Contents List of Acronyms xxxvii Teaching (Nano) Materials xli Learning (Nano) Materials xliii Guessing (Nano) Materials xliv About the Authors xlv Acknowledgements l Nanofood for Thought–Thinking about Nanochemistry, Nanoscience, Nanotechnology and Nanosafety lii Chapter 1 Nanochemistry Basics 3 1.1 The Roots of Nanochemistry in Materials Chemistry 3 1.2 Synthesis of Materials and Nanomaterials 5 1.3 Materials Self-Assembly 9 1.4 Big Bang to the Universe 10 1.5 Why Nano? 10 1.6 What Do we Mean by Large and Small Nanomaterials? 11 1.7 Do it Yourself Quantum Mechanics 12 1.8 What is Nanochemistry? 13 1.9 Molecular vs. Materials Self-Assembly 13 1.10 What is Hierarchical Assembly? 14 Nanochemistry: A Chemical Approach to Nanomaterials By Geoffrey A. Ozin, Andre´C. Arsenault and Ludovico Cademartiri r Geoffrey A. Ozin, Andre´C. Arsenault and Ludovico Cademartiri 2009 Published by the Royal Society of Chemistry, www.rsc.org xxiii xxiv Contents 1.11 Directing Self-Assembly 15 1.12 Supramolecular Vision 15 1.13 Genealogy of Self-Assembling Materials 16 1.14 Unlocking the Key to Porous Solids 19 1.15 Learning from Biominerals – Form is Function 22 1.16 Can You Curve a Crystal? 24 1.17 Patterns, Patterns Everywhere 25 1.18 Synthetic Creations with Natural Form 26 1.19 Two-Dimensional Assemblies 28 1.20 SAMs and Soft Lithography 31 1.21 Clever Clusters 32 1.22 Extending the Prospects of Nanowires 34 1.23 Coercing Colloids 35 1.24 Mesoscale Self-Assembly 38 1.25 Materials Self-Assembly of Integrated Systems 40 References 41 Nanofood for Thought – Materials Chemistry, Nanochemistry, Genealogy, Materials Self-Assembly, Length Scales 53 Chapter 2 Chemical Patterning and Lithography 57 2.1 Lord’s Prayer on the Head of a Pin 57 2.2 Soft Lithography 58 2.3 What are Self-Assembled Monolayers? 60 2.4 The Science and Art of Soft Lithography 61 2.5 Patterning Wettability? 63 2.6 Condensation Figures 65 2.7 Microlens Arrays 65 2.8 Nanoring Arrays 67 2.9 SAM Registration 69 2.10 Patterning the Solid State 69 2.11 Primed for Printing Polymers 73 2.12 Beyond Molecules – Transfer Printing of Thin Films 74 2.13 Microcontact Printing Living Bacteria 75 2.14 Electrically Contacting SAMs 76 2.15 SAM Crystal Engineering 78 2.16 Learning From Nature’s Biocrystal Engineering 80 2.17 Wet Stamping – The Incredible Shrinking Liesegang Rings 83 2.18 Wet Etch Patterns 85 2.19 Colloidal Microsphere Patterns 87 2.20 SAM Patterned Opal Marble Arrays 88 Contents xxv 2.21 Switching SAM Function 89 2.22 Patterning by Photocatalysis 90 2.23 Reversibly Switching SAMs 91 2.24 Electrowettability Switch 92 2.25 Metamorphic Mold – Adjustable Microtopography PDMS 95 2.26 Sweet Chips 96 2.27 All Fall Down in a Row Lithography 97 2.28 Nanoskiving 99 2.29 Patterning Nanochannel Alumina Membranes With Single Channel Resolution 100 References 103 Nanofood for Thought – Soft Lithography, SAMs, Patterning 112 Chapter 3 Layer-by-Layer Self-Assembly 117 3.1 Building One Layer at a Time 117 3.2 Electrostatic Superlattices 117 3.3 Organic Polyelectrolyte Multilayers 119 3.4 Layer-by-Layer Smart Windows 120 3.5 How Thick is Thin? 121 3.6 Assembling Metallopolymers 122 3.7 Directly Imaging Polyelectrolyte Multilayers 122 3.8 Polyelectrolyte–Colloid Multilayers 124 3.9 Graded Composition LbL Films 125 3.10 LbL MEMS 126 3.11 Trapping Active Proteins 128 3.12 Protein Laden Porous LbL Multilayers 129 3.13 Layering on Curved Surfaces 130 3.14 Microcrystal Packaging – Polyelectrolyte Coated Crystal Drug Delivery Systems 132 3.15 Hydrolytically Degradable LbL Films for Drug Delivery 134 3.16 Nanobaloons – New Generation Ultrasound Contrast Agents 135 3.17 Crystal Engineering of Oriented Zeolite Film 138 3.18 Zeolite-Ordered Multicrystal Arrays 141 3.19 Crosslinked Crystal Arrays 142 3.20 Tunable Structural Color in Multilayer Bragg Stacks 143 3.21 2D LbL Structural Color 145 3.22 Layering with Topological Complexity 147 3.23 Patterned Multilayers 149 3.24 Non-Electrostatic Layer-by-Layer Assembly 150 xxvi Contents 3.25 Low-Pressure Layers 151 3.26 Layer-by-Layer Self-Limiting Reactions 152 References 152 Nanofood for Thought – Designer Monolayers, Multilayers, Materials Flatland 162 Chapter 4 Nanocontact Printing and Writing – Stamps and Tips 167 4.1 Sub-100 nm Soft Lithography 167 4.2 Extending Microcontact Printing 168 4.3 Putting on the Pressure 169 4.4 Defect Patterning – Topologically Directed Etching 171 4.5 Below 50 nm Nanocontact Printing 172 4.6 Nanocontact Writing – Dip Pen Nanolithography 173 4.7 DPN of Silicon 174 4.8 DPN on Glass 175 4.9 Nanoscale Writing on Semiconductor Nanowires 176 4.10 Sol–Gel DPN 177 4.11 Soft Patterning of Hard Magnets 178 4.12 Writing Molecular Recognition 179 4.13 DPN Written Protein Recognition Nanostructures 181 4.14 HIV Detection Using DPN Arrays 182 4.15 Patterning Bioconstructions 183 4.16 Eating Patterns – Enzyme DPN 185 4.17 Electrostatic DPN 186 4.18 Electrochemical DPN 186 4.19 SPM Nano––Electrochemistry 187 4.20 Beyond DPN – Electrowhittling Nanostructures 189 4.21 Nanospinning Fibers 190 4.22 OLED Tip – AFM with a Nanoscale Scanning Light Probe 191 4.23 Hot Tips – DPN Soldering Iron 193 4.24 Combi Nano – DPN Combinatorial Libraries 193 4.25 50,000 Tips Go Sailing by, Go Sailing by in the Morning 196 4.26 Nanoblotters 197 4.27 Nanoscale Patterning of PDMS Stamps the DPN Way 198 4.28 Scanning Probe Contact Printing (SP-CP) 200 4.29 Dip Pen Nanolithography Stamp TIP – Beyond DPN CP 202 4.30 Best of Both Worlds 203 4.31 The Nanogenie is out of the Bottle 203 Contents xxvii References 204 Nanofood for Thought – Sharper Chemical Patterning Tools 210 Chapter 5 Nanorod, Nanotube, Nanowire Self-Assembly 215 5.1 Building Block Assembly 215 5.2 Templating Nanowires 216 5.3 Modulated Diameter Gold Nanorods 217 5.4 Modulated Composition Nanorods 218 5.5 Barcoded Nanorod Orthogonal Self-Assembly 221 5.6 Nanodisk Codes 224 5.7 Sir SERS 226 5.8 Self-Assembling Nanorods 227 5.9 Magnetic Nanorods Bunch Up 229 5.10 Magnetic Nanorods and Magnetic Nanoclusters 230 5.11 An Irresistible Attraction for Biomolecules 232 5.12 Hierarchically Ordered Nanorods 233 5.13 Nanorod Devices 235 5.14 Nanotubes from Nanoporous Templates 236 5.15 Layer-by-Layer Nanotubes from Nanorods 238 5.16 Synthesis of Single Crystal Semiconductor Nanowires 239 5.17 Vapor–Liquid–Solid Synthesis of Nanowires 240 5.18 What Controls Nanowire-Oriented Growth? 241 5.19 Marrying Plasmonics and Catalytics 242 5.20 Nanowire Quantum Size Effects 244 5.21 Single-Source Precursors 245 5.22 Supercritical Fluid–Liquid–Solid Synthesis 245 5.23 Ultrathin Nanowires-Nanothermoelectrics 246 5.24 Zoo of Nanowire Compositions and Architectures 250 5.25 Got the Nanoneedle 251 5.26 Manipulating Nanowires 252 5.27 Blowing Nanotube and Nanowire Bubbles Everywhere 254 5.28 Crossed Semiconductor Nanowires – Smallest LED 257 5.29 Nanowire Diodes and Transistors 259 5.30 Nanowire Sensors 260 5.31 Catalytic Nanowire Electronics 261 5.32 Nanowire Heterostructures 262 5.33 Longitudinal Nanowire Superlattices 263 5.34 Nanoscale Ionics: Ion-Exchange of Nanorods 266 5.35 Axial Nanowire Heterostructures 269 5.36 Nanowires Branch Out 269 xxviii Contents 5.37 Coaxially Gated Nanowire Transistor 272 5.38 Vertical Nanowire Field Effect Transistors 273 5.39 Integrated Metal–Semiconductor Nanowires – Nanoscale Electrical Contacts 274 5.40 Photon-Driven Nanowire Laser 276 5.41 Electrically Driven Nanowire Laser 278 5.42 Nanowire UV Photodetectors 279 5.43 Simplifying Complex Nanowires 279 5.44 Nanowire Casting of Single-Crystal Nanotubes 281 5.45 Solution-Phase Routes to Nanowires 283 5.46 Spinning Nanowire Devices 285 5.47 Hollow Nanofibers by Electrospinning 286 5.48 Carbon Nanotubes 288 5.49 Carbon Nanotube Structure and Electrical Properties 289 5.50 Gone Ballistic 291 5.51 Carbon Nanotube Nanomechanics 292 5.52 Carbon Nanotube Chemistry 293 5.53 Carbon Nanotubes All in a Row 296 5.54 Carbon Nanotube Photonic Crystal 298 5.55 Putting Carbon Nanotubes Exactly Where You Want Them 300 5.56 The Nanowire Pitch Challenge 301 5.57 Integrated Nanowire Nanoelectronics 303 5.58 Silicon Nanowire Solar Cells – Self-Powered Nanoelectronics 305 5.59 See-Through Nanoelectronics Circuits 306 5.60 Piezoelectric Nanowire Electrical Nanogenerators 307 5.61 Carbon Nanotube Radio Receiver 310 5.62 Silicon Nanowire NEMS: Very High Frequency Resonators and Ultra High Sensitivity Mass Monitors 311 5.63 Nanowires that Never Forget 312 5.64 A Small Thought at the End of a Large Chapter 315 References 315 Nanofood for Thought – Wires, Rods, Tubes, Low Dimensionality 330 Chapter 6 Nanocrystal Synthesis and Self-Assembly 335 6.1 Building-Block Assembly 335 6.2 When is a Nanocrystal a Nanocluster or a Nanoparticle? 336 6.3 Synthesis of Capped Semiconductor Nanocrystals 336 6.4 Electrons and Holes in Nanocrystal Boxes 339 Contents xxix 6.5 Nanocluster Phase Transformations 342 6.6 Watching Nanocrystals Grow 343 6.7 Nanocrystals in Nanobeakers 345 6.8 Capped Gold Nanocrystals – Nanonugget Rush 346 6.9 At Last a Single Crystal X-Ray Diffraction Structure of a Thiolate Ligand-Capped Gold Nanocluster 348 6.10 Alkanethiolate Capped Nanoclusters Diagnostics 350 6.11 Periodic Table of Capped Nanocrystals 351 6.12 There’s Gold in Them Thar Hills! 352 6.13 Capped Nanocrystal Architectures and Morphologies 353 6.14 Alkanethiolate Capped Silver Nanocrystal Superlattice 353 6.15 Active Plasmonics – Tunable Silver Nanocrystal Superlattices 355 6.16 Crystals of Nanocrystals 357 6.17 Getting Nanocrystal Superlattices to Conduct 358 6.18 Synergy in Nano 360 6.19 What if you Don’t