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Measurement of the Band Bending and Surface Dipole at Chemically Functionalized Si(111)/Vacuum Interfaces

Gleason-Rohrer, David C. and Brunschwig, Bruce S. and Lewis, Nathan S. (2013) Measurement of the Band Bending and Surface Dipole at Chemically Functionalized Si(111)/Vacuum Interfaces. Journal of Physical Chemistry C, 117 (35). pp. 18031-18042. ISSN 1932-7447. doi:10.1021/jp401585s.

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The core-level energy shifts observed using X-ray photoelectron spectroscopy (XPS) have been used to determine the band bending at Si(111) surfaces terminated with Si–Br, Si–H, and Si–CH3 groups, respectively. The surface termination influenced the band bending, with the Si 2p3/2 binding energy affected more by the surface chemistry than by the dopant type. The highest binding energies were measured on Si(111)–Br (whose Fermi level was positioned near the conduction band at the surface), followed by Si(111)–H, followed by Si(111)–CH3 (whose Fermi level was positioned near midgap at the surface). Si(111)–CH3 surfaces exposed to Br2(g) yielded the lowest binding energies, with the Fermi level positioned between midgap and the valence band. The Fermi level position of Br2(g)-exposed Si(111)–CH3 was consistent with the presence of negatively charged bromine-containing ions on such surfaces. The binding energies of all of the species detected on the surface (C, O, Br) shifted with the band bending, illustrating the importance of isolating the effects of band bending when measuring chemical shifts on semiconductor surfaces. The influence of band bending was confirmed by surface photovoltage (SPV) measurements, which showed that the core levels shifted toward their flat-band values upon illumination. Where applicable, the contribution from the X-ray source to the SPV was isolated and quantified. Work functions were measured by ultraviolet photoelectron spectroscopy (UPS), allowing for calculation of the sign and magnitude of the surface dipole in such systems. The values of the surface dipoles were in good agreement with previous measurements as well as with electronegativity considerations. The binding energies of the adventitious carbon signals were affected by band bending as well as by the surface dipole. A model of band bending in which charged surface states are located exterior to the surface dipole is consistent with the XPS and UPS behavior of the chemically functionalized Si(111) surfaces investigated herein.

Item Type:Article
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URLURL TypeDescription material
Brunschwig, Bruce S.0000-0002-6135-6727
Lewis, Nathan S.0000-0001-5245-0538
Additional Information:© 2013 American Chemical Society. Received: February 13, 2013; Revised: July 8, 2013; Published: July 10, 2013. We gratefully acknowledge the National Science Foundation (CHE-0911682 and CHE-1214152), the Molecular Materials Research Center of the Beckman Institute at the California Institute of Technology, and Toyota for support of this work.
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Caltech Beckman InstituteUNSPECIFIED
Issue or Number:35
Record Number:CaltechAUTHORS:20131120-160424952
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Official Citation:Measurement of the Band Bending and Surface Dipole at Chemically Functionalized Si(111)/Vacuum Interfaces David C. Gleason-Rohrer, Bruce S. Brunschwig, and Nathan S. Lewis The Journal of Physical Chemistry C 2013 117 (35), 18031-18042
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:42604
Deposited By: Katherine Johnson
Deposited On:21 Nov 2013 00:16
Last Modified:10 Nov 2021 16:25

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