CN115449769B - High-temperature-resistant low-diffusion alloy film for copper matrix and preparation method thereof - Google Patents
High-temperature-resistant low-diffusion alloy film for copper matrix and preparation method thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 189
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 167
- 238000009792 diffusion process Methods 0.000 title claims abstract description 157
- 239000011159 matrix material Substances 0.000 title claims abstract description 125
- 239000000956 alloy Substances 0.000 title claims abstract description 85
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title description 13
- 239000010410 layer Substances 0.000 claims abstract description 240
- 230000004888 barrier function Effects 0.000 claims abstract description 80
- 238000004544 sputter deposition Methods 0.000 claims description 58
- 238000005530 etching Methods 0.000 claims description 40
- 239000000758 substrate Substances 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 10
- 229910000943 NiAl Inorganic materials 0.000 claims description 7
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 7
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims description 6
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Classifications
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- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- 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
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
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- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/129—Flame spraying
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- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/131—Wire arc spraying
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- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a high-temperature-resistant low-diffusion alloy film for a copper matrix, which comprises an intermediate layer and a diffusion barrier layer which are alternately arranged on the copper matrix, wherein the total number of layers of the intermediate layer and the diffusion barrier layer is 2-48, and the modulation ratio of the intermediate layer to the diffusion barrier layer is 1:1-5. According to the invention, the high-temperature-resistant low-diffusion alloy film is formed by alternately arranging the intermediate layers and the diffusion barrier layers on the copper matrix, the intermediate layers play a transitional role, the diffusion barrier layers effectively relieve the high-temperature oxidation and diffusion problems of the copper matrix, the interlayer binding force is excellent, the binding force with the matrix is good, and the film has excellent high-temperature oxidation resistance and diffusion barrier performance under a thinner thickness, so that the copper matrix can maintain stable high-temperature conductivity.
Description
Technical Field
The invention belongs to the technical field of protective coatings, and particularly relates to a high-temperature-resistant low-diffusion alloy film for a copper matrix and a preparation method thereof.
Background
Copper and copper alloys have excellent high electrical and thermal conductivity, good mechanical properties and corrosion resistance and are widely used in the fields of integrated circuit lead frames, instruments and meters, high-energy motors, computer communication, and technical and precision mechanical manufacturing. However, copper is extremely easily oxidized in high-temperature air (> 200 ℃) to cause blackening of copper cores/copper wires, and the generated oxide film is not protective, and the copper wires are rapidly oxidized and lose conductivity at a temperature exceeding 400 ℃. The temperature continues to rise, copper atoms and an outer protective layer or an oxidation resistant layer can have serious interdiffusion, so that the conductivity is obviously reduced, even voltage among copper wires is attenuated, voltage breakdown is caused, and the performance and the reliability of the device are seriously affected.
Under some special high-temperature use environments, such as large-scale oil drilling motor wires, turbine generator rotor wires, electric locomotive overhead wires and the like, copper wires/copper alloy materials are required to have high-strength and high-conductivity performances, better high-temperature resistance and reduced diffusion performances under the application background. Therefore, how to improve the oxidation resistance of the copper conductor and inhibit the interdiffusion at high temperature to ensure the stable high-temperature conductivity of the copper conductor is a difficult problem which needs to be solved in order to meet the development requirements of advanced power equipment.
To improve the surface properties of pure copper, copper surfaces are typically covered. This can be achieved by diffusing specific elements (Ti, si and Al) into the surface layer of copper. Wang Gongxing et al used nickel plating and slurry pack aluminizing to prepare Ni structure at 800 deg.C for 12 hr 2 Al 3 Is a single-phase percolated layer. The method can oxidize for 250 hours in the air at 1000 ℃ and still maintain good high-temperature oxidation resistance. However, because Cu and Al have large solid solubility and various intermediate compound phases exist, the internal diffusion is serious in high-temperature service, and the copper conductor, especially micro-copper conductor, can be greatly reducedConductivity of the fine copper wire.
The patent application number 202111360394.8 discloses a low-interdiffusion high-temperature oxidation resistant coating for copper conductors and a preparation method thereof, wherein Cr or a Cr alloy with a Cr atom percentage not lower than 95% is used, the coating with Cr as a main component can maintain low diffusivity with a Cu matrix at high temperature, and meanwhile, cr has excellent oxidation resistance. But Cr coating forms Cr with O element in environment 2 O 3 A layer capable of preventing the O element from continuing to diffuse to the substrate and forming a gaseous CrO under high temperature conditions 3 Escaping, so that the Cr coating is continuously consumed and destroyed, and the problem also limits the oxidation resistance of the Cr coating. And compared with the multi-element multi-layer coating or gradient coating, the single-layer coating has columnar microstructure and intrinsic defects such as pinholes, pores, microcracks, transient grain boundaries and the like, and the service life of the coating can be reduced.
Therefore, a high-temperature-resistant low-diffusion alloy film for a copper matrix and a preparation method thereof are needed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-temperature-resistant low-diffusion alloy film for a copper matrix aiming at the defects of the prior art. The thin film comprises the intermediate layers and the diffusion barrier layers which are alternately arranged on the copper matrix, wherein the intermediate layers play a role in transition, the diffusion barrier layers effectively relieve the problems of high-temperature oxidation and diffusion of copper conductors, the interlayer binding force is excellent, the binding force with the matrix is good, and the thin film has excellent high-temperature oxidation resistance and diffusion barrier performance under a thinner thickness, so that the copper matrix can keep stable high-temperature conductive performance.
In order to solve the technical problems, the invention adopts the following technical scheme: the high-temperature-resistant low-diffusion alloy film for the copper matrix is characterized by comprising an intermediate layer and a diffusion barrier layer which are alternately arranged on the copper matrix, wherein the total number of layers of the intermediate layer and the diffusion barrier layer is 2-48, the modulation ratio of the intermediate layer to the diffusion barrier layer is 1:1-5, the intermediate layer is a Ti layer, and the diffusion barrier layer is a NiCrAl layer.
According to the invention, the intermediate layer and the diffusion barrier layer are alternately arranged on the copper matrix, the intermediate layer plays a role in transition, and the diffusion barrier layer effectively relieves the problems of high-temperature oxidation and diffusion of the copper conductor, so that the copper matrix can maintain stable high-temperature conductivity;
according to the invention, the Ti layer is adopted as the intermediate layer, the NiCrAl layer is adopted as the diffusion barrier layer, and based on the research on Ti/Cu solid phase interface diffusion, the atomic diffusion flow is Cu diffusion and enters Ti when Ti and Cu are subjected to solid phase diffusion below 700 ℃, and Ti is seldom diffused and enters Cu, so that the Ti is adopted as the transition intermediate layer, the NiCrAl is prevented from back diffusion to a Cu substrate and affecting Cu conductivity, compact oxide can be formed at high temperature due to Cr and Al elements, the O element is prevented from diffusing inwards to erode a matrix, meanwhile, the Ni and Cr can inhibit the diffusion between the NiCrAl and the Cu matrix at high temperature, and meanwhile, the requirements of oxidation resistance and low diffusion under the high temperature of a copper conductor are met, the NiCrAl layer is also a high-temperature-resistant, oxidation-resistant and low-diffusion coating with good oxidation resistance, and a novel material design with material performance of 1+1>2 is realized by matching with the Ti intermediate layer in view of a unique heterogeneous interface effect of a multilayer structure, so that a film with better oxidation resistance and mechanical property is obtained;
the invention is based on the characteristic that the NiCrAl layer is almost incompatible with Cu, has good Cu migration resistance at high temperature, has excellent oxidation resistance because of Cr and Al elements, uses Ti as an intermediate layer, avoids back diffusion of Ti and NiCrAl to a Cu substrate and influences Cu conductivity, can not only remarkably solve the serious oxidation problem faced by high-temperature application of a copper conductor, but also solve the problem of conductivity reduction caused by mutual diffusion of films/matrixes when other high-temperature protective films are applied to the copper conductor, so that a copper matrix can keep stable high-temperature conductivity;
the thickness of the alloy film is controlled by controlling the total layer number of the intermediate layer and the diffusion barrier layer, so that the alloy film is suitable for different use requirements, the modulation ratio is an important parameter for reflecting the stoichiometric ratio of materials in the preparation of the multilayer film, a group of alternately arranged intermediate layers and diffusion barrier layers are manufactured to be a modulation period, the modulation ratio is the sputtering time of the intermediate layers and the diffusion barrier layers in the modulation period, and the thickness ratio of the intermediate layers and the diffusion barrier layers in the film is controlled by controlling the sputtering time, so that the alloy film meets the use requirements of different conditions.
The high-temperature-resistant low-diffusion alloy film for the copper matrix is characterized in that the intermediate layer can be a Ni layer, a Cr layer, an Al layer or a Zr layer; the NiCrAl layer consists of the following components in atomic percent: 45-55% of Ni, 25-35% of Cr and 20-30% of Al.
The intermediate layer can also be a Ni layer, a Cr layer, an Al layer or a Zr layer, the functions of the Ni layer, the Cr layer, the Al layer or the Zr layer and the Ti layer are the same, the Ni layer, the Cr layer, the Al layer or the Zr layer are used as transition layers to increase the film-based bonding strength of the surface NiCrAl layer, but when the interface between Ti and Cu is diffused below 700 ℃, the atomic diffusion flow is that Cu diffuses into Ti, and the Ti rarely diffuses into Cu, so that Ti is preferred, and other metal films diffuse into Cu due to the difference of diffusion coefficients of the metal films and Cu, the efficiency is different, and different intermediate layers are selected according to the actual working conditions;
the invention controls the components of Ni 45% -55%, cr 25% -35% and Al 20% -30% because the low content of Al and Cr in the components can cause the lack of sufficient high-temperature oxidation resistance, and the Al in the film component is used as Al 2 O 3 The film forming element has the most obvious influence on the high-temperature oxidation resistance of the film, the proper Al content can improve the high-temperature oxidation resistance of the film, but simultaneously the film embrittles due to excessive addition of Al, and the proper Cr element in the film obviously improves the hot corrosion resistance of the film, and simultaneously greatly reduces the content required by selective oxidation of the Al element, thereby accelerating the Al on the surface of the film 2 O 3 The film can be formed, the film can be prevented from being degraded due to the mutual diffusion of elements, the proper Ni content can improve the thermal stability of the film, particularly the corrosion resistance of the film in the severe environment, and the film has better comprehensive performance, can resist high-temperature oxidation and has certain heat corrosion resistance, and meanwhile, the film has the effect of preventing the mutual diffusion of elements from being degraded.
The high-temperature-resistant low-diffusion alloy film for the copper matrix is characterized in that the thickness of each intermediate layer and the thickness of each diffusion barrier layer are 20-1000 nm, and the total thickness of the film is 1.0-3.0 mu m.
According to the invention, the total thickness of the film is controlled to be 1.0-3.0 mu m, the film keeps high thermal stability and diffusion barrier performance, the film thickness is too small, the film is insufficient to have enough high temperature resistance and prevent diffusion with matrix elements, the film bonding capability is poor due to the fact that the film is too large in thickness, the preparation time is too long, the manufacturing cost is increased, the film density is increased, matrix use is affected, the thickness of the middle layer and the diffusion barrier layer is 20-1000 nm in a corresponding modulation period, the middle layer is not required to be too thick, the isolation effect can be achieved at the lowest 20nm, the diffusion between the NiCrAl layer and the matrix is prevented, the binding force of the film is improved, the film thickness is not controlled well due to the fact that the film thickness is too small, the film is mainly a NiCrAl layer, when the film is used for improving high resistance, the film stress is too large or film defects are generated when the film thickness exceeds 1000nm, and film failure is accelerated.
In addition, the invention also provides a method for preparing the high-temperature-resistant low-diffusion alloy film for the copper matrix, which is characterized by comprising the following steps of:
etching the copper matrix in a vacuum environment to obtain an etched copper matrix; the etching power is 150-250W, and the etching time is 5-10 min;
alternately sputtering the surface of the etched copper matrix obtained in the first step by using a metal target and an alloy target to prepare an intermediate layer and a diffusion barrier layer, so as to obtain a copper matrix with a high-temperature-resistant low-diffusion alloy film; the metal target is a Ti target, a Ni target, a Cr target, an Al target or a Zr target; the alloy target is a NiCrAl target, and the alloy target can be more than two of a NiCr target, a NiAl target and a CrAl target.
Before coating, the surface of the copper matrix is subjected to ion etching cleaning in a vacuum state to remove gas and dirt adsorbed on the surface, so that real surface atoms are thoroughly exposed, and meanwhile, the temperature of the surface of the matrix is slightly increased, thereby being beneficial to film nucleation and enhancing the bonding strength of the film and the matrix;
according to the invention, a Ti target, a Ni target, a Cr target, an Al target or a Zr target is selected to prepare different intermediate layers respectively, so that the method is suitable for different preparation requirements, the NiCrAl target is directly used as an alloy target to prepare a diffusion barrier layer, or more than two of the NiCr target, the NiAl target and the CrAl target are used to prepare a NiCr layer, a NiAl layer and a CrAl layer respectively so as to form a NiCrAl ternary alloy layer, and the NiCrAl ternary alloy layer has the advantages of heat resistance, high-temperature oxidation resistance and corrosion resistance, compact structure, better cohesiveness with a matrix material, realization of use conditions at higher temperature, better protection of the matrix performance, controllable constituent parts of the film, corrosion resistance and the like;
the method comprises the steps of firstly grinding and polishing a substrate by sand paper before sputtering, ultrasonically cleaning, drying and etching the polished substrate, and removing impurities of the substrate; the ultrasonic cleaning method comprises the following steps: sequentially ultrasonically cleaning the raw materials in acetone and ethanol for 10min, and drying.
The method is characterized in that in the first step, the etching is performed under vacuum degree of less than 3×10 -3 Pa, and the temperature of the copper matrix is 20-250 ℃. The invention properly heats the copper matrix and etches the copper matrix, thereby improving the etching and cleaning efficiency.
The method is characterized in that the sputtering in the second step is magnetron sputtering, the metal target adopts a direct current power supply, the power is 60-120W, the alloy target adopts a radio frequency power supply, the power is 80-180W, the direct current bias voltage on the copper substrate is 0-150V, and the sputtering is performed under the conditions that the air pressure is 1.5 Pa-2.5 Pa and the argon flow is 10-30 sccm. The metal target is a direct current power supply, the alloy target is a radio frequency power supply, the alloy target is a magnetic substance because of Ni content, stable glow discharge is more easily formed by using the radio frequency power supply, sputtering power has great influence on the deposition rate of a film, the sputtering phenomenon cannot be generated because the energy of incident ions cannot reach the sputtering threshold value of the target if the power is too small, or the deposition speed is too slow, a film layer structure is loose, particles are large, the power is too large, the film layer is broken because of the increase of stress in the film layer, the deposited microstructure can be greatly influenced, the direct current power supply is adopted by the metal target, the power is 60W-120W, the range of 80W-180W intervals of the radio frequency target is adopted, and the prepared film is compact and uniform; the magnetron sputtering is facilitated by applying the direct-current bias, and the scattering effect on sputtered atoms is weak by controlling the pressure and introducing argon, so that the film has better binding force and keeps higher growth rate.
The method is characterized in that in the first step, the copper substrate is copper or copper alloy.
The method is characterized in that the total sputtering time of the metal target in the second step is 2 min-30 min, and the total sputtering time of the alloy target is 2 min-90 min. The invention controls the modulation ratio by controlling the time of the metal target sputtering and the alloy target sputtering, and the total time is different because the alternation times are determined, so that the time of the metal target sputtering and the time of the alloy target sputtering are different, namely the thicknesses of the intermediate layer and the diffusion barrier layer which are alternately distributed are controlled, when the thicknesses of the intermediate layer and the diffusion barrier layer are the same, the intermediate layer is thicker, the diffusion barrier layer element can be better prevented from diffusing into the copper matrix, the electric conductivity and the heat conductivity of the copper matrix are influenced, and when the diffusion barrier layer is thicker than the intermediate layer, the serious oxidization problem faced by the high-temperature application of the copper matrix is solved, and the copper matrix has better high-temperature resistance, oxidation resistance and corrosion resistance.
The method is characterized in that the alternate sputtering is carried out for 1 time in the second step, a single-layer high-temperature-resistant low-diffusion alloy film is obtained on the copper substrate, the alternate sputtering is carried out for 2-24 times, and a multi-layer high-temperature-resistant low-diffusion alloy film is obtained on the copper substrate. The invention realizes the preparation of the single-layer high-temperature-resistant low-diffusion alloy film and the multi-layer high-temperature-resistant low-diffusion alloy film by controlling the times of alternate sputtering, wherein the single-layer alloy film has simple preparation process, stable performance and uniform and convenient control components, but the single-layer film can directly corrode a matrix through gaps among crystal grains, pinholes, slits and other defects in the film, penetrate into a film base interface, the coating diffusion barrier capability is weaker, and the interfaces among the multi-layer alloy films can prevent the growth of columnar crystals and refine crystal grains, thereby improving the plastic deformation capability, inhibiting the formation and the expansion of cracks, improving the corrosion resistance and the diffusion barrier capability of the film, and determining the layer number of the film according to actual use requirements.
The method is characterized in that the film is prepared by arc ion plating, flame spraying or plasma spraying. The alloy film of the invention can be prepared by sputtering, and the intermediate layer and the diffusion barrier layer can be alternately arranged on the copper matrix by adopting arc ion plating, flame spraying or plasma spraying.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the high-temperature-resistant low-diffusion alloy film is formed by the intermediate layers and the diffusion barrier layers which are alternately arranged on the copper matrix, the intermediate layers play a role in transition, the diffusion barrier layers effectively relieve the high-temperature oxidation and diffusion problems of the copper conductor, the interlayer binding force is excellent, the binding force with the copper matrix is better, the surfaces of the intermediate layers and the diffusion barrier layers with different layer thickness ratios are uniform and compact, almost no defects and particles exist, no obvious difference exists, and the film has excellent high-temperature oxidation resistance and diffusion barrier performance under a thinner thickness, so that the copper matrix can keep stable high-temperature conductivity.
2. According to the invention, ti is used as an intermediate layer, reverse diffusion of Ti and NiCrAl to a Cu substrate is avoided, cu conductivity is influenced, niCrAl is used as a diffusion barrier layer, niCrAl is almost insoluble with Cu, and the copper substrate has good Cu migration resistance at high temperature, so that not only can the serious oxidization problem faced in high-temperature application of a copper conductor be remarkably solved, but also the problem of conductivity reduction caused by inter-diffusion of a coating/substrate when other high-temperature protective coatings are applied to the copper conductor can be solved, and the copper substrate can maintain stable high-temperature conductivity.
3. According to the invention, the magnetron sputtering is used for alternately sputtering the pure metal intermediate layer and the alloy diffusion barrier layer, the deposited coating interface is obvious, the deposition efficiency and the film adhesion are improved by controlling the sputtering condition, the obtained film is ensured to have smooth surface and compact structure, the film component is consistent with the target component, the preparation process is simple, the controllability is high, the environment is protected, and the problems of waste water and exhaust of the traditional electroplating Ni and Cr are avoided.
4. The film and the preparation method of the film are applied to copper wires, copper matrixes and the like in the high-temperature field, the comprehensive service effect is far better than that of other common protective coating systems such as nickel-based protective coatings, aluminizing, thermal spraying coatings and the like, and the film and the preparation method of the film are used in stability under different application environments such as bending/winding and the like, so that the oxidation problem of copper conductors and the diffusion problem at high temperature are effectively relieved, and the stable high-temperature conductivity of the film and the film is ensured.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a schematic structural diagram of a high temperature resistant low diffusion alloy film for copper substrates according to the present invention.
FIG. 2 is a morphology of a copper matrix with a high temperature resistant low diffusion alloy film obtained in example 1 of the present invention.
FIG. 3 is an SEM image of a copper matrix having a high temperature resistant low diffusion alloy film according to example 1 of the present invention.
FIG. 4 is a graph showing the morphology of a copper substrate with a high temperature resistant low diffusion alloy film obtained in example 2 of the present invention.
FIG. 5 is an SEM image of a copper matrix with a high temperature resistant low diffusion alloy film according to example 2 of the present invention.
FIG. 6 is an SEM image of a cross section of a copper matrix with a high temperature resistant low diffusion alloy film according to example 2 of the present invention.
Fig. 7 is an SEM image of the copper matrix with the high temperature resistant low diffusion alloy film obtained in example 2 of the present invention after heat resistance test.
Fig. 8 is an enlarged view at a of fig. 7.
Fig. 9 is an EDS spectrum of the copper matrix with the high temperature resistant low diffusion alloy film obtained in example 2 of the present invention after heat resistance test.
FIG. 10 is a graph showing the morphology of a copper substrate with a high temperature resistant low diffusion alloy film obtained in example 2 of the present invention after scratch test.
FIG. 11 is a graph showing the load-friction force curve obtained by scratch test of a copper substrate with a high temperature resistant low diffusion alloy film obtained in example 2 of the present invention.
Detailed Description
Fig. 1 is a schematic structural diagram of a high-temperature-resistant low-diffusion alloy film for a copper matrix, and as can be seen from fig. 1, a middle layer 2 is uniformly arranged around the copper matrix 1, and a diffusion barrier layer is uniformly arranged outside the middle layer 2.
Example 1
In the embodiment, the total number of layers for preparing the intermediate layer and the diffusion barrier layer is 12, the modulation ratio of the intermediate layer to the diffusion barrier layer is 1:1, the intermediate layer is a Ti layer, the diffusion barrier layer is an alloy film of a NiCrAl layer, and the copper matrix is a T1 copper wire.
The embodiment comprises the following steps:
sequentially ultrasonically cleaning a polished copper matrix in acetone and absolute ethyl alcohol for 10min, then rapidly drying by using a blower, fixing the copper matrix on a sample table of a magnetron sputtering vacuum coating chamber, and etching in a vacuum environment to obtain an etched copper matrix; the etching power is 250W, and the etching time is 5min; the etching is performed under vacuum degree of less than 5×10 -3 Pa, and the temperature of the copper matrix is 20 ℃;
step two, argon is introduced into a vacuum coating chamber, the bias voltage for etching the copper matrix is set to be 150V, pre-sputtering is carried out for 1min, and then 1 Ti target and 2 NiCrAl targets are adopted to deposit 6 periods in sequence, so that the copper matrix with the high-temperature-resistant low-diffusion alloy film is obtained; wherein the argon flow is 10sccm, the working air pressure is 1.5Pa, the power is 120W, the time of each sputtering of the Ti target is 10min, the power is 180W, the time of each sputtering is 10min, the sputtering temperature is room temperature, and the rotating speed of the etched copper matrix in the sputtering process is 15r/min.
The nicrall layer prepared in this example was tested to consist of the following atomic percent: ni:55%, cr:25% and Al:20%, the thickness of each intermediate layer is 100nm, the thickness of each diffusion barrier layer is 150nm, the total thickness of the film is 1.55 mu m, the binding force of the base film is 22N by adopting a scratch method, the interface of the film is complete after 300h heat-resistant treatment at 500 ℃, the structure is kept compact and smooth, and the film has better high-temperature oxidation resistance and heat resistance.
Fig. 2 is a morphology diagram of the copper matrix with the high temperature resistant low diffusion alloy film obtained in this example, and it can be seen from fig. 2 that the copper matrix with the high temperature resistant low diffusion alloy film presents silvery white metallic luster, has smooth and flat surface, and has no obvious adverse phenomena such as pinholes, peeling, wrinkles, falling off, and the like.
Fig. 3 is an SEM image of the copper matrix with the high temperature resistant low diffusion alloy film obtained in this example, and it can be seen from fig. 3 that the surface of the copper matrix is relatively uniform and dense after being coated, and almost no obvious cracks, defects and particles are generated.
Example 2
In the embodiment, the total number of layers for preparing the intermediate layer and the diffusion barrier layer is 24, the modulation ratio of the intermediate layer to the diffusion barrier layer is 1:1, the intermediate layer is a Ti layer, the diffusion barrier layer is an alloy film of a NiCrAl layer, and the copper matrix is TU1 oxygen-free copper sheet.
The embodiment comprises the following steps:
sequentially ultrasonically cleaning a polished copper matrix in acetone and absolute ethyl alcohol for 10min, then rapidly drying by using a blower, fixing the copper matrix on a sample table of a magnetron sputtering vacuum coating chamber, and etching in a vacuum environment to obtain an etched copper matrix; the etching power is 150W and the etching time is 50min; the etching is performed under vacuum degree of less than 5×10 -3 Pa, and the copper matrix temperature is 250 ℃;
step two, argon is introduced into a vacuum coating chamber, the bias voltage for etching the copper matrix is set to be 0V, pre-sputtering is carried out for 1min, and then 1 Ti target and 2 NiCrAl targets are adopted to deposit 12 periods in sequence, so that the copper matrix with the high-temperature-resistant low-diffusion alloy film is obtained; wherein the argon flow is 20sccm, the working air pressure is 2.1Pa, the power is 100W, the time of each sputtering of the Ti target is 5min, the power is 150W, the time of each sputtering is 5min, the sputtering temperature is room temperature, and the rotating speed of the etched copper matrix in the sputtering process is 15r/min.
The nicrall layer prepared in this example was tested to consist of the following atomic percent: ni:50%, cr:30% and Al:20%, the thickness of each intermediate layer is 60nm, the thickness of each diffusion barrier layer is 120nm, the total thickness of the film is 2.15 mu m, the binding force of the base film is 23N by adopting a scratch method, the interface of the film is complete after 300h heat-resistant treatment at 500 ℃, the structure is kept compact and smooth, and the film has better high-temperature oxidation resistance and heat resistance.
Fig. 4 is a morphology diagram of the copper matrix with the high temperature resistant low diffusion alloy film obtained in this example, and it can be seen from fig. 4 that the copper matrix with the high temperature resistant low diffusion alloy film presents silvery white metallic luster, has smooth and flat surface, and has no obvious adverse phenomena such as pinholes, peeling, wrinkles, falling off, and the like.
Fig. 5 is an SEM image of the copper matrix with the high temperature resistant low diffusion alloy film obtained in this example, and it can be seen from fig. 5 that the surface of the copper matrix is relatively uniform and dense after being coated, and almost no obvious cracks, defects and particles are generated.
Fig. 6 is an SEM image of a cross section of a copper matrix with a high temperature resistant low diffusion alloy film obtained in this example, and as can be seen from fig. 6, the film thickness is 1-3 μm, the average thickness is 2.15 μm, the film has obvious columnar crystals, the film thickness is uniform, and the bonding between the film and the copper matrix and between the films is stable and tight.
Fig. 7 is an SEM image of the copper substrate with the high temperature resistant low diffusion alloy film obtained in this embodiment after heat resistance test, fig. 8 is an enlarged image of a portion a of fig. 7, and fig. 9 is an EDS spectrum of the copper substrate with the high temperature resistant low diffusion alloy film obtained in this embodiment after heat resistance test, it can be seen from fig. 7, fig. 8 and fig. 9 that the interface of the coating after heat resistance treatment is complete, the structure is kept compact and flat, the high temperature oxidation resistance is better, the O element and Cr element are distributed on the surface of the coating in a large amount, and the Cu element is distributed in a small amount in the barrier layer, which indicates that Cr can effectively protect Cu oxidation, and has a good Cu diffusion barrier capability.
Fig. 10 is a morphology diagram of a copper substrate with a high temperature resistant low diffusion alloy film obtained in this example after scratch test, fig. 11 is a load-friction force graph obtained in this example after scratch test of the copper substrate with a high temperature resistant low diffusion alloy film, and as can be seen from fig. 10 and 11, the amplification factor of fig. 10 is 30 times, the film substrate binding force is tested by using an automatic scratch tester, the termination load is 100N for 60 seconds, scratches with a length of 5mm are obtained on the surface of the copper substrate with a high temperature resistant low diffusion alloy film, real-time recording is performed on the sound signal and the friction force in the experimental process, the scratch track is gradually enlarged, no noise signal is generated, obvious fluctuation appears in the friction force graph when the scratch time reaches about 15 seconds, and at this time, the scratch load is about 23N, and the film layer shows excellent film substrate binding force and plasticity.
Example 3
In the embodiment, the total number of layers for preparing the intermediate layer and the diffusion barrier layer is 48, the modulation ratio of the intermediate layer to the diffusion barrier layer is 1:1.5, the intermediate layer is a Ti layer, the diffusion barrier layer is an alloy film of a NiCrAl layer, and the copper matrix is H96 brass wire.
The embodiment comprises the following steps:
sequentially ultrasonically cleaning a polished copper matrix in acetone and absolute ethyl alcohol for 10min, then rapidly drying by using a blower, fixing the copper matrix on a sample table of a magnetron sputtering vacuum coating chamber, and etching in a vacuum environment to obtain an etched copper matrix; the etching power is 200W and the etching time is 8min; the etching is performed under vacuum degree of less than 5×10 -3 Pa, and the copper matrix temperature is 200 ℃;
step two, argon is introduced into a vacuum coating chamber, the bias voltage for etching the copper matrix is set to be 100V, pre-sputtering is carried out for 1min, and then 1 Ti target and 2 NiCrAl targets are adopted to deposit 24 periods in sequence, so that the copper matrix with the high-temperature-resistant low-diffusion alloy film is obtained; wherein the argon flow is 30sccm, the working air pressure is 2.5Pa, the power is 120W, the time of each sputtering of the Ti target is 2min, the power is 180W, the time of each sputtering is 3min, the sputtering temperature is room temperature, and the rotating speed of the etched copper matrix in the sputtering process is 15r/min.
The nicrall layer prepared in this example was tested to consist of the following atomic percent: ni:45%, cr:25% and Al:30%, the thickness of each intermediate layer is 30nm, the thickness of each diffusion barrier layer is 100nm, the total thickness of the film is 3.00 mu m, the binding force of the base film is 30N by adopting a scratch method, the interface of the film is complete after 300h heat-resistant treatment at 500 ℃, the structure is kept compact and smooth, and the film has better high-temperature oxidation resistance and heat resistance.
Example 4
In the embodiment, the total number of layers for preparing the intermediate layer and the diffusion barrier layer is 2, the modulation ratio of the intermediate layer to the diffusion barrier layer is 1:3, the intermediate layer is a Ti layer, the diffusion barrier layer is an alloy film of a NiCrAl layer, and the copper matrix is a T2 copper wire.
The embodiment comprises the following steps:
sequentially ultrasonically cleaning a polished copper matrix in acetone and absolute ethyl alcohol for 10min, then rapidly drying by using a blower, fixing the copper matrix on a sample table of a magnetron sputtering vacuum coating chamber, and etching in a vacuum environment to obtain an etched copper matrix; the etching power is 250W and the etching time is 10min; the etching is performed under vacuum degree of less than 5×10 -3 Pa, and the copper matrix temperature is 200 ℃;
step two, argon is introduced into a vacuum coating chamber, the bias voltage for etching the copper matrix is set to be 150V, pre-sputtering is carried out for 1min, and then 1 cycle of deposition is carried out by adopting 1 Ti target and 2 NiCrAl targets in sequence, so that the copper matrix with the high-temperature-resistant low-diffusion alloy film is obtained; wherein the argon flow is 20sccm, the working air pressure is 2.1Pa, the power of the Ti target is 60W, the time of each sputtering of the Ti target is 30min, the power of the NiCrAl target is 80W, the time of each sputtering is 90min, the sputtering temperature is room temperature, and the rotating speed of the etched copper matrix in the sputtering process is 15r/min.
The nicrall layer prepared in this example was tested to consist of the following atomic percent: ni:45%, cr:30% and Al:25%, the thickness of each intermediate layer is 500nm, the thickness of each diffusion barrier layer is 1500nm, the total thickness of the film is 2.0 mu m, the binding force of the base film is 25N by adopting a scratch method, the interface of the film is complete after 300h heat-resistant treatment at 500 ℃, the structure is kept compact and smooth, and the film has better high-temperature oxidation resistance and heat resistance.
Example 5
In the embodiment, the total number of layers for preparing the intermediate layer and the diffusion barrier layer is 2, the modulation ratio of the intermediate layer to the diffusion barrier layer is 1:3, the intermediate layer is a Ti layer, the diffusion barrier layer is an alloy film of a NiCrAl layer, and the copper matrix is TU1 oxygen-free copper.
The embodiment comprises the following steps:
sequentially ultrasonically cleaning a polished copper matrix in acetone and absolute ethyl alcohol for 10min, then rapidly drying by using a blower, fixing the copper matrix on a sample table of a magnetron sputtering vacuum coating chamber, and etching in a vacuum environment to obtain an etched copper matrix; the etching power is 250W and the etching time is 10min; the etching is performed under vacuum degree of less than 5×10 -3 Pa, and the copper matrix temperature is 100 ℃;
step two, argon is introduced into a vacuum coating chamber, the bias voltage for etching the copper matrix is set to be 150V, pre-sputtering is carried out for 1min, and then 1 cycle of deposition is carried out by adopting 1 Ti target and 2 NiCrAl targets in sequence, so that the copper matrix with the high-temperature-resistant low-diffusion alloy film is obtained; wherein the argon flow is 30sccm, the working air pressure is 2.5Pa, the power is 120W, the time of each sputtering of the Ti target is 30min, the power is 180W, the time of each sputtering is 90min, the sputtering temperature is room temperature, and the rotating speed of the etched copper matrix in the sputtering process is 15r/min.
The nicrall layer prepared in this example was tested to consist of the following atomic percent: ni:45%, cr:35% and Al:20%, the thickness of each intermediate layer is 300nm, the thickness of each diffusion barrier layer is 900nm, the total thickness of the film is 1.2 mu m, the binding force of the base film is 20N by adopting a scratch method, the interface of the film is complete after 300h heat-resistant treatment at 500 ℃, the structure is kept compact and smooth, and the film has better high-temperature oxidation resistance and heat resistance.
Example 6
In the embodiment, the total number of layers for preparing the intermediate layer and the diffusion barrier layer is 2, the modulation ratio of the intermediate layer to the diffusion barrier layer is 1:3, the intermediate layer is a Cr layer, the diffusion barrier layer is an alloy film of a NiCrAl layer, and the copper matrix is TP1 deoxidized copper.
The embodiment comprises the following steps:
sequentially ultrasonically cleaning a polished copper matrix in acetone and absolute ethyl alcohol for 10min, then rapidly drying by using a blower, fixing the copper matrix on a sample table of a magnetron sputtering vacuum coating chamber, and etching in a vacuum environment to obtain an etched copper matrix; the etching power is 250W and the etching time is 10min; the etching is performed under vacuum degree of less than 5×10 -3 Pa, and the copper matrix temperature is 200 ℃;
step two, argon is introduced into a vacuum coating chamber, bias voltage for etching a copper matrix is set to be 150V, pre-sputtering is carried out for 1min, and then 1 Cr target, a NiCr target and a NiAl target are adopted to deposit for 1 period in sequence, so that the copper matrix with the high-temperature-resistant low-diffusion alloy film is obtained; wherein the argon flow is 20sccm, the working air pressure is 2.1Pa, the power of the Cr target is 120W, the time of each sputtering of the Cr target is 30min, the power of the NiCr target and the NiAl target is 180W, the time of each sputtering is 90min, the sputtering temperature is room temperature, and the rotating speed of the etched copper matrix in the sputtering process is 15r/min.
The nicrall layer prepared in this example was tested to consist of the following atomic percent: ni:55%, cr:25% and Al:20%, the thickness of each intermediate layer is 500nm, the thickness of each diffusion barrier layer is 1000nm, the total thickness of the film is 1.5 mu m, the binding force of the base film is 25N by adopting a scratch method, the interface of the film is complete after 300h heat-resistant treatment at 500 ℃, the structure is kept compact and smooth, and the film has better high-temperature oxidation resistance and heat resistance.
Example 7
This embodiment differs from embodiment 6 in that: a NiAl target and a CrAl target are used as alloy targets.
Example 8
The total number of layers of the intermediate layer and the diffusion barrier layer prepared by adopting arc ion plating is 10, the modulation ratio of the intermediate layer to the diffusion barrier layer is 1:1, the intermediate layer is a Ni layer, the diffusion barrier layer is an alloy film of a NiCrAl layer, and the copper matrix is H96 brass.
Example 9
The total number of layers of the intermediate layer and the diffusion barrier layer prepared by flame spraying is 14, the modulation ratio of the intermediate layer to the diffusion barrier layer is 1:2, the intermediate layer is an Al layer, the diffusion barrier layer is an alloy film of a NiCrAl layer, and the copper matrix is HNi-5 nickel brass.
Example 10
The total number of layers of the intermediate layer and the diffusion barrier layer prepared by adopting plasma spraying is 4, the modulation ratio of the intermediate layer to the diffusion barrier layer is 1:5, the intermediate layer is a Zr layer, the diffusion barrier layer is an alloy film of a NiCrAl layer, and the copper matrix is H70 brass.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (9)
1. The high-temperature-resistant low-diffusion alloy film for the copper matrix is characterized by comprising an intermediate layer and a diffusion barrier layer which are alternately arranged on the copper matrix, wherein the total number of layers of the intermediate layer and the diffusion barrier layer is 2-48, the modulation ratio of the intermediate layer to the diffusion barrier layer is 1:1-5, the intermediate layer is a Ti layer, and the diffusion barrier layer is a NiCrAl layer; the NiCrAl layer consists of the following components in atomic percent: 45-55% of Ni, 25-35% of Cr and 20-30% of Al.
2. The high temperature resistant low diffusion alloy film for copper substrate according to claim 1, wherein the thickness of each of the intermediate layer and the diffusion barrier layer is 20nm to 1000nm, and the total thickness of the film is 1.0 μm to 3.0 μm.
3. A high temperature resistant low diffusion alloy film for copper substrates according to any one of claims 1 or 2, wherein the film is prepared by arc ion plating, flame spraying or plasma spraying.
4. A method for producing the high temperature resistant low diffusion alloy film for copper substrate according to any one of claims 1 or 2, characterized by comprising the steps of:
etching the copper matrix in a vacuum environment to obtain an etched copper matrix; the etching power is 150-250W, and the etching time is 5-10 min;
alternately sputtering the surface of the etched copper matrix obtained in the first step by using a metal target and an alloy target to prepare an intermediate layer and a diffusion barrier layer, so as to obtain a copper matrix with a high-temperature-resistant low-diffusion alloy film; the metal target is a Ti target; the alloy target is a NiCrAl target, and the alloy target can be more than two of a NiCr target, a NiAl target and a CrAl target.
5. The method of claim 4, wherein the etching in step one is performed at a vacuum level of less than 3X 10 - 3 Pa, and the temperature of the copper matrix is 20-250 ℃.
6. The method of claim 4, wherein the sputtering in the second step is magnetron sputtering, the metal target is a direct current power supply, the power is 60-120 w, the alloy target is a radio frequency power supply, the power is 80-180 w, the direct current bias voltage on the copper substrate is 0-150 v, and the sputtering is performed under the conditions that the air pressure is 1.5-2.5 pa, and the argon flow is 10-30 sccm.
7. The method of claim 4, wherein in step one the copper substrate is copper or a copper alloy.
8. The method according to claim 4, wherein the total time of sputtering the metal target in the second step is 2 min-30 min, and the total time of sputtering the alloy target is 2 min-90 min.
9. The method according to claim 4, wherein the alternate sputtering is performed 1 time to obtain a single-layer high-temperature-resistant low-diffusion alloy film on the copper substrate, and the alternate sputtering is performed 2 to 24 times to obtain a multi-layer high-temperature-resistant low-diffusion alloy film on the copper substrate.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008078667A1 (en) * | 2006-12-22 | 2008-07-03 | Toshio Narita | Alloy coating film, method for production of alloy coating film, and heat-resistant metal member |
| CN109136844A (en) * | 2018-10-12 | 2019-01-04 | 佛山科学技术学院 | A kind of rose gold plate and its preparation process |
| GB201903373D0 (en) * | 2019-03-12 | 2019-04-24 | Rolls Royce Plc | Method of forming a diffusion bonded joint |
| CN110690186A (en) * | 2019-10-11 | 2020-01-14 | 陕西科技大学 | Micro-through-hole Cu-based CVD diamond heat-sink sheet and preparation method thereof |
| CN111020573A (en) * | 2019-12-05 | 2020-04-17 | 沈阳工业大学 | Heat-conducting anti-corrosion composite film layer based on copper surface and preparation method |
| CN112376098A (en) * | 2020-10-26 | 2021-02-19 | 江苏源泉智能装备科技有限公司 | Method for electroplating molybdenum-copper alloy surface |
| CN113699485A (en) * | 2021-08-26 | 2021-11-26 | 沈阳理工大学 | High-entropy oxide diffusion barrier film and preparation process and application thereof |
| CN114086122A (en) * | 2021-11-26 | 2022-02-25 | 江苏科技大学 | Ceramic-based gradient plating layer based on high film-substrate binding force on copper substrate and preparation method thereof |
| CN114231914A (en) * | 2021-11-17 | 2022-03-25 | 中国科学院金属研究所 | Low-interdiffusion and high-temperature-oxidation-resistant coating for copper conductor and preparation method thereof |
| WO2022062102A1 (en) * | 2020-09-23 | 2022-03-31 | 广东省科学院新材料研究所 | Diffusion-resistant high-entropy alloy coating material, heat resistant coating material, preparation method therefor, and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005023122A1 (en) * | 2005-05-19 | 2006-11-23 | Infineon Technologies Ag | Integrated circuit arrangement with layer stack and method |
| WO2008100281A2 (en) * | 2006-07-24 | 2008-08-21 | American Superconductor Corporation | High temperature superconductors having planar magnetic flux pinning centers and methods for making the same |
| US7893006B2 (en) * | 2007-03-23 | 2011-02-22 | American Superconductor Corporation | Systems and methods for solution-based deposition of metallic cap layers for high temperature superconductor wires |
| US9279187B2 (en) * | 2009-11-11 | 2016-03-08 | Southwest Research Institute | Method for applying a diffusion barrier interlayer for high temperature components |
| US8790791B2 (en) * | 2010-04-15 | 2014-07-29 | Southwest Research Institute | Oxidation resistant nanocrystalline MCrAl(Y) coatings and methods of forming such coatings |
-
2022
- 2022-10-28 CN CN202211334090.9A patent/CN115449769B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008078667A1 (en) * | 2006-12-22 | 2008-07-03 | Toshio Narita | Alloy coating film, method for production of alloy coating film, and heat-resistant metal member |
| CN109136844A (en) * | 2018-10-12 | 2019-01-04 | 佛山科学技术学院 | A kind of rose gold plate and its preparation process |
| GB201903373D0 (en) * | 2019-03-12 | 2019-04-24 | Rolls Royce Plc | Method of forming a diffusion bonded joint |
| CN110690186A (en) * | 2019-10-11 | 2020-01-14 | 陕西科技大学 | Micro-through-hole Cu-based CVD diamond heat-sink sheet and preparation method thereof |
| CN111020573A (en) * | 2019-12-05 | 2020-04-17 | 沈阳工业大学 | Heat-conducting anti-corrosion composite film layer based on copper surface and preparation method |
| WO2022062102A1 (en) * | 2020-09-23 | 2022-03-31 | 广东省科学院新材料研究所 | Diffusion-resistant high-entropy alloy coating material, heat resistant coating material, preparation method therefor, and application thereof |
| CN112376098A (en) * | 2020-10-26 | 2021-02-19 | 江苏源泉智能装备科技有限公司 | Method for electroplating molybdenum-copper alloy surface |
| CN113699485A (en) * | 2021-08-26 | 2021-11-26 | 沈阳理工大学 | High-entropy oxide diffusion barrier film and preparation process and application thereof |
| CN114231914A (en) * | 2021-11-17 | 2022-03-25 | 中国科学院金属研究所 | Low-interdiffusion and high-temperature-oxidation-resistant coating for copper conductor and preparation method thereof |
| CN114086122A (en) * | 2021-11-26 | 2022-02-25 | 江苏科技大学 | Ceramic-based gradient plating layer based on high film-substrate binding force on copper substrate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 耐高温抗氧化的优质喷涂材料镍铬铝复合粉;刘维祥;有色金属(冶炼部分)(第02期);全文 * |
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