In the last decade, many studies applied surface analysis techniques (SEM, XPS and SIMS) to understand the formation of SEI layers on Li-ion battery electrodes. This work was meant as a comparative model study of the SEI layer formation, which combined in situ SEM imaging with TOF SIMS depth profiling of four samples of the same graphite electrode material, which was subjected to different charge–discharge cycling schemes in a Li-ion battery. Besides comparing compositions of sub-surface regions of these differently processed electrodes, we wanted to know whether these compositions depend on after-cycling sample preparation, in particular if a brief exposure of these samples to air would affect the compositions measured by TOF SIMS. We found that the exposure to air (1) increases secondary ion yield for all species, and (2) changes shapes of SIMS depth profiles for some key species. For selected samples, we also conducted a comparison between the conventional single beam TOF-SIMS depth profiling and a high resolution dual beam depth profiling and found that the former approach can detect the same features in depth profiles as the latter one. We interpreted this as an indication that the sample surface morphology (high roughness) could be a limiting factor in this SEI study, suggesting that specially designed model samples with smooth surfaces are a better choice for future studies.

Is a U.S. Department of Energy laboratory managed by UChicago Argonne, LLC. This work is supported by NASA through grant NNH09AM48I, and by the U.S. Department of Energy, Office of Science, Materials Sciences and Engineering Division. Use of the Center for Nanoscale Materials was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. Depth Profiling of Genesis Diamond-on-Silicon Collectors: Direct Comparison Between Front side and Backside Approaches

We report on a combination of imaging mass spectrometry (MS) and scanning electron microscopy (SEM) developed in a custom designed time-of-flight (TOF) MS instrument with laser post-ionization of sputtered atoms. Elemental (by MS) and topographical (by SEM) mapping of surfaces of heavily contaminated Si collectors from the NASA Genesis sample return mission enabled obtaining much more accurate and detailed depth distribution of the Solar Wind Mg and Ca implanted in these collectors. This is because the cleanest areas were identified by the SEM/MS mapping, and high resolution sputter depth profiling at these locations revealed near-surface (0-15 nm) depth distribution of Mg and Ca, that were used for more accurate fluence calculations of these Solar Wind species. MS imaging was virtually nondestructive at primary ion fluence 10(12) cm(-2), causing no effect on accuracy and precision of quantitative depth profiling that followed the imaging. We also demonstrate importance of such an approach by directly comparing high resolution depth profiles measured on clean areas versus arbitrarily selected areas. (C) 2014 Elsevier B.V. All rights reserved.

Ionized and neutral clusters were desorbed from spangold, a polycrystalline ternary alloy with composition Au7Cu5Al4, using both a femtosecond laser beam and an energetic ion beam and the resulting time of flight mass spectra compared. Neutral clusters containing up to 7 atoms were ejected by the 15 key Ar+ beam whereas only smaller positively and negatively charged clusters were observed from the laser ablated spangold surface.Laser ionization mass spectrometry (LIMS) positive ion spectra were dominated by Al containing cluster ions whereas Au containing ions dominated the negative LIMS spectrum. An odd-even variation in LIMS cluster yield was observed, consistent with previous results and due to fragmentation of photoionized clusters. The laser sputtered neutral mass spectrometry (laser SNMS) spectrum showed that larger desorbed clusters were gold rich. The cluster signals also followed a power law dependence with cluster size with the exponent value of 6-7.6 for sputtered mixed clusters being greater than that found from sputtering of pure elements, similar to the result found previously in the Cu-Au system. (C) 2014 Elsevier B.V. All rights reserved.

The Genesis mission was the first mission returning solar material to Earth since the Apollo program [1,2]. Unfortunately the return of the space craft on September 8, 2004 resulted in a crash landing, which shattered the samples into small fragments and exposed them to desert soil and other debris. Thus only small fragments of the original collectors are available, each having different degrees of surface contamination. Thorough surface cleaning is required to allow for subsequent analysis of solar wind material embedded within. An initial cleaning procedure was developed in coordination with Johnson Space Center which focused on removing larger sized particulates and a thin film organic contamination acquired during collection in space [3]. However, many of the samples have additional residues and more rigorous and/or innovative cleaning steps might be necessary. These cleaning steps must affect only the surface to avoid leaching and re-distribution of solar wind material from the bulk of the collectors. To aid in development and identification of the most appropriate cleaning procedures each sample has to be thoroughly inspected before and after each cleaning step. Laboratory based total reflection X-ray fluorescence (TXRF) spectrometry lends itself to this task as it is a non-destructive and surface sensitive analytical method permitting analysis of elements from aluminum onward present at and near the surface of a flat substrate [4]. The suitability of TXRF has been demonstrated for several Genesis solar wind samples before and after various cleaning methods including acid treatment, gas cluster ion beam, and CO2 snow jet [5 - 7]. The latter one is non-invasive and did show some promise on one sample [5]. To investigate the feasibility of CO2 snow jet cleaning further, several flown Genesis samples were selected to be characterized before and after CO2 snow application with sample 61052 being discussed below.

In materials science and engineering it is often necessary to obtain quantitative measurements of surface topography with micrometer lateral resolution. From the measured surface, 3D topographic maps can be subsequently analyzed using a variety of software packages to extract the information that is needed.In this article we describe how white light interferometry, and optical profilometry (OP) in general, combined with generic surface analysis software, can be used for materials science and engineering tasks. In this article, a number of applications of white light interferometry for investigation of surface modifications in mass spectrometry, and wear phenomena in tribology and lubrication are demonstrated. We characterize the products of the interaction of semiconductors and metals with energetic ions (sputtering), and laser irradiation (ablation), as well as ex situ measurements of wear of tribological test specimens.Specifically, we will discuss:i. Aspects of traditional ion sputtering-based mass spectrometry such as sputtering rates/yields measurements on Si and Cu and subsequent time-to-depth conversion.ii. Results of quantitative characterization of the interaction of femtosecond laser irradiation with a semiconductor surface. These results are important for applications such as ablation mass spectrometry, where the quantities of evaporated material can be studied and controlled via pulse duration and energy per pulse. Thus, by determining the crater geometry one can define depth and lateral resolution versus experimental setup conditions.iii. Measurements of surface roughness parameters in two dimensions, and quantitative measurements of the surface wear that occur as a result of friction and wear tests.Some inherent drawbacks, possible artifacts, and uncertainty assessments of the white light interferometry approach will be discussed and explained.

Rapid Communications in Mass SpectrometryVolume 27, Issue 24 p. 2828-2832 Letter to the Editor Dual-beam versus single-beam depth profiling: Same sample in same instrument S. V. Baryshev, Corresponding Author S. V. Baryshev Materials Science Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL, 60439 USACurrent address: Euclid TechLabs LLC, 5900 Harper Rd., Solon, OH 44139, USA; and High Energy Physics Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL 60439, USA. Correspondence to: S. V. Baryshev, Materials Science Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL 60439, USA. E-mail: [email protected]Search for more papers by this authorN. G. Becker, N. G. Becker Materials Science Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL, 60439 USA Department of Physics, Illinois Institute of Technology, 3101 S. Dearborn St., Chicago, IL, 60616 USASearch for more papers by this authorA. V. Zinovev, A. V. Zinovev Materials Science Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL, 60439 USASearch for more papers by this authorC. E. Tripa, C. E. Tripa Materials Science Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL, 60439 USASearch for more papers by this authorI. V. Veryovkin, I. V. Veryovkin Materials Science Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL, 60439 USASearch for more papers by this author S. V. Baryshev, Corresponding Author S. V. Baryshev Materials Science Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL, 60439 USACurrent address: Euclid TechLabs LLC, 5900 Harper Rd., Solon, OH 44139, USA; and High Energy Physics Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL 60439, USA. Correspondence to: S. V. Baryshev, Materials Science Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL 60439, USA. E-mail: [email protected]Search for more papers by this authorN. G. Becker, N. G. Becker Materials Science Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL, 60439 USA Department of Physics, Illinois Institute of Technology, 3101 S. Dearborn St., Chicago, IL, 60616 USASearch for more papers by this authorA. V. Zinovev, A. V. Zinovev Materials Science Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL, 60439 USASearch for more papers by this authorC. E. Tripa, C. E. Tripa Materials Science Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL, 60439 USASearch for more papers by this authorI. V. Veryovkin, I. V. Veryovkin Materials Science Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL, 60439 USASearch for more papers by this author First published: 11 November 2013 https://doi.org/10.1002/rcm.6749Citations: 3 Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat REFERENCES 1 S. V. Baryshev, A. V. Zinovev, C. E. Tripa, M. J. Pellin, Q. Peng, J. W. Elam, I. V. Veryovkin. High-resolution secondary ion mass spectrometry depth profiling of nanolayers. Rapid Commun. Mass Spectrom. 2012, 26, 2224. 10.1002/rcm.6344 CASPubMedWeb of Science®Google Scholar 2 G. Gillen. 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Sputter depth profile analysis of interfaces. Reports Prog. Phys. 1998, 61, 827. 10.1088/0034-4885/61/7/002 CASWeb of Science®Google Scholar 11 Y. Kataoka, K. Yamazaki, M. Shigeno, Y. Tada, K. Wittmaack. Surface roughening of silicon under ultra-low-energy cesium bombardment. Appl. Surf. Sci. 2003, 203–204, 43. 10.1016/S0169-4332(02)00650-5 CASWeb of Science®Google Scholar 12 S. Hofmann, A. Zalar, E. H. Cirlin, J. J. Vajo, H. J. Mathieu, P. Panjan. Interlaboratory comparison of the depth resolution in sputter depth profiling of Ni/Cr multilayers with and without sample rotation using AES, XPS, and SIMS. Surf. Interface Anal. 1993, 20, 621. 10.1002/sia.740200803 CASWeb of Science®Google Scholar 13 T. J. Ormsby, D. P. Chu, M. G. Dowsett, G. A. Cooke, S. B. Patel. The advantages of normal incidence ultra-low energy secondary ion mass spectrometry depth profiling. Appl. Surf. Sci. 1999, 144–145, 292. 10.1016/S0169-4332(98)00812-5 Web of Science®Google Scholar 14 T. Sasaki, N. Yoshida, M. Takahashi, M. Tomita. The optimization of incident angles of low-energy oxygen ion beams for increasing sputtering rate on silicon samples. Appl. Surf. Sci. 2008, 255, 1357. 10.1016/j.apsusc.2008.05.024 CASWeb of Science®Google Scholar 15 I. V. Veryovkin, C. E. Tripa, A. V. Zinovev, B. V. King, M. J. Pellin, D. S. Burnett. Sensitive multielement RIMS depth profiling of Genesis Solar Wind collectors, in Proceedings 41st Lunar and Planetary Science Conference 2010, Abstract #2579. Google Scholar Citing Literature Volume27, Issue2430 December 2013Pages 2828-2832 ReferencesRelatedInformation

We report results of high-resolution sputter depth profiling of an alternating MgO/ZnO nanolayer stack grown by atomic layer deposition (ALD) of ≈5.5 nm per layer. We used an improved dual beam time-of-flight secondary ion mass spectrometer to measure 24Mg+ and 64Zn+ intensities as a function of sample depth. Analysis of depth profiles by the mixing–roughness–information model yields a 1.5 nm nanolayer interfacial roughness within the MgO/ZnO multilayer. This finding was cross-validated using specular x-ray reflectivity. Such an analysis further suggested that the 1.5 nm roughness corresponds to native/jig-sawed interfacial roughness rather than interfacial interdiffusion during the ALD growth.

White light interferometry (WLI) can be used to obtain surface morphology information on dimensional scale of millimeters with lateral resolution as good as similar to 1 mu m and depth resolution down to 1 nm. By performing true three-dimensional imaging of sample surfaces, the WLI technique enables accurate quantitative characterization of the geometry of surface features and compares favorably to scanning electron and atomic force microscopies by avoiding some of their drawbacks.In this paper, results of using the WLI imaging technique to characterize the products of ion sputtering experiments are reported. With a few figures, several example applications of the WLI method are illustrated when used for (i) sputtering yield measurements and time-to-depth conversion, (ii) optimizing ion beam current density profiles, the shapes of sputtered craters, and multiple ion beam superposition and (iii) quantitative characterization of surfaces processed with ions.In particular, for sputter depth profiling experiments of Mg-25, Ca-44 and Cr-53 ion implants in Si (implantation energy of 1 keV per nucleon), the depth calibration of the measured depth profile curves determined by the WLI method appeared to be self-consistent with TRIM simulations for such projectile-matrix systems. In addition, high depth resolution of the WLI method is demonstrated for a case of a Genesis solar wind Si collector surface processed by gas cluster ion beam: a 12.5 nm layer was removed from the processed surface, while the transition length between the processed and untreated areas was 150 mu m. (C) 2012 Elsevier B. V. All rights reserved.

Introduction: NASA Genesis Mission samples made of a number of ultrapure materials, which captured the solar wind (SW), pose a serious challenge for analytical approaches to reveal solar elemental and isotopic abundances at high precision and accuracy. The difficulties are generally known to be (i) surface contamination due to brown stain and/or the crash landing and (ii) ultralow/trace concentrations of the implanted elements (~1 ppb/parts of ppb) which are distributed within the first 100 nm depth from the collectors surface. Mass spectrometry (MS) based on ion sputtering proved to be an inestimable method in the Genesis project [1]. The combination of factors (i) and (ii) requires of MS approaches to have the highest possible depth resolution (in addition to the highest possible sensitivity) to accurately distinguish between surface terrestrial contamination and the implanted SW. For a number of SW elements having high terrestrial abundances, this is possibly the only way to restore the correct depth profile curves yielding to correct fluence calculations. In this work, we report results on Genesis Si flight samples obtained by laser post-ionization secondary neutral mass spectrometry (LPI SNMS) based on dual beam depth profiling with low energy normal incidence sputtering (lenisDB). Being an approach of ultimate depth resolution, coupled with preliminary Genesis sample surface SNMS mapping and secondary electron microscopy (SEM) imaging, lenisDB allowed us to (i) resolve the SW depth profile from the surface contamination and (ii) find analytical cleaner (sweet) spots, i.e. surface areas of lowest initial contamination levels, and so uncover a fine structure of the nearsurface SW depth distribution (essentially pronounced in Mg), which we attribute to radiation enhanced diffusion towards the surface. Experimental: In SARISA [2] we combined two separate ion beams; one of low energy and normal incidence for ultimate depth resolution (~0.5 nm) ion milling and another for elemental analysis with high lateral resolution (~10 μm). This arrangement is an advanced version of known dual beam depth profiling [3] and should be called in our case lenisDB (Fig.1). The principle of LPI SNMS is as follows. Sputtered neutrals are converted into photo-ions for further time-of-flight (TOF) MS analysis by resonantly enhanced multi-photon ionization with tunable Tisapphire lasers by the scheme as reported in [4]. Such a scheme allows us, in general, to detect simultaneously Mg, Ca and Cr.

We report results of high-resolution TOF SIMS (time of flight secondary ion mass spectrometry) depth profiling experiments on a nanolayered structure, a stack of 16 alternating MgO and ZnO ~5.5 nm layers grown on a Si substrate by atomic layer deposition. The measurements were performed using a newly developed approach implementing a low energy direct current normally incident Ar+ ion beam for sample material removal by sputtering (250 eV and 500 eV energy), in combination with a pulsed 5 keV Ar+ ion beam at 60{\deg} incidence for TOF SIMS analysis. By this optimized arrangement, a noticeably improved version of known dual-beam (DB) approach to TOF SIMS depth profiling is introduced, which can be called gentleDB. We apply the mixing-roughness-information model to detailed analysis of experimental results. It reveals that the gentleDB approach allows ultimate depth resolution by confining the ion beam mixing length to about 2 monolayers. This corresponds to the escape depth of secondary ions, the fundamental depth resolution limitation in SIMS. Other parameters deduced from the measured depth profiles indicate that a single layer thickness equals to 6 nm so that "flat" layer thickness d is of 3 nm and interfacial roughness {\sigma} is of 1.5 nm thus yielding d+2\bullet{\sigma}=6 nm. In essence, we have demonstrated that the gentleDB TOF SIMS depth profiling with noble gas ion beams is capable of revealing structural features of a stack of nanolayers, resolving its original surface and estimating the roughness of interlayer interfaces, which is difficult to obtain by traditional approaches.