Molecular Beam Epitaxy: Applications to Key Materials

MOLECULAR BEAM EPITAXY

Applications to Key Materials

Robin F.C. Farrow

IBM Almaden Research Center, San Jose, California

Table of Contents

Cover image

Title page

Copyright

MATERIALS SCIENCE AND PROCESS TECHNOLOGY SERIES

Preface

Contributors

Chapter 1: The Technology and Design of Molecular Beam Epitaxy Systems

1.0 INTRODUCTION

2.0 MOLECULAR BEAM EPITAXY

3.0 MBE SYSTEM DEVELOPMENT

4.0 VACUUM

5.0 MBE COMPONENTS: SOURCES

6.0 MBE COMPONENTS: SHUTTERS AND BEAM INTERRUPTORS

7.0 MBE COMPONENTS: SUBSTRATE HEATER DESIGNS

8.0 TEMPERATURE MEASUREMENT AND CONTROL

9.0 FLUX MONITORING TECHNIQUES

10.0 PREPARATION, DIAGNOSTICS AND ANALYSIS

11.0 MBE SYSTEM DESIGN: RETROSPECT AND PROSPECT

12.0 PROCESS AND SYSTEM AUTOMATION

Chapter 2: Molecular Beam Epitaxy of High-Quality GaAs and AlGaAs

8.0 ISOELECTRONIC AND UNINCORPORATED DOPANTS

9.0 SURFACE PRESERVATION

10.0 PREPARATION OF AN MBE SYSTEM FOR THE GROWTH OF HIGH PURITY III/V SEMICONDUCTORS

11.0 CHARACTERIZATION TECHNIQUES FOR EPITAXIAL SEMICONDUCTOR LAYERS

12.0 IMPURITY ENERGY LEVELS IN GaAs AND AlGaAs

ACKNOWLEDGMENTS

Chapter 3: Gas-Source Molecular Beam Epitaxy: GaxIn1−xAs1-yPy/InP MBE with Non-elemental Sources. Heterostructures and Device Properties

1.0 INTRODUCTION

2.0 CHEMISTRY

3.0 GROUP V GAS SOURCES

4.0 THE MBE AND GAS HANDLING SYSTEMS

5.0 PROCEDURES

6.0 SINGLE BULK LAYERS

7.0 QUANTUM WELL AND SUPERLATTICE STUDIES

ACKNOWLEDGMENTS

Chapter 4: Molecular Beam Epitaxy of Wide Gap II-VI Semiconductor Heterostructures

1.0 GENERAL INTRODUCTION

2.0 CdTe-BASED HETEROSTRUCTURES

3.0 ZnSe-BASED HETEROSTRUCTURES

4.0 SUMMARY

ACKNOWLEDGMENT

Chapter 5: Elemental Semiconductor Heterostructures—Growth, Properties, and Applications

1.0 INTRODUCTION

2.0 GROWTH OF SI1−xGex ALLOYS

3.0 STABILITY OF Si1−xGex FILMS

4.0 LONG RANGE ORDER IN THE SI1−xGex SYSTEM

5.0 DEVICE APPLICATIONS OF Si1−xGex ALLOYS

6.0 CONCLUSIONS

ACKNOWLEDGEMENTS

Chapter 6: MBE Growth of High Tc Superconductors

1.0 INTRODUCTION

2.0 OXIDE MBE SYSTEMS

3.0 SPECIFIC HIGH Tc MATERIALS AND DEMONSTRATED SYNTHESIS CAPABILITIES

4.0 FUTURE DIRECTIONS

5.0 CONCLUSIONS

ACKNOWLEDGMENTS

Chapter 7: MBE Growth of Artificially-Layered Magnetic Metal Structures

1.0 INTRODUCTION

2.0 SEEDED EPITAXY OF MAGNETIC METALS

3.0 STRUCTURAL AND MAGNETIC PROPERTIES OF ARTIFICIALLY-LAYERED MAGNETIC METAL STRUCTURES

4.0 CONCLUSIONS

ACKNOWLEDGMENTS

Chapter 8: Reflection High Energy Electron Diffraction Studies of the Dynamics of Molecular Beam Epitaxy

1.0 INTRODUCTION

2.0 DIFFRACTION GEOMETRY

3.0 DIFFRACTION FUNDAMENTALS

4.0 DIFFRACTION MEASUREMENTS

5.0 SIMPLE GROWTH MODELS

6.0 CONCLUSION

ACKNOWLEDGMENTS

APPENDIX: TWO-LEVEL DIFFRACTION

Index

Copyright

Copyright © 1995 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: 94-31247

ISBN: 0-8155-1371-2

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

Molecular beam epitaxy : applications to key materials / edited by

Robin F. C. Farrow

p. cm.

Includes bibliographical references and index.

ISBN 0-8155-1371-2

1. Molecular beam epitaxy. I. Farrow, R. F. C.

QC611.6.M64M644 1995

621.3815′2–dc20 94-31247

CIP

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, 2nd 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, Second 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

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

MOLECULAR BEAM EPITAXY: edited by Robin F. C. Farrow

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: 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

SEMICONDUCTOR INDUSTRIAL HYGIENE HANDBOOK: by Michael E. Williams and David G. Baldwin

Preface

Molecular beam epitaxy was initially developed by J. R. Arthur and A. Y. Cho[1][2] for growth of GaAs and GaAs/AlxGa1-xAs structures. It has subsequently been extended to an ever-widening variety of materials while maintaining key advantages over other techniques of epitaxial film growth such as chemical vapor deposition (CVD), liquid phase epitaxy (LPE), metal-organic vapor phase epitaxy (MOVPE), and related techniques. These advantages include the ability to control growth reproducibly to atomic monolayer dimensions and to monitor the growth process in real time. For example, the ultra-high vacuum growth environment of MBE makes it possible to study the dynamics of the growth process itself using modulated molecular beam techniques and RHEED (reflection high energy electron diffraction). In addition, other in-situ techniques such as XPD (X-ray photoelectron diffraction) can be used to examine the formation of interfaces and film growth modes.

In this volume, we have set out to describe the use of MBE for a range of key materials systems which are of interest for both technological and fundamental reasons. Prior books on MBE have provided an introduction to the basic concepts and techniques of MBE, and emphasise growth and characterization of GaAs-based structures. Our aim in this book is somewhat different; it is to demonstrate the versatility of the technique by showing how it can be utilized to prepare and explore a range of distinct and diverse materials. The impact of MBE in each of these materials systems has been both beneficial and considerable. In Table 1, milestones in the chronological development of MBE are shown. Those in bold type are topics which form the basis of the chapters of this volume. In each of these areas, MBE is making considerable impact in terms of both devices and solid state physics. In several instances, the discovery of new physical phenomena was made possible by MBE synthesis of specific structures. For example, the observation by Dingle et al.[6] in 1978 of enhanced electron mobility in modulation-doped GaAs led to the subsequent discovery by Tsui et al.[9] of the fractional quantized Hall effect in a two-dimensional electron gas. Similarly, the discovery[14] in 1988 of GMR (giant magnetoresistance) in MBE-grown Fe/Cr multilayers has enlivened the old field of magnetism and magnetic materials, and is leading to GMR-based devices such as rotation sensors and magnetic recording heads. Likewise, MBE techniques permit artificial layering of high-Tc oxide superconducting films and provide a promising route to device structures and metastable phases which are difficult to access by more conventional growth techniques. In the field of II-VI semiconductors, the preparation[15] by MBE of high-conductivity, p-type ZnSe films, utilizing a nitrogen plasma source, provided the technological breakthrough to II-VI blue-green lasers. Similarly, the development of heterostructures of elemental semiconductors has been accelerated by the application of MBE to Si1-xGexSi heterostructures. We hope that the excitement of these developments and their implications is conveyed by the series of chapters in the present volume. Finally, the editor wishes to thank J. R. Arthur for his help and advice in planning this book, and is most grateful for the efforts and time which the contributors have put into their respective chapters.

Table 1

Milestones in the Development of MBE

January 1995

Robin F.C. Farrow,     San Jose, California

REFERENCES

1. Arthur, J.R. J. Appl. Phys. 1968;39:4032.

2. Cho, A.Y. Surf. Sei. 1969;17:494. J. Appl. Phys. 1970;41:2780. J. Appl. Phys. 1971;42:2074.

3. Cho, A.Y., Arthur, J.R. Somorjai, G., McCaldin, J.M., eds. Prog, in Solid State Chem, 10. Pergammon Press: New York, 1975:157.

4. Ploog, K. Freyhardt, H.C., eds. Crystals, Growth, Properties and Appl, 3. Springer-Verlag: Berlin-Heidelberg, 1980:73.

5. Kasper, E., Herzog, H.J., Kibbel, H. Appl. Phys. 1975;8:199.

6. Dingle, R., Störmer, H.L., Gossard, A.C., Wiegmann, W. Appl. Phys. Lett. 1978;33:665.

7. Panish, M.B. J. Electrochem. Soc. 1980;127:2729.

8. See chapter 1 of this volume.

9. Tsui, D.C., Störmer, H.L., Gossard, A.C. Phys. Rev. Lett. 1982;48:1559.

10. Neave, J.H., Joyce, B.A., Dobson, P.J., Norton, N. Appl. Phys. Lett. 1983;A31:1.

11. Van Hove, J.M., Lent, C.S., Pukite, P.R., Cohen, P.I. J. Vac. Sei. Technol. 1983;B1:741.

12. Bean, J.C., Feldman, L.C., Fiory, A.T., Nakahara, S., Robinson, I.K. J. Vac. Sei. Technol. 1984;A2:436.

13. People, R., Bean, J.C., Lang, D.V., Sergent, A.M., Störmer, H.L., Wecht, K.W., Lynch, R.T., Baldwin, K. Appl. Phys. Lett. 1985;45.

14. Webb, C., Weng, S.-L., Eckstein, J.N., Missert, N., Char, K., Schlom, D.G., Hellman, E.S., Beasley, M.R., Kapitulnik, A., Harris, J.S., Jr. Appl. Phys. Lett. 1987;51:1191. Kwo, J., Hsieh, T.C., Fleming, R.M., Hong, M., Liou, S.H., Davidson, B.A., Feldman, L.C. Phys. Rev. 1987;B36:4036.

15. Binasch, G., Grunberg, P., Saurenbach, F., Zinn, W. Phys. Rev. 1989;B39:4828. Saurenbach, F., Barnas, J., Binasch, G., Vohl, M., Grunberg, P., Zinn, W. Thin Solid Films. 1989;175:317. Van Dau, F.N., Fert, A., Etienne, P., Baibich, M.N., Broto, J.M., Chazelas, J., Creuzet, G., Friederich, A., Hurdequint, H., Redoules, J.P., Massies, J. Journale de Physique. 1988;49:C8–1633. Baibich, M.N., Broto, J.M., Fert, A., Nguyen Van Dau, F., Petroff, F., Etienne, P., Creuzet, G., Friederich, A., Chazelas, J. Phys. Rev. Lett. 1988;61:2472.

16. Park, R.M., Troffer, M.B., Rouleau, C.M., De Puydt, J.M., Haase, M.A. Appl. Phys. Lett. 1990;57:2127.

17. See Ch. 2 of this volume.

Contributors

Philip I. Cohen,     Department of Electrical Engineering, University of Minnesota, Minneapolis, Minnesota

Robin F.C. Farrow,     IBM Almaden Research Center, San Jose, California

Robert L. Gunshor,     School of Electrical Engineering, Purdue University, West Lafayette, Indiana

Gerald R. Harp,     Department of Physics, Ohio University, Athens, Ohio

James S. Harris, Jr.,     Department of Electrical Engineering, Stanford University, Stanford, California

Subramanian S. Iyer,     IBM Thomas J. Watson Research Center, Yorktown Heights, New York

Vijay P. Kesan,     IBM Thomas J. Watson Research Center, Yorktown Heights, New York

Leslie A. Kolodziejski,     Department of Electrical Engineering and Computer Science, Massachusetts Institute of Technology, Cambridge, Massachusetts

Richard A. Kubiak,     The Department of Physics, University of Warwick, Coventry, England

Eric C. Larkins,     Department of Electrical Engineering, Stanford University, Stanford, California

Ronald F. Marks,     IBM Research Division, Almaden Research Center, San Jose, California

Simon M. Newstead,     The Department of Physics, University of Warwick, Coventry, England

Arto V. Nurmikko,     Division of Engineering and Department of Physics, Brown University, Providence, Rhode Island

Nubuo Otsuka,     Materials Engineering, Purdue University, West Lafayette, Indiana

Morton B. Panish,     AT&T Bell Laboratories, Murray Hill, New Jersey

Stuart P. Parkin,     IBM Research Division, Almaden Research Center, San Jose, California

Gale S. Petrich,     Department of Electrical Engineering and Computer Science, Massachusetts Institute of Technology, Cambridge, Massachusetts

Thomas A. Rabedeau,     Stanford Synchrotron, Radiation Laboratory, Stanford, California

Darrell G. Schlom,     Department of Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania

Philip Sullivan,     Fisons Instruments Inc., Danvers, Massachusetts

Henryk Temkin,     Electrical Engineering Department, Colorado State University, Fort Collins, Colorado

Michael F. Toney,     IBM Research Division, Almaden Research Center, San Jose, California

Dieter Weller,     IBM Research Division, Almaden Research Center, San Jose, California

Gregory J. Whaley,     Phillips LMS, Colorado Springs, Colorado

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.

1

The Technology and Design of Molecular Beam Epitaxy Systems

Richard A. Kubiak, Simon M. Newstead and Philip Sullivan

1.0

INTRODUCTION

In essence, MBE is little more than a UHV-based evaporation method. In practice, it is a material deposition technique capable of predictably and reproducibly yielding material with impurity levels below ten parts per billion, with unprecedented control over the precision with which the composition and doping of the structure can be tailored.[1]–[10] Some of these attributes are intrinsic to the MBE process, e.g., slow growth rates and low deposition temperatures. Others, such as material quality and purity, rely on the technology employed.

Much of the rapid development of MBE, particularly in the last five years, can be ascribed to the willingness of manufacturers of vacuum equipment to come to grips with the complex and often unique instrumentation involved.[11] In particular, the rapid changes in market requirements from custom-made special ultra-high vacuum evaporators to dedicated high-throughput MBE instruments have been effectively challenged, and the results have met with considerable success within the semiconductor industry. In this chapter, we chart the progress made in MBE system technology and thereby illustrate current design practice. The development of MBE related components, system geometries, and the MBE process will be covered. Although the physics of growth mechanisms and growth methodology are dealt with elsewhere in this book, we briefly consider these aspects where pertinent to the discussion. Where rigorous referencing is difficult, the authors unashamedly draw from their own biased experience.

2.0 MOLECULAR BEAM EPITAXY

To put in perspective the technology discussed in this chapter, we briefly consider the MBE process and those epitaxial materials currently being addressed.

MBE involves the generation of fluxes of constituent matrix and doping species (molecular beam) and their reaction at the substrate to form an ordered overlayer (epitaxy). Figure 1 shows a schematic representation of the process, and its components. Elemental or compound constituents are heated (if in the liquid or solid state) or introduced (if gaseous) to cause mass transfer from the flux generators to the substrate, via the vapor phase. To maintain the high purity and integrity of the deposit, stringent vacuum conditions are needed. MBE is essentially a line-of-sight technique from source to substrate, and the fluxes of constituents (and thus the composition of the material perpendicular to the growth direction) can be temporally modulated either by altering the evaporation/introduction conditions, or by physically interrupting the beam using rapid-action mechanical shutters.

Figure 1 Schematic representation of the MBE process and control interface. The evaporation procedure, flux incidence on the substrate, vacuum, and process diagnostics are controlled by a supervisory operator or computer. The MBE process is supplemented by ex situ substrate preparation and wafer introduction procedures.

A key attribute of MBE is the precision with which the composition and doping of a structure can be tailored, such that atomically abrupt features can be produced. Examples are to be found throughout this book. To achieve this level of control within realistic time spans, deposition rates centered around one atomic layer (a monolayer) per second are used. This places constraints on the operational temperatures of sources, and the speeds with which shutters are required to operate.

From the above, the key features to be addressed in a discussion of technology associated with the MBE process are:

1. Vacuum requirements

2. MBE components

• sources

• shutters

• substrate heating and manipulation

3. MBE diagnostic and analytical facilities

However, to offer a viable MBE process, other pertinent areas include:

4. Factors governing MBE chamber design

5. Throughput considerations

6. Automation

7. Modern manufacturing methods

This chapter deals with the design of components and systems used in MBE. Unfortunately, a generic MBE system configuration does not exist, since this depends on the nature of the deposit and the behavior of the constituent source materials. Nevertheless, Table 1 identifies three methodological areas into which most MBE activities can be categorized, and gives examples of material systems to which each area applies. Also included in Table 1 is a list of the sources encountered in each area (though all are not required for a given material system), and the section in which they are described in this chapter.

Table 1

Types of source employed in each of the three methodological divisions of MBE (a particular application would not usually require the use of all types of source listed within the appropriate division).

Notes: 1. HTCSC = High Tc superconductors

2. Temperatures are maximum values

The most active area of MBE is in GaAs/AxGa1−xAs applications deposited using conventional condensed phase (solid or liquid) sources. A schematic of a commercially available III-V:MBE system, described in detail in subsequent sections, is shown in Fig. 2. The equipment used also lends itself to epitaxy of other III-V, II-VI and IV-VI semiconductors, provided that the vapor pressures of the source materials at temperatures below 1200°C are sufficiently high for evaporation from K-cells (effusion furnaces). The evaporation plane in these systems is near-horizontal so that the sources are angled to prevent stray deposits (e.g., from chamber walls and shutters) from falling vertically into the crucible. The severity of this problem has not, however, been demonstrated. The current generation of III-V:MBE systems is capable of accommodating standard 50 mm and 75 mm wafer sizes processed individually. More recently, 100 mm capability has become available, also offering the possibility of depositing onto three 50 mm wafers simultaneously. Larger scale systems are discussed in Sec. 12.

Figure 2 Schematic of a III-V:MBE system. The deposition chamber on the left is fitted with up to 8 thermal effusion (K-cells) and other sources (see Secs. 5.1, 5.2, 5.3, 5.5, and 5.6) configured to achieve optimal uniformity of deposit (see Sec. 12). Shutters (Sec. 6) can interrupt the flux to yield rapid changes in composition or doping. The deposition chamber is connected via an in-line gate valve to the preparation chamber, in which substrate storage and diagnostics can be performed, and to a fast entry chamber (Secs. 2 and 3). Ultra high vacuum conditions are maintained throughout the system to achieve high material quality (see Sec. 3). The MBE system shown handles platens capable of accommodating one 100-mm, one 75-mm or three 50-mm wafers. (Courtesy VG Semicon.)

The second methodological area of MBE activities relates to deposition of III-V’s using gaseous source materials, Gas Source MBE. This new technology offers a variety of potential advantages over conventional MBE in terms of control and accuracy over fluxes, indefinite source material lifetime, and suitability to scaling. In general, conventional III-V:MBE systems are used for GSMBE with the K-cells replaced by gas effusion and hydride cracker sources, and appropriate pumping for the process added. This approach does not necessarily represent the optimum system design for this technology, but no doubt the recent increase in activity in the area can largely be ascribed to the ease with which gas sources can be retrofitted to conventional MBE systems.

The remaining MBE activities relate to materials requiring source temperatures in excess of those attainable with K-cells, necessitating electron beam evaporation (MBE of Si and related materials, metals, and superconductors). By their nature, electron beam evaporators dictate the need for a vertical evaporation geometry, with the substrate in the horizontal plane. This permits the substrate to be maintained in the horizontal plane throughout the MBE system, providing simplified handling of the larger wafer sizes, particularly in the case of Si:MBE (75 to 200 mm diameter). A schematic of a Si-MBE system is shown in Fig. 3.

Figure 3 Schematic of an MBE system used for deposition of Si and related materials, metals, and superlattices. The matrix evaporation sources are electron beam evaporators (Sec. 5.4), although thermal effusion (Sec. 5.1), ion beam (Sec. 5.7) and other species specific (Sec. 5.1) sources can be fitted for matrix and doping flux generation. The deposition geometry is configured to achieve optimal uniformity of deposit (see Sec. 12). Shutters (Sec. 6) can interrupt the flux to yield rapid changes in composition or doping. The deposition chamber is connected via an in-line gate valve to the preparation chamber, in which substrate storage and diagnostics can be performed, and to a fast entry chamber (Secs. 2 and 3). Ultra high vacuum conditions are maintained throughout the system to achieve high material quality (see Sec. 3). The MBE system shown handles wafers up to 150 mm diameter without the need for wafer holders. (Courtesy VG Semicon.)

3.0

MBE SYSTEM DEVELOPMENT

To aid in an understanding of current MBE methodology and system designs (such as shown in Figs. 2 and 3), it is useful to take a brief look at the historical development of the MBE process.

The first MBE systems incorporated evaporation and substrate heating facilities, and some diagnostic and analytical equipment into a single stand-alone vacuum chamber. In many respects, the MBE sources employed were natural developments of high vacuum precursors, refined to ensure compatibility with the UHV environment. The presence of diagnostic and analytical equipment expedited improved understanding of the epitaxial processes involved (just as use of these techniques today offers assistance to the MBE practitioner in establishing optimized or reproducible deposition conditions). Deposition sample areas used in the early systems were small (typically less than several cm²). The small source volumes employed (several cc’s) were adequate when replenished each time the system was vented for the loading of a new substrate. Aside from limiting throughput of samples (to a maximum of one sample a day for the most agile of operators!), the need for air exposure of the system between each deposition run resulted in poor and irreproducible material quality[12][13] because system venting contaminated the sources, precluded a thorough de-gassing of sources prior to growth, and exposed the substrate to a poor vacuum during system bake-out.

Borrowing from the technology of other vacuum processing, throughput and material quality were improved by use of a Fast Entry Lock (FEL) for introduction of substrates into, and removal of processed samples from, the MBE deposition region.[14] A valve between the FEL and deposition chamber ensured high vacuum integrity in the deposition region while the FEL was vented to air. Transfer of samples between the two vacuum chambers was performed when the pressure in the FEL was better than 10−6 mbar. Although several methods of sample transfer were reported (such as insertion of substrate manipulators into the deposition region,[15] and transfer of entire substrate heater assemblies,[14] the preferred methods proved to be those which required introduction of the substrate and a minimal substrate holder (if any at all), thus minimizing contamination of the deposition environment by outgassing of air-exposed surfaces. With this development, the UHV lifetime of the MBE system became limited only by cell depletion times, typically extending to several tens of microns of material. Reliability of MBE components became of paramount importance!

In addition to dramatically enhancing throughput and the convenience of system operation, the use of FEL’s significantly improved material quality. The substrate manipulator, source cells and materials were held under vacuum for extended time periods (typically several weeks) leading to thorough outgassing. K-cells could be maintained at temperatures 50 to 100°C below their normal operating range when not in use, preventing recontamination by residual gases, and extending crucible lifetime for such materials as Al, which tends to crack boron nitride crucibles if it is allowed to solidify rapidly. Substrates were no longer subjected to extended bake-out periods, but were introduced into the clean deposition area as required. The benefits of load-locked operation are apparent in modern MBE systems, in which the first few samples grown after system bake-out provide for conditioning of the system, with higher quality material being achieved during the second, third or subsequent growth runs.[16][17]

Recent MBE system designs[10] interpose a preparation chamber between the deposition chamber and FEL, as shown in Figs. 2 and 3. Samples are no longer introduced into the FEL individually, but in batches of typically ten. After evacuation of the FEL, the samples are transferred into the preparation chamber parking stage, where, once the FEL has been isolated, they are stored under UHV conditions. Transfer of a sample into the deposition chamber thus does not require exposure of the air-exposed FEL to the deposition chamber, minimizing contamination of the deposition environment. The preparation chamber also provides a UHV environment in which samples can be pre-processed (e.g., heated to sub-growth temperatures to de-gas the sample) or analyzed.

Component-specific load-locks have also been used for MBE component maintenance. For example, the UHV lifetime of III-V:MBE can be extended by reloading the most rapidly depleted sources (usually As and P). Retraction of these sources into small volume load-lock chambers that can be isolated from the deposition chamber with a valve, permits venting and reloading of the cell without disturbing the deposition environment. Before reinsertion into its deposition position, the load-lock station may be briefly baked, and the source cell de-gassed. Most MBE practitioners would still bake the entire system to ensure vacuum cleanliness after reintroduction of the source cell. The use of component load-locks can expedite simplified and rapid system turn-round, and maintain high material quality, since all other components remain outgassed under UHV.

Another lesson transferred from high vacuum deposition techniques to increase throughput in MBE systems is use of substrate movement. The simplest form of motion, namely rotation, is used in MBE.[18] (More complex motions such as planetary[19] are avoided in MBE, even for multi-wafer systems, due to the limitations in bearing lubrication technology in UHV, see Sec. 4.2) Sample rotation significantly improves the uniformity over the sample areas used,[18][19] and, even for non-optimized source/substrate geometries, increases the area over which acceptable deposition uniformity occurs. The optimization of MBE system geometries is discussed in Sec. 11.

4.0 VACUUM

4.1 Vacuum Requirements for MBE

Vacuum provides a unique environment in which materials can be prepared, characterized, and modified, and thus plays an important role in a wide range of technologies.[20]–[30] The quality of the vacuum required (i.e., both the residual gas pressure and its composition) depends on the influence of the residual gases on the process. It is instructive, therefore, to consider the vacuum requirements for MBE.

The behavior of gases as a function of pressure is described by the Kinetic Theory of Gases.[31] This yields important relationships between gas pressure, molecular density, the mean-free path of molecules (the distance they travel between collisions with one another), and the impingement rate of molecules on a surface (such as the chamber walls, or a substrate); see Fig. 4. A useful reference unit is the monolayer, which corresponds to coverage of a flat surface by one atomic layer. Given that a flat crystalline surface has between 10¹⁴ and 10¹⁵ atoms cm−2, Fig. 4 indicates that a pressure of approximately 10−6 mbar corresponds to an impingement rate which would lead to addition of one monolayer in one second, if all incident species (assumed to be atoms) adsorbed onto the surface. In general, residual gas species are sufficiently volatile not to adsorb onto a surface. However, in the case of a newly deposited surface, free chemical bonds can enhance the adsorbtion of residual gases, leading either to their incorporation as an impurity, or to disruption of the growth process.

Figure 4 The relationship between the fundamental units encountered in vacuum technology.

Given that the growth rates used in MBE correspond to approximately 1 monolayer sec−1 the pressure levels required during MBE can be estimated. As an example, let us consider the requirements for the level of carbon in MBE-grown GaAs. C is a common component of several major residual gases (CO, CO2, CH4 and other hydrocarbons), and is also an effective p-type dopant and deep level in GaAs. For many device applications, C levels in GaAs below 10¹⁴ cm−3 are required, i.e., an impurity level of 1 atom in 10⁸. Taking this worst case as the ratio of the impingement rates of C-bearing residual gas species (i.e., 10−6 of a monolayer sec−1) and growth species (1 monolayer sec−1), a maximum permissible pressure of C-bearing gases in the vacuum of 10−6/10−8 = 10−14 mbar or below is indicated.[3] The sticking coefficients of C-bearing species are fortuitously much less than unity, and although total permissible pressures perhaps as high as 10−11 mbar could be tolerated, even this level represents an exacting requirement of vacuum quality. Similar arguments apply to incorporation of all other residual gas constituents in any MBE-deposìted material. In practice, then, MBE practitioners cannot afford to permit any compromise in achieving clean UHV conditions. Indeed, it is the availability of the UHV environment which makes MBE essential to many deposition processes, particularly in semiconductor applications where the purity of the material is paramount. Furthermore, MBE practice involves care in siting and use of hot filaments (e.g., ion gauges) relative to the growth region to minimize the presence of excited gas species with potentially enhanced reactivities with the depositing surface.[4]

4.2 The Ultra-High Vacuum System

There are potentially four major sources of gas in a vacuum system:

1. High vapor pressure materials, and materials with poor thermal or chemical stability. These can generally be discounted, because materials used in construction of MBE systems are selected to ensure high vacuum quality (i.e., minimized partial pressures of deleterious species). Nevertheless, the MBE process may necessitate use of high vapor pressure source materials (e.g., As and P in III-V:MBE), which may lead to cross contamination of sources, and impart a high load on the pumps.

2. Gas adsorbed onto surfaces during air exposure. This is the main source of concern in achieving UHV. A surface exposed to air accumulates several monolayers of chemisorbed and physisorbed gases (see Fig. 5),[19][25][29][30] which slowly de-gas, precluding rapid pump-down of the vacuum system. Several hours, or even days, may be necessary to achieve pressures below 10−7 mbar (depending on exposure history). Therefore, UHV systems are routinely baked[21][30] after each air exposure to temperatures of about 250°C, to accelerate the desorption, leaving, after eight hours or more, a conditioned low vapor pressure surface. On cooling to ambient temperatures, pressures of the order of 10−11 mbar and below can be achieved. An alternative method of stimulating gas desorption from vacuum surfaces (particularly water vapor) is irradiation with UV light.[32] This method alone cannot achieve the stringent UHV levels required within the MBE deposition chamber, but is useful for speedy de-gassing of entry locks and introduced wafers. Venting of vacuum systems to dry nitrogen rather than air greatly reduces gas adsorption, and reduces the times needed for pumping, baking, and de-gassing the components. MBE components which need to be operated at high temperatures (e.g., filaments, source cells) are outgassed at temperatures higher than those of operation (but, in the case of source cells, within the vapor pressure constraints of the source materials) either during bake-out, or just prior to use.

Figure 5 A representation of the coverage of gases sorbed onto an air-exposed stainless steel surface. The uppermost water-rich layer is weakly physisorbed and is easily removed by baking at temperatures below 120°C, or by irradiation with UV light. The remaining chemisorbed gases necessitate higher temperatures (in excess of 200°C) to promote efficient desorption, or reaction with the stainless steel to form a stable low vapor pressure surface. Gases dissolved in the near surface of the stainless steel are also removed by baking.

3. Dissolved gases or impurities within the constructional materials which diffuse to the surface and desorb. Such materials can be conditioned by heating in vacuo, as #2 above. The generation of hydrogen during evaporation of Si and metals under UHV is an example.

4. Poor vacuum integrity due to leaks. This is addressed by employing suitable constructional materials and methods.[21]–[30] Early UHV systems were manufactured from glass or quartz.[20] However, the need for easy access into the larger chamber volumes in current use (which imposes large stresses on chamber walls due to the pressure differential) has stimulated the maturation of a UHV technology based on stainless steel,[21]–[30] and, more recently, aluminum alloys.[28][30][33] Access into the chambers is facilitated by removable flanges.[25]–[27] Small flanges (usually up to 300 mm port size) use flat copper gaskets as a seal, into which knife-edges on the flanges bite, known as Conflat seals. Larger flanges are generally compression seals, using annealed Au, Cu, or Al wire rings. To minimize outgassing, chambers are often internally electropolished which reduces the vacuum surface area by between two and five times. Argon-arc welding of stainless tubes or plates to form chambers minimizes inclusions and oxidation at welds, and realizes high weld penetration to ensure strength, absence of leaks and low permeability.[27][30] Grades of stainless steel are selected for high molybdenum (e.g., 316 grade) and low carbon (e.g., 304 and 316 grades) content to minimize chromium diffusion at welds.[27][30]

Chambers and pumps are interconnected by valves which permit isolation of the various sections of the system (e.g., of the pump during chamber venting). Several types of valves have been developed, capable of withstanding many resealing cycles (in the range 100–30,000 depending on the design constraints). Valves with metal (copper, gold or silver) sealing faces are used where the valves need to be closed during bake-out. For example, between the chambers and permanently plumbed roughing lines (which are outside the bake-out zone), small conductance (up to 100 l/s) right angle valves permit bake-out of the entire UHV portion of the system. To stop oxidation of the sealing material, both sides of the valve must be maintained under vacuum during bake-out. Since transfer of samples between chambers requires linear motion usually through large apertures to accommodate current wafer sizes (typically 100–300 mm diameter), so-called gate valves are employed. Although these gate valves are of all-metal construction to ensure UHV comparability, elastomer O-rings are most frequently used for valve sealing.[35][36] The most commonly used O-ring material, Viton, can be baked to temperatures of 250°C provided not in compression, i.e., the valves need to be open during bake-out. Being reasonably soft, and having a small compression set, Viton is tolerant of ingress of evaporant dust (present in large quantities in MBE). Being of narrow cross-section (100–150 mm between flanges), gate valves also have high conductances making them ideal for valving pumps. Gate valves with metal sealing rings are also available for applications necessitating valve closure during bake-out, for example to preclude cross-contamination between chambers. Such all-metal valves are prone to leaking due to ingress of evaporant dust, and large bore metal sealing gate valves needed for pumping and sample transfer (150 mm and larger) are costly. Other materials, potentially offering the benefits of both metal and elastomer seals (e.g., Kalrez) are under investigation.[35][36]

Other key components (e.g., electrical, water, liquid nitrogen and rotary/linear motion feedthroughs) conform to conventional UHV practice.[37] Viewports, which are used for process and sample transfer observation and pyrometry, are generally shuttered with a mechanical flap to prevent ‘fogging by evaporant species. Kodial or a similar borosilicate glass is generally used. However, glassware has been shown to generate volatile boron compounds[38] for which the SiO2 surface of Si wafers has an affinity. The boron compounds do not desorb during oxide removal, and can lead to p-type doping at the substrate/epilayer interface in Si:MBE.P⁹l Quartz viewports (employing direct quartz to metal seals, and not graded through glass) eliminate the B-doping problem,[39][40] but large quartz viewports capable of withstanding bake-out temperatures of 250°C are expensive. The use of other types of glass, or of transparent viewport coatings may provide a simpler solution. Glass provides a versatile electrical insulation material for conductors and components operating at temperatures below 300°C (except in Si-MBE for the above reason). The choice of suitable, stable and low vapor pressure metals for use as heater filaments and heat shields is restricted to refractory elements such as tungsten, tantalum, and molybdenum. These are available at purities better than 99.9%, and in various forms including wire, rod, and foil. Tungsten is extensively used for filaments, but is unsuitable for K-cell and other applications containing confined heaters because, being brittle, thermal stressing can lead to failure. Tantalum, which is less affected by thermal cycling, has become more commonly used for these heaters. Tantalum can be easily welded. Of the three metals, molybdenum is the least difficult to machine, and is thus used for larger support components and threaded components (e.g., nuts and bolts). Mo looses its machinability after thermal cycling, cannot be welded, and requires more thorough outgassing than W or Ta due to formation of volatile oxides. Mo material has to be selected for MBE usage, since commercially available Mo formed by sintering is laminar and difficult to outgas thoroughly. Arc cast" Mo is preferred. Other refractory metals, e.g., rhenium, are prohibitively expensive. The key vacuum, mechanical and electrical characteristics of these metals can be found in Refs. 21–30.

Insulation of filaments (e.g., inside K-cells and substrate heaters) has been performed using quartz, beryllium oxide, alumina, and hot pressed boron nitride. Unfortunately, these materials have been shown to contribute contaminant fluxes in MBE environments[41]–[43] due to thermal and chemical (e.g., reduction by the filaments) instability, or the presence of volatile impurities (e.g., BO in BN). Pyrolytic boron nitride[44] (pBN) is now used almost exclusively as an electrical insulator in contact with or near heaters. pBN is considerably less convenient than alumina, because the method of manufacture (pyrolysis in a CVD reactor) permits only simple shapes, and fine dimensional tolerance is difficult to achieve. pBN is also soft, brittle, and delaminates under mechanical stress. Despite these shortcomings, pBN is a near ideal material for MBE by virtue of its high purity, chemical and thermal stability, and non-porous structure. Nevertheless, care is required during extended high temperature treatment to prevent contamination of pBN caused by decomposition of C-bearing species from the residual gases.[45] Some care is required in its use in Si:MBE, since some thermal/chemical decomposition occurs at temperatures above 1300°C, which can lead to B-doping.[46]

The need for motion (e.g., substrate rotation, sample movement around the UHV system) necessitates bearings capable of sustained operation in UHV for both the manipulator and rotary feedthrough. All-stainless-steel ball races are available, compatible with the UHV environment and high temperature bake-out. Unfortunately, greases and other lubricants developed for high vacuum (down to 10–8 mbar) are not compatible with the clean, hydrocarbon-free environment required for MBE, and proprietary bearing lubrication processes have been developed by most UHV companies. Also bearings using dissimilar metals are becoming available. The need for high-speed rotation of ever increasing sizes of substrate platens poses a challenge to MBE practitioners and manufacturers alike. These are however being addressed as discussed in Sec. 8.

4.3 Pumping

Aside from sources of gas in vacuum systems, the other factor influencing the level of vacuum attainable is the efficacy of pumping. The ideal UHV pump would have a high pumping speed for all gases (i.e., would be non-selective) and would itself not contribute to the gas load in the system. For MBE, pumping is achieved by combination of several pumps, aimed at eliminating the most damaging gaseous components and dealing with technology-specific gas loads, for example, H2 in GSMBE. Pumps fall into two classes, primary pumps used to achieve and maintain UHV under quiescent conditions, Table 2, and secondary pumps, which provide pumping appropriate to the process, Table 3. In many instances, the same pump provides both functions.

Table 2

(a). Primary UHV capture pumps used in each methodological division of MBE.

Table 3

Secondary UHV pumps, fitted to deal with process-specific gas loads and to provide highly effective pumping of condensable vapors.

Primary pumps (Table 2) are of two types. Capture pumps collect gas by gettering/implantation (sputter ion[26][47][48] and titanium sublimation[26][30] pumps) and freezing of the gas (cryo-pumps[49]–[53]); the gas remains trapped within the UHV system pump. Throughput (diffusion[22][26][30][54]–[56] and turbomolecular[28][57]–[59]) pumps compress the vacuum gas to a vented outlet held at 10³ mbar or below, where it is removed by a backing pump. Detailed discussions of their operation can be found in the expert texts referenced above. UHV pumps are normally connected to UHV chambers via high conductance valves[34] which permit isolation and continued operation of the pumps while the UHV chamber is vented to air. The merits of this arrangement are in maintaining cleanliness of the pump, promoting easy and rapid pumpdown, and, if automated, serving as a safety barrier in case of vacuum or pump failure (e.g., to prevent oil contamination from turbo or diffusion pumps).

Table 2

(b). Primary UHV throughput pumps used in each methodological division of MBE.

As is apparent from Tables 2 and 3, the upper pressure at which most UHV pumps will operate is approximately 10−3 mbar. Table 4 lists the pumps available for evacuation of vacuum systems to this level and for backing throughput pumps, and presents their characteristics. Rotary pumps[23][26][30][60] are generally not used for roughing MBE systems due to the potential for oil contamination by backstreaming. Liquid nitrogen cooled sorption pumps[23][30][61] provide for oil-free evacuation, although care is needed to ensure that sorbate dust does not enter the UHV chamber. The large volume of MBE chambers necessitates two or more sorption pumps to be used sequentially for evacuation to below 10−3 mbar. Alternatively, the chambers can be pre-evacuated to approximately 100 mbar (removing 85% of the gas) prior to sorption pumping by use of compressed-air Venturi or oil-free rotary vane pumps. The use of pre-evacuation can greatly expedite the speed, cleanliness, and cost of evacuation. Evacuation (and venting to air) is performed slowly to minimize turbulence (at pressures between atmospheric and 50 mbar), which could cause contamination of sources due to redistribution of particles of deposit or dust.

Table 4

Roughing and Backing Pumps. Combinations of roughing pumps are used to evacuate chambers to the pressures at which primary UHV pumps can operate (∼10³ mbar, see text). Backing pumps are used to clear the gas loads at the outlets of throughput-type primary UHV pumps.

Tables 5 and 6 summarize the most common combinations of pumps used in the deposition and appendage chambers respectively, in the three methodological areas of MBE. With the exception of gas source MBE (and systems handling phosphorus or mercury), primary pumping by ion-sputter plus titanium sublimation pumps (TSP) suffice to achieve UHV. There is some evidence that operation of TSP filaments during MBE deposition can be detrimental to III-V[62] and Si[63] material quality, although whether this is inherent to TSP operation, or circumstantial, is unclear. The provision of secondary pumping via liquid nitrogen cryopanels is essential for many MBE processes (see Sec. 4.4), and further addition of a cryopump helps to minimize partial pressures of other damaging residual gas species (e.g., CO, CH4). In some cases (e.g., Si:MBE) cryopumps have been successfully used as the primary UHV pump.[51][52] To date, throughput pumps have generally, though not always,[64] been avoided in MBE due to the potential for oil contamination of the deposition environment. The recent development of oil-free turbomolecular (using magnetic levitation of the rotor) and rotary pumps[65] removes this objection (albeit presently at high cost).

Table 5

Common combinations of growth-chamber pumping used in the three methodological divisions of MBE.

(Most frequent pump listed first. Common additions or options in parentheses. Additions indicated by *.)

Table 6

Common pumping arrangements for ancillary MBE chambers.

For gas source MBE (and solid source MBE of P-bearing materials), the high gas loads of process gases and hydrogen, and the toxic nature of the gas products necessitates throughput pump use. The safety aspects associated with handling of the toxic and pyrophoric source gases necessitate stringent safety procedures and exhaust scrubbing. The process gases are corrosive and degrade oils and bearings, therefore turbomolecular and rotary pumps are provided with nitrogen gas ballast to dilute the gases, and specially selected oils to maximize service times (typically between 1 and 3 months depending on throughput and type of source gas). To further assist rotary pump operation, phosphorus and metal-organic trapping is performed in the backing line using molecular sieve and activated charcoal, and the backing line is designed to permit easy servicing of the filters and pumps. Diffusion pumps using polyphenylether oils (such as Santavac 5) have been found to be resistant to corrosion from most process gases encountered in GSMBE. The availability of oil-free turbo-molecular and rotary pumps may expedite future development of simpler pumping systems for these processes.

MBE of materials containing mercury presents unique problems due to the large volumes of Hg needed for growth. Mercury diffusion pumps are employed.

4.4 Cryopanelling

Liquid nitrogen cryopanels provide very large pumping speeds for condensable gases, particularly H2O and heavier hydrocarbons, and also, though less effectively, for CO2.[66] Provision of extensive cryopanelling surrounding the deposition region is an essential secondary pump for achieving high quality with some materials,[1]–[7] e.g., Al-bearing compounds are water sensitive. Cryopanelling is therefore a key design requirement for MBE systems used in the first two methodological areas presented in Table 1. The whole deposition region is surrounded by cryopanelling, with minimal apertures provided for access of components and for substrate transfer. Careful design of the MBE geometry is needed to preclude localized heating of the cryopanel by sources, and of the cryopanel to ensure wide channels for effective liquid nitrogen flow and escape of nitrogen gas. Hot spots, caused by trapping of thermally insulating gaseous nitrogen behind the stainless steel (which itself has a poor thermal conductivity), can attain temperatures in excess of 400°C; Mn-doping of GaAs has been observed due to local heating of a cryopanel.[41][42] This effect can be circumvented by forcing liquid nitrogen flow through the panels. Care is required in construction of the cryopanel, ensuring adequate strength to withstand frequent thermal cycling from 77 K to ambient (and occasional bake-out) temperatures.

In applications employing electron beam evaporators (the third area of MBE presented in Table 1), the need for liquid-nitrogen cooled cryopanels remains controversial, even if adequately designed to tolerate the significantly higher thermal loads encountered. In Si:MBE, liquid nitrogen cryopanelling is ineffective at collecting the main gas load (H2) and with the most material-damaging gas species (CO and CH4). Furthermore, those residual and outgassed species condensed on the cryopanel can be liberated during process by electron-induced desorbtion stimulated by reflected and secondary electrons from the electron beam evaporators, giving rise to artificially high partial pressures during process.[63][67] Another problem with certain materials, notably Si, is the formation of loose powdery deposits on liquid-nitrogen cooled surfaces, which migrate around the vacuum vessel due to poor adhesion. The fine dust thus generated can become charged, again due to electrons in the chamber, and adhere to Si substrates, giving rise to defects.[68] In these applications, water cooled panels are considered preferable by some, though by no means all, manufacturers and users, since build-up of outgassed species does not occur within the deposition region, and more stable deposits accumulate. The water cooling does, however, need to be very efficient to preclude occurrence of hot spots on the chamber wall or panel, and thereby ensure adequate gettering of volatile dopants, as used in MBE of Si and related materials. The use of closed-loop refrigerators with water/methanol (or glycol) mixture can improve cooling efficiency by proving sub-zero (centigrade) temperatures to the panels. Nevertheless, primary and secondary pumping external to the deposition area must be enhanced to compensate for the loss of the liquid nitrogen surface.

4.5 System Manufacture

A great deal of care is excercised by MBE practitioners and manufacturers to achieve the clean vacuum conditions necessary for MBE. Chamber materials (stainless steel sheet and tube) are cleaned after each stage of handling and machining, particularly prior to welding stages to preclude inclusions. The completed chambers are thoroughly degreased using solvents and proprietary procedures[25][69] (often based on methods developed originally for the vacuum valve industry) and checked for leak-tightness an all welds.

Typically, MBE system construction starts with assembly of chambers and pumps onto their support frames. During construction, care is exercised in handling the vacuum components (chambers, cryopanels, pumps, etc.) to avoid contamination from oil, grease, or by human contact. A semi-clean environment is employed, consistent with the need for heavy equipment, e.g., hoists. With the exception of ion gauges and a mass spectrometer, all ports are fitted with blank flanges, and after leak checking, the system is baked at 250°C or higher, preferably into an external coupled UHV pump. On achieving satisfactory leak-free vacuum performance, the MBE system pumps are started, and the system is rebaked. The empty vacuum system should achieve specification pressure (the x-ray limit of commonly used ion gauges of 3 × 10−11 mbar), and should have a clean residual gas spectrum (dominated by H2, with small CO and H2O peaks, and negligible levels of hydrocarbons). This procedure may need to be repeated if vacuum quality is not sufficiently clean for acceptance of MBE components.

The constructional materials for MBE components are treated with even more care than the chambers. All materials and machined components are initially thoroughly degreased. Various components are treated in a vacuum furnace to further clean and condition their surfaces. Assembly of the MBE components takes place under clean room conditions. Prior to loading into the MBE system, the components generally go through vacuum checks and de-gassing. K-cells (without crucibles) are inserted into a dedicated UHV outgassing system, baked to 250°C, and operated at their maximum temperature (1400–1600°C, depending on design) until acceptable vacuum conditions can be achieved. Crucibles are then inserted, and the complete cell re-outgassed. This is often restricted to 1200°C and for a limited time period in the case of pBN crucibles, due to the build up of C on the pBN surface.[45] The substrate manipulators also undergo testing of operation at maximum temperatures and rotational speeds. These components are then introduced into the clean MBE system. The system is once again baked and complete operation of the system is tested.

With the exception of the filament assemblies and the source materials, electron beam evaporators operate at near ambient temperatures. Since these sources cannot be tested empty, they are inserted into the MBE system at an early stage of system construction after cleaning to UHV standards, and performing electrical and mechanical checks.

Introduction of new components into an operating MBE system can cause disruption of the MBE environment, and degradation of the conditioned state of the system, often leading to degraded material quality. New or repaired components should, if time permits, be thoroughly outgassed either in a separate, dedicated UHV chamber, or in the preparation chamber of the MBE system to minimize any disruption of the MBE environment.

5.0 MBE COMPONENTS: SOURCES

A variety of sources are employed for flux generation in MBE, and their design depends on the nature of the source materials. A list of sources, used respectively for matrix and dopant flux generation is presented in Tables 7 and 8. These tables describe the main characteristics of each source, their areas of application, and examples of source materials employed.

Table 7

Principal characteristics of the matrix flux sources used in MBE.

Table 8

Principle characteristics of the dopant flux sources used in MBE.

MBE sources have the following requirements:

1. The flux should be free of contaminants generated by the constructional materials.

2. The source should operate at a temperature which is as low as possible, commensurate with obtaining the desired flux, to minimize contamination of the flux by outgassing.

3. The source should permit good and reproducible control of the flux.

4. The source should be capable of providing a wide dynamic range of flux (e.g., over five orders of magnitude for dopants).

5. Response times to programmed changes in source conditions (e.g., temperatures, gas flow) should be rapid.

6. The flux distribution emanating from the source should be commensurate with the MBE system geometry to obtain optimized deposit uniformity (see Sec. 12.1)

7. The source design should be rugged and reliable.

The following sections describe in detail the evolution and design of MBE sources listed in Tables 7 and 8, using the above criteria in assessing the efficacy of individual source designs.

5.1 K-cells (also known as Thermal Effusion Sources or MBE Furnaces)

K-cells can justifiably be termed the work-horse of MBE, since they are used in nearly all MBE systems to evaporate matrix and/or dopant materials. The designs of K-cells have changed as new constructional materials have become available, and as factors affecting material quality and cell performance have become better understood.

A K-cell comprises a crucible containing the solid or liquid evaporant, which is radiatively heated (see the basic schematic of Fig. 6). The electrically insulated heater filaments are wound non-inductively, either spirally or from end-to-end, to prevent magnetic interference of electron diffraction facilities in the MBE system. A thermocouple, carefully positioned to ensure intimate contact with the crucible, registers the source material temperature and can, via a feed-back loop, control the power to the heater and thus the temperature of the source (see Secs. 8.1 and 9.1). After calibration, the source temperature can thus be used to maintain a constant flux intensity, although frequent recalibration is found to be necessary because of source material depletion, redistribution of the charge, and changes in the thermal environment. Several layers of refractory metal foil wrapped around the entire cell minimize heat losses from the cell wall, the major heat loss being from the effusion aperture.

Figure 6 Schematic of the key components of a K-cell. A crucible containing the condensed phase source material is radiatively heated, and its temperature is monitored and controlled by a thermocouple. Early designs of K-cell had an end-cap with a restricting effusion aperture, as shown, to provide a well-characterized beam flux profile.

Knudsen[70] first analyzed the theory of effusion of a flux from a source with a small (compared with the mean-free path) exit aperture in which the vapor and condensed phase are kept in near-equilibrium. The beam flux density J (molecules cm−2s−1), at a distance L from such a source can be expressed as:[71]

Eq. (1)

where r is the effusion aperture radius, p is the vapor pressure of cell in mbar, and M is the molecular weight of the source material. The temperature dependence in the denominator of Eq. (1) is small compared with that of p (see, for example, the vapor pressure data collated by Honig and Kramer,[72] and references therein), thus J increases essentially exponentially with source temperature. The beam flux distribution from such a source is predictable,[71][73][74] and independent of the quantity of material in the cell. Early MBE source designs approximated to this Knudsen evaporation condition (hence the term K-cell); the crucibles were manufactured from graphite with a tight fitting end-cap (removable for cell loading) providing the small effusion aperture (Fig. 6). To provide electrical isolation of the heater filaments from the electrically conducting graphite crucible, the heater was completely enclosed in insulation.

As MBE evolved, several limitations with this design became apparent, resulting in incremental improvements:

1. The large area of contact between the completely enclosed filament and its insulators could produce flux contamination. As noted in Sec. 4.2, quartz and beryllium oxide cause Si and Be-doping[41][42] of GaAs, as well as providing deleterious background oxygen. Even alumina, and the more thermally and chemically stable pBN, undergo slight decomposition[43] when in contact with filaments operating at high temperatures (greater than 1200°C). Minimizing heater-generated contamination of the flux was addressed by preventing line-of-sight between the heater assembly and the substrate, and designs for completely enclosed heaters have been reported.[75] Modern designs follow this practice, and event though using pBN extensively within the heater assembly, contact between pBN and filaments is minimized, for example, by using of self-supporting heaters (see below).

2. Graphite