APPARATUS AND METHOD FOR DEPOSITING HYDROGEN-FREE TA-C LAYERS ON WORKPIECES AND WORKPIECE

Abstract

An apparatus for the manufacture of at least substantially hydrogen-free ta-C layers on substrates, which includes a vacuum chamber, which is connectable to an inert gas source and a vacuum pump, a support device in the vacuum chamber, at least one graphite cathode having an associated magnet arrangement forming a magnetron that serves as a source of carbon material, a bias power supply for applying a negative bias voltage to the substrates on the support device, at least one cathode power supply for the cathode, which is connectable to the at least one graphite cathode and to an associated anode and which is designed to transmit high power pulse sequences spaced at intervals of time, with each high power pulse sequence comprising a series of high frequency DC pulses adapted to be supplied, optionally after a build-up phase, to the at least one graphite cathode.

Claims

1.-33. (canceled)

34. A method for manufacturing substantially hydrogen-free ta-C layers on a substrate using a magnetron sputtering apparatus, the magnetron sputtering apparatus including a vacuum chamber in communication with an inert gas source and a vacuum pump; at least one graphite cathode having a front surface disposed within the vacuum chamber; a magnet arrangement associated with and disposed behind the at least one graphite cathode and comprising a center pole of a first polarity and outside poles of an opposite polarity surrounding the center pole and generating a closed loop magnetic tunnel in front of the cathode thereby forming a magnetron, the graphite cathode serving as a source of carbon material; a bias power supply; and at least one unipolar cathode power supply for the at least one graphite cathode, which is connectable to the at least one graphite cathode and to an associated anode, wherein the method comprises: a) providing the substrate to the vacuum chamber; b) evacuating the vacuum chamber with the vacuum pump; c) providing an inert gas that does not include hydrogen to the vacuum chamber from the inert gas source; d) applying a negative bias voltage to the substrate from the bias power supply, the negative bias voltage being less than 150 V at an average bias current that is in a range of 1.8 A to 9 A, and e) transmitting macro pulses to the cathode from unipolar cathode power supply, wherein the macro pulses each include a sequence of high power micro pulses, the macro pulses each have a duration in the range of 10 to 5000 sec and are spaced at intervals of time with a pulse repetition frequency in the range of 1 Hz to 2 kHz, each sequence of high power micro pulses includes a series of high frequency DC power pulses adapted to be supplied to the at least one graphite cathode with the high frequency DC power pulses having a peak power in the range from 100 kW to at least 2 megawatt, the micro pulses each have a total duration including the time during which the power to the cathode is switched on in the range from 2 to 25 sec and the time during which the power to the cathode is switched off in the range from 6 to 1000 sec, the average power of the macro pulses average over a longer period of time including a plurality of macro pulses is comparable with the power of a DC sputtering system with a constant DC power, and the substantially hydrogen-free ta-C layers have a hardness selected in the range of 1546 HV to 4890 HV.

35. The method claim 34, wherein the intervals between the high power pulse sequences are selected using a program.

36. The method of claim 34, wherein the series of high frequency DC pulses are supplied to the at least one graphite cathode after a build-up phase.

37. The method of claim 34, wherein the pulse repetition frequency lies in the range from 1 Hz to 1.5 kHz.

38. The method of claim 34, wherein the pulse repetition frequency lies in the range from 1 Hz to 30 Hz.

39. The method of claim 34, further comprising forming a bond layer on the substrate before depositing the substantially hydrogen-free ta-C layer.

40. The method of claim 34, wherein the substrate is formed from a material selected from the group consisting of steel, 100 Cr6 steel, titanium, titanium alloys, aluminum alloys, ceramic materials, and WC.

41. A substrate having a ta-C layer that is manufactured according to the method of claim 34.

42. The method of claim 34, further comprising heating the substrate to a temperature in the range of 99 to 199 C.

43. The method of claim 34, wherein a pulse length of the high frequency DC pulses is in the range of 652 to 656 s.

44. The method according to claim 34, wherein the duration of each micro pulse is in the range of 1 to 100 sec.

45. The method according to claim 34, wherein the average DC power lies in the range of 7 to 250 kW.

Description

[0048] The invention will now be explained in more detail with reference to the accompanying drawings in which are shown:

[0049] FIG. 1 a schematic view of a cathode sputtering apparatus for depositing ta-C coatings,

[0050] FIG. 2 a cross-section through a modified version of the vacuum chamber of the apparatus of FIG. 1,

[0051] FIG. 3 a schematic view of a cathode power supply for use in the apparatus of FIG. 1 or 2,

[0052] FIGS. 4A-4C schematic diagram of the high power DC pulse sequences used to investigate the manufacture of the ta-C coating by magnetron sputtering,

[0053] FIG. 5A a bar graph showing hardness as a function of various parameters as recited in Table 2, and

[0054] FIG. 5B a bar graph showing hardness as a function of various parameters as recited in Table 3.

[0055] In all drawings the same reference numerals have been used for the same components or features or for components having the same function and the description given for any particular component will not be repeated unnecessarily unless there is some distinction of importance. Thus a description given once for a particular component or feature will apply to any other component given the same reference numeral.

[0056] Referring first to FIG. 1 a vacuum coating apparatus is 10 is shown for coating a plurality of substrates or workpieces 12. The apparatus includes a vacuum chamber 14 of metal, which in this example has two oppositely disposed magnetron cathodes 16 which are each provided with a high power impulse power supply 18 (of which only one is shown here) for the purpose of generating ions of a material which is present in the gas phase in the chamber 14, i.e. inert gas ions and/or ions of the materials of which the respective cathodes are formed. The workpieces 12 are mounted on a support device in the form of a table 20 which rotates in the direction of the arrow 22 by means of an electric motor 24. The electric motor drives a shaft 26 which is connected to the table 20. The shaft 26 passes through a lead-through 28 at the base of the chamber 14 in a sealed and isolated manner which is well known per se. This permits one terminal 30 of the bias power supply 32 to be connected via a lead 27 to the workpiece support 20 and thus to the workpieces. This substrate bias power supply 32 is shown here with the letters BPS an abbreviation for bias power supply. The BPS is preferably equipped with HIPIMS-biasing capability, as described in the EP application 07724122.2 published as WO2007/115819, in particular with regard to the embodiment of FIGS. 1 to 3.

[0057] Biasing can also be done by pulsed biasing or RF-biasing. Pulsed biasing can be synchronized with the HIPIMS-cathode pulses (also described in WO2007/115819). Good results can be achieved with the HIPIMS-DC biasing described in connection with FIGS. 1 to 3 of WO2007/115819. For thicker coatings, HIPIMS biasing may be an issue because of more or less non-conductivity of the coating.

[0058] In this example the metallic housing of the vacuum chamber 14 is connected to ground and this is at the same time the positive terminal of the apparatus. The positive terminal(s) of the high impulse cathode power supply(ies) 18 is/are likewise connected to the housing 14 and thus to ground 36 as well as the positive terminal of the bias power supply 32.

[0059] A connection stub 40 is provided at the top of the vacuum chamber 14 (but could be at located at other locations as well) and can be connected via a valve 42 and a further line 44 to a vacuum system for the purpose of evacuating the treatment chamber 14. The vacuum system is not shown but well known in this field. A further line 50, which serves for the supply of an inert gas, especially argon to the vacuum chamber 14, is likewise connected to the top of the vacuum chamber 14 via a valve 48 and a further connection stub 46. For dopants, additional gas supply systems 43, 45, 47 can be used.

[0060] Vacuum coating apparatus of the generally described kind are known in the prior art and frequently equipped with two or more cathodes 16. For example a vacuum coating apparatus is available from the company Hauzer Techno Coating BV in which the chamber has a generally square shape in cross-section with one cathode at each of the four sides. This design has one side designed as a door permitting access to the chamber 14. In another design the chamber is approximately octagonal in cross-section with two doors which each form three sides of the chamber. Each door can carry up to three magnetrons and associated cathodes 16. A typical vacuum coating apparatus includes a plurality of further devices which are not shown in the schematic drawings of this application. Such further devices comprise items such as dark space shields, heaters for the preheating of the substrates and sometimes electron beam sources or plasma sources in diverse designs. Finally, it is also possible to provide arc cathodes with respective arc power supplies in the same chamber in addition to magnetron cathodes. When using the apparatus air is first extracted from the vacuum chamber 14 by the vacuum pumping system via the line 44, the valve 42 and the line 40 and the argon is supplied via the line 50, the valve 48 and the connection stub 50. The chamber and the workpieces are preheated during pump-down to drive out any volatile gases or compounds which adhere to the workpieces or chamber walls.

[0061] The inert gas (argon) which is supplied to the chamber is always ionized to an initial extent, for example by cosmic radiation and splits up into ions and electrons.

[0062] By generating a sufficiently high voltage on the work pieces, a glow discharge can be generated on the workpieces. The argon ions are attracted to the workpieces and collide there with the material of the workpieces, thus etching the workpieces.

[0063] Alternatively, Ar ions can be generated by a plasma source. The generated ions can be attracted to the workpieces by a negative substrate bias voltage and can then etch the workpieces.

[0064] As soon as the etching treatment has been carried out the coating mode can be switched on. For a sputter discharge, during deposition the cathodes will be activated. Ar-ions are colliding with the target and knock atoms out of the target. Electrons are ejected from the target due to sputtering and are accelerated by the dark space voltage gradient. With their energy they can collide with Ar atoms, where secondary electrons will be emitted and help to maintain the discharge. Each of the cathodes is provided with a magnet system (not shown in FIG. 1 which is well known per se and which normally generates a magnetic tunnel in the form of a closed loop which extends over the surface of the associated cathode. This tunnel formed as a closed loop forces the electrons to move around the loop and collide with argon atoms causing further ionization in the gas atmosphere of the vacuum chamber 14. This in turn causes further ionization in the chamber from the material of the associated cathode and the generation of further argon ions. During deposition these ions can be attracted to the substrates by the applied negative bias voltage of for example 120 V to 1200 V and strike the surface of the workpieces with appropriate energy to control the coating properties.

[0065] In case of a HIPIMS discharge, a different discharge mode is effective. The number of ions increases dramatically and as a consequence the target material particles knocked out from the target will be ionized. This is not the case for a normal sputter discharge. As a consequence gases present in the chamber will be highly ionized as well. This is beneficial when dopants are applied.

[0066] The power supply to the cathode or cathodes causes a flux of ions of the material of the cathode to move into the space occupied by the workpieces 12 and to coat them with the material of the respective cathode. The structure of the coating is influenced by the applied negative bias voltage that influences the movement of ions towards the workpieces.

[0067] Sputtering processes are known in diverse forms. There are those that operate with a constant voltage at the cathodes and a constant negative voltage at the workpieces and this is termed DC magnetron sputtering. Pulsed DC sputtering is likewise known in which at least one of the cathodes is operated in a pulsed mode, i.e. pulsed power is applied to the cathode by a pulsed power supply.

[0068] A special form of a pulsed discharge is the HIPIMS discharge. In a HIPIMS mode the power which is supplied to each cathode during a power impulse can be much higher than the power of a DC sputtering mode because there are substantial intervals between each pulse and the average power remains the same as for DC puttering. The limiting constraint on the power is the amount of heat that can be dissipated at the cathode before this overheats.

[0069] In recent times the cathodes are no longer supplied with a constant power but rather with power impulses of much higher power but only in relatively short pulses. This leads to a higher ionization in the vacuum chamber and improved coatings. For example, in well known HIPIMS sputtering (high power impulse magnetron sputtering), each power pulse can have a duration of say 10 s and a pulse repetition time is used of say 200 s, (corresponding to a pulse repetition frequency of 5000 Hz, i.e. a spacing between impulses of 190 s). These values are only given as an example and can be varied in wide limits. For example, an impulse duration can be selected between 10 s and 4 ms and a pulse repetition time between 200 s and 1 s. As the time during which a very high peak power is applied to the cathodes is short the average power can be kept to a moderate level equivalent to that of a DC sputtering process. It has however been found that by the application of high power impulses at the cathode these operate in a different mode in which a very high degree of ionization of the ions arises which are ejected from the cathodes, with this degree of ionization, which is material dependent, lying in the range between 40% and indeed up to 90%. As a result of this high degree of ionization, many more ions are attracted by the workpieces and arrive there with higher velocities which lead to denser coatings and make it possible to achieve completely different and better coating properties then regular sputtering or arc coating.

[0070] The fact that the power is supplied in power peaks means however that relatively high currents flow in the bias power supply during these power peaks and the current take up cannot be readily supplied by a normal power supply.

[0071] In order to overcome this difficulty WO 2007/115819 describes a solution as shown in FIG. 1 of this application in which an additional voltage source 60 is provided which is best realized by a capacitor. The capacitor 60 is charged by a customary bias power supply to the desired output voltage. When a power impulse arrives at one of the cathodes from the HIPIMS power supply 18 then this leads to an increased material flow of ions, essentially ions of the cathode material to the workpieces 12 and this signifies an increase of the bias current at the bias power supply via the workpiece support 20 and the line 27. A normal bias power supply could not deliver such a peak current when it is designed for constant DC operation instead of HIPIMS operation. However, the capacitor 62, which is charged by the bias power supply to the desired voltage in the periods between the power impulses, is able to keep the desired bias at the substrates constant within narrow limits and to supply the required current which only cases a small degree of discharging of the capacitor. In this way, the bias voltage remains at least substantially constant.

[0072] By way of example the discharge can take place in such a way that a bias of 50V drops during the power pulses to 40V.

[0073] As HIPIMS sputtering has developed there have been some proposals to use special high power pulse sequences instead of single power pulses. In accordance with the present invention it has surprisingly been found that with HIPIMS+OSC power supplies excellent hydrogen-free ta-C coatings can be formed from a graphite cathode when such pulse sequences are used with parameters in particular ranges.

[0074] In the simplest form of the present invention one of the cathodes 16 is a graphite cathode for supplying the carbon by magnetron sputtering and the other is a Cr, Ti or Si target for supplying a bond layer material. Possibly, other materials could also be used for a bond layer.

[0075] All the depositions of ta-C layers investigated were performed using workpieces on a table 20 of 850 mm diameter. To ensure good adhesion of the hard hydrogen-free carbon layer on the substrate, the apparatus initially used a standard ARC adhesion layer such as is used when depositing ta-C by carbon arc. It will not be described in detail because it is not the preferred solution and the arc process is in any case well known.

[0076] FIG. 2 shows a view of the vacuum chamber of FIG. 1 in a cross-section perpendicular to the vertical axis with additional detail but without the workpieces. The chamber also has four cathodes, two of Cr as a bond layer material and two of graphite for forming the ta-C layer.

[0077] The two cathodes 16 labelled also C are of graphite and have magnet arrangements with centre poles of polarity north (N) and outside poles of polarity south (S) to generate the well known magnetic tunnel of a magnetron. The cathodes have the shape of elongate rectangles when viewed face on and are shown here in a cross-section perpendicular to their long axis. Instead of having SNS polarity as shown, they could have NSN polarity as shown for the magnet arrangements for the Cr cathodes at the top and bottom of FIG. 2. The CR cathodes 16 would then have magnet arrangements with SNS polarity.

[0078] The magnet arrangements can be moved in the direction of the respective double arrows 82 towards and away from the respective cathodes 16. This is an important control parameter for the operation of the HIPIMS cathodes.

[0079] The idea is for the magnetrons to have alternating polarities going around the vacuum chamber 14. This means, with an even number of cathodes that the magnetic poles always alternate, i.e. N, S, N, S, N, S, N, S, N, S, N, S, when going around the chamber. This leads to an enhanced magnetic confinement of the plasma. A similar magnetic confinement can also be achieved if all cathodes have the same polarities, say NSN. Then it is necessary to operate with auxiliary S poles between the adjacent magnetrons to obtain a similar N, S, N, S, N arrangement around the chamber. It will be appreciated that the described arrangements only work with an even number of magnetrons. However, it is also possible to obtain a similar effect with an odd number of magnetrons either by making some poles stronger than others or by the use of auxiliary poles. Such designs to obtain a closed plasma are well known and documented in various patent applications.

[0080] What FIG. 2 also shows is four rectangular coils 80 positioned like the magnets with the SNS poles or NSN poles outside of the chamber 14. The coils form electromagnets and have the same polarity as the outer magnets for the respective cathodes 16. These electromagnetic coils 80 enable the magnetic flux in front of the cathodes 16 and inside the chamber 14, to be varied.

[0081] FIG. 3 shows the principle circuit for a special HIPIMS+OSC cathode power supply 18. It has a source 80 of constant voltage Vin (which can be varied) which is connected across a capacitor 82. A lead 84 goes from the negative terminal of the source of constant power 80 and of the capacitor 82 to the respective cathode 16. A second lead 85 goes from the positive terminal of the source of constant power 80 to the anode. In most cases the anode will be the grounded wall of the vacuum chamber 14. An additional anode is sometimes provided in the vacuum chamber 14 adjacent to the cathode 16 and can be advantageous. The reference numeral 86 designates an electronically controllable switch with a programmable electronic control 88. The electronic control 88 can be controlled by various programs called pulse files to vary the parameters of the pulse sequences provided for each high power pulse sequence by opening and closing the electronic switch 86, which can for example be an IBGT or similar device. It is to be noted that switch 86 plays a role in the extinguishing of an (undesired) arc discharge on the cathode. Also it is to be noted that the equipment allows for a combination as well as a separation of the voltage control switches. It is for example possible that the controls for the voltage Vin on capacitor 82 can be used for the control of the output voltage according to the macro-pulse programming, which of course also needs to be switched off immediately in case of arc detection. Therefore it should be noted that the switch is drawn as a functional device, which can correspond to one or more distributed components in the actual device.

[0082] The electronic control 88, which can be thought of as a microprocessor or microcontroller, is also able to operate a further electronic switch 90. This switch is used as a crowbar, which together with switch 86 will be switched on if an arc occurs on the cathode. This switch will preferentially be connected directly between the output terminals of cathode and anode (14 and 16) in order to dissipate as much stored energy from capacitors and inductances as possible for fastest switching off.

[0083] An LC circuit 92 is connected into the lead 84 so that the power applied during each high power pulse sequence can be modified at the resonant frequency of the LC circuit, which is preferably also a tunable LC circuit capable of operating at various resonant frequencies.

[0084] It should be noted that for reasons which are not well understood the plasma in side the vacuum chamber acts as complicated electrical load with non-linear characteristics which lead to the waveforms explained below with reference to FIGS. 4A to 4C. It has been found that by increasing the frequency resonant conditions can be created, leading to high oscillations of current and power. Hence, the oscillating voltage after the initial build up phase of each high power pulse sequence is an oscillating unipolar voltage which does not alternate from positive to negative polarity but always has the same negative DC polarity, albeit of an oscillating nature.

[0085] The most characteristic properties from a process point of view of the pulse unit used here, as described in connection with FIG. 3 is that a wide range of possible pulse shapes can be generated. The pulse unit described allows variations of the off times, such as long off times of the voltage pulses within a pulse package, i.e. within one high frequency pulse sequence (macro-pulse). Due to the long off time of the voltage the cathode current also returns to zero. This is illustrated in the oscilloscope trace of the FIG. 4 recordings shown below. Three different pulse files are shown of which the characteristics are given in Table I below.

[0086] In Table 1 some parameters are given that have been applied for the respective pulse file (column 1 in Table 1). Pulse files are the programs for the macro-pulses. In this example the macro-pulses have been built up from micro-pulses in a here called ignition part (column 2-6) and a here called highly ionized part (column 11). In column 12 is the total time of the macro-pulse mentioned. Details about the columns of table 1 are explained by the first line: the pulse file concerned here is named 35. In the ignition part of the macro-pulse, 4 repetitive pulse cycles have been programmed (column 5), where each individual cycle consists of a micro-pulse. For each micro-pulse the voltage is switched by means of switch 86 to the output for 3 s (voltage on) followed by a period of 40 s in which the voltage is switched off. This on/off cycle is repeated 4 times (column 5), which leads to a duration (column 2) of 172 s (440+43). The frequency of 23 kHz indicated in column 6 is derived from the periodicity of 43 s, determined by the sum of column 3 and 4.

[0087] After the ignition period, a highly ionized period follows. Here the micro-pulse consists of 30 sec off (column 9) and 14 sec on (column 10). The period of this micro-pulse is therefore 44 sec, corresponding to 22.7 kHz (column 11). The number of micro-pulses programmed in the highly ionized part, is 11 (column 10), resulting in a duration of the highly ionized period of 484 sec (column 8, calculated from columns 11 and the sum of column 9 and 10). The total duration of the macro-pulse in column 12 is 656 sec, which is calculated from the sum of all micro-pulse periods. In this case it is the sum of the durations of the ignition period (column 2) and of the highly ionized period (column 7).

TABLE-US-00001 Col. 1 Col. 2 Col. 3 Col. 4 Col. 6 Col. 7 Col. 8 Col. 9 Col. 11 Col. 12 pulse t_ign t_ign_ t_ign_ Col. 5 f_ign t_H1 t_H1_ t_H1_ Col. 10 f_H1 t_pulse file (s) off on #_ign (Hz) (s) off on #_H1 (Hz) (s) 35 172 40 3 4 23256 484 30 14 11 22727 656 42 172 40 3 4 23256 480 6 10 30 62500 652 43 172 40 3 4 23256 480 10 14 20 41667 652

[0088] Table 1

[0089] Every pulse starts with an ignition pulse. After the ignition pulse, pulse file 35 generates pulses with long off times, while pulse file 42 generates pulses with short off times. Pulse file 43 has intermediate off times. This can also be seen in the oscilloscope recordings of FIGS. 4A to 4C.

[0090] For pulse file 35 the cathode current has the largest oscillations and it actually drops down to zero. It is noteworthy that the bias current also has the largest oscillations, as can be expected, but the off time is still not large enough for the bias current to drop down back to zero.

[0091] In FIG. 4A-4C the displayed signals are the cathode voltage, the topmost trace which is labelled 1 at the left hand side, the bias current which is the trace that starts at the left hand side in the middle at approximately the level labelled T and drops to the lowest position, and the cathode current which starts at the lowest position at the left hand side labelled 2 and rises to the middle position. This description of the traces can most easily be followed in FIGS. 4B and 4C and then read over into FIG. 4A. The scaling in the oscillogram is 100 sec/DIV for the (horizontal) time scale, whereas for the vertical scale for the signals is set to 160 Amps/DIV for cathode current, 10 Amps/DIV for the bias current, and 700 Volt/DIV for the cathode voltage. DIV is used here as an abbreviation for Division and one DIV gives the height of one of the boxes subdivided into five smaller graduations It should be noted that the level labelled 1 corresponds to zero volts. The value labelled T is actually the zero level for the bias current (i.e. there is an offset from the value labelled T to the start of the curve for the bias current of a few amps which can be calculated from the scale of the graphs). The position labelled 2 is the zero value for the cathode current.

[0092] In the enlarged oscillogram of FIG. 4A o the bottom of page 21 is the parameter setting of the pulse files according table 1 recognizable. As an example: the trace for the cathode current in FIG. 4A shows that the ignition part lasts 172 sec, whereas counting of the last 2 divisions of the highly ionized part contains somewhat less then 5 cycles. In the latter case 5 cycles would last 220 sec according to Table 1, column 8 and 9.

[0093] Process Parameters: Pulse File and Magnetic Field

[0094] In order to scan the process window the three shown pulse files were used to deposit hydrogen-free carbon layers. In addition the magnetic field was changed by putting the magnetic board, i.e. the holder of the permanent magnets, either in the front or back position, as symbolised by the arrow 82. In the front position the horizontal field strength (parallel to the carbon target surface) is approximately 600 Gauss. The back position results in a magnetic field strength of approximately 300 Gauss. One of the most interesting properties of the coating is the hardness. In Table 2 below the hardness result of the 6 deposited coatings (3 pulse files2 magnetic field strengths) is shown. The results are also shown in the bar graph of FIG. 5A. Other characteristic process parameters (maximum temperature, peak cathode current, peak bias current, average bias current) and the coating thickness are also given. All depositions ran for 12 hours, unless otherwise indicated.

TABLE-US-00002 TABLE 2 Hardness as a function of several parameters Pulse Max. Avg. Max Max Hardness Run Pulse length Magnet temp. Bias lbias cath. Thickness HVpl number File (s) position in C. current current current in m 10 mN 7 35 656 front 188 7.5 44 520 1.07 4394 8 35 656 back 149 4.6 26 350 1.45 3417 9 42 652 back 99 1.8 26 368 1.2 1546 10 42 652 front 120 3.2 42 416 0.81 3812 11 43 652 front 141 4.4 44 512 0.93 3851 12 43 652 back 117 2.9 36 496 1.07 2727

[0095] TABLE 2 in indicated as a table above and as a bar graph in FIG. 5. The most important conclusion to be drawn from this table is that pulse files with the longest off-time in the high ionization part (all pulse files had the same ignition part) gave the hardest coating (pulse file 35), whereas shorter off times result in softer coatings (pulse file 42 with shortest off time gives softest coating).

[0096] A stronger magnetic field results in a harder coating. For each individual pulse file this correlates with the peak bias current and the peak cathode current. It should be noted however that for different pulse files this correlation is lost. For example, pulse file 35 with magnets in back position has a peak bias current of 26 A and a coating hardness of 3400 Vickers, and pulse file 43 with magnets in back position has a peak bias current of 36 A and a hardness of only 2700 Vickers. This is possibly caused by the peak cathode current. It is known that the height of the peak cathode current is one of the dominating parameters for the ionization of the cathode material. The increase in bias current is probably related to an additional ionization of Ar gas.

[0097] From this first scan of parameters it is concluded that the best result can be obtained with the strongest magnetic field (magnets in front) and the longest off time in the pulse package (pulse file 35).

[0098] Process Parameters: Argon Flow, UBM Coil Current, and Bias Voltage

[0099] Other process parameters which can influence the coating properties are the maximum temperature, the process pressure, the UBM coil current, and the bias voltage. To investigate the effect these parameters have on the coating properties, the coating of run 7 (pulse file 35, magnets in front, 400 sccm Ar, 2 A UBM coil current, 100 V bias) was taken as the reference.

[0100] The effect on the coating hardness of these parameters is shown in Table 3 below and illustrated also in the bar graph of FIG. 5B.

TABLE-US-00003 TABLE 3 Influence of variation of pressure (by Ar flow), coil current and bias voltage. Pressure Max. Average Max. Max. Avg. run Ar Coil Bias pulse in 10.sup.3 Temp. bias bias cath. Power Thickness HVpl # (sccm) (A) Volt. file mbar in C. curent current current in kW in m 10 mN 7 400 2 100 35 2.47 188 7.5 44 520 9 1.07 4394 16 400 4 100 35 2.53 199 9 49 384 7 0.089 4890 17 400 4 150 35 2.48 188 6.1 32 384 7 0.69 4319

[0101] Increasing the coil current from 2 A to 4 A (which increases the ionization because of the stronger unbalancing effect on the cathodes) has a positive effect on the coating hardness. Also the peak bias current, and therefore the coating temperature, goes up in this case. Under these conditions a coating hardness of almost 4900 Vickers was achieved, which is the best result obtained so far. Further investigations have to be done and will probably add more information to these coatings.

[0102] Probably it makes no sense to increase the bias voltage combined with increased coil currents. It is likely that there is an optimum for the combination off higher coil currents and higher bias voltages. The optimum is in this case probably lower than 150 V.

SUMMARY AND RECOMMENDATIONS

[0103] From the current scan of the process parameters it can be concluded that the best result is obtained by depositing with long off times of the voltage pulses within the pulse package or sequence. Depositing with higher UBM coil currents results in the deposition of a hydrogen-free carbon coating with the highest measured hardness so far (almost 4900 Vickers). Thus, the following recommendations can be given: [0104] Use higher UBM coil current (e.g. 6 A) [0105] Use a lower negative bias voltage [0106] Find an optimum for the combination of coil current and bias voltage. [0107] Also it is conceivable that adding small amounts of C2H2 and thus permitting a small proportion of hydrogen in the coating (less than about 1%) could be beneficial. [0108] Introduction of other dopants could be beneficial for the tribological properties, even though it does not necessarily lead to a higher hardness.

[0109] When an optimum coating from this parameter window has been obtained then attention should be paid to the base layer or bond layer. It seems that improvements can be made by: [0110] Replacing the carbon arc ion etch by a HIPIMS carbon ion etch or by other bond layers produced by regular sputtering. [0111] Deposition of the hard hydrogen-free carbon layer on top of a (standard) DLC coating could be beneficial for tribological systems, but also for other wear systems as referred to above.