Atomic Force Microscopy, Scanning Nearfield Optical Microscopy and Nanoscratching: Application to Rough and Natural Surfaces

301 Pages·2006·25.94 MB·English

by  Professor Dr. Gerd Kaupp (auth.)

NanoScience and Technology
NanoScience and Technology
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velopmentsinthisemergingdisciplinearecoveredbycomprehensiveandtimelybooks.
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G. Kaupp
Atomic Force Microscopy,
Scanning Nearfield
Optical Microscopy
and Nanoscratching
Application to Rough and Natural Surfaces
With239 Figures and 7 Tables
123
ProfessorDr.GerdKaupp
UniversityofOldenburg,DepartmentofChemistry
Diekweg 15, D-26188, Edewecht, Germany
[email protected]
SeriesEditors:
ProfessorDr.PhaedonAvouris
IBMResearchDivision,NanometerScaleScience&Technology
ThomasJ.WatsonResearchCenter,P.O.Box218
YorktownHeights,NY10598,USA
ProfessorDr.BharatBhushan
OhioStateUniversity
NanotribologyLaboratoryforInformationStorageandMEMS/NEMS(NLIM)
Suite255,AckermanRoad650,Columbus,Ohio43210,USA
ProfessorDr.,Dres.h.c.KlausvonKlitzing
Max-Planck-Institutfu¨rFestko¨rperforschung,Heisenbergstrasse1
70569Stuttgart,Germany
ProfessorHiroyukiSakaki
UniversityofTokyo,InstituteofIndustrialScience,4-6-1Komaba,Meguro-ku
Tokyo153-8505,Japan
ProfessorDr.RolandWiesendanger
Institutfu¨rAngewandtePhysik,Universita¨tHamburg,Jungiusstrasse11
20355Hamburg,Germany
ISSN1434-4904
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Preface
The introduction of the scanning tunneling microscope (STM) for electri-
cally conducting surfaces by Binnig and Rohrer in 1981 was followed by the
invention of atomic force microscopy in 1986 by Binnig, Quate, and Ger-
ber also for nonconductive samples. The initial interest was in atomic and
molecular resolution, and it rightfully continues also with building molecu-
lar machines by atomic-scale manipulation and industrial applications in the
field of high-density data storage on ultraflat surfaces. The latter topic also
usesthevarioustechniquesofscanningnear-fieldopticalmicroscopy(SNOM)
for surfaces without roughness. It was not until 1990 that the capabilities
of AFM for the third dimension started to become recognized, even though
commercial instruments were available since 1989, but funding of projects
aiming for submicroscopic characterization of topology was still not achiev-
able then and early publications were impeded by referees and editors. Many
authors in the first half of the 1990s did not even give a z-scale to their plots
but stressed only on the lateral resolution on top of 3D objects. It was not
appreciated then that most industrial and biological applications would be
on real-world samples at ambient conditions rather than with artificial test
samplesunderhighvacuum,orwithotherartificialtreatment.Similarexperi-
enceswereencounteredwithSNOMwhenanewinstrumentbecameavailable
in 1995 with the capability of reliable scanning on rough real-world surfaces
withheightdifferencesofmorethanamicrometer,andagainsimilarlyin1999
when two-dimensional transducers were added to nanoindentation equipment
enablingnanoscratchingfornovelnanomechanicaltesting.Theearlypioneers
whoimmediatelyrecognizedtheunprecedentedcapabilitiesandnecessitiesfor
real-worldapplicationswereagainnotgrantedthefundingfortheinitialbasic
research but had to privately purchase all of these instruments and were left
aloneinestablishingthefoundationsforscientificandindustrialuse.Funding
was only granted for applied research after the basics had been pioneered.
However the initially disliked topology is by far the most important topic in
practical and industrial applications of AFM and SNOM, and the new quan-
titative treatment that has been empirically developed in nanoscratching for
VI Preface
allkindsofsolidmaterialsisrevolutionizingthefield.Thelatteralsoprovided
the entry for quantitative treatments of nanoindentation, which was unduly
regarded as the “smaller-scale microindentation” and therefore relied on the
multiparameter iterative data treatment of Oliver and Pharr from 1992 that
was adopted in the ISO 14577 standard.
This book is devoted to the practical and industrial applications of the
nanotechniques AFM, SNOM, nanoindentation, and nanoscratching for real-
world samples in ambient environment. It does so in four independent chap-
ters. It also deals with theory as far as it is necessary for the practitioner
and as far as new physical effects, laws, and relations have been empirically
found, deduced, or derived and that are not covered in previous reviewing
booksormonographsonthesubjectsifavailable.Furtherscanningprobemi-
croscopy techniques (SPM) that have not yet been developed for application
to real-world surfaces are not covered. They are treated in the cited books.
The present book does not treat atomic and molecular resolution, molecular
Langmuir–Blodgett films (notwithstanding molecular steps on rough crystal
surfaces), atomic or molecular machines, and further nanotechnology devices
that exclude (significant) topology. Exhaustive treatises on these subjects are
available and there is no need for repeating them. None of the books with
particular emphasis on theory on the basis of model systems and simulations
treat the special requirements and additional expertise for reliable scanning
on (high) topology with AFM and SNOM or for quantitative measurements
innanoindentation,andnosuchtreatmentexistedfornanoscratchingwithits
wealth of information on mechanical properties of industrial interest.
Practical applications from almost all sciences, industries, and daily life
are collected, described, and cited with particular emphasis on the topology
of the real-world surfaces and on the quantitative study of nanomechanical
properties on the basis of new standards for all kinds of materials. Unfor-
tunately, many authors who are scanning now AFM on rough surfaces, after
AFMisdirectlyconnectedtomuchlessresolving(confocal)microscopy,donot
still stress the topology properties in the abstracts of their papers. Therefore,
some highly relevant reports must have been inevitably lost in the literature
retrievaloftheauthor.Buttheauthortriedhisbesttoapproachasmanydif-
ferent applications as possible and hopes that he did not miss any important
fields of practical application.
Thebookintendstoclosethegapbetweentheoryandpracticeofthefour
major tools for nanotechnology and to further advance the interest of indus-
try in SNOM on rough surfaces, nanoscratching, and nanoindentation. AFM
and microindentation are already widely accepted, although the latter on the
basis of a multiparameter iterative ISO standard, while quantitative treat-
ments with highly improved information and reliability on the basis of simple
apparentlyuniversallawswouldbeobtainedfromnanoindentation.Thebook
should therefore be of interest to students and scientists in academia and
industry in all fields of surface investigations not only in natural and life sci-
encesorindustrialengineering,butalsoinapparentlyunrelatedfieldssuchas
Preface VII
astrophysics, historical sciences, arts, forensics, jurisdiction, etc. The purpose
of the book is to give a systematic physical and technical background on the
basis of well-documented experimental results on all kinds of materials sur-
faces using uncomplicated robust equipment in ambient atmosphere. It does
so also with the probably most exhaustive collection of varied applications
from the literature beyond the atomic and molecular resolution issues, while
previous treatises restrict their application parts largely to DNA imaging or
sectioning and industrial data storage aspects. AFM, SNOM on rough sur-
faces,nanoindentation,andnanoscratchingwillcertainlyenjoyarapidfurther
development with applications to real-world problems.
Oldenburg,
February 2006 Gerd Kaupp
Contents
1 Atomic Force Microscopy.................................. 1
1.1 Introduction ............................................ 1
1.2 Basics of Contact AFM .................................. 2
1.3 Instrumental............................................ 3
1.4 Validity Checks ......................................... 9
1.5 Artifacts ............................................... 11
1.6 Surface Scratching and Plowing, Liquids on the Surface ...... 17
1.7 Molecular Steps ......................................... 22
1.8 Ambient Surface Modifications ............................ 27
1.9 Chemical Surface Modeling and Typical Shapes of Topologic
Features................................................ 31
1.9.1 Volcano or Cone Type ............................. 31
1.9.2 Islands........................................... 32
1.9.3 Craters .......................................... 38
1.9.4 Pool Basin Type .................................. 43
1.9.5 Prismatic Floes ................................... 44
1.9.6 Heights and Valleys................................ 48
1.9.7 Fissures .......................................... 50
1.9.8 Bricks ........................................... 52
1.10 Shear-Force AFM ....................................... 56
1.11 Further Fields of Practical Application ..................... 62
1.11.1 Biology and Medicine .............................. 63
1.11.2 Pharmacy ........................................ 64
1.11.3 Polymers......................................... 65
1.11.4 Ceramics ......................................... 65
1.11.5 Mineralogy and Geology ........................... 66
1.11.6 Metallurgy and Corrosion .......................... 68
1.11.7 Catalysis ......................................... 69
1.11.8 Forensics ......................................... 70
1.11.9 Historical Objects ................................. 70
X Contents
1.12 Electromagnetic AFM.................................... 71
1.13 Conclusions............................................. 71
References .................................................. 73
2 Scanning Near-Field Optical Microscopy................... 87
2.1 Introduction ............................................ 87
2.2 Foundations of SNOM ................................... 88
2.3 Equipment ............................................. 95
2.4 Optical Resolution....................................... 97
2.5 Dependence of the Reflectance Enhancement
from the Shear Force.....................................102
2.6 Artifacts ...............................................106
2.6.1 Tip Breakage During Scanning ......................106
2.6.2 Stripes Contrast...................................108
2.6.3 Inverted Derivative of the Topology in the Optical
Response.........................................110
2.6.4 Inverted Contrast .................................112
2.6.5 Displaced Optical Contrast .........................113
2.6.6 Local Far-Field Light Concentration .................115
2.6.7 Topologic Artifacts ................................115
2.7 Application of SNOM in Solid-State Chemistry..............118
2.8 Physical-State SNOM Contrast............................125
2.9 Technical Applications ...................................127
2.9.1 SNOM on Dental Alloys............................127
2.9.2 SNOM on Glazed Paper............................129
2.9.3 SNOM on Blood Bags .............................132
2.9.4 Quality Assessment of Metal Sol Particles for SERS
by SNOM ........................................134
2.10 Applications of SNOM in Biology and Medicine .............135
2.10.1 Prehistoric Bacterium, Pyrite Formation upon
Petrification ......................................136
2.10.2 SNOM on a Human Tooth..........................136
2.10.3 SNOM on Polymer Beads ..........................139
2.10.4 SNOM on Cryo Microtome Cuts of Rabbit Heart [61] ..139
2.10.5 SNOM on Stained and Unstained Shrimp Eye
Preparations [61] ..................................144
2.10.6 SNOM in Cancer Research [61]......................146
2.11 Near-Field Spectroscopy..................................149
2.11.1 Direct Local Raman SNOM ........................150
2.11.2 SERS SNOM .....................................151
2.11.3 Near-Field Infrared Spectroscopy and Scanning
Near-Field Dielectric Microscopy ....................153
2.11.4 Fluorescence SNOM ...............................154
2.12 Nanophotolithography ...................................163
2.13 Digital Microscopy for Rough Surfaces .....................168
Contents XI
2.14 Conclusions.............................................169
References ..................................................171
3 Nanoindentation...........................................177
3.1 Introduction ............................................177
3.2 Equipment .............................................177
3.3 Foundations of the Nanoindentation Technique..............179
3.3.1 General Remarks..................................179
3.3.2 Load–Displacement Curves .........................179
3.3.3 Anisotropy and Far-Reaching Response ..............182
3.4 Elastic and Plastic Parameters ............................184
3.4.1 Nanohardness.....................................185
3.4.2 Reduced Elastic Modulus...........................186
3.4.3 Contact Area and Contact Height ...................187
3.4.4 Stiffness and Compliance ...........................189
3.4.5 The Unloading Iteration Process ....................189
3.5 Improved Indentation Parameters .........................193
3.6 Linear Plots for the Loading Curves – the New Universal
Exponent 3/2 ...........................................198
3.7 Phase Transitions .......................................204
3.8 The Work of Indentation and its Anisotropy ................206
3.9 Recent Approaches to Nanoindentation at Highest
Resolution..............................................210
3.10 Nanoindentations with Highly Anisotropic Organic
Crystals................................................211
3.11 Nanoindentations with Organic Polymers...................218
3.12 Concluding Remarks.....................................221
References ..................................................223
4 Nanoscratching ............................................229
4.1 Introduction ............................................229
4.2 Foundations of the Nanoscratching Technique ...............232
4.3 Equipment .............................................234
4.4 The Appearance of Nanoscratches .........................237
4.5 Quantitative Treatment of Nanoscratching..................238
4.5.1 The Relation of Lateral and Normal Force............238
4.5.2 Scratch Work Considerations and Mathematical
Justification of the F ∼F3/2 Relation...............244
L N
4.5.3 Phase Transitions .................................246
4.5.4 The Relation of Lateral Force and Normal
Displacement: Consistency of the New 3/2
Exponential Relationships in Nanoscratching and
Nanoindentation ..................................252
4.5.5 Scratch Resistance.................................252
4.5.6 Anisotropy in Nanoscratches........................255