de Mello Donegá Nanoparticles

Workhorses of Nanoscience
1. Auflage 2014
ISBN: 978-3-662-44823-6
Verlag: Springer
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 303 Seiten

This book can be roughly divided into three parts: fundamental physico-chemical and physical principles of Nanoscience, chemistry and synthesis of nanoparticles, and techniques to study nanoparticles. The first chapter is concerned with the origin of the size dependence of the properties of nanomaterials, explaining it in terms of two fundamental nanoscale effects. This chapter also serves as a general introduction to the book, briefly addressing the definition and classification of nanomaterials and the techniques used to fabricate and study them. Chapter 2 lays out the theoretical framework within which to understand size effects on the properties of semiconductor nanocrystals, with particular emphasis on the quantum confinement effect. The optical properties of metal nanoparticles and metal nanostructures (periodic lattices) are discussed in Chapter 3. Chapter 4 is devoted to nanoporous materials, treating in detail their synthesis, structure and functional properties, as well as the physical properties of liquids confined in nanopores. The preparation methods, characterization techniques, and applications of supported nanoparticles are covered in Chapter 5. The sixth Chapter presents the essential physical-chemical concepts needed to understand the preparation of colloidal inorganic nanoparticles, and the remarkable degree of control that has been achieved over their composition, size, shape and surface. The last four Chapters are dedicated to a few selected characterization techniques that are very valuable tools to study nanoparticles. Chapter 7 concentrates on electron microscopy techniques, while Chapter 8 focuses on scanning probe microscopy and spectroscopy. Electron paramagnetic resonance (EPR) based spectroscopic techniques and their application to nanoparticles are explored in Chapter 9. Finally, Chapter 10 shows how solution Nuclear Magnetic Resonance (NMR) spectroscopic techniques can be used to unravel the surface chemistry of colloidal nanoparticles.

After degrees in Chemistry (BSc, 1986; MSc, 1990) from the State University of São Paulo (Brazil), Celso de Mello Donega moved to the Netherlands, where he worked under the supervision of Prof. George Blasse from 1991 to 1994, being awarded a PhD degree in Chemistry from Utrecht University in 1994. Upon his return to Brazil in 1995, he was appointed Associate Professor at the Federal State University of Pernambuco. He moved back to the Netherlands in 2000 to join the Condensed Matter and Interfaces Group of the Debye Institute for Nanomaterials Science at Utrecht University, where he currently holds a tenured Associate Professor position. His expertise is in the field of synthesis and optical spectroscopy of luminescent materials. His research is focused on the chemistry and optoelectronic properties of nanomaterials, with particular emphasis on colloidal nanocrystals and heteronanocrystals.

Autoren/Hrsg.

de Mello Donegá, Celso

Inhaltsverzeichnis

1;Preface;6
2;Contents;9
3;1 The Nanoscience Paradigm: ``Size Matters!'';11
3.1;Abstract;11
3.2;1.1 What Is Different About the Nanoscale?;11
3.2.1;1.1.1 Finite Size Effects I: Spatial Confinement;12
3.2.2;1.1.2 Finite Size Effects II:;14
3.3;1.2 Nanomaterials: and Classification;15
3.3.1;1.2.1 What Are Nanomaterials?;15
3.3.2;1.2.2 Types;16
3.4;1.3 The Nanoscale Tool Box;17
3.4.1;1.3.1 Techniques to Make Nanoparticles;17
3.4.1.1;1.3.1.1 Bottom-up Approaches;17
3.4.2;1.3.2 Techniques to Study Nanoparticles;19
3.5;1.4 Exercises;21
3.6;References;21
4;2 Size Effects on Semiconductor Nanoparticles;23
4.1;Abstract;23
4.2;2.1 Introduction;23
4.3;2.2 Electronic Structure of Bulk Semiconductors;25
4.4;2.3 Electronic Transitions in Bulk Semiconductors;28
4.5;2.4 Electronic;31
4.5.1;2.4.1 : Nanocrystal as a Small Crystal;31
4.5.1.1;2.4.1.1;36
4.5.1.2;2.4.1.2 Shape Effects;37
4.5.2;2.4.2 Nanocrystal as a Large Molecule: Building Up Atom by Atom;38
4.6;2.5 Optical Transitions in a Semiconductor Nanoparticle;43
4.7;2.6 Exciton Relaxation and Recombination;46
4.8;2.7 Excitons in Semiconductor Heteronanostructures;50
4.9;2.8 Size Effects on the Electronic Structure of Nanocrystals: Semiconductors in Comparison to Metals;54
4.10;2.9 Applications of Semiconductor Nanoparticles;55
4.11;2.10 Outlook;58
4.12;2.11 Exercises;58
4.13;References;60
5;3 Metal Nanoparticles for Microscopy and Spectroscopy;62
5.1;Abstract;62
5.2;3.1 Introduction;62
5.3;3.2 The Optical Response of Bulk Metals;64
5.3.1;3.2.1 The Drude Model for a Free Electron Plasma;64
5.3.2;3.2.2 The Dielectric Function of Ag and Au in Reality;66
5.3.3;3.2.3 Comparison of Metals;67
5.4;3.3 Scattering by Small Particles;68
5.4.1;3.3.1 Polarizability of a Small;68
5.4.2;3.3.2 Extinction and Scattering Cross Sections;70
5.4.3;3.3.3 Spheroids;73
5.5;3.4 Applications of Single Metal Nanoparticles;75
5.5.1;3.4.1 Optical Detection of a Single Particle;76
5.5.2;3.4.2 A Metal Particle as an Optical Label;79
5.5.3;3.4.3 Optical Trapping;80
5.5.4;3.4.4 Biosensing;81
5.5.5;3.4.5 Emission Enhancements;84
5.6;3.5 Clusters and Lattices of Metal Nanoparticles;86
5.6.1;3.5.1 Plasmon Hybridization;87
5.6.2;3.5.2 Validating Plasmon Hybridization Intuition;90
5.6.3;3.5.3 Observation and Use of Dark Modes;92
5.6.4;3.5.4 Narrow Gaps Yield High Fields;93
5.6.5;3.5.5;96
5.6.6;3.5.6 Lattices of Plasmonic;99
5.7;3.6 Exercises;103
5.8;References;105
6;4 Nanoporous Materials and Confined Liquids;108
6.1;Abstract;108
6.2;4.1 Introduction;108
6.3;4.2 Classes of Nanoporous Materials;110
6.3.1;4.2.1;110
6.3.2;4.2.2 Metal-Organic and Organic Microporous Materials;113
6.3.3;4.2.3 Disordered Mesoporous;114
6.3.4;4.2.4;116
6.3.5;4.2.5;118
6.4;4.3 Liquids Confined in Nanopores;119
6.4.1;4.3.1 Wetting;120
6.4.2;4.3.2 Capillarity and Capillary Condensation;121
6.4.3;4.3.3 Gas Physisorption;124
6.4.4;4.3.4 Changes in Melting Behaviour;125
6.4.5;4.3.5;125
6.5;4.4 Outlook;127
6.6;4.5 Exercises;127
6.7;References;129
7;5 Supported Nanoparticles;130
7.1;Abstract;130
7.2;5.1 Preparation Strategies;130
7.2.1;5.1.1 Precursor Solution;132
7.2.2;5.1.2;134
7.2.3;5.1.3;135
7.3;5.2 Characterization;136
7.4;5.3 Supported Nanoparticles as Catalysts;138
7.4.1;5.3.1;140
7.4.2;5.3.2 Nanoparticle Stability;142
7.4.3;5.3.3;143
7.5;5.4 Nanomaterials for and Storage;144
7.5.1;5.4.1 Gas Separation;144
7.5.2;5.4.2 Reversible;146
7.6;5.5 Outlook;150
7.7;5.6 Exercises;150
7.8;References;152
8;6 The Challenge of Colloidal Nanoparticle Synthesis;153
8.1;Abstract;153
8.2;6.1 Introduction;153
8.3;6.2 Colloidal Nanoparticles: When the Whole Is Greater than the Sum of Its Parts;154
8.3.1;6.2.1 The Inorganic Core;155
8.3.2;6.2.2 The Organic Shell;156
8.3.3;6.2.3 The Organic&hx2013;Inorganic Interface and;159
8.4;6.3 Colloidal Nanoparticle Synthesis;162
8.4.1;6.3.1 Synthesis Methodologies;162
8.4.2;6.3.2 The Hidden Variable: Adventitious Impurities;166
8.4.3;6.3.3 Colloidal Nanoparticle Synthesis: Fundamental Concepts;167
8.4.3.1;6.3.3.1 : The Monomer Formation;170
8.4.3.2;6.3.3.2 Nucleation Stage;171
8.4.3.2.1;Homogeneous Nucleation;171
8.4.3.2.2;Sec13;175
8.4.3.3;6.3.3.3;177
8.4.3.3.1;Oriented Attachment and Shape Control;178
8.4.3.3.2;Growth by;179
8.4.3.3.3;Homoepitaxial;183
8.4.3.3.4;Heteroepitaxial Growth and Shape Control;188
8.5;6.4 Outlook;192
8.6;6.5 Exercises;193
8.7;References;193
9;7 Electron Microscopy Techniques;198
9.1;Abstract;198
9.2;7.1 Introduction: Imaging Nanoparticles with Electrons;198
9.3;7.2 Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM);199
9.3.1;7.2.1;201
9.4;7.3 Two Imaging;202
9.5;7.4 Electron Diffraction;204
9.6;7.5 Advanced Imaging---Contrast Modes;207
9.7;7.6 Electron Tomography: 3-Dimensional Imaging;211
9.8;7.7 Analytical EM: Chemical Mapping, EDX and;216
9.8.1;7.7.1 Energy-Dispersive;217
9.8.2;7.7.2;218
9.9;7.8 Cryo-TEM: Frozen-in Nanoparticles and Their Assemblies;220
9.10;7.9 In situ TEM: Gas Exposure and Heating;223
9.10.1;7.9.1 In Situ Gas Exposure;223
9.10.2;7.9.2 In Situ Heating;224
9.11;7.10 Outlook: Quantitative and Dynamic EM;225
9.12;7.11 Exercises;226
9.13;References;227
10;8 Scanning Probe Microscopy and Spectroscopy;229
10.1;Abstract;229
10.2;8.1 Introduction;229
10.3;8.2 Microscopy and Spectroscopy of Colloidal Quantum Dots;230
10.3.1;8.2.1 Why Perform Microscopy and Spectroscopy on Single Nanocrystals?;230
10.3.2;8.2.2 Scanning Tunneling Microscopy and the Double-Barrier Tunnel Junction;231
10.3.3;8.2.3 Electron-Electron Interactions in Nanocrystals;236
10.3.4;8.2.4 Comparison Between Optical and;238
10.3.5;8.2.5 Charge Sensing with Atomic Force Microscopy;239
10.3.6;8.2.6 Sample Preparation;241
10.4;8.3 Examples of Typical STM experiments with Nanocrystals;243
10.4.1;8.3.1 Electronic Structure of PbSe Nanocrystals;243
10.4.2;8.3.2 Measuring the Size of a Nanocrystal;244
10.4.3;8.3.3 Acquisition and Processing of Spectroscopic Measurements;245
10.4.4;8.3.4 Identification of the Transport Regime;246
10.4.5;8.3.5;248
10.4.6;8.3.6 Charge Sensing;250
10.4.7;8.3.7 Symmetry of the Energy Levels;253
10.4.8;8.3.8 Elastic or;253
10.4.9;8.3.9 Dot-in-Rod Heteronanocrystals;255
10.5;8.4 Exercises;256
10.6;Acknowledgments;258
10.7;References;258
11;9 Electron Paramagnetic Resonance Based Spectroscopic Techniques;262
11.1;Abstract;262
11.2;9.1 Fundamentals;262
11.2.1;9.1.1 Detected Electron Paramagnetic Resonance (ESE-EPR);263
11.2.2;9.1.2 Electron-Nuclear Double Resonance (ENDOR);264
11.2.3;9.1.3 Optically Detected Magnetic Resonance (ODMR);264
11.3;9.2 Applications to Nanomaterials;265
11.3.1;9.2.1 ZnO Nanocrystals;266
11.3.1.1;9.2.1.1 The Identification of the Binding Core of Shallow Donors and Deep s in ZnO Nanocrystals by EPR and ENDOR;266
11.3.1.2;9.2.1.2 Probing the Wave Function of Shallow Donors in ZnO Nanocrystals and Confinement Effects;270
11.3.1.3;9.2.1.3 Dynamic Nuclear Polarization of Nuclear Spins in ZnO Nanocrystals;272
11.3.1.4;9.2.1.4 ODMR via in ZnO Nanocrystals;274
11.4;9.3 Outlook;275
11.5;9.4 Exercises;276
11.6;Acknowledgments;276
11.7;References;277
12;10 Solution NMR Toolbox for Colloidal Nanoparticles;278
12.1;Abstract;278
12.2;10.1 Introduction;278
12.3;10.2 One-Dimensional NMR Spectroscopy (1D NMR);279
12.3.1;10.2.1 Exciting Spins;279
12.3.2;10.2.2;281
12.3.3;10.2.3 Quantification;282
12.4;10.3 Diffusion Ordered Spectroscopy (DOSY);284
12.4.1;10.3.1 The Basics;284
12.4.2;10.3.2;286
12.4.3;10.3.3 in DOSY;287
12.5;10.4;288
12.5.1;10.4.1 Screening for Ligands;288
12.5.2;10.4.2 Recognizing Ligands in Fast Exchange;291
12.6;10.5 The Solution NMR Toolbox in Action: Octylamine Stabilized CdSe NPs;291
12.6.1;10.5.1 Octylamine Stabilized CdSe NPs;292
12.6.2;10.5.2;293
12.6.3;10.5.3 of Octylamine;294
12.7;10.6 Outlook;296
12.8;10.7 Exercises;296
12.9;References;297
13;Index;299