Semiconductor and Metal Nanocrystals Synthesis and Electronic and Optical Properties edited by Victor I. Klimov Los Alamos National Laboratory Los Alamos, New Mexico, U.S.A. MARCEL MARCEL DEKKER, INC. NEW YORK BASEL
Preface Contributors Hi xiii Part I. Semiconductor Nanocrystals (Nanocrystal Quantum Dots) 1. "Soft" Chemical Synthesis and Manipulation of Semiconductor Nanocrystals 1 Jennifer A. Hollingsworth and Victor I. Klimov I. Introduction 1 II. Colloidal Nanosynthesis 4 Inorganic Surface Modification 14 IV. Shape Control 24 V. Phase Transitions and Phase Control 37 VI. Nanocrystal Doping 42 VII. Nanocrystal Assembly and Encapsulation 51 References 61 2. Electronic Structure in Semiconductor Nanocrystals 65 David J. Norris I. Introduction 65 II. Theoretical Framework 68 Cadmium Selenide Nanocrystals 77 IV. Beyond CdSe 96 References 99 vii
VIII 3. Fine Structure and Polarization Properties of Band-Edge Excitons in Semiconductor Nanocrystals 103 Al. L. Efros I. Introduction 103 II. Fine Structure of the Band-Edge Exciton in CdSe Nanocrystals 104 Fine Structure of the Band-Edge Excitons in Magnetic Fields 120 IV. Experiment 124 V. Discussion and Conclusions 137 Appendix: Calculation of the Hole g Factor 138 References 140 Intraband Spectroscopy and Dynamics of Colloidal Semiconductor Quantum Dots 143 Phillipe Guyot-Sionnest, Moonsub Shim, and Congjun Wang I. Introduction 143 II. Background 144 Experimental Observations of the Intraband Absorption in Colloidal Quantum Dots 146 IV. Intraband Absorption Probing of Carrier Dynamics 149 V. Conclusions 155 References 155 5. Charge Carrier Dynamics and Optical Gain in Nanocrystal Quantum Dots: From Fundamental Photophysics to Quantum Dot basing 159 Victor I. Klimov I. Introduction 159 II. Energy Structures and Intraband Relaxation in NQDs 161 Carrier Trapping at Interface States and Excited-State Absorption in NQDs 175 IV. Multiparticle Effects and Optical Gain in NQDs 185 V. Optical Amplification and basing in NQDs 199 VI. Conclusions and Outlook 209 References 212
IX Optical Dynamics in Single Semiconductor Quantum Dots 215 К. Т. Shimizu and M. G. Bawendi I. II. 111. IV. V. VI. Introduction Single-Quantum-Dot Spectroscopy Spectral Diffusion and Fluorescence Intermittency Correlation Between Spectral Diffusion and Blinking "Power-Law" Blinking Statistics Conclusions References 215 216 218 220 226 237 238 Electrical Properties of Semiconductor Nanocrystals 239 David S. Ginger and Neil C. Greenham I. Introduction 239 II. Theory of Electron Transfer Between Localized States 242 Experimental Techniques 248 IV. Nanocrystals and Photoinduced Electron Transfer 251 V. Charge Transport in Nanocrystal Films 265 VI. Nanocrystal-Based Devices 276 VII. Conclusions 283 References 284 Tunneling and Optical Spectroscopy of Semiconductor Nanocrystal Quantum Dots: Single-Particle and Ensemble Properties 289 Uri Banin and Oded Millo I. Introduction 289 II. General Comparison Between Tunneling and Optical Spectroscopy of QDs 293 Correlation Between Optical and Tunneling Spectra of InAs Nanocrystal QDs 298 IV. Junction Symmetry Effects on the Tunneling Spectra 311 V. Tunneling and Optical Spectroscopy of Core-Shell Nanocrystal QDs 316 VI. QD Wave-Function Imaging 320 VII. Concluding Remarks 323 References 323
X III-V Quantum Dots and Quantum Dot Arrays: Synthesis, Optical Properties, Photogenerated Carrier Dynamics, and Applications to Photon Conversion 327 Arthur J. Nozik and Olga I. Micic I. II. IV. V. VI. Introduction Synthesis of Quantum Dots Unique Optical Properties Relaxation Dynamics of Photogenerated Carriers inqds Quantum-Dot Arrays Applications: Quantum-Dot Solar Cells References 327 328 340 357 363 372 378 Part II. Metal Nanocrystals 10. Synthesis and Fabrication of Metal Nanocrystal Superlattices 387 R. Christopher Doty, Michael B. Sigman, Jr., Cynthia A. Stowell, Parag S. Shah, Aaron E. Saunders, and Brian A. Korgel I. Introduction 387 II. Nanocrystal Characterization 394 Superlattice Formation 401 IV. Physical Consequences of Superlattice Order 411 V. Conclusions and Future Work 417 References i 417 11. Optical Spectroscopy of Surface Plasmons in Metal Nanoparticles 421 Stephan Link and Mostafa A. El-Sayed I. Introduction 421 II. Size, Shape, and Composition Dependence of Surface Plasmon Resonances 422 Dephasing of the Surface Plasmon Resonance 432 IV. Nonradiative Decay of the Surface Plasmon Resonance After Laser Excitation 434 V. Photothermal Shape Changes of Gold Nanorods 437 VI. Summary and Conclusions 449 References 450
XI 12. Time-Resolved Spectroscopy of Metal Nanoparticles 453 Gregory V. Hartland I. Introduction 453 II. Experimental: Synthesis and Laser Techniques 454 Coherent Excitation of Acoustic Vibrational Modes 456 IV. Gold Nanorods 463 V. Bimetallic Nanoparticles 464 VI. Summary and Conclusions 468 References 469 Index 473