Nanoscale Domain Stability in Organic Monolayers on Metals

[+] Author and Article Information
Z. Suo, Y. F. Gao

Mechanical and Aerospace Engineering Department and Princeton Materials Institute, Princeton University, Princeton, NJ 08544  

G. Scoles

Chemistry Department and Princeton Materials Institute, Princeton University, Princeton, NJ 08544

J. Appl. Mech 71(1), 24-31 (Mar 17, 2004) (8 pages) doi:10.1115/1.1640366 History: Received September 04, 2002; Revised July 08, 2003; Online March 17, 2004
Copyright © 2004 by ASME
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Grahic Jump Location
When a metal is in contact with an alkanethiol solution, the alkanethiol molecules adsorb on the metal surface to form a monolayer. The structure of a HS(CH2)4OH molecule is illustrated.
Grahic Jump Location
The free energy of mixing for a monolayer composed of two molecular species, A and B. The pair has a large enthalpy of mixing, so that the free energy of mixing has two wells at Cα and Cβ, corresponding to two phases. When the average concentration of the monolayer, C0, is between the two wells, to reduce the free energy, the monolayer separates into the two phases.
Grahic Jump Location
The contact potential U=ϕβ−ϕα causes an electrostatic field in the air, a positive charge on the metal surface under domain β, and a negative charge under domain α. Represent the domain size by the period λ.
Grahic Jump Location
(a) The charge Q accumulated under either domain increases linearly with the contact potential between the two domains, U=ϕβ−ϕα. The area of the triangle is the electrostatic energy stored in the space occupied by the air. The slope of the line is inverse of the capacitance of the system. (b) The Q-U lines for two domain sizes, λ12. At a constant voltage, the smaller the domain size, the larger the charge, namely, Q1>Q2. (c) In a parallel-electrode capacitor, the electric interaction causes the attraction between two electrodes. To keep the two electrodes in place, one has to apply a pair of forces to pull the electrodes apart.
Grahic Jump Location
The boundary conditions at the interfacial object between the air and the bulk of the metal
Grahic Jump Location
(a) The concentration field initially fluctuates with small amplitude around the average concentration C0=0.5, and evolves into a pattern of meandering stripes. (b) The concentration field initially fluctuates with small amplitude around the average concentration C0=0.4, and evolves into a pattern of dots.




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