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of Nanotechnology Bharat Bhushan (Ed.)

h\\\ Edition With 1325 Figures and 100 Tables

4y Sprin er

Contents

List of Abbreviations XXXIII

1 Introduction to Nanotechnology Bharat Bhushan 1 1.1 Nanotechnology- Definitionsand Examples 2 1.2 History and Early Research Expenditures 6 1.3 Governance of the National Nanotechnology Initiative 7 l.k Nanotechnology R&D Funding Since 2001 8 1.5 Worldwide R&D Investments and Output 11 1.6 Translation of Basic Research to Technology Commercialization .... 15 1.7 Nanoscience and Nanotechnology Education 16 1.8 Summary and Outlook 17 1.9 Organization of the Handbook 18 References 18

Part A Micro/Nanofabrication Techniques

2 Molecule-Based Devices Francisco M. Raymo 23 2.1 Chemical Approaches to Nanostructured Materials 2k 2.2 Molecular Switches and Logic Gates 28 2.3 Solid-State Devices 35 l.k Conclusions and Outlook k6 References kl

3 introduction to Micro-/Nanofabrication Gemma Rius, Antoni Baldi, Babak Ziaie, Massood Z. Atashbar 51 3.1 Basic Microfabrication Techniques 52 3.2 MEMS Fabrication Techniques 62 3.3 Nanofabrication Techniques lk l.k Summary and Conclusions 82 References 82

k 3-D Nanostructure Fabrication by Focused-ion Beam, Electron- and Laser Beam Shinji Matsui, Hiroaki Misawa, Quan Sun 87 ^.1 Various 3-D Nanostructure Fabrication Techniques 88 k.l 3-D Nanostructure Fabrication by Focused Ion Beam 88 k.3 3-D Nanostructure Fabrication by Electron Beam 97 k.k 3-D Nanostructure Fabrication by Laser 103 References 109

5 Nanoimprint Lithography Helmut Schift, Anders Kristensen 113 5.1 Emerging Nanopatterning Methods 115 5.2 Nanoimprint Process 119 5.3 Tools and Materials for Nanoimprint 125

5.4 Applications 132 5.5 Conclusion and Outlook 137 References 138

6 Stamping Technlques for Micro- and Nanofabrication John A. Rogers, Etienne Menard 143 6.1 High-Resolution Stamps 144 6.2 Microcontact Printing 146 6.3 Nanotransfer Printing 148 6.4 Applications 152 6.5 Conclusions 159 References 159

7 Materials Aspects of Micro- and Nanoelectromechanicai Systems Christian A. Zorman 163 7.1 Silicon and its Commonly-Used Derivatives 163 7.2 Germanium-Based Materials 170 7.3 Metals 171 7.4 Semiconductorsfor Harsh Environment Applications 173 7.5 QaAs, InP and Related lll-V Materials 178 7.6 Piezoelectric Materials 180 7.7 Polymer Materials 183 7.8 Future Trends 185 References 185

Part B Nanomaterial and Nanostructures

8 Carbon Nanotubes MarcMonthioux, PhilippeSerp, Brigitte Caussat, Emmanuel Flahaut, Manitra Razafinimanana, Flavien Valensi, Christophe Laurent, Alain Peigney, David Mesguich, Alicia Weibel, Wolfgang Bacsa, Jean-Marc Broto 193 8.1 Structure of Carbon Nanotubes 194 8.2 Synthesis of Carbon Nanotubes 199 8.3 Growth Mechanisms of Carbon Nanotubes 210 8.4 Properties of Carbon Nanotubes 213 8.5 Carbon Nanotube-Based Nano-Objects (Carbon Meta-Nanotubes). 217 8.6 Carbon-Nanotube-Containing Materials (Composites) 223 8.7 Current Applications of Carbon Nanotubes (on the Market) 227 8.8 Toxicity and Environmental Impact of Carbon Nanotubes 231 8.9 Concluding Remarks 233 References 233

9 Nanowires Mildred S. Dresselhaus, Marcie R. Black, Vincent Meunier, Oded Rabin 249 9.1 Synthesis 250 9.2 Characterization and Physical Properties of Nanowires 262 9.3 Applications 282 9.4 Concluding Remarks 290 References 290

10 Nanoribbons Toshiaki Enoki, Shintaro Sato 303 10.1 Graphene Nanoribbons 303 10.2 Electronic and Magnetic Properties 305 10.3 Characterizations 310 10.it Syntheses: Top-Down Methods and Bottom-Up Methods 317 10.5 Potential Applications 324 10.6 Conclusions 330 References 331

11 Nanoparticies and Their Applications Seyedsina Moeinzadeh, Esmaiel Jabbari 335 11.1 Overview 335 11.2 NPs Classification and Synthesis 336 11.3 Properties of NPs 348 I I A Applications of NPs 351 11.5 Summary 353 References 353

12 Graphene Aravind Vijayaraghavan, Maria Mut 363 12.1 Methods of Production 365 12.2 Properties 369 12.3 Characterization 372 12.4 Applications 376 12.5 Conclusions and Outlook 385 References 386

PartC MEMS/NEMS

13 MEMS/NEMS Devices and Applications Philip X.-L. Feng, Darrin J. Young, Christian A. Zorman 395 13.1 MEMS Devices and Applications 397 13.2 NEMS Devicesand Applications 415 13.3 Challenges and Perspectives 425 References 426

U Single-Wailed Carbon Nanotube Sensor Concepts Cosmin I. Roman, Thomas Helbling, Miroslav Haluska, Christofer Hierold . 431 14.1 Sensor Design Considerations 432 14.2 Sensor Fabrication: SWNT Synthesis and Integration 439 14.3 Summary of State-of-the-Art, Applications Examples 445 14.4 Concluding Remarks 451 References 451

15 Nanomechanical Cantilever Array Sensors Hans Peter Lang, Martin Hegner, Christoph Gerber 457 15.1 Technique 458 15.2 Cantilever Array Sensors 459 15.3 Modes of Operation 460 15.4 Microfabrication 464

15.5 Measurement Setup 465 15.6 Functionalization Techniques 468 15.7 Applications 470 15.8 Conclusions and Outlook 476 References 477

16 Microfluidic Devices and Their Applications Aditya Aryasomayajula, Pouriya Bayat, Pouya Rezai, P. Ravi Selvaganapathy 487 16.1 Preface 487 16.2 Historical Developments 489 16.3 Dominant Phenomenon and Micro-Nanofluidic Design 491 16.4 Fabrication of Micro-Nanofluidic Devices 496 16.5 Applications 504 16.6 Outlook and Future Directions 521 References 522

17 Microfluidic Micro/Nano Droplets Gopakumar Kamalakshakurup, Derek Vallejo, Abraham Lee 537 17.1 Introduction to Micro/Nano Droplet Microfluidic Technologies 537 17.2 Overview ofCurrent Trends in Droplet Microfluidic Technologies ... 546 17.3 Fundamental Designs and Techniques for Microfluidic

Generation of Droplets 547 17.4 Microfluidic Micro-/Nanodroplet Applications 550 17.5 Conclusion 556 References 556

18 Nanorobotics BradleyJ. Nelson, Lixin Dong 559 18.1 Overview of Nanorobotics 560 18.2 Actuation at Nanoscales 561 18.3 Nanorobotic Manipulation Systems 563 18.4 Nanorobotic Assembly 568 18.5 Applications 576 References 580

Part D BioMEMS/NEMS

19 Applications of MEMS to Cell Biology Georg E. Fantner, Pascal D. Odermatt, Haig Alexander Eskandarian 587 19.1 Biological Background 588 19.2 High Resolution Microscopy Methods for Live Cell Imaging 592 19.3 Measuring Mechanical Properties on Living Cells 593 19.4 Cancer Detection Using Nanomechanical Sensors 596 19.5 Measurement of Cell Adhesion Using Cantilever Based Force Sensor 599 19.6 Manipulation of Cells Using MEMS Cantilevers 602 19.7 Mass Measurements of Single Cells Using Resonant Cantilevers 603 19.8 Characterization of Antibiotic Action Using MEMS Devices 606 19.9 Conclusions and Outlook 609 References 609

20 Contact-free Mechanica! Manipulation of Biological Materials Jörg Schnauß, Josef A. Käs, David M. Smith 617 20.1 Interaction of Laser Light with Biological Material 618 20.2 Optical and MagneticTweezersfor Single-Molecule Manipulations 621 20.3 Optical and Electric Forces for the Manipulation of Whole Cells 629 20.4 Hydrodynamic Shear Forces for the Manipulation of Single Cells ... 636 20.5 Conclusion and Outlook 638 References 638

21 Nano-Particles for Bfomedicaf Applications Paolo Decuzzi, Alessandro Coclite, Aeju Lee, Anna Lisa Palange, Daniele Di Mascolo, uro Chiappini, Helder A. Santos, Maria Laura Coluccio, Gerardo Perozziello, Patrizio Candeloro, Enzo Di Fabrizio, Francesco Gentile 643 21.1 Ove rview 644 21.2 Rational Design of Nanoconstructs 646 21.3 Multifunctional Polymerie Nanoconstructs 650 21.4 Sensing and Drug Delivery with Porous Silicon Nanomaterials 655 21.5 Nanomedicine Synthesis by Microfluidics Technology 662 21.6 Electroless Formation of Metal Nanoparticle Aggregates 669 21.7 2-D and 3-D Optical Nanostructures 677 References 681

22 Biological Molecules in Therapeutic Nanodevices Stephen C. Lee, Bharat Bhushan 693 22.1 Definitions and Scope 694 22.2 Assembly Approaches 700 22.3 Sensing Devices 710 22.4 Concluding Remarks: Barriers to Practice 717 References 718

Part E Nanometrology

23 Scanning Probe Microscopy -Principle of Operation, Instrumentation and Probes Bharat Bhushan, Othmar Marti 725 23.1 Scanning Tunneling Microscope 727 23.2 Atomic Force Microscope 731 23.3 AFM Instrumentation and Analyses 747 23.4 Conclusion 763 References 763

24 Low-Temperature Scanning Probe Microscopy Mehmet Z. Baykara, Markus Morgenstern, Alexander Schwarz, Udo D. Schwarz 769 24.1 Microscope Operation at Low Temperatures 771 24.2 Instrumentation 772 24.3 Scanning Tunneling Microscopy and Spectroscopy 773 24.4 Scanning Force Microscopy and Spectroscopy 788 24.5 Summary 799 References 799

XXVI Contents

25 Biomedica! Sensing with the Atomic Force Microscope Constanze Lamprecht, Jürgen Strasser, Melanie Koehler, Sandra Posch, Yoojin Oh, Rong Zhu, Lilia A. Chtcheglova, Andreas Ebner, Peter Hinterdorfer 809 25.1 Topographical Imaging of Biological Samples 810 25.2 Single-Molecule Force Spectroscopy (SMFS) 814 25.3 Simultaneous Topography and Recognition Imaging (TREC) 821 25 .4 AFM Biomedical Sensing - Examples 827 25.5 Perspectives and Concluding Remarks 836 References 837

26 Superresolution Microscopy Tom D. Muster 845 26.1 Overview 845 26.2 Scanning Aperture Techniques 849 26.3 4-Pi Microscopy 853 26.4 Enhancement/Depletion Techniques 854 26.5 Photoactivated Localization 856 26.6 Structured Illumination 858 26.7 Light-Sheet Microscopy 862 26.8 Comparison of Techniques for Live-Cell Imaging 863 26.9 Summa ry 864 References 864

Part F Bio/Nanotribology and Bio/Nanomechanics

27 Nanotribology, Nanomechanics and Materials Characterization BharatBhushan 869 27.1 Description of AFM/FFM and Various MeasurementTechniques 871 27.2 Surface Imaging, Friction, and Adhesion 882 27.3 Micro/Nanoscale Wear and Scratching, Local Deformation,

and Nanofabrication/Nanomachining 906 27.4 Indentation 915 27.5 Boundary Lubrication 919 27.6 Conclusion 928 References 929

28 Surface Forces and Nanorheology of Molecularly Thin FÜms Dong Woog Lee, Marina Ruths, Jacob N. Israelachvili 935 28.1 Types of Surface Forces 936 28.2 Methods Used to Study Surface Forces 938 28.3 Normal Forces Between Dry (Unlubricated) Surfaces 941 28.4 Normal Forces Between Surfaces in Liquids 942 28.5 Adhesion and Capillary Forces 951 28.6 Introduction: Different Modes of Friction 956 28.7 Relationship Between Adhesion and Friction 957 28.8 Liquid Lubricated Surfaces 966 28.9 Effects of Nanoscale Texture on Friction 976 References 978

29 Atomic Scale Friction Phenomena Enrico Gnecco, Remy Pawlak, Marcin Kisiel, Thilo Glatzel, Ernst Meyer 987 29.1 Friction Force Microscopy in Selected Environments 988 29.2 The Prandtl-Tomlinson Model 993 29.3 Friction Experiments on the Atomic Scale 996 29.4 Thermal Effects on Atomic Friction 998 29.5 Friction on the Manometer Scale 999 29.6 Wearon the Atomic Scale 1002 29.7 Noncontact Friction 1003 29.8 Single Molecule Friction 1005 29.9 Conclusion 1008 References 1008

30 Computer Simulat ions of Nanometer-Scaie Sndentation and Friction Susan B. Sinnott, Seong-Jun Heo, Donald W. Brenner, Judith A. Harrison, Douglas L. Irving 1013 30.1 Computational Details 1014 30.2 Indentation 1019 30.3 Friction and Lubrication 1033 30.4 Conclusions 1058 References 1058

31 Cellular Nanomechanics Roger D. Kamm, Jan Lammerding, Mohammad R. K. Mofrad 1069 31.1 Overview 1069 31.2 Structural Components of a Cell 1071 31.3 Experimental Methods 1077 31.4 Theoretical and Computational Descriptions 1082 31.5 Mechanics of Subcellular Structures 1086 31.6 Current Understanding and Future Needs 1095 References 1096

32 Nanomechanicai Properties of Nanostructures and Scale Effects Bharat Bhushan 1101 32.1 Experimental Techniques for Measurement of Mechanical

Properties of Nanostructures 1103 32.2 Experimental Results and Discussion 1109 32.3 Finite Element Analysis of Nanostructures with Roughness

and Scratches 1125 32.4 Summary 1131 32.A Appendix: Fabrication Procedure for the Double-Anchored

and Cantilever Beams 1132 References 1134

Part G Molecularly-Thick Films for Lubrication

33 Nanotriboiogy of Ultrathin and Hard Amorphous Carbon Films Bharat Bhushan 1141 33.1 Description of Commonly Used Deposition Techniques 1145 33.2 Chemical Characterization and Effect of Deposition Conditions

on Chemical Characteristics and Physical Properties 1149 33.3 Micromechanical and Tribological Characterizations

of Coatings Deposited by Various Techniques 1154 33.4 Conclusion 1174 References 1175

34 Seff-Ässembfed Monoiayers for Nanotriboiogy and Surface Protection Bharat Bhushan 1179 34.1 Background 1179 34.2 A Primer on Organic Chemistry 1182 34.3 Self-Assembled Monoiayers: Substrates, Spacer Chains,

and End Groups in the Molecular Chains 1186 34.4 Contact Angle and Nanotribological Properties of SAMs 1189 34.5 Conclusion 1209 References 1210

35 Nanoscale Boundary Lubrication Studies Bharat Bhushan 1215 35.1 Nanodeformation, Molecular Conformation, Spreading,

Nanotribological and Electrical Studies, and Environmental Effects of Commonly Used PFPE Lubricant Films 1216

35.2 Nanotribological, Electrical, and Chemical Degradations Studies and Environmental Effects in Novel PFPE Lubricant Films .. 1233

35.3 Nanotribological and Electrical Studies of lonic Liquid Films 1242 35.4 Conclusion 1257 References 1258

Part H Biomimetks and Bioinspired Surfaces

36 Plant Surfaces: Structures and Functions for Biomimetic Applications Wilhelm Barthlott, Matthias Mail, Bharat Bhushan, Kerstin Koch 1265 36.1 500 Million Years of Evolution for Innovative Technologies 1266 36.2 Chemistry of Plant Surfaces 1270 36.3 Structuring of Plant Surfaces:

Hierarchical Architecture Between Nano- and Macrostructures 1279 36.4 Physical Basis of Surface Wetting 1285 36.5 Superhydrophilic and Superhydrophobic Plant Surfaces 1286 36.6 Functional Diversity of Plant Surfaces 1289 36.7 Biomimetic Application 1294 36.8 Living Prototypes: Evolution of Plant Surfaces and Biodiversity 1297 36.9 Conclusions v 1298 References 1298

37 Bioinspired Nanostructured Antibiofouling and Anti-inorganic Surfaces Bharat Bhushan 1307 37.1 Fields Susceptible to Fouling 1307 37.2 Biofouling and Inorganic Fouling Formation Mechanisms 1310 37.3 Antifouling Strategies from Living Nature 1313 37.4 Antifouling: Curreht Prevention and CleaningTechniques 1315 37.5 Bioinspired Rice Leaf Surfaces for Antifouling 1318 37.6 Closure 1324 References 1324

Part i Micro/Nanodevice Reiiability

38 MEMS/NEMS and BioMEMS/BioNEMS: Tribology, Mechanics, Materials and Devices Bharat Bhushan 1331 38.1 MEMS/NEMS Basics 1332 38.2 Nanotribology and Nanomechanics Issues in MEMS/NEMS

and BioMEMS/BioNEMS 1336 38.3 Nanotribology and Nanomechanics Studies of Silicon

and Related Materials 1352 38.4 Lubrication Studiesfor MEMS/NEMS 1359 38.5 Nanoscale Friction, Wear, and Mechanical Behavior

of Nano-Objects 1365 38.6 Nanotribological Studies of Biological Molecules

on Polystyrene and Silicon Surfaces and Coated Polymer Surfaces.. 1376 38.7 Trajectory of Submicron Particies for Therapeutics and Diagnostics. 1390 38.8 Component-Level Studies 1392 38.9 Conclusion 1403 38.A Appendix: Micro/Nanofabrication Techniques 1404 References 1407

39 Friction and Wear in Micro- and Nanomachines Maarten P. de Boer, Sameer S. Shroff, Frank l/l/. DelRio, 1/1/. Robert Ashurst. 1417 39.1 From Single- to Multiple-Asperity Friction 1419 39.2 Rate-State Friction 1422 39.3 Putting MEMS Friction to Use:

Making Motors and Friction Instruments 1429 39.4 Wear and Tribopolymer Evolution in Micro- and Nanoswitches .... 1430 39.5 Concluding Remarks 1432 References 1432

40 FaiSure Mechanisms in MEMS/NEMS Devices 1/1/. Merlijn van Spengen, Robert Modlihski, Robert Puers, Anne Jourdain.. 1437 40.1 Failure Modes and FaiIure Mechanisms 1438 40.2 Stiction and Charge-Related Failure Mechanisms 1439 40.3 Creep, Fatigue, Wear, and Packaging-Related Failures 1445 40.4 Conclusions 1454 References 1454

XXX Contents

41 Mechanical Properties of Micromachined Structures Hamid Kahn 1459 41.1 Measuring Mechanical Properties of Films on Substrates 1459 41.2 Micromachined Structures for Measuring Mechanical Properties.... 1460 41.3 Measurements of Mechanical Properties 1471 41.4 Summary 1475 References 1476

42 High Volume Manufacturing and Fleld Stability of MEMS Products T. Kieran Nunan, Mark 6. da Silva 1481 42.1 High-Volume Manufacturing Strategy 1482 42.2 Robust Design for Volume Manufacturing 1491 42.3 Stable Field Performance 1496 42.4 Internet of Things (loT) 1498 42.5 Conclusions and Outlook 1503 References 1503

43 Packaging and Reliability Issues in Micro/Nano Systems Yu-Chuan Su, Jongbaeg Kim, Yu-Ting Cheng, Mu Chiao, Liwei Lin 1505 43.1 Introduction to MEMS Packaging 1505 43.2 Hermetic and Vacuum Packaging 1511 43.3 Emerging Packaging Approaches 1518 43.4 Thermal Issues and Packaging Reliability 1526 43.5 Future Trends and Summary 1533 References 1534

Part J Nanotechnoiogy and Society and Education

44 Nanotechnologies in Societal Context Barbara Herr Harthorn 1543 44.1 AssessingTechnological Progress in Societal Terms 1545 44.2 Nanotechnologies and Upstream Societal Engagement 1547 44.3 Ethics 1549 44.4 Governance, Law and Regulation 1550 44.5 Public Perceptions and Participation in Decision-Making 1552 44.6 Integrating the Societal with the Technical 1553 44.7 Concluding Remarks 1554 References 1554

45 Environment, Health and Safety Issues in Nanotechnoiogy Rui Chen, Chunying Chen 1559 45.1 Impacts of the Development of Nanotechnoiogy

on Environment, Health, and Safety Issues 1559 45.2 Current Progress of the Most Important Nanomaterials 1562 45.3 Physicochemical Characteristics of Nanoparticles

that Determine theToxicity Impacts 1569 45.4 Novel Techniques and Biomarker Development in Nanotoxicology. 1574 45.5 Conclusion and Perspectives 1580 References 1580

46 Nanoscience and Nanotechnology Convergence William S. Bainbridge 1587 46.1 Background 1587 46.2 Convergence with Society 1591 46.3 Concepts and Methods 1595 46.4 Convergence in Education 1598 46.5 Conclusions 1600 References 1600

47 Global Perspectives of Nanotechnology Education Kurt Winkelmann, Bharat Bhushan 1603 47.1 Growth and Trends of Nanotechnology Education 1605 kl.2 Primary and Secondary Education 1608 47.3 Vocational Education Training 1610 47.4 Undergraduate Education 1611 47.5 Graduate Education 1614 47.6 Teacher Professional Development 1616 47.7 Informal Education 1618 47.8 Summary and Outlook 1620 References 1622

About the Authors 1625 Detailed Contents 1645 Subject Index 1671