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
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/0021—Reactive sputtering or evaporation
  • C23C14/0036—Reactive sputtering
• • 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
  • C23C14/0021—Reactive sputtering or evaporation
  • C23C14/0036—Reactive sputtering
  • C23C14/0068—Reactive sputtering characterised by means for confinement of gases or sputtered material, e.g. screens, baffles
• • 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
  • C23C14/08—Oxides

Definitions

• the invention is related to the method of application, deposition or coating of material, most frequently using a low-voltage arc, or material de-dusting, typically using magnetron sputtering, in cases where the surface conductivity of the cathode is reduced by the so-called cathode poisoning. Material is released from this cathode for deposition on the coated substrate, the surface of which is supposed to be protected and/or functionally treated, and where such degraded, or poisoned (as the case may be) cathode impairs the quality of deposition of the protective and/or functional layers.
• the fundamental problem in achieving a stable and economical process of coating layers with low electrical conductivity, for example oxide, is to prevent poisoning of the cathode, which results in reduced speed of deposition in the PVD methods and also - in the case of the low-voltage arc - increased production of macroparticles, and thus generally overall instability of the process.
• the aim of the invention is to achieve a new method of creating protective or functional layers, during which the so-called poisoning of the cathode is prevented.
• subject matter of the invention consists of application of a thin layer with sufficient electrical conductivity to an electrode, which serves as a working cathode, from which it is evaporated using a low-voltage arc or de-dusted by means of cathode sputtering.
• an electrode which serves as a working cathode
• the working cathode is coated with an electrically conductive material by an auxiliary coating source during the process of deposition of the - protective and functional layers on the substrates in order to increase the electrical conductivity of the surface of this working cathode.
• a method of creating protective and functional layers using the PVD method from a cathode with reduced surface electrical conductivity by means of application from the working coating source, where the principle is that a material is applied to the substrate, but this material is applied from the working coating source made as a rotating working cathode, and the rotating working cathode is coated during the process from an auxiliary coating source with a material with sufficient electrical conductivity where the coat layer applied to the surface of the rotating working cathode has greater electrical conductivity than the surface of this rotating working cathode that is otherwise created during processes without using the coating of the rotating working cathode from an auxiliary coating source.
• the auxiliary coating source is modified as a rotating auxiliary cathode.
• Another advantage is the use of a low-voltage arc or magnetron sputtering to apply the material to the substrate from the rotating working cathode.
• Another advantage is modification of the rotating auxiliary cathode to be used for coating of the working cathode by means of a low-voltage arc or magnetron sputtering. It is also advantageous to apply the coat from the rotating auxiliary cathode to the rotating working cathode in a different atmosphere than the application of the material from the rotating working cathode to the substrate.
• the layer from the rotating auxiliary cathode is applied to the rotating working cathode in a largely non-reactive atmosphere and if the layer from the rotating working cathode to the substrate is applied in a largely reactive atmosphere.
• the reactive atmosphere can contain oxygen.
• an advantage is if the material of the rotating working cathode is Al; a great advantage can be if the material of the rotating working cathode is an Al-Cr alloy, with the content of Cr ranging between 0.01 to 80 % of the atomic weight.
• An advantage is if the material of the rotating auxiliary cathode is Cr; a great advantage is if the material of the rotating auxiliary cathode is an alloy containing at least partially one of the following elements: Al, Ti, V, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ag, Hf, Ta, W, Au.
• the method is advantageous particularly in situations where the surface of the evaporated material of this working cathode is poorly conductive as a result of the "poisoning" by the reactive gas or a deposition from the gaseous phase, which results in uneven evaporation or de-dusting of this material.
• This is usually accompanied by process instabilities and, in the case of arc, it results in increased production of macroparticles with the subsequent increased roughness of the surfaces of the substrates coated.
• Use of the technology according to the invention leads to a maintained sufficient and even electrical conductivity of this working cathode, which results in the process stability and, in the case of evaporation by a low-voltage arc, in significant elimination of the production of macroparticles.
• a suitable material with sufficient electrical conductivity is applied to a surface of the working cathode with insufficient electrical conductivity, e.g., to a surface poisoned by oxygen, nitrogen, layer containing carbon, etc. by an auxiliary coating source in a sufficiently inert atmosphere.
• a suitable material includes but is not limited to chromium because it is sufficiently electrically conductive in the metallic state as well as in partially oxidized state, i.e., in the form of sub-oxides. Application of this layer increases electrical conductivity of the surface, which results in significant stabilization of the burning of the low-voltage arc as well as magnetron sputtering.
• the surface of the working cathode is continuously poisoned during the application from the working cathode, which results in instabilities.
• the low-voltage arc will subsequently create channels with better conductivity on the surface, between which macroparticles, particularly large macroparticles are emitted in increased measure.
• the result is a layer deposited on the substrates with high roughness, and the useful life of this working cathode is also significantly reduced.
• the working pressure is instable and the deposition speed is reduced.
• the simplest way to create a layer with sufficient electrical conductivity on the working cathode is evaporation of the suitable material using a low-voltage arc or magnetron sputtering from the auxiliary cathode in a sufficiently inert atmosphere and the deposition thereof on the working cathode of the arc evaporation equipment or on the working cathode of the magnetron for magnetron cathodic sputtering.
• the technology is primarily designed for application of layers of oxide but it can be used also for other types of layers, e.g., layers containing nitride and carbon, in which the deposition of the poorly conductive polymer carbon layer on the surface of the working cathode causes similar problems.
• the advantage of the system with rotating cathodes is that it is possible to apply a layer with sufficient electrical conductivity to other part of the working cathode than the one, from which the material of this working cathode is evaporated on the samples, or the coated products, so the auxiliary source of material for the creation of the layer with sufficient electrical conductivity on the working cathode does not have to be placed in the area between the working cathode and the substrates, products, samples or tools coated.
• the coating source can also be placed in a screened chamber with sufficiently inert gas.
• the method can be used in two different ways
• One of the ways is a two-stage process, which consists of two recurring steps: Within the first step, a layer with sufficient electrical conductivity from the auxiliary coating source is applied to the surface of the working cathode in a sufficiently inert atmosphere. Within the second step, the material of the working cathode is evaporated to the product, sample or substrate coated, using a low-voltage arc or cathodic sputtering, e.g., using a magnetron, in a reactive atmosphere, which gradually poisons the surface of the working cathode.
• the parameters of the discharge e.g., voltage of the arc, pressure of the reactive gas, etc., or set empirically by determining the optimal duration, i.e., the process is interrupted and the first step is repeated before the poisoned surface has been created, i.e., application of the layer with sufficient conductivity to the working cathode.
• Example 1 A specific example of the two-stage process is described in Example 1.
• the second way is a continuous process: In this case the two steps are combined.
• the working cathode as well as the auxiliary coating source are located within one shielding.
• the inert gas is discharged to the area between the evaporated working cathode and the auxiliary coating source, and the reactive gas to the area of the chamber.
• Example 2 A specific example of the continuous process is described in Example 2.
• the main advantage of the continuous process as opposed to the two-stage process is the 2-3 times higher speed of coating and the improved homogeneity of the chemical composition.
• the auxiliary coating source and the working 1 eathode can be designed for operation based on a low-voltage arc or magnetron.
• An advantage is if the shape of the working cathode is cylindrical rotary form.
• the shape of the cathode of the auxiliary coating source can be cylindrical rotary or planar form.
• the auxiliary cathode 1 is made of Cr; the working cathode 2 is made of Al.
• the two cathodes take turns in burning.
• the inlet of both gases here is, by example, at a point 8; the chamber pumping is at a point 9.
• the low-voltage arc is burning on the auxiliary cathode 1 with Cr-based material, and Cr is applied to the working cathode 2 made of Al-based material, in the direction 10., as shown on figure No. 1.
• Rotary shielding 3 ⁇ or rotary shielding 4 is always turned in such position as to apply the maximum amount of the evaporated material from the auxiliary cathode 1 to the working cathode 2.
• the shielding 7 prevents application of the coat from the auxiliary cathode 1 to the substrates 6, or products, samples or tools during this stage of the process.
• Example 2 Preparation of the layer (AI,Cr) 2 ⁇ 3 in a continuous process
• Example 2a Preparation of the layer (AI,Cr) 2 ⁇ 3 in a continuous process
• the auxiliary cathode ⁇ is made of Cr-based material; the working cathode 2 is made of Al-based material. During the coating process itself, the two cathodes burn at the same time.
• Ar is taken in through the inlet 8a; O 2 is taken in through the inlet 8b.
• Inert gas, Ar is taken into the area between the cathodes 1 and 2 through the shielding 3a, through the above-mentioned inlet 8a.
• Evaporation of the auxiliary cathode 1 occurs in a sufficiently inert atmosphere.
• Evaporation of the working cathode 2 occurs in a mixture of an inert gas, Ar, and a reactive gas, O 2 .
• the advantage of the method according to Example 2 as opposed to the method according to Example 1 is the higher (two to three times higher) rate of growth and improved homogeneity of the chemical composition of the deposited layer.
• Both cathodes are located on the side of the chamber, by example in the chamber door, and the auxiliary cathode 1, which is located within the shielding flown through by the inert gas, e.g., Ar, the material with sufficient electrical conductivity is evaporated to the working cathode 2 from the side and, at the same time, the mixed material, e.g., Al and Cr, is applied from the working cathode 2, made of e.g., of Al, to the substrates in the reaction chamber, e.g., with O 2 or a mixture of O 2 and Ar.
• the working cathode 2 made of e.g., of Al
• the material of the auxiliary cathode 1 can also be a different conductive material; the material of the working cathode 2 can also be an Al alloy, e.g., Al-Cr alloy, AISi alloy, or any other suitable material creating oxides or nitrides, e.g., Zr, Ti, etc.
• Al alloy e.g., Al-Cr alloy, AISi alloy, or any other suitable material creating oxides or nitrides, e.g., Zr, Ti, etc.
• the currents of the arcs can range between 30 - 600 A.
• the technology can be combined also with the technology of pulse arc or magnetron.
• the working pressures can differ significantly; for application in an oxide atmosphere the partial pressure of oxygen can range from 0.1 to 10 Pa.
• the method according to the invention is applicable for the application of protective or functional coatings on various substrates or products, samples or tools.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Physical Vapour Deposition (AREA)

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Citations (7)

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• 2009
  • 2009-07-28 CZ CZ2009-504A patent/CZ305038B6/cs not_active IP Right Cessation
• 2010
  • 2010-07-27 WO PCT/CZ2010/000082 patent/WO2011012093A1/en active Application Filing
  • 2010-07-27 EP EP10763585A patent/EP2478126A1/en not_active Ceased

Patent Citations (7)

Non-Patent Citations (3)

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