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Title: Molecular Anchors for Self-Assembled Monolayers on ZnO: A Direct Comparison of the Thiol and Phosphic Acid Moieties

Abstract

Two of the most promising schemes for attaching organic molecules to metal oxides are based on the chemistry of the thiol and phosphonic acid moieties. We have made a direct comparison of the efficacy of these two molecular anchors on zinc oxide by comparing the chemical and physical properties of n-hexane derivatives of both. The surface properties of polycrystalline ZnO thin films and ZnO(000)-O crystals modified with 1-hexanethiol and 1-hexanephosphonic acid were examined with a novel quartz crystal microbalance (QCM)-based flow cell reactor, angle-resolved and temperature-dependent photoelectron spectroscopy, and contact angle measurements. A means of using ammonium chloride as a probe of molecule-ZnO interactions is introduced and used to ascertain the relative quality of self-assembled monolayers (SAMs) based on thiols and phosphonic acids. QCM data shows that a phosphonic acid-anchored alkyl chain only six carbons long can provide significant corrosion protection for ZnO against Bronsted acids, reducing the etch rate relative to the bare ZnO surface by a factor of more than nine. In contrast, we find that monolayers from the analogous molecule hexanethiol are more defective as revealed by their higher ionic permeability and lower hydrophobicity. Substrate attenuation X-ray photoelectron spectroscopy (XPS) experiments were used to determine the thicknessmore » of SAMs formed by the two hexane derivatives and it was found that SAMs from phosphonic acids were approximately twice as thick as those formed by hexanethiol. The thermal stability of the two linking groups was also explored and we find that previous claims of highly stable alkanethiolate monolayers on ZnO are suspect. Taken as a whole, our results indicate that the phosphonic acid moiety is preferred over thiols for the attachment of short alkyl groups to ZnO.« less

Authors:
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
975386
DOE Contract Number:  
AC36-08GO28308
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry C
Additional Journal Information:
Journal Volume: 113; Journal Issue: 42, 2009; Journal ID: ISSN 1932-7447
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; AMMONIUM CHLORIDES; ATTENUATION; CHAINS; CHEMISTRY; CORROSION PROTECTION; HEXANE; MICROBALANCES; OXIDES; PERMEABILITY; PHOSPHONIC ACIDS; PHOTOELECTRON SPECTROSCOPY; PHYSICAL PROPERTIES; PROBES; QUARTZ; STABILITY; SUBSTRATES; SURFACE PROPERTIES; THICKNESS; THIN FILMS; THIOLS; X-RAY PHOTOELECTRON SPECTROSCOPY; ZINC OXIDES; Solar Energy - Photovoltaics

Citation Formats

Perkins, C L. Molecular Anchors for Self-Assembled Monolayers on ZnO: A Direct Comparison of the Thiol and Phosphic Acid Moieties. United States: N. p., 2009. Web. doi:10.1021/jp906013r.
Perkins, C L. Molecular Anchors for Self-Assembled Monolayers on ZnO: A Direct Comparison of the Thiol and Phosphic Acid Moieties. United States. doi:10.1021/jp906013r.
Perkins, C L. Thu . "Molecular Anchors for Self-Assembled Monolayers on ZnO: A Direct Comparison of the Thiol and Phosphic Acid Moieties". United States. doi:10.1021/jp906013r.
@article{osti_975386,
title = {Molecular Anchors for Self-Assembled Monolayers on ZnO: A Direct Comparison of the Thiol and Phosphic Acid Moieties},
author = {Perkins, C L},
abstractNote = {Two of the most promising schemes for attaching organic molecules to metal oxides are based on the chemistry of the thiol and phosphonic acid moieties. We have made a direct comparison of the efficacy of these two molecular anchors on zinc oxide by comparing the chemical and physical properties of n-hexane derivatives of both. The surface properties of polycrystalline ZnO thin films and ZnO(000)-O crystals modified with 1-hexanethiol and 1-hexanephosphonic acid were examined with a novel quartz crystal microbalance (QCM)-based flow cell reactor, angle-resolved and temperature-dependent photoelectron spectroscopy, and contact angle measurements. A means of using ammonium chloride as a probe of molecule-ZnO interactions is introduced and used to ascertain the relative quality of self-assembled monolayers (SAMs) based on thiols and phosphonic acids. QCM data shows that a phosphonic acid-anchored alkyl chain only six carbons long can provide significant corrosion protection for ZnO against Bronsted acids, reducing the etch rate relative to the bare ZnO surface by a factor of more than nine. In contrast, we find that monolayers from the analogous molecule hexanethiol are more defective as revealed by their higher ionic permeability and lower hydrophobicity. Substrate attenuation X-ray photoelectron spectroscopy (XPS) experiments were used to determine the thickness of SAMs formed by the two hexane derivatives and it was found that SAMs from phosphonic acids were approximately twice as thick as those formed by hexanethiol. The thermal stability of the two linking groups was also explored and we find that previous claims of highly stable alkanethiolate monolayers on ZnO are suspect. Taken as a whole, our results indicate that the phosphonic acid moiety is preferred over thiols for the attachment of short alkyl groups to ZnO.},
doi = {10.1021/jp906013r},
journal = {Journal of Physical Chemistry C},
issn = {1932-7447},
number = 42, 2009,
volume = 113,
place = {United States},
year = {2009},
month = {1}
}