CN109280895A - A kind of preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion - Google Patents
A kind of preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000000137 annealing Methods 0.000 claims abstract description 15
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 238000005468 ion implantation Methods 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- 238000005530 etching Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000002513 implantation Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 2
- 238000001771 vacuum deposition Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 14
- 230000008021 deposition Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000000280 densification Methods 0.000 abstract description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract 1
- 230000035946 sexual desire Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 37
- 239000011888 foil Substances 0.000 description 32
- 238000010998 test method Methods 0.000 description 25
- 150000002500 ions Chemical class 0.000 description 14
- 229910052750 molybdenum Inorganic materials 0.000 description 14
- 238000009792 diffusion process Methods 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 11
- 238000007747 plating Methods 0.000 description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011733 molybdenum Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- FSVVWABMXMMPEE-UHFFFAOYSA-N molybdenum silver Chemical compound [Mo][Ag][Mo] FSVVWABMXMMPEE-UHFFFAOYSA-N 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 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
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000011536 re-plating Methods 0.000 description 1
- 239000011734 sodium Substances 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
- 239000006104 solid solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/48—Ion implantation
-
- 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
-
- 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
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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- H01L31/042—PV modules or arrays of single PV cells
- H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
- H01L31/0504—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module
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Abstract
The present invention provides a kind of preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion.This method uses ion implantation technique to inject Ag first in Mo layer surface, forms Mo/Ag alloy-layer；Then Ag layers are deposited using magnetron sputtering technique, using high energy silver ion in magnetron sputtering process to the bombardment effect of Mo layer surface, deposition obtains the Ag layer of smooth densification；Finally by annealing, promote the phase counterdiffusion of the interface Mo/Ag atom, forms metallurgical bonding.Mo/Ag laminar composite obtained has the high interface binding power of high-densit sexual desire, can be used for compactness and the demanding occasion of interface cohesion, for example, being used for spacecraft solar battery mutually in flakes etc..
Description
Technical field
The present invention relates to technical field of composite materials, and in particular to a kind of Mo/Ag layer of high-densit, high interface cohesion
The preparation method of shape composite material.
Background technique
Series-parallel and electric current the extraction of spacecraft solar array is all by mutually realizing in flakes.Silver
(Ag) there is excellent electric conductivity and good weldability, be often used as space solar cell battle array interconnection sheet material.
The aircraft of Low Earth Orbit operation faces the influence of the environmental conditions such as elemental oxygen, high/low temperature alternation, ion irradiation,
Using be mutually easy to happen under the influence of severe environmental conditions in flakes made of pure Ag foil oxidation degrade, the failure such as fatigue cracking,
Seriously constrain the long-life reliability service of aircraft.Molybdenum (Mo) has low thermal expansion coefficient, good electric conductivity and high temperature
The advantages of the two, is combined by preparing Mo-Ag laminar composite, is to solve space interconnection sheet material to support by mechanical strength
The effective way of anti-high and low-temp impact and atomic oxygen erosion.But since molybdenum money kind metal is non-solid-solution, it is hardly formed alloy,
Therefore it is a major challenge that preparation, which has the molybdenum silver laminar composite of good interface bond strength,.Prepare Mo/Ag both at home and abroad at present
Laminar composite mainly passes through electric plating method.
Chinese patent 201110008862.5 discloses solar battery mutually in flakes with molybdenum/silver laminar metal matrix composite
With preparation process, by injecting Ag in molybdenum foil surface ion, it is multiple that the method that Ag layers of re-plating obtains molybdenum silver layer shape Metal Substrate
Condensation material, bond strength 460gf.Chinese patent 201210444359.9 discloses a kind of method of molybdenum foil electroplating surface silver,
But the related data of molybdenum silver interface bond strength is not provided.Although can be invaded elemental oxygen is resisted at Ag layers of molybdenum foil electroplating surface
Erosion has the effect of certain, but it also has the defect of itself.Usual electroplated coating compactness is poor, and there is skies for inside
Position, defect, in Low earth orbit environment, elemental oxygen can enter inside by these defects of coating material and carry out to it
It corrodes, slowly atomic oxygen erosion still can generate serious destruction to performance mutually in flakes for a long time in this way.In addition, plating
Waste water, exhaust gas and the waste residue generated in the process will cause damage to natural environment and human health, while also increase enterprise
Pollution treatment cost.
Summary of the invention
Technical purpose of the invention is to provide a kind of preparation method of Mo/Ag laminar composite, and this method is at Mo layers
Surface uses ion implantation technique to inject Ag first, forms Mo/Ag alloy-layer, and then magnetron sputtering deposits Ag layers, finally carries out
Annealing technology processing, is successfully prepared the Mo/Ag laminar composite of high-densit, high interface cohesion, solves at present in molybdenum layer
Surface using Mo/Ag layers made from electroplating technology it is not fine and close, interface cohesion is poor the problems such as.
That is, technical solution provided by the invention are as follows: the Mo/Ag laminar composite of high-densit, the high interface cohesion of one kind
Preparation method, in Mo layer surface ion implanting Ag first, then uses magnetron sputtering with (referred to as Mo layers) of stratiform Mo for matrix
Technology deposits Ag layers, is finally made annealing treatment.
Compared with prior art, coupled ion injection technique, magnetron sputtered deposition technology and annealing technology of the present invention obtain
Mo/Ag laminar composite, has the following beneficial effects:
(1) firstly, injecting Ag in Mo layer surface using ion implantation technique, in ion implantation process, Ag ion beam exists
Mo layer surface is bombarded with very high kinetic energy under accelerating field effect, generates sputtering and injection effect, which send out Mo layer surface
Raw distortion of lattice and irradiation damage, and the Ag ion for injecting surface is promoted to spread to Mo layers of subsurface stratum, it is formed closely in Mo layer surface
Surface alloying layer can significantly improve molybdenum/silver interface binding power.
(2) then, Ag layers are deposited using magnetron sputtered deposition technology, utilizes high energy Ag ion pair Mo in magnetron sputtering process
The bombardment effect on foil surface, can cause the raising of Mo foil temperature, and higher base reservoir temperature is conducive to Ag film and Mo layers of atom
Phase counterdiffusion further enhances the binding force of Mo layers with Ag layers, improves densification to form diffusion bond and chemical bonding
Degree, obtains the Ag film of smooth densification；
(3) finally, atom active can be improved in high temperature in this process, further promotes Mo/Ag using annealing
The phase counterdiffusion of interface atom realizes the good alloying in interface, to more improve the interface cohesion of Mo and Ag
Intensity improves the compactness of composite material.
(4) in addition, traditional electroplating technology can bring the noxious materials such as strong acid, highly basic, cyanide during plating Ag layers
Problem of environmental pollution, and magnetron sputtering belongs to environmentally protective coating technique, and coating process is under vacuum state, not with water
Or hydrogen generate chemical change and generate harmful chemical, whole process comply fully with environmental protection specification and demand, without pollution treatment at
This, with good economic efficiency and social benefit.
(5) therefore, there is high compactness, Gao Jie using the Mo/Ag laminar composite being prepared of the invention
Face binding force can be used for compactness and the demanding occasion of interface cohesion, for example, mutual for spacecraft solar battery
In flakes etc..
On the basis of the above, the present inventor further takes following advantageous measure:
Preferably, before carrying out ion implanting Ag, to Mo layers of progress surface etching treatment, to improve Mo layers of surface
Roughness increases the real contact area of Mo layers with Ag layers, improves film-substrate cohesion.The lithographic method is unlimited, is included in
It is performed etching in etching liquid.It is further preferred that Mo layers of progress surface cleaning processing before etching.
In the process of Mo layer surface ion implanting Ag specifically: Mo is placed in the vacuum cavity of ion implantation apparatus, with
Metal Ag starts ion implanting Ag as cathode material after vacuumizing.
Preferably, being evacuated to less than 1 × 10-3Pa。
Preferably, the injecting voltage is 20KV~80KV.
Preferably, the implantation dosage is 1 × 1017~5 × 1017ions/cm2。
Ag layers of process is deposited using magnetron sputtering technique specifically: treated that Mo is placed on vacuum by ion implanted Ag
In plated film cavity, using metal Ag as target, using high-purity Ar as working gas after being vacuumized to cavity, unbalanced pulse DC power supply,
Ag film is deposited in Mo layer surface.
Preferably, being evacuated to 2 × 10 to cavity-3Pa~5 × 10-3Pa。
Preferably, the operating air pressure remains 0.1~1.0Pa.
Preferably, the Ag target power output is 500~1000W.
Preferably, Ag film sedimentation time is 3-5h.
Preferably, applying back bias voltage appropriate to Mo layers, the bombardment of Ag ion pair Mo layer surface on the one hand can be enhanced
Cleaning action can effectively remove the gas and pollutant of the absorption of Mo layer surface, further increase Ag film adhesive strength；Another party
Face, under the acceleration of back bias voltage, high energy Ag ion has stronger atomic migration ability after reaching Mo layer surface, can disappear
Except the columnar crystal structure that Ag film is loose, generate uniformly, fine and close, imporous particle crystal structure, block elemental oxygen to inside film
The channel of erosion further increases the resistance to elemental oxygen corrosive nature of Ag film.The substrate negative voltage preferably -70V~-
100V。
Preferably, being cooled to room temperature under vacuum conditions after to Ag film deposition, then deflates and begin to speak to take out, i.e.,
Obtain Mo/Ag laminar composite.
As a kind of implementation, annealing process are as follows: Mo/Ag laminar composite is placed in high temperature process furnances,
It anneals under high-purity argon gas atmosphere.Purity of argon is preferably 99.99% or more.Ar pressure is preferably a standard atmospheric pressure.
Annealing temperature is preferably 700~900 DEG C.Annealing time is preferably 2~5h.
Detailed description of the invention
Fig. 1 is the cross section structure figure of the Mo/Ag laminar composite prepared in the embodiment of the present invention 1；
Fig. 2 is the section SEM shape appearance figure of the Mo/Ag laminar composite prepared in the embodiment of the present invention 1；
Fig. 3 is that the Mo/Ag laminar composite section prepared in the embodiment of the present invention 1 is composed along the Elemental redistribution of depth direction
Figure；
Fig. 4 is the Mo/Ag laminar composite interface bond strength extension test curve prepared in the embodiment of the present invention 1；
Fig. 5 is that the Mo/Ag laminar composite section prepared in comparative example 1 is composed along the Elemental redistribution of depth direction
Figure；
Fig. 6 is the Mo/Ag laminar composite interface bond strength extension test curve prepared in comparative example 1.
Specific embodiment
Below with reference to embodiment, present invention is further described in detail, it should be pointed out that embodiment described below purport
It is being convenient for the understanding of the present invention, and is not playing any restriction effect to it.
Embodiment 1:
In the present embodiment, Mo/Ag laminar composite is prepared by matrix of Mo foil, preparation method includes the following steps:
(1) Mo foil pre-treatment
Degreaser will be soaked in having a size of 50mm × 50mm × 0.02mm molybdenum foil after sand paper grinding process, in into
Row ungrease treatment, the degreaser are NaOH, Na2CO3With Na2SiO3The mixed solution of composition, wherein NaOH, Na2CO3With Na2SiO3
Mass ratio be NaOH:Na2CO3: Na2SiO3=3:2:1.Mo foil surface is rinsed with a large amount of deionized waters after ungrease treatment.Again will
Mo foil is placed in 10% H2SO4It etches 10 minutes in solution, is rinsed after taking-up with deionized water, then be placed in deionized water ultrasonic
Wave cleans 20 minutes, and taking-up is dried stand-by.
(2) Ag ion implanting
By step (1) treated Mo foil on the workpiece position of ion implantation apparatus vacuum cavity, chamber vacuum is evacuated in advance
1.0×10-3Pa；The rotation of workpiece position is opened, to guarantee implantation homogeneity.Triggering set of frequency be 10Hz, adjust minor arc voltage to
Minor arc electric current is 0.8A, first opens inhibition electric current, then open extracted current, increases extraction voltage to target voltage 40KV, start Ag from
Son injection, dosage to be implanted reach target dose 3 × 1017ions/cm2Afterwards, stop injection.
(3) magnetron sputtering deposits Ag film
It will Mo foil be placed in vacuum coating cavity by step (2) treated.The metal Ag for being 99.99% with purity is
Target, using high-purity Ar as working gas, cavity forvacuum to 2 × 10-3Mo foil is cleaned using Ar plasma after Pa or less
Processing 30 minutes, is then turned on pulse dc power, carries out Ag film deposition, deposition parameter on Mo foil surface are as follows: Ag target sputters function
Rate is 800W, and bias is -100V, operating air pressure 0.2Pa, sedimentation time 4 hours, deposits the Ag film of 5 μ m-thicks on Mo foil surface.
It after deposition, is cooled to room temperature under vacuum conditions, then deflates and begin to speak to take out, obtain composite material.
(4) it makes annealing treatment
The composite material obtained after step (3) processing is placed in high temperature process furnances, is 99.999% argon gas in purity
It anneals under atmosphere, pressure is a standard atmospheric pressure.With the heating rate of 5 DEG C/min from room temperature to 800 DEG C, heat preservation 4 is small
When.Then, room temperature is cooled to the furnace, i.e. acquisition Mo/Ag laminar composite.
Following observation and test are carried out to Mo/Ag laminar composite obtained above:
(1) section SEM is observed
The cross-sectional sample of the Mo/Ag laminar composite is prepared using focused ion beam (FIB) technology, and uses scanning electron
Microscope (SEM) observes sample in cross section structure.As shown in Figure 1, sample in cross section structure is divided into three layers, layer 1 is in FIB sample making course
The Pt layer of plating, layer 2 are Ag film, and 5 microns of Ag film thickness, layer 3 is Mo foil.It will be seen from figure 1 that the interface cohesion of Ag film and Mo foil
Intact, flawless occurs.
Fig. 2 gives sample in cross section SEM shape appearance figure, it can be seen that Ag film is brilliant in fine and close particle without column crystal feature
Structure, this is because the bombardment effect of high energy particle promotes Ag atom in the expansion on surface during magnetron sputtering deposits Ag
Transfer ability is dissipated, its columnar growth mode has been interrupted, forms fine and close microstructure.
(2) cross sectional elements distribution tests
The Mo/Ag laminar composite element is measured along the distribution situation of depth direction using EDS.As shown in Fig. 2, in Mo
Sufficient elements diffusion is realized with the interface of Ag, thickness of diffusion layer shows that interface forms good metallurgy up to 2 microns
In conjunction with.
(3) interface bond strength is tested
The interface knot of the Mo/Ag laminar composite is tested using the disbonded test method in national standard GB/T 5270-2005
Close intensity.The sample having a size of 1cm × 1cm is made in Mo/Ag laminar composite, by the two sides the Ag and Mo FM of sample
It is 1cm × 1cm that 1000 binders are pasted on two sections respectively, and extension test exemplar is made among the aluminium bar that length is 5cm.With
INSTRON-5567 universal testing machine carries out extension test to exemplar, and extension test is carried out in room temperature, and tensile speed is
5mm/min.Tensile strength test curve is as shown in figure 3, maximum load is 3360N, tensile strength 42.8Mpa.Observe section
It was found that fracture occurs in the interface of glue and Ag film, and Ag film does not fall off from Mo foil, shows that Ag film and Mo foil interface are realized
Metallurgical bonding, has very excellent bond strength, and bond strength is greater than the bond strength 42.8MPa of binder.
Embodiment 2:
In the present embodiment, matrix is identical with the matrix in embodiment 1, deposits Ag layers of preparation Mo/ in the matrix surface
Ag laminar composite, preparation method are specific as follows:
(1) identical as step (1) in embodiment 1；
(2) Ag ion implanting
By step (1) treated Mo foil on the workpiece position of ion implantation apparatus vacuum cavity, chamber vacuum is evacuated in advance
1.0×10-3Pa；The rotation of workpiece position is opened, to guarantee implantation homogeneity.Triggering set of frequency be 10Hz, adjust minor arc voltage to
Minor arc electric current is 0.8A, first opens inhibition electric current, then open extracted current, increases extraction voltage to target voltage 60KV, start Ag from
Son injection, dosage to be implanted reach target dose 5 × 1017ions/cm2Afterwards, stop injection.
(3) identical as step (3) in embodiment 1；
(4) identical as step (4) in embodiment 1；
Following observation and test are carried out to Mo/Ag laminar composite obtained above:
(1) section SEM is observed
Test method is identical as the test method in embodiment 1.
Test result is similar with the test result in embodiment 1, and display sample in cross section structure is divided into three layers, and layer 1 is FIB system
The Pt layer of plating during sample, layer 2 are Ag film, and layer 3 is Mo foil, and the interface cohesion of Ag film and Mo foil is intact, and flawless occurs.And
And Ag film is without column crystal feature, in fine and close particle crystal structure.
(2) cross sectional elements distribution tests
Test method is identical as the test method in embodiment 1.
Test result is similar with the test result in embodiment 1, and the interface for being shown in Mo and Ag realizes sufficient member
Element diffusion, thickness of diffusion layer show that interface forms good metallurgical bonding up to 1.5 microns.
(3) interface bond strength is tested
Test method is identical as the test method in embodiment 1.
Test result is similar with the test result in embodiment 1, and display maximum load is 3610N, and tensile strength is
46MPa.Observe section discovery, fracture occurs in the interface of glue and Ag film, and Ag film does not fall off from Mo foil, show Ag film and
Mo foil interface realizes metallurgical bonding, has very excellent bond strength.
Embodiment 3:
In the present embodiment, matrix is identical with the matrix in embodiment 1, deposits Ag layers of preparation Mo/ in the matrix surface
Ag laminar composite, preparation method are specific as follows:
(1) identical as step (1) in embodiment 1；
(2) identical as step (2) in embodiment 1；
(3) magnetron sputtering deposits Ag film
It is identical essentially identical with step (3) in embodiment 1, except that substrate bias is decreased to -70V；
(4) identical as step (4) in embodiment 1；
Following observation and test are carried out to Mo/Ag laminar composite obtained above:
(1) section SEM is observed
Test method is identical as the test method in embodiment 1.
Test result shows that sample in cross section structure is divided into three layers, and layer 1 is the Pt layer of plating in FIB sample making course, and layer 2 is Ag
Film, illustrates that reducing bias causes reverse sputtering effect to weaken, Ag film thickness increases, under coating consistency by about 5.8 μm of Ag film thickness
Drop.
(2) cross sectional elements distribution tests
Test method is identical as the test method in embodiment 1.
Test result is similar with the test result in embodiment 1, and the interface for being shown in Mo and Ag realizes sufficient member
Element diffusion, shows that interface forms good metallurgical bonding.
(3) interface bond strength is tested
Test method is identical as the test method in embodiment 1.
Test result is similar with the test result in embodiment 1, and display maximum load is 2820N, and tensile strength is
35.9MPa.Section discovery is observed, fracture occurs in the interface of glue and Ag film, and Ag film does not fall off from Mo foil, shows Ag film
Metallurgical bonding is realized with Mo foil interface, there is excellent bond strength.But compared with Example 1, due to substrate bias
Reducing, particle bombardment energy reduces, and Ag atom weakens in the transfer ability of coating surface, and cause coating structure consistency to decline,
Ag/Mo interface binding power reduces.
Embodiment 4:
In the present embodiment, matrix is identical with the matrix in embodiment 1, deposits Ag layers of preparation Mo/ in the matrix surface
Ag laminar composite, preparation method are specific as follows:
(1) identical as step (1) in embodiment 1；
(2) identical as step (2) in embodiment 1；
(3) identical as step (3) in embodiment 1；
(4) it makes annealing treatment
It is identical essentially identical with step (4) in embodiment 1, except that holding temperature is increased to 900 DEG C.
Following observation and test are carried out to Mo/Ag laminar composite obtained above:
(1) section SEM is observed
Test method is identical as the test method in embodiment 1.
Test result is similar with the test result in embodiment 1, and display sample in cross section structure is divided into three layers, and layer 1 is FIB system
The Pt layer of plating during sample, layer 2 are Ag film, and layer 3 is Mo foil, and the interface cohesion of Ag film and Mo foil is intact, and flawless occurs.And
And Ag film is without column crystal feature, in fine and close particle crystal structure.
(2) cross sectional elements distribution tests
Test method is identical as the test method in embodiment 1.
Test result is similar with the test result in embodiment 1, and the interface for being shown in Mo and Ag realizes sufficient member
Element diffusion, thickness of diffusion layer is up to 2.5 microns, compared with Example 1, illustrates that higher annealing temperature promotes interface element expansion
It dissipates, shows that interface forms metallurgical bonding.
(3) interface bond strength is tested
Test method is identical as the test method in embodiment 1.
Test result is similar with the test result in embodiment 1, and display maximum load is 3780N, and tensile strength is
48.1MPa.Section discovery is observed, fracture occurs in the interface of glue and Ag film, and Ag film does not fall off from Mo foil, shows Ag film
Metallurgical bonding is realized with Mo foil interface, there is very excellent bond strength.Compared with Example 1, illustrate higher move back
Fiery temperature further promotes interface element diffusion, improves interface bond strength.
Comparative example 1:
(1) identical as step (1) in embodiment 1；
(2) identical as step (2) in embodiment 1；
(3) Ag film is electroplated
The present embodiment selects sulphite silver-plated, and plating solution is prepared with deionized water.With step (2) note Ag treated Mo foil
For cathode, with silver strip (purity 99.9999%, size 200mm × 200mm × 1.5mm) for anode, pH value is 6~7.Plating Ag matches
Side and electroplating parameter are as follows: AgNO330g/L, Na2SO3100g/L, NaH2PO435g/L, sodium citrate 35g/L, thiosemicarbazide
8g/L, 25 DEG C of temperature, current density 0.45Adm2。
(4) identical as step (4) in embodiment 1；
Following observation and test are carried out to Mo/Ag laminar composite obtained above:
(1) section SEM is observed
Test method is identical as the test method in embodiment 1.
Fig. 5 gives the Cross Section Morphology figure that plating prepares Ag/Mo composite material, it can be seen that plating Ag film is in apparent column
The compactness of shape crystal structure, Ag film is poor.
(2) cross sectional elements distribution tests
Test method is identical as the test method in embodiment 1.
Test result is similar with the test result in embodiment 1, and the interface for being shown in Mo and Ag realizes elements diffusion,
Thickness of diffusion layer shows that interface forms metallurgical bonding up to 1 micron.
(3) interface bond strength is tested
Test method is identical as the test method in embodiment 1.
Test results are shown in figure 6: maximum load 1084N, tensile strength 13.8MPa.Its bond strength is much smaller than
The film substrate bond strength for the magnetron sputtering deposition Ag film preparation Ag/Mo composite material that embodiment 1-4 is provided.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in spirit of the invention,
Supplement or similar fashion substitution etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion, it is characterized in that: in Mo layer surface
Then ion implanting Ag first deposits Ag layers using magnetron sputtering technique, is finally made annealing treatment.
2. the preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion as described in claim 1, feature
It is: before carrying out ion implanting Ag, to Mo layers of progress surface etching treatment.
3. the preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion as claimed in claim 2, feature
It is: to Mo layers of progress surface cleaning processing before etching.
4. the preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion as described in claim 1, feature
Be: in the process of Mo layer surface ion implanting Ag are as follows: Mo is placed in the vacuum cavity of ion implantation apparatus, using metal Ag as
Cathode material is evacuated to less than 1 × 10-3Start ion implanting Ag after Pa；
Preferably, the injecting voltage is 20KV~80KV；
Preferably, the implantation dosage is 1 × 1017~5 × 1017ions/cm2。
5. the preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion as described in claim 1, feature
It is: Ag layers of process is deposited using magnetron sputtering technique are as follows: treated that Mo is placed on vacuum coating cavity by ion implanted Ag
In, using metal Ag as target, 2 × 10 are evacuated to cavity-3Pa~5 × 10-3Using high-purity Ar as working gas after Pa, open
Pulse dc power deposits Ag film in Mo layer surface；
Preferably, the operating air pressure remains 0.1~1.0Pa；
Preferably, Ag film sedimentation time is 3-5h.
6. the preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion as described in claim 1, feature
Be: the Ag target power output is 500~1000W.
7. the preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion as described in claim 1, feature
It is: during depositing Ag layers using magnetron sputtering technique, to Mo layers of application back bias voltage.
8. the preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion as claimed in claim 6, feature
Be: the substrate negative voltage is -70V~-100V.
9. the preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion as described in claim 1, feature
It is: is made annealing treatment under high-purity argon gas atmosphere；
Annealing temperature is preferably 700~900 DEG C；
Annealing time is preferably 2~5h.
10. utilizing high-densit, high interface cohesion made from preparation method described in any claim in claim 1 to 9
Mo/Ag laminar composite is used for spacecraft solar battery mutually in flakes.
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