Abstract
Vibrational sum-frequency generation (VSFG) spectroscopy was used to investigate the orientation and azimuthal anisotropy of the C-H stretching modes for propynyl-terminated Si(111) surfaces, Si - C=C - CH3. VSFG spectra revealed symmetric and asymmetric C-H stretching modes in addition to a Fermi resonance mode resulting from the interaction of the asymmetric C-H bending overtone with the symmetric C-H stretching vibration. The polarization dependence of the C-H stretching modes was consistent with the propynyl groups oriented such that the Si - C=C- bond is normal to the Si(111) surface. The azimuthal angle dependence of the resonant C-H stretching amplitude revealed no rotational anisotropy for the symmetric C-H stretching mode and a 3-fold rotational anisotropy for the asymmetric C-H stretching mode in registry with the 3-fold symmetric Si(111) substrate. The results are consistent with the expectation that the C-H stretching modes of a -CH3 group are decoupled from the Si substrate due to a -C=C- spacer. In contrast, the methyl-terminated Si(111) surface, Si-CH3, was previously reported to have pronounced vibronic coupling of the methyl stretch modes to the electronic bath of bulk Si. Vacuum-annealing of propynyl-terminated Si(111) resulted in increased 3-fold azimuthal anisotropy for the symmetric stretch, suggesting that removal of propynyl groups from the surface upon annealing allowed the remaining propynyl groups to tilt away from the surface normal into one of three preferred directions toward the vacated neighbor sites.
| Original language | English |
|---|---|
| Pages (from-to) | 16872-16878 |
| Number of pages | 7 |
| Journal | Journal of Physical Chemistry C |
| Volume | 121 |
| Issue number | 31 |
| DOIs | |
| Publication status | Published - Aug 10 2017 |
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ASJC Scopus subject areas
- Electronic, Optical and Magnetic Materials
- Energy(all)
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
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Vibrational Sum-Frequency Spectroscopic Investigation of the Structure and Azimuthal Anisotropy of Propynyl-Terminated Si(111) Surfaces. / Dhar, Purnim; Plymale, Noah T.; Malyk, Sergey; Lewis, Nathan S; Benderskii, Alexander V.
In: Journal of Physical Chemistry C, Vol. 121, No. 31, 10.08.2017, p. 16872-16878.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Vibrational Sum-Frequency Spectroscopic Investigation of the Structure and Azimuthal Anisotropy of Propynyl-Terminated Si(111) Surfaces
AU - Dhar, Purnim
AU - Plymale, Noah T.
AU - Malyk, Sergey
AU - Lewis, Nathan S
AU - Benderskii, Alexander V.
PY - 2017/8/10
Y1 - 2017/8/10
N2 - Vibrational sum-frequency generation (VSFG) spectroscopy was used to investigate the orientation and azimuthal anisotropy of the C-H stretching modes for propynyl-terminated Si(111) surfaces, Si - C=C - CH3. VSFG spectra revealed symmetric and asymmetric C-H stretching modes in addition to a Fermi resonance mode resulting from the interaction of the asymmetric C-H bending overtone with the symmetric C-H stretching vibration. The polarization dependence of the C-H stretching modes was consistent with the propynyl groups oriented such that the Si - C=C- bond is normal to the Si(111) surface. The azimuthal angle dependence of the resonant C-H stretching amplitude revealed no rotational anisotropy for the symmetric C-H stretching mode and a 3-fold rotational anisotropy for the asymmetric C-H stretching mode in registry with the 3-fold symmetric Si(111) substrate. The results are consistent with the expectation that the C-H stretching modes of a -CH3 group are decoupled from the Si substrate due to a -C=C- spacer. In contrast, the methyl-terminated Si(111) surface, Si-CH3, was previously reported to have pronounced vibronic coupling of the methyl stretch modes to the electronic bath of bulk Si. Vacuum-annealing of propynyl-terminated Si(111) resulted in increased 3-fold azimuthal anisotropy for the symmetric stretch, suggesting that removal of propynyl groups from the surface upon annealing allowed the remaining propynyl groups to tilt away from the surface normal into one of three preferred directions toward the vacated neighbor sites.
AB - Vibrational sum-frequency generation (VSFG) spectroscopy was used to investigate the orientation and azimuthal anisotropy of the C-H stretching modes for propynyl-terminated Si(111) surfaces, Si - C=C - CH3. VSFG spectra revealed symmetric and asymmetric C-H stretching modes in addition to a Fermi resonance mode resulting from the interaction of the asymmetric C-H bending overtone with the symmetric C-H stretching vibration. The polarization dependence of the C-H stretching modes was consistent with the propynyl groups oriented such that the Si - C=C- bond is normal to the Si(111) surface. The azimuthal angle dependence of the resonant C-H stretching amplitude revealed no rotational anisotropy for the symmetric C-H stretching mode and a 3-fold rotational anisotropy for the asymmetric C-H stretching mode in registry with the 3-fold symmetric Si(111) substrate. The results are consistent with the expectation that the C-H stretching modes of a -CH3 group are decoupled from the Si substrate due to a -C=C- spacer. In contrast, the methyl-terminated Si(111) surface, Si-CH3, was previously reported to have pronounced vibronic coupling of the methyl stretch modes to the electronic bath of bulk Si. Vacuum-annealing of propynyl-terminated Si(111) resulted in increased 3-fold azimuthal anisotropy for the symmetric stretch, suggesting that removal of propynyl groups from the surface upon annealing allowed the remaining propynyl groups to tilt away from the surface normal into one of three preferred directions toward the vacated neighbor sites.
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U2 - 10.1021/acs.jpcc.7b05256
DO - 10.1021/acs.jpcc.7b05256
M3 - Article
AN - SCOPUS:85027331171
VL - 121
SP - 16872
EP - 16878
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 31
ER -