Francis Leonard Deepak · Alvaro Mayoral Raul Arenal Editors Advanced Transmission Electron Microscopy Applications to Nanomaterials Advanced Transmission Electron Microscopy Francis Leonard Deepak (cid:129) Alvaro Mayoral Raul Arenal Editors Advanced Transmission Electron Microscopy Applications to Nanomaterials Editors Francis Leonard Deepak Alvaro Mayoral International Iberian Nanotechnology Advanced Microscopy Laboratory Laboratory Nanoscience Institute of Aragon Braga , Portugal University of Zaragoza Zaragoza , Spain Raul Arenal Advanced Microscopy Laboratory Nanoscience Institute of Aragon University of Zaragoza Zaragoza , Spain ISBN 978-3-319-15176-2 ISBN 978-3-319-15177-9 (eBook) DOI 10.1007/978-3-319-15177-9 Library of Congress Control Number: 2015939736 Springer Cham Heidelberg New York Dordrecht London © Springer International Publishing Switzerland 2015 T his work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifi cally the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfi lms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specifi c statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. T he publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained herein or for any errors or omissions that may have been made. Printed on acid-free paper S pringer International Publishing AG Switzerland is part of Springer Science+Business Media (www.springer.com) Pref ace T he book entitled Advanced Transmission Electron Microscopy: Applications to Nanomaterials is an effort to try to bring an update in the fi eld of nanomaterials that have been explored employing s tate - of -t he - art electron microscopic techniques. Electron microscopy has undergone remarkable changes since the invention of the transmission electron microscope (TEM) in 1931 by Max Knoll and Ernst Ruska (Nobel Prize in Physics 1986). The invention of the TEM was a major signifi cant effort to move forward, in terms of spatial resolution, from optical microscopes that were predominant in that era. The efforts and achievements in the fi eld of aberration corrected microscopes would not have happened today if not for the vision of Otto Scherzer who predicted that the limiting factor in the resolution of the microscopes originated from spherical and chromatic aberrations (S pherical and Chromatic Correction of Electron Lenses , Optik, 1947 and J . Appl. Phys. , 1949). The dream of imaging atoms without the “blur” of the optics owes its efforts to several people and projects in this fi eld. The importance on several such developments and building of new prototype corrector optics as well as providing the theoretical and experimental understanding towards achieving atomic resolution has been highlighted with the award of the Wolf prize in Physics (2011) to Harald Rose, Maximilian Haider, and Knut Urban. I n parallel, there have been signifi cant advances in the development of analytical methods—EDS and EELS, 3D techniques, electron tomography, in situ electron microscopy, advances in sample preparation, data detection, monochromators, etc. Simultaneously, there has been an explosion in the kind of materials that are being explored under the electron microscope to obtain both qualitative and quantitative information. The materials include carbon in all kinds of forms, boron nitride, and other carbon-based nanomaterials, metal, and metal oxide nanoparticles, highly beam-sensitive structures: zeolites and mesoporous materials; all of it with the fi nal purpose of pushing the information limit down to the single structural bricks con- forming matter that is the single atoms (or atomic column). Owing to this kind of information, many properties which remained unknown until now can be explained better than before, thereby allowing for enhanced material design. v vi Preface T he chapters in this book have been organized in order to bring an update to the fi eld both in terms of the advanced techniques as well as to enhance the understand- ing of nanomaterials under the electron microscope. The fi rst chapter Aberration Corrected Electron microscopy of Nanoparticles (Miguel José Yacamán, Ulises Santiago, and Sergio Mejía-Rosales) provides an introduction to the fi eld of electron microscopy, spectroscopy, diffraction, and aberration- corrected electron microscopy. This chapter highlights the signifi cant historical advances that have been made in the fi eld of transmission electron micros- copy and highlights a few specifi c examples related to clusters and nanoparticles. This is followed by the chapter entitled E lectron Diffraction and Crystal Orientation Phase Mapping Under Scanning Transmission Electron Microscopy (Francisco Ruiz-Zepeda, J. Alejandro Arizpe-Zapata, Daniel Bahena, Arturo Ponce, and Domingo Garcia) which highlights the use of STEM for purposes of electron dif- fraction and phase mapping of nanostructured and thin fi lm materials. The subse- quent chapter Advanced Electron Microscopy in the Study of Multimetallic Nanoparticles (Nabraj Bhatatrai, Subarna Khanal, J. Jesus Velazquez-Salazar, and Miguel Jose-Yacaman) explores the area of bimetallic/multimetallic nanoparticles as investigated by advanced electron microscopic techniques. The fourth chapter Zeolites and Ordered Mesoporous Materials Under the Electron Microscope (Alvaro Mayoral, Yasuhiro Sakamoto, and Isabel Diaz) deals with the most impor- tant heterogeneous catalysts which are the zeolites. In addition, it also covers the other big family of ordered porous structures, silica mesoporous materials, showing the capabilities of advanced electron microscopy methods to tackle the problem of the beam-sensitive materials. The fi fth chapter L ocal TEM Spectroscopic Studies on Carbon - and Boron Nitride - Based Nanomaterials (Raul Arenal and Odile Stephan) explores local spectroscopy (including chemical analyses and the study of physical properties) on nanostructures based on carbon and other related materials (boron nitride, BxCyNz). The sixth chapter 3 D - Nanometric Analyses via Electron Tomography: Application to Nanomaterials (Simona Moldovan, Raul Arenal, and Ovidiu Ersen) provides a critical update in the fi eld of electron tomography, while the seventh chapter I n Situ TEM of Carbon Nanotubes (Pedro M. F. J. Costa and Paulo J. Ferreira) provides a current update in the fi eld of in situ electron micros- copy studies that have been carried out focusing especially on carbon nanotubes. The fi nal chapter Physical Characterization of Nanomaterials in Dispersion by Transmission Electron Microscopy in a Regulatory Framework (Jan Mast, Eveline Verleysen, and Pieter-Jan De Temmerman) addresses the different steps required to analyze dispersed nanomaterials to obtain homogeneous and stable dispersions of colloidal nanomaterials and powders while exploring a descriptive, qualitative as well as quantitative analysis on the TEM images. It is hoped that this book will be suitable not only for an audience that uses advanced electron microscopic techniques in their current day-to-day investigations of nanomaterials for various applications but also for materials scientists, physi- cists, and chemists who carry out active research in nanoscience and nanotechnol- ogy. In addition, the topics and the chapters, which are written by the various Preface vii authors, are aimed at a beginner who intends to pursue such investigations for his/ her study. Finally, there is a tremendous and signifi cant pileup of new information in terms of advances in instrumentation, techniques, methodologies, etc. and we have sought to address some of these major topics that we thought necessary to highlight at the present point of time. Braga, Portugal Francis Leonard Deepak Zaragoza, Spain Alvaro Mayoral Zaragoza, Spain Raul Arenal (All the Editors contributed equally to the fi nal output of this book). Contents 1 Aberration-Corrected Electron Microscopy of Nanoparticles ............. 1 Miguel José Yacamán , Ulises Santiago , and Sergio Mejía-Rosales 2 Electron Diffraction and Crystal Orientation Phase Mapping Under Scanning Transmission Electron Microscopy............................. 31 Francisco Ruiz-Zepeda , J. Alejandro Arizpe-Zapata , Daniel Bahena , Arturo Ponce , and Domingo I. Garcia-Gutierrez 3 Advanced Electron Microscopy in the Study of Multimetallic Nanoparticles ................................................................ 59 Nabraj Bhattarai , Subarna Khanal , J. Jesus Velazquez-Salazar , and Miguel Jose-Yacaman 4 Zeolites and Mesoporous Crystals Under the Electron Microscope ................................................................................................. 93 Alvaro Mayoral , Yasuhiro Sakamoto , and Isabel Diaz 5 Local TEM Spectroscopic Studies on Carbon- and Boron Nitride-Based Nanomaterials ................................................ 139 Raul Arenal and Odile Stephan 6 3D Nanometric Analyses via Electron Tomography: Application to Nanomaterials .................................................................. 171 Simona Moldovan , Raul Arenal , and Ovidiu Ersen 7 In Situ TEM of Carbon Nanotubes ......................................................... 207 Pedro M. F. J. Costa and Paulo J. Ferreira 8 Physical Characterization of Nanomaterials in Dispersion by Transmission Electron Microscopy in a Regulatory Framework ..................................................................... 249 Jan Mast , Eveline Verleysen , and Pieter-Jan De Temmerman Index ................................................................................................................. 271 ix