High‐resolution secondary ion mass spectrometry depth profiling of nanolayers

Baryshev, Sergey V.; Zinovev, A. V.; Tripa, C. E.; Pellin, Michael J.; Peng, Qing; Elam, Jeffrey W.; Veryovkin, I. V.

doi:10.1002/rcm.6344

Cited by 14 publications

(25 citation statements)

References 38 publications

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“…One attempt to improve mass resolution in TOF-SIMS using Ar-GCIB involves applying delayed extraction, an essential technique in TOF mass spectrometry. [17][18][19][20][21][22][23][24][25][26][27][28] In the conventional static extraction mode (standard mode) of TOF-SIMS analysis, the width of the primary ion pulse directly affects the start accuracy of the TOF measurement, regardless of whether the analysis is performed with Ar-GCIB or with a liquid metal ion gun. This is because the pulsed primary ions desorb the secondary ions while the extraction field is already switched on, as shown in Scheme 1(a).…”

Section: Resultsmentioning

confidence: 99%

Improved mass resolution and mass accuracy in TOF-SIMS spectra and images using argon gas cluster ion beams

Shon¹,

Yoon²,

Moon³

et al. 2016

Biointerphases

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The popularity of argon gas cluster ion beams (Ar-GCIB) as primary ion beams in time-of-flight secondary ion mass spectrometry (TOF-SIMS) has increased because the molecular ions of large organic- and biomolecules can be detected with less damage to the sample surfaces. However, Ar-GCIB is limited by poor mass resolution as well as poor mass accuracy. The inferior quality of the mass resolution in a TOF-SIMS spectrum obtained by using Ar-GCIB compared to the one obtained by a bismuth liquid metal cluster ion beam and others makes it difficult to identify unknown peaks because of the mass interference from the neighboring peaks. However, in this study, the authors demonstrate improved mass resolution in TOF-SIMS using Ar-GCIB through the delayed extraction of secondary ions, a method typically used in TOF mass spectrometry to increase mass resolution. As for poor mass accuracy, although mass calibration using internal peaks with low mass such as hydrogen and carbon is a common approach in TOF-SIMS, it is unsuited to the present study because of the disappearance of the low-mass peaks in the delayed extraction mode. To resolve this issue, external mass calibration, another regularly used method in TOF-MS, was adapted to enhance mass accuracy in the spectrum and image generated by TOF-SIMS using Ar-GCIB in the delayed extraction mode. By producing spectra analyses of a peptide mixture and bovine serum albumin protein digested with trypsin, along with image analyses of rat brain samples, the authors demonstrate for the first time the enhancement of mass resolution and mass accuracy for the purpose of analyzing large biomolecules in TOF-SIMS using Ar-GCIB through the use of delayed extraction and external mass calibration.

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Section: Resultsmentioning

confidence: 99%

Improved mass resolution and mass accuracy in TOF-SIMS spectra and images using argon gas cluster ion beams

Shon¹,

Yoon²,

Moon³

et al. 2016

Biointerphases

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“…Although already used by several authors, the effect of a delayed extraction on the resulting mass spectra has never been fully described, much less so in the case of biological tissue imaging. In the present work, a detailed study of the different primary ion beam focusing modes of a TOF‐SIMS instrument has been performed, with extensive comparisons of mass and spatial resolutions on rat cerebellum sections, and with the aim of obtaining with delayed extraction the best compromise between mass resolution, spatial resolution, and acquisition time.…”

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confidence: 99%

“…[38,39] In TOF-SIMS it can also be used to compensate for the departure time of secondary ions when using long primary ion bunches as in the present case of the BA mode if the ion velocity distribution is not too large. Several authors have mentioned the use of a delayed extraction: in the case of ions produced after ion/surface collisions, [40] in depth profiling of Langmuir-Blodgett [41] and of peptides films, [42] in the analysis of eukaryotic cells preserved in trehalose, [43] in the analysis of human skin remains, [17] in the depth profiling of nanostructured layers, [44] in sputtering of silicate glasses, [45] and in the study of topographic and field effects. [46] Although already used by several authors, [17,[40][41][42][43][44][45][46] the effect of a delayed extraction on the resulting mass spectra has never been fully described, much less so in the case of biological tissue imaging.…”

mentioning

confidence: 99%

“…Several authors have mentioned the use of a delayed extraction: in the case of ions produced after ion/surface collisions, [40] in depth profiling of Langmuir-Blodgett [41] and of peptides films, [42] in the analysis of eukaryotic cells preserved in trehalose, [43] in the analysis of human skin remains, [17] in the depth profiling of nanostructured layers, [44] in sputtering of silicate glasses, [45] and in the study of topographic and field effects. [46] Although already used by several authors, [17,[40][41][42][43][44][45][46] the effect of a delayed extraction on the resulting mass spectra has never been fully described, much less so in the case of biological tissue imaging. In the present work, a detailed study of the different primary ion beam focusing modes of a TOF-SIMS instrument has been performed, with extensive comparisons of mass and spatial resolutions on rat cerebellum sections, and with the aim of obtaining with delayed extraction the best compromise between mass resolution, spatial resolution, and acquisition time.…”

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confidence: 99%

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Time‐of‐flight secondary ion mass spectrometry imaging of biological samples with delayed extraction for high mass and high spatial resolutions

Vanbellingen

Elie

Eller

et al. 2015

Rapid Comm Mass Spectrometry

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RationaleIn Time‐of‐Flight Secondary Ion Mass Spectrometry (TOF‐SIMS), pulsed and focused primary ion beams enable mass spectrometry imaging, a method which is particularly useful to map various small molecules such as lipids at the surface of biological samples. When using TOF‐SIMS instruments, the focusing modes of the primary ion beam delivered by liquid metal ion guns can provide either a mass resolution of several thousand or a sub‐µm lateral resolution, but the combination of both is generally not possible.MethodsWith a TOF‐SIMS setup, a delayed extraction applied to secondary ions has been studied extensively on rat cerebellum sections in order to compensate for the effect of long primary ion bunches.ResultsThe use of a delayed extraction has been proven to be an efficient solution leading to unique features, i.e. a mass resolution up to 10000 at m/z 385.4 combined with a lateral resolution of about 400 nm. Simulations of ion trajectories confirm the experimental determination of optimal delayed extraction and allow understanding of the behavior of ions as a function of their mass‐to‐charge ratio.ConclusionsAlthough the use of a delayed extraction has been well known for many years and is very popular in MALDI, it is much less used in TOF‐SIMS. Its full characterization now enables secondary ion images to be recorded in a single run with a submicron spatial resolution and with a mass resolution of several thousand. This improvement is very useful when analyzing lipids on tissue sections, or rare, precious, or very small size samples. © 2015 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd.

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“…We have extended our work on the orthogonal milling dualbeam (gentleDB) depth profiling described in an earlier paper in this journal. [1] The gentleDB strategy is compared here with the single-beam (SB) approach (both conventional and mesa [2] ) with an emphasis on ion-beam-induced effects, especially ion beam mixing, and its critical role in providing high level of quantification in secondary ion mass spectrometry (SIMS). Many empirical correlations between the type, incidence angle, and energy of primary ion species and the SIMS depth resolution have been reported, with discussions mostly in terms of depth profile parameters called leading and trailing lengths.…”

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confidence: 99%