Surface composition of poly(styrene-d8-styrene) random copolymers studied by static secondary ion mass spectroscopy

Affrossman, S.; Hartshorne, Mark; Jérôme, Robert; Munro, H.S.; Pethrick, R. A.; Petitjean, S.; Vilar, M. Rei

doi:10.1021/ma00072a017

Cited by 24 publications

(36 citation statements)

References 4 publications

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“…2 [27][28][29] and tandem mass spectrometry. 30,31 However, in the case of end groups containing heteroatoms (Si, S, Br, …), several extra peaks are present in the spectra.…”

Section: Resultsmentioning

confidence: 99%

Evidence of simple intramolecular rearrangement at polymer end groups in secondary ion mass spectrometry

Eynde

Oike

Hamada

et al. 1999

Rapid Commun. Mass Spectrom.

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Polystyrenes with various end groups were analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS). These end groups were obtained by termination of the active anionic group by sulfonate or chlorosilane derivatives. Characteristic end group fragments for each sulfonate derivative were observed. On the one hand, for PS capped by methyl sulfonate, or -(CH(2))(4)-O-SO(2)-CH(3), almost complete end group fragment is observed at m/z 95 and a [O-SO(2)-CH(3)](-) molecular structure. On the other hand, when PS is terminated by silyl methyl sulfonate, or -Si(CH(3))(2)-(CH(2))(3)-O-SO(2)-CH(3), the most characteristic fragment in the fingerprint secondary ion mass spectrum is located at m/z 153 with [Si(CH(3))(2)-O-SO(2)-CH(3)](+) and the complete end group peak, [Si(CH(3))(2)-(CH(2))(3)-O-SO(2)-CH(3)](+), at m/z 201, is absent. According to the molecular structure, characteristic end group secondary ions can be emitted as complete or rearranged fragments. Various silylalkyl alcohol or sulfonate functionalities are analyzed and fragmentation pathways are discussed. To our knowledge, this is the first time that such rearrangement at silyl functions has been observed and demonstrated in fingerprint secondary ion mass spectra. Copyright 1999 John Wiley & Sons, Ltd.

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“…2 [27][28][29] and tandem mass spectrometry. 30,31 However, in the case of end groups containing heteroatoms (Si, S, Br, …), several extra peaks are present in the spectra.…”

Section: Resultsmentioning

confidence: 99%

Evidence of simple intramolecular rearrangement at polymer end groups in secondary ion mass spectrometry

Eynde

Oike

Hamada

et al. 1999

Rapid Commun. Mass Spectrom.

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“…10,11,25 Time-of-flight ͑ToF͒ SIMS was used to characterize the degree of deuterium substitution in the dPS ͑ d ͒. 11,26 For this, Si ͑100͒wafers were cut into 1 ϫ 1 cm 2 squares, soaked in BakerClean JTB-111 ͑J. T. Baker͒ for 30 min, and then rinsed with de-ionized ͑DI͒ water.…”

Section: A Materials and Sample Preparationmentioning

confidence: 99%

“…11 Mass spectra were collected from three different spots and were subsequently analyzed using the WINCADENCE commercial software. The tropylium ion ͑C 7 H 7 + ͒ was the species used for determining d , as this molecular ion has minimal mass fractionation effects among the various isotopic permutations 15,26 and negligible background interferences. The positive secondary ion mass spectrum of dPS from 96 to 99 Da is shown in Fig.…”

Section: B Time-of-flight Sims Analysismentioning

confidence: 99%

Mass fractionation of carbon and hydrogen secondary ions upon Cs+ and O2+ bombardment of organic materials

Harton

Zhu

Stevie

et al. 2007

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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A phenomenon known as mass fractionation has been probed in organic materials using secondary ion mass spectrometry (SIMS). Mass fractionation occurs because two isotopes of a particular species (i.e., identical number of protons, but different number of neutrons) do not have identical secondary ion yields in a constant chemical environment. Two primary ion probes, Cs+ and O2+, have been utilized with detection of negative and positive secondary ions, respectively, using a magnetic sector mass spectrometer. These two analysis conditions have been found to yield considerably different mass fractionation effects as a result of different sputtering and ionization mechanisms. Also, as determined previously with SIMS analysis of inorganic materials, the lower molecular weight species carbon and hydrogen are particularly susceptible to mass fractionation effects. Because organic materials are primarily composed of carbon and hydrogen, and because isotopic labeling is often utilized to accurately analyze such materials, knowledge of these effects in organic materials is essential for quantitative SIMS analysis.

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“…X \ X* ] E(n ] p) (8) where E is the matrix of residuals. The basic idea of PCR is to use this instead of X in T r any linear regression ;…”

Section: Multivariate Analysismentioning

confidence: 99%

“…6 Another problem is the isotopic distribution of the fragments that should be included in the quantiÐcation to obtain an improvement of the results. 8 The more fundamental approach to the quantiÐcation should be based on the complete understanding of the secondary ion emission phenomena induced by ion-beam interaction with polymer surfaces. Although this goal is far from being reached, some progress has been obtained recently in the understanding of the macromolecular fragmentation schemes by using tandem mass spectrometry13 or by measuring the kinetic energy distribution of the molecular fragments.14 Computer simulations of the sputtering and secondary emission could give quantitative results but these methods are restricted, up to now, to a few small molecules adsorbed on speciÐc metallic substrates.…”

Section: Introductionmentioning

confidence: 99%

ToF-SIMS quantification of polystyrene spectra based on principal component analysis (PCA)†

Eynde

Bertrand

1997

Surf. Interface Anal.

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Monodisperses polystyrenes (PS) with molecular weight (Mn) ranging from 850 to 20000 g mol‐1 and with different butyl end‐groups have been analysed by time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). Only the fingerprint part of the spectra (m/z<200) has been considered. This part comes from the fragmentation of the macromolecules and this is the only contribution in the secondary ion spectra of bulk polymers. In a former study, it has been shown that Mn has a significant influence on the PS secondary molecular ion intensities. It was found that not only the end‐group characteristic ion intensities are modified for Mn<50000 g mol‐1, but also those related to main chain fragments. In this study, the possibility to use this effect to quantify the molecular weight of the macrochains at the surface is investigated. Because the quantification method should preferably include all the information contained in the spectra (over 150 peaks), statistical methods are needed. Principal component analysis is applied to these ToF‐SIMS data. Principal component analysis builds the best linear combination of the variables, namely the principal components that describe the greatest amount of variation of the sample set. It is found that only one principal component is required to account for the molecular weight variations and a second one allows the samples to be discriminated depending on their butyl end‐groups. Whatever the PS end‐groups (linear, secondary or tertiary butyl), the correlation found between the first principal component and the sample molecular weight leads to the definition of a universal curve that allows the molecular weight determination for an unknown monodisperse PS sample. © 1997 John Wiley & Sons, Ltd.

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Surface composition of poly(styrene-d8-styrene) random copolymers studied by static secondary ion mass spectroscopy

Cited by 24 publications

References 4 publications

Evidence of simple intramolecular rearrangement at polymer end groups in secondary ion mass spectrometry

Evidence of simple intramolecular rearrangement at polymer end groups in secondary ion mass spectrometry

Mass fractionation of carbon and hydrogen secondary ions upon Cs+ and O2+ bombardment of organic materials

ToF-SIMS quantification of polystyrene spectra based on principal component analysis (PCA)†

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