Probing temperature-dependent behaviour in self-assembled monolayers by ac-impedance spectroscopy

Literature Information

Publication Date 2001-05-03
DOI 10.1039/B100457N
Impact Factor 3.676
Authors

Samuel H. Gyepi-Garbrah, Roberta Šilerová


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Abstract

Gold electrodes modified by monolayers of three different long-chain thiol derivatives were studied by electrochemical impedance spectroscopy with a [Fe(CN)6]4−/3− redox probe over a wide temperature range. The impedance characteristics of a bare gold electrode are compared to those of the same electrode modified with n-hexadecanethiol, n-octadecanethiol, and 11-mercaptoundecanoic acid, all between 15°C and 65°C. A strong temperature dependence of the films' electrical features was observed. All films show markedly different behaviour below and above a characteristic temperature specific to each film. It was possible to model bare gold and the thiol-modified electrodes with the Randles circuit over the whole temperature range examined, except for the 11-mercaptoundecanoic acid-modified electrode below its characteristic temperature, which required a different equivalent circuit. Cyclic voltammetry was used to verify the characteristic temperature of each film. The results are interpreted in terms of a two-dimensional phase transition in these monolayers. The possible nature of this phase transition is discussed.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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