|
|
xi | |
Foreword |
|
xvii | |
Introduction |
|
xix | |
|
Part I Principles of Multiphoton Absorption |
|
|
1 | (94) |
|
1 Rapid Laser Optical Printing in 3D at a Nanoscale |
|
|
|
|
|
|
|
|
3 | (1) |
|
1.2 3D (Nano)polymerization: Linear Properties |
|
|
4 | (6) |
|
1.2.1 Photocure and Thermal Cure of Photoresists |
|
|
5 | (1) |
|
1.2.2 Tight Light Focusing |
|
|
6 | (2) |
|
1.2.3 Optical Properties at High Excitation: From Solid to Plasma |
|
|
8 | (2) |
|
|
10 | (3) |
|
1.3 3D (Nano)polymerization: Nonlinear Properties |
|
|
13 | (4) |
|
1.3.1 Strongest Optical Nonlinearities |
|
|
13 | (2) |
|
1.3.2 Avalanche Versus Multiphoton Excitation |
|
|
15 | (2) |
|
|
17 | (1) |
|
1.5 Conclusions and Outlook |
|
|
18 | (7) |
|
|
19 | (1) |
|
|
19 | (6) |
|
2 Characterization of 2PA Chromophores |
|
|
25 | (40) |
|
|
|
|
25 | (1) |
|
2.2 Description of Nonlinear Absorption and Refraction Processes |
|
|
26 | (5) |
|
2.2.1 Two-Photon Absorption and Bound-Electronic Nonlinear Refraction |
|
|
26 | (2) |
|
2.2.2 Excited-State Absorption and Refraction |
|
|
28 | (3) |
|
2.3 Methods for Measurements of NLA and NLR |
|
|
31 | (24) |
|
|
31 | (1) |
|
2.3.1.1 Nonlinear Transmission |
|
|
31 | (1) |
|
|
32 | (7) |
|
2.3.1.3 Determining Nonlinear Response from Pulse-width Dependence of Z-Scans |
|
|
39 | (2) |
|
2.3.1.4 White-Light-Continuum Z-Scan (WLC Z-Scan) |
|
|
41 | (2) |
|
2.3.1.5 Other Variants of the Z-Scan Method |
|
|
43 | (2) |
|
|
45 | (1) |
|
2.3.2.1 Excitation--Probe Methods |
|
|
45 | (3) |
|
2.3.2.2 White-Light-Continuum (WLC) Excite--Probe Spectroscopy |
|
|
48 | (3) |
|
2.3.2.3 Degenerate Four-Wave Mixing (DFWM) |
|
|
51 | (2) |
|
2.3.2.4 Two-Photon-Absorption-Induced Fluorescence Spectroscopy |
|
|
53 | (2) |
|
2.3.2.5 Fluorescence Anisotropy |
|
|
55 | (1) |
|
2.4 Examples of Use of Multiple Techniques |
|
|
55 | (4) |
|
|
56 | (1) |
|
|
57 | (2) |
|
|
59 | (1) |
|
|
60 | (5) |
|
|
60 | (1) |
|
|
60 | (5) |
|
3 Modeling of Polymerization Processes |
|
|
65 | (30) |
|
|
|
|
65 | (1) |
|
3.2 Basic Laser Polymerization Chemistry and Kinetic Equations |
|
|
66 | (3) |
|
3.3 Phenomenological Polymerization Threshold and Spatial Resolution |
|
|
69 | (6) |
|
3.4 Effect of Fluctuations on the Minimum Feature Size |
|
|
75 | (8) |
|
3.5 Diffusion of Molecules |
|
|
83 | (7) |
|
3.5.1 Diffusion of the Growing Chains |
|
|
84 | (2) |
|
3.5.2 Diffusion of Inhibitor: Diffusion-Assisted Direct Laser Writing |
|
|
86 | (4) |
|
|
90 | (5) |
|
|
91 | (1) |
|
|
91 | (4) |
|
Part II Equipment and Techniques |
|
|
95 | (38) |
|
4 Light Sources and Systems for Multiphoton Lithography |
|
|
97 | (14) |
|
|
|
|
97 | (1) |
|
4.2 Ultrashort-Pulse Lasers |
|
|
98 | (2) |
|
4.3 Laboratory Systems and Processing Strategy |
|
|
100 | (5) |
|
4.4 Further Processing Considerations |
|
|
105 | (6) |
|
|
108 | (3) |
|
5 STED-Inspired Approaches to Resolution Enhancement |
|
|
111 | (22) |
|
|
|
111 | (2) |
|
5.2 Stimulated Emission Depletion Fluorescence Microscopy |
|
|
113 | (4) |
|
5.3 Stimulated Emission Depletion in Multiphoton Lithography |
|
|
117 | (5) |
|
|
122 | (1) |
|
5.5 Inhibition Based on Photoinduced Electron Transfer |
|
|
123 | (3) |
|
5.6 Absorbance Modulation Lithography |
|
|
126 | (1) |
|
5.7 Challenges for Two-Color, Two-Photon Lithography |
|
|
127 | (1) |
|
|
128 | (5) |
|
|
128 | (1) |
|
|
128 | (5) |
|
|
133 | (132) |
|
6 Photoinitiators for Multiphoton Absorption Lithography |
|
|
135 | (32) |
|
|
|
6.1 Introduction for Photoinitiators for Multiphoton Absorption Lithography |
|
|
135 | (6) |
|
6.1.1 Multiphoton Absorption Lithography |
|
|
135 | (1) |
|
6.1.2 Photoinitiators for Multiphoton Absorption Lithography |
|
|
135 | (1) |
|
6.1.2.1 History of the Design of Two-Photon Initiators |
|
|
135 | (1) |
|
6.1.2.2 Property of Two-Photon Initiators |
|
|
136 | (1) |
|
6.1.3 Characterization of Two-Photon Initiators |
|
|
137 | (3) |
|
6.1.4 Molecular Design for Photoinitiators |
|
|
140 | (1) |
|
6.2 Centrosymmetric Photoinitiators |
|
|
141 | |
|
6.3 Noncentrosymmetric Photoinitiators |
|
|
153 | |
|
6.4 Application of Photoinitiators in Multiphoton Absorption Lithography |
|
|
156 | (4) |
|
|
162 | (5) |
|
|
163 | (1) |
|
|
163 | (4) |
|
7 Hybrid Materials for Multiphoton Polymerization |
|
|
167 | (16) |
|
|
|
|
167 | (1) |
|
|
168 | (1) |
|
7.3 Silicate Hybrid Materials |
|
|
169 | (2) |
|
7.4 Composite Hybrid Materials |
|
|
171 | (2) |
|
7.5 Surface and Bulk Functionalization |
|
|
173 | (2) |
|
|
175 | (1) |
|
|
176 | (7) |
|
|
176 | (7) |
|
8 Photopolymers for Multiphoton Lithography in Biomaterials and Hydrogels |
|
|
183 | (38) |
|
|
|
|
|
183 | (3) |
|
8.2 Multiphoton Lithography (MPL) for Photopolymerization |
|
|
186 | (2) |
|
8.3 MPL Equipment for Biomaterial Fabrication |
|
|
188 | (1) |
|
8.4 Chemistry for MPL Photopolymerizations |
|
|
189 | (13) |
|
8.4.1 Photopolymerization |
|
|
189 | (2) |
|
8.4.2 Photoinitiator Selection |
|
|
191 | (2) |
|
8.4.3 Photopolymer Chemistries |
|
|
193 | (1) |
|
8.4.3.1 Macromer Chemistries |
|
|
193 | (1) |
|
8.4.3.2 Photochemical Polymerization and Degradation |
|
|
194 | (8) |
|
8.5 Biomaterial Fabrication |
|
|
202 | (1) |
|
8.6 Biomaterial Modulation |
|
|
203 | (3) |
|
8.7 Biological Design Constraints |
|
|
206 | (2) |
|
|
208 | (1) |
|
|
209 | (12) |
|
|
210 | (11) |
|
9 Multiphoton Processing of Composite Materials and Functionalization of 3D Structures |
|
|
221 | (44) |
|
|
|
|
|
|
|
221 | (4) |
|
9.2 Polymer--Organic Composites |
|
|
225 | (5) |
|
9.2.1 Fluorescent-Dye-Doped Organic Microstructures |
|
|
225 | (2) |
|
9.2.2 Organic Composites for Lasing Microstructures |
|
|
227 | (1) |
|
9.2.3 Organic Composites for Electrically Conductive Microstructures |
|
|
227 | (2) |
|
9.2.4 Other Optically Active Microstructures |
|
|
229 | (1) |
|
9.3 Multiphoton Processing of Oxide-Based Materials |
|
|
230 | (5) |
|
|
231 | (1) |
|
|
231 | (1) |
|
|
232 | (1) |
|
|
232 | (1) |
|
|
233 | (1) |
|
|
234 | (1) |
|
|
234 | (1) |
|
9.4 Multiphoton Processing of Metallic Composites and Materials |
|
|
235 | (11) |
|
9.4.1 Thermal Evaporation |
|
|
236 | (1) |
|
|
236 | (1) |
|
9.4.3 Magnetron Sputtering |
|
|
236 | (1) |
|
9.4.4 Chemical Vapor Deposition |
|
|
237 | (1) |
|
9.4.5 Functionalization by Attachment of Nanoparticles |
|
|
238 | (1) |
|
9.4.6 Electroless Metallization from Solution |
|
|
239 | (3) |
|
9.4.7 Multiphoton Lithography of Nanoparticles Supported in a Polymer Matrix |
|
|
242 | (2) |
|
9.4.8 Direct Writing of Continuous-Metal Microstructures |
|
|
244 | (1) |
|
9.4.9 Metal Backfilling by Electroplating |
|
|
245 | (1) |
|
9.5 Multiphoton Processing of Semiconductor Composites and Materials |
|
|
246 | (2) |
|
9.5.1 Structures Functionalized with Nanoparticles |
|
|
246 | (1) |
|
9.5.2 Structures Functionalized using NP-Polymer Composites |
|
|
246 | (1) |
|
9.5.3 Structures Functionalized by In Situ NP Formation |
|
|
247 | (1) |
|
9.5 A Structures Functionalized by NP Coating |
|
|
248 | (6) |
|
9.5.5 Structures Functionalized by Silicon Inversion |
|
|
250 | (2) |
|
9.5.6 Functional Structures Fabricated in Bulk Chalcogenide Glasses |
|
|
252 | (1) |
|
9.5.7 Structures Fabricated in ChG Film |
|
|
252 | (2) |
|
9.5.8 Structures Fabricated in ChG--NP Composites |
|
|
254 | (1) |
|
|
254 | (11) |
|
|
255 | (1) |
|
|
255 | (10) |
|
|
265 | (88) |
|
10 Fabrication of Waveguides and Other Optical Elements by Multiphoton Lithography |
|
|
267 | (30) |
|
|
|
|
|
|
|
267 | (1) |
|
10.2 Acrylate Monomers for Multiphoton Lithography |
|
|
268 | (9) |
|
|
277 | (3) |
|
10.4 Sol--Gel-Derived Resins |
|
|
280 | (4) |
|
10.5 Cationic Polymerization and Stereolithography |
|
|
284 | (3) |
|
10.6 Materials Based on Multiphoton Photochromism |
|
|
287 | (5) |
|
|
292 | (5) |
|
|
292 | (1) |
|
|
292 | (5) |
|
11 Fabricating Nano and Microstructures Made by Narrow Bandgap Semiconductors and Metals using Multiphoton Lithography |
|
|
297 | (18) |
|
|
|
|
|
297 | (1) |
|
11.2 Fabrication of 3D Structures Made by PbSe with Multiphoton Lithography |
|
|
298 | (6) |
|
11.2.1 Challenges of Multiphoton Lithography with Top-Down Approach for Narrow Electronic Bandgap Semiconductors |
|
|
298 | (1) |
|
11.2.2 Photoresin Development |
|
|
299 | (3) |
|
11.2.3 Two-Photon Lithography of PbSe Structures |
|
|
302 | (1) |
|
11.2.4 Confirmation of PbSe Formation |
|
|
303 | (1) |
|
11.3 Fabrication of Silver Structures with Multiphoton Lithography |
|
|
304 | (6) |
|
11.3.1 Principle of Resolution Improvement by Increasing Photosensitivity in Photoreduction |
|
|
305 | (1) |
|
11.3.2 Photosensitivity Enhancement by Tuning Laser Wavelength |
|
|
305 | (3) |
|
11.3.3 Dot Size Model Based on Photosensitivity |
|
|
308 | (2) |
|
11.3.4 Further Increase the Photosensitivity with an Electron Donor |
|
|
310 | (1) |
|
|
310 | (5) |
|
|
312 | (1) |
|
|
312 | (3) |
|
12 Microfluidic Devices Produced by Two-Photon-Induced Polymerization |
|
|
315 | (20) |
|
|
|
315 | (1) |
|
12.2 Fabrication of Movable Micromachines |
|
|
316 | (4) |
|
12.3 Optically Driven Micromachines |
|
|
320 | (5) |
|
12.4 Microfluidic Devices Driven by a Scanning Laser Beam |
|
|
325 | (2) |
|
12.5 Microfluidic Devices Driven by a Focused Laser Beam |
|
|
327 | (3) |
|
12.6 Microfluidic Devices Driven by an Optical Vortex |
|
|
330 | (1) |
|
|
331 | (4) |
|
|
332 | (3) |
|
13 Nanoreplication Printing and Nanosurface Processing |
|
|
335 | (18) |
|
|
13.1 Introduction: Limitations of Multiphoton Lithography |
|
|
335 | (1) |
|
13.2 Micro-transfer Molding (μTM) |
|
|
336 | (2) |
|
13.3 μTM of Complex Geometries |
|
|
338 | (1) |
|
13.4 Nano-replication of Other Materials |
|
|
339 | (3) |
|
13.5 Nanosurface Metallization Processing |
|
|
342 | (2) |
|
13.6 Nanosurface Structuring via Ablation |
|
|
344 | (5) |
|
13.7 Conclusion and Future Directions |
|
|
349 | (4) |
|
|
351 | (2) |
|
Part V Biological Applications |
|
|
353 | (24) |
|
14 Three-Dimensional Microstructures for Biological Applications |
|
|
355 | (22) |
|
|
|
|
|
|
355 | (2) |
|
14.2 3D Structures for Cells Studies |
|
|
357 | (6) |
|
14.3 Biocompatible Materials |
|
|
363 | (5) |
|
14.4 Scaffolds for Bacterial Investigation |
|
|
368 | (3) |
|
14.5 Microstructures for Drug Delivery |
|
|
371 | (3) |
|
|
374 | (3) |
|
|
374 | (3) |
Index |
|
377 | |