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Nano Research 2024, 17(5): 4231-4243 https://doi.org/10.1007/s12274-023-6292-8
Review Article | Open Access | Issue | Published: 01 December 2023

Odd-even effects in the structure and properties of aryl-substituted aliphatic self-assembled monolayers

Show Author's Information Piotr Cyganik1,  Andreas Terfort2,  Michael Zharnikov3( )
Jagiellonian University, Faculty of Physics, Astronomy and Applied Computer Science, Smoluchowski Institute of Physics, Łojasiewicza 11, 30-348 Kraków, Poland
Institut für Anorganische und Analytische Chemie, Universität Frankfurt, Max-von-Laue-Straße 7, 60438 Frankfurt, Germany
Applied Physical Chemistry, Heidelberg University, Im Neuenheimer Feld 253, 69120 Heidelberg, Germany
Keywords:
self-assembled monolayers, odd-even-effects, molecular films, surface and interface engineering
Topics:
Carbon films Self assembled monolayersThin films
Cite this article:
Cyganik P, Terfort A, Zharnikov M. Odd-even effects in the structure and properties of aryl-substituted aliphatic self-assembled monolayers. Nano Research, 2024, 17(5): 4231-4243. https://doi.org/10.1007/s12274-023-6292-8
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Abstract Full text About this article

Self-assembled monolayers (SAMs) represent an important tool in context of nanofabrication and molecular engineering of surfaces and interfaces. The properties of functional SAMs depend not only on the character of the tail groups at the SAM-ambient interface, but are also largely defined by their structure. In its turn, the latter parameter results from a complex interplay of the structural forces and a variety of other factors, including so called odd-even effects, viz. dependence of the SAM structure and properties on the parity of the number (odd or even) of individual building blocks in the backbone of the SAM constituents. The most impressive manifestation of the odd-even effects is the structure of aryl-substituted alkanethiolate SAMs on Au(111) and Ag(111), in which, in spite of the fact that the intermolecular interaction is mostly determined by the aryl part of the monolayers, one observes a pronounced dependence of molecular inclination and, consequently, the packing density of the SAM-forming molecules on the parity of number of methylene units in the alkyl linker. Here we review the properties of the above systems as well as address fundamental reasons behind the odd-even effects, including the existence of a so-called bending potential, which is frequently disregarded in analysis of the structure-building forces. The generality of the odd-even effects in SAMs is additionally supported by the recent data for SAMs on GaAs, scanning tunneling microscopy data for SAMs on Ag(111), and the data for the monolayers with selenolate and carboxyl anchoring groups on Au(111) and Ag(111). The implications of these effects in terms of the control over the packing density and orientation of the tail groups at the SAM-ambient interface, structural perfection, polymorphism, temperature-driven phase transitions, and SAM stability toward such factors as ionizing radiation, exchange reaction, and electrochemical desorption are discussed. These implications place the odd-even effects as an important tool for the design of functional SAMs in context of specific applications.


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About this article

Odd-even effects in the structure and properties of aryl-substituted aliphatic self-assembled monolayers

Show Author's information Piotr Cyganik1, Andreas Terfort2, Michael Zharnikov3( )
Jagiellonian University, Faculty of Physics, Astronomy and Applied Computer Science, Smoluchowski Institute of Physics, Łojasiewicza 11, 30-348 Kraków, Poland
Institut für Anorganische und Analytische Chemie, Universität Frankfurt, Max-von-Laue-Straße 7, 60438 Frankfurt, Germany
Applied Physical Chemistry, Heidelberg University, Im Neuenheimer Feld 253, 69120 Heidelberg, Germany

Abstract

Self-assembled monolayers (SAMs) represent an important tool in context of nanofabrication and molecular engineering of surfaces and interfaces. The properties of functional SAMs depend not only on the character of the tail groups at the SAM-ambient interface, but are also largely defined by their structure. In its turn, the latter parameter results from a complex interplay of the structural forces and a variety of other factors, including so called odd-even effects, viz. dependence of the SAM structure and properties on the parity of the number (odd or even) of individual building blocks in the backbone of the SAM constituents. The most impressive manifestation of the odd-even effects is the structure of aryl-substituted alkanethiolate SAMs on Au(111) and Ag(111), in which, in spite of the fact that the intermolecular interaction is mostly determined by the aryl part of the monolayers, one observes a pronounced dependence of molecular inclination and, consequently, the packing density of the SAM-forming molecules on the parity of number of methylene units in the alkyl linker. Here we review the properties of the above systems as well as address fundamental reasons behind the odd-even effects, including the existence of a so-called bending potential, which is frequently disregarded in analysis of the structure-building forces. The generality of the odd-even effects in SAMs is additionally supported by the recent data for SAMs on GaAs, scanning tunneling microscopy data for SAMs on Ag(111), and the data for the monolayers with selenolate and carboxyl anchoring groups on Au(111) and Ag(111). The implications of these effects in terms of the control over the packing density and orientation of the tail groups at the SAM-ambient interface, structural perfection, polymorphism, temperature-driven phase transitions, and SAM stability toward such factors as ionizing radiation, exchange reaction, and electrochemical desorption are discussed. These implications place the odd-even effects as an important tool for the design of functional SAMs in context of specific applications.

Keywords: self-assembled monolayers, odd-even-effects, molecular films, surface and interface engineering

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Publication history

Received: 23 September 2023
Revised: 17 October 2023
Accepted: 26 October 2023
Published: 01 December 2023
Issue date: May 2024

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© The Author(s) 2023

Acknowledgements

Acknowledgements

The authors thank their coworkers and cooperation partners around the world, who have contributed to the research described in this review article. M. Z. acknowledges allocation of the beamtimes and valuable technical support during the experiments at BESSY I and BESSY II in Berlin and MAX IV in Lund. P. C. acknowledges the financial support from Alexander von Humboldt Foundation, The Leverhulme Trust, and Foundation for Polish Science. The researches described in this review were financially supported by BMBF, DFG, NSC Poland, and DAAD through a variety of projects.

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Copyright: © 2023 by the author(s). This article is an open access article distributed under Creative Commons Attribution License (CC BY 4.0), visit https://creativecommons.org/licenses/by/4.0/.

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