The Foundations of Vacuum Coating Technology

By Donald M. Mattox

The Foundations of Vacuum Coating Technology, Second Edition, is a revised and expanded version of the first edition, which was published in 2003. The book reviews the histories of the various vacuum coating technologies and expands on the history of the enabling technologies of vacuum technology, plasma technology, power supplies, and low-pressure plasma-enhanced chemical vapor deposition. The melding of these technologies has resulted in new processes and products that have greatly expanded the application of vacuum coatings for use in our everyday lives. The book is unique in that it makes extensive reference to the patent literature (mostly US) and how it relates to the history of vacuum coating. The book includes a Historical Timeline of Vacuum Coating Technology and a Historical Timeline of Vacuum/Plasma Technology, as well as a Glossary of Terms used in the vacuum coating and surface engineering industries.

• History and detailed descriptions of Vacuum Deposition Technologies
• Review of Enabling Technologies and their importance to current applications
• Extensively referenced text
• Patents are referenced as part of the history
• Historical Timelines for Vacuum Coating Technology and Vacuum/Plasma Technology
• Glossary of Terms for vacuum coating

• Language: English
• Publisher: Elsevier Science
• Release date: Aug 21, 2018
• ISBN: 9780128130858

Donald M. Mattox

Donald M. Mattox obtained his B.S degree in Physics from Eastern Kentucky State University. He served as a meteorologist and Air Weather Officer in the USAF during and after the Korean War. He then obtained a M.S. degree in Solid State Physics from the University of Kentucky in 1960. In 1961 he went to work at Sandia National Laboratories (SNL). Don was a manager and member of the Technical staff at SNL for 27 years and has been a consultant to the vacuum coating industry for over 28 years. In 1995 he was the recipient of the American Vacuum Society Albert Nerken Award "For his invention of the ion plating process and its continued development." In 2007 Don received the Society of Vacuum Coaters Nathaniel Sugerman Award “For his development of the ion plating process and long-term commitment to education in the vacuum coating community.” Don has published numerous papers and book chapters on the subject of Physical Vapor Deposition (PVD) processing and technology transfer from R&D to production. He is the author of Handbook of Physical Vapor Deposition (PVD) Processing (1st edition 1998, 2nd edition 2010) published by Elsevier and Foundations of Vacuum Coating Technology, published by William Andrew/Elsevier (1st edition 2003).

Book preview

The Foundations of Vacuum Coating Technology

Second Edition

Donald M. Mattox

Management Plus, Inc., Albuquerque, NM, United States

Table of Contents

Cover image

Title page

Copyright

Dedication

Biography

Foreword

Preface

Further Discussion

Acknowledgments

Chapter 1. About This Book

Abstract

Introduction

Terminology

Text References

References

Further Reading

Chapter 2. Vacuum Technology

Abstract

Introduction

Vacuum Pumps

Vacuum Chambers

Vacuum Sealing

Leak Detection and Residual Gas/Vapor Analysis

Vacuum Gauging

Chamber Cleaning and Conditioning

Conductance—Gas Manifold and Pumping Distribution

References

Further Reading

Chapter 3. Plasmas and Plasma Enhanced CVD

Abstract

Introduction: Plasmas

Plasma Generation

Plasma Diagnostics

Plasma Confinement

Some Applications of Plasmas in Vacuum Deposition

Introduction: Chemical Vapor Deposition and Plasma Enhanced CVD (PECVD)

Some Applications of PECVD

References

Further Reading

Chapter 4. Physical Sputtering and Sputter Deposition

Abstract

Introduction

Mechanism of Sputtering

Sputtered Surface (Target)

Reactive Sputtering

Chemical Sputtering

Sources for Physical Sputtering

Sputter Deposition

Some Applications of Sputter Deposition

References

Further Reading

Chapter 5. Thermal Evaporation and Deposition in Vacuum

Abstract

Introduction

Free Surface Evaporation (Langmuir Evaporation)

Evaporation/Sublimation Sources

Plasma-Activated Deposition

Deposition by Evaporation/Sublimation

Some Applications of Thermal Evaporation in Vacuum

References

Further Reading

Chapter 6. Cathodic Arc Vaporization and Cathodic Arc Vapor Deposition

Abstract

Introduction

Cathodic Arc Vaporization

Cathodic Arc Vapor Sources

Cathodic Arc Vapor Deposition (CAVD)

Some Applications of Arc Vapor Deposition

References

Further Reading

Chapter 7. Ion Plating

Abstract

Introduction

Sputter Cleaning and Bombardment Heating

Vapor Sources for Ion Plating

Gas Phase Nucleation

Bombardment Sources for Ion Plating

Reactive Deposition Under Bombardment Conditions

Some Bombardment Effects on Vacuum Deposited Coatings

Some Applications of Ion Plating

References

Further Reading

Chapter 8. Condensation, Nucleation, Interface Formation, and Film Growth

Abstract

Introduction

Condensation and Nucleation

Interface Formation

Growth of the Depositing Film

References

Further Reading

Appendix I. Historical Timeline

Appendix II. Glossary of Terms Used in Vacuum Coating

A

B

C

D

E

F

G

H

I

J

K

L

M

N

O

P

Q

R

S

T

U

V

W

X

Y

Z

Index

Copyright

William Andrew is an imprint of Elsevier

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Copyright © 2018 Elsevier Inc. All rights reserved.

No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions.

This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein).

Notices

Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.

Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility.

To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein.

British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library

Library of Congress Cataloging-in-Publication Data

A catalog record for this book is available from the Library of Congress

ISBN 978-0-12-813084-1

For Information on all William Andrew publications visit our website at https://www.elsevier.com/books-and-journals

Publisher: Matthew Dean

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Dedication

The author dedicates this work to his wife Vivienne, without whose unwavering support, encouragement, and excellent proofing skills this book would not have been written.

DC Diode Reactive Sputtering/Reactive Sputter Deposition Configuration

Copyright 2017 by Donald M. Mattox; Illustration by Linnea J. Dueker

Biography

Donald M. Mattox

Renowned engineer, educator, historian, and consultant on PVD processing

Don Mattox spent 27 years at Sandia National Laboratories (SNL) inventing, developing, and transferring vacuum coating technologies to the manufacturing sector. During that time he invented the ion plating process, was elected President of the American Vacuum Society (AVS) (1985), wrote many articles and book chapters on vacuum technology and vacuum coating technology and was selected for awards such as the Albert Nerken Award from the AVS. After retiring from SNL in 1989, he became more active in consulting and teaching as well as becoming the Technical Director of the Society of Vacuum Coaters (SVC) (1989–2006) and the Technical Director of the Association of Vacuum Equipment Manufacturers (AVEM) (1993–2007). He was awarded the Nathaniel Sugerman Award from the SVC in 2007. In 1998 he published the book Handbook of Physical Vapor Deposition (PVD) Processing (second edition, 2010). His professional life has spanned the years of many of the significant developments in vacuum coating processing and he developed an interest in the history of vacuum technology and the vacuum coating processes. This interest has resulted in numerous articles and the book Foundations of Vacuum Coating Technology (first edition, 2003) as well as this revised and expanded work. He is coprincipal of Management Plus, Inc. and further information on his background as well as his blog on vacuum coating processes may be found on <www.mpinm.com>.

Foreword

Dr. David A. Glocker, Isoflux Incorporated, retired, West Henrietta, NY, United States

In the preface to the First Edition of The Foundations of Vacuum Coating Technology, Don Mattox paraphrases George Santayana to say Those that do not know the history of their field are doomed to repeat its mistakes or end up in patent litigation. As Don then shows us, this lighthearted version of Santayana’s famous quote is based on an important truth: researchers are wise to understand the origins of their fields. Often the seminal publications contain the clearest explanations and manner of thinking about the major issues in a technology. Moreover, lines of inquiry that were unsuccessful decades ago can be very fruitful in light of new developments and familiarity with the history of one’s work often stimulates new ideas.

In addition to being recognized for his own important contributions, Don is a scholar of vacuum coating and uniquely qualified to write about its history. I was with him during a trip to Greece a number of years ago when he found a hand vacuum pump dating to the 1800s in a flea market, which he immediately bought and added to his hardware collection. His extensive personal library contains a number of books that are now difficult or impossible to find elsewhere. This knowledge and experience, gained over a career that has spanned more than 60 years, are reflected in the remarkable breadth of information one finds here.

The Second Edition differs from the original in a number of important ways. It begins with a chapter introducing the terminology of vacuum coating and containing information on many of the important reference sources that are available. I found the enlarged discussion on patents and copyrights particularly interesting. The descriptions of each of the major deposition techniques have been expanded and are now the subjects of individual chapters. Recent developments, such as high power impulse magnetron sputtering, have been added. There is a new chapter on arc vapor deposition (both cathodic and anodic) and the section on surface preparation has been incorporated into a much more comprehensive chapter on nucleation and growth. Many of the illustrations that appeared in the First Edition, which make the history come to life, still appear and new ones have been added. Perhaps most importantly, the Second Edition continues to offer an outstanding list of references that extends from the earliest work until the present day. The chapter on sputter deposition alone has over five hundred.

In updating The Foundations of Vacuum Coating Technology, Don Mattox has done the field a tremendous service by helping to assure that we don’t lose contact with the origins of our technology. In addition to its practical value, it’s also very entertaining and should be part of every vacuum coater’s library.

April 2018

Preface

Donald M. Mattox, Management Plus, Inc., Albuquerque, NM, United States

We are living in a Golden Age of Surface Engineering where we can modify the properties of surfaces to perform a desired function. There are many ways to accomplish that modification but vacuum coating is one that has advanced greatly in the last 50 years. The beginning of the vacuum coating era really began in earnest with the development of the incandescent filament light bulb in the 1860s and the development of gaseous electronics in the late 1800s. The need for better vacuum environments and better filaments drove both vacuum technology and vacuum coating in the lamp industry. Plasma-assisted vacuum coating techniques were a major advance in vacuum coatings in the 1960s. Professor Allan Matthews has discussed those advances as a series of waves with the first wave beginning in the mid-1960s with the use of concurrent ion bombardment to modify the properties of atomistically depositing films in vacuum.

In the 1970s developments in the semiconductor industry and in tribology promoted the development of low-pressure plasma-enhanced chemical vapor deposition processes (LP-PECVD), which, in turn, assisted in the development of complex vacuum coatings by hybrid processes that combine several different vacuum coating processes into one. For example, the use of LP-PECVD together with plasma-assisted physical vapor deposition (PVD) allows the reactive deposition of coatings of complex materials such as the metal carbonitrides that are used for tribological applications as well as for hard, wear resistant decorative coatings. The use of plasmas and concurrent ion bombardment allows these hybrid processes to take place at relatively low substrate temperatures.

The use of vacuum coatings for demanding applications emphasized the need for understanding the nucleation, growth, and interface formation in vacuum coating processes. These studies led to the design and development of complex vacuum coatings such as composite, graded-composition, and layered (laminate) vacuum coating structures. This, in turn, promoted the use of plasmas for modifying the substrate surface before depositing the vacuum coating. Examples include: plasma nitriding a steel surface before depositing a hard coat and plasma treating a polymer surface before coating in order to enhance the apparent adhesion. The field of vacuum coating is continually evolving, and new coating designs, processes, materials, and applications provide a fertile field for the historian.

The subject of this work is the early history of the enabling technologies for vacuum coating processes. This book is not meant to be an up-to-date treatment of the individual subjects but rather is an attempt to identify the early work on the technologies, which is often neglected in contemporary treatments. References include patents as well as technical papers since often a patent is the first disclosure (sometimes the only disclosure) of the original work. Patents seldom cite relevant technical literature and technical papers seldom cite relevant patent literature. Patents often describe the early knowledge and thinking about a subject. Using Cited by in internet searches on technical papers and Patent citations and Referenced by in internet searches on patents often allows the previous and subsequent development and understanding of a subject to be more fully developed.

Further Discussion

For a more comprehensive discussion of some aspects of the history of vacuum coating technology and its enabling technologies, the reader is referred to a series of articles by the author provided in the References/Articles and Chapters section of Chapter 1 of this book.

Acknowledgments

The author would like to thank Dave Glocker for his review of this work and his comments, which are to be found in the Foreword to this book. Writing such a broad-ranging history has been very challenging and the author assumes responsibility for any errors of commission or omission.

Chapter 1

About This Book

Abstract

This work is meant to portray the historical aspects of the subject of vacuum coating rather than the more contemporary aspects. This chapter discusses the details of what is covered and what is not covered. The book is unique in that it references a great deal of patent literature. The types of references used are discussed and examples provided as to how they affect history. History is in the eyes of the author so it is not expected that everyone will agree as to the weight that is given to each subject particularly patents. From the Preface of the first edition:

Those that do not know the history of their field are doomed to repeat its mistakes or end up in patent litigation.

G. Santayana, paraphrased

Keywords

History; terminology; source of references

Introduction

This work portrays the subject of vacuum coating from an historical perspective. For more contemporary aspects the reader is referred to more recent journals, proceedings, and books dedicated to the subject of interest.

Vacuum coating has evolved as an important industrial process in the past 65 years. In the last 50 years vacuum coating has allowed numerous new applications to be developed. Vacuum coating is normally associated with vaporization from a solid or liquid surface. However, it should be recognized that the use of chemical vapor precursors such as hydrocarbon compounds has become more important as a condensing vapor source in hybrid vacuum deposition processes, using both vaporization of a solid/liquid along with the decomposition of the chemical vapor precursor.

The advancements in the enabling technologies of vacuum technology (Chapter 2: Vacuum Technology), together with advancements in plasma technology and electrical power supplies (Chapter 3: Plasmas and Plasma Enhanced CVD) are discussed. Appendix 1 provides an historical timeline of both vacuum deposition and vacuum and plasma technology. Other enabling technologies of surface preparation [1–3] and processing environments such as clean rooms [4,5] will not be discussed. It should be noted that the successful production of a product not only depends on the deposition process but upon all aspects of the process flow from the incoming material to the final packaging. Fig. 1.1 shows a flowchart that not only shows the processing flow but also the decisions about vacuum equipment and processing that must be made during the development phase (also see Ref. [6]). The reproducibility of the process depends on controlling the process parameters within the parameter windows.

Figure 1.1 Flowchart of the vacuum coating processing sequence. This chart includes the equipment and process decisions that are relevant to developing a vacuum coating process. <http://www.mpinm.com> Process Flow diagram for PVD processing [6].

Terminology

Vacuum Deposition–Vacuum Coating–Physical Vapor Deposition–Chemical Vapor Deposition

Vacuum deposition is accomplished by vaporizing a solid or liquid in good vacuum such that the vapor deposits as atoms or molecules on the surface to be coated. If vaporization does not take place in a good vacuum the vapors condense in the vapor phase by multibody collisions to form particulates (soot). The term Physical Vapor Deposition (PVD) was first used in 1955 by C.F. Powell et al. in the book Vapor-Plating: The Formation of Coatings by Vapor-Deposition Techniques to differentiate PVD from Chemical Vapor Deposition (CVD) [7]. In PVD the vaporization is from a solid or liquid surface. CVD is when the material to be deposited comes from a chemical vapor precursor. If a plasma is used to aid the CVD process it is called plasma-enhanced CVD (PECVD) or in some cases plasma deposition. The rational for this PVD/CVD distinction was discussed in the Preface of the 1966 book Vapor Deposition edited by C.F. Powell et al. [8]. The term PVD was not widely used until the 1990s but instead the process was more generally called Vacuum Deposition (e.g., Ref. [9]).

The term vacuum coating covers both PVD and low-pressure CVD such as PECVD. The hybrid vacuum coating process of PVD and PECVD (PVD/PECVD) began to be developed and applied to products in the early 1970s with the introduction of the ion plating process where plasma activation of CVD precursors takes place at low pressures (Chapter 3: Plasmas and Plasma Enhanced CVD). By having ion bombardment during deposition the substrate surface may directly heated. Activation and heating both promote chemical reactions on the surface (Chapter 7: Ion Plating).

Thin Film Versus Coating

The literature on vacuum deposition uses the terms thin film and coating often without any definition. Early uses of vacuum coatings were for reflecting surfaces and antireflection films, both of which only require film thicknesses on the order of a quarter of the wavelength of visible light or about 1500 Å (150 nm), so it seems logical to call these film thicknesses thin films. As the vacuum deposits became thicker, for tribological purposes for instance, it would have been logical to call them thick films but that terminology has a specific meaning in hybrid microelectronic technology [10]. Therefore the term vacuum coating seemed to be a good compromise.

Units of Pressure

There are different units for the pressure in a vacuum environment used in different countries and in different disciplines. The most common system of units are the centimeter-gram-second (CGS), the meter-kilogram-second (mks), the foot-pound-second (fps), and the customary system of units. In the United States a customary system of units (pounds per square inch—psi and inches Hg—inHg {aeronautical}) are generally used, though the US Metric Conversion Act was passed in 1975 which was supposed to encourage changing to the metric system. Among scientists the International Standard (SI) units are used and some journals will not accept any other unit system in their papers. The SI system has basic units such as the meter (m), kilogram (kg), second (s), Ampere (A), and Kelvin temperature (K) and derived units such as Newton (N) for force, Joule (J) for heat, and Pascal (Pa) for pressure.

The first units used for pressure was millimeters of mercury (mmHg) which became 1 mmHg=1 Torr, named after Torricelli. In vacuum technology the use of milliTorr (1/1000 of a Torr) (0.133 Pa) is often used and in some literature 1/1000 mmHg is called a micron.

The International Standard Atmosphere (ISO) is taken to be 101,325 Pa (1.01325 bar; 14.6959 psi; 29.92 inchesHg; 760 mmHg) at 15°C. The common units of pressure in meteorology are the millibar (mb), and the hectopascal (hPa).¹

Text References

This work is meant to be more historical than contemporary though many contemporary references are provided along with the historical references. The author has striven to give the earliest references to a particular subject. The source of references may be divided into the categories of: (1) books and book chapters, (2) periodic journals and transactions, (3) proceedings of conferences and meetings, (4) patents, (5) documents, such as reports and magazines, (6) the Internet (Blogs, YouTube, etc.), and (7) others, such as oral histories and private communications.

Books and Book Chapters

Book references were the earliest references for vacuum technology. Often early books were published by the author to disseminate their work since few scientific journals were available in the 16th and 17th century. Today very few technical books have single authors but are rather collections of chapters written by different authors who have expertise in the subject being covered in that chapter. Portions of early books or the whole book are often available on the Internet (e.g., Google Books) [11].

Periodic Journals and Transaction Articles

Articles in periodic journals may or may not be peer-reviewed. Emphasis on peer reviewing and refereeing of articles for journals has mostly developed since the 1950s [12,13]. The use of the title transaction for a group of articles was and sometimes is used the way proceedings is often used today. Often transactions are not peer-reviewed.

In 1660 King Charles II founded the Royal Society of London in England to promote the theory and application of science. In 1662 the newly formed Royal Society of London for Improving Natural Knowledge was granted a charter to publish by King Charles II and on March 6, 1665, the first issue of Philosophical Transactions was published under the editorship of Henry Oldenburg, who was also the Secretary of the Society. The first volumes of what was the world’s first scientific journal were very different from today’s journal, but in essence it served the same function; namely, to inform the Fellows of the Society and other interested readers of the latest scientific discoveries. As such, Philosophical Transactions established the important principles of scientific priority and peer review, which have become the central foundations of scientific journals ever since. In 1886 the breadth and scope of scientific discovery had increased to such an extent that it became necessary to divide the journal into two, Philosophical Transactions A and B, covering the physical sciences and the life sciences, respectively.

The first scientific society, in what became the United States, was the American Philosophical Society, which was founded in 1743 under the leadership of Benjamin Franklin. The Transactions of the American Philosophical Society began publication in 1771. Up to that time most American scientists published in European journals. In 1819 Benjamin Silliman, who has been called the father of American scientific education, started publishing the American Journal of Science and Arts (AJSA). The AJSA is the oldest journal still published in the United States and is now known as the American Journal of Science and publishes mainly on geology. The term arts was used for what we now call technology well into the 20th century and the term is still used in the patent literature.

Many early papers on vacuum coating were published in the Journal of the Electrochemical Society (JES), which began in 1853. The Journal of the Optical Society of America (JOSA) began publishing in 1917. The journal Vacuum began publishing in January 1951 in England. The American Vacuum Society (AVS) was formed in 1953 to provide a forum for those interested in the scientific and industrial development of vacuum equipment and processes in the United States [14–19]. Initially the papers of the AVS annual symposium were published in the form of transactions. The AVS began publishing the Journal of Vacuum Science and Technology (JVST) in 1964. In 1983 the journal was split into two sections, A—devoted to vacuum, surfaces, and films, and B—devoted to microelectronics, processing, and phenomena. In 1967 the journal Thin Solid Films began publication. In 1986 Surface and Coating Technology began publication; the name morphed from Electrodeposition and Surface Treatment {1972} then Surface Technology {1976}. In 1973 the Société Francaise des Ingénieurs et Techniciens du Vide (1945) became the Société Francaise du Vide (SFV) in 1973. In 1974 the French Vacuum Society (SFV) began publishing the journal Le Vide: les couches minces (The Vacuum: Thin Films).

Unfortunately many journal papers may only be accessed by subscription to the journal or payment per article to get behind a paywall. This is changing as more research grants specify that the work be published with open access. The open access may be immediate or it may be after a short period of time, or it may be for a short period of time and then behind a paywall. Sometimes searching several sources will locate a site where the article is not behind the paywall.

Proceedings, Conferences, and Meetings

Some conferences publish proceedings that are archived and others do not. Sometimes the proceedings are only available to the members. For example, the Society of Vacuum Coaters (SVC) has published the proceedings of their annual technical conference since 1957. Since 2013 select papers from the SVC technical conference have been peer-reviewed and published in Surface and Coating Technology while nonpeer-reviewed (original) versions are published in the SVC Proceedings.²

In some cases select papers from the conference are published in a journal. For example, peer-reviewed papers from the International Conference on Metallurgical Coatings and Thin Films (ICMCT) conference are published in Thin Solid Films and Surface and Coating Technology.³

More and more conference papers are only published in digital format with no print copies. A unique variation of the digital publication is the proceedings of the Plasma Surface Engineering (PSE) conference. The PSE conference is a biannual conference that was started in 1984 and is held in Garmisch-Partenkirchen, Germany. The conference is organized by the European Joint Committee on Plasma and Ion Surface Engineering. Beginning in 2006 the abstracts and author contacts of the conference papers have been published on the PSE website <www.pse-conferences.net/previous-conferences.html>. If you want to know more about a paper you need to contact the author directly.

Patents and Copyrights

Patents and copyrights are called Intellectual Property (IP) and the IP laws differ between countries. IP is country specific and unless there is an agreement between countries IP is not recognized between countries. Generally patents expire over a specified period of time. In the United States the patent expires after 20 years, but a copyright may last for much longer. For example in the United States the tune Happy birthday to you was copyrighted in 1893 and music companies have been collecting royalties on its commercial use ever since by continuously renewing the copyright.

In the United States use may be made of copyrighted materials under the Fair use doctrine. Fair use provides for the legal, unlicensed citation or incorporation of copyrighted material in another author’s work. Examples of fair use in United States copyright law include commentary, search engines, criticism, parody, news reporting, research, and scholarship. The proper application of fair use is evaluated using a four-factor test:

1. The purpose and character of the use, including whether such use is of a commercial nature or is for nonprofit educational purposes;

2. The nature of the copyrighted work;

3. The amount and substantiality of the portion used in relation to the copyrighted work as a whole; and

4. The effect of the use upon the potential market for or value of the copyrighted work.

In the United States and some other countries, material generated using government funding is not copyrighted and may be used by anyone.⁴

Patents play an important role in the history of the development of vacuum coating but are generally ignored in the peer-reviewed technical/scientific literature though they often contain a detailed discussion of the fundamentals that are the background to the patent. Sometimes authors of technical papers also submit patent applications and both are referenced in this book. Inventors often don’t publish their work in the scientific literature. Examples of such inventors are Thomas Edison, who had around 1000 patents but no journal papers, and Willis Whitfield, the inventor of the Ultra-clean room, [4] who never published in the technical literature except for some conference proceedings. A problem with researching patents is that the titles are often not very descriptive and the language is often archaic. For example, patent literature uses the word art for what we would now call technology.

In this book, patents are referenced by the inventor(s) full name(s), patent title, patent number, priority date (if different from the filing date), filing date, and publication date. Often there is a statement as to the assignment of the original patent. In some cases, what is published in the patent literature is not revealed in the technical literature for many years when it is independently disclosed (see e.g., Berghaus/Mattox—Chapter 7: Ion Plating).

When acquiring a patent on the Internet not only are patent citations of previous patents that have been examined on the subject of the patent are provided but also nonpatent citations such as technical articles, that are relevant to the patent may be given in the patent. The patent often includes a referenced by section that gives subsequent patents that refer to the patent. This section is similar to the Science Citation Index (SCI—first issued in 1964) that was published for a selected group of scientific journals. More recently the Science Citation Index Expanded (SCI-E) covers more than 8500 journals and covers the years 1900-to-present. Modern citation indexes are based on the Shepard’s Citations used by the US law profession for finding relevant case law and other legal authority. In 1873 the Shepard’s Citations legal service was started by Frank Shepard. In law the term Shepardizing refers to the process of referring to Shepard’s Citations.

The concept of the modern patent began in England in 1624. The patent system of the United States as well as other countries evolved from that concept [22,23]. Until 2013 the United States operated under a first to invent (conceive) principle, while other countries used first to file. Under the first-to-invent system, when two inventors file a patent application for the same invention, the patent office should identify and award the patent to the inventor who was first to conceive and diligently reduce the invention to practice, even if the first inventor was not the first to file a patent application. Usually this determination is decided in the court-of-law. In 2013 in the United States passed the America Invents Act (AIA), which changed the US patent law from a first-to-invent system to a first-to-file system more in line with other industrial nations.

An example how this change would have changed vacuum coating history is that of the patent for the planar magnetron sputtering source. In July 1973 John F. Corbani, filed a patent (pat. #3878085) which was granted in 1975, and in January 1974 John S. Chapin filed a patent (pat. #4166018) which was granted in 1979. They both described the planar magnetron. Chapin was able to swear behind Corbani’s patent using a laboratory notebook entry witnessed by R.L. Cormia of AIRCO, which predated Corbani’s patent filing. Under the new patent rules John Corbani would be credited with the invention not John Chapin. The situation is further complicated by the fact that W. Knauer published a planar magnetron sputtering design in his ion pump patent (#3216652—fig. 3) granted in 1965. This would allow the Chapin/Corbani (C/C) patents to have been challenged if someone had wanted to go to court over it. The C/C patents could be challenged using Knauer’s patent as prior art and obviousness since Knauer used the planar magnetron configuration to sputter deposit a film in an ion pump to getter gases.

Patents are only protected in countries in which they are patented and in countries that had signed a reciprocal copyright agreement. To broaden the protection the United Nations established the World Intellectual Property Organization (WIPO) in 1967. The WIPO monitors the Patent Cooperation Treaty, which provides a common procedure for filing applications across its contracting member countries (presently about 185 countries). Filing an international patent application preserves the right to file in other member states for 1 year thus eliminating the need to file a large number of patents simultaneously. A WIPO international patent number is prefaced by WO. Patent litigation is the means by which disputes over the use of patented designs or processes is resolved.⁵

Documents/Magazine Articles, etc.

In the United States, the National Technical Information Service (NTIS) provides indexing to US government-sponsored research and is the central source for the sale of unclassified US government-sponsored work. The National Technical Reports Library (NTRL) was created by the NTIS as a means of disseminating scientific and technical information produced by federal and international sources (www.ntrl.ntis.gov). In the United States, the Defense Technical Information Center (DTIC) is also a source of unclassified documents from the US Department of Defense (www.dtic.mil).

Internet—YouTube, Blogs, etc.

One of the most recent sources of information is YouTube. For example if you want to know about magnetron sputtering you may search on YouTube magnetron sputtering and watch a video of an animation and explanation of the process. Note: Sometimes they are not entirely correct or they are incomplete, so beware. Wikipedia is often criticized but the author of this book finds that, if the subject is not controversial, it can be a good place to start a search.

References

1. Mattox DM. Preparation and cleaning of vacuum surfaces, Ch 4.9. In: Hoffman DM, Singh B, Thomas III JH, eds. Handbook of Vacuum Science and Technology. Academic Press 1998;553–606.

2. Mattox DM. Surface preparation for vacuum surfaces and vacuum coating, Chapter 21. In: Mattox DM, Mattox VH, eds. 50 Years of Vacuum Coating Technology and the Growth of the Society of Vacuum Coaters. SVC 2007;151–154.

3. Mattox DM. A Short History: In Situ Cleaning in Vacuum for Physical Vapor Deposition (PVD) Bulletin, Society of Vacuum Coaters Fall 2014;50–53.

4. W.J. Whitfield, Ultra-Clean Room, USP 3158457 (filed 14 May 1962; published 24 Nov. 1964) (assigned US Atomic Energy Commission).

5. Mattox DM. Another 50th Anniversary that is Important to the Vacuum Coating Industry Bulletin, Society of Vacuum Coaters Spring 2013;6.

6. <http://www.mpinm.com> Process Flow diagram for PVD processing.

7. Powell CF, Campbell JE, Gonser BW. Vapor-Plating, The Formation of Coatings by Vapor-Deposition Techniques (Electrochemical Society) John Wiley 1955.

8. Powell CF, Oxley JH, Blocher Jr JM, eds. Vapor Deposition. Electrochemical Society, John Wiley 1966.

9. Holland L. Vacuum Deposition of Thin Films Chapman & Hall 1956.

10. Harper CA, ed. Handbook of Thick Film Hybrid Microelectronics. McGraw-Hill 1974.

11. <www.google.com/googlebooks/about/>.

12. Baldwin M. In referees we trust. Phys Today. 2017;70(2):44–49.

13. Discussion, Phys. Today 70 (10) (October 2017) 15–18.

14. Schleuning HW. The first twenty years of the American Vacuum Society. J Vac Sci Technol. 1973;10.

15. Vossen JL, Hammond N. The American Vacuum Society. J Vac Sci Technol. 1983;13:1351.

16. Lafferty JM. History of the American Vacuum Society and the International Union of Vacuum Science, Technique and Application. J Vac Sci Technol. 1984;A2:104.

17. Lafferty JM. History of the International Union for Vacuum Science, Technique, and Applications: Review Article. J Vac Sci Technol. 1987;A5(4):405.

18. Singleton JH. The American Vacuum Society at 40. Vacuum Science and Technology: Pioneers of the 20th Century New York, NY: AIP Press; 1993;1.

19. 50 years of the AVS (1953–2003) AVS web site: <http://www2.avs.org/historybook/default.asp>.

20. D.M. Mattox, V.H. Mattox (Eds.), 50 Years of Vacuum Coating Technology and the Growth of the Society of Vacuum Coaters, SVC, 2007.

21. D.M. Mattox, V.H. Mattox, Retrospectives about the Society of Vacuum Coaters (SVC) on their 60th Anniversary, Vacuum Technology and Coating, Part 1 (July 2017) 33 <http://bt.e-ditionsbyfry.com/publication/?i=423100#{%22issue_id%22:423100,%22page%22:32}> and Part II (August 2017) 36. .

22. L.H. Campbell, The patent system of the United States so far as it relates to the granting of patents. <http//www.myoutbox.net/pocamp.htm>, (2002) 1–19.

23. Dobyns KW. The Patent Office Pony: A History of the Early Patent Office Sergeant Kirkland’s Press 1997.

24. D.T. Wei, A.W. Louderback, Method of Fabricating Multi-Layer Optical Films, USP 41412958 (filed 13 April 1978; published 6 March 1979) (assigned Litton Systems).

25. <http://openjurist.org/82/f3d/1559/Litton-systems-inc-v-Honeywell-inc>, July 3, 1996.

26. <http://openjurist.org/238/f3d/1376/Litton-systems-inc-v-Honeywell-inc>, February 5, 2001.

27. K.L. Chopra, M.R. Randett, High Current Duoplasmatron Having an Aperature Anode Comprising a Metal of High Magnetic Permeability, USP 3409529 (filed 7 July 1967; published 5 Nov. 1968) (assigned Kennecott Copper Corp.).

28. Private communication from K.L. Chopra on October 6, 2017.

29. G. Gautherin, C. Schwebel, C. Weissmantel, in: 7th International Conference on Solid Surfaces 1977 Vienna (Austria) (1977) 1449.

30. Gautherin G, Bouchier D, Schwebel C. High-vacuum deposition methods involving superthermal free particles, Ch 5. In: Klabunde KJ, ed. Thin Films From Free Atoms and Particles. Academic Press 1985;203–255.

31. Mattox DM. Bibliography: PVD (and related) books. Bulletin, Society of Vacuum Coaters Fall 2012;33–36.

Further Reading

Early Vacuum Deposition Books [31]

A Discussion on: The Making of Reflecting Surfaces, Optical Society, Fleetwood Press, 1920.

I.C. Gardner, F.A. Case, The Making of Mirrors by the Deposition of Metals on Glass, Bureau of Standards circular #389 (USA) 1931.

The Application of Metallic Fluoride Reflection Reduction Films to Optical Elements, (Record of a Conference held at the Frankford Arsenal in October, 1943. Available from SVC.org/HistoryofVacuumCoating/Historical-Papers.cfm.

H. Mayer, Physik dünner Schichten (Physics of Thin Layers) Teil 1, 1950 und II (1955) Wissenschaftliche Verlagsgesellschaft, Stuttgart, 1950, 1955.

1. Holland L. Vacuum Deposition of Thin Films Chapman & Hall 1956.

M. Auwärter, Ergebnisse der Hochvakuumtechnik und der Physik dünner Schichten (Results of the high vacuum technique and the physics of thin films), Wissenschaftliche Buchgesellschaft, 1957.

2. Structure and Properties of Thin Films. In: Neugebauer CA, Newkirk JB, Vermilyea DA, eds. Proceedings of an International Conference held September 9–11, 1959. John Wiley 1959.

3. Hass G, ed. Physics of Thin Films, vol 1, Advances in Research and Development. Academic Press 1963; first of Thin Film Series by Academic Press.

Thin Films (papers presented at a seminar of the American Society for Metals October 19 and 20, 1963), chaired by H.G.F. Wilsdorf, ASM, 1964.

4. Anderson JC, ed. The Use of Thin Films in Physical Investigations: NATO Advanced Studies Institute, 1965. Academic Press 1966.

B.S. Danilin, Vacuum Deposition of Thin Films, Moscow, 1967. English Translation: Foreign Technology Div. Wright-Patterson AFB, Accession number: AD0698198; FTD-MT-24-490, 1969 (in Russian).

5. Berry RW, Hall PM, Harris MT, eds. Thin Film Technology. Van Nostrand, Reinhold 1968.

6. Chopra KL. Thin Film Phenemona McGraw-Hill 1969.

7. Maissel LI, Glang R, eds. Handbook of Thin Film Technology. McGraw-Hill 1970; (reissued 1983).

8. Lewis B, Anderson JC. Nucleation and Growth of Thin Films Academic Press 1979.

Books

1. Mattox DM. The Foundations of Vacuum Coating Technology (first ed.) Noyes/William Andrew/Elsevier 2003.

2. Mattox DM, Mattox VH, eds. 50 Years of Vacuum Coating Technology and the Growth of the Society of Vacuum Coaters. SVC 2007.

3. Mattox DM. Handbook of Physical Vapor Deposition, (PVD) Processing second ed. Elsevier 2010.

Articles and Chapters

A. Anders, Tracking down the origin of arc plasma science. I. Early pulsed and oscillating discharges, IEEE Trans. Plasma Sci. 30(4) (2003), 1052.; A. Anders, II: Early continuous discharges, IEEE Trans. Plasma Sci. 31(4) (2003) 1060

1. Greene JE. Tracing the 5000-year recorded history of inorganic thin films from ~3000 BC to the early 1900s AD. Appl Phys Rev. 2014;1 0411302.

2. Greene JE. Tracing the recorded history of thin-film sputter deposition: from the 1800s to 2017. J Vac Sci Technol. 2017;A35 05C204/60.

M. Ingram, Google’s victory in book-scanning case is a huge win for Fair Use, (October 16, 2016). Available at <http://fortune.com/2015/10/16/google-fair-use/>. Also in Wikipedia.

3. Lafferty JM. History of the American vacuum society and the international union for vacuum science, technique, and applications. J Vac Sci Technol. 1984;A2:104.

4. Mattox DM. Foundations of vacuum coating technology: the stories behind the facts, in 46th Annual Technical Conference Proceedings. Society of Vacuum Coaters 2003;11–20.

Series of articles by Donald M. Mattox in the Bulletin of the Society of Vacuum Coaters:

A Short History: Deposition by Thermal Evaporation in Vacuum, Bulletin, Society of Vacuum Coaters (Spring 2018) 46–57.

A Short History: Sources of Physical Sputtering, Bulletin, Society of Vacuum Coaters (Fall/Winter 2017), 54–63.

A Short History: Physical Sputtering, Bulletin, Society of Vacuum Coaters (Summer 2017) 43–52.

A Short History: Vacuum in the 17th Century: The Beginning of Experimental Sciences, Bulletin, Society of Vacuum Coaters (Spring 2017), 40–47.

A Short History: Vacuum Sealing - Greases, Oils, Cements, Elastomers, and Metals, Bulletin, Society of Vacuum Coaters (Fall/Winter 2016), 36–42.

A Short History: The Role of Mercury in Vacuum and PVD Technology, Bulletin, Society of Vacuum Coaters (Summer 2016), 44–47.

A Short History: Adhesion, Interface formation, and Stress in PVD Coatings, Bulletin, Society of Vacuum Coaters, (Spring 2016), 32–37.

A Short History: Vacuum Chambers for PVD, Bulletin, Society of Vacuum Coaters (Fall 2015), 38–45.

A Short History: Magnetron Sputter Deposition, Bulletin, Society of Vacuum Coaters, (Summer 2015), 42–45.

A Short History: Film Deposition by Pulsed Laser Deposition (PLD), Bulletin, Society of Vacuum Coaters (Spring 2015), 38–39.

A Short History: In situ Cleaning in Vacuum for Physical Vapor Deposition (PVD), Bulletin, Society of Vacuum Coaters (Fall 2014), 50–53.

A Short History: Ultrafine (nano-) Particles Formed in Vacuum, Bulletin, Society of Vacuum Coaters, (Summer 2014), 54–56.

A Short History: Reactive Evaporation, Bulletin, Society of Vacuum Coaters (Spring 2014), 50–51.

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¹Meteorology: The international unit for measuring atmospheric pressure is the hectopascal (1 hPa=100 Pa=1 mb=0.75 Torr). The millibar (mb) is still often used in weather reports and forecasts for the public, but the unit hectopascal is increasingly being used. The distribution of pressure is vital information for meteorologists who need pressure readings taken at the same time in many different places. For consistency, a pressure reading is adjusted to a datum of mean sea level to take account of the reduced pressure at locations above sea level (1 hPa at or near sea level is equivalent to approximately 7.5-m elevation change).

The highest atmospheric pressure ever recorded was 1085.7 hPa (adjusted to sea level) (814.3 Torr) in Tosontsengel, Mongolia in 2001, which is 7% higher than the standard atmosphere. The lowest pressure ever recorded was 870 hPa (652.6 Torr) in the eye of Super Typhoon Tip in 1979 (as determined by a weather reconnaissance aircraft), which is 14% less than the standard atmosphere. For comparison a good vacuum cleaner can generate a vacuum about 20% less than the ambient atmospheric pressure. Wind is caused by a pressure gradient in the atmosphere and the max wind speed ever recorded was 301±20 mph during the Moore, OK tornado of May 3, 1999.

²SVC [20]: The SVC was formed in 1957 to provide a forum for developments in the industrial production and application of vacuum coatings. The SVC Annual Technical Conference Proceedings began to be published in 1957. Proceedings papers after 1990 are available on the SVC website. Papers before 1990 are available upon request from SVC. The SVC also publishes the Bulletin three times a year and contains technical articles of interest to the vacuum coating industry and news. Publication of the Bulletin began in 2004. Retrospectives about the Society of Vacuum Coaters (SVC) on SVC’s 60th Anniversary were published by Donald M. Mattox and Vivienne Harwood Mattox in Vacuum Technology & Coating in July and August 2017 [21].

³ICMCTF: ICMCTF is an annual topical conference of the Advanced Surface Engineering Division (ASED) of the AVS. The roots of the ICMCTF began with the Vacuum Metallurgical Division (VMD) of the AVS, which was the first division (1961) of the AVS. The VMD division conference was initially interested in vacuum melting and degassing.

In 1974 the VMD organized a conference on Structure/Property Relationships in Thick Films and Bulk Coatings. The conference covered a broad range of coating technologies including: PVD, CVD, thermal spray (plasma, arc-wire, and D-gun), and electrolytic deposition. Rointan Framroze (Ron) Bunshah was the organizer and Program Chairman. In 1975 a second conference was held. The proceedings of both of those conferences were published in the AVS Journal of Vacuum Science and Technology (JVST) volumes 11(4) and 12(4) and as hardcover books. These conferences met with so much success it was decided to have an annual conference on metallurgical coatings so the International Conference on Metallurgical Coatings (ICMC) was born.

In 1976 the first ICMC meeting with that title was held in San Francisco and selected (peer-reviewed) papers from the meeting were published as volumes 39 and 40 of Thin Solid Films (Elsevier) and in a two-volume hardcover book form. The early ICMC meetings included a number of papers using coating techniques other than PVD. Beginning in 1987 selected (peer-reviewed) papers from the conference appeared in Thin Solid Films (TSF) and in Surface