Secondary Ion Mass Spectrometry E-Book

Paul van der Heide

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 697

Veröffentlichungsjahr: 2014

Beschreibung

Serves as a practical reference for those involved in Secondary Ion Mass Spectrometry (SIMS)
• Introduces SIMS along with the highly diverse fields (Chemistry, Physics, Geology and Biology) to it is applied using up to date illustrations
• Introduces the accepted fundamentals and pertinent models associated with elemental and molecular sputtering and ion emission
• Covers the theory and modes of operation of the instrumentation used in the various forms of SIMS (Static vs Dynamic vs Cluster ion SIMS)
• Details how data collection/processing can be carried out, with an emphasis placed on how to recognize and avoid commonly occurring analysis induced distortions
• Presented as concisely as believed possible with All sections prepared such that they can be read independently of each other

Leseprobe

Table of Contents

Cover

Title Page

Copyright

Foreword

Preface

Acknowledgments

List of Constants

Chapter 1: Introduction

1.1 Matter and The Mass Spectrometer

1.2 Secondary Ion Mass Spectrometry

1.3 Summary

Section I: Principles

Chapter 2: Properties of Atoms, Ions, Molecules, and Solids

2.1 The Atom

2.2 Electronic Structure of Atoms and Ions

2.3 Summary

Chapter 3: Sputtering and Ion Formation

3.1 The Fundamentals of Sims

3.2 Sputtering

3.3 Ionization/Neutralization

3.4 Summary

Section II: Practices

Chapter 4: Instrumentation Used in SIMS

4.1 The Science of Measurement

4.2 Hardware

4.3 Summary

Chapter 5: Data Collection and Processing

5.1 The Art of Measurement

5.2 Sample Preparation and Handling

5.3 Data Collection

5.4 Data Processing

5.5 Summary

Appendix A

A.1 Periodic Table of the Elements

A.2 Isotopic Masses, Natural Isotope Abundances, Atomic Weights, and Mass Densities of the Elements

A.4 Work–Function Values of Elemental Solids

A.5 SIMS Detection Limits of Selected Elements

A.6 Charged Particle Beam Transport

A.7 Some Statistical Distributions of Interest

A.8 SIMS Instrument Designs

A.9 Additional Sims Methods of Interest

A.10 Additional Spectroscopic/Spectrometric Techniques

A.11 Additional Microscopies

A.12 Diffraction/Reflection Techniques of Interest

Technique Acronym List

Abbreviations Commonly used in SIMS

Glossary of Terms

Questions and Answers

References

Index

End User License Agreement

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Guide

Cover

Table of Contents

Preface

Section I: Principles

Chapter 1: Introduction

List of Illustrations

Figure 1.1

Figure 1.2

Figure 1.3

Figure 1.4

Figure 1.5

Figure 2.1

Figure 2.2

Figure 2.3

Figure 2.4

Figure 2.5

Figure 2.6

Figure 2.7

Figure 2.8

Figure 3.1

Figure 3.2

Figure 3.3

Figure 3.4

Figure 3.5

Figure 3.6

Figure 3.7

Figure 3.10

Figure 3.8

Figure 3.9

Figure 3.11

Figure 3.14

Figure 3.12

Figure 3.13

Figure 3.15

Figure 3.16

Figure 3.17

Figure 3.18

Figure 3.19

Figure 3.20

Figure 3.21

Figure 3.22

Figure 3.23

Figure 3.24

Figure 3.25

Figure 3.26

Figure 3.27

Figure 3.28

Figure 3.29

Figure 3.30

Figure 3.31

Figure 3.32

Figure 3.33

Figure 3.34

Figure 3.35

Figure 3.36

Figure 3.37

Figure 3.38

Figure 3.39

Figure 3.40

Figure 3.41

Figure 3.42

Figure 4.1

Figure 4.2

Figure 4.3

Figure 4.4

Figure 4.5

Figure 4.6

Figure 4.7

Figure 4.8

Figure 4.9

Figure 4.10

Figure 4.11

Figure 4.12

Figure 4.13

Figure 4.14

Figure 4.15

Figure 4.16

Figure 4.17

Figure 4.18

Figure 4.19

Figure 5.1

Figure 5.2

Figure 5.3

Figure 5.4

Figure 5.5

Figure 5.6

Figure 5.7

Figure 5.8

Figure 5.9

Figure 5.10

Figure 5.11

Figure 5.12

Figure 5.13

Figure 5.14

Figure 5.15

Figure 5.16

Figure 5.17

Figure 5.18

Figure 5.19

Figure 5.20

Figure 5.21

Figure 5.22

Figure 5.23

Figure 5.24

Figure 5.25

Figure 5.26

Figure A.1

Figure A.2

Figure A.3

Figure A.4

Figure A.5

Figure A.6

Figure A.7

Figure A.8

Figure A.9

Figure A.10

Figure A.11

Figure A.12

List of Tables

Table 2.1

Table 2.2

Table 3.1

Table 3.2

Table 3.3

Table 4.1

Table 4.2

Table 4.3

Table 4.4

Table 4.5

Table 4.6

Secondary Ion Mass Spectrometry

An Introduction to Principles and Practices

Paul van der Heide

Copyright © 2014 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New Jersey

Published simultaneously in Canada

No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, [phone], fax [phone], or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, [phone], fax [phone], or online at http://www.wiley.com/go/permissions.

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Library of Congress Cataloging-in-Publication Data:

Van der Heide, Paul, 1962– author.

Secondary ion mass spectrometry : an introduction to principles and practices / Paul van der Heide.

pages cm

Includes bibliographical references and index.

Summary: ``This is presented in a concise yet comprehensive manner to those wanting to know more about the technique in general as opposed to advanced sample specific procedures/applications''– Provided by publisher.

ISBN 978-1-118-48048-9 (hardback)

1. Secondary ion mass spectrometry. I. Title.

QD96.S43V36 2014

543′.65–dc23

2014011448

Foreword

Development of the techniques Secondary Ion Mass Spectrometry (SIMS) and Secondary Neutral Mass Spectrometry (SNMS) during the last three decades ranks as one of the most important advances in Chemical Physics and Surface Science.

Information derivable from these techniques is of vital importance in the understanding of the atomic, molecular, ionic, solid-state, and electronic processes that occur at the surface and within the bulk of materials. The dynamics of ion and neutral species, as they approach, penetrate, charge-exchange, diffuse, dissociate (molecules and molecular ions), and sputter some of the substrate atoms, molecules, ions, and clusters, provides a wealth of information. Some of this information cannot be obtained by any other means. Although SIMS is now moving out of adolescence into a stage of maturity, there is still much to be learned about the mechanisms and applications of SIMS and SNMS.

This book provides both a pedagogic function and a research need. The pedagogic function is particularly evident in the early chapters. These chapters are written at the level of senior undergraduates or beginning graduate students with backgrounds in Chemistry, Physics, and/or Engineering. Many spectra and illustrative diagrams are included to exemplify the discussions. The research function is particularly evident in Chapter 3. These chapters contain state-of-the-art quantum mechanical and classical treatments as well as new experimental processes that are at the brink of current research.

The approach has been to amalgamate theory and experiment throughout this book. Both classical and quantum models are used as they are both important in understanding the sputtering, ionization, neutralization, quantification, dissociation, implantation, chemical reactions, and cluster formation that are encountered in the sputtering process.

J. Wayne Rabalais

Distinguished Professor of Chemistry and Physics

Lamar University

P. O. Box 10022

Beaumont, Texas 77710, USA

Preface

Secondary Ion Mass Spectrometry (SIMS) is a microanalytical technique used to understand the composition (isotopic, elemental, and/or molecular) of any predefined microvolume from any solid or made to be solid region. This region can include a solid's surface, the interface between two or more chemically distinct solids, and/or any internal volume of the solid. Some examples of fields in which SIMS has been applied (listed in order of application), or is being introduced to, include:

The Material Sciences. As an example, SIMS is the technique of choice for defining dopant distributions in the semiconductor industry. SIMS is also applied in the energy, plastics, and automotive industries and so on.

The Earth Sciences (Geochemistry, Atmospheric Chemistry, etc.) along with Archeology, Chronology, and Cosmochemistry. Note: SIMS is the benchmark for dating polychronic zircon populations.

The Biosciences inclusive of Pathology and Proteomics, along with Metabolomics, Lipidomics, and Pharmacology. This arises from the ability to image elemental and molecular distributions over submicron regions.

In addition, SIMS has experienced extensive growth and sophistication within each of these divergent fields over the past few decades, with its commercialization resulting in the availability of numerous instrument types and geometries with price tags ranging from several hundred thousand US dollars to several million US dollars. As a result, SIMS is now considered the most heavily used of the ion spectrometries for examining submicron scale regions on or within any solid material.

SIMS derives compositional information by directing a focused energetic ion beam at the surface of interest. These ions, referred to as primary ions, induce the emission of atoms and molecules from the solid's surface, a small percentage of which exist in the ionized state. The emitted ions, referred to as secondary ions, are then collected and passed through a mass spectrometer, hence the name secondary ion mass spectrometry.

The popularity of SIMS stems from its ability to:

measure any isotope of any element (H-U) from any solid (conductors through insulators). Note: Liquids can also be examined if frozen

examine molecular ions exiting a solid's surface along with their fragmentation patterns, with some novel chemical experiments also possible

record many elements/molecules to high sensitivity, high dynamic range, and extensive detection limits (some elements to sub parts per billion levels)

define the location of elements/molecules with a spatial resolution of 1 µm or better and depth resolution values reaching or even exceeding 1 nm

collect the needed data with relative ease and, in most cases, minimal sample preparation.

Indeed, the full potential of SIMS is yet to be realized. As an example, the recent introduction of large cluster primary ion sources has allowed for the mapping of organic molecules in all Three Dimensions (3D) to levels not possible with any other technique. Likewise, the incorporation of Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass filters has allowed for unprecedented mass resolution values (>100,000) to be reached. These are but a few of the new areas being researched.

The areas being researched are probably best exemplified in the types of manuscripts reported at the International Conference on Secondary Ion Mass Spectrometry, i.e. in 1991, over 60% were devoted to atomic secondary ion emissions, where as 20 years later, over 60% covered molecular emissions. This shift also illustrates the maturity in the use and understanding of atomic secondary ion emissions. Indeed, SIMS when used in this manner is applied more heavily than any other area with most applications seen within the industrial sector. Indeed, the refinement of industry-specific practices (in some cases, these are considered intellectual property) has resulted in this form of SIMS being used more like a metrology-based technique.

That being said, SIMS remains a technique lacking a complete understanding of the physics (fundamentals) leading up to the recorded signal. Indeed, there is no one model that describes all secondary ion emissions from all surfaces.

The inspiration for this book arose when teaching both the fundamental and the practical aspects of SIMS. More precisely, this arose on realizing how the collective works and experiences could be funneled into a book that could further facilitate this transfer of knowledge. The premise used in putting together this book was easily attainable answers to all of the questions asked over the years. For example, how is it that SIMS can probe molecular distributions as a function of depth when the sputtering process is known to introduce severe damage to the lattice structure?1 In adhering to this premise, all sections are prepared such that they can be read independently of each other, all equations are presented using the most commonly used units, and all fundamental aspects are discussed using classical analogies, where possible, over the more correct quantum mechanics descriptions.

This book is subdivided into two broad sections following a brief introduction (Chapter 1). These sections cover the following:

Fundamental aspects (Chapters 2 and 3). This not only covers the process of sputtering and ionization (those responsible for secondary ion formation/survival) but also presents a brief description of solids, atoms, and molecules as well as the parameters used in describing secondary ion formation/survival.

Analytical aspects (Chapters 4 and 5). This covers various instrument types, configurations, and setup conditions required for various specific types of analyses encountered. The more common data acquisition modes and data conversion practices in both Static SIMS and Dynamic SIMS are covered.

A brief compilation of other analytical techniques is then presented in Appendix A along with tables and additional concepts of interest to those in the field of SIMS.

The diverse topics covered are presented as simply and concisely as believed possible with the main emphasis given to attaining a practical understanding of all aspects of SIMS. It is also understood that for many analytical applications, knowledge of the underlying theory is not necessary. Knowledge of both is, however, useful in setting up new analytical protocols, examining new areas of application, and of course, in fundamental studies. This knowledge also provides for the ability to recognize, understand, and even predict the nature of various distortions that may be introduced during SIMS analysis. This, in turn, will allow for a more effective translation of the recorded data into maps representative of the original compositional variations.

It is hoped that this book will find use as an effective stepping stone to the wealth of information presently available on this technique, from the numerous journal articles to some of the more detailed books covering more specific application areas. Some examples of existing tests include Time-of-Flight (TOF)-SIMS (Vickerman and Briggs 2012), Cluster SIMS (Mahoney 2013), and SIMS in the Earth Sciences (Fayek et al. 2009). Moreover, there are the general surface analysis texts, with some examples including those by Riviere and Myhra (2009), Vickerman and Gilmore 2009, and O'Conner et al. 2003.

Riviere JC, Myhra S.

Handbook of Surface and Interfacial Analysis: Methods for Problem-Solving

. 2nd ed. New York: CRC Press; 2009.

Vickerman JC, Briggs D.

TOF-SIMS: Surface Analysis by Mass Spectrometry

. 2nd ed. Chichester, UK: IM Publications; 2012.

1

 The possibility of depth profiling organic molecular species, and so mapping such species in all three dimensions, arises from the fact that large cluster ion-induced sputtering can, under optimized conditions, induce the removal of the entire damaged region per sputter cycle (the damaged region resulting from the sputtering event is also minimized) such that the exposed underlying surface is effectively damage free. In addition, many large cluster ions tend to evaporate from the sputtered region during/following the sputtering event.

Acknowledgments

Although this book has profited from many people, there are several, in particular, whose names more than deserve mention. First of all, a special thanks goes to Kim van der Heide for the support provided during the many iterations of this project and for being a first draft editor. Secondly, I need to express a deep level of appreciation to Wayne Rabalais for the invaluable tips, support, encouragement, and discussions provided over the years. Finally, I would like to indicate my gratitude to Paul Ronsheim, Michel Schuhmacher, Nathan Havercroft, Scott Bryan, and Christopher Penley for the useful discussions and additional information.

Thank you all.

List of Constants

Boltzmann's constant

k

B

1.381 × 10

−23

J K

−1

or

8.616 × 10

−5

eV K

−1

Elementary charge

q

1.602 × 10

−19

C

Mass of electron

m

e

9.109 × 10

−31

kg

Mass of neutron

m

n

1.675 × 10

−27

kg

Mass of proton

m

p

1.673 × 10

−27

kg

Planks constant

h = .

2

π

6.626 × 10

−34

J s or

4.136 × 10

−15

eV s

Speed of light

c

2.98 × 10

8

m s

−1

or

2.98 × 10

10

cm s

−1