Glow Discharge Plasmas in Analytical Spectroscopy Glow Discharge Plasmas in Analytical Spectroscopy Editedby R. Kenneth Marcus Clemson University,Clemson, SC, USA and Jose´ A. C. 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Includesbibliographicalreferencesandindex. ISBN0-471-60699-5(alk.paper) 1.Emissionspectroscopy.2.Glowdischargs.3.Solids—Surfaces—Spectra.I.Marcus, R.Kenneth.II.Broekaert,J.A.C.,1948– QD96.E46G462003 543(cid:1).0858—dc21 2002072636 BritishLibraryCataloguinginPublicationData AcataloguerecordforthisbookisavailablefromtheBritishLibrary ISBN0-471-60699-5 Typesetin10/12ptTimesbyLaserwordsPrivateLimited,Chennai,India PrintedandboundinGreatBritainbyTJInternational,Padstow,Cornwall Thisbookisprintedonacid-freepaperresponsiblymanufacturedfromsustainableforestry inwhichatleasttwotreesareplantedforeachoneusedforpaperproduction. Dedicated to our family, friends and colleagues for their support through the years ... RKM JACB Contents Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi List of Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 R. K.Marcusand J.A. C. Broekaert 1.1 Rationale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1.2 Glow Discharge Devices: Basic Operating Principles. . . . . . . . 3 1.3 Glow Discharge Devices: Scope of Application . . . . . . . . . . . 6 1.4 Volume Outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 1.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 2 Optical Emission Spectrometry with Glow Discharges . . . . . . . . 15 J.A. C. Broekaert 2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 2.2 Glow Discharges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 2.3 Atomic Emission Spectrometry . . . . . . . . . . . . . . . . . . . . . . 36 2.4 Material Ablation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49 2.5 Analyses with Glow Discharge Atomic Emission Spectrometry . 55 2.6 Other Methods of Analysis and Outlook . . . . . . . . . . . . . . . . 63 2.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 3 Mass Spectrometry of Glow Discharges . . . . . . . . . . . . . . . . . . 71 W.W. Harrison, C. Yangand E. Oxley 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71 3.2 Fundamentals of Mass Spectrometry . . . . . . . . . . . . . . . . . . 75 3.3 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 3.4 Qualitative Considerations . . . . . . . . . . . . . . . . . . . . . . . . . 91 3.5 Quantitative Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 3.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 3.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 viii Contents 4 Radio Frequency Glow Discharges . . . . . . . . . . . . . . . . . . . . . . 97 R. K.Marcus 4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97 4.2 Radio Frequency Glow Discharge (rf-GD) Operation Principles. 99 4.3 Comparisons with dc-Powered Glow Discharge Sources . . . . . 101 4.4 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 4.5 Analytical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . 112 4.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136 4.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136 5 Depth Profile Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141 A. Bengtson 5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141 5.2 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142 5.3 Practical Aspects and Results . . . . . . . . . . . . . . . . . . . . . . . 144 5.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153 5.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154 6 Numerical Modeling of Analytical Glow Discharges . . . . . . . . . . 155 A. Bogaerts and R. Gijbels 6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155 6.2 Description of the Models . . . . . . . . . . . . . . . . . . . . . . . . . 157 6.3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . 170 6.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202 6.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203 7 Application of Glow Discharge Optical Emission Spectrometry in the Steel Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207 K.Kakita 7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207 7.2 Measurement Traceability of Coating Weight and Chemical Composition by GD-OES. . . . . . . . . . . . . . . . . . . . . . . . . . 208 7.3 Method of Coating Analysis by GD-OES . . . . . . . . . . . . . . . 209 7.4 Depth Profiles of Coatings by GD-OES . . . . . . . . . . . . . . . . 213 7.5 Factors Affecting Depth Profiles . . . . . . . . . . . . . . . . . . . . . 217 7.6 Validation and Verification of Calibration Graphs . . . . . . . . . . 225 7.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229 8 Surfaces, Thin Films and Coatings . . . . . . . . . . . . . . . . . . . . . . 231 R. Payling, P. Chapon, K. Shimizu, R. Passetemps, A. Jadin, Y. Bourgeois, K.Crener,M. Aeberhardand J.Michler 8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231 8.2 Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232 8.3 Thin Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238 Contents ix 8.4 Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243 8.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251 8.6 Acknowledgements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251 8.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251 9 Comparison of Glow Discharge Atomic Spectrometry with Other Surface Analysis Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . 253 K.Wagatsuma 9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253 9.2 Surface Analysis Methods Competitive with Glow Discharge Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256 9.3 Analytical Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263 9.4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272 10 Analysis of Samples of Nuclear Concern with Glow Discharge Atomic Spectrometry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273 M.Betti 10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273 10.2 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274 10.3 Practical Aspects and Results . . . . . . . . . . . . . . . . . . . . . . . 277 10.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288 10.5 Acknowledgements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289 10.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290 11 Analysis of Nonconducting Materials by dc Glow Discharge Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293 A. Bogaerts, W. Schellesand R. Van Grieken 11.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293 11.2 Use of a Conducting Host Matrix . . . . . . . . . . . . . . . . . . . . 294 11.3 Use of a Conducting Secondary Cathode . . . . . . . . . . . . . . . 301 11.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311 11.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 314 12 Standards and Reference Materials for Glow Discharge Spectroscopies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317 M.R. Winchester 12.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317 12.2 Practical Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318 12.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331 12.4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332 13 Analysis of Liquid Samples Using Glow Discharge Spectroscopies 335 R. K.Marcus 13.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335