Nanoconfined electrochemical nucleation of crystalline molecular monolayers on graphite substrates

Daniel E. Hooks, Christopher M. Yip, Michael Ward

Research output: Contribution to journalArticle

Abstract

Real-time in situ atomic force microscopy (AFM) has been employed to examine the electrochemical nucleation of epitaxially oriented, crystalline monolayers of bis(ethylenedithiolo)tetrathiafulvalene triiodide, (ET)2I3, on the basal plane of highly oriented pyrolytic graphite electrodes decorated with circular, single-layer-deep pits created by thermal etching. The nucleation of the monolayers in the pits is inhibited compared to the contiguous terraces. The time required for pit filling scales inversely with pit diameter, with nucleation completely suppressed in pits with diameters less than 100 nm. The suppression of growth in the pits can be attributed to the surface discontinuity created by the pit edge that prevents surface diffusion of ET growth units from the surrounding terrace to the pit. Consequently, growth of nuclei in the pits is limited by the amount of ET arriving in the pit by diffusion directly from solution. Numerical simulations of aggregate growth in pits illustrate the influences of transport and the finite boundary created by pit wall on the evolution of aggregate shape and size during growth, while revealing the most probable locations for nucleation within the pit. These studies illustrate the convenience of investigating nucleation processes triggered by electrochemically driven changes in redox state, the advantage of AFM for probing nucleation in the nanoscale-confined environments, and the role of transport in nucleation of ordered films.

Original languageEnglish (US)
Pages (from-to)9958-9965
Number of pages8
JournalJournal of Physical Chemistry B
Volume102
Issue number49
StatePublished - Dec 3 1998

Fingerprint

Graphite
Monolayers
Nucleation
graphite
nucleation
Crystalline materials
Substrates
Atomic force microscopy
Graphite electrodes
Surface diffusion
Etching
atomic force microscopy
pyrolytic graphite
surface diffusion
Computer simulation
discontinuity
tetrathiafulvalene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Nanoconfined electrochemical nucleation of crystalline molecular monolayers on graphite substrates. / Hooks, Daniel E.; Yip, Christopher M.; Ward, Michael.

In: Journal of Physical Chemistry B, Vol. 102, No. 49, 03.12.1998, p. 9958-9965.

Research output: Contribution to journalArticle

@article{4ff29f4b9587416c8d878f52129e0537,
title = "Nanoconfined electrochemical nucleation of crystalline molecular monolayers on graphite substrates",
abstract = "Real-time in situ atomic force microscopy (AFM) has been employed to examine the electrochemical nucleation of epitaxially oriented, crystalline monolayers of bis(ethylenedithiolo)tetrathiafulvalene triiodide, (ET)2I3, on the basal plane of highly oriented pyrolytic graphite electrodes decorated with circular, single-layer-deep pits created by thermal etching. The nucleation of the monolayers in the pits is inhibited compared to the contiguous terraces. The time required for pit filling scales inversely with pit diameter, with nucleation completely suppressed in pits with diameters less than 100 nm. The suppression of growth in the pits can be attributed to the surface discontinuity created by the pit edge that prevents surface diffusion of ET growth units from the surrounding terrace to the pit. Consequently, growth of nuclei in the pits is limited by the amount of ET arriving in the pit by diffusion directly from solution. Numerical simulations of aggregate growth in pits illustrate the influences of transport and the finite boundary created by pit wall on the evolution of aggregate shape and size during growth, while revealing the most probable locations for nucleation within the pit. These studies illustrate the convenience of investigating nucleation processes triggered by electrochemically driven changes in redox state, the advantage of AFM for probing nucleation in the nanoscale-confined environments, and the role of transport in nucleation of ordered films.",
author = "Hooks, {Daniel E.} and Yip, {Christopher M.} and Michael Ward",
year = "1998",
month = "12",
day = "3",
language = "English (US)",
volume = "102",
pages = "9958--9965",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "49",

}

TY - JOUR

T1 - Nanoconfined electrochemical nucleation of crystalline molecular monolayers on graphite substrates

AU - Hooks, Daniel E.

AU - Yip, Christopher M.

AU - Ward, Michael

PY - 1998/12/3

Y1 - 1998/12/3

N2 - Real-time in situ atomic force microscopy (AFM) has been employed to examine the electrochemical nucleation of epitaxially oriented, crystalline monolayers of bis(ethylenedithiolo)tetrathiafulvalene triiodide, (ET)2I3, on the basal plane of highly oriented pyrolytic graphite electrodes decorated with circular, single-layer-deep pits created by thermal etching. The nucleation of the monolayers in the pits is inhibited compared to the contiguous terraces. The time required for pit filling scales inversely with pit diameter, with nucleation completely suppressed in pits with diameters less than 100 nm. The suppression of growth in the pits can be attributed to the surface discontinuity created by the pit edge that prevents surface diffusion of ET growth units from the surrounding terrace to the pit. Consequently, growth of nuclei in the pits is limited by the amount of ET arriving in the pit by diffusion directly from solution. Numerical simulations of aggregate growth in pits illustrate the influences of transport and the finite boundary created by pit wall on the evolution of aggregate shape and size during growth, while revealing the most probable locations for nucleation within the pit. These studies illustrate the convenience of investigating nucleation processes triggered by electrochemically driven changes in redox state, the advantage of AFM for probing nucleation in the nanoscale-confined environments, and the role of transport in nucleation of ordered films.

AB - Real-time in situ atomic force microscopy (AFM) has been employed to examine the electrochemical nucleation of epitaxially oriented, crystalline monolayers of bis(ethylenedithiolo)tetrathiafulvalene triiodide, (ET)2I3, on the basal plane of highly oriented pyrolytic graphite electrodes decorated with circular, single-layer-deep pits created by thermal etching. The nucleation of the monolayers in the pits is inhibited compared to the contiguous terraces. The time required for pit filling scales inversely with pit diameter, with nucleation completely suppressed in pits with diameters less than 100 nm. The suppression of growth in the pits can be attributed to the surface discontinuity created by the pit edge that prevents surface diffusion of ET growth units from the surrounding terrace to the pit. Consequently, growth of nuclei in the pits is limited by the amount of ET arriving in the pit by diffusion directly from solution. Numerical simulations of aggregate growth in pits illustrate the influences of transport and the finite boundary created by pit wall on the evolution of aggregate shape and size during growth, while revealing the most probable locations for nucleation within the pit. These studies illustrate the convenience of investigating nucleation processes triggered by electrochemically driven changes in redox state, the advantage of AFM for probing nucleation in the nanoscale-confined environments, and the role of transport in nucleation of ordered films.

UR - http://www.scopus.com/inward/record.url?scp=0000448524&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000448524&partnerID=8YFLogxK

M3 - Article

VL - 102

SP - 9958

EP - 9965

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 49

ER -