Nanochemistry : a chemical approach to nanomaterials

International interest in nanoscience research has flourished in recent years, as it becomes an integral part in the development of future technologies. The diverse, interdisciplinary nature of nanoscience means effective communication between disciplines is pivotal in the successful utilization of the science. Nanochemistry: A Chemical Approach to Nanomaterials is the first textbook for teaching nanochemistry and adopts an interdisciplinary and comprehensive approach to the subject. It presents a basic chemical strategy for making nanomaterials and describes some of the principles of materials self-assembly over 'all' scales. It demonstrates how nanometre and micrometre scale building blocks (with a wide range of shapes, compositions and surface functionalities) can be coerced through chemistry to organize spontaneously into unprecedented structures, which can serve as tailored functional materials. Suggestions of new ways to tackle research problems and speculations on how to think about assembling the future of nanotechnology are given. Primarily designed for teaching, this book will appeal to graduate and advanced undergraduate students. It is well illustrated with graphical representations of the structure and form of nanomaterials and contains problem sets as well as other pedagogical features such as further reading, case studies and a comprehensive bibliography.

Reviews 1

Choice Review

Although this book, like most in nanotechnology, touts the interdisciplinary nature of the field, the subtitle is significant and accurate. Other books may organize topics primarily by techniques of synthesizing materials or the physical properties of nanomaterials; Ozin and Arsenault (both, Univ. of Toronto) describe both materials and methods of synthesis in chemical terms wherever possible. This provides not merely a different descriptive framework, but in many instances detailed molecular-level accounts of nanomaterials that explain their properties. This nanochemical approach seems likely to be of great value to those looking to synthesize new materials with specific properties. The book is generally well written with many descriptions of interesting and potentially useful applications of nanomaterials. Several of these applications are in special chapters on patterning, printing, and colored materials. There are a large number of exceptionally lucid illustrations and extensive chapter references. A colorful standout in the crowded field of books on nanotechnology. Summing Up: Highly recommended. Graduate students through professionals. D. Bantz University of Alaska

List of Acronyms	p. xxv
Teaching (Nano)Materials	p. xxix
Learning (Nano)Materials	p. xxxi
About the Authors	p. xxxiii
Acknowledgements	p. xxxvii
Nanofood for Thought - Thinking about Nanochemistry, Nanoscience, Nanotechnology and Nanosafety	p. xxxix
Chapter 1 Nanochemistry Basics	p. 1
1.1 Materials Self-Assembly	p. 1
1.2 Big Bang to the Universe	p. 2
1.3 Why Nano?	p. 2
1.4 What do we Mean by Large and Small Nanomaterials?	p. 3
1.5 Do it Yourself Quantum Mechanics	p. 4
1.6 What is Nanochemistry?	p. 5
1.7 Molecular vs. Materials Self-Assembly	p. 5
1.8 What is Hierarchical Assembly?	p. 6
1.9 Directing Self-Assembly	p. 6
1.10 Supramolecular Vision	p. 7
1.11 Geneology of Self-Assembling Materials	p. 8
1.12 Unlocking the Key to Porous Solids	p. 11
1.13 Learning from Biominerals - Form is Function	p. 14
1.14 Can you Curve a Crystal?	p. 16
1.15 Patterns, Patterns Everywhere	p. 17
1.16 Synthetic Creations with Natural Form	p. 18
1.17 Two-Dimensional Assemblies	p. 20
1.18 SAMs and Soft Lithography	p. 23
1.19 Clever Clusters	p. 24
1.20 Extending the Prospects of Nanowires	p. 26
1.21 Coercing Colloids	p. 27
1.22 Mesoscale Self-Assembly	p. 31
1.23 Materials Self-Assembly of Integrated Systems	p. 32
1.24 References	p. 33
Nanofood for Thought - Nanochemistry, Genealogy Materials Self-Assembly, Length Scales	p. 45
Chapter 2 Chemical Patterning and Lithography	p. 49
2.1 Soft Lithography	p. 49
2.2 What are Self-Assembled Monolayers?	p. 50
2.3 The Science and Art of Soft Lithography	p. 52
2.4 Patterning Wettability?	p. 54
2.5 Condensation Figures	p. 55
2.6 Microlens Arrays	p. 56
2.7 Nanoring Arrays	p. 58
2.8 Patterning the Solid State	p. 59
2.9 Primed for Printing Polymers	p. 61
2.10 Beyond Molecules - Transfer Printing of Thin Films	p. 63
2.11 Electrically Contacting SAMS	p. 64
2.12 SAM Crystal Engineering	p. 66
2.13 Learning from Nature's Biocrystal Engineering	p. 68
2.14 Colloidal Microsphere Patterns	p. 71
2.15 Switching SAM Function	p. 71
2.16 Patterning by Photocatalysis	p. 73
2.17 Reversibly Switching SAMs	p. 74
2.18 Electrowettability Switch	p. 76
2.19 Sweet Chips	p. 77
2.20 All Fall Down in a Row Lithography	p. 79
2.21 References	p. 80
Nanofood for Thought - Soft Lithography, SAMs, Patterning	p. 89
Chapter 3 Layer-by-Layer Self-Assembly	p. 95
3.1 Building One Layer at a Time	p. 95
3.2 Electrostatic Superlattices	p. 95
3.3 Organic Polyelectrolyte Multilayers	p. 97
3.4 Layer-by-Layer Smart Windows	p. 97
3.5 How Thick is Thin?	p. 99
3.6 Assembling Metallopolymers	p. 99
3.7 Directly Imaging Polyelectrolyte Multilayers	p. 100
3.8 Polyelectrolyte-Colloid Multilayers	p. 101
3.9 Graded Composition LbL Films	p. 103
3.10 LbL MEMS	p. 104
3.11 Trapping Active Proteins	p. 106
3.12 Layering on Curved Surfaces	p. 106
3.13 Crystal Engineering of Oriented Zeolite Film	p. 108
3.14 Zeolite-Ordered Multicrystal Arrays	p. 110
3.15 Crosslinked Crystal Arrays	p. 111
3.16 Layering with Topological Complexity	p. 112
3.17 Patterned Multilayers	p. 113
3.18 Non-Electrostatic Layer-by-Layer Assembly	p. 115
3.19 Low Pressure Layers	p. 116
3.20 Layer-by-Layer Self-Limiting Reactions	p. 117
3.21 References	p. 118
Nanofood for Thought - Designer Monolayers, Multilayers, Materials Flatland	p. 126
Chapter 4 Nanocontact Printing and Writing - Stamps and Tips	p. 131
4.1 Sub-100 nm Soft Lithography	p. 131
4.2 Extending Microcontact Printing	p. 131
4.3 Putting on the Pressure	p. 133
4.4 Defect Patterning - Topologically Directed Etching	p. 135
4.5 Below 50 nm Nanocontact Printing	p. 136
4.6 Nanocontact Writing - Dip Pen Nanolithography	p. 137
4.7 DPN of Silicon	p. 138
4.8 DPN on Glass	p. 139
4.9 Nanoscale Writing on Seminconductor Nanowires	p. 140
4.10 Sol-Gel DPN	p. 141
4.11 Soft Patterning of Hard Magnets	p. 142
4.12 Writing Molecular Recognition	p. 143
4.13 DPN Writing Protein Recognition Nanostructures	p. 145
4.14 Patterning Bioconstructions	p. 145
4.15 Eating Patterns - Enzyme DPN	p. 147
4.16 Electrostatic DPN	p. 148
4.17 Electrochemical DPN	p. 148
4.18 SPM Nano-Electrochemistry	p. 149
4.19 Beyond DPN - Whittling Nanostructures	p. 151
4.20 Combi Nano - DPN Combinatorial Libraries	p. 151
4.21 Nanoplotters	p. 153
4.22 Nanoblotters	p. 154
4.23 Scanning Probe Contact Printing (SP-CP)	p. 155
4.24 Dip Pen Nanolithography Stamp Tip - Beyond DPN CP	p. 157
4.25 Best of Both Worlds	p. 157
4.26 The Nanogenie is out of the Bottle	p. 158
4.27 References	p. 158
Nanofood for Thought - Sharper Chemical Patterning Tools	p. 164
Chapter 5 Nanorod, Nanotube, Nanowire Self-Assembly	p. 167
5.1 Building Block Assembly	p. 167
5.2 Templating Nanowires	p. 167
5.3 Modulated Diameter Gold Nanorods	p. 168
5.4 Modulated Composition Nanorods	p. 170
5.5 Barcoded Nanorod Orthogonal Self-Assembly	p. 173
5.6 Self-Assembling Nanorods	p. 176
5.7 Magnetic Nanorods Bunch Up	p. 177
5.8 Magnetic Nanorods and Magnetic Nanoclusters	p. 178
5.9 An Irresistable Attraction for Biomolecules	p. 181
5.10 Hierarchically Ordered Nanorods	p. 183
5.11 Nanorod Devices	p. 184
5.12 Nanotubes from Nanoporous Templates	p. 186
5.13 Layer-by-Layer Nanotubes from Nanorods	p. 188
5.14 Synthesis of Single Crystal Semiconductor Nanowires	p. 189
5.15 Vapor-Liquid-Solid Synthesis of Nanowires	p. 189
5.16 What Controls Nanowire-Oriented Growth?	p. 191
5.17 Supercritical Fluid-Liquid-Solid Synthesis	p. 191
5.18 Nanowire Quantum Size Effects	p. 193
5.19 Zoo of Nanowire Compositions and Architectures	p. 195
5.20 Single-Source Precursors	p. 195
5.21 Manipulating Nanowires	p. 196
5.22 Crossed Semiconductor Nanowires - Smallest LED	p. 199
5.23 Nanowire Diodes and Transistors	p. 201
5.24 Nanowire Sensors	p. 201
5.25 Catalytic Nanowire Electronics	p. 203
5.26 Nanowire Heterostructures	p. 204
5.27 Longitudinal Nanowire Superlattices	p. 206
5.28 Axial Nanowire Heterostructures	p. 207
5.29 Nanowires Branch Out	p. 209
5.30 Coaxially Gated Nanowire Transistor	p. 209
5.31 Vertical Nanowire Field Effect Transistors	p. 212
5.32 Integrated Metal-Semiconductor Nanowires - Nanoscale Electrical Contacts	p. 215
5.33 Photon-Driven Nanowire Laser	p. 216
5.34 Electrically Driven Nanowire Laser	p. 218
5.35 Nanowire UV Photodetectors	p. 220
5.36 Simplifying Complex Nanowires	p. 220
5.37 Nanowire Casting of Single-Crystal Nanotubes	p. 222
5.38 Solution-Phase Routes to Nanowires	p. 223
5.39 Spinning Nanowire Devices	p. 226
5.40 Hollow Nanofibers by Electrospinning	p. 227
5.41 Carbon Nanotubes	p. 229
5.42 Carbon Nanotube Structure and Electrical Properties	p. 229
5.43 Gone Ballistic	p. 231
5.44 Carbon Nanotube Nanomechanics	p. 233
5.45 Carbon Nanotube Chemistry	p. 233
5.46 Carbon Nanotubes All in a Row	p. 236
5.47 Carbon Nanotube Photonic Crystal	p. 238
5.48 Putting Carbon Nanotubes Exactly Where You Want Them	p. 240
5.49 The Nanowire Pitch Challenge	p. 242
5.50 Integrated Nanowire Nanoelectronics	p. 244
5.51 A Small Thought at the End of a Large Chapter	p. 246
5.52 References	p. 246
Nanofood for Thought - Wires, Rods, Tubes, Low Dimensionality	p. 260
Chapter 6 Nanocluster Self-Assembly	p. 265
6.1 Building-Block Assembly	p. 265
6.2 When is a Nanocluster a Nanocrystal or Nanoparticle?	p. 266
6.3 Synthesis of Capped Semiconductor Nanoclusters	p. 266
6.4 Electrons and Holes in Nanocluster Boxes	p. 268
6.5 Watching Nanoclusters Grow	p. 270
6.6 Nanocrystals in Nanobeakers	p. 271
6.7 Nanocluster Semiconductor Alloys and Beyond	p. 273
6.8 Nanocluster Phase Transformation	p. 274
6.9 Capped Gold Nanoclusters - Nanonugget Rush	p. 275
6.10 Alkanethiolate Capped Nanocluster Diagnostics	p. 277
6.11 Periodic Table of Capped Nanoclusters	p. 278
6.12 There's Gold in Them Thar Hills!	p. 278
6.13 Water-Soluble Nanoclusters	p. 279
6.14 Capped Nanocluster Architectures and Morphologies	p. 281
6.15 Alkanethiolate Capped Silver Nanocluster Superlattice	p. 282
6.16 Crystals of Nanocrystals	p. 284
6.17 Beyond Crystal of Nanocrystals - Binary Nanocrystal Superlattices	p. 285
6.18 Capped Magnetic Nanocluster Superlattice - High Density Data Storage Materials	p. 286
6.19 Alloying Core-Shell Magnetic Nanoclusters	p. 287
6.20 Soft Lithography of Capped Nanoclusters	p. 288
6.21 Organizing Nanoclusters by Evaporation	p. 289
6.22 Electroluminescent Semiconductor Nanoclusters	p. 289
6.23 Full Color Nanocluster-Polymer Composites	p. 291
6.24 Capped Semiconductor Nanocluster Meets Biomolecule	p. 293
6.25 Nanocluster DNA Sensors - Besting the Best	p. 296
6.26 Semiconductor Nanoclusters Extend and Branch Out	p. 297
6.27 Branched Nanocluster Solar Cells	p. 299
6.28 Tetrapod of Tetrapods - Towards Inorganic Dendrimers	p. 300
6.29 Golden Tips - Making Contact with Nanorods	p. 301
6.30 Flipping a Nanocluster Switch	p. 303
6.31 Photochromic Metal Nanoclusters	p. 304
6.32 Carbon Nanoclusters - Buckyballs	p. 306
6.33 Building Nanodevices with Buckyballs	p. 307
6.34 Carbon Catalysis with Buckyball	p. 308
6.35 References	p. 309
Nanofood for Thought - Nanoclusters, Nanocrystals, Quantum Dots, Quantum Size Effects	p. 320
Chapter 7 Microspheres - Colors from the Beaker	p. 325
7.1 Nature's Photonic Crystals	p. 325
7.2 Photonic Crystals	p. 325
7.3 Photonic Semiconductors	p. 327
7.4 Defects, Defects, Defects	p. 328
7.5 Computing with Light	p. 328
7.6 Color Tunability	p. 330
7.7 Transferring Nature's Photonic Crystal Technology to the Chemistry Laboratory	p. 330
7.8 Microsphere Building Blocks	p. 331
7.9 Silica Microspheres	p. 331
7.10 Latex Microspheres	p. 332
7.11 Multi-Shell Microspheres	p. 332
7.12 Basics of Microsphere Self-Assembly	p. 333
7.13 Microsphere Self-Assembly - Crystals and Films	p. 334
7.14 Colloidal Crystalline Fluids	p. 336
7.15 Beyond Face Centered Cubic Packing of Microspheres	p. 337
7.16 Templates - Confinement and Epitaxy	p. 338
7.17 Photonic Crystal Fibers	p. 340
7.18 Photonic Crystal Marbles	p. 340
7.19 Optical Properties of Colloidal Crystals - Combined Bragg-Snell Laws	p. 343
7.20 Basic Optical Properties of Colloidal Crystals	p. 343
7.21 How Perfect is Perfect?	p. 345
7.22 Cracking Controversy	p. 346
7.23 Synthesizing a Full Photonic Band Gap	p. 348
7.24 Writing Defects	p. 349
7.25 Getting Smart with Planar Defects	p. 350
7.26 Switching Light with Light	p. 353
7.27 Internal Light Sources	p. 353
7.28 Photonic Inks	p. 354
7.29 Color Oscillator	p. 357
7.30 Photonic Crystal Sensors	p. 357
7.31 Colloidal Photonic Crystal Solar Cell	p. 359
7.32 Thermochromic Colloidal Photonic Crystal Switch	p. 360
7.33 Liquid Crystal Photonic Crystal	p. 361
7.34 Encrypted Colloidal Crystals	p. 363
7.35 Gazing into the Photonic Crystal Ball	p. 365
7.36 References	p. 365
Nanofood for Thought - Colloidal Assembly, Colloidal Crystals, Colloidal Crystal Devices, Structural Color	p. 373
Chapter 8 Microporous and Mesoporous Materials from Soft Building Blocks	p. 379
8.1 Escape from the Zeolite Prison	p. 379
8.2 A Periodic Table of Materials Filled with Holes	p. 380
8.3 Modular Self-Assembly of Microporous Materials	p. 381
8.4 Hydrogen Storage Coordination Frameworks	p. 383
8.5 Overview and Prospects of Microporous Materials	p. 384
8.6 Mesoscale Soft Building Blocks	p. 385
8.7 Micelle Versus Liquid Crystal Templating Paradox	p. 387
8.8 Designing Function into Mesoporous Materials	p. 387
8.9 Tuning Length Scales	p. 388
8.10 Mesostructure and Dimensionality	p. 390
8.11 Mesocomposition - Nature of Precursors	p. 390
8.12 Mesotexture	p. 391
8.13 Periodic Mesoporous Silica-Polymer Hybrids	p. 392
8.14 Guests in Mesopores	p. 393
8.15 Capped Nanocluster Meets Surfactant Mesophase	p. 394
8.16 Marking Time in Mesostructured Silica - New Approach to Optical Data Storage	p. 396
8.17 Sidearm Mesofunctionalization	p. 397
8.18 Organics in the Backbone	p. 398
8.19 Mesomorphology - Films, Interfaces, Mesoepitaxy	p. 400
8.20 Stand Up and Be Counted	p. 402
8.21 Mesomorphology - Spheres, Other Shapes	p. 404
8.22 Mesomorphology - Patterned Films, Soft Lithography, Micromolding	p. 406
8.23 Mesomorphology - Morphosynthesis of Curved Form	p. 408
8.24 Chiral Surfactant Micelles - Chiral Mesoporous Silica	p. 410
8.25 Mesopore Replication	p. 413
8.26 Mesochemistry and Topological Defects	p. 414
8.27 Mesochemistry - Synthesis in "Intermediate" Dimensions	p. 415
8.28 References	p. 418
Nanofood for Thought - Soft Blocks Template Hard Precursors, Holey Materials	p. 430
Chapter 9 Self-Assembling Block Copolymers	p. 435
9.1 Polymers, Polymers Everywhere in Nanochemistry	p. 435
9.2 Block Copolymer Self-Assembly - Chip Off the Old Block	p. 435
9.3 Nanostructured Ceramics	p. 437
9.4 Nano-objects	p. 439
9.5 Block Copolymer Thin Films	p. 439
9.6 Electrical Ordering	p. 442
9.7 Spatial Confinement of Block Copolymers	p. 442
9.8 Nanoepitaxy	p. 444
9.9 Block Copolymer Lithography	p. 444
9.10 Decorating Block Copolymers	p. 446
9.11 A Case of Wettability	p. 447
9.12 Nanowires from Block Copolymers	p. 449
9.13 Making Micelles	p. 451
9.14 Assembling Inorganic Polymers	p. 453
9.15 Harnessing Rigid Rods	p. 453
9.16 Supramolecular Assemblies	p. 455
9.17 Supramolecular Mushrooms	p. 456
9.18 Structural Color from Lightscale Block Copolymers	p. 458
9.19 Block Copolypeptides	p. 459
9.20 Block Copolymer Biofactories	p. 461
9.21 References	p. 462
Nanofood for Thought - Block Copolymer Self-Assembling Nanostructures	p. 468
Chapter 10 Biomaterials and Bioinspiration	p. 473
10.1 Nature did it First	p. 473
10.2 To Mimic or to Use?	p. 474
10.3 Faux Fossils	p. 475
10.4 Nature's Siliceous Sculptures	p. 476
10.5 Ancient to Modern Synthetic Morphology	p. 477
10.6 Biomimicry	p. 478
10.7 Biomineralization and Biomimicry Analogies	p. 479
10.8 Learning from Nature	p. 481
10.9 Viral Cage Directed Synthesis of Nanoclusters	p. 482
10.10 Viruses that Glitter	p. 483
10.11 Polynucleotide Directed Nanocluster Assembly	p. 484
10.12 DNA Coded Nanocluster Chains	p. 485
10.13 Building with DNA	p. 487
10.14 Bacteria Directed Materials Self-Assembly	p. 489
10.15 Using a Virus that is Benign, to Align	p. 491
10.16 Magnetic Spider Silk	p. 492
10.17 Protein S-Layer Masks	p. 493
10.18 Morphosynthesis - Inorganic Materials with Complex Form	p. 496
10.19 Echinoderm vs. Block Copolymers	p. 498
10.20 Fishy Top-Down Photonic Crystals	p. 499
10.21 Aluminophosphates Shape Up	p. 501
10.22 Better Bones Through Chemistry	p. 502
10.23 Mineralizing Nanofibers	p. 504
10.24 Biological Lessons in Materials Design	p. 505
10.25 Surface Binding Through Directed Evolution	p. 505
10.26 Nanowire Evolution	p. 508
10.27 Biomolecular Motors - Nanomachines Everywhere	p. 508
10.28 How Biomotors Work	p. 510
10.29 Kinesin - Walk Along	p. 512
10.30 ATPase - Biomotor Nanopropellors	p. 515
10.31 (Bio)Inspiration	p. 516
10.32 References	p. 517
Nanofood for Thought - Organic Matrix, Biomineralization, Biomimetics, Bioinspiration	p. 527
Chapter 11 Self-Assembly of Large Building Blocks	p. 531
11.1 Self-assembling Supra-micron Shapes	p. 531
11.2 Synthesis Using the "Capillary Bond"	p. 532
11.3 Crystallizing Large Polyhedral-Shaped Building Blocks	p. 533
11.4 Self-Assembling 2D and 3D Electrical Circuits and Devices	p. 533
11.5 Crystallizing Micron-Sized Planar Building Blocks	p. 534
11.6 Polyhedra with Patterned Faces that Autoconstruct	p. 536
11.7 Large Sphere Building Blocks Self-Assemble into 3D Crystals	p. 540
11.8 Synthetic MEMS?	p. 541
11.9 Magnetic Self-Assembly	p. 541
11.10 Dynamic Self-Assembly	p. 543
11.11 Autonomous Self-Assembly	p. 544
11.12 Self-Assembly and Synthetic Life	p. 547
11.13 References	p. 548
Nanofood for Thought - Static and Dynamic, Capillary Bond, Shape Assembly	p. 550
Chapter 12 Nano and Beyond	p. 553
12.1 Assembling the Future	p. 553
12.2 Microfluidic Computing	p. 554
12.3 Fuel Cells - Hold the Membrane	p. 554
12.4 Curved Prints	p. 554
12.5 Beating the Ink Diffusion Dilemma	p. 555
12.6 Tip of the Pyramid	p. 556
12.7 Biosensing Membranes	p. 556
12.8 Crossing Nanowires	p. 556
12.9 Complete Crystallographic Control	p. 557
12.10 Down to the Wire	p. 557
12.11 Shielded Nanowires	p. 558
12.12 Writing 3D Nanofluidic and Nanophotonic Networks	p. 559
12.13 Break-and-Glue Transistor Assembly	p. 560
12.14 Turning Nanostructures Inside-out	p. 560
12.15 Confining Spheres	p. 560
12.16 Escape from the Silica and Polystyrene Prison	p. 562
12.17 Smart Dust	p. 562
12.18 Light Writing for Light Guiding	p. 562
12.19 Nanoring Around the Collar	p. 563
12.20 A Meso Rubbed Right	p. 563
12.21 Fungus with the Midas Touch	p. 564
12.22 Self-assembled Electronics	p. 565
12.23 Gears Sink Their Teeth into the Interface	p. 565
12.24 Materials Retro-assembly	p. 566
12.25 Matter that Matters - Materials of the "Next Kind"	p. 568
12.26 References	p. 571
Nanofood for Thought - Nano Potpourri	p. 574
Chapter 13 Nanochemistry Nanolabs	p. 579
Appendix A Origin of the Term "Self-Assembly"	p. 585
Appendix B Cytotoxicity of Nanoparticles	p. 589
Appendix C Walking Macromolecules Through Colloidal Crystals	p. 593
Appendix D Patterning Nanochannel Alumina Membranes With Single Channel Resolution	p. 597
Appendix E Muscle Powered Nanomachines	p. 599
Appendix F Bacteria Power	p. 603
Appendix G Chemically Driven Nanorod Motors	p. 607
Subject Index	p. 611

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