Modern Electroplating

737 Pages·2016·82.3 MB·English

by  Schlesinger M.

MODERN ELECTROPLATING
MODERN ELECTROPLATING
Fifth Edition
Edited by
MORDECHAY SCHLESINGER
Universityof Windsor, Windsor Ontario, Canada
MILAN PAUNOVIC
IBMT.J.Watson ResearchCenter, Yorktown Heights,NY (Retired)
Sponsoredby
THEELECTROCHEMICALSOCIETY,INC.Pennington,NewJersey
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Moderneletroplating /editedbyMordechaySchlesinger,MilanPaunovic.–5thed.
p.cm.–(TheECSseriesoftextsandmonographs;52)
Includesindex.
Summary:‘‘Electroplatingisthecoatingofanelectricallyconductiveobjectwithalayerofmetalusingelectricalcurrentresultinginathin,smooth,even
coatofmetalontheobject.Thistextcoversthemethodsandapplicationsofelectrochemicaldepositionofmetals,alloys,semiconductors,andconductive
polymers.Itprovidespracticaladviceandsometheorticalbackgroundtothoseenteringthefieldofelectrodeposition.Likepreviouseditions,thefifthedition
willbethefirststopreferecefortheelectroplatingconmmunity.Thisfullyupdatededitionincludessignificantadvancesinthefield,fromemerging
electrodepostiontechniquestoelectroplatinginmedicalanddatastorageindustries’’–Providedbypublisher.
ISBN978-0-470-16778-6(hardback)
1. Electroplating. I. Schlesinger, Mordechay. II.Paunovic,Millan.
TS670.M554 2010
671.7’32–dc22
PrintedintheUnitedStatesofAmerica
10 9 8 7 6 5 4 3 2 1
CONTENTS
PREFACE vii
PREFACE TO THE FOURTHEDITION ix
CONTRIBUTORS xi
CONVERSIONFACTORS xiii
GRAPHICAL CONVERSIONS xv
THE ELECTROCHEMICAL SOCIETYSERIES xvii
1 FundamentalConsiderations 1
MilanPaunovic,MordechaySchlesinger,andDexterD.Snyder
2 Electrodeposition ofCopper 33
JackW.DiniandDexterD.Snyder
3 Electrodeposition ofNickel 79
GeorgeA.DiBari
4 Electrodeposition ofGold 115
PaulA.Kohl
5 Electroless and Electrodeposition ofSilver 131
MordechaySchlesinger
6 Tinand TinAlloys for Lead-Free Solder 139
YunZhang
7 Electrodeposition ofChromium 205
NenadV.MandichandDonaldL.Snyder
8 Electrodeposition ofLead andLead Alloys 249
ManfredJordan
9 Electrodeposition ofTin–LeadAlloys 265
ManfredJordan
10 Electrodeposition ofZinc and Zinc Alloys 285
Rene´ Winand
v
vi CONTENTS
11 Electrodeposition ofIron and Iron Alloys 309
MasanobuIzaki
12 Palladium Electroplating 327
JosephA.Abys
13 Electrochemical Deposition Process for ULSI Interconnection Devices 369
TetsuyaOsakaandMasahiroYoshino
14 Electrodeposition ofSemiconductors 383
T.E.Schlesinger,KrishnanRajeshwar,andNormaR.DeTacconi
15 Depositionon Nonconductors 413
MordechaySchlesinger
16 Conductive Polymers:Electroplatingof Organic Films 421
TetsuyaOsaka,ShinichiKomaba,andToshiyukiMomma
17 Electroless Deposition ofCopper 433
MilanPaunovic
18 Electroless Deposition ofNickel 447
MordechaySchlesinger
19 Electrochemical Synthesis ofMetal Alloys for Magnetic Recording Systems 459
AtsushiSugiyama,MasahiroYoshino,TakumaHachisu,andTetsuyaOsaka
20 Electroless Deposition ofPalladium and Platinum 477
IzumiOhno
21 Electroless Deposition ofGold 483
YutakaOkinakaandMasaruKato
22 Electroless Deposition ofAlloys 499
IzumiOhno
23 Preparation for Deposition 507
DexterD.Snyder
24 Manufacturing Tools 513
TomRitzdorf
25 Monitoring and Control 527
TomRitzdorf
26 Environmental Aspects of Electrodeposition 555
MichaTomkiewicz
27 Applications toMagnetic Recording and Microelectronic Technologies 573
StankoR.Brankovic,NatasaVasiljevic,andNikolayDimitrov
28 Microelectromechanical Systems 617
GiovanniZangari
29 Analysisof Electroplated Films UsingDual-Beam FIB/SEM andTEM Techniques 637
XianyingMeng-Burany
30 Ionic Liquid Treatments for Enhanced Corrosion Resistance of Magnesium-Based Substrates 665
RobertPetro,MordechaySchlesinger,andGuang-LingSong
APPENDIX 687
INDEX 701
PREFACE
Ours is the information age. Consequently, the demand for “Applications to Magnetic Recording and Microelectronic
high-performance, low-cost, and nonvolatile information Technologies” by Brankovic, Vasiljevic, and Dimitrov;
storagesystemsisonaconstantrise.Thereareagreatvariety “Microelectromechanical Systems” by Zangari; “Analysis
of information storage systems, with varying degrees of of Electroplated Films Using Dual-Beam FIB/SEM and
developmentandcommercialization.Thoseinclude,butare TEMTechniques”byMeng-Burany;and“IonicLiquidTreat-
not limited to, magnetic tape drives, hard disc drives, ments for Enhanced Corrosion Resistance of Magnesium-
magneticfloppydiscdrives,magneto-optic(MO)discdrives, BasedSubstrates”byPetro,Schlesinger,andSong.Theseand
phasechangeopticdiscdrives,semiconductorflushmemory, most other changes, including the publication of the new
magnetic random-access memory (RAM), and holographic secondeditionin2006ofFundamentalsofElectrochemical
optical storage. Electrochemical deposition techniques are Deposition,reflectthepresenttendencyoftheapplicationsof
essentialintheproductionofmostoftheabove.This,among electroplatingmoreandmoreinthearenaofnanoelectronics
manyothers,istheraisond’eˆtreforthepresent(fifth)andthe in particular and nanotechnology in general as alluded to
earlier (fourth)editions. above.Typically,itmaybeobservedthatwhereasthefourth
The fourth edition of Modern Electroplating appeared editioniscomprisedof26chaptersonabout800pages,the
some10yearsago.Agreatdealofprogresshastakenplacein present edition contains 30 chapters and is about the same
thoseyearsintheareaofelectrochemicalplatingandrelated numberofsubstantiallyenlargedpages.Inthiseditionasin
fields. It is these developments that make this new edition thepreviousthechaptersareself-containedinthatthosemay
both desirable and necessary. Those profound changes are bereadinanyorderthatthereaderfindsuseful.Thanksare
reflectedinthepresenteditioninanumberofdifferentways. duetotheover30contributors/authorswhomadethisedition
Essentially, all chapters were rewritten, some by different possible.
authors, and/or updated. Unfortunately, two authors who
contributed to the fourth edition (Drs. Rolf Wyle and Ned MORDECHAYSCHLESINGER
Mandich) have since passed on. Two chapters have been
removed altogether and new ones are replacing them. The WindsorOntario,Canada
two new chapters are titled “Electrochemical Deposition
MILAN PAUNOVIC
Process for ULSI Interconnection Devices” by Osaka and
Yoshinoand“ElectrochemicalSynthesisofMetalAlloysfor
PortWashington,NewYork
Magnetic Recording Systems” by Sugiyama, Yoshino,
Hachisu, and Osaka. Four new chapters have been added:
vii
PREFACE TO THE FOURTH EDITION
In planning this new edition of Modern Electroplating, we opto-etectronics; and sensors of most types. In addition, a
have realized from the start that it would be impossible to number of key industries, such as the automotive industry,
includeinonevolumeboththefundamentalaspectsandthe employmethodsofelectroplating.Thisissoevenwhenother
technologyitself.Forthisreasonwehavedecidedtopublish methodssuchasevaporationandsputteringCVD(chemical
the recent developments in the science of deposition in a vapor deposition) are an option. Electroplating is therefore
separate volume titled Fundamentals of Electrochemical often used for reasonsof economy and/or convenience.
Deposition. That volume was published in November Thisvolumeisdividedinto26chapters.Afterathree-part
1998. Therefore, the present volume includes only a brief introductory chapter by Paunovic, Schlesinger, and Weil
summary offundamental technological advancements, and come 13 chapters dealing with the electrodeposition of
thisis presented inthe first,introductory chapter. copper (Dini), nickel (DiBari), gold (Kohl), silver
SincethelasteditionofModernElectroplatingin1975, (Schlesinger), tin (Abys et al.). chromium (Snyder et al.),
electrochemical deposition has evolved from an ill-defined lead and alloys (Jordan), tin-lead alloys (Jordan), zinc and
area, as the Preface to the previous edition calls it, into an alloys(Winand),ironandalloys(Izaki),palladiumandalloys
exactscience.Thisdevelopmentis,inthefirstplace,seenas (Abys et al.), nickel and cobalt alloys (DiBari), and semi-
responsible for the ever-increasing number and widening conductors(T.E.Schlesinger).Closingthisseriesofchapters
typesofapplicationsofthisbranchofpracticalscienceand is one on deposition on nonconductors (Schlesinger), and
engineering. conductive polymers (Osaka et al.). Next come 6 chapters
Themostsignificantdevelopmentsinanyfieldofscience dealing with electroless deposition of copper (Paunovic),
ortechnologyingeneral,andinelectrochemistryinpartic- nickel(Schlesinger),cobalt(Osaka),palladiumandplatinum
ular,aremadebythosewhopossessagoodunderstandingof (Ohno), gold (Okinaka), and electroless alloys (Ohno).
thefundamentalaspectsofthediscipline,whichinthiscaseis Finally, 4 chapters close the book, and these are on prepa-
electrochemicaldeposition.We,theeditors,founditneces- ration for deposition (Dexter Snyder), manufacturing
saryandhighlydesirabletoseekandpresenttothereadera technologies (Turner), manufacturing control (Turner), and
companionvolumethat,forallintentsandpurposes,makes environmental considerations (Tomkiewicz).
essentially a completely new contribution and not just a In the preface to Fundamentals of Electrochemical De-
revisedversionoftheearliereditions.Thus,forthesakeof position we stated that it may be considered a lucky coin-
illustration,thepresenteditionincludesachapterdevotedto cidence that thisvolumeis published close tothe time that
theelectrodepositionofsemiconductors.Anotherdealswith copper interconnection technology is introduced in the mi-
environmentalissues.Last,butnotleast,inthisconnection, croelectronicindustry.Thisisstillthecase.Therehasbeena
neitheroftheeditorsnorthevastmajorityofthecontributors trulyrevolutionarychangefromphysicaltoelectrochemical
wereassociated with anyof the earlier editions. techniquesintheproductionofmicroconductorsonsilicon,
Technologicalareasinwhichthepossessionoftechnical anddevelopmentsinelectrochemicaldepositionareboundto
knowledgeofelectroplatingisfoundtobeessentialinclude generateandmaintaininthetwenty-firstcenturyanincreased
all aspects of electronics; macro-, micro-, and nano-optics; interestandurgentneedforup-to-dateinformationregarding
ix
x PREFACETOTHEFOURTHEDITION
thetechnology.Thepresent volumetogetherwith theFun- Ourthanksandheartfeltgratitudegotomanymembersof
damentalsvolumeshouldbeofgreathelpinunderstanding theElectrochemicalSocietyandinparticulartothoseofthe
these advancements. Electrodeposition Division. Our thanks also go to our re-
The chapters were written by different authors and so spectivefamiliesfortheirpatienceandunderstandingduring
differences in style and approach will be evident. We the the hectic long hours we spent in preparing this volume.
editorshavetriedtosmooththosedifferenceswithoutchang-
ingthebasicmessagepresentineachchapter.Wealsointend MOROECHAYSCHLESINOER
this volume to be a useful reference for practitioners of
depositionaswellasforindividualswhoareabouttoenter WindsorOntario.Canada
thismodernever-evolvingfieldofpracticalknowledge.For
MILANPAUNOVIC
this reason each chapter is complete and may be read and
consulted separately, and certainly the book can be read in
YorktownHeights.NewYork
anyorder.
CONTRIBUTORS
Joseph A. Abys Cookson Electronics–Enthone Inc., Xianying Meng-Burany UniversityofWindsor,Windsor,
Orange, CT ON, Canada
StankoR.Brankovic CullenCollegeofEngineering,Uni- Tetsuya Osaka Waseda University, Tokyo,Japan
versityofHouston, Houston, TX
Izumi Ohno Tokyo Institute of Technology, Tokyo, Japan
Jack W. Dini Lawrence Livermore National Laboratory, (Retired)
Livermore,CA (Retired)
Yutaka Okinaka Waseda University, Tokyo,Japan
George A. DiBari INCO,SaddleBrook,NJ (Retired)
Milan Paunovic IBM T J Watson Research Center, York-
Norma R. de Tacconi University of Texas at Arlington, town Heights, NY
Arlington, TX
Robert Petro University of Windsor, Windsor, ON,
Nikolay Dimitrov Department of Chemistry, Binghamton Canada
University–SUNY, Binghamton, NY
Krishnan Rajeshwar University of Texas at Arlington,
Takuma Hachisu Waseda University, Tokyo,Japan Arlington,TX
Masanobu Izaki Toyohashi University of Technology, Tom Ritzdorf Semitool, Inc., Kalispell, MT
Toyohashi,Japan
Mordechay Schlesinger University of Windsor, Windsor,
Manfred Jordan Dr. Ing. Max Schlotter, Geislingen/ ON, Canada
Steige,Germany
DexterD.Snyder GMResearchandDevelopmentCenter,
Paul A. Kohl School of Chemical Engineering, Georgia Warren, MI (Retired)
Institute ofTechnology, Atlanta, GA
Donald L. Snyder ATOTech, Cleveland, OH
SinichiKomaba DepartmentofAppliedChemistry,Tokyo
T.E. Schlesinger CarnegieMellon University,Pittsburgh,
University of Science, Shinjuku-ku, Tokyo,Japan
PA
Masaru Kato Kanto Chemical Co., Soka Saitama-ken,
Atsushi Sugiyama Waseda University,Tokyo,Japan
Japan
Guang-LingSong GMResearchandDevelopmentCenter,
Nenend V.Mandich (Deceased)
Warren, MI
Toshiyuki Momma Waseda University,Tokyo,Japan
xi
xii CONTRIBUTORS
Micha Tomkiewicz Department of Physics, Brooklyn Masahiro Yoshino Waseda University, Tokyo,Japan
College–CUNY, Brooklyn,NY
Yun Zhang Cookson Electronics–Enthone Inc., Orange,
Natasa Vasiljevic Physics Department, University of CT
Bristol, Bristol, UK
Giovanni Zangari UniversityofVirginia,Charlottesville,
Rene´ Winand UniversityofBruxelles,Bruxelle,Belgium VA
(Retired)