CN110872692A - Molybdenum-silver laminated composite material, and preparation method and application thereof - Google Patents
Molybdenum-silver laminated composite material, and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- FSVVWABMXMMPEE-UHFFFAOYSA-N molybdenum silver Chemical compound [Mo][Ag][Mo] FSVVWABMXMMPEE-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 145
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 142
- 239000011733 molybdenum Substances 0.000 claims abstract description 142
- 229910052751 metal Inorganic materials 0.000 claims abstract description 137
- 239000002184 metal Substances 0.000 claims abstract description 129
- 229910052709 silver Inorganic materials 0.000 claims abstract description 116
- 239000004332 silver Substances 0.000 claims abstract description 113
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 108
- 238000000151 deposition Methods 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 69
- 239000000758 substrate Substances 0.000 claims abstract description 62
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 51
- 230000008569 process Effects 0.000 claims abstract description 36
- 239000013077 target material Substances 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 27
- 238000000137 annealing Methods 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 78
- 239000011651 chromium Substances 0.000 claims description 76
- 239000011888 foil Substances 0.000 claims description 50
- 230000008021 deposition Effects 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 43
- 229910052759 nickel Inorganic materials 0.000 claims description 30
- 229910052804 chromium Inorganic materials 0.000 claims description 26
- 238000011282 treatment Methods 0.000 claims description 25
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 20
- 238000009792 diffusion process Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 15
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- 239000011261 inert gas Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 abstract description 184
- 239000011229 interlayer Substances 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 28
- 238000009713 electroplating Methods 0.000 description 19
- 238000010998 test method Methods 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 238000001771 vacuum deposition Methods 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
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- 230000000694 effects Effects 0.000 description 9
- 238000007747 plating Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011156 metal matrix composite Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
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- 238000002513 implantation Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000010849 ion bombardment Methods 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
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- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
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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
- C23C14/06—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
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/34—Sputtering
- C23C14/3435—Applying energy to the substrate during sputtering
- C23C14/345—Applying energy to the substrate during sputtering using substrate bias
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
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Abstract
The invention discloses a molybdenum-silver laminated composite material, a preparation method and application thereof. The preparation method comprises the following steps: at least placing a molybdenum substrate and a metal target material with good solid solubility with molybdenum in a vacuum environment, and depositing a metal intermediate layer on the surface of the molybdenum substrate by a direct-current magnetron sputtering method; placing at least a molybdenum substrate and a metal silver target material, the surfaces of which are provided with metal intermediate layers, into a vacuum environment, and depositing and forming a silver layer on the surfaces of the metal intermediate layers by a direct-current magnetron sputtering method; and annealing the obtained molybdenum substrate-metal intermediate layer-silver layer composite structure, so that the metal elements forming the metal intermediate layer are continuously diffused into the molybdenum substrate and the silver layer. The method can successfully prepare the silver/metal interlayer/molybdenum laminated composite material, is environment-friendly, has high process stability, and can be produced in a large scale; and the obtained molybdenum silver laminar composite material has high density, excellent bonding strength, excellent oxidation corrosion resistance and thermal fatigue resistance.
Description
Technical Field
The invention relates to a preparation method of a molybdenum-silver laminated composite material, in particular to a silver film/metal intermediate layer/molybdenum composite material and a preparation method and application thereof, belonging to the technical field of composite materials.
Background
The atomic oxygen resistance and the thermal fatigue resistance of the interconnected sheet material of the space solar cell array directly influence the high reliability, long service life and safe operation of the solar cell array of the low-orbit spacecraft. Molybdenum is a natural choice for thermal shock and thermal fatigue resistance due to its excellent electrical conductivity, excellent heat resistance, high temperature mechanical properties, low coefficient of thermal expansion and high coefficient of thermal conductivity. In addition, the reaction rate of molybdenum with atomic oxygen is almost zero, i.e., molybdenum is not affected by atomic oxygen corrosion. Because of these characteristics, molybdenum is well suited as an aerospace vehicle solar cell array interconnect material. However, the melting point of pure molybdenum can reach 2620 ℃, and the solar cell electrode is made of pure silver or silver gold-plating material, and the melting point is only about 1000 ℃. Because the melting points are not matched, the two materials cannot form effective welding, and therefore molybdenum/silver composite materials are prepared by laminating molybdenum and silver to reduce the surface melting point of metal molybdenum so as to realize melt-resistant welding with the silver. The molybdenum/silver composite material has excellent conductivity, weldability, atomic oxygen resistance and thermal fatigue resistance, and is the latest generation of interconnection sheet material for the solar cell array of the foreign low-orbit spacecraft.
However, the molybdenum and the silver belong to systems without mutual solid solution, so that an alloy substance is difficult to form, and the Mo/Ag layered metal matrix composite material is difficult to prepare. At present, Mo/Ag laminated metal matrix composite materials are prepared at home and abroad mainly by an electroplating method, and a silver layer directly deposited by an electroplating process is generally insufficient in binding force and poor in quality. Currently, the industry generally adopts a pre-plating or impact plating method to solve the problem of difficult molybdenum electroplating, i.e., a very thin metal layer (such as chromium, nickel, gold, rhodium, platinum, etc.) capable of forming an alloy with molybdenum is electroplated on the surface of molybdenum, and then silver electroplating is performed after high-temperature heat treatment. For example, CN103681952A discloses a process for preparing a molybdenum/platinum/silver layered metal matrix composite for a space vehicle, in which a platinum intermediate layer and a silver layer are sequentially electroplated on the surface of a molybdenum foil, and a molybdenum/platinum/silver layered metal matrix composite is prepared after two high-temperature heat treatments, so as to obtain a welding strength of 324 gf. Patent CN103668368A discloses a preparation process of molybdenum/palladium/silver layered metal matrix composite, which uses palladium as a connecting layer between molybdenum foil and silver, and prepares the molybdenum/palladium/silver layered composite through electroplating and multiple annealing processes, wherein the welding strength reaches 416 gf. However, the electroplating process needs a plurality of high-temperature heat treatment processes, is very complicated and has insufficient strength. Moreover, the electroplated silver layer has defects of the electroplated silver layer, the electroplated coating is generally in a columnar crystal structure and has poor compactness, vacancies and defects exist in the electroplated coating, and atomic oxygen can enter the electroplated coating through the defects of the plated material to corrode the electroplated coating in a low-earth orbit environment, so that the slow atomic oxygen corrosion for a long time can still seriously damage the performance of the interconnection piece. In addition, waste water, waste gas and waste residue produced in the electroplating process can cause damage to the natural environment and human health, and simultaneously, the pollution treatment cost of enterprises is increased.
Disclosure of Invention
The invention mainly aims to provide a molybdenum-silver laminated composite material and a preparation method thereof, thereby overcoming the defects in the prior art.
The invention also aims to provide application of the molybdenum-silver laminated composite material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides a preparation method of a molybdenum-silver laminated composite material, which comprises the following steps:
at least placing a molybdenum substrate and a metal target material with good solid solubility with molybdenum in a vacuum environment, and depositing a metal intermediate layer on the surface of the molybdenum substrate by a direct-current magnetron sputtering method;
placing at least a molybdenum substrate and a metal silver target material, the surfaces of which are provided with metal intermediate layers, into a vacuum environment, and depositing and forming a silver layer on the surfaces of the metal intermediate layers by a direct-current magnetron sputtering method; and
and annealing the obtained molybdenum substrate-metal intermediate layer-silver layer composite structure, so that the metal elements forming the metal intermediate layer are continuously diffused into the molybdenum substrate and the silver layer.
In some embodiments, the preparation method specifically comprises: placing the pretreated molybdenum substrate in a vacuum cavity, taking metal with good solid solubility with molybdenum as a target material, taking protective gas as working gas, and pre-vacuumizing to 5 multiplied by 10-3And (3) treating the molybdenum substrate for 20-30 min by using plasma under Pa, then starting a pulse direct-current power supply, and depositing at least on the surface of the molybdenum substrate by using a direct-current magnetron sputtering method to form a metal intermediate layer.
In some embodiments, the preparation method specifically comprises: and after the deposition of the metal intermediate layer is finished, starting a metal silver target pulse direct current power supply by taking metal silver as a target and protective gas as working gas, and depositing at least on the surface of the metal intermediate layer by a direct current magnetron sputtering method to form a flat and compact silver layer.
The embodiment of the invention also provides the molybdenum-silver laminated composite material prepared by the method, which comprises a molybdenum layer, a silver layer and a metal intermediate layer, wherein the metal intermediate layer is made of metal with good solid solubility with molybdenum, and the metal with good solid solubility with molybdenum continuously diffuses into the molybdenum layer and the silver layer at least from the bonding interface of the molybdenum layer and the silver layer.
The embodiment of the invention also provides application of the molybdenum-silver laminated composite material in preparation of a solar cell array interconnection sheet material of a spacecraft.
The embodiment of the invention also provides a spacecraft solar cell array interconnection sheet material which comprises the molybdenum-silver laminated composite material.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the preparation method of the molybdenum-silver laminated composite material, the intermediate layer is made of metal elements such as chromium and nickel which have good solid solubility with molybdenum and silver and are low in price, so that the intermediate layer can form firm diffusion interfaces with the molybdenum and the silver respectively, the molybdenum and the silver which are not dissolved in solid solution originally form strong bonding through the connection of the intermediate layer, meanwhile, the intermediate layer can relieve the difference of thermal expansion coefficients between the molybdenum and the silver, the stress at the interface is relaxed, and the bonding force between the molybdenum and the silver is greatly enhanced;
2) the preparation method of the molybdenum-silver laminated composite material provided by the invention adopts a magnetron sputtering technology, and the metal intermediate layer and the silver layer are sequentially deposited on the surface of molybdenum to successfully prepare the silver/metal intermediate layer/molybdenum laminated composite material;
3) the traditional electroplating process can bring the problem of environmental pollution of toxic substances such as strong acid, strong base, cyanide and the like in the process of plating a metal intermediate layer and a silver layer, and magnetron sputtering belongs to a green environment-friendly coating technology, the coating process is in a vacuum state, no chemical change is generated with water or hydrogen to generate harmful chemical substances, the whole process completely meets the environmental protection specification and requirements, no pollution control cost is generated, and good economic benefit and social benefit are achieved;
4) the molybdenum silver laminar composite material provided by the invention has the advantages of high density, excellent bonding strength, excellent oxidation corrosion resistance and thermal fatigue resistance.
Drawings
FIG. 1 is a sectional SEM structural diagram of a Mo/Cr/Ag layered composite material prepared in example 1 of the invention.
FIG. 2 is a depth-wise distribution spectrum of Mo/Cr/Ag layered composite material prepared in example 1 of the present invention.
FIG. 3 is a tensile test graph of the interfacial bonding strength of the Mo/Cr/Ag layered composite material prepared in example 1 of the present invention.
FIG. 4 is a cross-sectional view of a Mo/Ag composite material prepared by electroplating in comparative example 1 of the invention.
FIG. 5 is a tensile test graph of interfacial bonding strength of a Mo/Ag composite material prepared by electroplating in comparative example 1 of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to propose the technical solution of the present invention, and further explain the technical solution, the implementation process and the principle thereof, etc.
The magnetron sputtering technology is used as a green coating process, has the advantages of high deposition efficiency, high film layer density, strong binding force of a coating and a matrix, no pollution, high production efficiency, mass production and the like, and is widely applied to the fields of aerospace, electronics, materials and the like. Based on the above, on the basis of ensuring good conductivity and atomic oxygen resistance of the interconnector material, the invention uses the metal elements such as chromium, nickel and the like which have good solid solubility with molybdenum and silver and low price as the intermediate layer, and adopts the magnetron sputtering technology to replace the traditional electroplating technology to prepare the molybdenum/chromium (nickel)/silver laminated composite material, so that the molybdenum/chromium (nickel)/silver laminated composite material has excellent compactness and bonding force.
In summary, the technical scheme of the application is mainly as follows: firstly, a magnetron sputtering technology is adopted, a metal intermediate layer (such as chromium, nickel and the like) with good solid solubility with molybdenum and silver is deposited on the surface of molybdenum, then a smooth and compact silver layer is deposited on the surface of the metal intermediate layer by utilizing the magnetron sputtering technology, and finally, the mutual diffusion of atoms at two interfaces of the molybdenum/metal intermediate layer and the metal intermediate layer/silver is promoted through annealing treatment, so that good metallurgical bonding is formed.
As one aspect of the technical solution of the present invention, a method for preparing a mo-ag layered composite material (also referred to as ag/metal interlayer/mo layered composite material) includes:
at least placing a molybdenum substrate and a metal target material with good solid solubility with molybdenum in a vacuum environment, and depositing a metal intermediate layer on the surface of the molybdenum substrate by a direct-current magnetron sputtering method;
placing at least a molybdenum substrate and a metal silver target material, the surfaces of which are provided with metal intermediate layers, into a vacuum environment, and depositing and forming a silver layer on the surfaces of the metal intermediate layers by a direct-current magnetron sputtering method; and
and annealing the obtained molybdenum substrate-metal intermediate layer-silver layer composite structure, so that the metal elements forming the metal intermediate layer are continuously diffused into the molybdenum substrate and the silver layer.
In some embodiments, the preparation method specifically comprises: placing the pretreated molybdenum substrate in a vacuum cavity, taking metal with good solid solubility with molybdenum as a target material, taking protective gas as working gas, and pre-vacuumizing to 5 multiplied by 10-3And (3) treating the molybdenum substrate for 20-30 min by using plasma under Pa, then starting a pulse direct-current power supply, and depositing at least on the surface of the molybdenum substrate by using a direct-current magnetron sputtering method to form a metal intermediate layer.
Further, when the metal intermediate layer is deposited, the process conditions adopted by the direct current magnetron sputtering method comprise: before depositing the metal intermediate layer, the chamber is vacuumized to be lower than 5 multiplied by 10-3Pa, the working gas pressure is kept at 0.1-1.0 Pa, the power of the metal target material which has good solid solubility with molybdenum is 500-1000W, and the negative bias of the substrate is-70-100V.
Further, the deposition time of the metal intermediate layer is 10-30 min.
Further, the metal having good solid solubility with molybdenum includes, but is not limited to, chromium, nickel, and the like. According to the invention, metal elements with good solid solubility with molybdenum and silver are selected as the intermediate layer, so that the intermediate layer and the molybdenum and the silver form firm diffusion interfaces, and the molybdenum and the silver which are not dissolved in solid solution originally form strong combination through the connection of the intermediate layer. Meanwhile, the intermediate layer can relieve the difference of the thermal expansion coefficients of molybdenum and silver, and relax the stress at the interface, so that the bonding force between the molybdenum and the silver is greatly enhanced.
In the process of depositing the metal intermediate layer (chromium, nickel and the like) by adopting a magnetron sputtering deposition technology, a chromium or nickel ion beam bombards the surface of the Mo layer with high kinetic energy under the action of an accelerating electric field to generate a shallow implantation effect, the shallow implantation effect enables the surface of the Mo layer to generate lattice distortion and damage and promotes the chromium or nickel ions implanted into the surface to diffuse to the subsurface layer of the Mo layer, and a near-surface alloy layer is formed on the surface of the Mo layer, so that the interface bonding force of chromium/molybdenum or nickel/molybdenum can be obviously improved. In the process of further depositing the silver layer by magnetron sputtering, high-energy Ag ions can also generate a shallow injection effect on the surface of the chromium or nickel intermediate layer, so that the interface bonding force of silver/chromium or silver/nickel is improved.
Furthermore, the metal intermediate layer is not suitable to be too thick, the thickness is 200-600 nm, otherwise, the interface is easy to embrittle, and the interface bonding force between the molybdenum substrate and the silver layer is reduced.
Furthermore, the number n of the metal targets with good solid solubility with molybdenum is not limited, preferably, the number n of the metal targets is more than or equal to 2 and less than or equal to 4, and the metal targets are preferably symmetrically distributed by taking the substrate as the center.
Preferably, the purity of the metal target material with good solid solubility with molybdenum is more than 99.9%.
Preferably, the protective gas comprises an inert gas, such as argon, and the purity is selected to be above 99.9%.
In some embodiments, the preparation method specifically comprises: and after the deposition of the metal intermediate layer is finished, starting a metal silver target pulse direct current power supply by taking metal silver as a target and protective gas as working gas, and depositing at least on the surface of the metal intermediate layer by a direct current magnetron sputtering method to form a flat and compact silver layer.
Further, the thickness of the silver layer is 3-5 μm.
Further, when depositing the silver layer, the process conditions adopted by the direct current magnetron sputtering method include: evacuating the chamber to below 5 × 10 before depositing Ag film-3Pa, the working gas pressure is kept at 0.1-1.0 Pa, the power of the metal silver target material is 500-1000W, and the negative bias of the substrate is-70-100V.
In the process of depositing the metal intermediate layer and the silver film by magnetron sputtering, the negative bias is applied to the substrate, so that deposited ions can obtain high kinetic energy to generate a bombardment effect on the surface of the film. The high-energy ions have stronger atom migration capability after reaching the surface of the film, can avoid generating a loose columnar crystal structure and generate a uniform, compact and pore-free granular crystal structure, thereby blocking a channel for the atomic oxygen to corrode the film and improving the atomic oxygen corrosion resistance of the Ag film.
Further, the deposition time of the silver layer is 3-5 hours.
Furthermore, the number m of the metallic silver targets is not limited, preferably, the number m of the metallic silver targets is more than or equal to 2 and less than or equal to 4, and the metallic silver targets are preferably symmetrically distributed by taking the substrate as the center.
Preferably, the metallic silver target has a purity of 99.9% or more.
Preferably, the protective gas comprises an inert gas, such as argon, and the purity is selected to be above 99.9%.
Further, the preparation method further comprises the following steps: and after the deposition of the silver layer is finished, cooling to room temperature in a vacuum environment, then exhausting gas, opening a cavity and discharging to obtain the molybdenum substrate-metal interlayer-silver layer composite structure (also called Mo/metal interlayer/Ag layered composite material).
In the process of depositing the metal intermediate layer (chromium, nickel and the like) and silver by adopting a magnetron sputtering deposition technology, the temperature of the Mo foil can be increased by utilizing the bombardment effect of high-energy Ag ions on the surface of the Mo foil, the higher substrate temperature is favorable for mutual diffusion of atoms at the interface of the film layer and the substrate, and the bonding force between the film layer and the substrate is further enhanced; meanwhile, the higher substrate temperature can also improve the horizontal migration capability of the silver atoms on the surface of the film layer, thereby improving the density of the film layer.
The process adopts the magnetron sputtering intermediate layer on the surface of the molybdenum foil and the magnetron sputtering silver layer on the surface of the intermediate layer, the whole process belongs to a dry process, the preparation of the intermediate layer and the preparation of the silver layer can be completed in sequence in the same equipment, and the process is simple; and the magnetron sputtering technology is a green environment-friendly technology and does not relate to the problem of environmental protection.
In some embodiments, the preparation method specifically comprises: and annealing the obtained molybdenum substrate-metal interlayer-silver layer composite structure in a protective atmosphere under the pressure of 101.3 kPa. In the annealing treatment process, the high temperature can improve the atom activity, promote the mutual diffusion of atoms at the interface of the molybdenum/metal intermediate layer and the metal intermediate layer/silver, realize the alloying at the interface and further improve the interface bonding strength of the Mo and the Ag.
Further, the temperature of the annealing treatment is 700-900 ℃, and the time is 2-5 hours.
In some embodiments, the method of making further comprises: the surface of the molybdenum substrate is pretreated, and then the metal intermediate layer is formed on the surface of the molybdenum substrate in a deposition mode.
Further, the pre-processing comprises: and sequentially carrying out degreasing, cleaning, etching, ultrasonic cleaning and drying treatment on the surface of the molybdenum substrate. The acid liquor etching in the pretreatment process of the molybdenum substrate can improve the roughness of the surface of the molybdenum substrate, increase the actual contact area of the molybdenum substrate and a silver layer and improve the film-substrate binding force.
Preferably, the molybdenum substrate includes a molybdenum foil, but is not limited thereto.
Preferably, the thickness of the molybdenum foil is 10-30 μm.
In some more specific embodiments, the preparation process of the molybdenum-silver laminated composite material includes pretreatment of a molybdenum foil, magnetron sputtering deposition of a metal intermediate layer (chromium, nickel, etc.), magnetron sputtering deposition of an Ag film, and annealing treatment under protection of an inert atmosphere, which includes the following steps:
In order to ensure the bonding strength between the silver film and the molybdenum foil, the molybdenum foil needs to be subjected to surface treatment before the test, and the process flow is as follows: degreasing → cleaning → etching → ultrasonic cleaning → drying. The specific process comprises the steps of soaking a molybdenum foil with the purity of 99.5% and the thickness of 10-30 microns in oil removing liquid, taking out the molybdenum foil, soaking and washing the molybdenum foil with deionized water, then placing the molybdenum foil into etching liquid for etching, ultrasonically cleaning the molybdenum foil with deionized water after etching, and finally drying the molybdenum foil with nitrogen.
Placing the Mo foil pretreated in the step 1 in a vacuum coating cavity, pre-vacuumizing to 5 x 10 by taking chromium, nickel or other metal elements with high solid solubility with molybdenum with the purity of 99.99 percent as a target material and high-purity Ar as a working gas-3Pa or less, etcAnd after the plasma treatment is carried out for 20-30 minutes, starting a pulse direct current power supply, and carrying out metal intermediate layer deposition on the surface of the Mo foil.
And after the deposition of the metal intermediate layer is finished, continuing to perform the next step of magnetron sputtering the silver film without leaving the vacuum chamber.
And (3) starting an Ag target pulse direct current power supply by taking metal Ag with the purity of 99.99% as a target material and high-purity Ar as working gas, and continuing magnetron sputtering on the surface of the metal intermediate layer deposited in the step (2) to deposit an Ag film.
And after the deposition of the Ag film is finished, cooling to room temperature in a vacuum environment, then exhausting gas, opening the cavity and discharging to obtain the Mo/metal interlayer/Ag laminated composite material.
Step 4 annealing treatment
And (3) placing the Mo/metal interlayer/Ag layered composite material treated in the step (3) in a high-temperature tube furnace, annealing in an argon atmosphere with the purity of 99.999% and the pressure of one standard atmosphere, and obtaining the Mo/Ag layered composite material after annealing treatment.
The traditional electroplating process can bring the problem of environmental pollution of toxic substances such as strong acid, strong base, cyanide and the like in the process of plating a metal intermediate layer and a silver layer, and magnetron sputtering belongs to a green environment-friendly coating technology, the coating process is in a vacuum state, no chemical change is generated with water or hydrogen to generate harmful chemical substances, the whole process completely meets the environmental protection specification and requirements, no pollution control cost is generated, and good economic benefit and social benefit are achieved; compared with the prior electroplating and multi-channel high-temperature heat treatment process, the process disclosed by the invention can ensure the excellent bonding strength between molybdenum and silver by only one-step heat treatment, simplifies the process links and improves the production efficiency.
In conclusion, the preparation method of the molybdenum-silver laminated composite material provided by the invention is environment-friendly, has high process stability, can realize large-scale production, and solves the problems of incompact plating layer, poor interface combination, environment-friendliness and the like of the existing molybdenum foil surface silver electroplating process.
As another aspect of the technical solution of the present invention, the molybdenum-silver layered composite material prepared by the method comprises a molybdenum layer, a silver layer, and a metal intermediate layer, wherein the material of the metal intermediate layer comprises a metal having good solid solubility with molybdenum, and the metal having good solid solubility with molybdenum continuously diffuses into the molybdenum layer and the silver layer at least from the bonding interface between the molybdenum layer and the silver layer.
Furthermore, the thickness of the diffusion layer diffused into the molybdenum layer and the silver layer is 0.8-1.6 mu m.
Further, the metal having good solid solubility with molybdenum includes, but is not limited to, chromium, nickel, and the like.
Further, the thickness of the metal intermediate layer is 200-600 nm.
The molybdenum-silver laminar composite material provided by the invention has high density, excellent bonding strength (more than 35MPa), and excellent oxidation corrosion resistance (the cumulative flux of atomic oxygen irradiation is 2.5 multiplied by 10)21Per cm2Mass loss is not more than 0.0002g) and thermal fatigue resistance (-100 to +100 ℃ high and low temperature alternating cycle times > 100).
The invention adopts the magnetron sputtering technology, and can obtain a high-density film layer due to the special high-energy ion bombardment effect. The high density can reduce the defects of cracks, pores and the like in the film layer, block the channel of the atomic oxygen eroded to the inside of the film layer and improve the atomic oxygen resistance of the film layer. In addition, the shallow implantation effect and the temperature rise effect brought by the high-energy ion bombardment in the magnetron sputtering process can further promote the atom diffusion at the interface of the film layer and the substrate, and improve the bonding strength of the film and the substrate. The film-substrate bonding strength of the finally obtained silver film/metal intermediate layer/molybdenum composite material is more than 3 times of that of the electroplating process.
As another aspect of the technical scheme of the invention, the invention relates to an application of the molybdenum-silver laminated composite material in preparation of a solar cell array interconnection sheet material of a spacecraft.
Correspondingly, the invention also provides a spacecraft solar cell array interconnection sheet material which comprises the molybdenum-silver laminated composite material.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.
Example 1
(1) Mo foil pretreatment
Polishing molybdenum foil with size of 50mm × 50mm × 0.02mm with sand paper, and soaking in degreasing solution (NaOH: Na)2CO3：Na2SiO3Mixed solution of 3:2: 1) was subjected to degreasing treatment. After degreasing, the surface of the Mo foil is washed by a large amount of deionized water. Then the Mo foil is placed in 10% H2SO4Etching in the solution for 10 minutes, taking out, washing with deionized water, placing in deionized water, ultrasonically cleaning for 20 minutes, taking out, and airing for later use.
(2) Magnetron sputtering deposition of Cr intermediate layer
And (3) placing the Mo foil treated in the step (1) in a vacuum coating cavity. Taking metal Cr with the purity of 99.99 percent as a target material and high-purity Ar as working gas, and pre-vacuumizing to 5 multiplied by 10-3And Pa below, after plasma cleaning treatment for 30 minutes, starting a Cr target pulse direct-current power supply, and depositing a Cr intermediate layer on the surface of the Mo foil. The sputtering power of the Cr target was 800W, the bias voltage was-70V, the working gas pressure was 0.1Pa, and the deposition time was 20min, and a Cr layer (hereinafter referred to as Mo/Cr composite material) was deposited on the surface of the Mo foil.
(3) Magnetron sputtering deposition of Ag films
And (3) placing the Mo/Cr composite material treated in the step (2) in a vacuum coating cavity. Using metal Ag with purity of 99.99% as target material, using high-purity Ar as working gas, pre-vacuumizing to 5X 10-3And (4) below Pa, after plasma cleaning treatment for 30 minutes, starting a pulse direct-current power supply, and depositing an Ag film on the surface of the Cr layer. The sputtering power of the Ag target is 800W, the bias voltage is-70V, the working pressure is 0.1Pa, and the deposition time is 5 hours. After deposition is finished, cooling to room temperature in a vacuum environment, then exhausting gas, opening a cavity and discharging.
(4) Annealing treatment
And (4) placing the composite material treated in the step (3) in a high-temperature tube furnace, and annealing in an argon atmosphere with the purity of 99.999 percent, wherein the pressure is one standard atmosphere. The temperature is raised from room temperature to 700 ℃ at the temperature raising rate of 5 ℃/min, and the temperature is kept for 5 hours. Cooling to room temperature along with the furnace to obtain the Mo/Cr/Ag layered composite material.
(5) Cross-section SEM observation of Mo/Cr/Ag layered composite material
A cross-sectional sample of the Mo/Cr/Ag layered composite material is prepared by using a Focused Ion Beam (FIB) technology, and the cross-sectional structure of the sample is observed by using a Scanning Electron Microscope (SEM). As shown in fig. 1, the cross-sectional structure of the sample is divided into three layers, wherein the layer 1 is an Ag film and the film thickness is 5 micrometers; layer 2 is an intermediate layer of Cr, about 0.4 microns thick; layer 3 is a Mo foil. As can be seen from FIG. 1, the interface bonding of Ag/Cr and Cr/Mo is perfect without cracks.
(6) Cross-section element distribution test of Mo/Cr/Ag laminated composite material
And measuring the distribution condition of the Mo/Cr/Ag laminated composite material elements along the depth direction by adopting EDS. As shown in FIG. 2, sufficient elemental diffusion was achieved at the interface of Mo/Cr and Cr/Ag to a thickness of 1.5 microns, indicating that a good metallurgical bond was formed at the interface.
(7) Interface bonding strength test of Mo/Cr/Ag laminated composite material
The interface bonding strength of the Mo/Cr/Ag layered composite material is tested by adopting a stripping test method in the national standard GB/T5270-. Preparing Mo/Cr/Ag laminated composite material into a sample with the diameter of 10mm, and respectively adhering Ag and Mo sides of the sample to two cross sections with FM1000 adhesive
A tensile test sample was prepared from a 5cm long aluminum rod. And (3) carrying out a tensile test on the sample piece by using an INSTRON-5567 universal material testing machine, wherein the tensile test is carried out at room temperature and the tensile speed is 5 mm/min. The tensile strength test curve is shown in FIG. 3, the maximum load is 3372N, and the tensile strength is 43 MPa. The fracture was observed to occur at the interface between the binder and the Ag film, which did not come off the Mo foilThe method shows that metallurgical bonding is realized at the interface of the Ag film and the Mo foil, and the Ag film and the Mo foil have very excellent bonding strength which is 43MPa higher than that of the bonding agent and the silver film.
Example 2
In this embodiment, the substrate is completely the same as the substrate in embodiment 1, and a Cr intermediate layer and an Ag layer are sequentially deposited on the surface of the substrate to prepare the Mo/Cr/Ag layered composite material, wherein the preparation method specifically comprises the following steps:
(1) same as in step (1) in example 1;
(2) magnetron sputtering deposition of Cr intermediate layer
And (3) placing the Mo foil treated in the step (1) in a vacuum coating cavity. Taking metal Cr with the purity of 99.99 percent as a target material and high-purity Ar as working gas, and pre-vacuumizing to 5 multiplied by 10-3And Pa below, after plasma cleaning treatment for 30 minutes, starting a Cr target pulse direct-current power supply, and depositing a Cr intermediate layer on the surface of the Mo foil. The sputtering power of the Cr target was 500W, the bias voltage was-85V, the working gas pressure was 0.5Pa, and the deposition time was 10min, and a Cr layer (hereinafter referred to as Mo/Cr composite material) was deposited on the surface of the Mo foil.
(3) Magnetron sputtering deposition of Ag films
And (3) placing the Mo/Cr composite material treated in the step (2) in a vacuum coating cavity. Using metal Ag with purity of 99.99% as target material, using high-purity Ar as working gas, pre-vacuumizing to 5X 10-3And (4) below Pa, after plasma cleaning treatment for 30 minutes, starting a pulse direct-current power supply, and depositing an Ag film on the surface of the Cr layer. The sputtering power of the Ag target was 500W, the bias voltage was-85V, the working pressure was 0.5Pa, and the deposition time was 4 hours. After deposition is finished, cooling to room temperature in a vacuum environment, then exhausting gas, opening a cavity and discharging.
(4) Annealing treatment
Same as in step (4) in example 1.
(5) Cross-sectional SEM Observation
The test method was the same as that in example 1.
The test results were similar to those in example 1, and showed that the cross-sectional structure of the sample was divided into three layers, layer 1 being an Ag film, the film thickness being about 3 μm; layer 2 is an intermediate layer of Cr, about 0.2 microns thick; layer 3 is a Mo foil. The interface of Ag/Cr and Cr/Mo is well combined without cracks. Moreover, the Ag film has no columnar crystal characteristics and is in a compact granular crystal structure.
(2) Cross-sectional element distribution test
The test method was the same as that in example 1.
The test results are similar to those in example 1 and show that sufficient elemental diffusion is achieved at the interface of Mo/Ni and Ni/Ag, but the diffusion layer thickness is thinner, about 0.8 microns, due to the thinner Cr interlayer.
(3) Interfacial bond strength test
The test method was the same as that in example 1.
The test results were similar to those in example 1, and showed a maximum load of 2766N and a tensile strength of 35.2 MPa.
Example 3
In this embodiment, the substrate is completely the same as the substrate in embodiment 1, and a Cr intermediate layer and an Ag layer are sequentially deposited on the surface of the substrate to prepare the Mo/Cr/Ag layered composite material, wherein the preparation method specifically comprises the following steps:
(1) same as in step (1) in example 1;
(2) magnetron sputtering deposition of Cr intermediate layer
And (3) placing the Mo foil treated in the step (1) in a vacuum coating cavity. Taking metal Cr with the purity of 99.99 percent as a target material and high-purity Ar as working gas, and pre-vacuumizing to 5 multiplied by 10-3And Pa below, after plasma cleaning treatment for 30 minutes, starting a Cr target pulse direct-current power supply, and depositing a Cr intermediate layer on the surface of the Mo foil. The sputtering power of the Cr target was 1000W, the bias was-100V, the working gas pressure was 1.0Pa, and the deposition time was 30min, and a Cr layer (hereinafter referred to as Mo/Cr composite material) was deposited on the surface of the Mo foil.
(3) Magnetron sputtering deposition of Ag films
And (3) placing the Mo/Cr composite material treated in the step (2) in a vacuum coating cavity. Using metal Ag with purity of 99.99% as target material, using high-purity Ar as working gas, pre-vacuumizing to 5X 10-3Pa below, after plasma cleaning for 30min, turning on pulsed DCAnd (4) performing Ag film deposition on the surface of the Cr layer by using a power supply. The sputtering power of the Ag target is 1000W, the bias voltage is-100V, the working pressure is 1.0Pa, and the deposition time is 4 hours. After deposition is finished, cooling to room temperature in a vacuum environment, then exhausting gas, opening a cavity and discharging.
(4) Annealing treatment
And (4) placing the composite material treated in the step (3) in a high-temperature tube furnace, and annealing in an argon atmosphere with the purity of 99.999 percent, wherein the pressure is one standard atmosphere. The temperature is raised from room temperature to 900 ℃ at the temperature raising rate of 5 ℃/min, and the temperature is kept for 2 hours. Cooling to room temperature along with the furnace to obtain the Mo/Cr/Ag layered composite material.
(5) Cross-sectional SEM Observation
The test method was the same as that in example 1.
The test results were similar to those in example 1, and showed that the cross-sectional structure of the sample was divided into three layers, layer 1 being an Ag film, the film thickness being about 5 μm; layer 2 is an intermediate layer of Cr, about 0.6 microns thick; layer 3 is a Mo foil. The interface of Ag/Cr and Cr/Mo is well combined without cracks. Moreover, the Ag film has no columnar crystal characteristics and is in a compact granular crystal structure.
(2) Cross-sectional element distribution test
The test method was the same as that in example 1.
The test results were similar to those in example 1, showing that sufficient elemental diffusion was achieved at the interface of Mo/Ni and Ni/Ag to a diffusion layer thickness of 1.6 microns.
(3) Interfacial bond strength test
The test method was the same as that in example 1.
The test results were similar to those in example 1, showing a maximum load of 3222N and a tensile strength of 41 MPa.
Example 4
In this embodiment, the substrate is completely the same as the substrate in embodiment 1, and a Ni intermediate layer and an Ag layer are sequentially deposited on the surface of the substrate to prepare the Mo/Ni/Ag layered composite material, wherein the preparation method specifically comprises the following steps:
(1) same as in step (1) in example 1;
(2) magnetron sputtering deposition of Ni intermediate layer
And (3) placing the Mo foil treated in the step (1) in a vacuum coating cavity. Using metal Ni with purity of 99.99% as target material, using high-purity Ar as working gas, pre-vacuumizing to 5X 10-3And Pa below, after plasma cleaning treatment for 30 minutes, starting a Ni target pulse direct-current power supply, and depositing a Ni intermediate layer on the surface of the Mo foil. The Ni target was sputtered at a sputtering power of 500W under a bias of-100V under a working gas pressure of 1.0Pa for a deposition time of 30 minutes to deposit a Ni layer (hereinafter referred to as Mo/Ni composite material) on the surface of the Mo foil.
(3) Magnetron sputtering deposition of Ag films
And (3) placing the Mo/Ni composite material treated in the step (2) in a vacuum coating cavity. Using metal Ag with purity of 99.99% as target material, using high-purity Ar as working gas, pre-vacuumizing to 5X 10-3And Pa below, after plasma cleaning treatment for 30 minutes, starting a pulse direct current power supply, and depositing an Ag film on the surface of the Ni layer. The sputtering power of the Ag target was 500W, the bias voltage was-100V, the working pressure was 1.0Pa, and the deposition time was 3 hours. After deposition is finished, cooling to room temperature in a vacuum environment, then exhausting gas, opening a cavity and discharging.
(4) Annealing treatment
And (4) placing the composite material treated in the step (3) in a high-temperature tube furnace, and annealing in an argon atmosphere with the purity of 99.999 percent, wherein the pressure is one standard atmosphere. The temperature is raised from room temperature to 800 ℃ at the temperature raising rate of 5 ℃/min, and the temperature is kept for 4 hours. Cooling to room temperature along with the furnace to obtain the Mo/Ni/Ag layered composite material.
The Mo/Ni/Ag laminated composite material prepared by the method is observed and tested as follows:
(1) cross-sectional SEM Observation
The test method was the same as that in example 1.
The test results were similar to those in example 1, and showed that the cross-sectional structure of the sample was divided into three layers, layer 1 was an Ag film, and the film thickness was 3.5 μm; layer 2 is a Ni interlayer, about 0.3 microns thick; layer 3 is a Mo foil. The interface of Ag/Ni and Ni/Mo is well combined without cracks. Moreover, the Ag film has no columnar crystal characteristics and is in a compact granular crystal structure.
(2) Cross-sectional element distribution test
The test method was the same as that in example 1.
The test results are similar to those in example 1 and show that sufficient elemental diffusion is achieved at the interface of Mo/Ni and Ni/Ag, with a diffusion layer thickness of up to 1 micron, indicating that a good metallurgical bond is formed at the interface.
(3) Interfacial bond strength test
The test method was the same as that in example 1.
The test results were similar to those in example 1, and showed 3120N maximum load and 39.7MPa tensile strength.
Example 5
In this embodiment, the substrate is completely the same as the substrate in embodiment 1, and a Ni intermediate layer and an Ag layer are sequentially deposited on the surface of the substrate to prepare the Mo/Ni/Ag layered composite material, wherein the preparation method specifically comprises the following steps:
(1) same as in step (1) in example 1;
(2) magnetron sputtering deposition of Ni intermediate layer
And (3) placing the Mo foil treated in the step (1) in a vacuum coating cavity. Using metal Ni with purity of 99.99% as target material, using high-purity Ar as working gas, pre-vacuumizing to 5X 10-3And Pa below, after plasma cleaning treatment for 20 minutes, starting a Ni target pulse direct-current power supply, and depositing a Ni intermediate layer on the surface of the Mo foil. The Ni target was sputtered at a sputtering power of 1000W under a bias of-70V under a working gas pressure of 0.1Pa for a deposition time of 30 minutes to deposit a Ni layer (hereinafter referred to as Mo/Ni composite material) on the surface of the Mo foil.
(3) Magnetron sputtering deposition of Ag films
And (3) placing the Mo/Ni composite material treated in the step (2) in a vacuum coating cavity. Using metal Ag with purity of 99.99% as target material, using high-purity Ar as working gas, pre-vacuumizing to 5X 10-3And Pa below, after plasma cleaning treatment for 30 minutes, starting a pulse direct current power supply, and depositing an Ag film on the surface of the Ni layer. The sputtering power of the Ag target is 1000W, the bias voltage is-70V, the working pressure is 0.1Pa, and the deposition time is 5 hours. After deposition, cooling in vacuum environmentAnd (5) cooling to room temperature, then discharging the gas, opening the cavity and discharging the furnace.
(4) Annealing treatment
And (4) placing the composite material treated in the step (3) in a high-temperature tube furnace, and annealing in an argon atmosphere with the purity of 99.999 percent, wherein the pressure is one standard atmosphere. Raising the temperature from room temperature to 900 ℃ at the temperature raising rate of 5 ℃/min, and preserving the temperature for 5 hours. Cooling to room temperature along with the furnace to obtain the Mo/Ni/Ag layered composite material.
The Mo/Ni/Ag laminated composite material prepared by the method is observed and tested as follows:
(1) cross-sectional SEM Observation
The test method was the same as that in example 1.
The test results were similar to those in example 1, and showed that the cross-sectional structure of the sample was divided into three layers, layer 1 was an Ag film, and the film thickness was 5.4 μm; layer 2 is a Ni interlayer, about 0.5 microns thick; layer 3 is a Mo foil. The interface of Ag/Ni and Ni/Mo is well combined without cracks. Moreover, the Ag film has no columnar crystal characteristics and is in a compact granular crystal structure.
(2) Cross-sectional element distribution test
The test method was the same as that in example 1.
The test results are similar to those in example 1 and show that sufficient elemental diffusion is achieved at the interface of Mo/Ni and Ni/Ag, with a diffusion layer thickness of up to 1.4 microns, indicating that a good metallurgical bond is formed at the interface.
(3) Interfacial bond strength test
The test method was the same as that in example 1.
The test results were similar to those in example 1, showing a maximum load of 3580N and a tensile strength of 45.3 MPa.
Comparative example 1
(1) Same as in step (1) in example 1;
(2) electroplating Ag film
And (3) electroplating an Ag film on the molybdenum foil treated in the step (1). The comparative example selects sulfite for silver plating, and the plating solution is prepared by deionized water. Using the Mo foil treated by Ag injection in the step (2) as a cathode and using a silver sheet(purity 99.9999%, size 200mm x 1.5mm) as anode, pH 6-7. The formula and the electroplating parameters of the Ag plating are as follows: AgNO330g/L，Na2SO3100g/L，NaH2PO435g/L, 35g/L sodium citrate, 8g/L thiosemicarbazide, 25 ℃ temperature, 0.45 A.dm current density2。
(3) Same as step (4) in example 1;
the Mo/Ag laminated composite material prepared by the method is observed and tested as follows:
(1) cross-sectional SEM Observation
The test method was the same as that in example 1.
FIG. 4 shows the cross-sectional morphology of Mo/Ag layered composite material prepared by electroplating, which shows that the electroplated Ag film is in an obvious columnar crystal structure and has poor compactness.
(2) Cross-sectional element distribution test
The test method was the same as that in example 1.
The test results were similar to those in example 1, showing that no significant elemental diffusion phenomenon occurred at the interface of Mo and Ag, indicating that no good metallurgical bond was formed at the interface.
(3) Interfacial bond strength test
The test method was the same as that in example 1.
The test results are shown in fig. 5: the maximum load was 1084N and the tensile strength was 13.8 MPa. The bonding strength is much less than the film-based bonding strength of the magnetron sputter deposited Mo/Cr/Ag and Mo/Ni/Ag layered composites provided in examples 1 and 2.
In conclusion, according to the technical scheme, the preparation method provided by the invention adopts the magnetron sputtering technology, and the silver/metal intermediate layer/molybdenum laminated composite material is successfully prepared by sequentially depositing the metal intermediate layer and the silver layer on the molybdenum surface.
In addition, the inventors have also conducted experiments with other raw materials and conditions, etc. listed in this specification, in the manner of examples 1 to 5, and have also succeeded in producing a silver/metal interlayer/molybdenum layered composite material having high density, excellent bonding strength, and excellent resistance to oxidation corrosion and thermal fatigue.
It should be noted that, in the present context, an element defined by the phrase "comprising … …" does not exclude the presence of other identical elements in steps, processes, methods or experimental facilities including the element.
It should be understood that the above preferred embodiments are only for illustrating the present invention, and other embodiments of the present invention are also possible, but those skilled in the art will be able to adopt the technical teaching of the present invention and equivalent alternatives or modifications thereof without departing from the scope of the present invention.
Claims (10)
1. A preparation method of a molybdenum-silver laminated composite material is characterized by comprising the following steps:
at least placing a molybdenum substrate and a metal target material with good solid solubility with molybdenum in a vacuum environment, and depositing a metal intermediate layer on the surface of the molybdenum substrate by a direct-current magnetron sputtering method;
placing at least a molybdenum substrate and a metal silver target material, the surfaces of which are provided with metal intermediate layers, into a vacuum environment, and depositing and forming a silver layer on the surfaces of the metal intermediate layers by a direct-current magnetron sputtering method; and
and annealing the obtained molybdenum substrate-metal intermediate layer-silver layer composite structure, so that the metal elements forming the metal intermediate layer are continuously diffused into the molybdenum substrate and the silver layer.
2. The method according to claim 1, comprising: placing the pretreated molybdenum substrate in a vacuum cavity, taking metal with good solid solubility with molybdenum as a target material, taking protective gas as working gas, and pre-vacuumizing to 5 multiplied by 10-3Plasma processing for 20-30 min under Pa, then starting a pulse direct current power supply, and performing a direct current magnetron sputtering method toAnd depositing a metal intermediate layer on the surface of the molybdenum substrate.
3. The preparation method according to claim 2, wherein the process conditions adopted by the direct current magnetron sputtering method when depositing the metal intermediate layer comprise: the vacuum degree in the vacuum cavity is less than 5 multiplied by 10-3Pa, the working gas pressure is 0.1-1.0 Pa, the power of the metal target material which has good solid solubility with molybdenum is 500-1000W, and the negative bias of the substrate is-70-100V; and/or the deposition time of the metal intermediate layer is 10-30 min.
4. The method of claim 2, wherein: the metal with good solid solubility with molybdenum comprises chromium and/or nickel; and/or the thickness of the metal intermediate layer is 200-600 nm; and/or the number of the metal target materials with good solid solubility with molybdenum is n, n is more than or equal to 2 and less than or equal to 4, and the metal target materials are preferably symmetrically distributed by taking the matrix as the center; and/or the protective gas comprises an inert gas.
5. The method according to claim 2, comprising: after the deposition of the metal intermediate layer is finished, starting a metal silver target pulse direct current power supply by taking metal silver as a target and protective gas as working gas, and depositing at least on the surface of the metal intermediate layer by a direct current magnetron sputtering method to form a flat and compact silver layer; preferably, the thickness of the silver layer is 3-5 μm.
6. The preparation method according to claim 5, wherein the process conditions adopted by the DC magnetron sputtering method in depositing the silver layer comprise: the vacuum degree in the vacuum cavity is less than 5 multiplied by 10-3Pa, the working gas pressure is 0.1-1.0 Pa, the metal silver target material power is 500-1000W, and the matrix negative bias is-70-100V; and/or the deposition time of the silver layer is 3-5 h; and/or the number of the metal silver target materials is m, m is more than or equal to 2 and less than or equal to 4, and the metal silver target materials are preferably symmetrically distributed by taking the matrix as the center; and/or the protective gas comprises an inert gas.
7. The production method according to any one of claims 1 to 6, characterized by comprising: annealing the obtained molybdenum substrate-metal interlayer-silver layer composite structure in a protective atmosphere under the pressure of 101.3 kPa; preferably, the annealing treatment temperature is 700-900 ℃, and the time is 2-5 h;
and/or, the preparation method further comprises the following steps: firstly, pretreating the surface of a molybdenum substrate, and then depositing on the surface of the molybdenum substrate to form the metal intermediate layer; preferably, the pretreatment comprises: sequentially carrying out degreasing, cleaning, etching, ultrasonic cleaning and drying treatment on the surface of the molybdenum substrate; preferably, the molybdenum substrate comprises a molybdenum foil, and the thickness of the molybdenum foil is 10-30 μm.
8. The molybdenum-silver laminated composite material prepared by the method of any one of claims 1 to 7, which comprises a molybdenum layer and a silver layer, and is characterized by further comprising a metal intermediate layer, wherein the material of the metal intermediate layer comprises a metal with good solid solubility with molybdenum, and the metal with good solid solubility with molybdenum continuously diffuses into the molybdenum layer and the silver layer at least from the bonding interface of the molybdenum layer and the silver layer; preferably, the metal having good solid solubility with molybdenum comprises chromium and/or nickel; preferably, the thickness of the metal intermediate layer is 200-600 nm; preferably, the thickness of the diffusion layer diffused into the molybdenum layer and the silver layer is 0.8 to 1.6 μm.
9. Use of the molybdenum silver laminate composite of claim 8 in the preparation of a spacecraft solar cell array interconnect material.
10. A spacecraft solar cell array interconnect sheet material comprising the molybdenum silver laminate composite of claim 8.
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