ECR Ce Aun a CL! arry Carter sity of Minnesota, Minneapolis, Minnesota | ., want to leam about electron microscopy from specimen prepa. Transmission Electron Mic (the ultimate limitation) or via the instrument or how to use TEM comprehensive text in 20 ea AU eae aan nara eter ae ea a cg Cc een Ceo See Re ea eae tern Deena ree eS em GRE CRON LES reo Pana ne er eS ae Ry Coes [DP on ae ke Pe ee = ea aedasb coe cL ape Sone PeiiecUneec Rte aa hooey Hier ea ene orien acerca er eg eu ACs Pe ee ger ee cic nena ct Ty ifohianrtete ranean ni ici ane Perea eer tama ULL ‘opists and it breaks new ground in a number of ways. This ieee 7 RePEc ATL RL men in REO Re ar retical oer sera OMT PME Lah occ ca thee Pesan Se eect meter acceding Tr ona ie Serer er eee reed ct EL air annie pail STU ernie Mn te CM Ca Hea pond Loe eae ttahaeieban tr ererana teres tl am enter RA STA abt rai ene ag trina iene Scale inlets en Crees ae UOC RCES EMC Ic MUMS A a Ce ron microscopy. Drawing on their many years of experience in Hemia, Professors Williams and Carter have painstakingly crafted a ce ae Soe eee led Pye URC un eis Siete RC lester 4-unit course. There is scholarship throughout. . . . The writ- ieee ener aE cl Seg See Rens MCN kk Ue Pete est un Re Ru aay Iron microscopist in the physical soiences, and to interpret the eee Rick ceu er Rao a fm Oe TS cee ae ee eT ee ieee mien trae tea rea) sR Electronique du Centre National de la Recherche eran etey oh aS Mca ne PPR ca Rm RUC Rod ;—diagrams which are clear and to the point; comforting words Meee ae Meee acc Se eas Pree OR ca WRU RR a Ul | 0 ee eer age Ra | j per eet esr eos } eee er ua NH enn er eae oF PBOSDSUSe4 aR Lon SVM) ISBN 0-aDb-4s3aPreface Sse How is this book any different from the many other books ‘hat deal with TEM? It has several unique features, but the most distinguishing one, we believe, is that it can really be described as a “textbook —that is, one designed to be used primarily in the classroom rather than in the research labo: fatory. We have constructed the book as a series of rela- tively small chapters (with a few notable exceptions!). The contents of many chapters can be covered in a typical lec- ture of 50 to 75 minutes. The style is informal for easier reading; it resembles an oral lecture rather than the formal ‘writing you would encounter when reading research papers. 1m our experience, the TEM books currently avail- able fall into three major categories. They may be too theo: retical for many materials science students; they attempt to cover all kinds of electon microscopy in one volume, ‘Which makes it difficult to include sufficient theory on any ‘one technique; or they are Himited in the TEM topics they cover. The rapid development of the TEM field has meant that many of the earlier books must automaticaly be placed inthe third category. Although these books are often invala- able in teaching, we have not found them generally suitable as the course textbook in a senior-year undergraduate or first-year graduate course introducing TEM, so we have en- Aeavored to fill this perceived gap. ‘Since this text is an introduction to the whole sub- ject of TEM, we incorporate all aspects of a modern TEM into an integrated whole. So, rather than separating out the broad-beam and convergent-beam aspects of the subject Athe traditional structural analysis or imaging versus the “chemical” analysis or “new” techniques), we teat these two aspects as different sides of the same coin. Thus scan: ning-beam (STEM) imaging is just another way to form an image in a TEM. There is no reason to regard “conven- tional” bright-field and “conventional” dark-field imaging 8 any more fundamental ways of imaging the specimen than annular dark-field imaging —or even secondary-elec- tron or STEM Z-contrast modes. Similarly, convergent- beam and scanning-beam diffraction are integral parts of electron diffraction, and are complementary to selected: area diffraction, Inelastic electron scattering is the source fof both Kikuchi lines and characteristic X-rays. So we don’t deliberately split off “conventional” microscopy from “analytical” microscopy. Our approach is to thread two fundamental ques~ tions throughout the text. Why should we use a particular technique? How do we put the idea into practice? We attempt to establish a sound theoretical basis where necessary, although not always giving all the details. We then use this knowledge to build a solid understanding of hhow we use the instrument. The text is illustrated with ex- amples from across the fields of materials science and en- ‘gineering and, where possible, a sense of the history of the ‘technique is introduced. We keep references to a minimum and generally accepted concepts are not specifically cred- ited, although numerous classical general references are included. “We both have extensive teaching and research back- grounds in all aspects of TEM comprising diffraction, imaging, and microanalysis. Our research in TEM of mate- rials spans metals, ceramics, composites, and semiconduc- tors. We each bring more than 25 years of TEM experience to the book, and have contributed to the training of a gener~ ation of (we hope) skilled electron microscopists. We found that writing the book broadened our own knowledge con- siderably and was actually fun on some occasions. We hope ‘you experience the same reactions after reading it. Lastly, we encourage you to send us any comments, (positive or negative). We can both be reached by email: dbwl @lehigh.edu and carter@cems.umn.edu ixAcknowledgments We have spent the best part of a decade in the conception and gestation of this text and such an endeavor can’t be ac- complished in isolation, Our first acknowledgments must be to our wives, Margie and Bryony, and our families, who have borne the brunt of our absences from home (and occa sionally the brunt of our presence, also!) ‘We have both been fortunate to work with other mi croscopists, post-doctoral associates, and graduate students who have taught us much and contributed significantly to the examples in the text. We would like to thank a few of these colleagues directly: Dave Ackland, Ian Anderson, Charlie Betz, John Bruley, Dov Cohen, Ray Coles, Vinayak Dravid, Joe Goldstein, Brian Hebert, Jason Heffelfinger, Join Hunt, Matt Johnson, Vicki Keast, Ron Liu, Charlie Lyman, Stuart McKean, Joc Michael, Grant’ Norton, Sundar Ramamurthy, René Rasmussen, Kathy Repa, Al Romig, David A. Smith, Changmo Sung, Caroline Swat sor, Ken Vecchio, and Mike Zemyan. In addition, many other colleagues and friends in the fields of microscopy and microanalysis have helped withthe book (even if they weren’t aware of it). These include: Ron Anderson, Jim Bentley, Geoff Campbell, Graham Cliff, David Cockayne, the late Chuck Fiori, Peter Goodhew, Ron Gaonsky, Peter Hawkes, David Joy, Roar Kilaas, Gordon Lovimer, Harald Millejans, Dale Newbury, Mike O’Keefe, Jolin Steeds, Peter Swann, Gareth Thomas, Patrick Veyssiére, Nestor Zaluzec, and Elmar Zeitler. In addition, many other Iisroscopists kindly provided the figures that we acknowl- ‘edge individually inthe list atthe end of the book. We have received financial support for our mi- ‘erwscopy studies through several federal agencies; without this support none of the research that underpins the con- tents of this book would have been accomplished. In par- ticular, DBW wishes to acknowledge the National Science Foundation (Division of Materials Research) for almost 20 years of continuous funding, the National Aeronautics and Space Administration, the Department of Energy (Ba- sic Energy Sciences), Sandia National Laboratories, and the Materials Research Center at Lehigh, which supports the microscopy laboratory. Portions of the text were writ- ten while DBW was on sabbatical or during extended visits to Chalmers University, Giteborg, with Gordon Dunlop and Hans Nordén; the Max Planck Instiut fr Metall forschung, Stuttgart, with Manfred Ruble; and Los Alamos National Laboratory, with Terry Mitchell. CBC wishes to acknowledge the Department of Energy (Basic Energy Sci- ences), the National Science Foundation (Division of Ma- terials Research), the Center for Interfacial Engineering at the University of Minnesota, the Materials Science Center at Comell University, and the SHaRE Program at Oak Ridge National Laboratories. This text was started while CBC was with the Department of Materials Science and Engineering at Cornell University Despite our common scientific beginnings as under- sraduates in Chris’s College, Cambridge, we learned our trade under different microscopists; DBW with Jeff Eding- ton in Cambridge and CBC with Sit Peter Hirsch and Mike Whelan in Oxford. Not surprisingly, the classical texts by these renowned microscopists are referred to throughout this book. They influenced our own views of TEM tremen- ously, unavoidably contributing to any bias in our opin- ions, notation, and approach to the whole subject.List of Acronyms The field of TEM is a rich source of acronyms, behind which we hide both simple and esoteric concepts. While the gen- ‘eration of new acronyms can be a source of original thinking (e.g., see ALCHEMD), it undoubtedly makes for easier com- ‘munication in many cases and certainly reduces the length of voluminous textbooks. You have to master this strange lan- ‘guage before being accepted into the community of microscopists, so we present a comprehensive listing that you should memorize. ACF absorption correction factor AID analog to digital (converter) ADF annular dark field AEM analytical electron microscope/microscopy AES Auger electron spectrometer/spectroscopy AFF _aberration-free focus ALCHEMI atom location by channeling-enhanced micro- analysis ANL Argonne National Laboratory APB _anti-phase domain boundary ASU Arizona State University ATW atmospheric thin window BF bright field BFP back focal plane BSE__ backscattered electron BSED _backscattered-electron diffraction BZB_Brillouin-zone boundary C(1,2,etc.) condenser (1, 2, ete.) lens CB_ coherent bremsstrahlung CBED convergent-beam electron diffraction CBIM convergent-beam imaging CCD. charge-coupled device CCF cross-correlation function CCM _charge-collection microscopy CDF centered dark field CF coherent Fresnel/Foucault CFEG cold field-emission gun xi CL _cathodoluminescence CRT cathode-ray tube CS crystallographic shear CSL coincident-site lattice DF dark field DOS density of states DP diffraction pattern DQE detection quantum efficiency DSTEM dedicated scanning transmission electron micro- scope/microscopy DISA desktop spectrum analyzer EBIC electron beam-induced currenticonductivity EELS _clectron energy-loss spectrometry EFI energy-filtered imaging ELNES energy-loss near-edge structure ELP _energy-loss program (Gatan) EMMA electron microscope microanalyzer EMS electron microscopy image simulation EPMA electron probe microanalyzer ESCA electron spectroscopy for chemical analysis, ESI_ electron spectroscopic imaging EXAFS extended X-ray absorption fine structure EXELFS extended energy-loss fine structure FCF fluorescence correction factor FEG _field-emission gun FET field-effect transistor FFT fast Fourier transformWw FOLZ first-order Laue zone FSE fast secondary electron PIP file transfer protocol FWHM full width at half maximum FWTM full width at tenth maximum GB_ grain boundary GCS "generalized cross section GIF Gatan image filter GOS generalized oscillator strength HAADF high-angle annular dark field HOLZ higher-order Laue zone HPGe high-purity germanium HRTEM high-resolution transmission electron micro- scope/microscopy HV high vacuum HVEM "high voltage electron microscope/microscopy IDB _ inversion domain boundary IEEE International Electronics and Electrical Engineering IG _ intrinsic Ge IVEM intermediate voltage electron microscope/micro- scopy K-M_Kossel-Méllenstedt LEED LLs LuT low-energy electron diffraction linear least-squares look-up table MC_ minimum contrast MCA. multichannel analyzer MDM minimum detectable mass MLS multiple least-squares MMF minimum mass fraction MSDS material safety data sheets NCEMSS National Center for Electron ulation system NIH_ National Institutes of Health NIST _ National Institute of Standards and Technology ictoscopy sim- OR_ orientation relationship OTEDP oblique-textured electron diffraction pattern PB phase boundary P/B_peak-to-background ratio. PEELS parallel electron energy-loss spectrometer/spec- trometry PIMS Precision Ion-Milling System®® PIPS Precision fon-Polishing System® PM photomultiplier POA. phase-object approximation LIST OF ACRONYMS QHRTEM quantitative high-resolution transmission elec- ‘ton microscopy RB translation boundary (yes, it does!) RCP rocking-beam channeling patterns RDF radial distribution function REM _ reflection electron microscope/microscopy RHEED _ reflection high-energy electron diffraction RHF relativistic Hartree-Fock RHFS relativistic Hartree-Fock-Slater SAD selected-area diffraction SE_ secondary electron SEELS serial electron energy-loss spectrometer/spec- trometry SEM _ scanning electron microscope/microscopy SF stacking fault SHRLI simulated high-resolution lattice images SIMS _ secondary ion mass spectrometry SIN signal-to-noise ratio SOLZ second-order Laue zone SRM _ standard reference material ‘STEM _ scanning transmission electron microscope/micro- scopy STM scanning tunneling microscope/microscopy TB. twin boundary TEM transmission electron microscope/microscopy TMBA too many bloody acronyms UHV ultrahigh vacuum UTW ultrathin window VIF voltage to frequency (converter) VLM _ visible-light microscope/microscopy WB _ weak beam WBDF weak-beam dark field WDS _ wavelength-dispersive spectrometer/spectrometry WP whole pattern WPOA weak-phase object approximation WWW World Wide Web XANES _ X-ray absorption near-edge structure XEDS | X-ray energy-dispersive spectrometer/spectrometry XRD X-ray diffraction YBCO yttrium-barium-copper oxide YAG - yttrium-aluminum gamet ZAP atomic number, absorption, fluorescence (correc tion) ZAP _zone-axis pattern ZOLZ zero-order Laue zoneList of Symbols ‘We use a large number of symbols, Because we are constrained by the limits of our own and the Greek alphabets we often use the same symbol for different terms, which can confuse the unwary. We have tried to be consistent where possible but undoubtedly we have not always succeeded. The following (not totaly inclusive) list may help if you remain confused after reading the text. relative transition probability ‘ay Bohr radius a,b,c lattice vectors a*,b#, c¥ reciprocal lattice vectors amplitude of scattered beam. amperes, absorption correction factor active area of the detector Richardson's constant atomic weight Angstrom Bloch wave amplitude A(U) aperture function >> Bb >a b beam-broadening parameter ‘edge component of the Burgers vector Burgers vector of partial dislocation Burgers vector of total dislocation beam direction magnetic field strength background intensity B(U) aberration function oe bos. ¢ velocity of light © contrast composition CC, astigmatism aberration coefficient CC. chromatic aberration coefficient C,-Bcomponent of Bloch wave xv G spherical aberration coefficient Gy. fraction of X atoms on specific sites Cy amplitude of direct beam C,_ combination of the elastic constants (Ed) scherzer (Cd laser 4 beam (probe) diameter 4 diameter of spectrometer entrance aperture spacing of moiré fringes 4. interplanar spacing 4, effective source size 4, diffraction-limited beam diameter 4, Gaussian beam diameter due KE interplanar spacing dj, smallest resolvable image distance dj, smallest resolvable object distance 4,” spherical-aberration limited beam diameter dq effective entrance aperture diameter at recording plane dz thickness ofa diffracting slice dvldQ. differential cross section of one atom D_ change in focus D_ distance from projector crossover to recording plane D_ electron dose Dig, depth of focus Day depth of field Dj, D,__tie-line points on dispersion surfaces in presence of defectcharge on the electron energy electric field Young's modulus spatial coherence envelope chromatic aberration envelope critical ionization energy |, displacement energy "x ionization energy for K-shell electron ;, _tonization energy for L-shell electron total energy energy loss £,, average energy loss , plasmon energy loss E, plasmon energy threshold energy E,_ beam energy E(U) envelope function E(u) envelope function for chromatic aberration Ew) envelope function for specimen drift E,(u) envelope function for the detector Eu) envelope function for the source E,(u) envelope function for specimen vibration Ff focal length ‘Ae) strength of object at point x,y “AO) atomic scattering factor/amplitude {f, scattering factor for X-rays f(s) residual of least-squan F Fano factor F fluorescence correction factor F Lorentz force F,_ fraction of B alloying clement F. special value of F(@) when 0 is the Bragg angle FP) Fourier transform of plasmon intensity Fw) Fourier teansform of fir) FO) Fourier transform of elastic intensity F(1) Fourier transform of single-scattering intensity FQ) structure factor fit diffraction vector (magnitude of K at the Bragg angle) (0) intensity of image at point (x,y) G Bragg reflection G radius of a HOLZ ring G gige Glu) Fourier transform of g(r) ‘ft Planck’s constant ‘distance from specimen to the aperture (6) contrast transfer function (hke) Miller indices of aerystal plane HkE indices of diffraction spots from ke plane LIST OF SYMBOLS H_ spacing of the reciprocal-lattice planes parallel to the electron beam H(u) Fourier transform of A(r) 1 imensity I intrinsic line width of the detector i, emission current i filament heating current J, intensity in the diffracted beam J Keshell intensity above background 1(k) kinematical intensity Jy intensity inthe first plasmon peak J, total transmitted intensity 1, imtensity in the zero-loss peak Jy_ittensity in the direct beam I) low-loss spectrum intensity current density i magnitude of the wave vector Kk Boltzmann’s constant k kilo k, _k-vector of the incident wave K,K-vector of the diffracted wave Kye Cliff-Lorimer factor KR’ bulk modulus, K Kelvin K_ Kramers constant K- sensitivity factor K inner core shell/characteristic X-ray line/ionization edge K change in k due to diffraction K, magnitude of K at the Bragg angle Ky. kernel camera tength m_number of focal increments m, rest mass of the electron M- magnification M_ mega ‘M,_ angular magnification ‘M, transverse magnification M,,M, tie-line points on dispersion surfaces n integer ni free-electron density vector normal to the surface n, number of electrons in the ionized subshell N noise N-number of counts N-number of atoms per unit area N hekee| TiSTOF SYMBOLS. N(E) number of bremsstrahlung photons of energy E N, Avogadro's number ©. direct beam p pico p momentum p integer P. peak intensity P_ FWHM of a randomized electronic pulse generator Py._ probability of K-shell ionization Plz) scattering matrix for a slice of thickness z Q number of scattering events per unit distance Q cross section radius distance a wave propagates power term to fit background in EELS spectrum. yy image translation distance rr, lattice vector rh reciprocal lattice vector ‘ry astigmatism disk radius 1 chromatic-aberration disk radius ym Spherical-aberration disk radius re. minimum disk radius 1," theoretical disk radius lattice vector in strained crystal 1, maximum radius of DP in focal plane of spectrometer R crystal latice vector R countrate R_ resolution of XEDS detector R distance on screen between diffraction spots R, lattice displacement vector excitation error or deviation parameter 5, excitation error due to defect 5,(6,) excitation error in the z direction Sigg “effective excitation error distance from the specimen to detector S- signal 5 standard deviation for n measurements st steradians {shift vector between the ZOLZ and the HOLZ 1" absorption path length Tw) _objective-lens transfer function T.g(w) effective transfer function object distance W_ unit vector along the dislocation line u* vector normal to the ZOLZ. 4 displacement field UT overvoltage U, Fourier component of the perfect-crystal potential image distance v velocity of an electron V_ accelerating voltage 'Y potential energy V, the volume of the unit cell V; inner potential of cavity V;_ projected potential through the thickness of the speci- V(r) erystal inner potential T absolute temperature T Tesla Ty period of rotation (UVW) indices of a crystal direction UVW indices of beam direction w 6, (excitation error x extinction distance) x. times x distance x. times (magnification) xyz atom coordinates X FWHM due to detector parallax shift in the image displacement at the specimen specimen height (distance along the optic axis) Z__ atomic number/atomic number correction factor Greek symbols 8 phase shift due to defect, semiangle of incidence/convergence X-ray take-off angle i,q, optimum convergence semiangle 8 B brightness B ratio of electron velocity to light velocity B_ semiangle of collection By optimum collection semiangle ‘y degree of spatial coherence phase of direct beam A. changeldifference A. width of energy window ‘Ad phase difference ‘A0, angles between Kossel-Méllenstedt fringes jg difference in mass-absorption coefficients AE’ energy spread Ag, plasmon line width 4f " maximum difference in focus Afgge Aberration-free (defocus ‘fe minimum contrast defocus fen, optimum defocusAfi Scherzer defocus Alt” relative depth in specimen AI change in intensity Ap parallax shift AV. change in the inner potential ‘Ar path difference ‘Ax half-width of image of undissociated screw disloca- tion Ax., resolution at Scherzer defocus Ac” change in height angle between detector normal and line from detector to specimen 8 diameter of disk image 8 diffuseness of interface 5 fluorescence enhancement ratio 8 precipitate/matrix misfit & angle of deflection & detector efficiency © energy to create an electron-hole pair strain 5 permittivity of free space (dielectric constant) ‘1(8) phase of the atomic scattering factor 11 phase change v- Poisson's ratio @ work function ‘Dye X-ray emission from element A in an isolated thin film angle between Kikuchi line and diffraction spot angle between two Kikuchi line pairs angle between wo planes angle of tit between stereo images phase of a wave * “complex conjugate of amplitude of the diffracted beam 7 amplitude of the direct beam 6, angle of deflection of the beam (02) depth distribution of X-ray production X% Wave vector outside the specimen %q Wave vector which terminates on the point G in rec rocal space Yo Wave vector which terminates on the point O in recip- rocal space x(u)phase-distortion function Seeoseos ke thermal conductivity LST OF SYMBOLS & extinction distance for diffracted beam "absorption parameter extinction distance for direct beam & absorption-modified &, A mean-free path wavelength A, coherence length plasmon nes fee path ye igs of Ewald sphere ao Ht refractive index w/p mass absorption coefficient 0%) Bloch function v frequency amplitude of a wave Wt total wave function Yo" total wave function angle between directions density 6, information limit due to chromatic aberration (r) radial distribution function pf mass thickness 2 area of a pixel ‘© scattering cross section of one atom standard deviation o stress ionization cross section for K-shell electron total scattering cross section 04(BA) partial ionization cross section © scattering semiangle 0, Bragg angle 6, cut-off semiangle ©, characteristic scattering semiangle 6, screening parameter T detector time constant t dwell time © fluorescence yield ©, cyclotron frequency ©, plasmon frequency Q. solid angle of collection ® convolution (multiply and integrate)Contents 1m Basics 1m The Transmission Electron Microscope Chapter Preview Eee 1.1. Why Use Electrons? 1.L.A. An Extremely Brief History 1.1.B. Microscopy and the Concept of Resolution 1.1.C. Interaction of Electrons with Matter 1.1.D. Depth of Field 1.L.E. Diffraction 1.2. Limitations of the TEM 1.2.A. Sampling - 1.2.B. Interpreting Transmission Images... 1.2.C. Electron Beam Damage and Safety -1.2.D. Specimen Preparation . 1.3. Different Kinds of TEMs : 1.4, Some Fundamental Properties of Electrons 15. Microscopy on the Intemet/World Wide Web 1.5.A. Microscopy and Microanalysis-Related WWW Sites Fi Microscopy and Microanalysis Software Chapter Summary . References . 1 2m Scattering and Diffraction Chapter Preview... 2.1. Why Are We Interested in Electron Scattering? . 2.2. Terminology of Scattering . : 2.3. The Characteristics of Electron Scattering . 2.4. The Interaction Cross Section . 2.5. The Mean Free Path 2.6. The Differential Cross Section 19 24 22, 23 24 25 28 2.1. Other Factors Affecting Scattering 2.8. Comparison to X-ray Diffraction 2.9. Fraunhofer and Fresnel Diffraction 2.10. Diffraction of Light from Slits 2.11. Coherent Interference 2.12. A Word about Angles... 2.13. Electron Diffraction Patterns Chapter Summary References . 3. m Elastic Scattering Chapter Preview . 3.L.Particles and Waves ..... 3.2. Mechanisms of Elastic Scattering 3.3. Scatter from Isolated Atoms 3.4. The Rutherford Cross Section .... 3.5. Modifications to the Rutherford Cross Se 3.6. Coherency of the Rutherford-Scattered Electrons sees 3.7. The Atomic Scattering Factor 3.8. The Origin of (8) 3.9. The Structure Factor F(0) . 3.10. Simple Diffraction Concepts . 3.10.A. Interference of Electron Waves... 3.10.B. Diffraction Equations Chapter Summary ... References 4 m Inelastic Scattering and Beam Damage Chapter Preview 4.1, Which Inelastic Processes Occur in the TEM? 4.2. X-ray Emission .. 4.2.4, Characteristic X-rays 4.2.B. Bremsstrahlung X-rays ..... xix 26 26 a 27 28 30 30 31 33 38 37 37 38 39 39 40 41 42 43 44 45 46 47 49 SI 51 52. 564.3. Secondary Electron Emission 4.3.A. Slow Secondary Electrons 4.3.B, Fast Secondary Electrons 4.3.C. Auger Electrons .. 4.4, Blectron-Hole Pairs and Cathodoluminescence (CL) 4.5, Plasmons and Phonons 4.6. Beam Damage 4.6.4. Electron Dose 4.6.B. Specimen Heating 4.6.C. Beam Damage in Polymers 4.6.D. Beam Damage in Covalent and Ionic Crystals, 4.6.E, Beam Damage in Metals 4.6. Sputtering .... Chapter Summary References 5 m@ Electron Sources Chapter Preview 5.1. The Physics of Different Electron Sources 5.1.4. Thermionic Emission 5.1.B. Field Emission 5.2. The Characteristics of the Electron Beam 5.2.A. Brightness 5.2.B. Temporal Coherency and Energy Spread . 5.2.C. Spatial Coherency and Source Size 5.2.D. Stability 5.3. Blectron Guns : 5.3.4. Thermionic Guns 5.3. Field-Emission Guns (FE 5.4, Comparison of Guns 5.5. Measuring Your Gun Characteristics 5.5.8. Beam Current 5.5.B. Convergence Angle 5.5.C. Calculating the Beam Diameter 5.5.D, Measuring the Beam Diameter 5.5.E. Energy Spread . 5.5.F. Spatial Coherency . 5.6. What kV Should You Use? Chapter Summary References 6 m Lenses, Apertures, and Resolution Chapter Preview 6.1, Why Learn about Lenses? 6.2. Light Optics and Electron Optics 6.2.4, How to Draw a Ray Diagram 6.2.B. The Principal Optical Elements 6.2.C. The Lens Equation 6.2.D. Magnification, Demagnification, and Focus 37 37 38 58 39 ca 61 62 6 62 3 683 65 65 65 67 oo od 70 70 70 n n n n 16 n B 8 8 9 9 82 82 82 83 85 87 87 88 89 90 90 ‘CONTENTS: 6.3, Blectron Lenses 91 6.3.A. Polepieces and Coils 91 6.3.B. Different Kinds of Lenses . 92 6.3.C. Electron Ray Paths through Magnetic Fields : 3 6.3.D. Image Rotation and the Eucentic Plane 95 6.3.E. Deflecting the Beam . 95 64, Apertures and Diaphragms 95 6.5. Real Lenses and Their Problems 7 6.5.A. Spherical Aberration ” 6.5.B. Chromatic Aberration 98 6.5.C. Astigmatism 98 6.6. The Resolution of the Electron Lens (and Ultimately of the TEM) . . 99 6.6.A, Theoretical Resolution 99 6.6.B. Spherical Aberration-Limited Resolution (The Practical Resolution) ... 100 6.6.C. Confusion in the Definitions of Resolution 101 6.7. Depth of Focus and Depth of Field... 102 Chapter Summary .. : 103 References. 104 7 m Howto “See” Electrons Chapter Preview 105 7.1. Bleetron Detection and Display 107 7.2. Viewing Screens 108 7.3. Blectron Detectors . cee 108 7.3.A, Semiconductor Detectors 108 73.B. Scintillator-Photomulkiplier Detectors ... 110 7A.C.TV Camere and Chage-Compled Devices . ut 7.3.D. Faraday Cup 12 7.4, Which Detector Do We Use for Which Signal?” 12 7.5. Image Recording na 7.5.A. Photographic Emulsions 4 7.5.B. Other Image Recording Methods 14 7.6. Comparison of Scanning Images and Static TEM Images 1s Chapter Summary us References 15 8 m Pumps and Holders Chapter Preview : 17 8.1, Vacuums 119 8.2, Roughing Pumps 119 8.3. High/Ultra-High Vacuum Pumps 120 8.3.A. Diffusion Pumps 120 8.3.B. Turbomolecular Pumps 120 8.3.C. Ion Pumps ... 121 8.3.D. Cryogenic (Adsorption) Pumps 121‘CONTENTS: 8.4, The Whole System .... 8.5.Leak Detection . 8.6. Contamination: Hydrocarbons and ‘Water Vapor 8.7. Specimen Holders and Stages 88. Side-Entry Holders - 8.9. Top-Entry Holders 8.10. Different Types of Holders Chapter Summary References 9m The Instrument Chapter Preview . 9.1. The Ilumination System . 9.1.A. TEM Operation Using a Parallel Beam 9.1.B. Convergent-Beam (S)TEM Mode... 9.1.C. Translating and Tilting the Beam 9.1.D. Alignment . : 9.1.8. Condenser Lens Defects 9.1.F. Calibration 9.2. The Objective Lens and Stage 9.3, Forming Diffraction Patterns and Images: ‘The TEM Imaging System 9.3.4. Selected-Area Diffraction ‘i 9.3.B. Bright-Field and Dark-Field Imaving 9.3.C. Centered DF Operation .. 9.4. Forming Diffraction Patterns and Images: ‘The STEM Imaging System 9.4.4. Bright-Field STEM Images 9.4.B. Dark-Field STEM Images .. 9.4.C. Annular DF Images .. 9.4.D. Magnification in STEM 9.5, Alignment and Stigmation 9.5.4. Lens Rotation Centers 9.5.B. Correction of Astigmatism in the Imaging Lenses 9.6. Calibration of the Imaging System . 9.6.4. Magnification Calibration 9.6.B. Camera-Length Calibration 9.6.C. Rotation of the Image Relative to the Diffraction Pattern 9.6.D. Analysis of TEM Images and Diffraction Patterns : 9.7. Other Calibrations Chapter Summary References 10 m Specimen Preparation Chapter Preview ae 10.1. Safety : 10.2, Self-Supporting Disk or Use a Grid? 10.3. Preparing a Self-Supporting Disk for Final Thinning : 122 123 123 124 124 125 125 128 129 131 133 133 133 135 136 137 138 139 140 140 142 143 144 144 145 145 146 147 147 147 148 148 150 1st 151 151 153 153 155 137 158 159 10.3.A. Creation of a Thin Slice from the Bulk Sample 10.3.B, Cutting the Disk 10.3. Prethinning the Disk 10.4, Final Thinning of the Disk 10.4.4. Electropolishing 10.48. Ion Milling . 10.5. Cross-Section Specimens 10.6. Specimens on Grids/Washers 10,6. Electropolishing —The Window Method for Metals and Alloys « 10.6. Ultramicrotomy Bae 10.6.C. Grinding and Crushing . 10.6. Replication and Extraction 10.6. Cleaving 10.6F. The 90° Wedge 10.66. Lithography 10.61. Preferential Chemical Etching .- 10.7. Storing Specimens Chapter Summary References raction 11 m Diffraction Patterns Chapter Preview 11.1, Why Use Diffraction in the TEM? 11.2. The TEM, Diffraction Cameras, and the TV .. 11.3. Scattering from a Plane of Atoms 11.4, Scattering from a Crystal 11.5. Meaning of n in Brage’s Law 11.6. A Pictorial Introduction to Dynamical Effects. 11.7. Use of Indices in Diffraction Patterns 11.8, Practical Aspects of Diffraction-Pattern Formation 11.9, More on Selected-Area Diffraction Patterns Chapter Summary .... References 12. @ Thinking In Resiprocel Space Chapter Preview 12.1. Why Introdice Another Lattice? 12.2. Mathematical Definition of the Reciprocal Lattice 123. The Vector g. 12.4. The Laue Equations and Their Relation (0 Bragg’s Law 12.5. The Ewald Sphere of Reflection . 12.6. The Excitation Error . 12.7. Thin-Foil Effect and the Effect of Accelerating Voltage 159 159 160 161 161 162 165 166 166 167 167 168 168 169 169 169 170 170 m2 77 179 179 181 182 184 185 185 185 186 189 189 191 193 193 194 195 196 197 199Chapter Summary References 13 m Diffracted Beams Chapter Preview 13.1. Why Calculate Intensities? 13.2, The Approach 133. The Amplitude ofa Diffracted Beam 13.4, The Characteristic Length 135. The Howie-Whelan Equations 13.6. Reformulating the Howie-Whelan Equations 13.7. Solving the Howie-Whelan Equations 13.8. The Importance of 0 and 2 13.9. The Total Wave Amplitude 13.10. The Effective Excitation Error 13.11. The Column Approximation 13.12. The Approximations and Simplifications 13.13. The Coupled Harmonic Oscillator Analog Chapter Summary References 14m Bloch Waves Chapter Preview 14.1. Wave Equation in TEM 14.2. The Crystal 14.3. Bloch Functions 14.4, Schrédinger’s Equation for Bloch Waves 14.5. The Plane-Wave Amplitudes 14.6. Absorption of Bloch Waves Chapter Summary References, 15 m Dispersion Surfaces Chapter Preview 15.1. Introduction : 15.2. The Dispersion Diagram when U, 15.3. The Dispersion Diagram when U! 0 15.4, Relating Dispersion Surfaces and Diffraction Patterns 15.5. The Relation between U, ,£,, and s, 15.6. The Amplitudes of Block Waves 15.7, Extending to More Beams 15.8. Dispersion Surfaces and Defects Chapter Summary References 16 m_ Diffraction from Crystals Chapter Preview 16.1. Review of Diffraction from a Primitive Lattice 16.2. Structure Factors: The Idea 200 200 201 203, 203 204 205, 206 207 207 208 209 210 210 2 212 212 213 21s 217 217 219 219 21 23 23 224 ns 27 228 228 29 232 233, 234 235, 235 236 237 239 240 CONTENTS: 16.3. Some Important Structures: bec, fee, and hep ......... 16.4. Extending fec and hep to Include a Basis, 165, Applying the bee and fec Analysis to Simple Cubie . 16.6. Extending hep to TiAl : 16.7. Superlattice Reflections and Imaging 16.8. Diffraction from Long-Period ‘Superlatices 16.9. Forbidden Reflections : 16.10. Using the International Tables Chapter Summary References 17m Diffraction from Small Volumes Chapter Preview 17.1. Introduction 17.1.4. The Summation Approach . 17.1.B. The Integration Approach 17.2. The Thin-Foil Effect 17.3. Diffraction from Wedge-Shaped Specimens 17.4, Diffraction from Planar Defects 17.5. Diffraction from Particles 11.6. Diffraction from Dislocations, Individually and Collectively ...... 17.1. Diffraction and the Dispersion Surface Chapter Summary References 18 m Indexing Diffraction Patterns Chapter Preview 18.1. Choosing Your Technique . 18.2. Experimental Techniques . 18,3. The Stereographic Projection 18.4, Indexing Single-Crystal Diffraction Patterns 18.5. Ring Patterns from Polycrystalline Materials 18.6, Ring Patterns from Amorphous Materials 18.7. Double Diffraction 18.8. Orientation of the Specimen 18.9. Orientation Relationships 18.10. Computer Analysis Chapter Summary , References 19 m_ Kikuchi Diffraction Chapter Preview 19.1. The Origin of Kikuchi Lines 19.2. Kikuchi Lines and Bragg Scattering 19.3. Constructing Kikuchi Maps 241 242 243, 244 244 246 247 247 249 249 251 253 254 255 256 256 258 259 261 262 263 265 267 267 269 am 273 274 278 280 280 285, 286 286 289 291 291 293‘CONTENTS| 19.4, Crystal Orientation and Kikuchi Maps 1955. Setting the Value ofs, .. 19.6. Intensities "i Chapter Summary . References 20 m Obtaining CBED Patterns Chapter Preview 20.1. Why Use a Convergent Beam?» 20.2, Obtaining CBED Patterns 20.2.A. Comparing SAD and CBED 20.2.B. CBED in TEM : 20.2.C. Choosing the C2 Aperture 20.2.D. Choosing the Camera Length 20.2.E. Focusing Your Pattern. 20.2.F. Choice of Beam Size ..... 20.2.G, Effect of Specimen Thickness 20.2.H. Final Adjustment . 20.2.1. CBED in STEM Mode 20.3. Zero-Order and Higher-Order Laue-Zone Diffraction : 20.3.4. ZOLZ Patterns 20.3.B. HOLZ Patterns 20.3.C. Indexing HOLZ Patterns 20.4. Kikuchi Lines in CBED Patterns 20.5. HOLZ Lines 20.5.A. The Relationship between HOLZ Lines and Kikuchi Lines 20,5.B. Acquiring HOLZ Lines 20.5.C. Indexing HOLZ Lines Chapter Summary . References, 21 m Using Convergent-Beam Techniques Chapter Preview ....... : 21.1. Thickness Determination 21.2, Unit-Cell Determination 21.2.4, Experimental Considerations 21.2.B. The Importance of the HOLZ-Ring Radius 21.2.C. Determining the Lattice Centering 21.3. Symmetry Determination 21.3.A. Introduction to Symmetry Concepts 21.3.B. Friedel’s Law... a 21.3.C. Looking for Symmetry in Your Patterns 21.3.D. Point-Group Determination 21.3.B. Space-Group Determination 21.4. Lattice Parameter, Strain, and Composition Analysis 21.5. Determination of Enantiomorphism 21.6. Convergent-Beam Imaging ... 295 296 297 298 298 301 303 304 304 305 305 306 306 307 308 308 308 309 309 309 301 314 315 315 315 317 318 318 319 321 323 323 323, 325 326 326 328 328 330 332 338 341 341 21.7. Scanning-Beam Diffraction ..........+ 21.8. Other Methods of Microdifiraction . Chapter Summary References Mm Imaging 22m Imaging in the TEM Chapter Preview 22.1. What Is Contrast? 22.2. Principles of Image Contrast 22.2.A. Images and Diffraction Patterns 22.2.B. Use of the Objective Aperture or the STEM Detector: BF and DF Images 22.3. Mass-Thickness Contrast 22.3.A. Mechanism of Mass-Thickness Contrast 22.3.B. TEM Images 22.3.C, STEM Images 22.3.D. Specimens Which Show ‘Mass-Thickness Contrast 22.3.8. Quantitative Mass-Thickness Contrast. ceesee 22.4. Z Contrast : 22.8. TEM Diffraction Contrast .- 2.5.4. Two-Beam Conditions 22.5.B. Setting the Deviation Parameter, 5 22.8.C. Setting Up a Two-Beam CDF Image . 22.5.D. Relationship between the Image and the Diffraction Pattern 22.6, STEM Diffraction Contrast . . Chapter Summary... References 23m Thickness and Bending Effects Chapter Preview Gac0000 23.1. The Fundamental Ideas . 23.2. Thickness Fringes 23.3. Thickness Fringes and the Diffraction Pattern 23.4, Bend Contours (Annoying Artfact, Useful Tool, and Valuable Insight) . 23.5. ZAPs and Real- Space Costllogaphy 23.6. Hillocks, Dents, or Saddles 23.7. Absorption Effects 23.8. Computer Simulation of Thickness Fringes 23.9. Thickness-Fringe/Bend-Contour Interactions 341 343. 344 345 349 351 351 351 351 353 353 354 355 357 397 358 361 361 361 361 363 364 366 366 367 369 369 371 372 373 374 374 375 37523.10. Other Effects of Bending Chapter Summary ,. References 24 m Planar Defects Chapter Preview 24.1. Translations and Rotations. : 24.2. Why Do Translations Produce Contrast? 24.3. The Scattering Matrix ‘i 24.4. Using the Scattering Matrix 24.5. Stacking Faults in foc Materials, 24.5.A. Why fee Materials? 24.5.B. Some Rules . 24.5.C. Intensity Calculations . 24.5.D. Overlapping Faults 24.6. Other Translations: 1 and 8 Fringes 24.7, Phase Boundaries 24.8, Rotation Boundaries 24.9. Diffraction Patterns and Dispersion Surfaces . 24.10, Bloch Waves and BF/DF Image Pairs 24.11. Computer Modeling 24.12. The Generalized Cross Section 24.13. Quantitative Imaging ... 24.13.A. Theoretical Basis and Parameters 24.13.B. Apparent Extinction Distance 24.13.C. Avoiding the Column Approximation 24.13.D. The User Interface Chapter Summary References 25 m Strain Fields Chapter Preview 25.1. Why Image Strain Fields? 25.2, Howie-Whelan Equations .. 25.3, Contrast from a Single Dislocation 25.4. Displacement Fields and Ewald’s Sphere 25.5. Dislocation Nodes and Networks . 25.6. Dislocation Loops and Dipoles 25.7. Dislocation Pairs, Arrays, and Tangles 25.8, Surface Effects . 25.9. Dislocations and Interfaces 25.10. Volume Defects and Particles 25.11. Simulating Images ............ 25.11.A. The Defect Geometry 25.11.B. Crystal Defects and Calculating the Displacement Field 25.11.C. The Parameters Chapter Summary References 376 377 378 379 381 382 383, 384 385 386 386 387 388 389 301 391 391 393 304 395, 396 396 397 397 398, 398, 398 401 403 403 405 408 409 409 4ul a2 413 417 418 418 418 419 419 420 ‘CONTENTS 26 m Weak-Beam Dark-Field Microscopy Chapter Preview 26.1, Intensity in WBDF Images S 26.2. Setting s, Using the Kikuchi Pattern . 26.3. How to Do WBDF Goan 26.4. Thickness Fringes in Weak-Beam Images 26.5. Imaging Strain Fields 26.6, Predicting Dislocation Peak Positions 26.7. Phasor Diagrams 26.8. Weak-Beam Images of Dissociated Dislocations oon 26.9. Other Thoughts 26.9.A. Thinking of Weak-Beam Diffraction as a Coupled Pendulum 26,9.B. Bloch Waves . 26.9.C. If Other Reflections Are Present 26.9.D. The Future . Chapter Summary .. References 27 m@ Phase-Contrast Images Chapter Preview . fg 27.1. Introduction 5 27.2. The Origin of Lattice Fringes 27.3, Some Practical Aspects of Latice Fringes 273.A.fs=0 een 27138. ifs #0 : 27.4, On-Axis Lattice-Fringe Imaging 27.5. Moiré Patterns . ee 27.5.4. Translational Moiré Fringes 27.5.B. Rotational Moiré Fringes 27.5.C. General Moiré Fringes 27.6. Experimental Observations of Moiré Fringes 27.6.4. Translational Moiré Patterns 27.6.B. Rotational Moiré Fringes 27.6.C. Dislocations and Moié Fringes . 27.6.D. Complex Moiré Fringes 27.7. Fresnel Contrast 27.7.A, The Fresnel Biprism: 27.7.B. Magnetic-Domain Walls 27.8. Fresnel Contrast from Voids or Gas Bubbles 27.9. Fresnel Contrast from Lattice Defects 27.9.A. Grain Boundaries 27.9.B. End-On Dislocations Chapter Summary References 28 m High-Resolution TEM Chapter Preview 28.1. The Role of an Optical System 28.2. The Radio Analogy 421 423 423 425 426 427 428 430 432 436 436 436 437 437 438 438 439 441 441 442 442 442 442 444 445, 445 445 445 446 447 447 448 450 450 451 431 452 453, 453 435 455 457 459 459—_—_—_—_—_—_=—=_———_ ‘CONTENTS: 28.3. The Specimen 28.4. Applying the WPOA to the TEM 28.5. The Transfer Function 28.6. More on x(u), sin x(u), and cos xi) 28.7. Scherzer Defocus 28.8. Envelope Damping Functions 28.9. Imaging Using Passbands 28.10. Experimental Considerations 28.11. The Future for HRTEM . . 28.12. The TEM as a Linear System 28.13. FEGTEMs and the Information Limit 28.14. Some Difficulties in Using an FEG . 28.15. Selectively Imaging Sublattices 28.16. Interfaces and Surfaces . 28.17. Incommensurate Structures 28.18. Quasicrystals 28.19. Single Atoms Chapter Summary References 29 m Image Simulation Chapter Preview 29.1. Simulating Images . . 29.2. The Multislice Method . 29.3. The Reciprocal-Space Approach 29.4. The FFT Approach ......... 29.5. The Real-Space Approach .. 29.6. Bloch Waves and HRTEM Simulation 29.7. The Ewald Sphere Is Curved .. : 29.8. Choosing the Thickness of the Slice .. 29.9. Beam Convergence Bboeo 29.10. Modeling the Structure 29.11. Surface Grooves and Simulating Fresnel Contrast ..... 29.12. Calculating Images of Defects 29.13. Simulating Quasicrystals 29.14. Bonding in Crystals . Chapter Summary References 30 m Quantifying and Processing HRTEM Images Chapter Preview 30.1. What Is Image Processing? 30.2, Processing and Quantifying Images 30.3. A Cautionary Note 30.4. Image Input 3055. Processing Techniques 30.5.4. Fourier Fitering and Reconstruction - 30.5.B. Analyzing Diffractograms 30.5.C. Averaging Images and Other Techniques . 2 485 461 462 462 463 465 466 467 468 469 470 470 43 475 476 478 479 480 481 481 483 485, 485 487 488 488 489 490 490 491 492 493 494 496 497 497 499 S01 501 502 502 502 502 508 30.5.D. Kernels . 30.6. Applications 30.6.A. Beam-Sensitive Materials 30.6.B. Periodic Images . 30.6.C. Correcting Drift 30.6.D. Reconstructing the Phase 30.6.B. Diffraction Patterns 30.6.F. Tilted-Beam Series 30.7. Automated Alignment 30.8. Quantitative Methods of Image Analysis 30.9. Pattern Recognition in HRTEM. 30.10. Parameterizing the Image Using QUANTITEM 30.10.A. The Example of a Specimen ‘with Uniform Composition . .. 30.10.B. Calibrating the Path of R 30.10.C. Noise Analysis 30.11. Quantitative Chemical Lattice Imaging... 30.12, Methods of Measuring Fit 30.13. Quantitative Comparison of Simulated and Experimental HRTEM Images 30.14, A Fourier Technique for Quantitative Analysis . 30.15. Real or Reciprocal Space? 30.16. The Optical Bench . .. Chapter Summary . References . 31m Other Imaging Techniques Chapter Preview 31.1 Stereo Microscopy . 31.2. 26D Microscopy . 31.3. Magnetic Specimens 31.3.A. The Magnetic Correction 31.3.B. Lorentz Microscopy 31.4. Chemically Sensitive Images 31.5. Imaging with Diffusely Scattered Electrons 31.6. Surface Imaging 31.6.A. Reflection Electron Microscopy 31.6.B. Topographic Contrast 31.7. High-Order BF Imaging 31.8. Secondary-Electron Imaging 31.9. Backscattered-Electron Imaging 31.10. Charge-Collection Microscopy and Cathodoluminscence .. 31.11, Electron Holography 31.12. In situ TEM: Dynamic Experiments 31.13. Other Variations Possible in a STEM Chapter Summary References 507 507 507 508, 508, 508 508 510 sit 512 513 514 sia 516 516 318 518 521 523 523 924 526 526 529 531 532 534 534 535 538 538 540 340 540 S41 S41 542 543 543 546 547 548 548_ EE owl IV m Spectrometry 32 m X-ray Spectrometry Chapter Preview 32.1. X-ray Analysis: Why Bother? - 32.2. Basic Operational Mode : 32.3. The Energy-Dispersive Spectrometer 324. Semiconductor Detectors 32.4.4. How Does XEDS Work? 32.4.B. Different Kinds of Windows 32.4.C. Intrinsic Germanium Detectors 32.5, Pulse Processing and Dead Time 32.6, Resolution of the Detector 32.7. What You Should Know about Your XEDS 32.7.A. Detector Variables. 32.7.B. Processing Variables 32.7.C. Artifacts Common to XEDS Systems : 32.8. Wavelength-Dispersive Spectrometers Chapter Summary References 33m The XEDS-TEM Interface Chapter Preview 3.1. The Requirements 33.2. The Collimator 33.2.A. Collection Angle 33.2.B, Take-Off Angle 33.2.C. Orientation of the Detector to the Specimen 33.3, Protecting the Detector from Intense Radiation 33.4, System X-rays and Spurious X-rays 33.4.4. Pre-Specimen Effects 33.4.B. Post-Specimen Scatter 33.4.C, Coherent Bremsstrahlung 33.5, Peak-to-Background Ratio . Chapter Summary : References 34 Mm Qualitative X-ray Analysis Chapter Preview 34.1. Microscope Variables 34.2. Acquiring a Spectrum 34,3, Peak Identification 34.4, Peak Visibility ‘Chapter Summary References 35 ™ Quantitative X-ray Microanaly: Chapter Preview 35.1. Historical Perspective 35.2, The Cliff-Lorimer Ratio Technique 553 555 5955 558 559 559 560 562 563, 564 565 565 566 568 570 S71 572 573 515 575 S75 576 317 578 578 578 580 583, 583 584 585 987 589 589 590 593 595 595 597 599 600 CONTENTS 35.3, Practical Steps for Quantitative Microanalysis 600 35.3.A. Background Subtraction .. 601 35.3.B. Peak Integration 603 35.4. Determining k Factors 605 35.4.8. Experimental Determination of kj, ... 605 35.4.B. Errors in Quantification 606 35.4.C. Calculating kxg 609 35.5, Absorption Correction, 612 35.6, Extrapolation Techniques for Absorption Correction - 614 35.7. The Fluorescence Correction 61s 35.8. ALCHEMI 616 35.9. Examples: Profiles and Maps 617 Chapter Summary . . 619 References . 619 36m Spatial Resolution and Minimum Detectability Chapter Preview 621 36.1. Why Is Spatial Resolution Important? 623 36.2. Definition of Spatial Resolution 623 36.3. Beam Spreading 624 364. The Spatial Resolution Equation 625 36.5. Measurement of Spatial Resolution 626 36.6. Thickness Measurement + 628 36.6.4. TEM Methods 628 36.6.B. Contamination-Spot Separation Method . 629 36.6.C. X-ray Spectrometry Methods - 630 36.6.D, Electron Energy-Loss Spectrometry Methods 63 36.6.B. Convergent-Beam Diffraction Method 631 36.7. Minimum Detectability . 631 36.7.A. Experimental Factors Affecting the MMF 632 36.7.B. Statistical Criterion for the MMF 632 36.7.C. Comparison with Other Definitions .. 633 36.7.D. Minimum Detectable Mass 634 Chapter Summary 634 References 634 37 m Electron Energy-Loss Spectrometers Chapter Preview 637 37.1. Why Do Electron Energy-Loss Spectrometry? 639 37.2. The Magnetic Prism: A Spectrometer and aLens 640 37.2.A, Focusing the Spectrometer 641 37.2.B. Calibrating the Spectrometer 642 37.3. Acquiring a Spectrum 642 37.3.A. Serial Collection 642‘CONTENTS 37.3.B, Parallel Collection 37.3.C. Spectrometer Dispersion 37.3.D. Spectrometer Resolution 37.3.E. Point-Spread Function 37.4. Image and Diffraction Modes 37.4.A, Spectrometer Collection Angle 37.4.B. Spatial Selection 37.5. What You Need to Know about Your PEELS 37.6. Imaging Spectrometers Chapter Summary References 38 m The Energy-Loss Spectrum Chapter Preview 38.1, A Few Basic Concepts, 38.2. The Zero-Loss Peak 38.3. The Low-Loss Spectrum 38.3.4. Plasmons 38.3.B. Inter- and Intra-Band Transitions 38.4, The High-Loss Spectrum 38.4.. Inner-Shell Ionization 38.4.B. Ionization-Edge Characteristics 38.5. Artifacts in the Spectrum Chapter Summary References 39. m_ Microanalysis with lonization-Loss Electrons ‘Chapter Preview 39.1. Choice of Operating Parameters 39.2. What Should Your Spectrum Look Like? 39.3. Qualitative Microanalysis 39.4, Quantitative Microanalysis 39.4.A. Derivation of the Equations for Quantification 39.4.B. Background Subtraction 644 645 645 646 646 647 649 649 650 651 651 653 655 656 656 656 658 658 658 662 664 665 666 667 669 670 on on 673 674 39.4.C. Edge Integration 39.4.D. The Zero-Loss Integral 39.4.E. The Partial Jonization Cross Section 39.5. Measuring Thickness from the Energy-Loss Spectrum 39.6. Deconvolution 39.7. Correction for Convergence of the Incident Beam 39.8, The Effect of the Specimen Orientation 39.9, Spatial Resolution 39.10. Detectability Limits Chapter Summary References 40 m Everything Else in the Spectrum Chapter Preview 40.1. Fine Structure inthe Ionization Edges 40.1.A. ELNES 40.1.B, EXELFS 40.2. The Low-Loss Spectrum 40.2.A. Plasmon Losses 40.2.B. Dielectric-Constant Determination 40.2.C. Band-Gap and Inter-Band ‘Transitions 40.2.D. Angle-Resolved EELS 40.3. Energy Filtered and Spectrum Imaging 40.3.A, STEM Digital Imaging 403.8, TEM Analog Imaging Chapter Summary References Index ‘Acknowledgements for Figures 676 676 676 678 680 682 682 682 683, 684 684 687 689 689 694 696 696 697 698, 698, 699 700 700 703, 703, 705 7Transmission Electron Microscopy A Textbook for Materials ScienceThe Transmission Electron Microscope 1.1. Why Use Electrons? .... 1.1.A. An Extremely Brief History : 1.1.8. Microscopy and the Concept of Resolution 1.1.C. Interaction of Electrons with Matter 1.1.D. Depth of Field . 1.1.£. Diffraction . 1 Limitations of the TEM . -2.A. Sampling ....... 1.2.B. Interpreting Transmission Images 1.2.C. Electron Beam Damage and Safety 1.2.D. Specimen Preparation . . Different Kinds of TEMs ....... : |. Some Fundamental Properties of Electrons . Microscopy on the Internet/World Wide Web . 1.5.A. Microscopy and Microanalysis-Related WWW 1.5.B. Microscopy and Microanalysis Software . CHAPTER PREVIEW A typical commercial transmission electron microscope (TEM) costs about $2 for each electron volt of energy in the beam, and if you add on all the options, it can cost about $4-5 per eV. As you'll see, we use beam enor, gies in the range from 100,000-400,000 eV, so a TEM becomes an extremely expensive piece of equipment Consequently, there have to be very sound scientific reasons for investing such a large amount of money in One microscope. In this chapter (which is just a brief overview of many of the concepts that we'll talk about in Getall throughout the book) we start by introducing you to some of the historical development of the TEM be- Cause the history is intertwined with some of the reasons why you need to use a TEM to characterize mater als. Other reasons for using TEM appeared as the instrument developed, Unfortunately, coupled with the adh Vantages are some serious drawbacks, which limit the microscope performance, and you must be just as ‘ware of the instrument's limitations as you are of its advantages, 50 we summarize these also. ‘ATEM can appear in several different forms, all of which are described by different acronyms such as HRTEM, STEM, and AEM, and we'll introduce you to these different instruments, We'll also use the same acronym to denote both the technique (microscopy) and the instrument (microscope). We regard all ofthe df. 3a Tm Basics ferent types of TEM as simply variations on a basic theme and that is why only “TEM” is in the book title. We will describe some of the basic physical characteristics of the electron. Throughout the book youll have to con- front some physics and mathematics every now and again. The reason for this is because understanding what we can do with a TEM and why we operate it in certain ways is governed by the fundamental physics of elec- trons, how electrons are controlled by magnetic fields in the microscope, and how electrons interact with ma- terials. Finally, we will summarize some of the most popular computer software packages for TEM. We will refer to many of these throughout the text. We are including them in the first chapter to emphasize the role of the ‘computer in today's TEM analysis.The Transmission Electron Microscope 1.1. WHY USE ELECTRONS? Why should we use an electron microscope? Histori- cally, TEMs were developed because of the limited im- age resolution in light microscopes, which is imposed by the wavelength of visible light. Only after electron mi- ccroscopes were developed was it realized that there are ‘many other equally sound reasons for using electrons, most of which are utilized to some extent in a modern TEM. By way of introduction to the topic let's look at how the TEM developed and the pros and cons of using such an instrument, 1.1.A. An Extremely Brief History Louis de Broglie (1925) first theorized that the electron had wave-like characteristics, with a wavelength substan- tially less than visible light. Then Davisson and Germer (1927) and Thompson and Reid (1927) independently car- ried out their classic electron diffraction experiments hich demonstrated the wave nature of electrons. It didn’t take long for the idea of an electron microscope to be pro- posed, and the term was first used in the paper of Knoll and Ruska (1932). In this paper they developed the idea of electron lenses into a practical reality, and demonstrated electron images taken on the instrument shown in Figure 1.1. This was a most crucial step, for which Ruska received the Nobel Prize, somewhat late, in 1986. Within a year of Knoll and Ruska’s publication, the resolution limit of the light microscope was surpassed. Ruska, surprisingly, re- vealed that he hadn’t heard of de Broglie's ideas about electron waves and thought that the wavelength limit didn't apply to electrons. TEMs were developed by com- mercial companies only four years later. The Metropolitan- Vickers EMI was the first commercial TEM. It was built in the UK in 1936, but apparently it didn’t work very well and regular production was really started by Siemens and Halske in Germany in 1939, TEMs became widely avail- able from several other sources (Hitachi, JEOL, Philips and RCA, inter alia) after the conclusion of World War I For materials scientists a most important develop- ‘ment took place in the late 1940s when Heidenreich (1949) first thinned metal foils to electron transparency. This work ‘was followed up by Bollman in Switzerland and Hirsch and co-workers in Cambridge. Because so much of the early ‘TEM work examined metal specimens, the word “foil” has come to be synonymous with “specimen.” In addition, the Cambridge group also developed the theory of electron fraction contrast with which we can now identify, often in a quantitative manner, all known line and planar erystal de- fects in TEM images. This theoretical work is summarized in a formidable but essential text often referred to as the “Bible” of TEM (Hirsch et al. 1977). For the materials sci- centist, practical applications of the TEM for the solution of materials problems were pioneered in the United States by ‘Thomas and first clearly expounded in his text (Thomas 1962). Other materials-oriented texts followed, e.g., Eding- ton (1976) and Thomas and Goringe (1979). Today, TEMs constitute arguably the most efficient and versatile tools for the characterization of materials. If ‘you want to read a history of the TEM, the book by Marton (1968) is a compact, personal monograph and that edited by Hawkes (1985) contains a series of individual reminis- ccences. Fujita (1986) emphasizes the contribution of Japan to the development of the instrument. The field is now at the point where many of the pioneers have put their mem- irs down on paper, or Festschrifts have been organized in their honor (¢.g., Cosslett 1979, Ruska 1980, and Hashimoto 1986) which detail their contributions over the decades, and compile some useful overview papers of the field. If you enjoy reading about the history of science, we strongly recommend the review of Fifty Years of Electron Diffraction, edited by Goodman (1981), and Fifty Years of X-ray Diffraction, edited by Ewald (1962). (The spelling of, X-ray is discussed in the CBE Manual, 1994,)Figure 1.1. The clecton microscope built by Rusks and Knoll in ‘Berlin nthe early 1930s, 1.1.B. Microscopy and the Concept of Resolution When asked what a “microscope” is, most people would answer that it is an instrument for magnifying things too ‘small to see with the naked eye, and most likely they would be referring to the visible-light microscope, Because of the general familiarity with the concept of the light micro scope, we will draw analogies between electron and visi- ble-light microscopes wherever it’s instructive The smallest distance between two points that we can resolve with our eyes is about 0.1-0.2 mm, depending ‘on how good our eyes are, and assuming that there’s suffi- cient illumination to see by. This distance is the resolution or resolving power of our eyes. So any instrument that can show us pictures (or “images” as we'll refer to them) re- veiling detail finer than 0.1 mm could be described as a microscope, and its highest useful magnification is gov- ered by its resolution. A major attraction to the early de- velopers of the TEM was that, since electrons are smaller than atoms, it would be possible, at least theoretically, to build @ microscope that could “see” detail well below the atomic level. The idea of being able to “see” with electrons may be confusing to you. Our eyes are not sensitive to electrons. If a beam of high-energy electrons was aimed into your eye, you would most likely be blinded as the electrons killed the retinal cells, but you wouldn't see any- thing! So an integral part of any electron microscope is a viewing screen of some form, which translates electron in- tensity to light intensity, and which we observe or record photographically. We'll discuss these screens and other ‘ways of recording electron images in Chapter 7. 1m Basics The resolution of a TEM means different things for different functions of the instrument, and we'll discuss ‘them in the appropriate chapters. Its easiest to think of the image resolution in TEM in terms of the classical Rayleigh criterion for light microscopy, which states that the smallest distance that can be resolved, 8, is given approximately by 61h, = 2s a. In equation 1.1, 1 is the wavelength of the radiation, the reftactive index of the viewing medium, and B isthe semi- angle of collection of the magnifying lens. For the sake of simplicity we can approximate sin B (which is sometimes called the numerical aperture) to unity and so the resolu- tion is equal to about half the wavelength of light. For {green light in the middle of the visible spectrum, 2-is about '550 nm (5500 A), and so the resolution of a good light mi- croscope is about 300 nm. In TEMs we can approximate sO a @ more convenient Using convoluted Dhrases tke he nanometer.” the resolution in equation 1.1:to 0.614/B which, as we'll see later, is very small Now although 300 nm is a small dimension to us it corresponds to about 1000 atom diameters, and therefore ‘many of the features that control the properties of materials are on a scale well below the resolution of the light micro- scope. So there's a real need to image detail down to the atomic level if we want to understand the properties of ma- terials, and that's a major reason why TEMS are 0 useful. This limit of light microscopy was well understood at the turn of this century and prompted Emst Abbe, one of the giants in the field, to complain that “it is poor comfort to hope that human ingenuity will find ways and means of ‘overcoming this limit.” (He was right to be so depressed. because he died in 1905, some 20 years before de Broglie’s, ingenuity solved the problem.) Now de Broglie’s famous equation shows that the wavelength of electrons is related to their energy, E, and if we ignore relativistic effects we can show approximately (and exactly in Section 1.4 below) that a~ 12 2)1 THE TRANSMISSION ELECTRON MICROSCOPE, Figure 1.2. A in boundary in spinel stepping from one (11) plane to another parallel plane. The white dots ate columns of stom. The ‘change in atomic orientation across the tvin boundary ean be readily seen, even if we do not know what eaues the white dots or why, indeed, they ae white. In this equation Fis in electron volts (eV) and 2 in nm, Re~ ‘member that we should be precise in our use of the units V and eV: the former represents the accelerating voltage of the microscope while. the latter refers to the energy of the electrons in the microscope. So for a 100-keV electron, we find that 2 ~ 4 pm (0.004 nm), whici is much smaller than the diameter of an atom, We'll see later that we are nowhere near building ‘TEMS that approach this wavelength limit of resolution, because we can’t make perfect electron lenses (see Chapter 6). But progress was rapid after Ruska’s early work on lenses and, since the mid-1970s, many commercial TEMS hhave been capable of resolving individual columns of atoms in crystals, creating the field of “high-resolution transmission electron microscopy,” or HRTEM, which we'll discuss in Chapter 28. A typical HRTEM image is shown in Figure 1.2. The advantages of shorter wave- lengths led in the 1960s to the development of high voltage electron microscopes (HVEMS), with accelerating poten- tials between 1 MV and 3 MY. In fact, most of these instru- ments were used to introduce controlled amounts of radia- tion damage into specimens in an attempt to simulate nuclear reactor environments, but changes in the emphasis of energy research mean there is not much call for such in- struments today. While we can still improve the resolution by incremental amounts, the drive for much better resolu- tion is now no longer paramount and the TEM is develop- ing in other ways. In fact, only one HVEM (1 MY) for HRTEM imaging was constructed in the 1980s and three 1.25-MV machines in the 1990s, Intermediate voltage electron microscopes (IVEMs) were introduced in the 1980s. These TEMs operate at 300 or 400 kY, but still offer very high resolution, clase to that achieved at 1 MV. 1.1.C. Interaction of Electrons with Matter Electrons are one type of “ionizing radiation,” which is the general ferm given to radiation that is capable of removing one of the tightly bound inner-shell electrons from the at= tractive field of the nucleus. One of the advantages to using ionizing radiation is that it produces a wide range of secondary signals from the specimen, and some of these are summarized in Figure 1.3 ‘Many of these signals are used in “analytical electron mi- croscopy,” or AEM, giving us chemical information and a Jot of other detail about our samples. AEM uses X-ray en- ergy dispersive spectrometry (XEDS) and electron energy- Joss spectrometry (EELS). For example, Figure 1.44 is an ‘X-ray spectrum from a very small region of a TEM speci- men showing characteristic peaks which identify the ele. ‘ments present. We can transform such spectra into quanti- tative data describing elemental changes associated with inhomogeneous microstructures as also shown in Figures 1.4B and C. This aspect comprises Part IV of the book. In ‘contrast, microscopes using nonionizing radiation such as visible light usually only generate light (but not much heat, which is good). AEMs generally offer improved perfor- ‘mance at intermediate voltages, similar to HRTEMS, In order to get the best signal out of our specimens ‘we have to put the best signal in, and so the electron source is critical. We are now very accomplished in this respect as you'll see in Chapter 5, so modem TEMS are very good Incident Secondary nigrkvteam Seconda Bockacatered eleetons (HSE) Geen ays Auger electrons Visibe “ah a ‘Asorbed! lecto-hole kerons -— — win Soo nremsalang Elsially Inelsically seated Dae catered tectons ea Sectors Figure 1.3. Sigals generated when high-energy beam of electrons imteracis witha thin specimen, Most of thete signals canbe detested in different types of TEM. The directions shown for each signal do nota rays represent the physical diction ofthe signal but indicate, na el tive manner, where the signal is strongest or wher itis detected,