List of Contributors XI
Foreword XVII
Introduction XIX
Part I Principles of Multiphoton Absorption 1
1 Rapid Laser Optical Printing in 3D at a Nanoscale 3
Albertas ukauskas, Mangirdas Malinauskas, Gediminas Seniutinas, and Saulius Juodkazis
1.1 Introduction 3
1.2 3D (Nano)polymerization: Linear Properties 4
1.2.1 Photocure andThermal Cure of Photoresists 5
1.2.2 Tight Light Focusing 6
1.2.3 Optical Properties at High Excitation: From Solid to Plasma 8
1.2.4 Heat Accumulation 10
1.3 3D (Nano)polymerization: Nonlinear Properties 13
1.3.1 Strongest Optical Nonlinearities 13
1.3.2 Avalanche Versus Multiphoton Excitation 15
1.4 Discussion 17
1.5 Conclusions and Outlook 18
Acknowledgments 19
References 19
2 Characterization of 2PA Chromophores 25
EricW. Van Stryland and David J. Hagan
2.1 Introduction 25
2.2 Description of Nonlinear Absorption and Refraction Processes 26
2.2.1 Two-Photon Absorption and Bound-Electronic Nonlinear Refraction 26
2.2.2 Excited-State Absorption and Refraction 28
2.3 Methods for Measurements of NLA and NLR 31
2.3.1 Direct Methods 31
2.3.1.1 Nonlinear Transmission 31
2.3.1.2 Z-Scan 32
2.3.1.3 Determining Nonlinear Response from Pulse-width Dependence of Z-Scans 39
2.3.1.4 White-Light-Continuum Z-Scan (WLC Z-Scan) 41
2.3.1.5 Other Variants of the Z-Scan Method 43
2.3.2 Indirect Methods 45
2.3.2.1 Excitationâ"Probe Methods 45
2.3.2.2 White-Light-Continuum (WLC) Exciteâ"Probe Spectroscopy 48
2.3.2.3 Degenerate Four-Wave Mixing (DFWM) 51
2.3.2.4 Two-Photon-Absorption-Induced Fluorescence Spectroscopy 53
2.3.2.5 Fluorescence Anisotropy 55
2.4 Examples of Use of Multiple Techniques 55
2.4.1 Squaraine Dye 56
2.4.2 Tetraone Dye 57
2.5 Other Methods 59
2.6 Conclusion 60
Acknowledgments 60
References 60
3 Modeling of Polymerization Processes 65
Alexander Pikulin and Nikita Bityurin
3.1 Introduction 65
3.2 Basic Laser Polymerization Chemistry and Kinetic Equations 66
3.3 Phenomenological PolymerizationThreshold and Spatial Resolution 69
3.4 Effect of Fluctuations on the Minimum Feature Size 75
3.5 Diffusion of Molecules 83
3.5.1 Diffusion of the Growing Chains 84
3.5.2 Diffusion of Inhibitor: Diffusion-Assisted Direct LaserWriting 86
3.6 Conclusion 90
Acknowledgements 91
References 91
Part II Equipment and Techniques 95
4 Light Sources and Systems for Multiphoton Lithography 97
Ulf Hinze and Boris Chichkov
4.1 Laser Light Sources 97
4.2 Ultrashort-Pulse Lasers 98
4.3 Laboratory Systems and Processing Strategy 100
4.4 Further Processing Considerations 105
References 108
5 STED-Inspired Approaches to Resolution Enhancement 111
John T. Fourkas
5.1 Introduction 111
5.2 Stimulated Emission Depletion Fluorescence Microscopy 113
5.3 Stimulated Emission Depletion in Multiphoton Lithography 117
5.4 Photoinhibition 122
5.5 Inhibition Based on Photoinduced Electron Transfer 123
5.6 Absorbance Modulation Lithography 126
5.7 Challenges for Two-Color, Two-Photon Lithography 127
5.8 Conclusions 128
Acknowledgments 128
References 128
Part III Materials 133
6 Photoinitiators for Multiphoton Absorption Lithography 135
Mei-Ling Zheng and Xuan-Ming Duan
6.1 Introduction for Photoinitiators for Multiphoton Absorption Lithography 135
6.1.1 Multiphoton Absorption Lithography 135
6.1.2 Photoinitiators for Multiphoton Absorption Lithography 135
6.1.2.1 History of the Design of Two-Photon Initiators 135
6.1.2.2 Property of Two-Photon Initiators 136
6.1.3 Characterization of Two-Photon Initiators 137
6.1.4 Molecular Design for Photoinitiators 140
6.2 Centrosymmetric Photoinitiators 141
6.3 Noncentrosymmetric Photoinitiators 153
6.4 Application of Photoinitiators in Multiphoton Absorption Lithography 156
6.5 Conclusion 162
Acknowledgment 163
References 163
7 Hybrid Materials for Multiphoton Polymerization 167
Alexandros Selimis and Maria Farsari
7.1 Introduction 167
7.2 Solâ"Gel Preparation 168
7.3 Silicate Hybrid Materials 169
7.4 Composite Hybrid Materials 171
7.5 Surface and Bulk Functionalization 173
7.6 Replication 175
7.7 Conclusions 176
References 176
8 Photopolymers for Multiphoton Lithography in Biomaterials and Hydrogels 183
Mark W. Tibbitt, Jared A. Shadish, and Cole A. DeForest
8.1 Introduction 183
8.2 Multiphoton Lithography (MPL) for Photopolymerization 186
8.3 MPL Equipment for Biomaterial Fabrication 188
8.4 Chemistry for MPL Photopolymerizations 189
8.4.1 Photopolymerization 189
8.4.2 Photoinitiator Selection 191
8.4.3 Photopolymer Chemistries 193
8.4.3.1 Macromer Chemistries 193
8.4.3.2 Photochemical Polymerization and Degradation 194
8.5 Biomaterial Fabrication 202
8.6 Biomaterial Modulation 203
8.7 Biological Design Constraints 206
8.8 Biologic Questions 208
8.9 Outlook 209
References 210
9 Multiphoton Processing of Composite Materials and Functionalization of 3D Structures 221
Casey M. Schwarz, Christopher N. Grabill, Jennefir L. Digaum, Henry E.Williams, and Stephen M. Kuebler
9.1 Overview 221
9.2 Polymerâ"Organic Composites 225
9.2.1 Fluorescent-Dye-Doped Organic Microstructures 225
9.2.2 Organic Composites for Lasing Microstructures 227
9.2.3 Organic Composites for Electrically Conductive Microstructures 227
9.2.4 Other Optically Active Microstructures 229
9.3 Multiphoton Processing of Oxide-Based Materials 230
9.3.1 Titanium Dioxide 231
9.3.2 Zinc Oxide 231
9.3.3 Zirconium Dioxide 232
9.3.4 Iron Oxide 232
9.3.5 Tin Dioxide 233
9.3.6 Germanium Dioxide 234
9.3.7 Silicon Dioxide 234
9.4 Multiphoton Processing of Metallic Composites and Materials 235
9.4.1 Thermal Evaporation 236
9.4.2 e-Beam Evaporation 236
9.4.3 Magnetron Sputtering 236
9.4.4 Chemical Vapor Deposition 237
9.4.5 Functionalization by Attachment of Nanoparticles 238
9.4.6 Electroless Metallization from Solution 239
9.4.7 Multiphoton Lithography of Nanoparticles Supported in a Polymer Matrix 242
9.4.8 DirectWriting of Continuous-Metal Microstructures 244
9.4.9 Metal Backfilling by Electroplating 245
9.5 Multiphoton Processing of Semiconductor Composites and Materials 246
9.5.1 Structures Functionalized with Nanoparticles 246
9.5.2 Structures Functionalized using NPâ"Polymer Composites 246
9.5.3 Structures Functionalized by In Situ NP Formation 247
9.5.4 Structures Functionalized by NP Coating 248
9.5.5 Structures Functionalized by Silicon Inversion 250
9.5.6 Functional Structures Fabricated in Bulk Chalcogenide Glasses 252
9.5.7 Structures Fabricated in ChG Film 252
9.5.8 Structures Fabricated in ChGâ"NP Composites 254
9.6 Conclusion 254
Acknowledgments 255
References 255
Part IV Applications 265
10 Fabrication ofWaveguides and Other Optical Elements by Multiphoton Lithography 267
Samuel Clark Ligon, Josef Kumpfm¼ller, Niklas Pucher, J¼rgen Stampfl, and Robert Liska
10.1 Introduction 267
10.2 Acrylate Monomers for Multiphoton Lithography 268
10.3 Thiolâ"Ene Resins 277
10.4 Solâ"Gel-Derived Resins 280
10.5 Cationic Polymerization and Stereolithography 284
10.6 Materials Based on Multiphoton Photochromism 287
10.7 Conclusions 292
Acknowledgments 292
References 292
11 Fabricating Nano and Microstructures Made by Narrow Bandgap Semiconductors and Metals using Multiphoton Lithography 297
Min Gu, Zongsong Gan, and Yaoyu Cao
11.1 Introduction 297
11.2 Fabrication of 3D Structures Made by PbSe with Multiphoton Lithography 298
11.2.1 Challenges of Multiphoton Lithography with Top-Down Approach for Narrow Electronic Bandgap Semiconductors 298
11.2.2 Photoresin Development 299
11.2.3 Two-Photon Lithography of PbSe Structures 302
11.2.4 Confirmation of PbSe Formation 303
11.3 Fabrication of Silver Structures with Multiphoton Lithography 304
11.3.1 Principle of Resolution Improvement by Increasing Photosensitivity in Photoreduction 305
11.3.2 Photosensitivity Enhancement by Tuning LaserWavelength 305
11.3.3 Dot Size Model Based on Photosensitivity 308
11.3.4 Further Increase the Photosensitivity with an Electron Donor 310
11.4 Conclusions 310
Acknowledgments 312
References 312
12 Microfluidic Devices Produced by Two-Photon-Induced Polymerization 315
Shoji Maruo
12.1 Introduction 315
12.2 Fabrication of Movable Micromachines 316
12.3 Optically Driven Micromachines 320
12.4 Microfluidic Devices Driven by a Scanning Laser Beam 325
12.5 Microfluidic Devices Driven by a Focused Laser Beam 327
12.6 Microfluidic Devices Driven by an Optical Vortex 330
12.7 Future Prospects 331
References 332
13 Nanoreplication Printing and Nanosurface Processing 335
Christopher N. LaFratta
13.1 Introduction: Limitations of Multiphoton Lithography 335
13.2 Micro-transfer Molding (μTM) 336
13.3 μTM of Complex Geometries 338
13.4 Nano-replication of Other Materials 339
13.5 Nanosurface Metallization Processing 342
13.6 Nanosurface Structuring via Ablation 344
13.7 Conclusion and Future Directions 349
References 351
Part V Biological Applications 353
14 Three-Dimensional Microstructures for Biological Applications 355
Adriano J. G. Otuka, Vinicius Tribuzi, Daniel S. Correa, and Cleber R. Mendon§a
14.1 Introduction 355
14.2 3D Structures for Cells Studies 357
14.3 Biocompatible Materials 363
14.4 Scaffolds for Bacterial Investigation 368
14.5 Microstructures for Drug Delivery 371
14.6 Final Remarks 374
References 374
Index 377
