WO2015147213A1 - Conducteur, et interconnecteur de cellule solaire - Google Patents

Conducteur, et interconnecteur de cellule solaire Download PDF

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Publication number
WO2015147213A1
WO2015147213A1 PCT/JP2015/059475 JP2015059475W WO2015147213A1 WO 2015147213 A1 WO2015147213 A1 WO 2015147213A1 JP 2015059475 W JP2015059475 W JP 2015059475W WO 2015147213 A1 WO2015147213 A1 WO 2015147213A1
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Prior art keywords
interconnector
solder layer
solder
coating layer
thickness
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PCT/JP2015/059475
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English (en)
Japanese (ja)
Inventor
直哉 佐脇
木村　圭一
將元 田中
中塚　淳
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新日鉄住金マテリアルズ株式会社
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Priority to JP2016510506A priority Critical patent/JPWO2015147213A1/ja
Publication of WO2015147213A1 publication Critical patent/WO2015147213A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/19—Soldering, e.g. brazing, or unsoldering taking account of the properties of the materials to be soldered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0016—Brazing of electronic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/008—Soldering within a furnace
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/36—Electric or electronic devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/08—Non-ferrous metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/08—Non-ferrous metals or alloys
    • B23K2103/12—Copper or alloys thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/18—Dissimilar materials
    • 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

Definitions

  • the present invention relates to a conductor and a solar cell interconnector.
  • Solar power generation is a power generation method that converts infinite solar energy directly into electrical energy. For this reason, power generation using solar cells has been actively developed in recent years as a technology for greatly reducing energy problems, and the market has been greatly expanded.
  • a solar cell employing a single crystal silicon substrate or the like includes a plurality of substrates (hereinafter referred to as solar cells) having a size of about 5 to 6 inches square.
  • the solar cells are connected to each other by current collecting wiring.
  • a solar cell collects the electric energy produced
  • a melt liquid phase bonding using solder is often employed as a connection between the solar battery cell and the current collecting wiring.
  • This current collecting wiring is called a solar cell interconnector (hereinafter referred to as an interconnector), and is formed of a rectangular copper wire (tape copper wire) covered with solder. In this interconnector, the coated solder is melted (reflowed) and joined to the mating electrode on the solar battery cell.
  • connection using a film containing conductive particles (contact film) instead of solder or a paste containing conductive particles has been devised.
  • the interconnector used in this connection method does not require thick solder, but it is desirable that the copper wire be subjected to some surface treatment in consideration of bonding properties and corrosion resistance.
  • the interconnector 100 is mounted on the solar cell 101.
  • the interconnector 100 is mechanically and electrically joined to the electrode 104 formed on the surface of the solar battery cell 102 by solder, contact film, or conductive paste.
  • line mounting the form of joining and mounting with other materials in the longitudinal direction of the side surface of the metal.
  • the interconnectors 100a and 100b are line-mounted on the front surface 103 of the solar battery cell 102a and the back surface of the solar battery cell 102b disposed adjacent to the L direction of the solar battery cell 102a.
  • the front surface 103 refers to a surface facing in the positive direction of the D direction
  • the back surface refers to a surface facing in the negative direction of the D direction.
  • the interconnectors 100c and 100d are line-mounted on the front surface 103 of the solar battery cell 102b and the back surface of the solar battery cell 102c.
  • the solar cells 102a, 102b, and 102c are electrically connected in series by being connected by the interconnectors 100a, 100b, 100c, and 100d.
  • the interconnectors 100a and 100b are arranged at an appropriate interval in the W direction.
  • the current collecting interconnectors 100c and 100d are arranged at an appropriate interval in the W direction.
  • thermal stress is generated due to the difference between the thermal expansion coefficient of silicon forming the solar battery cell and the thermal expansion coefficient of copper forming the interconnector.
  • the linear expansion coefficients near room temperature are 16.6 ⁇ 10 ⁇ 6 (K ⁇ 1 ) for copper and 3 ⁇ 10 ⁇ 6 (K ⁇ 1 ) for silicon. If copper and silicon are bonded at 200 ° C., a length difference of about 0.26% occurs. Actually, thermal stress is generated between copper and silicon, which causes warpage of the solar battery cell. Thus, since the ratio of the thermal expansion coefficient of copper and the thermal expansion coefficient of silicon is as large as about 5 times, the solar cell may be deformed and damaged by the generated thermal stress.
  • a solar cell is an energy device that outputs generated power as a current
  • the cross-sectional area of the interconnector and the area of the connecting surface between the interconnector and the solar cell take into account the amount of current flowing through the interconnector. It is necessary to decide.
  • the substrate used for the solar battery cell has been made thinner. For example, a very thin silicon substrate such as a thickness of 180 ⁇ m has been used as a solar battery cell. For this reason, the damage of the solar battery cell due to thermal stress has become a bigger problem (Patent Document 1).
  • the solder coated on this type of interconnector is Sn-Pb alloy solder.
  • the solder should be lead-free from the environmental point of view, but Sn-Pb alloys are used in the majority of photovoltaic modules due to problems of bondability and melting point.
  • the melting point of Sn-37 wt% Pb solder which is a commonly used Sn-Pb alloy solder, is 183 ° C, and Sn-3.0 wt% Ag-0.5 wt% Cu (used most often in lead-free solder)
  • the melting point of SAC305) is 219 ° C.
  • the SAC 305 needs to be reflowed and bonded at a higher temperature, and as described above, the risk of damage to the solar battery cell is increased, so that there is a problem that the yield decreases.
  • SAC305 is also inferior in wettability (bondability) to electrodes compared to Sn—Pb solder.
  • Sn-Bi alloys and Sn-In alloys are eutectic Sn-57 wt% Bi and Sn-49 wt% In, with melting points as low as 139 ° C and 120 ° C, respectively. It is being studied as a connector covering material. Moreover, since the wettability with respect to an electrode is inferior, there are many cases where about 2% by weight of silver is added. However, the problem of bondability has not been eliminated, and the spread has not progressed.
  • solder layer does not directly contribute to the bonding to the electrodes, but it is desirable that the copper wire be subjected to some surface treatment in consideration of bonding properties and corrosion resistance, and the tin alloy may be coated. It is almost.
  • the conductive particles of the contact film or conductive paste As the conductive particles of the contact film or conductive paste, silver, nickel, Sn-Bi alloy is used, but the contact resistance between the conductive particles and the surface coating material of the interconnector needs to be low.
  • a solder material such as a Sn-Bi alloy has a higher contact resistance than noble metals such as gold and silver due to the effect of surface oxidation.
  • there is a type of conductive paste in which Sn—Bi particles are used as conductive particles, in which at least a part of Sn—Bi particles is melted and joined. Such a conductive paste has the same wettability problem as an interconnector that reflows and joins solder.
  • the present invention provides a conductor and a solar cell interconnector that can improve the wettability during reflow of a solder formed of a Sn-Bi-based alloy and improve the bondability to a contact film or a conductive paste.
  • the purpose is to do.
  • the conductor according to the present invention includes a core portion formed of copper, a solder layer formed on the surface of the core portion, and a coating layer formed on the surface of the solder layer, It is formed of a Sn-Bi alloy containing 16% by weight or more and 60% by weight or less of bismuth or a Sn-In alloy containing 10% by weight or more and 55% by weight or less of indium, and has a thickness of 0.3 ⁇ m or more and 40 ⁇ m or less.
  • the coating layer is made of silver, has a thickness of 0.05 ⁇ m or more and 0.5 ⁇ m or less, and a coverage of the coating layer with respect to the solder layer is 90 area% or more.
  • the solar cell interconnector according to the present invention is characterized by using the above-mentioned conductor.
  • a coating layer formed of silver and having a thickness of 0.05 ⁇ m or more and 0.5 ⁇ m or less wetting at the time of reflow of a solder formed of a Sn—Bi alloy or a Sn—In alloy
  • a solder formed of a Sn—Bi alloy or a Sn—In alloy it is possible to improve the bondability to contact films and conductive pastes.
  • An interconnector 10A as a conductor shown in FIG. 1 includes a tape-shaped core portion 12A formed of copper, and a solder layer formed of Sn—Bi alloy or Sn—In alloy on the surface of the core portion 12A. 14A and a coating layer 16A made of silver so as to cover the solder layer 14A.
  • the interconnector 10A according to the embodiment of the present invention can be applied to both a type in which the solder layer 14A is reflowed and joined and a type in which the solder layer 14A is joined with a contact film or a conductive paste.
  • the conductor is not limited to a tape shape, but may be a round wire shape.
  • An interconnector 10B shown in FIG. 2 with a reference numeral corresponding to FIG. 1 includes a round wire-shaped core portion 12B made of copper.
  • the interconnectors 10A and 10B are different only in shape, the common contents will be described for the interconnector 10A.
  • the interconnector 10A is a wire and is a rectangular wire macroscopically (the interconnector 10B is a round wire macroscopically).
  • a wide surface that is, a surface generally referred to as a tape surface
  • Other opposing surfaces that is, generally referred to as side surfaces
  • the thickness refers to the macroscopic length between the tape surfaces, that is, the maximum value
  • the width refers to the maximum value between the side surfaces.
  • the width direction is also referred to as the short direction.
  • the core portion 12A is formed of a metal mainly composed of copper. Since it is used as a conductive material, high conductivity is required, so the purity of copper is preferably 99.8% or more. JIS standards include oxygen-free copper (C1020), tough pitch copper (C1100), and phosphorus deoxidized copper (C1201, C1220, C1221). Further, the metal mainly composed of copper may contain inevitable impurities, and an alloy element may be added to improve mechanical properties and adhesion with a solder layer 14A described later. Furthermore, the core portion 12A is preferably in a sufficiently annealed state (O material in the JIS standard) so as to reduce the yield strength.
  • the core portion 12A generally has a thickness of 0.1 mm to 0.3 mm and a width of 1 mm to 3 mm.
  • the core portion 12B generally has a diameter in the range of 0.05 mm to 0.5 mm.
  • the core portion 12A contains inevitable impurities in copper and elements intentionally added to obtain additional effects.
  • examples of the latter include zinc, nickel, aluminum, calcium, silver, chromium, zirconium, tin, manganese, and rare earth elements in this embodiment, but are not limited thereto.
  • silver and aluminum are also conceivable as other options for the core 12A, but the cost is low for silver, the conductivity is high for aluminum, and the thermal expansion coefficient is closer to that of silicon. Copper is selected because it is easy to apply Sn-Bi alloy plating.
  • the core 12A may be a rectangular wire and the core 12B may be a round wire.
  • the core portion 12 ⁇ / b> A has a first surface 18 corresponding to the tape surface and a second surface 20 formed on the opposite side of the first surface 18.
  • the solder layer 14A is formed on at least one of the first surface 18 and the second surface 20 because the core portion 12A is a flat wire. In the case of this embodiment, it is formed on the entire circumference of the core portion 12 ⁇ / b> A including the first surface 18 and the second surface 20.
  • the solder layer 14B is formed on the entire circumference since the core portion 12B is a round wire.
  • the bismuth contained in the Sn-Bi based alloy constituting the solder layer 14A and the indium contained in the Sn-In based alloy are characterized in that the problem of toxicity is smaller than that of lead.
  • the bismuth concentration of the Sn—Bi alloy and the indium concentration of the Sn—In alloy in the solder layer 14A are 16% by weight to 60% by weight and 10% by weight to 55% by weight, respectively, in terms of melting point and bondability. Need to be.
  • the reason for limiting the concentration range for each alloy will be described.
  • the temperature of the liquidus becomes 215 ° C or higher, compared to 219 ° C for Sn-3.0% by weight Ag-0.5% by weight Cu for general non-lead solder.
  • the advantage is lost in that respect.
  • the bismuth concentration is less than 16% by weight, the superiority in terms of wettability and bondability is lost even for an interconnector in which silver is added to the solder layer.
  • the higher upper limit concentration of bismuth is desirable in terms of cost, but it should be 57% by weight or less, which is a eutectic composition, and 60% by weight or less even considering errors. If the concentration of bismuth exceeds 60% by weight, the liquidus increases and the wettability and mechanical properties as solder deteriorate.
  • the bismuth concentration is more preferably 36% by weight or more and 51% by weight or less. If it is 36% by weight, the liquidus temperature is 180 ° C. or lower, and the melting point is lower than that of eutectic solder (melting point 183 ° C.), which is more advantageous in terms of preventing cell damage due to thermal stress. On the other hand, if it exceeds 51% by weight, the embrittlement of the solder due to an increase in the bismuth concentration occurs, and the soundness of the joint with the electrode starts to deteriorate.
  • the indium concentration is less than 10% by weight, the temperature of the liquidus becomes 215 ° C or higher, which is the junction temperature point compared to 219 ° C for Sn-3.0% by weight Ag-0.5% by weight Cu for general lead-free solder.
  • the advantage is lost.
  • the concentration is less than the lower limit as described above, superiority is lost in terms of wettability and bondability with respect to an interconnector in which silver is added to the solder layer.
  • the upper limit concentration of indium needs to be 55% by weight or less in consideration of an error from the eutectic composition.
  • concentration of indium exceeds 55% by weight, the liquidus temperature rises, and wettability and mechanical properties as solder deteriorate.
  • the indium concentration is more preferably 28% by weight or more and 52% by weight or less. If the indium concentration is 28% by weight or more, the liquidus temperature is 180 ° C or less, which is a low melting point for eutectic solder (melting point 183 ° C), which is advantageous in preventing damage to solar cells due to thermal stress. Therefore, it is more preferable. Further, if the indium concentration exceeds 55 wt%, solder embrittlement occurs due to an increase in indium concentration, and the soundness of bonding with the electrode starts to deteriorate, so 55 wt% or less is preferable.
  • the solder layer 14A has a thickness of 0.3 ⁇ m or more and 40 ⁇ m or less.
  • the average thickness converted from the basis weight is used as the thickness of the solder layer 14A.
  • the difference between the weight of the core portion 12A before forming the solder layer 14A and the weight after forming the solder layer 14A, the density of the alloy constituting the solder layer 14A, and the solder layer 14A are formed. Calculate from the surface area of the site.
  • the thickness of the solder layer 14A is such that the solder layer 14A is entirely formed on the first surface 18 and the second surface 20. Unless otherwise specified, the thicknesses formed on the first surface 18 and the second surface 20 are used. In practice, as shown in FIG. 1, since the thickness is thick at the central portion in the width direction of the tape surface, the actual thickness of the solder layer 14A at the central portion is often larger than the average thickness converted from the basis weight. Since the core portion 12B is a round wire, the average thickness converted from the basis weight of the solder layer 14B is a value close to the actual thickness of the solder layer 14B.
  • the solder layer 14A may be thin, but a thickness of 0.3 ⁇ m or more is necessary to maintain the corrosion resistance.
  • the thickness of the solder layer 14A is less than 0.3 ⁇ m, the core portion 12A is exposed when a damage or a pinhole occurs during handling or joining on the solar battery cell. If it does so, a battery will be formed between copper which is a constituent element of coating layer 16A, and a constituent element of core part 12A, copper will corrode electrochemically, and copper oxide will be formed.
  • the solder layer 14A may be made of Sn-Bi or Sn-In alloy to which copper is added in an amount of 0.3 wt% to 0.7 wt%. Thereby, while melting
  • solder layer 14A may contain phosphorus added as an antioxidant on the surface of the solder hot dipping bath in the above alloy.
  • solder layer 14A of the present embodiment elements other than copper and phosphorus are not particularly excluded and may be added as necessary and may contain inevitable impurities.
  • silver is not particularly required to be added, but it is added in advance as long as the silver concentration in the Sn-Bi alloy layer or Sn-In alloy layer after reflow does not exceed 3 wt%. May be.
  • the covering layer 16A is made of silver.
  • Silver is a chemically stable metal compared to Sn—Bi alloys and Sn—In alloys, and prevents oxidation. Thereby, the coating layer 16A can extend the storage period (lifetime) of the interconnector 10A. Silver forming the coating layer 16A may contain inevitable impurities.
  • the wettability at the time of melting can be improved and the bonding property can be improved.
  • Silver has the effect of suppressing the oxidation of the surface of the solder layer 14A and locally lowering the melting point of the interface between the solder layer 14A and the coating layer 16A.
  • the electrode of the solar battery cell is formed of silver, but the silver is Sn-Bi-based on the entire surface of the solder layer 14A during reflow by being in close contact with the solder layer 14A as the coating layer 16A rather than the electrode.
  • the above effect can be obtained more reliably.
  • the bismuth concentration of the solder layer 14A is 16% by weight or more or the indium concentration is 10% by weight or more, there is a remarkable effect. Further, this effect is more remarkable than when the same amount of silver is added to the solder layer in advance because silver concentrates on the surface of the solder layer when the solder layer is melted by reflow.
  • the thickness of the coating layer 16A is 0.05 ⁇ m or more and 0.5 ⁇ m or less.
  • the weight per unit area is also used in this specification for the thickness of the coating layer 16A. When the thickness is within the above range, wettability can be improved.
  • the coating layer 16A is preferably thin from the viewpoint of cost, but when the thickness of the coating layer 16A is less than 0.05 ⁇ m, the above effect cannot be obtained sufficiently, so it is necessary that the thickness is 0.05 ⁇ m or more.
  • the coverage of the coating layer 16A with respect to the solder layer 14A is 90 area% or more, a good bonding state can be obtained even if the solder layer 14A is exposed on the surface. This is because, in the case where there is a part where silver is partially uncoated, if the coverage is 90 area% or more, the silver diffuses also in the uncoated part, and the effect of the coating layer 16A can be sufficiently obtained. . However, if the covering rate of the covering layer 16A is less than 90% by area, the above effect cannot be obtained sufficiently.
  • the ratio of the thickness of the solder layer 14A and the coating layer 16A is not particularly limited as long as it is within the above-mentioned thickness range, but the silver concentration when the coating layer 16A is completely dissolved in the solder layer 14A is 2% by weight. More preferably, the thickness ratio is as follows. With such a thickness ratio, not only the effect of the coating layer 16A can be obtained, but also the cost of the coating layer can be suppressed.
  • the interconnector 10A is such that, after the solder layer 14A is melted by reflow, the silver constituting the coating layer 16A is efficiently dissolved in the Sn—Bi, Sn—In alloy. It is possible to improve the thermal fatigue characteristics of the interface with the.
  • the coating layer 16A prevents oxidation of the surface, so that a good peel strength can be obtained. That is, the interconnector 10A can obtain high joint reliability. Further, since the contact resistance with the conductive particles can be reduced by preventing the oxidation of the surface, the interconnector 10A can improve the power generation efficiency of the solar cell. Furthermore, when Sn—Bi alloy is used as the conductive particles in the conductive paste, the coating layer 16A improves the wettability at the time of melting, similar to the interconnector 10A of the type that reflows the solder layer 14A. Bondability can be improved.
  • the above effect can be obtained if the coating layer 16A has a thickness of 0.05 ⁇ m to 0.5 ⁇ m and a coverage of 90 area% or more. It is done. Even if the thickness of the coating layer 16A is greater than 0.5 ⁇ m, it is considered that the effect is obtained, but from the viewpoint of cost, 0.5 ⁇ m is the upper limit.
  • the ratio of the solder layer 14A and the coating layer 16A is not particularly limited, and the effect of the present invention can be obtained as long as the thickness is within the above-described range. .
  • the tape surface on the side opposite to the surface to be joined with the electrode is different from the type that is connected by reflowing the solder.
  • the coating layer 16A remains without melting.
  • the reflectance of sunlight of the interconnector 10A on the light receiving side of the solar cell is higher than that of the interconnector 10A of the type that reflows the solder layer 14A. Further, the sunlight that reaches the interconnector 10A is reflected and does not reach the solar battery cell directly. The light reflected by the interconnector 10A is rereflected by the difference in refractive index at the glass or resin interface of the solar battery, and reaches the solar battery cell with a certain probability. Therefore, the interconnector 10A having a high reflectance can improve the power generation efficiency of the solar cell.
  • Silver is the metal with the highest reflectivity among metals.
  • the interconnector 10A according to the embodiment of the present invention can increase the reflectance of sunlight of the interconnector 10A by forming the coating layer 16A of 0.05 ⁇ m or more in thickness with silver.
  • the reflectance of silver is more than 20% higher than tin and bismuth.
  • the coating ratio of the coating layer 16A to the solder layer 14A is 90% by area or more, so that the reflectance of sunlight can be increased more reliably.
  • the coverage is less than 90 area%, the contact resistance with the conductive particles increases, and the effect of improving the reflectance is offset, so that the power generation efficiency cannot be sufficiently improved.
  • the core portion 12A is a flat wire, it can be formed by rolling the plate material to a predetermined thickness and appropriately performing slit processing. Since the core portion 12B is a round wire, it can be formed by swaging and drawing a round bar-shaped copper alloy. Since the core portion 12A thus formed has a high yield strength due to work hardening, it is desirable that the core portion 12A be recrystallized and softened by using heat in the step of forming the solder layer 14A described later.
  • a solder layer 14A is formed on the surface of the core 12A.
  • the solder layer 14A can be formed by hot dipping. In the hot dipping, the core portion 12A is continuously passed through the plating tank, and the surface of the core portion 12A is plated with Sn—Bi and Sn—In alloy.
  • the thickness of the solder layer 14A with respect to the core portion 12A and the interval between the core portions 12A in the width direction are determined by arranging a drawing die having a hole with an appropriate shape at the outlet where the core portion 12A exits from the surface of the molten plating solution.
  • Adjustment can be made by passing through a drawing die or by spraying an inert gas or the like immediately after plating from a nozzle called a wiping nozzle to blow off excess molten metal.
  • the solder layer 14A is not limited to the above hot dipping but may be formed by wet plating.
  • a coating layer 16A is formed on the solder layer 14A.
  • the coating layer 16A can be formed by wet plating such as electroplating or electroless plating, or dry plating such as sputtering or vapor deposition.
  • the coating layer 16A is generally cost-effective and generally formed by wet plating.
  • an oxygen-free copper plate JIS ⁇ C1020 1 / 2H material with a purity of 99.96 wt% or more and a thickness of 1.2 mm was cold-rolled to 0.2 mm, then slitted to a width of 1.5 mm, and a cross-section of 0.2 mm x 1.5 mm A tape-shaped core part was produced.
  • this core portion was passed through a hot dipping bath having various bath compositions, and a solder layer having a thickness of 15 ⁇ m or 20 ⁇ m on one side was formed on the surface of the core portion.
  • the hot-dip plating bath used to form the solder layer has a bismuth concentration of 10%, 15%, 16%, 36%, 51%, 57%, 60%, 63% by weight. 8 types of Sn-Bi alloy baths and 5 types of Sn-In alloy baths with indium concentrations of 10%, 28%, 40%, 52%, and 55% by weight were prepared. . Further, for the hot dip plating baths having bismuth concentrations of 10 wt%, 15 wt%, and 16 wt%, another hot dip plating bath to which silver was further added to 2 wt% was prepared.
  • the core portion fed out from the bobbin was heated to 600 ° C. and then passed through a tubular furnace in which N 2 -5% by volume H 2 gas was passed. Thereafter, the core was passed through the hot dipping bath without being exposed to the outside air and wound around a bobbin.
  • the thickness of the solder layer is set to 20 ⁇ m on one side by blowing argon gas from the wiping nozzle provided above the hot dipping bath to the core coming out from the liquid surface of the hot dipping bath and controlling the flow rate of the gas. Adjusted.
  • the temperature of the hot dipping bath was adjusted according to the concentration of bismuth and indium, and was set to a temperature obtained by adding 20 ° C. to the liquidus temperature of each hot dipping bath. When silver is added to the hot dip bath, the liquidus temperature decreases, but in this case as well, the hot dip bath temperature is defined by the bismuth concentration.
  • the composition of the plated solder layer was the same as the composition of the hot dipping bath used for forming the solder layer. The same was true for the examples produced later.
  • the table also shows the bismuth concentration of the solder layer.
  • a silver coating layer having a thickness of 0.05 ⁇ m to 0.5 ⁇ m and a coverage of 89 area% to 100 area% with respect to the solder layer was formed by electroplating.
  • the coverage was adjusted by controlling the current density and the line speed during electroplating. In order to improve the coverage, the current density may be decreased or the line speed may be decreased.
  • the coverage was measured by taking a photograph of the surface of the interconnector with an optical microscope at a magnification of 50 times in 5 fields or more, and dividing the area of the area where the coating layer was formed by image processing by the total surface area. . The measurement results are shown in the “Coverage” column.
  • solar cell strings were prepared for a total of 42 types of interconnectors including interconnectors not formed with a coating layer, and the bondability was examined.
  • Solar cell strings were produced using an automatic wiring device. This automatic wiring device reflows the solder to join the solar cells and the interconnector. First, an interconnector is placed on a solar cell on a preheated cell table and held down with a pin. Next, hot air is blown to melt the solder layer of the interconnector, thereby joining the solar cells and the interconnector. In this way, solar cell strings in which three solar cells were connected in series were produced.
  • the solar cell used is a polycrystalline silicon substrate having a size of 156 mm ⁇ 156 mm and a thickness of 200 ⁇ m.
  • An electrode to which the interconnector is joined is formed on each surface of the solar battery cell. Two electrodes are arranged in parallel on each surface. This electrode is made of silver and has a width of 2 mm.
  • the temperature at which the solder layer was reflowed and joined to the electrode was varied depending on the composition of the Sn-based alloy of the solder layer.
  • the cell table temperature was a temperature obtained by reducing the liquidus temperature of the solder layer by 40 ° C.
  • the hot air set temperature was a temperature obtained by adding 130 ° C. to the liquidus temperature of the solder layer.
  • the time for pressing with a pin was 3 seconds. The above condition is defined as condition 1.
  • Examples 1 to 22 all had a liquidus temperature of 214 ° C. or lower and a good bonding state. On the other hand, in Comparative Examples 3 to 11 and 14 to 20, the bonding state deteriorated. In Comparative Examples 1, 2, 12, and 13, the bonding state was good, but the liquid phase temperature was 215 ° C. or higher because the bismuth concentration was 15% by weight or less. There is no advantage in terms of bonding temperature.
  • the interconnector having a coating layer thickness of 0.3 ⁇ m was capable of sound joining in a range where the bismuth concentration was 51% by weight or less.
  • the higher the concentration the lower the bonding temperature. Therefore, the amount of strain due to the difference in the thermal expansion coefficient between the solar cells and the interconnector can be reduced.
  • the bismuth concentration exceeds 51% by weight, the solder becomes brittle, so that the soundness of the joint is deteriorated.
  • the upper limit of the bismuth concentration in this example was 60% by weight.
  • Comparative Examples 12 to 14 2% by weight of silver was added to the solder layer.
  • the concentration was the same as in Comparative Examples 12 to 14, and the basis weight of silver may be considered the same.
  • bonding was good while the bismuth concentration was low, but partial peeling occurred when the bismuth concentration was 16% by weight.
  • the reason why the bonding state of Example 1 having the same bismuth concentration was sound was that high concentration of silver was present at the bonding interface and efficiently contributed to solder wetting.
  • the coverage of the coating layer is 90 area% or more, it can be a macroscopically sound joined state or a sound joined state. It could be confirmed.
  • a tough pitch copper wire JIS C1100 1 / 2H material with a purity of 99.9% by weight or more and ⁇ 1.2 mm was rolled to produce a tape-shaped core having a cross section of 0.16 mm ⁇ 2.0 mm.
  • the tape surface is parallel and flat, but the side surface is curved.
  • this core portion was passed through a hot dipping bath having various bath compositions, and a solder layer having a thickness of 40 ⁇ m on one side was formed on the surface of the core portion.
  • the produced hot-dip plating bath has a bismuth concentration of 40% by weight, a copper concentration of 0.2% by weight, 0.3% by weight, 0.5% by weight, 0.7% by weight, 0.8% by weight, and the balance from Sn and inevitable impurities.
  • Sn-Bi-Cu hot dipping bath the concentration of indium is 30 wt%, the concentration of copper is 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.7 wt%, 0.8 wt%, the rest is Sn And a Sn—In—Cu hot dipping bath comprising inevitable impurities.
  • the hot dipping was performed in the same manner as in the first example.
  • the temperature of the hot dipping bath was 195 ° C. This temperature is a temperature obtained by adding 20 ° C. to the liquidus temperature of the hot dipping bath. When copper is added, the liquidus temperature decreases, but in this case as well, the temperature of the hot dipping bath is defined by the concentration of bismuth and the concentration of indium.
  • a silver coating layer having a predetermined thickness and coverage was formed on the solder layer thus prepared by electroplating.
  • solar cell strings were prepared for a total of 23 types of interconnectors with varying thickness, coverage, and copper addition, including interconnectors that did not have a coating layer. Examined.
  • the solar cell strings were produced in the same manner as in the first example.
  • the cell table temperature was set to 100 ° C.
  • the hot air set temperature was set to 270 ° C.
  • the temperature was set lower than the optimum bonding temperature.
  • the time for pressing with a pin was 3 seconds.
  • the above condition is defined as condition 2.
  • the joining state when the copper concentration of the solder layer is changed is the joining state when the copper concentration is in the range of 0.3 wt% to 0.7 wt%. And 0.5% by weight was the best. This is presumably because the liquidus of the Sn—Bi—Cu alloy and Sn—In—Cu decreased and the bonding temperature was the lowest when the copper concentration was 0.5 wt% or less. As shown in Examples 23, 27, 33, and 37, the bonding state deteriorated when the copper concentration was outside the above range. The reason why the bonding state deteriorated at a copper concentration of 0.8% by weight is thought to be that the liquidus temperature increased and that the Sn-Bi-Cu alloy and Sn-In-Cu alloy became brittle. It is done.
  • the thickness of the coating layer was compared. As a result, the thickness of the coating layer was 0.05 ⁇ m to 0.5 ⁇ m. At that time, the bonding state was good. Even if the thickness exceeds 0.5 ⁇ m, it is expected that there will be an effect, but from the viewpoint of cost, the optimum thickness is 0.05 ⁇ m to 0.5 ⁇ m.
  • an oxygen-free copper plate (JIS C1020 % 1 / 2H material) with a purity of 99.96 wt% or more and a thickness of 1.0 mm is cold-rolled to 0.2 mm, then slitted to a width of 1.3 mm, and a cross-section of 0.22 mm x 1.3 mm A tape-shaped core part was produced.
  • this core portion was passed through a hot dipping bath having various bath compositions, and a solder layer was formed on the surface of the core portion.
  • a hot dipping bath having various bath compositions, and a solder layer was formed on the surface of the core portion.
  • Sn-Bi alloy baths with bismuth concentrations of 16%, 36%, and 51% by weight, or indium concentrations of 10%, 30%, and 55% by weight.
  • the Sn-In alloy bath was used.
  • the hot dipping was performed in the same manner as in the first example.
  • the temperature of the hot dipping bath is 234 ° C, 200 ° C, 170 ° C, and the indium concentration is 10%, 30%, and 55% by weight when the bismuth concentration is 16%, 36%, and 51%, respectively.
  • the thickness was reduced to about 0.2 mm by rolling to produce a copper wire having a cross section with a solder layer formed of 0.2 mm ⁇ 1.3 mm.
  • a silver coating layer having a predetermined thickness and coverage was formed on the solder layer thus prepared by electroplating.
  • a total of 19 types of interconnectors including interconnectors without a coating layer were prepared and the bondability was examined.
  • the thickness of the solder layer and the coating layer was determined by observing the cross-section of the interconnector with a scanning electron microscope and measuring the thickness of the tape surface. At this time, it was confirmed that the solder layer and the coating layer were also coated on the side surfaces.
  • the interconnector and the solar battery cell were joined using an acrylic resin conductive paste containing silver conductive particles.
  • the solar cell used was a polycrystalline silicon substrate having a size of 156 mm ⁇ 156 mm and a thickness of 200 ⁇ m.
  • An electrode to which the interconnector is joined is formed on each surface of the solar battery cell. Three electrodes are arranged in parallel on each surface. This electrode is made of silver and has a width of 1.3 mm.
  • a conductive paste was applied on a solar cell electrode with a dispenser.
  • interconnectors were arranged along the electrodes, and temporarily joined by placing them in a furnace heated to 130 ° C. for 3 minutes while uniformly applying a load of 2N per interconnector. Thereafter, the interconnector was temporarily joined to the opposite surface in the same manner. Furthermore, it hold
  • This temperature is lower than the eutectic temperature of the Sn—Bi alloy and is a condition that does not cause a liquid phase in the solder between the interconnector and the electrode interface.
  • the solar reflectance of the interconnector on the light-receiving surface side joined to the solar cell was measured using a near infrared visible light spectrophotometer.
  • the evaluation results are shown in the “sunlight reflectance” column of Table 3.
  • the solar reflectance was in accordance with the measurement method of JIS A5759.
  • Bondability was evaluated by a 45 ° peel test.
  • 45 ° peel test a solar cell is fixed at an angle of 45 ° from the horizontal plane, the end of the interconnector is peeled off and held on the chuck, and pulled straight onto the load cell (perpendicular to the horizontal plane) and applied to the load cell while peeling off. The force was measured.
  • the average load obtained at the time of peeling is defined as the peel strength. The measurement results are shown in “Peel Strength” in Table 3.
  • Example 38 to 49 since the thickness of the coating layer was 0.05 ⁇ m or more and the coverage was 90 area% or more, the solar reflectance exceeded 80%, and the cell efficiency was improved. Further, in Examples 38 to 49, since the thickness of the solder layer was 0.3 ⁇ m or more, no exposure of the core portion was observed.
  • Comparative Examples 29 to 32 since the coating layer was 0.03 ⁇ m or less, high cell efficiency was not obtained as compared with the Examples.
  • Comparative Examples 29 and 30 since the thickness of the solder layer was 0.2 ⁇ m, exposure of the core portion was observed on the tape surface after bonding.
  • Comparative Examples 31 to 34 no exposure of the core was observed when the thickness of the solder layer was 0.3 ⁇ m or more. From this, it can be said that at least the thickness of the solder layer is 0.3 ⁇ m or more in order to ensure the corrosion resistance. Further, in the case of Comparative Example 35 without the solder layer, exposure of the core part was observed even when the thickness of the coating layer was 0.05 ⁇ m.
  • the corrosion resistance deteriorates because there is no sacrificial anticorrosive effect of the solder layer.
  • the thickness of the coating layer must be increased, which is disadvantageous in terms of cost. Furthermore, when the coverage of the coating layer was less than 90% by area, sufficient solar reflectance and cell efficiency could not be obtained.
  • the peel strength varies greatly depending on the presence or absence of the coating layer, and a good strength was obtained particularly when the thickness of the coating layer was 0.05 ⁇ m or more. High values of power generation efficiency as solar cells were obtained by having a coating layer. This is an effect due to good electrical contact between the conductive particles and the interconnector.
  • the interconnector has a solder layer thickness of 0.3 ⁇ m or more, a coating layer thickness of 0.05 ⁇ m or more, and a coating layer coverage of 90 area% or more, the corrosion resistance can be ensured and the bonding reliability is high. It was found that a high-efficiency solar cell module can be produced.
  • the temperature of the hot dipping bath was adjusted according to the concentration of bismuth and indium, and was set to a temperature obtained by adding 20 ° C. to the liquidus temperature of each hot dipping bath.
  • a silver coating layer having a predetermined thickness and coverage was formed on the solder layer thus prepared by electroplating.
  • solar cell strings were prepared for a total of 13 types of interconnectors with varying thickness, coverage, and copper addition, including interconnectors that did not have a coating layer. Examined.
  • Solar cell strings were produced using an automatic wiring device.
  • the solar cell used was a polycrystalline silicon substrate having a size of 156 mm ⁇ 156 mm and a thickness of 200 ⁇ m.
  • An electrode to which the interconnector is joined is formed on each surface of the solar battery cell. Three electrodes are arranged in parallel on each surface. This electrode is made of silver and has a width of 0.3 mm.
  • the temperature at which the solder layer was reflowed and joined to the electrode was varied depending on the composition of the Sn-based alloy of the solder layer.
  • the cell table temperature was a temperature obtained by reducing the liquidus temperature of the solder layer by 40 ° C.
  • the hot air set temperature was a temperature obtained by adding 130 ° C. to the liquidus temperature of the solder layer.
  • the time for pressing with a pin was 3 seconds. The above condition is defined as condition 1.
  • the bonding state was evaluated based on the machine operation stop and bonding state. X that could hardly be joined and automatic continuous operation of the machine was not possible x, solar cell strings were formed but partially peeled during handling ⁇ , macroscopically sound, The fillet indicating that the solder has been wet is not partially formed or there is an unbonded portion. It is shown in the “Joint state at 1” column. When the evaluation was ⁇ or ⁇ , it was determined to be acceptable.
  • the liquidus temperature was 214 ° C. or lower, and the bonding state was good. Therefore, it was found that the effects of the present invention can be obtained even when the cross-sectional shape is a round line.
  • the present invention is not limited to the above-described embodiment, and can be appropriately changed within the scope of the gist of the present invention.
  • the conductor is applied to the interconnector.
  • the present invention is not limited to this, and may be applied as another semiconductor mounting conductor such as a tab wire or a general conductor. it can.

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Abstract

La présente invention concerne un conducteur et un interconnecteur de cellule solaire qui sont capables d'améliorer la mouillabilité pendant la refusion d'une soudure formée à partir d'un alliage Sn-Bi, et qui sont capables d'améliorer des propriétés de liaison par rapport à un film de contact et une pâte conductrice. La présente invention est caractérisée en ce qu'elle est équipée : d'une partie d'âme (12A) formée à partir de cuivre; une couche de soudure (14A) formée sur la surface de la partie d'âme; et une couche de revêtement (16A) formée sur la surface de la couche de soudure (14A). La présente invention est en outre caractérisée en ce que : la couche de soudure (14A) est formée à partir d'un alliage Sn-Bi comportant entre 16 % en poids et 60 % en poids de bismuth, et présente une épaisseur comprise entre 0,3 et 40 µm inclus; la couche de revêtement (16A) est formée à partir d'argent et présente une épaisseur comprise entre 0,05 et 0,5 µm inclus; et le recouvrement de la couche de soudure (14A) par la couche de revêtement (16A) est d'au moins 90 % en surface.
PCT/JP2015/059475 2014-03-26 2015-03-26 Conducteur, et interconnecteur de cellule solaire WO2015147213A1 (fr)

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Cited By (3)

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JPWO2017134784A1 (ja) * 2016-02-03 2018-04-12 三菱電機株式会社 太陽電池モジュール及びその製造方法
CN112151631A (zh) * 2020-09-18 2020-12-29 浙江晶科能源有限公司 焊带、光伏组件以及焊带的制备方法
KR20230076427A (ko) * 2021-11-24 2023-05-31 주식회사 제이에이치머티리얼즈 블랙 버스바 및 그 제조방법

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JP2005353549A (ja) * 2004-06-14 2005-12-22 Hitachi Cable Ltd リード線及びその製造方法並びに太陽電池アセンブリ
JP2007046150A (ja) * 2005-04-06 2007-02-22 Misuzu:Kk 電子部品用リード線及び該リード線よりなるフラットケーブル
JP2007141930A (ja) * 2005-11-15 2007-06-07 Neomax Material:Kk 太陽電池用電極線材及びその製造方法
JP2008168339A (ja) * 2006-12-14 2008-07-24 Hitachi Cable Ltd 太陽電池用めっき線及びその製造方法
JP2013211266A (ja) * 2012-02-29 2013-10-10 Nippon Steel & Sumitomo Metal テープ状導電材料、太陽電池用インターコネクター及び太陽電池モジュール

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JP2000156450A (ja) * 1998-11-19 2000-06-06 Hitachi Cable Ltd 電子部品用リード
JP2001155548A (ja) * 1999-11-29 2001-06-08 Hitachi Cable Ltd 電子部品用リード線
JP2005216749A (ja) * 2004-01-30 2005-08-11 Hitachi Cable Ltd フラットケーブル用導体及びその製造方法並びにフラットケーブル
JP2005353549A (ja) * 2004-06-14 2005-12-22 Hitachi Cable Ltd リード線及びその製造方法並びに太陽電池アセンブリ
JP2007046150A (ja) * 2005-04-06 2007-02-22 Misuzu:Kk 電子部品用リード線及び該リード線よりなるフラットケーブル
JP2007141930A (ja) * 2005-11-15 2007-06-07 Neomax Material:Kk 太陽電池用電極線材及びその製造方法
JP2008168339A (ja) * 2006-12-14 2008-07-24 Hitachi Cable Ltd 太陽電池用めっき線及びその製造方法
JP2013211266A (ja) * 2012-02-29 2013-10-10 Nippon Steel & Sumitomo Metal テープ状導電材料、太陽電池用インターコネクター及び太陽電池モジュール

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2017134784A1 (ja) * 2016-02-03 2018-04-12 三菱電機株式会社 太陽電池モジュール及びその製造方法
CN112151631A (zh) * 2020-09-18 2020-12-29 浙江晶科能源有限公司 焊带、光伏组件以及焊带的制备方法
CN112151631B (zh) * 2020-09-18 2022-07-05 浙江晶科能源有限公司 焊带的制备方法
KR20230076427A (ko) * 2021-11-24 2023-05-31 주식회사 제이에이치머티리얼즈 블랙 버스바 및 그 제조방법
KR102612746B1 (ko) 2021-11-24 2023-12-12 주식회사 제이에이치머티리얼즈 블랙 버스바 및 그 제조방법

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