Thin Solid Films 365 (2000) 4348 www.elsevier.

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Frequency response in pulsed DC reactive sputtering processes

L.B. Jonsson, T. Nyberg, I. Katardjiev, S. Berg*
The Angstrom laboratory, Uppsala university, P.O. Box 534, 751 21 Uppsala, Sweden Received 30 April 1999; received in revised form 24 November 1999; accepted 24 November 1999

Abstract By simple arguments as well as results from a recently developed computer simulation model we have found out that for high frequency pulsed DC reactive sputtering the target poisoning does not reect the periodicity of the pulsed DC power supply. The degree of target poisoning does not change markedly during a single duty cycle. The degree of poisoning essentially exhibits the same continuous time independent behavior as observed for the conventional continuous reactive sputtering process. Furthermore, it is shown that the distribution width of the transit times for sputtered atoms by far exceeds the period time for pulsed DC frequencies higher than 510 kHz. This causes a large overlap between sputter eroded material between consecutive pulses during processing resulting in an essentially continuous arrival rate of sputtered atoms to the substrate surface. This implies also that the deposition rate will be constant and will not follow the pulsed sputter erosion variation from the target. These ndings show that, with respect to lm stoichiometry and homogeneity, the high frequency pulsed DC reactive sputtering process behaves identically as the continuous reactive sputtering process. No chemical reaction effects or gas gettering variations will follow the periodicity of the pulsed DC power supply at high frequencies. q 2000 Elsevier Science S.A. All rights reserved.
Keywords: Pulsed DC; Reactive sputtering

1. Introduction Sputtering is probably the most popular metal thin lm deposition process. There exist commercially available codes [1,2] enabling the user to calculate the distribution of sputtered material at the substrate surface. These programs take into consideration the shape of the erosion track at the magnetron target, the energy- and angulardistributions of the sputtered atoms, the scattering of the latter via gas-phase collisions as well as the geometry of the processing chamber. Reactive sputtering can be used to deposit insulating thin lms. Performing DC magnetron sputtering from a pure metal target in an ambient of Ar and oxygen may result in the formation of a metal oxide insulating coating on the substrate. However, the presence of oxygen in the processing chamber, unfortunately, may also result in some oxidation of the metal target surface. The thin oxide coating at the target may be charged by the bombarding ions. This will result in microarcing at this surface. During such arcing microparticles may be formed resulting in a coating with microparticles inclusions. This is of course undesirable. To overcome this problem it has become quite popular to
* Corresponding author. Tel.: 1 46-18-471-3084. E-mail address: soren.berg@Angstrom.uu.se (S. Berg)

supply the DC power in the form of high negative pulses interrupted by small positive pulses (arc suppression) [3,4]. In this way the charge at the oxide surface on the target may be neutralized by attracting electrons during the positive part of the duty cycle. It has been shown that properly matched positive and negative pulses may allow for arc free reactive sputter deposition of insulating materials from pure metal targets. One might suspect that the DC-pulsed reactive sputter deposition process may create different processing conditions than those obtained in the traditional continuous RFor DC-magnetron sputtering. We have observed that there is surprisingly little reported about the basic understanding of the physical and chemical mechanisms for the DC pulsed technique. In fact we have not found any article in the literature that penetrates in detail how the pulsed DC reactive sputtering process deviates from the continuous reactive sputtering process. Our group has worked intensively with modeling and experimental studies of the reactive sputtering technique for the last 1015 years. The computer simulation model for the reactive sputtering process that was originally suggested by Berg et al. [58] has probably become the most generally accepted description of this process. As a natural continuation of our work concerning reactive sput-

0040-6090/00/$ - see front matter q 2000 Elsevier Science S.A. All rights reserved. PII: S 0040-609 0(99)01116-5

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tering we have also initiated both experimental and theoretical studies of the pulsed DC process. It is the purpose of these studies to obtain a more detailed understanding of some of the basic physical and chemical processes that take place with this relatively new processing technique. In pulsed DC reactive sputtering erosion of the target only takes place during the negative part of the duty cycle. One might suspect that the positive part of the duty cycle offers an additional time for reactions with the sputter eroded metal atoms and the reactive gas at the substrate as well as at the target surface. This is a signicant difference in processing conditions as compared to the continuous sputtering process. It is the purpose of this article to clarify how the conditions at the target and substrate will differ during pulsed DC reactive sputtering as compared to continuous reactive sputter deposition. The differences (and similarities) between the two cases are explained and illustrated by simple and well known accepted physical and chemical effects. 2. Arc suppression During DC reactive sputter deposition of e.g. an oxide from an elemental metal target in a mixture of argon and oxygen an insulating oxide lm may be formed on the target surface. This insulating layer will be charged by the positive ions that are accelerated in the plasma and collected on this surface. If the insulating layer could sustain an innite electric eld strength this layer would ultimately be charged to the applied power supply voltage Va. As a consequence, there would be no potential left to accelerate ions and electrons in the plasma and the plasma would therefore disappear and the sputtering process will stop. However, the insulating lm at the target can normally withstand an electric eld strength of up to 110 MV/cm before electrical breakdown in the layer will occur. During such a breakdown (micro-arcing) small particles may be ejected from the arcing tracks. These micro particles may reach the substrate and become imbedded in the growing lm. This will most probably be detrimental to the intended lm properties. A DC pulsed power supply can create conditions that eliminate the arcing at the target. The voltage build up VD on the insulating layer may be limited by interrupting the negative voltage and applying a short positive pulse to the target. This positive pulse will attract electrons to the target. This ux of negative particles will discharge fully or partially the insulating layer on the target. In this way arcing can be avoided. In Fig. 1 is shown a simplied drawing of the surface of the metal target during reactive DC sputtering. Included in Fig. 1 is also a schematic drawing of the time dependent target bias during pulsed DC reactive sputtering. We recall the simple arguments for selecting a suitable pulse frequency when operating the reactive sputtering
Fig. 1. Schematic of the target surface during reactive DC sputtering of an insulating material. The dielectric layer is charged by positive ions causing a voltage build up, VD, across the insulating layer with thickness d. Also shown is a schematic of the time dependent target voltage, Va, during pulsed DC reactive sputtering.

process with a pulsed DC power supply. As a rst order approximation the dielectric layer on the target may be described as a parallel plate capacitor where the dielectric layer represents the thickness (d) between the parallel plates. The voltage build up (VD) on this capacitor will follow the simple relation Q VD C 1 where Q is the charge on the capacitor C formed by the dielectric. The capacitor C can be expressed as C 110 A=d and the voltage VD can be written as VD Fd 3 where F is the electric eld strength in the dielectric layer. Due to the ion current density J (during the negative part of a duty cycle) charge will be collected in the capacitor. The charge build up can be written Q JAt 4 where t is the time that the constant current density J has passed current to the dielectric layer. Combining Eqs. (1)(4) will result in an expression for F F J=110 t 5 Assuming a relative dielectric constant 1 < 5, an average ion current density J < 20 mA/cm 2 and that arcing will occur when the dielectric has been charged to a critical eld strength F < 5 MV/cm will result in a maximum charging time t10 24 s before the critical eld strength is 2

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reached. This corresponds to a minimum pulse repetition frequency of approx. 10 kHz to avoid arcing. However, to assure absolute arc-free operation practical operating DC pulse frequencies use to be in the region of 50100 kHz. These simple `school-book calculations' serve to clarify why it is necessary to choose a relatively high operating frequency for the pulsed DC reactive sputtering process. In the following sections we will predict in some detail how the target and substrate conditions will vary during one duty cycle of the operating pulse frequency. 3. Target erosion 3.1. Negative period It is interesting to calculate how much the conditions at the target may change during a single period of the DC pulse duty cycle. It has been claimed that it is possible to preferentially `clean' the target (sputter removal of possible oxide formation) during the negative voltage period of the duty cycle [9]. There are reasons to believe, however, that this statement is not correct for the frequencies normally used in pulsed DC processing. It is quite easy to estimate the possible degree of change of target poisoning by calculating the possible maximum sputter erosion from the target during one single period of the DC pulse repetition frequency. At moderate target to substrate distances and low pressures the target erosion rate needed to supply a substrate deposition rate of 10 4 A/min may be ten times greater 5 <10 A/min. The sputter erosion from the target surface by one single pulse at 100 kHz pulse frequency will thus be 105 =60 1025 < 0:017 A/pulse. This sputter erosion corresponds to the removal of ,0.5% of a monolayer. This result points out that the change in degree of target poisoning by sputter erosion of some oxide can not be signicantly affected during the negative period (sputter erosion period) of one single duty cycle. At steady state DC pulsed reactive sputter processing, however, all consecutive pulses (by denition) will affect the process identically. Therefore at steady state processing no detectable variation in target poisoning will take place during the negative parts of the duty cycles. If the target poisoning varies ,0.5% one may truly consider the degree of target poisoning to be constant and not vary according to the applied pulsed DC frequency. 3.2. Positive period During the positive part of the duty cycle electrons are collected at the target surface. Due to the lower mass of the electrons as compared to ions the mobility of the electrons will be much higher than the mobility of the ions. The discharge current (positive period) will therefore typically be much higher than the charging current (negative period). Therefore the discharge may take place in a much shorter

time than the charging time. Due to this difference in mobility we may assume that the discharge may take place in 10% of the charging time. For a 100 kHz DC pulse repetition frequency the positive period of a duty cycle may be <1 ms. A typical partial pressure of a reactive gas during reactive sputter deposition may be in the region of 1 mTorr. This corresponds to a ux of reactive gas to all surrounding surfaces <5 1021 m 22 s 21. The number of reactive molecules that may reach the target surface during one positive pulse (10 26 s) will thus be <5 10 15 m 22. This corresponds to ,0.1% of the atomic density of a typical target surface. If all of the incoming reactive molecules would react with the target metal atoms less than 0.1% of the target atoms should be `converted' to compound surface molecules (dielectric). This simple calculation indicates clearly that the degree of `poisoning' of the target surface will not change markedly (,0.1%) during the positive part of one duty cycle. As in Section 3.1 we may consider the degree of poisoning to be constant also during the positive parts of the duty cycles. From these simple calculations we may conclude that the pulsed DC reactive sputtering technique will not cause a pulsed behavior of the target poisoning. The conditions at the target will basically remain constant (time independent) as in continuous DC sputtering. This result may come as a surprise to many users of the pulsed DC reactive sputtering process. The degree of target poisoning during one duty cycle does not reect the shape of the pulse from the pulsed DC power supply. It should be pointed out that these results of course are only valid for relatively high pulse repetition frequencies. 3.3. Target poisoning at different frequencies We have developed a computer simulation program that calculates the time dependent behavior of some key parameters (partial pressure of the reactive gas, sputter erosion rate from the target, degree of target poisoning etc.) during pulsed DC reactive sputtering [10]. The simulations are based on basic gas kinetics and straightforward material balance calculations. For the compound growth mechanism at the target it is assumed that gettering of reactive gas onto metal contributes to form the rst monolayer of compound. Further gettering contributes to form a second monolayer of compound and so on until a dened maximum number of atomic layers has been reached. Moreover, sputtering is assumed to remove the top atomic layer. For a detailed model description we refer to previous articles [58,10]. With this program, it is possible to predict the outcome of varying the repetition frequency of the pulsed DC power supply. In Fig. 2a,b is shown results from such simulations for sputtering of Al in an atmosphere of Ar and O2. Fig. 2a) shows the build up of the poisoned layer (Al2O3) at the Altarget as a function of time for a repetition frequency of only 1 Hz (low frequency mode). The calculations assume that we start with a `clean' metallic Al-target at t 0. From t 0 it

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frequency. The variation in the degree of poisoning of the target in Fig. 2b is so small that it can not be resolved by the eye. Therefore, in an insert in Fig. 2b is shown a magnication of a few duty cycles. In this magnication it can be seen that the variation in the degree of target poisoning in one single duty cycle is less than 0.3%. The results from the calculations shown in Fig. 2a,b strongly support the simple estimations made in Sections 3.1 and 3.2. For frequencies over 100 Hz the variation of the target poisoning in a single duty cycle will decrease even further [10]. At 100 kHz the calculations predict that the variations for all practical purposes may be considered to be zero. The results presented so far clearly indicate that in the high frequency mode of operation of the pulsed DC reactive sputtering process no time dependent variation of the poisoning of the target will be expected. The degree of poisoning will not vary according to the applied DC pulse frequency. In addition, the degree of target poisoning will approach the same level as for the corresponding continuous reactive sputtering process operating at a constant power level identical to the average power level of the pulsed DC process.

Fig. 2. Simulations of the target compound layer thickness for a pulsed DC sputtering with a repetition frequency of 1 Hz (a) and 100 Hz (b). At t 0 the target is in pure metallic state. It is seen that the variations (in steadystate) for 100 Hz are negligible.

4. Material deposition at the substrate 4.1. Time of ight of the sputtered atoms In the continuous reactive sputtering process the ux of sputtered atoms from the target will arrive continuously at the substrate. In the pulsed DC reactive sputtering process, however, the sputter erosion condition is quite different. At rst sight one may expect the lm growth conditions to vary in a periodic way corresponding to the pulse frequency of the pulsed DC power. However, there are strong reasons to believe that this is not necessary always the case. Metal atoms (and/or compound molecules) sputtered from the target exhibit a kinetic energy distribution. A typical energy of a sputtered atom may be <15 eV. For e.g. sputtered Al atoms this energy corresponds to a velocity of about 36000 m/s. At small processing pressure some sputtered Al atoms may travel between the target and the substrate essentially without any collisions. Assuming a target to substrate distance of e.g. 0.1 m the time of ight for these sputter eroded Al atoms between the target and the substrate will be <2040 ms. It should be noted that this time interval is longer than a single duty cycle (10 ms) for a 100 kHz pulsed DC reactive sputtering process. A large fraction of the out sputtered atoms have an energy ,5 eV. These atoms will exhibit an even longer time of ight between the target and the substrate. Furthermore, at normal sputtering operation pressure signicant scattering of the sputtered atoms with the argon gas also takes place. This scattering process causes a further delay of the transit time of the sputtered atoms. Both the energy and angular distribution of the sputtered

takes a certain time to reach steady state processing conditions. We dene that steady state has been reached when two consecutive periods become identical. In this calculation it takes <15 s to reach steady state. It can be seen that at this low frequency the thickness of the Al2O3 layer on top of the Altarget surface markedly follows the power variations from the pulsed DC power supply. At steady state the thickness of this poisoned layer (Al2O3) varies <^20% within a duty cycle. We have found [10] that if the frequency is further decreased the thickness variation of the poisoned layer will increase further. At low frequencies it is thus possible to obtain conditions at the target and the substrate that reect the periodicity of the pulsed DC power supply. Some scientists have successfully made use of this effect to add an extra control possibility of the average composition of the deposited lm [11]. However, one must keep in mind that arcing may easily occur at these low frequencies. It is, therefore, necessary to use an arc suppression unit in series with the low frequency power supply. Fig. 2b shows an identical simulation but for a pulse repetition frequency of 100 Hz For this `high frequency mode' of operation the calculations indicate that there are almost no variations in the degree of poisoning of the target in a duty cycle when the process has reached steady state (t . 15 s). At this frequency the curve does not exhibit a large zigzag shape as observed for the 1 Hz repetition

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atoms and the gas scattering will contribute to a broadening of the transit time distribution. A Monte Carlo based computer simulation of the distribution of transit times for sputtered atoms for a 0.1 m distance between the target and the substrate has been carried out. Only atoms arriving at the substrate within a radii of 5 cm from the symmetry axis have been considered. The calculations have been carried out for two different targets, Al and W. The energy distribution of the sputter eroded atoms used in the calculations are shown in Fig. 3. Due to the higher sublimation energy of W the escape energy is somewhat higher for W atoms than for Al atoms. The Ar pressure during processing was assumed to be 5 mTorr. The results of the calculations of the transit time distribution from sputter erosion from an Al or W target, respectively, are shown in Fig. 4. The latter indicates that sputtered Al atoms are more rapidly thermalized by gas scattering with Ar atoms than the W atoms. Therefore, the transit time distribution for sputtered Al atoms is shifted towards higher values. Note, however, that the width of these distributions <0.51 ms which is signicantly broader than the period time (1020 ms) for a single period in normal pulsed DC processing (50100 kHz). The distribution curves also illustrate that the majority of the sputtered atoms have a transit time exceeding by far 2040 ms, the latter corresponding to a straight collisionless transit between the target and the substrate. These results conrm that the energy- and angle- distributions of the sputtered atoms as well as collisions with gas molecules cannot be neglected in describing the `real' effective transit time for sputtered atoms. Fig. 5 shows the arrival time distribution of all Al atoms sputter eroded during the negative period (100 ms) of one duty cycle for a 5 kHz pulse repetition frequency having a 50% negative voltage duration time of the total duty cycle. This gure clearly illustrates that the distribution in arrival time at the substrate is signicantly wider than the sputter erosion time interval of one single period of the pulsed DC frequency. The short time interval between two consecutive pulses (200 ms) during processing indicates that there will

Fig. 4. The transit time distribution for aluminum and tungsten atoms.

be a large overlap between arrival times of Al atoms sputter eroded by two consecutive pulses. At steady state processing the pulsed sputter eroded material from the target will be collected at the substrate. This will result in an overall distribution of arrival of sputtered atoms that is the sum of the overlapping contributions from a large number of consecutive pulses. Fig. 6 shows this net arrival time distribution, obtained from integration of consecutive distributions as shown in Fig. 5 for a repetition frequency of 5 kHz. The results in Fig. 6 illustrate the somewhat surprising overall effect that the pulsed sputter erosion of atoms from the target will result in an almost continuous deposition rate of atoms at the substrate. This smearing effect, in addition to the results shown in Sections 3.1 and 3.2. (no time dependent stoichiometry variation of the target surface) strongly support the expectation that there will be a constant time independent deposition of material from the target onto the substrate. Neither will there be any compositional variation during lm growth correlated to the shape of the pulsed DC power supply. We may thus conclude that for the DC pulsed reactive sputter deposition process the deposition conditions at the substrate will be constant (time independent) as in continuous DC sputtering. It should be noted, however, that the results of Fig. 6 are only valid for high frequencies where the distribution in transit times for sputtered material is comparable to or larger than the sputter erosion period of a single duty cycle.

Fig. 3. The energy distributions for sputtered aluminum and tungsten atoms. Due to the higher surface binding energy of tungsten, its energy distribution is shifted to higher values.

Fig. 5. The arrival time distribution for aluminum atoms sputtered during a single pulse (dash curve).

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Fig. 6. The net arrival time distribution (in steady-state) for aluminum atoms sputtered during the dashed pulses (f 5 kHz).

inuence the reaction kinetics between metal target atoms and adsorbed molecules of the reactive gas. Furthermore, for identical average power supplied to the target the peak power is always higher for the pulsed DC process as compared to the continuous process. This will give rise to a higher plasma density during the sputter erosion part of the duty cycle in the pulsed plasma system. These two effects may generate conditions that have not been taken into account in this work. These effects can be simulated by modifying some of the parameters in the computer simulations. As far as we have found out, however, it is unlikely that these effects should change the process behavior to deviate signicantly from what has been described in this article. Acknowledgements This work has been nancially supported by the Swedish Research Council for Engineering Sciences (TFR) and the Swedish Foundation for Strategic Research (SSf). References
[1] J.P. Biersack, L.G. Haggmark, Nuclear Instrum. Methods Phys. Res. 174 (1980) 257. [2] SIMBAD - Thin Film Process Simulator. #318,11315-87 Avenue, Edmonton, Alberta, Canada T6G 2T9: Alberta Microelectronic Center, 1997. [3] S. Schiller, K. Goedicke, J. Reschke, V. Kirchhoff, S. Schneider, F. Milde, Surf. Coat. Technol. 61 (1993) 331. [4] H. Ohsaki, Y. Tachibana, J. Shimizu, T. Oyama, Thin Solid Films 281/282 (1996) 213. [5] S. Berg, H.-O. Blom, T. Larsson, C. Nender, J. Vac. Sci. Technol. A 5 (1987) 202. [6] S. Berg, T. Larsson, C. Nender, H.-O. Blom, J. Appl. Phys. 63 (1988) 887. [7] S. Berg, C. Nender, J. Physique IV C5 (1995) 45. [8] S. Berg, T. Nyberg, H.-O. Blom, C. Nender, Handbook of Thin Film Process Technology, Institute of Physics Publishing, Bristol, UK, 1998. [9] J. Sellers, Surf. Coat. Technol. 98 (1998) 1245. [10] L.B. Jonsson, T. Nyberg, S. Berg, J. Vac. Sci Technol. A ( in press Mar/April 2000). [11] F. Perry, A. Billard, C. Frantz, Surf. Coat. Technol. 94/95 (1997) 339.

However, this is certainly the case for a pulse repetition frequency of 50100 kHz normally used in pulsed DC reactive sputter processing. 5. Conclusions By some simple but straightforward arguments and calculations we have illustrated that for high frequency pulsed DC reactive sputtering the target poisoning as well as the substrate deposition rate and lm composition do not reect the periodicity of the pulsed DC power supply. These processing parameters will exhibit the same continuous time independent behavior as previously observed for the continuous reactive sputtering process. This nding indicates that the processing behavior (reactive gas gettering, hysteresis etc.) at high pulse repetition rates will be very similar to the continuous reactive sputtering. Results from more sophisticated computer simulation calculations conrm this prediction. We agree to, as earlier have been suggested, that the positive pulses primarily serve to supply electrons to the target surface to prevent the harmful charging of possible formed insulating layers on the target surface. In this way arc free reactive sputter deposition of insulating thin lms may be carried out. On the other hand, however, one cannot rule out that the intense short electron bombardment of the target does not