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Ion Beam Modification of Metals: Compositional and Microstructural Changes

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Ion Beam Modification of Metals: Compositional and Microstructural Changes Progress in Surface Science, Vol. 32, pp. 211-332 0079-6816/89 $0.00 + .50 Printed in the U.S.A. All rights reserved. Copyright © 1990 Pergamon Press plc ION BEAM MODIFICATION OF METALS: COMPOSITIONAL AND MICROSTRUCTURAL CHANGES GARY S. WAS Departments of Nuclear Engineering and Materials Science and Engineering, University of Michigan, Ann Arbor, M148109 Abstract Ion implantation has become a highly developed tool for modifying the structure and properties of metals and alloys. In addition to direct implantation, a variety of other ion beam techniques such as ion beam mixing, ion beam assisted deposition and plasma source ion implantation have been used increasingly in recent years. The modifications constitute compositional and microstructural changes in the surface of the metal. This leads to alterations in physical properties (transport, optical, corrosion, oxidation), as well as mechanical properties (strength, hardness, wear resistance, fatigue resistance). The compositional changes brought about by ion bombardment are classified into recoil implantation, cascade mixing, radiation-enhanced diffusion, radiation-induced segregation, Gibbsian adsorption and sputtering which combine to produce an often complicated compositional variation within the implanted layer and often, well beyond. Microstructurally, the phases present are often altered from what is expected from equilibrium thermodynamics giving rise to order- disorder transformations, metastable ~ (crystalline, amorphous or quasicrystalline) phase formation and growth, as well as densification, grain growth, formation of a preferred texture and the formation of a high density dislocation network. All these effects need to be understood before one can determine the effect of ion bombardment on the physical and mechanical properties of metals. This paper reviews the literature in terms of the compositional and microstructural changes induced by ion bombardment, whether by direct implantation, ion beam mixing or other forms of ion irradiation. The topics are introduced as well as reviewed, making this a more pedogogical approach as opposed to one which treats only recent developments. The aim is to provide the tools needed to understand the consequent changes in physical and mechanical properties. 211 212 G.S. WAS Contents 1. Introduction 213 2. Ion Beam Modification Techniques 214 3. Compositional Changes 218 A. Recoil implantation 220 B. Cascade mixing 224 C. Chemical effects 229 D. Radiation-enhanced diffusion 233 E. Radiation-induced segregation 239 E Gibbsian adsorption 256 G. Sputtering 258 H. Phenomenological model for surface composition changes 262 I. Implant redistribution during ion implantation 268 4. Microstructural Changes 270 A. Phase stability 271 B. Metastable phases 286 C. Additional microstructural effects of ion implantation 314 5. Summary 322 References 324 Abbreviations AES Auger electron spectroscopy bcc body centered cubic CSRO Chemical short range order DM Displacement mixing fcc face centered cubic GA Gibbsian adsorption hcp hexagonal close packed IBAD Ion beam assisted deposition IBM Ion beam mixing PS Preferential sputtering PSII Plasma source ion implantation RED Radiation enhanced diffusion RIS Radiation-induced segregation TEM Transmission electron microscopy TSRO Topological short range order ION BEAM MODIFICATION OF METALS 213 1. Introduction The use of ion beams for altering the properties of materials was pioneered in the 1960s with the introduction of electrically active elements into silicon and other semiconducting materials [1]. It became widely adopted by the microelectronics industry in the 1970s and has developed into a well established and precision industry [2]. The first application of ion implantation into metals was reported in 1969 by Dearnaley [3] at the Harwell Laboratory, who addressed the possibility of improving mechanical and corrosion behavior of steels that are of relevance to the nuclear industry. Rapidly thereafter, the attributes of ion implantation as a surface modification technique became realized and activity in ion implantation of metals mushroomed. In comparison with alternative surface modification techniques, ion implantation has a number of advantages: 1) the process is inherently low temperature and thermal distortion of components is not a problem, 2) since ion implantation is not a coating process, there is no interface that may become susceptible to decohesion due to mechanical stress or corrosion, 3) dimensional changes are negligible on an engineering tolerance scale, being on the order of a few tens of nanometers, 4) surface polish is improved due to preferential sputter erosion of asperities, 5) the implanted atoms are dispersed on a microscopic (and sometimes on an atomic) level producing the most efficient and beneficial effect of the additive, and 6) significant compressive surface stresses are produced which will partially compensate externally imposed tensile stresses and lengthen component life against creep or fatigue failure by surface initiated cracking. In addition to these practical attributes, a more general attribute of the implantation process is that it is a non-equilibrium process. As a result the implanted target may form non-equilibrium or metastable phases or microstructures. The study of these microstructures has generated a great deal of interest with regard to the mechanical and physical properties they possess. For example, the superior corrosion properties which accompany formation of an amorphous surface are of tremendous interest because of the ease with which amorphization can occur in specific systems. Similarly, the mechanical properties of these phases as well as metastable microstructures is of significant interest. Numerous examples exist on the hardening of alloys by ion implantation and ion beam mixing. In many cases, this translates into improved friction and wear properties of well-known engineering materials. The change in microstructure of the alloy surface has also been found to strongly affect the fatigue and creep behavior of the component - 214 G.$. WAS mechanical responses which are often associated with bulk properties of the sample rather than surface properties. However, all of the observed property changes in metals are due to either compositional, microstructural or topographical changes in the alloy. We must therefore, seek to understand how ion implantation induces these changes before we can hope to understand their effects on the mechanical or physical properties of alloys. Having accomplished this, we may then look forward to this technique becoming a useful and reliable processing tool for the metals industry. The purpose of this paper is to present an introduction and a review of the state of ion beam surface modification of metals for property improvements. As just discussed, property improvements can only be understood through a thorough knowledge of the compositional and microstructural changes induced by ion bombardment of metals. Therefore, this topic is divided into two parts. In this, the first part, compositional and microstructural effects of ion bombardment in metals are reviewed. The processes which govern the composition profile of the implanted specie; sputtering, displacement mixing, radiation enhanced diffusion, radiation induced segregation, Gibbsian adsorption and preferential sputtering, and the microstructural development; phase stability, metastable phase formation, amorphization, dislocation dynamics, precipitation, grain growth, etc. are discussed and reviewed. The second part will review the chemical; corrosion and oxidation, and mechanical; hardness, wear, fatigue, property changes brought about by the compositional and microstructural changes discussed here. The intent is not merely to survey the current literature, but to present a coherent and semiquantitative description and analysis of the physical processes occurring during, or as a result of the ion bombardment process. Hence, a balance is struck between the development of physical models and surveying the current literature, resulting in a more pedagogical presentation. 2, Ion Beam Modification Techniques The modification of metal surfaces by ion beams can be accomplished by a variety of methods, each with its own advantages for particular situations. The principal methods include 1) direct ion implantation, 2) ion beam mixing, 3) ion beam assisted deposition and 4) plasma ion implantation and are shown schematically in Figs. 1-4. Each of these will be briefly described and considered with respect to its advantages and disadvantages. ION BEAM MODIFICATIONOF METALS 215 © @ 6) Fig. 1. Schematic representation Fig. 2. Schematic representation of direct ion implantation. of the ion beam mixing process (IBM). A w A v ~et a flux Plasma sheath A w Fig. 3. Schematic representation Fig. 4. Schematic representation of ion beam assisted deposition of the plasma source ion implant (IBAD). ation process (PSII). 216 G.S. WAS Direct ion implantation is accomplished by bombarding the target with a beam of ions in the energy range from a few hundred keV to several MeV. The beam is usually monoenergetic, contains a single charge state and is generally (but not always) mass analyzed. Due to the stochastic nature of the elastic collision process, the ions come to rest in a Gaussian distribution with the mean of the Gaussian centered about Rp, the projected range, with the FWHM ~ 2.35ARp where ARp is the standard deviation from the mean. Although seemingly a very simple process,
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