handbook of Surface and interface Analysis

Transcription

1 handbook of Surface and interface Analysis Methods for Problem-Solving edited by j. С Riviere AEA Technology Oxford, England S. Myhra Griffith University Nathan Queensland, Australia ж M A R C E L D E К К E R MARCEL DEKKER, INC. NEW YORK BASEL HONG KONG

2 Preface About the Contributors 1. Introduction /. C. Riviere and S. Myhra 1. A spectrum of practitioners 2. Trends in surface and interface 3. The intended audience 4. The structure of the volume 2. Elements of Problem-Solving 5. Myhra and J. C. Riviere 1. Introduction 2. Surface, interface, and bulk 3. The problem-solving sequence

3 vi Contents 3.1. Identification of the problem and formation of an initial hypothesis Identification of the essential variable(s) Reduction of the problem as far as possible without losing essential information Selection of the technique(s) likely to provide the crucial information by the most reliable and economic route Choice of methodology(ies) consistent with the selection of technique(s) Acquisition and processing of data of adequate quantity and quality Interpretation of the data Review and evaluation Presentation Practical matters in problem-solving for surfaces and interfaces Specimen handling, preparation and configuration Ex situ preparation In situ preparation Specimen configuration Technique destructiveness Quality assurance, best practice and good housekeeping How to Use This Book Myhra and J. C. Riviere 1. Introduction Definitions Decision-making in problem-solving Acronyms and jargon 26 Table 4.1: Acronyms: Techniques for surfaces and interfaces 29 Table 4.2: Acronyms: Surface and interface methodologies 31 Table 4.3: Acronyms and trade names: Compounds 32 Table 4.4: Acronyms: Miscellaneous 33 Table 4.5: Definitions: Miscellaneous Finding the information 31 Table 4.6: Choices and decisions: Specimen configuration and preparation 34 Table 4.7: Choices and decisions: Instrumental aspects 35 Table 4.8: Surface and interface techniques: Information and methods 37 Table 4.9: Surface and interface techniques: Characteristics and attributes 40 Table 4.10: Classes, functions and applications of materials: Key words and locations 46

4 vii 4. Spectroscopic Techniques: X-Ray Photoelectron Spectroscopy, Auger Electron Spectroscopy, and Ion Scattering Spectroscopy 57 Gar B. Hoflund 1. X-ray photoelectron spectroscopy (XPS) Introduction and history Experimental equipment and data collection X-ray sources Energy analyzers Energy calibration Data processing Sample configuration Sample treatment 1.3. Spectral features and interpretation Determination of composition from XPS data Determination of chemical state Additional features in XPS spectra 1.4. Spatially resolved XPS 2. Aug er electron spectroscopy (AES) Introduction and history Experimental equipment and data collection Electron sources Energy analyzers Spectral features and interpretation Associated methodologies Depth profiling with AES Angle-resolved AES (ARAES) Scanning Auger microscopy (SAM) 3. Ion scattering spectroscopy (ISS) Introduction and history Experimental equipment and data collection Spectral features and interpretation General features Background and neutralization Multiple scattering Multiply charged ion scattering Choice of primary ion Hydrogen and carbon Elemental sensitivity Energy resolution Peak shape Quantification Data processing Depth profiling Referem ;es HI

5 viii Contents 5. Compositional Analysis by Auger Electron and X-ray Photoelectron Spectroscopy 159 Graham C. Smith 1. Introduction Spectral interpretation XPS spectra Elemental line energies Photoelectron line shapes Chemical shifts Curve fitting Auger electron spectra Elemental line energies Chemical shifts X-ray-excited Auger electron spectra Quantitative of structural analysis Quantification and homogeneous samples Use of sensitivity factors Measurement of intensity Modified sensitivity factors for improved quantification Quantification of XPS data Quantification of AES data Statistical errors in quantification Analysis of specimens with spatially varying compositions Analysis of specimens with compositional variations in depth 201 References Ion Beam Techniques: Surface Mass Spectrometry 209 Birgit Hagenhoff and Derk Rading 1. Principles Physical effects of ion induced sputtering Sputtering Ionization Formation of molecular species Instrumentation Primary-ion bombardment Mass analyzers Add-ons Typical spectra Typical characteristics of SSIMS spectra Typical characteristics of SNMS spectra Useful definitions in SSIMS and SNMS General SSIMS 222

6 ix SNMS Use of noble metal substrates Performance summary Operational methodology The analytical question Spatial location Identification and peak assignment Quantification Use of internal standards (Sub)monolayer coverages Organic multilayers Problem solving Defects in car paint CI diffusion in polymer materials Monitoring of surface modifications Residues on glass Summary and outlook 249 References 251 In-depth Analysis: Methods for Depth Profding 255 F. Renters 1. Introduction Sample preparation Nondestructive in-depth analysis Rutherford backscattering spectrometry (RBS) Basic principles Quantitative analysis Application of RBS Angle-resolved AES and XPS Basic principles Applications Summary Destructive depth profiling Ion guns AES and XPS Basic principles Quantitative analysis Depth determination-conversion Depth resolution Improvement in AES sputter depth profiling Summary of optimized depth profiling conditions foraes/xps Improvement of depth resolution by sample rotation Chemical depth profiles using AES Glow discharge optical emission spectroscopy (GDOES) 279

7 X Contents Basic principles Quantitative analysis Recent improvements in GDOES SIMS Basic principles Quantitative analysis Applications Optimum conditions for performing SIMS depth profiling Bombarding conditions: ions Angle of incidence Effect of the choice of gas in SIMS Choice of ion beam energy Interferences in SIMS depth profiling SNMS Basic principles Quantification in SNMS Applications Discussion and general conclusion Typical problems that might be encountered when sputter profiling, and their solutions Key parameters/considerations for choice of the appropriate analysis method 289 References 290 Ion Beam Effects in Thin Surface Films and Interfaces 297 /. Bertöti, M. Menyhard, and A. Toth 1. Introduction Low-energy atomic mixing Auger depth profiling Multilayer systems High-resolution depth profiling equipment Characteristic depth profiles Evaluation of Auger depth profiles Sputtering-induced surface roughness Intrinsic surface roughness of interfaces Calculation of the surface concentration Atomic mixing Energy dependence of ion mixing Interpretation of the depth profiles Particle-beam-induced chemical alterations Thin surface films of inorganic compounds TiN layers Metal oxides Cr-O-Si cermet films 327

8 xi 3.2. Thin surface films of polymers Aromatic poly(ether sulfone) Aromatic polyimide Organosilicon polymers 338 References Surface Modification by Ion Implantation 347 D. M. Rück. 1. Introduction Physical processes Ion implantation: instrumentation and procedures Methods for characterisation of implanted layers Phase analysis by Mössbauer spectroscopy General aspects Depth-selective CEMS Examples of the application of ion implantation Improved surface properties in medical endoprothesis Introduction Results Discussion and conclusions Modification of chromium layers by nitrogen ion implantation Introduction Experimental procedures Results Conclusions Waveguide structures by ion irradiation of polymeric materials Introduction Generation of urn structures Buried waveguide layers Coupling between device and fiber: fiber-chip coupling Conclusions and further developments 387 References Introduction to Scanned Probe Microscopy 395 S. Myhra 1. Introduction Essential elements of SPM Brief history of SPM The SPM family tree Physical principles 402

9 xii Contents 2.1. STM/STS SFM Force-distance spectroscopy Technical implementation of SPM instrumentation Generic features and elements Spatial positioning and control Gap control loop Raster implementation and control Noise and drift management Environmental control Data management Specifics for some SPM techniques STM/STS specifics SFM specifics SFM probes: general considerations SFM probes: design criteria Probe calibration and image artefacts Determination of normal spring constant Determination of lateral spring constant Resonance frequency Aspect ratio Radius of curvature of tip Determination of tip height and tilt Problem-solving with SPM Manipulation on the nanoscale with SPM 442 References Metallurgy R. K. Wild 1. Introduction 1.1. Strength of materials 1.2. Failure mechanisms 1.3. Segregation Thermal Irradiation assisted 2. Analytical methods for determining grain boundary segregation Introduction Metallographically polished specimens Chemical etching SIMS Autoradiography Intergranular fracture Impact at low temperature AES XPS

10 xiii Hydrogen charging Charging methods Impact and slow tensile fracture Transmission electron microscopy Production of a thin foil Field emission gun STEM Parallel electron energy loss spectroscopy Energy dispersive X-ray analysis Comparison of AES and FEGSTEM Time-of-flight atom probe Cracks in metals and alloys 477 References Microelectronics and Semiconductors 485 E. Paparazzo 1. Introduction Techniques Surface specificity Elemental specificity Chemical sensitivity Destructiveness Quantification Spatial resolution Surface charging and other considerations Josephson junctions Problem specification Experimental approach: choice of techniques and specimen configuration Results AES analysis XPS analysis Discussion Oxidation of InxGai_ x AsyPi_ y semiconductors by NO Problem specification Experimental approach: choice of technique and specimen configuration Results AES analysis SAM and scanning ELS analysis Discussion Si/Si0 2 interface Problem specification Experimental approach: choice of technique and specimen configuration 511

11 xiv Contents 5.3. Results Effects of Ar + bombardment Interfacial suboxides Surface-hydrated species 5.4. Discussion Effects of Ar + bombardment and suboxides Surface-hydrated species InP/Si02 system 6.1. Problem specification 6.2. Experimental approach: choice of technique and specimen configuration 6.3. Results 6.4. Discussion erences Minerals, Ceramics, and Glasses 543 R. St. C. Smart Introduction Information required: analytical techniques Analysis strategy Minerals Phase structures Surface structures Surface sites Grain boundaries and intergranular films Depth profiles Adsorption Surface reactions Surface modification Ceramics 5.1. Phase structures 5.2. Surface structures 5.3. Surface sites 5.4. Grain boundaries and intergranular films 5.5. Depth profiles 5.6. Adsorption 5.7. Surface reactions 5.8. Surface modification Glasses 6.1. Surface composition 6.2. Surface sites 6.3. Depth profiles 6.4. Adsorption 6.5. Surface reactions

12 XV 6.6. Surface modification 596 References 598 Composites 605 P.M. A. Sherwood 1. Introduction Presenting fibers for surface analysis Presentation of multiple fibers for analysis Problems in the study of conducting fibers The question of fiber decomposition Presenting composites for surface analysis Surface analytical techniques for composites and fibers X-ray diffraction FTIR and Raman spectroscopies SEM STM and AFM Wavelength dispersive X-ray emission in an electron microprobe Surface energy Titrimetric methods Mass spectrometry SIMS Ion scattering spectroscopy X-ray photoelectron spectroscopic studies of composites and fibers Introduction The question of surface charging Depth profiling of carbon composites and fibers Decomposition of surface functionality during spectral collection XPS data analysis and interpretation of core chemical shifts Fitting С Is spectra Detailed fitting considerations The use of monochromatic X-radiation Fitting О Is spectra Fitting N Is spectra Interpreting the valence-band spectrum Using calculations to predict valence-band spectra Understanding the valence-band spectra of carbon fibers The use of UV rather than X-radiation Interfacial studies Concluding comments 638 References 640

13 Corrosion and Surface Analysis: An Integrated Approach Involving Spectroscopic and Electrochemical Methods 643 N. S. Mclntyre, R. D. Davidson, I. Z. Hyder, and A. M. Brennenstiihl 1. Introduction Types of corrosion process Corrosion and surfaces Protocols for corrosion film analysis Preliminary sample handling Contaminants Preliminary examination Cross sectioning of oxide surface films Pressure restrictions on sample analysis SEM and EDS analyses XPS AES SIMS Other methods Background to the problem: A working hypothesis Experimental strategy Electrochemical techniques for surface corrosion studies Basic electrode kinetics Electrochemical techniques Linear polarization Anodic polarization Electrochemical impedance spectroscopy Results and assessment Initial characterization Boiler simulation corrosion experiments Contrived corrosion experiments on Monel Electrochemical measurements at ph Microscopy studies of oxides from ph 10 exposures Elemental and chemical compositions of oxides formed at ph Electrochemical and microscopy studies of alloys exposed to ph Conclusions 693 References 696 Problem-Solving Methods in Tribology with Surface-Specific Techniques 697 C. Donnet 1. Tribology and surface-related phenomena 697

14 xvii 2. Surface analysis requirements for tribology Overview Dimensional criterion Time-scale criterion Information criterion Physicochemical and structural information Surface morphology Physical, mechanical and frictional surface and interface properties Generic studies Ultrathin boundary lubricant films Tribochemistry of antiwear additives in boundary lubrication Ex situ surface analytical investigations In vivo pre mortem surface analytical investigations In situ post mortem surface analytical investigations in Ultrahigh Vacuum Tribochemical activity of nascent surfaces Influence of the nature of the surface on the tribochemistry of various tribo-materials Effect of adsorbate monolayers on dry friction Tribochemistry of SiC/SiC under a partial pressure of oxygen Relationship of durability to microstructure of IBAD M0S2 coatings Frictionless sliding of pure M0S2 in UHV Tribology of carbonaceous coatings Tribochemistry of Ceo coatings Synthesis and conclusion 741 Acronyms 743 References Catalyst Characterization 747 W. E. S. Unger and T. Gross 1. Introduction Applicability of surface spectroscopies in catalyst characterization Sample damage Sample preparation Charging of insulator surfaces by the probe Chemical-state analysis with XPS by fingerprinting and reference to databases or chemical-state plots Chemical state analysis with SIMS by fingerprinting Miscellaneous The molecular probe approach: assessment of acid-base properties 769

15 8.2. Alloying at bimetallic supported catalysts In-depth analysis Quantitative surface analysis of catalysts: composition, dispersion and coverage 772 References 776 Adhesion Science and Technology 781 /. F. Watts 1. Introduction Characteristics of the solid substrate Organic contamination Oxide films at metal surfaces Carbon fiber composite materials Failure analysis: identification of the locus of failure Adhesion to brass Adhesion of organic coatings to steel Zinc surfaces Aluminum alloys Composite materials Ceramics Summary Probing the buried interface Organosilane adhesion promoters Acid-base interactions in adhesion Evaluation of acid-base interactions in adhesion The XPS chemical shift and acid-base interactions The use of vapor phase probes for the determination of-андв Quantitative acid-base characteristics of the polymer Acid-base properties of inorganic surfaces Concluding remarks Computer chemistry and molecular modeling Future prospects 825 References 828 Archaeomaterials 835 E. Paparazzo 1. Introduction Choice of techniques for the study of archeomaterials Bulk techniques Surface-specific techniques: XPS and SAM Roman lead pipe fistula Description of material and specimen Results Discussion 852

16 xix 4. Roman leaded bronzes Specification of the problem Results Discussion 867 References 868 Appendix 1. Physical Constants and Conversion Factors 871 Appendix 2. Data for the Elements and Isotopes 873 Appendix 3. Less Commonly Used Techniques for Analysis of Surfaces and Interfaces 885 Gar B. Hoflund and J. C. Riviere 1. Ultraviolet photoemission spectroscopy (UPS) 885 References Electron energy loss spectroscopy (ELS) 889 References Electron-stimulated desorption (ESD) 892 References Vibrational spectroscopies Infrared techniques Attenuated total reflectance (ATR) Reflection absorption infrared spectroscopy (RAIRS) Electron impact technique High-resolution electron energy loss spectroscopy (HREELS) 899 References 902 Appendix 4. Core-Level Binding Energies, Auger Kinetic Energies, and Modified Auger Parameters for Some Chemical Elements in Various Compounds 903 References 905 Appendix 5. Documentary Standards in Surface Analysis: The Way of the Future? J. Harris 1. Introduction ISO technical committee 201 on surface chemical analysis Structure of ISO technical committee ISO technical committee 201 sub-committees ISO TC201 Working Groups Conclusions 924 References 927 Index 929