Table Of ContentSpringer Series in Surface Sciences 52
Karsten Hinrichs
Editors
Klaus-Jochen Eichhorn
Ellipsometry of
Functional Organic
Surfaces and Films
Second Edition
Springer Series in Surface Sciences
Volume 52
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
Karsten Hinrichs Klaus-Jochen Eichhorn
(cid:129)
Editors
Ellipsometry of Functional
Organic Surfaces and Films
Second Edition
123
Editors
Karsten Hinrichs Klaus-Jochen Eichhorn
Leibniz-Institut für Analytische Abteilung Analytik
Wissenschaften – ISAS –e.V. Leibniz-Institut für Polymerforschung
Berlin Dresdene.V.
Germany Dresden,Sachsen
Germany
ISSN 0931-5195 ISSN 2198-4743 (electronic)
SpringerSeries inSurface Sciences
ISBN978-3-319-75894-7 ISBN978-3-319-75895-4 (eBook)
https://doi.org/10.1007/978-3-319-75895-4
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Foreword
Given the increasingly important role of spectroscopic ellipsometry (SE) as a
real-time, non-perturbing, monitoring, and characterization tool in numerous
technological and biomedical applications, the editors, authors, and Springer are
commendedforpublishingthe2ndeditionofthismonograph,whichisdedicatedto
significantapplicationsofSEtofunctionalorganicsurfacesandthinfilms.Retained
topics from the first edition cover the adsorption of biomolecules at liquid–solid
interfaces, smart polymer surfaces and thin films for sensor applications, charac-
terization of nanoparticles and nanostructured surfaces and thin films, thin-film
organic semiconductors for photovoltaics and light emitters, and recent develop-
ments of SE instrumentation and related techniques over an extended optical
bandwidth.
New topics that appear in the 2nd edition include SE studies of bonding of
biomolecules on self-assembled monolayers, structure and interactions of hydrated
polymer thin films, ellipsometry of solvent-induced swelling at soft polymer
interfaces, optical properties of anisotropic thin films of organic dye aggregates,
relationship between morphology and optical properties of conjugated polymers,
and polarons in conducting polymers.
This updated monograph is a welcome contribution to the expanding ellip-
sometry literature.
New Orleans, USA R. M. A. Azzam
University of New Orleans
v
Acknowledgements
Theeditorswouldliketoacknowledgeallauthorsfortheircontributionsandmany
valuable discussions, and Arnulf Röseler for his lasting support in helping for
understanding of the ellipsometric world. In addition, this book would not have
been possible without the motivation and support of our families; KJE thanks his
wifeSigrunandhischildrenSusanneandJörg,andKHthankshiswifeClaudiaand
hisdaughterDaria.Forpermanenttechnicalsupportinthepreparationofthebook,
we are indebted to I. Engler and E. Bittrich.
Berlin, Germany Karsten Hinrichs
Dresden, Germany Klaus-Jochen Eichhorn
vii
Contents
1 Ellipsometry: A Survey of Concept. . . . . . . . . . . . . . . . . . . . . . . . . 1
Christoph Cobet
1.1 Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Historical Context. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3 Measurement Principles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3.1 Data Recording and Evaluation Steps . . . . . . . . . . . . 5
1.3.2 Determination of W and D . . . . . . . . . . . . . . . . . . . . 8
1.3.3 Fresnel Coefficients. . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.4 Dielectric Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.4.1 Dispersion Models—Lorentz Oscillator . . . . . . . . . . . 19
1.4.2 Inhomogeneous Media and Structured Interfaces . . . . 21
1.5 Ellipsometric Configurations . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.5.1 Null-Ellipsometer . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.5.2 Rotating Polarizer/Analyzer. . . . . . . . . . . . . . . . . . . . 23
1.5.3 Rotating Compensator. . . . . . . . . . . . . . . . . . . . . . . . 23
1.5.4 Photo-Elastic Modulator Ellipsometer . . . . . . . . . . . . 24
1.5.5 Dual Rotating Compensator . . . . . . . . . . . . . . . . . . . 24
1.5.6 Reflection Anisotropy Spectroscopy. . . . . . . . . . . . . . 25
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Part I Biomolecules at Surfaces
2 Adsorption of Proteins at Solid Surfaces. . . . . . . . . . . . . . . . . . . . . 31
Hans Arwin
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.1.1 Historical Background . . . . . . . . . . . . . . . . . . . . . . . 31
2.1.2 Opportunities and Challenges . . . . . . . . . . . . . . . . . . 32
2.1.3 Objectives and Outline . . . . . . . . . . . . . . . . . . . . . . . 33
2.2 Methodology—Experimental Aspects. . . . . . . . . . . . . . . . . . . 34
ix
x Contents
2.3 Methodology—Modeling Aspects . . . . . . . . . . . . . . . . . . . . . 35
2.3.1 Strategies to Determine Both Thickness
and Refractive Index. . . . . . . . . . . . . . . . . . . . . . . . . 35
2.3.2 Spectral Representations of Protein Layers. . . . . . . . . 38
2.3.3 Determination of Surface Mass Density . . . . . . . . . . . 38
2.4 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.4.1 Protein Adsorption and Dynamics on Model
Surfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.4.2 Studies of Protein Layer Structure . . . . . . . . . . . . . . . 39
2.4.3 Protein Layer Based Biosensing . . . . . . . . . . . . . . . . 43
2.4.4 Other Applications . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.5 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3 DNA Structures on Silicon and Diamond . . . . . . . . . . . . . . . . . . . . 49
Simona D. Pop, Karsten Hinrichs, Sylvia Wenmackers,
Christoph Cobet, Norbert Esser and Dietrich R. T. Zahn
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.2 Dielectric Function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.3 Applications to Thin Biomolecular Films . . . . . . . . . . . . . . . . 54
3.3.1 Single DNA Bases . . . . . . . . . . . . . . . . . . . . . . . . . . 54
3.3.2 Single- and Double-Stranded DNA Molecules . . . . . . 56
3.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4 Thickness and Beyond. Exploiting Spectroscopic Ellipsometry
and Atomic Force Nanolithography for the Investigation
of Ultrathin Interfaces of Biologic Interest . . . . . . . . . . . . . . . . . . . 63
Pietro Parisse, Ilaria Solano, Michele Magnozzi, Francesco Bisio,
Loredana Casalis, Ornella Cavalleri and Maurizio Canepa
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
4.2 Optical Ellipsometry of Ultrathin Interfaces: Difference
Spectra. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
4.3 Atomic Force Nanolithography: Notes on Principles
and Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
4.4 Application of SE and Atomic Force Lithography Methods
to Ultrathin Soft Matter Films: Case Studies. . . . . . . . . . . . . . 79
4.4.1 Bio-Inert SAMs: Nanoshaving. . . . . . . . . . . . . . . . . . 79
4.4.2 Specific Immobilisation of Proteins on SAMs:
Grafting. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.5 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Contents xi
Part II Smart Polymer Surfaces and Films
5 Glass Transition of Polymers with Different Architectures
in the Confinement of Nanoscopic Films. . . . . . . . . . . . . . . . . . . . . 97
Michael Erber, Martin Tress, Eva Bittrich, Lars Bittrich
and Klaus-Jochen Eichhorn
5.1 Polymers: A Unique Class of Materials and Their Physical
Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
5.2 Nanoscopic Polymer Films versus Bulk Polymers. . . . . . . . . . 99
5.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
5.2.2 True or Mimicked Confinement Effects . . . . . . . . . . . 100
5.2.3 Make a Long Controversial Story Short:
Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
5.3 Comparison of Analytical Methods for the Determination
of Glass Transition of Polymers in Thin Polymer Films . . . . . 101
5.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
5.3.2 Ellipsometry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
5.3.3 Broadband Dielectric Spectroscopy . . . . . . . . . . . . . . 102
5.3.4 AC-calorimetry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
5.3.5 Other Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
5.4 Concepts of the Determination of Glass Transition
Applying Ellipsometry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
5.4.1 Single Wavelength Ellipsometry . . . . . . . . . . . . . . . . 104
5.4.2 Spectroscopic vis-Ellipsometry (SE). . . . . . . . . . . . . . 105
5.5 Glass Transition in Thin Polymeric Films in Dependence
of Film Thickness – Some Exclusive Examples . . . . . . . . . . . 109
5.5.1 Effect of Polymer Architecture and Functional
Groups. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
5.5.2 Effect of Interfacial Interactions Between Polymer
and Substrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
5.6 Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
6 Polymer Brushes, Hydrogels, Polyelectrolyte Multilayers:
Stimuli-Responsivity and Control of Protein Adsorption . . . . . . . . 115
Eva Bittrich, Andreas Furchner, Meike Koenig, Dennis Aulich,
Petra Uhlmann, Karsten Hinrichs and Klaus-Jochen Eichhorn
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
6.2 Ellipsometry on Swellable, Stimuli-Responsive Surface
Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
6.2.1 Hydrophilic Polymer Brushes . . . . . . . . . . . . . . . . . . 119
6.2.2 Hydrogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
6.2.3 Polyelectrolyte Multilayers . . . . . . . . . . . . . . . . . . . . 128
6.3 Concepts of Determining the Adsorbed Amount of Protein
on Different Polymer Films . . . . . . . . . . . . . . . . . . . . . . . . . . 129
