CN101273463A - Process for producing electrode wire for solar battery - Google Patents
Process for producing electrode wire for solar battery Download PDFInfo
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- CN101273463A CN101273463A CNA200680035619XA CN200680035619A CN101273463A CN 101273463 A CN101273463 A CN 101273463A CN A200680035619X A CNA200680035619X A CN A200680035619XA CN 200680035619 A CN200680035619 A CN 200680035619A CN 101273463 A CN101273463 A CN 101273463A
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- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 80
- 238000007747 plating Methods 0.000 claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims description 76
- 230000004927 fusion Effects 0.000 claims description 60
- 239000010410 layer Substances 0.000 claims description 47
- 229910052802 copper Inorganic materials 0.000 claims description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 44
- 239000012530 fluid Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 14
- 239000002344 surface layer Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 9
- 239000010944 silver (metal) Substances 0.000 claims description 9
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 6
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 4
- 239000010946 fine silver Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 36
- 239000004065 semiconductor Substances 0.000 abstract description 24
- 238000000137 annealing Methods 0.000 abstract description 12
- 230000008646 thermal stress Effects 0.000 abstract description 9
- 229910000679 solder Inorganic materials 0.000 abstract description 7
- 238000007654 immersion Methods 0.000 abstract 1
- 239000011162 core material Substances 0.000 description 107
- 238000003466 welding Methods 0.000 description 31
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- 229910045601 alloy Inorganic materials 0.000 description 23
- 239000002356 single layer Substances 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
To provide a process for producing an electrode wire for a solar battery that can easily produce an electrode wire for a solar battery, which can easily be plastically deformed by thermal stress produced in a semiconductor substrate to prevent damage caused by thermal stress, without providing a softening annealing step. [MEANS FOR SOLVING PROBLEMS] A process for producing an electrode wire, comprising a core fabrication step of fabricating a material for a core into a strip-shaped core (2) and a molten solder plating step of immersing the core (2) in a molten solder bath and pulling up the core (2) to form molten solder plating layers(3A) and (3B) on the surface of the core (2). In the molten solder plating step, the temperature of the molten solder bath is brought to 250 C or above and 380 C or below, the core immersion time is 6 to 10 sec when the bath temperature is 250 C or above and below 280 C; is 3 to 10 sec when the bath temperature is 280 C or above and 350 C or below; or is 3 to 5 sec when the bath temperature is above 350 C and 380 C or below.
Description
Technical field
The present invention relates to use the manufacture method of using the electrode wire of lead-in wire as the connection of solar cell.
Background technology
As shown in Figure 3, solar cell comprises the semiconductor substrate 11 that formed by the Si semiconductor with PN junction, the surface electrode 12 of a plurality of wire of be arrangeding in parallel with the surface of above-mentioned semiconductor substrate 11 and the connection that is connected with above-mentioned a plurality of surface electrodes 12 be with lead-in wire 13.Above-mentioned connection is welded in the mode of intersecting with above-mentioned a plurality of surface electrodes 12 with lead-in wire 13 adheres on the scolder band of formation.Usually, for the electromotive force that obtains expecting a plurality of solar cells are connected in series and are used.Being connected in series of solar cell carried out in the following manner, on the surface electrode of a solar cell, be welded to connect a surface (lower surface), another surface (upper surface) be welded on the backplate with big zone of solar cell of adjacency with lead-in wire.
In the prior art, use to above-mentioned connection and comprise core with the electrode wire of lead-in wire 13 and in the fusion plating weldering (solder plating) of its surperficial lamination layer, this core is that the copper cash to the circular cross-section that is formed by tough pitch copper (tough-pitch copper) rolls, and is that the conquassation copper cash of band plate-like forms by conquassation.Above-mentioned fusion plating layer forms by above-mentioned conquassation copper cash being carried out fusion plating weldering.Fusion plating weldering be by pickling etc. the surface of conquassation copper cash is cleaned after, this conquassation copper cash is implemented by the fusion weld feed liquid.
When being welded on above-mentioned electrode wire on the semiconductor substrate, heating-up temperature is strictly controlled near the low temperature of fusing point of welding material.Its reason is, and is because form the copper and the semi-conducting material that forms semiconductor substrate of the core of electrode wire, for example different with the coefficient of thermal expansion of silicon.That is, so that cause the as far as possible little mode of thermal stress that cracks on the semiconductor substrate of high price, welding electrode wire rod at low temperatures.
Used thickness is the above-mentioned semiconductor substrate about 300 μ m in the prior art, but in recent years, in order to reduce cost, has the tendency of thin-walled property, brings into use the semiconductor substrate about 250 μ m recently.Therefore, when during as the electrode wire of core, on semiconductor substrate, being easy to generate the problem of crackle when existing in welding with existing conquassation lead.In order to prevent such crackle, bring into use in recent years with the less conductive material of the thermal expansion difference of semiconductive material substrate as core.As such material, for example can enumerate record in the Japanese kokai publication sho 60-15937 communique (patent documentation 1), in that (represent composition: the two sides lamination in the intermediate layer that Fe-36%Ni) forms has also incorporate clad material of copper layer by invar (Inver) alloy as the alloy of Fe, Ni.Low heat expansion alloy as forming above-mentioned intermediate layer except that above-mentioned invar alloy, can also use section's watt (Kovar) (registered trade mark) alloy of Fe-Ni-Co alloy.
Patent documentation 1: Japanese kokai publication sho 60-15937 communique
Summary of the invention
With the electrode wire (be also referred to as " covering electrode wire ") of above-mentioned patent documentation 1 disclosed clad material as core, because can reduce the thermal stress that produces really on semiconductor substrate but alloy materials such as the higher Fe-Ni alloy of specific insulation, Fe-Ni-Co alloy form the intermediate layer, average resistance uprises, the problem of the generating efficiency step-down of solar cell so exist.
Therefore, present inventors have designed a kind of electrode wire, when welding this electrode wire on semiconductor substrate, in the process of setting of fusion welding, this electrode wire easily produces plastic deformation according to the thermal stress that produces on substrate, thereby prevents, suppresses the damage of semiconductor substrate.This electrode wire is for being below the 2.3 μ Ω cm with specific insulation and endurance is the electrode wire of the core of metal material more than the 19.6MPa, below the 85MPa or the clad material band plate-like that forms electrode wire.
When making such electrode wire, in the process of making core, on core, produce work hardening.Therefore, think be necessary with processing before the core the core raw material or heating furnaces such as shaft-type furnace, carry out softening annealing fully from the core that the core raw material are processed as band plate-like.But, in the manufacturing process that comprises such softening annealing operation, exist productivity poor and cause the high problem of manufacturing cost.
The present invention finishes in view of the above problems, it is a kind of on semiconductor substrate during the welding electrode wire rod that purpose is to provide, according to the thermal stress that on semiconductor substrate, produces plastic deformation easily, can prevent the manufacture method of electrode wire for solar battery of the damage of the semiconductor substrate that causes by the thermal stress that on semiconductor substrate, produces, utilize this method, the softening annealing operation is not set promptly can easily makes.
The manufacture method of electrode wire for solar battery of the present invention comprises: processing core raw material, the core manufacturing procedure of the core of manufacturing band plate-like; Mention after being immersed in the fusion weld feed liquid with the core that will be processed into band plate-like, on the surface of above-mentioned core, form the fusion plating welder preface of fusion plating layer.Above-mentioned core raw material are the Cu alloy, fine silver of principal component by fine copper or with Cu or are that the Ag alloy of principal component forms with Ag.In addition, in above-mentioned fusion plating welder preface, the use fluid temperature is the fusion weld feed liquid more than 250 ℃, below 380 ℃, the dip time of above-mentioned core at fluid temperature is more than 250 ℃, be 6～10 seconds during 280 ℃ of less thaies, at fluid temperature is to be 3～10 seconds more than 280 ℃, below 350 ℃ the time, surpasses 350 ℃ but be to be 3～5 seconds below 380 ℃ the time at fluid temperature.As above-mentioned fine copper, preferred oxygen is the following anaerobic fine copper of 20ppm.In the present invention, above-mentioned core and electrode wire, irrelevant with the length of its length, not only comprise core (core) or electrode wire (one-time electrode wire rod) that length is long, also comprise the core (secondary core) or the electrode wire (second electrode wire rod) that they are cut to suitable length.
Manufacturing method according to the invention, using fluid temperature is the fusion weld feed liquid of the high temperature more than 250 ℃, below 380 ℃, the mode that fully reduces with the endurance that makes core according to fluid temperature is set the dip time of core, therefore, heat can effectively utilize the heat effect of fusion welding from being passed to core fast with fusion welding that core directly contacts.As a result, can make the fusion plating weldering processing itself that core is implemented promptly have the effect of softening annealing.Therefore, even omit softening annealing operation to the core before core raw material or the electroplating processes, also can make the endurance of the core after the electroplating processes is below the 85MPa.Certainly, can make its specific insulation according to the prescribed material that forms core is below the 2.3 μ Ω cm.Thereby, electrode wire for solar battery according to the present invention's manufacturing, in the time of on being welded on semiconductor substrate, in the process of setting of scolder according to the thermal stress that results from semiconductor substrate and automatically plastic deformation can reduce or eliminate the thermal stress that results from semiconductor substrate.Therefore, be difficult on semiconductor substrate, crack.In addition, because specific insulation is below the 2.3 μ Ω cm, so excellent electric conductivity, generating efficiency is also excellent.
In addition, above-mentioned core manufacturing procedure is to use tabular clad material as the core raw material, and it is cut, and makes the operation of the core of band plate-like.In this case, as above-mentioned clad material, use to have the intermediate layer that forms as the Al alloy of main component by fine aluminium or with Al and at the first surface layer that forms as the Cu alloy of main component by fine copper or with Cu of its two sides superimposed layer and the material of second surface layer.As above-mentioned fine copper, preferred oxygen is the following anaerobic fine copper of 20ppm.
When using above-mentioned clad material, preferably above-mentioned first, second superficial layer is formed identical thickness with same material as the core raw material.Thus, the thermal deformation of the electrode wire in the time of can preventing to weld can further improve welding operation.In addition, the integral thickness of the relative clad material in preferred above-mentioned intermediate layer is more than 10%, below 50%.Be difficult to guarantee above-mentioned endurance as 10% of less than, when surpassing 50%, be difficult to guarantee above-mentioned specific insulation.
As mentioned above, manufacture method according to electrode wire for solar battery of the present invention, because the temperature according to fusion welding is flooded official hour with core, so heat can effectively be utilized the heat effect of fusion welding from being passed to core fast with fusion welding that core directly contacts.As a result, the fusion plating weldering processing itself that core is implemented reaches the effect of softening annealing, even omit the softening annealing before the electroplating processes, the endurance of the core after the electroplating processes is reduced fully.
Description of drawings
Fig. 1 is the cross-sectional view of first execution mode (single-layer electrodes wire rod) of electrode wire constructed in accordance.
Fig. 2 is the cross-sectional view of second execution mode (covering electrode wire) of electrode wire constructed in accordance.
Fig. 3 has the approximate three-dimensional map that connects with the solar cell of lead-in wire (electrode wire).
The explanation of symbol
1, the 1A electrode wire
2, the 2A core
3A, 3B fusion plating layer
4 intermediate layers
5A, 5B copper layer (first surface layer, second surface layer)
Embodiment
At first, the execution mode of the electrode wire made from reference to the description of drawings manufacturing method according to the invention.
Fig. 1 represents the single-layer electrodes wire rod 1 of first execution mode, and this single-layer electrodes wire rod 1 has the core 2 of band plate-like and plates layer 3A, 3B on the surface of this core 2 and the fusion of back side superimposed layer formation.Above-mentioned core 2 is below the 2.3 μ Ω cm by specific insulation and endurance is that low endurance metal more than the 19.6MPa, below the 85MPa forms.In addition, when electroplating processes,, in Fig. 1, omit record though on the side of above-mentioned core 2, also be formed with fusion plating layer inevitably.The expression other execution modes described later figure in too with its omission.
Metal material as forming above-mentioned core 2 can use conductivity, good copper material, the silver-colored material of weldability.Particularly,, can use fine copper, can use the copper alloy as main component in addition, for example contain Cu-Ni alloy, Cu-Mn alloy, the Cu-Ag alloy of the above Cu of above, the preferred 95mass% of 90mass% with Cu as copper material.In addition,, can use fine silver, can use the Ag alloy as main component in addition, for example contain the Ag-Cu alloy of the above Ag of above, the preferred 95mass% of 90mass% with Ag as silver-colored material.Particularly, from the viewpoint of material cost, preferably use fine copper.The purity of copper is high more good more, is preferably more than the 99.9mass%, or this above material.Because in impurity, the oxygen of trace promptly has the effect that improves endurance, so oxygen is few more good more, the anaerobic fine copper of oxygen amount below 20ppm such as oxygen-free copper (OFHC), vacuum melting copper are more suitable.
Fig. 2 represents the covering electrode wire 1A of second execution mode, and this covering electrode wire 1A has the core 2A of the band plate-like that is formed by clad material and fusion plating layer 3A, the 3B that forms at surface and the back side superimposed layer of this core 2A.Above-mentioned core 2A has the intermediate layer 4 that is formed by aluminium and the first surface layer 5A that is formed by the copper material lamination on its two sides, second surface layer 5B.The mean value that above-mentioned core 2A is adjusted to specific insulation be following and mean value endurance of 2.3 μ Ω cm be 19.6MPa above, below the 85MPa.
As above-mentioned aluminium, preferred Al amount be above about 99.0mass%, to be more preferably the Al amount be that above fine aluminium of 99.9mass% or Al amount are the above aluminium alloy of 98mass%.As above-mentioned Al alloy, for example can use JIS 1050,1060,1085,1080,1070,1N99,1N90.On the other hand,, can use fine copper, can use the copper alloy as main component in addition, for example contain the Cu-Ni alloy, Cu-Mn alloy, the Cu-Ag alloy that more than the 90mass%, preferably contain the above Cu of 95mass% with Cu as above-mentioned copper material.About fine copper, the preferred higher copper of purity, especially the oxygen amount is that the following anaerobic fine copper of 20ppm is more suitable.
The thickness in above-mentioned intermediate layer 4 is preferably set to more than 10%, below 50% of thickness of the integral body of core 2A.This is that average specific insulation surpasses 2.3 μ Ω cm when surpassing 50% on the other hand because the average endurance of clad material surpasses 85MPa when less than 10%.In addition, preferably the thickness of first, second superficial layer 5A, 5B is identical.By being same thickness, when welding, can prevent electrode wire generation thermal deformation.
Above-mentioned fusion plating layer 3A, 3B are that welding material about 130～300 ℃ forms by fusing point.As such welding material, for example can enumerate Sn-Pb alloy, Sn-(0.5～5mass%) Ag alloy, Sn-(0.5～5mass%) Ag-(0.3～1.0mass%) Cu alloy, Sn-(0.3～1.0mass%) Cu alloy, Sn-(1.0～5.0mass%) Ag-(5～8mass%) In alloys, Sn-(1.0～5.0mass%) Ag-(40～50mass%) Bi alloys, Sn-(40～50mass%) Bi alloys, Sn-(1.0～5.0mass%) Ag-(40～50mass%) Bi-(5～8mass%) In alloys.Because Pb is harmful and may pollute natural environment, so from the welding material of the Sn-Ag alloy of the preferred no Pb of antipollution viewpoint, Sn-Ag-Cu alloy, Sn-Cu alloy, Sn-Ag-In alloy, Sn-Ag-Bi alloy etc.In addition, in above-mentioned each welding material, in order to prevent the oxidation of fusion welding, add one or more the Ge of Gd, several～tens ppm of Ga, several～tens ppm of P, several～tens ppm that can be from about 50～200ppm.
Then, the manufacture method to the electrode wire of above-mentioned execution mode describes.
The core 2 of above-mentioned single-layer electrodes wire rod 1 can use the wire rod to circular cross-section to roll and the two sides is processed into tabular surface and the band plate spare that forms, or by the calendering slab, the individual layer calendering plate of thickness of slab attenuation is cut the band plate spare of making.Full reduction ratio when the wire rod (annealed material) of circular cross-section is depressed into the core of band plate-like is generally more than 60%.The square sectional material of the area that this full reduction ratio supposition equates with the sectional area of circular wire rod is that the initial material before depressing calculates.The wire rod of above-mentioned circular cross-section, individual layer calendering plate all constitute the core raw material of single-layer electrodes wire rod.Under the raw-material situation, when being processed into core, the core raw material on core, produce work hardening as core at the wire rod that adopts above-mentioned circular cross-section.In addition, adopting individual layer calendering plate under the raw-material situation,, also to produce work hardening so cut the core that forms thus because itself there is work hardening in the core raw material as core.Follow the work hardening of core of cutting slighter than raw-material work hardening.
On the other hand, the core of above-mentioned covering electrode wire is by being made to the cladding sheet cutting with same cross-sectional structure.Because cladding sheet does not carry out softening annealing, moderately there is work hardening, so by cutting, can not produce burr (バ リ), severing easily is a plurality of band plate spares, i.e. core.Above-mentioned cladding sheet constitutes the core raw material of covering electrode wire.
Overlap the aluminium sheet (annealed material), the copper coin (annealed material) that constitute each layer, should overlap material then and carry out cold weld or warm crimping, can easily make above-mentioned cladding sheet thus by a pair of depress roller.Further, the clad material of crimping is implemented pressure-sizing prolong, can carry out the thickness of slab adjustment in the mode of the target thickness of slab (being generally about 100～300 μ m) that becomes core.The reduction ratio that is used for the initial calendering of the above-mentioned coincidence material of crimping is generally more than 60%, is generally more than 60% to the full reduction ratio that becomes till the raw-material clad material of core from overlapping material, is preferably more than 75%, more preferably more than 85%.
The band plate spare that is made into from the core raw material is core (core) in the above described manner, does not implement softening annealing, directly carries out fusion plating weldering and handles.On above-mentioned core, handle the second electrode wire rod that the electrode wire (one-time electrode wire rod) that is formed with fusion plating layer is cut to suitable length usually, it is welded on the semiconductor substrate of used for solar batteries by fusion plating weldering.In the present invention, because the double as softening annealing is handled in fusion plating weldering, so there is no need before electroplating processes, to be provided with the softening annealing operation.
In fusion plating weldering was handled, electroplating temperature was that the temperature (fluid temperature) of fusion weld feed liquid is set at more than 250 ℃, below 380 ℃, is preferably the high temperature of ratio prior art more than 280 ℃, below 350 ℃.In addition, core is to the dip time of fusion weld feed liquid, and at fluid temperature be more than 250 ℃, be 6～10 seconds during 280 ℃ of less thaies, be to be 3～10 seconds more than 280 ℃, below 350 ℃ the time at fluid temperature, surpassing 350 ℃ but be to be 3～5 seconds below 380 ℃ the time.In each temperature range of fluid temperature, when dip time is prescribed a time limit less than the following of this dip time, core softening insufficient, on the other hand, when surpassing going up in limited time of this dip time, because Cu atom, Ag atom spread to electroplate liquid from the core surface, so the amount of the Cu that dissolves in the fusion welding of electroplate liquid, Ag increases.In such fusion welding that has changed was formed, the fusing point of scolder rose, and the welding temperature to semiconductor substrate also rises thereupon.Therefore, the welding operation variation of electrode wire.As mentioned above, when the amount of the Cu in the fusion welding, Ag increases, must adjust it and form, so be difficult to carry out stable operation.In addition, when fluid temperature surpassed 380 ℃, the diffusion of Cu atom was remarkable, and the composition of fusion welding is changed significantly.In addition, formed by clad material under the situation of core, when surpassing 380 ℃, generating the Cu-Al intermetallic compound between intermediate layer and superficial layer, bond strength descends, and is easy to generate splitting.But, under the situation that the existing fusion plating weldering that only with formation fusion plating layer is purpose is handled, fluid temperature is set at higher about 30～40 ℃ than the fusing point of solder alloy, in order to suppress as much as possible from the diffusion of being plated material, below dip time is restricted to about 1 second.Therefore, the dip time of above-mentioned execution mode is compared long enough with common dip time.
Below, enumerate embodiment, electrode wire of the present invention is specifically described, but the present invention is not limited to this embodiment.
Making has the various clad materials intermediate layer, thickness of slab 160 μ m of all thickness.Above-mentioned clad material is made with following method: by aluminium sheet (material JIS 1N90, Al:99.90mass%, annealed material) or invar alloy plate (Fe-36.5mass%Ni, annealed material) on the raw-material two sides, the intermediate layer of Gou Chenging, overlaps by no-oxygen copper plate (Cu:99.97mass%, O:15ppm, thickness of slab 1.0mm, annealed material) the superficial layer raw material of Gou Chenging, the reduction ratio crimping with 70% should overlap material, further with 50～80% reduction ratio this crimping material was carried out pressure-sizing and prolonged.The ratio of the thickness in the intermediate layer of the full reduction ratio from the coincidence material to clad material of each clad material, relative integral thickness is as shown in table 1.On the other hand, the full reduction ratio with 22% rolls the copper coin (thickness of slab 2mm) of above-mentioned oxygen-free copper, makes the Cu monolayer material (copper coin) of thickness of slab 160 μ m.Above-mentioned each clad material and Cu monolayer material constitute the core raw material respectively.
Then, each clad material and Cu monolayer material are cut respectively, make a core of the band plate-like of width 2mm, cut off an above-mentioned core, make a plurality of cores (secondary core) of length 150mm.
Further, clean with acetone after the surface of each core, (scolder is formed: Sn-3.5mass%Ag at fusion plating welding fluid, fusing point: 220 ℃, fluid temperature: 320 ℃) flooded for 5 seconds in, mention rapidly afterwards, on the surface of core, form fusion plating layer thus.The thickness of the fusion weld bed of material of the electrode wire of Zhi Zuoing is on each face of core about average out to 40 μ m like this.
To remove attached to the dissolving of the fusion on core plating layer from each electrode wire by chemical treatment, the core after using this to remove, the method for press the JISZ2241 defined, in the tension test that length direction stretches, mensuration endurance.In addition, according to the method for JISH0505 defined, measure the specific insulation of core.In table 1, represent measurement result in the lump.In table 1, be a sample with the identical electrode wire of core raw material, additional thereon specimen coding is distinguished each sample according to specimen coding.
In addition, make each sample electrodes wire rod respectively with the scolder band butt of silicon for solar cell substrate (thickness 200 μ m), kept one minute down at 260 ℃, thus electrode wire is welded on the aforesaid substrate.Above-mentioned scolder band adheres to the surface that is formed on substrate to pass through the mode that is formed at a plurality of surface electrodes on the silicon substrate.After welding, check on silicon substrate, whether to have produced crackle.In table 1, represent its result in the lump.
As shown in Table 1, no matter be single-layer type, cladding type, the endurance of the core of the electrode wire of embodiment (sample No.1,2,4) is below the 85MPa, therefore, even the thin silicon substrate of 200 μ m does not crack yet.On the other hand, about specific insulation, than the covering electrode wire (sample No.5) of the comparative example that is formed the intermediate layer by invar alloy, the electrode wire of embodiment is lower, confirms to have good electrical conductivity.
[table 1]
| Sample No. | Core material structure, material | The intermediate layer thickness ratio | Full reduction ratio % | Core endurance MPa | Specific insulation μ Ω cm | Silicon substrate cracks nothing: zero has: * |
| *1 | Cu/Al/Cu | 20％ | 95 | 80 | 2.0 | ○ |
| *2 | Cu/Al/Cu | 33％ | 90 | 76 | 2.2 | ○ |
| 3 | Cu/Al/Cu | 60％ | 85 | 64 | 2.6 | ○ |
| *4 | The Cu monolayer material | - | 95 | 82 | 1.8 | ○ |
| 5 | Cu/ invar alloy/Cu | 33％ | 93 | 135 | 2.3 | ○ |
Have on (notes) sample No.
*Be embodiment, No.3, the 5th, comparative example
Prepare the aluminium sheet (thickness of slab 0.5mm) identical, the copper coin (thickness of slab 1.0mm) of oxygen-free copper, make the clad material that final thickness of slab is 200 μ m with the foregoing description 1 material.Above-mentioned clad material is the above-mentioned copper coin of two side superimposed at above-mentioned aluminium sheet, the reduction ratio with 65～75% carries out crimping to this coincidence material, further this crimping material is carried out pressure-sizing and prolongs and make and obtain.Full reduction ratio from the coincidence material to clad material is 92%.On the other hand, the copper coin (thickness of slab 2.5mm) of calendering oxygen-free copper, the Cu monolayer material (copper coin) of making thickness 200 μ m.Afterwards, cut these clad materials and Cu monolayer material respectively, make a core of the band plate-like of width 2mm.Above-mentioned clad material and Cu monolayer material constitute the core raw material respectively.
Then, after utilizing acetone to clean the surface of each core, impregnated in the fusion plating welding fluid (scolder is formed: Sn-3.5mass%Ag, fusing point: 220 ℃, capacity 20kg), and mention rapidly, on the surface of a core, form fusion plating layer.Expression fusion plating welding rod spare (fluid temperature, dip time) in table 2.When carrying out electroplating processes, check the variation of the scolder composition of an every 6000m of core.Because the Cu concentration of the fusion welding in electroplate liquid is 3% when following, the fusing point of welding material does not produce substantial poor, is judged to be in the qualified benchmark so the Cu concentration during scolder formed is situation below 3%.
Then, cut off a plurality of cores (secondary core) that each core village makes length 150mm,, make electrode wire by carry out fusion plating weldering with the plating condition shown in the table 2.And, similarly to Example 1, check the endurance of the core after each electrode wire is removed fusion plating layer.In addition, each electrode wire is welded on the silicon for solar cell substrate (thickness 200 μ m), checks on the silicon substrate after the welding, whether to crack.In table 2, represent these investigation results in the lump.In table 2, be a sample with the core raw material electrode wire identical with the plating condition, additional thereon specimen coding is distinguished each sample by specimen coding.
According to table 2 as can be known, the plating condition is 280～350 ℃ of fluid temperatures, 3～10 seconds embodiment of dip time (sample No.8～10,14～16,24～26), or at 380 ℃ of electrode wires that flood 3 seconds embodiment (sample No.11,27) down of fluid temperature, no matter be single-layer type or cladding type, the endurance of core is below the 85MPa, even the thin silicon substrate of 200 μ m is also confirmed not crack.In addition, sample No.13 shows, even be that if dip time grows to 10 seconds, then the endurance of core also can fully descend, and can not crack on silicon substrate under 250 ℃ of this lower situations electroplating fluid temperature.
[table 2]
| Sample No. | Core material structure | Scolder liquid temp ℃ | Dip time sec | Scolder is formed in the variation benchmark: outside zero benchmark: * | Core endurance MPa | Silicon substrate cracks nothing: zero has: * | |
| 1 | Clad material | 250 | 2 | ○ | 230 | × | Comparative example |
| 2 | ″ | 280 | 2 | ○ | 220 | × | ″ |
| 3 | ″ | 320 | 2 | ○ | 220 | × | ″ |
| 4 | ″ | 350 | 2 | ○ | 210 | × | ″ |
| 5 | ″ | 380 | 2 | ○ | 200 | × | ″ |
| 6 | ″ | 400 | 2 | × | 80 | ○ | ″ |
| 7 | ″ | 250 | 3 | ○ | 220 | × | ″ |
| 8 | ″ | 280 | 3 | ○ | 83 | ○ | Embodiment |
| 9 | ″ | 320 | 3 | ○ | 82 | ○ | ″ |
| 10 | ″ | 350 | 3 | ○ | 82 | ○ | ″ |
| 11 | ″ | 380 | 3 | ○ | 81 | ○ | ″ |
| 12 | ″ | 400 | 3 | × | 80 | ○ | Comparative example |
| 13 | ″ | 250 | 10 | ○ | 82 | ○ | Embodiment |
| 14 | ″ | 280 | 10 | ○ | 81 | ○ | ″ |
| 15 | ″ | 320 | 10 | ○ | 80 | ○ | ″ |
| 16 | ″ | 350 | 10 | ○ | 78 | ○ | ″ |
| 17 | ″ | 380 | 10 | × | 76 | ○ | Comparative example |
| 18 | ″ | 250 | 12 | × | 82 | ○ | ″ |
| 19 | ″ | 280 | 12 | × | 80 | ○ | ″ |
| 20 | ″ | 320 | 12 | × | 80 | ○ | ″ |
| 21 | ″ | 350 | 12 | × | 78 | ○ | ″ |
| 22 | ″ | 380 | 12 | × | 76 | ○ | ″ |
| 23 | The Cu monolayer material | 250 | 3 | ○ | 220 | × | ″ |
| 24 | ″ | 280 | 3 | ○ | 85 | ○ | Embodiment |
| 25 | ″ | 320 | 3 | ○ | 84 | ○ | ″ |
| 26 | ″ | 350 | 3 | ○ | 84 | ○ | ″ |
| 27 | ″ | 380 | 3 | ○ | 83 | ○ | ″ |
| 28 | ″ | 400 | 3 | × | 82 | ○ | Comparative example |
Claims (6)
1. the manufacture method of an electrode wire for solar battery, it is the manufacture method that is coated with the electrode wire for solar battery of fusion plating layer on the surface of core, it is characterized in that, comprising:
Processing core raw material, the core manufacturing procedure of making the core of band plate-like; Mention after impregnated in the fusion weld feed liquid with the core that will be processed into band plate-like, on the surface of described core, form the fusion plating welder preface of fusion plating layer, wherein
Described core raw material are the Cu alloy of principal component or fine silver by fine copper or with Cu or are that the Ag alloy of principal component constitutes with Ag,
In described fusion plating welder preface, the fluid temperature that makes the fusion weld feed liquid is more than 250 ℃, below 380 ℃, the dip time that makes described core at fluid temperature is more than 250 ℃, be 6～10 seconds under the situation of 280 ℃ of less thaies, at fluid temperature is to be 3～10 seconds under the situation more than 280 ℃, below 350 ℃, surpasses 350 ℃ but be to be 3～5 seconds under the situation below 380 ℃ at fluid temperature.
2. the manufacture method of electrode wire for solar battery as claimed in claim 1 is characterized in that:
Described core raw material are that anaerobic fine copper below the 20ppm constitutes by oxygen.
3. the manufacture method of an electrode wire for solar battery, it is the manufacture method that is coated with the electrode wire for solar battery of fusion plating layer on the surface of core, it is characterized in that, comprising:
Processing core raw material, the core manufacturing procedure of making the core of band plate-like; Mention after impregnated in the fusion weld feed liquid with the core that will be processed into band plate-like, on the surface of described core, form the fusion plating welder preface of fusion plating layer, wherein
Described core manufacturing procedure is by using tabular clad material to constitute as described core raw material, operation that this clad material is cut to make core, described clad material is the two sides in the intermediate layer that the Al alloy that is main component forms by pure Al or with Al, it is the first surface layer that forms of the Cu alloy of main component and the material of second surface layer that lamination has by pure Cu or with Cu
In described fusion plating welder preface, the fluid temperature that makes the fusion weld feed liquid is more than 250 ℃, below 380 ℃, the dip time that makes described core at fluid temperature is more than 250 ℃, be 6～10 seconds under the situation of 280 ℃ of less thaies, at fluid temperature is to be 3～10 seconds under the situation more than 280 ℃, below 350 ℃, surpasses 350 ℃ but be to be 3～5 seconds under the situation below 380 ℃ at fluid temperature.
4. the manufacture method of electrode wire for solar battery as claimed in claim 3 is characterized in that:
Described first surface layer and second surface layer are that anaerobic fine copper below the 20ppm constitutes by oxygen.
5. as the manufacture method of claim 3 or 4 described electrode wire for solar battery, it is characterized in that:
The material of described first surface layer and second surface layer is identical with thickness.
6. as the manufacture method of each the described electrode wire for solar battery in the claim 3～5, it is characterized in that:
In the described clad material, its integral thickness relatively, the thickness in intermediate layer is more than 10%, below 50%.
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| JP5073386B2 (en) * | 2007-07-05 | 2012-11-14 | 株式会社Ｎｅｏｍａｘマテリアル | ELECTRODE WIRE FOR SOLAR CELL, ITS SUBSTRATE, AND METHOD FOR PRODUCING SUBSTRATE |
| JP5446188B2 (en) * | 2008-09-17 | 2014-03-19 | 新日鐵住金株式会社 | Interconnector for semiconductor wire mounting and interconnector for solar cell |
| JP2010205792A (en) | 2009-02-27 | 2010-09-16 | Hitachi Cable Ltd | Solar cell lead, method of manufacturing same, and solar cell using same |
| JP2010283138A (en) * | 2009-06-04 | 2010-12-16 | Hitachi Cable Ltd | Solar cell lead wire and method of manufacturing the same, and solar cell using the same |
| JP5397809B2 (en) * | 2009-10-21 | 2014-01-22 | 日立金属株式会社 | Solar cell |
| JP5831034B2 (en) * | 2011-08-17 | 2015-12-09 | 日立金属株式会社 | Manufacturing method of molten solder plating stranded wire |
| JP2013258305A (en) * | 2012-06-13 | 2013-12-26 | Toyo Kohan Co Ltd | Interconnector for solar cell, and solar cell with interconnector |
| KR101739404B1 (en) * | 2015-08-07 | 2017-06-08 | 엘지전자 주식회사 | Solar cell panel |
| KR102612746B1 (en) * | 2021-11-24 | 2023-12-12 | 주식회사 제이에이치머티리얼즈 | Black bus bar and manufacturing method thereof |
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| JPS59204547A (en) * | 1983-05-10 | 1984-11-19 | 日立電線株式会社 | Aluminum-copper clad material |
| JPS62242345A (en) * | 1986-04-14 | 1987-10-22 | Hitachi Cable Ltd | High-strength lead wire for semiconductor and manufacture thereof |
| JPH0783083B2 (en) * | 1987-07-13 | 1995-09-06 | 株式会社日立製作所 | Ceramic board having metal pins and method of manufacturing the same |
| JPH02215008A (en) * | 1989-02-16 | 1990-08-28 | Hitachi Cable Ltd | Manufacture of composite flat rectangular wire |
| JPH04116904A (en) * | 1990-09-07 | 1992-04-17 | Sony Chem Corp | Coil |
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| JPH1121660A (en) * | 1997-07-03 | 1999-01-26 | Hitachi Cable Ltd | Connecting wire for solar battery |
| JP2000113730A (en) * | 1998-10-05 | 2000-04-21 | Totoku Electric Co Ltd | Compound lightweight ribbon wire, insulated compound lightweight ribbon wire, and manufacture thereof |
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| JP3879666B2 (en) * | 2002-12-24 | 2007-02-14 | 日立電線株式会社 | Lead wire for solar cell connection |
| JP2004204257A (en) * | 2002-12-24 | 2004-07-22 | Hitachi Cable Ltd | Solder-plated composite rectangular conductor |
| JP4565650B2 (en) * | 2003-05-22 | 2010-10-20 | 株式会社Ｎｅｏｍａｘマテリアル | ELECTRODE WIRE, ITS MANUFACTURING METHOD, AND SOLAR CELL HAVING CONNECTION LEAD FORMED BY THE ELECTRODE WIRE |
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| JP4986615B2 (en) * | 2004-05-21 | 2012-07-25 | 株式会社Ｎｅｏｍａｘマテリアル | Solar cell electrode wire |
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| WO2007037184A1 (en) | 2007-04-05 |
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