CN103026499B - Solar cell lead wire and preparation method thereof - Google Patents
Solar cell lead wire and preparation method thereof Download PDFInfo
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- CN103026499B CN103026499B CN201180036496.2A CN201180036496A CN103026499B CN 103026499 B CN103026499 B CN 103026499B CN 201180036496 A CN201180036496 A CN 201180036496A CN 103026499 B CN103026499 B CN 103026499B
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- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 110
- 239000010949 copper Substances 0.000 claims abstract description 110
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000013078 crystal Substances 0.000 claims abstract description 59
- 239000002245 particle Substances 0.000 claims abstract description 51
- 238000000137 annealing Methods 0.000 claims abstract description 31
- 238000005097 cold rolling Methods 0.000 claims abstract description 25
- 238000003490 calendering Methods 0.000 claims abstract description 16
- 238000005098 hot rolling Methods 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000005096 rolling process Methods 0.000 claims description 11
- 150000001879 copper Chemical class 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 29
- 229910052710 silicon Inorganic materials 0.000 description 29
- 239000010703 silicon Substances 0.000 description 29
- 239000000463 material Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 11
- 230000008646 thermal stress Effects 0.000 description 10
- 238000005520 cutting process Methods 0.000 description 9
- 238000003754 machining Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 230000008602 contraction Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000005482 strain hardening Methods 0.000 description 4
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000005382 thermal cycling Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- 229910020836 Sn-Ag Inorganic materials 0.000 description 1
- 229910020888 Sn-Cu Inorganic materials 0.000 description 1
- 229910020988 Sn—Ag Inorganic materials 0.000 description 1
- 229910019204 Sn—Cu Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
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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
- 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
- H01L31/0512—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 made of a particular material or composition of materials
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- 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
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- Power Engineering (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Non-Insulated Conductors (AREA)
- Photovoltaic Devices (AREA)
- Conductive Materials (AREA)
- Metal Rolling (AREA)
Abstract
The invention provides the preparation method of a kind of solar cell lead wire and solar cell lead wire, even if this solar cell lead wire does not also break under long-term thermal cycle, long service life.This solar cell lead wire is made up of oxygen-free copper or tough pitch copper, it is characterized in that, the crystal particle diameter of skin section is more than 10 μm, less than 60 μm, and the crystal particle diameter of skin section is less than 80% of internal layer crystal particle diameter.The preparation method of this solar cell lead wire, it is characterized in that, to oxygen-free copper or tough pitch copper ingot bar carry out cold rolling after, intermediate annealing or the hot rolling of 1 second ~ 1 hour is implemented at 300 ~ 700 DEG C, then be 1 ~ 15% carry out cold rolling or cold-drawn calendering once to roll working modulus, be processed into lead-in wire, then this lead-in wire carried out to the annealing of 1 second ~ 1 hour at 200 ~ 500 DEG C.
Description
Technical field
The present invention relates to a kind of solar cell lead wire and preparation method thereof, by multiple element (solar cell device, Solarcells, hereinafter referred to as element) in the solar module that forms, described solar cell lead wire is suitable for being used as the wiring material between Connection Element.
Background technology
In solar cells, by lead-in wire, multiple element be made up of silicon wafer is connected in series, sufficient electromotive force can be obtained.This lead-in wire generally uses zinc-plated copper strap wire, and this copper strap wire is engaged by scolding tin with silicon wafer.
But silicon wafer occupies most of cost ratio of solar cell, in recent years in order to reduce preparation cost, carry out the thin-walled property of silicon wafer.If but made silicon wafer thinning, its intensity will decline.Particularly as shown in table 1, because silicon wafer is different with the thermal coefficient of expansion of copper cash, when High-temperature cooling when therefore connecting from scolding tin is to room temperature, due to the difference of thermal shrinking quantity, silicon wafer may be caused to bend and damage.In addition, the thermal stress produced by thermal cycle when using solar cell, also likely makes silicon wafer damage.Therefore, the demand of the little lead-in wire of the thermal stress produced between silicon wafer is constantly increased.In order to solve this demand, there has been proposed following method, by annealing fine copper, making its crystal particle diameter coarsening, reducing yield strength and copper cash is surrendered, thus reducing the method (see patent documentation 1) of thermal stress.
(table 1)
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2008-140787
Summary of the invention
The technical problem to be solved in the present invention
But, if make crystal particle diameter coarsening, be then difficult to avoid the intensity of copper cash self to decline.If the copper cash that working strength declines connects silicon wafer, this copper cash will bear the load of thermal cycle round the clock of solar cell continuously, causes producing microcrack, reduction of service life in the copper line surface with coarse grain.
Therefore, require, when not reducing lead-in wire intensity, to reduce the thermal stress produced when scolding tin connects.
The technological means of technical solution problem
The present inventor etc., by carrying out suitable processing and suitable heat treatment to copper cash, making the crystal particle diameter miniaturization of copper line surface, successfully enhancing crack resistance, even if so far invented Long-Time Service, the solar cell lead wire of the long service life that surface also can not crack.
Solar cell lead wire of the present invention is made up of oxygen-free copper or tough pitch copper (toughpitchcopper), and the crystal particle diameter of its skin section is more than 10 μm, less than 60 μm, and the crystal particle diameter of skin section is less than 80% of internal layer crystal particle diameter.
The solar cell lead wire be made up of described oxygen-free copper or tough pitch copper, especially preferably the crystal particle diameter of its skin section is more than 10 μm, less than 40 μm, and the crystal particle diameter of skin section is less than 50% of internal layer portion crystal particle diameter.
Solar cell lead wire between the element of connection solar module of the present invention, is made up of oxygen-free copper or tough pitch copper, and the crystal particle diameter of its skin section is more than 10 μm, less than 60 μm, the total amount of described skin section thickness is 5% ~ 50% of copper strap wire thickness.
Solar cell lead wire between the element of connection solar module of the present invention, is made up of oxygen-free copper or tough pitch copper, preferred below the 150MPa of 0.2% yield strength of this lead-in wire.
The preparation method of solar cell lead wire of the present invention, it is characterized in that, to oxygen-free copper or tough pitch copper ingot bar implement cold rolling after, intermediate annealing or the hot rolling of 1 second ~ 1 hour is implemented at 300 ~ 700 DEG C, then be 1 ~ 15% carry out cold rolling or cold-drawn calendering once to roll the working modulus of (1 パ ス), be processed into lead-in wire, at 200 ~ 500 DEG C, then carry out the annealing of 1 second ~ 1 hour.
In the preparation method of described solar cell lead wire, working modulus of once rolling that is cold rolling or cold-drawn calendering is 1 ~ 15%, and preferably its working modulus total amount is more than 20%.
Invention effect
The lead-in wire be made up of oxygen-free copper or tough pitch copper of the present invention, because its skin section is fine-grain layer, therefore improve the tolerance of the thermal cycle load born during solar cell is used, not easily deterioration, there is the excellent effect extending solar cell useful life.
And, the lead-in wire that the present invention is made up of oxygen-free copper or tough pitch copper, because its internal layer portion remains coarse grain, the yield strength of (copper cash) entirety that therefore goes between is little, the thermal stress produced when being connected with silicon wafer scolding tin can be relaxed, the bending of wafer can be prevented or break, there is the excellent effect that can be easy to be interconnected solar cell.
Accompanying drawing explanation
Fig. 1 is the accompanying drawing about cutting preparation method.
Fig. 2 is the accompanying drawing about circle line preparation method.
Embodiment
Solar cell lead wire of the present invention, is made up of oxygen-free copper or tough pitch copper, and the crystal particle diameter of its skin section is more than 10 μm, less than 60 μm, and the crystal particle diameter of skin section is less than 80% of the crystal particle diameter of internal layer.
The present invention forms fine structure by making skin section, improves crack resistance, compared with existing product, extends the useful life to thermal cycle load.If the crystal particle diameter of skin section is less than 10 μm, yield strength increases, therefore not preferred, if in addition more than 0.6 μm, crack resistance is abundant not, not preferably.From improving the viewpoint balanced between crack resistance and suppression yield strength, particularly preferably the upper limit of skin section particle diameter is less than 40 μm.
In addition, different from making the size of crystal grain in internal layer portion in skin section.This difference in size is that the crystal particle diameter of skin section is less than 80% of internal layer crystal particle diameter.In the present invention, form fine skin section by crystal grain, improve crack resistance, compared with skin section, make internal layer portion form thick crystal grain layer, thus the yield strength suppressing copper cash (lead-in wire) overall increases.
The crystal particle diameter that invention provides for skin section is be less than internal layer crystal particle diameter 80%.If the crystal particle diameter of skin section exceedes 80% of internal layer portion crystal particle diameter, although the crack resistance of improve, yield strength too increases, and causes alleviating thermal stress when being connected with silicon wafer scolding tin, therefore not preferred.In addition, from improving crack resistance and suppressing the balance between yield strength to be considered, preferably making the crystal particle diameter of skin section be less than 50% of internal layer portion crystal particle diameter, by being set smaller than 50%, thermal stress when being connected with silicon wafer scolding tin can be alleviated well.
Solar cell lead wire of the present invention, the thickness total amount of its skin section is preferably 5% ~ 50% of lead-in wire (copper cash) thickness.
If the thickness of the skin section that crystal particle diameter is fine is blocked up, the yield strength of copper cash entirety increases, and easily produces and break when being connected with silicon wafer scolding tin.On the other hand, if skin section is excessively thin, the effect improving crack resistance diminishes, and breaks in the face of thermal cycle load can produce, and therefore preferably the thickness of skin section is overall 5% ~ 50%.
The solar cell lead wire be made up of oxygen-free copper or tough pitch copper of the present invention is that 0.2% yield strength of lead-in wire (copper cash) is preferably the solar cell lead wire of below 150MPa.
If yield strength is excessive, when being connected with silicon wafer scolding tin, the thermal stress produced by coefficient of thermal expansion differences, causes silicon wafer to damage.But, if yield strength value is little, then easily cause the plastic deformation to thermal stress, therefore can reduce the load that silicon wafer is born, can prevent from breaking.In order to not make silicon wafer damaged, the load that silicon wafer is born can be reduced, in order to prevent breaking, preferred below the 150MPa of 0.2% yield strength of material.
The preparation method of solar cell lead wire of the present invention, can prepare by following either method, thin plate is cut into proper width, forms flat; Or stretch or pressure rolling circle line, make it form round wire or flat.In addition, the shape as lead-in wire can be circle, rectangle etc., and without particular determination, but from the viewpoint of the scolding tin connectivity with element, comparatively ideal is flat.
Below, embodiments of the present invention are described.
The preparation method of copper strap wire used for solar batteries of the present invention, following method can be used to be prepared: make the ingot bar of oxygen-free copper or tough pitch copper form thin plate by calendering, then this thin plate is cut into proper width, make its method forming flat (hereinafter referred to as cutting preparation method); Or pressure rolling circle line, make its method being formed as flat (hereinafter referred to as circle line preparation method).In addition, make its method being formed as circle line (hereinafter, referred to as circle line preparation method) also can prepare the lead-in wire of round line with the calendering circle line that stretches, but its performance and lenticular wire are extremely similar, therefore in this manual, have only carried out following explanation to lenticular wire.
First, with reference to Fig. 1, cutting preparation method is described.
pretreatment procedure 1(homogenizes heat treatment step)
The ingot bar of oxygen-free copper or tough pitch copper is implemented to homogenize heat treatment.At 900 DEG C, such as keep the process that homogenizes of about 30 minutes.
pretreatment procedure 2(hot-rolled process)
Homogenize after process, carry out hot rolling, water-cooled, facing cut, make the copper coin that thickness of slab is about 10mm.
any operation of cold rolling process 1()
Be that the sheet material of about 10mm is cold-rolled to given size by thickness.This operation is any operation, can omit.
intermediate annealing operation (any operation)
When having carried out cold rolling process 1, with energized or batch type heat treatment, at 300 ~ 700 DEG C, carry out the intermediate annealing of 1 second ~ 1 hour.This operation is the subsidiary any operation of above-mentioned cold rolling process 1, can omit.
cold rolling process 2
To the sheet material of pretreatment procedure 2 or the sheet material through intermediate annealing operation have been carried out, further with the working modulus of once rolling be 1 ~ 15% carry out cold rolling, formed regulation thickness.In addition, through intermediate annealing operation when, the general working rate being annealed to cold rolling process 2 end from centre is desirably made to be more than 20%.
cutting processing
The copper flat board being calendered to specific thickness is carried out cutting processing, forms the flat wire shape of Rack.
final annealing operation
Finally, by energized or batch type heat treatment at 200 ~ 500 DEG C, the copper strap wire after cutting is carried out to the annealing of 1 second ~ 1 hour.
zinc-plated operation
As required, implement zinc-plated to the copper strap wire prepared.
Then, with reference to Fig. 2, circle line preparation method is described.
pretreatment procedure (preparation section of wire rod)
By belt wheel method (ベ Le ト & ホ イ ー Le method), two-tape method, up-drawing method, the oxygen-free copper of melting or tough pitch copper are made the wire rod (wire rod) that diameter is about 8mm, or, by hot extrusion method etc., ingot bar is made the wire rod (wire rod) that diameter is about 8mm.
any operation of cold working operation 1()
By obtained wire rod cold-drawn or be cold-rolled to given size.This operation is any operation, can omit.
intermediate annealing operation (any operation)
When carried out cold-drawn or cold rolling, by energized or batch type heat treatment, will the wire rod of given size be stretched to, at 300 ~ 700 DEG C, carry out the intermediate annealing of 1 second ~ 1 hour.This operation is the subsidiary any operation of above-mentioned cold working operation 1, can omit.
cold working operation 2
To the wire rod of pretreatment procedure be have passed through or have passed through the wire rod of intermediate annealing operation, carry out the cold-drawn calendering or cold rolling of 1 ~ 15%, make copper strap wire.In addition, when have passed through intermediate annealing operation, the general working rate being annealed to cold rolling process 2 end from centre is desirably made to be more than 20%.
final annealing operation
After being configured as flat type copper wire, by energized or batch type heat treatment, at 200 ~ 500 DEG C, carry out the annealing of 1 second ~ 1 hour.
zinc-plated operation
As required, implement zinc-plated to the copper strap wire made.
To the sheet material after having carried out intermediate annealing in above-mentioned cold rolling process 2 or wire rod (when there is no need below to distinguish them, being only called copper material), implement the cold rolling or cold-drawn calendering of 1 ~ 15%.If implement the light processing of 1 ~ 15% to copper material, then distortion concentrates on the surface of copper material, and its inside can not deform substantially, and the machining deformation produced in copper material is uneven.
Then in cold rolling process, carry out the final annealing process of 200 ~ 500 DEG C, the part that in skin section, machining deformation is many, because the nucleus of recrystallization is many, crystal particle diameter is fine, does not produce the interior layer of machining deformation, and its crystallographic grain is thick.
About copper strap wire, the copper strap wire that crystal particle diameter is fine, its crack resistance is high, but yield strength is also high.In the present invention, only the crystal particle diameter of skin section is fine, and the crystal grain in internal layer portion is thick, and therefore overall yield strength declines.Thus can alleviate when being connected with silicon wafer scolding tin, because of the stress that thermal contraction produces.
In addition, the copper strap wire that machining deformation is many, its recrystallization particle diameter becomes fine, can form the product of crack resistance excellence.
Final annealing is carried out at 200 ~ 500 DEG C.When annealing temperature is below 200 DEG C, fully can not carry out recrystallization, thus not preferred.In addition, if annealed with the high temperature of annealing temperature higher than 500 DEG C, be out of shape many top layers and extreme recrystallization grains coarsening phenomenon can occur, cause the crystal particle diameter of skin section thicker than internal layer portion, cause crack resistance to decline to a great extent, thus not preferred.
In addition, if the once calendering working modulus in cold rolling process 2 is more than 20%, then owing to processing deeply to inner, form relatively uniform structure, if but entirety is fine structure, yield strength increases, then, when carrying out scolding tin connection, generation is broken.In addition, if form overall thick structure, then the crack resistance of copper line surface declines, and therefore breaks in the face of long-term thermal cycle load can produce.
Once calendering working modulus in cold rolling process 2 is larger, and the region producing machining deformation is more, and the thickness of the skin section that crystal grain reduces is thickening.If the thickness on the top layer that this crystal grain is fine is excessively thin, then the raising effect of crack resistance will diminish, and breaks in the face of thermal cycle can produce.In addition, if the skin section thickness of fine grain size is blocked up, then the yield strength value of copper cash entirety increases, and can produce break when scolding tin connects.Even if when general working rate is identical, once rolls working modulus with increase and reduce to roll and process compared with number of times, it is desirable to reduce once to roll working modulus and increase calendering processing number of times.
As the material forming tin coating, Sn class solder can be used.As the second composition, exemplify Pb, In, Bi, Ag, Cu of more than interpolation 0.1 quality %, but in order to preventing pollution environment, use Sn-Ag, Sn-Ag-Cu, Sn-Cu, the Sn-Ag-In etc. without Pb ideally.
Embodiment
, based on embodiment, the present invention is described below, but the present invention is not limited thereto.The present invention, adopts oxygen-free copper and tough pitch copper two kinds of fine copper to implement, and is prepared with following two preparation conditions: obtained flat by cutting calendering copper coin and obtained flat by calendering dish line.
First, the preparation method being obtained flat by cutting is described.After casting oxygen-free copper, at 900 DEG C, carry out the process that homogenizes of 30 minutes, then carry out hot rolling.The final pressure rolling temperature making hot rolling is 500 ~ 800 DEG C, calendering rate is 30%.After hot rolling, carry out water-cooled, facing cut, obtain the copper coin that thickness of slab is 10mm.Then, be 20% carry out cold rolling with the working modulus of once rolling, at 300 ~ 700 DEG C, carry out intermediate annealing.Then carry out, repeatedly with cold rolling (operation 2) that the working modulus of once rolling is 1 ~ 15%, making thickness of slab be 0.2mm.After cold rolling, at 200 ~ 500 DEG C, carry out the heat treatment of 30 minutes.Then, be cut to the width of 2mm, and be impregnated in the solder bath of the Sn-3%Ag-0.5%Cu remained at 250 DEG C, implement about 20 μm zinc-plated, make and treat examination material (lead-in wire).
The method being prepared lenticular wire by dish line is then described.
To the dish line be made up of oxygen-free copper of the diameter 8mm obtained with belt wheel method, implement cold-drawn or be cold-rolled to specified diameter, then carrying out the intermediate annealing of 300 ~ 700 DEG C.Now with once roll be 20% working modulus carry out.Then repeatedly once roll be 1 ~ 15% cold working, formed thickness of slab be the lenticular wire of 0.2mm, at 200 ~ 500 DEG C, carry out the heat treatment of 30 minutes.And this lenticular wire be impregnated in the solder bath of the Sn-3%Ag-0.5%Cu remained at 250 DEG C, implement about 20 μm zinc-plated, be made and treat examination material (lead-in wire).
Respectively treat that examination material carries out following evaluation to what prepare.
(1) crystal particle diameter of skin section,
(2) crystal particle diameter of central part,
(3) ratio of the crystal particle diameter of top layer and internal layer,
(4) thickness proportion shared by top layer,
(5) 0.2% yield strengths,
(6) what cause because of thermal contraction when judging that scolding tin connects breaks,
(7) breaking of thermal cycling test is judged.
The mensuration of crystal particle diameter is the longitudinal section using intersection method to measure lenticular wire.
Measure the thickness of skin section at the center of lenticular wire Width, it accounts for the thickness proportion of ratio shared by skin section of integral thickness.
What following judgement scolding tin caused because of thermal contraction when connecting breaks, will when examination material scolding tin is connected on the silicon plate of 150mm × 150mm, thickness of slab 0.18mm, judges whether silicon wafer breaks with microscopic examination.
Breaking of following judgement thermal cycling test, carries out 10000 thermal cycling tests of 20 DEG C to 150 DEG C, judges to treat whether examination material surface cracks with microscopic examination.Judge that not producing the sample broken completely is designated as "○", produce the sample broken and be designated as "×", represent in table 2,3.
(table 2-1)
(table 2-2)
(table 2-3)
(table 2-4)
Table 2-1 ~ 4 represent by the lenticular wire of the obtained oxygen-free copper of cutting wait try material.The internal layer crystal particle diameter of embodiment 1 ~ 328 is thick, and therefore yield strength value is little, does not also break when being connected with silicon wafer scolding tin, and skin section crystal particle diameter is fine, therefore reveals tolerance to long thermal cycle load meter.Now, the working modulus of once rolling is larger, and machining deformation is more deep to inner, and therefore the thickness of skin section has the tendency thickened, the working modulus r(% once rolled) and skin depth ratio d(%) between, the basic relation setting up d=3r+3.In addition, embodiment 73 ~ 96,121 ~ 168,193 ~ 248,273 ~ 328, the general working rate after intermediate annealing is 20%, and the crystal particle diameter of skin section is also less than 40 μm, especially miniaturization.
On the contrary, because the final annealing temperature of comparative example 1 ~ 56 is too high, the crystal grain producing the many skin section of machining deformation, than internal layer more coarsening, therefore declines to the tolerance of thermal cycle load.In addition, because the heat treatment of comparative example 57 ~ 63 is insufficient, yield strength is large, when being therefore connected with silicon wafer scolding tin, because thermal contraction silicon wafer occurs damaged.
(table 3-1)
(table 3-2)
(table 3-3)
(table 3-4)
Table 3-1 ~ 4 represent by wire rod prepare the lenticular wire of oxygen-free copper wait try material.Embodiment 329 ~ 656, because the crystal particle diameter in internal layer portion is thick, therefore yield strength value is little, breaks when being connected with silicon wafer scolding tin, and due to the crystal particle diameter on top layer fine, therefore also tolerance is shown to Long Time Thermal circulating load.Now, because the working modulus of once rolling is larger, the more deep inside of machining deformation, therefore the thickness of skin section has thickening tendency, the working modulus r(% once rolled) and skin depth ratio d(%) between, the basic relation setting up d=3r+3.In addition, the general working rate of embodiment 401 ~ 424,449 ~ 496,521 ~ 576,601 ~ 656 after intermediate annealing is 20%, and the crystal particle diameter on top layer is also less than 40 μm, especially miniaturization.
On the contrary, because the final annealing temperature of comparative example 65 ~ 120 is too high, the crystal grain therefore producing the many skin section of machining deformation, than internal layer more coarsening, therefore declines to the tolerance of thermal cycle load.In addition, because the heat treatment of comparative example 121 ~ 127 is insufficient, therefore yield strength is large, because thermal contraction causes silicon wafer damaged when being connected with silicon wafer scolding tin.
As mentioned above, the lead-in wire be made up of oxygen-free copper or tough pitch copper of the present invention, because skin section is fine crystal layer, is therefore improved to the tolerance of the thermal cycle load born in solar cell use, not easily deterioration, has the excellent effect in the useful life extending solar cell.
And, the lead-in wire be made up of oxygen-free copper or tough pitch copper of the present invention, because its internal layer portion remains thick crystal grain, the yield strength of (copper cash) entirety that therefore goes between is little, the thermal stress produced when being connected with silicon wafer scolding tin can be alleviated, the bending of wafer can be prevented and break, there is the excellent effect being easy to be interconnected solar cell.
Claims (18)
1. a solar cell lead wire, be interconnected between its element for solar module, there is the copper cash be made up of oxygen-free copper or tough pitch copper, it is characterized in that, the average crystal particle diameter of the skin section of this copper cash is more than 10 μm and less than 60 μm, and the average crystal particle diameter of the skin section of described copper cash is less than 80% of described copper cash internal layer portion crystal particle diameter, and 0.2% yield strength of described copper cash is less than 150MPa.
2. solar cell lead wire according to claim 1, is characterized in that, also has tin coating in the periphery of described copper cash.
3. solar cell lead wire according to claim 2, is characterized in that, described tin coating adds the Sn class scolding tin that more than 0.1 quality % to be selected from Pb, In, Bi, Ag, Cu any one to be formed.
4. the solar cell lead wire according to Claims 2 or 3, is characterized in that, the thickness of described tin coating is 20 μm.
5. a solar cell lead wire, be interconnected between its element for solar module, there is the copper cash be made up of oxygen-free copper or tough pitch copper, it is characterized in that, the average crystal particle diameter of the skin section of this copper cash is more than 10 μm and less than 40 μm, and the average crystal particle diameter of the skin section of described copper cash is less than 50% of the internal layer portion crystal particle diameter of described copper cash.
6. solar cell lead wire according to claim 5, is characterized in that, 0.2% yield strength of described copper cash is below 150MPa.
7. the solar cell lead wire according to claim 5 or 6, is characterized in that, also has tin coating in the periphery of described copper cash.
8. solar cell lead wire according to claim 7, is characterized in that, described tin coating adds the Sn class scolding tin that more than 0.1 quality % to be selected from Pb, In, Bi, Ag, Cu any one to be formed.
9. solar cell lead wire according to claim 7, is characterized in that, the thickness of described tin coating is 20 μm.
10. solar cell lead wire according to claim 8, is characterized in that, the thickness of described tin coating is 20 μm.
11. 1 kinds of solar cell lead wires, be interconnected between its element for solar module, there is the copper cash be made up of oxygen-free copper or tough pitch copper, it is characterized in that, the average crystal particle diameter of the skin section of this copper cash is more than 10 μm and less than 60 μm, and the average crystal particle diameter of the skin section of described copper cash is less than 80% of described copper cash internal layer portion crystal particle diameter, and the thickness of the skin section of described copper cash is 5% ~ 50% of described copper cash integral thickness.
12. solar cell lead wires according to claim 11, is characterized in that, also have tin coating in the periphery of described copper cash.
13. solar cell lead wires according to claim 12, is characterized in that, described tin coating adds the Sn class scolding tin that more than 0.1 quality % to be selected from Pb, In, Bi, Ag, Cu any one to be formed.
14. solar cell lead wires according to claim 12, is characterized in that, the thickness of described tin coating is 20 μm.
15. solar cell lead wires according to claim 13, is characterized in that, the thickness of described tin coating is 20 μm.
The preparation method of 16. 1 kinds of solar cell lead wires, it is characterized in that, to the ingot bar of oxygen-free copper or tough pitch copper implement cold rolling after, intermediate annealing or the hot rolling of 1 second ~ 1 hour is implemented at 300 ~ 700 DEG C, then be 1 ~ 15% repeatedly carry out repeatedly cold rolling or cold-drawn calendering with the working modulus of once rolling, be processed into copper cash, and this copper cash implemented to the annealing of 1 second ~ 1 hour at 200 ~ 500 DEG C.
The preparation method of 17. solar cell lead wires as claimed in claim 16, is characterized in that, is that the working modulus summation of the cold rolling or cold-drawn calendering that 1 ~ 15% carries out is for more than 20% with the working modulus of once rolling.
The preparation method of 18. solar cell lead wires according to claim 16 or 17, it is characterized in that, zinc-plated operation is implemented in the periphery also with the copper cash after described annealing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2010192190 | 2010-08-30 | ||
| JP2010-192190 | 2010-08-30 | ||
| PCT/JP2011/069593 WO2012029772A1 (en) | 2010-08-30 | 2011-08-30 | Solar cell lead wire and method of manufacturing thereof |
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| CN103026499A CN103026499A (en) | 2013-04-03 |
| CN103026499B true CN103026499B (en) | 2016-01-20 |
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| JP (2) | JP5041455B2 (en) |
| KR (1) | KR101479431B1 (en) |
| CN (1) | CN103026499B (en) |
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| WO (1) | WO2012029772A1 (en) |
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| TWI495131B (en) * | 2010-08-30 | 2015-08-01 | Furukawa Electric Co Ltd | Cable for solar cell and method for manufacturing the same |
| JP5569330B2 (en) * | 2010-10-20 | 2014-08-13 | 日立金属株式会社 | Cable for music / video |
| JP6147077B2 (en) * | 2013-05-10 | 2017-06-14 | 古河電気工業株式会社 | Rolled copper foil and method for producing rolled copper foil |
| EP3057123B1 (en) * | 2013-10-07 | 2021-12-08 | Furukawa Electric Co., Ltd. | Joining structure comprising layers with different average crystal grain sizes for a semiconductor chip |
| CN104818443A (en) * | 2015-04-03 | 2015-08-05 | 北京科技大学 | Short-process efficient production method of copper-sliver alloy wire |
| KR101992001B1 (en) * | 2016-11-03 | 2019-06-24 | 엘에스전선 주식회사 | Solder composition for circular wire of solar cell module and cirfular wire for solar cell module having a solder plating layer formed from the same |
| JP6805789B2 (en) * | 2016-12-13 | 2020-12-23 | 三菱マテリアル株式会社 | Copper bar |
| CN107299245A (en) * | 2017-06-19 | 2017-10-27 | 河北德田半导体材料有限公司 | Semiconductor-sealing-purpose silver alloy wire and preparation method thereof |
| CN109935651B (en) * | 2019-04-08 | 2022-01-07 | 保定易通光伏科技股份有限公司 | Photovoltaic solder strip and manufacturing method thereof |
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| CN101572276A (en) * | 2004-08-13 | 2009-11-04 | 日立电线株式会社 | Flat conductor for solar battery and manufacturing method thereof and connection wire for solar battery |
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| JP2907415B2 (en) * | 1993-10-06 | 1999-06-21 | 日本製箔株式会社 | Manufacturing method of ultra-thin soft copper foil |
| JP2001262296A (en) * | 2000-03-17 | 2001-09-26 | Nippon Mining & Metals Co Ltd | Rolled copper foil and its manufacturing process |
| JP3731815B2 (en) * | 2001-05-31 | 2006-01-05 | 日鉱金属加工株式会社 | Phosphor bronze and heat treatment method thereof |
| JP2008140787A (en) | 2006-10-10 | 2008-06-19 | Hitachi Cable Ltd | Solder plating wire for solar cell and its manufacturing method |
| JP2008098315A (en) | 2006-10-11 | 2008-04-24 | Hitachi Cable Ltd | Solder plating wire for solar cell and its production process |
| JP4656100B2 (en) * | 2007-07-23 | 2011-03-23 | 日立電線株式会社 | Solder-plated wire for solar cell and manufacturing method thereof |
| JP4725688B2 (en) * | 2008-04-25 | 2011-07-13 | 三菱マテリアル株式会社 | Material for interconnector for solar cell and interconnector for solar cell |
| JP2010100890A (en) * | 2008-10-23 | 2010-05-06 | Hitachi Cable Ltd | Copper alloy strip for connector |
| TWI495131B (en) * | 2010-08-30 | 2015-08-01 | Furukawa Electric Co Ltd | Cable for solar cell and method for manufacturing the same |
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| CN101572276A (en) * | 2004-08-13 | 2009-11-04 | 日立电线株式会社 | Flat conductor for solar battery and manufacturing method thereof and connection wire for solar battery |
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| JP2013033957A (en) | 2013-02-14 |
| JP5041455B2 (en) | 2012-10-03 |
| WO2012029772A1 (en) | 2012-03-08 |
| CN103026499A (en) | 2013-04-03 |
| TW201222848A (en) | 2012-06-01 |
| JPWO2012029772A1 (en) | 2013-10-28 |
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| TWI495131B (en) | 2015-08-01 |
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