JP5410628B1 - Dye-sensitized solar cell element - Google Patents

Abstract

Disclosed is a dye-sensitized solar cell element having excellent durability.
A dye-sensitized solar cell includes a first base material having a transparent substrate, a second base material facing the first base material, and a first base material. And an annular sealing portion that joins the second base material, and the second base material is flexible and is embedded in the sealing portion so as to be joined to the sealing portion. And a main body part inside the joining edge part, and the joining edge part has a biting part that extends away from the transparent substrate and bites into the sealing part.
[Selection] Figure 1

Description

  The present invention relates to a dye-sensitized solar cell element.

  As a photoelectric conversion element, a dye-sensitized solar cell element has attracted attention because it is inexpensive and can provide high photoelectric conversion efficiency, and various developments have been made on the dye-sensitized solar cell element.

  The dye-sensitized solar cell element includes at least one dye-sensitized solar cell, and the dye-sensitized solar cell includes a conductive substrate and an annular sealing portion that connects a counter substrate such as a counter electrode. Yes.

  In such a dye-sensitized solar cell element, the peripheral edge of the counter electrode is generally substantially parallel to the opposing conductive substrate (see, for example, Patent Document 1 below).

JP 2008-153180 A

  However, the dye-sensitized solar cell element described in Patent Document 1 still has room for improvement in terms of durability.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a dye-sensitized solar cell element having excellent durability.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors first considered that the peripheral edge portion of the counter electrode was embedded in the sealing portion. In this case, the sealing portion is bonded not only to the surface on the conductive substrate side but also to the surface on the opposite side of the conductive substrate with respect to the peripheral portion of the counter electrode, and the bonding area increases. . However, there was still room for improvement in terms of durability. Therefore, as a result of further earnest studies, the present inventors have found that the above-described problems can be solved by the following invention.

  That is, the present invention has at least one dye-sensitized solar cell, and the dye-sensitized solar cell includes a first base material having a transparent substrate, a second base material facing the first base material, An annular sealing portion that joins the first base material and the second base material, and the second base material has flexibility and is embedded in the sealing portion, thereby the sealing portion. An annular joint edge joined to the joint edge and a body part inside the joint edge, the joint edge extending so as to be separated from the transparent substrate and biting into the sealing part It is a dye-sensitized solar cell element which has a part.

  According to this dye-sensitized solar cell element, when the dye-sensitized solar cell element is placed in a high temperature environment, the space formed by the first base material, the second base material, and the sealing portion is thermally expanded. At this time, a stress to be pulled out from the sealing portion in which the second base material is embedded is applied to the joint edge portion of the second base material. Here, the joining edge portion has a biting portion that extends away from the transparent substrate and bites into the sealing portion. In other words, the biting part extends from the base end part on the main body part side toward the tip part so as to be separated from the transparent substrate. That is, a part of the sealing part exists on the main body side with respect to the biting part, and a part of the sealing part is in contact with the biting part. Furthermore, since the biting portion extends so as to be separated from the transparent substrate, a sufficient distance between the biting portion and the first base material can be ensured. That is, the thickness of the sealing part between the biting part and the first base material can be sufficiently ensured. For this reason, the adhesiveness of the biting part with respect to a 1st base material can be strengthened. Therefore, even if a stress is applied to pull out the biting portion along the first base material, the movement of the biting portion is sufficiently suppressed by the sealing portion. From the above, the joining edge portion is sufficiently suppressed from being pulled out from the sealing portion. As a result, it is possible to have excellent durability.

  In the dye-sensitized solar cell element, the encroaching portion is inclined with respect to the surface of the transparent substrate of the first base material, and an inclined portion extending so as to be separated from the transparent substrate as the distance from the main body portion increases. It is preferable to have.

  In this case, the amount of the sealing portion present on the main body portion side with respect to the inclined portion is larger than that in the case where the biting portion is configured by a protruding portion extending so as to be orthogonal to the surface of the transparent substrate. When the biting part is pulled out, the resistance becomes larger. Therefore, the joint edge portion is particularly sufficiently suppressed from being pulled out from the sealing portion. As a result, it is possible to have particularly excellent durability.

  In the dye-sensitized solar cell element, it is preferable that the biting portion further includes a protrusion provided at the tip of the inclined portion so as to face the side opposite to the first base material.

  In this case, even if the dye-sensitized solar cell element is placed in a high-temperature environment and a stress is applied to pull out the biting portion along the first base material, the tip of the inclined portion is opposite to the first base material. Since the protruding portion is provided so as to face, the movement of the biting portion is more sufficiently suppressed by the sealing portion. Therefore, the joint edge portion is more sufficiently suppressed from being pulled out from the sealing portion.

  In the said dye-sensitized solar cell element, it is preferable that the said joint edge part has a connection part which connects the said biting part and the said main-body part, and the said connection part extends so that the said transparent substrate may be met.

  When the dye-sensitized solar cell element is placed in a high temperature environment and the space formed by the first base material, the second base material, and the sealing portion is thermally expanded, the main body portion faces toward the side opposite to the first base material. Becomes convex. In this case, it is possible to increase the angle formed by the joining edge portion and the main body portion as compared with the case where there is no connection portion. For this reason, it is suppressed more fully that a tear arises between a joining edge part and a main-body part.

  In the said dye-sensitized solar cell element, it is preferable that a part of said main-body part is a convex bending part bent so that it may become convex toward the said 1st base material opposite side.

  When the dye-sensitized solar cell element is placed in an environment with a large temperature change, the space between the first base material, the second base material, and the sealing portion expands or contracts. At this time, even if an excessive stress is applied to the second base material and the second base material is about to be in a tension state, a part of the main body portion of the second base material is a convex bent portion, Is absorbed by the convex flexure. For this reason, the stress applied to the interface between the joining edge portion of the second base material and the sealing portion can be sufficiently reduced. For this reason, even if the dye-sensitized solar cell element is placed in an environment with a large temperature change, it can have excellent durability.

  The dye-sensitized solar cell element further includes an oxide semiconductor layer provided on the first base material, the first base material includes a first electrode, and the second base material includes a second electrode. In addition, it is preferable that the remaining part of the main body has a concave bent portion that is bent so as to be recessed toward the oxide semiconductor layer side.

  In this case, since the remaining part of the main body part has the concave bent part, the distance between the first electrode and the second electrode can be reduced. For this reason, the dye-sensitized solar cell element can have excellent photoelectric conversion characteristics.

  In the said dye-sensitized solar cell element, it is preferable that the said convex bending part is arrange | positioned in the position adjacent to the said joining edge part.

  Stress is likely to be applied to the interface between the joining edge portion and the sealing portion. In that respect, when the convex bent portion is disposed at a position adjacent to the joint edge, it is possible to effectively suppress application of excessive stress to the joint edge.

In the present invention, the second base material is “flexible” means that both edges on the long side of the sheet-like second base material of 50 mm × 200 mm in an environment of 20 ° C. (each having a width of 5 mm). ) Is fixed horizontally with a tension of 1 N, and the maximum deformation rate of the second base material when the load of 20 g is applied to the center of the second base material exceeds 20%. Here, the maximum deformation rate is the following formula:
Maximum deformation rate (%) = 100 × (maximum displacement / sheet-like second base material thickness)
The value calculated based on Therefore, for example, when a sheet-like second base material having a thickness of 0.04 mm is bent by applying a load as described above and the maximum deformation amount becomes 0.01 mm, the maximum deformation rate becomes 25%, and this sheet The shaped second substrate will have flexibility.

  According to the present invention, a dye-sensitized solar cell element having excellent durability is provided.

It is sectional drawing which shows 1st Embodiment of the dye-sensitized solar cell element of this invention. It is a top view which shows a part of 1st Embodiment of the dye-sensitized solar cell element of this invention. It is a fragmentary sectional view which shows the 2nd base material of FIG. It is a top view which shows the pattern of the transparent conductive film in the dye-sensitized solar cell element of FIG. It is a top view which shows the 1st integrated sealing part of FIG. It is a top view which shows the 2nd integrated sealing part of FIG. It is sectional drawing along the VII-VII line of FIG. It is the elements on larger scale of FIG. It is a top view which shows the working electrode which formed the connection part for fixing a back seat | sheet. It is a top view which shows the 1st integrated sealing part formation body for forming the 1st integrated sealing part of FIG. It is a top view which shows a part of 2nd Embodiment of the dye-sensitized solar cell element of this invention. It is a top view which shows a part of 3rd Embodiment of the dye-sensitized solar cell element of this invention. It is a top view which shows a part of 4th Embodiment of the dye-sensitized solar cell element of this invention. It is sectional drawing which shows a part of 5th Embodiment of the dye-sensitized solar cell element of this invention. It is sectional drawing which shows a part of 6th Embodiment of the dye-sensitized solar cell element of this invention. It is sectional drawing which shows a part of 7th Embodiment of the dye-sensitized solar cell element of this invention. It is sectional drawing which shows a part of 8th Embodiment of the dye-sensitized solar cell element of this invention. It is a fragmentary sectional view which shows 9th Embodiment of the dye-sensitized solar cell element of this invention.

  Hereinafter, preferred embodiments of the dye-sensitized solar cell element of the present invention will be described in detail with reference to FIGS. FIG. 1 is a sectional view showing a preferred embodiment of the dye-sensitized solar cell element of the present invention, and FIG. 2 is a plan view showing a part of the preferred embodiment of the dye-sensitized solar cell element of the present invention. 3 is a partial sectional view showing the second substrate of FIG. 1, FIG. 4 is a plan view showing a pattern of the transparent conductive film in the dye-sensitized solar cell module of FIG. 1, and FIG. 5 is a first integrated piece of FIG. FIG. 6 is a plan view showing the second integrated sealing portion of FIG. 1, FIG. 7 is a cross-sectional view taken along line VII-VII of FIG. 2, and FIG. FIG. 9 is a partially enlarged view of FIG. 7, and FIG.

  As shown in FIG. 1, a dye-sensitized solar cell module (hereinafter sometimes referred to as “DSC module”) 100 as a dye-sensitized solar cell element includes a plurality (four in FIG. 1) of dye-sensitized solar cells. It has a battery (hereinafter also referred to as “DSC”) 50 and a back sheet 80 provided so as to cover the back side of DSC 50. As shown in FIG. 2, the plurality of DSCs 50 are connected in series by a conductive material 60P. Hereinafter, for convenience of description, the four DSCs 50 in the DSC module 100 may be referred to as DSCs 50A to 50D.

  As shown in FIG. 1, each of the plurality of DSCs 50 includes a working electrode 10 having a conductive substrate 15, a counter electrode 20 facing the conductive substrate 15, and an annular sealing that joins the conductive substrate 15 and the counter electrode 20. 30A. A cell space formed by the conductive substrate 15, the counter electrode 20, and the annular sealing portion 30 </ b> A is filled with an electrolyte 40.

  As shown in FIG. 3, the counter electrode 20 includes a metal substrate 21 and a catalyst layer 22 provided on the working electrode 10 side of the metal substrate 21 to promote a catalytic reaction. In two adjacent DSCs 50, the counter electrodes 20 are separated from each other. The counter electrode 20 has flexibility. In the present embodiment, the counter electrode 20 constitutes the second base material and the second electrode.

  As shown in FIGS. 1 and 2, the working electrode 10 includes a conductive substrate 15 and at least one oxide semiconductor layer 13 provided on the conductive substrate 15. The conductive substrate 15 includes a transparent substrate 11, a transparent conductive film 12 provided on the transparent substrate 11, an insulating material 33 provided on the transparent substrate 11, and a connection terminal 16 provided on the transparent conductive film 12. have. The oxide semiconductor layer 13 is disposed inside the annular sealing portion 30A. The transparent substrate 11 is used as a common transparent substrate for the DSCs 50A to 50D. In the present embodiment, the conductive substrate 15 constitutes the first base material and the first electrode.

  As shown in FIGS. 2 and 4, the transparent conductive film 12 is composed of transparent conductive films 12 </ b> A to 12 </ b> F provided in a state of being insulated from each other. That is, the transparent conductive films 12A to 12F are arranged with the groove 90 interposed therebetween. Here, the transparent conductive films 12A to 12D constitute the plurality of DSCs 50A to 50D, respectively. The transparent conductive film 12E is arranged so as to be bent along the sealing portion 30A. The transparent conductive film 12F is an annular transparent electrode film 12 for fixing the peripheral edge 80a of the back sheet 80 (see FIG. 1).

  As shown in FIG. 4, each of the transparent conductive films 12 </ b> A to 12 </ b> D includes a rectangular main body portion 12 a having a side edge portion 12 b and a protruding portion 12 c that protrudes laterally from the side edge portion 12 b of the main body portion 12 a. Have.

  As shown in FIG. 2, the protruding portion 12c of the transparent conductive film 12C among the transparent conductive films 12A to 12D extends from the protruding portion 12d and the protruding portion 12d that protrude laterally with respect to the arrangement direction X of the DSCs 50A to 50D. And a counter part 12e facing the main body part 12a of the adjacent DSC 50D via the groove 90.

  Also in the DSC 50B, the protruding portion 12c of the transparent conductive film 12B has a protruding portion 12d and a facing portion 12e. Also in the DSC 50A, the protruding portion 12c of the transparent conductive film 12A has a protruding portion 12d and a facing portion 12e.

  The DSC 50D is already connected to the DSC 50C, and there is no other DSC 50 to be connected. For this reason, in the DSC 50D, the protruding portion 12c of the transparent conductive film 12D does not have the facing portion 12e. That is, the protruding portion 12c of the transparent conductive film 12D is configured only by the overhang portion 12d.

  However, the transparent conductive film 12D connects the first current extraction part 12f for extracting the current generated in the DSC module 100 to the outside, the first current extraction part 12f, and the main body part 12a, and the transparent conductive films 12A to 12C. And a connecting portion 12g extending along the side edge portion 12b. The first current extraction portion 12f is disposed around the DSC 50A and on the opposite side of the transparent conductive film 12B with respect to the transparent conductive film 12A.

  On the other hand, the transparent conductive film 12E also has a second current extraction portion 12h for extracting the current generated in the DSC module 100 to the outside. The second current extraction portion 12h is around the DSC 50A and is formed of a transparent conductive film. It is arranged on the opposite side to the transparent conductive film 12B with respect to 12A. The first current extraction portion 12f and the second current extraction portion 12h are arranged adjacent to each other through the groove 90 around the DSC 50A. Here, the groove 90 is formed along the first groove 90A formed along the edge of the main body 12a of the transparent conductive film 12, and the edge of the portion of the transparent conductive film 12 excluding the main body 12a. The second groove 90 </ b> B intersects with the peripheral edge 80 a of the backsheet 80.

  Moreover, as shown in FIG. 2, the connection terminal 16 is provided on each protrusion part 12c and transparent conductive film 12E of transparent conductive films 12A-12C. Each connection terminal 16 is connected to the conductive material 60P, and is sealed outside the sealing portion 30A, extending along the sealing portion 30A, and from the conductive material connecting portion 16A to the outside of the sealing portion 30A. And a conductive material non-connecting portion 16B extending along the portion 30A. In the present embodiment, in the transparent conductive films 12A to 12C, at least the conductive material connection portion 16A of the connection terminals 16 is provided on the facing portion 12e of the protrusion 12c, and the main body portion of the adjacent DSC 50 to be connected. 12a. In the transparent conductive film 12E, the conductive material connection portion 16A of the connection terminals 16 faces the main body portion 12a of the adjacent DSC 50A to be connected. The width of the conductive material non-connecting portion 16B is narrower than the width of the conductive material connecting portion 16A. Here, the widths of the conductive material connecting portion 16A and the conductive material non-connecting portion 16B are constant. Note that the width of the conductive material connecting portion 16A is the length in the direction orthogonal to the extending direction of the conductive material connecting portion 16A and means the narrowest width among the widths of the conductive material connecting portion 16A. The width of the portion 16B is the length in a direction orthogonal to the extending direction of the conductive material non-connecting portion 16B and means the narrowest width among the widths of the conductive material non-connecting portion 16B.

  The conductive material connecting portion 16A of the connection terminal 16 provided on the protruding portion 12c of the transparent conductive film 12C in the DSC 50C and the metal substrate 21 of the counter electrode 20 in the adjacent DSC 50D are connected via the conductive material 60P. The conductive material 60P is disposed so as to pass over the sealing portion 30A. Similarly, the conductive material connecting portion 16A of the connecting terminal 16 in the DSC 50B and the metal substrate 21 of the counter electrode 20 in the adjacent DSC 50C are connected via the conductive material 60P, and adjacent to the conductive material connecting portion 16A of the connecting terminal 16 in the DSC 50A. The metal substrate 21 of the counter electrode 20 in the DSC 50B is connected via a conductive material 60P, and the conductive material connection portion 16A of the connection terminal 16 on the transparent conductive film 12E and the metal substrate 21 of the counter electrode 20 in the adjacent DSC 50A are conductive material 60P. Connected through.

  External connection terminals 18a and 18b are provided on the first current extraction portion 12f and the second current extraction portion 12h, respectively.

  Further, as shown in FIG. 8, the counter electrode 20 includes an annular joint edge portion 20a that is embedded in the seal portion 30A and joined to the seal portion 30A, and a main body portion 20b inside the joint edge portion 20a. Have. Here, the joining edge portion 20a has a biting portion that extends from the boundary between the joining edge portion 20a and the main body portion 20b so as to be separated from the conductive substrate 14 and bites into the sealing portion 30A. In the present embodiment, the biting portion is configured by an inclined portion 23 that is inclined with respect to the surface of the transparent substrate 11 of the conductive substrate 15 and extends away from the transparent substrate 11 as the distance from the main body portion 20b increases.

  As shown in FIG. 1, the sealing part 30A is provided so as to overlap the annular first sealing part 31A provided between the conductive substrate 15 and the counter electrode 20, and the first sealing part 31A. It has the 2nd sealing part 32A which clamps the joining edge part 20a of the counter electrode 20 with 1 sealing part 31A. Then, as shown in FIG. 5, adjacent first sealing portions 31 </ b> A are integrated to form a first integrated sealing portion 31. In other words, the first integrated sealing portion 31 includes an annular portion (hereinafter referred to as “annular portion”) 31 a that is not provided between two adjacent counter electrodes 20 and two adjacent counter electrodes 20. A portion (hereinafter referred to as a “partition portion”) 31 b that is provided between them and partitions the inner opening 31 c of the annular portion 31 a. Further, as shown in FIG. 6, the second sealing portions 32 </ b> A are integrated between the adjacent counter electrodes 20 to constitute a second integrated sealing portion 32. The second integrated sealing portion 32 is provided between an annular portion (hereinafter referred to as “annular portion”) 32 a that is not provided between two adjacent counter electrodes 20 and two adjacent counter electrodes 20. And a portion (hereinafter referred to as “partition portion”) 32b that partitions the inner opening 32c of the annular portion 32a.

  Further, as shown in FIG. 1, a glass is interposed between the first sealing portion 31 </ b> A and the groove 90 so as to enter the groove 90 between the adjacent transparent conductive films 12 </ b> A to 12 </ b> F and straddle the adjacent transparent conductive film 12. An insulating material 33 made of frit is provided. More specifically, the insulating material 33 enters the first groove 90A formed along the edge of the main body 12a of the transparent conductive film 12 in the groove 90, and the main body forming the first groove 90A. The edge of the portion 12a is also covered.

  As shown in FIG. 7, the width P of the bonding portion between the surface of the counter electrode 20 on the conductive substrate 15 side and the partition portion 31 b of the first integrated sealing portion 31 is the same as that of the counter electrode 20 on the conductive substrate 15 side. It is narrower than the width Q of the bonding portion between the surface and the annular portion 31 a of the first integrated sealing portion 31. Furthermore, the width R of the partition part 31 b of the first integrated sealing part 31 is 100% or more and less than 200% of the width T of the annular part 31 a of the first integrated sealing part 31.

  The second integrated sealing portion 32 includes a main body portion 32 d provided on the opposite side of the counter electrode 20 from the working electrode 10, and an adhesive portion 32 e provided between the adjacent counter electrodes 20. The second integrated sealing portion 32 is bonded to the first integrated sealing portion 31 by an adhesive portion 32e.

  As shown in FIG. 1, a back sheet 80 is provided on the conductive substrate 15. The backsheet 80 includes a laminate 80A including a weather resistant layer and a metal layer, and an adhesive portion 80B that is provided on the opposite side of the laminate 80A from the metal layer and adheres to the conductive substrate 15 via the connecting portion 14. Including. Here, the bonding portion 80B is for bonding the back sheet 80 to the conductive substrate 15, and as long as it is formed on the peripheral portion of the stacked body 80A as shown in FIG. However, the bonding portion 80B may be provided on the entire surface on the DSC 50 side of the stacked body 80A. The peripheral edge portion 80a of the back sheet 80 is connected to the transparent conductive films 12D, 12E, and 12F of the transparent conductive film 12 through the connecting portion 14 by the bonding portion 80B. Here, the bonding portion 80B is separated from the sealing portion 30A of the DSC 50. The connecting portion 14 is also separated from the sealing portion 30A. The space inside the back sheet 80 and outside the sealing portion 30A is not filled with the electrolyte 40.

  As shown in FIG. 2, in the transparent conductive film 12D, the current collector wiring 17 having a lower resistance than that of the transparent conductive film 12D extends so as to pass through the main body portion 12a, the connection portion 12g, and the current extraction portion 12f. . The current collecting wiring 17 is arranged so as not to intersect the connecting portion 14 between the back sheet 80 and the conductive substrate 15. In other words, the current collecting wiring 17 is disposed on the inner side than the connecting portion 14.

  As shown in FIG. 2, bypass diodes 70A to 70D are connected in parallel to the DSCs 50A to 50D, respectively. Specifically, the bypass diode 70A is fixed on the partition part 32b of the second integrated sealing part 32 between the DSC 50A and the DSC 50B, and the bypass diode 70B is a second integrated between the DSC 50B and the DSC 50C. The bypass diode 70C is fixed on the partition part 32b of the second integrated sealing part 32 between the DSC 50C and the DSC 50D. The bypass diode 70D is fixed on the sealing portion 30A of the DSC 50D. A conductive material 60Q is fixed to the metal substrate 21 of the counter electrode 20 so as to pass through the bypass diodes 70A to 70D. The conductive material 60P branches from the conductive material 60Q between the bypass diodes 70A and 70B, between the bypass diodes 70B and 70C, and between the bypass diodes 70C and 70D, and the conductive material connecting portion 16A on the transparent conductive film 12A, the transparent conductive film The conductive material connecting portion 16A on 12B and the conductive material connecting portion 16A on the transparent conductive film 12C are connected to each other. A conductive material 60P is also fixed to the metal substrate 21 of the counter electrode 20 of the DSC 50A, and the conductive material 60P connects the bypass diode 70A and the conductive material connection portion 16A of the connection terminal 16 on the transparent conductive film 12E. . Further, the bypass diode 70D is connected to the transparent conductive film 12D through the conductive material 60P.

  A desiccant (not shown) is provided on the counter electrode 20 of each DSC 50.

  According to the DSC module 100, the DSC module 100 is placed in a high temperature environment, and the space formed by the conductive substrate 15, the counter electrode 20, and the sealing portion 30A is thermally expanded. At this time, a stress is applied to the bonding edge 20a of the counter electrode 20 to be pulled out from the sealing portion 30A in which it is embedded. Here, the joining edge portion 20a has an inclined portion 23 as a biting portion that extends from the boundary between the joining edge portion 20a and the main body portion 20b so as to be separated from the transparent substrate 11 and bites into the sealing portion 30A. In other words, the inclined portion 23 extends away from the transparent substrate 11 from the proximal end portion on the main body portion 20b side toward the distal end portion. That is, a part of the sealing part 30 </ b> A exists on the main body part 20 b side with respect to the inclined part 23, and a part of the sealing part 30 </ b> A is in contact with the inclined part 23. In particular, the amount of the sealing portion 30A existing on the main body portion 20b side with respect to the inclined portion 23 is larger than that in the case where the biting portion is constituted by a protruding portion extending perpendicular to the surface of the transparent substrate 11, and this sealing The stop portion 30A becomes a larger resistance when the biting portion is pulled out. The inclined portion 23 extends away from the transparent substrate 11. Specifically, the inclined portion 23 is inclined with respect to the surface of the transparent substrate 11 of the conductive substrate 15 and extends away from the transparent substrate 11 as the distance from the main body portion 20b increases. For this reason, a sufficient distance between the inclined portion 23 and the conductive substrate 15 can be secured. In other words, the thickness of the sealing portion 30A between the inclined portion 23 and the conductive substrate 15 can be sufficiently ensured. For this reason, the adhesiveness of the inclined portion 23 to the conductive substrate 15 can be strengthened. Accordingly, even if a stress is applied to pull the inclined portion 23 along the conductive substrate 15, the movement of the inclined portion 23 is sufficiently suppressed by the sealing portion 30A. From the above, the joining edge portion 20a is sufficiently suppressed from being pulled out from the sealing portion 30A. As a result, the DSC module 100 can have excellent durability.

  In the DSC module 100, a groove 90 is formed along the edge of the transparent conductive film 12, and the groove 90 is an edge of the main body 12a of the transparent conductive film 12 disposed inside the annular sealing portion 30A. The first groove 90A is formed along the first groove 90A. The insulating material 33 made of glass frit enters the first groove 90A, and the insulating material 33 also covers the edge of the main body portion 12a forming the first groove 90A. For this reason, even if a crack is formed along the groove 90 in the transparent substrate 11 and below the groove 90, and the crack is connected to the edge of the main body 12 a, the crack is sealed. Intrusion of moisture from the outside of the stop 30A is sufficiently suppressed by the insulating material 33. In particular, in the DSC module 100, since the insulating material 33 that covers the edge of the main body portion 12a that forms the first groove 90A and enters the first groove 90A is made of glass frit, the insulating material 33 is made of resin. Compared to high sealing performance. For this reason, the DSC module 100 can have excellent durability.

  In the DSC module 100, the sealing portion 30A and the insulating material 33 are arranged so as to overlap each other. For this reason, compared with the case where the insulating material 33 is arrange | positioned so that it may not overlap with 30 A of sealing parts, the area of the part which contributes to electric power generation seen from the light-receiving surface side of the DSC module 100 can be increased more. . For this reason, an aperture ratio can be improved more.

  In the DSC module 100, the first current extraction unit 12f and the second current extraction unit 12h are disposed around the DSC 50A and on the opposite side of the transparent conductive film 12B from the transparent conductive film 12A. The first current extraction portion 12f and the second current extraction portion 12h of the transparent conductive film 12F are arranged adjacent to each other via the groove 90. Therefore, in the DSC module 100, the external connection terminals 18a and 18b can be arranged adjacent to each of the first current extraction unit 12f and the second current extraction unit 12h. Therefore, the number of connectors for taking out current from the external connection terminals 18a and 18b to the outside can be reduced to one. That is, if the first current extraction part 12f is arranged on the opposite side of the transparent conductive film 12C with respect to the transparent conductive film 12D, the first current extraction part 12f and the second current extraction part 12h are arranged greatly apart from each other. Therefore, the external connection terminals 18a and 18b are also arranged far apart. In this case, in order to take out the current from the DSC module 100, two connectors are required: a connector connected to the external connection terminal 18a and a connector connected to the external connection terminal 18b. However, according to the DSC module 100, since the external connection terminals 18a and 18b can be arranged adjacent to each other, only one connector is required. For this reason, according to the DSC module 100, space saving can be achieved. Further, when the DSC module 100 is used under low illuminance, the generated current is small. Specifically, the generated current is 2 mA or less. Therefore, the second current in which a part of the transparent conductive film 12D of the DSC 50D on one end side of the DSCs 50A and 50D at both ends of the DSCs 50A to 50D is electrically connected to the metal substrate 21 of the counter electrode 20 of the DSC 50A on the other end side. Even if it arrange | positions as the 1st electric current extraction part 12f via the groove | channel 90 next to the extraction part 12h, the fall of the photoelectric conversion performance of the DSC module 100 can fully be suppressed.

  In the DSC module 100, the DSCs 50A to 50D are arranged in a line along the X direction, and the DSC 50A and 50D at both ends of the DSCs 50A to 50D include the transparent conductive film 12D of the DSC 50D at one end of the sealing portion 30A. It has a main body part 12a provided on the inner side, a first current extraction part 12f, and a connection part 12g for connecting the main body part 12a and the first current extraction part 12f. Therefore, DSC 50A and DSC 50D, which are a part of DSCs 50A to 50D, are folded back halfway, and DSC 50A is used to connect two adjacent DSCs 50 to each other as compared to the case where DSC 50A and DSC 50D are arranged adjacent to each other. It becomes possible to further shorten the installation area of the connection terminals 16 provided along the arrangement direction (X direction in FIG. 2) of ˜50D, and to further reduce the space. Also, according to the DSC module 100, when the DSC module 100 is used in a low illumination environment, the generated current is usually small, so the DSC module 100 connects the main body portion 12a and the first current extraction portion 12f. Even if it has the 1st connection part 12g to perform, the fall of a photoelectric conversion characteristic can fully be suppressed.

  Further, in the DSC module 100, the current collecting wiring 17 is disposed so as not to intersect the connecting portion 14 between the back sheet 80 and the conductive substrate 15. In general, the current collector wiring 17 is porous and has air permeability, and gas such as water vapor can pass therethrough. The current collector wiring 17 is connected to the back sheet 80 and the conductive substrate 15. If it is arranged so as not to intersect the portion 14, it is possible to prevent water vapor and the like from entering the space between the back sheet 80 and the conductive substrate 15 through the current collecting wiring 17 from the outside. As a result, the DSC module 100 can have excellent durability. Moreover, since the current collection wiring 17 has resistance lower than transparent conductive film 12D, even if a generated current becomes large, the fall of a photoelectric conversion characteristic can fully be suppressed.

  Furthermore, when the DSC module 100 is placed in an environment where the temperature change is large, the connection terminal 16 is less likely to be peeled off from the protruding portion 12 c of the transparent conductive film 12 as the connection terminal 16 is narrower. In that respect, in the DSC module 100, the conductive material non-connecting portion 16B of the connection terminals 16 has a narrower width than the conductive material connecting portion 16A connected to the conductive material 60P. For this reason, the conductive material non-connecting portion 16 </ b> B of the connection terminal 16 is difficult to peel off from the protruding portion 12 c of the transparent conductive film 12. Therefore, even if the conductive material connecting portion 16A is peeled off from the protruding portion 12c of the transparent conductive film 12, the conductive material non-connecting portion 16B is not peeled off from the transparent conductive film 12 and can maintain the connection to the transparent conductive film 12. It becomes. Even if the conductive material connecting portion 16A is peeled off from the protruding portion 12c of the transparent conductive film 12, the DSC module 100 can operate normally. Therefore, according to the DSC module 100, connection reliability can be improved. In addition, the conductive material 60P connected to the metal substrate 21 of the counter electrode 20 in one of the two adjacent DSCs 50 is connected to the conductive material connection portion 16A on the protruding portion 12c in the other DSC 50, and the conductive material connection portion. 16A is provided outside the sealing portion 30A on the protruding portion 12c. That is, two adjacent DSCs 50 are connected to each other outside the sealing portion 30A. For this reason, according to the DSC module 100, it is possible to improve the aperture ratio.

  Further, in the DSC module 100, in the DSC 50 connected to the adjacent DSC 50 among the DSCs 50A to 50D, the projecting portion 12c extends from the main body portion 12a to the side and extends from the protruding portion 12d to the adjacent DSC 50. Of the connection terminal 16 and at least the conductive material connection portion 16A is provided on the facing portion 12e.

  In this case, since at least the conductive material connection portion 16A of the connection terminals 16 is provided on the facing portion 12e facing the main body portion 12a of the adjacent DSC 50, at least the conductive material connection portion 16A of the connection terminals 16 is Unlike the case where it is not provided on the facing portion 12e facing the main body portion 12a of the adjacent DSC 50, the conductive material 60P connected to the conductive material connecting portion 16A crosses the metal substrate 21 of the counter electrode 20 of the adjacent DSC 50. Can be sufficiently prevented. As a result, it is possible to sufficiently prevent a short circuit between adjacent DSCs 50.

  In the DSC module 100, the conductive material connecting portion 16A and the conductive material non-connecting portion 16B are both arranged along the sealing portion 30A. For this reason, compared with the case where the electrically conductive material connection part 16A and the electrically conductive material non-connection part 16B are arranged along the direction away from the sealing part 30A, the space required for the connection terminal 16 can be omitted.

  Furthermore, in the DSC module 100, the adhesive portion 80B of the back sheet 80 is separated from the sealing portion 30A of the DSC 50. For this reason, it is sufficiently suppressed that the adhesive portion 80B contracts at a low temperature to pull the sealing portion 30A and an excessive stress is applied to the interface between the sealing portion 30A and the conductive substrate 15 or the counter electrode 20. The In addition, even at a high temperature, it is sufficiently suppressed that the bonding portion 80B expands and pushes the sealing portion 30A to apply an excessive stress to the interface between the sealing portion 30A and the conductive substrate 15 or the counter electrode 20. The That is, excessive stress is sufficiently suppressed from being applied to the interface between the sealing portion 30 </ b> A and the conductive substrate 15 or the counter electrode 20 at both high and low temperatures. For this reason, the DSC module 100 can have excellent durability.

  Furthermore, in the DSC module 100, the width P of the bonding portion between the surface of the counter electrode 20 on the conductive substrate 15 side and the partition portion 31 b of the first integrated sealing portion 31 is equal to the width of the counter electrode 20 on the conductive substrate 15 side. It is narrower than the width Q of the bonding portion between the surface and the annular portion 31 a of the first integrated sealing portion 31. For this reason, the aperture ratio in the DSC module 100 can be improved more sufficiently. In the DSC module 100, the adjacent first sealing portions 31 </ b> A and the adjacent second sealing portions 32 </ b> A are integrated between the adjacent counter electrodes 20. Here, if the adjacent first sealing portions 31 </ b> A are not integrated, two adjacent sealing portions are exposed to the atmosphere between the adjacent DSCs 50. On the other hand, in the DSC module 100, since the adjacent first sealing portions 31A are integrated, there is one sealing portion exposed to the atmosphere between the adjacent DSCs 50. That is, since the 1st integrated sealing part 31 is comprised by the annular part 31a and the partition part 31b, the sealing part exposed with respect to air | atmosphere between adjacent DSC50 is the partition part 31b. There is only one place. Further, since the first sealing portions 31A are integrated with each other, the penetration distance of moisture and the like from the atmosphere to the electrolyte 40 is extended. For this reason, it is possible to sufficiently reduce the amount of moisture and air entering from the outside of the DSC 50 between the adjacent DSCs 50. That is, the sealing performance of the DSC module 100 can be sufficiently improved. Further, according to the DSC module 100, the adjacent first sealing portions 31A are integrated. For this reason, the width P of the bonding portion between the surface of the counter electrode 20 on the side of the conductive substrate 15 and the partition portion 31b of the first integrated sealing portion 31 is the same as that of the surface of the counter electrode 20 on the side of the conductive substrate 15. Even if it is narrower than the width Q of the bonding portion between the integrated sealing portion 31 and the annular portion 31a, a sufficient sealing width can be secured in the partition portion 31b. That is, according to the DSC module 100, the adhesive strength between the first sealing portion 31A and the conductive substrate 15 and the adhesive strength between the first sealing portion 31A and the counter electrode 20 are sufficiently increased while improving the aperture ratio. It becomes possible to enlarge. As a result, the aperture ratio can be improved, and when the DSC module 100 is used at a high temperature, the electrolyte 40 expands and an excessive stress is applied from the inside to the outside of the first sealing portion 31A. Also, peeling of the first sealing portion 31A from the conductive substrate 15 and the counter electrode 20 can be sufficiently suppressed, and excellent durability can be achieved.

  Furthermore, in the DSC module 100, the width R of the counter electrode 20 and the partition portion 31b of the first integrated sealing portion 31 is 100% or more and less than 200% of the width T of the annular portion 31a of the first integrated sealing portion 31. It has become. In this case, in the partition part 31b of the first integrated sealing part 31, the width of the partition part 31b is 100% or more of the width T of the annular part 31a. In comparison with the case where the width R of the partition portion 31b is less than 100% of the width T of the annular portion 31a, the penetration distance of moisture and the like from the atmosphere to the electrolyte 40 is further extended. For this reason, it can suppress more fully that a water | moisture content penetrate | invades from the exterior through the partition part 31b between adjacent DSC50. On the other hand, compared with the case where the width R of the partition part 31b exceeds 200% of the width T of the annular part 31a, the aperture ratio can be further improved.

  In the DSC module 100, the second sealing portion 32A is bonded to the first sealing portion 31A, and the joining edge portion 20a of the counter electrode 20 is formed by the first sealing portion 31A and the second sealing portion 32A. It is pinched. For this reason, even if the stress in the direction away from the working electrode 10 acts on the counter electrode 20, the separation is sufficiently suppressed by the second sealing portion 32A. Further, since the partition portion 32b of the second integrated sealing portion 32 is bonded to the first sealing portion 31A through the gap S between the adjacent counter electrodes 20, the counter electrodes 20 of the adjacent DSCs 50 are in contact with each other. Is reliably prevented.

  Next, the working electrode 10, the connecting part 14, the photosensitizing dye, the counter electrode 20, the sealing part 30A, the electrolyte 40, the conductive materials 60P and 60Q, the back sheet 80, and the desiccant will be described in detail.

(Working electrode)
The material which comprises the transparent substrate 11 should just be a transparent material, for example, As such a transparent material, glass, such as borosilicate glass, soda lime glass, white plate glass, quartz glass, polyethylene terephthalate (PET), for example , Polyethylene naphthalate (PEN), polycarbonate (PC), and polyethersulfone (PES). The thickness of the transparent substrate 11 is appropriately determined according to the size of the DSC module 100 and is not particularly limited, but may be in the range of 50 to 10,000 μm, for example.

Examples of materials included in the transparent conductive film 12 include tin-doped indium oxide (Indium-Tin-Oxide: ITO), tin oxide (SnO ₂ ), and fluorine-doped tin oxide (Fluorine-doped-Tin-Oxide: FTO). Examples include conductive metal oxides. The transparent conductive film 12 may be a single layer or a laminate of a plurality of layers containing different conductive metal oxides. When the transparent conductive film 12 is composed of a single layer, the transparent conductive film 12 preferably includes FTO because it has high heat resistance and chemical resistance. The transparent conductive film 12 may further include glass frit. The thickness of the transparent conductive film 12 may be in the range of 0.01 to 2 μm, for example.

Moreover, the resistance value of the connection part 12g of transparent conductive film 12D among the transparent conductive films 12 is not particularly limited, but is preferably equal to or less than the resistance value represented by the following formula (1).
Resistance value = number of DSCs 50 connected in series × 120Ω (1)

  In this case, compared with the case where the resistance value of the connection part 12g exceeds the resistance value represented by said Formula (1), the performance fall of the DSC module 100 can fully be suppressed. In the present embodiment, since the number of DSCs 50 is 4, the resistance value represented by the above formula (1) is 480Ω, and thus the resistance value of the connecting portion 12g is preferably 480Ω or less.

  The thickness of the insulating material 33 is 10-30 micrometers normally, Preferably it is 15-25 micrometers.

  The connection terminal 16 includes a metal material. Examples of the metal material include silver, copper, and indium. You may use these individually or in combination of 2 or more types.

  Moreover, although the connection terminal 16 may be comprised with the material same as the electrically conductive material 60P, or may be comprised with a different material, it is preferable that it is comprised with the same material.

  In this case, since the connection terminal 16 and the conductive material 60P are made of the same material, the adhesion between the connection terminal 16 and the conductive material 60P can be more sufficiently improved. For this reason, the connection reliability in the DSC module 100 can be further improved.

  In the connection terminal 16, the width of the conductive material non-connecting portion 16B is not particularly limited as long as it is smaller than the width of the conductive material connecting portion 16A, but is preferably 1/2 or less of the width of the conductive material connecting portion 16A.

  In this case, the connection reliability in the DSC module 100 can be further improved as compared with the case where the width of the conductive material non-connecting portion 16B exceeds 1/2 of the width of the conductive material connecting portion 16A.

  The width of the conductive material connecting portion 16A is not particularly limited, but is preferably 0.5 to 5 mm, and more preferably 0.8 to 2 mm.

The oxide semiconductor layer 13 is composed of oxide semiconductor particles. Examples of the oxide semiconductor particles include titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), zinc oxide (ZnO), tungsten oxide (WO ₃ ), niobium oxide (Nb ₂ O ₅ ), and strontium titanate (SrTiO ₃ ). , Tin oxide (SnO ₂ ), indium oxide (In ₃ O ₃ ), zirconium oxide (ZrO ₂ ), thallium oxide (Ta ₂ O ₅ ), lanthanum oxide (La ₂ O ₃ ), yttrium oxide (Y ₂ O ₃ ) , Holmium oxide (Ho ₂ O ₃ ), bismuth oxide (Bi ₂ O ₃ ), cerium oxide (CeO ₂ ), aluminum oxide (Al ₂ O ₃ ), or two or more thereof.

  The oxide semiconductor layer 13 is usually composed of an absorption layer for absorbing light, but may be composed of an absorption layer and a reflective layer that reflects light transmitted through the absorption layer and returns it to the absorption layer.

  The thickness of the oxide semiconductor layer 13 may be, for example, 0.5 to 50 μm.

(Connecting part)
The material constituting the connecting portion 14 is not particularly limited as long as the back sheet 80 and the transparent conductive film 12 can be bonded. Examples of the material constituting the connecting portion 14 include a glass frit and a sealing portion. A resin material similar to the resin material used for 31A can be used. Especially, it is preferable that the connection part 14 is a glass frit. Since the glass frit has a higher sealing performance than the resin material, it is possible to effectively suppress intrusion of moisture and the like from the outside of the back sheet 80.

(Photosensitizing dye)
Examples of the photosensitizing dye include a ruthenium complex having a ligand containing a bipyridine structure, a terpyridine structure, and the like, and organic dyes such as porphyrin, eosin, rhodamine, and merocyanine.

(Counter electrode)
As described above, the counter electrode 20 includes the metal substrate 21 and the conductive catalyst layer 22 that is provided on the working electrode 10 side of the metal substrate 21 and promotes the reduction reaction on the surface of the counter electrode 20. However, the joining edge portion 20a may be composed of only the metal substrate 21.

  The metal substrate 21 is made of a corrosion-resistant metal material such as titanium, nickel, platinum, molybdenum, tungsten, aluminum, and stainless steel. The thickness of the metal substrate 21 is appropriately determined according to the size of the DSC module 100 and is not particularly limited, but may be, for example, 0.005 to 0.1 mm.

  The catalyst layer 22 is composed of platinum, a carbon-based material, a conductive polymer, or the like. Here, carbon nanotubes are suitably used as the carbon-based material.

  Moreover, the counter electrode 20 has the inclination part 23 embedded in 30 A of sealing parts, and the main-body part 20b inside it as mentioned above. Here, the angle formed by the inclined portion 23 and the surface of the transparent substrate 11 is not particularly limited as long as it is greater than 0 ° and less than 90 °, but is preferably 5 ° to 45 °. In this case, the durability of the DSC module 100 can be effectively improved.

(Sealing part)
The sealing unit 30A includes a first sealing unit 31A and a second sealing unit 32A.

  Examples of the material constituting the first sealing portion 31A include a modified polyolefin resin containing, for example, an ionomer, an ethylene-vinyl acetic anhydride copolymer, an ethylene-methacrylic acid copolymer, an ethylene-vinyl alcohol copolymer, and ultraviolet curing. Examples thereof include resins and resins such as vinyl alcohol polymers.

  The thickness of 31A of 1st sealing parts is 40-90 micrometers normally, Preferably it is 60-80 micrometers.

  The width P of the bonded portion between the counter electrode 20 and the partition portion 31b is preferably 25% or more and less than 100% of the width Q of the bonded portion between the counter electrode 20 and the annular portion 31a of the first integrated sealing portion 31. In this case, compared with the case where the width | variety P of an adhesion part is less than 25% of the width | variety Q of an adhesion part, it becomes possible to have more outstanding durability. The width P of the bonding portion is more preferably 30% or more of the width Q of the bonding portion, and further preferably 40% or more.

  In the DSC module 100, the width R of the partition part 31b of the first integrated sealing part 31 is preferably 100% or more and less than 200% of the width T of the annular part 31a of the first integrated sealing part 31. 120 to 180% is more preferable.

  In this case, a large aperture ratio and excellent durability can be balanced.

  As the material constituting the second sealing portion 32A, for example, an ionomer, an ethylene-vinyl acetic anhydride copolymer, an ethylene-methacrylic acid copolymer, an ethylene-vinyl alcohol copolymer, as in the first sealing portion 31A. Examples thereof include resins such as modified polyolefin resins, UV curable resins, and vinyl alcohol polymers.

  The thickness of the second sealing portion 32A is usually 20 to 45 μm, preferably 30 to 40 μm.

(Electrolytes)
The electrolyte 40 contains a redox couple such as I ⁻ / I ₃ ^— and an organic solvent. As an organic solvent, acetonitrile, methoxyacetonitrile, methoxypropionitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, γ-butyrolactone, valeronitrile, pivalonitrile, glutaronitrile, methacrylonitrile, isobutyronitrile, Phenylacetonitrile, acrylonitrile, succinonitrile, oxalonitrile, pentanitrile, adiponitrile and the like can be used. Examples of the redox pair include I ⁻ / I ₃ ^— and redox pairs such as bromine / bromide ions, zinc complexes, iron complexes, and cobalt complexes. The electrolyte 40 may use an ionic liquid instead of the organic solvent. As the ionic liquid, for example, a known iodine salt such as a pyridinium salt, an imidazolium salt, or a triazolium salt, and a room temperature molten salt that is in a molten state near room temperature is used. Examples of such room temperature molten salts include 1-hexyl-3-methylimidazolium iodide, 1-ethyl-3-propylimidazolium iodide, dimethylimidazolium iodide, ethylmethylimidazolium iodide, and dimethylpropyl. Imidazolium iodide, butylmethylimidazolium iodide, or methylpropyl imidazolium iodide is preferably used.

  In addition, the electrolyte 40 may use a mixture of the ionic liquid and the organic solvent instead of the organic solvent.

An additive can be added to the electrolyte 40. As the _{additive, LiI, I 2, 4-} t- butylpyridine, guanidinium thiocyanate, 1-methylbenzimidazole, 1-butyl-benzimidazole and the like.

Further, as the electrolyte 40, a nano-composite gel electrolyte, which is a pseudo-solid electrolyte formed by kneading nanoparticles such as SiO ₂ , TiO ₂ , carbon nanotubes, etc. into the electrolyte, may be used, and polyvinylidene fluoride may be used. Alternatively, an electrolyte gelled with an organic gelling agent such as a polyethylene oxide derivative or an amino acid derivative may be used.

The electrolyte 40 includes an oxidation-reduction pair consisting of I ⁻ / I ₃ ^—, and the concentration of I ₃ ⁻ is preferably 0.006 mol / liter or less, and is 0 to 6 × 10 ⁻⁶ mol / liter. More preferably, it is more preferably 0-6 × 10 ⁻⁸ mol / liter. In this case, since the concentration of I ₃ ⁻ carrying electrons is low, the leakage current can be further reduced. For this reason, since an open circuit voltage can be increased more, a photoelectric conversion characteristic can be improved more.

(Conductive material)
For example, metal films are used as the conductive materials 60P and 60Q. As a metal material constituting the metal film, for example, silver or copper can be used.

(Back sheet)
As described above, the back sheet 80 is provided on the surface of the laminate 80A including the weather resistant layer and the metal layer, and the DSC 50 side of the laminate 80A, and bonds the laminate 80A and the connecting portion 14 together. 80B.

  The weather resistant layer may be made of, for example, polyethylene terephthalate or polybutylene terephthalate.

  The thickness of the weather resistant layer may be, for example, 50 to 300 μm.

  The metal layer should just be comprised with the metal material containing aluminum, for example. The metal material is usually composed of aluminum alone, but may be an alloy of aluminum and another metal. Examples of other metals include copper, manganese, zinc, magnesium, lead, and bismuth. Specifically, 1000 series aluminum obtained by adding a trace amount of other metals to 98% or more pure aluminum is desirable. This is because the 1000 series aluminum is cheaper and more workable than other aluminum alloys.

  Although the thickness of a metal layer is not specifically limited, For example, what is necessary is just 12-30 micrometers.

  The stacked body 80A may further include a resin layer. Examples of the material constituting the resin layer include butyl rubber, nitrile rubber, thermoplastic resin, and the like. These can be used alone or in combination of two or more. The resin layer may be formed on the entire surface of the metal layer opposite to the weather-resistant layer, or may be formed only on the peripheral edge.

  Examples of the material constituting the bonding portion 80B include butyl rubber, nitrile rubber, and thermoplastic resin. These can be used alone or in combination of two or more. The thickness of the bonding portion 80B is not particularly limited, but may be, for example, 300 to 1000 μm.

(desiccant)
The desiccant may be in the form of a sheet or granular. Any desiccant may be used as long as it absorbs moisture, and examples of the desiccant include silica gel, alumina, and zeolite.

  Next, a method for manufacturing the DSC module 100 will be described with reference to FIGS. 4, 9 and 10. 10 is a plan view showing a first integrated sealing portion forming body for forming the first integrated sealing portion of FIG.

  First, a laminate in which a transparent conductive film is formed on one transparent substrate 11 is prepared.

  As a method for forming the transparent conductive film, a sputtering method, a vapor deposition method, a spray pyrolysis (SPD) method, a CVD method, or the like is used.

  Next, as shown in FIG. 4, grooves 90 are formed in the transparent conductive film, and transparent conductive films 12 </ b> A to 12 </ b> F that are disposed in an insulating state with the grooves 90 interposed therebetween are formed. Specifically, the four transparent conductive films 12A to 12D corresponding to the DSCs 50A to 50D are formed so as to have a rectangular main body 12a and a protrusion 12c. At this time, with respect to the transparent conductive films 12A to 12C corresponding to the DSCs 50A to 50C, the projecting portion 12c extends not only from the overhanging portion 12d but also from the overhanging portion 12d to form a facing portion 12e facing the main body portion 12a of the adjacent DSC 50. It is formed so that it also has. The transparent conductive film 12D includes not only the rectangular main body 12a and the overhanging portion 12d, but also the first current extraction portion 12f and a connection portion 12g that connects the first current extraction portion 12f and the main body portion 12a. To form. At this time, the first current extraction portion 12f is formed to be disposed on the opposite side of the transparent conductive film 12B with respect to the transparent conductive film 12A. Further, the transparent conductive film 12E is formed so that the second current extraction portion 12h is formed. At this time, the second current extraction portion 12h is disposed on the opposite side of the transparent conductive film 12A with respect to the transparent conductive film 12A, and is disposed adjacent to the first current extraction portion 12f via the groove 90. Form.

The groove 90 can be formed by a laser scribing method using, for example, a YAG laser or a CO ₂ laser as a light source.

  Thus, the transparent conductive film 12 is formed on the transparent substrate 11.

  Next, a precursor of the connection terminal 16 composed of the conductive material connection portion 16A and the conductive material non-connection portion 16B is formed on the protruding portion 12c of the transparent conductive films 12A to 12C. Specifically, the precursor of the connection terminal 16 is formed so that the conductive material connection portion 16A is provided on the facing portion 12e. Also, the precursor of the connection terminal 16 is formed on the transparent conductive film 12E. The precursor of the conductive material non-connecting portion 16B is formed to be narrower than the width of the conductive material connecting portion 16A. The precursor of the connection terminal 16 can be formed, for example, by applying a silver paste and drying it.

  Furthermore, the precursor of the current collection wiring 17 is formed on the connection part 12g of transparent conductive film 12D. The precursor of the current collecting wiring 17 can be formed, for example, by applying a silver paste and drying it.

  Also, precursors for external connection terminals 18a and 18b for taking out current to the outside are formed on the first current extraction part 12f and the second current extraction part 12h of the transparent conductive film 12A, respectively. The precursor of the terminal for external connection can be formed, for example, by applying a silver paste and drying it.

  Further, the precursor of the insulating material 33 made of glass frit is formed so as to enter the first groove 90A formed along the edge of the main body 12a and also cover the edge of the main body 12a. The insulating material 33 can be formed, for example, by applying and drying a paste containing glass frit.

  Further, in order to fix the back sheet 80, the annular connecting portion 14 is surrounded by the annular conductive portion 14 so as to surround the insulating material 33 and pass through the transparent conductive film 12D, the transparent conductive film 12E, and the transparent conductive film 12F. A precursor is formed.

  Furthermore, the precursor of the oxide semiconductor layer 13 is formed on each main body part 12a of the transparent conductive films 12A to 12D. The precursor of the oxide semiconductor layer 13 can be formed by printing a porous oxide semiconductor layer forming paste containing oxide semiconductor particles and then drying the paste.

  The oxide semiconductor layer forming paste includes a resin such as polyethylene glycol and a solvent such as terpineol in addition to the oxide semiconductor particles.

  As a method for printing the oxide semiconductor layer forming paste, for example, a screen printing method, a doctor blade method, a bar coating method, or the like can be used.

  Finally, the precursor of the connection terminal 16, the precursor of the insulating material 33, the precursor of the connecting portion 14, and the precursor of the oxide semiconductor layer 13 are baked together to form the connecting terminal 16, the insulating material 33, and the connecting portion 14. And the oxide semiconductor layer 13 are formed.

  At this time, the firing temperature varies depending on the types of oxide semiconductor particles and glass frit, but is usually 350 to 600 ° C., and the firing time also varies depending on the types of oxide semiconductor particles and glass frit, but usually 1 to 5 times. It's time.

  Thus, as shown in FIG. 9, the connecting portion 14 for fixing the back sheet 80 is formed, and the working electrode 10 having the conductive substrate 15 is obtained.

  Next, a photosensitizing dye is supported on the oxide semiconductor layer 13 of the working electrode 10. For this purpose, the working electrode 10 is immersed in a solution containing a photosensitizing dye, the photosensitizing dye is adsorbed on the oxide semiconductor layer 13, and then the excess photosensitizer is added with the solvent component of the solution. The photosensitizing dye may be adsorbed to the oxide semiconductor layer 13 by washing away the dye and drying it. However, even if the photosensitizing dye is adsorbed to the oxide semiconductor layer 13 by applying a solution containing the photosensitizing dye to the oxide semiconductor layer 13 and then drying the solution, the photosensitizing dye can be absorbed into the oxide semiconductor layer 13. 13 can be carried.

  Next, the electrolyte 40 is disposed on the oxide semiconductor layer 13.

  Next, as shown in FIG. 10, a first integrated sealing portion forming body 131 for forming the first integrated sealing portion 31 is prepared. The first integrated sealing portion forming body 131 prepares one sealing resin film made of the material constituting the first integrated sealing portion 31, and the sealing resin film according to the number of DSCs 50. It can be obtained by forming a rectangular opening 131a. The first integrated sealing portion forming body 131 has a structure in which a plurality of first sealing portion forming bodies 131A are integrated.

  Then, the first integrated sealing portion forming body 131 is bonded onto the conductive substrate 15. At this time, the first integrated sealing portion forming body 131 is bonded to the conductive substrate 15 so as to overlap the insulating material 33 constituting the conductive substrate 15. The first integrated sealing portion forming body 131 can be adhered to the conductive substrate 15 by heating and melting the first integrated sealing portion forming body 131. The first integrated sealing portion forming body 131 is bonded to the conductive substrate 15 so that the main body portion 12 a of the transparent conductive film 12 is disposed inside the first integrated sealing portion forming body 131.

  On the other hand, the same number of counter electrodes 20 as the number of DSCs 50 are prepared.

  The counter electrode 20 is obtained by forming a conductive catalyst layer 22 that promotes a reduction reaction on the surface of the counter electrode 20 on the metal substrate 21 to obtain a counter electrode forming substrate. It can obtain by pressing with the metal mold | die which can obtain the shape of the counter electrode 20 as shown in FIG.

  Next, another first integrated sealing portion forming body 131 described above is prepared. And each of the some counter electrode 20 is bonded together so that each opening 131a of the 1st integrated sealing part formation body 131 may be plugged up.

  Next, the first integrated sealing portion forming body 131 bonded to the counter electrode 20 and the first integrated sealing portion forming body 131 bonded to the working electrode 10 are superposed to form a first integrated sealing portion forming body. 131 is heated and melted under pressure. Thus, the first integrated sealing portion 31 is formed between the working electrode 10 and the counter electrode 20. At this time, the width P of the bonding portion between the surface of the counter electrode 20 on the conductive substrate 15 side and the partition portion 31b of the first integrated sealing portion 31 is equal to the surface of the counter electrode 20 on the conductive substrate 15 side. The 1st integrated sealing part 31 is formed so that it may become narrower than the width | variety Q of the adhesion part with the annular part 31a of the integrated sealing part 31. FIG. Further, the first integrated sealing is performed such that the width R of the partition portion 31b of the first integrated sealing portion 31 is not less than 100% and less than 200% of the width T of the annular portion 31a of the first integrated sealing portion 31. A portion 31 is formed. The formation of the first integrated sealing portion 31 may be performed under atmospheric pressure or under reduced pressure, but is preferably performed under reduced pressure.

  Next, the 2nd integrated sealing part 32 is prepared (refer FIG. 6). The second integrated sealing portion 32 has a structure formed by integrating a plurality of first sealing portions 32A. The second integrated sealing portion 32 can be obtained by preparing a single sealing resin film and forming the rectangular openings 32c corresponding to the number of DSCs 50 in the sealing resin film. The second integrated sealing portion 32 is bonded to the counter electrode 20 so as to sandwich the joining edge portion 20a of the counter electrode 20 together with the first integrated sealing portion 31. The adhesion of the second integrated sealing portion 32 to the counter electrode 20 can be performed by heating and melting the second integrated sealing portion 32.

  Examples of the sealing resin film include ionomers, ethylene-vinyl acetic anhydride copolymers, modified polyolefin resins containing ethylene-methacrylic acid copolymers, ethylene-vinyl alcohol copolymers, ultraviolet curable resins, and vinyls. Examples thereof include resins such as alcohol polymers. The constituent material of the sealing resin film for forming the second integrated sealing portion 32 has a higher melting point than the constituent material of the sealing resin film for forming the first integrated sealing portion 31. It is preferable. In this case, since the second sealing portion 32A is harder than the first sealing portion 31A, it is possible to effectively prevent contact between the counter electrodes 20 of the adjacent DSCs 50. In addition, since the first sealing portion 31A is softer than the second sealing portion 32A, the stress applied to the sealing portion 30A can be effectively relieved.

  Next, the bypass diodes 70 </ b> A, 70 </ b> B, and 70 </ b> C are fixed to the partition part 32 b of the second sealing part 32. The bypass diode 70D is also fixed on the sealing portion 30A of the DSC 50D.

  Then, the conductive material 60Q is fixed to the metal substrate 21 of the counter electrode 20 of the DSCs 50B to 50C so as to pass through the bypass diodes 70A to 70D. Furthermore, each conductive material 60Q between the bypass diodes 70A and 70B, between the bypass diodes 70B and 70C, between the bypass diodes 70C and 70D, the conductive material connection portion 16A on the transparent conductive film 12A, and the conductive material connection portion on the transparent conductive film 12B. A conductive material 60P is formed so as to connect 16A and the conductive material connecting portion 16A on the transparent conductive film 12C. Further, the conductive material 60P is fixed to the metal substrate 21 of the counter electrode 20 of the DSC 50A so as to connect the conductive material connecting portion 16A on the transparent conductive film 12E and the bypass diode 70A. Further, the transparent conductive film 12D and the bypass diode 70A are connected by the conductive material 60P.

  At this time, as the conductive material 60P, a paste containing a metal material constituting the conductive material 60P is prepared, and this paste is applied from the counter electrode 20 to the conductive material connection portion 16A of the connection terminal 16 of the adjacent DSC 50 and cured. . For the conductive material 60Q, a paste containing a metal material constituting the conductive material 60Q is prepared, and this paste is applied on each counter electrode 20 so as to connect adjacent bypass diodes, and is cured. At this time, as the paste, it is preferable to use a low-temperature curable paste that can be cured at a temperature of 90 ° C. or less from the viewpoint of avoiding an adverse effect on the photosensitizing dye.

  Finally, a back sheet 80 is prepared, and the peripheral edge 80 a of the back sheet 80 is bonded to the connecting portion 14. At this time, the back sheet 80 is disposed so that the adhesive portion 80B of the back sheet 80 and the sealing portion 30A of the DSC 50 are separated from each other.

  The DSC module 100 is obtained as described above.

  In the above description, in order to form the connection terminal 16, the insulating material 33, the connecting portion 14, and the oxide semiconductor layer 13, the precursor of the connecting terminal 16, the precursor of the insulating material 33, and the precursor of the connecting portion 14. Body, the precursor of the oxide semiconductor layer 13 is baked in a lump, but the connection terminal 16, the insulating material 33, the connecting portion 14, and the oxide semiconductor layer 13 are separately fired. May be formed.

  The present invention is not limited to the above embodiment. For example, in the above-described embodiment, the DSCs 50A to 50D are arranged in a line along the X direction in FIG. 2, but like the DSC module 200 shown in FIG. The DSC 50A and the DSC 50D may be arranged so that they are adjacent to each other. In this case, unlike the DSC module 100, the transparent conductive film 12D does not require the connection portion 12g to be provided between the main body portion 12a and the first current extraction portion 12f. For this reason, it is not necessary to provide the current collection wiring 17 either.

  Moreover, in the said embodiment, although the 2nd groove | channel 90B which cross | intersects the connection part 14 of the back seat | sheet 80 and the electroconductive board | substrate 15 is not covered with the insulating material 33 which consists of glass frit, the DSC module 300 shown in FIG. As described above, the second groove 90B is preferably covered with an insulating material 33 made of glass frit. In FIG. 12, the back sheet 80 is omitted. As shown in FIG. 12, when the second groove 90 </ b> B intersects the connecting portion 14, moisture may enter the space between the back sheet 80 and the conductive substrate 15 through the second groove 90 </ b> B. It becomes possible. In this case, the insulating material 33 enters the second groove 90 </ b> B, and the insulating material 33 covers the edge of the transparent conductive film 12 except for the main body portion 12 a, so that the inner side from the outer side of the back sheet 80. Moisture penetration into the water is sufficiently suppressed. For this reason, the water | moisture content which penetrate | invaded into the space between the backsheet 80 and the electroconductive board | substrate 15 fully suppresses entering the inside of 30 A of sealing parts through 30 A of sealing parts. For this reason, it is possible to sufficiently suppress a decrease in durability of the DSC module 300.

Furthermore, in the said embodiment, although the 1st electric current extraction part 12f and the 2nd electric current extraction part 12h are arrange | positioned around the DSC50A side, as shown to the DSC module 400 shown in FIG. And the 2nd electric current extraction part 12h may be arrange | positioned around the DSC50D side. In this case, the 1st electric current extraction part 12f is provided so that it may protrude to the outer side of 30 A of sealing parts on the opposite side to DSC50C with respect to the main-body part 12a of transparent conductive film 12D. On the other hand, the second current extraction portion 12h is provided on the opposite side of the DSC 50C with respect to the main body portion 12a of the transparent conductive film 12D. A connecting portion 12i as a second connecting portion extends along the transparent conductive films 12A to 12D, and the connecting portion 12i connects the second current extraction portion 12f and the metal substrate 21 of the counter electrode 20 of the DSC 50A. Yes. Specifically, the current collection wiring 417 is provided on the connection portion 12i along the connection portion 12i, and the current collection wiring 417 and the conductive material 60P extending from the bypass diode 70A are connected. The DSC module 400 can also save space while having excellent photoelectric conversion characteristics. In this case, the resistance value of the connection portion 12i is preferably equal to or less than the resistance value represented by the following formula (1), as in the above embodiment.
Resistance value = number of DSCs 50 connected in series × 120Ω (1)

  Moreover, in the said embodiment, although the biting part contained in the joining edge part 20a is comprised by the inclination part 23, as shown in FIG. 14, the biting part is the inclination part 23, the inclination part 23, and the main-body part 20b. And a connecting portion 24 that connects the two. Here, the connecting portion 24 extends along the conductive substrate 15.

  When the DSC module 100 is placed in a high temperature environment and the space formed by the conductive substrate 15, the counter electrode 20, and the sealing portion 30 </ b> A is thermally expanded, the main body portion 20 b protrudes toward the side opposite to the conductive substrate 15. Become. In this case, it is possible to increase the angle formed by the joining edge portion 20a and the main body portion 20b as compared with the case where the connecting portion 24 is not provided. For this reason, it is more fully suppressed that a tear arises between the joining edge part 20a and the main-body part 20b.

  Furthermore, in the said embodiment, although the biting part contained in the joining edge part 20a is comprised by the inclination part 23, as shown in FIG. 15, it is orthogonal to the surface of the transparent substrate 11, as shown in FIG. You may be comprised by the projection part 25 extended and the connection part 24 which connects the projection part 25 and the main-body part 20b.

  Here, as shown in FIG. 16, the biting portion is preferably provided with an inclined portion 23 between the protruding portion 25 and the connecting portion 24. That is, the protrusion 25 is preferably provided at the tip of the inclined portion 23. In this case, even when the DSC module 100 is placed in a high temperature environment and a stress is applied to pull out the biting portion along the conductive substrate 15, the tip of the inclined portion 23 faces away from the conductive substrate 15. Thus, the protrusion 25 is provided so that the movement of the inclined portion 23 is more sufficiently suppressed by the sealing portion 30A. Therefore, the joining edge portion 20a is more sufficiently suppressed from being pulled out from the sealing portion 30A.

  Furthermore, in the said embodiment, as shown in FIG. 17, some main-body parts 20b of the counter electrode 20 become the convex bending part 20c bent so that it may become convex toward the electroconductive board | substrate 15, and the other side. Preferably it is. That is, as shown in FIG. 17, it is preferable that the height H1 of the convex bent portion 20c from the transparent substrate 11 is larger than the height H2 of the joining edge portion 20a from the transparent substrate 11. When the DSC module 100 is placed in an environment with a large temperature change, the space between the conductive substrate 15, the counter electrode 20, and the sealing portion 30A expands or contracts. At this time, even if an excessive stress is applied to the counter electrode 20 and the counter electrode 20 tends to be in a tensioned state, a part of the main body portion 20b of the counter electrode 20 is a convex bending portion 20c, so that the stress is a convex bending. Absorbed by the part 20c. For this reason, the stress applied to the interface between the joining edge 20a of the counter electrode 20 and the sealing portion 30A can be sufficiently reduced. For this reason, even if the DSC module 100 is placed in an environment with a large temperature change, it is possible to have excellent durability.

  In FIG. 17, the convex flexure 20c is annular. Here, as shown in FIG. 17, the convex bending part 20c is arrange | positioned in the position adjacent to the joining edge part 20a. Stress is likely to be applied to the interface between the joining edge portion 20a and the sealing portion 30A. In that respect, if the convex bending part 20c is arrange | positioned in the position adjacent to the joining edge part 20a, it can suppress effectively that an excessive stress is added to the joining edge part 20a.

  Moreover, it is preferable that the remainder of the main-body part 20b has the concave bending part 20d bent so that it may dent toward the porous oxide semiconductor layer 13 side. That is, it is preferable that the height H3 of the concave bent portion 20d is smaller than the height H2 of the joining edge portion 20a. In this case, since the remaining part of the main body 20b has the concave bent portion 20d, the distance between the electrodes of the conductive substrate 15 and the counter electrode 20 can be reduced. For this reason, the DSC module 100 can have excellent photoelectric conversion characteristics. In FIG. 17, the concave bent portion 20 d is arranged inside the annular convex bent portion 20 c. In FIG. 17, the concave bent portion 20d may not be provided. That is, the height H2 of the joining edge portion 20a from the transparent substrate 11 may be equal to the height H3 of the concave bent portion 20d from the transparent substrate 11. In FIG. 17, the convex flexure 20c does not necessarily have to be provided at a position adjacent to the joint edge 20a, and may be provided at a position separated from the joint edge 20a.

  Moreover, in the said embodiment, although the groove | channel 90 has the 2nd groove | channel 90B, the 2nd groove | channel 90B does not necessarily need to be formed.

  Moreover, in the said embodiment, although the width | variety of the conductive material connection part 16A and the conductive material non-connection part 16B of the connection terminal 16 is made constant, the width | variety of the conductive material connection part 16A and the conductive material non-connection part 16B is respectively connected. It may change along the extending direction of the terminal 16. For example, the width of the conductive material non-connecting portion 16B monotonically increases from the end farthest from the conductive material connecting portion 16A toward the end closest to the conductive material connecting portion 16A. The width may monotonously increase from the end portion on the 16B side toward the end portion farthest from the conductive member non-connecting portion 16B.

  Moreover, in the said embodiment, although the electrically-conductive material connection part 16A and the electrically-conductive material non-connection part 16B are provided along the sealing part 30A, respectively, these are formed so that it may extend in the direction away from the sealing part 30A. May be. However, in this case, it is preferable that the conductive material connecting portion 16A is disposed at a position closer to the sealing portion 30A than the conductive material non-connecting portion 16B. In this case, the conductive material 60P can be made shorter.

  Alternatively, in the connection terminals 16 formed on the transparent conductive films 12A to 12C, the conductive material non-connecting portion 16B may be disposed so as to be orthogonal to the conductive material connecting portion 16A.

  Further, it may be equal to or smaller than the width of the conductive material connecting portion 16A and the conductive material non-connecting portion 16B.

  In the above embodiment, the second sealing portion 32A is bonded to the first sealing portion 31A. However, the second sealing portion 32A may not be bonded to the first sealing portion 31A.

  Furthermore, in the said embodiment, although 30 A of sealing parts are comprised by 31 A of 1st sealing parts and 32 A of 2nd sealing parts, 32 A of 2nd sealing parts may be abbreviate | omitted.

  Moreover, in the said embodiment, the width P of the adhesion part of the counter electrode 20 and the partition part 31b of the 1st integrated sealing part 31 is the adhesion part of the counter electrode 20 and the annular part 31a of the 1st integrated sealing part 31. Although it is narrower than the width Q, the width P of the bonding portion may be equal to or greater than the width Q of the bonding portion.

  Furthermore, in the said embodiment, the width | variety R of the partition part 31b of the 1st integrated sealing part 31 is 100% or more of the width | variety T of the annular part 31a of the 1st integrated sealing part 31, and less than 200%. However, the width R of the partition part 31b may be less than 100% of the width T of the annular part 31a of the first integrated sealing part 31, or 200% or more.

  In the above embodiment, the back sheet 80 and the transparent conductive film 12 are bonded via the connecting portion 14 made of glass frit. However, the back sheet 80 and the transparent conductive film 12 are not necessarily connected via the connecting portion 14. Need not be glued together.

  Furthermore, in the said embodiment, although the connection part 14 and the insulating material 33 are spaced apart, it is preferable that these are all comprised and integrated with the glass frit. In this case, even if moisture enters in the space between the back sheet 80 and the conductive substrate 15, the interface between the connecting portion 14 and the conductive substrate 15, between the sealing portion 30 </ b> A and the conductive substrate 15. No interface exists. Further, both the insulating material 33 and the connecting portion 14 are made of glass frit, and have higher sealing performance than that of resin. For this reason, the penetration | invasion of the water | moisture content through the interface between the connection part 14 and the electroconductive board | substrate 15 and the interface between the insulating material 33 and the electroconductive board | substrate 15 can fully be suppressed.

  Moreover, in the said embodiment, although the insulating material 33 consists of glass frit, the material which comprises the insulating material 33 should just have melting | fusing point higher than the material which comprises 30 A of 1st sealing parts. For this reason, examples of such a material include glass frit, thermosetting resins such as polyimide resins, and thermoplastic resins. Among these, it is preferable to use a thermosetting resin. In this case, even if the sealing portion 30A becomes fluid at high temperatures, the insulating material 33 is less likely to be fluidized at high temperatures than when it is made of a thermoplastic resin, as in the case of glass frit. For this reason, the contact between the conductive substrate 15 and the counter electrode 20 is sufficiently suppressed, and a short circuit between the conductive substrate 15 and the counter electrode 20 can be sufficiently suppressed.

  Moreover, in the said embodiment, although the electroconductive board | substrate 15 has the insulating material 33, it does not need to have the insulating material 33. FIG. In this case, the sealing portion 30 </ b> A and the first integrated sealing portion 31 </ b> A are joined to the transparent substrate 11, the transparent conductive film 12, or the connection terminal 16. Here, the conductive substrate 15 may not have the connection terminal 16. In this case, the sealing portion 30 </ b> A and the first integrated sealing portion 31 </ b> A are bonded to the transparent substrate 11 or the transparent conductive film 12.

  Furthermore, in the said embodiment, although several DSC50 is connected in series, you may connect in parallel.

  Further, in the above embodiment, a plurality of DSCs 50 are used. However, in the present invention, only one DSC may be used.

  Moreover, in the said embodiment, although the number of DSC50 is four, what is necessary is just one or more, and is not limited to four. When there are a plurality of DSCs 50 as described above, it is preferable to arrange the DSCs 50 in a certain direction as shown in FIG. 2 rather than when a part of the DSCs 50A to 50D is turned back halfway as shown in FIG. When the DSCs 50 are arranged in a certain direction as described above, it is possible to select either an even number or an odd number as the number of DSCs 50, the number of DSCs 50 can be freely determined, and the degree of freedom in design is improved. be able to.

  Moreover, in the said embodiment, although the counter electrode 20 comprises the 2nd base material, it replaces with the counter electrode 20 as a counter substrate like DSC500 shown in FIG. 18, and the joining edge part embedded in the sealing part 30A An insulating substrate 501 configured by 501a and a main body portion 501b inside the joining edge portion 501a may be used. In this case, the structure body 502 is disposed in a space between the insulating substrate 501, the sealing portion 31a, and the conductive substrate 15. The structure body 502 is provided on the surface of the conductive substrate 15 on the insulating substrate 501 side. The structure 502 includes a porous oxide semiconductor layer 13, a porous insulating layer 503, and a counter electrode 520 in this order from the conductive substrate 15 side. An electrolyte is disposed in the space. The electrolyte is impregnated into the porous oxide semiconductor layer 13 and the porous insulating layer 503. As the electrolyte, the same electrolyte as the electrolyte 40 can be used. Here, as the insulating substrate 501, for example, a glass substrate or a resin film can be used. As the counter electrode 520, the same electrode as the counter electrode 20 can be used. Alternatively, the counter electrode 520 may be formed of a single porous layer containing, for example, carbon. The porous insulating layer 503 is mainly for preventing physical contact between the porous oxide semiconductor layer 13 and the counter electrode 520 and impregnating the electrolyte 40 therein. As such a porous insulating layer 503, for example, a fired body of an oxide can be used. Note that in the DSC 500 illustrated in FIG. 18, only one structure 502 is provided in the space between the sealing portion 31a, the conductive substrate 15, and the insulating substrate 501, but a plurality of structures 502 are provided. It may be. Further, the porous insulating layer 503 is provided between the porous oxide semiconductor layer 13 and the counter electrode 520, but between the conductive substrate 15 and the counter electrode 520 so as to surround the porous oxide semiconductor layer 13. May be provided. Even with this configuration, physical contact between the porous oxide semiconductor layer 13 and the counter electrode 520 can be prevented. In FIG. 18, the biting portion is constituted by an inclined portion, but the biting portion may be constituted by an inclined portion and a connecting portion as in the case where the counter substrate is constituted by the game 20. In addition, the projection part and the connection part may be used. Here, as the inclined portion, the same one as the inclined portion 23 can be used. Moreover, as a projection part, the thing similar to the projection part 25 can be used. Furthermore, it is preferable that a protrusion provided to face the opposite side of the transparent substrate 11 is provided at the tip of the inclined portion, as in the case where the counter substrate is configured by the counter electrode 20.

  Hereinafter, the content of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Example 1
First, a laminate was prepared by forming a transparent conductive film made of FTO having a thickness of 1 μm on a transparent substrate made of glass having a thickness of 1 mm. Next, as shown in FIG. 4, CO ₂ to form a groove 90 on the transparent conductive film 12 by a laser (Universal System Co. V-460), to form a transparent conductive film 12A-12F. At this time, the width of the groove 90 was 1 mm. Each of the transparent conductive films 12A to 12C was formed so as to have a rectangular main body portion of 4.6 cm × 2.0 cm and a protruding portion protruding from one side edge portion of the main body portion. The transparent conductive film 12D was formed to have a 4.6 cm × 2.1 cm rectangular main body portion and a protruding portion protruding from one side edge of the main body portion. Further, of the transparent conductive films 12A to 12D, the projecting portions 12c of the three transparent conductive films 12A to 12C extend from the one side edge portion 12b of the main body portion 12a and the projecting portion 12d, and are adjacent to each other. The conductive film 12 is constituted by a facing portion 12e facing the main body portion 12a. In addition, the protrusion 12c of the transparent conductive film 12D is configured only by the overhanging portion 12d protruding from the one side edge portion 12b of the main body portion 12a. At this time, the length of the overhang portion 12d in the overhang direction (direction orthogonal to the X direction in FIG. 2) was 2.1 mm, and the width of the overhang portion 12d was 9.8 mm. The width of the facing portion 12e was 2.1 mm, and the length of the facing portion 12e in the extending direction was 9.8 mm.

  Further, the transparent conductive film 12D is formed to have not only the main body portion 12a and the protruding portion 12c, but also the first current extraction portion 12f and a connection portion 12g that connects the first current extraction portion 12f and the main body portion 12a. did. The transparent conductive film 12E was formed to have the second current extraction part 12h. At this time, the width of the connecting portion 12g was 1.3 mm, and the length was 59 mm. Further, the resistance value of the connecting portion 12g was measured by a four-terminal method and found to be 100Ω.

  Next, the precursor of the connection terminal 16 composed of the conductive material connection portion 16A and the conductive material non-connection portion 16B was formed on the protruding portion 12c of the transparent conductive films 12A to 12C. Specifically, the precursor of the connection terminal 16 is provided such that the precursor of the conductive material non-connecting portion 16B is provided on the overhanging portion 12d so that the precursor of the conductive material connecting portion 16A is provided on the facing portion 12e. Formed. At this time, the precursor of the conductive material non-connecting portion 16B was formed to be narrower than the width of the conductive material connecting portion 16A. The precursor of the connection terminal 16 was formed by applying and drying a silver paste (“GL-6000X16” manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) by screen printing.

  Furthermore, the precursor of the current collection wiring 17 was formed on the connection part 12g of transparent conductive film 12D. The precursor of the current collector wiring 17 was formed by applying a silver paste by screen printing and drying.

  In addition, precursors of external connection terminals 18a and 18b for taking out current to the outside were formed on the first current extraction portion 12f and the second current extraction portion 12h of the transparent conductive film 12A, respectively. The precursor of the terminal for external connection was formed by applying a silver paste by screen printing and drying.

  Furthermore, the precursor of the insulating material 33 made of glass frit was formed so as to enter the first groove 90A and cover the edge of the main body part 12a forming the first groove 90A. The insulating material 33 was formed by applying and drying a paste containing glass frit by screen printing. At this time, the edge of the transparent conductive film covered with the insulating material 33 was a portion 0.2 mm from the groove 90.

  Further, in order to fix the back sheet 80, in the same manner as the insulating material 33, an annular ring made of glass frit is formed so as to surround the insulating material 33 and pass through the transparent conductive film 12D, the transparent conductive film 12E, and the transparent conductive film 12F. The precursor of the connection part 14 was formed. At this time, the precursor of the connecting portion 14 was formed so that the precursor of the current collecting wiring 17 was disposed inside thereof. Moreover, the connection part 14 was formed so that the 1st electric current extraction part and the 2nd electric current extraction part may be arrange | positioned on the outer side. The connecting part 14 was formed by applying and drying a paste containing glass frit by screen printing.

  Furthermore, the precursor of the oxide semiconductor layer 13 was formed on each main body part 12a of the transparent conductive films 12A to 12D. The precursor of the oxide semiconductor layer 13 is a porous oxide semiconductor layer forming paste containing titania (“PST-21NR” manufactured by JGC Catalysts & Chemicals Co., Ltd.) three times by screen printing, dried, and further titania. It was formed by applying a porous oxide semiconductor layer forming paste (“PST-400C” manufactured by JGC Catalysts & Chemicals Co., Ltd.) by screen printing, followed by drying.

Next, a precursor of the connection terminal 16, a precursor of the current collector wiring 17, a precursor of the external connection terminals 18a and 18b, a precursor of the insulating material 33, a precursor of the connecting portion 14, a precursor of the insulating material 33, The precursor of the oxide semiconductor layer 13 was baked at 500 ° C. for 15 minutes to form the connection terminal 16, the current collector wiring 17, the external connection terminals 18 a and 18 b, the connecting portion 14, the insulating material 33, and the oxide semiconductor layer 13. . Thus, the working electrode 10 having the connecting portion 14 and the conductive substrate 15 was obtained. At this time, the width of the conductive material connection portion of the connection terminal 16 was 1.0 mm, and the width of the conductive material non-connection portion was 0.3 mm. Further, the length along the extending direction of the conductive material connecting portion was 7.0 mm, and the length along the extending direction of the conductive material non-connecting portion was 7.0 mm. The dimensions of the current collector wiring 17, the external connection terminals 18 a and 18 b, the connecting portion 14, and the oxide semiconductor layer 13 were as follows.

Current collecting wiring 17: thickness 4 μm, width 200 μm, length 79 mm along the X direction in FIG. 2, length 21 mm along the direction orthogonal to the X direction in FIG.
External connection terminals 18a and 18b: thickness 20 μm, width 2 mm, length 7 mm
Connection part 14: thickness 50 μm, width 3 mm
Oxide semiconductor layer 13: thickness 14 μm, length 17 mm in the X direction in FIG. 2, length 42.1 mm in the direction perpendicular to the X direction in FIG.

  Next, the working electrode is immersed overnight in a dye solution containing 0.2 mM of a photosensitizing dye composed of N719 and a solvent in which acetonitrile and tert-butanol are mixed at a volume ratio of 1: 1. Then, it was taken out and dried, and a photosensitizing dye was supported on the oxide semiconductor layer.

  Next, on the oxide semiconductor layer, in a solvent composed of 3-methoxypropionitrile, hexylmethylimidazolium iodide 2M, n-methylbenzimidazole 0.3M, and guanidinium thiocyanate 0.1M are formed. The electrolyte was applied and dried to place the electrolyte.

  Next, a first integrated sealing portion forming body for forming the first sealing portion was prepared. The first integrated sealing portion forming body prepares one sealing resin film made of maleic anhydride-modified polyethylene (trade name: Binnel, manufactured by DuPont) of 8.0 cm × 4.6 cm × 50 μm, It was obtained by forming four rectangular openings in the sealing resin film. At this time, each opening has a size of 1.7 cm × 4.4 cm × 50 μm, the width of the annular portion is 2 mm, and the width of the partition portion that partitions the inner opening of the annular portion is 2.6 mm. The 1st integrated sealing part formation body was produced.

  Then, after the first integrated sealing portion forming body is overlaid on the insulating material 33 constituting the conductive substrate 15, the first integrated sealing portion forming body is bonded to the insulating material 33 by heating and melting. I let you.

Next, four counter electrodes were prepared. Two of the four counter electrodes were prepared as follows. That is, first, a catalyst layer made of platinum having a thickness of 5 nm was formed on a 4.6 cm × 1.9 cm × 40 μm titanium foil by sputtering to prepare a counter electrode forming substrate. At this time, the catalyst layer was not formed on the 1 mm width portion of the peripheral edge of the counter electrode forming substrate. The obtained counter electrode forming substrate was processed by pressing it with a mold capable of obtaining the shape of the counter electrode 20 as shown in FIG. In this way, a counter electrode was obtained. Of the four counter electrodes, the remaining two counter electrodes were prepared as follows. That is, first, a catalyst layer made of platinum having a thickness of 5 nm was formed on a 4.6 cm × 2.0 cm × 40 μm titanium foil by sputtering to prepare a counter electrode forming substrate. At this time, the catalyst layer was not formed on the 1 mm width portion of the peripheral edge of the counter electrode forming substrate. It processed by pressing with the metal mold | die which can obtain the shape of the counter electrode 20 as shown in FIG. 8 with respect to the obtained counter electrode formation board | substrate. In this way, a counter electrode was obtained. In the obtained counter electrode, the peripheral edge portion was inclined with respect to the surface of the inner main body portion. Further, another one of the first integrated sealing portion forming body is prepared, and the first integrated sealing portion forming body is a surface facing the working electrode of the counter electrode on the peripheral edge portion of the counter electrode. Bonding was performed in the same manner as described above. Then, the first integrated sealing portion forming body bonded to the working electrode and the first integrated sealing portion forming body bonded to the counter electrode are opposed to each other, and the first integrated sealing portion forming bodies are overlapped with each other. Combined. In this state, the first integrated sealing portion forming body was heated and melted while pressurizing the first integrated sealing portion forming body. Thus, the first sealing portion was formed between the working electrode and the counter electrode. At this time, the width P of the adhesive portion between the partition portion of the first integrated sealing portion and the surface on the conductive substrate side of the counter electrode, the conductive substrate of the annular portion and the counter electrode of the first integrated sealing portion The width Q of the adhesive portion with the side surface, the width R of the partition portion of the first integrated sealing portion, and the width T of the annular portion were as follows.

P = 1.0mm
Q = 2.0mm
R = 2.6mm
T = 2.2mm

  Next, a second integrated sealing part was prepared. The second integrated sealing portion is prepared by preparing a sealing resin film made of maleic anhydride-modified polyethylene (trade name: Binnel, manufactured by DuPont) of 8.0 cm × 4.6 cm × 50 μm. It was obtained by forming four rectangular openings in the stopping resin film. At this time, each opening has a size of 1.7 cm × 4.4 cm × 50 μm, the width of the annular portion is 2 mm, and the width of the partition portion that partitions the inner opening of the annular portion is 2.6 mm. A second integrated sealing portion was prepared. The second integrated sealing portion was bonded to the counter electrode so as to sandwich the peripheral edge portion of the counter electrode together with the first integrated sealing portion. At this time, the first integrated sealing portion and the second integrated sealing portion were bonded to the counter electrode and the first integrated sealing portion by heating and melting while pressing the second integrated sealing portion against the counter electrode. At this time, the peripheral edge portion of the counter electrode was embedded in the integrated sealing portion formed by the first integrated sealing portion and the second integrated sealing portion. Specifically, the peripheral edge bites into the sealing portion so as to face the opposite side of the transparent substrate, is inclined with respect to the surface of the transparent substrate, and extends away from the transparent substrate as the distance from the main body portion increases. An inclined part was formed.

  Next, the desiccant sheet was affixed with the double-sided tape on the metal substrate of each counter electrode. The dimensions of the desiccant sheet were 1 mm thick × 3 cm long × 1 cm wide, and a zeo sheet (trade name, manufactured by Shinagawa Kasei Co., Ltd.) was used as the desiccant sheet.

  Next, as shown in FIG. 2, bypass diodes 70 </ b> A to 70 </ b> C are respectively provided in the three partition portions of the second integrated sealing portion, and a low-temperature curing type silver paste (Dotite D500 manufactured by Fujikura Kasei Co., Ltd.) is used. It fixed by apply | coating so that it might connect with the metal substrate 21 of the counter electrode 20 from the terminal of both ends. Further, among the four DSCs 50A to 50D, the bypass diode 70D is connected to the annular part of the second integrated sealing part of the DSC 50D, and the low-temperature curing type silver paste is connected to the counter electrode from one of the terminals at both ends of the diode. It was fixed by applying as follows. Thus, the conductive material 60Q was formed so as to connect the two adjacent bypass diodes to the four bypass diodes 70A to 70D. At this time, the conductive material 60Q was formed by curing the low temperature curable silver paste at 30 ° C. for 12 hours. As the bypass diode, RB751V-40 manufactured by ROHM was used.

  Further, a low temperature curing type silver paste (Dotite D-500, manufactured by Fujikura Kasei Co., Ltd.) is used so as to connect each conductive material 60Q between the bypass diodes and the conductive material connecting portions on the three transparent conductive films 12A to 12C. The conductive material 60P was formed by applying and curing. Further, with respect to the bypass diode 70A, the conductive material 60P was formed by applying and curing the low-temperature curable silver paste so as to be connected to the conductive material connecting portion on the transparent conductive film 12E. At this time, the conductive material 60P was formed by curing the low temperature curable silver paste at 30 ° C. for 12 hours.

  Next, butyl rubber (“Aikamelt” manufactured by Aika Kogyo Co., Ltd.) was applied onto the connecting portion 14 with a dispenser while heating at 200 ° C. to form a precursor of the bonded portion. On the other hand, a laminate is prepared by laminating a film (thickness 50 μm) made of polybutylene terephthalate (PBT) resin film (thickness 50 μm), aluminum foil (thickness 25 μm) and binel (trade name, manufactured by DuPont) in this order. did. And it piled up on the peripheral part of this laminated body 80A, and the precursor of the adhesion part 80B, and pressurized for 10 seconds. In this way, a back sheet 80 composed of the bonding portion 80B and the laminated body 80A was obtained at the connecting portion 14. A DSC module was obtained as described above.

(Example 2)
A DSC module was produced in the same manner as in Example 1 except that a connecting portion was provided between the main body portion and the inclined portion, and this connecting portion was formed so as to extend along the transparent substrate.

(Example 3)
The same as in Example 2 except that instead of the inclined portion, a projection is provided at the tip of the connecting portion so as to face the opposite side of the transparent substrate and extends perpendicular to the surface of the transparent substrate. Thus, a DSC module was produced.

Example 4
A DSC module was produced in the same manner as in Example 1 except that a protrusion provided to face the opposite side of the transparent substrate was formed at the tip of the inclined portion.

(Example 5)
When the first integrated sealing portion forming body is heated and melted while being pressurized, the heating and melting is performed while pressing the inside of the annular portion adjacent to the bonding edge in the main body of the counter electrode. A DSC module was produced in the same manner as in Example 1 except that an annular convex bent portion was formed at a position adjacent to the concave bent portion and a concave bent portion was formed inside the annular bent portion.

(Example 6)
A DSC module was produced in the same manner as in Example 5 except that the amount of the applied electrolyte was increased from 20 μL to 45 μL so that the concave bent portion was not formed.

(Example 7)
When the first integrated sealing portion forming body is heated and melted while being pressurized, the inner portion of the annular portion adjacent to the joint edge portion of the main body portion of the counter electrode and a part of the annular portion (the U-shaped portion) ) While pressing, a straight convex bent portion is formed in a part of the annular portion adjacent to the joint edge of the counter electrode, and a concave bent portion is formed at a position facing the convex bent portion. A DSC module was produced in the same manner as in Example 5 except that.

(Comparative Example 1)
When preparing the counter electrode, no processing is performed on the counter electrode forming substrate, and the counter electrode forming substrate is used as it is as the counter electrode, so that the joint edge of the counter electrode is parallel to the surface of the transparent substrate. A DSC module was produced in the same manner as in Example 1 except that it was extended.

(Characteristic evaluation)
(durability)
For the DSC modules obtained in Examples 1 to 7 and Comparative Example 1, the photoelectric conversion efficiency (η ₀ ) was measured. Then, about the DSC module obtained in Examples 1-7 and the comparative example 1, the photoelectric conversion efficiency ((eta)) after performing the heat cycle test according to JISC8938 was also measured. And the following formula:
Retention rate of photoelectric conversion efficiency (%) = η / η ₀ × 100
Based on the above, the retention rate of photoelectric conversion efficiency (photoelectric conversion retention rate) was calculated. The results are shown in Table 1.

  As shown in Table 1, it was found that the DSC modules of Examples 1 to 7 showed a higher photoelectric conversion retention rate than the DSC module of Comparative Example 1.

  From the above, it was confirmed that the DSC module of the present invention has excellent durability.

DESCRIPTION OF SYMBOLS 11 ... Transparent substrate 13 ... Oxide semiconductor layer 15 ... Conductive substrate (1st base material, 1st electrode)
20, 520 ... Counter electrode (second base material, second electrode)
20a ... Joining edge portion 20b ... Main body portion 20c ... Convex-shaped bending portion 20d ... Concave-shaped bending portion 23 ... Inclined portion (biting portion)
24 ... Connection part 25 ... Protrusion part (cutting-in part)
30A ... Sealing part 50, 50A-50D ... Dye-sensitized solar cell 100, 200, 300, 400, 500 ... Dye-sensitized solar cell module (dye-sensitized solar cell element)
501 ... Insulating substrate (second base material)
520 ... Counter electrode

Claims (5)

Having at least one dye-sensitized solar cell;
The dye-sensitized solar cell is
A first base material having a transparent substrate;
A second substrate facing the first substrate;
An annular sealing portion for joining the first base material and the second base material,
The second substrate has flexibility;
An annular joining edge joined to the sealing part by being embedded in the sealing part;
A main body part inside the joining edge part,
The joint edges, have a biting portion bites into the sealing portion extends so as to be separated with respect to said transparent substrate,
The biting portion is inclined with respect to the surface of the transparent substrate of the first base material, and from the main body portion
A dye-sensitized solar cell having an inclined portion that extends away from the transparent substrate as it moves away, and further includes a protrusion provided at the tip of the inclined portion so as to face the side opposite to the first base material. element. The joint edge portion has a connecting portion that connects the biting portion and the main body portion,
The dye-sensitized solar cell element according to claim 1 , wherein the connecting portion extends along the transparent substrate. 3. The dye-sensitized solar cell element according to claim 1, wherein a part of the main body portion is a convex bending portion that is bent so as to protrude toward the side opposite to the first base material. An oxide semiconductor layer provided on the first substrate;
The first substrate is composed of a first electrode;
The second substrate is composed of a second electrode;
The dye-sensitized solar cell element according to claim 3 , wherein the remaining portion of the main body portion has a concave bent portion that is bent so as to be recessed toward the oxide semiconductor layer side. The dye-sensitized solar cell element according to claim 3 or 4 , wherein the convex bent portion is disposed at a position adjacent to the joining edge portion.

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