CN101393947A - Process and device for coating silver on molybdenum foil used for solar cell paddle of aerospace aircraft - Google Patents
Process and device for coating silver on molybdenum foil used for solar cell paddle of aerospace aircraft Download PDFInfo
- Publication number
- CN101393947A CN101393947A CNA2008101528122A CN200810152812A CN101393947A CN 101393947 A CN101393947 A CN 101393947A CN A2008101528122 A CNA2008101528122 A CN A2008101528122A CN 200810152812 A CN200810152812 A CN 200810152812A CN 101393947 A CN101393947 A CN 101393947A
- Authority
- CN
- China
- Prior art keywords
- silver
- ion
- molybdenum foil
- treatment
- molybdenum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a silver electroplating technology for molybdenum foils used for panel substrate interconnecting flakes of solar cells of a space craft. The technology comprises the steps of molybdenum foils buffing and degreasing treatment, acid cleaning activation treatment, silver metal plasma injection, high temperature annealing treatment, silver leaching treatment, silver electroplating, EDS testing on the constituents of an electroplated layer, shape and morphology SEM observation, passivation for the electroplated molybdenum foils, and testing on the conductibility and the weldability of the electroplated molybdenum foils. The vacuum metal plasma injection technology provided by the invention comprises the following steps: injecting metallic elements as per certain energy and dosage into the molybdenum foil interconnecting flake material processed by buffing, degreasing treatment and acid cleaning activation treatment; carrying out silver leaching treatment after vacuum high temperature annealing; and carrying out non-cyanide silver electroplating so as to achieve a silver plating layer on the molybdenum foils, which is characterized by seamlessness, fine and round crystal grains and dense structure. The passivation treatment for the electroplated molybdenum foils gives the silver plating layer the ability to prevent the silver plating layer from being corroded by sulfide. Meanwhile, the conductibility and the weldability of electroplated aluminum foils are greatly improved without being affected by the passivation treatment.
Description
Technical field
The present invention relates to surface treatment technology of material, particularly a kind of aerospace craft solar cell windsurfing sheet of interconnect is specially the technology of new aerospace craft solar cell windsurfing sheet of interconnect with the molybdenum foil electrosilvering with molybdenum foil silver plating process and device.
Background technology
Molybdenum and molybdenum alloy are a kind of exotic materials, at high temperature can keep higher intensity.Simultaneously, it also has high thermal conductivity and low thermal coefficient of expansion, and thermal shock resistance is good.The conductivity of this material and resistance to wear are also fine.Because above-mentioned advantage, molybdenum and molybdenum alloy are widely used in aerospace field, wherein just comprise the molybdenum foil that is used for aerospace craft (satellite, airship and space station) solar array sheet of interconnect.But the solderability of molybdenum is relatively poor relatively and can strong oxidation during high temperature, and this oxide-film has no protective action, and for aerospace craft solar energy sailboard sheet of interconnect material, good weldability and conductivity are indispensable.For addressing this problem, need to electroplate modification on the molybdenum surface.Because silver has a good brazing property, therefore silver-plated improving solderability in the molybdenum surface electrical usually, and reduce or prevent the oxidation of molybdenum.
Because often there is native oxide in the molybdenum surface, mainly is MoO
3, this oxide can disturb the absorption of coating.Simultaneously, it is very difficult to form alloy (solid solution) between molybdenum and the silver, reason is that molybdenum solubility in silver is very little, at 1600 ℃, the solubility of molybdenum in silver only is 5% approximately, and alloys such as AgMO30 in the market, AgMo50, AgMo65 and AgMo75 are and adopt the manufacturing of powder metallurgic method high temperature sintering.Therefore, bigger in the silver-plated difficulty of molybdenum surface electrical, directly silver-plated often adhesion is not firm, and quality of coating is relatively poor.The way that solves molybdenum electrosilvering difficulty generally is to adopt the way of preplating or strike plating to plate the thin metal (as chromium, nickel, gold, rhodium, platinum etc.) of one deck earlier on the surface, electroplate through continuing again after the high-temperature heat treatment, technology is comparatively loaded down with trivial details, and the combination of silvering and molybdenum foil is also bad.In addition, have the bibliographical information nickel preplating that electric conductivity is caused adverse effect, gold, rhodium, platinum then also can strengthen cost.Therefore be necessary to study a kind of new on the molybdenum foil surface technology of electrosilvering.
It is a kind of process for treating surface that grows up the eighties in last century that metal plasma is injected modification technology.It is directly metal ion to be injected the material that needs modification, and the metal-modified layer that obtains no sharp interface, has very high bond strength improves its surperficial conductivity.Simultaneously, at injection process intermediate ion bundle material surface is also had the bombardment effect, this bombardment effect often can be removed the oxide of material surface.Material is electroplated on this basis, it is better to obtain quality again, the electrodeposited coating that bond strength is high.Obviously, the metal plasma injection technique can solve the difficult problem of the silver-plated existence of molybdenum foil surface electrical, comprises that the molybdenum foil surface exists native oxide and molybdenum silver to be difficult to form solid solution.
Summary of the invention
The object of the present invention is to provide silver plating process and the device of a kind of aerospace craft solar cell windsurfing sheet of interconnect with molybdenum foil, adopt the metal plasma injection technology that silver ion is injected into through in the molybdenum foil after degreasing, pickling and the cleaning, high annealing carries out electrosilvering with soaking after silver is handled again, carry out Passivation Treatment at last, thereby obtain the tiny slyness of crystal grain, compact structure and the strong silver coating of resisting sulfide corrosion ability, the conductivity of molybdenum foil improves, good weldability.
A kind of aerospace craft solar cell windsurfing sheet of interconnect provided by the invention with the electrosilvering technology of molybdenum foil mainly comprise molybdenum foil preliminary treatment, ion injection, The high temperature anneal, soak silver-colored processing, electrosilvering and Passivation Treatment, concrete steps:
1) the pure molybdenum foil test piece of sheet of interconnect is finished preliminary treatment through polishing, ungrease treatment, washing, sulfuric acid solution pickling, washing;
The purpose that ungrease treatment is handled is the surface state homogeneous that makes test piece, and removes partial oxide film and greasy dirt.Test piece after the ungrease treatment will be washed repeatedly through flowing water.Clean back test piece surface water membrane stage homogeneous, do not hang liquid, be the degreasing success, can carry out next procedure.
Test piece after the degreasing is put into 10% dilution heat of sulfuric acid and is carried out acid-wash activation and handle, and with the oxide on further removing test piece surface, could obtain to combine with substrate good coating like this.Simultaneously, the cleaning on molybdenum sheet of interconnect surface is for the acquisition of condition of high vacuum degree in the ion implantor and keep extremely importantly, and cleaning surfaces can also obtain good ion and inject effect.Test piece after the activation processing also will be washed repeatedly through flowing water, and uses washed with de-ionized water.
2) on ion implantor silver ion is injected molybdenum foil test piece (sheet of interconnect), take out the back of spending the night in the vacuum chamber;
On the high current ion implantor silver ion is injected in the molybdenum foil sheet of interconnect, sample is taken out in the back of spending the night in vacuum chamber.Specifically be that Ag metal ion with doses and energy is injected in the Mo sheet of interconnect; Be infused on the metal plasma implanter and carry out.Need set the negative electrode in metal plasma source and triggering pressure and the beam current density between the arc voltage between the anode, trigger electrode and the negative electrode during injection.For preventing that ion implantor from frequently sparking occurring and damaging machine, destruction vacuum and retardance injection process, the minimum that should be set in the energy starting the arc is pressed in arc voltage and triggering, and the later stage can constantly be adjusted.For accelerating injection process, beam current density should suitably be transferred greatly, should turn down in case high voltage arc appears in ion implantor.And implantation dosage and injection energy carry out according to the value that realizes design.Described ion implantation process technological parameter is: arc voltage rises to 60V, triggers voltage rise to 80V, and negative pressure rises to 2KV, and high pressure rises to 50KV, constantly regulates in the injection process and triggers frequency, and keeping beam current density is 2.0～2.5 μ Acm
-2About, injection period vacuum degree remain on 1 * 10
-3Below the Pa.The dosage of the injection of described silver ion is 1.7 * 10
17Ions/cm
2, the injection energy is 105keV.
3) in high vacuum furnace, be 1 * 10 in vacuum degree
-3Insulation was annealed in 2 hours under Pa and the 700 ℃ of temperature;
Mo paper tinsel specimen surface after the Ag ion injects has very big stress, inject back specimen surface atom simultaneously and all be noncrystalline state, so need carry out annealing in process to the sample after injecting, to eliminate internal stress, make amorphous Ag be converted into the Ag of crystalline state simultaneously, this equally distributed crystalline state Ag makes the electrosilvering ion be more prone at the molybdenum foil surface crystallization, and coating crystal grain also diminishes, and this is complete to obtaining, compact crystallization, the Ag coating that is evenly distributed are helpful.Annealing temperature determines to the definition of crystalline transformation according to stress relief annealing and amorphous, and insulation hour is determined according to reality.
4) under 42-48 ℃, will carry out the surface through the silver-colored solution of the molybdenum test piece immersion pH=4 behind silver ion injection, the high annealing and soak silver;
Soak silver-colored processing and can further improve the throwing power of molybdenum foil silver.This step comprises the preparation of soaking silvering solution and soaks silver and handle.During preparation, silver nitrate and thiocarbamide are used deionized water dissolving respectively, two kinds of solution are mixed put into same container then, constantly be stirred to till the white precipitate dissolving.Regulate the pH value of mixed solution with hydrochloric acid.When soaking silver and handling, silver ion is injected and the molybdenum foil test piece behind high annealing is immersed in silvering solution, the upset molybdenum foil makes that to soak silver layer even, till the silver of test piece surface coverage one deck white.The test piece of soaking behind the silver must be through the flushing repeatedly of flowing water.The described liquor argenti nitratis ophthalmicus that soaks silvering solution prescription: 15g/L, saturated thiourea solution, 200-220g/L, hydrochloric acid adjust pH=4 of 1:1.
5) use through silver ion injection, high annealing and soak the silver-colored molybdenum foil test piece of handling to be negative electrode, silver foil is an anode, carries out electrosilvering in the silver salt plating bath;
The present invention selects for use sulphite silver-plated, the main silver nitrate of solution composition, sodium sulfite, sodium dihydrogen phosphate, natrium citricum.During plating, be anode with silver, passing through ion injection, high annealing and soaking the silver-colored molybdenum foil of handling is negative electrode, and the pH value of regulating electroplate liquid is 6～7, and temperature is room temperature 18-35 ℃, and current density is 0.4-2A/dm
2In order to make electrodeposited coating crystal grain tiny, add the additive thiosemicarbazide.
Described silver salt plating bath:
AgNO
3 30g/L
Na
2SO
3 100g/L
NaH
2PO
4 35g/L
Natrium citricum 35g/L
Thiosemicarbazide 8g/L.
6) the silver-plated molybdenum foil test piece that obtains is placed on carried out passivation time 4 minutes in the passivating dip, dry naturally subsequently;
Because the thermodynamic (al) instability of silvering itself, especially when containing sulfide in the natural environment atmosphere and exist, can produce the corrosion variable color at humidity, salt fog.This corrosion can have a strong impact on its electric conductivity and solderability, causes the decline of silvering quality, thereby influences the Performance And Reliability of machine product.Therefore, often need behind the material electrosilvering, carry out Passivation Treatment to improve the ability of its resisting sulfide corrosion.The present invention adopts the organic compound passivation, just in straight chain that contains sulphur, nitrogen active group or heterocyclic compound solution, flood certain hour, silver generates the extremely thin silver complex film of one deck with the organic substance effect, silvering and corrosive medium are kept apart, reach the purpose that prevents variable color and anti-sulfide corrosion.Because this silver complex film is very thin, is unlikely to influence conductivity and solderability.Passivating dip composition of the present invention comprises benzotriazole (B.T.A), KI, 1-phenyl 5-mercapto tetrazole, and the pH value is controlled in 5～6 scopes during passivation, and temperature is a room temperature, about 4 minutes of time.
The present invention carries out following test:
1) electroplate liquid performance test
1. by the stability of placing naturally and electroplate liquid is tested in the heating experiment.Wherein, placing naturally is the plating bath long-time placement naturally in air that will newly prepare, the time of record from beginning to becoming turbid; The heating experiment then is the plating bath that disposes newly, is heated to 50 ℃ in permanent water-bath, the time of record from beginning to becoming turbid.
2. adopt far and near cathode method to measure the covering power of electroplate liquid.
3. measure deposition velocity with the weightening finish method, press the Coating composition analysis result and calculate the coating average thickness.
2) the composition EDS of electrodeposited coating detects.The Oxford ISIS4.0EDS test surfaces composition that adopts Britain to produce detects electroplating effect.
3) electrodeposited coating pattern SEM observation.Adopt PHILIPS XL30 environmental scanning electron microscope to observe the specimen surface pattern, comprise electrodeposited coating grain size, shape, whether complete sum densification on the structure.
The purpose of above-mentioned two tests is to check the effect of electroplating technology.
4) anti-vulcanized sodium corrosion test.The purpose of this experiment is to check the effect of Passivation Treatment.The present invention adopts Na is put in silver-plated molybdenum foil test piece
2Make the mode of its accelerated corrosion in the solution of S constant concentration, detect the corrosion resistant degree of silver-plated molybdenum foil test piece.Adopt the three-electrode system electro-chemical test, obtain its polarization resistance in sodium sulfide solution.
5) adopt heating quenching method to check the adhesive strength of silvering and molybdenum foil.In Ovenized resistance furnace, heat, be incubated 1.5-2h down at 200 ℃.After heating, take out sample and drop into quenching in the water that temperature is a room temperature immediately, cold cycling 4 times.To being chilled to the sample inspection of room temperature, coating does not have peeling or peels off to qualified, otherwise is chosen as defective.
6) test of the molybdenum foil sheet of interconnect conductivity after the passivation.For aerospace craft (satellite, airship and space station) solar cell windsurfing sheet of interconnect material, good electrical conductivity is one of basic requirement.Conductivity should be able to obtain very big improvement behind electrosilvering, but because Passivation Treatment has generated the extremely thin silver-colored complexing film of one deck on its surface, conductivity might be affected, therefore, must carry out the conductivity test to the molybdenum foil sheet of interconnect after the passivation.The present invention adopts the two electrical measurement four point probe testers of SDY-5 type to measure the conductivity of sample.For reducing the influence that measure error causes, each sample is surveyed five points, averages then.
7) electroplate the test of molybdenum foil sheet of interconnect solderability.For aerospace craft solar cell windsurfing sheet of interconnect material, one of requirement that good solderability is also basic.Just because of the solderability of pure molybdenum foil is relatively poor, thus it is carried out electrosilvering improving its solderability, and Passivation Treatment also might impact solderability, so be necessary last solderability is tested.This experiment employing is spread area-method and is tested.The scolder of spreading area-method and being certain mass is placed on the sample to be tested surface, drip last several rosin isopropyl alcohol solder flux, be placed on and be heated to 200 ℃ on the heating plate, keep 2min, take off sample, with planimeter inspection and calculating scolder spreading area (the rosin joint face can not count in the lump), it is bigger to spread area then, and plating weldability better.More easy to operate for experiment is had, accident test weld material spreading area after cooling, but survey diameter D or average diameter (being generally circle or ellipse after the fusing) after the solder fusing diffusion, D is bigger, the expression welding performance better, otherwise poorer.
The present invention adopts the metal plasma injection technique, in conjunction with traditional electrosilvering technology, a kind of new aerospace craft solar cell windsurfing sheet of interconnect molybdenum foil electrosilvering technology is provided, thereby obtain the tiny slyness of crystal grain, compact structure and the strong silver coating of resisting sulfide corrosion ability, the conductivity of molybdenum foil improves, and solderability is good.
Description of drawings
Fig. 1: silver ion of the present invention injects molybdenum foil device schematic diagram.
Fig. 2: covering power testing apparatus schematic diagram of the present invention.
Fig. 3: electrodeposited coating EDS collection of illustrative plates of the present invention.
Fig. 4: the SEM surface topography of sheet of interconnect molybdenum foil silver coating of the present invention is observed.
Fig. 5: electro-chemical test system schematic diagram of the present invention.
Fig. 6: the response curve of sample polarization resistance in Na2S solution after the passivation of the present invention.
Fig. 7: solderability test schematic diagram of the present invention.
Embodiment
With accompanying drawing the present invention is described in detail in conjunction with the embodiments.
Fig. 1 injects molybdenum foil device schematic diagram for silver ion, wherein, and 1-ion source, 2-ion beam, 3-flood chamber, 4-sample, 5-target disc, 6-vacuum diffusion pump, 7-holding pump, 8-mechanical pump, 9-high pressure and system's control cubicle.The building block of this ion implantor comprises that ion source, vacuum impregnating are entered the room, target disc, vacuum system, high pressure and control cubicle.Wherein, vacuum system is made up of diffusion pump, holding pump and mechanical pump again, and vacuum system is directly entered the room with vacuum impregnating and is connected by valve; Target disc is arranged in flood chamber; Ion source is positioned at the flood chamber top, tilts relative with target disc.During injection, ion source is added with arc voltage, triggers and press and high pressure.
Main operational steps is as follows:
1, be that the pure molybdenum foil test piece of 50mm * 40mm * 0.1mm is carried out at first wanting earlier through the fine sandpaper polishing to specification, so that the surface state homogeneous of test piece, and remove partial oxide film.Subsequently test piece is immersed in degreaser
(NaOH:Na
2CO
3: Na
2SiO
3The mixed solution of=3:2:1) carry out ungrease treatment in, the test piece after the ungrease treatment will be washed repeatedly through flowing water.Clean back test piece surface water membrane stage homogeneous, do not hang liquid, be the degreasing success.
2, the test piece after the degreasing is put into 10% sulfuric acid solution and is carried out acid-wash activation and handle, and with the oxide on further removing test piece surface, makes test piece expose pure molybdenum lattice.Test piece after the activation processing also will be washed repeatedly through flowing water, and uses washed with de-ionized water.
3, the MEVVAIIA-H source strength that is infused in of silver ion is wandered about as a refugee and is carried out (Institute of Low Energy Nuclear Physics, Beijing Normal University's production) on the sub-implanter among the present invention, and this implanter is with reference to shown in the accompanying drawing 1, and the technological parameter selection result is listed in the table 1.
Table 1 Ag ion implantation technology parameter
The injection process schematic diagram is seen Fig. 1.During injection, open metal ion implantation machine vacuum chamber 3, sheet of interconnect silver foil sample 4 is put on the target disc 5, start vacuum system and vacuumize, vacuum system is by vacuum diffusion pump 6, holding pump 7, and mechanical pump 8 is formed, and vacuum system is connected with valve with flood chamber.Begin to take out low vacuum earlier, after rough vacuum reaches below the 1Pa, with diffusion pump 6 pumping high vacuums, when condition of high vacuum degree reaches 1 * 10 with mechanical pump 8
-3Behind the Pa, begin to regulate technological parameter.
At first open ion source 1 preheating 5 minutes, on high pressure and system's control cubicle 9, arc voltage is risen to 60V (the arc voltage table value of reading) then, trigger voltage rise to 80V (triggering the pressure table value of reading).With arc voltage and trigger to press transferred after, rise negative pressure to 2KV, high pressure rises to 50KV, triggers to begin injection work.Injection process is constantly regulated the triggering frequency, and keeping beam current density is 2.0～2.5 μ Acm
-2About, injection period vacuum degree remain on 1 * 10
-3Below the Pa.
After injecting end, sample is not taken out earlier, be placed in the vacuum chamber and spend the night, open vacuum chamber then and take out sample.
4, adopt high vacuum sintering furnace, at high vacuum state (1 * 10
-3Pa) annealing in process was carried out in insulation in 2 hours and under 700 ℃ of temperature.
5, carry out the silver leaching process preliminary treatment to the silver ion injection and through the molybdenum foil test piece surface of high-temperature vacuum annealing.The process for preparation that soaks silvering solution is: take by weighing a certain amount of silver nitrate and thiocarbamide (chemical pure), use deionized water dissolving respectively, making liquor argenti nitratis ophthalmicus concentration is 15g/L, and thiourea solution concentration is 200-220g/L (saturation condition).Same container is put in two kinds of solution mixing, constantly be stirred to till the white precipitate dissolving.With the hydrochloric acid of 1:1 the pH value of mixed solution is adjusted to 4.The solution for preparing is sunken to the bottom if any excessive thiocarbamide, belongs to normal phenomenon, need not filter.The temperature of soaking silver is controlled at 42-48 ℃.
To be immersed in through the molybdenum foil test piece that above-mentioned operation is handled well in the silvering solution, the upset molybdenum foil makes that to soak silver layer even, till the silver of test piece surface coverage one deck white.The test piece of soaking behind the silver must to avoid bringing coating bath into soaking silvering solution, be polluted plating bath through the flushing repeatedly of flowing water.
6, electroplate
(1) the present invention selects for use sulphite silver-plated, and used all ingredients is chemical pure, and plating bath is prepared with deionized water.Negative electrode is silver ion injection, high annealing and soaks the molybdenum foil test piece that silver is handled that anode uses silver foil.
(2) acidity is little to the apparent state influence of coating, but its discoloration-resisting is had certain influence, and pH is more suitable about 6.5.For ease of practical operation, the present invention is controlled at the pH value between the 6-7.
Silver-plated prescription and process conditions are
AgNO
3 30g/L
Na
2SO
3 100g/L
NaH
2PO
4 35g/L
Natrium citricum 35g/L
Thiosemicarbazide 8g/L
pH 6.5
25 ℃ of temperature
Current density 0.4-2Adm
2
Wherein, thiosemicarbazide is an additive.
(3) bath stability property testing
1. place experiment naturally
In container, put into the plating bath of the new configuration of 50mL, long-time placement naturally in air, the time of record from beginning to becoming turbid.
2. heating experiment
In the uncovered beaker of 100mL, contain the plating bath of the new configuration of 50mL, in permanent water-bath, be heated to 50 ℃, the time of record from beginning to becoming turbid.
The bath stability experimental result shows, places experiment naturally and precipitation still do not occur through 1 month plating bath; Precipitation do not occur through 80 hours plating baths in the heating experiment, this plating bath that shows that the present invention prepares has good stable.
(4) test covering power
Measure covering power with far and near cathode method.Aqueduct is the transparent organic glass beaker, and it is the molybdenum foil of 30 μ m that negative electrode adopts thickness, is of a size of 50 * 50mm, working surface is light smoothly, the non-working surface epoxy sealing, the orificed anode pure silver foil of use and negative electrode same size, the experiment electric current is 2A, as shown in Figure 2,10-anode, 11-plating bath, 12-nearly negative electrode, 13-negative electrode far away, 14-power supply.
The taking-up negative electrode cleans up after at room temperature electroplating 30min, dry 15min in 105-115 ℃ baking oven, accurately the weightening finish m of the nearly negative electrode far away of weighing
1And m
2
Covering power T is calculated as follows:
K is far and near negative electrode and the ratio of anode spacing in the formula, and 5:1 is adopted in this experiment.
The result shows, the covering power T=92.9% of the used plating bath of the present invention.
(5) mensuration of deposition velocity.
Measure deposition velocity with the weightening finish method, press the Coating composition analysis result and calculate the coating average thickness.
V is a deposition velocity in the formula, and 1 is the sedimentary deposit size, and t is a sedimentation time.
Experimental result shows, among the present invention used galvanoplastic at room temperature, cathode-current density D
k=3A.dm
-2The time, deposition velocity is 90-110 μ mh
-1
7, energy spectrum analysis
The silver-colored electrodeposited coating EDS in molybdenum foil surface can see Fig. 3 by spectrogram.By power spectrum Fig. 3 as can be seen, the electrodeposited coating of this experiment mainly is made of silver element, and silver successfully has been electroplated onto the surface of molybdenum sheet of interconnect.
8, silvering ESEM morphology observation
Fig. 4 is a silvering pattern SEM photo.As can be seen from Figure 4, the crystallization of gained coating is careful, the crystal grain slyness, and crystal grain is evenly distributed.
9, Passivation Treatment
Because silver coating very easily reacts and variable color with airborne sulphur, therefore need it is carried out the passivation test.Passivation technology is:
Benzotriazole (B.T.A) 5g/L
KI (KI) 2g/L
1-phenyl 5-mercapto tetrazole 0.5g/L
pH 5-6
Temperature 25
Time 4min
Naturally dry after passivation is intact.
10, anti-vulcanized sodium corrosion test
The present invention adopts Na is put in silver-plated molybdenum foil test piece
2Make the mode of its accelerated corrosion in the solution of S constant concentration, detect the corrosion resistant degree of silver-plated test piece.
Electro-chemical test adopts three-electrode system, schematic diagram as shown in Figure 5,15-Na wherein
2S solution, W are sample to be tested, and R is saturated calomel electrode (SCE), and A is the stainless steel auxiliary electrode.Auxiliary electrode is a stainless steel electrode, adopts saturated calomel electrode (SCE) as reference electrode.Work electrode is the pure molybdenum foil of silver-plated front and back, and work electrode working face area is 20 * 20mm
2, non-working surface epoxy sealing, working media are 1%Na
2S solution.Before the experiment, sample at Na
2Soak 30min in the S solution, make its surface state stable.Test for 25 ± 3 times in room temperature.Test macro is made up of the PARSTAT2273 electro-chemical test system and the PowerSuite software of PRINCETON company.
Polarization curve is being measured in+10mV linear polarization scope with respect to corrosion potential-10mV.Potential scanning speed is 0.166mV/s.
Fig. 6 for sheet of interconnect sample after the passivation at Na
2The response curve of polarization resistance in the S solution, obtain passivation by this curve after sample at Na
2Polarization resistance in the S solution (Rp) is 86.472 Ω .cm
2, and the polarization resistance that unpassivated is handled is 31.632 Ω .cm
2Sheet of interconnect after this explanation passivation has stronger anti-Na
2The ability of S corrosion.Actual observation finds that also sheet of interconnect appearance color does not change.
11, adopt the adhesive strength of heating quenching method check silvering and molybdenum foil.The molybdenum foil of electrosilvering before and after the passivation is put into Ovenized resistance furnace heat, be incubated 1.5-2h down at 200 ℃.After heating, take out sample and drop into quenching in the water that temperature is a room temperature immediately, cold cycling 4 times.To being chilled to the sample inspection of room temperature, the electrosilvering molybdenum foil did not all have foaming (layer), nothing decortication (falling), flawless, acomia wrinkle, does not have be full of cracks before and after the result showed passivation.
12, conductivity test before and after the sheet of interconnect passivation
The present invention adopts the two electrical measurement four point probe testers of SDY-5 type to measure the conductivity of sheet of interconnect passivation front and back.For reducing the influence that measure error causes, each sample is surveyed five points, averages then.
The scope of this apparatus measures silicon chip resistivity is 0.001-200 Ω .cm (can expand), and the measuring range of measuring square resistance is 0.01-2000 Ω .cm (can expand); Thickness of sample requires to being no more than 3.00mm; The full-size d of sample stage is 100mm (J-2B) and 200mm) (J-51); The analog circuit test error is smaller or equal to the 0.3%+1 word; The overall measurement maximum relative error is smaller or equal to+5%; The overall measurement standard uncertainty is smaller or equal to 5%; Power supply is an alternating current, and operating voltage is 220V+10%, and power is less than 25W.The conductivity average out to 1.82 * 10 of the pure molybdenum foil of electrosilvering not
7Ω
-1M
-1, and the conductivity average out to 6.5 * 10 of the molybdenum foil of electrosilvering
7Ω
-1M
-1, be 6.31 * 10 through the sample conductivity after the Passivation Treatment
7Ω
-1M
-1This explanation electrosilvering is remarkable to improving molybdenum foil conductivity effect, and Passivation Treatment is little to the conductivity influence.
13, sheet of interconnect welding performance test
The present invention adopts and spreads the area-method test.
The scolder of spreading area-method and being certain mass is placed on sample to be tested (the silver-plated molybdenum foils before and after the passivation) surface, drip last several rosin isopropyl alcohol solder flux, be placed on and be heated to 200 ℃ on the heating plate, keep 2min, take off sample,, as illustrate shown in Figure 7 then with planimeter inspection and calculating scolder spreading area (the rosin joint face can not count in the lump), the 16-matrix, the 17-scolder.Assessment method: it is bigger to spread area, and plating weldability better.More easy to operate for experiment is had, accident test weld material spreading area after cooling, but survey diameter D after the solder fusing diffusion or average diameter (owing to be generally circle or ellipse after the fusing, measure its long section footpath), D is bigger, represents welding performance better, otherwise poorer.
The scolder that adopts is the soldering silk of stanniferous 40% φ 2.0; Solder flux is 25% the neutral solder flux of rosin isopropyl alcohol.The results are shown in Table 2.
Table 2 molybdenum foil welding performance test result
The result shows, the sample solderability after silver-plated all is greatly improved than pure molybdenum foil, has reached requirement.Simultaneously, test result shows that also the passivation experiment of organic substance BTA also causes welding performance slightly to descend, and is little to the welding performance impact when significantly improving the silver coating decay resistance.
Claims (9)
1, a kind of aerospace craft solar cell windsurfing sheet of interconnect is with the electrosilvering technology of molybdenum foil, it is characterized in that mainly comprising molybdenum foil preliminary treatment, ion injection, The high temperature anneal, soak silver-colored processing, electrosilvering and Passivation Treatment, concrete steps:
1) the pure molybdenum foil test piece of sheet of interconnect is finished preliminary treatment through polishing, ungrease treatment, washing, sulfuric acid solution pickling, washing;
2) on ion implantor silver ion is injected the molybdenum foil test piece, take out the back of spending the night in the vacuum chamber;
3) in high vacuum furnace, be 1 * 10 in vacuum degree
-3Insulation was annealed in 2 hours under Pa and the 700 ℃ of temperature;
4) under 42-48 ℃, silver ion injects pH=4 is also immersed in the back through the molybdenum test piece of high annealing the silvering solution that soaks, and silver is soaked on the surface again handle;
5) use through silver ion injection, high annealing and soak the silver-colored molybdenum foil test piece of handling to be negative electrode, silver foil is an anode, carries out electrosilvering in the silver salt plating bath;
6) obtaining silver-plated molybdenum foil test piece is placed on and carries out passivation time in the passivating dip and dry naturally after 4 minutes.
2,, it is characterized in that described sulfuric acid solution is 10% sulfuric acid solution according to the described technology of claim 1.
3,, it is characterized in that described pure molybdenum foil test piece is 50 * 40 * 0.1mm according to the described technology of claim 1.
4,, it is characterized in that described ion implantation process technological parameter is according to the described technology of claim 1:
Arc voltage rises to 60V, triggers voltage rise to 80V, and negative pressure rises to 2KV, and high pressure rises to 50KV, constantly regulates in the injection process and triggers frequency, and keeping beam current density is 2.0～2.5 μ Acm
-2, injection period vacuum degree remain on 1 * 10
-3Below the Pa.
5, according to the described technology of claim 1, the dosage that it is characterized in that the injection of described silver ion is 1.7 * 10
17Ions/cm
2, the injection energy is 105keV.
6,, it is characterized in that the described liquor argenti nitratis ophthalmicus that soaks silvering solution prescription: 15g/L, saturated thiourea solution, 200-220g/L, salt acid for adjusting pH value=4 of 1:1 according to the described technology of claim 1.
7,, it is characterized in that described silver salt plating bath and technological parameter according to the described technology of claim 1:
AgNO
3 30g/L
Na
2SO
3 100g/L
NaH
2PO
4 35g/L
Natrium citricum 35g/L
Thiosemicarbazide 8g/L
pH 6-7
25 ℃ of temperature
Current density 0.4-2Adm
2
8,, it is characterized in that the composition of described passivating dip according to the described treatment process of claim 1:
Benzotriazole (B.T.A) 5g/L KI (KI) 2g/L
1-phenyl 5-mercapto tetrazole 0.5g/L pH 5-6
25 ℃ of time 4min of temperature.
9, the ion implantor device that uses in the described technology of a kind of claim 1 is characterized in that it is the high current ion implantor, and the building block of this ion implantor comprises that ion source, vacuum impregnating are entered the room, target disc, vacuum system, high pressure and control cubicle.Wherein, vacuum system is made up of diffusion pump, holding pump and mechanical pump again, and vacuum system is directly entered the room with vacuum impregnating and is connected by valve; Target disc is arranged in flood chamber; Ion source is positioned at the flood chamber top, tilts relative with target disc.During injection, ion source is added with arc voltage, triggers and press and high pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101528122A CN101393947B (en) | 2008-11-05 | 2008-11-05 | Process and device for coating silver on molybdenum foil used for solar cell paddle of aerospace aircraft |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101528122A CN101393947B (en) | 2008-11-05 | 2008-11-05 | Process and device for coating silver on molybdenum foil used for solar cell paddle of aerospace aircraft |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101393947A true CN101393947A (en) | 2009-03-25 |
| CN101393947B CN101393947B (en) | 2010-12-08 |
Family
ID=40494133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101528122A Expired - Fee Related CN101393947B (en) | 2008-11-05 | 2008-11-05 | Process and device for coating silver on molybdenum foil used for solar cell paddle of aerospace aircraft |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101393947B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140618A (en) * | 2011-01-17 | 2011-08-03 | 天津大学 | Mutual non-solid-solution system metal infiltration process and device based ion implantation radiation damage |
| CN102169912A (en) * | 2011-01-17 | 2011-08-31 | 天津大学 | Mo/Ag laminated metal matrix composite for solar cell interconnected sheet and preparation process thereof |
| CN103681952A (en) * | 2013-08-20 | 2014-03-26 | 天津大学 | A preparation technique for spacecraft-used molybdenum/platinum/silver/ layered metal matrix composite materials |
| CN103668368A (en) * | 2013-11-20 | 2014-03-26 | 天津大学 | Preparation process of molybdenum/palladium/silver laminar metal matrix composite |
| CN103692147A (en) * | 2013-11-22 | 2014-04-02 | 天津大学 | Direct bonding connection technology of mutual non-solid-solution metal |
| CN103887363A (en) * | 2012-12-19 | 2014-06-25 | 上海空间电源研究所 | Method for forming atomic oxygen resistant interconnection piece for solar cell circuit |
| CN106048534A (en) * | 2016-06-03 | 2016-10-26 | 南通市申海工业技术科技有限公司 | Surface treatment process of molybdenum foil for spaceflight interconnection piece |
| CN109280895A (en) * | 2017-07-20 | 2019-01-29 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion |
-
2008
- 2008-11-05 CN CN2008101528122A patent/CN101393947B/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169912A (en) * | 2011-01-17 | 2011-08-31 | 天津大学 | Mo/Ag laminated metal matrix composite for solar cell interconnected sheet and preparation process thereof |
| CN102140618B (en) * | 2011-01-17 | 2012-11-07 | 天津大学 | Mutual non-solid-solution system metal infiltration process based on ion implantation radiation damage and electrode material |
| CN102169912B (en) * | 2011-01-17 | 2013-04-03 | 天津大学 | Mo/Ag laminated metal matrix composite for solar cell interconnected sheet and preparation process thereof |
| CN102140618A (en) * | 2011-01-17 | 2011-08-03 | 天津大学 | Mutual non-solid-solution system metal infiltration process and device based ion implantation radiation damage |
| CN103887363A (en) * | 2012-12-19 | 2014-06-25 | 上海空间电源研究所 | Method for forming atomic oxygen resistant interconnection piece for solar cell circuit |
| CN103681952B (en) * | 2013-08-20 | 2016-01-13 | 天津大学 | The preparation technology of spacecraft molybdenum/platinum/silver laminar metal matrix composite |
| CN103681952A (en) * | 2013-08-20 | 2014-03-26 | 天津大学 | A preparation technique for spacecraft-used molybdenum/platinum/silver/ layered metal matrix composite materials |
| CN103668368A (en) * | 2013-11-20 | 2014-03-26 | 天津大学 | Preparation process of molybdenum/palladium/silver laminar metal matrix composite |
| CN103668368B (en) * | 2013-11-20 | 2016-04-13 | 天津大学 | The preparation technology of molybdenum/palladium/silver laminar metal matrix composite |
| CN103692147A (en) * | 2013-11-22 | 2014-04-02 | 天津大学 | Direct bonding connection technology of mutual non-solid-solution metal |
| CN103692147B (en) * | 2013-11-22 | 2015-11-04 | 天津大学 | The Direct Bonding Joining Technology of not solid solution metal mutually |
| CN106048534A (en) * | 2016-06-03 | 2016-10-26 | 南通市申海工业技术科技有限公司 | Surface treatment process of molybdenum foil for spaceflight interconnection piece |
| CN109280895A (en) * | 2017-07-20 | 2019-01-29 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101393947B (en) | 2010-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101393947B (en) | Process and device for coating silver on molybdenum foil used for solar cell paddle of aerospace aircraft | |
| CN107313084B (en) | A kind of alkaline non-cyanide plate silver plating solution and silver-coating method | |
| CN102169912B (en) | Mo/Ag laminated metal matrix composite for solar cell interconnected sheet and preparation process thereof | |
| CN108570703A (en) | Preparation method of tungsten/copper laminated composite material based on tungsten sheet surface nanocrystallization | |
| CN110016700B (en) | Surface-enhanced Raman spectrum silver-plated active substrate and preparation method thereof | |
| CN104630837A (en) | Electroplating liquid and electroplating method of anthraquinone dye system acid copper plating | |
| CN105063685A (en) | Nickel plated copper product containing nickel-cobalt alloy clad layer, and preparation method and application thereof | |
| CN102234800A (en) | Aluminum alloy rare earth passivating liquid taking chlorine salt as accelerator and use method thereof | |
| CN103668368A (en) | Preparation process of molybdenum/palladium/silver laminar metal matrix composite | |
| KR101270770B1 (en) | Electroplating method for printed circuit board | |
| CN107304479B (en) | A kind of coating method of silumin | |
| Ding et al. | Electrochemical migration behavior and mechanism of PCB-ImAg and PCB-HASL under adsorbed thin liquid films | |
| CN105200465A (en) | Thiazine dye system acidic copper electroplating solution and electroplating method | |
| CN113737267B (en) | Electrolyte plasma polishing electrolyte of nickel-based superalloy and polishing method thereof | |
| CN103681952A (en) | A preparation technique for spacecraft-used molybdenum/platinum/silver/ layered metal matrix composite materials | |
| Yao et al. | Effects of ceramic coating by micro-plasma oxidation on the corrosion resistance of Ti–6Al–4V alloy | |
| Fang et al. | Determination of the composition of viscous liquid film on electropolishing copper surface by XPS and AES | |
| CN105734534A (en) | Preparation method of coating alloy for metal connectors of SOFCs | |
| CN105316719A (en) | Electroplate liquid and electroplate method for cyanide-free gold plating of thallium-contained sulfite | |
| US3627650A (en) | Method for producing a chromium-tungsten coating on tungsten for protection against oxidation at elevated temperatures | |
| Feng et al. | Effect of Na4P2O7· 10H2O as complexing agent on deposition behavior and property of electroless Ni-P coating on ZK61M magnesium alloy | |
| De Rose et al. | Adhesion improvement for solder interconnection of wet chemically coated aluminum surfaces | |
| Liu et al. | Electroless Nickel Plating and Process Simulation for Surface Treatment | |
| Wang et al. | Preparation and characterization of a bilayer Cr-C/Ni-P coating on aluminum 5052 as bipolar plates | |
| Guo et al. | A study on preparation of ultra-thin localized Au coating by laser-induced electrodeposition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101208 Termination date: 20111105 |