36 Springer Series in Chemical Physics Edited by Robert Gomer ~---- Springer Series in Chemical Physics Editors: V. I. Goldanskii R. Gomer F. P. Schafer 1. P. Toennies Atomic Spectra and Radiative Transitions 19 Secondary Ion Mass Spectrometry By 1.1. Sobelmann SIMS III 2 Surface Crystallography by LEED Editors: A. Benninghoven, J. Giber, Theory, Computation and Structural J. Laszlo, M. Riedel, H. W. Werner Results. By M. A. Van Hove, S. Y. Tong 20 Chemistry and Physics of Solid 3 Advances in Laser Chemistry Surfaces IV Editor: A. H. Zewail Editors: R. Vanselow, R. Howe 4 Picosecond Phenomena 21 Dynamics of Gas-Surface Interaction Editors: C. V. Shank, E. P. Ippen, Editors: G. Benedek, U. Valbusa S. L. Shapiro 22 Nonlinear Laser Chemistry 5 Laser Spectroscopy Multiple-Photon Excitation Basic Concepts and Instrumentation By V. S. Letokhov By W. Demtriider 2nd Printing 23 Picosecond Phenomena III 6 Laser-Induced Processes in Editors: K. B. Eisenthal, R. M. Hochstrasser, Molecules Physics and Chemistry W. Kaiser, A. Laubereau Editors: K.L. Kompa, S.D. Smith 24 Desorption Induced by Electronic 7 Excitation of Atoms and Broadening Transitions DIET I Editors: N. H. Tolk, of Spectral Lines By 1.1. Sobelman, M. M. Traum, J. C. Tully, T. E. Madey L. A. Vainshtein, E. A. Yukov 25 Ion Formation from Organic Solids 8 Spin Exchange Editor: A. Benninghoven Principles and Applications in 26 Semiclassical Theories of Molecular Chemistry and Biology Scattering By B. C. Eu By Yu.N. Molin, K.M. Salikhov, 27 EXAFS and Near Edge Structures K. I. Zamaraev Editors: A. Bianconi, L. Incoccia, S. Stipcich 9 Secondary Ions Mass Spectrometry 28 Atom in the Strong Light Field SIMS II Editors: A. Benninghoven, ByN.B. Delone, V.P. Krainov C. A. Evans, Jr., R. A. Powell, 29 Gas Flow in Nozzles R. Shimizu. H. A. Storms By U. Pirumov, G. Roslyakov lO Lasers and Chemical Change 30 Theory of Slow Atomic Collisions By A. Ben-Shaul, Y. Haas, By E. E. Nikitin, S. Ya. Umanskii K. L. Kompa, R. D. Levine 31 Reference Data on Atoms, Molecules, II Liquid Crystals of One-and and Ions By A. A. Radzig, B. M. Smirnov Two-Dimensional Order 32 Adsorption Processes on Semiconductor Editors: W. Helfrich. G. Heppke and Dielectric Surfaces I 12 Gasdynamic Laser By S. A. Losev By V. E Kiselev, O. V. Krylov 13 Atomic Many-Body Theory 33 Surface Studies with Lasers By I. Lindgren, J. Morrison Editors: ER. Aussenegg, A. Leitner, M.E. Lippitsch 14 Picosecond Phenomena II 34 Inert Gases Potentials, Dynamics, and Energy Editors: R. M. Hochstrasser, Transfer in Doped Crystals W. Kaiser, C. V. Shank Editor: M. Klein 15 Vibrational Spectroscopy of Adsorbates Editor: R. E Willis 35 Chemistry of Solid Surfaces V Editors: R. Vanselow, R. Howe 16 Spectroscopy of Molecular Excitions 36 Secondary Ion Mass Spectrometry, By V. L. Broude, E. I. Rashba, SIMS IV E.E Sheka Editors: A. Benninghoven, J. Okano, 17 Inelastic Particle-Surface Collisions R. Shimizu, H. W. Werner Editors: E. Taglauer, W. Heiland 18 Modelling of Chemical Reaction Systems Editors: K. H. Ebert, P. Deuflhard, W. Jager Secondary Ion Mass Spectrometry SIMSIV Proceedings of the Fourth International Conference, Osaka, Japan, November 13-19, 1983 Editors: A. Benninghoven, 1. Okano, R Shimizu, and H. W Werner With 415 Figures Springer-Verlag Berlin Heidelberg New York Tokyo 1984 Professor Dr. A. Benninghoven Professor Dr. R Shimizu Phsysikalisches Inst. der Universitat MUnster, Department of Applied Physics, D4400 MUnster, Fed. Rep. of Germany Osaka University, Osaka 565, Japan Professor Dr. 1. Okano Dr. H. W. Werner College of General Education, Philips Research Laboratories, Eindhoven Osaka University, Osaka 560, Japan The Netherlands v: International Organizing Committee: A. Benninghoven (Chairman), T. Cherepin, C. A. Evans, Jr., K. F. J. Heinrich, J. Okano, G. Slodzian, H. W. Werner Local Organizing Committee: 1. Okano (Chairman), T. Ichinokawa, H. Kamada, S. Maruse, K. Masuda, S. Namba, T. Noda, K. Ogata, Y. Omori, Y. Sakaki, K. Sanbongi, R. Shimizu, G. Shinoda, M. Someno, E. Sugata. Sponsored by: Japan Society for the Promotion of Science, The Commemorative Association for the Japan World Exposition, Yamada Science Foundation, Shimadzu Science Foundation Series Editors Professor Vitalii 1. Goldanskii Professor Dr. Fritz Peter Schafer Institute of Chemical Physics Max-Planck-Institut flir Academy of Sciences Biophysikalische Chemie Vorobyevskoye Chaussee 2-b D-3400 Gottingen-Nikolausberg Moscow V-334, USSR Fed. Rep. of Germany Professor Robert Gomer Professor Dr. J. Peter Toennies The James Franck Institute Max-Planck-Institut flir Stromungsforschung The University of Chicago BottingerstraJ3e 6-8 5640 Ellis Avenue D-3400 Gottingen Chicago, IL 60637, USA Fed. Rep. of Germany ISBN-13: 978-3-642-82258-2 e-ISBN-13: 978-3-642-82256-8 DOl: 10.1 007/978-3-642-82256-8 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically those oftranslatioll, reprinting, reuse of illustrations, broadcasting, reproduction by photocopying machine or similar means, and storage in data banks. Under § 54 of the German Copyright Law where copies are made for other than private use, a fee is payable to "Verwertungsgesellschaft Wort", Munich. © by Springer-Verlag Berlin Heidelberg 1984 Softcover reprint of the hardcover 15t edition 1984 The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Offset printing: Beltz Offsetdruck, 6944 Hemsbach/Bergstr. Bookbinding: J. Schaffer OHG, 6718 Griinstadt 2153/3130-543210 Preface This volume contains full proceedings of the Fourth International Conference on Secondary Ion Mass Spectrometry (SIMS-IV), held in the Minoo-Kanko Hotel, Osaka, Japan, from November 13th to 19th, 1983. Coordinated by a local or ganizing committee under the auspices of the international organizing com mittee, it followed earlier conferences held in MUnster (1977), Stanford (1979), and Budapest (1981). The conference was attended by about 250 participants from 18 countries, and 130 papers including 24 invited ones were presented. Reflecting the rap idly expanding activities in the SIMS field, informative papers were pre sented containing up-to-date information on SIMS and various related fields. The proceedings focussed upon six main issues: (1) Fundamentals of sput tering and secondary ion formation. (2) Recent progress in instrumentation, including submicron SIMS and image processing. (3) SIMS combined with other surface analysis techniques. (4) Outstanding SIMS-related analytical methods such as laser-microprobe SIMS, sputtered neutral mass spectrometry, mass spectrometry of sputtered neutrals by multi-photon resonance ionization, and accelerator-based SIMS. (5) Organic SIMS and FAB which has recently become a rapidly expanding technique in pharmacy, biotechnology, etc. (6) Appl ica tions of SIMS to various fields such as metallurgy, geology, and biology, including depth profiling of semiconductors, and analysis of inorganic mate rials. As a venue for the exchange of ideas and information concerning all the above issues, the conference proved a great success. The first meeting for organizing SIMS-IV was arranged by the Technical Committee for Microbeam Analysis (Chairman, Prof. S. Maruse) of the Japan Society for Promotion of Science (JSPS) in response to a request made by the international organizing committee at the Budapest conference. At this meet ing I was asked to establish a local organizing committee and act as chair man. The local organizing committee then appointed Prof. Y. Sakaki as chair man of the fund-raising committee and Profs. G. Shinoda, E. Sugata, and K. Sanbongi as advisers. The success of this conference was due in great part to the efforts of the fund-raising commmittee and to the financial support received from the Japan Society for Promotion of Science, the Commemorative Association for the Japan World Exposition, the Yamada Foundation, the Shimadzu Science Foundation, and from industry. We are also indebted to both the internation al and the local organizing committees for the technical advice and support they furnished. Our warm thanks go out too for the efforts made by the exec utive committee members, particularly Dr. H. Nishimura,who devotedly handled all the arrangements for sending out circulars, p~oducing abstracts, regis tration, hotel accommodation, and managing the accounts of the conference. v The technical assistance and support given by the JSPS Technical Committee for Microbeam Analysis from the beginning stages of organizing the confer ence were most helpful and are gratefully acknowledged. Finally, on behalf of the local organizing committee, I would like to ex tend our deepest appreciation to all the participants who made this confer ence such a successful and fruitful one. Osaka, Japan Jun Okano January 1984 (Chairman of organization for SIMS-IV) VI Contents Part I Fundamentals * Fundamentals of Sputtering. By P. Sigmund ................•........... 2 Sputtered Atom Yields and Ionization Probabilities of Binary Alloys 2 Under O Bombardment. By K. Tsunoyama and T. Suzuki (With 2 Figures) 8 Sputtering and Secondary Ion Yields of Ti-Al Alloys Subjected to Oxygen Ion Bombardment. By K. Inoue, Y. Taga, and K. Satta (With 4 Figures) ........................................................ 11 Outermost Surface Composition of Au-Cu Alloys Under Ion Bombardment of Different Current Densities of Ar+ Ions. By H.J. Kang and R. Shimizu (With 3 Figures) .................................................. 14 Secondary Dimer Ion Emission Probability in Sputtering Cu-Ni Alloy By F. Honda, Y. Fukuda, and K. Nakajima (With 4 Figures) ......•..•. 17 Empirical Formula for Sputtering Yield and Z2 Dependence of Its QValues By Y. Yamamura, S. Nakagawa, and S. Enoki (With 4 Figures) ........ 20 * Molecular Dynamics Computer Simulation Investigation of Target Damage Created by Ion Bombardment. By D.E. Harrison, Jr., W.A. Mason, and R.P. Webb (With 3 Figures) ........................................ 24 Simulation of Ion Sputtering Process on the Binary Alloy By T. Koshikawa, T. Ikuta, and R.S. Li (With 3 Figures) 31 Secondary Ion Emission from Si Subjected to Oxygen Ion Bombardment dy T. Ohwaki, Y. Taga, and K. Satta (With 4 Fi gures) . . .. . . . .. . .... 35 Surface Structure of Oxidized Metals Bombarded by Incident Ions By Y. Sekimoto, Y. Igarashi, and T. Kawata (With 5 Figures) ....... 38 The Effect of Energetic Electrons on the Secondary Ion Emission By Zhu Ang-Ru and Wu Xe-Ling (With 1 Figure) ........ .............. 41 Influence of Alkali Metals on the Negative Secondary Ion Emission from Silicon. By W. Frentrup, t1. Griepentrog, H. Klose, G. Kreysch, and U. Mueller-Jahreis (With 3 Figures) .....................•......... 43 * Invited paper VII Secondary Ion Emission Peculiarities at Metal Interfaces By M.A. Vasilyev and S.P. Chenakin (With 2 Figures) 46 * Intensities and Energy Spectra of Secondary Ions Sputtered from Fe-Al Alloys by Ar+ Ion Bombardment in Ultrahigh Vacuum By R.-L. Inglebert and J.-F. Hennequin (With 3 Figures) ........... 49 CF;: An Alternative Primary Beam Source for the Sensitive Detection of Electropositive Elements in SIMS. By W. Reuter .................... 54 Hydrogen Ion Bombardment in Secondary Ion f1ass Spectrometry By V.T. Cherepin, A.A. Kosyachkov, and I.N. Makeeva (With 2 Figures) 57 Electron Tunneling and the Emission of Secondary Ions from Silicon Surfaces. By M.L. Yu (With 3 Figures) ............................. 60 Detection of Sputtered Neutrals by Multiphoton Resonance Ionization By F.M. Kimock, J.P. Baxter, D.L. Pappas, P.H. Kobrin, and N. Winograd (With 1 Figure) .......................................... 63 The Energy Dependence of the Ionisation Coefficient in SIMS By R.F. Garrett, R.J. MacDonald, and D.J. O'Connor (With 4 Figures) 66 Accurate ~1easurement of Energy Distri bution Curves of Secondary Ions by UHV-IMMA. By O. Tsukakoshi, K. Komatsu, and S. Komiya (With 4 Figures) ........................................................ 70 Energy Distribution of Positive Secondary Ions from Pure Elements and Amorphous Alloys. By M. Riedel and H. DUsterhoft (With 2 Figures) 73 Energy Distribution of Secondary Ions Emitted from Silicate Minerals By J. Okano and H. Nishimura (With 3 Figures) ..................... 76 A Retarding-Accelerating Energy Analyser for SIMS. By Cha Liang-Zhen, Xue Zu-Qing, Zheng Zhao-Jia, Tong Yu-Qing, and Wu Yong-Qing (With 4 Figures) ........................................................ 79 Part II Quantification * Current Status of Sputtered Ion Emission Models. By P. Williams 84 LTE Quantification of SIMS of Ni-Cr Alloy By S. Tamaki and H. Matsuda (With 3 Figures) 85 Simplified IMISR Method with Computer Data Acquisition. By J. Giber, A. Solydom, D. Marton, and I. Barsony ............................. 89 Relative Sensitivity Factor of Compound Semiconductor by SIMS By K. Kusao, K. Tsukamoto, Y. Yoshioka, and F. Konishi (With 3 Figures) ........................................................ 92 Quantitative Ion Probe Analysis of Oxidized Surface Using N2 Primary Ion. By J. Murayama, N. Usuki, and N. Fujino (With 4 Figures) ..... 95 Oxygen Effect on Secondary Ion Yield in Oxygen-Doped Silicon By Y. Homma, H. Tanaka, and Y. Ishii (With 4 Figures) ............. 98 VIII *T he Role of Standards in Secondary Ion Mass Spectrometry By D.E. Newbury and D. Simons (With 2 Figures) .................... 101 SIMS Quantitative Analysis of Impurities in GaAs Using Multi-Element- Doped GaAs. By S. Kurosawa, Y. Homma, T. Tanaka, and M. Yamawaki (With 3 Figures) .................................................. 107 SIMS Quantitative Analysis of Gallium in Silicon by Using Ion-Implanted Samples for Standards. By H. Yamaguchi, Y. Honma, J. Kashiwakura, and K. Koike (With 5 Figures) ..................................... 110 Part III Instrumentation * Ion Gun Systems for Submicron SIMS. By H. Liebl (With 3 Figures) 114 * Submicron Ion Probes. By N. Anazawa and R. Aihara (With 3 Figures) 119 Optimization of High Brightness Cs Ion Source and Ion Optics for UHV- IMMA. By K. Komatsu, O. Tsukakoshi, T. Katagawa, and S. Komiya (With 4 Figures) .................................................. 124 A New Type Surface Ionization Source with an Additional Mode of Electrohydrodynamic Ionization for SIMS. By T. Okutani, M. Fukuda, T. Noda, H. Tamura, and H. Watanabe (With 4 Figures) .............. 127 A Study of Argon Ion Gun in SIMS. By Wang Jian-Hua, Li You-Zhe, Chen Pi-Jin, Long Zhi-Qiao, Ho Xiao-Fang, Zhang Quan-Zhen, and Zhang Zhen-Xiang (With 6 Figures) ................................. 130 * Liquid Metal Ion Sources for Scanning SIMS By F.G. Ruedenauer (With 4 Figures) ............................... 133 SIMS with Very High Spatial Resolution Using Liquid Metal Ion Sources By A.R. Waugh, A.R. Bayly, and K. Anderson (With 5 Figures) 138 Development of High Performance Ion Microanalyzer. By E. Izumi, Y. Kato, M. Yano, Y. Arima, and H. Tamura (With 2 Figures) 141 MIQ-156 MARK II A Highly Advanced and Versatile Quadrupole SIMS Instrument, with Dual Primary Ion Source By F. Simondet and P. Staib (With 5 Figures) ...................... 144 Development of Shielded Ion Microprobe Analyser for Irradiated Fast Reactor Fuel and Material Examination. By Y. Enokido, M. Mizuno, S. Yamanouchi, K. Kohno, and T. Itaki (With 2 Figures) ............ 147 Parameters Influencing Ion Intensities for Quadrupole SIMS Instruments By M. Kotera and D.B. Wittry (With 4 Figures) ..................... 150 * Isotopic Measurements at High Mass Resolution by Electrostatic Peak Switching. By G. Slodzian, J.C. Lorin, R. Dennebouy, and A. Havette (With 6 Figures) .................................................. 153 * Laser Microprobe Mass Spectrometry. By D.S. Simons (With 2 Figures) 158 Metastable Molecular Ion Emission from Semiconductor Surfaces Under N2 Laser Irradiation. By A. Kasuya and Y. Nishina (l~ith 3 Figures) 164 IX Laser-Induced Sputtering from CdS and GaAs. By H. Fukano, A. Namiki, Y. Yasuda, T. Nakamura, and T. Noda (l~ith 3 Figures) .............. 167 * SIMS at Higher Energies. By A.E. Litherland, J.C. Rucklidge, G.C. Wilson, W.E. Kieser, L.R. Kilius, and R.P. Beukens (With 2 Figures) 170 The Radiocarbon Measurement with the Tandem Accelerator at Nagoya University. By T. Nakamura, H. Yamashita, N. Nakai, T. Sakase, S. Sato, and A. Sakai (With 2 Figures) ............................ 175 * Image Processing SIMS. By G.H. Morrison and M.G. Moran (Hith 2 Figures) 178 Evaluation of Metal Interaction by Color Display SIMS Techni~ue By Y. r~ashiko, K. Tsutsumi, H. Koyama, and S. Kawazu (With3Figures) 183 A Comparison of Camera-Based and Quantized Detectors for Image Processing on an Ion Microscope. By R.W. adom, D.H. Hayne, and C.A. Evans, Jr. (With 4 Figures) ....................................... 186 Automation of an Ion Microprobe Mass Analyzer By T. Suzuki and K. Tsunoyama (With 3 Figures) 189 Part I V Combined and Static SIMS * Ultra-High Vacuum SIMS: A Pilgrim's Journey Through History By S. Komiya ...................................................... 194 * Single Crystal Surface Structure Studies with Static SIMS By E. Bauer and S. Prigge (With 2 Figures) ........................ 201 Ion Dose Effect in Thin Film Formation on Nb(lOO) By T. Koshikawa, S. Prigge, and E. Bauer (With 4 Figures) 206 A Low-Energy SIMS Investigation on Thermal Diffusion on Vapor-Deposited Nickel on Copper Substrate By H. Yamamoto, T. Kikuchi. and K. Furuya (With 2 Figures) ........ 210 * SIMS Combined with Other Methods of Surface Analysis. By O. Ganschow (With 3 Figures) •••••....•....•....•.•.....•.......••...•...•..... 213 Combined SIMS and Electron Spectroscopy Investigation of the Chemical State of Some Ion-Implanted Transition Metals and Steels By W.M. Bone, T.M. Barlak, I.L. Singer, R.A. Jeffries, and R.J. Colton (With 3 Figures) ........................................... 221 SIMS-Auger Analysis of Organic Films on Gallium Arsenlde By M. Hatada and K. Matsuda (With 3 Figures) ...................... 225 SIMS and AES Studies of Ni-Zn Alloys. By Y. Fukuda (With 5 Figures) 228 The Application of SIMS and Other Surface Techniques to the Study of Antimony-Doped Tin Oxide Surfaces. By G.B. Hoflund, P.H. Holloway, and W.H. Hocking (With 3 Figures) ................................. 231 Silver Catalyst for Partial Oxidation of Methanol. Reaction Path and Catalyst Poisoning by Iron. A Combined SIMS, TOMS, AES, XPS and ISS Study. By R. Jede, E. Manske, L.D. An, O. Ganschow, U. Kaiser, L. Wiedmann, and A. Benninghoven (With 6 Figures) ................. 234 x