Table Of ContentSpringer Series in Surface Sciences 65
Sascha Sadewasser
Editors
Thilo Glatzel
Kelvin Probe Force
Microscopy
From Single Charge Detection to Device
Characterization
Springer Series in Surface Sciences
Volume 65
Series editors
Roberto Car, Princeton University, Princeton, NJ, USA
Gerhard Ertl, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany
Hans-Joachim Freund, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin,
Germany
Hans Lüth, Peter Grünberg Institute, Forschungszentrum Jülich GmbH, Jülich,
Germany
Mario Agostino Rocca, Dipartimento di Fisica, Università degli Studi di Genova,
Genova, Italy
This series covers the whole spectrum of surface sciences, including structure and
dynamicsofcleanandadsorbate-coveredsurfaces,thinfilms,basicsurfaceeffects,
analytical methods and also the physics and chemistry of interfaces. Written by
leading researchers in the field, the books are intended primarily for researchers in
academia and industry and for graduate students.
More information about this series at http://www.springer.com/series/409
Sascha Sadewasser Thilo Glatzel
(cid:129)
Editors
Kelvin Probe Force
Microscopy
From Single Charge Detection to Device
Characterization
123
Editors
Sascha Sadewasser Thilo Glatzel
International Iberian Department ofPhysics
Nanotechnology Laboratory University of Basel
Braga Basel
Portugal Switzerland
ISSN 0931-5195 ISSN 2198-4743 (electronic)
SpringerSeries inSurface Sciences
ISBN978-3-319-75686-8 ISBN978-3-319-75687-5 (eBook)
https://doi.org/10.1007/978-3-319-75687-5
LibraryofCongressControlNumber:2018931494
©SpringerInternationalPublishingAG2018
Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission
orinformationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar
methodologynowknownorhereafterdeveloped.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfrom
therelevantprotectivelawsandregulationsandthereforefreeforgeneraluse.
The publisher, the authors and the editors are safe to assume that the advice and information in this
book are believed to be true and accurate at the date of publication. Neither the publisher nor the
authorsortheeditorsgiveawarranty,expressorimplied,withrespecttothematerialcontainedhereinor
for any errors or omissions that may have been made. The publisher remains neutral with regard to
jurisdictionalclaimsinpublishedmapsandinstitutionalaffiliations.
Printedonacid-freepaper
ThisSpringerimprintispublishedbytheregisteredcompanySpringerInternationalPublishingAG
partofSpringerNature
Theregisteredcompanyaddressis:Gewerbestrasse11,6330Cham,Switzerland
Foreword
AtomicForceMicroscopyAFManditsOff-springs:TheUltimateToolkitsfor
Nanoscience and Technology
Nature is the best example of a system functioning on the nanometer scale, where
the involved materials, energy consumption, and data handling are optimized. The
emergence ofAtomic Force Microscopy (AFM)31 years ago inthe then-fledgling
field of nanotechnology led to a shift of paradigm in the understanding and per-
ception of matter at its most fundamental level. It undoubtedly has opened new
avenues in physics, chemistry, biology, and medicine and still is inspiring
researchersaroundtheworldtestifiedsofarbymorethan350’000scientificarticles
inpeer-reviewedjournals(accordingtothewebofscience).Thehighflexibilityof
AFMtoimage,probe,andmanipulatematerialswithunprecedentedresolutionand
to be combined with other technologies made it the most powerful and versatile
toolkit in nanoscience and technology of today. As a consequence, new revolu-
tionary concepts stimulated a number of new technologies.
Kelvin probe force microscopy emerged quite early in the history of AFM and
showed the enormous potential of the method impacting surface science on the
atomic scale to a great extent ever since. The new edition “Kelvin Probe Force
Microscopy—FromSingleChargeDetectiontoDeviceCharacterization”givesthe
reader an overview of the dramatic developments in the last decade taking the
technique into diverse fields of applications and beyond.
Basel, Switzerland Christoph Gerber
July 2017
v
Preface
Seven years have passed since the first volume “Kelvin probe force microscopy—
Measuring and compensating electrostatic forces” has been published in 2011. It
presentedthefirstbookdedicatedsolelytoKelvinprobeforcemicroscopy(KPFM),
about 20 years after the invention of KPFM in 1991 by Nonnenmacher et al.
The book gave an overview and good starting point for newcomers to the field,
providedin-depthdescriptionsoftheunderlyingtechniques,andpresentedavariety
of examples for applications. Since then we have seen a strongly increased
development of KPFM techniques, an improved understanding of the involved
physical principles, and a multitude of new applications in numerous fields.
Therefore,wefeelitisagoodtimetosummarizetherecentadvancesintoasecond
volume of the book, which is entitled “Kelvin Probe Force Microscopy—From
Single Charge Detection to Device Characterization”. The subtitle reflects the
remarkable development that KPFM has seen in the recent 5 to 10 years. Several
new techniques have been developed providing measurements of the surface
potentialthatarefaster,freeofcapacitivecross-talk,andwithbetterresolutionand
noiselevel.KPFMinliquidenvironments,improvedtheoreticalunderstanding,and
time-resolved KPFM are other major steps that have given new impulses to the
field. Another important development is the imaging of electrostatic forces at
atomic and intramolecular scale, providing fundamental insights into organic and
inorganicmatter.Alltheseadvanceshavepavedthegroundforthecharacterization
and the progress of knowledge in material science and device applications.
Motivated by these developments and opportunities, KPFM and electrostatic
force microscopy (EFM) have received increasing attention in the scientific liter-
ature and at scientific conferences and workshops. Large conferences on materials
science (e.g., the annual spring and fall meetings of the (European) Materials
ResearchSociety)havehostedseveraldedicatedsymposiawhereKPFMandEFM
played a significant role. Conferences specialized to certain types of device con-
cepts (e.g., solar cells, nanowires, nanoelectronis, etc.) typically have dedicated
sessions for scanning probe microscopy where KPFM and EFM have a large
impact. In addition, specialized conferences (e.g., the annual nc-AFM conference)
vii
viii Preface
and numerous smaller workshops typically hold sessions devoted to these
techniques.
In view of these advances and interest in the local characterization of electrical
surfacepropertiesbyKPFM,wefeelthatitisagoodtimetoprovideareviewofthe
state-of-the-artofthefieldintheformofthepresentbook.Weaimatsummarizing
and describing the advances and recent applications in this second volume, again
providing a first contact for newcomers into the field and also an overview with
in-depth discussions of specific techniques or applications for the specialist.
Volume 2 contains 15 completely new chapters and starts with a fully revised
chapter giving an introduction to the principles of the technique. The book is
structured into four parts, covering “Experimental Methods and Technical
Aspects”, “Data Interpretation and Theoretical Aspects”, “Application to Device
Characterization”, and “Atomic Scale Experiments”. We could win the leading
scientistsandresearcherstocontributetheirexpertiseinthevariouschaptersandwe
thank them for their efforts and contributions.
We hope that the reader finds the book a useful resource in the daily work, an
inspirationtotryoutnewtechniquesandapplications,andtogobeyondthecurrent
state-of-the-art in the field of electrostatic and Kelvin probe force microscopy.
Braga, Portugal Sascha Sadewasser
Basel, Switzerland Thilo Glatzel
Contents
Part I Experimental Methods and Technical Aspects
1 Experimental Technique and Working Modes . . . . . . . . . . . . . . . . 3
Sascha Sadewasser and Thilo Glatzel
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2 Non-contact Atomic Force Microscopy . . . . . . . . . . . . . . . . . . 4
1.3 Electrostatic Force Microscopy . . . . . . . . . . . . . . . . . . . . . . . . 8
1.4 Kelvin Probe Force Microscopy. . . . . . . . . . . . . . . . . . . . . . . . 10
1.4.1 AM-KPFM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.4.2 FM-KPFM. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.4.3 Technical Realization . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.4.4 Other Modes and Additional Experimental Options . . . 16
1.5 Additional Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2 Dissipation Modulated Kelvin Probe Force
Microscopy Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
Yoichi Miyahara and Peter Grütter
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.2 Theory. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.2.1 Review of Theory of Frequency Modulation Atomic
Force Microscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.2.2 Analysis of Electrostatic Force with AC Bias
Voltage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.3 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.4 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.4.1 Validation of D-KPFM Theory . . . . . . . . . . . . . . . . . . 35
2.4.2 Illustrative Example of D-KPFM Imaging . . . . . . . . . . 38
2.4.3 Comparison of Different KPFM Techniques. . . . . . . . . 40
2.4.4 Dynamic Response of D-KPFM . . . . . . . . . . . . . . . . . 44
ix
x Contents
2.5 Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3 Dynamic Modes in Kelvin Probe Force Microscopy: Band
Excitation and G-Mode. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Stephen Jesse, Liam Collins, Sabine Neumayer, Suhas Somnath
and Sergei V. Kalinin
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3.2 Principles of EFM and KPFM. . . . . . . . . . . . . . . . . . . . . . . . . 51
3.3 Classic KPFM Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3.4 Dynamic KPFM Without DC Bias Feedback . . . . . . . . . . . . . . 56
3.5 Band Excitation KPFM. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.5.1 Open Loop BE-KPFM . . . . . . . . . . . . . . . . . . . . . . . . 60
3.5.2 Half Harmonic BE-KPFM . . . . . . . . . . . . . . . . . . . . . 63
3.5.3 Photothermal BE-KPFM. . . . . . . . . . . . . . . . . . . . . . . 65
3.5.4 Force Volume BE-KPFM . . . . . . . . . . . . . . . . . . . . . . 67
3.6 Time Resolved KPFM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.7 G-Mode KPFM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
3.7.1 Classical Analysis Approach: Digital Heterodyne
Detection. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3.7.2 Physics Based Analysis: Recovery
of Force-Voltage Dependence . . . . . . . . . . . . . . . . . . . 80
3.7.3 Information Based Analysis: Data Mining . . . . . . . . . . 81
3.7.4 General Dynamic Mode . . . . . . . . . . . . . . . . . . . . . . . 82
3.8 KPFM Spectroscopies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.8.1 Contact KPFM. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.9 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
4 Practical Aspects of Kelvin Probe Force Microscopy
in Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
Kei Kobayashi and Hirofumi Yamada
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
4.2 Electric Double Layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
4.3 Capacitive Force. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
4.4 Electrostatic Force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
4.5 Surface Charge Measurement by Force Mapping . . . . . . . . . . . 112
4.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
5 Time-Resolved Electrostatic and Kelvin Probe
Force Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
Sascha Sadewasser and Nicoleta Nicoara
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
