NANOSCALE MATERIALS
NANOSCALE MATERIALS edited by Luis M. Liz-Marzán Universidade de Vigo Spain Prashant V. Kamat University of Notre Dame U.S.A. KLUWER ACADEMIC PUBLISHERS NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW
ebook ISBN: 0-306-48108-1 Print ISBN: 1-4020-7366-6 2004 Kluwer Academic Publishers New York, Boston, Dordrecht, London, Moscow Print 2003 Kluwer Academic Publishers Dordrecht All rights reserved No part of this ebook may be reproduced or transmitted in any form or by any means, electronic, mechanical, recording, or otherwise, without written consent from the Publisher Created in the United States of America Visit Kluwer Online at: and Kluwer's ebookstore at: http://kluweronline.com http://ebooks.kluweronline.com
To Neha, Neeta, Pedro and Sofía
CONTENTS NANOSCALE MATERIALS 1 Luis M. Liz-Marzán and Prashant V. Kamat CHEMICALLY FUNCTIONALIZED METAL NANOPARTICLES: SYNTHESIS, PROPERTIES AND APPLICATIONS 5 Eugenii Katz, Andrew Shipway, and Itamar Willner SYNTHESIS AND PROPERTIES OF MONOLAYER CAPPED METAL NANOPARTICLES 1 2 3 Functionalized Metal Nanoparticles in Organic Phases Functionalized Metal Nanoparticles in Aqueous Systems Chemical Activities of Functionalized Metal Nanoparticles and their Stepwise Modifications SYNTHESIS AND PROPERTIES OF POLYMER-CAPPED METAL NANOPARTICLES CONTROLLING THE SIZE AND COMPOSITION OF THE METALLIC CORES OF NANOPARTICLES CATALYTIC, ELECTROCHEMICAL AND PHOTOCHEMICAL PROPERTIES OF FUNCTIONALIZED METAL NANOPARTICLES 1 Catalytic Properties of Functionalized Metal Nanoparticles 2 Electrochemical Properties of Functionalized Metal Nanoparticles 3 Photochemical Properties of Functionalized Metal Nanoparticles 4 Recognition, Specific Association, and Sensoric Operation of Functionalized Metal Nanoparticles FUNCTIONALIZED METAL NANOPARTICLE ARRAYS ON SURFACES 1 Preparation of Functionalized Metal Nanoparticles Arrays on Surfaces 2 Patterning of Functionalized Metal Nanoparticles Arrays 5 6 7 10 14 16 19 22 23 25 30 32 37 37 46
viii CONTENTS 8. 9. 3 Sensoric Applications of Functionalized Metal Nanoparticles Arrays 4 Photoelectrochemical Applications of Functionalized Metal Nanoparticles Arrays 5 Functional Devices Based on Electronic Properties of Metal Nanoparticles Arrays CONCLUSIONS AND PERSPECTIVES ACKNOWLEDGMENT 50 56 58 63 64 64 METAL NANOPARTICLES FOR CATALYSIS 79 Naoki Toshima 8. METALS AS CATALYSTS PREPARATION OF METAL NANOPARTICLES CHARACTERIZATION OF METAL NANOPARTICLE CATALYSTS EFFECT OF STRUCTURES ON CATALYSIS OF METAL NANOPARTICLES 1 Size of Metal Nanoparticles 2 Bimetallic Structure EFFECT OF POLYMER FIELD ON CATALYSIS OF METAL NANOPARTICLES CONCLUDING REMARKS AND FUTURE ASPECTS 79 80 81 85 86 86 88 92 94 94 ULTRAFAST DYNAMICS OF METAL NANOSPHERES AND NANORODS 97 Min Hu and Gregory V. Hartland EXPERIMENTAL TECHNIQUES RESULTS AND DISCUSSION 1 2 3 4 Coherent Vibrational Motion in Nanospheres: Observations and Excitation Mechanism Heat Dissipation for Gold Particles in Aqueous Solution Mode Softening at High Temperature Vibrational Modes of Nanorods SUMMARY AND CONCLUSIONS ACKNOWLEDGEMENTS 97 100 101 101 104 106 110 114 115 115
CONTENTS ix RADIATION EFFECTS IN NANOPARTICLE SUSPENSIONS 119 Dan Meisel ENERGY DEPOSITION IN PARTICLE SUSPENSIONS EXPERIMENTAL PROCEDURES ESCAPE OF ELECTRONS INTO THE AQUEOUS PHASE ESCAPE OF HOLES INTO THE AQUEOUS PHASE INTERFACIAL CAPTURE HYDROGEN YIELDS 8. RADIOLYSIS AS A SYNTHETIC TOOL 9. CONCLUSIONS 10. ACKNOWLEDGEMENT 1 119 121 123 124 125 126 127 130 131 132 132 SYNTHESIS OF NANOPARTICLES IN MICROEMULSIONS 135 M. A. López-Quintela, J. Rivas, M. C. Blanco, and C. Tojo MICROEMULSIONS 1 2 3 4 5 6 Autocatalysis 7 Concentration 8 Droplet Size MONTE CARLO SIMULATION 1 2 3 4 5 MECHANISM OF FORMATION OF PARTICLES IN Intermicellar Material Exchange Droplet Volume Fraction Film Flexibility Nucleation and Growth Processes Ripening Study of Nucleation and Growth Processes Influence of the Concentration Influence of the Film Flexibility Influence of the Reactant Excess Influence of the Interdroplet Material Exchange EXAMPLES CONCLUSIONS AND FUTURE PERSPECTIVES ACKNOWLEDGEMENTS 135 136 136 139 140 142 143 143 144 144 144 144 146 147 149 150 152 153 153 153
x CONTENTS CHEMICAL ASPECTS OF SEMICONDUCTOR NANOCRYSTALS 157 Tito Trindade STRUCTURAL, ELECTRONIC AND OPTICAL PROPERTIES CHEMICAL SYNTHESIS OF SEMICONDUCTOR NANOCRYSTALS 1 General Concepts 2 Controlled Precipitation in Confined Spaces 3 MolecularPrecursors Routes 4 Cluster Building-Up Approach SURFACE CHEMISTRY AND ASSEMBLY METHODS 1 Nanocrystals Surface Modification 2 Nanocrystals Assemblies CONCLUSIONS AND OUTLOOK 157 158 162 162 164 166 168 169 169 172 175 176 8. SPECTROELECTROCHEMISTRY OF SEMICONDUCTOR COLLOID QUANTUM DOTS 181 Philippe Guyot-Sionnest CHARGING AND SEMICONDUTOR QUANTUM DOTS SPECTROELECTROCHEMISTRY OF COLLOID QUANTUM DOTS CONCLUSIONS ACKNOWLEDGEMENTS 181 182 183 187 187 188 9. NANOPARTICLES WITH POLYMERIC SURFACES FILLERS AND MODELS FOR ULTRASOFT COLLOIDS 191 Wolfgang Schärtl SYNTHESIS OF MODEL PARTICLES COMPATIBILITY OF COLLOIDAL PARTICLES AND LINEAR CHAINS ULTRASOFT COLLOIDS IN COLOID-POLYMER-BLENDS 1 2 Spherical Micellar Brushes with Colloidal Particle Character Spherical Micellar Brushes Behaving Like Hyperbranched Polymers CONCLUDING REMARKS ACKNOWLEDGMENTS 191 192 194 198 198 204 206 206 206
CONTENTS xi 10. PROPERTIES OF NIPAM-BASED INTELLIGENT MICROGEL PARTICLES: INVESTIGATED USING SCATTERING METHODS 209 Thomas Hellweg MICROGEL PREPARATION 1 Synthesis of PNIPA Microgels 2 Sample Preparation for Scattering Experiments SCATTERING METHODS 1 Dynamic Light Scattering 2 Small Angle Neutron Scattering 3 Static Light Scattering 4 Characterization of Microgel Based Colloidal Crystals 5 Internal Dynamics of Microgels Studied by Neutron Spin-Echo Spectroscopy SUMMARY AND OUTLOOK ACKNOWLEDGMENTS 209 210 210 210 211 213 216 217 219 220 222 223 223 1 DESIGN OF NANOSCALE MATERIALS USING SILICA-COATED METAL NANOCOLLOIDS 227 Luis M. Liz-Marzán 8. 9. MODELLING OF OPTICAL PROPERTIES 1 Dilute Dispersions 2 Thin Films THIN FILMS THROUGH LAYER-BY-LAYER ASSEMBLY NANOPARTICLE ASSEMBLY ON COLLOID SPHERES DOPED GLASS FROM COATED NANOPARTICLES ORDERED THREE-DIMENSIONAL ASSEMBLIES Wet Colloidal Crystals Solid Opals Inverse Opals from Particles CONCLUSIONS AND OUTLOOK ACKNOWLEDGMENTS 227 229 229 231 232 234 236 238 238 240 241 244 244 244 1 FABRICATION OF INORGANICNANOCOMPOSITES USING SELF-ASSEMBLY AND SOL-GEL PROCESSING 247 S. Tamil-Selvan 247
xii CONTENTS 8. 9. 10. 1 2 3 4 5 Quantum Size Effects in Nanocrystals Polymer Nanocomposites Sol-Gel Processing Photonic Glasses Silica Particles GOLD-POLYPYRROLE CORE-SHELL NANOCOMPOSITES THROUGH SELF-ASSEMBLY OF BLOCK-COPOLYMERS NONLINEAR OPTICAL PROPERTIES OF COMPOSITES LUMINESCENCE OF SILICA COMPOSITES PHOTOPHYSICS OF QUANTUM DOTS HIGHLY LUMINESCENT QD-GLASSES SILICA-COATED QUANTUM DOTS SUMMARY AND OUTLOOK ACKNOWLEDGEMENTS 248 248 248 249 250 251 253 255 258 259 262 266 266 267 1 ORGANIZATION OF LAYER-BY-LAYER ASSEMBLED NANOCOMPOSITES: FUNCTIONAL EFFECTS IN PHOTONICS AND BIOMATERIALS 273 Nicholas A. Kotov and Luis M. Liz-Marzán LAYER-BY-LAYER ASSEMBLY ORDERING OF THE LBL ASSEMBLED NANOMATERIALS 1 Sequence Effects in Nanoparticle Multilayers LATERAL ORDERING IN LBL FILMS 1 Improvement of Packing Density of Nanoparticles in the Adsorption Layer by Surface Modification Improvement of Packing Density by Assembly Conditions Effect Of Lateral Ordering On The Materials Functions 2 3 CONCLUSIONS 273 273 275 275 284 284 286 289 296 297 1 NEW APPLICATIONS AND PROPERTIES OF LANGMUIR- BLODGETT FILMS 303 Inmaculada Prieto, María Teresa Martín, and Luis Camacho LIQUID CRYSTALS 1 Alignment Properties of Langmuir-Blodgett Films in Liquid Crystal Cells Studies of Liquid Crystalline Phase Rheology in Langmuir Films 2 LUMINESCENCE PROPERTIES: ORGANIC LIGHT-EMITTING DIODES 303 306 308 311 312
CONTENTS 1 2 3 The Light Phenomenon and Devices Background on LED Formation by Using Organic Materials Lifetime, Efficiency, and Thickness of OLEDs MAGNETIC PROPERTIES 1 2 3 Magnetic Nanoparticles Purely Organic Magnetic Monolayers and Films Hybrid Organic-Inorganic Materials NONLINEAR OPTICAL PROPERTIES 1 2 Scope and Phenomenon Properties of Organic Materials for NLO Devices xiii 312 314 316 320 321 324 325 326 326 327 330 1 ASSEMBLIES OF MAGNETIC PARTICLES 335 Michael Hilgendorff and Michael Giersig THEORY 1 Forces Influencing the Colloid Stability Evolution of Nanoparticles in a Colloidal Solution The Theory of Drying WET CHEMICAL SYNTHESIS OF MAGNETIC NANOPARTICLES 1 Iron Oxide Metals ASSEMBLING MAGNETIC PARTICLES 1 Magnetophoretic Deposition Technique (MDT) 2 Nano Sphere Lithography (NSL) 3 Electrostatic Self-Assembly (ESA) CONCLUSIONS ACKNOWLEDGMENT 335 337 338 345 346 347 349 350 352 352 357 364 365 365 366 1 MAGNETIC NANOSTRUCTURES FROM CLUSTERS 371 A. Perez, V. Dupuis, J. Tuaillon-Combes, L. Bardotti, B. Prével, P. Mélinon, M. Jamet, W. Wernsdorfer, and B. Barbara MAGNETIC NANOSTRUCTURE PREPARATION BY LECBD STRUCTURES AND MORPHOLOGIES OF CLUSTER-ASSEMBLED FILMS MAGNETIC PROPERTIES OF INDIVIDUAL CLUSTERS AND CLUSTER-ASSEMBLED FILMS 1 MicroSQUID Magnetometry Studies of Individual Magnetic Nanoclusters 2 MicroSQUID Magnetometry Studies of 2D Clusters Assemblies, 371 373 375 382 382
xiv CONTENTS 3 Below the 2D-Percolation Threshold 386 MicroSQUID Magnetometry Studies of 2D Clusters Assemblies, Above the 2D-Percolation Threshold 388 Magnetic Properties of Thick Cluster Assembled Films 388 4 FUNCTIONALIZED MAGNETIC NANOSTRUCTURES FROM MIXED CLUSTERS CONCLUSIONS 390 392 392 1 MAGNETIC THIN FILMS 395 Michael Farle 8. FILM GROWTH MAGNETIC MOMENT (T = 0K) MAGNETIC ANISOTROPY ENERGY DENSITY (T = 0K) 1 Microscopic Origin 2 Surface and Interface Anisotropy TEMPERATURE DEPENDENT PHENOMENA CONCLUSION ACKNOWLEDGEMENT 395 396 398 405 408 412 417 419 419 420 18. THREE-DIMENSIONAL PHOTONIC CRYSTALS MADE FROM COLLOIDS 423 A. Imhof OPTICAL PROPERTIES OF PHOTONIC CRYSTALS 1 Propagation of Light in Photonic Crystals 2 Experimental Probes of Photonic Crystals FABRICATION OF PHOTONIC CRYSTALS 1 Nanofabrication 2 Self-Assembly Methods 3 Colloidal Crystal Templating 4 Directed Self-Assembly: More Order and Different Lattices 5 The Effects of Disorder ENGINEERING OF COLLOIDAL PARTICLES: CORE-SHELL, METALLO-DIELECTRIC, AND ANISOTROPIC COLLOIDS CONCLUSIONS ACKNOWLEDGEMENTS 423 425 425 429 433 433 435 436 440 442 443 446 446 447
CONTENTS xv 19. FUNDAMENTALS AND TECHNOLOGICAL ASPECTS OF CARBON NANOTUBES 455 Shekhar Subramoney SYNTHESIS OF CARBON NANOTUBES STRUCTURE OF CARBON NANOTUBES PHYSICAL PROPERTIES AND APPLICATIONS OF CARBON NANOTUBES 1 Mechanical Properties 2 Electronic Properties APPLICATIONS INVOLVING CARBON NANOTUBES 1 Carbon Nanotube-Based Field Emitters 2 Single-Electron Field Effect Transistors THE FUTURE OF CARBON NANOTUBES 455 456 460 463 463 466 468 468 469 470 471 20. MOLECULAR ASSEMBLY OF FULLERENES AS NANOCLUSTERS AND NANOSTRUCTURED FILMS 475 Prashant V. Kamat and K. George Thomas PREPARATION OF FULLERENE NANOCLUSTERS AND NANOSTRUCTURED FILMS PROPERTIES OF FULLERENE CLUSTERS 1 2 3 Absorption and Emission Characteristics Size and Shape of Clusters Photoinduced Electron Transfer between Fullerene Clusters and Electron Donors NANOSTRUCTURED FULLERENE FILMS 1 2 3 Electrophoretic Deposition Fullerene Functionalized Gold Clusters And Films Nanostructured Films of APPLICATIONS 1 2 ACKNOWLEDGEMENT Electrocatalytic Aspects Photoelectrochemical Conversion of Light Energy 475 476 478 478 479 480 482 483 484 486 486 487 488 491 491 INDEX 495
PREFACE The unique electronic and chemical properties of nanoparticles have drawn the attention of chemists, physicists, biologists and engineers who wish to use them for the development of next generation nanodevices. Organized nanoassemblies of inorganic nanoparticles and organic molecules are building blocks of nanodevices, whether they are designed to perform molecular level computing, sense the environment or improve the catalytic properties of a material. The key to creation of these hybrid nanostructures lies in understanding the chemistry at a fundamental level. This book serves as a reference book for advanced graduate students and active researchers by providing fundamental understanding of many nanoscopic materials. Scientists and engineers who wish to diversify their research into nanoscience and nanotechnology will find this book extremely useful. The rapidly evolving field of nanoscience has come out of its infancy and is paving its way into novel technological applications. The topics chosen for this book provide a global perspective into the status of an extremely active research field. Constantly evolving methodologies and techniques provide new dimensions to this field every year. Though many issues are still being debated, the general interest in nanoscience will continue to grow during the coming decade. Luis M. Liz-Marzán Prashant V. Kamat
ACKNOWLEDGMENTS We thank all the contributors to this book for their extra effort in presenting state-of-art developments in their areas of expertise. This book would have not been possible without them. Additionally, we need to acknowledge the patience of our families, specially our wives (Charo and Shobha), which allowed us to spend time on the preparation of the book at the cost of not being with them.