π* ← π Shakeup Satellites for the Analysis of Structure and Bonding in Aromatic Polymers by X-Ray Photoelectron Spectroscopy
- 1 February 1986
- journal article
- research article
- Published by SAGE Publications in Applied Spectroscopy
- Vol. 40 (2), 224-232
- https://doi.org/10.1366/0003702864509565
Abstract
The applications of ESCA to polymer surface analysis include the use of the secondary final-state effects which lead to satellite structure near the core-level photoemission (PE) lines. Specifically, unsaturated and aromatic functionalities in organic compounds and polymers lead to π* ← π shakeup peaks of less than 10 eV lower kinetic energy (higher binding energy). In the surface analysis of polymers, these features can be utilized for qualitative analysis, identification of the presence and structure of aromatic bonding, and quantitative analysis in determining the amount of a particular block or the aromatic containing function in the near-surface region. Carbon Is shakeups are most often used, but the present study includes detailed qualitative and quantitative analysis of shakeup structures from PE lines from each type of atom in hydrocarbon-, siloxane-, and sulfur-containing polymers. These results show the importance of including the shakeup intensity in quantitative peak area calculations and in peak fitting of complex PE envelopes. These studies prove in a variety of systems that the effects of third-row atoms on the final state lead to the presence of shakeup features in atoms with orbitals which do not participate in the aromatic orbital initial state, thus complicating interpretation of structure from the presence of these features. Results from the siloxane and sulfone polymers indicate that previously held assumptions about the nature of the initial-state molecular orbital may overlook the contribution of empty 3d orbitals or increased charge density on the Si or S atom which would spread the pi orbitals to the oxygen in the aromatic siloxane or sulfone systems. Finally, analysis of these features can provide quantitative analysis of polymeric surface structure by monitoring the relative intensity of the feature to the main PE line.Keywords
This publication has 26 references indexed in Scilit:
- π* ← π Shakeup phenomena in organic polymers with backbone aromatic functionalityJournal of Electron Spectroscopy and Related Phenomena, 1984
- Transition from Adiabatic to Sudden Core-Electron Excitation:on Ni(100)Physical Review Letters, 1983
- Shake-up transitions in the X-ray photoelectron spectra of some five-membered heterocycles containing two heteroatomsSpectrochimica Acta Part A: Molecular Spectroscopy, 1982
- Energy-gain satellite structure in the C(1s) x-ray photoemission spectra of organic macromoleculesSolid State Communications, 1978
- Satellite structure in the x-ray photoelectron spectra of gaseous furan, pyrrole, and thiophenThe Journal of Chemical Physics, 1977
- An ESCA study of the electronic structure of solid benzene.Molecular Physics, 1977
- ESCA studies of polymers. XIII. Shake‐up phenomena in substituted polystyrenesJournal of Polymer Science: Polymer Chemistry Edition, 1977
- Some aspects of shake-up phenomena in some simple polymer systemsJournal of Electron Spectroscopy and Related Phenomena, 1976
- ESCA studies of polymers. VII. Shake‐up phenomena in some alkane–styrene copolymersJournal of Polymer Science: Polymer Chemistry Edition, 1976
- Electron Shake-Off Resulting from-Shell Ionization in Neon Measured as a Function of Photoelectron VelocityPhysical Review B, 1965