Layer system with at least one mixed crystal layer of a multi-oxide

Abstract

A PVD layer system for the coating of workpieces encompasses at least one mixed-crystal layer of a multi-oxide having the following composition: (Me1.sub.1-xMe2.sub.x).sub.2O.sub.3, where Me1 and Me2 each represent at least one of the elements Al, Cr, Fe, Li, Mg, Mn, Nb, Ti, Sb or V. The elements of Me1 and Me2 differ from one another. The crystal lattice of the mixed-crystal layer in the PVD layer system has a corundum structure which in an x-ray diffractometrically analyzed spectrum of the mixed-crystal layer is characterized by at least three of the lines associated with the corundum structure. Also disclosed is a vacuum coating method for producing a mixed-crystal layer of a multi-oxide, as well as correspondingly coated tools and components.

Claims

1. A vacuum coating method for producing a mixed-crystal layer of a multi-oxide on a workpiece, comprising the steps of: depositing a coating on the workpiece with a first arc- or sputtering-source electrode, constituting an alloy target, and a second electrode in an oxygenous process-gas atmosphere; and simultaneously feeding said source electrode with a direct current or direct voltage as well as a pulsed or alternating current or a pulsed or alternating-current voltage, characterized in that composition of the alloy target essentially corresponds to that of the mixed-crystal layer and that the latter is deposited with a corundum structure by arc evaporating the alloy target, wherein said mixed-crystal layer of said multi-oxide comprises areas of at least one element of said alloy target.

2. Method as in claim 1, characterized in that the composition of the metals in the mixed-crystal layer, when scaled to the total metal content, does not differ for the respective constituent metals by more than 10 at % from the concentrations in the target composition.

3. Method as in claim 2, characterized in that the composition does not differ by not more than 5 at % from the concentrations in the target composition.

4. Method as in claim 2, characterized in that the composition does not differ by not more than 3 at % from the concentrations in the target composition.

5. Method as in claim 1, characterized in that the source is an arc source and that the second electrode is separated from the arc source or constitutes the anode of the arc source.

6. Method as in claim 5, characterized in that both electrodes are connected to and powered by a single pulsed-current power supply.

7. Method as in claim 6, characterized in that the second electrode serves as the cathode of another arc vaporizing source which latter as well is connected to and powered by a DC power supply.

8. Method as in claim 6, characterized in that the second electrode serves as the cathode of a sputtering source, which latter as well is connected to and powered by a power supply.

9. Method as in claim 8, characterized in that the sputtering source is a magnetron source.

10. Method as in claim 8, characterized in that the power supply is a DC power supply.

11. Method as in claim 6, characterized in that the second electrode is in the form of an evaporation crucible and is powered as the anode of a low voltage arc evaporator.

12. Method as in claim 7, characterized in that the DC power supply and the pulsed current supply are decoupled by means of an electrical decoupling filter.

13. Method as in claim 12, characterized in that the electrical decoupling filter contains at least one hold-off diode.

14. Method as in claim 7, characterized in that the DC power supply is operated with a base current in a manner whereby the plasma discharge at the sources is maintained in an essentially continuous mode.

15. Method as in claim 14, characterized in that the sources are the arc evaporation sources.

16. Method as in claim 1, characterized in that the pulsed current or pulsed voltage power supply is operated with pulse edges whose pulse slopes are steeper than 2.0 V/ns, leading to a high-power discharge.

17. Method as in claim 16, characterized in that the pulse slopes are at least in the range from 0.02 V/ns to 2.0 V/ns.

18. Method as in claim 16, characterized in that the pulse slopes are at least in the range from 0.1 V/ns to 1.0 V/ns.

19. Method as in claim 1, characterized in that the pulsed current power supply is operated at a frequency in the range from 1 kHz to 200 kHz.

20. Method as in claim 1, characterized in that the pulsed current power supply is operated with a varying pulse-width ratio setting.

21. Method as in claim 1, characterized in that a pulsed magnetic field is applied on at least one arc source.

22. Method as in claim 21, characterized in that the magnetic field is pulsed by the pulsed current or by part of the pulsed current of the arc source.

23. Method as in claim 1, characterized in that at least one arc source is either not cooled or is heated.

24. Method as in claim 1, characterized in that the sources are operated with a process gas that has at least 80% of oxygen.

25. Method as in claim 24, characterized in that the process gas has 90% of oxygen.

26. Method as in claim 24, characterized in that the process gas consists 100% of oxygen.

27. Method as in claim 1, characterized in that the coating temperature is set below 650 C.

28. Method as in claim 27, characterized in that the coating temperature is set below 550 C.

Description

EXAMPLES AND FIGURES

(1) The following will explain this invention with the aid of examples and with reference to the exemplary figures which illustrate the following:

(2) FIG. 1 X-ray spectra of (Al.sub.1-xCr.sub.x).sub.2O.sub.3 layers;

(3) FIG. 2 Lattice parameters of (Al.sub.1-xCr.sub.x).sub.2O.sub.3 layers;

(4) FIG. 3 Temperature pattern of the lattice parameters;

(5) FIG. 4 Oxidation pattern of a TiAlN layer;

(6) FIG. 5 Oxidation pattern of a TiCN layer;

(7) FIG. 6 Oxidation pattern of a TiCN/(Al.sub.1-xCr.sub.x).sub.2O.sub.3 layer;

(8) FIG. 7 Detail of a (Al.sub.1-xCr.sub.x).sub.2O.sub.3 layer.

(9) The example per test #1), described below in more detail, covers a complete coating cycle according to the invention, employing a weak, essentially vertical magnetic field in the area of the target surface.

(10) The workpieces were placed in appropriately provided double- or triple-rotatable holders, the holders were positioned in the vacuum processing chamber, whereupon the vacuum chamber was pumped down to a pressure of about 10.sup.4 mbar.

(11) For generating the process temperature, supported by radiation heaters, a low voltage arc (LVA) plasma was ignited between a baffle-separated cathode chamber housing a hot cathode and the anodic workpieces in an argon-hydrogen atmosphere.

(12) The following heating parameters were selected:

(13) TABLE-US-00001 Discharge current (LVA) 250 A Argon flow 50 sccm Hydrogen flow 300 sccm Process pressure 1.4 10.sup.2 mbar Substrate temperature approx. 550 C. Process duration 45 min

(14) Those skilled in the art will be familiar with possible alternatives. As a matter of preference the substrate was connected as the anode for the low voltage arc and also preferably pulsed in unipolar or bipolar fashion.

(15) As the next procedural step the etching was initiated by activating the low voltage arc between the filament and the auxiliary anode. Here as well, a DC-, pulsed DC- or AC-operated MF or RF power supply can be connected between the workpieces and frame ground. By preference, however, a negative bias voltage was applied to the workpieces.

(16) The following etching parameters were selected:

(17) TABLE-US-00002 Argon flow 60 sccm Process pressure 2.4 10.sup.3 mbar Discharge current, LVA 150 A Substrate temperature approx. 500 C. Process duration 45 min Bias 200-250 V

(18) The next procedural step consisted in the coating of the substrate with an AlCrO layer and a TiAlN interface layer. If higher ionization is needed, all coating processes can be assisted by means of the low voltage arc plasma.

(19) For the deposition of the TiAlN interface layer the following parameters were selected:

(20) TABLE-US-00003 Argon flow 0 sccm (no argon added) Nitrogen flow Pressure-regulated to 3 Pa Process pressure 3 10.sup.2 mbar DC source current TiAl 200 A Coil current of the source 1 A magnetic field (MAG 6) DC substrate bias U = 40 V Substrate temperature approx. 550 C. Process duration 120 min

(21) For the transition of about 15 min to the actual functional layer the AlCr arc sources were switched on with a DC source current of 200 A, with the positive pole of the DC source connected to the annular anode of the source and to frame ground. During that phase a DC substrate bias of 40 V was applied to the substrate. 5 minutes after activation of the AlCr (50/50) targets the oxygen inflow was started and was then ramped up within 10 min from 50 to 1000 sccm. At the same time the TiAl (50/50) targets were turned off and the N.sub.2 was reduced back to approx. 100 sccm. Just before the introduction of oxygen the substrate bias was switched from DC to bipolar pulses and increased to U=60 V. That completed the interface layer and the transition to the functional layer. The targets were powder-metallurgically produced targets. Alternatively, melt-metallurgical targets may be used as well. To reduce the spattering rate, monophase targets as described in DE 19522331 may be used.

(22) The coating of the substrate with the actual functional layer took place in pure oxygen. Since aluminum oxide constitutes an insulating layer, either a pulsed or an AC bias supply was used.

(23) The key functional-layer parameters were selected as follows:

(24) TABLE-US-00004 Oxygen flow 1000 sccm Process pressure 2.6 10.sup.2 mbar DC source current, AlCr 200 A Coil current of the source 0.5 A, which generated on the target magnetic field (MAG 6) surface a weak, essentially vertical field of approx. 2 mT (20 Gs). Substrate bias U = 60 V (bipolar, 36 s negative, 4 s positive) Substrate temperature approx. 550 C. Process duration 60 to 120 min

(25) The process described yielded well-bonded, hard layers. Comparison tests of the coating on lathe-work and milling tools revealed a product life significantly improved over traditional TiAlN coatings, although the surface roughness was clearly higher than the roughness values of optimized pure TiAlN coatings.

(26) The test examples #2 to #22 shown in Table 1 refer to simple layer systems according to the invention, each consisting of a double oxide layer of the (Al.sub.1-xCr.sub.x).sub.2O.sub.3 type produced at a coating temperature of between 450 and 600 C. The remaining parameters were identical to the parameters described above for producing the functional layer. The stoichiometric component of the layer composition was measured by Rutherford backscattering spectrometry (RBS). The largest deviation from the target alloy composition shown in column 2 was encountered in tests #10 to #12, with a deviation of 3.5 percentage points at a 70/30 Al/Cr ratio. The metal components of the layer are scaled to the total metal content of the oxide. In terms of the stoichiometry of the oxygen, however, there were somewhat greater deviations of up to over 8%. All layers nevertheless exhibited a clearly corundum-like lattice structure. Preferably, therefore, layers produced according to the invention should have an oxygen-related stoichiometry shortage of 0 to 10% since even with an oxygen deficit of as much as 15% the desired lattice structure will be obtained.

(27) FIG. 1 A to C show typical corundum structures of (Al.sub.1-xCr.sub.x).sub.2O.sub.3 layers produced at 550 C. in accordance with the invention, with targets of varying alloys as indicated in tests #18 (Al/Cr=25/75), #14 (50/50) and #3 (70/30). The measurements and analyses were obtained by x-ray diffractometry with the parameter selections described in more detail under Measuring Methodology, above. In the illustration any correction for background noise was dispensed with. Lattice parameters can be determined by other means as well, such as electron diffraction spectrometry. Due to the decreasing layer thickness from FIGS. 1A to 1C, from 3.1 to 1.5 m, there is a strong increase of the unmarked substrate lines relative to the dash-marked layer lines of the corundum structure. But even in spectrum C, the linear presentation of the Y-axis notwithstanding, 7 lines can still be clearly associated with the corundum lattice. The remaining lines belong to the basic tungsten carbide metal (WC/Co alloy). Of course, for an unambiguous association of the crystal lattice and the determination of the lattice constants, at least 3 and preferably 4 to 5 lines should be uniquely identifiable.

(28) The crystal structure of the layers is compact-grained, in large measure with an average crystallite size of less than 0.2 m. Only in cases of large chromium concentrations and at coating temperatures of 650 C. were crystallite sizes found to be between 0.1 and 0.2 m.

(29) For the tests #2 to #22, FIG. 2 shows the lattice constants a (solid line) and c (dashed line) of the (Al.sub.1-xCr.sub.x).sub.2O.sub.3 crystal lattice plotted above the stoichiometric chromium content and comparing them with the dotted straight lines determined by three values DB1 to DB3 from the ICDD (International Center for Diffraction Data), applying Vegard's Law. Over the entire concentration range the maximum deviation from the ideal Vegard's straight line is 0.7 to 0.8%. Measurements taken on other multi-oxide layers showed similar results, with deviations for the parameters indicated amounting to a maximum of 1%. This suggests very low intrinsic stress in the mixed-crystal layer, which is why, in contrast to many other PVD layers, it is possible to deposit these coatings with a greater layer thickness for instance between 10 and 30 m, in some cases even up to 40 m, with good bonding qualities. Larger stress patterns in the layer were obtained only by applying greater substrate voltages (>150) and/or by using an Ar/O.sub.2 mixture of the process gas with a high Ar component. Since for many applications it is especially the multilayer systems, described in more detail below, that are well suited, it is possible within a wide range to adjust, where necessary, the layer stress values by selecting perhaps a multistratum interface layer and/or cover layer between the workpiece and the mixed-crystal layer. For example, this allows for the selection of higher residual compressive stress values to increase the hardness of the coating for hard-metal machining processes. For industrial applications involving a high level of abrasive wear, thick layer systems with layers more than 10 or 20 m thick can be produced economically, with the mixed-crystal layer preferably having a thickness of more than 5 and especially more than 8 m.

(30) Parallel tests were performed on mixed-crystal layers 2 m thick, employing the methods described above (Stoney's bending strip method and bending disk method). The layer stress values measured ranged from stress-free to minor compressive and tensile stress values less than or equal to 0.5 GPa. However, thicker PVD coatings can still be deposited with layers exhibiting a somewhat higher layer stress of about 0.8 GPa. Another possibility consists in a sequence of thin layers (1 m) deposited with alternating tensile and compressive stress, constituting a multilayer system.

(31) As shown in Table 2, test #2, the temperature and oxidation resistance of the corundum structure of the deposited (Al.sub.1-xCr.sub.x).sub.2O.sub.3 layers was tested by heating coated carbide metal test objects with an elevated Co content to a temperature of 1000 and, respectively, 1100 C. over a period of 50 minutes, then holding them there for 30 minutes and finally cooling them to 300 C. over a time span of 50 minutes. Once cooled to room temperature, the lattice constants were reevaluated. According to the phase diagram [W. Sitte, Mater. Sci. Monogr., 28A, React. Solids 451-456, 1985] referred to in Phase Equilibria Diagrams Volume XII Oxides published by the American Ceramic Society, there is a miscibility gap in the range between about 5 and 70% aluminum, i.e. (Al.sub.0.05-0.7Cr.sub.x0.95-0.30).sub.2O.sub.3 for temperatures up to about 1150 C., which would predict a segregation of the (Al.sub.1-xCr.sub.x).sub.2O.sub.3 mixed crystal into Al.sub.2O.sub.3 and Cr.sub.2O.sub.3 and an (Al.sub.1-xCr.sub.x).sub.2O.sub.3 mixed crystal of some other composition. From that diagram it is also evident that with the process according to this invention it is possible to shift the thermodynamic formation temperature for (Al.sub.1-xCr.sub.x).sub.2O.sub.3 mixed-crystal layers from 1200 C. to between 450 and 600 C. Surprisingly it was also found that the mixed-crystal layers produced by this inventive method experience only minimal changes in their lattice constants as a result of the glow process and that there is no segregation into their binary components. The maximum deviation, shown in FIG. 3, of the value of the lattice parameters a and of the red hot sample, measured after the coating process at room temperature, is about 0.064% while the maximum deviation of value c is 0.34%. For various other multi-oxides as well, the measurements revealed an extraordinary thermal stability of the layer with a minor deviation of the lattice constants by 1 to 2% at the most.

(32) FIGS. 4 and 5 show the results of oxidation tests on conventional layer systems based on an REM fracture pattern of a TiAlN and a TiCN layer, heated to 900 C. as described above and then glowed at that temperature for 30 minutes in an oxygen atmosphere. In a range of over 200 nm the TiAlN layer reveals a distinct alteration of its surface structure. A thin outer layer, consisting essentially of aluminum oxide and having a thickness of between 130 and 140 nm, is followed by a porous aluminum-depleted layer with a thickness of between 154 and 182 nm. Much poorer yet is the oxidation pattern of the TiCN layer in FIG. 5 which, subjected to the same treatment, has oxidized right down to the base material and reveals an incipient layer separation on the right side in the illustration. The layer is coarse-grained and no longer features the columnar structure of the original TiCN layer.

(33) FIG. 6 and FIG. 7 show the results of identical oxidation tests on a TiCN layer protected by an (Al.sub.0.7Cr.sub.0.3).sub.2O.sub.3 layer, about 1 m thick, according to this invention. FIG. 6 is a 50,000 magnification of the interlaminar bonding. The known columnar structure of the TiCN layer and the slightly finer crystalline (Al.sub.0.7Cr.sub.0.3).sub.2O.sub.3 layer are clearly recognizable. The crystallite size of the aluminum/chrome oxide layer can be further refined by using targets with a higher Al content. FIG. 7 is a 150,000 magnification of the interlaminar bond, with the TiCN layer still visible only at the bottom edge of the image. Compared to the layers in FIG. 4 and FIG. 5 the reaction zone of the (Al.sub.0.5Cr.sub.0.5).sub.2O.sub.3 layer with a height H2 of maximally 32 nm is substantially narrower, having a dense structure without detectable pores. A series of comparison tests with different mixed-crystal layers according to the invention revealed that, unlike other, prior-art, oxide layers, they protect the intermediate layers underneath, thus giving the entire layer system excellent heat and oxidation resistance. It is generally possible to use for this purpose all inventive mixed-crystal layers which in the oxidation test described do not form reaction zones larger than 100 nm. The preferred mixed-crystal layers are those with reaction zones between 0 and 50 nm.

(34) The hardness values of the (Al.sub.0.5Cr.sub.0.5).sub.2O.sub.3 layers were determined to be about 2000 HV.sub.50. Measurements performed on other multi-oxides such as (Al.sub.0.5Ti.sub.0.3Cr.sub.0.2).sub.2O.sub.3, or (Al.sub.0.6Ti.sub.0.4).sub.2O.sub.3, (V.sub.0.5Cr.sub.0.5).sub.2O.sub.3, (Al.sub.0.2Cr.sub.0.8).sub.2O.sub.3, on their part yielded values between 1200 and 2500 HV.

(35) Tables 3 to 6 list additional multilayer implementations of the layer system according to the invention. Process parameters for producing AlCrO and AlCrON mixed-crystal layers on a 4-source coating system (RCS) are shown in Table 7 while corresponding process parameters for producing individual strata for various support layers are shown in Table 8.

(36) The tests #23 to #60 in Tables 3 and 4 refer to layer systems in which the oxidic mixed-crystal layer is of a corundum structure throughout and is mostly formed as a monolayer. Only in tests #25, #29 and #31 the mixed-crystal layer is formed from two consecutive individual strata of different chemical compositions. In test #29 the only difference between the mixed-crystal layers is their respective Al/Cr ratio.

(37) The tests #61 to #107 in Tables 5 and 7 refer to layer systems in which the mixed-crystal layer is composed of 5 to as many as 100 very thin strata measuring between 50 nm and 1 m. In these cases, there may be alternating oxidic mixed-crystal layers of a corundum structure with different chemical compositions and corresponding mixed-crystal layers with different layer systems.

(38) In comparison tests on various turning and milling tools, the layers used in tests #23, #24 and #61 to #82 proved clearly superior in turning and milling applications over conventional layer systems such as TiAlN, TiN/TiAlN and AlCrN. Even when compared to CVD coatings, tool product-life improvements were achieved in the milling arena and in some lathe applications.

(39) Although, as stated above, analyses and tests have already been conducted on a substantial number of layer systems, those skilled in the art will use conventional measures, where necessary, to adapt certain characteristics of the inventive layer system to specific requirements. For example, one may consider adding further constituent elements to individual or all layers of the system but in particular to the mixed-crystal layer. Elements known to improve for instance the heat resistance at least of nitridic layers include Zr, Y, La or Ce.

(40) TABLE-US-00005 TABLE 1 Depos'n Glow Stoichiometric V- Target Temp. Temp. Component Cr/ Lattice Constants d No. [Al/Cr] [ C.] [ C.] Cr Al O (Cr + Al) a c c/a [m] DB1- Al.sub.2O.sub.3 0.00 2.00 3.00 0.00 4.75870 12.99290 2.7303 DB2 - 90/10 0.20 1.80 3.00 0.10 4.78550 13.05900 2.7289 2 70/30 550 0.59 1.41 3 0.30 4.85234 13.26296 2.7333 3 70/30 550 0.60 1.40 2.80 0.30 4.85610 13.24587 2.7277 1.5 4 70/30 600 0.61 1.39 3.00 0.31 4.84603 13.23092 2.7303 3.3 5 70/30 550 0.62 1.38 2.75 0.31 4.85610 13.24587 2.7277 3.0 6 70/30 550 0.64 1.36 3.1 0.32 4.85610 13.24587 2.7277 3.1 7 70/30 550 0.63 1.37 2.90 0.32 4.85612 13.23089 2.7246 2.9 8 70/30 550 0.67 1.33 2.8 0.34 4.88443 13.15461 2.6932 2.7 9 70/30 550 0.68 1.32 2.95 0.34 4.86815 13.15461 2.7022 10 70/30 550 0.67 1.33 3 0.34 4.85610 13.24587 2.7277 1.9 11 70/30 550 0.67 1.33 2.95 0.34 4.84804 13.23103 2.7292 2.5 12 70/30 550 0.67 1.33 2.85 0.34 4.83993 13.24192 2.7360 2.5 13 50/50 500 1.01 0.99 2.80 0.51 4.89218 13.32858 2.7245 4.1 14 50/50 550 1.04 0.96 2.95 0.52 4.88403 13.31746 2.7267 1.9 15 50/50 600 1.06 0.94 2.95 0.53 4.87996 13.33965 2.7336 3.5 16 25/75 600 1.52 0.48 2.85 0.76 4.92028 13.44988 2.7336 17 25/75 500 1.54 0.46 2.8 0.77 4.92464 13.43581 2.7283 4.5 18 25/75 550 1.53 0.47 2.8 0.77 4.92053 13.44655 2.7327 3.1 19 0/100 550 2.00 0.00 2.80 1.00 4.95876 13.58287 2.7392 21 0/100 450 2.00 0.00 2.85 1.00 4.97116 13.58280 2.7323 2.0 22 0/100 500 2.00 0.00 2.75 1.00 4.97116 13.59412 2.7346 1.7 DB3 - Cr.sub.2O.sub.3 2.00 0.00 3.00 1.00 4.95876 13.59420 2.7415

(41) TABLE-US-00006 TABLE 2 Depos'n Glow Target Temp Temp. Lattice Constants V-No. [Al/Cr] [ C.] [ C.] a c c/a 2 70/30 550 RT 4.85030 13.24484 2.7307 2 70/30 550 1000 4.85339 13.22837 2.7256 2 70/30 550 1100 4.84727 13.20028 2.7232 Test objects: Hard metal

(42) TABLE-US-00007 TABLE 3 Mixed-Crystal Layer Monolayer Intermediate Layer Corundum Bonding Layer Hard Metal Layer Structure V-No. [(Me1Me2)X] d [m] [(Me1Me2)X] d [m] [(Me1Me2)X] d [m] TiN TiAlN (Al.sub..5Cr.sub..5).sub.2O.sub.3 wo TiAlN (Al.sub..5Cr.sub..5).sub.2O.sub.3 TiN TiAlN (Al.sub..5Cr.sub..5).sub.2O.sub.3 TiN TiCN (Al.sub..65Cr.sub..35).sub.2O.sub.3 TiN (Al.sub..65Cr.sub..35).sub.2O.sub.3 TiCN (Al.sub..7Cr.sub..3).sub.2O.sub.3 TiN TiAlN (Al.sub..7Cr.sub..3).sub.2O.sub.3 TiN TiC (Al.sub..7Cr.sub..3).sub.2O.sub.3 TiN TiAlN (Al.sub..7Fe.sub..3).sub.2O.sub.3 TiN (Al.sub..6Fe.sub..4).sub.2O.sub.3 TiN TiCN (Al.sub..6Fe.sub..4).sub.2O.sub.3 TiCN (Al.sub..1Fe.sub..9).sub.2O.sub.3 wo TiAlN (Al.sub..1Fe.sub..9).sub.2O.sub.3 wo wo (Al.sub..5Fe.sub..5).sub.2O.sub.3 wo wo (Al.sub..5Fe.sub..5).sub.2O.sub.3 TiN wo (Al.sub..5V.sub..5).sub.2O.sub.3 VN VCN (Al.sub..5V.sub..5).sub.2O.sub.3 VN (Al.sub..5V.sub..5).sub.2O.sub.3 CrN CrC Cr.sub.2O.sub.3 CrN CrCN Cr.sub.2O.sub.3 CrN wo Cr.sub.2O.sub.3 CrN wo Cr.sub.2O.sub.3 AlCrN wo (Al.sub..2Cr.sub..8).sub.2O.sub.3 Mixed-Crystal Layer Monolayer Other Oxide Layer Cover Layer d DS1 DS2 V-No. [(Me1Me2)X] [m] [(Me1Me2)X] d [m] [(Me1Me2)X] d [m] wo wo Wo wo wo Wo (Al.sub..7Cr.sub..3).sub.2O.sub.3 (Al,Cr,Zr).sub.2O.sub.3+x ZrO.sub.2 ZrN (Al,Cr).sub.2O.sub.3 AlCrN AlCrN AlCrN TiN AlVN AlVN CrN CrN CrN AlCrN

(43) TABLE-US-00008 TABLE 4 Mixed-Crystal Layer Monolayer Intermediate Layer Corundum Other Oxide Cover Layer Bonding Layer Hard Metal Layer Structure Layer DS1 DS2 V- d d d d d d No. [(Me1Me2)X] [m] [(Me1Me2)X] [m] [(Me1Me2)X] [m] [(Me1Me2)X] [m] [(Me1Me2)X] [m] [(Me1Me2)X] [m] 46 CrN 0.3 AlCrON 5.0 (Al.sub..02Cr.sub..08).sub.2O.sub.3 3.0 47 CrN 0.5 AlCrN 3.0 (Al.sub..05Cr.sub..85).sub.2O.sub.3 3.0 (Al.sub..7Cr.sub..3).sub.2O.sub.3 1.0 CrN 2.0 48 AlCrN 0.5 AlCrON 5.0 (Al.sub..05Cr.sub..85).sub.2O.sub.3 3.0 49 TiN 0.8 TiAlN 4.0 (Al.sub..5Ti.sub..5).sub.2O.sub.3 4.0 TiN 1.0 50 wo TiAlN 6.0 (Al.sub..5Ti.sub..5).sub.2O.sub.3 2.0 51 TiN 0.3 TiCN 8.0 (Al.sub..7Ti.sub..3).sub.2O.sub.3 4.0 52 wo TiAlN 3.0 (Al,Mg,Ti).sub.2O.sub.3 3.0 53 TiN 0.5 AlMgTiN 6.0 (Al,Mg,Ti).sub.2O.sub.3 4.0 54 TiN 5.0 (Al,Mg,Ti).sub.2O.sub.3 3.0 TiN 2.0 55 TiN 0.3 (Al,Mg,Ti)ON 5.0 (Al,Mg,Ti).sub.2O.sub.3 2.0 56 AlCrN 0.2 (Al,Mg,Ti)ON 1.0 (Al,Mg,Ti).sub.2O.sub.3 6.0 57 TiN 1.0 (Al,Fe,Ti).sub.2O.sub.3 5.0 TiN 0.5 58 TiN 1.0 TiCN 6.0 (Al,Fe,Ti).sub.2O.sub.3 2.0 TiN 1.0 59 TiN 1.0 TiAlN 4.0 (Al,Fe,Ti).sub.2O.sub.3 4.0 60 TiCN 4.0 (Al,Fe,Ti).sub.2O.sub.3 2.0

(44) TABLE-US-00009 TABLE 5 Mixed-Crystal Layer as Multilayer Intermediate Layer Corundum Bonding Layer Hard Metal Layer Structure V-No. [(Me1Me2)X] d [m] [(Me1Me2)X] d [m] [(Me1Me2)X] d [m] 61 TiN 0.2 TiAlN 3.0 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.100 62 wo TiAlN 2.0 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.500 63 TiN 0.3 TiAlN 3.0 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.100 64 TiN 0.3 TiAlN 4.0 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.050 65 TiN 0.3 TiAlN 3.0 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.100 66 TiN 0.3 TiAlN 6.0 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.200 67 TiN 0.3 TiAlN 3.0 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.200 68 TiN 0.3 TiAlN 4.0 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.200 69 TiN 0.3 TiAlN 3.0 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.200 70 TiN 0.3 TiAlN 2.0 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.200 71 TiN 0.3 TiAlN 2.0 (Al.sub..5Cr.sub..5).sub.2O.sub.3 0.100 72 TiN 0.2 TiCN 6.0 (Al.sub..5Cr.sub..5).sub.2O.sub.3 0.100 73 wo TiCN 3.0 (Al.sub..5Cr.sub..5).sub.2O.sub.3 0.500 74 TiN 0.3 TiCN 12.0 (Al.sub..5Cr.sub..5).sub.2O.sub.3 0.100 75 TiN 0.3 TiCN 8.0 (Al.sub..5Cr.sub..5).sub.2O.sub.3 0.050 76 TiN 0.3 TiCN 4.0 (Al.sub..5Cr.sub..5).sub.2O.sub.3 0.100 77 TiN 0.3 TiCN 3.0 (Al.sub..5Cr.sub..5).sub.2O.sub.3 0.200 78 TiN 0.3 TiCN 6.0 (Al.sub..4Cr.sub..5).sub.2O.sub.3 0.200 79 TiN 0.3 TiCN 3.0 (Al.sub..4Cr.sub..6).sub.2O.sub.3 0.200 80 TiN 0.3 TiCN 2.0 (Al.sub..4Cr.sub..6).sub.2O.sub.3 0.200 81 TiN 0.3 TiCN 3.0 (Al.sub..4Cr.sub..6).sub.2O.sub.3 0.200 82 TiN 0.3 TiC 4.0 (Al.sub..4Cr.sub..6).sub.2O.sub.3 0.100 83 TiN 0.5 TiAlN 3.0 (Al.sub..4Cr.sub..6).sub.2O.sub.3 0.300 84 TiN 0.4 TiAlN 2.0 (Al.sub..7Cr.sub..3).sub.2O.sub.3 0.200 85 TiN 0.3 wo (Al.sub..6V.sub..4).sub.2O.sub.3 0.200 86 VN 0.4 VCN 4.0 (Al.sub..6V.sub..4).sub.2O.sub.3 0.200 Mixed-Crystal Layer as Multilayer Cover Layer Other ML Layer DS1 DS2 V- d No. d d No. [(Me1Me2)X] [m] MLs [(Me1Me2)X] [m] [(Me1Me2)X] [m] 61 AlCrN 0.100 50.0 AlCrN 0.5 62 AlCrN 0.500 10.0 63 AlCrN 0.050 100.0 AlCrN 0.2 64 AlCrN 0.050 100.0 65 ZrO.sub.2 0.300 10.0 ZrN 1.0 66 Ta.sub.2O.sub.5 0.100 30.0 TaN 0.6 67 Nb.sub.2O.sub.5 0.500 10.0 NbN 1.0 68 V.sub.2O.sub.5 0.100 50.0 69 Al.sub.$$Cr.sub..2).sub.2O.sub.3 0.050 30.0 AlCrN 0.2 70 (Al,V).sub.2O.sub.3 0.050 30.0 AlVN 0.2 71 TiAlN 0.100 50.0 72 0.100 0.100 50.0 AlCrN 0.5 73 AlCrN 0.500 10.0 74 AlCrN 0.050 100.0 AlCrN 0.2 75 AlCrN 0.050 100.0 76 ZrO.sub.2 0.300 10.0 ZrN 1.0 77 Ta.sub.2O.sub.6 0.100 30.0 TaN 0.5 78 Nb.sub.2O.sub.5 0.500 10.0 NbN 1.0 79 V.sub.2O.sub.3 0.100 50.0 80 (Al,Cr).sub.2O.sub.3 0.050 30.0 AlCrN 0.2 81 (Al,Zr).sub.2O.sub.3 0.050 30.0 AlZrN 0.2 82 AlCrN 0.050 100.0 TiN 0.2 83 (Al,Cr,Zr).sub.2O.sub.3$$ 0.300 ZrN 1.0 ZrN 0.5 84 (Al,Cr).sub.2O.sub.3 0.200 10.0 AlCrN 0.5 85 AlVN 0.100 TiN 0.3 86 (Al,Cr).sub.2O.sub.3 0.100

(45) TABLE-US-00010 TABLE 6 Mixed-Crystal Layer as Multilayer Intermediate Layer Corundum Bonding Layer Hard Metal Layer Structure V-No. [(Me1Me2)X] d [m] [(Me1Me2)X] d [m] [(Me1Me2)X] d [m] 87 CrN 0.5 CrC 4.0 Cr.sub.2O.sub.3 0.200 88 CrN 0.5 CrCN 6.0 Cr.sub.2O.sub.3 0.200 89 CrN 0.5 wo Cr.sub.2O.sub.3 1.000 90 CrN 0.5 wo Cr.sub.2O.sub.3 0.050 91 CrN 0.5 wo Cr.sub.2O.sub.3 0.050 92 AlCrN 0.3 wo (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.100 93 CrN 0.3 AlCrON 5.0 (Al.sub..5Cr.sub..5).sub.2O.sub.3 0.200 94 CrN 0.5 AlCrN 3.0 (Al.sub..5Cr.sub..5).sub.2O.sub.3 1.000 95 AlCrN 0.5 AlCrON 5.0 (Al.sub..5Cr.sub..5).sub.2O.sub.3 0.050 96 TiN 0.8 TiAlN 4.0 (Al.sub..5Ti.sub..5).sub.2O.sub.3 0.100 97 wo TiAlN 6.0 (Al.sub..1Ti.sub..0).sub.2O.sub.3 0.050 98 TiN 0.3 TiCN 8.0 (Al.sub..1Ti.sub..0).sub.2O.sub.3 0.200 99 wo TiAlN 3.0 (Al,Mg,Ti).sub.2O.sub.3 0.100 100 TiN 0.5 AlMgTiN 6.0 (Al,Mg,Ti).sub.2O.sub.3 0.500 101 TiN 5.0 (Al,Mg,Ti).sub.2O.sub.3 0.100 102 TiN 0.3 (Al,Mg,Ti)ON 5.0 (Al,Mg,Ti).sub.2O.sub.3 0.050 103 AlCrN 0.2 (Al,Mg,Ti)ON 1.0 (Al,Mg,Ti).sub.2O.sub.3 0.100 104 TiN 1.0 (Al,Fe,Ti).sub.2O.sub.3 0.200 105 TiN 1.0 TiCN 6.0 (Al,Fe,Ti).sub.2O.sub.3 0.200 106 TiN 1.0 TiAlN 4.0 (Al,Fe,Ti).sub.2O.sub.3 0.200 107 TiCN 4.0 (Al,Fe,Ti).sub.2O.sub.3 0.200 Mixed-Crystal Layer as Multilayer Cover Layer Other ML Layer DS1 DS2 d No. d d V-No. [(Me1Me2)X] [m] MLs [(Me1Me2)X] [m] [(Me1Me2)X] [m] 87 CrN 0.300 5.0 CrN 2.0 88 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.100 10.0 CrN 1.0 89 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.500 5.0 90 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.050 200.0 91 CrN 0.050 100.0 92 CrN 0.400 8.0 AlCrN 1.0 93 (Al.sub..7Cr.sub..3).sub.2O.sub.3 0.100 10.0 94 (Al.sub..7Cr.sub..3).sub.2O.sub.3 0.500 5.0 CrN 0.5 CrN 2.0 95 (Al.sub..7Cr.sub..3).sub.2O.sub.3 0.050 200.0 96 TiAlN 0.200 30.0 TiN 1.0 97 TiAlN 0.300 10.0 98 (Al.sub..7Cr.sub..3).sub.2O.sub.3 0.100 20.0 99 0.100 0.100 40.0 100 AlCrN 0.500 12.0 101 AlCrN 0.050 50.0 102 AlCrN 0.050 30.0 103 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.300 15.0 104 Nb.sub.2O.sub.3 0.500 20.0 TiN 0.5 105 V.sub.2O.sub.3 0.100 20.0 TiN 0.5 106 (Al.sub..65Cr.sub..35).sub.2O.sub.3 0.100 10.0 107 (Al,Me).sub.2O.sub.3 0.050 15.0

(46) TABLE-US-00011 TABLE 7 I-Source 1 I-S.2 I-S.3 I-S.4 U-base-bp O2 N2 p T Material [A] [A] [A] [A] [V] [sccm] [sccm] [Pa] [ C.] AlCrO 200 200 60 1000 2.6 550 C. AlCrOAlCrN 200 200 60 1000 1000 2.6 550 C. Multilayer Coil current of the source magnetic system 0.5 to 1 A

(47) Coil current of the source magnetic system 0.5 to 1 A

(48) TABLE-US-00012 TABLE 8 I-Source 1 I-S.2 I-S.3 I-S.4 U-Bias DC Ar C2H2 N2 p T Material [A] [A] [A] [A] [V] [sccm] [sccm] [sccm] [Pa] [ C.] TiAlN 200 200 40 Pressure 3 550 C. regulated TiN 180 180 100 Pressure 0.8 550 C. regulated TiCN 190 190 100 420 15-125 500-150 2.5-2.0 550 C. AlCrN 200 200 100 1000 2.6 550 C. AlMeN 140 140 80 600 0.8 500 C. AlMeCN 220 220 120 300 10-150 Pressure 2.5 600 C. regulated Coil current of the source magnetic system 0.1 to 2 A

(49) Coil current of the source magnetic system 0.1 to 2 A