Vacuum 85 (2011) 1125e1129

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Vacuum
journal homepage: www.elsevier.com/locate/vacuum

Ion implantation techniques for non-electronic applications

J.A. Garca*, R.J. Rodrguez
AIN-Centro de Ingeniera Avanzada de Supercies, 31191 Cordovilla, Pamplona, Spain

a r t i c l e i n f o
Article history: Accepted 23 December 2010 Keywords: Ion implantation Plasma immersion Biocompatibility Tribology

a b s t r a c t
Ion implantation techniques have been used to improve surface properties for over more than four decades. Metallurgical application of ion beam techniques was rst reported in the 70s by Harwell laboratory (UK), and by the Naval Research Laboratory (USA), mainly focused to nitrogen implantation of steels. From those rst results to today ion implantation techniques have been introduced in many different applications for industrial sectors such as the aeronautical and biomedical. This paper presents some of the most important actual applications of ion implantation techniques. Different strategies of conventional Ion Implantation (II), Low energy-High Temperature Ion Implantation (LEHT), and Plasma Immersion Ion Implantation (PIII) are studied and compared in terms of modied surface properties and industrial application niches. Furthermore, the reported results show how these different treatments have a big potential for research in smart and nano-functional surfaces in applications including biomaterials and many other specic developments. 2011 Elsevier Ltd. All rights reserved.

1. Introduction Ion implantation techniques for semiconductor applications were developed in Bell Laboratories by Kingsbury and Ohl in the early 1950s [1,2]. The rst non-electronic applications for ion beam modication of materials dates back to the work in the Harwell Laboratories in the 70s by Dearnaley and collaborators [3] and in the Naval Research Laboratory by Hirvonen et al. [4]. In those early works nitrogen implantation was shown to be a useful procedure to improve tribological and corrosion properties of the different steels [5e7]. In the 80s ion implantation techniques were employed to carry out modications on many other technological metal alloys, like titanium and aluminium. These investigations were gathered into a brief collection of some excellent reviews [8,9]. From these early works, some technical and economical limitations were found for scaling ion beam technologies in real industrial applications. Some of the most important drawbacks of ion beam treatments are the line of sight treatment (beam and target scanning are mandatory for three-dimensional parts), low ion current, and complex equipment which result in too long and too expensive treatments, limiting them to applications of very high added value.

These important problems for scaling ion implantation were partially solved in the 80s by the emerging plasma immersion ion implantation technique. Although the origin of this technology is in the early 80s in the Mission Research Corporation by Adler and coworkers [10], the birth of Plasma Immersion is associated with Conrad and co-workers in 1987 [11,12]. In these studies nitrogen implantation was successfully employed for improving wear and corrosion resistance of aluminium and steels, providing conformal implantation at high temperatures. In the following decades both ion bombardment techniques have been widely explored in terms of applications and possible industrial niches. Developments of less complex equipment and specic solutions have been one of the more successful research lines to provide scale-up of ion implantation. 2. Plasma immersion implantation and Line-of-Sight implantation The fundamental difference between Ion Beam Implantation (II) and Plasma Immersion Ion Implantation (PIII) is the fact that, in PIII, the target is an active part of the system, where it is biased at pulsed high voltage, but in II the target is completely isolated from the ion beam generation. Concerning the implantation process and parameters both treatments have relevant differences. On one hand, II is a complete ballistic process where kinetic energy from ions is the cause for ion implantation into the target. On the other hand PIII is a combined treatment where temperature and voltage

* Corresponding author. Tel.: 34 948421101; fax: 34 948421100. E-mail address: jagarcia@ain.es (J.A. Garca). 0042-207X/$ e see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.vacuum.2010.12.024

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J.A. Garca, R.J. Rodrguez / Vacuum 85 (2011) 1125e1129 Table 1 Comparison of plasma immersion ion implantation versus ion beam implantation. Ion implantation Geometry Temperature Thickness Batch time Ion energy Ion current Industrial scaling Line of sight Room temperature 0.1 micron 10e100 h 10e1000 kV 1e100 mA Low Plasma immersion Conformal 400  C 0.05e10 microns 0.1e2 h 0.1e100 kV 100e1000 mA Medium

3. Applications of ion beam implantation Recent work on ion beam implantation, other than electronic and magnetic applications, is focused on the treatment of different materials and alloys for specic applications (customized research). In this way corrosion and tribological applications are being fullled with, for example, implantation of CoCr alloys for biomedical applications, and implantation of polymers.
Fig. 1. Range of temperatures and thickness for the conventional Plasma Nitriding, Plasma Immersion Ion Implantation and Ion Beam Implantation.

3.1. Tribology and corrosion Wear resistance and control of friction coefcient are the topics most studied in research on ion implantation of metals and alloys [13e17]. Nitrogen implantation covers more than 90% of applications showing excellent results in terms of hardness, and wear resistance improvement. The performance of Nitrogen implanted metals shows a clear dependence with the nitrogen implanted dose, with hardness increasing with the implanted dose. Moreover it is possible to determine a saturation dose in nitrogen implantation of metal depending on the implanted material and the ion (Fig. 3). Corrosion resistance can be improved by means of Chromium ion implantation and by implantation of rare earth ions [18]. 3.2. Biomedical applications Knowledge of bactericide effects of some elements like silver date back to the Roman civilization. Ion beam implantation allows very thin layers to be formed with content of silver and other bactericide elements in the form of nano-precipitates. By means of this strategy it is possible to increase the bactericide effect of a material by introducing silver, copper and other elements into biomedical materials such as stainless steels, titanium alloys and CoCr alloys, without decreasing their hardness and corrosion resistance [19]. 3.3. Polymers Light ion implantation into polymers is a very useful technique to modify their surface properties. Depending on the implanted ion and implantation parameters (energy and dose), different effects can be obtained. The lighter is the implanted ion the higher is the supercial hardness of the implanted layer. Moreover the higher is the implantation energy the higher is the supercial hardness. This result can be explained taking into account that the hardness increase is due to a cross linking effect of the polymeric chains induced by ionization produced by ion implantation. In this way it is clear that the lighter the implanted ion the higher is the electronic energy transfer. Hydrogen, Helium and other low mass ions are the selected ones for these applications [20,21]. On the contrary ion implantation of not so light ions produces graphitisation of the outer surface of the polymer, inuencing other important properties such as electrical conductivity and reduction of friction coefcients.

are carefully selected to obtain the desired implantation prole, so the temperature is a fundamental parameter in PIII, dominating in many cases the nal implantation prole (Fig. 1). Ion energy is the other key parameter in ion implantation, especially in II where it is the only parameter affecting implantation prole for a given ion species and target material. In the case of PIII ion energy is not as important as temperature and typical implantation energies range from a few volts to no more than 40 kV (Fig. 1). In these two Figs. 1 and 2 II and PIII are compared in terms of thickness and temperature and thickness and ion energy, and conventional plasma nitriding has been included for comparison with a conventional industrial treatment. Besides batch temperature and ion voltage, other important characteristics of both kinds of treatment are gathered in Table 1 in terms of implantation requirements (3D implantation or scanning of the target) and ion current that can be obtained for both methods. For PIII usually we have a 100 times bigger current than for conventional II, offering lower batch times and, consequently, a much cheaper and scalable treatment.

Fig. 2. Range of ion energies and thickness for the conventional Plasma Nitriding, Plasma Immersion Ion Implantation and Ion Beam Implantation.

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Fig. 3. Hardness in GPa for unimplanted and nitrogen implanted IV, V and VI metallic elements. Low dose is below 4 1017 ion/cm2 and high dose is below 8 1017 ion/cm2.

3.4. Successful cases at AIN The Centre of Advance Surface Energy started to work with ion implantation techniques in 1989. From this date to now many different industrial applications have been tested [22]. Examples amongst those successful cases include high dose nitrogen implantation of stainless steel blades for the food industry (blades for peeling asparagus and cutting vegetables). In the paper industry, nitrogen implantation of cutting and punching tools increases the life durability by more than three times. A high dose carbon implantation on special bearings (for aeronautical applications) produces an important decrease in friction coefcient and an increase in the load bearing capacity of the system. When the saturation dose is reached (up to 8 1017 ion/cm2) a carbon rich thin layer appeared on top of the surface reducing friction and wear [23].

arise due to the high exibility of the technique. From the more general denition of plasma immersion ion implantation A plasma inside a vacuum chamber with a pulsed biased substrate holder it is possible to have different hybrid processes [24]. In Fig. 4 there is a schematic diagram showing the different treatments that can be achieved by plasma implantation techniques. Using the PIII chamber it is possible to use a oating potential (non- biased process), the so called plasma nitriding, and high energy low temperature ion implantation. Moreover, combining plasma sources with cathodic arcs or magnetron sources, we are able to deposit coatings by means of a PVD process, obtaining excellent results in terms of adhesion, due to the implantation prior to the layer growth [25].. Finally DLC coatings and also ceramic coatings can be deposited by CVD using the plasma immersion system [26]. All these possibilities, very well described by Anders [27], indicate that the Plasma immersion process has a role as a Super Hybrid Process 4.1. Tribology and corrosion Tribology and corrosion applications were the rst objectives of PIII research from the early work from Conrad [12] to the present day. Meanwhile plasma nitriding at moderate temperatures (below 400  C) and low ion energies provides a thick nitride layer (up to 10 microns) and then a very high wear resistance for high load situations [28]. The majority of published work on plasma nitriding has stainless steels or chromium-containing alloys as substrates [29]. Plasma nitriding below 400  C does not cause precipitation of Cr, so there is no reduction in corrosion resistance which is a clear

4. Application of plasma immersion ion implantation Plasma immersion ion implantation has many denominations PIII, PBII, PSII, PIII&D, depending of the researcher and to the specic characteristics of each process. These different names also

20

Ni (concentration in atomic percent)

18 16 14 12 10 8 6 4 2 0 0 20 40 60

10kV 20kV 30kV

80

Depth (nm)
Fig. 4. Scheme of the different possibilities for ion implantation and deposition techniques. (PN: Plasma Nitriding; CVD: Chemical Vapor Deposition; PVD: Physical Vapor Deposition; II: Ion Implantation; PBII: Plasma Based Ion Implantation). Fig. 5. Compositional proles for Oxygen implanted into stainless steel at energies of 10 keV, 20 keV and 30 keV.

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Concentration (atomic percent)

70 60 50 40 30 20 10 0 0 2 4 6 8 10 12 14

Co

Cr N

Mo

16

Depth (m)
Fig. 6. Nitrogen prole for the CoCr alloy after nitriding.

advantage over conventional plasma nitriding at higher temperatures. Recent papers, such as Pichon et al. [30], explore the role of the different implantation parameters (bias, content of hydrogen, temperature) to obtain the desired nitrogen prole. In these articles the important role of the thickness of the dynamic oxide layer is revealed, and the competitive process between implantation and re-sputtering plus out-diffusion, is clearly explained by Moller et al. [31]. 4.2. Biomedical applications In last decade PIII has been widely used to improve biocompatibility of different materials. The majority of this work was focused on nitrogen implantation of NiTi shape memory alloy, Titanium, titanium alloys and CoCr alloys [32e35]. By means of nitrogen implantation, the cited works show how biocompatibility improves, by making tests of corrosion and product migration in different simulated body uids, and also measuring friction and wear. These papers report a dramatic increase in wear resistance without a decrease in corrosion resistance, but there are already some aspects to be improved. In the case of nitriding of CoCr alloys, one of the alloys often employed for hip prostheses, increases in wear resistance and corrosion resistance were reported [36]. Here a signicant increase in Co content in the uid after the wear test was found which could be explained by the nitrogen implantation causing migration of Co to the most outer surface. 4.3. Successful cases at AIN The most important application carried out at AIN in PIII is focused on biomedical devices and relates to oxygen implantation of coronary stents (stainless steel). By means of oxygen implantation of these prostheses, heavy ions (Ni, Mo, and Cr) go deeper into the material as shown in Fig. 5, where it is possible to observe atomic concentration of Ni after oxygen implantation. As a consequence of this, migration tests show a reduction of the concentration of these ions in blood of more than 50%. Another interesting application is the plasma nitriding of CoCr alloys for total hip replacement. At AIN we implant a layer of more than 12 microns in a high density cathodic arc plasma as shown in Fig. 6. By means of this treatment wear resistance increases by more than a factor 10. 5. Summary and future trends From the rst experiment in 1970 to now, ion implantation has been shown to be a powerful tool for improving surface properties and for developing new surface functionalities. Tool protection and

increases in durability were the rst objectives for ion implantation in the early studies. These early studies were made using conventional ion implantation which is a line-of-site process and provides solutions for relatively small samples. More recently the advent of Plasma Ion Implantation has offered treatment of 3-dimensional samples at much higher rates which has opened up new commercially-viable possibilities. Today the researchers look for new applications such as improvements in biocompatibility. Future trends depend very strongly on the possibility of scaling equipment to industrial application. Researchers must now work to develop suitable treatments without losing the economical perspective. Acknowledgements The authors acknowledge the Ministry of Science & Innovation of Spain and the Navarresse Government for the co-funding of the project CONSOLIDER-FUNCOAT CSD2008-0023 and the project Ni-TOOLS MAT2007-6655. References
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