Synthesis, Characterization, and Reactivity of Ethynyl- and Propynyl-Terminated Si(111) Surfaces
Abstract
Ethynyl- and propynyl-terminated Si(111) surfaces synthesized using a two-step halogenation/alkylation method have been characterized by transmission infrared spectroscopy (TIRS), high-resolution electron energy-loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED), atomic-force microscopy (AFM), electrochemical scanning–tunneling microscopy (EC-STM) and measurements of surface recombination velocities (S). For the ethynyl-terminated Si(111) surface, TIRS revealed signals corresponding to ethynyl ≡C–H and C≡C stretching oriented perpendicular to the surface, HREELS revealed a Si–C stretching signal, and XPS data showed the presence of C bound to Si with a fractional monolayer (ML) coverage (Φ) of Φ_(Si–CCH) = 0.63 ± 0.08 ML. The ethynyl-terminated surfaces were also partially terminated by Si–OH groups (Φ_(Si–OH) = 0.35 ± 0.03 ML) with limited formation of Si^(3+) and Si^(4+) oxides. For the propynyl-terminated Si(111) surface, TIRS revealed the presence of a (C–H)CH_3 symmetric bending, or "umbrella," peak oriented perpendicular to the surface, while HREELS revealed signals corresponding to Si–C and C≡C stretching, and XPS showed C bound to Si with Φ_(Si–CCCH_3) = 1.05 ± 0.06 ML. The LEED patterns were consistent with a (1 × 1) surface unit cell for both surfaces, but room-temperature EC-STM indicated that the surfaces did not exhibit long-range ordering. HCC–Si(111) and CH_3CC–Si(111) surfaces yielded S values of (3.5 ± 0.1) × 10^3 and (5 ± 1) × 10^2 cm s^(–1), respectively, after 581 h exposure to air. These observations are consistent with the covalent binding of ethynyl and propynyl groups, respectively, to the Si(111) surface.
Additional Information
© 2015 American Chemical Society. Received: May 26, 2015, Revised: July 7, 2015, Publication Date (Web): July 10, 2015. We acknowledge the National Science Foundation Grant No. CHE-1214152 and the Molecular Materials Research Center of the Beckman Institute at the California Institute of Technology for support. N.T.P. acknowledges support from the NSF for a Graduate Research Fellowship. Support for Y.-G.K. and M.P.S. to perform the EC-STM experiments was provided by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. We thank Dr. Leslie E. O'Leary, Dr. Ronald L. Grimm, and Mr. Christopher W. Roske for helpful discussions. The authors declare no competing financial interest.Attached Files
Supplemental Material - jp5b05028_si_001.pdf
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Additional details
- Eprint ID
- 59887
- DOI
- 10.1021/acs.jpcc.5b05028
- Resolver ID
- CaltechAUTHORS:20150825-113614153
- NSF
- CHE-1214152
- Caltech Beckman Institute
- NSF Graduate Research Fellowship
- Joint Center for Artificial Photosynthesis (JCAP)
- Department of Energy (DOE)
- DE-SC0004993
- Created
-
2015-08-25Created from EPrint's datestamp field
- Updated
-
2021-11-10Created from EPrint's last_modified field
- Caltech groups
- Kavli Nanoscience Institute, JCAP