ENCYCLOPEDIA OF MATERIALS CHARACTERIZATION C. Richard Brundle Charles A. Evans, Jr. Shaun Wilson a MAT E R I A LS CHARACTER SERIES SURFACES, INTERFACES, THIN FILMS + ENCYCLOPEDIA OF MATERIALS CHARACTERIZATION MATERIALS CHARACTERIZATION SERIES Surfaces, Interfaces, Thin Films Series Editors: C. Richard Brundle and Charles A. Evans, Jr. Series Titles Encyclopedia of Materiah Characterization, C. Richard Brundle, Characterization of Mekth and Alloys, Paul. H. Holloway and P. N. Characterization of Ceramics, Ronald E. Loehman Characterimtion of Pobmers, Ned J. Chou, Stephen P. Kowalczyk, Characterization in Silicon Processing, Yale Strausser Characterization in Compound Semiconductor Processing, Yale Strausser Characterization of Integraed Circuit Packaging Materiah, Thomas M. Moore and Robert G. McKenna Characterization of Cadytic Materiah, Israel E. Wachs Characterization of Composite Materiah, Hatsuo Ishida Characterization of Optical Materiah, Gregory J. Exarhos Characterization of Tribological Materiah, William A. Glaeser Characterization of Organic Thin Films, Abraham Ulman Charles k Evans, Jr., and Shaun Wilson Vaidyanathan Ravi Sard, and Ho-Ming Tong ENCYCLOPEDIA OF MLATERIALS CHARACTERIZATION Surfaces, Interfaces, Thin Films EDITORS C Ricbard Brundle Charles A. Evans, Jr. Sbaun Wihon MANAGING EDITOR Lee E. Fitzpatrick BUTTERWORTH-HEINEMANN Boston London Oxford Singapore Sydney Toronto Wellington MANNING Greenwich This book was acquired, developed, and produced by Manning Publications Co. Copyright Q 1992 by Butxetworch-Heinemann, a division of Reed Publishing CUSA) Inc Au rights rad No parc of this publicarion may be reproduced, scored in a retried system, or transmitted, in any form or by means. electronic, mechanical, photocopying, or orherwise, without prior written permission of the publisher. Recognizing the importance of preserving what has been written, it is the policy of Butterworth-Heinemann and of Manning to have the books they publish printed on acid-free paper, and we exert our best &m to that end. Library of Congress Cataloging-in-Publication Data Brundle, C. R. Encyclopedia of materials characterization: surfaces, interfaces, thin films/C. Richard Brundle, Charles A. Evans, Jr., Sham Wilson. p. un (Materials characterization series) Indudes bibliographical refrrenoa and index. ISBN CL7506-9168-9 1. Surfaces (Tedmoology)-Tes~ I. Evans, Charlak 11. Wilson, Shaun. 111. Title. IV. Series. TA418.7.B73 I992 92-14999 620’.4Pdc20 CIP Butterworth-Heinemann 80 Montvale Avenue Stoneham, MA02180 Manning Publications Co. 3 his Street Greenwich, CT 06830 109 8 7 6 5 4 3 Printed in the Unired States ofAmerica Contents Preface to Series ix Preface x Acronyms Glossary xi Contributors xvi INTRODUCTION AND SUMMARIES 1.0 Introduction I Technique Summaries 7-56 IMAGING TECHNIQUES (MICROSCOPY) 2.0 Introduction 57 2.1 Light Microscopy 60 2.2 Scanning Electron Microscopy, SEM 70 2.3 Scanning Tunneling Microscopy and 2.4 Transmission Electron Microscopy, TEM 99 Scanning Force Microscopy, STM and SFM 85 ELECTRON BEAM INSTRUMENTS 3.0 Introduction 117 3.1 Energy-Dispersive X-Ray Spectroscopy, EDS 120 3.2 Electron Energy-Loss Spectroscopy in the Transmission Electron Microscope, EELS 135 3.3 Cathodoluminescence, CL 149 3.4 Scanning Transmission Electron Microscopy, STEM 161 3.5 Electron Probe X-Ray Microanalysis, EPMA 175 V STRUCTURE DETERMINATION BY DIFFRACTION AND SCATTERING 4.0 Introduction 193 4.1 X-Ray Diffraction, XRD 198 4.2 Extended X-Ray Absorption Fine Structure, EXAFS 214 4.3 Su&ce Extended X-Ray Absorption Fine Structure and Near Edge X-Ray Absorption Fine Structure, SEXAFS/NEXAFS Auger Electron Difiction, XPD and AED 227 4.4 X-Ray Photoelectron and 4.5 Low-Energy Electron Diffraction, LEED 252 4.6 Reflection High-Energy Electron Diffraction, WEED 264 240 ELECTRON EMISSION SPECTROSCOPIES 5.0 Introduction 279 5.1 X-Ray Photoelectron Spectroscopy, XPS 282 5.2 Ultraviolet Photoelectron Spectroscopy, UPS 300 5.3 Auger Electron Spectroscopy, AES 310 5.4 Reflected Electron Energy-loss Spectroscopy, REELS 324 X-RAY EMISION TECHNIQUES 6.0 Introduction 335 6.1 X-Ray Fluorescence, XRF 338 6.2 Total Reflection X-Ray Fluorescence Analysis, TXRF 349 6.3 Particle-Induced X-Ray Emission, PIXE 357 VISIBLE/W EMISSION, REFLECTION, AND ABSORPTION 7.0 Introduction 371 7.1 Photoluminescence, PL 373 7.2 Modulation Spectroscopy 385 7.3 Variable Angle Spectroscopic Ellipsometry, VASE 401 VIBRATIONAL SPECTROSCOPIES AND NMR 8.0 Introduction 413 8.1 Fourier Transform Infrared Spectroscopy, FTIR 416 8.2 RamanSpectroscopy 428 8.3 High-Resolution Electron Energy Loss Spectroscopy, HREELS 4-42 8.4 Solid State Nuclear Magnetic Resonance, NMR 460 vi Contents ION SCATTERING TECHNIQUFS 9.0 Introduction 473 9.1 Rutherford Backscattering Spectrometry, RBS 476 9.2 Elastic Recoil Spectrometry, ERS 488 9.3 Medium-Energy Ion Scattering with Channeling and Blocking, MEIS 502 9.4 Ion scattering Spectroscopy, Iss 514 MASS AND OPTICAL SPECTROSCOPIES 10.0 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 Introduction 527 Dynamic Secondary Ion Mass Spectrometry, Dynamic SIMS Static Secondary Ion Mass Spectrometry, Static SIMS 549 Surfice Analysis by her Ionization, SAL1 Sputtered Neutral Mass Spectrometry, SNMS Laser Ionization Mass Spectrometry, LIMS Spark Source Mass Spectrometry, SSMS 598 Glow-Discharge Mass Spectrometry, GDMS 609 Inductively Coupled Plasma Mass Spectrometry, ICPMS Inductively Coupled Plasma-Optical Emission Spectroscopy, ICP-OES 633 532 559 586 571 624 NEUTRONANDNUCLEARTECHNIQUES 1'1.0 Introduction 645 1 1 .I Neutron Diffraction 648 11.2 Neutron Reflectivity 660 11.3 Neutron Activation Analysis, NAA 671 11.4 Nuclear Reaction Analysis, NRA 680 PHYSICAL AND MAGNETIC PROPERTIES 12.0 Introduction 695 12.1 Surface Roughness: Measurement, Formation by Sputtering, Impact on Depth Profiling 698 12.2 Optical Scatterometry 711 12.3 Magneto-optic Kerr Rotation, MOJSE 723 12.4 Physical and Chemical Adsorption Measurement of Solid Surface Areas 736 Contents vii [...]... LIMS ;E20ll 11 .2 ;l;g;v SSMS 11 .3 NAA 11 .4 NRA Optical 12 .2 scatternmetry 12 .3 M O U 12 .4 Adsorption 1. 5 nm * 10 0nm 3 P 10 0 nm 5w 5 P 0 0 0 * Bulk Width probed (typical) un 2pm cm cm mm mm TkCe capability (typical) 50 PPm 1- 100ppm 0.05 ppm ppt-ppb PPt PPb Types of solid sample (typical) Flat conductors Al l % iii v) 0 5 'E! m, I Notes 2 3 - - 3 - Flatpolymer films N - 3 N - PPt-PPm 10 -lOOppm Ta... 0. 01- 10% 0. 01% 0 %1 % -0 1 50 ppm -1% 0 2 nm PPb-PPm All, mostly sernicond Y 3 1 Y a a m 1Pn 0 o 0 m a m 1 nm a 3A 1o ow Few % All, m s l polymer oty Y 3 2 Y 3A 10 0 nrn PPb-PPrn AU, mostly inorg Y 3 3 N Compilation of Comparative Information on the AnalyticalTechniques Discussedin This Volume 0, 6 Maill ~ n l l a t i ~ Depth probed (typical) ArrideTechnique No 10 .4 10 .5 10 .6 10 .7 10 .8 10 .9 2 0 0 C 0 : z... SEXAFS NEXAFS XPD All m e STEM EPMA XRD EXAFS 0.2 pn m m TEM 3.4 3.5 4 .1 4.2 4.3 4.3 4.4 4.5 4.6 5 .1 5.2 5.3 (typical) Variable SFM 3.3 T p of solid sample 05 pm mm mm 10 0 ppm mm Few % mm 15 0 prn 0 .1 mrn 0.02 mm 15 0 pm mm 10 0 nrn Few% 10 Cun Bulk* lnm 1nm 3nm 1 nm lnm 3nm 1 nm 2 nm 3% Few % 1% - 1% - 0 .1% Crystalline All Surface and adsorbate Surface and adsorbate Single crystal Single crystal Single... m m e e e 1pm 20 nm* 1Ml 5 nm 0.5 pn 1 nm 500 ppm Few% 1Cun PPm All; sunicond usually Y 1 3 N - All; e200 nm thick All; flat best Y Y N YIN 3 3 2 3 2 1 3 3 3 3 2 2 1 3 1 iA 10 0 nm* lnm lpm e 1 Y Cond, coated ins Conductors All All;e200 nm thick AU;Z > 5 All; e30 nm thick 10 nm-pm e m e UPS AES 1 e e EDS XPS N m EELS SEXAFS NEXAFS XPD All m e STEM EPMA XRD EXAFS 0.2 pn m m TEM 3.4 3.5 4 .1 4.2 4.3 4.3... address the needs of the practical materials user, with an emphasis on the newer areas of surfice, interface, and thin film microcharacterization The Series is composed of the leading volume, Enychpedia of Materialj Characterization,and a set of about 10 subsequent volumes concentrating on characterization of individual materials classes In the Encyclopedia, 50 brief articles (each 10 -18 pages in length)... SIMS 10 .3 SALI Y N Y Y lw a 8.3 RBS ERS MEIS 9.4 ISS Dynamic 10 .1 SIMS All Trace heavy metals All Few Pn PKE Photoluminescence Modulation spectrosmpy VASE FTIR Raman Scattering 9 .1 9.2 9.3 All 10 0 nm rm n un 10 0 pn XRF TXRF mm 1% AU;flat cond best All; not all elements Y 3 3 N N 3 3 N All YlN3 H containing Y All; usually single crystal Y 3 All Y - 2 3 3 3 Y N N Y Bulk m To 2 pn 0 3A 0. 01- 10% 0. 01% 0 %1. .. Compilationof Comparative Information on the AnalyticalTechniques Discussedin This Volume Main information Article Technique No 5.4 6 .1 6.2 6.3 7 .1 7.2 7.3 8 .1 8.2 REELS a 2 3 3 3 1 3 3 N Y Y Y N 1 2 N a a NMR a a m 10 0 pm PPrn All, semicond usually N 2 3 N un 20 pm Variable Flat thin h All N N 2 2 3 1 Y Y llrm Variable All N 2 2 Y 2 nm a a 1 Pm Fewp a 8.4 VI All, semicond usually - Fewpm a HREELS 10 .2 static... Yes, in the near-edge structure of edge profiles information Depth profiling None, the specimen is already thin capabilities Quantification Without standards +fl0-20% at.; with standards 1- 2% at Detection limits -lo- 21 g Depth probed Thickness of specimen ( 2000 A) I Lateral resolution 1 nm -10 pm, depending on the diameter of the incident electron probe and the thickness of the specimen - Imaging Capabilities... sophistication and accessories: 1 means < $50k 2 means $50-300k; 3 means >$300k."-" means no mmplcre commercia instrument Usup:Numbers refer to usage for anaylsis of solid materials 1 means Extensive; 2 means medium; 3 means not common Tim capz6iliy:Guide only Often very material/wnditions dependent "-" means not used for trace components 3 Y 3 Y 1 3 Y 1 2 2 N N 2 Light Microscopy 1. 2 .1 The light microscope... $300,000- $1, 500,000 Size 10 0 fL2to a major lab 10 INTRODUCTION AND SUMMARIES Chapter 1 Energy-Dispersive X-Ray Spectroscopy (EDS) 1. 3 .1 When the atoms in a material are ionized by a high-energy radiation they emit characteristic X rays EDS is an acronym describing a technique of X-ray spectroscopy that is based on the collection and energy dispersion of characteristic X rays An EDS system consists of a . MEIS 502 9.4 Ion scattering Spectroscopy, Iss 514 MASS AND OPTICAL SPECTROSCOPIES 10 .0 10 .1 10 .2 10 .3 10 .4 10 .5 10 .6 10 .7 10 .8 10 .9 Introduction 527 Dynamic Secondary Ion Mass. 586 5 71 624 NEUTRONANDNUCLEARTECHNIQUES 1& apos ;1. 0 Introduction 645 1 1 .I Neutron Diffraction 648 11 .2 Neutron Reflectivity 660 11 .3 Neutron Activation Analysis, NAA 6 71 11 .4 Nuclear. un (Materials characterization series) Indudes bibliographical refrrenoa and index. ISBN CL7506- 916 8-9 1. Surfaces (Tedmoology)-Tes~ I. Evans, Charlak 11 . Wilson, Shaun. 11 1. Title.