Infrared and X-ray photoelectron spectroscopic studies of the reactions of hydrogen-terminated crystalline Si(111) and Si(100) surfaces with Br2, I2, and ferrocenium in alcohol solvents

Joel A. Haber, Nathan S Lewis

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98 Citations (Scopus)

Abstract

The reaction chemistry of H-terminated crystalline Si(111) and Si(100) surfaces in CH3OH, CD3OD, CF3(CH2)3OH, C4H9OH, and C4D9OD solutions containing ferrocenium (Fc+)-BF4, I2, or Br2 was monitored using X-ray photoelectron (XP) spectroscopy and infrared (IR) spectroscopy. Addition of the one-electron oxidant Fc+, or addition of the oxidizing species I2 or Br2, produced diagnostic changes in the IR spectra that clearly indicated formation of surficial Si-OR groups. XPS data confirmed the conclusions of the IR studies: Under our reaction conditions, no detectable reaction occurred without the presence of the oxidant. The data are consistent with oxidative activation of the surficial Si-H bonds toward nucleophilic attack by the alcohols. The reaction chemistry was generally similar on (111)-and (100)-oriented Si surfaces, although some differences were observed in the ratio of reaction products on the two different surface orientations. Alkoxylated surfaces were also prepared by a two-step process in which the surface was first chlorinated and then reacted with LiOCH3, LiOCD3, or LiO(CH2)3CF3. The data indicate that formation of silicon-halogen bonding alone is not sufficient to provide a robust correlation between the electronic and chemical properties of such crystalline Si surfaces and that formation of silicon-alkoxyl bonds is a common motif for surfaces often used in electronic and electrochemical studies of Si.

Original languageEnglish
Pages (from-to)3639-3656
Number of pages18
JournalJournal of Physical Chemistry B
Volume106
Issue number14
DOIs
Publication statusPublished - Apr 11 2002

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Photoelectrons
Hydrogen
photoelectrons
alcohols
Alcohols
Crystalline materials
Infrared radiation
X rays
hydrogen
x rays
Silicon
Oxidants
X ray photoelectron spectroscopy
chemistry
Halogens
silicon
ferrocenium
Reaction products
electronics
chemical properties

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Infrared and X-ray photoelectron spectroscopic studies of the reactions of hydrogen-terminated crystalline Si(111) and Si(100) surfaces with Br2, I2, and ferrocenium in alcohol solvents",
abstract = "The reaction chemistry of H-terminated crystalline Si(111) and Si(100) surfaces in CH3OH, CD3OD, CF3(CH2)3OH, C4H9OH, and C4D9OD solutions containing ferrocenium (Fc+)-BF4, I2, or Br2 was monitored using X-ray photoelectron (XP) spectroscopy and infrared (IR) spectroscopy. Addition of the one-electron oxidant Fc+, or addition of the oxidizing species I2 or Br2, produced diagnostic changes in the IR spectra that clearly indicated formation of surficial Si-OR groups. XPS data confirmed the conclusions of the IR studies: Under our reaction conditions, no detectable reaction occurred without the presence of the oxidant. The data are consistent with oxidative activation of the surficial Si-H bonds toward nucleophilic attack by the alcohols. The reaction chemistry was generally similar on (111)-and (100)-oriented Si surfaces, although some differences were observed in the ratio of reaction products on the two different surface orientations. Alkoxylated surfaces were also prepared by a two-step process in which the surface was first chlorinated and then reacted with LiOCH3, LiOCD3, or LiO(CH2)3CF3. The data indicate that formation of silicon-halogen bonding alone is not sufficient to provide a robust correlation between the electronic and chemical properties of such crystalline Si surfaces and that formation of silicon-alkoxyl bonds is a common motif for surfaces often used in electronic and electrochemical studies of Si.",
author = "Haber, {Joel A.} and Lewis, {Nathan S}",
year = "2002",
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T1 - Infrared and X-ray photoelectron spectroscopic studies of the reactions of hydrogen-terminated crystalline Si(111) and Si(100) surfaces with Br2, I2, and ferrocenium in alcohol solvents

AU - Haber, Joel A.

AU - Lewis, Nathan S

PY - 2002/4/11

Y1 - 2002/4/11

N2 - The reaction chemistry of H-terminated crystalline Si(111) and Si(100) surfaces in CH3OH, CD3OD, CF3(CH2)3OH, C4H9OH, and C4D9OD solutions containing ferrocenium (Fc+)-BF4, I2, or Br2 was monitored using X-ray photoelectron (XP) spectroscopy and infrared (IR) spectroscopy. Addition of the one-electron oxidant Fc+, or addition of the oxidizing species I2 or Br2, produced diagnostic changes in the IR spectra that clearly indicated formation of surficial Si-OR groups. XPS data confirmed the conclusions of the IR studies: Under our reaction conditions, no detectable reaction occurred without the presence of the oxidant. The data are consistent with oxidative activation of the surficial Si-H bonds toward nucleophilic attack by the alcohols. The reaction chemistry was generally similar on (111)-and (100)-oriented Si surfaces, although some differences were observed in the ratio of reaction products on the two different surface orientations. Alkoxylated surfaces were also prepared by a two-step process in which the surface was first chlorinated and then reacted with LiOCH3, LiOCD3, or LiO(CH2)3CF3. The data indicate that formation of silicon-halogen bonding alone is not sufficient to provide a robust correlation between the electronic and chemical properties of such crystalline Si surfaces and that formation of silicon-alkoxyl bonds is a common motif for surfaces often used in electronic and electrochemical studies of Si.

AB - The reaction chemistry of H-terminated crystalline Si(111) and Si(100) surfaces in CH3OH, CD3OD, CF3(CH2)3OH, C4H9OH, and C4D9OD solutions containing ferrocenium (Fc+)-BF4, I2, or Br2 was monitored using X-ray photoelectron (XP) spectroscopy and infrared (IR) spectroscopy. Addition of the one-electron oxidant Fc+, or addition of the oxidizing species I2 or Br2, produced diagnostic changes in the IR spectra that clearly indicated formation of surficial Si-OR groups. XPS data confirmed the conclusions of the IR studies: Under our reaction conditions, no detectable reaction occurred without the presence of the oxidant. The data are consistent with oxidative activation of the surficial Si-H bonds toward nucleophilic attack by the alcohols. The reaction chemistry was generally similar on (111)-and (100)-oriented Si surfaces, although some differences were observed in the ratio of reaction products on the two different surface orientations. Alkoxylated surfaces were also prepared by a two-step process in which the surface was first chlorinated and then reacted with LiOCH3, LiOCD3, or LiO(CH2)3CF3. The data indicate that formation of silicon-halogen bonding alone is not sufficient to provide a robust correlation between the electronic and chemical properties of such crystalline Si surfaces and that formation of silicon-alkoxyl bonds is a common motif for surfaces often used in electronic and electrochemical studies of Si.

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