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TECHNICAL PAPERS

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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References

Schreiber,  F., 2000, “Structure and Growth of Self-Assembling Monolayer,” Prog. Surf. Sci., 65, pp. 151–256.
Ulman, A., 1991, An Introduction to Ultrathin Organic Films: From Langmuir-Blodgett to Self-Assembly, Academic Press, Boston.
Dubois,  L. H., and Nuzzo,  R. G., 1992, “Synthesis, Structure, and Properties of Model Organic-Surfaces,” Annu. Rev. Phys. Chem., 43, pp. 437–463.
Bain,  C. D., and Whitesides,  G. M., 1989, “Formation of Monolayers by the Coadsorption of Thiols on Gold-Variation in the Length of the Alkyl Chain,” J. Am. Chem. Soc., 111, pp. 7164–7175.
Kumar,  A., Biebuyck,  H. A., and Whitesides,  G. M., 1994, “Patterning Self-Assembled Monolayers—Applications in Materials Science,” Langmuir, 10, pp. 1498–1511.
Delmarche,  E., Schmid,  H., Bietsch,  A., Larsen,  N. B., Rothuizen,  H., Michel,  B., and Biebuyck,  H., 1998, “Transport Mechanisms of Alkanethiols During Microcontact Printing on Gold,” J. Phys. Chem. B, 102, pp. 3324–3334.
Xia,  Y., Rogers,  J.A., Paul,  K. E., and Whitesides,  G. M., 1999, “Unconventional Methods for Fabricating and Patterning Nanostructures,” Chem. Rev., 99, pp. 1823–1848.
Barrena,  E., Ocal,  C., and Salmeron,  M., 1999, “Evolution of the Structure and Mechanical Stability of Self-Assembled Alkanethiol Islands on Au (111) due to Diffusion and Ripening,” J. Chem. Phys., 111, pp. 9797–9802.
Tamada,  K., Hara,  M., Sasabe,  H., and Knoll,  W., 1997, “Surface Phase Behavior of n-Alkanethiol Self-Assembled Monolayers Adsorbed on Au (111): An Atomic Force Microscope Study,” Langmuir, 13, pp. 1558–1566.
Stranick,  S. J., Parikh,  A. N., Tao,  Y. T., Allara,  D. L., and Weiss,  P. S., 1994, “Phase-Separation of Mixed-Composition Self-Assembled Monolayers Into Nanometer-Scale Molecular Domains,” J. Phys. Chem., 98, pp. 7636–7646.
Stranick,  S. J., Atre,  S. V., Parikh,  A. N., Wood,  M. C., Allara,  D. L., Winograd,  N., and Weiss,  P. S., 1996, “Nanometer-Scale Phase Separation in Mixed Composition Self-Assembled Monolayers,” Nanotechnology, 7, pp. 438–442.
Hobara,  D., Ota,  M., Imabayashi,  S., Niki,  K., and Kakiuchi,  T., 1998, “Phase Separation of Binary Self-Assembled Thiol Monolayers Composed of 1-Hexadecanethiol and 3-Mercaptopropionic Acid on Au (111) Studied by Scanning Tunneling Microscopy and Cyclic Voltammetry,” J. Electroanal. Chem., 444, pp. 113–119.
Kern,  K., Niehus,  H., Schatz,  A., Zeppenfeld,  P., Goerge,  J., and Comsa,  G., 1991, “Long-Range Spatial Self-Organization in the Adsorbate-Induced Restructuring of Surfaces: Cu {110}-(2×1)O,” Phys. Rev. Lett., 67, pp. 855–858.
Leibsle,  F. M., Flipse,  C. F. J., and Robinson,  A. W., 1993, “Structure of the Cu {100}-(2×2)N Surface: A Scanning-Tunneling-Microscopy Study,” Phys. Rev. B, 47, pp. 15,865–15,868.
Parker,  T. M., Wilson,  L. K., Condon,  N. G., and Leibsle,  F. M., 1997, “Epitaxy Controlled by Self-Assembled Nanometer-Scale Structures,” Phys. Rev. B, 56, pp. 6458–6461.
Brune,  H. M., Giovannin,  K., Bromann,  K., and Kern,  K., 1998, “Self-Organized Growth of Nanostructure Arrays on Strain-Relief Patterns,” Nature (London), 394, pp. 451–453.
Pohl,  K., Bartelt,  M. C., de la Figuera,  J., Bartelt,  N. C., Hrbek,  J., and Hwang,  R. Q., 1999, “Identifying the Forces Responsible for Self-Organization of Nanostructures at Crystal Surfaces,” Nature (London), 397, pp. 238–241.
Plass,  R., Last,  J. A., Bartelt,  N. C., and Kellogg,  G. L., 2001, “Self-Assembled Domain Patterns,” Nature (London), 412, pp. 875–875.
Ellmer,  H., Repain,  V., Rousset,  S., Croset,  B., Sotto,  M., and Zeppenfeld,  P., 2001, “Self-Ordering in Two Dimensions: Nitrogen Adsorption on Copper (100) Followed by STM at Elevated Temperature,” Surf. Sci., 476, pp. 95–106.
Petty, M. C., 1996, Langmuir-Blodgett Films, Cambridge University Press, Cambridge, UK.
McConnell,  H. M., 1991, “Structures and Transitions in Lipid Monolayers at the Air-Water Interface,” Annu. Rev. Phys. Chem., 42, pp. 171–195.
Benvegnu,  D. J., and McConnell,  H. M., 1992, “Line Tension Between Liquid Domains in Lipid Monolayers,” J. Phys. Chem., 96, pp. 6820–6824.
Andelman,  D., Brochard,  F., and Joanny,  J.-F., 1987, “Phase-Transitions in Langmuir Monolayers of Polar-Molecules,” J. Phys. Chem., 86, pp. 3673–3681.
Seul,  M., and Andelman,  D., 1995, “Domain Shapes and Patterns: The Phenomenology of Modulated Phases,” 267 , pp. 476–483.
Alerhand,  O. L., Vanderbilt,  D., Meade,  R. D., and Joannopoulos,  J. D., 1988, “Spontaneous Formation of Stress Domains on Crystal Surfaces,” Phys. Rev. Lett., 61, pp. 1973–1976.
Ng,  K.-O., and Vanderbilt,  D., 1995, “Stability of Periodic Domain Structures in a Two-Dimensional Dipolar Model,” Phys. Rev. B, 52, pp. 2177–2183.
Hannon,  J. B., Tersoff,  J., and Tromp,  R. M., 2002, “Surface Stress and Thermodynamic Nanoscale Size Selection,” Science, 295, pp. 299–301.
Suo,  Z., and Lu,  W., 2000, “Composition Modulation and Nanophase Separation in Binary Epilayer,” J. Mech. Phys. Solids, 48, pp. 211–232.
Lu,  W., and Suo,  Z., 2001, “Dynamics of Nanoscale Pattern Formation of an Epitaxial Monolayer,” J. Mech. Phys. Solids, 49, pp. 1937–1950.
Mate,  C. M., Kao,  C.-T., and Somorjai,  G. A., 1988, “Carbon-Monoxide Induced Ordering of Adsorbates on the Rh (111) Crystal—Surface—Importance of Surface Dipole-Moments,” Surf. Sci., 206, pp. 145–168.
Stone,  H. A., and Ajdari,  A., 1998, “Hydrodynamics of Particles Embedded in a Flat Surfactant Layer Overlying a Subphase of Finite Depth,” J. Fluid Mech., 369, pp. 151–173.
Folkers,  J. P., Laibinis,  P. S., Whitesides,  G. M., and Deutch,  J., 1994, “Phase-Behavior of 2-Component Self-Assembled Monolayers of Alkanethiolates on Gold,” J. Phys. Chem., 98, pp. 563–571.
Imabayashi,  S., Hobara,  D., and Kakiuchi,  T., 2001, “Voltammetric Detection of the Surface Diffusion of Adsorbed Thiolate Molecules in Artificially Phase-Separated Binary Self-Assembled Monolayers on a Au (111) Surface,” Langmuir, 17, pp. 2560–2563.
Ashcroft, N. W., and Mermin, N. D., 1976, Solid State Physics, Saunders College Publications, Philadelphia, PA.
Evans,  S. D., and Ulman,  A., 1990, “Surface-Potential Studies of Alkyl-Thiol Monolayers Adsorbed on Gold,” Chem. Phys. Lett., 170, pp. 462–466.
Evans,  S. D., Urankar,  E., Ulman,  A., and Ferris,  N., 1991, “Self-Assembled Monolayers of Alkanethiols Containing a Polar Aromatic Group—Effects of the Dipole Position on Molecular Packing, Orientation, and Surface Wetting Properties,” J. Am. Chem. Soc., 113, pp. 4121–4131.
Landau, L. D., Lifshitz, E. M., and Pitaevskii, L. P., 1984, Electrodynamics of Continuous Media, 2nd Ed., Butterworth Heinemann, New York.
Cahn,  J. W., and Hilliard,  J. E., 1958, “Free Energy of a Nonuniform System. 1. Interfacial Free Energy,” J. Chem. Phys., 28, pp. 258–267.
Gao,  Y. F., Lu,  W., and Suo,  Z., 2002, “A Mesophase Transition in a Binary Monolayer on a Solid Surface,” Acta Mater., 50, pp. 2297–2308.
Berger,  R., Delamarche,  E., Lang,  H. P., Gerber,  C., Gimzewski,  J. K., Meyer,  E., and Güntherodt,  H.-J., 1997, “Surface Stress in Self-Assembly of Alkanethiols on Gold,” Science, 276, pp. 2021–2024.
Chen,  L. Q., and Wang,  Y. Z., 1996, “The Continuum Field Approach to Modeling Microstruct. Evol.,” JOM 48, pp. 13–18.
Lu,  W., and Suo,  Z., 2002, “Symmetry Breaking in Self-Assembled Monolayers on Solid Surface. I. Anisotropic Surface Stress,” Phys. Rev. B, 65 Paper No. 085401.
Lu,  W., and Suo,  Z., 2002, “Symmetry Breaking in Self-Assembled Monolayers on Solid Surface. II. Anisotropic Substrate Elasticity,” Phys. Rev. B, 65 Paper No. 205418.
Gao,  Y. F., and Suo,  Z., 2003, “The Orientation of the Self-Assembled Monolayer Stripes on a Crystalline Substrate,” J. Mech. Phys. Solids, 51147–167.
Chou,  S. Y., and Zhuang,  L., 1999, “Lithographically Induced Self-Assembly of Periodic Polymer Micropillar Arrays,” J. Vac. Sci. Technol. B, 17, pp. 3197–3202.
Schäffer,  E., Thurn-Albrecht,  T., Russell,  T. P., and Steiner,  U., 2000, “Electrically Induced Structure Formation and Pattern Transfer,” Nature (London), 403, pp. 874–877.
Suo,  Z., and Liang,  J., 2001, “Theory of Lithographically Induced Self-Assembly,” Appl. Phys. Lett., 78, pp. 3971–3973.
Gao,  Y.F., and Suo,  Z., 2003, “Guided Self-Assembly of Molecular Dipoles on a Substrate Surface,” J. Appl. Phys., 93, pp. 4276–4282.
Suo, Z., and Hong, W., 2004, “Programmable Motion and Assembly of Molecules on Solid Surfaces,” publication 150, www.deas.harvard.edu/suo.

Figures

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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