Interfacial Effects on the Band Edges of Functionalized Si Surfaces in Liquid Water
Abstract
By combining ab initio molecular dynamics simulations and many-body perturbation theory calculations of electronic energy levels, we determined the band edge positions of functionalized Si(111) surfaces in the presence of liquid water, with respect to vacuum and to water redox potentials. We considered surface terminations commonly used for Si photoelectrodes in water splitting experiments. We found that, when exposed to water, the semiconductor band edges were shifted by approximately 0.5 eV in the case of hydrophobic surfaces, irrespective of the termination. The effect of the liquid on band edge positions of hydrophilic surfaces was much more significant and determined by a complex combination of structural and electronic effects. These include structural rearrangements of the semiconductor surfaces in the presence of water, changes in the orientation of interfacial water molecules with respect to the bulk liquid, and charge transfer at the interfaces, between the solid and the liquid. Our results showed that the use of many-body perturbation theory is key to obtain results in agreement with experiments; they also showed that the use of simple computational schemes that neglect the detailed microscopic structure of the solid–liquid interface may lead to substantial errors in predicting the alignment between the solid band edgesmore »
- Authors:
-
- Department of Chemistry, University of California, Davis, California 95616, United States, Lawrence Livermore National Laboratory, Livermore, California 94551, United States
- Lawrence Livermore National Laboratory, Livermore, California 94551, United States
- The Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United States
- Publication Date:
- Research Org.:
- Univ. of California, Davis, CA (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Univ. of Chicago, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1165322
- Alternate Identifier(s):
- OSTI ID: 1392319
- Grant/Contract Number:
- SC0008938; AC52-07NA27344; CHE-0802907
- Resource Type:
- Published Article
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Name: Journal of the American Chemical Society Journal Volume: 136 Journal Issue: 49; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Pham, Tuan Anh, Lee, Donghwa, Schwegler, Eric, and Galli, Giulia. Interfacial Effects on the Band Edges of Functionalized Si Surfaces in Liquid Water. United States: N. p., 2014.
Web. doi:10.1021/ja5079865.
Pham, Tuan Anh, Lee, Donghwa, Schwegler, Eric, & Galli, Giulia. Interfacial Effects on the Band Edges of Functionalized Si Surfaces in Liquid Water. United States. https://doi.org/10.1021/ja5079865
Pham, Tuan Anh, Lee, Donghwa, Schwegler, Eric, and Galli, Giulia. Wed .
"Interfacial Effects on the Band Edges of Functionalized Si Surfaces in Liquid Water". United States. https://doi.org/10.1021/ja5079865.
@article{osti_1165322,
title = {Interfacial Effects on the Band Edges of Functionalized Si Surfaces in Liquid Water},
author = {Pham, Tuan Anh and Lee, Donghwa and Schwegler, Eric and Galli, Giulia},
abstractNote = {By combining ab initio molecular dynamics simulations and many-body perturbation theory calculations of electronic energy levels, we determined the band edge positions of functionalized Si(111) surfaces in the presence of liquid water, with respect to vacuum and to water redox potentials. We considered surface terminations commonly used for Si photoelectrodes in water splitting experiments. We found that, when exposed to water, the semiconductor band edges were shifted by approximately 0.5 eV in the case of hydrophobic surfaces, irrespective of the termination. The effect of the liquid on band edge positions of hydrophilic surfaces was much more significant and determined by a complex combination of structural and electronic effects. These include structural rearrangements of the semiconductor surfaces in the presence of water, changes in the orientation of interfacial water molecules with respect to the bulk liquid, and charge transfer at the interfaces, between the solid and the liquid. Our results showed that the use of many-body perturbation theory is key to obtain results in agreement with experiments; they also showed that the use of simple computational schemes that neglect the detailed microscopic structure of the solid–liquid interface may lead to substantial errors in predicting the alignment between the solid band edges and water redox potentials.},
doi = {10.1021/ja5079865},
journal = {Journal of the American Chemical Society},
number = 49,
volume = 136,
place = {United States},
year = {Wed Nov 26 00:00:00 EST 2014},
month = {Wed Nov 26 00:00:00 EST 2014}
}
https://doi.org/10.1021/ja5079865
Web of Science
Works referenced in this record:
Probing the electronic structure of liquid water with many-body perturbation theory
journal, February 2014
- Pham, T. Anh; Zhang, Cui; Schwegler, Eric
- Physical Review B, Vol. 89, Issue 6
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Preparation of air-stable, low recombination velocity Si(111) surfaces through alkyl termination
journal, September 2000
- Royea, William J.; Juang, Agnes; Lewis, Nathan S.
- Applied Physics Letters, Vol. 77, Issue 13
Band offsets and dielectric properties of the amorphous Si 3 N 4 /Si(100) interface: A first-principles study
journal, June 2013
- Anh Pham, T.; Li, Tianshu; Nguyen, Huy-Viet
- Applied Physics Letters, Vol. 102, Issue 24
The ionization potential of aqueous hydroxide computed using many-body perturbation theory
journal, July 2014
- Opalka, Daniel; Pham, Tuan Anh; Sprik, Michiel
- The Journal of Chemical Physics, Vol. 141, Issue 3
Self-consistent hybrid functional for condensed systems
journal, May 2014
- Skone, Jonathan H.; Govoni, Marco; Galli, Giulia
- Physical Review B, Vol. 89, Issue 19
Well-Defined Carboxyl-Terminated Alkyl Monolayers Grafted onto H−Si(111): Packing Density from a Combined AFM and Quantitative IR Study
journal, January 2006
- Faucheux, Anne; Gouget-Laemmel, Anne Chantal; Henry de Villeneuve, Catherine
- Langmuir, Vol. 22, Issue 1
Computational Search for Single-Layer Transition-Metal Dichalcogenide Photocatalysts
journal, September 2013
- Zhuang, Houlong L.; Hennig, Richard G.
- The Journal of Physical Chemistry C, Vol. 117, Issue 40
The absolute electrode potential: an explanatory note (Recommendations 1986)
journal, January 1986
- Trasatti, S.
- Pure and Applied Chemistry, Vol. 58, Issue 7
Improving accuracy and efficiency of calculations of photoemission spectra within the many-body perturbation theory
journal, February 2012
- Nguyen, Huy-Viet; Pham, T. Anh; Rocca, Dario
- Physical Review B, Vol. 85, Issue 8
Dependence of Water Dynamics on Molecular Adsorbates near Hydrophobic Surfaces: First-Principles Molecular Dynamics Study
journal, April 2014
- Lee, Donghwa; Schwegler, Eric; Kanai, Yosuke
- The Journal of Physical Chemistry C, Vol. 118, Issue 16
Will Solar-Driven Water-Splitting Devices See the Light of Day?
journal, September 2013
- McKone, James R.; Lewis, Nathan S.; Gray, Harry B.
- Chemistry of Materials, Vol. 26, Issue 1
Combined Theoretical and Experimental Study of Band-Edge Control of Si through Surface Functionalization
journal, March 2013
- Li, Yan; O’Leary, Leslie E.; Lewis, Nathan S.
- The Journal of Physical Chemistry C, Vol. 117, Issue 10
Aligning electronic energy levels at the interface
journal, August 2010
- Cheng, Jun; Sprik, Michiel
- Physical Review B, Vol. 82, Issue 8
Prediction of semiconductor band edge positions in aqueous environments from first principles
journal, June 2011
- Wu, Yabi; Chan, M. K. Y.; Ceder, G.
- Physical Review B, Vol. 83, Issue 23
Bulk and surface characterization of the silicon electrode
journal, June 1981
- Madou, M. J.; Loo, B. H.; Frese, K. W.
- Surface Science, Vol. 108, Issue 1
Towards an assessment of the accuracy of density functional theory for first principles simulations of water
journal, January 2004
- Grossman, Jeffrey C.; Schwegler, Eric; Draeger, Erik W.
- The Journal of Chemical Physics, Vol. 120, Issue 1
First-Principles Theory of Quasiparticles: Calculation of Band Gaps in Semiconductors and Insulators
journal, September 1985
- Hybertsen, Mark S.; Louie, Steven G.
- Physical Review Letters, Vol. 55, Issue 13
Electronic excitations: density-functional versus many-body Green’s-function approaches
journal, June 2002
- Onida, Giovanni; Reining, Lucia; Rubio, Angel
- Reviews of Modern Physics, Vol. 74, Issue 2
Towards an assessment of the accuracy of density functional theory for first principles simulations of water. II
journal, September 2004
- Schwegler, Eric; Grossman, Jeffrey C.; Gygi, François
- The Journal of Chemical Physics, Vol. 121, Issue 11
Solar Water Splitting Cells
journal, November 2010
- Walter, Michael G.; Warren, Emily L.; McKone, James R.
- Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473
Chemical and electronic characterization of methyl-terminated Si(111) surfaces by high-resolution synchrotron photoelectron spectroscopy
journal, July 2005
- Hunger, Ralf; Fritsche, Rainer; Jaeckel, Bengt
- Physical Review B, Vol. 72, Issue 4
Electronic Band Structures of Molybdenum and Tungsten Dichalcogenides by the GW Approach
journal, March 2012
- Jiang, Hong
- The Journal of Physical Chemistry C, Vol. 116, Issue 14
Towards an exact description of electronic wavefunctions in real solids
journal, December 2012
- Booth, George H.; Grüneis, Andreas; Kresse, Georg
- Nature, Vol. 493, Issue 7432
Communication: Electronic structure of the solvated chloride anion from first principles molecular dynamics
journal, May 2013
- Zhang, Cui; Pham, Tuan Anh; Gygi, François
- The Journal of Chemical Physics, Vol. 138, Issue 18
Correlation of photocurrent-voltage curves with flat-band potential for stable photoelectrodes for the photoelectrolysis of water
journal, November 1976
- Bolts, Jeffrey M.; Wrighton, Mark S.
- The Journal of Physical Chemistry, Vol. 80, Issue 24
calculations using the spectral decomposition of the dielectric matrix: Verification, validation, and comparison of methods
journal, April 2013
- Pham, T. Anh; Nguyen, Huy-Viet; Rocca, Dario
- Physical Review B, Vol. 87, Issue 15
Passivation and Secondary Functionalization of Allyl-Terminated Si(111) Surfaces
journal, February 2008
- Plass, Katherine E.; Liu, Xueliang; Brunschwig, Bruce S.
- Chemistry of Materials, Vol. 20, Issue 6
Water Confined in Nanotubes and between Graphene Sheets: A First Principle Study
journal, January 2008
- Cicero, Giancarlo; Grossman, Jeffrey C.; Schwegler, Eric
- Journal of the American Chemical Society, Vol. 130, Issue 6
Ideal hydrogen termination of the Si (111) surface
journal, February 1990
- Higashi, G. S.; Chabal, Y. J.; Trucks, G. W.
- Applied Physics Letters, Vol. 56, Issue 7
Electronic Structure of Aqueous Sulfuric Acid from First-Principles Simulations with Hybrid Functionals
journal, July 2014
- Wan, Quan; Spanu, Leonardo; Gygi, Francois
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 15
First principles scheme to evaluate band edge positions in potential transition metal oxide photocatalysts and photoelectrodes
journal, January 2011
- Toroker, Maytal Caspary; Kanan, Dalal K.; Alidoust, Nima
- Physical Chemistry Chemical Physics, Vol. 13, Issue 37, p. 16644-16654
Synthesis and Characterization of Mixed Methyl/Allyl Monolayers on Si(111) †
journal, November 2010
- O’Leary, Leslie E.; Johansson, Erik; Brunschwig, Bruce S.
- The Journal of Physical Chemistry B, Vol. 114, Issue 45
Electronic excitations in light absorbers for photoelectrochemical energy conversion: first principles calculations based on many body perturbation theory
journal, January 2013
- Ping, Yuan; Rocca, Dario; Galli, Giulia
- Chemical Society Reviews, Vol. 42, Issue 6
Properties of metal–water interfaces studied from first principles
journal, December 2009
- Schnur, Sebastian; Groß, Axel
- New Journal of Physics, Vol. 11, Issue 12