Scanning Electrochemical Microscopy

661 Pages·2001·8.76 MB·English

by  Allen J. Bard, Michael V. Mirkin

ISBN: 0-8247-0471-1
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PREFACE
Alittlemorethantenyearshaveelapsedsincepublicationofthefirstpapers
describing the fundamentals of scanning electrochemical microscopy
(SECM). During this decade, the field of SECM has evolved substantially.
The technique has been used in a variety of ways, for example, as an elec-
trochemical tool to study heterogeneous and homogeneous reactions, for
high-resolutionimagingofthechemicalreactivityandtopographyofvarious
interfaces, and for microfabrication. Quantitative theoretical models have
been developed for different modes of the SECM operation. The first com-
mercial SECM instrument was introduced in 1999. The SECM technique is
now used by a number of research groups in many different countries. We
think the time has come to publish the first monograph, providing compre-
hensive reviews of different aspects of SECM.
The first five chapters of this book contain experimental and theoretical
background, which is essential for everyone working in this field:principles
of SECM measurements (Chapter 1), instrumentation (Chapter 2), prepara-
tion of SECM ultramicroelectrodes (Chapter 3), imaging methodologies
(Chapter 4), and theory (Chapter 5). Other chapters are dedicatedtospecific
applications and are self-contained. Although some knowledge of electro-
chemistry and physical chemistry is assumed, the key ideas are discussedat
the level suitable for beginning graduate students.
Through the addition of submicrometer-scale spatial resolution, SECM
greatly increases the capacity of electrochemical techniques to characterize
interfaces and measure local kinetics. In this way, it has proved useful for
a broad range of interdisciplinary research. Various applications of SECM
are discussed in this book, from studies of biological systems, to sensors,to
probing reactions at the liquid/liquid interface. Although we did not intend
topresentevenabriefsurveyofthosediverseareasofresearch,eachchapter
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iv Preface
provides sufficient details to allow a specialist to evaluate the applicability
of the SECM methods for solving a specific problem. We hope it will be
useful to all interested in learning about this technique and applying it.
We would like to thank our students, co-workers, and colleagues who
have done so much to develop SECM. The future for this technique, which
is unique among scanning probe methods in its quantitative rigor and its
ability to study with ease samples in liquid environments, continues to be a
bright one.
Allen J. Bard
Michael V. Mirkin
CONTENTS
Preface iii
Contributors ix
1 INTRODUCTIONAND PRINCIPLES 1
Allen J. Bard
I. Background of Scanning Electrochemical Microscopy 1
II. Principles of SECM 2
III. Applications of SECM 9
References 15
2 INSTRUMENTATION 17
David O. Wipf
I. Introduction 17
II. Overview of the SECMApparatus 18
III. Commercial SECM Instrument Implementation 42
IV. Tip Position Modulation Instrumentation 44
V. Constant-Current Mode Instrumentation 44
VI. Experimental Difficulties in DataAcquisition 53
VII. Accessory Equipment for SECM 59
Appendix; Suppliers 66
References 71
v
vi Contents
3 THE PREPARATION OF TIPS FOR SCANNING
ELECTROCHEMICAL MICROSCOPY 75
Fu-Ren F. Fan and Christophe Demaille
I. Introduction 75
II. Preparation Techniques 75
III. Nondisk Tips and Tip Shape Characterization 104
References 107
4 SECM IMAGING 111
Fu-Ren F. Fan
I. Introduction 111
II. Principle and Methodology of SEM Imaging 111
III. Images in Solutions 115
IV. Images in HumidAir 124
V. Conclusions and Future Projections 139
References 141
5 THEORY 145
Michael V. Mirkin
I. Introduction 145
II. Feedback Mode of SECM Operation 145
III. Generation/Collection (G/C) Mode of SECM Operation 165
IV. SECM of More Complicated Chemical Systems 170
V. Numerical Solution of SECM Diffusion Problems
Using PDEase2 Program Package 182
List of Symbols 193
References 198
6 HETEROGENEOUS ELECTRON TRANSFER REACTIONS 201
Kai Borgwarth and Ju¨rgen Heinze
I. Introduction 201
II. Principles 203
III. Studies of Heterogeneous Electron Transfer 217
IV. Applications 234
V. Conclusion and Outlook 237
References 238
Contents vii
7 KINETICS OF HOMOGENEOUS REACTIONS COUPLED
TO HETEROGENEOUS ELECTRON TRANSFER 241
Patrick R. Unwin
I. Introduction 241
II. EC Processes 244
i
III. EC Processes 270
2i
IV. ECE/DISP Processes 283
References 297
8 CHARGE-TRANSFERAT THE LIQUID/LIQUID INTERFACE 299
Michael V. Mirkin and Michael Tsionsky
I. Introduction 299
II. Electron Transfer 301
III. Ion Transfer at the ITIES 325
IV. Processes with Coupled Homogeneous Reactions 336
References 339
9 IMAGING MOLECULAR TRANSPORTACROSS
MEMBRANES 343
Bradley D. Bath, Henry S. White, and Erik R. Scott
I. Introduction 343
II. Principles of Imaging Porous Membranes 346
III. Applications 365
IV. Future Directions 392
References 394
10 POTENTIOMETRIC PROBES 397
Guy Denuault, Ge´za Nagy, and Kla´ra To´th
I. Introduction 397
II. Basic Theory 415
III. Properties and Behavior of Ion-Selective Probes 417
IV. Potentiometric Measurements in Scanning Probe
Microscopies Other than SECM 422
V. Potentiometric Measurements in SECM 423
VI. Conclusion 441
References 442
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11 BIOLOGICAL SYSTEMS 445
Benjamin R. Horrocks and Gunther Wittstock
I. Approaches to Imaging Biological and Biochemical
Systems 445
II. SelectedApplications 463
III. Conclusion and Outlook 504
IV. Abbreviations,Acronyms, and Symbols 510
References 512
12 PROBING REACTIONSAT SOLID/LIQUID INTERFACES 521
Julie V. Macpherson and Patrick R. Unwin
I. Introduction 521
II. Measurement of Adsorption/Desorption Kinetics and
Surface Diffusion Rates 523
III. Dissolution Kinetics of Ionic Single Crystals 536
IV. Corrosion Studies 573
V. Conclusions 588
References 590
13 MICRO-AND NANOPATTERNING USING THE
SCANNING ELECTROCHEMICALMICROSCOPE 593
Daniel Mandler
I. Patterning by the Direct Mode of the SECM 594
II. Patterning by the Feedback Mode of the SECM 603
III. PerspectiveApproaches 623
References 625
14 CONCLUSIONSAND PROSPECTS 629
Allen J. Bard
I. Combining SECM with Other Techniques 629
II. Novel Interfaces 634
III. Instrumentation Improvements 636
References 637
Index 639
CONTRIBUTORS
ALLEN J. BARD The University of Texas at Austin,Austin, Texas
BRADLEY D. BATH ALZACorporation, Mountain View, California
KAI BORGWARTH Institute for Physical Chemistry,Albert Ludwig
University of Freiburg, Freiburg, Germany
CHRISTOPHE DEMAILLE The University of Texas at Austin,Austin,
Texas
GUY DENUAULT University of Southampton, Southampton, England
FU-REN F. FAN The University of Texas at Austin,Austin, Texas
JU¨RGEN HEINZE Albert Ludwig University of Freiburg, Freiburg,
Germany
BENJAMIN R. HORROCKS University of Newcastle upon Tyne,
Newcastle upon Tyne, United Kingdom
JULIE V. MACPHERSON University of Warwick, Coventry, England
DANIEL MANDLER The Hebrew University of Jerusalem, Jerusalem,
Israel
MICHAELV. MIRKIN Queens College–City University of New York,
Flushing, New York
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