HANDBOOK OF DEPOSITION TECHNOLOGIES FOR FILMS AND COATINGS Science, Technology and Applications Second Edition Edited by Rointan F Bunshah University of California at Los Angeles Los Angeles, California np NOYES PUBLICATIONS Park Ridge, New Jersey, U.S.A Copyright © 1994 by Noyes Publications No part of this book may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording or by any information storage and retrieval system, without permission in writing from the Publisher Library of Congress Catalog Card Number: 93-30751 ISBN: 0-8155-1337-2 Printed in the United States Published in the United States of America by Noyes Publications Mill Road, Park Ridge, New Jersey 07656 10 9 8 7 6 5 4 3 2 1 Library of Congress Cataloging-in-Publication Data Handbook of deposition technologies for films and coatings / edited by Rointan F Bunshah 2nd ed p cm Rev ed of: Deposition technologies for films and coatings c1982 Includes bibliographical references and index ISBN 0-8155-1337-2 1 Coating processes I Bunshah, R F (Rointan Framroze) II Title: Deposition technologies for films and coatings TP156.C57H38 1994 667' 9 dc20 9 3 -30751 CIP DEDICATION This volume is dedicated to Professor John Thornton for his many pioneering contributions to thin film science and technology which have inspired so many of the scientists and engineers working in this field vii MATERIALS SCIENCE AND PROCESS TECHNOLOGY SERIES Editors Rointan F Bunshah, University of California, Los Angeles (Series Editor) Gary E McGuire, Microelectronics Center of North Carolina (Series Editor) Stephen M Rossnagel, IBM Thomas J Watson Research Center (Consulting Editor) Electronic Materials and Process Technology HANDBOOK OF DEPOSITION TECHNOLOGIES FOR FILMS AND COATINGS, Second Edition: edited by Rointan F Bunshah CHEMICAL VAPOR DEPOSITION FOR MICROELECTRONICS: by Arthur Sherman SEMICONDUCTOR MATERIALS AND PROCESS TECHNOLOGY HANDBOOK: edited by Gary E McGuire HYBRID MICROCIRCUIT TECHNOLOGY HANDBOOK: by James J Licari and Leonard R Enlow HANDBOOK OF THIN FILM DEPOSITION PROCESSES AND TECHNIQUES: edited by Klaus K Schuegraf IONIZED-CLUSTER BEAM DEPOSITION AND EPITAXY: by Toshinori Takagi DIFFUSION PHENOMENA IN THIN FILMS AND MICROELECTRONIC MATERIALS: edited by Devendra Gupta and Paul S Ho HANDBOOK OF CONTAMINATION CONTROL IN MICROELECTRONICS: edited by Donald L Tolliver HANDBOOK OF ION BEAM PROCESSING TECHNOLOGY: edited by Jerome J Cuomo, Stephen M Rossnagel, and Harold R Kaufman CHARACTERIZATION OF SEMICONDUCTOR MATERIALS, Volume 1: edited by Gary E McGuire HANDBOOK OF PLASMA PROCESSING TECHNOLOGY: edited by Stephen M Rossnagel, Jerome J Cuomo, and William D Westwood HANDBOOK OF SEMICONDUCTOR SILICON TECHNOLOGY: edited by William C O’Mara, Robert B Herring, and Lee P Hunt HANDBOOK OF POLYMER COATINGS FOR ELECTRONICS, 2nd Edition: by James Licari and Laura A Hughes HANDBOOK OF SPUTTER DEPOSITION TECHNOLOGY: by Kiyotaka Wasa and Shigeru Hayakawa HANDBOOK OF VLSI MICROLITHOGRAPHY: edited by William B Glendinning and John N Helbert CHEMISTRY OF SUPERCONDUCTOR MATERIALS: edited by Terrell A Vanderah CHEMICAL VAPOR DEPOSITION OF TUNGSTEN AND TUNGSTEN SILICIDES: by John E J Schmitz ELECTROCHEMISTRY OF SEMICONDUCTORS AND ELECTRONICS: edited by John McHardy and Frank Ludwig v vi Contents Series HANDBOOK OF CHEMICAL VAPOR DEPOSITION: by Hugh O Pierson DIAMOND FILMS AND COATINGS: edited by Robert F Davis ELECTRODEPOSITION: by Jack W Dini HANDBOOK OF SEMICONDUCTOR WAFER CLEANING TECHNOLOGY: edited by Werner Kern CONTACTS TO SEMICONDUCTORS: edited by Leonard J Brillson HANDBOOK OF MULTILEVEL METALLIZATION FOR INTEGRATED CIRCUITS: edited by Syd R Wilson, Clarence J Tracy, and John L Freeman, Jr HANDBOOK OF CARBON, GRAPHITE, DIAMONDS AND FULLERENES: by Hugh O Pierson Ceramic and Other Materials—Processing and Technology SOL-GEL TECHNOLOGY FOR THIN FILMS, FIBERS, PREFORMS, ELECTRONICS AND SPECIALTY SHAPES: edited by Lisa C Klein FIBER REINFORCED CERAMIC COMPOSITES: edited by K S Mazdiyasni ADVANCED CERAMIC PROCESSING AND TECHNOLOGY, Volume 1: edited by Jon G P Binner FRICTION AND WEAR TRANSITIONS OF MATERIALS: by Peter J Blau SHOCK WAVES FOR INDUSTRIAL APPLICATIONS: edited by Lawrence E Murr SPECIAL MELTING AND PROCESSING TECHNOLOGIES: edited by G K Bhat CORROSION OF GLASS, CERAMICS AND CERAMIC SUPERCONDUCTORS: edited by David E Clark and Bruce K Zoitos HANDBOOK OF INDUSTRIAL REFRACTORIES TECHNOLOGY: by Stephen C Carniglia and Gordon L Barna CERAMIC FILMS AND COATINGS: edited by John B Wachtman and Richard A Haber Related Titles ADHESIVES TECHNOLOGY HANDBOOK: by Arthur H Landrock HANDBOOK OF THERMOSET PLASTICS: edited by Sidney H Goodman SURFACE PREPARATION TECHNIQUES FOR ADHESIVE BONDING: by Raymond F Wegman FORMULATING PLASTICS AND ELASTOMERS BY COMPUTER: by Ralph D Hermansen HANDBOOK OF ADHESIVE BONDED STRUCTURAL REPAIR: by Raymond F Wegman and Thomas R Tullos CARBON–CARBON MATERIALS AND COMPOSITES: edited by John D Buckley and Dan D Edie CODE COMPLIANCE FOR ADVANCED TECHNOLOGY FACILITIES: by William R Acorn Contributors Rointan F Bunshah Department of Materials Science and Engineering University of California at Los Angeles Los Angeles, California Jan-Otto Carlsson Department of Chemistry Upsala University Upsala, Sweden Joseph E Greene Coordinated Science Laboratory University of Illinois at UrbanaChampaign Urbana, Illinois Bret L Halpern Jet Process Corporation New Haven, Connecticut Donald M Mattox Society of Vacuum Coaters Albuquerque, New Mexico Gary E McGuire Microelectronics Center of North Carolina Research Triangle Park, North Carolina Jerome C Schmitt Jet Process Corporation New Haven, Connecticut Morton Schwartz Electrochemical/Metal Finishing Consultant Los Angeles, California Arthur Sherman Consultant Palo Alto, California xiii xiv Contents Contributors John A Thornton* Coordinated Science Laboratory University of Illinois at UrbanaChampaign Urbana, Illinois * Robert C Tucker, Jr Praxair Surface Technologies, Inc Indianapolis, Indiana Professor Thornton died unexpectedly in November, 1987 NOTICE To the best of our knowledge the information in this publication is accurate; however the Publisher does not assume any responsibility or liability for the accuracy or completeness of, or consequences arising from, such information This book is intended for informational purposes only Mention of trade names or commercial products does not constitute endorsement or recommendation for use by the Publisher Final determination of the suitability of any information or product for use contemplated by any user, and the manner of that use, is the sole responsibility of the user We recommend that anyone intending to rely on any recommendation of materials or procedures mentioned in this publication should satisfy himself as to such suitability, and that he can meet all applicable safety and health standards Preface to the Second Edition A decade after the first edition of this volume was published, a second edition is being brought out partly due to the excellent response to the first edition and also to update the many improvements in deposition technologies, the mechanisms and applications The entire volume has been extensively revised and contains 50% or more new material Five entirely new chapters have been added The organization of the book has also been changed in the following respects: 1 Considerably more material has been added in Plasma Assisted Vapor Deposition Processes 2 A new chapter on Metallurgical Coating Applications has been added The chapter in the first edition on Polymeric Coating techniques has been omitted as it deserves a volume by itself Large topics such as coatings technology in microelectronics, diamond films, etc., have been treated in separate volumes in this series Although there are some new competing volumes dealing with selected topics on the materials science of thin films, this volume remains the only comprehensive treatment of the entire subject of Deposition Technology Applications of films and coatings spans the entire gamut of science and technology Generic application areas include electronic, magnetic, optical, mechanical, chemical and decorative applications New deposition technologies such as arc evaporation, unbalanced magnetron sputtering, ion beam assisted deposition, and metal-organic CVD have come on stream for critical applications In this post cold war era, many economic solutions to engineering problems will necessarily involve coatings, e.g., battery materials for the emerging electric car industry ix x Preface Contents The core subjects are the basic technologies for the deposition of films and coatings These are the Physical Vapor Deposition (PVD) Processes consisting of Evaporation, Sputtering, and Ion Plating; Chemical Vapor Deposition (CVD) and Plasma-Assisted Chemical Vapor Deposition (PACVD); Electrodeposition and Electroless Plating; Thermal Spraying, Plasma Spraying and Detonation Gun Technologies Chapters on other subjects common to the above technologies are included These are: Adhesion of Coatings, Cleaning of Substrates, Role of Plasmas in Deposition Processes, Structure of PVD Deposits, Growth and Structure of PVD Films, Mechanical and Tribological Properties of PVD Deposits, Elemental and Structural Characterization Techniques, and Metallurgical Coatings A relatively new development, Jet Vapor Deposition Process, was added as the last chapter in the book during the page proof stage because of its novelty We hope that this volume will be useful to the multitude of disciplines represented by the workers in this field and provide a source for future developments University of California Los Angeles, California June, 1993 Rointan F Bunshah Preface to the First Edition Almost universally in high technology applications, a composite material is used where the properties of the surface are intentionally different from those of the core Thus, materials with surface coatings are used in the entire crosssection of applications ranging from microelectronics, display devices, chemical corrosion, tribology including cutting tools, high temperature oxidation/ corrosion, solar cells, thermal insulation and decorative coatings (including toys, automobile components, watch cases, etc.) A large variety of materials is used to produce these coatings They are metals, alloys, refractory compounds (e.g., oxides, nitrides, carbides), intermetallic compounds (e.g., GaAg) and polymers in single or multiple layers The thickness of the coatings ranges from a few atom layers to millions of atom layers The microstructure and hence the properties of the coatings can be varied widely and at will, thus permitting one to design new material systems with unique properties (A material system is defined as the combination of the substrate and coating.) Historically, coating technology evolved and developed in the last 30 years in several industries, i.e., decorative coatings, microelectronics and metallurgical coatings They used similar techniques but only with the passage of time have the various approaches reached a common frontier resulting in much useful cross-fertilization That very vital process is proceeding ever more strongly at this time With this background in mind, a short course on Deposition Technologies and their applications was developed and given on five consecutive occasions in the last three years This volume is based on the material used in the course xi 874 Deposition Technologies for Films and Coatings of formation 215 volume 711 Free jet 853 Free-exciton (FE) recombination 842 Frequency effects on RF plasma 466 Fresnel reflection coefficient 834 Fretting corrosion 767 wear 781 Friction 783 and wear 781 and wear coatings 42 coefficient of 784 FTIR measuring epitaxial layer 839 Full-density coatings 158 Functional characterization 672 coatings 41 G Ga Auger transition 795 GaAs anodic oxidation of 810 growth 723 sputtering of 298 Galvanic cell 768 corrosion 661, 770 Gas charging 143 control equipment 630 dispensing system 411 in a deposited film 380 pumping 380 states 418 Gas flow calculations 420 dynamics 417 patterns 420 proportional counter 827 rate controls stoichiometry 494 Gas jet deposition 37 Gasdynamic deposition source 849 Gaseous anodization 49 Gate 859 Geometrical thickness measurement of 689 GexSi1-x alloys on Si(100) 728 Glow discharge 52, 461, 849 cleaning 100 DC 301 evaporation 52 low-pressure 301 plasma 55, 59, 70, 76 polymerization 77 sputter jet 855 sputtering 327 Gold 850, 854 Graded interface 237 Grain boundaries 721 boundary 39 growth mechanism 736 size 719 size can vary 577 Grain boundaries weak 240 Grashof number 418 Grit blasting 632 Growth adsorption-induced 452 area-selective 446 kinetics 707 mixed-mode 728 modes 708 rate 848 single phase vapor 442 substrate-activated 449 three-dimensional 708, 710 two-dimensional 708, 721 Growth mechanism of PVD films 224 Gyro radius 67 H Hall-Petch relationship 249, 253, 576 Halogen solvents 124 Handling of prepared surfaces 147 Index Hard coating tool wear-life improvement by 786 Hardness 591 of higher velocity coatings 648 of metal and alloy deposits 244 values for various deposits 539 varies with deposition temperature 255 Hardness testing 695 Haring-Blum %TP 518 Harmonic electrical spraying 52 Heat treatment of Ni3P or Ni3B 554 Heating sources 370 the substrate 415 Hertz-Knudsen equation 167 Heteroepitaxial films are often pseudomorphic 725 High temperature protective metallic coatings 779 High temperature corrosion 42 History of evaporated thin films 158 Hollow-cathode ion sources 327 Homogeneous nucleation 409 Homogeneous reaction control 429 Host-guest 848, 860 Hot hollow cathode discharge beam 187 electron beam gun 188 Hot wall reactor 413 Hot-cathode triode sputtering systems 305 Hot-wall PECVD reactors 468 Humidity in clean room 116 Hybrid processes 501 Hydriding 409 Hydrogen charge 368 overvoltage 517 reduction cleaning 130 Hydrophilic wetting method 51 Hydrosonic agitation 529 cleaning 128 875 I Impact erosion 782 Impact mobility 749 Impurities in deposits 256 in plating solutions 529 In 747 Induction heated sources 180 Inelastic collisions 60 Inelastic mean free path 791, 799 Inert coatings 770 Inert gas entrapped 291 shroud 623 Inhibitive coatings 770 Injection rate reactive-gas 330 Integrated electronics 849 Interface characterization of 679 during CVD is unstable 443 formation 350, 678 trap density 859 types 678 Interfacial regions classified 374 Intergranular corrosion 767 Intermetallic compounds 409 deposition of 205 Interphase 678 Ion bombardment 93 bombardment during deposition 750 carburizing 49 current 324 current monitor 194 hollow-cathode source 327 implantation 53 implantation accelerators 348 irradiation 97, 333, 743 irradiation effects 744, 759 mixing 683 mobility 72 nitriding 49 replenishment 522 876 Deposition Technologies for Films and Coatings scrubbing 134, 354 source 350 Ion beam assisted deposition 53 Ion beam deposition 52 Ion implantation 53 Ion plating 53, 77 advantages and disadvantages 389 applications 389 barrel-plating 388 chemical ion plating 348 control of 385 control parameters 354 DC plasma conditions 354 defined 346 discharge 77 history 346, 348 IAD 348 IBED 348 IVD 388 monitoring of 385 problem areas 386 process 162 process parameters 358 process specifications 385 pulsed 383, 387 reactive 348, 373 rules 349 sputter 348 stages 349 vacuum 348 Ion-assisted chemical etching 367 Ion-assisted molecular-beam epitaxy 743 Ion-beam sputtering 327 Ion/surface interactions 708 low-energy 743 Ionic migration 522 Ionization 56, 69 balances 77 potential 56 rate of 80 Ionization gauge rate monitor 194 Ionized gas 55 IR absorption bands of O and C 839 Iron alloy films corrosion resistance 775 Irradiation during film growth 743 Irradiation-induced effects 755 Island coalescence 714 Island growth 224, 716 Islands In 730 secondary 714 J Jet boundary 854 conditions 860 independence 855 sonic 848 source 849 Jet in low vacuum 849, 853, 856, 861 Jet Vapor Deposition (JVD) 848 JVD 848, 853, 856, 859, 861 JVD sources 849 microwave 859 sputtering 856 K Kinetic energy (KE) emitted photoelectrons Krytonation 368 797 L LaB6 791 Lamellae thickness of 253 Lamellar microstructure 663 Laminate composites 253 structure 253 Larmor radius 67 Laser ablation 192 Laser induced evaporation 192 Lattice atom displacement 363 constant 725 defects 368 strain 378, 680, 694 Index Laves phase 641 Li-doped Si detector 825, 826 Life-tests accelerated 674 operational 674 Limit 708 Low-contaminant materials 116 Low-energy ion irradiation 707 Low-pressure plasma deposition (LPPD) process 218 Low-temperature deposition 732, 860 Lubricant coatings 42 Lubrication coatings 785 M Mach disc 853 Macroparticle removal of 191 Magnesium alloys anodizing of 568 Magnetic contrast type I, II 828 Magnetic fields and plasma particles 67 Magnetic moment 828 Magnetic sector spectrometer 804, 833 Magnetron discharge sources 84 enhanced plasma 140 Magnetron discharge 84 Magnetrons 279, 281, 306, 326 advantages and disadvantages 358 cylindrical 311 discharge 357 double-ended RF 326 geometries 497 sputtering of a source 387 unbalanced 333 Manufacturing advantages of JVD 856 Masking techniques 633 877 Mass spectrometer quadrupole 804 Mass spectrometers magnetic sector 804 Mass transfer coefficient 524 Mass transport across a boundary layer 428 control 429 of ions 522 Material cost 856 Materials multicomponent 292 Materials conservation 43 Maxwellian velocity distribution 62 MCrAlY 663 coating process steps 780 Mean free path defined 56 of electrons 303, 791 Mean residence time 714 Measurement in situ 673 of adhesion 671, 682 of density 697 of electrical resistivity 671 of electromigration 697 of films and coatings 671 of resistivity 696 of stability 672 pressure 171 thickness of films and coatings 671 Mechanical properties 647 See also Test techniques of laminates 254 of thick condensates 244 of thin films 241 Mechanical scrubbing 125 Mechanically functional applications 41 Metal ions deposition of 522 Metal-nitride-semiconductor (MNS) capacitor 859 Metallic contaminates 117 impurities 530 878 Deposition Technologies for Films and Coatings Metallic coatings deposition of 772 Metalliding 50 Metallographic apparent porosity 647 Metallurgical properties 39 Metastable species 90 Metastable phases 491 Metastable species 90, 499 Metering of liquids 413 Methyl Red 860 Microbalances 196 Microhardness measurement 592, 695 Microlaminate composites thermal conductivity of 781 Microlaminates 858 Micromixing 856 Microstructural development mechanisms 741 difference between coatings 637 evolution 707, 708, 732 Microstructure 38 evolution 224, 730 evolution of 730 of films 375 of PVD condensates 224 of thick single phase films 226 Microstructures columnar 732, 733 Microthrowing power 523 Microwave discharge 77, 356, 849 plasma generation 139 Migration charge-induced 810 Mobilities low-adatom 733 Mobility 64 of ions 65, 302 Model capillarity 711 droplet 711 TLK 438 Models, nonlinear of the reactive sputtering 332 Modified surface definition of 669 Modulus of rupture 650 Molecular beam epitaxy 52 Molecular beam epitaxy (MBE) 722 Molecular bombarding species 286 Molecular dynamic simulations 754 Molecular flow of species 488 Molecular-dynamic simulations 733 Momentum exchange 65, 289, 291 collisions 64 cross section 58 Momentum transfer 353, 363 Monitoring of deposited mass 196 Monitoring of specific film properties 196 Monitors optical 196 resistance 196 Monochromator with x-ray source 798 Monolayer per pass 856 Monte Carlo simulations 733, 736, 754 Morphology large-grained columnar 228 of films 375 of thick single phase films 226 structural 227 Motion of charged particle 66 Movchan-Demchishin model 230 Multifilament tows 859 Multiple internal reflections 839 Multiple jet, moving substrate 852, 856, 861 Multiple sources 201 N Nano-particles 37 Negative glow 301 Negative glow region 82 Negative ion emission 297 Negative ions 89 Nernst equation 513 Index Ni and Cr depth profile of 794 Ni on Si interactions 817 Ni-Cr-Fe electrophoretic deposition of 548 Nickel composite electroless 557 containing P or B 551 deposition of 230 electrodeposits 577 Nitridation of UHV cleaned surfaces 151 Nitriding 49, 403 NixPy compounds 551 Noble metals 860 Non-destructive evaluation (NDE) 675 Novel coatings 848 Nozzle pressure 849 Nuclear fuels 44 Nuclear reaction analysis (NRA) 819 Nucleation 438, 707, 710 3-D 710 activation barrier 711 control 429 density 374, 677 heterogeneous 452, 711 kinetics 743 kinetics model 713 secondary 716 two-dimensional 722, 724, 725 Nucleation sites preferential 744 Nuclei size 716 Number density of Au nuclei on NaCl 715 of ion-irradiation-induced 744 surface site 710 O Optical emission 304 Optical monitors 196 Optically functional applications 41 Optics nonlinear 849 Orbiting frequency 66 Organic impurities 530 Orientation crystallographic 380 Oscillations plasma 75 Outgassing after fluid cleaning 132 Overlay coating definition of 669 Overlay coatings 31 Overvoltage 515 Oxidation cleaning 128 high temperature 776 Oxidation states ability to distinguish 800 Oxide films 410 Oxygen plasma cleaning 144 P PACVD 495 Palladium adhesion dependent on 571 Partial pressure affects growth of films 494 Particle impingement rate monitor 194 Particles lenticular 617, 621 Particulate contamination 114 deposition processes 36 origin of 111 removal 120 Parting corrosion 767 Parylene 861 Paschen curves 80 relation 77, 83 Passivation 859 of clean surfaces 151 PAVD film growth by 493 879 880 Deposition Technologies for Films and Coatings PECVD 461 conditions for silicon nitride 473 dual frequency reactor 475 films 481 Peel test 688 Penning discharge 75 ionization 91 Penning ionization 141, 359 Periodic reverse 532 Phase diagrams 407 Phosphorus content of deposits 553 Photoelectron (PE) transitions 799 Photoelectron spectroscopy 797 Photoluminescence (PL) spectroscopy 841 Physical sputtering of a surface 143 Physical vapor deposition processes 160 See also Deposition techniques Pickling 121, 536 Pierce gun 185 Piezoceramic wafers 858 Pitting corrosion 767 PL practical range of 843 primary application of 842 Planar diodes 83, 301 Planar magnetron 279, 316 Plasma 55 activation 360 chemistry 140, 359 cleaning 134 defined 186, 351 density 335 diagnostic techniques 492 discharge operating conditions 81 enhancement 358 etching 77, 145 frequency 69 gas velocities 618 generation of 135, 351 glow discharge 55, 76 methods of creating 467 microwave 356 monitoring of 385 near the substrate surface 384 oscillations 75 oxidation 49 parameters 493, 494 polymerization 53, 93 processing 351 properties of 351, 360 RF 355 sheath 69, 70 spraying 36 temperature 618, 622 torch 618, 621 uniformity 384 variables 488 volume chemistry 492, 499 Plasma electron beam gun 186 Plasma excitation geometries 221 Plasma excitation modes 221 Plasma rings 312, 315 Plasma-Assisted CVD 50 Plasma-assisted CVD 743 conditions 92 Plasma-assisted deposition limitations of 499 Plasma-assisted etching 93 Plasma-enhanced CVD 461 Plating cell 508 laser-enhanced 535 on plastics 570 operations 536 variables 528 Platinum coatings 776 PLD See Deposition techniques Point of entry of powder 620 Poisoning of sputter cathode 330 Polarization 515 effects 520 Polycrystalline silicides 830 Pores 409 Porosimetry 699 Porosity 698 Index decreased by ion irradiation 753 in coatings 647 tests 700 Position equivalency 674 Positive column region 83 Post-deposition processing 680 Post-plating treatments 538 Potential floating 70 negative 276 Powder dispensers 630 size distribution 622 temperature 620 used for plasma 632 velocity 620 Prandtl number 418 Precursor species 492 Precursors chemical vapor 373 toxic 849 Predominance diagrams 407 Preferential sputtering 366 Preferred orientation 746, 750, 756 Presheath 72 Primary electrons 302 Primary ions for SIMS 806 Primary-ion deposition (PID) 743 Printed circuit board plating of 571 Printing process 51 Process control 194 Process parameters control of 494 Processes for MCrAlY coatings 780 wet-chemical See Wet-chemical Production capability 159 Professional organizations 676 Properties of deposited coating 38 Property measurements of films and coatings 682 Pseudomorphism 728 Pulse plating 532 881 Pulse-counting 826 Pulsed laser deposition (PLD) 192 Pulsed plating effects of 534 Pump chemical 416 water-ring 416 Pumping systems 171 Purification of metals by evaporation 256 PVD See Deposition techniques microstructure of condensates 224 process terminology 32 processes 160 vs CVD 165 PVD processes classification of 487 PVDF piezoelectric membrane 860 Pycnometry 698 Pyroelectric infrared detectors 858 Pyrolysis 50 PZT 856, 858, 859 Q Quadrupole mass spectrometer R Radiation hardness 859 Random walk of a helium atom 854 Rare-gas crystals growth of 724 Rate control 199 of chemical reaction in a plasma 493 of dissociation 495 Rate monitors crystal oscillator 196 ion current 194 ionization gauge 194 microbalances 196 of deposited mass 196 particle impingement 194 spectroscopic 195 804 882 Deposition Technologies for Films and Coatings Rate-controlling steps 216 Rate-determining reactions in CVD 436 Rate-limiting in CVD 428 Ratio of ring diameters 831 Rayleigh number 418 RBS sensitivity limit of 818 spectrum 816 used to normalize SIMS 810 Reaction CVD 403 kinetics 215 mechanisms in CVD 436 rate 63 resistance 431 Reactive evaporation 52 gas 330 ion etching 98, 145 ion plating 53 plasma cleaning 144 plasma etching 367 sputtering 328 Reactive evaporation model 215 process 213 Reactive ion plating (RIP) processes 218 Reactor cold wall 414 CVD 413 geometry 420 hot wall 413 Recoil implantation 348, 369, 754 Recombination of electron-hole pairs 841 Recombination rate constant 855 Recontamination 111 Recrystallization 716, 721, 741 during coalescence 716 Recycling of reactants 417 Redeposition of sputtered material 375 Reducing agent 550, 553 Reduction reactions 403 Reflected power 324 Reflection coefficients 835 of ions 290 Reflection high-energy electron diffraction (RHEED 722 Refraction indices of 834 Refractive index 837 Refractory compounds 209, 254 deposition of 209 mechanical properties of 254 Refractory materials evaporation of 370 Refractory metals area-selective deposition 449 Relative characterization 672 Research needed 40 Residual stress 237, 645 in deposits 237 Residue contamination 117 Resistance heated sources 175 Resistance monitors 196 Resistivity of films and coatings 696 Resonance ionization spectroscopy (RIS) 812 Resputtering rate 375, 377 Reynold’s number 418 RF planar-diode 319 plasma reactor 466 power supplies 355 sputtering 279, 318 RF activation 220 RF discharge 76, 85, 322, 355 advantages and disadvantages 356 capacitively coupled 355 plasma generation 138 RHEED 722 RHEED oscillations 723, 724 Rhodamine 860 Room temperature deposition 634 Index Roughness can not be determined 838 of coatings 636 of surface 633 Rutherford backscattering spectroscopy (RBS) 812 S S-gun magnetron 306 Sacrificial layer 151 Safety 152 Salt concentration cell 769 Saturated hydrogen electrode 513 Saturation flux density 593 Scanning electron microscopy 822 Scattering energy 812 Scratch test 688 Scrubbers exhaust 417 Scrubbing 125 Secondary electron emission coefficient 82, 352 Secondary electrons 302, 308 energy distribution of 822 Secondary ion mass spectroscopy (SIMS) 803 Secondary ions generation of 806 Secondary nucleation 714, 716 rate 747 Selected area diffraction (SAD) 830 Selective deposition by CVD 445 Self-accelerated gun 182 See Electron beam gun Self-bias negative 462 Self-limiting growth 450 Self-mating characteristics 658 Self-shadowing 733 Self-sputtering 366 Self-supported shapes 158 Self-welding 659 SEM resolution of 822 Semiconductor microelectronic processing 861 883 Semiconductors 201 Sensitization of a surface 149 Shear strength 643 test 688 Sheath 74 capacitance 324 includes dark spaces 461 plasma 70 potential 137, 467 thickness 72 Sheath potential 354 Sheet resistance 696 Shroud inert gas 623 Si 728, 730 thermally induced defects in 844 Silicon dioxide by PECVD 478 Silicon nitride by PECVD 472 etch rate 859 films 859 interface trap density 859 radiation hardness 859 SIMS detection limit of 810 RBS is used to calibrate 810 spectrum 806 voltage range 806 SiN 859 Single rod-fed electron beam source 202 Smut 122 Snell’s Law 834 Snow scrubs 120 Sodium contamination 117 Solid state reactions during CVD 401 Solution wear 783 Solvent cleaning 123 systems 125 Sonic gas flow 855 Sonic jet in a low-vacuum fast flow 848 884 Deposition Technologies for Films and Coatings Sources See Vapor sources for electron beam evaporation 383 hollow-cathode 327 ion 327 of depositing species 369 of energetic particles 350 of ions 350 reaction with evaporants 178 Space charge sheaths 70 Spark-hardening 50 Specifications and standards professional organizations 676 Spectroscopic ellipsometry 837 Spectroscopic methods 195 Spectroscopy 797 Splat 637 Spray cleaning 126 Spraying processes 51 Sputter cleaning 143, 349 Sputter deposition 52, 275, 722 applications of 279 flux profiles 316 forward 361 history of 283 magnetron 333 of multicomponent materials 292 parameters 496 process variants 497 universality of 276, 279 Sputter deposition modes reactive sputtering 328 Sputter deposition technology variations 276 Sputter-assisted laser ionization (SALI) 811 Sputter-deposited films composition of 292 Sputtered as dimers 297 clusters 297 molecules 297 species 296, 298, 299 Sputtering 52 bias 332 cost of 282 DC 279 defined 275 deposition rate 304 direct 486 efficiency 291 efficiency of 286 erosion rate 288 glow discharge 297, 327, 849 in N2 332 ion plating 371 ion-beam 327 mechanisms 284 mechanisms of 284 of alloys 294 of alloys and compounds 279, 293 of compound semiconductors 298 of molecular species 297 of PTFE (Teflon) 279 physical 353, 364 preferential 365 process 163 See also Deposition techniques rate 285, 289, 330 reactive 328, 486 RF 279 targets See Targets with reactive species 295 Sputtering systems balanced 324 bias sputtering 332 configurations 278 in-line 314 ion-beam 327 load-lock 281 magnetron 325 magnetrons 281, 306 magnetrons, cylindrical 311 multisource 280 operating conditions 311 parallel-plate diode 278 planar diode 281, 301, 303, 305 planar-diode 278 RF 318, 324 RF planar-diode 319 selection of 282 single-ended 324 targets 282 Index triode 279 triode discharge 305 with magnetrons 279 Sputtering yield 285, 286, 287, 365 defined 286, 364 dependence on angle of incidence 287 dependence on ion species 295 expression for 289 influenced by surface topography 296 SIMS 806 Stabilizers added to chlorinated solvents 124 Stabilizing for electrodeposition 537 Stainless steel corrosion resistance 775 STEM 828 Sticking coefficient 257, 329 Sticking probability 329 Storage of prepared surfaces 147 Strain-to-fracture 650 Stranski-Krastanov 728 growth mode 708 Stress 409, 592, 644, 733 calculation of 691 for chromium deposits 590 growth 680 in continuous films 721 in deposits 237 in electroless Ni-P alloys 553 in films and coatings 691 in growing film 361 in PECVD films 473 in the near-surface region 369 in-plane tensile 733 measurements 593 mechanical 683 residual growth 378 varies with phophorus 554 Stress wave adhesion tests 688 Stress-corrosion cracking 767 Strike 350 885 Strikes before plating 537 Strip processing line 170 Stripline 170 Structure zone model 39 Structure-zone diagram 736 Structure-zone diagrams 708 Sublimation 370 sources 176 Substrate bias influences structure 494 preparation 632 preparation defined 108 Substrate motion 851, 856 Superalloy 778, 780 Superconducting film growth 192 Supercritical nuclei 714 Supersaturation 444, 713, 725 degree of 719 in CVD 442 ratio 711 Surface coverage 380 diffusion 440 effects of bombardment 368 engineering 27 kinetics control 429, 432 modification 150 morphology 367, 442 preparation 677 preparation for ion plating 349 profilometer 690 protection 849 reaction control 433 Surface Acoustic Wave porosity measurement 700 Surface Charge Analysis See SCA Surface energy 715 Surface free energy 711 Surface mobility 229 Synthesis of compounds 224 of unusual, complex materials 849 SZD 738, 739, 741 886 Deposition Technologies for Films and Coatings T TaC-Fe-Ni electrophoretic deposition of 548 Target poisoning 496 Target voltage 489 Targets 295 composite sputtering 294 for sputtering 282 hot-pressed 295 non-conducting 321 polycrystalline or amorphous 300 poorly conducting 295 semiconducting 297 sputter 383 TEM scanning 828 Temperature control 629 detonation gun 626 during CVD 401 gas 70 profiles 427 Temperature Coefficient of Resistivity (TCR) 696 Tensile bond strength 643 strength 592 stress 691 test 688 Tensile properties of metals and alloy deposits 244 of thin film 242 TEOS films 479 Terrace lengths 723 Test techniques of mechanical properties 241 Texture of evaporated deposits 236 Thermal barriers 663 decomposition 403 evaporation 370 expansion coefficient 695 properties of coatings 663 Thermal stress adhesion test 689 Thermally sensitive membranes 860 Thermionic Gun 183 Thermodynamic calculations 405 control of CVD 429 wear 783 Thermoelectron emitter system 357 Thick films 31 Thick single phase films microstructure and morphology of 226 Thickness and uniformity 858 coating 617 control 199 measurement of 689, 698 Thin films 31 Three body collisions 855 Three-dimensional growth 708 Throwing power 32, 381, 489 of a solution 518 TiC deposition of 216, 222 microhardness of 255 Time of atomic rearrangements 754 TiN 757 by reactive magnetron sputter 741 Titanium anodizing of 568 deposition of 229 Tool wear-life improvement by hard coating 786 Topographical evolution 294 Tows 859 Toxic metal precursors 856 Transition mechanism 331 Transition zone temperatures 228 Zone T 226 Transmission electron microscopy (TEM) 828 Transport of species 488 Trapping 368 Tribology 781 Index Triode 279, 282 configuration 357 discharge devices 305 hot-cathode 305 sputtering systems 305 Triode configuration 220 Tungsten alloy electrodeposition 544 deposited by CVD 32, 450 Tungsten carbide-cobalt 659 Turnaround time 856 Two-dimensional growth 708 Ultimate electrons 310 Ultrasonic agitation 528 cleaning 127 Unbalanced magnetron 333 Uniform deposit thickness 168, 172, 851 plasma density 386 Uniformity 858 of plasma 384 Uniformly coated 857 induction heated 180 multiple 201 resistance-heated 175 rod-fed 202 sonic jet in low-vacuum fast flow 848 sublimation 177 wire-fed 202 Vaporization 849 Variables in plasma deposition processes 488 Velocity carrier 849 distribution 60, 62 drift 64 of powder 621 Video-RHEED 750 Void density 753 Volatilization of elemental metal 856 Volatilization cleaning 130 Volmer-Weber growth mode 708 Volume free energy 711 Volume reactions 92 V W Vacuum arc vaporization 371 chamber configurations 282 chamber pressure 276 deposition and electroplating 507 evaporation theory 166 system for ion plating 381 Vacuum chamber 169 Vacuum pump 416 Vacuum pumping system 171 Vapor contamination 116 degreasers 126 equilibrium pressure 710 species generation 488, 494 Vapor pressure equilibrium 166 Vapor sources 849 arc 189 electron beam heated 181 Wall jet 853, 854 Water ultrapure 118 Water break test 133 Wavelength dispersive x-ray (WDX) 826 Wear 781, 785 Wear resistance 648, 653 of electroless nickel 555 Wear-life improvement by hard coating Welding processes 51 Wetting angle 111, 133 Wetting processes 50 Wirefeed jet 854 sources 857 Witness plates 673 Woods nickel strike 538 U 887 786 888 Deposition Technologies for Films and Coatings Work function 797 Work-accelerated gun 182 See Electron beam gun X X-ray analysis in STEM 834 emission 825 source 797 X-ray fluorescence (XRF) 690 XPS 797 detection limit for 802 Y YBCO film deposition 193, 194 Yield secondary ion 806, 811 Z Zinc coatings 773 complexed with cyanide 514 Zirconia as a thermal barrier 780 Zn deposition conditions 774 Zone T 226 Zones defined 737 Zone T 739 ... Library of Congress Cataloging-in-Publication Data Handbook of deposition technologies for films and coatings / edited by Rointan F Bunshah 2nd ed p cm Rev ed of: Deposition technologies for films. .. and Lee P Hunt HANDBOOK OF POLYMER COATINGS FOR ELECTRONICS, 2nd Edition: by James Licari and Laura A Hughes HANDBOOK OF SPUTTER DEPOSITION TECHNOLOGY: by Kiyotaka Wasa and Shigeru Hayakawa HANDBOOK. .. MATERIALS AND PROCESS TECHNOLOGY HANDBOOK: edited by Gary E McGuire HYBRID MICROCIRCUIT TECHNOLOGY HANDBOOK: by James J Licari and Leonard R Enlow HANDBOOK OF THIN FILM DEPOSITION PROCESSES AND TECHNIQUES: