ultrahigh vacuum (UHV). This UHV‐FLIG allows Ar⁺ ions of primary energy down to 50 eV to be provided with high current intensity. The developed UHV‐FLIG was sufficiently compact, being ～30 cm long, to be attached to a commercial surface analytical instrument. The performance of the UHV‐FLIG was measured by attaching it to a scanning Auger electron microprobe (JAMP‐10, Jeol), the base pressure of which in the analysis chamber was ～1 × 10^?7 Pa. The vacuum condition of ～5 × 10^?6 Pa was maintained during operation of the UHV‐FLIG without a differential pumping facility. Current density ranged from 41 to 138 µA cm^?2 for Ar⁺ ions of primary energy 100–500 eV at the working distance of 50 mm. This ensures a sputtering rate of ～10 nm h^?1 with 100 eV Ar⁺ ions for Si, leading to depth profiling of high resolution in practical use. Copyright © 2003 John Wiley & Sons, Ltd.     

Preferential sputtering observed in Auger electron spectroscopy sputter depth profiling of AlAs/GaAs superlattice using low‐energy ions

Auger electron spectroscopy (AES) sputter depth profiling of an ISO reference material of the GaAs/AlAs superlattice was investigated using low‐energy Ar⁺ ions. Although a high depth resolution of ～1.0 nm was obtained at the GaAs/AlAs interface under 100 eV Ar⁺ ion irradiation, deterioration of the depth resolution was observed at the AlAs/GaAs interface. The Auger peak profile revealed that the enrichment of Al due to preferential sputtering occurred during sputter etching of the AlAs layer only under 100 eV Ar⁺ ion irradiation. In addition, a significant difference in the etching rates between the AlAs and GaAs layers was observed for low‐energy ion irradiation. Deterioration of the depth resolution under 100 eV Ar⁺ ion irradiation is attributed to the preferential sputtering and the difference in the etching rate. The present results suggest that the effects induced by the preferential sputtering and the significant difference in the etching rate should be taken into account to optimize ion etching conditions using the GaAs/AlAs reference material under low‐energy ion irradiation. Copyright © 2005 John Wiley & Sons, Ltd.     

Dissociative Electron Attachment to the Nitroamine HMX (Octahydro-1,3,5,7-Tetranitro-1,3,5,7-Tetrazocine)

In the present study, dissociative electron attachment (DEA) measurements with gas phase HMX, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, C₄H₈N₈O₈, have been performed by means of a crossed electron-molecular beam experiment. The most intense signals are observed at 46 and 176 u and assigned to NO₂ ^? and C₃H₆N₅O₄ ^?, respectively. Anion efficiency curves for 15 negatively charged fragments have been measured in the electron energy region from about 0–20 eV with an energy resolution of ~0.7 eV. Product anions are observed mainly in the low energy region, near 0 eV, arising from surprisingly complex reactions associated with multiple bond cleavages and structural and electronic rearrangement. The remarkable instability of HMX towards electron attachment with virtually zero kinetic energy reflects the highly explosive nature of this compound. Substantially different intensity ratios of resonances for common fragment anions allow distinguishing the nitroamines HMX and royal demolition explosive molecule (RDX) in negative ion mass spectrometry based on free electron capture.      

High resolution auger electron spectroscopy for materials characterization

High resolution Auger microanalysis has become a widely applied technique in various fields of materials research. Its submicrometer spatial resolution is shown as being advantageous for surface, interface and thin film analysis. Limitations of the lateral resolution are outlined with respect to influences of electron backscattering, detection sensitivity, sample drift, beam heating and other electron induced processes. High in-depth resolution is linked with high spatial resolution for optimized depth profiling by sputtering. Crater edge profiling with scanning Auger microscopy is particularly useful for obtaining a three-dimensional microanalysis. Some examples demonstrate the capabilities and limitations in the analysis of precipitates, fracture surfaces and multilayer structures.     

IonCCD™ for Direct Position-Sensitive Charged-Particle Detection: from Electrons and keV Ions to Hyperthermal Biomolecular Ions

A novel, low-cost, pixel-based detector array (described elsewhere Sinha and Wadsworth (76(2), 1) is examined using different charged particles, from electrons to hyperthermal (<100 eV) large biomolecular positive and negative ions, including keV small atomic and molecular ions. With this in mind, it is used in instrumentation design (beam profiling), mass spectrometry, and electron spectroscopy. The array detector is a modified light-sensitive charge-coupled device (CCD) that was engineered for direct charged-particle detection by replacing the semiconductor part of the CCD pixel with a conductor Sinha and Wadsworth (76(2), 1). The device is referred to as the IonCCD. For the first time, we show the direct detection of 250-eV electrons, providing linearity response of the IonCCD to the electron beam current. We demonstrate that the IonCCD detection efficiency is virtually independent from the particle energy (250 eV, 1250 eV), impact angle (45^o, 90^o) and flux. By combining the IonCCD with a double-focusing sector field mass spectrometer (MS) of Mattauch-Herzog geometry (MH-MS), we demonstrate fast data acquisition. Detection of hyperthermal biomolecular ions produced using an electrospray ionization source (ESI) is also presented. In addition, the IonCCD was used as a beam profiler to characterize the beam shape and intensity of 15 eV protonated and deprotonated biomolecular ions at the exit of an rf-only collisional quadrupole. This demonstrates an ion-beam profiling application for instrument design. Finally, we present simultaneous detection of 140 eV doubly protonated biomolecular ions when the IonCCD is combined with the MH-MS. This demonstrates the possibility of simultaneous separation and micro-array deposition of biological material using a miniature MH-MS.