AlN-based hard material layer on an object made of metal, cemented carbide, cermet or ceramic, and method for manufacturing the same.

Abstract

The present invention relates to the field of materials engineering and relates to an AlN-based hard material layer on an object made of metal, cemented carbide, cermet or ceramic and a method for its production. The problem of the invention is to provide an AlN-based hard material layer which has increased hardness and wear resistance and can be produced in a time- and cost-effective manner. According to the invention, an AlN-based hard material layer is provided, which is a single-layer or multi-layer layer system, at least one layer of the single-layer or multi-layer layer system is an AlN-based hard material layer with a hexagonal crystal lattice structure, which hexagonal crystal lattice structure is <002> The hard material layer has an oxygen-doped texture formed thereon, the oxygen doping being present in the range of 0.01 atomic % to 15 atomic %. The hard material layer can be used as a wear protection layer for a cutting tool.

Description

Technical Field

[0001] The present invention relates to the technical field of materials engineering, and relates to an AlN-based hard material layer on an object composed of metal, cemented carbide, cermet or ceramics and a method for manufacturing the same. The AlN-based hard material layer according to the present invention has a high degree of texture and is oxygen-doped, and can be used, for example, as a wear protection layer for cutting tools, a protection layer for turbine blades, or a diffusion barrier for microelectronics.

[0002] AlON layers are known from the prior art and are mainly used as dielectric layers and in resistive change memories for microelectronics. Here, this layer is manufactured by a variety of CVD (thermal CVD, RTP-MOCVD) and PVD processes.

[0003] Japanese Patent Application Laid-Open No. 2001-287104 discloses one or more coating materials containing aluminum oxynitride. The aluminum oxynitride layer consists of an Al-O-N solid solution, a crystalline Al-O-N compound, or a mixture of both. Furthermore, AlN may be mixed therein.

[0004] German Patent Application Publication No. 102010052687 discloses a layer system of a polycrystalline aluminum nitride and aluminum oxynitride, preferably on a substrate such as HSS or cemented carbide. Here, a layer structure composed of a plurality of layers is disclosed, and preferably includes an oxynitride layer composed of the elements Cr, Al, O and N with a layer thickness of 0.3 to 2.5 micrometers.

[0005] U.S. Patent No. 4336305 discloses a ceramic throw-away chip having at least one thin coating of Al2O3 or AlON disposed on the surface by a CVD process.

[0006] International Publication No. 2012126031 describes a combination of a TiAlN layer and a second layer consisting of AlON and optionally carbon, in which case Al can be partially replaced with other metals.

[0007] A drawback of known solutions from prior art is the insufficient hardness and wear resistance of the manufactured AlN hard material layer. AlN-based hard material layers from prior art exhibit a hardness of approximately 2000 HV. Furthermore, the manufacturing of such AlN-based hard material layers is time-consuming and costly.

[0008] The objective is to provide an AlN-based hard material layer with improved hardness and wear resistance. The present invention is also based on the objective of providing a time- and cost-effective thermal CVD process for manufacturing an AlN hard material layer.

[0009] The aforementioned problems are resolved by the features of the claims, and the present invention also encompasses combinations of individual dependent claims in the sense of an AND connection, as long as they are not mutually exclusive.

[0010] According to the present invention, the aforementioned problem is solved by an AlN-based hard material layer on an object made of a metal, cemented carbide, cermet or ceramic, wherein the AlN-based hard material layer is a single-layer or multi-layer system manufactured by a CVD process without plasma excitation, and at least one layer of the single-layer or multi-layer system is an AlN-based hard material layer having a hexagonal lattice structure, and the hexagonal lattice structure is <002> This is resolved by a hard material layer having an oxygen-doped texture formed thereon, wherein the oxygen doping is present in the range of 0.01 atomic% to 15 atomic% and is not directly lattice-bonded in the hexagonal crystal structure.

[0011] Advantageously, the texture has a texture coefficient TC of >2.5 to 8. Also advantageously, the texture is formed in a columnar shape.

[0012] Advantageously, the AlN-based hexagonal hard material layer has an Al content of ≥45 atomic%.

[0013] Furthermore, the h-AlN-based hard material layer has a thickness of 5 to 40 μm.

[0014] In one advantageous embodiment of the present invention, at least one h-AlN-based hard material layer is formed to be nanocrystalline, and particularly advantageously, the crystal size is 5 nm to 100 nm.

[0015] Furthermore, the nanocrystalline h-AlN-based hard material layer may, particularly advantageously, have amorphous components, and very, particularly advantageously, it may contain oxygen doping of 0.01 atomic% to 25 atomic%.

[0016] Advantageously, at least one h-AlN-based hard material layer has a hardness of 2500 HV [0.01] to 2800 HV [0.01].

[0017] More advantageously, the h-AlN-based hard material layer may be provided to include doping with Zr, Si, Hf, Ta and / or Ti.

[0018] In one advantageous embodiment, there is at least one bonding layer, intermediate layer and / or cover layer, which are particularly advantageously made of nitrides, carbides, carbonitrides, oxycarbides, oxycarbonitrides of Group 4-6 transition elements of PSE, or oxides of Al or Zr. In a very particular advantage, the bonding layer, intermediate layer and / or cover layer are TiN, TiCN, TiAlN and / or combinations thereof.

[0019] The present invention also provides a method for manufacturing an AlN-based hard material layer on an object made of metal, cemented carbide, cermet, or ceramic, wherein a textured oxygen-doped h-AlN-based hard material layer is deposited from a gas phase of AlCl3, H2, N2, NH3, CO, and / or CO2 at a temperature of 850°C to 1050°C and a pressure of 0.1kPa to 30kPa by a thermal CVD process without plasma excitation in a CVD reactor, wherein CO and / or CO2 are supplied separately to the CVD reactor through a separate gas feed.

[0020] Advantageously, NH3 is supplied separately to the CVD reactor to generate a gas phase, and particularly advantageously, a gas phase containing 0.2% to 2% by volume of CO and / or CO2 is deposited.

[0021] Similarly advantageously, an AlN-based hard material layer is deposited from a gas phase containing 0.30% to 2% by volume of NH3.

[0022] In one advantageous embodiment of the present method, before depositing the h-AlN-based hard material layer, at least one bonding layer, intermediate layer and / or cover layer is deposited, consisting of nitrides, carbides, carbonitrides, oxycarbides, oxycarbonitrides of Group 4 to 6 transition elements of PSE, or oxides of Al or Zr, and these layers are deposited, very particularly advantageously, as bonding layers, intermediate layers and / or cover layers having TiN, TiCN, TiAlN and / or combinations thereof.

[0023] The present invention provides a textured oxygen-doped h-AlN-based hard material layer that is manufactured efficiently in terms of time and cost by a thermal CVD process without plasma excitation, and has improved hardness and wear resistance.

[0024] According to the present invention, always <002> A pure AlN-based hard material layer having a hexagonal lattice structure texture formed in a specific direction is provided. To obtain the hexagonal lattice structure of the AlN hard material layer, it is proposed to introduce CO and / or CO2 into the CVD coating chamber through a separate gas feed, specifically by a CVD process without plasma excitation, thereby doping the hexagonal lattice structure with oxygen as intended. Here, direct lattice bonding of oxygen does not occur. Therefore, unlike the prior art, the h-AlN-based hard material layer does not contain oxygen components due to impurities or leaks in the CVD reactor, and the oxygen doping that affects the morphological properties is achieved as intended, without direct lattice bonding only to the interstitial sites.

[0025] As a result, a novel, highly textured oxygen-doped h-AlN hard material layer is provided, exhibiting high hardness of up to 2800 HV [0.01] and high wear resistance. Surprisingly, the incorporation of a specific proportion of oxygen during layer deposition can favorably influence the structure and properties of the h-AlN-based hard material layer according to the present invention.

[0026] This is achieved by providing and manufacturing an AlN-based hard material layer having a textured surface and containing oxygen doping in the range of 0.01 atomic% to 15 atomic%, thereby exhibiting high hardness and excellent wear resistance due to its hexagonal lattice structure.

[0027] In the present invention, texture should be understood as the crystallographic orientation of crystals in an oxygen-doped h-AlN-based hard material layer grown on a substrate by a CVD process according to the present invention without plasma excitation. Here, the texture is preferably formed in a columnar shape, and each columnar structure has a substantially hexagonal, and therefore honeycomb-like, shape.

[0028] Since the texture of the oxygen-doped h-AlN-based hard material layer having a high degree of texture is formed in a columnar shape, internal stress is generated by the direct contact of the juxtaposed columns in the AlN-based hard material layer according to the present invention, and this internal stress brings about the strengthening of the hard material layer, and thus a significant improvement in hardness and wear resistance.

[0029] According to the present invention, at least one layer of the oxygen-doped AlN-based layer system has a hexagonal lattice structure having a texture formed in <002>.

[0030] The single-layer or multi-layer texture according to the present invention can be represented by a texture coefficient TC.

[0031] Here, the texture coefficient TC is calculated by the following formula in accordance with JCPDS 0-25-1133:

Equation

[0032] For this calculation, the following eight atomic planes are used: <100>, <002>, <101>, <102>, <110>, <103>, <200>, <112>.

[0033] The TC of the oxygen-doped h-AlN-based hard material layer having a high degree of texture according to the present invention is preferably >2.5 to 8.

[0034] The solution according to the present invention provides a novel oxygen-doped h-AlN-based hard material layer on an object composed of metal, cemented carbide, cermet or ceramics, wherein the h-AlN-based hard material layer is a single-layer or multi-layer layer system. <​​In a multilayer system, at least one h-AlN-based hard material layer of the system may be formed to be nanocrystalline. The nanocrystalline layer is particularly finely granular and has a crystallite size of 5 nm to 100 nm. Such a nanocrystalline AlN-based hard material layer may further contain amorphous components and may advantageously have oxygen doping of 0.01 atomic% to 25 atomic%.

[0036] It is particularly advantageous if one or more bonding layers, intermediate layers, and / or cover layers are present between the object to be coated and the oxygen-doped h-AlN-based hard material layer according to the present invention. By pre-depositing one or more bonding layers, intermediate layers, or cover layers, much better adhesion of the oxygen-doped h-AlN-based hard material layer according to the present invention to objects made of metals, cemented carbides, cermets, or ceramics can be achieved.

[0037] By depositing one or more intermediate layers between the binder layer and the cover layer, an improvement in the hardness of the entire layer system, particularly the binder layer, is achieved.

[0038] By applying one or more cover layers, further improvements in oxidation resistance and enhanced bonding of the h-AlN-based hard material layer subsequently placed thereon become possible. Furthermore, a reduction in friction between the oxygen-doped h-AlN-based hard material layer with a high degree of texture and the workpiece is achieved, thereby significantly improving, for example, the service life of the wear protection layer. Advantageously, the bonding layer, intermediate layer, or cover layer consists of nitrides, carbides, carbonitrides, oxycarbides, oxycarbonitrides of PSE group 4-6 transition elements, or oxides of Al or Zr.

[0039] Particularly advantageously, the binder layer, intermediate layer, and / or cover layer may be composed of TiN, TiCN, TiAlN, and / or combinations thereof. To ensure good adhesion to the object being coated, for example, the binder layer may be made of TiN. To improve hardness, for example, an intermediate layer made of TiCN may be deposited on the binder layer. Furthermore, to further improve the adhesion of the h-AlN-based hard material layer according to the present invention, an additional cover layer made of TiN may be provided on the intermediate layer.

[0040] The hexagonal lattice structure of the AlN-based hard material layer according to the present invention, combined with the intended use of CO and / or CO2 as an additional oxygen source in a CVD coating apparatus, along with the texture according to the present invention, achieves particularly high hardness values ​​of 2500 HV [0.01] to 2800 HV [0.01] with a high Al elemental content of ≥45 atomic%, thereby improving oxidation resistance, which in turn positively impacts wear resistance, especially at high temperatures.

[0041] The h-AlN-based hard material layer is advantageous if it has additional doping of Zr, Si, Hf, Ta, and / or Ti. By introducing small amounts of Zr, Si, Hf, Ta, and / or Ti, heterogeneous atoms are introduced into the hexagonal lattice structure, thereby improving the hardness and wear resistance of the h-AlN-based hard material layer.

[0042] The improved wear properties of the textured and oxygen-doped h-AlN-based hard material layer according to the present invention are achieved by a thermal CVD process without plasma excitation, by depositing this layer in a CVD reactor from a gas phase consisting of AlCl3, H2, N2, and NH3 with CO and / or CO2 added as intended, at a temperature of 850°C to 1050°C and a pressure of 0.1kPa to 30kPa.

[0043] It was found to be advantageous to first mix the reactive gas phase required for coating in a CVD reactor and then deposit it directly onto the substrate there.

[0044] To supply the gas phase into a CVD reactor, it is advantageous to deliver NH3 to the reactor chamber through a separate gas supply device. Supplying the gas phase components separately has the advantage that the gas phase has a much higher reactivity at the moment of deposition in the reactor, thus reducing the risk of premature reaction within the gas supply device. Furthermore, supplying the reaction gases separately to the CVD reactor allows for individual and easy adjustment of the gas phase composition, particularly the control of the supply of NH3, CO2, and / or CO.

[0045] It was also found to be advantageous to deposit a gas phase containing 0.2% to 2.0% by volume of CO and / or CO2. By adding CO and / or CO2 as intended, oxygen is incorporated into the AlN-based hard material layer as intended without direct lattice bonding to the hexagonal lattice structure. This, in particular, leads to improved oxidation resistance of the h-AlN-based hard material layer. Advantageously, the gas phase can further contain doping of Zr, Si, Hf, Ta and / or Ti, which are incorporated into the hexagonal lattice structure of the h-AlN-based hard material layer during deposition.

[0046] Surprisingly, we found that when the deposited gas phase contains NH3 in a proportion of 0.3% to 2.0% by volume, a texturing intensity with a high texture coefficient TC of >2.5 to 8 can be achieved.

[0047] In summary, the present invention provides a novel, highly textured, oxygen-doped h-AlN-based hard material layer exhibiting high hardness up to 2800 HV [0.01] and high wear resistance. Surprisingly, the targeted incorporation of a specific percentage of oxygen during layer deposition positively influences the structure and properties of the h-AlN-based hard material layer according to the present invention. A novel LPCVD process enables the fabrication of the layer in a temperature range of 850°C to 1050°C.

[0048] The present invention will be described in detail below with reference to several embodiments and accompanying drawings. [Brief explanation of the drawing]

[0049] [Figure 1] This is an X-ray diffraction pattern of an oxygen-doped h-AlN layer with a high degree of texture, manufactured by CVD according to Embodiment Example 1. [Figure 2] This figure shows a TEM image of an oxygen-doped h-AlN-based hard material layer with a high degree of texture according to Embodiment Example 1. [Figure 3] This figure shows the TEM-EDX analysis of an oxygen-doped h-AlN-based hard material layer with a high degree of texture according to Embodiment Example 1. [Figure 4] This is an X-ray diffraction pattern of an oxygen-doped h-AlN-based hard material layer with a high degree of texture, manufactured by CVD according to Embodiment Example 2. [Figure 5] This figure shows a TEM image of an oxygen-doped h-AlN-based hard material layer with a high degree of texture according to Embodiment Example 2. [Figure 6] This figure shows the TEM-EDX analysis of an oxygen-doped h-AlN-based rigid material layer with a high degree of texture according to Embodiment Example 2. [Figure 7] This figure shows a cross-sectional SEM image of an oxygen-doped h-AlN-based hard material layer with a high texture and a thickness of 40 μm according to Embodiment Example 3. [Figure 8] This figure shows the EDX analysis of an oxygen and silicon-doped h-AlN-based hard material layer with a high degree of texture, manufactured by CVD according to Embodiment Example 4. [Figure 9] This figure shows the EDX analysis of an oxygen and zirconium-doped h-AlN-based hard material layer with a high texture, manufactured by CVD according to Embodiment Example 5. [Figure 10] This figure shows the wear test of an oxygen-doped h-AlN-based hard material layer with a high degree of texture according to Embodiment 1, Embodiment 4, and Embodiment 5.

[0050] Embodiment Example 1 A highly textured oxygen-doped h-AlN-based hard material layer is deposited as a cover layer on a WC / Co cemented carbide throwaway chip pre-coated with a 5 μm thick TiN / TiCN / TiN layer system serving as a bonding layer, intermediate layer, and cover layer, using a thermal CVD process without plasma excitation. The coating process is carried out in a high-temperature walled CVD reactor with an inner diameter of 75 mm. The CVD coating is performed in a gas phase consisting of 0.46 vol% AlCl3, 0.31 vol% NH3, 0.72 vol% CO2, 4.80 vol% N2, and 93.71 vol% H2. The deposition temperature is 900°C and the process pressure is 6 kPa. After 90 minutes of coating, a highly textured 5.2 μm thick oxygen-doped h-AlN-based hard material layer is obtained.

[0051] Layer analysis using X-ray imaging revealed the presence of an h-AlN phase, and its crystals exhibited a highly textured state. <002> It is growing in the direction of the grain. The texture coefficient TC is 7.2. TEM testing combined with elemental analysis as shown in Figures 2 and 3 revealed that the h-AlN phase is doped with 13 atomic percent oxygen. The microhardness measured using a Vickers indenter was 2690 HV [0.01].

[0052] Elemental analysis using TEM revealed the following elemental content: 47 atomic% Al, 39.5 atomic% N, 13 atomic% O, and 0.5 atomic % Cl.

[0053] Embodiment Example 2 On a WC / Co cemented carbide throwaway chip pre-coated with a 5 μm thick TiN / TiCN / TiN layer system serving as a bonding layer, intermediate layer, and cover layer, a layer of highly textured, nanocrystalline, amorphous, oxygen-doped h-AlN-based hard material is deposited as a cover layer by a thermal CVD process. The coating process is carried out in a high-temperature walled CVD reactor with an inner diameter of 75 mm. The CVD coating is performed in a gas phase consisting of 0.46 vol% AlCl3, 0.42 vol% NH3, 0.61 vol% CO2, 4.68 vol% N2, and 93.83 vol% H2. The deposition temperature is 850°C and the process pressure is 6 kPa. After 90 minutes of coating, a 6.0 μm thick, nanocrystalline, highly textured, oxygen-doped h-AlN-based hard material layer containing amorphous components is obtained.

[0054] Layer analysis using X-ray imaging revealed the presence of the h-AlN phase as shown in the X-ray diffraction pattern in Figure 4, and its crystals exhibited a highly textured state. <002> It is growing in the direction of the grain. The texture coefficient TC is 4.2. TEM testing combined with elemental analysis as shown in Figures 5 and 6 revealed that the h-AlN phase is doped with 24 atomic percent oxygen. The microhardness measured using a Vickers indenter was 2580 HV [0.01].

[0055] Elemental analysis using TEM revealed the following elemental content: 45 atomic% Al, 30.5 atomic% N 24 atomic% O, and 0.5 atomic % Cl.

[0056] Embodiment Example 3 A highly textured oxygen-doped h-AlN-based hard material layer is deposited as a cover layer on a WC / Co cemented carbide throwaway chip pre-coated with a 1 μm thick TiN bonded layer by a thermal CVD process. The coating process is carried out in a high-temperature walled CVD reactor with an inner diameter of 75 mm. The CVD coating is performed in a gas phase consisting of 0.46 vol% AlCl3, 0.45 vol% NH3, 0.58 vol% CO2, 4.80 vol% N2, and 93.71 vol% H2. The deposition temperature is 1000°C and the process pressure is 6 kPa. After 150 minutes of coating, a highly textured oxygen-doped h-AlN-based hard material layer with a thickness of 40.0 μm is obtained.

[0057] Layer analysis using X-ray imaging revealed the presence of an h-AlN phase, and its crystals exhibited a highly textured state. <002> It is growing in the direction of the grain. The texture coefficient TC is 5.4. From the cross-sectional SEM test shown in Figure 7, a 40 μm thick h-AlN-based hard material layer with a high degree of texture was confirmed. The microhardness measured using a Vickers indenter was 2760 HV [0.01].

[0058] Embodiment Example 4 A highly textured oxygen and silicon-doped h-AlN-based hard material layer is deposited as a cover layer on a WC / Co cemented carbide throwaway tip pre-coated with a 5 μm thick TiN / TiCN / TiN layer system serving as a bonding layer, intermediate layer, and cover layer, using a thermal CVD process. The coating process is carried out in a high-temperature walled CVD reactor with an inner diameter of 75 mm. The CVD coating is performed in a gas phase consisting of 0.46 vol% AlCl3, 0.06 vol% SiCl4, 0.31 vol% NH3, 0.72 vol% CO2, 4.80 vol% N2, and 93.65 vol% H2. The deposition temperature is 900°C and the process pressure is 6 kPa. After 90 minutes of coating, a highly textured 4.8 μm thick oxygen and silicon-doped h-AlN-based hard material layer is obtained.

[0059] Layer analysis using X-ray imaging revealed the presence of an h-AlN phase, and its crystals exhibited a highly textured state. <002> It is growing in the direction of the grain. The texture coefficient TC is 3.7. As shown in Figure 8, EDX testing of the cross section revealed oxygen and silicon doping into the highly textured h-AlN layer. The microhardness measured using a Vickers indenter was 2610 HV [0.01].

[0060] Embodiment Example 5 A highly textured oxygen and zirconium-doped h-AlN-based hard material layer is deposited as a cover layer on a WC / Co cemented carbide throwaway tip pre-coated with a 5 μm thick TiN / TiCN / TiN layer system serving as a bonding layer, intermediate layer, and cover layer, using a thermal CVD process. The coating process is carried out in a high-temperature walled CVD reactor with an inner diameter of 75 mm. The CVD coating is performed in a gas phase consisting of 0.46 vol% AlCl3, 0.04 vol% ZrCl4, 0.31 vol% NH3, 0.72 vol% CO2, 4.80 vol% N2, and 93.67 vol% H2. The deposition temperature is 1030°C and the process pressure is 6 kPa. After 90 minutes of coating, a highly textured 4.5 μm thick oxygen and zirconium-doped h-AlN-based hard material layer is obtained.

[0061] Layer analysis using X-ray imaging revealed the presence of an h-AlN phase, and its crystals exhibited a highly textured state. <002> It is growing in the direction of the grain. The texture coefficient TC is 4.1. As shown in Figure 9, EDX testing of the cross section revealed oxygen and zirconium doping into the h-AlN-based hard material layer with a high degree of texture. The microhardness measured using a Vickers indenter was 2650 HV [0.01].

Claims

1. An AlN-based hard material layer on an object made of metal, cemented carbide, cermet, or ceramics, wherein the AlN-based hard material layer is a single-layer or multi-layer system, and at least one layer of the single-layer or multi-layer system is an AlN layer having a hexagonal lattice structure, the hexagonal lattice structure has an oxygen-doped texture formed in <002>, the oxygen doping is present in the range of 0.01 atomic% to 15 atomic%, and is not directly lattice-bonded in the hexagonal lattice structure, the texture has a texture coefficient TC of >2.5 to 8, and the Al content is ≥45 atomic%, the hard material layer.

2. The hard material layer according to claim 1, wherein the texture is formed in a columnar shape.

3. The hard material layer according to claim 1 or 2, wherein the h-AlN-based hard material layer has a layer thickness of 5 to 40 μm.

4. An AlN-based hard material layer on an object made of metal, cemented carbide, cermet, or ceramics, wherein the AlN-based hard material layer is a single-layer or multi-layer system, at least one layer of the single-layer or multi-layer system is an AlN layer having a hexagonal lattice structure, the hexagonal lattice structure has an oxygen-doped texture formed in <002>, the at least one h-AlN-based hard material layer is formed to be nanocrystalline, the oxygen doping is present in the range of 0.01 atomic% to 25 atomic%, and is not directly lattice-bonded in the hexagonal lattice structure, the texture has a texture coefficient TC of >2.5 to 8, and the Al content is ≥45 atomic%, in a hard material layer.

5. The hard material layer according to claim 4, wherein the crystal size is 5 nm to 100 nm.

6. The hard material layer according to claim 4 or 5, wherein the h-AlN-based hard material layer has a layer thickness of 5 to 40 μm.

7. The hard material layer according to any one of claims 1 to 6, wherein the h-AlN-based hard material layer includes doping with Zr, Si, Hf, Ta and / or Ti.

8. A hard material layer according to any one of claims 1 to 7, wherein at least one h-AlN-based hard material layer has a hardness of 2500 HV [0.01] to 2800 HV [0.01].

9. The hard material layer according to any one of claims 1 to 8, wherein at least one bonding layer, intermediate layer and / or cover layer is present between the object, which is composed of a metal, cemented carbide, cermet or ceramic, and the h-AlN-based hard material layer.

10. The hard material layer according to claim 9, wherein the bonding layer, intermediate layer and / or cover layer are made of nitrides, carbides, carbonitrides, oxycarbides, oxycarbonitrides, or oxides of Al or Zr of transition elements of groups 4 to 6 of the periodic table.

11. The rigid material layer according to claim 9 or 10, wherein the bonding layer, intermediate layer and / or cover layer is TiN, TiCN, TiAlN and / or a combination thereof.

12. A method for manufacturing an AlN-based hard material layer on an object made of metal, cemented carbide, cermet or ceramic, wherein the AlCl layer is produced by a thermal CVD process without plasma excitation in a CVD reactor. ３ , H ２ , N ２ NH ３ , CO and / or CO ２ From the gas phase, a textured oxygen-doped h-AlN-based hard material layer is deposited at a temperature of 850°C to 1050°C and a pressure of 0.1 kPa to 30 kPa, during which CO and / or CO ２ This is supplied separately to the CVD reactor through a separate gas feed, and 0.30% to 2% by volume of NH ３ A method that uses a gas phase containing gas.

13. To generate the gas phase, NH ３ The method according to claim 12, wherein the gas is supplied separately to the CVD reactor through a separate gas feed.

14. The method according to claim 12 or 13, wherein, prior to the deposition of the h-AlN-based hard material layer, at least one bonding layer, intermediate layer and / or cover layer is deposited on the object made of the metal, cemented carbide, cermet or ceramic, comprising nitrides, carbides, carbonitrides, oxycarbides, oxycarbonitrides of transition elements from groups 4 to 6 of the periodic table, or oxides of Al or Zr.

15. The method according to claim 14, comprising depositing a binding layer, an intermediate layer and / or a cover layer having TiN, TiCN, TiAlN and / or a combination thereof.

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