Analytical Transmission Electron Microscopy and Scanning Transmission Electron Microscopy Techniques for the Characterization of Nanomaterial Composition, Phase and Crystallinity

Abstract The production and use of manufactured nanomaterials (NMs) have been increasing dramatically for the past few years. Because there are nearly unlimited possibilities for the types of NMs that may be created, heterogeneity and complexity in both composition and structure are expected. In addition, manufactured NMs undergo compositional and structural transformation processes in response to the interaction(s) with their surrounding environment, as well as with that environment as it changes through time. In this chapter, we will introduce and discuss how to identify and characterize chemical composition and crystal structure (and therefore the exact phase or phases) of manufactured NMs (parent forms) as well as their transformed ones (daughter forms) by using analytical transmission electron microscopy (analytical TEM) and scanning transmission electron microscopy (STEM). For this specific purpose, in this chapter, we discuss TEM and STEM techniques for compositional and structural analyses, the applications and limits, the data acquisition and analysis methods, as well as sample preparation procedures in detail. The purpose of this chapter is to make these instruments and techniques much more accessible and familiar to nonexperts in electron microscopy. Manufactured NMs, such as TiO 2 , metals and metal oxides and sulphides will be used for examples throughout this chapter. In addition, examples of naturally occurring NMs will be used for crystal structural analyses, as well as crystal structure refinements.

[1]  Andrew M. Minor,et al.  Focused Ion Beam Microscopy and Micromachining , 2007 .

[2]  R. Averback,et al.  Effect of viscous flow on ion damage near solid surfaces. , 1994, Physical review letters.

[3]  Bernd Kabius,et al.  Electron microscopy image enhanced , 1998, Nature.

[4]  Alfred Wagner,et al.  High Resolution Focused Ion Beams: FIB and Its Applications , 2003 .

[5]  Lucille A. Giannuzzi,et al.  Introduction to focused ion beams : instrumentation, theory, techniques, and practice , 2010 .

[6]  R. Egerton.  Electron energy-loss spectroscopy in the TEM , 2008 .

[7]  David B. Williams,et al.  Transmission Electron Microscopy: A Textbook for Materials Science , 1996 .

[8]  J. Miao,et al.  Electron tomography at 2.4-ångström resolution , 2012, Nature.

[9]  B. Baker,et al.  Fibxtem— Focussed Ion Beam Milling for TEM Sample Preparation , 1991 .

[10]  G. Botton,et al.  Materials science applications of HREELS in near edge structure analysis and low-energy loss spectroscopy. , 2003, Ultramicroscopy.

[11]  H. W. Werner,et al.  Secondary Ion Mass Spectrometry: Basic Concepts, Instrumental Aspects, Applications and Trends , 1987 .

[12]  Michael F. Hochella,et al.  Characterization and environmental implications of nano- and larger TiO(2) particles in sewage sludge, and soils amended with sewage sludge. , 2012, Journal of environmental monitoring : JEM.

[13]  L. Fitting Kourkoutis,et al.  Atomic-Scale Chemical Imaging of Composition and Bonding by Aberration-Corrected Microscopy , 2008, Science.

[14]  R. Wirth.  Focused Ion Beam (FIB): Applications in Micro- and Nanoanalysis in Geosciences and Applied Mineralogy , 2005 .

[15]  Mitsuhiro Murayama,et al.  Integrated approaches of x-ray absorption spectroscopic and electron microscopic techniques on zinc speciation and characterization in a final sewage sludge product. , 2014, Journal of environmental quality.

[16]  M. Hodson,et al.  Characterization of mineral surfaces using FIB and TEM: A case study of naturally weathered alkali feldspars , 2007 .

[17]  M. Nastasi,et al.  Ion-Solid Interactions: Fundamentals and Applications , 1996 .

[18]  Mitsuhiro Murayama,et al.  Discovery and characterization of silver sulfide nanoparticles in final sewage sludge products. , 2010, Environmental science & technology.

[19]  P. Nellist,et al.  Towards sub-0.5 A electron beams. , 2003, Ultramicroscopy.

[20]  V. Mittal,et al.  Visualization of Organic–Inorganic Nanostructures in Liquid , 2012 .

[21]  J. M. Cowley,et al.  Transmission Electron Microscopy of Synthetic 2- and 6-Line Ferrihydrite , 2000 .

[22]  Bernd Kabius,et al.  A way to higher resolution: spherical-aberration correction in a 200 kV transmission electron microscope , 1999 .

[23]  Niven Monsegue,et al.  Nanopores in hematite (α-Fe2O3) nanocrystals observed by electron tomography , 2013 .

[24]  Tsuda,et al.  Refinement of crystal structural parameters using two-dimensional energy-filtered CBED patterns. , 1999, Acta crystallographica. Section A, Foundations of crystallography.

[25]  J. Banfield,et al.  Ultrastructure, aggregation-state, and crystal growth of biogenic nanocrystalline sphalerite and wurtzite , 2004 .

[26]  J. Dubochet,et al.  Cryo-electron microscopy of vitrified specimens , 1988, Quarterly Reviews of Biophysics.

[27]  R. Wirth,et al.  Focused ion beam (FIB): A novel technology for advanced application of micro- and nanoanalysis in geosciences and applied mineralogy , 2004 .

[28]  Y. Ikuhara,et al.  Atomic-scale imaging of individual dopant atoms in a buried interface. , 2009, Nature materials.

[29]  H. Moor.  Theory and practice of high pressure freezing. , 1987 .

[30]  O. Krivanek,et al.  Automated processing of parallel-detection EELS data , 1991 .

[31]  C. Bulle-lieuwma,et al.  Novel scheme for the preparation of transmission electron microscopy specimens with a focused ion beam , 1993 .

[32]  Knut W Urban.  Is science prepared for atomic-resolution electron microscopy? , 2009, Nature materials.

[33]  M. Lee.  Transmission electron microscopy (TEM) of Earth and planetary materials: A review , 2010, Mineralogical Magazine.

[34]  K. Urban,et al.  Studying Atomic Structures by Aberration-Corrected Transmission Electron Microscopy , 2008, Science.

[35]  Ondrej L. Krivanek,et al.  Towards sub-Å electron beams , 1999 .

[36]  P. Sigmund.  Theory of Sputtering. I. Sputtering Yield of Amorphous and Polycrystalline Targets , 1969 .

[37]  L. Giannuzzi,et al.  2 keV Ga+ FIB Milling for Reducing Amorphous Damage in Silicon , 2005, Microscopy and Microanalysis.

[38]  S. Pennycook,et al.  Depth sectioning with the aberration-corrected scanning transmission electron microscope. , 2006, Proceedings of the National Academy of Sciences of the United States of America.

[39]  J. Rimstidt,et al.  The enigmatic iron oxyhydroxysulfate nanomineral schwertmannite: Morphology, structure, and composition , 2012 .

[40]  R. Wirth,et al.  Focused Ion Beam (FIB) combined with SEM and TEM: Advanced analytical tools for studies of chemical composition, microstructure and crystal structure in geomaterials on a nanometre scale , 2009 .

[41]  P. Schattschneider,et al.  Energy loss magnetic chiral dichroism : A new technique for the study of magnetic properties in the electron microscope (invited) , 2008 .

[42]  M. Chi,et al.  Aberration Corrected and Monochromated STEM/TEM for Materials Science , 2007, Microscopy and Microanalysis.

[43]  Joachim Mayer,et al.  TEM Sample Preparation and FIB-Induced Damage , 2007 .

[44]  O. Krivanek,et al.  An electron microscope for the aberration-corrected era. , 2008, Ultramicroscopy.

[45]  P. Sigmund.  A mechanism of surface micro-roughening by ion bombardment , 1973 .

[46]  John M. Cowley,et al.  Applications of electron nanodiffraction , 2004 .

[47]  B. Rand,et al.  Quantitative valence plasmon mapping in the TEM: viewing physical properties at the nanoscale. , 2003, Ultramicroscopy.

[48]  P. Bland,et al.  Preparation of TEM samples by focused ion beam (FIB) techniques: applications to the study of clays and phyllosilicates in meteorites , 2003, Mineralogical Magazine.

[49]  D. Muller.  Structure and bonding at the atomic scale by scanning transmission electron microscopy. , 2009, Nature materials.

[50]  P Sigmund,et al.  スパッタの理論 I 非晶質のスパッタ収量と多結晶ターゲット , 1969 .

[51]  M. O'Keefe.  Seeing atoms with aberration-corrected sub-Angström electron microscopy. , 2008, Ultramicroscopy.

[52]  Nigel D. Browning,et al.  EELS in the STEM: Determination of Materials Properties on the Atomic Scale , 1997, MICRO 1997.

[53]  J Verbeeck,et al.  Model based quantification of EELS spectra. , 2004, Ultramicroscopy.

[54]  Peter Hartel,et al.  Advancing the Hexapole Cs-Corrector for the Scanning Transmission Electron Microscope , 2006, Microscopy and Microanalysis.

[55]  E. Mugnaioli,et al.  Accurate and precise lattice parameters by selected-area electron diffraction in the transmission electron microscope , 2009 .