Electronic Structure of Poly(dimethylsilane) and Polysilane Studied by XPS, UPS, and Band Calculation
- 1 February 1988
- journal article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 61 (2) , 351-358
- https://doi.org/10.1246/bcsj.61.351
Abstract
The valence electronic structures of poly(dimethylsilane)(PDMS) (Si(CH3)2)n and polysilane (SiH2)n were studied. PDMS was experimentally studied by X-ray photoelectron spectroscopy (XPS) and UV photoelectron spectroscopy (UPS), and band calculations were performed for both compounds. The observed spectral features and calculated band structures were assigned and discussed through a comparison with theoretical and experimental results for oligomers and other polymers. These analyses have demonstrated how the electronic structures of these compounds are correlated through factors such as (i) change in the chain length, (ii) methylation, and (iii) the substitution of Si by C. PDMS has a small ionization energy (5.9 eV) almost as low as that of poly(p-phenylene) (5.6 eV). This small value comes from the combined contribution from the small electronegativity of silicon, σ-conjugation, and the inductive effect of methyl groups. The small ionization energy and large σ-conjugation explain the reported high conductivity of PDMS and its derivatives upon acceptor doping.This publication has 43 references indexed in Scilit:
- The polysilane high polymersJournal of Organometallic Chemistry, 1986
- Effects of polysilane formation on the optical and electrical properties of binary Si:H alloysPhysical Review B, 1985
- Phenylmethylpolysilanes: formable silane copolymers with potential semiconducting propertiesJournal of the American Chemical Society, 1981
- Infrared and Raman spectra of the silicon-hydrogen bonds in amorphous silicon prepared by glow discharge and sputteringPhysical Review B, 1977
- Photoelectron spectra and molecular properties. LI. Ionization potentials of silanes SinH2n+2Journal of the American Chemical Society, 1976
- Electronic structure of silanes in the semi-empirical equivalent orbital methodTheoretical Chemistry Accounts, 1975
- Photoelectron spectra of polysilanes. Conformational analyses of tetra-and penta-silaneJournal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics, 1975
- Intermolecular donation of a .sigma.-electron from group IVb catenates to tetracyanoethylene. Evidence of electron paramagnetic resonance and charge-transfer spectraJournal of the American Chemical Society, 1973
- Charge-transfer complexing between permethylpolysilanes and tetracyanoethyleneJournal of the American Chemical Society, 1973
- Bond‐Bond Interaction in PolysilanesAngewandte Chemie International Edition in English, 1971