JP2018006498A - Photoelectric conversion element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoelectric conversion element capable of improving an opening ratio.SOLUTION: The present invention relates to a photoelectric conversion element 100 comprising at least one photoelectric conversion cell 50, a first external connection terminal 70a for taking a current out of the at least one photoelectric conversion cell 50, a second external connection terminal 70b for taking a current out of the at least one photoelectric conversion cell 50, and a connector 60 for taking the currents out of the first external connection terminal 70a and second external connection terminal 70b, and characterized in that: the connector 60 has a connector body part 61, a first connector terminal 62a, and a second connector terminal 62b; the first external connection terminal 70a is provided outside an annular sealing part 30 of one photoelectric conversion cell 50 of the at least one photoelectric conversion cell 50 and at a first transparent conductive part 12 of a first conductive substrate 10; and the second external connection terminal 70b is provided on a metal substrate 21 of a second conductive substrate 20 of one photoelectric conversion cell 50 of the at least one photoelectric conversion cell 50.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a photoelectric conversion element.

  As a photoelectric conversion element, a photoelectric conversion element using a dye has attracted attention because it is inexpensive and can provide high photoelectric conversion efficiency.

  As a photoelectric conversion element using such a dye, a dye-sensitized solar cell element including a photoelectric conversion cell and two external connection terminals for taking out current from the photoelectric conversion cell is known (Patent Document 1 below). reference). In Patent Document 1 below, a photoelectric conversion cell is a ring-shaped electrode that joins a transparent conductive substrate having a transparent conductive layer, a counter electrode having a metal substrate facing the transparent conductive substrate, and the transparent conductive substrate and the counter electrode. It has been disclosed that two external connection terminals are provided on the transparent conductive layer of the transparent conductive substrate and outside the annular sealing portion. Further, Patent Document 1 below discloses that a connector is connected to the two external connection terminals.

JP 2014-211951 A

  However, the photoelectric conversion element described in Patent Document 1 has the following problems. That is, in the above Patent Document 1, two external connection terminals for connecting the connector are provided on the transparent conductive substrate. Therefore, a space for two external connection terminals is required on the transparent conductive substrate. In order to ensure the space for two external connection terminals, the opening area of the sealing part had to be reduced. For this reason, the photoelectric conversion element described in Patent Document 1 has room for improvement in terms of preventing a decrease in the aperture ratio.

  This invention is made | formed in view of the said situation, and it aims at providing the photoelectric conversion element which can improve an aperture ratio.

  In order to solve the above problems, the present invention provides at least one photoelectric conversion cell, a first external connection terminal for taking out current from the at least one photoelectric conversion cell, and taking out current from the at least one photoelectric conversion cell. A second external connection terminal and a connector for extracting current from the first external connection terminal and the second external connection terminal, wherein the photoelectric conversion cell has a first conductive substrate, and the first conductive The conductive substrate includes a transparent substrate and a first transparent conductive portion provided on the transparent substrate, the second conductive substrate includes a metal substrate, and the sealing portion includes a resin seal containing a resin. A connector main body, a first connector terminal provided on the connector main body, fixed to the first external connection terminal, provided on the connector main body, and the second external Connection A second connector terminal fixed to the child, wherein the first external connection terminal is outside the annular sealing portion of one photoelectric conversion cell of the at least one photoelectric conversion cell, and The metal substrate of the second conductive substrate of one of the at least one photoelectric conversion cells provided in the first transparent conductive portion of the first conductive substrate, and the second external connection terminal. It is a photoelectric conversion element provided on the top.

  According to this photoelectric conversion element, the first external connection terminal is outside the annular sealing portion of one photoelectric conversion cell of at least one photoelectric conversion cell, and the first transparent conductive material of the first conductive substrate. And the second external connection terminal is provided on the metal substrate of the second conductive substrate of one of the at least one photoelectric conversion cells, and the first connector terminal of the connector is the first external terminal. Connected to the connection terminal, the second connector terminal is connected to the second external connection terminal. That is, in order to take out an electric current from a photoelectric conversion cell via a connector, it becomes possible to make only the 1st external connection terminal the external connection terminal provided in the 1st transparent conductive part of a 1st conductive substrate. For this reason, it is not necessary to provide a space for providing the second external connection terminal on the first conductive substrate and outside the annular sealing portion. Accordingly, the opening area inside the sealing portion can be increased, and the aperture ratio of the photoelectric conversion element can be improved.

  The photoelectric conversion element preferably further includes an adhesive portion that bonds the connector main body portion and the first conductive substrate and has a smaller linear expansion coefficient than the resin sealing portion of the sealing portion.

  In this case, when the photoelectric conversion element is placed in an environment with a large temperature change, the resin sealing portion of the sealing portion expands and contracts and the thickness of the sealing portion increases. At this time, the bonding portion has a linear expansion coefficient smaller than that of the resin sealing portion of the sealing portion, and the connector main body portion and the first conductive substrate are bonded by the bonding portion. For this reason, even if the connector main body portion of the connector attempts to move away from the first conductive substrate, the bonding portion sufficiently suppresses the connector main body portion from moving away from the first conductive substrate. For this reason, the movement of the connector main body sufficiently suppresses excessive stress from being applied between the first connector terminal and the first external connection terminal and between the second connector terminal and the second external connection terminal. The peeling of the first connector terminal from the first external connection terminal and the peeling of the second connector terminal from the second external connection terminal are sufficiently suppressed. As a result, according to the photoelectric conversion element of the present invention, it is possible to have excellent durability even in an environment where the temperature change is large.

  In the photoelectric conversion element, the adhesive portion includes a main body portion and an overhang portion protruding from the main body portion, and the overhang portion includes the connector main body portion and the metal substrate of the second conductive substrate. Are preferably adhered.

  In this case, when the photoelectric conversion element of the present invention is placed in an environment with a large temperature change, the sealing portion expands and contracts and the thickness of the sealing portion changes. At this time, the bonding portion has a linear expansion coefficient smaller than the linear expansion coefficient of the sealing portion, and the protruding portion of the bonding portion bonds the connector main body portion and the metal substrate of the second conductive substrate. For this reason, for example, even if the metal substrate of the second conductive substrate tries to move in the direction approaching the first conductive substrate, the metal substrate is sufficiently suppressed from moving in the direction approaching the first transparent conductive portion. For this reason, it is more sufficiently suppressed that excessive stress is applied between the second external connection terminal and the second connector terminal due to the movement of the metal substrate, and separation of the second connector terminal from the second external connection terminal is sufficiently performed. It is suppressed. As a result, according to the photoelectric conversion element of the present invention, it is possible to have more excellent durability even in an environment with a large temperature change.

  In the photoelectric conversion element, it is preferable that the metal substrate of the second conductive substrate includes titanium, and the second external connection terminal includes a metal, a resin, and carbon.

  In this case, the second external connection terminal is difficult to peel from the metal substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the photoelectric conversion element which can improve an aperture ratio is provided.

It is a top view which shows 1st Embodiment of the photoelectric conversion element of this invention. FIG. 2 is an end view of a partially cut surface along the line II-II in FIG. 1. FIG. 3 is a partially enlarged view of FIG. 2. It is a top view which shows the 1st electroconductive board | substrate of the photoelectric conversion element of FIG. It is a top view which shows the state which provided the oxide semiconductor layer and the sealing part in the 1st conductive substrate of FIG. It is a top view which shows 1 process of the manufacturing method of the photoelectric conversion element of FIG. It is a partial cut surface end view which shows a part of 2nd Embodiment of the photoelectric conversion element of this invention. It is a partial cut surface end view which shows a part of 3rd Embodiment of the photoelectric conversion element of this invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to FIGS. 1 is a plan view showing one embodiment of a photoelectric conversion element of the present invention, FIG. 2 is a sectional end view taken along the line II-II in FIG. 1, and FIG. 3 is a partially enlarged view of FIG. 4 is a plan view showing a first conductive substrate of the photoelectric conversion element of FIG. 1, and FIG. 5 is a plan view showing a state where an oxide semiconductor layer and a sealing portion are provided on the first conductive substrate of FIG. is there.

  As illustrated in FIGS. 1 to 5, the photoelectric conversion element 100 extracts one photoelectric conversion cell 50, a first external connection terminal 70 a for extracting current from the photoelectric conversion cell 50, and a current from the photoelectric conversion cell 50. And a connector 60 for taking out current from the first external connection terminal 70a and the second external connection terminal 70b.

  As shown in FIG. 2, the photoelectric conversion cell 50 includes a first conductive substrate 10, a second conductive substrate 20 facing the first conductive substrate 10, and an oxide provided on the first conductive substrate 10. A semiconductor layer 13; an electrolyte 40 provided between the first conductive substrate 10 and the second conductive substrate 20; an annular sealing portion 30 that joins the first conductive substrate 10 and the second conductive substrate 20; It has. The electrolyte 40 is filled in a cell space formed by the first conductive substrate 10, the second conductive substrate 20, and the sealing unit 30.

  As shown in FIGS. 2 to 4, the first conductive substrate 10 includes a transparent substrate 11 and a transparent conductive layer 12 as a first transparent conductive portion provided on the transparent substrate 11.

  As shown in FIG. 2, the oxide semiconductor layer 13 is disposed inside the sealing portion 30. Further, a dye is adsorbed on the oxide semiconductor layer 13.

  As shown in FIG. 2, the sealing unit 30 is provided on the first conductive substrate 10. The sealing unit 30 includes an inorganic sealing unit 30B made of an inorganic material, and a resin sealing unit 30A that connects the inorganic sealing unit 30B and the second conductive substrate 20 and contains a resin. . As shown in FIG. 5, the sealing portion 30 has a quadrangular ring shape when viewed along the thickness direction, and the quadrangular annular sealing portion 30 includes four linear portions 30 a and two 4 crossing portions 30b formed by extending and intersecting the linear portions 30a, and one corner portion 30c of the four crossing portions 30b opposite to the oxide semiconductor layer 13 is provided. 30d is cut out.

  As shown in FIG. 2, the second conductive substrate 20 includes a metal substrate 21 serving as a substrate and an electrode, and a conductive substrate that is provided on the first conductive substrate 10 side of the metal substrate 21 and contributes to the reduction of the electrolyte 40. And a catalyst layer 22. The second conductive substrate 20 has a quadrangular shape when viewed along its thickness direction, and one of the four corners is cut away (see FIG. 1). The corner portion of the first conductive substrate 10 is exposed by cutting out the corner portion and cutting out the corner portion from one of the four intersection portions 30b of the sealing portion 30.

  The first external connection terminal 70 a is provided on the transparent conductive layer 12 of the first conductive substrate 10 outside the annular sealing portion 30 of the photoelectric conversion cell 50. On the other hand, the second external connection terminal 70 b is provided on the metal substrate 21 of the second conductive substrate 20 of the photoelectric conversion cell 50.

  On the other hand, as shown in FIG. 3, the connector 60 includes a connector main body 61, a first connector terminal 62 a provided in the connector main body 61, and a second connector terminal 62 b provided in the connector main body 61. Yes. The first connector terminal 62a is fixed to the first external connection terminal 70a by the first fixing portion 80a, and the second connector terminal 62b is fixed to the second external connection terminal 70b by the second fixing portion 80b.

  In addition, an adhesive portion 90 is provided on the first conductive substrate 10. The bonding portion 90 bonds the connector main body portion 61 and the first conductive substrate 10 and has a smaller linear expansion coefficient than the sealing portion 30. In the present embodiment, the bonding portion 90 includes a main body portion 90a and an overhang portion 90b protruding from the main body portion 90a. The overhang portion 90b is a metal substrate of the connector main body portion 61 and the second conductive substrate 20. 21 is bonded.

  According to the photoelectric conversion element 100, the first external connection terminal 70 a is provided on the transparent conductive layer 12 of the first conductive substrate 10 of the photoelectric conversion cell 50 outside the annular sealing portion 30 of the photoelectric conversion cell 50. The second external connection terminal 70b is provided on the metal substrate 21 of the second conductive substrate 20 of the photoelectric conversion cell 50, and the first connector terminal 62a of the connector 60 is connected to the first external connection by the first fixing portion 80a. The second connector terminal 62b is fixed to the second external connection terminal 70b by the second fixing portion 80b. That is, in order to take out current from the photoelectric conversion cell 50 via the connector 60, it is possible to use only the first external connection terminal 70a as the external connection terminal provided on the transparent conductive layer 12 of the first conductive substrate 10. For this reason, it is not necessary to provide a space for providing the second external connection terminal 70 b on the first conductive substrate 10 and outside the annular sealing portion 30. Accordingly, the opening area inside the sealing portion 30 can be increased, and the aperture ratio of the photoelectric conversion element 100 can be improved.

  Further, when the photoelectric conversion element 100 is placed in an environment with a large temperature change, the resin sealing portion 30A of the sealing portion 30 expands and contracts, and the thickness of the sealing portion 30 changes. At this time, the bonding portion 90 has a linear expansion coefficient smaller than the linear expansion coefficient of the resin sealing portion 30A of the sealing portion 30, and the connector main body 61 and the first conductive substrate 10 are bonded by the bonding portion 90. Has been. For this reason, even if the connector main body 61 of the connector 60 tries to move away from the first conductive substrate 10, the bonding portion 90 is sufficient for the connector main body 61 to move away from the first conductive substrate 10. To be suppressed. For this reason, excessive stress is applied between the first connector terminal 62a and the first external connection terminal 70a and between the second connector terminal 62b and the second external connection terminal 70b due to the movement of the connector body 61. Is sufficiently suppressed, and separation of the first connector terminal 62a from the first external connection terminal 70a and separation of the second connector terminal 62b from the second external connection terminal 70b are sufficiently suppressed. As a result, according to the photoelectric conversion element 100, it is possible to have excellent durability even in an environment with a large temperature change.

  Further, in the photoelectric conversion element 100, the bonding portion 90 has a main body portion 90a and a protruding portion 90b that protrudes from the main body portion 90a, and the protruding portion 90b is a metal of the connector main body portion 61 and the second conductive substrate 20. It is provided between the substrate 21. For this reason, when the photoelectric conversion element 100 is placed in an environment with a large temperature change, the resin sealing portion 30A of the sealing portion 30 expands and contracts, and the thickness of the sealing portion 30 changes. At this time, the bonding portion 90 has a linear expansion coefficient smaller than the linear expansion coefficient of the sealing portion 30, and the protruding portion 90 b of the bonding portion 90 is connected to the connector main body portion 61 and the metal substrate 21 of the second conductive substrate 20. Is glued. For this reason, for example, even if the metal substrate 21 of the second conductive substrate 20 tries to move in the direction approaching the first conductive substrate 10, the metal substrate 21 is sufficiently suppressed from moving in the direction approaching the transparent conductive layer 12. The Therefore, the movement of the metal substrate 21 can more sufficiently suppress the application of excessive stress between the second external connection terminal 70b and the second connector terminal 62b, and the second connector terminal 62b from the second external connection terminal 70b can be suppressed. Peeling is sufficiently suppressed. As a result, according to the photoelectric conversion element 100, it is possible to have more excellent durability even in an environment with a large temperature change.

  Furthermore, in the photoelectric conversion element 100, the second connector terminal 62 b of the connector 60 is fixed to the second external connection terminal 70 b on the metal substrate 21 of the second conductive substrate 20, while the 4 in the rectangular annular sealing portion 30. The first external connection on the transparent conductive layer 12 of the first conductive substrate 10 exposed by the cutout of the corner portion 30d opposite to the oxide semiconductor layer 13 at one of the cross portions 30b. The first connector terminal 62a of the connector 60 is fixed to the terminal 70a. Here, as shown in FIG. 5, the length w2 of the diagonal lines of the four intersecting portions 30c is longer than the width w1 of the linear portions 30a. For this reason, even if the corner part 30d on the opposite side to the oxide semiconductor layer 13 is cut out at one of the four intersection parts 30c, the sealing width at the intersection part 30c is equal to that of the linear part 30a. An excessive reduction in the sealing width can be prevented. Therefore, in order to secure the sealing width of the annular sealing portion 30, it is not necessary to reduce the area of the inner opening of the sealing portion. Therefore, a decrease in the aperture ratio of the photoelectric conversion element 100 can be sufficiently prevented.

  Next, the first conductive substrate 10, the second conductive substrate 20, the oxide semiconductor layer 13, the sealing portion 30, the electrolyte 40, the dye, the first external connection terminal 70a, the second external connection terminal 70b, the connector 60, The 1st fixing | fixed part 80a, the 2nd fixing | fixed part 80b, and the adhesion part 90 are demonstrated in detail.

<First conductive substrate>
The first conductive substrate 10 includes a transparent substrate 11 and a transparent conductive layer 12 provided on the transparent substrate 11.

  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 Insulating materials such as polyethylene naphthalate (PEN), polycarbonate (PC), and polyethersulfone (PES). The thickness of the transparent substrate 11 is appropriately determined according to the size of the photoelectric conversion element 100 and is not particularly limited, but may be in the range of 50 to 40,000 μm, for example.

Examples of the material constituting the transparent conductive layer 12 include conductive metal oxides such as tin-added indium oxide (ITO), tin oxide (SnO ₂ ), and fluorine-added tin oxide (FTO). The transparent conductive layer 12 may be a single layer or a laminate of a plurality of layers made of different conductive metal oxides. When the transparent conductive layer 12 is composed of a single layer, the transparent conductive layer 12 is preferably composed of FTO because it has high heat resistance and chemical resistance. The thickness of the transparent conductive layer 12 may be in the range of 0.01 to 2 μm, for example.

<Second conductive substrate>
As described above, the second conductive substrate 20 includes the metal substrate 21 serving as a substrate and an electrode, and the conductive catalyst layer 22.

  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 photoelectric conversion element 100 and is not particularly limited, but may be, for example, 0.005 to 4 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. Note that the second conductive substrate 20 may not have the catalyst layer 22 when the metal substrate 21 has a catalytic function (for example, when it contains carbon or the like).

<Oxide semiconductor layer>
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 ), or two or more thereof.

  The thickness of the oxide semiconductor layer 13 is usually 2 to 40 μm, preferably 10 to 30 μm.

<Sealing part>
As described above, the sealing unit 30 includes the inorganic sealing unit 30B and the resin sealing unit 30A.

  The inorganic sealing part 30B is not particularly limited as long as it is made of an inorganic material, and examples of the inorganic material constituting the inorganic sealing part 30B include glass and ceramics.

  The resin sealing portion 30A is not particularly limited as long as the resin sealing portion 30A is made of a material containing a resin. Examples of the resin constituting the resin sealing portion 30A include thermoplastic resins such as modified polyolefin resins and vinyl alcohol polymers. Examples thereof include resins and ultraviolet curable resins. Examples of modified polyolefin resins include ionomers, ethylene-vinyl acetic anhydride copolymers, ethylene-methacrylic acid copolymers, and ethylene-vinyl alcohol copolymers. These resins can be used alone or in combination of two or more.

<Electrolyte>
The electrolyte 40 includes, for example, a redox pair such as iodide ion (iodine ion) / polyiodide ion and an organic solvent. As the organic solvent, acetonitrile, methoxyacetonitrile, methoxypropionitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, γ-butyrolactone, valeronitrile, pivalonitrile and the like can be used. Examples of the redox pair include iodide ions / polyiodide ions (for example, I ⁻ / I ₃ ⁻ ), and redox pairs such as bromide ions (bromine ions) / polybromide ions, zinc complexes, iron complexes, and cobalt complexes. It is done. The iodide ion / polyiodide ion can be formed by iodine (I ₂ ) and a salt (ionic liquid or solid salt) containing iodide (I ⁻ ) as an anion. When using an ionic liquid having an iodide as an anion, only iodine should be added. When using an ionic liquid other than an organic solvent or an anion as an anion, an anion such as LiI or tetrabutylammonium iodide is used. A salt containing iodide (I ⁻ ) may be added.

  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, 1-ethyl-3-methylimidazolium iodide, 1, 2 -Dimethyl-3-propylimidazolium iodide, 1-butyl-3-methylimidazolium iodide, or 1-methyl-3-propylimidazolium 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. Examples of the additive include LiI, 4-t-butylpyridine, guanidinium thiocyanate, 1-methylbenzimidazole, 1-butylbenzimidazole 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 preferably includes an oxidation-reduction pair composed of iodide ions / polyiodide ions (for example, I ⁻ / I ₃ ⁻ ), and the concentration of polyiodide ions is preferably 0.006 mol / liter or less. In this case, since the concentration of polyiodide ions that carry 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. In particular, the concentration of polyiodide ions is preferably 0.005 mol / liter or less, more preferably 0 to 6 × 10 ⁻⁶ mol / liter, and 0 to 6 × 10 ⁻⁸ mol / liter. Is more preferable. In this case, the color of the electrolyte 40 can be made inconspicuous when the photoelectric conversion element 100 is viewed from the light incident side of the first conductive substrate 10.

<Dye>
Examples of the dye include a photosensitizing dye such as a ruthenium complex having a ligand containing a bipyridine structure, a terpyridine structure, or the like, an organic dye such as porphyrin, eosin, rhodamine, or merocyanine, and an organic- Examples include inorganic composite dyes. For example, CH ₃ NH ₃ PbX ₃ (X = Cl, Br, I) is used as the lead halide perovskite. Here, when using a photosensitizing dye as a dye, the photoelectric conversion element 100 becomes a dye-sensitized photoelectric conversion element, and the photoelectric conversion cell 50 becomes a dye-sensitized photoelectric conversion cell.

  Among the above dyes, a photosensitizing dye composed of a ruthenium complex having a ligand containing a bipyridine structure or a terpyridine structure is preferable. In this case, the photoelectric conversion characteristics of the photoelectric conversion element 100 can be further improved.

<First external connection terminal>
The first external connection terminal 70a 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.

<Second external connection terminal>
The second external connection terminal 70b includes a metal and a resin. As the metal material, the same material as the metal material included in the first external connection terminal 70a can be used.

  The second external connection terminal 70b may further include a non-metallic conductive material. Examples of non-metallic conductive materials include carbon and conductive polymers. You may use these individually or in combination of 2 or more types.

  However, when the metal substrate 21 of the second conductive substrate 20 contains titanium, the second external connection terminal 70b preferably further contains carbon in addition to the metal and the resin. In this case, the second external connection terminal 70b is difficult to peel from the metal substrate 21. For this reason, the durability of the photoelectric conversion element 100 is further improved.

<Connector>
As described above, the connector 60 includes the connector main body 61, the first connector terminal 62a, and the second connector terminal 62b.

  The connector body 61 is made of an insulating material, for example. Examples of the insulating material include an inorganic insulating material such as glass and an organic insulating material such as resin.

  The connector main body 61 includes a bottom facing the bonding portion 90, a top opposite to the bottom, and a side connecting the bottom and the top.

  The connector main body 61 has an insertion port (not shown), but has a convex portion for inserting into the insertion port of the connector mounted on the circuit board instead of the insertion port. Also good.

  The first connector terminal 62a and the second connector terminal 62b extend from the bottom of the connector main body 61 in FIG. 2, but the first connector terminal 62a and the second connector terminal 62b are respectively from the side of the connector main body 61. It may extend.

<First fixing part>
The 1st fixing | fixed part 80a should just be comprised with the material which can fix the 1st connector terminal 62a to the 1st external connection terminal 70a, and this material usually contains a metal and resin. Examples of the metal include silver and solder. Examples of the resin include a polyester resin and an epoxy resin. The carbon content in the first fixing portion 80a is not particularly limited, but is preferably smaller than the carbon content in the first external connection terminal 70a. In this case, the adhesiveness of the 1st fixing | fixed part 80a with respect to the 1st external connection terminal 70a can be improved more, and the connector 60 can be more strongly bonded to the 1st external connection terminal 70a.

<Second fixing part>
The 2nd fixing | fixed part 80b should just be comprised with the material which can fix the 2nd connector terminal 62b to the 2nd external connection terminal 70b, and this material contains a metal and resin normally. Examples of the metal include silver and solder. The carbon content in the second fixing portion 80b is not particularly limited, but is preferably smaller than the carbon content in the second external connection terminal 70b. In this case, the adhesiveness of the 2nd fixing | fixed part 80b with respect to the 2nd external connection terminal 70b can be improved more, and the connector 60 can be more strongly and strongly bonded to the 2nd external connection terminal 70b.

<Adhesive part>
The bonding part 90 has a linear expansion coefficient larger than that of the resin sealing part 30A of the sealing part 30, and is made of a material capable of bonding the connector 60 and the first conductive substrate 10. As such a material, in addition to a resin similar to the resin contained in the resin sealing portion 30A, a thermosetting resin such as an epoxy resin, or an inorganic material such as glass can be used. When the resin sealing portion 30A is made of a thermoplastic resin, a curable resin such as an ultraviolet curable resin or a thermosetting resin or an inorganic material is preferably used.

  The ratio R of the linear expansion coefficient of the adhesive portion 90 to the linear expansion coefficient of the resin sealing portion 30A is not particularly limited as long as it is smaller than 1, but is preferably 0.1 to 0.9, 0.3 More preferably, it is -0.7.

  Next, a method for manufacturing the above-described photoelectric conversion element 100 will be described with reference to FIGS. FIG. 6 is a plan view showing a series of steps in the method for producing the photoelectric conversion element of FIG.

  First, as shown in FIG. 4, a first conductive substrate 10 formed by forming a transparent conductive layer 12 on one transparent substrate 11 is prepared.

  As a method for forming the transparent conductive layer 12, a sputtering method, a vapor deposition method, a spray pyrolysis method, a CVD method, or the like is used.

  Next, the oxide semiconductor layer 13 is formed over the transparent conductive layer 12. The oxide semiconductor layer 13 may be formed by printing an oxide semiconductor layer forming paste and then baking it.

  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 described above.

  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.

  The firing temperature varies depending on the material of the oxide semiconductor particles, but is usually 350 to 600 ° C., and the firing time also varies depending on the material of the oxide semiconductor particles, but is usually 1 to 5 hours.

  Next, a rectangular annular inorganic sealing portion 30 </ b> B is formed on the transparent conductive layer 12. The inorganic sealing portion 30B may be formed by printing an inorganic sealing portion forming paste containing an inorganic material and then baking it. However, the inorganic sealing portion 30 </ b> B is formed so that the outer corner portion is cut away when viewed along the thickness direction.

  The inorganic sealing part forming paste contains a resin such as polyethylene glycol and a solvent such as terpineol in addition to the inorganic material described above.

  As a printing method of the inorganic sealing portion forming paste, for example, a screen printing method, a doctor blade method, a bar coating method, or the like can be used.

  Although the firing temperature varies depending on the material of the inorganic material, it is usually 400 to 600 ° C., and the firing time also varies depending on the material of the inorganic material, but is usually 0.5 to 5 hours.

  Next, an annular sealing portion forming body is prepared. The sealing part forming body can be obtained, for example, by preparing a sealing resin film and forming one rectangular opening in the sealing resin film.

  And this sealing part formation body is adhere | attached on the inorganic sealing part 30B. At this time, adhesion of the sealing portion forming body to the inorganic sealing portion 30B can be performed, for example, by heating and melting the sealing portion forming body.

  Thus, a structure is obtained (see FIG. 5).

  Next, a dye is adsorbed on the surface of the oxide semiconductor layer 13 of the structure. For this purpose, the working electrode is immersed in a solution containing a dye, the dye is adsorbed to the oxide semiconductor layer 13, and then the excess dye is washed away with the solvent component of the solution and dried. A dye may be adsorbed on the oxide semiconductor layer 13. However, the dye may be adsorbed to the oxide semiconductor layer 13 by applying a solution containing the dye to the oxide semiconductor layer 13 and then drying the solution.

  Next, the electrolyte 40 is prepared.

  Next, the electrolyte 40 is disposed on the oxide semiconductor layer 13. The electrolyte 40 can be disposed by a printing method such as screen printing.

  Next, a quadrangular second conductive substrate forming body for forming the second conductive substrate 20 is prepared. And the corner | angular part which is not joined to the cross | intersection part 30c of the sealing part 30 among the four corner | angular parts in this 2nd conductive substrate formation body is specified, and this corner | angular part is excised. Thus, the second conductive substrate 20 is obtained. Here, the excision of the corners of the second conductive substrate forming body can be performed using, for example, a laser processing method or a wire processing method. When the corner portion of the second conductive substrate forming body is excised using the laser processing method, for example, a pulse laser light source is used as the laser light source.

The wavelength of the laser beam may be 1000 nm or more, preferably 1000-20.
It is 00 nm, More preferably, it is 1000-1200 nm.

The pulse width of the laser light is not particularly limited, but is usually 150 ns or less, preferably 100 ns or less. However, the pulse width of the laser light is preferably 5 ns or more.

  The irradiation energy per unit scanning distance of the laser light is preferably 0.01 to 0.3 J / mm, and more preferably 0.06 to 0.09 J / mm.

The number of excisions per location may be one time or a plurality of times, but one time is preferable from the viewpoint of production efficiency.

  Next, after arrange | positioning this 2nd electroconductive board | substrate 20 so that the opening of the sealing part 30 may be plugged up among the said structures, it bonds together with the sealing part 30. FIG. At this time, the bonding of the second conductive substrate 20 to the sealing portion 30 is performed, for example, under reduced pressure.

  Next, the first external connection terminal 70 a is formed on the transparent conductive layer 12 of the first conductive substrate 10 and outside the sealing portion 30. On the other hand, the second external connection terminal 70 b is formed on the metal substrate 21 of the second conductive substrate 20.

  Next, the connector 60 is prepared.

  Then, the first connector terminal 62a of the connector 60 is fixed to the first external connection terminal 70a by the first fixing portion 80a. On the other hand, the second connector terminal 62b of the connector 60 is fixed to the second external connection terminal 70b by the second fixing portion 80b.

  Finally, the connector 60 and the first conductive substrate 10 are bonded by the bonding portion 90. For example, when the bonding portion 90 is made of an ultraviolet curable resin, after bonding the ultraviolet curable resin as a raw material of the bonding portion 90 so as to come into contact with the connector 60 and the first conductive substrate 10, What is necessary is just to harden a raw material by irradiating a raw material with an ultraviolet-ray.

  The photoelectric conversion element 100 is obtained as described above.

  The present invention is not limited to the above embodiment. For example, in the above embodiment, the bonding portion 90 includes the main body portion 90a and the overhang portion 90b, but the bonding portion 90 does not include the overhang portion 90b as in the photoelectric conversion element 200 illustrated in FIG. Good. That is, the adhesion part 90 may be comprised only by the main-body part 90a.

  Moreover, in the said embodiment, although the photoelectric conversion element 100 has the adhesion part 90 which adhere | attaches the connector 60 and the 1st electroconductive board | substrate 10, like the photoelectric conversion element 300 shown in FIG. The adhesive portion 90 is not necessarily required.

  In the above embodiment, the first conductive substrate 10 includes the transparent substrate 11, and the oxide semiconductor layer 13 is provided on the transparent substrate 11 via the transparent conductive layer 12. It may be provided on the metal substrate 21 of the second conductive substrate 20. However, in this case, the catalyst layer 22 is provided on the transparent conductive layer 12 of the first conductive substrate 10.

  Furthermore, in the said embodiment, although the sealing part 30 is comprised with the inorganic sealing part 30B and the resin sealing part 30A, the sealing part 30 may be comprised only with resin sealing part 30A.

  Furthermore, in the said embodiment, although the sealing part 30 is a square ring shape, the sealing part 30 should just be cyclic | annular, the polygonal ring except a square ring may be sufficient, and an annular | circular shape may be sufficient.

  In the above embodiment, the first external connection terminals 70 a are provided at the corners of the rectangular first conductive substrate 10, but the first external connection terminals 70 a are provided on the first conductive substrate 10. As long as it is provided on the outer side of the annular sealing part 30 on one transparent conductive part, it may be provided between the corners of the rectangular first conductive substrate 10.

  Moreover, in the said embodiment, although the photoelectric conversion element 100 has the one photoelectric conversion cell 50, the photoelectric conversion element may be provided with two or more photoelectric conversion cells 50. FIG. In this case, for example, the first external connection terminal 70 a is fixed to the first transparent conductive portion of the first conductive substrate 10 of one photoelectric conversion cell 50 among the plurality of photoelectric conversion cells 50. The second external connection terminal 70 b is fixed to the metal substrate 21 of the second conductive substrate 20 of another one photoelectric conversion cell 50.

DESCRIPTION OF SYMBOLS 10 ... 1st conductive substrate 11 ... Transparent substrate 12 ... Transparent conductive layer (1st transparent conductive part)
DESCRIPTION OF SYMBOLS 20 ... 2nd electroconductive board | substrate 21 ... Metal substrate 30 ... Sealing part 30A ... Resin sealing part 50 ... Photoelectric conversion cell 60 ... Connector 61 ... Connector main-body part 62a ... 1st connector terminal 62b ... 2nd connector terminal 70a ... 1st DESCRIPTION OF SYMBOLS 1 External connection terminal 70b ... 2nd external connection terminal 90 ... Adhesion part 100,200 ... Photoelectric conversion element

Claims (4)

At least one photoelectric conversion cell;
A first external connection terminal for taking out a current from the at least one photoelectric conversion cell;
A second external connection terminal for taking out a current from the at least one photoelectric conversion cell;
A connector for taking out current from the first external connection terminal and the second external connection terminal;
The photoelectric conversion cell is
A first conductive substrate;
A second conductive substrate facing the first conductive substrate;
An annular sealing portion for joining the first conductive substrate and the second conductive substrate;
The first conductive substrate has a transparent substrate, and a first transparent conductive portion provided on the transparent substrate,
The second conductive substrate comprises a metal substrate;
The sealing part has a resin sealing part containing resin,
The connector is
A connector body,
A first connector terminal provided in the connector body and fixed to the first external connection terminal;
A second connector terminal provided on the connector main body and fixed to the second external connection terminal;
The first external connection terminal is provided on the first transparent conductive portion of the first conductive substrate outside the annular sealing portion of one of the at least one photoelectric conversion cells. And
The photoelectric conversion element in which the second external connection terminal is provided on the metal substrate of the second conductive substrate of one of the at least one photoelectric conversion cells.   The photoelectric conversion element according to claim 1, further comprising an adhesive portion that adheres the connector main body portion and the first conductive substrate and has a smaller linear expansion coefficient than the resin sealing portion of the sealing portion. The adhesive portion is
The main body,
A projecting portion that projects from the main body,
The photoelectric conversion element according to claim 2, wherein the overhanging portion bonds the connector main body portion and the metal substrate of the second conductive substrate. The metal substrate of the second conductive substrate includes titanium;
The photoelectric conversion element according to claim 1, wherein the second external connection terminal includes a metal, a resin, and carbon.

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