32

Cathodic Arc Plasma Deposition

32.1 Introduction ......................................................................32-1 32.2 Cathodic Arc Plasma Deposition Process .......................32-1 32.3 Cathodic Arc Sources........................................................32-3 32.4 Cathodic Arc Emission Characteristics ...........................32-3 32.5 Microdroplets ....................................................................32-4 32.6 Recent Developments........................................................32-5 References .....................................................................................32-7

H. Randhawa
Vac-Tec Systems, Inc.

32.1 Introduction
The cathodic arc plasma deposition (CAPD) method1,2 of thin lm deposition belongs to a family of ion plating processes that includes evaporative ion plating3,4 and sputter ion plating.5,6 However, the CAPD process involves deposition species that are highly ionized and posses higher ion energies than other ion plating processes. All the ion plating processes have been developed to take advantage of the special process development features and to meet particular requirements for coatings, such as good adhesion, wear resistance, corrosion resistance, and decorative properties. The cathodic arc technique, having proved to be extremely successful in cutting tool applications, is now nding much wider ranging applications in the deposition of erosion resistance, corrosion resistance, decorative coatings, and architectural and solar coatings.

32.2 Cathodic Arc Plasma Deposition Process

In the CAPD process, material is evaporated by the action of one or more vacuum arcs, the source material being the cathode in the arc circuit (Figure 32.1). The basic coating system consists of a vacuum chamber, a cathode and an arc power supply, an arc ignitor, an anode, and substrate bias power supply. Arcs are sustained by voltages in the range of 15 to 50 V, depending on the source material; typical arc currents in the range of 30 to 400 A are employed. When high currents are used, an arc spot splits into multiple spots on the cathode surface, the number depending on the cathode material. This is illustrated in Figure 32.2 for a titanium source. In this case, an average arc current/arc spot is about 75 A. The arc spots move randomly on the surface of the cathode, typically at speeds of the order of tens of meters per second. The arc spot motion and speed can be further inuenced by external means such as magnetic elds, gas pressures during coatings, and electrostatic elds. Materials removal from the source occurs as a series of rapid ash evaporation events as the arc spot migrates over the cathode surface. Arc spots, which are sustained as a result of the material plasma generated by the arc itself, can be controlled with appropriate boundary shields and/or magnetic elds.

32-1
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Coatings Technology Handbook, Third Edition

Gas Inlet

Arc Supply () (+) To Anode

Arc Source () To Pump (+) Arc Supply

To Anode

Substrate

() Bias Supply (+) ??

?? ??

??

FIGURE 32.1 Schematic of a cathode arc deposition system.

FIGURE 32.2 Number of arc spots on the titanium cathode arc source as a function of arc current.

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32-3

CAPD is markedly different from the physical vapor deposition process. Some of its characteristic features are as follows: 1. 2. 3. 4. The material plasma is generated by one or more arc spots. A high percentage (30 to 100%) of evaporation material is ionized. The ions exist in multiple charge states (e.g., in case of Ti, Ti+, Ti2+, Ti3+, etc.). The ions possess very high kinetic energies (10 to 100 eV).

These characteristics of CAPD result in deposits that are of superior quality in comparison to other plasma processes. Some of these advantages are as follows: 1. Good quality lms over a wide range of deposition conditions (e.g., stoichiometric reached lms with enhanced adhesion and lm density can be obtained over a wide range of reactive gas pressures and evaporation rates) 2. High deposition rates for metals, alloys, and compounds with excellent coating uniformity 3. Low substrate temperature 4. Retention of alloy composition from source to deposit 5. Ease of producing reacted compound lms

32.3 Cathodic Arc Sources

A schematic cross section of a cathodic arc source is shown as an inset in Figure 32.1, in a photograph of a typical large area source. The arc source comprises a cathode (source material), an anode, an arc ignitor, and a means of arc connement. The method of arc connement is a key factor in arc source design and conguration. Cathodes using magnetic elds or boundary shields are limited to small sizes of the order of a few inches in diameter. This limits the uniformity attained from such sources. It is generally necessary to use a multitude of such sources to obtain a reasonable coating quality. Arc sources employing connement passive boarders (Figure 32.3) with predetermined electronic characteristics may be built much larger and over a wide range of sizes. Such cathode sources provide good uniformity over a wide range of substrate sizes in various industrial applications. Typical thickness uniformity observed using an 8 in. 24 in. titanium cathode at a source to substrate distance of 10 in. was approximately 10% over a at area measuring 5 in. 20 in. Furthermore, the target utilization of such arc sources exceeds 70% much higher in comparison to the magnetron sputtering source (N 40%).

32.4 Cathodic Arc Emission Characteristics

The cathodic arc results in a plasma discharge within the material vapor released from the cathode surface. The arc spot is typically a few micrometers in size and carries current densities as high as 10 A/m2. This high current density causes ash evaporation of the source material, and the resulting evaporant consists of electrons, ions, neutral vapor atoms, and microdroplets. Emissions from the cathode spots are illustrated in Figure 32.4. The electrons are accelerated toward the cloud of positive ions. The emissions from the cathode spots split into a number of spots. The average current carried per spot depends on the nature of the cathode material. The extreme physical conditions present within cathode spots are listed in Table 32.1. It is likely that almost 100% of the material may be ionized within the cathode spot region. These ions are ejected in a direction almost perpendicular to the cathode surface. The microdroplets, however, have been postulated to leave the cathode surface at angles up to about 30 above the cathode plane. The microdroplet emission is a result of extreme temperatures and forces that are present within emission craters. The microdroplet emission is greater for metals with low boiling points. Figure 32.5 shows such results for copper, chromium, and tantalum.

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Coatings Technology Handbook, Third Edition

FIGURE 32.3 Typical large-area cathodic arc source.

32.5 Microdroplets
Microdroplets are emitted as one of the products of the ash evaporation events. In an uncontrolled situation, very high microdroplet densities may be produced and deposited onto the substrates. The microdroplets are found to be metal-rich in composition in the case of reacted compound lms. Microdroplet size and density can be controlled in the arc deposition process. Parameters and source design are the key factors that inuence the density and size of the microdroplets. As previously reported, microdroplet density and size vary with the material. Zirconium nitride lms, deposited under the same conditions as titanium nitride, exhibit a much lower density of much smaller microdroplets (N 0.1 to 0.2 m). It is believed that the smaller microdroplets result from the higher melting point and low vapor pressure of zirconium coupled with the higher arc spot velocity observed on a zirconium cathode surface. The higher arc spot velocity results in a low mean residence time of the arc spot on a given localized area; thus, it minimizes localized overheating and, hence, the size and density of the microdroplets. The arc motion of a conventional arc source was studied using a very high speed photographic technique. The arc speed was measured to be approximately 8 m/sec. The application of suitable external magnetic elds was found to enhance the arc speed to 17 m/sec. A corresponding reduction in macroparticles was observed. The source design as well as the operating gas pressure during deposition had an effect on the microdroplet emission. A new arc source using these modied microdroplets could be totally illuminated. This is illustrated for lms of titanium and zirconium nitrides and titanium dioxide, as shown in Figure 32.6.

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Cathodic Arc Plasma Deposition

32-5

Anode Cathode + Ion Cloud Electrons

Metal Ions

Metal Vapor Metal Ions

Droplets

Neutral Atoms

FIGURE 32.4 Emission characteristics of a cathodic arc source. TABLE 32.1 Physical Conditions: Cathode Arc Spot
Temperature (K) Pressure, Mpa Power density, W/cm2 Electric eld, V/cm1 Current density, A/cm2 4 103104 0.110 107109 104105 106108

32.6 Recent Developments

A major interest in the cathodic arc process until recently has been in the deposition of hard coatings for tribology, wear, and decorative applications. Deposition, characterization, and performance evaluations of nitrites, carbides, and carbonitrites of several materials [Ti, Zr, Hf, (TiAl), (TiZr)(Ti6Al4V), etc.] using the cathodic arc deposition process have been investigated in detail and will not be discussed here. Some of the most recent developments involve deposition of oxides and multicomponent materials for architectural glass, solar reduction applications, barrier lms, and so on. Thin lms of tin, zirconium nitride, titanium dioxide, zirconium dioxide, oxide of copper, and other metallic materials have been investigated for these applications. Films of TiO2 and ZrO2 were deposited in a reactive mode using an oxygengas mixture. ZrO2 and TiO2 lms with very low absorption (<5%) in the visible light range and excellent adhesion to plastics and glass substrates have been deposited. In fact, TiO2 lms with a sharp cutoff at approximately 400 nm were found to be very suitable for UV lters.

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Coatings Technology Handbook, Third Edition

1.50 kv Cu

30 kv 002 Cr

1.00 kv Ta

30 kv 014

FIGURE 32.5 Microdroplet emission from metals having different melting points.

1.50 kv TiN ZrN

30 kv 003

TiO2

FIGURE 32.6 Scanning electron micrographs showing surface topography of various lms using modied arc technology.

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TiN and ZrN lms deposited by cathodic arc have also been investigated for architectural glass coatings. The deposition rates and stoichiometry control were found to be superior to magnetron sputtering. A deposition rate as high as 10 times that of magnetron sputtering for production scale was demonstrated. Multicomponent lms consisting of Inconel and NiCrAlY alloys have also been successfully deposited at rates as high as 1 mm/min. The lm composition as analyzed by spectroscopic techniques (e.g., ESCA and AES) was found to be within 10 to 15% of the source material. This makes cathodic arc an excellent choice for multicomponent materials. The cathodic arc deposition process has proved to be capable of fullling the most exacting demands in applications as diverse as tool coatings, decorative coatings, architectural glass coatings, and turbine engine coatings. Developments are continuing to broaden the range of various potential applications of the cathodic arc.

References
1. H. Randhawa and P. C. Johnson, A review, Surf. Coat. Technol., 31, 303 (1987). 2. J. L. Vossen and W. Kem, Eds., Thin Film Processes. New York: Academic Press, 1978. 3. J. A. Thornton, in Deposition Technologies for Films and Coatings. R. F. Bunshah, Ed. Park Ridge, NJ: Noyes Publications, 1982. 4. W. M. Mullarie, U.S. Patent No. 4,430,184 (1984). 5. H. Randhawa and P. C. Johnson, Surf. Coat. Technol., 33, 53 (1987). 6. H. Randhawa, presented at ASM International Strategic Machining and Materials Conference, Orlando, FL, 1987.

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