JP2011222140A - Electronic device and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electronic device and manufacturing method thereof which can sufficiently maintain durability even when placed under an environment with a large temperature change.SOLUTION: An electronic device 100 includes a first substrate 1, a second substrate 2 disposed opposite to the first substrate 1, a part 3 to be sealed disposed between the first substrate 1 and the second substrate 2, and a sealing part 4 joining the first substrate 1 and the second substrate 2 together and provided in a periphery of the part 3 to be sealed, having outer resin sealing parts 4a by which at least a part along the periphery of the part 3 to be sealed of the sealing part 4 is fixed to each of the first substrate 1 and the second substrate 2, and an intermediate resin sealing part 4b disposed so as to be interposed by the outer resin sealing parts 4a between the first substrate 1 and the second substrate 2. The outer resin sealing parts 4a and the intermediate resin sealing part 4b contain resin, and a melt flow rate of the intermediate resin sealing part 4b is larger than a melt flow rate of the outer resin sealing parts 4a.

Description

  The present invention relates to an electronic device and a method for manufacturing the same.

  Known electronic devices include photoelectric conversion elements such as dye-sensitized solar cells and organic thin film solar cells, and display elements such as liquid crystal display devices and EL display devices.

  As such an electronic device, an insulating spacer is disposed between a pair of bases, and the insulating spacer is bonded to the pair of bases with a sealing material so that the sealing performance is good and a short circuit is hardly caused. Devices have been proposed (see, for example, Patent Document 1). In this Patent Document 1, it is disclosed that an inorganic material such as glass, alumina, quartz or the like, or an organic material such as polyethylene is used as an insulating spacer, and an acrylic resin, glass frit or the like is used as a sealing material (Example) ).

JP 2007-194075 A

  However, the functional device described in Patent Document 1 has the following problems.

  In other words, the functional device described in Patent Document 1 may be placed in an environment where the temperature changes greatly, such as outdoors, where temperatures vary greatly between day and night. In particular, a functional device such as a solar cell is highly likely to be placed in an environment with a large temperature change such as outdoors. At this time, the pair of substrates, the sealing material, and the spacer repeat thermal expansion and thermal contraction. Here, when the spacer is made of an inorganic material such as glass, the linear expansion coefficient between the sealing material and the base is usually different, so that the interface between the sealing material and the spacer or the interface between the sealing material and the base is different. Excessive stress is applied. Even when the spacer is made of resin, an excessive stress may be applied to the interface between the sealing material and the spacer or the interface between the sealing material and the substrate. For this reason, as a result of a decrease in the adhesion and adhesion between the sealing material and the spacer, the sealing performance of the functional device is reduced, and the durability cannot be maintained.

  Therefore, an object of the present invention is to provide an electronic device that can sufficiently maintain durability even when placed in an environment with a large temperature change, and a manufacturing method thereof.

  In order to solve the above problems, the present inventor has conducted extensive research on the cause of failure to sufficiently maintain the durability of an electronic device even when placed in an environment with a large temperature change. As a result, the inventor is disposed between a pair of substrates. It was thought that the fact that the insulating spacer is harder than the sealing material may not sufficiently maintain the durability of the electronic device even when placed in an environment with a large temperature change. That is, the present inventor considered that the spacer is harder than the sealing material, so that stress generated in the electronic device with temperature change may be concentrated on the interface between the sealing material and the spacer. Therefore, the present inventors have further studied and found that the above-described problems can be solved by the following invention.

  That is, the present invention includes a first base material, a second base material disposed opposite to the first base material, a sealed portion disposed between the first base material and the second base material, The first base material and the second base material are connected to each other, and a sealing part provided around the sealed part is provided, and the sealing part is provided along the periphery of the sealed part. At least a part between the first base material and the second base material, and the outer side resin seal part fixed between the first base material and the second base material. An intermediate resin sealing portion disposed so as to be sandwiched between the outer resin sealing portion and the intermediate resin sealing portion, and the melt flow rate of the intermediate resin sealing portion is the outer resin. It is a photoelectric conversion device characterized by being larger than the melt flow rate of a sealing part.

  According to this electronic device, since the melt flow rate of the intermediate resin sealing portion is larger than the melt flow rate of the outer resin sealing portion, the intermediate resin sealing portion is softer than the outer resin sealing portion. For this reason, when an electronic device is placed in an environment with a large temperature change, even if stress is applied to the interface between the outer resin sealing portion and the intermediate resin sealing portion in the sealing portion, the intermediate resin is soft. It is absorbed by the sealing part and sufficiently relaxed. Therefore, according to the electronic device of the present invention, it is possible to sufficiently suppress the decrease in the adhesion and adhesion between the outer resin sealing portion and the intermediate resin sealing portion, and the leakage of the sealed portion or the outside It is possible to sufficiently suppress the intrusion of moisture into the portion to be sealed. Therefore, durability can be maintained even when the electronic device is placed in an environment with a large temperature change.

  The intermediate resin sealing part preferably contains an acid-modified polyolefin.

  In this case, the adhesion between the intermediate resin sealing portion and the outer resin sealing portion becomes strong, and at the interface between the outer resin sealing portion and the intermediate resin sealing portion, leakage of the sealed portion or external sealing Infiltration of moisture into the stop can be more sufficiently suppressed.

  The intermediate resin sealing part preferably contains acid-modified polyethylene. Since acid-modified polyethylene has a relatively low melting point compared to other acid-modified polyolefins, it becomes softer than the outer resin-encapsulated portion compared to the case where other acid-modified polyolefins are used. For this reason, when an electronic device is placed in an environment with a large temperature change, even if stress is applied to the interface between the outer resin sealing portion and the intermediate resin sealing portion in the sealing portion, the stress is more sufficiently Alleviated.

  The intermediate resin sealing portion may include at least one selected from the group consisting of polyvinyl alcohol and an ethylene-vinyl alcohol copolymer.

  Since these resins have a high gas barrier property, leakage of the sealed portion or entry of moisture from the outside into the sealed portion can be more sufficiently suppressed in the intermediate resin sealing portion.

  The outer resin sealing portion preferably contains at least one selected from the group consisting of acid-modified polyolefins and ultraviolet curable resins.

  In this case, the adhesion between the first base material and the second base material and the outer resin sealing portion becomes strong, and at each interface, leakage of the sealed portion or moisture from the outside to the sealed portion. Infiltration can be more sufficiently suppressed.

  The outer resin sealing portion preferably contains acid-modified polyethylene. Acid-modified polyethylene has a relatively low melting point among acid-modified polyolefins. For this reason, compared with the case where acid-modified polyolefin other than acid-modified polyethylene is used as the outer resin sealing portion, the stress generated at the interface between the outer resin sealing portion and the first base material or the second base material is further alleviated. can do.

  The outer resin sealing portion may include at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymer.

  Since these resins have a high gas barrier property, leakage of the sealed portion or entry of moisture from the outside into the sealed portion can be more sufficiently suppressed in the outer resin sealing portion.

  The electronic device has a boundary between the first base material and the sealing portion, a boundary between the second base material and the sealing portion, the intermediate portion on a side opposite to the sealed portion with respect to the sealing portion. It is preferable that a covering portion that covers at least a boundary between the resin sealing portion and the outer resin sealing portion is further provided, and the covering portion includes a second resin.

  In this case, leakage of the sealed portion or entry of moisture from the outside into the sealed portion is suppressed not only by the sealed portion but also by the covering portion. In particular, the interface leakage between the sealing part and the first base material, the interface between the sealing part and the second base material, and the sealed part passing through the interface between the intermediate resin sealing part and the outer resin sealing part. Or the penetration | invasion of the water | moisture content to the to-be-sealed part from the outside is effectively suppressed by the coating | coated part.

  In the electronic device, the first base material may be a first electrode, and the second base material may be a second electrode.

  In an electronic device in which the first base material is a first electrode and the second base material is a second electrode, the first electrode is formed of a porous oxide semiconductor layer and the porous oxide semiconductor layer And a protruding portion that is provided so as to protrude above the conductive film and is disposed so as to be sandwiched between the outer resin sealing portion and the conductive film. It is preferable that the portion to be sealed is made of an inorganic material and is an electrolyte.

  In this case, since the protruding portion made of an inorganic material is provided so as to protrude on the conductive film, the protruding portion functions to seal the electrolyte as the sealed portion together with the sealing portion. And since a protrusion part consists of inorganic materials, it has higher sealing ability than the outer side resin sealing part and intermediate resin sealing part containing resin. For this reason, compared with the case where the 1st electrode does not have a projection part, the leakage of an electrolyte or the penetration | invasion of the water | moisture content to the to-be-sealed part from the exterior can be suppressed more fully.

  Here, the projecting portion is constituted by a wiring portion fixed on the conductive film, the wiring portion is made of an inorganic material, and the current collecting wiring provided on the conductive film, and the current collecting wiring It is preferable to have a wiring protective layer to cover.

  In this electronic apparatus, the protruding portion is disposed so as to be sandwiched between the outer resin sealing portion and the conductive film. And a projection part has a wiring part, and a wiring part has a current collection wiring and the wiring protective layer which covers current collection wiring. That is, the current collection wiring is arranged so as to overlap the sealing portion along the direction connecting the first electrode and the second electrode in a state protected from the electrolyte by the wiring protective layer. Thus, since the current collection wiring is not provided outside the sealing portion, and further, the current collection wiring is not provided inside the sealing portion, the current collection wiring is provided on the light incident surface of the first electrode. And the area occupied by the sealing portion can be minimized, and incident light shielded by the current collecting wiring and the sealing portion can be minimized. Therefore, the light receiving area can be enlarged and high photoelectric conversion efficiency can be obtained.

  In the electronic device in which the first base material is the first electrode and the second base material is the second electrode, the second electrode includes a counter electrode substrate, a catalyst film provided on the counter electrode substrate, and the catalyst. A projection provided on the membrane so as to be sandwiched between the outer resin sealing portion and the catalyst membrane, the projection made of an inorganic material, The stop is preferably an electrolyte.

  In this case, since the protruding portion made of an inorganic material is provided so as to protrude on the catalyst film, the protruding portion functions to seal the electrolyte as the sealed portion together with the outer resin sealing portion. And since a protrusion part consists of inorganic materials, it has higher sealing ability than the outer side resin sealing part and intermediate resin sealing part containing resin. For this reason, compared with the case where a 2nd electrode does not have a protrusion part, the leakage of an electrolyte or the penetration | invasion of the water | moisture content to the to-be-sealed part from the exterior can be suppressed more fully.

  Moreover, this invention is the 1st which forms the 1st sealing part containing an outer side resin sealing part in the 1st cyclic | annular site | part in the said 1st base material which prepares a 1st base material and a 2nd base material. A sealing portion forming step, a second sealing portion forming step of forming a second sealing portion including an outer resin sealing portion in a second annular portion of the second base material, the first base material, and the A second base material is bonded, and a sealing part is formed by adhering the first sealing part and the second sealing part between the first base material and the second base material, and the sealing is performed. A sealing portion forming step of disposing a sealing portion so as to be surrounded by the stopper, the first base material, and the second base material, and at least one of the first sealing portion and the second sealing portion One has an intermediate resin sealing portion provided on the outer resin sealing portion, and the intermediate resin sealing portion and the outer resin sealing portion include a resin. Wherein a method for producing an intermediate resin sealing portion photoelectric conversion device melt flow rate being greater than the melt flow rate of the outer resin sealing portion.

  According to this manufacturing method, the melt flow rate of the intermediate resin sealing portion is larger than the melt flow rate of the outer resin sealing portion. For this reason, the intermediate resin sealing portion is softer than the outer resin sealing portion. Therefore, when the obtained electronic device is placed in an environment with a large temperature change, even if stress is applied to the interface between the outer resin sealing portion and the intermediate resin sealing portion in the sealing portion, the stress is soft. It is absorbed by the intermediate resin sealing portion and sufficiently relaxed. Therefore, according to the method for manufacturing an electronic device of the present invention, a decrease in adhesion and adhesion between the outer resin sealing portion and the intermediate resin sealing portion is sufficiently suppressed, and leakage of the sealed portion or from the outside is prevented. Intrusion of moisture into the sealed portion is sufficiently suppressed, and as a result, an electronic device that can maintain durability even when placed in an environment with a large temperature change can be obtained. In addition, since the melt flow rate of the intermediate resin sealing portion is higher than the melt flow rate of the outer resin sealing portion, the intermediate resin is bonded to the first sealing portion and the second sealing portion in the sealing portion forming step. The fluidity of the sealing part is higher than that of the outer resin sealing part. For this reason, when the first sealing portion and the second sealing portion are bonded, even if foreign matters such as foreign matters adhere to the first sealing portion and the second sealing portion, the first sealing portion and the second sealing portion The second sealing portion is easily bonded while containing impurities by the intermediate resin sealing portion. For this reason, it becomes possible to strengthen the adhesion between the first sealing portion and the second sealing portion.

  The sealing portion forming step is preferably performed in a reduced pressure space.

  In this case, when the obtained electronic device is taken out from the decompression space to the atmosphere, the sealed portion is in a negative pressure state with respect to the outside air. As a result, the electronic device receives atmospheric pressure from the outside, and the state in which the first base material and the second base material exert a pressing force on the sealing portion is maintained, and the volatile component in the sealed portion Leakage is sufficiently suppressed.

  In the method for manufacturing an electronic device, the first base material may be a first electrode, and the second base material may be a second electrode.

  Here, the first electrode includes a porous oxide semiconductor layer, the sealed portion is an electrolyte, and the manufacturing method includes the porous layer between the preparation step and the sealing portion forming step. A dye carrying step for carrying a photosensitizing dye on the oxide semiconductor layer; and on the first electrode and inside the first sealing part or on the second electrode and on the second sealing part. An electrolyte layer forming step of forming an electrolyte layer by disposing the electrolyte inside, wherein the electrolyte layer forming step includes at least one of the first sealing portion forming step and the second sealing portion forming step. It is performed later, and in the sealing portion forming step, the sealing portion is preferably formed by melting the first sealing portion and the second sealing portion while applying pressure.

  According to the manufacturing method, at least one of the first sealing portion forming step and the second sealing portion forming step is performed before the electrolyte layer forming step. For this reason, for example, when only the first sealing portion forming step is performed before the electrolyte layer forming step among the first sealing portion forming step and the second sealing portion forming step, the first sealing portion is defined as the first electrode. When forming in the 1st cyclic | annular site | part in, the volatile component in electrolyte is not adhering to the 1st cyclic | annular site | part, and the wettability of the surface is not falling. Therefore, the resin adheres firmly to the first annular portion, and the first sealing portion is firmly fixed to the first annular portion.

  On the other hand, the sealing part forming step is performed after the electrolyte layer forming step. For this reason, normally, with melting of the first sealing portion and the second sealing portion, a part of the electrolyte evaporates, and wetting between the first sealing portion and the second sealing portion. It is thought that the nature is lowered. In addition, it is considered that the electrolyte adheres on the first sealing portion and the second sealing portion during the electrolyte layer forming step, and wettability between the first sealing portion and the second sealing portion is lowered. .

  However, as described above, since the melt flow rate of the intermediate resin sealing portion is higher than the melt flow rate of the outer resin sealing portion, in the sealing portion forming step, the first sealing portion and the second sealing portion are In bonding, the intermediate resin sealing portion has higher fluidity than the outer resin sealing portion. Therefore, when the first sealing portion and the second sealing portion are adhered, even if foreign matters such as foreign matters are attached to the first sealing portion and the second sealing portion, The second sealing portion includes the impurities in the intermediate resin sealing portion and is bonded. For this reason, the 1st sealing part and the 2nd sealing part strengthen the adhesion between the 1st sealing part and the 2nd sealing part by the intermediate resin sealing part which included impurities. It becomes possible.

  Thus, according to the manufacturing method, the first sealing portion is firmly fixed to the first annular portion of the first electrode, and the second sealing portion is firmly fixed to the second annular portion of the second electrode. Is done. Further, the first sealing portion and the second sealing portion are also firmly bonded to each other. Therefore, in the obtained electronic device, leakage of volatile components in the electrolyte is more sufficiently suppressed. Furthermore, it is possible to more sufficiently suppress moisture from entering the electrolyte from the outside. Therefore, according to the method for manufacturing an electronic device according to the present invention, it is possible to manufacture an electronic device that can sufficiently suppress a temporal decrease in photoelectric conversion efficiency.

  In the electrolyte layer forming step, the electrolyte layer includes the electrolyte on the first electrode and inside the first sealing portion, or on the second electrode and inside the second sealing portion. It is preferable that the first sealing portion or the second sealing portion is overflowed and overflowed to the outside of the first sealing portion or the second sealing portion.

  In this case, the electrolyte can be sufficiently injected into the first sealing portion or the second sealing portion. Further, when forming the sealing portion by bonding the first sealing portion and the second sealing portion, air can be sufficiently removed from the space surrounded by the first electrode, the second electrode, and the sealing portion. it can. As a result, a decrease in photoelectric conversion efficiency over time can be sufficiently suppressed.

  In the electrolyte layer forming step, the electrolyte layer is preferably formed on the first electrode and inside the first sealing portion.

  In this case, the sealing step is performed after the electrolyte has sufficiently spread to the porous details of the porous oxide semiconductor layer. For this reason, air in the porous oxide semiconductor layer is sufficiently suppressed from appearing as bubbles, and a decrease in photoelectric conversion efficiency with time can be sufficiently suppressed.

  In the manufacturing method, the first electrode is provided so as to protrude from a porous oxide semiconductor layer, a conductive film in which the porous oxide semiconductor layer is formed, and the conductive film, and the first annular shape. It is preferable that the protruding portion is made of an inorganic material, and the sealed portion is an electrolyte.

  In this case, since the protruding portion made of an inorganic material is provided so as to protrude on the conductive film, the protruding portion functions to seal the electrolyte layer as the sealed portion together with the sealing portion. And since a protrusion part consists of inorganic materials, it has higher sealing ability than the 1st sealing part and 2nd sealing part containing resin. For this reason, compared with the case where a 1st electrode does not have a protrusion part, the leakage of an electrolyte or the penetration | invasion of the water | moisture content to the electrolyte from the exterior can be suppressed more fully.

  In the above manufacturing method, the second electrode has a counter electrode substrate, a catalyst film provided on the counter electrode substrate, and a protruding portion that is provided so as to protrude on the catalyst film and forms the second annular portion. And it is preferable that the said protrusion part consists of inorganic materials, and the said to-be-sealed part is an electrolyte.

  In this case, since the protruding portion made of an inorganic material is provided so as to protrude on the catalyst film, the protruding portion functions to seal the electrolyte layer as the sealed portion together with the sealing portion. And since a protrusion part consists of inorganic materials, it has higher sealing ability than the 1st sealing part and 2nd sealing part containing resin. For this reason, compared with the case where a 2nd electrode does not have a protrusion part, the leakage of electrolyte can be suppressed more fully.

  In the manufacturing method, it is preferable that at least one of the first electrode and the second electrode has flexibility.

  In this case, compared with the case where neither the first electrode nor the second electrode has flexibility, when the first electrode and the second electrode are taken out from the reduced pressure space and placed under the atmospheric pressure, the first electrode and the second electrode can be used. The flexible electrode is deflected by the atmospheric pressure, and the distance between the first electrode and the second electrode can be reduced. As a result, the characteristics are further improved as compared with the case where neither the first electrode nor the second electrode has flexibility.

  In the present invention, the value of the melt flow rate (hereinafter abbreviated as “MFR”) is a value measured under conditions of 190 ° C. and 2.16 kgs in accordance with ASTM D1238. However, when accurate measurement of MFR is difficult under the condition of 190 ° C., the value measured under the condition of 210 ° C. shall be said.

  ADVANTAGE OF THE INVENTION According to this invention, the electronic device which can fully maintain durability, even when it puts in the environment with a large temperature change, and its manufacturing method are provided.

It is sectional drawing which shows one Embodiment of the electronic device which concerns on this invention. It is sectional drawing which shows the 1st electrode of FIG. It is sectional drawing which shows the 2nd electrode of FIG. It is a top view which shows the 1st electrode of FIG. It is sectional drawing which shows 1 process of one Embodiment of the manufacturing method of the electronic device which concerns on this invention. It is a top view which shows the 2nd electrode of FIG. It is sectional drawing which shows the other process of one Embodiment of the manufacturing method of the electronic device which concerns on this invention. It is sectional drawing which shows the further process of one Embodiment of the manufacturing method of the electronic device which concerns on this invention. It is sectional drawing which shows the further another process of one Embodiment of the manufacturing method of the electronic device which concerns on this invention. It is sectional drawing which shows 1 process of other embodiment of the manufacturing method of the electronic device which concerns on this invention. It is sectional drawing which shows the modification of the 1st electrode of FIG. It is sectional drawing which shows the modification of the 2nd electrode of FIG.

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

<First Embodiment>
First, a first embodiment of an electronic apparatus according to the present invention will be described with reference to FIGS. FIG. 1 is a cross-sectional view showing a dye-sensitized solar cell which is an embodiment of an electronic apparatus according to the invention. 2 is a sectional view showing the first electrode of FIG. 1, FIG. 3 is a sectional view showing the second electrode of FIG. 1, FIG. 4 is a plan view showing the first electrode of FIG. 2, and FIGS. FIG. 9 to FIG. 9 are cross-sectional views each showing one step of the manufacturing method of the present embodiment. FIG. 6 is a plan view showing the second electrode of FIG.

  As shown in FIG. 1, the dye-sensitized solar cell 100 includes a working electrode 1 and a counter electrode 2 disposed to face the working electrode 1. The working electrode 1 carries a photosensitizing dye. The working electrode 1 and the counter electrode 2 are connected by a sealing portion 4. The cell space surrounded by the working electrode 1, the counter electrode 2, and the sealing portion 4 is filled with an electrolyte, and the electrolyte layer 3 is formed by this electrolyte. The electrolyte layer 3 is disposed between the working electrode 1 and the counter electrode 2, and the sealing portion 4 is provided around the electrolyte layer 3. In the present embodiment, the working electrode 1 is a first base material and also a first electrode. The counter electrode 2 is a second base material and also a second electrode. The electrolyte layer 3 corresponds to the portion to be sealed.

  The working electrode 1 includes a transparent substrate 6, a transparent conductive film 7 provided on the counter electrode 2 side of the transparent substrate 6, and a porous oxide semiconductor layer 8 provided on the transparent conductive film 7. The photosensitizing dye is supported on the porous oxide semiconductor layer 8 in the working electrode 1. The counter electrode 2 includes a counter electrode substrate 9 and a conductive catalyst film 10 that is provided on the working electrode 1 side of the counter electrode substrate 9 and promotes a reduction reaction on the surface of the counter electrode 2.

  The sealing part 4 connects the working electrode 1 and the counter electrode 2, an outer resin sealing part 4 a fixed to the working electrode 1, an outer resin sealing part 4 a fixed to the counter electrode 2, and these outer sides It is comprised with the intermediate | middle resin sealing part 4b arrange | positioned so that it may be pinched | interposed between the resin sealing parts 4a. The outer resin sealing portion 4 a on the working electrode 1 side is fixed on the surface of the working electrode 1 on the porous oxide semiconductor layer 8 side, that is, on the surface of the transparent conductive film 7. The outer resin sealing portion 4 a on the counter electrode 2 side is fixed on the surface of the catalyst film 10 of the counter electrode 2. Both the outer resin sealing portion 4a and the intermediate resin sealing portion 4b contain resin, and the MFR of the intermediate resin sealing portion 4b is larger than the MFR of the outer resin sealing portion 4a.

  According to this dye-sensitized solar cell 100, since the MFR of the intermediate resin sealing portion 4b is larger than the MFR of the outer resin sealing portion 4a, the intermediate resin sealing portion 4b is softer than the outer resin sealing portion 4a. . For this reason, when the dye-sensitized solar cell 100 is placed in an environment with a large temperature change, even if stress is applied to the interface between the outer resin sealing portion 4a and the intermediate resin sealing portion 4b in the sealing portion 4. The stress is absorbed by the soft intermediate resin sealing portion 4b and sufficiently relaxed. Therefore, according to the dye-sensitized solar cell 100, it can fully suppress that the adhesiveness and adhesiveness of the outer side resin sealing part 4a and the intermediate resin sealing part 4b fall, and electrolyte leakage and external Invasion of moisture from can be sufficiently suppressed. Therefore, durability can be maintained even when the dye-sensitized solar cell 100 is placed in an environment with a large temperature change.

  Next, the manufacturing method of the dye-sensitized solar cell 100 described above will be described.

[Preparation process]
First, a working electrode (first electrode) 1 and a counter electrode (second electrode) 2 are prepared.

(Working electrode)
The working electrode 1 can be obtained as follows (FIG. 2).

  First, a transparent conductive film 7 is formed on the transparent substrate 6 to form a laminate. As a method for forming the transparent conductive film 7, a sputtering method, a vapor deposition method, a spray pyrolysis (SPD) method, a CVD method, or the like is used. Of these, the spray pyrolysis method is preferable from the viewpoint of apparatus cost.

  The material which comprises the transparent substrate 6 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), polyethersulfone (PES) and the like. The thickness of the transparent substrate 6 is appropriately determined according to the size of the dye-sensitized solar cell 100 and is not particularly limited, but may be in the range of 50 μm to 10000 μm, for example.

Examples of the material constituting the transparent conductive film 7 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 7 may be a single layer or a laminate of a plurality of layers made of different conductive metal oxides. When the transparent conductive film 7 is composed of a single layer, the transparent conductive film 7 is preferably composed of FTO because it has high heat resistance and chemical resistance. Moreover, it is preferable to use a laminated body composed of a plurality of layers as the transparent conductive film 7 because the characteristics of each layer can be reflected. Among these, it is preferable to use a laminate of a layer made of ITO and a layer made of FTO. In this case, the transparent conductive film 7 having high conductivity, heat resistance and chemical resistance can be realized. The thickness of the transparent conductive film 7 may be in the range of 0.01 μm to 2 μm, for example.

  Next, a paste for forming a porous oxide semiconductor layer is printed on the transparent conductive film 7 obtained as described above. The porous 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 printing method of the paste for forming the porous oxide semiconductor layer, for example, a screen printing method, a doctor blade method, a bar coating method, or the like can be used.

  Next, the porous oxide semiconductor layer forming paste is baked to form the porous oxide semiconductor layer 8 on the transparent conductive film 7. The firing temperature varies depending on the oxide semiconductor particles, but is usually 350 ° C. to 600 ° C., and the firing time also varies depending on the oxide semiconductor particles, but is usually 1 to 5 hours.

Examples of the oxide semiconductor particles include titanium oxide (TiO ₂ ), zinc oxide (ZnO), tungsten oxide (WO ₃ ), niobium oxide (Nb ₂ O ₅ ), 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 oxide semiconductor particles composed of two or more of these. The average particle diameter of these oxide semiconductor particles is 1-1000 nm, the surface area of the oxide semiconductor covered with the dye is increased, that is, the field for photoelectric conversion is increased, and more electrons are generated. Is preferable. Here, it is preferable that the porous oxide semiconductor layer 8 is configured by a stacked body in which oxide semiconductor particles having different particle size distributions are stacked. In this case, it becomes possible to cause reflection of light repeatedly in the laminated body, and light can be efficiently converted into electrons without escaping incident light to the outside of the laminated body. The thickness of the porous oxide semiconductor layer 8 may be, for example, 0.5 to 50 μm. In addition, the porous oxide semiconductor layer 8 can also be comprised with the laminated body of the several semiconductor layer which consists of a different material.

(Counter electrode)
On the other hand, the counter electrode 2 can be obtained as follows (FIG. 3).

  That is, first, the counter electrode substrate 9 is prepared. Then, the catalyst film 10 is formed on the counter electrode substrate 9. As a method for forming the catalyst film 10, a sputtering method, a vapor deposition method, or the like is used. Of these, sputtering is preferred from the viewpoint of film uniformity.

  The counter electrode substrate 9 is made of, for example, a corrosion-resistant metal material such as titanium, nickel, platinum, molybdenum, or tungsten, a conductive oxide such as ITO or FTO, carbon, or a conductive polymer. The thickness of the counter electrode substrate 9 is appropriately determined according to the size of the dye-sensitized solar cell 100 and is not particularly limited, but may be, for example, 0.005 mm to 0.1 mm.

  The catalyst film 10 is made of platinum, a carbon-based material, a conductive polymer, or the like.

[First sealing portion forming step]
Next, as shown in FIGS. 4 and 5, the first sealing is performed on the first annular portion C1 of the working electrode 1 on the surface of the transparent conductive film 7 and surrounding the porous oxide semiconductor layer 8. Part 4A is formed. 4 A of 1st sealing parts are comprised from the outer side resin sealing part 4a fixed to the 1st cyclic | annular site | part C1 of the transparent conductive film 7, and the intermediate | middle resin sealing part 4b provided on it. Here, both the outer resin sealing portion 4a and the intermediate resin sealing portion 4b contain a resin, and the intermediate resin sealing portion 4b has an MFR larger than the MFR of the outer resin sealing portion 4b. Use.

[Second sealing portion forming step]
On the other hand, as shown in FIGS. 6 and 7, the second sealing portion 4 </ b> B is formed in the second annular portion C <b> 2 that is a portion on the surface of the catalyst film 10 in the counter electrode 2. The second sealing portion 4B is composed of an outer resin sealing portion 4a that is fixed to the second annular portion C2 of the catalyst film 10.

  The resin contained in the outer resin sealing portion 4a may be any resin as long as it is a resin. For example, an acid-modified polyolefin, polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, or an ultraviolet curable resin is used as such a resin. be able to. These can be used alone or in combination of two or more.

(Outside resin sealing part)
When the outer resin sealing portion 4a is a thermoplastic resin such as acid-modified polyolefin, polyvinyl alcohol, or ethylene-vinyl alcohol copolymer, the outer resin sealing portion 4a uses a ring-shaped sheet made of the resin as a working electrode. It can form by arrange | positioning in the 1st 1st cyclic | annular site | part C1 or the 2nd cyclic | annular site | part C2 of the counter electrode 2, and fuse | melting and adhere | attaching. When the outer resin sealing portion 4a is an ultraviolet curable resin, the outer resin sealing portion 4a has the precursor of the ultraviolet curable resin as the first annular portion C1 of the working electrode 1 or the second annular portion C2 of the counter electrode 2. After coating, it can be formed by irradiating and curing with ultraviolet rays.

  As the resin of the outer resin sealing portion 4a, acid-modified polyolefin or ultraviolet curable resin is preferable among the above resins. When an acid-modified polyolefin or an ultraviolet curable resin is used as the resin contained in the outer resin sealing portion 4a, the adhesion between the working electrode 1 and the transparent conductive film 7 or the counter electrode 2 becomes strong, and at each interface, the electrolyte Leakage and entry of moisture from the outside into the electrolyte can be more sufficiently suppressed. Among the acid-modified polyolefins, acid-modified polyethylene is preferable. Acid-modified polyethylene has a relatively low melting point among acid-modified polyolefins. For this reason, compared with the case where acid-modified polyolefin other than acid-modified polyethylene is used as the outer resin sealing portion 4a, the stress generated at the interface between the outer resin sealing portion 4a and the working electrode 1 or the counter electrode 2 is further alleviated. be able to. Among acid-modified polyolefins, acid-modified polyethylene has particularly high stability to electrolytes. For this reason, the outer side resin sealing part 4a can maintain physical properties, such as the softness | flexibility and adhesiveness of resin which are contained in the outer side resin sealing part 4a over a long period of time.

  Further, the resin contained in the outer resin sealing portion 4a may be polyvinyl alcohol or an ethylene-vinyl alcohol copolymer. Since these have high gas barrier properties, leakage of the electrolyte and entry of moisture from the outside into the electrolyte can be more sufficiently suppressed in the outer resin sealing portion 4a. The above-described resins may be used alone as the resin for the outer resin sealing portion 4a, but may be a mixture or laminate of two or more.

(Intermediate resin sealing part)
The resin contained in the intermediate resin sealing part 4b may be any resin as long as it has a higher MFR than the outer resin sealing part 4a. For example, acid-modified polyolefin, polyvinyl alcohol, ethylene-vinyl alcohol It can be appropriately selected from polymers.

  When the intermediate resin sealing portion 4b is a thermoplastic resin such as acid-modified polyolefin, polyvinyl alcohol, or ethylene-vinyl alcohol copolymer, the intermediate resin sealing portion 4b is formed on the outer resin sealing portion 4a. It can be formed by arranging an annular sheet made of resin and then melting and bonding.

  As the resin contained in the intermediate resin sealing portion 4b, acid-modified polyolefin is preferable. In this case, the adhesion with the outer resin sealing portion 4a is strengthened, and at the interface between the outer resin sealing portion 4a and the intermediate resin sealing portion 4b, the leakage of the electrolyte and the intrusion of moisture into the electrolyte from the outside It can be suppressed sufficiently. In addition to the reasons described above, since the acid-modified polyolefin is very stable with respect to the electrolyte, the physical properties such as flexibility and adhesiveness of the resin contained in the intermediate resin sealing portion 4b can be maintained over a long period of time. . Furthermore, since acid-modified polyolefin has a relatively low melting point compared to polyvinyl alcohol or ethylene-vinyl alcohol copolymer, it also has the following advantages. That is, since the acid-modified polyolefin has a relatively low melting point compared to other acid-modified polyolefins, the intermediate resin sealing portion 4b is more than the outer resin sealing portion 4a compared to polyvinyl alcohol or an ethylene-vinyl alcohol copolymer. It becomes even softer. For this reason, when the dye-sensitized solar cell 100 is placed in an environment with a large temperature change, even if stress is applied to the interface between the outer resin sealing portion 4a and the intermediate resin sealing portion 4b in the sealing portion 4. As compared with the case where polyvinyl alcohol or ethylene-vinyl alcohol copolymer is used as the intermediate resin sealing portion 4b, the stress is more relaxed. Further, since the acid-modified polyolefin has a relatively low melting point compared to polyvinyl alcohol or ethylene-vinyl alcohol copolymer, the outer resin sealing portion 4a and the resin of the intermediate resin sealing portion 4b are melt-bonded at a relatively low temperature. It becomes easy. The acid-modified polyolefin means one obtained by random copolymerization, alternating copolymerization, block copolymerization, or graft copolymerization of an olefin with an acid, or one obtained by neutralizing these with a metal ion. As the acid-modified polyolefin, for example, ethylene-methacrylic acid copolymer, ionomer, maleic anhydride-modified polyethylene, and maleic anhydride-modified polypropylene can be used. Here, for example, maleic anhydride-modified polypropylene is an acid-modified olefin obtained by graft copolymerization of maleic anhydride.

  The resin contained in the intermediate resin sealing portion 4b is more preferably acid-modified polyethylene. Since acid-modified polyethylene has a relatively low melting point compared to other acid-modified polyolefins, the intermediate resin sealing part 4b is much softer than the outer resin sealing part 4a compared to other acid-modified polyolefins. For this reason, when the dye-sensitized solar cell 100 is placed in an environment with a large temperature change, even if stress is applied to the interface between the outer resin sealing portion 4a and the intermediate resin sealing portion 4b in the sealing portion 4. As compared with the case where other acid-modified polyolefin is used as the intermediate resin sealing portion 4b, the stress is more relaxed.

  Further, the resin contained in the intermediate resin sealing portion 4b may be polyvinyl alcohol or an ethylene-vinyl alcohol copolymer. Since these resins have high gas barrier properties, leakage of the electrolyte and entry of moisture from the outside into the electrolyte can be more sufficiently suppressed in the intermediate resin sealing portion 4b.

  The resin of the outer resin sealing part 4a and the intermediate resin sealing part 4b is preferably a different acid-modified polyolefin. In this case, since the outer resin sealing portion 4a and the intermediate resin sealing portion 4b have the same kind of unsaturated carbon chain in each molecule, the compatibility is good, and the first sealing portion is formed in the sealing portion forming step described later. It is excellent in adhesiveness and adhesiveness between 4A and the 2nd sealing part 4B.

  The resin of the outer resin sealing portion 4a and the intermediate resin sealing portion 4b is more preferably the same resin selected from the group of acid-modified polyolefins. For example, the resin constituting the outer resin sealing portion 4a and the resin constituting the intermediate resin sealing portion 4b are composed of the same ionomer, or the resin constituting the outer resin sealing portion 4a and the intermediate resin sealing portion 4b are configured. A combination of the same resins made of the same maleic anhydride-modified polypropylene is desirable.

  Further, the resin contained in the intermediate resin sealing portion 4b and the outer resin sealing portion 4a is more preferably acid-modified polyethylene. In this case, acid-modified polyethylene is particularly stable with respect to electrolyte among acid-modified polyolefins. For this reason, the intermediate resin sealing part 4b and the outer resin sealing part 4a can maintain physical properties such as flexibility and adhesiveness of the resin contained in the intermediate resin sealing part 4b and the outer resin sealing part 4a over a long period of time. . Furthermore, since acid-modified polyethylene has a relatively low melting point compared to other acid-modified polyolefins, the resin of the outer resin sealing portion 4a and the resin of the intermediate resin sealing portion 4b are easily melted and bonded at a relatively low temperature. Further, when the resin of the outer resin sealing portion 4a and the intermediate resin sealing portion 4b are different types of acid-modified polyethylene, since the respective monomers are ethylene, the compatibility is good, and the first sealing is performed in the sealing portion forming step described later. It is excellent in adhesiveness and adhesiveness between the stop portion 4A and the second sealing portion 4B.

  Here, the acid-modified polyethylene means one obtained by random copolymerization, alternating copolymerization, block copolymerization, or graft copolymerization of an acid with polyethylene, or one obtained by neutralizing these with metal ions. As an example, an ethylene methacrylic acid copolymer is obtained by copolymerizing ethylene and methacrylic acid, and is an acid-modified polyethylene. An ionomer obtained by neutralizing an ethylene methacrylic acid copolymer with a metal ion is also an acid-modified polyethylene. Become.

  The resin of the outer resin sealing portion 4a and the intermediate resin sealing portion 4b is more preferably the same resin selected from the group of acid-modified polyethylene. For example, the resin constituting the outer resin sealing portion 4a and the resin constituting the intermediate resin sealing portion 4b are composed of the same ionomer, or the resin constituting the outer resin sealing portion 4a and the intermediate resin sealing portion 4b are configured. A combination of the same resin made of the same maleic anhydride-modified polyethylene is desirable.

  Here, the same resin includes resins having different molar ratios as well as resins having the same molar ratio of acid monomers for modifying polyethylene to ethylene repeating units. For example, an ethylene methacrylic acid copolymer having a molar ratio of acid monomer to ethylene repeating units of 5% and an ethylene methacrylic acid copolymer having a molar ratio of acid monomer to ethylene repeating units of 10% are the same resin. In this case, since the melting point, MFR, and other various thermal properties of the resin used are close, it is easy to melt and bond each other at the same timing. Therefore, compared with the case of using resins having significantly different melting points and MFRs, it is easy to control the melting and heating time, and the sealing part forming step described later can be easily performed.

  Specifically, the following are mentioned as a combination of the outer side resin sealing part 4a and the intermediate | middle resin sealing part 4b. For example, the resin contained in the outer resin sealing portion 4a is made of a binel that is maleic anhydride-modified polyethylene, and the resin contained in the intermediate resin sealing portion 4b is made of a nucleurel that is an ethylene-methacrylic acid copolymer, or Examples thereof include a combination in which the resin contained in the outer resin sealing portion 4a is made of high Milan, which is an ionomer, and the resin contained in the intermediate resin sealing portion 4b is made of nucleol, which is an ethylene-methacrylic acid copolymer.

  The resin contained in the outer resin sealing portion 4a contains at least one of polyvinyl alcohol or ethylene-vinyl alcohol copolymer, and the resin contained in the intermediate resin sealing portion 4b is polyvinyl alcohol or ethylene-vinyl. In the case of containing at least one kind of alcohol copolymer, since a very small amount of water is present at the interface between the outer resin sealing portion 4a and the intermediate resin sealing portion 4b, both are dissolved and bonded in the vicinity of the interface. In addition, leakage of the electrolyte and entry of moisture from the outside into the electrolyte can be further suppressed.

  In the intermediate resin sealing portion 4b and the outer resin sealing portion 4a, the difference in MFR between them is preferably 1 g / 10 min or more, and the difference in both MFR is more preferably 2.5 g / 10 min or more, 25 g / 10 min. The combination is as follows. When the difference in MFR between the intermediate resin sealing portion 4b and the outer resin sealing portion 4a is within the above range, the following advantages are obtained. That is, when the difference in MFR between the two is 1 g / 10 min or more, the stress relaxation between the intermediate resin sealing portion 4 b and the outer resin sealing portion 4 a during the heat cycle is compared to the case where the difference is less than 1 g / 10 min. Happens more effectively. Moreover, when the difference between the two MFRs is 2.5 to 25 g / 10 min, the stress relaxation effect becomes more conspicuous as compared to the case where the above range is not satisfied.

  In addition, the resin contained in the outer resin sealing portion 4a and the intermediate resin sealing portion 4b may be composed only of a resin, or may be composed of a resin and an inorganic filler.

[Dye support process]
Next, a photosensitizing dye is supported on the porous oxide semiconductor layer 8 of the working electrode 1. For this purpose, the working electrode 1 is immersed in a solution containing a photosensitizing dye, the dye is adsorbed on the porous oxide semiconductor layer 8, and then the excess dye is washed away with the solvent component of the solution. The photosensitizing dye may be adsorbed on the porous oxide semiconductor layer 8 by drying. However, even if the photosensitizing dye is adsorbed to the porous oxide semiconductor film by applying a solution containing the photosensitizing dye to the porous oxide semiconductor layer 8 and then drying, the photosensitizing dye is porous. It can be supported on the oxide semiconductor layer 8.

  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.

[Electrolyte layer forming step]
Next, as shown in FIG. 8, the electrolyte is disposed on the working electrode 1 and inside the first sealing portion 4 </ b> A to form the electrolyte layer 3. The electrolyte layer 3 can be obtained by injecting or printing the electrolyte on the working electrode 1 and inside the first sealing portion 4A.

  Here, when the electrolyte is liquid, it is preferable to inject the electrolyte until it overflows beyond the first sealing portion 4A and outside the first sealing portion 4A. In this case, the electrolyte can be sufficiently injected inside the first sealing portion 4A. In addition, when the sealing portion 4 is formed by bonding the first sealing portion 4A and the second sealing portion 4B, air is sufficiently supplied from the cell space surrounded by the working electrode 1, the counter electrode 2, and the sealing portion 4. This can be eliminated, and the photoelectric conversion efficiency can be sufficiently improved. In addition, even if the adhesion part of 1st sealing part 4A gets wet with electrolyte by inject | pouring until electrolyte overflows outside the 1st sealing part 4A exceeding 1st sealing part 4A, 1st sealing part Since the MFR of the intermediate resin sealing portion 4b of 4A is larger than the MFR of the outer resin sealing portion 4a and has higher fluidity, the first sealing portion 4A and the second sealing portion 4B are melted. At the time of bonding, the intermediate resin sealing portion 4b easily includes an electrolyte and impurities. For this reason, when the first sealing portion 4A and the second sealing portion 4B are bonded, it is difficult for an electrolyte to exist at the interface between the first sealing portion 4A and the second sealing portion 4B, and the first sealing portion 4A. And the 2nd sealing part 4B adhere | attaches firmly.

The electrolyte is usually composed of an electrolytic solution, and the electrolytic solution includes an oxidation-reduction pair such as I ⁻ / I ₃ ^— and an organic solvent. As the organic solvent, acetonitrile, methoxyacetonitrile, methoxypropionitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, γ-butyrolactone, and the like can be used. Examples of the redox pair include I ⁻ / I ₃ ⁻ and bromine / bromide ion pairs. The dye-sensitized solar cell 100 is an electrolytic solution that includes a volatile solute such as I ⁻ / I ₃ ⁻ as an oxidation-reduction pair and an organic solvent such as acetonitrile, methoxyacetonitrile, and methoxypropionitrile that easily volatilizes at high temperatures. This is particularly effective when used as an electrolyte. In this case, the change in the internal pressure of the cell space is particularly large due to the change in the ambient temperature around the dye-sensitized solar cell 100, and the interface between the sealing part 4 and the counter electrode 2, and the sealing part 4 and the working electrode 1. This is because the electrolyte easily leaks from the interface. A gelling agent may be added to the volatile solvent. The electrolyte may be composed of an ionic liquid electrolyte composed of a mixture of an ionic liquid and a volatile component. Also in this case, the change in the internal pressure of the cell space increases due to the change in the ambient temperature around the dye-sensitized solar cell 100. 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. As such a room temperature molten salt, for example, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide is preferably used. As the volatile component, the above and an organic solvent, 1-methyl-3-methyl imidazolium iodide, _LiI, and the like I 2, 4-t-butylpyridine. Further, as the electrolyte 3, a nanocomposite ionic gel electrolyte, which is a pseudo-solid electrolyte formed by kneading nanoparticles such as SiO ₂ , TiO ₂ , and carbon nanotubes in the ionic liquid electrolyte, may be used. An ionic liquid electrolyte gelled using an organic gelling agent such as vinylidene chloride, polyethylene oxide derivative, or amino acid derivative may be used.

[Sealing part forming step]
Next, as shown in FIG. 9, the working electrode 1 and the counter electrode 2 are opposed to each other, and the first sealing portion 4A and the second sealing portion 4B are overlapped. Then, the first sealing portion 4A and the second sealing portion 4B are bonded to each other by melting the first sealing portion 4A and the second sealing portion 4B while applying pressure. At this time, the intermediate resin sealing portion 4b is bonded to the outer resin sealing portion 4a on the working electrode 1 side and the outer resin sealing portion 4a on the counter electrode 2 side. Thus, the working electrode 1 and the counter electrode 2 are bonded together to form the sealing portion 4 between the working electrode 1 and the counter electrode 2, and the electrolyte is surrounded by the working electrode 1, the counter electrode 2, and the sealing portion 4. Layer 3 is formed (see FIG. 1). In the present embodiment, the first sealing portion 4A and the second sealing portion 4B are bonded together under atmospheric pressure.

  At this time, pressurization of the first sealing portion 4A and the second sealing portion 4B is usually performed at 1 to 50 MPa, preferably 2 to 30 MPa, more preferably 3 to 20 MPa.

  Moreover, the temperature at which the first sealing portion 4A and the second sealing portion 4B are melted is the outer resin sealing portion 4a and the intermediate resin sealing portion that form the first sealing portion 4A and the second sealing portion 4B. The melting point is 4b or higher. When the temperature is lower than the melting point of the outer resin sealing portion 4a and the intermediate resin sealing portion 4b, the outer resin sealing portion 4a and the intermediate resin sealing portion 4b are not melted. The sealing part 4 cannot be formed by bonding the parts 4b.

  However, the temperature at which the outer resin sealing portion 4a and the intermediate resin sealing portion 4b are melted is preferably equal to or lower than (the melting point of the resin contained in the outer resin sealing portion 4a + 200 ° C.). If the temperature exceeds (the melting point of the resin contained in the outer resin sealing portion 4a + 200 ° C.), the resin contained in the outer resin sealing portion 4a and the intermediate resin sealing portion 4b may be decomposed by heat.

  Thus, the dye-sensitized solar cell 100 is obtained, and the manufacture of the dye-sensitized solar cell 100 is completed.

  According to the method for manufacturing the dye-sensitized solar cell 100 described above, the MFR of the intermediate resin sealing portion 4b is larger than the MFR of the outer resin sealing portion 4a. For this reason, the intermediate resin sealing portion 4b is softer than the outer resin sealing portion 4a. For this reason, when the obtained dye-sensitized solar cell 100 is placed in an environment with a large temperature change, stress is applied to the interface between the outer resin sealing portion 4a and the intermediate resin sealing portion 4b in the sealing portion 4. However, the stress is absorbed by the soft intermediate resin sealing portion 4b and sufficiently relaxed. Therefore, according to the method of manufacturing the dye-sensitized solar cell 100, the decrease in the adhesion and adhesiveness between the outer resin sealing portion 4a and the intermediate resin sealing portion 4b is sufficiently suppressed, and the leakage of the electrolyte and from the outside It is possible to obtain the dye-sensitized solar cell 100 in which the penetration of moisture into the electrolyte is sufficiently suppressed, and as a result, durability can be maintained even when placed in an environment with a large temperature change.

  In the present embodiment, the first sealing portion 4A and the second sealing portion 4B are formed before the electrolyte layer 3 is formed. For this reason, when forming the 1st sealing part 4A in the 1st cyclic | annular part C1 of the working electrode 1, the volatile component in electrolyte is not adhering to the 1st cyclic | annular part C1, and the wettability of the surface falls. Not done. Therefore, the thermoplastic resin is firmly bonded to the first annular portion C1, and the first sealing portion 4A is firmly fixed to the first annular portion C1. Further, even when the second sealing portion 4B is formed in the second annular portion C2 of the catalyst film 10, the volatile component in the electrolyte is not attached on the surface of the catalyst film 10, and the wettability of the surface is reduced. Not done. Therefore, the thermoplastic resin is firmly bonded to the second annular portion C2 of the catalyst film 10, and the second sealing portion 4B is firmly fixed to the second annular portion C2 of the catalyst film 10.

  On the other hand, the sealing portion 4 is formed before the electrolyte layer 3 is formed. For this reason, normally, with melting the first sealing portion 4A and the second sealing portion 4B, a part of the electrolyte is evaporated, and the first sealing portion 4A and the second sealing portion 4B It is considered that the wettability between the two decreases. In addition, the electrolyte adheres on the first sealing portion 4A and the second sealing portion 4B during the electrolyte layer forming step, and the wettability between the first sealing portion 4A and the second sealing portion 4B decreases. It is also possible.

  However, as described above, since the MFR of the intermediate resin sealing portion 4b is higher than the MFR of the outer resin sealing portion 4a, in the sealing portion forming step, the first sealing portion 4A and the second sealing portion 4B are In bonding, the intermediate resin sealing portion 4b has higher fluidity than the outer resin sealing portion 4a. For this reason, when bonding the first sealing portion 4A and the second sealing portion 4B, foreign matters (for example, an electrolyte) such as impurities are attached to the first sealing portion 4A and the second sealing portion 4B. In addition, the intermediate resin sealing portion 4b is easily bonded to the outer resin sealing portion 4a of the second sealing portion 4A while containing the impurities. For this reason, it becomes possible to strengthen the adhesion between the first sealing portion 4A and the second sealing portion 4B.

  Thus, according to the method for manufacturing the dye-sensitized solar cell 100, the first sealing portion 4A is firmly fixed to the first annular portion C1 of the working electrode 1, and the second sealing portion 4B is the counter electrode 2. It is firmly fixed to the second annular portion C2. Further, the first sealing portion 4A and the second sealing portion 4B are also firmly bonded. Therefore, in the obtained dye-sensitized solar cell 100, leakage of volatile components in the electrolyte is more sufficiently suppressed. Furthermore, it is possible to more sufficiently suppress moisture from entering the electrolyte from the outside. Therefore, according to the method for manufacturing the dye-sensitized solar cell 100, it is possible to manufacture a dye-sensitized solar cell that can sufficiently suppress a temporal decrease in photoelectric conversion efficiency.

  In the present embodiment, in the electrolyte layer forming step, the electrolyte layer 3 is formed on the working electrode 1 and inside the first sealing portion 4A. For this reason, the sealing portion 4 is formed after the electrolyte has sufficiently spread to the porous details of the porous oxide semiconductor layer 8. For this reason, air in the porous oxide semiconductor layer 8 is sufficiently suppressed from appearing as bubbles, and the photoelectric conversion efficiency can be more sufficiently improved.

Second Embodiment
Next, 2nd Embodiment of the manufacturing method of the dye-sensitized solar cell which concerns on this invention is described with reference to drawings.

  The manufacturing method according to the present embodiment is such that the first sealing portion 4A and the second sealing portion 4B are bonded in the reduced pressure space. Is different from the manufacturing method of the first embodiment, which is performed under atmospheric pressure. In addition, the same code | symbol is attached | subjected to the component same or equivalent to 1st Embodiment, and the overlapping description is abbreviate | omitted.

  In this case, when the resulting dye-sensitized solar cell 100 is taken out into the atmosphere, the electrolyte layer 3 can be in a negative pressure state with respect to the outside air. For this reason, the dye-sensitized solar cell 100 receives atmospheric pressure from the outside, and the state where the working electrode 1 and the counter electrode 2 apply pressing force to the sealing portion 4 is maintained. As a result, leakage of volatile components in the electrolyte layer 3 can be more sufficiently suppressed.

  The decompression space can be formed as follows, for example.

  That is, first, the working electrode 1 provided with the first sealing portion 4A is housed in a decompression vessel having an opening. Subsequently, an electrolyte is injected into the first sealing portion 4 </ b> A to form the electrolyte layer 3. Thereafter, the counter electrode 2 provided with the second sealing portion 4B is further accommodated in the decompression container, the working electrode 1 and the counter electrode 2 are opposed to each other in the decompression container, and the first sealing portion 4A and the second sealing portion 4 The sealing part 4B is overlaid. Next, the opening of the decompression container is closed with a flexible sheet made of a resin such as PET, and a sealed space is formed in the decompression container. Then, the sealed space is decompressed by, for example, a vacuum pump through an exhaust hole (not shown) formed in the decompression container. Thus, a decompression space is formed.

  When the decompression space is formed in this way, the counter electrode 2 is pressed by the flexible sheet. Along with this, the first sealing portion 4A and the second sealing portion 4B are sandwiched and pressurized by the working electrode 1 and the counter electrode 2. At this time, when the decompression container is heated and the first sealing portion 4A and the second sealing portion 4B are melted while being pressurized, the first sealing portion 4A and the second sealing portion 4B are bonded and sealed. A stop 4 is formed.

  At that time, the pressure in the reduced pressure space is usually in the range of 50 Pa or more and less than 1013 hPa, preferably 50 to 800 Pa, and more preferably 300 to 800 Pa.

  In particular, when the organic solvent contained in the electrolyte is a volatile solvent, the pressure in the reduced pressure space is preferably 700 to 1000 Pa, and more preferably 700 to 800 Pa. When the pressure is within the above range, the volatilization of the organic solvent is further suppressed when the electrolyte layer 3 is formed inside the first sealing portion 4A as compared with the case where the pressure is outside the above range, and In the dye-sensitized solar cell 100, the working electrode 1, the counter electrode 2 and the sealing portion 4 are more firmly fixed to each other, and the electrolyte layer 3 is less likely to leak.

  In addition, when the electrolyte includes an ionic liquid, the ionic liquid does not volatilize. Therefore, unlike the case where the electrolyte includes a volatile solvent, it is not necessary to increase the pressure in the decompression space in consideration of volatilization of the electrolyte. For this reason, the pressure in decompression space should just be 50-700Pa.

  Further, when the electrolyte includes a gel electrolyte, the case where the main component of the precursor to be gelled is a volatile system and the case where the main component of the precursor is a volatile system is different. It is preferably 50 to 700 Pa in the case of ˜800 Pa and an ionic liquid system. Therefore, when the electrolyte layer 3 contains a gel electrolyte, the pressure in the reduced pressure space is preferably 50 to 800 Pa.

  Moreover, when forming the sealing part 4 in a decompression space as mentioned above, it is preferable that at least one of the working electrode 1 and the counter electrode 2 has flexibility.

  In this case, compared to the case where neither the working electrode 1 nor the counter electrode 2 has flexibility, the flexibility of the working electrode 1 and the counter electrode 2 when the working electrode 1 and the counter electrode 2 are taken out from the reduced pressure space and placed under atmospheric pressure. It becomes possible to bend the electrode between the working electrode 1 and the counter electrode 2 to be narrowed by the atmospheric pressure. As a result, compared with the case where neither the working electrode 1 nor the counter electrode 2 has flexibility, the photoelectric conversion efficiency is performed more efficiently and the photoelectric conversion efficiency is further improved.

  The present invention is not limited to the above embodiment. For example, in the above embodiment, the electrolyte layer 3 is formed inside the first sealing portion 4A provided on the working electrode 1, but the electrolyte layer 3 is on the counter electrode 2 as shown in FIG. Then, it may be formed inside the second sealing portion 4B provided on the counter electrode 2.

  Further, in the above embodiment, the first sealing portion 4A and the second sealing portion 4B are formed before the electrolyte layer 3 is formed. However, the second sealing portion 4B forms the electrolyte layer 3. It may be performed at the same time or after the electrolyte layer 3 is formed. However, when the electrolyte layer 3 is formed inside the second sealing portion 4B provided on the counter electrode 2, the second sealing portion 4B needs to be formed before the electrolyte layer 3 is formed. In this case, the first sealing portion 4A need not be formed before the electrolyte layer 3 is formed, and may be formed simultaneously with the electrolyte layer 3, or after the electrolyte layer 3 is formed and sealed. It may be formed before the portion 4 is formed. At this time, the dye carrying step is also performed before the sealing portion 4 is formed.

  Moreover, in the said embodiment, it may replace with the working electrode 1 and may use the working electrode 101 which further has the protrusion part 13A which consists of an inorganic material so that it may protrude on the transparent conductive film 7, as shown in FIG. This protruding portion 13A is a portion where the first sealing portion 4A is formed, and forms a first annular portion C1.

  In this case, since the protruding portion 13 </ b> A made of an inorganic material is provided so as to protrude on the transparent conductive film 7, it functions to seal the electrolyte layer 3 together with the sealing portion 4. Moreover, since the protruding portion 13A is made of an inorganic material, it has a higher sealing ability than the first sealing portion 4A and the second sealing portion 4B made of a thermoplastic resin. For this reason, compared with the case where the working electrode 1 does not have the protruding portion 13A, the leakage of the electrolyte can be more sufficiently suppressed.

  Moreover, in the said embodiment, as shown in FIG. 12, the counter electrode 102 which further has the protrusion part 13B which consists of inorganic materials so that it may protrude on the catalyst film | membrane 10 can also be used. The protruding portion 13B is a portion where the second sealing portion 4B is formed, and forms a second annular portion C2.

  In this case, since the protruding portion 13 </ b> B made of an inorganic material is provided so as to protrude on the catalyst film 10, it functions to seal the electrolyte layer 3 together with the sealing portion 4. Moreover, since the protruding portion 13B is made of an inorganic material, it has a higher sealing ability than the first sealing portion 4A and the second sealing portion 4B made of a thermoplastic resin. For this reason, compared with the case where the counter electrode 2 does not have the protrusion part 13B, the leakage of electrolyte can be suppressed more fully.

  As the inorganic material constituting the protruding portions 13A and 13B, for example, an inorganic insulating material such as a lead-free transparent low-melting glass frit, or a metal material such as silver can be used. In particular, it is preferable that the wiring portion generally formed on the working electrode 1 also serves as the protruding portion 13A. In this case, the electrolyte is disposed between the working electrode 1 and the counter electrode 2. And 13 A of protrusion parts have a wiring part, and a wiring part has a current collection wiring and the wiring protective layer which covers current collection wiring. That is, the current collecting wiring is arranged so as to overlap the sealing portion 4 along the direction connecting the working electrode 1 and the counter electrode 2 in a state protected from the electrolyte by the wiring protective layer. As described above, the current collecting wiring is not provided outside the sealing portion 4, and further, the current collecting wiring is not provided inside the sealing portion 4. The area occupied by the wiring and the sealing portion 4 can be minimized, and incident light shielded by the current collecting wiring and the sealing portion 4 can be minimized. Therefore, the light receiving area can be enlarged and high photoelectric conversion efficiency can be obtained. Here, the current collecting wiring is made of a metal material such as silver, and the wiring protective layer is made of an inorganic insulating material such as a low melting point glass frit.

  Furthermore, in the said embodiment, although the 2nd sealing part 4B is comprised only from the outer side resin sealing part 4a, and does not contain the intermediate resin sealing part 4b, the 2nd sealing part 4B is an intermediate resin sealing part. 4b may be included.

  Furthermore, in the above embodiment, the intermediate resin sealing portion 4b has only one layer, but the intermediate resin sealing portion 4b may be a laminate of a plurality of intermediate resin sealing portions having different MFRs. . In this case, the intermediate resin sealing portion is laminated along the direction connecting the working electrode 1 and the counter electrode 2. Here, it is possible to effectively reduce the stress at each interface between the intermediate resin sealing portions by, for example, arranging the MFR of each layer in the laminated body of the intermediate resin sealing portions so as to increase sequentially from the counter electrode 2 side, for example. Therefore, it is preferable.

  Further, in the above embodiment, a covering portion that covers the boundary between the sealing portion 4 and the counter electrode 2 and the boundary between the sealing portion 4 and the working electrode 1 may be provided on the side opposite to the electrolyte layer 3. In this case, the covering portion includes the second resin. As the second resin, acid-modified polyolefin, ultraviolet curable resin, polyvinyl alcohol, or ethylene-vinyl alcohol copolymer can be used. When an acid-modified polyolefin or an ultraviolet curable resin is used as the second resin, adhesion with the working electrode 1, the counter electrode 2, and the sealing portion 4 becomes strong, and electrolyte leakage and electrolyte from the outside occur at each interface. Invasion of moisture into the water can be more sufficiently suppressed.

  Moreover, in the said embodiment, although a pigment | dye carrying | support process is performed after a 1st sealing part formation process from a viewpoint of reducing the thermal damage to a pigment | dye, a pigment | dye carrying | support process is performed before a 1st sealing part formation process. May be done.

  Furthermore, in the said embodiment, although the dye-sensitized solar cell is mentioned as an example of the electronic device of this invention, the electronic device of this invention is not restricted to a dye-sensitized solar cell, EL display apparatus, a liquid crystal display device, The present invention can also be applied to organic thin film solar cells, secondary batteries, and scintillator panels. For example, in an EL display device, a stacked body including an electrode and an EL layer is a sealed portion. In a liquid crystal display device, liquid crystal is a sealed portion.

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. In Tables 1 to 6, when it was difficult to measure the MFR at 190 ° C., an approximate range of the MFR was shown, and the MFR value measured at 210 ° C. was also shown. Further, in Tables 1 to 6, what is denoted as High Milan, Nuclerel, Binell, 05L04, 05L05, Soarnol, Exval, and 31x-101 are as follows.
(1) Ionomer made by High Milan Mitsui-DuPont Polychemical Co., Ltd. (2) Ethylene-methacrylic acid copolymer made by Nucleel Mitsui-DuPont Polychemical Co., Ltd. And maleic anhydride modified polypropylene (4) 05L04
Acid-modified polyethylene manufactured by Tosoh Corporation (molecular structure is branched compared to 05L05)
(5) 05L05
Acid-modified polyethylene manufactured by Tosoh Corporation (molecular structure is linear compared to 05L04)
(6) Soarnol Nippon Synthetic Chemical Industry Co., Ltd. ethylene-vinyl alcohol copolymer (7) EXEVAL Co., Ltd. Kuraray polyvinyl alcohol (8) 31x-101
Three bond UV curable resin

(Example 1)
First, a 10 cm × 10 cm × 4 mm FTO substrate was prepared. Subsequently, after applying a titanium oxide paste (Solaronix, Ti nanoixide T / sp) on the FTO substrate by a doctor blade method so that the thickness becomes 10 μm, it is put in a hot air circulation type oven. Firing was performed at 150 ° C. for 3 hours to form a porous oxide semiconductor layer on the FTO substrate to obtain a working electrode of 5 cm × 5 cm.

  On the other hand, the same FTO substrate as the working electrode was prepared as a counter electrode substrate. Then, a platinum catalyst film having a thickness of 10 nm was formed on the counter electrode substrate by sputtering to obtain a counter electrode.

  Thus, a working electrode and a counter electrode were prepared.

  Next, a square annular resin sheet in which an opening of 5 cm × 5 cm × 100 μm was formed in the center of a 6 cm × 6 cm × 100 μm sheet made of ionomer Himiran (melting point: 98 ° C.) was prepared. And this resin sheet was arrange | positioned in the cyclic | annular site | part surrounding the porous oxide semiconductor layer of a working electrode. The resin sheet was heated and melted at a melting temperature of 120 ° C. (hereinafter referred to as “melting temperature 1”) for 5 minutes to adhere to the annular portion, and the outer resin sealing portion was fixed to the annular portion.

  Subsequently, a square annular resin sheet having an opening of 5 cm × 5 cm × 100 μm formed at the center of a 6 cm × 6 cm × 100 μm sheet made of nucleol (melting point: 97 ° C.) which is an ethylene-methacrylic acid copolymer was prepared. .

  Then, this square annular resin sheet made of nucler was attached at a melting temperature of 110 ° C. (hereinafter referred to as “melting temperature 2”) immediately above the square annular resin sheet made of high Milan. Thus, the intermediate resin sealing portion was formed on the outer resin sealing portion, and the first sealing portion was formed.

  Next, the working electrode was immersed in a dehydrated ethanol solution in which 0.2 mM of N719 dye, which is a photosensitizing dye, was dissolved for 24 hours to support the photosensitizing dye on the working electrode.

  On the other hand, a square annular resin sheet having an opening of 5 cm × 5 cm × 100 μm formed in the center of a 6 cm × 6 cm × 100 μm sheet made of high Milan as an ionomer was prepared on the platinum catalyst film of the counter electrode. And this resin sheet was arrange | positioned in the cyclic | annular site | part on the platinum catalyst film | membrane of a counter electrode. The resin sheet was heated and melted at a melting temperature of 110 ° C. (hereinafter referred to as “melting temperature 3”) for 5 minutes to adhere to the annular portion, and the outer resin sealing portion was fixed.

  Subsequently, a square annular resin sheet was prepared in which an opening of 5 cm × 5 cm × 100 μm was formed in the center of a 6 cm × 6 cm × 100 μm sheet made of nucleol which is an ethylene-methacrylic acid copolymer.

  Then, this square annular resin sheet made of nucler was attached at a melting temperature of 110 ° C. (hereinafter referred to as “melting temperature 4”) immediately above the square annular resin sheet made of high Milan. Thus, the intermediate resin sealing portion was formed on the outer resin sealing portion, and the second sealing portion was formed.

  Next, the working electrode provided with the first sealing portion is arranged so that the surface of the FTO substrate on the porous oxide semiconductor layer side is horizontal, and a volatile solvent made of acetonitrile is provided inside the first sealing portion. As a main solvent, 0.05M of lithium iodide, 0.1M of lithium iodide, 0.6M of 1,2-dimethyl-3-propylimidazolium iodide (DMPII), and 0.02 of 4-tert-butylpyridine. An electrolyte containing 5M (referred to as “A” in Tables 1 and 2) was injected to form an electrolyte layer.

  Next, the counter electrode provided with the second sealing portion was opposed to the working electrode, placed in a reduced pressure environment of about 500 hPa, and the first sealing portion and the second sealing portion were overlapped. Then, under a reduced pressure environment, the brass frame having the same size as the sealing part is heated, the brass frame is arranged on the side opposite to the second sealing part of the counter electrode, and using a press machine, While the first sealing portion and the second sealing portion are pressurized at 5 MPa, they are locally heated and melted at a temperature of 160 ° C. (hereinafter referred to as “sealing temperature”) to form a sealing portion. Obtained. Then, this laminated body was taken out under atmospheric pressure. Thus, a dye-sensitized solar cell was obtained.

(Examples 2 to 14)
The resin constituting the outer resin sealing portion and the intermediate resin sealing portion of the first sealing portion and the MFR thereof, the resin constituting the outer resin sealing portion and the intermediate resin sealing portion of the second sealing portion and the MFR thereof, In addition, a dye-sensitized solar cell was produced in the same manner as in Example 1 except that the melting temperatures 1 to 4 and the sealing temperature were changed as shown in Table 1.

(Examples 15 to 20)
The resin constituting the outer resin sealing portion and the intermediate resin sealing portion of the first sealing portion and the MFR thereof, the resin constituting the outer resin sealing portion and the intermediate resin sealing portion of the second sealing portion and the MFR thereof, In addition, a dye-sensitized solar cell was produced in the same manner as in Example 1 except that the melting temperatures 1 to 4 and the sealing temperature were changed as shown in Tables 1 and 2.

  In addition, 31x-101 used as the outer resin sealing portion of the first sealing portion and the second sealing portion is an ultraviolet curable resin, and this ultraviolet curable resin is bonded to the annular portion of the working electrode and the counter electrode. In carrying out, after apply | coating to a cyclic | annular site | part, the ultraviolet curable resin was adhere | attached on the cyclic | annular site | part by making it harden | cure by irradiating an ultraviolet-ray (UV) in a low oxygen environment. For this reason, in Tables 1 and 2, the melting temperatures 1 and 3 are indicated as “−”.

(Examples 21 to 26)
The resin constituting the outer resin sealing portion and the intermediate resin sealing portion of the first sealing portion and the MFR thereof, the resin constituting the outer resin sealing portion and the intermediate resin sealing portion of the second sealing portion and the MFR thereof, In addition, a dye-sensitized solar cell was produced in the same manner as in Example 1 except that the melting temperatures 1 to 4 and the sealing temperature were changed as shown in Table 2.

  (Comparative Examples 1 to 5) The resin constituting the outer resin sealing portion and the intermediate resin sealing portion of the first sealing portion and its MFR, the outer resin sealing portion and the intermediate resin sealing portion of the second sealing portion A dye-sensitized solar cell was produced in the same manner as in Example 1 except that the resin and its MFR, the melting temperature 1 to 4 and the sealing temperature were changed as shown in Table 2.

(Comparative Example 6)
First, a working electrode was prepared in the same manner as in Example 1, and a dye was supported. On the other hand, a counter electrode was prepared in the same manner as in Example 1. And 31x-101 which is a precursor of a ultraviolet curable resin was apply | coated to the cyclic | annular part of a working electrode, and it hardened | cured by irradiating an ultraviolet-ray, and obtained the cyclic | annular 1st sealing part (outside resin sealing part). Subsequently, an electrolyte was disposed in the same manner as in Example 1 inside the first sealing portion. On the other hand, 31x-101 is applied to the annular portion of the counter electrode, the working electrode and the counter electrode are opposed to each other so as to overlap the first sealing portion, and then the second sealing is performed by irradiating 31x-101 with ultraviolet rays. Part (outside resin sealing part) was formed. In this way, a dye-sensitized solar cell was produced.

(Examples 27-52 and Comparative Examples 7-12)
As shown in Tables 3 and 4, the electrolyte is a volatile solvent composed of methoxypropionitrile as a main solvent, lithium iodide is 0.1M, iodine is 0.05M, and 4-tert-butylpyridine is 0.00. Dye-sensitized solar cells were produced in the same manner as in Examples 1 to 26 and Comparative Examples 1 to 6, except that the volatile electrolyte containing 5M was used (referred to as “B” in Tables 3 and 4).

(Examples 53 to 78 and Comparative Examples 13 to 18)
As shown in Table 5 and Table 6, the electrolyte was added to a volatile solvent composed of methoxypropionitrile, 0.1M lithium iodide, 0.05M iodine, and 0.5M 4-tert-butylpyridine. Example 1 except that 5% silica fine particles having an average particle diameter of 15 nm were added to the total weight of the product to change to a gelled electrolyte (referred to as “C” in Tables 5 and 6). 26, dye-sensitized solar cells were prepared in the same manner as in Comparative Examples 1 to 6, respectively.

に従って算出した。なお、光電変換効率の維持率が１００％を超えるものは、耐久試験後の変換効率が初期の変換効率よりも高いことを意味する。結果を表１〜６に示す。

[Characteristic evaluation]
About the dye-sensitized solar cell of Examples 1-78 and Comparative Examples 1-18, the characteristic evaluation was performed by conducting a durability test as follows. That is, in the durability test, the thermal cycle in which the ambient temperature is lowered to −40 ° C. and then raised to 90 ° C. according to JIS C8917 is applied to the dye-sensitized solar cells of Examples 1 to 78 and Comparative Examples 1 to 18. As a cycle, 200 cycles were performed. And the maintenance rate of photoelectric conversion efficiency is expressed by the following formula:

Calculated according to In addition, the thing whose maintenance rate of photoelectric conversion efficiency exceeds 100% means that the conversion efficiency after an endurance test is higher than the initial conversion efficiency. The results are shown in Tables 1-6.

  From the results shown in Tables 1 to 6, the dye-sensitized solar cells of Examples 1 to 78 are superior in terms of durability compared to the dye-sensitized solar cells of Comparative Examples 1 to 18 regardless of the type of electrolyte. I found out.

  Therefore, according to the electronic device of the present invention, it was confirmed that the durability could be sufficiently maintained even when placed in an environment with a large temperature change.

1,101 ... Working electrode (first electrode, first substrate)
2 ... Counter electrode (second electrode, second substrate)
3 ... electrolyte layer (sealed part)
4A ... 1st sealing part 4B ... 2nd sealing part 4 ... Sealing part 7 ... Transparent conductive film (conductive film)
DESCRIPTION OF SYMBOLS 8 ... Porous oxide semiconductor layer 9 ... Counter electrode substrate 10 ... Catalyst film 13A, 13B ... Projection part 100 ... Dye-sensitized solar cell C1 ... 1st cyclic | annular site | part C2 ... 2nd cyclic | annular site | part.

That is, the present invention includes a first base material, a second base material disposed opposite to the first base material, a sealed portion disposed between the first base material and the second base material, The first base material and the second base material are connected to each other, and a sealing part provided around the sealed part is provided, and the sealing part is provided along the periphery of the sealed part. At least a part between the first base material and the second base material, and the outer side resin seal part fixed between the first base material and the second base material. An intermediate resin sealing portion disposed so as to be sandwiched between the outer resin sealing portion and the intermediate resin sealing portion, and the melt flow rate of the intermediate resin sealing portion is the outer resin. It is an electronic device characterized by being larger than the melt flow rate of the sealing part.

Moreover, this invention is the 1st which forms the 1st sealing part containing an outer side resin sealing part in the 1st cyclic | annular site | part in the said 1st base material which prepares a 1st base material and a 2nd base material. A sealing portion forming step, a second sealing portion forming step of forming a second sealing portion including an outer resin sealing portion in a second annular portion of the second base material, the first base material, and the A second base material is bonded, and a sealing part is formed by adhering the first sealing part and the second sealing part between the first base material and the second base material, and the sealing is performed. A sealing portion forming step of disposing a sealing portion so as to be surrounded by the stopper, the first base material, and the second base material, and at least one of the first sealing portion and the second sealing portion One has an intermediate resin sealing portion provided on the outer resin sealing portion, and the intermediate resin sealing portion and the outer resin sealing portion include a resin. The melt flow rate of the intermediate resin sealing portion is a manufacturing method of an electronic device being greater than the melt flow rate of the outer resin sealing portion.

That is, the present invention includes a first base material, a second base material disposed opposite to the first base material, a sealed portion disposed between the first base material and the second base material, The first base material and the second base material are connected to each other, and a sealing part provided around the sealed part is provided, and the sealing part is provided along the periphery of the sealed part. At least a part between the first base material and the second base material, and the outer side resin seal part fixed between the first base material and the second base material. An intermediate resin sealing portion disposed so as to be sandwiched between the outer resin sealing portion and the intermediate resin sealing portion, and the melt flow rate of the intermediate resin sealing portion is the outer resin. a big electronic device than the melt flow rate of the sealing portion, wherein the electronic device is a dye-sensitized solar cells, organic thin-film solar cells, EL display devices Is an electronic device, which is a liquid crystal display device.

Moreover, this invention is the 1st which forms the 1st sealing part containing an outer side resin sealing part in the 1st cyclic | annular site | part in the said 1st base material which prepares a 1st base material and a 2nd base material. A sealing portion forming step, a second sealing portion forming step of forming a second sealing portion including an outer resin sealing portion in a second annular portion of the second base material, the first base material, and the A second base material is bonded, and a sealing part is formed by adhering the first sealing part and the second sealing part between the first base material and the second base material, and the sealing is performed. A sealing portion forming step of disposing a sealing portion so as to be surrounded by the stopper, the first base material, and the second base material, and at least one of the first sealing portion and the second sealing portion One has an intermediate resin sealing portion provided on the outer resin sealing portion, and the intermediate resin sealing portion and the outer resin sealing portion include a resin. Wherein the intermediate resin sealing portion of the melt flow rate is a manufacturing method of an electronic device being greater than the melt flow rate of the outer resin sealing portion, the electronic apparatus, the dye-sensitized solar cells, organic It is a manufacturing method of an electronic device which is a thin film solar cell, an EL display device, or a liquid crystal display device .

Claims (20)

A first substrate;
A second substrate disposed opposite to the first substrate;
A sealed portion disposed between the first base material and the second base material;
Connecting the first base material and the second base material, and having a sealing portion provided around the sealed portion,
At least a part of the sealing portion along the periphery of the sealed portion is
An outer resin sealing portion fixed to each of the first base material and the second base material;
An intermediate resin sealing portion disposed between the first base material and the second base material so as to be sandwiched between the outer resin sealing portions;
The outer resin sealing portion and the intermediate resin sealing portion include a resin,
The photoelectric conversion device, wherein a melt flow rate of the intermediate resin sealing portion is larger than a melt flow rate of the outer resin sealing portion.   The electronic device according to claim 1, wherein the intermediate resin sealing portion includes an acid-modified polyolefin.   The electronic device according to claim 1, wherein the intermediate resin sealing portion includes acid-modified polyethylene.   The electronic device according to claim 1, wherein the intermediate resin sealing portion includes at least one selected from the group consisting of polyvinyl alcohol and an ethylene-vinyl alcohol copolymer.   The electronic device according to any one of claims 1 to 4, wherein the outer resin sealing portion includes at least one selected from the group consisting of an acid-modified polyolefin and an ultraviolet curable resin.   The electronic apparatus according to claim 1, wherein the outer resin sealing portion includes acid-modified polyethylene.   The electronic device according to any one of claims 1 to 4, wherein the outer resin sealing portion includes at least one selected from the group consisting of polyvinyl alcohol and an ethylene-vinyl alcohol copolymer.   On the opposite side to the sealed portion with respect to the sealing portion, the boundary between the first base material and the sealing portion, the boundary between the second base material and the sealing portion, the intermediate resin sealing portion, and The electronic device according to claim 1, further comprising a covering portion that covers at least a boundary of the outer resin sealing portion, wherein the covering portion includes a second resin.   The electronic device according to any one of claims 1 to 8, wherein the first base material is a first electrode and the second base material is a second electrode.   The first electrode is provided so as to protrude from a porous oxide semiconductor layer, a conductive film on which the porous oxide semiconductor layer is formed, and the conductive film. The electronic device according to claim 9, further comprising: a protrusion disposed between the film and the film, wherein the protrusion is made of an inorganic material, and the sealed portion is an electrolyte.   The projecting portion is composed of a wiring portion fixed on the conductive film, the wiring portion is composed of an inorganic material, and current collecting wiring provided on the conductive film and wiring protection covering the current collecting wiring The electronic device according to claim 10, further comprising a layer.   The second electrode is provided so as to protrude on the counter electrode substrate, the catalyst film provided on the counter electrode substrate, and the catalyst film, and sandwiched between the outer resin sealing portion and the catalyst film. The electronic device according to any one of claims 9 to 11, wherein the protruding portion is made of an inorganic material, and the sealed portion is an electrolyte. A preparation step of preparing a first substrate and a second substrate;
A first sealing portion forming step of forming a first sealing portion including an outer resin sealing portion in the first annular portion of the first base material;
A second sealing portion forming step of forming a second sealing portion including an outer resin sealing portion in the second annular portion of the second base material;
Sealing formed by bonding the first base material and the second base material, and bonding the first sealing portion and the second sealing portion between the first base material and the second base material. And a sealing part forming step of arranging a sealed part so as to be surrounded by the sealing part, the first base material, and the second base material,
At least one of the first sealing portion and the second sealing portion has an intermediate resin sealing portion provided on the outer resin sealing portion,
The intermediate resin sealing portion and the outer resin sealing portion include a resin,
The method for manufacturing an electronic device, wherein a melt flow rate of the intermediate resin sealing portion is larger than a melt flow rate of the outer resin sealing portion.   The method for manufacturing an electronic device according to claim 13, wherein the first base material is a first electrode and the second base material is a second electrode. The first electrode includes a porous oxide semiconductor layer;
The sealed portion is an electrolyte;
Between the preparation step and the sealing portion formation step,
A dye carrying step of carrying a photosensitizing dye on the porous oxide semiconductor layer;
An electrolyte layer forming step of forming an electrolyte layer by disposing the electrolyte on the first electrode and inside the first sealing portion or on the second electrode and inside the second sealing portion. And further including
The electrolyte layer forming step is performed after at least one of the first sealing portion forming step and the second sealing portion forming step,
The method of manufacturing an electronic device according to claim 14, wherein in the sealing portion forming step, the sealing portion is formed by melting the first sealing portion and the second sealing portion while applying pressure.   In the electrolyte layer forming step, the electrolyte layer includes the electrolyte on the first electrode and inside the first sealing portion, or on the second electrode and inside the second sealing portion. The electron according to claim 15, wherein the electron is formed by injecting into a liquid and overflowing beyond the first sealing portion or the second sealing portion to the outside of the first sealing portion or the second sealing portion. Device manufacturing method.   The method for manufacturing an electronic device according to claim 15 or 16, wherein, in the electrolyte layer forming step, the electrolyte layer is formed on the first electrode and inside the first sealing portion. The first electrode is
The porous oxide semiconductor layer;
A conductive film on which the porous acid non-oxide semiconductor layer is formed;
The projection part which is provided so that it may protrude on the said electrically conductive film, and makes the said 1st cyclic | annular site | part, the said protrusion part consists of inorganic materials, and the said to-be-sealed part is electrolyte. The manufacturing method of the electronic device as described in any one. The second electrode is
A counter electrode substrate;
A catalyst film provided on the counter electrode substrate;
The projection part which is provided so that it may protrude on the said catalyst film, and makes the said 2nd cyclic | annular site | part, the said protrusion part consists of inorganic materials, and the said to-be-sealed part is electrolyte. The manufacturing method of the electronic device as described in any one. The method for manufacturing an electronic device according to claim 14, wherein at least one of the first electrode and the second electrode has flexibility.

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