I on I m p l a n t a t i on in S e m i c o n d u c t o rs SILICON AND GERMANIUM James W. Mayer Lennart Eriksson CALIFORNIA INSTITUTE OF TECHNOLOGY RESEARCH INSTITUTE FOR PHYSICS PASADENA, CALIFORNIA STOCKHOLM, SWEDEN and John A. Davies CHALK RIVER NUCLEAR LABORATORIES CHALK RIVER, CANADA A C A D E M IC P R E SS A SUBSIDIARY OF HARCOURT BRACE JOVANOVICH, PUBLISHERS N ew Y o rk L o n d on T o r o n to S y d n ey S an F r a n c i s co COPYRIGHT © 1970, BY ACADEMIC PRESS, INC. ALL RIGHTS RESERVED NO PART OF THIS BOOK MAY BE REPRODUCED IN ANY FORM, BY PHOTOSTAT, MICROFILM, RETRIEVAL SYSTEM, OR ANY OTHER MEANS, WITHOUT WRITTEN PERMISSION FROM THE PUBLISHERS. ACADEMIC PRESS, INC. Ill Fifth Avenue, New York, New York 10003 United Kingdom Edition published by ACADEMIC PRESS, INC. (LONDON) LTD. 24/28 Oval Road, London NW1 LIBRARY OF CONGRESS CATALOG CARD NUMBER: 75-107563 PRINTED IN THE UNITED STATES OF AMERICA 83 84 85 9 8 7 6 5 4 3 Many of the discussions that led to the writing of this book (and many of our experimental results) occurred at odd hours, weekends, and holidays. This book is dedicated, therefore, to our wives—Betty, Sylvia, and Flo— for their support, patience, and understanding. Preface Interest in ion implantation as a method to introduce atoms into the sur face layer of a solid has been growing steadily for at least a decade. Until a few years ago this interest was confined to a limited number of research laboratories where implantation was manifesting itself as a useful and versatile tool in many areas of atomic, nuclear, and solid-state physics. The marked upsurge of interest in ion implantation since 1966 can be attributed largely to its emergence as a potentially useful technique to produce electronic com ponents. Indeed, most of the current studies are being made in silicon. This monograph reviews the recent developments in ion implantation in silicon and germanium and emphasizes the basic aspects of these studies; we feel that experimental work on other semiconductor materials has not been carried through extensively enough to permit a comprehensive picture to emerge, and we have therefore limited our coverage of the subject to the two most studied elements. We have tried to cover in some detail each of the major basic aspects of experimental study: dopant distribution, radiation damage, dopant location, and electrical characteristics. This is not an historical survey; it is a guide to the more recent develop ments in the field. Because of this approach, we may not always have given credit to those pioneers in the field of ion-implantation doping who stimulated many of the later investigations. In this regard, the work of M. Bredov, J. O. McCaldin, D. Medved, W. King, and R. Ohl and their colleagues should be noted. It is our hope that this monograph will serve as a useful summary of the efforts to date in the field of ion implantation of semiconductors. It is aimed % at both the specialists in the implantation field and those in other fields who wish to acquaint themselves with the problems and merits of ion implantation. April 1970 xi Acknowledgments The writing of this book has grown out of a joint experimental program between the three authors, extending back to 1965 and involving five different research institutes. We are very deeply indebted to our many colleagues at these institutes for their encouragement, assistance, and criticism and for their stimulating discussions with us during our own in vestigations. In particular, we wish to mention F. Brown, L. Cheng, J. R. Parsons, D. Marsden, I. Mitchell, and J. L. Whitton at Chalk River Nuclear Laboratories (Canada); J. U. Andersen, E. B0gh, K. O. Nielsen, H. Schiott, and J. Lindhard at the University of Aarhus (Denmark). I. Bergstrom, K. Bjorkqvist, B. Domeij, G. Fladda, N. G. E. Johansson, and D. Sigurd at the Research Institute for Physics, Stockholm (Sweden); R. Baron, R. W. Bower, R. R. Hart, O. J. Marsh, and G. A. Shifrin at Hughes Research Laboratories (California); and S. T. Picraux and J. E. Westmoreland at the California Institute of Technology. In writing this book we acknowledge the major contributions of O. J. Marsh who collaborated in writing Chapter 5, R. W. Bower who wrote Chapter 6, and H. Schiott who furnished many of the range and straggling data in Chapter 2. The comments of P. Sigmund and F. Eisen on Chapter 3 were very valuable. A special acknowledgment is given to Mrs. N. Kosowicz for her secretarial assistance. The U.S.A.F. laboratories at Cambridge, Massachusetts and at Wright-Patterson Air Force base, Ohio, are acknowledged for their valuable support in stimulating many of these ion-implantation studies. Figures 2.3, 2.9a, 2.10, 2.15, 2.17, 2.19, 2.20, 2.23, 2.24, 2.26, 2.27, 2.30, 2.32, 3.14, 3.19, 3.21, 3.27, 3.31, 3.32, 4.9, 4.12, 4.13, 4.17, and 5.18 are reproduced by permission of the National Research Council of Canada from the Canadian Journal of Physics. Figure 2.4 is reproduced by permission of the National Research Council of Canada from the Canadian Journal of Chemistry. Figure 3.34 is reproduced by permission from C. Jech and R. Kelly, J. Phys. Chem. Solids 30, 465 (1969). New York, Pergamon Press. Figure 5.7 is reproduced from A. H. Clark and Κ. E. Manchester, Hall measurements of ion-implanted layers in silicon, Trans. TMS ΛΙΜΕ 242, 1173-1180 (1968). New York, American Institute of Mining, Metallurgical,and Petroleum Engineers. xiii 1 General Features of Ion Implantation Ion implantation is the introduction of atoms into the surface layer of a solid substrate by bombardment of the solid with ions in the keV to MeV energy range. The solid-state aspects are particularly broad because of the range of physical properties that are sensitive to the presence of a trace amount of foreign atoms. Mechanical, electrical, optical, magnetic, and superconducting properties are all affected and indeed may even be dominated by the presence of such foreign atoms. Use of implantation techniques affords the possibility of introducing a wide range of atomic species, thus making it possible to obtain impurity concentrations and distributions of particular interest; in many cases, these distributions would not be otherwise attainable. Recent interest in ion implantation has focused on the study of dopant behavior in implanted semiconductors and has been stimulated by the possi bilities of fabricating novel device structures in this way. We will therefore direct our attention to those factors which affect the electrical characteristics of implanted layers in silicon and germanium—such factors as range distribu tions of dopant species, lattice disorder, and location of dopant species on substitutional and interstitial sites in the lattice. The application of semiconductors in electronic circuitry has been based upon control of the thermal diffusion of dopant elements into semiconduct ing crystals, normally silicon. These dopants occupy silicon lattice sites and determine the electrical properties of the device. Their concentration is determined by the equilibrium solubility at the process temperature (900- 1100° C), and the distribution in depth is given by the diffusion constant and process time. Ion implantation provides an alternative method of introducing dopant atoms into the lattice. In this case, a beam of dopant ions accelerated through 1 2 / GENERAL FEATURES OF ION IMPLANTATION a potential of typically 10-100 kV is allowed to impinge on the semiconductor surface. The implantation system shown in Fig. 1.1 illustrates the basic elements required in this technique. Using different types of available ion sources, a wide variety of beams may be produced with sufficient intensity for implantation purposes: 1014-1015 ions/cm2 (less than a "monolayer") is a representative ion dose. Note that a mass-separating magnet is almost mandatory to eliminate unwanted species that often dominate the extracted beam. Beyond this, however, the basic instrumentation can be quite simple. An important aspect of the application of implantation to semiconductor technology, in contrast to diffusion processes, is that the number of implanted ions is controlled by the external system, rather than by the physical properties of the substrate. For example, dopants can be implanted at temperatures at which normal diffusion is completely negligible. Also, the dopant concentra tion is not limited by ordinary solubility considerations, and so a much wider variety of dopant elements may be used. Thus, one potential application of ion implantation is that it might allow the investigation of the properties of species which cannot be introduced into semiconductors by conventional means. ION Fig. 1.1. Schematic drawing of an ion-implantation system. A mass-separating magnet is used to select the ion species of interest. Beam-sweeping facilities are provided for large- area uniform implantations. LI RANGE DISTRIBUTIONS 3 The major factors governing the successful exploitation of ion implanta tion are the range distribution of the implanted atoms, the amount and nature of the lattice disorder that is created, the location of the implanted atoms with in the unit cell of the crystal, and (ultimately) the electrical characteristics that result from the implantation and subsequent annealing treatment. We will consider all of these factors briefly in the present chapter in order to obtain an overall picture of the problems involved. Subsequent chapters will then treat each one in detail. 1.1 Range Distributions One of the most important considerations, obviously, in any description of implantation processes is the depth (range) distribution of the implanted ions. In recent years, a large amount of experimental and theoretical work has been devoted to the task of understanding the energy-loss processes that govern the range distribution, and it is now possible to predict fairly accurately most of the factors involved. For example, a typical range distribution in an amorphous substrate is approximately Gaussian in shape, and may therefore be characterized by a mean range and a straggling about this mean value, as depicted in Fig. 1.2. As discussed in Chapter 2, both these quantities depend in a complex but predictable fashion on many variables. It is evident from Depth Depth Fig. 1.2. The depth distribution of implanted atoms in an amorphous target for the case in which the ion mass is less than or greater than the mass of the substrate atoms. To a first approximation the mean depth R depends on ion mass M and incident energy E, p x whereas the relative width AR/R of the distribution depends primarily on the ratio between P P ion mass and that of the substrate atoms, Μ. 2 4 1 GENERAL FEATURES OF ION IMPLANTATION Fig. 1.2 that implanted distributions contrast strongly with the monotonically decreasing profiles that are typical of diffusion processes. Furthermore, by varying the energy continuously during the implantation, one may achieve (in principle) almost any type of dopant profile. Typical values of the mean range for 100-keV ions are ~0.1 micron, whereas diffusion doping usually produces a mean depth of 1-10 microns. Numerous experiments have shown that in monocrystalline substrates, the range distribution depends strongly on the orientation of the crystal with respect to the implantation direction, i.e., on the "channeling effect." If an ion enters almost parallel to a major axis or plane, then a correlated series of collisions may steer it gently through the lattice, thus reducing its rate of energy loss and increasing its penetration depth. This may result in profiles of the type indicated in Fig. 1.3. In most implantations, only a small fraction of the implanted ions manage to stay channeled throughout their path, and the shape of such a distribution is sensitive to many factors that are difficult to control. 1.2 Lattice Disorder Other problems inherent in the use of implantation techniques arise from the lattice-disorder (Chapter 3) and radiation-damage effects produced by the incident ion. As an implanted ion slows down and comes to rest, it makes Fig. 1.3. The depth distribution of implanted atoms in a single crystal under conditions such that the beam is aligned with a major crystallographic axis. The shaded portion shows the distribution of perfectly "channeled" ions which penetrate nearly to the maximum channeling range R . The distribution of atoms is sensitive to many factors, such as beam max alignment, lattice vibrations, and surface disorder. The dashed curves indicate the type of distributions that might be obtained under typical implantation conditions in silicon and germanium. 1.2 LATTICE DISORDER 5 many violent collisions with lattice atoms, displacing them from their lattice sites. These displaced atoms can in turn displace others, and the net result is the production of a highly disordered region around the path of the ion, as shown schematically in Fig. 1.4 for the case of a heavy implanted atom at typically 10-100 keV. At sufficiently high doses, these individual disordered regions may overlap, and a noncrystalline or amorphous layer is formed. The isolated disordered regions and the amorphous layer have widely different anneal behavior. In the case of germanium and silicon, the isolated disordered regions anneal at moderate temperatures of approximately 200° and 300° C, respectively. The amorphous layers also anneal in a characteristic fashion, but at appreciably higher temperatures, i.e., at approximately 600° C in silicon and 400° C in germanium. It should be noted that even though both types of disorder can be annealed at temperatures well below those where diffusion of the dopant species occurs, there are still defects present. These defects are most evident in the growth of dislocations that occur in silicon at anneal temperatures above 600° C. If the implantation is performed at a temperature greater than approxi- Lattice Disorder Fig. 1.4. A schematic representation of the disorder produced in room-temperature implantations of heavy ions at energies of 10-100 keV. At low doses, the highly disordered regions around the tracks of the ions are spatially separated from each other. The volume of the disordered region is determined primarily by the stopping point of the ion and the range of the displaced lattice atoms (dashed arrows). At high doses, the disordered regions can overlap to form an amorphous layer.