X-ray photoelectron spectroscopic studies of interfacial chemistry at n-type Si/liquid junctions

Bruce J. Tufts, Amit Kumar, Ashish Bansal, Nathan S Lewis

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

The surface chemistry of n-type Si electrodes that had been etched, exposed to electrolyte, and electrochemically cycled has been probed using high-resolution X-ray photoelectron spectroscopy (XPS). n-Si surfaces etched in hydrofluoric acid-ethanol solutions (in air or N2 ambients) displayed spectra in the Si 2p region that were free of detectable substrate oxide signals (≤5 × 10-11 mol cm-2 SiO2; equivalent to ≤4% of a monolayer). Exposure of HF-C2H5OH etched or of 49% HF(aq) etched n-Si surfaces to an electrolyte solution containing CH3OH, dimethylferrocene (Me2Fc), and dimethylferricenium (Me2Fc+) generated very low levels, ≤(2 ± 1) × 10-10 mol cm-2 of silicon suboxides. Only sub-monolayer levels of SiOx, (4 ± 2) × 10-10 mol cm-2, were detected after electrochemical cycling of illuminated n-Si anodes in contact with CH3OH-Me2Fc+/0 electrolytes. Even n-Si photoanodes maintained at short circuit with the CH3OH-Me2Fc+/0 electrolyte for substantial periods (> 1000 C cm-2 anodic charge passed) formed less than a single monolayer of strained SiO2 at the silicon surface. Deliberate anodization of the Si surface in these electrolyte solutions yielded controlled amounts of thicker (8-10 Å) SiO2 overlayers; these overlayers provided a useful oxide for the formation of high-performance metal-insulator-semiconductor device structures. These studies demonstrate that HF-C2H5OH- or HF(aq)-etched n-Si surfaces are remarkably resistant to oxide formation during photoelectrochemical cycling in CH3OH-based electrolytes, and that the outstanding photoelectrochemical I-V properties of the n-Si/CH3OH-Me2Fc+/0 junction are not a result of formation of passivating oxide overlayers on the Si surface.

Original languageEnglish
Pages (from-to)4581-4592
Number of pages12
JournalJournal of Physical Chemistry
Volume96
Issue number11
Publication statusPublished - 1992

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Photoelectrons
Surface chemistry
Electrolytes
photoelectrons
chemistry
X rays
Oxides
electrolytes
Liquids
liquids
Monolayers
x rays
Silicon
oxides
Semiconductor device structures
Hydrofluoric Acid
Hydrofluoric acid
cycles
short circuits
Short circuit currents

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

X-ray photoelectron spectroscopic studies of interfacial chemistry at n-type Si/liquid junctions. / Tufts, Bruce J.; Kumar, Amit; Bansal, Ashish; Lewis, Nathan S.

In: Journal of Physical Chemistry, Vol. 96, No. 11, 1992, p. 4581-4592.

Research output: Contribution to journalArticle

Tufts, Bruce J. ; Kumar, Amit ; Bansal, Ashish ; Lewis, Nathan S. / X-ray photoelectron spectroscopic studies of interfacial chemistry at n-type Si/liquid junctions. In: Journal of Physical Chemistry. 1992 ; Vol. 96, No. 11. pp. 4581-4592.
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abstract = "The surface chemistry of n-type Si electrodes that had been etched, exposed to electrolyte, and electrochemically cycled has been probed using high-resolution X-ray photoelectron spectroscopy (XPS). n-Si surfaces etched in hydrofluoric acid-ethanol solutions (in air or N2 ambients) displayed spectra in the Si 2p region that were free of detectable substrate oxide signals (≤5 × 10-11 mol cm-2 SiO2; equivalent to ≤4{\%} of a monolayer). Exposure of HF-C2H5OH etched or of 49{\%} HF(aq) etched n-Si surfaces to an electrolyte solution containing CH3OH, dimethylferrocene (Me2Fc), and dimethylferricenium (Me2Fc+) generated very low levels, ≤(2 ± 1) × 10-10 mol cm-2 of silicon suboxides. Only sub-monolayer levels of SiOx, (4 ± 2) × 10-10 mol cm-2, were detected after electrochemical cycling of illuminated n-Si anodes in contact with CH3OH-Me2Fc+/0 electrolytes. Even n-Si photoanodes maintained at short circuit with the CH3OH-Me2Fc+/0 electrolyte for substantial periods (> 1000 C cm-2 anodic charge passed) formed less than a single monolayer of strained SiO2 at the silicon surface. Deliberate anodization of the Si surface in these electrolyte solutions yielded controlled amounts of thicker (8-10 {\AA}) SiO2 overlayers; these overlayers provided a useful oxide for the formation of high-performance metal-insulator-semiconductor device structures. These studies demonstrate that HF-C2H5OH- or HF(aq)-etched n-Si surfaces are remarkably resistant to oxide formation during photoelectrochemical cycling in CH3OH-based electrolytes, and that the outstanding photoelectrochemical I-V properties of the n-Si/CH3OH-Me2Fc+/0 junction are not a result of formation of passivating oxide overlayers on the Si surface.",
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AB - The surface chemistry of n-type Si electrodes that had been etched, exposed to electrolyte, and electrochemically cycled has been probed using high-resolution X-ray photoelectron spectroscopy (XPS). n-Si surfaces etched in hydrofluoric acid-ethanol solutions (in air or N2 ambients) displayed spectra in the Si 2p region that were free of detectable substrate oxide signals (≤5 × 10-11 mol cm-2 SiO2; equivalent to ≤4% of a monolayer). Exposure of HF-C2H5OH etched or of 49% HF(aq) etched n-Si surfaces to an electrolyte solution containing CH3OH, dimethylferrocene (Me2Fc), and dimethylferricenium (Me2Fc+) generated very low levels, ≤(2 ± 1) × 10-10 mol cm-2 of silicon suboxides. Only sub-monolayer levels of SiOx, (4 ± 2) × 10-10 mol cm-2, were detected after electrochemical cycling of illuminated n-Si anodes in contact with CH3OH-Me2Fc+/0 electrolytes. Even n-Si photoanodes maintained at short circuit with the CH3OH-Me2Fc+/0 electrolyte for substantial periods (> 1000 C cm-2 anodic charge passed) formed less than a single monolayer of strained SiO2 at the silicon surface. Deliberate anodization of the Si surface in these electrolyte solutions yielded controlled amounts of thicker (8-10 Å) SiO2 overlayers; these overlayers provided a useful oxide for the formation of high-performance metal-insulator-semiconductor device structures. These studies demonstrate that HF-C2H5OH- or HF(aq)-etched n-Si surfaces are remarkably resistant to oxide formation during photoelectrochemical cycling in CH3OH-based electrolytes, and that the outstanding photoelectrochemical I-V properties of the n-Si/CH3OH-Me2Fc+/0 junction are not a result of formation of passivating oxide overlayers on the Si surface.

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