Thin Solid Films 491 (2005) 1 17 www.elsevier.

com/locate/tsf

Review

Control of reactive sputtering processes

W.D. Sproul a,*, D.J. Christie b, D.C. Carter b
a

Reactive Sputtering Consulting, LLC, 3324 South Lemay Avenue, Fort Collins, CO 80525, USA b Advanced Energy Industries, Inc., 1625 Sharp Point Drive, Fort Collins, CO 80525, USA Available online 19 July 2005

Abstract The method of reactive gas control during reactive sputtering strongly influences the deposition rate and film properties of the compound being deposited. Flow control of the reactive gas is the simplest method, but since reactive sputtering is typically done in the compound or poisoned mode of the target, the deposition rate is low compared to the rate from the elemental target. In addition, the film properties produced by flow control reactive sputtering are less than optimal. Partial pressure control of the reactive gas is more complex than flow control because it requires active feedback control, but it allows operation of the process in the transition region between the elemental and poisoned states of the target. By operating in this region, higher deposition rates compared to flow control are achieved, and the film properties are improved. Reactive sputtering of insulating films requires the use of the right type of power to prevent arcing on the target, which is detrimental to the quality of the deposited films. Both pulsed dc and mid-frequency ac power prevent arcing during the reactive sputtering of insulating films. Arc prevention eliminates droplet ejection from the target and allows the reactive deposition to occur without large fluctuations in the reactive gas partial pressure, often a result of uncontrolled arcing. Ternary or quaternary compounds can be reactively sputtered using dual magnetron set-ups and multiple reactive gases. Multiple reactive gases present an additional control problem in that one of the reactive gases can trap the target in the poisoned mode unless the partial pressures of both reactive gases are individually controlled. Reactive sputtering with high power pulsed magnetron sputtering, which provides a high degree of ionization of the sputtered species, is possible for insulating films as long as the partial pressure of the reactive gas is controlled and arc detection and suppression is available on the power supply. D 2005 Elsevier B.V. All rights reserved.
Keywords: Reactive sputtering; Partial pressure control; Pulsed dc power; Mid-frequency ac power

Contents 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Introduction. . . . . . . . . . . . . . . . . . . . . . . . Flow control of the reactive gas . . . . . . . . . . . . . Partial pressure control of the reactive gas . . . . . . . . Comparison of mass flow and partial pressure controlled Power for reactive sputtering of insulating films . . . . . Reactive gas activation and distribution . . . . . . . . . Other approaches to reactive sputtering . . . . . . . . . Dual magnetron reactive co-sputtering . . . . . . . . . . Two-gas reactive sputtering . . . . . . . . . . . . . . . Small area reactive sputtering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . hysteresis curves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 2 3 6 9 12 13 13 13 15

* Corresponding author. E-mail addresses: bsproul@comcast.net (W.D. Sproul), Dave.Christie@aei.com (D.J. Christie), Dan.Carter@ei.com (D.C. Carter). 0040-6090/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.tsf.2005.05.022

W.D. Sproul et al. / Thin Solid Films 491 (2005) 1 17

11. HPPMS reactive 12. Conclusions . . Acknowledgements . . References . . . . . .

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1. Introduction Reactive sputtering is the sputtering of an elemental target in the presence of a gas that will react with the target material to form a compound. In one sense all sputtering is reactive because there are always residual gases in the chamber that will react with the sputtered species. However in reality, reactive sputtering occurs when a gas is purposely added to the sputtering chamber to react with the sputtered material. Examples are when oxygen is injected into the chamber with the sputtering of aluminum to form aluminum oxide or when nitrogen is added with the sputtering of titanium to form titanium nitride. Westwood [1] states, Reactive sputtering was developed in the 1950s to deposit the doped Ta N films for hybrid circuits [2]. Since that time, the use of reactive sputtering has proliferated, particularly over the past decade. It is used extensively by manufacturers of coated architectural glass, roll or web coatings, coated cutting tools, optical coatings, decorative and functional coatings for plumbing and hardware items, microelectronic devices (barrier layers, high k dielectrics, and resistive films), automotive windshields and mirrors, micro-electro-mechanical systems (MEMS) devices, surface acoustic wave devices, and transparent conductive oxides. All of us directly interface with many of these applications daily even though we may not know it. Over the years, many excellent reviews have been written about reactive sputtering [2 6]. The reader is encouraged to read these reviews to gain a more in-depth understanding of the reactive sputtering process than is given in this paper.

2. Flow control of the reactive gas The basic issue that must be faced during reactive sputtering is that the reactive gas combines with target material to form a compound. Ideally this reaction takes place on the surface of the substrate, but in reality it occurs not only at the substrate but also on the fixturing and chamber walls and on the target. It is the reaction on the target surface that leads to the classic reactive sputtering problem. The sputtering rate for the compound material that forms on the target is usually significantly less than the rate for the elemental target material. As the degree of target compound coverage increases, the deposition rate decreases. When the entire target surface is covered with the compound material, the target is said to be poisoned. It is

possible to reactively sputter compound materials from a poisoned target, but the rate of deposition is usually very low compared to the elemental deposition rate for the same amount of power delivered to the target. The control method used for the injection of the reactive gas into the sputtering chamber has a direct bearing on poisoning of the target. Historically mass flow control of the reactive gas has been the chosen delivery technique, but it very quickly leads to poisoning of the target. If the target power is kept constant as the flow of the reactive gas into the chamber is increased, initially the partial pressure of the reactive gas in the chamber (as measured by a differentially pumped mass spectrometer) remains very low as is shown in Fig. 1 for the titanium oxygen system. The oxygen partial pressure stays low with the lower flows because most of the gas reacts with the sputtered titanium and is being getter pumped. When the flow of the reactive gas reaches a sufficient level, in this case at point A at about 10.3 sccm, the partial pressure of the reactive gas suddenly increases to point B. This dramatic change in the partial pressure is a direct result of the poisoning of the target surface. Once the compound forms on the target surface, the deposition rate drops precipitously because of the lower sputtering rate for the compound material, and the result of this change in the deposition rate is that there is less sputtered target material to combine with the reactive gas. With less gettering of the reactive gas, its partial pressure increases. Any further increase in the reactive gas flow past point B just leads to a linear increase in its partial pressure, which is essentially parallel to but below the system pumping curve with the magnetron cathode off. When the flow of the reactive gas is decreased from point B, the partial pressure of the reactive gas does not return immediately to its previous low value. Instead the partial pressure remains high as the flow is decreased compared to when the flow was increasing until the compound layer on the surface of the target is broken through at point C due in part to decreased getter pumping by the chamber surfaces that are covered with the compound material. At this time, the flux of the sputtered elemental species increases rapidly due to its higher sputter yield, which results in a higher gettering rate for the reactive gas and a reduction in its partial pressure to point D. Trying to operate between points A and B in Fig. 1 with flow control of the reactive gas is very difficult if not impossible for most reactive systems. Any slight perturbation in the process such as from an arc event results in rapid poisoning of the target and an increase in the reactive gas partial pressure.

W.D. Sproul et al. / Thin Solid Films 491 (2005) 1 17

TiOx Flow Control Hysteresis

1.6

O2 Partial Pressure, mTorr

1.2 O2 Increasing O2 Decreasing 0.8

0.4

C D
0 0 4 8 O2 Flow, sccm
Fig. 1. Hysteresis curve for the reactive sputtering of TiOx using mass flow control of the reactive gas. Target power was 1.0 kW, and the argon pressure was 3.1 mTorr. Bipolar-pulsed dc power was used with a frequency of 100 kHz and a reverse time of 2.0 As.

A
12 16

It is now known that it is desirable to operate in this transition region between the elemental and poisoned states of the target to obtain high deposition rates and optimum film properties. However with flow control of the reactive gas, for most cases it is not possible to do so. There is a whole range of forbidden compositions that cannot be deposited with flow control of the reactive gas because the process jumps from a low partial pressure where the desired compound is usually very under-stoichiometric to a high partial pressure where the film composition is usually overstoichiometric. For flow control of the reactive gas for most cases, the process is unstable in this transition region. Okamoto and Serikawa [7] showed in 1986 that it is possible to change the shape of the reactive gas flow/partial curve by increasing the pumping speed of the system. As the pumping speed of the system is increased by increasing the pumping capacity of the system pumps, the hysteresis effect is reduced until eventually there is no hysteresis. There is just a linear relationship between the reactive gas flow and the partial pressure. With this technique, it is possible to avoid the hysteresis problems that normally occur without the high pumping speed. Even though increased pumping can circumvent the hysteresis problem, it comes at a high expense particularly in very large deposition systems. The cost of the extra pumps to achieve this effect is high as is the cost of operating the pumps. For these reasons, the high pumping speed approach is not used very often. It can require absurdly high pumping speeds, essentially 10 times those normally used today. Although the deposition rate is usually very low in the poisoned state, flow control of the reactive gas is still used in many production processes because once in the poisoned state, the process is very stable. The film

properties are reproducible, which is very important, but they may not be optimal. With flow control of the reactive gas, it may not be possible to optimize rate, reproducibility, and film properties.

3. Partial pressure control of the reactive gas In the early to mid-1980s, three different groups [8 10] demonstrated that it is possible to control the partial pressure of the reactive gas directly during reactive sputter deposition. Each group controlled the reactive gas partial pressure based on a different feedback signal. Schiller et al. [8] used an optical emission spectrometer (OES) signal from the sputtered material for their feedback signal. They found that the intensity of lines from the sputtered material decreased as the reactive gas partial pressure increased. This decrease in the optical intensity occurred as the erosion rate from the target decreased as more and more of the target became covered with the compound material. By using the optical signal as the feedback signal into their control system, they were able to maintain a constant partial pressure of the reactive gas during deposition. Sproul and Tomashek [9] integrated a mass spectrometer into their reactive gas partial pressure control system. They modified their mass spectrometer to provide a timely reactive gas feedback signal to their control system, and this control system was able to maintain constant partial pressure during the reactive deposition. They also recognized the importance of maintaining constant target power during deposition to maintain a constant deposition rate, and they modified their power supply to automatically maintain constant power.

W.D. Sproul et al. / Thin Solid Films 491 (2005) 1 17

Affinito and Parsons [10] were the first to report the use of cathode voltage as a feedback signal for controlling the reactive sputtering processes for aluminum nitride and aluminum oxide. They were successful in controlling the nitride process, but they reported that the oxide process was more difficult to control. Thus by the mid-1980s, the three basic feedback signals for controlling the partial pressure of the reactive gas during reactive sputter deposition were known. Today it is these same three signals that are commonly used for controlling the reactive sputtering process. There are pros and cons to each type of control signal. The mass spectrometer provides a direct reading of the particular reactive gas or gases being used in the process, which is not usually the case for the OES and cathode voltage control techniques. To be effective as the sensor for a reactive sputtering process, the spectrometer needs to update the feedback signal in a timely manner, which in practice for most reactive sputtering process means that the feedback signal needs to be updated in the range of every 32 64 ms otherwise stabilization of the feedback control loop may not be possible. Not all mass spectrometers are capable of this fast update time, but there are at least three commercially available units that can update the signal in the required time period. A drawback to the mass spectrometer is that signal intensity can drift with time, but all the peaks will typically drift together. The ratio of the peaks stays relatively constant with time, which can be used to compensate for the drift in the instrument. Another issue with the mass spectrometer is that oxygen can affect the performance of the ionizer particularly with high-pressure mass spectrometers. When oxygen is introduced into the ionizer, all signal intensities decrease in strength up to 30% over a 10 15 min period, which means that a high-pressure mass spectrometer is not a good sensor for oxygen in a reactive sputtering process. If oxygen is being used, it is recommended that a differentially pumped mass spectrometer with an open ion source be used. Due to the reduction in pressure, the differentially pumped mass spectrometer works reasonably well with oxygen. The differentially pumped mass spectrometer is also very effective in monitoring other gases in the chamber during deposition, and it can be very helpful in understanding what is going on during a reactive process. In particular, unintended introduction of a second reactive gas such as oxygen released from water vapor may be a problem for the reactive sputtering of many nitride coatings. For example if a chamber used for the reactive sputtering of titanium nitride is opened to the atmosphere to change samples and is not subsequently baked out before the start of the next reactive sputtering run, water vapor will be released from the walls and fixturing from heating effects of the process. The water vapor will crack in the plasma into hydrogen and oxygen, and the oxygen will combine with the sputtered species usually before the nitrogen will due to the high free energy of formation of the oxide compared to the nitride. An

oxynitride film will form instead of a pure nitride film. Most of the oxygen is consumed in the process, but the hydrogen is not and is easily monitored with the mass spectrometer. Depending on the amount of water vapor in the chamber, the color of this titanium oxynitride film will vary from a golden yellow for stoichiometric TiN to a light gold for some oxygen incorporation to an almost metallic looking film for a substantial amount of oxygen in the titanium oxynitride film. Both the optical emission spectrometer and the cathode voltage provide an indirect measure of the partial pressure of the reactive gas. Although it is possible in principle for an OES system to measure the reactive gas directly, in practice it is a wavelength from the sputtered species that is monitored because the emission lines from the reactive gas typically are quite weak and difficult to detect with respect to the metal lines. The intensity of the metal peak decreases as the partial pressure of the reactive gas increases, and the OES technique can be very effective as the sensor in a reactive sputtering process. Changes can be detected and updated on the order of every 10 ms. Like the mass spectrometer, the OES technique is not without its issues. As the target erodes, the intensity of the signal changes, and the optical fiber or other optics that look into the plasma may get coated with time. Similarly to the mass spectrometer, there can be drift issues for the line intensities from an optical emission spectrometer. For systems that involve motion of the substrates or magnets in the magnetron, this motion can affect the signal. This problem can be severe in a tool coating system where the substrates are ferrous materials. As the substrates move in front of the target(s), the magnetic field from the cathode interacts with the substrates, and the plasma intensity varies with the motion of the substrates. The assumption with an OES signal is that the decrease in its intensity is due to the presence of the reactive gas. However outgassing or a second reactive gas would also affect this signal making the OES signal from a target line a non-unique feedback signal. The target voltage can be a very effective feedback signal for a reactive sputtering process. In most reactive sputtering processes, the cathode voltage will change as the partial pressure of the reactive gas changes, and the magnitude of the change can be on the order of 100 150 V or more for the sputtering of aluminum or silicon with oxygen. However the cathode voltage can change for reasons other than a change in the reactive gas partial pressure. The cathode voltage is also affected by a change in temperature in the chamber, target erosion, a disappearing anode, outgassing or leaks, fluctuations in argon pressure, and other reactive gases. Changes to the cathode voltage can occur for many reasons and not just for a change in the reactive gas partial pressure. It, like the OES signal, is not unique feedback signal. The advantage of controlling the partial pressure of the reactive gas during a reactive sputtering process is that there is no forbidden region between the elemental and poisoned

W.D. Sproul et al. / Thin Solid Films 491 (2005) 1 17

states of the target, and an operating point can be chosen that optimizes both the desired film properties and the deposition rate. Fig. 2 shows the hysteresis curve for the reactive sputtering of titanium in an argon/oxygen atmosphere using partial pressure control of the oxygen reactive gas. The transition between the metallic state and the poisoned state is continuous. As the partial pressure of the reactive gas is increased, the amount of oxygen in the film increases, and the deposition rate decreases. There is an optimum operating point along this curve that maximizes both the deposition rate and delivers the desired property or properties of the deposited film. The shape of the hysteresis curve shown in Fig. 2 is typical of hysteresis curves generated with partial pressure control of the reactive gas. A similar curve for the reactive sputtering of aluminum in an argon/oxygen atmosphere is shown in Fig. 3. Shown along the transition curve between the elemental and the poisoned states are the index of refraction and deposition rate for different partial pressures. For the lowest partial pressure, the film is oxygen deficient as is noted by its index of refraction, but its deposition rate is 90% of the metal rate. Increasing the partial pressure from this point decreases both the index of refraction and the deposition rate. The optimal point for both index of refraction and rate occurs when the index is 1.66 and the rate is 71% of the metal rate. Any further increase in partial pressure beyond this point reduces the index of refraction below its optimal value. When the oxygen partial pressure is sufficiently high, the target is fully poisoned, and the rate and index from this region are the same as what is found when the target is fully poisoned under flow control of the reactive gas. The

deposition rate in the fully poisoned state for aluminum oxide is only 2 3% of the metal rate, which is a very significant reduction in rate. By operating at the partial pressure that produces the optimal index of refraction of 1.66, the deposition rate is more than 23 times higher than the poisoned rate and the film properties are better. Successful partial pressure control of the reactive gas requires a fast control loop. The partial pressure signal must be generated and processed quickly, and the response to any change must occur quickly. For many reactive sputtering processes, which includes most of the oxides, fast means that the total time to produce a feedback signal, process it, and produce a response should be less than 250 ms. Longer times result in an unstable process that oscillates between high and low partial pressures. Since the cathode voltage is an electrical signal, it has the fastest update time, potentially less than a few milliseconds. Optical signals typically are updated on the order of tens of milliseconds, as are mass spectrometer signals, and the time to process the feedback signal is very short compared to its update time. The response time to a change in the control signal emerging from the partial pressure controller is a critical issue. If the control signal is sent as a set point to a mass flow controller (MFC), the control process in most instances will not be able to maintain a constant partial pressure of the reactive gas in the transition region because the MFC responds too slowly. Typically MFCs take on the order of a half to 1 s to respond to a change because they must sense a change in the flow with a slow acting thermal sensor. The time to do so is much too long for effective partial pressure control.

TiOx Partial Pressure Control

10

Oxygen Flow, sccm

O2 PP Increasing O2 PP Decreasing

4 0 0.2 0.4 0.6 0.8 1 1.2 1.4

Oxygen Partial Pressure, mTorr

Fig. 2. Hysteresis curve for the reactive sputtering of TiOx using partial pressure control of the reactive gas. Target power was 1.0 kW, and the argon pressure was 3.1 mTorr. Bipolar-pulsed dc power was used with a frequency of 100 kHz and a reverse time of 2.0 As. From [41]. Used with permission from the Society of Vacuum Coaters.

W.D. Sproul et al. / Thin Solid Films 491 (2005) 1 17

AlOx: Partial Pressure Control

5
Metal rich, dark film 90% of metal rate Clear film: n = 1.66 71% of metal rate Clear film: n = 1.61 10% of metal rate

O2 Flow, sccm

2
Clear film: n = 1.57 2-3% of metal rate

PP Increasing PP Decreasing

0 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45

O2 Partial Pressure, mTorr

Fig. 3. The hysteresis curve for the reactive sputtering of aluminum in an argon/oxygen atmosphere using partial pressure control of the reactive gas. Target power was 1.0 kW, and the argon pressure was 3.1 mTorr. Bipolar-pulsed dc power was used with a frequency of 100 kHz and a reverse time of 2.0 As. From [42]. Used with permission from the Society of Vacuum Coaters.

To overcome the shortcomings of the MFC, it is necessary to control the inlet of the reactive gas into the chamber directly with a fast acting valve. Typically piezoelectric valves have a very fast response to a change in the controlling signal, and by controlling the valve directly it is possible to operate at any point along the transition region. Schiller et al. [8] and Sproul and Tomashek [9] recognized the need for this fast valve control, and their control systems directly controlled piezoelectric valves, which respond quickly enough as long as the valve is controlled directly. Today there are a few very fast acting MFCs that use a feed forward control design, and these MFCs can work successfully in a reactive gas partial pressure control system.

4. Comparison of mass flow and partial pressure controlled hysteresis curves For a partial pressure controlled reactive sputtering process operating in the transition region, the reactive gas partial pressure is usually 3 10% of the total system pressure. The reactive gas partial pressure for the reactive sputtering of oxides of aluminum, titanium, or silicon is typically in the low 104 Torr range. In contrast to this pressure range for partial pressure controlled processes, the partial pressure of the reactive gas in mass flow controlled reactive sputtering processes covers a very wide range of pressures from 20% to 50% of the total pressure, and sometimes the reactive gas pressure can be as high as 100% of the total pressure.

This difference in the reactive gas partial pressure based on whether it is mass flow or partial pressure controlled has an effect on the electrical response of the sputtering system. For example when constant power is applied to the cathode, the change in cathode voltage is quite different depending on the control method. For the TiOx system, the cathode voltage as a function of the reactive gas flow when reactive gas flow is the controlling variable is shown in Fig. 4. The cathode voltage initially increases as the O2 flow is increased, but there is a sharp increase in the cathode voltage followed by a decrease over the flow range of 10 11.5 sccm, which is the point during which the target becomes poisoned. Once the target is poisoned, the cathode voltage remains high even when the flow is reduced. It is not until the compound layer on the target surface is broken through that the cathode voltage returns to lower values corresponding to the metallic deposition mode. The plot of cathode voltage as a function of the reactive gas partial pressure when partial pressure is the controlling variable is shown in Fig. 5, which is quite different than the one shown in Fig. 4 for the flow control mode. With partial pressure control, the cathode voltage increases as the partial pressure increases for the titanium oxygen system, and the voltage change is almost 100 V for the change in O2 partial pressure shown. When the O2 partial pressure is reduced, the cathode voltage also decreases, and the initial and final voltages are the same. If the O2 partial pressure is increased beyond the point where the target is fully poisoned, the cathode voltage will decrease. Thus for a given cathode voltage, there can be two different partial pressures, which

W.D. Sproul et al. / Thin Solid Films 491 (2005) 1 17

TiOx Flow Control Hysteresis: Cathode Voltage vs. Flow

440

420

Cathode Voltage, volts

400

380

360

340
O2 PP Increasing - CV O2 PP Decreasing - CV

320 0 2 4 6 8 10 12

O2 Flow, sccm
Fig. 4. The cathode voltage as a function of the O2 flow during the reactive sputtering of TiOx using flow control of the reactive gas. Target power was 1.0 kW, and the argon pressure was 3.1 mTorr. Bipolar-pulsed dc power was used with a frequency of 100 kHz and a reverse time of 2.0 As.

would produce different deposition rates and different film properties. If the cathode voltage data from Fig. 4 is shown as a function of partial pressure (even though flow was the controlling variable), the plot takes on a different appearance as is shown in Fig. 6. Initially the cathode voltage increases with little or no change in reactive gas partial pressure, and then the cathode voltage continues to rise as the O2 partial pressure increases. The cathode

voltage reaches a peak value, which corresponds to the point where the target becomes poisoned, and then it decreases with further increases in reactive gas partial pressure. When the reactive gas partial pressure is decreased, it, for the most part, parallels the path taken on the increase of the partial pressure, but there is some separation of the two curves in the peak region. This separation could be due to implantation effects [11,12], to outgassing of water vapor from the chamber walls and

TiOx Hysteresis: Cathode Voltage vs. O2 Partial Pressure

400

380

Cathode Voltage, V

360

340
O2 PP Increasing O2 PP Decreasing

320

300

280 0 0.2 0.4 0.6 0.8 1 1.2 1.4

Oxygen Partial Pressure, mTorr

Fig. 5. The cathode voltage as a function of the O2 partial pressure during the reactive sputtering of TiOx using partial pressure control of the reactive gas. Target power was 1.0 kW, and the argon pressure was 3.1 mTorr. Bipolar-pulsed dc power was used with a frequency of 100 kHz and a reverse time of 2.0 As.

W.D. Sproul et al. / Thin Solid Films 491 (2005) 1 17

Effect of Flow on Partial Pressure and Cathode Voltage

430

Cathode Voltage, volts

410

390

370
O2 PP Increasing - CV O2 PP Decreasing - CV

350

330 0 1 2 3 4 5 6 7

O2 Partial Pressure, volts

Fig. 6. The cathode voltage as a function of the O2 partial pressure during the reactive sputtering of TiOx using flow control of the reactive gas. The data for this plot is from the same data set for the hysteresis run shown in Fig. 4. Target power was 1.0 kW, and the argon pressure was 3.1 mTorr. Bipolar-pulsed dc power was used with a frequency of 100 kHz and a reverse time of 2.0 As.

fixturing, or to drift in the instrument, which amounts to measurement error. How the cathode voltage changes as a function of reactive gas partial pressure depends on the material system. For example for the reactive sputtering of aluminum in an argon/oxygen atmosphere, the cathode voltage decreases as the partial pressure is increased as is shown in Fig. 7. Similar decreases in cathode voltage during reactive

sputtering for an increase in reactive gas partial pressure are also known for the aluminum nitrogen, silicon oxygen, silicon nitrogen, magnesium oxygen, and yttrium oxygen systems. Increases in cathode voltage during reactive sputtering for an increase in reactive gas partial pressure have also been observed in the titanium nitrogen, tantalum oxygen, yttrium nitrogen, and zirconium nitrogen systems. The change of the cathode voltage during

AlOx: Cathode Voltage vs O2 Partial Pressure

400

375

Cathode Voltage, V

350
Increasing PP Decreasing PP

325

300

275

250 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45

O2 Partial Pressure, mTorr

Fig. 7. The cathode voltage as a function of the O2 partial pressure during the reactive sputtering of AlOx using partial pressure control of the reactive gas. Target power was 1.0 kW, and the argon pressure was 3.1 mTorr. Bipolar-pulsed dc power was used with a frequency of 100 kHz and a reverse time of 2.0 As.

W.D. Sproul et al. / Thin Solid Films 491 (2005) 1 17

reactive sputtering as a function of the reactive gas partial pressure depends very much on the material system being deposited. A decrease in the cathode voltage as the partial pressure and hence target coverage is increased can be attributed to the compound on the target surface having a higher secondary electron emission coefficient than the elemental target surface. However, Lewis and Glocker [13] reported that an increase in the reactive gas partial pressure in the plasma could actually reduce the plasma density due to a subsequent reduction in the ionization collision cross section, which leads to an increase in the target voltage. For the titanium nitrogen and titanium oxygen systems, the cathode voltage initially increases with increasing reactive gas partial pressure, but as the partial pressure continues to increase the cathode voltage falls. This dual nature in the change of the cathode voltage as a function of the reactive gas partial pressure indicates that initially a reduction in plasma density is the dominating factor controlling cathode voltage. As the reactive gas partial pressure continues to increase, the plasma density increases, and the increase in secondary electron emission for the compound takes over and lowers the cathode voltage. The effect of target power on the hysteresis curves during the reactive sputtering of ZrNx using partial pressure control of the reactive gas shown in Fig. 8. As the power is increased, the flow is increased for a particular partial pressure. In addition, the partial pressure where the peak flow occurs prior to the first slope reversal increases as the power is increased. This apparent shift in partial pressure where the peak flow occurs is due to several factors. Part of

it is due to the increased getter pumping due to more target material being transported to the chamber surfaces. It is also due to the heating and rarefaction of the gases in front of the sputtering target from collisions with the sputtered species and also to an increase in the getter pumping efficiency. As the power is increased, the flux and energy of the sputtered species is increased, which leads to more energetic collisions with the gas atoms. Since the total pressure in the chamber is fixed, the heating of the gas species due to the collisions results in a reduction in the density of gas atoms right in front of the target [14]. However the mass spectrometer that is sensing the reactive gas partial pressure measures the partial pressure not at the target but next to the chamber wall where the gases are unheated. Since the control signal for the closed-loop control of the reactive gas comes from the mass spectrometer in this case, the reactive gas partial pressure must be increased in the chamber in general as the power is increased to overcome the heating and rarefaction in front of the target [15]. This apparent reactive gas partial pressure increase is an artifact of where the reactive gas partial pressure is measured.

5. Power for reactive sputtering of insulating films When an insulating film forms on the target surface, it can charge up. If the charge reaches the breakdown voltage for the insulating film, an arc will occur. Arcs usually result in droplets being ejected from the target surface, and these droplets degrade the film quality. Historically, to overcome these problems, radio frequency (rf) power has been used,

ZrNx Hysteresis at Different Power Levels

80

70

60

N2 Flow, sccm

50

40
5 kW - PP Increasing 5 kW - PP Decreasing 8 kW - PP Increasing 8 kW - PP Decreasing 10 kW - PP Increasing 10 kW - PP Decreasing

30

20

10 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6

N2 Partial Pressure, mTorr

Fig. 8. Reactive sputtering of ZrNx at different power levels using partial pressure control of the reactive gas. Work done in a Materials Research Corporation 902M in-line sputtering system using Inset cathodes. Total sputtering pressure was 8.0 mTorr, and substrate bias was 100 V.

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W.D. Sproul et al. / Thin Solid Films 491 (2005) 1 17

but rf power is more expensive to use than direct current (dc) power. RF power supplies cost more per watt than dc power supplies, and a matching network must be used in an rf system further adding to the overall cost. For an equivalent amount of power, the deposition rate with rf power is about half the rate for dc power [16]. DC power could be used for the reactive sputtering of insulating films if compound formation on the target surface could be avoided. It has been shown that if a box with a mesh opening is added around the sputtering target and the argon is introduced inside this case while the reactive gas is introduced next to the substrate, it is possible to use dc power for reactive sputtering of insulating films [17]. The disadvantages of this technique are that it is maintenance intensive and flakes from the coated mesh may break off and lower film quality. In addition, sputtering through a mesh reduces the deposition rate. In the early to mid-1990s, pulsed dc and mid-frequency alternating current (ac) power were introduced for reactive sputtering of insulating films. Both pulsed dc and midfrequency ac use a voltage reversal at the cathode to offset charge build up on the target surface. A schematic of pulsed dc power is shown in Fig. 9. With pulsed dc power, the polarity of the power delivered to the target is alternated between negative and positive. During a negative pulse, which is the normal condition for sputtering, ions are attracted to the target to eject target atoms, while during the positive pulse electrons from the plasma are attracted to the target to discharge any charged regions. Since the magnitude and duration of the negative pulse are greater than those for the positive pulse, this type of pulsed power is known as asymmetric pulsed dc power, and it is used most often for the reactive sputtering of insulating films. For pulsed dc sputtering of insulating films, the pulse frequency usually is in the range of 70 100 kHz, although the frequency can go as high as 350 kHz with the equipment available today. Besides the frequency, the second most important parameter to control with the pulsed dc power is the duty cycle, which is defined as the negative pulse time divided by the cycle time. Kelly et al. [18] and Carter et al.
Normal Sputtering

Arc Count vs. Time for Different Duty Factors

4000

Cumulative Arc Count

98%
3000

2000

94%
1000

88% 82% 70&76%

0 0 100 200 300

Time, minutes
Fig. 10. The effect of the duty cycle on arcing during the reactive sputtering of aluminum oxide from an aluminum target using asymmetric pulsed dc power. The target power was 750 W, the pulsing frequency was 60 kHz, and the argon pressure was 3.5 mTorr. From [19]. Used with permission from the Society of Vacuum Coaters.

[19] showed that if the duty cycle is 65 70% or less, then arcing will be suppressed even for long duration reactive deposition of insulating films as is shown in Fig. 10. One disadvantage with pulsed dc sputtering of insulating films is that the film can eventually cover all surfaces in the chamber. If this happens, the electrons from the plasma cannot return to the power supply, the cathode voltage will rise (if in constant power mode), and the plasma will eventually extinguish. This effect is known as a disappearing anode, but steps can be taken to prevent it from happening by protecting or hiding the anode [20,21]. Dual magnetron sputtering applies mid-frequency ac power to a pair of magnetrons as is shown in Fig. 11. One leg of the output of the power supply is wired to one target, and the other leg is wired to the other target. When one target is negative with respect to the plasma, the other side is positive and acts as the anode for the system. Then during the next half cycle of the power supply, the voltages are
Reverse Voltage Charge Scrub
e-

Ar+ 0V -500V

Pulsed DC
eeee-

Ar+

Fig. 9. Schematic of asymmetric pulsed dc power. During the negative pulse, ions are attracted to the target for sputtering, and during the positive pulse electrons are attracted to the target to offset any charge build up.

W.D. Sproul et al. / Thin Solid Films 491 (2005) 1 17

11

Fig. 11. Schematic drawing of the dual magnetron sputtering arrangement.

reversed and the target that was just the cathode and sputtered is now a clean anode in the racetrack region. There is always a clean anode even though the walls of the chamber are being coated with an insulating film, and there is no disappearing anode problem. Regions along the edges and center of the magnetron target where there is a built-up layer that may have acquired a charge during sputtering are discharged during the anode part of the cycle. The first reference to this dual magnetron technique came from Este and Westwood [16] in 1988, and Scherer et al. [22] applied it to a pair of planar magnetrons, which were located next to one another, for the reactive deposition of oxides and nitrides. Dual magnetron sputtering has been widely adopted by the architectural and automotive glass and roll coating industries where long deposition runs are the norm and where they must have a stable process for long periods of time. The ac frequency is nominally 40 kHz, but in some large ac power supplies the frequency is varied between 40 and 80 kHz to adjust the power delivered to the cathode by frequency modulation. Disadvantages to dual magnetron sputtering are that two magnetrons are required and that the racetrack current must be returned to its quasi-steady state value each half cycle. A voltage overshoot is the result, which produces a momentary stream of high-energy electrons that are accelerated toward the substrate. If the substrate is heat sensitive, this may be an issue. A relatively new power delivery approach extends the advantages of mid-frequency ac power to single magnetron systems. This technique is called Redundant Anode Sputtering or RAS [23]. RAS uses two auxiliary elements with a single cathode, each connected to a center-tapped

transformer as is shown schematically in Fig. 12. The auxiliary elements alternatively act as an anode or as an extra cathode. When this element is the extra cathode, it is sputter cleaned. The continuous voltage reversal on these two elements prevents charge build up from causing arcs. The center tapped transformer usually is driven with 40 kHz power, and the center tap is attached to the cathode. Power is applied to the cathode during each half cycle of the power supply, and the cathode is always negative with respect to the plasma except for a short period twice each cycle. During this time, the target potential is positive with respect to the plasma potential, and electrons are attracted to the target surface discharging any regions that may have acquired a charge. RAS offers the advantages of non-disappearing anodes along with charge mitigation both on the two anode elements and the target surface for a single magnetron system. Cost is reduced over a dual magnetron system. When one of the anode elements acts as a cathode, the material sputtered from the element could be a source of contamination in the deposited film. To overcome this issue, the two elements can be made of the same material as the target. The anode elements may need to be cooled because they are sputtered in a diode mode. There are other factors to consider when comparing pulsed dc, mid-frequency ac, and redundant anode sputtering. The cost per watt of power supplied is lowest for midfrequency ac and highest for pulsed dc, and the cost for RAS power falls between those two. In comparing the deposition rates for an equivalent amount of pulsed dc and midfrequency ac power, the rate will be higher for the pulsed dc

Fig. 12. Schematic drawing of the redundant anode sputtering (RAS) setup.

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process. In the dual cathode mid-frequency ac process, the electron current in the magnetic trap defined by the E B drift region above the racetrack must be re-established each half, which leads to greater dissipation of energy per cycle than is seen in the pulsed dc process. Unless the frequency of the pulsed dc process is less than about 10 kHz, the electron current above the racetrack does not decrease significantly between pulses, so the energy dissipated per cycle due to re-establishing the electron current is much less than for the ac process. Since the reduction in racetrack electron current is minimal for the pulsed dc processes, the voltage overshoot at the beginning of the negative part of the pulse is less for the pulsed dc process compared to the mid-frequency ac process, and a reduced energetic electron flux is emitted at the beginning of the pulse. Consequently, there is less substrate heating with pulsed dc power compared to the mid-frequency ac power. A big advantage for mid-frequency dual magnetron sputtering compared to pulsed dc and RAS is that the process has been scaled to very high power levels. Power supplies with a capacity in excess of 200 kW are available today, and they are used for the very large industrial applications such as architectural glass coating. Pulsed dc power supplies at these power levels are possible in principle, but the complexity and cost would be greater than for the mid-frequency ac power supplies. In the RAS process, there is no voltage overshoot during each half cycle of the ac power, which results in less noise in the process compared to pulsed dc and mid-frequency ac processes. The RAS process is still relatively new compared to pulsed dc and mid-frequency dual magnetron sputtering, and the number of applications where it has been used is limited compared to the other two processes. However where it has been used, the results have been very favorable. The maximum amount of power available today with RAS is only 30 kW, which may be limiting its application for the large industrial deposition processes. The RAS approach does require a dual anode arrangement, which may be not be fitted to the process equipment if it were not required to support the RAS approach. One very positive advantage for pulsed dc power has been reported by Kelly et al. [24]. In the pulsed dc frequency range of 100 350 kHz, the substrate bias current density is significantly increased compared to the current density observed with conventional dc power to the substrate, and the pulsed dc bias current does not saturate as the bias voltage is increased. The ability to control the substrate bias ion current density with the dc pulsing frequency is a new means to affect the structure and properties of the deposited film. An issue faced by all sputter power delivery systems is the need to detect and quench arcs. Even in the best of systems, arcs can and do occur. How the power supply handles the arc is the issue because if arcs are not stopped they lead to more arcs. Droplets are emitted from the arc zone, and these droplets damage the film. Most arcs are

initiated at the transition zone between the elemental part of the target and the insulating built-up area [25]. A stream of electrons is injected into the racetrack region of the target, and they are propelled in the E B direction with speeds on the order of 7.4 105 m s 1. An arc can be detected by sensing a drop in the cathode voltage or an increase in cathode current or by a combination of these two events. Once the arc is detected, the power supply should cut off power to the cathode and wait until the arc is cleared before resuming delivery of power. The amount of time that it waits does have a direct effect on a reactive sputtering process. In order to minimize the effect on the reactive sputtering process and the composition of the film, the power supply should detect and clear an arc very quickly. Christie and Seymour [26] showed that for a particular large area titanium oxide process, it is necessary to detect and clear an arc and return to full power in less than 1 ms. Even though an arc is detected and power is momentarily stopped, there is still power stored in the power delivery cable that must be dissipated before the effect of the arc event is over. The type and length of the cable both affect the amount of stored energy in the cable, and the system should be designed to minimize cable length and its inductance. The power supply and the type of power that it delivers are integral parts of the reactive sputtering process. Today using either pulsed dc or mid-frequency ac power, it is possible to prevent or greatly reduce arcing during reactive sputtering of insulating films. The combination of the right kind of power that prevents arcing with partial pressure control of the reactive gas is a very powerful tool for the high-rate reactive sputter deposition of insulating films. Arcing can also occur during the reactive sputter deposition of conductive films depending on the target purity. Oxide inclusions in aluminum targets or high iron concentrations in low purity titanium targets will result in arcing during reactive sputtering operations. The use of either pulsed dc or mid-frequency ac power will prevent arcing problems with these low purity targets, and the use of partial pressure control of the reactive gas will guarantee the highest deposition rates for the desired composition. The use of the right kind of power with reactive gas partial pressure control is the method recommended (by these authors) for all reactive sputtering applications.

6. Reactive gas activation and distribution Techniques that enhance the reaction of either the reactive gas or the sputtered species with one another may lower the partial pressure needed to produce the stoichiometric film with the optimum properties. Whether or not this reduction in the partial pressure will lead to an increase in the deposition rate while still producing the desired film depends on the interaction of the activated reactive gas with the target. Activation techniques include using substrate

W.D. Sproul et al. / Thin Solid Films 491 (2005) 1 17

13

bias, unbalanced magnetrons, or an external activation device such as an inductively coupled plasma source, a microwave source [27], or a laser. The distribution of the reactive gas in the chamber has always been a challenge with reactive sputtering, and Westwood has discussed many of the issues [28]. If the reactive gas is not distributed uniformly in the reactive zone both at the substrate and the target, the deposition rate and composition will vary across the substrate. Gas manifolds are recommended for uniformly distributing the reactive gas in the deposition zone. Contrary to what intuitive feel might suggest, the gas manifold should be made of tubing having a small diameter on the order of 6 mm, and all of the holes should be of uniform size and distributed equally. The recommended hole-size is 0.5 mm, and the distance between holes should be 50 mm. Larger diameter holes or nonuniform hole sizes will not give a uniform gas distribution, and smaller holes or larger tube diameters will inhibit the response time of the manifold making closed-loop control difficult. The problem of uniform gas distribution is particularly acute in large area coating applications such as architectural glass and roll coating where the length of the cathode can be as long as 3.5 m. Differences in deposition rate and pumping speed along the length of the cathode lead to differences in the reactive gas partial pressure over the length of the cathode. Once the length of the cathode exceeds 40 50 cm, it is recommended that multiple gas manifolds be used with different reactive gas partial pressures being delivered along the length of the cathode. Such an arrangement complicates the overall reactive gas control problem, but control systems exist today to handle multiple reactive gas zones for the same reactive gas [29,30].

and they maintain a constant cathode voltage by varying the power to the target using the cathode voltage as the feedback signal for controlling the power level. By adjusting the power to keep the cathode voltage constant, they are in effect maintaining a constant reactive gas partial pressure. This technique is subject to the same issues when the cathode voltage is used for the closed-loop control of the reactive gas partial pressure.

8. Dual magnetron reactive co-sputtering Co-sputtering allows the deposition of alloy materials without the need to manufacture an alloy target, and ternary compounds have been deposited by reactive co-sputtering [34,35]. Recently Christie [36] and Christie et al. [37] extended the Berg multi-component reactive sputtering model [38] to predict what would happen during the reactive co-sputtering titanium and aluminum targets in an argon/oxygen environment. With the model, they computed the deposition rate and composition as a function of reactive gas partial pressure. Experiments using pulsed dc power, regulated power to each target, and partial pressure control of the reactive gas were conducted. They showed that it is possible to vary the index of refraction continuously from 1.7 for nearly all Al2O3 to 2.3 for nearly all TiO2. The pulsed dc power prevented (or greatly reduced) arcing during deposition and provided independent power regulation to each cathode. The reactive gas partial pressure control provided stable operation in the transition region along with stabilization of the rate and index. Both are enabling technologies, which are required to gain control over deposition rate and composition for dual magnetron reactive co-sputtering.

7. Other approaches to reactive sputtering 9. Two-gas reactive sputtering Partial pressure control systems add a degree of complexity to the reactive sputtering problem that some people want to avoid even though good partial pressure control systems exist today. Scobey et al. have taken one alternative approach to reactive sputtering of insulating films [31] where they separated the metal sputter deposition step from the compound formation step. Substrates are mounted on a rotating holder, and in one part of the chamber, a thin metal layer on the order of 2.0 nm is sputter deposited. This layer is then turned into the desired compound in another part of the chamber by bombardment with energetic ions from an oxygen ion beam. A thick film is deposited by making multiple depositions of the metal layer followed by oxidation of each metal layer. Two groups, Gilboa et al. [32] and Xiong and Gupta [33] have taken an indirect path to control the partial pressure of the reactive gas during a reactive sputter deposition. Instead of varying the amount of gas flowing into the chamber, they use a fixed gas flow regulated with a mass flow controller, Another way to reactively sputter deposit ternary compounds is to sputter one target material in the presence of two reactive gases. Barankova et al. [39] first modeled twogas reactive sputtering with one target using flow control of the gases, and their model showed that it is possible for one of the two gases to trap the target in a poisoned mode. The only way to get out of this trapped state is to remove both reactive gases. Experiments verified the predictions of the model. Other groups such as Martin and Rousselot [40] also looked at two-gas reactive sputtering using mass flow control of the reactive gas, and their findings are similar to those of Barankova et al. In 2003, Berg et al. [41] expanded the two-gas reactive sputtering model to include partial pressure control of one or both of the reactive gases. Two-gas reactive sputtering is a more complex process than single-gas reactive sputtering, and the model showed that one gas affects the partial pressure of the other gas. Flow control of both gases leads to

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W.D. Sproul et al. / Thin Solid Films 491 (2005) 1 17

SiOxNy: Fixed O2 Flows, N2 Partial Pressure Varied

6

5
O2 6 sccm

O2 Partial Pressure

O2 10 sccm O2 12 sccm

O2 14 sccm

0 0 1 2 3 4 5 6 7 8

N2 Partial Pressure
Fig. 13. Reactive sputtering of SiOx Ny using oxygen flow control and nitrogen partial pressure control. The higher oxygen flows show an uncontrolled transition to a high partial pressure and poisoning of the target as the nitrogen partial pressure is increased. Sputtering conditions: 1 kW target power, pulsed dc power at 100 kHz with a 4.0 As reverse time, and an argon pressure of 3.0 mTorr. From [43]. Used with permission from the Society of Vacuum Coaters.

unstable operation, and flow control of one gas plus partial pressure control of the other gas can also be unstable. Partial pressure control of both gases is necessary for stable operation. Experimentally the predictions of the two-gas reactive sputtering model with pressure control of one or both gases have been verified [41 43]. To gain complete stability throughout the whole parameter space in a two-gas reactive sputtering process, the partial pressure of each reactive gas must be monitored. Individual feedback signals for each

reactive gas must be supplied, which usually means that a mass spectrometer provides the feedback signals since it can monitor multiple species simultaneously. Both gases affect the target voltage and the target material OES signals, and it is not possible to determine which of the two gases is responsible for a change in these signals. OES feedback signals can work if individual lines for each reactive gas are acquired, but this mode of operation is not the norm in industry today due to the low intensity of the reactive gas lines.

SiOxNy: Partial Pressure Control of Both Gases

16 500 450

Partial Pressure

12

400 350 300

250

Nitrogen PP
4

200 150 100 50

0 0 200

Oxygen PP
400 600 800

0 1000

Elapsed Time, sec

Fig. 14. Reactive sputtering of SiOx Ny using partial pressure control of both gases. There is no trapping, and there is a smooth transition between partial pressures. Sputtering conditions: 1 kW target power, pulsed dc power at 100 kHz with a 4.0 As reverse time, and an argon pressure of 3.0 mTorr. From [43]. Used with permission from the Society of Vacuum Coaters.

Cathode Voltage, volts

Cathode Voltage

W.D. Sproul et al. / Thin Solid Films 491 (2005) 1 17

15

To date, three two-gas reactive sputtering systems with a single target material have been investigated experimentally to show the effect of combined flow and partial pressure control or complete partial pressure control. These three are the Ti O N, Al O N, and Si O N material systems [41 43]. In those three systems, it was found that flow control of one gas with partial pressure control of the other gas could lead to a situation where one of the gases traps the target in a poisoned condition. This situation was more prevalent when oxygen was in the flow control mode while the nitrogen was in the partial pressure control mode. The mass spectrometer data showed as the partial pressure of the nitrogen was increased with a fixed oxygen flow, a point was reached where the partial pressure of the oxygen suddenly jumped to a high value as is shown in Fig. 13 for the SiOx Ny system [43]. When the nitrogen partial pressure was subsequently reduced, the oxygen partial pressure remained at its high partial pressure value. The cathode voltage data paralleled the mass spectrometer data for the trapping situation. When the oxygen partial pressure increased significantly, the cathode voltage was similar to that for a poisoned condition for an oxide film. Oxygen dominated the three oxynitride ternary systems investigated, and when the system went into a trapped mode, it was due to an oxide poisoning of the target. Partial pressure control of both reactive gases was required for the three reactively sputter deposited ternary systems to avoid the trapping situation. With partial pressure control of both reactive gases, there is a freedom to operate at any point in the two-gas parameter space as is shown in Fig. 14 for the SiOx Ny system [43]. Trapping does not occur with partial pressure control of both gases.

Small Area Sputtering Compound Formation

1

Fraction of Compound

0.8

At = 3 cm2

0.6

Substrate
0.4

Target
0.2

0 0 1 2 3 4 5 6 7

Reactive Gas Flow, sccm

Fig. 15. Small spot reactive sputtering showing that the desired compound forms at the substrate before it does on the target allowing flow control of the reactive gas to be used [44].

10. Small area reactive sputtering The reactive sputtering modeling work done by Berg and his colleagues has proven invaluable for understanding and improving reactive sputtering processes. Berg and Nyberg discovered from their model that there is a hysteresis free operation area with flow control of the reactive gas if the sputtering area is reduced to less than a critical size as is shown in Fig. 15 [44]. This hysteresis free operation holds for all target ion current densities. The sputtering area is the critical factor. This discovery is still quite new, but it holds promise for a simpler way to do reactive sputtering in the future.

11. HPPMS reactive sputtering High power pulsed magnetron sputtering (HPPMS), which was first introduced by Kouznetsov et al. [45 47], is a relatively new sputtering technique with the promise of generating highly ionized plasmas using essentially conventional magnetron sputtering equipment. With HPPMS, a

very large peak power, which can be on the order of megawatts, is delivered to the sputtering target in a very short period of time in the range of 100 150 As. Peak power densities on the target are of the order of 1 3 kW cm 2 at discharge voltages between 500 and 1000 V. The high peak power applied for a very short period of time produces a high degree of ionization of the sputtered species similar to an arc source, but it does so without generating macroparticles [45 47]. First applied to the deposition of metal films, it was soon combined with reactive sputtering for the reactive deposition of conducting CrN films. These HPPMS reactively deposited films showed improved film properties compared to CrN films deposited in a combined cathodic arc, reactive sputtering process [48]. Although HPPMS worked well for the deposition of metallic and conducting compound films, there was a question if it could be used for the reactive sputter deposition of insulating films. Recent work using an experimental HPPMS power supply with arc handling capabilities [36,49,50] combined with partial pressure control of the reactive gas demonstrated that it is definitely possible to reactively deposit insulating films using HPPMS power [51 53]. One of the challenges of the reactive HPPMS work was to minimize the effects of arcing during the reactive process. For materials such as ZrO2, Ta2O5, and TiO2 [52,53], the arcing was minimal and was easily handled by the arc detection and suppression circuitry of the experimental HPPMS power supply. The reactive deposition of Al2O3 was more difficult with respect to arcing during the process [51]. Target preparation and clean up was very important for removing any previous built-up layers around the outer edge and center of the target. During deposition, the arc handling capabilities of the power supply were very important to prevent arcing from getting out of control because, unless

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W.D. Sproul et al. / Thin Solid Films 491 (2005) 1 17 [11] D. Depla, A. Colpaert, K. Eufinger, A. Segers, J. Haemers, R. De Gryse, Vacuum 66 (2002) 9. [12] D. Depla, R. De Gryse, Surf. Coat. Technol. 183 (2004) 190. [13] M.A. Lewis, D.A. Glocker, J. Vac. Sci. Technol., A 7 (1989) 1019. [14] S.M. Rossnagel, J. Vac. Sci. Technol., A 6 (1988) 19. [15] William D. Sproul, Paul J. Rudnik, Thin Solid Films 171 (1989) 171. [16] G. Este, W.D. Westwood, J. Vac. Sci. Technol., A 6 (1988) 1845. [17] S. Maniv, C. Miner, W.D. Westwood, J. Vac. Sci. Technol. 18 (1981) 195. [18] P.J. Kelly, P.S. Henderson, R.D. Arnell, G.A Roche, D. Carter, J. Vac. Sci. Technol., A 18 (2000) 2890. [19] D. Carter, H. Walde, G. McDonough, G. Roche, 45th Annual Technical Conference Proceedings of the Society of Vacuum Coaters, Lake Buena Vista, Florida, 2002, p. 570, Note: papers from the Annual Technical Conference Proceedings of the Society of Vacuum Coaters are available from the Society of Vacuum Coaters, 71 Pinon Hill Place NE, Albuquerque, NM 87122 USA, Telephone: +1-505-856-7188. [20] Peter A. Sieck, Russell J. Hill, John L. Vossen, Stephen Schulz, U.S. Patent 5,683,558, November 4, 1997. [21] Clive H. Burton, Rodney Pratt, Frank Samson, Multi-Anode Device and Methods for Sputter Deposition, U.S. Patent 6,440,280 B1, August 27, 2002. [22] M. Scherer, J. Schmitt, R. Latz, M. Schanz, J. Vac. Sci. Technol., A 16 (1992) 1772. [23] A. Belkind, Z. Zhao, D. Carter, G. McDonough, G. Roche, R. Scholl, 44th Annual Technical Conference Proceedings of the Society of Vacuum Coaters, Philadelphia, Pennsylvania, 2001, p. 130. [24] P.J. Kelly, R. Hall, J. OBrien, J.W. Bradley, G. Roche, R.D. Arnell, Surf. Coat. Technol. 142 144 (2001) 635. [25] F.G. Tomasel, D. Carter, H. Walde, J.J. Gonzalez, G. McDonough, G.A. Roche, Plasma Sources Sci. Technol. 12 (2003) 139. [26] D.J. Christi, E.A. Seymour, 46th Annual Technical Conference Proceedings of the Society of Vacuum Coaters, San Francisco, California, 2003, p. 257. [27] L.A. Bartolomei, T. Read, U.S. Patent 5,849,1262, December 15, 1998. [28] William D. Westwood, Sputter Deposition, AVS, 120 Wall Street, 32nd Floor, New York, NY 10005, 2003, p. 207. [29] J. Strumpfel, G. Beister, D. Schulze, M. Krammer, M. Krammer, St. Rehn, 40th Annual Technical Conference Proceedings of the Society of Vacuum Coaters, 1997, p. 179. [30] F. Milde, G. Teschner, C. May, 44th Annual Technical Conference Proceedings of the Society of Vacuum Coaters, Philadelphia, Pennsylvania, 2001, p. 204. [31] Michael A. Scobey, Richard L. Seddon, James W. Seeser, R. Russel Austin, Paul M. LeFebvre, U.S. Patent 4,851,095, July 25, 1989. [32] Haim Gilboa, Roderick Mosley, Hiroji Hanawa, U.S. Patent, 5,108,569, April 28, 1992. [33] Wei Xiong, Subhadra Gupta, U.S. Patent 6,537,428, March 25, 2003. [34] C. Misiano, E. Simonetti, Vacuum 27 (1977) 403. [35] S. Kikkawa, M. Fujiki, M. Takahashi, F. Kanamaru, O. Funtai, J. Jpn. Soc. Powder Powder Metall. 44 (1997) 674. [36] D.J. Christie, Power Conversion and Control for Pulsed Magnetron Reactive Sputtering, Ph.D. Dissertation, Colorado State University, Fort Collins, Colorado, May 2004, p. 41. [37] D.J. Christie, W.D. Sproul, D.C. Carter, 46th Annual Technical Conference Proceedings of the Society of Vacuum Coaters, San Francisco, California, 2003, p. 393. [38] M. Moradi, C. Nender, S. Berg, H.-O. Blom, A. Belkind, Z. Orban, J. Vac. Sci. Technol., A 9 (1991) 619. [39] H. Barankova, S. Berg, C. P.Carlsson, Thin Solid Films 260 (1995) 181. [40] N. Martin, C. Rousselot, J. Vac. Sci. Technol., A 17 (1999) 2869. [41] W.D. Sproul, D.J. Christie, D.C. Carter, S. Berg, T. Nyberg, 46th Annual Technical Conference Proceedings of the Society of Vacuum Coaters, San Francisco, California, 2003, p. 98.

stopped, arcing leads to more arcing. It was the combination of the partial pressure control of the reactive gas with the special arc handling capabilities of the power supply that made it possible to reactively sputter oxide films with HPPMS power.

12. Conclusions Reactive sputtering is a viable method for depositing compound films from an elemental target, but the method of control of the reactive gas has a strong influence on the reactive deposition rate and the film properties. Flow control of the reactive gas, although simpler to implement, invariably produces low deposition rates compared to the deposition rate from the elemental target material. It also produces films with less than optimal properties. Partial pressure control of the reactive gas allows deposition of films in the transition region between the elemental and poisoned states of the target, which leads to higher deposition rates compared to flow control and better film properties. Insulating films can be reactively deposited without the debilitating effects of arcing as long as the right kind of power (either pulsed dc or mid-frequency ac) is used. Multiple gas reactive sputtering requires partial pressure control of each reactive gas to prevent trapping of the target in a poisoned mode, and HPPMS of insulating films is possible with partial pressure control of the reactive gas and arc detection and suppression in the power supply.

Acknowledgements The authors wish to acknowledge Karen Peterson, Randy Grilley, and Dan Doran for their help in running the many reactive sputtering experiments and for characterizing the reactively sputter deposited films. References
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