Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
  • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
  • C23C16/34—Nitrides
  • C23C16/342—Boron nitride
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/0641—Nitrides
  • C23C14/0647—Boron nitride
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
  • C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12014—All metal or with adjacent metals having metal particles
  • Y10T428/12021—All metal or with adjacent metals having metal particles having composition or density gradient or differential porosity
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12458—All metal or with adjacent metals having composition, density, or hardness gradient
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
  • Y10T428/12576—Boride, carbide or nitride component
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]

Definitions

• the invention relates to a layer composite on a substrate according to the preamble of claim 1. At least one layer of the composite layer contains cubic boron nitride.
• Cubic boron nitride is due to its excellent Materi ⁇ aleigenschaften and especially as a superhard material - after the diamond, the hardest material ever - particularly suitable as a wear protection layer for chip-giving tools such as chisels, cutting, milling or drilling tools and for forming tools to increase their service life and / or the processing speed in use.
• the big advantage of cubic boron nitride over diamond is its chemical resistance to ferrous materials.
• [1] describes cubic boron nitride layers, which are deposited via a plasma torch. With this technique, however, only small areas in the range of a few mm 2 can be coated. Also within this small coating area, the layer thickness distribution and the layer structure method are conditional extremely inhomogeneous. The layer thickness drops continuously to zero in the furrow region, and on the other hand there are coated regions in which the boron nitride is almost exclusively not deposited in the cubic region. Furthermore, a limited reproducibility is observed, which manifests itself in considerable fluctuation ranges of the growth rate. With regard to the tool and component coating, the required targeted rastering of the plasma torch jet in accordance with the complex tool and component geometries is extremely costly and practically impossible for above-mentioned reasons in a high quality.
• cubic boron nitride layers are produced without oxygen addition, whereby their residual stress was decomposed by high-energy argon ion implantation with an energy of 300,000 eV.
• high-energy argon ion implantation with an energy of 300,000 eV.
• cubic boron nitride layers with thicknesses of 1.3 ⁇ m could be produced.
• the area that can be exposed to the ion implantation is typically 1 cm 2
• the substrate volume is limited to 1 cm 3 and the range of the ions is about 180 nm.
• For the deposition of a 1.3 micron thick layer with an area of 1 cm 2 is then required for 7 cycles, consisting of coating,
• the object of the invention is therefore to suggest a layer composite in which boron nitride of at least one single layer is present in a cubic modification, has improved adhesion, and the abovementioned limitations and disadvantages, in particular for the coating of tools or other components, even with layer thicknesses above 2 ⁇ m or not at larger lateral dimensions.
• An essential feature of the invention relates to the targeted addition of oxygen in the deposition of a cubic boron nitride layer by adding oxygen into the process gas.
• the addition can be made, for example, by argon (Ar) and by an Ar: C> 2 gas mixture, where Ar is replaceable by another process gas, for example by helium (He), neon (Ne), krypton (Kr), xenon ( Xe) or nitrogen (N 2 ).
• Ar is replaceable by another process gas, for example by helium (He), neon (Ne), krypton (Kr), xenon ( Xe) or nitrogen (N 2 ).
• the oxygen can also be converted by an oxygen-containing target via a PVD process in the gas phase and separated from there.
• the oxygen occupies the N sites of the cubic boron nitride lattice, intercalates lattice sites, or accumulates in the grain boundaries between the crystallites. Basically, the oxygen influences the deposition kinetics in a positive way, so that surface and volume diffusion processes can be optimized and thus the residual stresses are reduced even more during the layer growth.
• Wear protection relevant thickness of at least 2 microns can be produced.
• the targeted addition of oxygen preferably takes place during the entire coating process.
• Oxygen-containing, cubic boron nitride layers can be prepared in principle with all PVD processes and all plasma-assisted CVD processes.
• the substrate serves as an electrode for the aforementioned electric field.
• the layer-forming particles may be:
• Oxygen (0) neutral, single or multiple ionized
• Molecules or clusters composed of boron, nitrogen and oxygen atoms neutral, mono- or poly-ionized
• He Helium
• Neon Ne
• Ar Argon
• Krypton Kr
• Xenon Xe
• group 0 of the Periodic Table noble gases, plasma atmosphere
• neutral mono- or poly-ionized
• ions with a certain energy Ei 0n and a certain current density ⁇ on must hit the substrate or the growing layer.
• These ions can be: Boron: single or multiple ionized,
• Nitrogen single or multiple ionized
• Oxygen single or multiple ionized
• the current densities and the energy need of the layering particles and the ions are chosen such that with regard to the ele ⁇ commentaries composition of the layer the following conditions are met •
• the concentration of other elementary particles except boron, 'Stick ⁇ material, oxygen, helium, neon, argon, krypton or xenon may be up to 5 at%, however, must be kept low if the particle formation of the cubic phase at a certain Concentration prevented and this concentration should be below 5 At%.
• all particles which strike the substrate or the growing layer with a certain current density and are incorporated in the layer define the total flux of the layer-forming particles ⁇ o .
• the average energy E 0 is defined.
• the average ion energy E 10n is defined.
• the ratio ⁇ i on / ⁇ o and di> e energies E 0 and Ej 0n must be chosen so that the cubic phase forms.
• FIG. 3 shows an AES overview spectrum of a 2550 nm thick oxygen-containing cubic boron nitride layer
• Fig. 4 shows an FTIR spectrum of a 1800 nm thick oxygen-containing, cubic boron nitride layer and Fig. 5 is an X-ray diffraction pattern of 1800 nm thick
• Oxygen-containing cubic boron nitride layer Oxygen-containing cubic boron nitride layer.
• oxygen-containing cubic boron nitride layers were successfully produced on planar silicon substrates, with layer thicknesses of 500 nm, 1.8 ⁇ m and 2.5 ⁇ m.
• the coating sources were magnetron sputtering units, an ECR ion gun and an ECR plasma source.
• the rotatable substrate holder was charged with a DC voltage or a high-frequency substrate bias and heated to 85O 0 C.
• All layers were grown on a silicon substrate as a three-layer system consisting of a boron-rich ion energy-graded adhesion layer (hexagonal boron nitride-oxygen layer, h-BN: O layer), a composition-graded boron nitride oxygen nucleation layer, and a cubic boron nitride Oxygen cover layer (c-BN: O cover layer) prepared in the order mentioned.
• a boron-rich ion energy-graded adhesion layer hexagonal boron nitride-oxygen layer, h-BN: O layer
• c-BN cubic boron nitride Oxygen cover layer
• the adhesive strength was increased by the deposition of the first single layer, the nucleation of the cubic phase was controlled by the deposition of the second single layer and the actual growth of c-BN: O was optimized by depositing the third single layer.
• Tab. 1 Individual and total layer thicknesses and the deposition times of the oxygen-containing cubic boron nitride layers.
• the production and process parameters for the individual layers listed in Tab. 1 are as follows, wherein the layer thicknesses are determined with the aid of scanning electron-sectional images and with the aid of surface profilometric measurements.
• the stoichiometric, hexagonal boron nitride target of a magnetron sputtering unit is subjected to 500 W HF target power and atomized in an Ar-C> 2 mixture.
• the gas mixture consists of 45 sccm Ar, 0 sccm N 2 , 3 sccm of an Ar-C> 2 gas mixture with a mixing ratio of Ar to O 2 of 80% to 20%.
• the working gas pressure is 0.26 Pa and the substrate temperature 350 ° C.
• the negative substrate bias amount has been increased from 0V in 30V increments to 330V at equidistant time intervals, and then to 350V.
• the stoichiometric, hexagonal boron nitride target of a magnetic atomizing unit is irradiated with 500 W HF target power. aufschlagt and atomized in an Ar-N 2 -O 2 mixture.
• the Substrat ⁇ temperature is 350 ° C and the amount of the negative Substrat ⁇ prestress 350 V.
• the gas mixture consists of 45 sccm Ar and 3 sccm of an Ar-O 2 gas mixture with a mixing ratio of Ar to O 2 from 80% to 20% ,
• the nitrogen gas is increased at equidistant time intervals from 0 sccm in 0.5 sccm increments to 5 sccm and then in 1 sccm increments to 10 sccm.
• the working gas pressure is initially at 0.26 Pa and at the end at 0.29 Pa.
• the stoichiometric, hexagonal boron nitride target of a magnetron sputtering unit is exposed to 500 W HF target power and atomized in an Ar-N 2 -O 2 mixture.
• the substrate temperature is 350 ° C and the amount of negative substrate bias is 350 V.
• the gas mixture consists of 45 sccm Ar, 3 sccm of an Ar-O 2 gas mixture with a mixing ratio of Ar to O 2 of 80% to 20% and 10 sccm N 2 .
• the working gas pressure is 0.29 Pa.
• the following procedure can be used in principle. If the layer does not contain a cubic phase for a chosen combination of ⁇ i on / ⁇ o ⁇ Eo and Ei 0n , then the ratio ⁇ Ion / ⁇ o and / or the energies Eo and E 10n must be chosen larger until the cubic Phase forms, but not so large that by sputtering effects on the surface no more auf ⁇ growing (see Fig. 1).
• Fig. 1 shows a diagram of the experimentally determined in the context of the embodiment relationship between the ion flux ⁇ i on i m ratio to the flow of the layer-forming particles ⁇ BN (corresponding to the aforementioned generally held flow of the layer-forming particles ⁇ o ) in dependence on the middle Ion energy Ei 0n -
• the diagram shows three parameter ranges 1 to 3.
• a cubic boron nitride oxygen layer (c-BN: O) deposits in the region 1, in a certain flux ratio ⁇ IO ⁇ / ⁇ BN or the average ion energy Eion reach a certain level.
• the substrate temperature T 3 must meet the following conditions during the coating process:
• T M / C _ B N O are: T s ⁇ T M , C -BM : O
• composition of the aforementioned individual layers was determined by means of AES (Auger electron spectroscopy).
• the spectrum shows three signals that can be assigned to the elements boron, nitrogen and oxygen.
• the elemental concentration results for boron at 48.6 at%, for nitrogen at 46.5 at% and for oxygen at 4.9 at%.
• FIG. 2 b shows, by way of example, an AES depth concentration profile of a layer composite given in Tab. 1 with a total thickness of 500 nm. From this, the homogeneous distribution of the element concentrations in the 300 nm thick oxygen-containing, cubic boron nitride cover layer can be determined as well as the element distribution in the adhesion promoter and the
• the electrical charge also increases in this analysis method. This complicates measurement and an accurate evaluation of the AES spectra, even if the charging of the analysis surface is at least partially compensated by the ion bombardment in combination with the offer of electrons. Therefore, in the composite layer with a total thickness of 2.55 ⁇ m, the BN: O layer had to be locally atomized by the ion beam down to the silicon substrate, forming a crater with a cross section similar to Gaussian distribution (crater profile). By scanning this mathematically describable crater profile, an accurate depth profiling could be performed, whereby charges are much easier degradable by a surface current over the crater profile to the silicon.
• Fig. 3 shows the above-mentioned overview spectrum on the crater profile, i. the elemental composition of the 2 micron thick oxygen-containing, cubic boron nitride cover layer of the listed in Tab. 1 2.55 micron thick BN: O layer.
• the boron concentration results to 49 At%, the nitrogen concentration to 46.3% and the Sauerstoff ⁇ concentration to 4.6 At%.
• this is in very good agreement with the elemental composition of the oxygen-containing, cubic boron nitride cover layer of the 500 nm thick BN: O layer and corresponds to the expectations due to the process in the deposition of the cover layers.
• the detection of the sp 3 -hybridized binding states takes place by means of infrared spectroscopy (FTIR, FIG. 4) and the detection of the cubic crystal structure by X-ray diffraction (XRD, FIG. 5).
• 4 shows a transmission infrared spectrum in the wavenumber range between 400 cm -1 and 8400 cm -1 .
• the BNB flexural vibration at approximately 780 cm -1 and the BN Stretching vibration observed at 1380 cm “1 , mainly from the
• Adhesive layer and the nucleation caused were ⁇ the.
• the oscillations are caused by layer thickness interferences.
• the 5 maxima at 7850 cm -1 , 6400 cm -1 , 5080 cm -1 , 3690 cm -1 and 2295 cm -1 and the four minimums between them can clearly be seen be estimated:
• the X-ray diffraction pattern which was taken in the grazing incidence, shows three signals which can be assigned to the c-BN: O. They correspond to the signals of (111) c-BN at 43.3 °, (220) c-BN at 74.1 ° and (311) c-BN at 89.8 °.
• the detection of the cubic, oxygen-containing boron nitride phase was provided by means of FTIR and XRD.
• the hardness was measured on an approximately 2 .mu.m thick, oxygen-containing, cubic boronitride layer.
• the layer hardness was found to be 59.2 GPa ⁇ 2.3 GPa at a maximum load of 2 mN, 59.6 GPa ⁇ 1.9 GPa at 5 mN and 60.5 GPa ⁇ 1.6 GPa at 10 mN, which corresponds to the theoretically expected value.

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• Inorganic Chemistry (AREA)
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• 2004
  • 2004-09-02 DE DE200410042407 patent/DE102004042407A1/de not_active Ceased
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