Patent Abstract:
A hard, wear-resistant aluminum nitride based coating of composition Al x Si y Me z N is proposed; x, y and z denote atomic fractions, the sum of which is between 0.95 and 1.05, and wherein Me is a metal dopant of group III to VIII and Ib transition metals or a combination thereof. The metal provides, during the coating process, an intrinsic electrical conductivity higher than the coating without the metal doping. The silicon content is in between 0.01≦y≦0.4 and the content of the metal dopant or dopants Me is 0.001≦z≦0.8, preferably 0.01≦z≦0.05 and most preferably 0.015≦z≦0.045.

Full Description:
FIELD OF THE INVENTION 
       [0001]    The present invention relates to a hard, wear-resistant aluminum nitride based coating, an article coated there with and a method for producing such a coating. 
       BACKGROUND OF THE INVENTION 
     Description of the Prior Art 
       [0002]    Layers based on Al 1-x Ti x N respectively based on Al 1-x Ti x Si y N are commonly used in a Ti/Al stoichiometry range near the maximum hardness. In the case of TiAlN, this stoichiometry corresponds approximately to Al 0.65 Ti 0.35 N. If an Al proportion exceeding these conditions, e.g. 75 to 85 at. % of metals, is selected, both hardness and wear resistance are known to break down rapidly. Essentially the same behaviour has been expected and found for Al 1-x Cr x N and similar hard materials. 
         [0003]    The existing knowledge about this softening is described in T. Suzuki, Y. Makino, M. Samandi and S. Miyake, J. Mater. Sci. 35 (2000), 4193 and A. Hörling, L. Hultman, M. Odén, J. Sjölén, L. Karlsson, Surf. Coat. Technol. 191 (2005) 384 and references cited therein. 
         [0004]    A typical coating is further known from JP-A-2003/225809. 
       SUMMARY OF THE INVENTION 
     Object of the Invention 
       [0005]    It is thus firstly the object of the invention to provide a hard coating which can be easily produced using cathodic arc evaporation technology and magnetron sputtering technology or a combination thereof. 
       DESCRIPTION OF THE INVENTION 
       [0006]    The invention achieves the object by a coating according to claim  1 . The measures of the invention firstly have the result that an article can be coated by the hard coating according to the present invention using cathodic arc evaporation technology without further handling of the chamber in which the process is performed. Additionally, the coating is surprisingly hard with respect to the parameters. 
         [0007]    The solution according to the present invention is based on the fact that at a further increase of the Al content of any Al 1-x Me x N system substantially beyond the composition prior known as the maximum hardness, to approximately more than 90 at. % of the total of elements except nitrogen, the hardness has been surprisingly found rising again. Furthermore, this tendency has been found as being enhanced in the presence of silicon. However, very close to pure AlN or Al 1-y Si y N, respectively, the layer hardness decreases again. This can be explained by the buildup of a non-conductive layer, resulting in the suppression of ion bombardment during deposition. 
         [0008]    Further details, features and advantages of the object of the invention are obtained from the following description of the relevant drawings wherein, for example, a method according to the present invention is explained. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0009]    The drawings are as follows: 
           [0010]      FIG. 1  is a view of the schematic arrangement of the targets in the chamber according to a first example according to the present invention; 
           [0011]      FIG. 2  is a view of the schematic arrangement of the targets in the chamber according to a second example according to the present invention; 
           [0012]      FIG. 3  is a cross-sectional view of an Al 0.91 Si 0.09 N layer showing the undesired formation of a weak columnar coating material due to the lack of ion bombardment; 
           [0013]      FIG. 4  is a cross-sectional view of an Al 0.86 Si 0.09 Cr 0.05 N layer showing the homogeneous and consistently fine structure achieved by maintaining coating conductivity by doping with a small amount of metal (in this case Cr); 
           [0014]      FIG. 5  is the diagram of the hardness dependence on coating stoichiometry for the Al 1-x Cr x Si ((1-x)/10) N system. Besides the main hardness maximum known already, an unexpected secondary hardness maximum is observed at very high (Al+Si) contents. The second curve (not this invention), of the comparison system Al 1-x Cr x N without silicon addition, shows a similar behaviour but generally lower hardness; 
           [0015]      FIG. 6  is the diagram of the hardness dependence on coating stoichiometry for the system Al 1-x Zr x Si ((1-x)/5) N. This curve shows that the region below 8 at. % dopant addition even yields the global hardness for this system. 
           [0016]      FIG. 7  is the diagram of metal drilling test using solid carbide drills of diameter 5 mm, under the following testing conditions: Drilling of blind holes in coldworking steel X155CrVMo12-1 (DIN 1.2379) in soft annealed state, depth of hole 15 mm, vc=70 m/min, feed=0.16 mm/rev, internal coolant emulsion 7%. 
           [0017]      FIG. 8  is the grazing incidence X-ray diffraction diagram of a typical coating according to the present invention of composition Al 0.834 Si 0.123 Cr 0.044 N 0.994 , in as-deposited state and after thermal treatment at 800° C. in nitrogen atmosphere for one hour. It illustrates the coexistance of both hexagonal and cubic phase in this system. The thermal stability of the nanocomposite crystallographic structure is proven by the similarity of the observed diffraction peaks before and after annealing at high temperatures. 
       
    
    
     DETAILED DESCRIPTION OF THE EMBODIMENTS OF THE INVENTION 
       [0018]    Layers were deposited predominantly by arc evaporation technology. AlN-based layers can be prepared from a single target or from several separated ones. The optimum layer is Al 1-x Me x Si y N, where the optimum Me content lies between 1 and 3 at. % and Si content between 3 and 10 at. % (this corresponds to x=0.02 to 0.06 and y=0.06 to 0.20). 
         [0019]    An example of single-cathode technology is described by means of  FIG. 1 . The Al 0.885 Si 0.10 Cr 0.015  target  10  is used for the main layer preparation, the pure Cr target  20  is used for cleaning process and for adhesion and optional base layer system, alone or in combination with target  10 . 
         [0020]    A two-cathode system is shown on  FIG. 2 . Electrode  30  consists of an AlSi alloy respectively pure Al, the metal electrode  40  is used for ion cleaning, to form the optional base layer, and is used, during the process, together with the AlSi (Al) to create the main Al 1-x Me x Si y N layer. 
         [0021]    When the metal dopant content is chosen too low (significantly less than 1 at. %) the process becomes unstable. In the case of pure AlN respectively AlSiN layers with an Al respectively AlSi metallic purity of minimum 99.5 weight %, wherein the demonstrated impurity is mainly Fe, the arc voltage grows up—at a nitrogen pressure of 2 Pa, 100 A arc current—from 30 V to more than 40 V during the process which influences both process stability and coating quality. The addition of either or both, conductive nitrides and metallic conductive materials, stabilize the evaporation process of AlSi respectively Al material in nitrogen or a nitrogen-based gas mixture atmosphere. The pure Al 1-y Si y N layer cross-section in comparison to an Al 1-x Cr x Si y N layer is shown on the  FIGS. 3 and 4 . The difference is considered being caused by insufficient conductivity of the layer during the process. The ion bombardment is not maintained which causes grain coarsening during film growth, resulting in bad mechanical properties. In the case of a CrAl target at a presence of 1 atomic percent of Cr in Al, the increase of the arc voltage during the process has been measured to be no more than 1 V. At a presence of 3 atomic percent of Cr the material shows no significant voltage increase at all during deposition resulting in a homogeneous structure, which yields good mechanical properties, i.e. wear resistance, important for the use of the coating. 
         [0022]      FIG. 5  shows the hardness dependence on coating stoichiometry for the system Al 1-x Cr x Si y N respectively Al 1-x Cr x N, and  FIG. 6  (Al 1-x Zr x Si y N) shows another dopant possibility and a higher silicon content. 
         [0023]    A remarkable finding is that the hardness of these coatings stays stable and even increases upon annealing at temperatures above the deposition temperature, as shown in table 1. 
         [0024]    This stability can be explained by the two-phase structure of this material, which contains both hexagonal AlN phase and another, cubic phase ( FIG. 8 ). This nanocomposite system remains practically unchanged after annealing for one hour at 800° C. in an inert atmosphere. This means an improvement for the use of such compounds as coatings for tooling applications, where high temperatures occur at the cutting edge. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Thermal stability of Al 1−x Cr x Si y N coatings on Hardmetal. 
               
               
                 The composition is given excluding nitrogen; the nitrogen content 
               
               
                 in all coatings was determined to be 50 ± 1 at. % by Rutherford 
               
               
                 backscattering Spectroscopy (RBS) analysis. 
               
             
          
           
               
                 Sample 
                 at. % 
                 at. % 
                 at. % 
                 Density 
                 Nanohardness [GPa] 
               
             
          
           
               
                 # 
                 Al 
                 Si 
                 Cr 
                 [g/cm3] 
                 as depos. 
                 annealed 800° C. 
               
               
                   
               
             
          
           
               
                 703 
                 90.5 
                 6.1 
                 3.4 
                 2.7 
                 40.5 
                 40.9 
               
               
                 763 
                 83.4 
                 12.3 
                 4.4 
                 3.1 
                 38.7 
                 40.8 
               
               
                 759 
                 84.2 
                 12.2 
                 3.7 
                 3.3 
                 37.3 
                 38.9 
               
               
                 767 
                 83.6 
                 12.3 
                 4.1 
                 3.6 
                 37.3 
                 38.8 
               
               
                 117 
                 76.9 
                 17.3 
                 4.8 
                 3.7 
                 38.3 
                 39.5 
               
               
                   
               
             
          
         
       
     
         [0025]    The process parameters of four examples as described above are shown in the following tables: 
       Example 1 
     Two-Cathode Solution (Arc Process) 
       [0026]      
         [0000]    
       
         
               
               
             
           
               
                   
               
             
             
               
                 Configuration: 
                 Target 1 Cr (partially shielded) 
               
               
                   
                 Target 2 Al 0.88 Si 0.12  alloy or blend 
               
               
                 Coating: 
                 Al 0.85 Si 0.10 Cr 0.05 N 
               
               
                 Coating thickness: 
                 3.0 μm 
               
               
                 Process sequence: 
                 Pumping to high vacuum P &lt; 1 × 10 − 5 hPa 
               
               
                   
                 Heating in vacuum to process temperature, e.g. 
               
               
                   
                 450° C. 
               
               
                   
                 Ar plasma etching, Ar flow 200 sccm, bias −750 
               
               
                   
                 V, 2 min 
               
               
                   
                 Arc metal ion etching, bias −1200 V, Cr 
               
               
                   
                 arc 60 A, Ar flow 15 sccm, 5 min 
               
               
                   
                 Adhesion layer, CrN, Cr current 120 A, 
               
               
                   
                 cathode 2 off P(N 2 ) 1 × 10 −2  hPa, bias −120 
               
               
                   
                 V, 5 min 
               
               
                   
                 Deposition, AlSi current 130 A, Cr 50 A, 
               
               
                   
                 P(N 2 ) 3 × 10 −2  hPa, bias −75 V 
               
               
                   
               
             
          
         
       
     
       Example 2 
     Single-Cathode Solution (Arc Process) 
       [0027]      
         [0000]    
       
         
               
               
             
           
               
                   
               
             
             
               
                 Configuration: 
                 Target 1 Ti 
               
               
                   
                 Target 2 Al 0.90 Si 0.08 Cr 0.02  alloy or blend 
               
               
                 Coating: 
                 Al 0.91 Si 0.06 Cr 0.03   
               
               
                 Coating thickness: 
                 2.5 μm 
               
               
                 Process sequence: 
                 Pumping to high vacuum P &lt; 1 × 10 −5  hPa 
               
               
                   
                 Heating in vacuum to process temperature e.g. 
               
               
                   
                 450° C. 
               
               
                   
                 Ar plasma etching, Ar flow 200 sccm, bias −750 
               
               
                   
                 V, 2 min 
               
               
                   
                 Arc metal ion etching, bias −900 V, 4 min, 
               
               
                   
                 Cr arc 55 A, Ar flow 15 sccm 
               
               
                   
                 Adhesion layer, TiN, current 125 A, P(N 2 ) 
               
               
                   
                 1 × 10 −2  hPa, bias −120 V; cathode 
               
               
                   
                 2 off, 2 min 
               
               
                   
                 Deposition AlSiCr 125 A, Ti off, P(N 2 ) = 
               
               
                   
                 3 × 10 −2  hPa, bias −75 V 
               
               
                 Optional base layer 
                 Ti current 120 A, cathode 2 off, P(N 2 ) 
               
               
                 before above 
                 1.0 × 10 −2  hPa, bias −75 V, 3 min 
               
               
                 deposition step: 
               
               
                   
               
             
          
         
       
     
       Example 3 
     Single-Cathode Solution with Gradient Interlayer (Arc Process) 
       [0028]      
         [0000]    
       
         
               
               
             
           
               
                   
               
             
             
               
                 Configuration: 
                 Target 1 Cr 
               
               
                   
                 Target 2 Al 0.82 Si 0.15 Cr 0.03  alloy or blend 
               
               
                 Coating: 
                 Al 0.84 Si 0.12 Cr 0.04 N 
               
               
                 Coating thickness: 
                 4.0 μm 
               
               
                 Process sequence: 
                 Pumping to high vacuum P &lt; 1 × 10 −5  hPa 
               
               
                   
                 Heating in vacuum to process temperature, 
               
               
                   
                 e.g. 475° C. 
               
               
                   
                 Ar plasma etching, Ar flow 200 sccm, bias −750 
               
               
                   
                 V, 1 min 
               
               
                   
                 Arc metal ion etching, bias −1000 V, 5 min, 
               
               
                   
                 Cr arc 60 A, Ar flow 15 sccm; 
               
               
                   
                 Adhesion layer (optional), CrN, Cr current 
               
               
                   
                 125 A, cathode 2 off, P(N 2 ) 1 × 10 −2  hPa, 
               
               
                   
                 bias −120 V, 2 min 
               
               
                   
                 Graded interlayer, Al 1−x Cr x Si ((1−x)/5.2) N, 
               
               
                   
                 P(N 2 ) 2 × 10 −2  hPa, bias −75 V; Cr 
               
               
                   
                 125 A −&gt; 75 A, AlSiCr 75 −&gt; 140 A, 
               
               
                   
                 5 min 
               
               
                   
                 Deposition, AlSiCr 130 A, cathode 1 off, 
               
               
                   
                 P(N 2 ) = 5 × 10 −2  hPa, bias −40 V 
               
               
                   
               
             
          
         
       
     
       Example 4 
     Two-Cathode Solution with Gradient Interlayer (Arc Process) 
       [0029]      
         [0000]    
       
         
               
               
             
           
               
                   
               
             
             
               
                 Configuration: 
                 Target 1 Zr (partially shielded) 
               
               
                   
                 Target 2 Al 0.82 Si 0.18  alloy or blend 
               
               
                 Coating: 
                 Al 0.835 Si 0.140 Zr 0.025 N 
               
               
                 Coating thickness 
                 3.0 μm 
               
               
                 Process sequence: 
                 Pumping to high vacuum P &lt; 1 × 10 − 5 hPa 
               
               
                   
                 Heating in vacuum to process temperature, 
               
               
                   
                 e.g. 450° C. 
               
               
                   
                 Ar plasma etching, Ar flow 200 sccm, bias −750 
               
               
                   
                 V, 1 min 
               
               
                   
                 Arc metal ion etching, bias −1200 V, 5 
               
               
                   
                 min, Zr arc 70 A, Ar flow 15 sccm 
               
               
                   
                 Adhesion layer (optional), ZrN, Zr current 
               
               
                   
                 120 A, cathode 2 off, P(N 2 ) 1.8 × 10 −2   
               
               
                   
                 hPa, bias −120 V, 2 min 
               
               
                   
                 Graded interlayer, Al 1−x Zr x Si ((1−x)/5.2) N, 
               
               
                   
                 P(N 2 ) 2 × 10 −2  hPa, bias −60 V; Zr 
               
               
                   
                 125 A −&gt; 60 A, AlSi 75 −&gt; 140 A, 10 min 
               
               
                   
                 Deposition AlSi current 140 A, Zr 60 A, 
               
               
                   
                 P(N 2 ) 2.5 × 10 −2  hPa, bias −60 V 
               
               
                   
               
             
          
         
       
     
       Example 5 
     Single-Cathode Sputter Solution (Sputter Process with Arc Bonding Layer) 
       [0030]      
         [0000]    
       
         
               
               
             
           
               
                   
               
             
             
               
                 Configuration: 
                 Target 1 Cr (arc target) 
               
               
                 Target 2 
                 Al 0.82 Si 0.15 Cr 0.03  alloy or blend (sputter 
               
               
                   
                 magnetron) 
               
               
                 Coating: 
                 Al 0.81 Si 0.14 Cr 0.05 N 
               
               
                 Coating thickness: 
                 2.0 μm 
               
               
                 Process sequence: 
                 Pumping to high vacuum P &lt; 1 × 10 −5  hPa 
               
               
                   
                 Heating in vacuum to process temperature, 
               
               
                   
                 e.g. 400° C. 
               
               
                   
                 Ar plasma etching, Ar flow 200 sccm, bias −750 
               
               
                   
                 V, 1 min 
               
               
                   
                 Arc metal ion etching, bias −1000 V, 5 min, 
               
               
                   
                 Cr arc 60 A, Ar flow 15 sccm 
               
               
                   
                 Adhesion layer (optional), CrN, Cr arc 
               
               
                   
                 current 125 A, cathode 2 off, P(N 2 ) 1 × 
               
               
                   
                 10 −2  hPa, bias −120 V, 2 min 
               
               
                   
                 Deposition, AlSiCr magnetron sputter target 
               
               
                   
                 10 kW, 
               
               
                   
                 cathode 1 (arc) off, P (Ar + N 2 ) = 
               
               
                   
                 2.2 × 10 −3  hPa, P(N 2 ) = 5 × 10 −4   
               
               
                   
                 hPa, bias −150 V. 
               
               
                   
               
             
          
         
       
     
         [0031]    It should be noted that the experimental conditions to execute the invention are generally disclosed in WO-A-02/50865 and EPA-1357577 by the same applicant which documents are included by reference into the disclosure of this application.

Technology Classification (CPC): 2