JP4780008B2 - Plating wire for solar cell and manufacturing method thereof - Google Patents

Description

  The present invention relates to a solar cell plating wire for connecting Si crystals of a solar cell and a method for manufacturing the same.

  Polycrystalline and single-crystal Si wafers are used for solar cells. As shown in FIG. 1, the connecting lead wires 2 are joined to predetermined regions of the Si wafer (solar cell 1) with solder, Through this, the generated power is transmitted. As shown in FIG. 3, there is a known example in which a pure Cu flat conductor such as tough pitch Cu or oxygen-free Cu is used for the conductor 3 and Sn—Pb eutectic solder is applied to the plating layer 4 (Patent Document). 1).

  In recent years, switching to a solder that does not contain Pb has been studied in consideration of the environment (Patent Document 2, etc.).

  The Si crystal wafer occupies most of the material cost among the members constituting the solar cell. Therefore, thinning of the Si crystal wafer has been studied. When the thinning is performed, the heating process at the time of joining the connection lead wire 2 and the solar battery cell 1 shown in FIG. Due to this temperature change, as shown in FIG. 2B, there arises a problem that the solar battery cell 1 is warped or damaged.

  In order to cope with this, there is an increasing demand for a material having low thermal expansion as a connecting lead wire. For example, as shown in Table 1, invar (Fe-36 mass% Ni), which is a low thermal expansion material, is used, and as shown in FIG. 4, the conductor 3 is formed with a cladding material (CIC) of Cu5 / Invar6 / Cu5. By using the connecting lead wire 2 in which the CIC conductor 3 is coated with a plating layer 4 (solder plating), thermal expansion matching with Si becomes possible. Table 1 shows the material properties of Cu / Invar / Cu clad material, Cu, Fe-36 mass% Ni (Invar), and Si.

  In addition, by reducing the 0.2% proof stress of conductors with high conductivity, it is possible to achieve thermal expansion matching with Si, and to reduce the cell warping force generated by conductor thermal contraction after solder connection. There is a lead wire (Patent Document 3).

Japanese Patent Laid-Open No. 11-21660 JP 2002-263880 A JP 2006-54355 A

  In the connection lead wire using the CIC shown in FIG. 4, the conductivity of the invar 6 is low (the volume resistivity is high), so that the conductivity of the entire CIC also decreases, and the power generation efficiency as a solar cell is reduced. There was a problem of falling.

  Moreover, in the solar cell lead wire described in Patent Document 3, in order to reduce the force of warping the cell, the 0.2% proof stress of the conductor in the solar cell lead wire provided with the plating layer is set to a certain reference value or less. There is a need. However, even if the conductor is manufactured under certain heat treatment conditions to make the 0.2% proof stress below a certain reference value, the crystal orientation is not necessarily constant, and the 0.2% proof stress of the product varies. Yield improvement was difficult.

  Furthermore, as a well-known method for reducing the 0.2% yield strength, there is a method of enlarging crystal grains by heat treatment. In general, when this method is employed, the oxygen-free Cu that tends to coarsen the crystal grains easily. Since (oxygen concentration ≦ 10 ppm) and high-purity Cu (99.9999%) are used as the conductor material of the solar cell lead wire, there is a problem that the material cost is increased.

  An object of the present invention is to provide a solar cell plating wire that has a low warpage of the Si cell and high conductivity even during thermal contraction after the solder connection with the Si cell. Another object of the present invention is to provide a method of manufacturing a plated wire for a solar cell that has a small variation in 0.2% proof stress required to reduce the warpage of the Si cell and that can be reduced in cost. There is to do.

In order to achieve the above object, the invention of claim 1 is a solar battery plating in which a plating layer is coated on a part or all of the surface of a conductor formed in a flat cross-sectional shape so as to be joined to a solar battery cell. In the wire, the crystal orientation (axis direction of the plating wire) of the central portion of the conductor is (211) orientation and (100) orientation, and the orientation ratio of (211) orientation is 30% or more
A 0.2% proof stress in a tensile test of the plated wire is 90 MPa or less .

  The invention according to claim 2 is the solar cell plating wire according to claim 1, wherein the conductor has a volume resistivity of 50 μΩ · mm or less.

  The invention according to claim 3 is the solar cell plating wire according to claim 1 or 2, wherein the conductor is made of pure copper.

  A fourth aspect of the present invention is the solar cell plating wire according to any one of the first to third aspects, wherein the conductor material is one of tough pitch Cu and phosphorus deoxidized Cu.

The invention according to claim 5 is the solar cell plated wire according to any one of claims 1 to 4 , wherein a 0.2% proof stress in a tensile test of the conductor is 70 MPa or less.

  According to a sixth aspect of the present invention, the plating layer contains 0.1 wt% of Sn-based solder or at least one element selected from Pb, In, Bi, Sb, Ag, Zn, Ni, and Cu as the second component. 6. The solar cell plated wire according to claim 1, which is a coating layer of Sn-based alloy solder including the above.

The invention according to claim 7 is a method for producing a plated wire for a solar battery in which a plating layer is coated on a part or all of the surface of a conductor formed in a rectangular cross section so as to be bonded to a solar battery cell. First of all, a rough drawing wire is prepared with a material, the rough drawing wire is drawn, and the drawn rough drawing wire is rolled or slitted to be formed into a rectangular cross section. Alternatively, annealing heat treatment is performed in a batch-type equipment, and the crystal orientation (axis direction of the plating wire) of the conductor is (211) orientation and (100) orientation, and the orientation ratio of (211) orientation is 30% or more A plated layer for a solar cell , wherein the surface of the conductor subjected to the annealing heat treatment is coated with a plating layer, and the 0.2% proof stress in a tensile test of the obtained plated wire is 90 MPa or less. It is a manufacturing method.

  The invention of claim 8 is the method for producing a plated wire for a solar cell according to claim 7, wherein the roughing wire is subjected to heat treatment with a current-carrying or batch-type equipment between the wire drawing steps.

  According to the plated wire for solar cell of the present invention, the Si cell is less warped and has high conductivity even during thermal contraction after the solder connection with the Si cell. Further, variation in 0.2% proof stress can be suppressed, and yield can be improved.

  Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.

  In general, when dissimilar metals having different thermal expansion coefficients are connected at a high temperature, a value obtained by integrating the thermal expansion coefficient and Young's modulus with the temperature change is a force for generating warpage. However, both members (solar cell plating wire, Si cell) connected like a solar cell are remarkably different in rigidity, or a conductor having a small cross-sectional area (for solar cell) when the connecting temperature is as high as 200 ° C. or higher. (Plating wire) yields, and the force due to the thermal expansion coefficient and Young's modulus does not directly generate warpage.

  If the yield stress of the conductor is small, the conductor is plastically deformed with a small force, and no further deformation resistance is obtained. Therefore, the plating wire for solar cells using a conductor having a small 0.2% proof stress, which is an index of plastic deformation, has an effect of reducing the amount of cell warpage after solder connection to the Si cell.

  However, there has been no provision for controlling the crystal structure of the conductor in order to accurately reduce the 0.2% yield strength of the conductor. As a result of intensive studies by the present inventors, by growing a certain crystal orientation at a predetermined ratio in the crystal orientation of the central portion of the conductor, it is possible to reduce 0.2% proof stress and to suppress variations thereof. I have found that I can achieve it.

  The solar cell plating wire according to a preferred embodiment of the present invention has a structure similar to that of the general solar cell plating wire 2 shown in FIG. 3, and a plating layer is formed on the entire surface of the conductor 3. 4 is coated. The conductor 3 of the plating wire for solar cell according to the present embodiment has the (211) orientation and the (100) orientation as the crystal orientation (axial orientation of the plating wire) at the center, and the orientation ratio of the (211) orientation. Is characterized by 30% or more.

  The 0.2% proof stress of the conductor 3 in the solar cell plated wire 2 is preferably 70 MPa or less, particularly preferably 40 to 70 MPa, and the 0.2% proof stress of the entire solar cell plated wire 2 is 90 MPa or less, particularly 60 to 90 MPa. desirable. The cross-sectional shape of the conductor 3 is preferably a rectangular type so that it can be easily connected to the Si cell 1 shown in FIG.

  The material of the conductor 3 is preferably a material having a relatively small volume resistivity. For example, as shown in Table 2, there are Au, Ag, Al, etc. in addition to Cu, and the 0.2% proof stress can be reduced. There is sex. Among these, Ag has the lowest volume resistivity and can maximize power generation efficiency. Further, Cu is preferable when cost reduction is prioritized, and Al is preferably selected when weight reduction is desired.

  As the kind of Cu, any of tough pitch Cu, oxygen-free Cu, phosphorus deoxidized Cu, and high-purity Cu (purity 99.9999% or more) can be used. In order to minimize the 0.2% yield strength, Cu having high purity is advantageous, that is, high purity Cu is selected. On the other hand, when it is desired to reduce the cost, tough pitch Cu or phosphorous deoxidized Cu is selected although the 0.2% proof stress is somewhat large because it contains impurities.

  Examples of the coating material for the plating layer 4 include solder plating and conventional plating generally used as a copper wire plating material. Further, the coating of the plating layer 4 may be a part of the conductor 3, for example, only the upper and lower surfaces of the conductor.

  As solder for solder plating, Sn-based solder or Sn-based alloy containing 0.1 wt% or more of at least one element selected from Pb, In, Bi, Sb, Ag, Zn, Ni, Cu as the second component A solder is mentioned, These solders may contain 1000 ppm or less of trace elements as the 3rd ingredient.

  Further, examples of conventional plating include metal materials containing at least one element selected from Ni, Ag, Sn, Zn, Cr, Au, Pd, Ru, and Pt. When this conventional plating is used as the plating layer 4, for example, bonding to the Si cell 1 is performed using a conductive adhesive.

  If the 0.2% proof stress of the conductor 3 is 70 MPa or less and the 0.2% proof stress of the entire solar cell plated wire 2 is 90 MPa or less, the Cu / Invar / Cu shown in FIG. This is because Si warpage can be reduced and a great effect can be obtained as compared with a conventional solar cell plating wire using a clad material (CIC).

  The solar cell assembly is obtained by connecting the solar cell plating wire 2 to a predetermined contact region (for example, an Ag plating region) of the Si cell 1 shown in FIG.

  Next, an example of the manufacturing method of the plating wire 2 for solar cells which concerns on this Embodiment is demonstrated.

  First, pure copper is dissolved as a conductor constituent material. Examples of the pure copper include tough pitch copper, phosphorus deoxidized Cu, oxygen-free Cu, and high-purity Cu (purity 99.9999% or more).

  Using this molten copper, a rough wire for copper is continuously produced. Moreover, a wire drawing process is given to this rough drawing line. Between these wire drawing processes, heat treatment (recrystallization treatment) is performed on the roughing wire using a current-carrying method or batch-type equipment. The wire drawing and recrystallization heat treatment may be repeated as appropriate.

  The drawn rough wire is subjected to rolling (or slitting) to produce a conductor 3 having a rectangular cross section. Thereafter, the flat conductor 3 is subjected to heat treatment (annealing treatment) using an energization method or batch-type equipment. By this processing and heat treatment, the crystal orientation of the central portion of the conductor 3 (axis direction of the plating wire) is oriented at a ratio of 30% or more in the (211) orientation, and the 0.2% proof stress of the conductor 3 is 70 MPa or less. Adjusted to

  After the heat treatment, the plating layer 4 is coated on the surface of the conductor 3 to obtain the solar cell plating wire 2 according to the present embodiment. The plating type and the plating thickness of the plating layer 4 are adjusted so that the 0.2% proof stress of the solar cell plating wire 2 is 90 MPa or less.

  The orientation ratio of the crystal orientation (211) in the central portion of the conductor 3 can be adjusted by adjusting, for example, the heat treatment temperature of the recrystallization heat treatment, the heat treatment time, and the processing conditions of the rolling process.

  As the processing method of the conductor 3, both rolling processing and slit processing are applicable. The method of rolling from a round wire and flattening can produce a long and uniform product. The slit method has the merit that it can cope with materials of various widths.

  Moreover, the wiring conductor for connecting solar cells and the solder plating wire according to the present invention may include a deformed portion that is easily deformed at a plurality of locations connected to the cell, and etching, pressing, and bending as processing methods. Any one or a plurality of them may be used in combination. Further, the processing may be applied to any of a material wire, a rolled wire obtained by rolling the material wire, and a foil-like wire obtained by slitting a plate material.

  As a heat treatment method for reducing the 0.2% proof stress, either an electric heating method or a batch heating method can be applied. The energization heating method is suitable for continuous and long processing, and the batch heating method is desirable when stable heat treatment is required. Further, from the viewpoint of preventing the conductor 3 from being oxidized, heat treatment may be performed using a furnace in a hydrogen reducing atmosphere.

  Next, the operation of the present embodiment will be described.

  According to the solar cell plating wire 2 according to the present embodiment, the crystal orientation (the axial orientation of the plating wire) of the central portion of the conductor 3 is oriented at a ratio of 30% or more in the (211) orientation. The variation in 0.2% proof stress of the conductor 3 itself is reduced, and the yield is improved. Moreover, since the 0.2% proof stress of the conductor 3 itself is lowered by orienting at a ratio of 30% or more in the (211) direction as described above, a cell warpage suppressing effect can also be obtained. In other words, the solar cell plated wire 2 can be controlled by precise control of the crystal structure of the conductor 3 to suppress a 0.2% reduction in yield strength and variations in characteristics, thereby generating heat shrinkage of the conductor after solder connection. In addition, the force for warping the cell can be reduced, and the yield of the product can be improved.

  Moreover, even if low-cost tough pitch Cu or phosphorus deoxidized Cu is used as the constituent material of the conductor 3, the same effect as that of oxygen-free Cu or high-purity Cu can be obtained, so that the product (plating wire 2 for solar cells) Cost reduction is possible. Furthermore, since the constituent material of the conductor 3 is pure copper, the electrical conductivity is better than when the CIC shown in FIG. 4 is used as a conductor.

  Further, the solder composition of the solder plating in the solar cell plating wire 2 has so far been required to be able to be connected at a low temperature in consideration of thermal expansion matching with the Si cell 1. By using it, it is also possible to use a Sn—Ag—Cu-based solder having a high connection temperature. Moreover, you may use a conductive adhesive instead of a solder connection.

  An embodiment of the present invention is shown below.

  The Cu conductor (rough drawing wire) was drawn, and heat treatment was performed on the rough drawing wire with a current-carrying system or batch-type equipment between the drawing processes. Thereafter, the rough drawn wire after wire drawing is further rolled and formed into a flat wire shape having a width of 2.0 mm and a thickness of 0.16 mm, annealed under predetermined conditions, and then the periphery thereof is Sn-3% Ag -Coated with 0.5% Cu-based lead-free solder, and as shown in Table 3, produces various types of solder-plated rectangular wires with different crystal orientations in the center of the conductor material (axial orientation of the lead wire center) (Samples 1 to 13).

  The crystal orientation was determined from the diffraction peak intensity ratio of the X-ray diffraction profile at the center of each solder plating coated rectangular wire cross section. The 0.2% yield strength was calculated by obtaining a 0.2% yield strength load from an SS curve obtained by a tensile test at a tensile rate of 20 mm / min, and dividing by the cross-sectional area of the conductor.

  As shown in Table 3, the 0.2% proof stress of the solder plating coated rectangular wires (samples 1 to 11) produced by controlling the crystal orientation was 10 MPa or less with a small difference (variation) between the maximum value and the minimum value. However, the 0.2% proof stress of the solder-plated rectangular wires (samples 12 and 13) produced by a conventional manufacturing method in which the crystal orientation is not controlled varies widely and is 20 MPa or more.

  Also, the solder-plated rectangular wires (samples 1 to 8) in which the crystal orientation of the conductor center portion (axial orientation of the lead wire center portion) is oriented at a ratio of 30% or more in the (211) orientation are 0% of the conductor. .2% proof stress is low and 70 MPa or less, while other solder-plated rectangular wires (samples 9 to 12) have a 0.2% proof stress.

  Furthermore, the warpage of the cell was investigated when each solder-coated rectangular wire having a 0.2% proof stress of 60, 70, 100, and 160 MPa was soldered to a Si cell having a length of 150 mm, a width of 150 mm, and a thickness of 200 μm. Table 4 shows the evaluation results of the cell warpage.

  As shown in Table 4, the amount of warpage of the cell is reduced as the 0.2% proof stress is decreased, and the tough pitch Cu is used as the conductor when the solder plating coated Cu flat wire has a 0.2% proof stress of 70 MPa. Compared with the conventional solder-plated Cu rectangular wire (sample 12, 0.2% proof stress is 160 MPa), the amount of warpage of the cell could be reduced to about ½.

  For comparison, a solder plating coated Cu rectangular wire (0.2% proof stress is 100 MPa) using Cu / Invar / Cu (ratio 2: 1: 2) as a conductor and a solder plating coated Cu having a 0.2% proof stress of 60 MPa. The warp of the cell when the flat wire was soldered to the Si cell was examined. Although the amount of warping of the former was about 3.0 mm, the amount of warping of the latter was about 1.5 mm, and it was confirmed that the cell warping was halved.

  If the amount of warpage is within this range (about 3.0 mm), it can be used as a lead wire for connecting solar cells.

It is a figure which shows the connection state of the solder plating rectangular wire to a photovoltaic cell. It is a figure which shows the connection state of the Si cell and the solder plating wire for solar cells, Fig.2 (a) has shown the state before solder connection, FIG.2 (b) has shown the state which the curvature generate | occur | produced after solder connection. It is a cross-sectional view of a general solar cell plating wire. It is a cross-sectional view of the plating wire for solar cells using CIC.

1 Solar cell (Si cell)
2 Plating wire for solar cell (Solder-plated flat wire)
3 Conductor 4 Plating layer 5 Cu
6 Invar

Claims (8)

In a solar cell plating wire in which a plating layer is coated on a part or all of the surface of a conductor formed in a rectangular cross section so as to be bonded to a solar battery cell, the crystal orientation (the axis of the plating wire) of the conductor Azimuth) is (211) azimuth and (100) azimuth, the orientation ratio of (211) azimuth is 30% or more , and 0.2% proof stress in the plated wire tensile test is 90 MPa or less. Plating wire for solar cells.   The plated wire for a solar cell according to claim 1, wherein the conductor has a volume resistivity of 50 μΩ · mm or less.   The solar cell plating wire according to claim 1, wherein the conductor is made of pure copper.   4. The solar cell plating wire according to claim 1, wherein the conductor material is one of tough pitch Cu and phosphorus deoxidized Cu. The plated wire for a solar cell according to any one of claims 1 to 4 , wherein a 0.2% yield strength in a tensile test of the conductor is 70 MPa or less.   The plating layer is Sn-based solder or Sn-based alloy solder containing 0.1 wt% or more of at least one element selected from Pb, In, Bi, Sb, Ag, Zn, Ni, and Cu as the second component. It is a coating layer, The plating wire for solar cells in any one of Claim 1 to 5. In the method of manufacturing a solar cell plating wire in which a plating layer is coated on a part or all of the surface of a conductor formed in a rectangular cross section so as to be bonded to a solar battery cell, first, roughing is performed using the conductor material. A wire is prepared, the rough drawn wire is drawn, and the drawn rough drawn wire is rolled or slitted to form a rectangular cross section, and then annealed with a current-carrying or batch-type equipment. heat treatment, I crystal orientation (axial direction of plated wire) is (211) orientation and (100) orientation der the central portion of the conductor, (at 211) orientation ratio of the orientation of 30% or more, the annealing A method for producing a plated wire for a solar cell, wherein the surface of the conductor subjected to heat treatment is coated with a plating layer, and the 0.2% proof stress in a tensile test of the obtained plated wire is 90 MPa or less .   The manufacturing method of the plating wire for solar cells of Claim 7 which heat-processes to the said rough drawing wire with an electricity supply system or a batch type installation between the processes of the said wire drawing process.

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