Metallized Plastics 3: Fundamental and Applied Aspects PDF
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METALLIZED PLASTICS 3 Fundamental and Applied Aspects METALLIZED PLASTICS 3 Fundamental and Applied Aspects Edited by K. L. Mittal Skill Dynamics, an IBM Company Thornwood, New York SPRINGER SCIENCE+BUSINESS MEDIA, LLC Llbrary of Congress Cataloglng-ln-Publlcatlon Data Metallized plastics 3 fundamental and applied aspects ! edited by K.L. MittaL p. cm. "Proceedings of the Thlrd Electrochemical Soclety Symposlum on Metallized Plastics, held October 13-18, 1991, in Phoenlx, Arizona" -T.p. verso. Includes blbllographical references and index. ISBN 978-1-4613-6510-5 ISBN 978-1-4615-3416-7 (eBook) DOI 10.1007/978-1-4615-3416-7 1. Plastic coatlngs--Con~resses. 1. Mlttal, K. L., 1945- II. Electrochemical Society Symposium an Metallized Plastics (3rd 1991 Phaenix, Ariz.) TP1175.M4M473 1992 668.4' 1--oc20 92-32962 CIP Proceedings of the Third Electrochemical Society Symposium on Me.tallized Plastics, held October 13-18, 1991, in Phoenix, Arizona ISBN 978-1-4613-6510-5 © 1992 Springer Science+Business Media New York Softcover reprint of the hardcover 1st edition 1992 Originally published by Plenum Press, New York in 1992 AH rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher PREFACE This volume chronicles the proceedings of the Third Symposium on Metallized Plastics: Fundamental and Applied Aspects held under the auspices of the Dielectric Science and Technology Division of the Electrochemical Society in Phoenix, Arizona, October 13-18, 1991. This series of symposia to address the subject of metallized plastics was initiated in 1988 and the premier symposium was held in Chicago, October 10-12, 1988, followed by the second event in Montreal, Canada, May 7-10, 1990. The rroceedings of these two symposia have been properly documented ,2. The third symposium was a huge success like the previous two events, and all this is testimonial to the brisk interest and high tempo of R&D activity in the fie14 of metallized plastics. This further bolsters our earlier thinking that there was a conspicuous need to hold symposia on this topic on a regular basis and the fourth is planned for May 16-21, 1993 in Honolulu, Hawaii. The study of metallized plastics constitutes an important human endeavor and as pointed out earlierl there are myriad applications of metallized plastics ranging from very commonplace to exotic. Also a survey of the recent literature will reveal that both the fundamental and applied aspects of metallized plastics are being pursued with great vigor. As for the present volume, it contains a total of 28 papers covering many facets of metallized plastics. It must be recorded here that all manuscripts were rigorously peer reviewed and all of them were suitably revised (some extensively, and some two times) before acceptance and inclusion in this volume. In o~her words, this book is not merely a collection of as-received manuscripts, rather it represents a compendium which has passed the peer scrutiny. It is divided into four parts as follows: Part I. Metallization Techniques and Properties of Metal Deposits; Part II. Investigation of Interfacial Interactions; Part III. Plastic Surface Modifications; and Part IV. Adhesion Aspects of Metallized Plastics. The topics covered include: polypyrrole precoat for the metallization of printed circuit boards; photoselective circuitization of dielectrics; application of metallized plastic electrodes for electrowinning of metals; scanning tunneling microscopy of metal/polymer interfaces; XPS investigation of metal/polymer systems; model systems for metal/polyimide interface; metal/polymer interface formation and adhesion; various plastic surface treatment and modification techniques; adhesion enhancement using ion processing; factors affecting adhesion of metal/polymer systems; electrochemical method to deduce mechanical and chemical adhesion components; and blister test, and nondestructive evaluation of adhesion. v I certainly hope that the present proceedings and the earlier two volumes will serve as a reference source for the latest information on the research and development activity and accomplishments in the field of metallized plastics. Acknowledgements: This section is always the fun part of writing the preface and it provides an opportunity to thank those who helped in a variety of ways. First and foremost it is my sincere pleasure to mention that this symposium was jointly organized by yours truly and Dr. John R. Susko of IBM Endicott and thanks are extended to him. Thanks are due to the appropriate officials of the Dielectric Science and Technology Division of the Electrochemical Society for sponsoring this event. I am thankful to the appropriate management of IBM Corporation for allowing us to organize this symposium and for me to edit this volume. Special appreciation goes .to my wife, Usha, for her help and understanding. My sincere thanks to the reviewers for their incisive comments and useful suggestions which definitely improved the contents and clarity of manuscripts; their time and efforts are deeply appreciated. Without the cooperation, interest and contributions of the authors, I would not have had the pleasure of making this book available. K.L. Mittal Skill Dynamics, an IBM Company 500 Columbus Ave. Thornwood, NY 10594 References 1. K.L. Mittal and J.R. Susko, editors, Metallized Plastics 1: Fundamental and Applied Aspects, Plenum Press, New York, 1989. 2. K.L. Mittal, editor, Metallized Plastics 2: Fundamental and Applied Aspects, Plenum Press, New York, 1991. VI CONTENTS PART I. METALLIZATION TECHNIQUES AND PROPERTIES OF METAL DEPOSITS The Application of a Polypyrrole Precoat for the Metallization of Printed Circuit Boards S. Gottesfeld, F.A. Uribe and S.P. Armes........................ 3 Photoselective Circuitization of Dielectrics Via Electroless Plating of Metals T.H. Baum, D.C. Miller and T.R. O'Toole ......................... 9 Plasma-Induced Deposition of Copper Films R. Padiyath, J. Seth, S.V. Babu and L.J. Matienzo ............... 19 The Effects of Substrate Functional Groups on Conventional and Novel E1ectroless Catalysts A.M. Mance, R.A. Waldo, S.W. Gaarenstroom and R.R. Witherspoon .. 29 Laser Speckle Detection of Surface Morphology in Molded Plastic Parts A.M. Mance, G.L. Eesley and J.Z. Stemple ........................ 43 Development of a Generic Method to Metallize Plastics T.A. Reddy, V.S. Nithianandam and S. Erhan ...................... 57 Palladium and Aluminum Thin Film Deposition on Thermally Sensitive Substrates from Organometallic Complexes S. Datta, Y.-G. Kim, P.A. Dowben, J.A. Glass, Jr., S.S. Kher, S.A. Peters, and J.T. Spencer ........................ 65 Application of Metallized Plastic Electrodes for Electrowinning of Metals B.E. El-Anadouli, S.E. Afifi, M.M. Saleh and B.G. Ateya ......... 73 PART II. INVESTIGATION OF INTERFACIAL INTERACTIONS Model Studies of the Interface Between Metals and Polyimides W.N. Unertl and R.G. Mack ....................................... 85 Scanning Tunneling Microscopy of Metal/Polymer Interfaces P. Bodo, J.R. Rasmusson and W.R. Salaneck ....................... 109 "In Situ" XPS Investigation of Polymers Metallized by Evaporation J.L. Droulas, Y. Jugnet and Tran Minh Duc ....................... 123 vii Model Systems for the Cr/Polyimide Interface A. Selmani, A. Ouhlal and A. Yelon .............................. 141 Interactions of Deposited Copper on COOH of ll-Mercaptoundecanoic Acid: An XPS Study D.E. King, A.W. Czanderna and D. Spaulding ...................... 149 XPS Investigation of the Interfacial Chemistry of Evaporated Silver on Plasma-Modified Polystyrene L.J. Gerenser and K.E. Goppert-Berarducci ....................... 163 The Chemistry of Metal/Polymer Interface Formation: Relevance to Adhesion R. W. Burger and L.J. Gerenser ................................... 179 PART III. PLASTIC SURFACE MODIFICATIONS A Study of Metallized Thermoplastic Films Following Gas Plasma Treatment R.J. Marnmone, M. Binder and W.L. Wade Jr ........................ 197 Influence of Surface Treatments on the Metallization of Thermostable Polymers A. Cros, H. Dallaporta, S. Lazare, F. Templier, J. Nechstchein, J. Palleau, H. Hiraoka and J. Torres ............ 201 Oxygen Plasma Treatment of Fluorinated Polyimide: An X-ray Photoelectron Spectroscopy Study N.C. Saha and L.-H. Chang ....................................... 215 A Static SIMS Study of the Chemical Modifications Induced by Plasma and Flame Treatments at the Surface of Polyolefins Y. De Puydt, D. Leonard and P. Bertrand ......................... 225 Aluminium Metallization of Polypropylene Films Pretreated by a N2 or NH3 Nonequilibrium Plasma. Study of the Interface and Adhesion Measurements F. Arefi, M. Tatoulian, V. Andre, J. Amouroux and G. Lorang ..... 243 Aluminum Metallization of Polyimide Substrate J. -K. Lin and N.C. Saha ......................................... 257 PART IV. ADHESION ASPECTS OF METALLIZED PLASTICS Adhesion Enhancement Using Ion Processing: Metallized Plastics A.A. Galuska .................................................... 267 The Influence of the Pretreatment on the Adhesion of Metallic Coatings on Plastics D. Mann, J. Fessmann, G. Kampschulte and K. Mertz ............... 295 Effect of the Polymeric Substrate Temperature on the Adhesion and Morphology of Metal Layers K. Nakamae, S. Tanigawa and K. yamaguchi ........................ 303 viii An Electrochemical Means of Probing a Metal/Polymer Interface--A Method for Deducing Mechanical and Chemical Adhesion Components B. R. Karas and D.F. Foust ...................................... 319 Measurement and Control of Interface Strength and Mechanical Properties of Coatings by Laser Spallation Experiment V. Gupta and J. yuan ............................................ 331 The Adhesion Strength of Metal/Polyimide and Polyimide/Silicon Interfaces as Determined by the Blister Test Y.Z. Chu, C.J. Durning, H.S. Jeong and R.C. White ............... 347 Non-destructive Evaluation of Adhesion at Metal-Insulator Interfaces Based on Extremely-Low-Frequency Dielectric Spectroscopy D. Narducci, J.J. Cuomo, D.L. Pappas and K. Sachdev ............. 365 About the Contributors .............................................. 385 Index ............................................................... 397 IX PART I. METALLIZATION TECHNIQUES AND PROPERTIES OF METAL DEPOSITS THE APPLICATION OF A POLYPYRROLE PRECOAT FOR THE METALLIZATION OF PRINTED CIRCUIT BOARDS Shimshon Gottesfeld, Francisco A. Uribe and Steven P. Armes* Electronics Research Group, Los Alamos National Laboratory Los Alamos, NM 87545 We describe a printed circuit (PC) board metallization process starting with the formation of a pre coat of polypyrrole (PPY) on the board followed by the direct electrodeposition of copper onto the polypyrrole-coated substrate. The polypyrrole film is applied to the insulating substrate by a single chemical polymerization step from an aqueous solution. The sheet resistivity of the polypyrrole precoat is typically of the order of a few hundred ohms/square, but this turns out to be a sufficiently low resistance to enable direct metal electrodeposition onto the PPY-coated substrate. INTRODUCTION Several authors have recently described various methods of application of thin films of conducting polymers to insulating substrates.1-4 The possibility of employing such conducting polymer coatings for the metallization of insulating substrates has been recently mentioned in the scientific4 as well as the patent literature.S The last two references describe for the first time processes where conducting polymer precoats are applied to an insulating substrate followed by the electrodeposition of a metal, particularly copper. Such processes can potentially provide a replacement for present-day insulator metallization technologies, particularly metallization of printed circuit board surfaces. These metallization technologies are based on an initial step of electro less metal deposition taking place on a catalyzed substrate surface. Drawbacks of the present-day technologies are the use of hazardous chemicals, particularly the formaldehyde used in the electroless copper deposition process, and the requirement of precious metal catalysts. To provide an attractive alternative metallization process based on a conducting polymer precoat, some obvious prerequisites are: (a) that the new conducting-polymer-based process would not itself involve hazardous chemicals, (b) that the initial process of polymer coating onto the insulating substrate be simple and result in a well adherent film, (c) that the polymer precoat be sufficiently conducting to * Permanent address: School of Chemistry, University of Sussex, Brighton BN!, 9QJ, UK Metallized Plastics 3: Fundamental and Applied Aspects Edited by K.L. Mittal. Plenum Press, New York, 1992 3
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