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Title: Epitaxy and chainlength dependent strain in self-assembled monolayers

Abstract

We use grazing incidence x-ray diffraction to systematically study the structure of an archetypal self-assembled monolayer as a function of the hydrocarbon chain length, n. The monolayers consists of n-alkyl thiol molecules, CH{sub 3}(CH{sub 2}){sub n{minus}1}SH (C{sub n}, 10{le}n{le}30), self-assembled on single crystal Au(111) surfaces. At room temperature, the 2D structure is described by a C(4{times}2) unit mesh for all chain lengths. However, we demonstrate that there is a systematic dependence of the tilt structure (i.e., the tilt angle and tilt direction) of the hydrocarbon chains as a function of the chain length. Furthermore, we show that the monolayer structures are characterized by distinct {open_quotes}long{close_quote}{close_quote} (n{ge}16) and {open_quotes}short{close_quote}{close_quote} (n{le}14) chain length regimes, as well as a smooth variation of the structural parameters within each regime. We associate these systematic structural changes with the conflicting requirements of epitaxy and molecular packing, and argue that the driving force is the changing intra-layer interaction strength (which is proportional to hydrocarbon chain length). We believe that these phenomena should be characteristic of the behavior of self-assembled monolayers, as well as the more general class of {open_quotes}soft/hard{close_quote}{close_quote} interfaces. {copyright} {ital 1997 American Institute of Physics.}

Authors:
;  [1];  [2];  [1]
  1. Physics Dept. and Princeton Materials Institute, Princeton University, Princeton, New Jersey 08544 (United States)
  2. Exxon Corporate Research, Annandale, New Jersey 08801 (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
OSTI Identifier:
435136
DOE Contract Number:  
AC02-76CH00016; FG02-93ER45503
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 106; Journal Issue: 4; Other Information: PBD: Jan 1997
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 40 CHEMISTRY; EPITAXY; STRAINS; MOLECULAR STRUCTURE; ORGANIC COMPOUNDS; X-RAY DIFFRACTION; DEFORMATION; GOLD; THIOLS; HYDROCARBONS; CHAINS

Citation Formats

Fenter, P, Eberhardt, A, Liang, K S, and Eisenberger, P. Epitaxy and chainlength dependent strain in self-assembled monolayers. United States: N. p., 1997. Web. doi:10.1063/1.473281.
Fenter, P, Eberhardt, A, Liang, K S, & Eisenberger, P. Epitaxy and chainlength dependent strain in self-assembled monolayers. United States. https://doi.org/10.1063/1.473281
Fenter, P, Eberhardt, A, Liang, K S, and Eisenberger, P. 1997. "Epitaxy and chainlength dependent strain in self-assembled monolayers". United States. https://doi.org/10.1063/1.473281.
@article{osti_435136,
title = {Epitaxy and chainlength dependent strain in self-assembled monolayers},
author = {Fenter, P and Eberhardt, A and Liang, K S and Eisenberger, P},
abstractNote = {We use grazing incidence x-ray diffraction to systematically study the structure of an archetypal self-assembled monolayer as a function of the hydrocarbon chain length, n. The monolayers consists of n-alkyl thiol molecules, CH{sub 3}(CH{sub 2}){sub n{minus}1}SH (C{sub n}, 10{le}n{le}30), self-assembled on single crystal Au(111) surfaces. At room temperature, the 2D structure is described by a C(4{times}2) unit mesh for all chain lengths. However, we demonstrate that there is a systematic dependence of the tilt structure (i.e., the tilt angle and tilt direction) of the hydrocarbon chains as a function of the chain length. Furthermore, we show that the monolayer structures are characterized by distinct {open_quotes}long{close_quote}{close_quote} (n{ge}16) and {open_quotes}short{close_quote}{close_quote} (n{le}14) chain length regimes, as well as a smooth variation of the structural parameters within each regime. We associate these systematic structural changes with the conflicting requirements of epitaxy and molecular packing, and argue that the driving force is the changing intra-layer interaction strength (which is proportional to hydrocarbon chain length). We believe that these phenomena should be characteristic of the behavior of self-assembled monolayers, as well as the more general class of {open_quotes}soft/hard{close_quote}{close_quote} interfaces. {copyright} {ital 1997 American Institute of Physics.}},
doi = {10.1063/1.473281},
url = {https://www.osti.gov/biblio/435136}, journal = {Journal of Chemical Physics},
number = 4,
volume = 106,
place = {United States},
year = {Wed Jan 01 00:00:00 EST 1997},
month = {Wed Jan 01 00:00:00 EST 1997}
}