Ellipsometry of Functional Organic Surfaces and Films (eBook)

Karsten Hinrichs received his PhD in solid state physics from the TU Berlin, Germany and he holds a habilitation degree in Physical Chemistry of the TU Dresden. Since 2000 he works as researcher at the Berlin Department of the Leibniz-Institut für Analytische Wissenschaften – ISAS – e. V.. Since 2012 he is the head of the working group In situ Spectroscopy. He became a member of the Graduate School of Analytical Sciences at Humboldt University Berlin in 2012 and since 2005 he is member of the board of the German Working Group Ellipsometry (www.akepdv.de). Currently he is member of the Society for Applied Spectroscopy (SAS), American Chemical Society (ACS) and German Physical Society (DPG).Karsten Hinrichs has undertaken several research periods to Prof. S. Minko's working group at the Clarkson University and the University of Georgia, U.S.A. since 2008.He was the program chair of the 7th International Conference in Spectroscopic Ellipsometry 2016 in Berlin and is a frequent contributor of articles and book chapters for renowned international journals. His research focusses on the optical analysis of functional surfaces and thin films and the development of new infrared spectroscopic measurement strategies with polarized light. Recent work was dedicated to structure-spectra correlations of functional films at solid liquid interfaces and infrared nanopolarimetric studies of structure and anisotropy of thin films and surfaces.Klaus-Jochen Eichhorn is head of the Analytical Department within the Institute of Macromolecular Chemistry at the Leibniz Institute of Polymer Research Dresden e. V., Germany (since 2000). In 1980 he received his Diploma in Chemistry from Friedrich-Schiller-University Jena, Germany, then he moved for a PhD position to Dresden University of Technology, Institute of Physical Chemistry and Electrochemistry where he finished his PhD studies on ellipsometry of iron and steel surfaces in model atmospheres in 1985. Since then Dr. Eichhorn has been working on the field of polymer chemistry and physics, especially polymer characterization using spectroscopic methods.Actual research topics include special techniques of vibrational spectroscopy to investigate the structure of bulk polymers and polymer interfaces, hyphenated techniques, in-situ spectroscopic ellipsometry to study thin layers and (nano)structured surfaces.Polymer brushes, materials for organic electronics, for sensor and biomedical applications, but also microplastic particles from the environment are in the focus of his recent studies.Klaus-Jochen Eichhorn is member of DAAS (German Workgroup of Analytical Spectroscopy) within the German Chemical Society/ Division of Analytical Chemistry. He is board member of the German Workgroup of Ellipsometry - Paul Drude e.V. and member of the program committee of the International Conference on Spectroscopic Ellipsometry (ICSE). He organized the 14th and 20th European Symposium on Polymer Spectroscopy (ESOPS 14 and 20) in 2002 and 2016 in Dresden and is member of the ESOPS International Advisory Board.

Foreword 6
Acknowledgements 7
Contents 8
Contributors 18
Introduction to Book Contents 22
References 25
1 Ellipsometry: A Survey of Concept 26
1.1 Classification 26
1.2 Historical Context 29
1.3 Measurement Principles 30
1.3.1 Data Recording and Evaluation Steps 30
1.3.2 Determination of and ? 33
1.3.3 Fresnel Coefficients 38
1.4 Dielectric Properties 44
1.4.1 Dispersion Models—Lorentz Oscillator 44
1.4.2 Inhomogeneous Media and Structured Interfaces 46
1.5 Ellipsometric Configurations 47
1.5.1 Null-Ellipsometer 48
1.5.2 Rotating Polarizer/Analyzer 48
1.5.3 Rotating Compensator 48
1.5.4 Photo-Elastic Modulator Ellipsometer 49
1.5.5 Dual Rotating Compensator 49
1.5.6 Reflection Anisotropy Spectroscopy 50
References 50
Biomolecules at Surfaces 53
2 Adsorption of Proteins at Solid Surfaces 54
2.1 Introduction 54
2.1.1 Historical Background 54
2.1.2 Opportunities and Challenges 55
2.1.3 Objectives and Outline 56
2.2 Methodology—Experimental Aspects 57
2.3 Methodology—Modeling Aspects 58
2.3.1 Strategies to Determine Both Thickness and Refractive Index 58
2.3.2 Spectral Representations of Protein Layers 61
2.3.3 Determination of Surface Mass Density 61
2.4 Applications 62
2.4.1 Protein Adsorption and Dynamics on Model Surfaces 62
2.4.2 Studies of Protein Layer Structure 62
2.4.3 Protein Layer Based Biosensing 66
2.4.4 Other Applications 69
2.5 Outlook 69
References 70
3 DNA Structures on Silicon and Diamond 72
3.1 Introduction 72
3.2 Dielectric Function 74
3.3 Applications to Thin Biomolecular Films 77
3.3.1 Single DNA Bases 77
3.3.2 Single- and Double-Stranded DNA Molecules 79
3.4 Summary 83
References 84
4 Thickness and Beyond. Exploiting Spectroscopic Ellipsometry and Atomic Force Nanolithography for the Investigation of Ultrathin Interfaces of Biologic Interest 86
4.1 Introduction 87
4.2 Optical Ellipsometry of Ultrathin Interfaces: Difference Spectra 89
4.3 Atomic Force Nanolithography: Notes on Principles and Application 99
4.4 Application of SE and Atomic Force Lithography Methods to Ultrathin Soft Matter Films: Case Studies 102
4.4.1 Bio-Inert SAMs: Nanoshaving 102
4.4.2 Specific Immobilisation of Proteins on SAMs: Grafting 107
4.5 Outlook 110
References 112
Smart Polymer Surfaces and Films 117
5 Glass Transition of Polymers with Different Architectures in the Confinement of Nanoscopic Films 118
5.1 Polymers: A Unique Class of Materials and Their Physical Properties 119
5.2 Nanoscopic Polymer Films versus Bulk Polymers 120
5.2.1 Introduction 120
5.2.2 True or Mimicked Confinement Effects 121
5.2.3 Make a Long Controversial Story Short: Conclusion 122
5.3 Comparison of Analytical Methods for the Determination of Glass Transition of Polymers in Thin Polymer Films 122
5.3.1 Introduction 122
5.3.2 Ellipsometry 122
5.3.3 Broadband Dielectric Spectroscopy 123
5.3.4 AC-calorimetry 123
5.3.5 Other Techniques 124
5.4 Concepts of the Determination of Glass Transition Applying Ellipsometry 125
5.4.1 Single Wavelength Ellipsometry 125
5.4.2 Spectroscopic vis-Ellipsometry (SE) 126
5.5 Glass Transition in Thin Polymeric Films in Dependence of Film Thickness – Some Exclusive Examples 130
5.5.1 Effect of Polymer Architecture and Functional Groups 130
5.5.2 Effect of Interfacial Interactions Between Polymer and Substrate 131
5.6 Summary and Outlook 133
References 134
6 Polymer Brushes, Hydrogels, Polyelectrolyte Multilayers: Stimuli-Responsivity and Control of Protein Adsorption 136
6.1 Introduction 137
6.2 Ellipsometry on Swellable, Stimuli-Responsive Surface Layers 140
6.2.1 Hydrophilic Polymer Brushes 140
6.2.2 Hydrogels 147
6.2.3 Polyelectrolyte Multilayers 149
6.3 Concepts of Determining the Adsorbed Amount of Protein on Different Polymer Films 150
6.4 Protein Adsorption on Different Types of Smart Polymer Brushes 153
6.4.1 Polymer Brushes Preventing Protein Adsorption 153
6.4.2 Protein Adsorption at Polyelectrolyte Brushes 155
6.5 Conclusion 160
References 161
7 Structure and Interactions of Polymer Thin Films from Infrared Ellipsometry 165
7.1 Introduction 165
7.2 Composition 167
7.3 Molecular Orientation 170
7.4 Hydrated Polymer Films 175
7.4.1 In Situ Infrared Ellipsometry 176
7.4.2 Polymer Films and Brushes in Aqueous Environments 177
7.4.3 Optical Effects and the Role of Water Bands 181
7.4.4 Structure and Interactions from Quantitative In Situ IR-SE 185
7.5 Future Prospects 187
References 189
8 In Situ Spectroscopic Ellipsometry in the Field of Industrial Membranes 192
8.1 Basics of Membrane Science and Technology 193
8.1.1 Principles of Membrane-Based Separations 193
8.1.2 Advantages and Challenges in Membrane Science and Technology 194
8.1.3 Characterization of Membranes 194
8.2 Experimental Configurations and Optical Models for In-Situ Ellipsometry for Thin Films and Membranes 195
8.2.1 Design of Measurement Chambers 195
8.2.2 Optical Modeling for Swelling Films and Membranes 197
8.3 Sorption and Diffusion of Small Molecule Penetrants in Membrane Polymers 198
8.3.1 Swelling and Diffusion Mechanisms in Thin Films 198
8.3.2 Glassy Versus Rubbery Membranes – Polymer Dynamics 200
8.3.3 Membrane Plasticization Studies 202
8.4 New Generation of Membrane Materials–Metal Organic Frameworks (MOFs) and Polymers of Intrinsic Microporosity (PIMs) 205
8.5 Towards Ellipsometry Applied Directly to Membranes 208
8.6 Outlook 212
References 212
Nanostructured Surfaces and Organic/Inorganic Hybrids 215
9 Systems of Nanoparticles with SAMs and Polymers 216
9.1 Introduction 216
9.2 Modeling Nanoparticles: The Mie–Lorenz Solution 218
9.3 Distinguishing NPs Based on Their Dielectric Functions 219
9.3.1 Plasmonic Nanoparticles 220
9.3.2 Quantum Dots 222
9.4 Nanoparticles in Polymer Matrices 223
9.5 Nanoparticles and Self-assembled Monolayers 226
9.6 Effective Medium Approximations 228
9.7 Surface Coverage of 2-D Films 231
9.8 SEIRA 233
9.8.1 SEIRA Substrates 234
9.8.2 SEIRA Optical Models 235
9.8.3 Recent Advances in SEIRA 237
9.9 Conclusions and Outlook 238
References 238
10 Detection of Organic Attachment onto Highly Ordered Three-Dimensional Nanostructure Thin Films by Generalized Ellipsometry and Quartz Crystal Microbalance with Dissipation Techniques 241
10.1 Introduction 242
10.2 Surface Preparation 246
10.2.1 Glancing Angle Deposition 246
10.2.2 Atomic Layer Deposition 247
10.3 Theory 248
10.3.1 Generalized Ellipsometry 248
10.3.2 Quartz Crystal Microbalance with Dissipation 251
10.3.3 Additional Experimental Considerations 252
10.4 Review of Work in the Field 252
10.4.1 Fibronectin Protein Adsorption 252
10.4.2 Decanethiol Chemisorption 255
10.4.3 Surface-Enhanced Birefringence Chromatography 257
10.5 Conclusion 260
References 260
11 Polarizing Natural Nanostructures 262
11.1 Introduction 262
11.2 Theoretical Details and Definitions 263
11.3 The Polarizing Environment 264
11.4 Polarization Sensitivity and Vision of Animals 266
11.5 Polarization by Animals 268
11.6 Polarized Light in Reflections from Beetles 269
11.7 Concluding Remarks 280
References 281
Thin Films of Organic Semiconductors for OPV, OLEDs and OTFT 284
12 Polymer Blends and Composites 285
12.1 Introduction 286
12.2 Organic Electronics Devices 287
12.3 Spectroscopic Ellipsometry for the Investigation of Optical and Electronic Properties of OE Nanolayers 290
12.3.1 Polymer: Fullerene Blends as Photoactive Layers for OPVs 291
12.3.2 PEDOT:PSS for Transparent Electrodes 299
12.4 Summary and Outlook 305
References 306
13 Small Organic Molecules 309
13.1 Introduction 309
13.2 Phthalocyanines and Molecular Orientation in Thin Films 310
13.3 Controlling the Molecular Orientation with a Molecular Template 319
13.4 Amorphous Organic Thin Films 322
13.5 Error Sources for Determination of Molecular Orientation 323
13.6 Ultra-Thin Films 326
References 329
14 Optical Dielectric Properties of Thin Films Formed by Organic Dye Aggregates 332
14.1 Introduction 332
14.2 Excitonic Properties and Molecular Structures of Organic Aggregates 333
14.3 Optical and Structural Properties of Molecular Aggregates 337
14.4 Conclusions and Outlook 345
References 345
15 Conjugated Polymers: Relationship Between Morphology and Optical Properties 347
15.1 Introduction 347
15.2 Basic Concepts 348
15.2.1 Structure and Optical Properties 349
15.2.2 Ellipsometry and Dielectric Function 350
15.3 Examples of Structural Variations 354
15.3.1 Conformation 354
15.3.2 Crystallinity 356
15.3.3 Anisotropy 358
15.4 Blending 359
15.5 Monitoring in Real Time 361
15.6 Summary 363
References 363
16 Polarons in Conjugated Polymers 366
16.1 Introduction 367
16.1.1 ?-Conjugation 367
16.1.2 Polarons and Metal-Insulator Transitions 369
16.1.3 Charge Injection 374
16.2 P3HT 375
16.2.1 Dielectric Function 375
16.2.2 Iodine Doping 377
16.3 Electrochemical Doping of P3HT 380
16.3.1 (Spectro-)Electrochemistry 381
16.3.2 In-situ Spectroelectrochemical Ellipsometry 382
16.4 MDMO-PPV - Iodine Doping 389
16.5 Polaron Formation in Push-Pull Polymers 391
16.6 Comments on Transmission (UV-VIS) and ATR Spectroscopy 393
References 397
Developments in Ellipsometric Real-Time/In-situ Monitoring Techniques 399
17 Coupling Spectroscopic Ellipsometry and Quartz Crystal Microbalance to Study Organic Films at the Solid–Liquid Interface 400
17.1 Introduction 401
17.2 Theory 402
17.2.1 Approaches to Analyze SE Data 402
17.2.2 Approaches to Analyze QCM-D Data 408
17.3 Practice 413
17.3.1 Experimental Setup 413
17.3.2 Data Acquisition Procedure 415
17.3.3 Data Analysis Procedure 416
17.4 Applications 419
17.4.1 Solvation and Swelling of Polymer Films 421
17.4.2 Calibration Curves 422
17.4.3 Trapped Solvent in Monolayers of Discrete Nanoscale Objects 423
17.5 Conclusions and Perspectives 424
References 425
18 TIRE and SPR-Enhanced SE for Adsorption Processes 427
18.1 Introduction 427
18.2 Theory 430
18.2.1 Surface Plasmon-Polaritons 430
18.2.2 Surface Plasmon-Polariton Resonances in Ellipsometric Mode 433
18.3 Ellipsometric Setups for TIRE 435
18.4 Applications 436
18.4.1 TIRE for Bioadsorption Processes and Biosensing 436
18.4.2 Biolayer Imaging with TIRE 437
18.4.3 TIRE for Gas Adsorption Studies 440
18.5 Concluding Remarks and Outlook 441
References 441
19 In-Line Quality Control of Organic Thin Film Fabrication on Rigid and Flexible Substrates 444
19.1 Introduction 444
19.2 Adaptation of Spectroscopic Ellipsometry to r2r Fabrication Processes 445
19.3 Optical Properties of OE Nanomaterials by In-Line SE 450
19.3.1 Inorganic Barrier Layers 450
19.3.2 PEDOT:PSS Transparent Electrodes 453
19.3.3 Multilayer Structures onto PET Rolls 459
19.3.4 P3HT:PCBM Nanolayers 460
19.4 Summary and Outlook 462
References 463
20 Application of In-Situ IR-Ellipsometry in Silicon Electrochemistry to Study Ultrathin Films 466
20.1 Introduction 467
20.2 Geometry for In-Situ Electrochemical and IR-Ellipsometric Measurements on Si Surfaces 467
20.3 Preconditioning of the Si Surface by H-Termination 469
20.4 Grafting from Diazonium Compound 470
20.5 Oxidation as Consequence of Side Reactions 474
20.6 Molecular Orientation 475
20.7 Thickness Determination of the NB Film 475
20.8 IRSE Investigation of the Maleimidobenzene Modified Si Surface 476
20.9 Thickness Determination of the MB Film 477
20.10 Summary of the IRSE Investigations of Si Surfaces Modified by Diazonium Cations 477
20.11 Deposition of Ultra-Thin Polymeric Layers from Pyrrole 478
20.12 Doping of PANI Films with PSS 483
20.13 Summary 484
References 484
Infared Spectroscopic Methods for Characterization of Thin Organic Films 487
21 Characterization of Thin Organic Films with Surface-Sensitive FTIR Spectroscopy 488
21.1 Introduction 489
21.2 Attenuated Total Reflection (ATR) 490
21.3 Infrared Spectroscopy in Transmission and Reflection Modes 495
21.3.1 Transmission Mode 495
21.3.2 Reflection Mode 497
21.3.3 Polarization Modulation Infrared Reflection Absorption Spectroscopy 498
21.4 IR Spectroscopic Ellipsometry: IRSE 501
21.5 Summary 505
References 506
22 Brilliant Infrared Light Sources for Micro-ellipsometric Studies of Organic Thin Films 509
22.1 Introduction 509
22.2 Infrared Synchrotron Beamlines for Spectroscopic Ellipsometry Applications 510
22.3 Applications 512
22.3.1 Mesoscopic Samples: Biosensors and Single Flake Graphene 512
22.3.2 Nano Patterned Films: Polymer Brushes 515
22.4 Summary and Outlook 518
22.4.1 Femtosecond-Laser Based Broad Band Sources 519
22.4.2 Fourth Generation Broad Band IR/THz Light Sources 520
References 521
Optical Constants 523
23 Common Polymers and Proteins 524
24 Organic Materials for Optoelectronic Applications 531
Index 541