TWI629802B - Photoelectric conversion element, electric module and method for producing photoelectric conversion element - Google Patents

Abstract

A photoelectric conversion element, comprising: a first electrode having a transparent conductive film formed on a surface of a substrate; a semiconductor layer formed on the surface of the transparent conductive film; and a second electrode separated from the substrate. An opposing conductive film is formed on the plate surface of the other substrate that is disposed to be opposed to each other at a distance from the transparent conductive film; and an electrolyte is sealed between the first electrode and the second electrode. And at least one of the one substrate and the other substrate is bent or bent inside the outer peripheral wall portion sealing the electrolyte, and protrudes toward the other substrate or the one substrate arranged oppositely.

Description

Photoelectric conversion element, electric module and manufacturing method of photoelectric conversion element

The invention relates to a method for manufacturing a photoelectric conversion element, an electric module and a photoelectric conversion element.

In recent years, solar cells have attracted attention as a power generation device instead of fossil fuels, and the development of silicon (Si) solar cells and dye-sensitized solar cells has been continuously promoted. In particular, a dye-sensitized solar cell has been extensively researched and developed as a cheap and easy mass-producer for its structure and manufacturing method (for example, the following Patent Document 1).

As shown in FIG. 11, the dye-sensitized solar cell 100 described in Patent Document 1 includes a first electrode 104 having a transparent conductive film 102 formed on a surface of a transparent substrate 101 and a surface formed on the surface of the transparent conductive film 102. A semiconductor layer 103 carrying a pigment; a second electrode 107 having an opposite conductive film 106 formed on the opposite substrate 105 so as to face the transparent conductive film 102; and a sealing material 108 surrounding the semiconductor layer 103 and The outer peripheral wall portion of the first electrode 104 is bonded to the outer peripheral wall portion of the second electrode 107 to form an internal space S and seal the internal space S; and an electrolyte 109 is injected into the internal space S.

[Patent Document 1] Japanese Patent Laid-Open No. 2011-49140

Furthermore, in general, since the dye-sensitized solar cell 100 must fill the internal space S with a large amount of the electrolytic solution 109 to prevent bubbles from entering the internal space S, the transparent substrate 101 and the opposing substrate 105 are bent near the center of the internal space S. The shape of the bulge is increased, and the thickness of the layer of the electrolyte 109 is larger than that of the portion where the sealing material 108 is disposed.

However, in a dye-sensitized solar cell, if the electrolytic solution 109 is thick near the center of the internal space S, the incident light reaching the semiconductor layer 103 through the electrolytic solution 109 is reduced, and the moving distance of electrons to the semiconductor layer 103 Increase, so there is a problem that the efficiency of the redox reaction decreases.

Therefore, the present invention has been made in view of the above problems, and an object thereof is to provide a photoelectric conversion element that suppresses a decrease in incident light and a decrease in efficiency of a redox reaction.

The photoelectric conversion element of the present invention is characterized by comprising: a first electrode having a transparent conductive film formed on a surface of a substrate; a semiconductor layer formed on the surface of the transparent conductive film; and a second electrode provided between the first electrode and the substrate. An opposite conductive film is formed on the plate surface of the other substrate that is disposed opposite to each other at a distance from the transparent conductive film; and an electrolyte is sealed between the first electrode and the second electrode. And at least one of the one substrate and the other substrate is bent or bent inside the outer peripheral wall portion sealing the electrolyte, and protrudes toward the other substrate or the one substrate arranged oppositely.

According to this configuration, at least one of the one substrate and the other substrate is bent or bent inside the outer peripheral wall portion that seals the electrolyte, so that the inner side of the outer peripheral wall portion can be provided with The strength of the bend in the direction opposite to the direction of the protrusion. Therefore, it is possible to prevent one substrate and the other substrate from bulging in a direction away from each other. Moreover, one substrate can be bent to be close to the opposite substrate. Therefore, it is possible to reduce the distance between one substrate and another substrate, to prevent the reduction of incident light due to the thickening of the layer of the electrolyte, and to realize the efficiency of the redox reaction caused by the shortening of the moving distance of the electrons.

At least one of the above-mentioned one substrate and the other substrate of the present invention may be configured to include a side wall portion disposed on the inside of the outer peripheral wall portion sealing the electrolyte toward the opposite substrate. Or the substrate is bent and formed along the outer peripheral wall portion; and the inner side wall portion is formed inside the front end of the side wall portion; and the side wall portion is inclined with respect to the outer peripheral wall portion.

According to this configuration, one substrate or the other substrate is bent, whereby the strength of the bending in a direction crossing the bending direction can be increased. Therefore, it is possible to prevent one substrate and the other substrate from bulging in a direction away from each other. Moreover, the distance between one substrate and the other substrate can be reduced to prevent a decrease in incident light due to the thickening of the layer of the electrolyte, and to realize the efficiency of the redox reaction caused by the shortening of the moving distance of the electrons.

The above-mentioned one substrate of the present invention may have a configuration in which it is bent on the inside of the peripheral wall portion where the electrolyte is sealed.

According to this configuration, one substrate is prevented from being bent so as to be swollen in a direction away from the opposite substrate. In addition, since one substrate is bent to be close to the opposite substrate, the distance between one substrate and the other substrate can be reduced and the redox reaction can be performed efficiently.

In the present invention, at least one of the one substrate or the other substrate protruding toward the other substrate or the one substrate is preferably formed of a resin film.

According to this configuration, the above-mentioned photoelectric conversion element can be easily and efficiently manufactured.

In the photoelectric conversion element of the present invention, it is preferable that the outer peripheral wall portion of the one substrate and the outer peripheral wall portion of the other substrate are connected by a sealing material, and the sealing material and the bent or bent outer periphery are connected. The corners facing the inside of the wall are chamfered.

According to this configuration, since the bending angle or bending angle of the one substrate and / or the other substrate that is bent or bent inside the outer peripheral wall portion can be made gentle, it is not easy to face the transparent conductive film and / or the opposite direction. The conductive film is damaged or cracked.

In the photoelectric conversion element of the present invention, the sealing material may be chamfered along a bent or curved shape inside the outer peripheral wall portion.

According to this configuration, the one substrate and / or the other substrate can be bent or bent along the chamfered sealing material.

The electrical module of the present invention is characterized by being provided with a plurality of any one of the above-mentioned photoelectric conversion elements.

According to the present invention, it is possible to obtain an electric module that performs any of the above functions and functions.

The method for manufacturing any one of the above-mentioned photoelectric conversion elements is characterized in that at least one of the one substrate and the other substrate protruding toward the other substrate or the one substrate is formed by performing press processing.

According to the present invention, the above-mentioned photoelectric conversion element can be easily manufactured.

It is preferable that the method for manufacturing any one of the photoelectric conversion elements is to form a semiconductor layer and apply compressive internal stress to the one substrate to bend the one substrate.

According to this configuration, the one substrate can be easily bent.

The semiconductor layer of the present invention is preferably formed by an aerosol deposition method.

According to this method, a substrate can be easily bent.

According to the present invention, since the reduction of the incident light and the reduction of the efficiency of the redox reaction can be suppressed, the effect of improving the power generation efficiency of the photoelectric conversion element and the electric module is exerted.

In addition, according to the method for manufacturing a photoelectric conversion element of the present invention, there is an effect that the photoelectric conversion element of the present invention can be easily manufactured.

1A, 1B, 1C, 1D ‧‧‧ solar cells (photoelectric conversion elements)

2‧‧‧ a substrate

2a‧‧‧board surface

2p‧‧‧ peripheral wall

3‧‧‧ transparent conductive film

3a‧‧‧ surface

4‧‧‧ semiconductor layer

5‧‧‧The first electrode

6‧‧‧ another substrate

6a‧‧‧board surface

6p‧‧‧ peripheral wall

7‧‧‧ Opposite conductive film

7a‧‧‧ surface

8‧‧‧ 2nd electrode

11‧‧‧ Electrolyte (electrolyte)

15‧‧‧ sidewall

16‧‧‧ inner wall

50‧‧‧ Corner

FIG. 1 is a cross-sectional view schematically showing a photoelectric conversion element according to a first embodiment of the present invention.

FIG. 2 is a perspective view schematically showing a substrate of a photoelectric conversion element according to the first embodiment of the present invention.

FIG. 3 is a cross-sectional view schematically showing a part of the manufacturing steps of the photoelectric conversion element according to the first embodiment of the present invention.

FIG. 4 is a cross-sectional view schematically showing a part of the manufacturing steps of the photoelectric conversion element according to the first embodiment of the present invention.

FIG. 5 is a cross-sectional view schematically showing a part of the manufacturing steps of the photoelectric conversion element according to the first embodiment of the present invention.

FIG. 6 is a cross-sectional view schematically showing a part of the manufacturing steps of the photoelectric conversion element according to the first embodiment of the present invention.

FIG. 7 is a cross-sectional view schematically showing a part of the manufacturing steps of the photoelectric conversion element according to the first embodiment of the present invention.

FIG. 8 is a cross-sectional view schematically showing a part of the manufacturing steps of the photoelectric conversion element according to the first embodiment of the present invention.

Fig. 9 is a sectional view schematically showing a photoelectric conversion element according to a second embodiment of the present invention.

10 (a) to (c) are cross-sectional views schematically showing a photoelectric conversion element shown as an embodiment of the present invention.

Fig. 11 is a sectional view showing a conventional photoelectric conversion element.

Fig. 12 is a sectional view schematically showing a photoelectric conversion element according to a third embodiment of the present invention.

Fig. 13 is a sectional view schematically showing a photoelectric conversion element according to a third embodiment of the present invention.

Hereinafter, taking the case where the photoelectric conversion element is a dye-sensitized solar cell as an example, each embodiment of the photoelectric conversion element and the electric module of the present invention will be described with reference to the drawings.

(First Embodiment)

As shown in FIG. 1, a dye-sensitized solar cell (photoelectric conversion element) (hereinafter referred to as a “solar cell”) 1A includes a first electrode 5 including a transparent conductive film 3 formed on a plate surface 2 a of a substrate 2, A semiconductor layer 4 formed on the surface 3a of the transparent conductive film 3; and a second electrode 8 on the plate surface 6a of the other substrate 6 disposed opposite to the substrate 2 at a distance from the substrate 2 to face the transparent conductive film 3 A facing conductive film 7 is formed in a direction-oriented manner.

In addition, between the first electrode 5 and the second electrode 8 is a state in which a separator 9 is interposed, and a sealing material 10 is provided between the outer peripheral wall portion 2p of one substrate 2 and the outer peripheral wall portion 6p of the other substrate 6. The first electrode 5 and the second electrode 8 are sealed in a frame shape so as to surround the outer periphery, and the sealed internal space S is filled with the electrolytic solution 11.

Here, as shown in FIG. 1 and FIG. 2, a substrate 2 is bent toward the other substrate 6 disposed on the inside of the outer peripheral wall portion 2 p sealing the electrolyte solution 11, and the inner wall portion of the outer peripheral wall portion 2 p is bent. 15 and 16 protrude toward the other substrate 6.

Specifically, a substrate 2 is provided with an outer peripheral wall portion 2p formed with a specific width dimension d which enters the inner specific dimension from the outer edge e of the substrate 2; and a side wall portion 15 which faces the other side from the inner side of the outer peripheral wall portion 2p. A base plate 6 is bent and erected obliquely (hanging down) along the outer peripheral wall portion 2p; and an inner side wall portion 16 is bent again at the front end of the side wall portion 15 to block the area surrounded by the front end of the side wall portion 15 And a convex portion 17 protruding toward the other substrate 6 is formed.

One substrate 2 and the other substrate 6 are components of the abutment of the transparent conductive film 3 and the opposite conductive film 7, respectively, for example, by polyethylene naphthalate (PEN), polyethylene terephthalate (PET) and other transparent thermoplastic resin materials.

In addition, one substrate 2 and the other substrate 6 may be formed into a film shape.

The transparent conductive film 3 is formed on the substantially entire surface of the plate surface 2 a of a substrate 2.

The material of the transparent conductive film 3 is, for example, indium tin oxide, zinc oxide, or the like.

The semiconductor layer 4 has a function of receiving and transmitting electrons from a sensitizing dye described below, and is formed on the surface 3 a of the transparent conductive film 3 by a semiconductor made of a metal oxide. Examples of the metal oxide include titanium oxide (TiO ₂ ), zinc oxide (ZnO), and tin oxide (SnO ₂ ).

The semiconductor layer 4 carries a sensitizing dye. The sensitizing dye is composed of an organic dye or a metal complex dye. As an organic pigment, various organic pigments, such as a coumarin system, a polyene system, a cyanine system, a hemicyanine system, and a thiophene system, can be used, for example. As the metal complex dye, for example, a ruthenium complex can be preferably used.

As described above, the transparent conductive film 3 is formed on one plate surface 2 a of a substrate 2, and the semiconductor layer 4 formed on the surface 3 a of the transparent conductive film 3 is provided to constitute the first electrode 5.

The opposite conductive film 7 is formed on substantially the entire surface of the plate surface 6 a of the other substrate 6.

The material of the opposite conductive film 7 is, for example, indium tin oxide (ITO), zinc oxide, or the like. A catalyst layer 18 made of carbon paste, platinum, or the like is arbitrarily provided on the surface of the opposite conductive film 7.

As described above, the opposite conductive film 7 is formed on one plate surface 6 a of the other substrate 6, and the catalyst layer 18 is formed on the surface of the opposite conductive film 7 to constitute the second electrode 8.

The second electrode 8 is arranged so that the opposed conductive film 7 faces the transparent conductive film 3 and faces the first electrode 5.

The first electrode 5 and the second electrode 8 are staggered in one direction so that the end portion 3h of the transparent conductive film 3 and the end portion 7h of the opposed conductive film 7 protrude from both ends of the solar cell 1A, respectively. These end portions 3h and 7h constitute terminals of the first electrode 5 and the second electrode 8.

The method of extracting the current is not limited to the configuration of this embodiment.

As the sealing material 10, a hot-melt resin or the like can be used.

The sealing material 10 is arranged in a frame shape on the surface 3a of the transparent conductive film 3 located on the outer peripheral wall portion 2p or on the surface of the opposite conductive film 7 located on the outer peripheral wall portion 6p, and the first electrode 5 and the first electrode 5 are heated and pressed. The second electrodes 8 are connected to each other.

As the separator 9 shown in FIG. 1, a sheet such as a nonwoven fabric having a large number of holes (not shown) through which the sealing material 10 and the electrolytic solution (electrolyte) 11 pass is used.

As the electrolyte solution 11, for example, a non-aqueous solvent such as acetonitrile or propionitrile is used; and a supporting electrolyte solution such as lithium iodide is mixed with a liquid component such as an ionic liquid such as dimethylpropylimidazolium iodide or butylmethylimidazolium iodide. A solution made with iodine. Also, to prevent reverse electron movement In the reaction, the electrolytic solution 11 may also include a third butylpyridine.

The solar cells 1A having the above-described configuration are connected in series or in parallel to form an electrical module.

Next, a manufacturing method of the solar cell 1A will be described using FIGS. 3 to 9.

The manufacturing method of the solar cell 1A according to the first embodiment includes: (1) an electrode plate forming step; (II) bonding the first electrode 5 and the second electrode 8 to form an internal space S therebetween, and the internal space S The sealing bonding step, (III) a liquid injection hole forming step, (IV) a liquid injection step, and (V) a liquid injection hole sealing step. Each step will be described below.

(1) <Electrode plate formation step>

A first electrode 5 and a second electrode 8 are formed in the electrode plate forming step. As shown in FIG. 3, the first electrode 5 forms a transparent conductive film 3 on a plate surface 2 a of a substrate 2 and is on the surface of the transparent conductive film 3. A semiconductor layer 4 is formed at 3 a. As shown in FIG. 4, the second electrode 8 forms an opposite conductive film 7 on a plate surface 6 a of the other substrate 6, and further forms a catalyst layer 18. Specifically, the first electrode 5 and the second electrode 8 are formed as follows.

As shown in FIG. 3, as a substrate 2, a plate-like member formed on the inside of the substrate and having a convex portion 17 protruding toward one plate surface is used as the substrate 2. The manufacturing method of the plate-shaped member provided with the convex part 17 is not specifically limited, It can shape | mold suitably by pressure processing, injection molding, etc.

The entire surface of the plate surface 2a of a substrate 2 is sputter-plated with indium tin oxide (ITO) or the like to form a transparent conductive film 3.

The semiconductor layer 4 is formed, for example, by applying a paste containing sinterable titanium oxide to the surface 3a of the transparent conductive film 3 by masking, printing, or the like, and thereafter at a temperature of about 120 ° C. By firing, it becomes porous. The semiconductor layer 4 is formed of PET or the like. In the case of a structured film material, it may be formed on the surface 3a of the transparent conductive film 3 by a low-temperature film-forming method that does not require firing, such as an aerosol deposition method or a cold spray method.

After the semiconductor layer 4 is formed, the semiconductor layer 4 is immersed in a sensitizing dye solution obtained by dissolving the sensitizing dye in a solvent, and the semiconductor layer 4 carries the sensitizing dye. In addition, the method of carrying the sensitizing dye on the semiconductor layer 4 is not limited to the above, and a method of continuously charging, dipping, and lifting while moving the semiconductor layer 4 in the sensitizing dye solution is also adopted.

With the above, the first electrode 5 shown in FIG. 3 is obtained.

As shown in FIG. 4, the second electrode 8 is formed by sputtering ITO, zinc oxide, platinum, or the like on one surface 6a of another substrate 6 made of polyethylene terephthalate (PET) or the like to make the opposite conductive. The film 7 is formed into a film. The opposite conductive film 7 may be formed by a printing method, a spray method, or the like. A carbon slurry is formed on the surface of the opposite conductive film 7 to form a catalyst layer 18.

(II) <Laminating step>

As shown in FIG. 5 and FIG. 6, the bonding step is to arrange the first electrode 5 and the second electrode 8 to face each other, and to attach the outer peripheral wall portions 2 p and 6 p to each other by the sealing material 10 to bond the first electrode. The step of forming an internal space S sealed between 5 and the second electrode 8.

[Arrangement of sealing material 10 and member for forming injection hole]

Specifically, as shown in FIG. 5, a sheet-shaped sealing material 10 formed in a frame shape having a specific width dimension is arranged on the outer peripheral wall portion 6 p so as to surround the catalyst layer 18.

Thereafter, the liquid injection hole forming member 19 is disposed so as to protrude from the outer peripheral wall portion 6 p of the other substrate 6 across the sealing material 10.

In addition, as the member 19 for forming a liquid injection hole, a moldable resin sheet formed into a short strip shape was used.

As a mold release resin sheet, polyester, polyethylene terephthalate, polybutylene terephthalate, etc. can be used, for example.

[Lamination of substrates]

Then, the second electrode 8 is brought into contact with the first electrode 5 in a state where the separator 9 is interposed so that the transparent conductive film 3 and the opposed conductive film 7 face each other.

[Next steps]

In the next step, the outer peripheral wall portions 2p and 6p shown in FIG. 5 after the first electrodes 5 and the second electrodes 8 are bonded together are heated and pressurized in the lamination direction to wait. At this time, since the heat-resistant temperature of the member 19 for forming a liquid injection hole is higher than the melt-hardening temperature of the sealing material 10 and is excellent in non-adhesion, it does not adhere to the sealing material 10 that contacts the member 19 for forming a liquid injection hole. Therefore, both surfaces of the member 19 for forming a liquid injection hole are not in contact with the first electrode 5 and the second electrode 8.

At this time, as shown in FIG. 5, the first electrode 5 and the second electrode 8 are staggered and bonded in one direction (direction of arrow Y), and the transparent conductive film 3 and the opposite conductive film are made as shown in FIG. 6. 7 Protrudes from both ends of the first electrode 5 and the second electrode 8 after bonding to form terminals 5t and 8t.

(III) <Step for forming injection hole>

In the liquid injection hole forming step, as shown in FIG. 7, the liquid injection hole forming member 19 (refer to FIG. 6) protruding from the outer peripheral wall portion 6 p of the other substrate 6 is extracted, and the internal space S is opened to form an injectable electrolytic solution.液 11 的 液 孔 21。 The liquid injection hole 21.

Through the above steps, a bonded body 1a having an internal space S formed between the first electrode 5 and the second electrode 8 is obtained.

(IV) <Infusion step>

In the liquid injection step, the joint body 1a obtained in the above step is placed under a reduced pressure environment. The liquid injection hole 21 is immersed in a container (not shown) that holds the electrolytic solution 11, and the electrolytic solution 11 is injected into the internal space S in a large amount as the electrolytic solution overflows by evacuation.

(V) <Step for sealing the injection hole>

Thereafter, in the liquid injection hole sealing step, after the electrolyte 11 is injected, the liquid injection hole 21 is closed with an adhesive or the like to seal the internal space S (see FIG. 8). At this time, since one substrate 2 is formed with a convex portion 17 that is bent along the outer peripheral wall portion 2p and protrudes toward the other substrate 6, the one substrate 2 is provided with a ridge line 17a (also formed on the substrate) formed by the bending. 17a), the strength of the bending in the direction (that is, the direction orthogonal to the bending direction). Therefore, even if the electrolytic solution 11 is filled in a large amount and sealed so that bubbles do not enter the internal space S, a substrate 2 can resist the force that is intended to bulge outward in the thickness direction due to the electrolytic solution 11, thereby keeping the inner side wall portion 16 flat. .

As described above, the solar cell 1A shown in FIG. 1 in which the inner wall portion 16 of a substrate 2 is kept flat is obtained.

In this way, according to the solar cell 1A or the electrical module in which the solar cells 1A are connected in series or in parallel, as shown in FIG. 1, a substrate 2 is bent and the inner wall portion 16 protrudes toward the other substrate 6. Therefore, the thickness dimension of the internal space S into which the electrolytic solution 11 is injected can be reduced as much as possible, and the inner wall portion 16 can be given a strength to resist the bending outward in the thickness direction by bending a substrate 2.

Therefore, even if a large amount of electrolyte 11 is injected into the internal space S, a substrate 2 can be prevented from bulging outward at the center of the internal space S, and the thickness of the internal space S of the layer forming the electrolyte 11 can be maintained as much as possible. Reduced fixed size. Furthermore, according to the configuration of the present invention, it is possible to obtain the effect that the loss of incident light caused by the increase in the thickness of the layer of the electrolyte solution 11 at the central portion of the internal space S can be prevented, and the electron Moving distance The longer the distance becomes, the lower the efficiency of the redox reaction is.

A substrate 2 is bent at an obtuse angle between the side wall portion 15 and the outer peripheral wall portion 2 p and between the side wall portion 15 and the inner side wall portion 16. Therefore, compared with the case where one substrate 2 is bent vertically or at an acute angle to form the convex portion 17, the convex portion can be easily formed by press working. In addition, by bending a substrate 2 into an obtuse angle, the following effect can be obtained: the wall thickness of the substrate 2 can be prevented from becoming thin at the bent portion, so that the strength determined by the thickness can be maintained and bent as much as possible .

Furthermore, it is preferable that one substrate 2 and / or the other substrate 6 be formed of a resin film (for example, the thickness of the film is 25 μm to 200 μm). In this case, an effect can be obtained in that, for example, the above-mentioned resin film is transported by a roll-to-roll method, and the substrate is bent or bent in the process, thereby improving production efficiency.

Furthermore, even if one substrate 2 and / or the other substrate 6 is formed of such a resin film, the rigidity of the substrate can be reinforced by bending or bending the one substrate 2 and / or the other substrate 6 so that It can effectively prevent the reduction of the photoelectric conversion efficiency caused by the bending and bulging of one substrate 2 and the other substrate 6.

In addition, since the side wall portion 15 and the outer peripheral wall portion 2p and the side wall portion 15 and the inner side wall portion 16 are bent at an obtuse angle, it is possible to easily form the entire surface of the transparent conductive film 3 facing the inner space S. Effect of the semiconductor layer 4. Therefore, according to the solar cell 1A or an electrical module in which the solar cells 1A are connected in series or in parallel, an effect that a redox reaction can be performed over a larger area can be obtained.

Next, a second embodiment of the present invention will be described using FIG. 9. In this embodiment, the same components as those in the first embodiment are denoted by the same reference numerals and descriptions thereof are omitted, and only differences from the first embodiment will be described.

In this embodiment, a curved surface is formed on one substrate 2 so as to protrude slightly toward the other substrate 6, and is constructed and manufactured in the same manner as in the first embodiment except that it is a curved surface.

According to this configuration, the curved surfaces 2 a and 2 b are formed on one substrate 2 so as to slightly protrude toward the other substrate 6, that is, the other substrate 6 is bent backward. Therefore, even if a large amount of electrolyte 11 is filled into the internal space S, a pressure on a substrate 2 to be bulged to the outside due to the electrolyte 11 can be resisted by the bending of a substrate 2 to prevent a substrate 2 from The central portion of the internal space S bulges outward.

In addition, one of the substrates 2 having a slightly curved shape can be formed on a surface of a substrate 2 by a powder spraying method (for example, an aerosol deposition method) in addition to a well-known formation method such as screen printing. This is also easily and efficiently formed.

That is, fine particles made of an oxide semiconductor are dispersed in nitrogen (N ₂ ), and fine particles made of an oxide semiconductor are sprayed from a nozzle toward a substrate 2 at high speed, so that a semiconductor layer 4 is formed on a transparent conductive film 3 of a substrate 2. . At this time, the microparticles made of an oxide semiconductor are formed into a film while heat is applied to a substrate 2 and then cooled, or the oxide semiconductor particles are extended while a substrate 2 is stretched under tension. Forming a film, and then releasing the tension, thereby shrinking a substrate 2 with a plate surface 2b on the side opposite to the side where the fine particles made of an oxide semiconductor are formed, thereby allowing a substrate 2 to face the plate surface 2a Bend in a protruding way (compressing internal stress).

In addition, the size of particles such as fine particles made of an oxide semiconductor may be in a range of 5 nm to 1000 nm, more preferably in a range of 10 nm to 500 nm, and even more preferably 15 nm to 50 nm.

In addition, the curvature of the curved surfaces 2a and 2b of a substrate 2 may be in the range of 0.01 to 0.1, which is ideal. The range is 0.03 ~ 0.06.

Therefore, in this embodiment, as in the case of the first embodiment, the following effects can be obtained: the thickness of the internal space S of the layer forming the electrolytic solution 11 can be reduced as much as possible, and a substrate 2 can be prevented from facing outward. The bulge can suppress the increase of the loss of incident light caused by the thickness of the layer of the electrolytic solution 11 and can prevent the reduction of the redox reaction caused by the increase of the moving distance of the electrons.

In addition, according to this embodiment, it is possible to easily manufacture the slightly curved substrate 2 to the first electrode 5, so that the manufacturing cost of the solar cell 1B can be suppressed, and the loss of incident light and the efficiency of the redox reaction are good. Solar cell 1B or an electrical module in which solar cells 1B are connected in series or in parallel.

Furthermore, in the above-mentioned first and second embodiments, a configuration is adopted in which one substrate 2 is bent to form the convex portion 17 or the substrate 2 is bent. However, the other substrate 6 may be bent or bent. Of the composition. Furthermore, both the one substrate 2 and the other substrate 6 can be bent or bent and bonded to each other so as to protrude toward the other substrate 6 or the one substrate 2 to produce a solar cell 1C (see FIG. 10 (b )). In the case where both the one substrate 2 and the other substrate 6 are bent or bent, and are attached in such a manner as to protrude toward the other substrate 6 or the one substrate 2, the following effect can be obtained, that is, the internal space S can be The thickness is set as small as possible, and bending of both the one substrate 2 and the other substrate 6 can be prevented.

Next, a third embodiment of the present invention will be described using FIG. 12 and FIG. 13. In this embodiment, the same components as those in the first embodiment are denoted by the same reference numerals and descriptions thereof are omitted, and only differences from the first embodiment will be described.

In this embodiment, as shown in FIG. 12, the outer peripheral wall portion 2p of one substrate 2 and the other substrate The sealing material 10 adjoining between the outer peripheral wall portions 6p is chamfered at a corner 50 facing the inner side of the outer peripheral wall portion 2p, and is constructed and manufactured in the same manner as in the first embodiment.

In the photoelectric conversion element 1D, the inside of the sealing material 10 surrounding the internal space S is formed as an inclined surface 51 of a corner portion 50 of the sealing material 10 indicated by an imaginary line that is chamfered and descends toward the internal space S.

With this configuration, the inclination angle of the side wall portion 15 of one substrate 2 can be made gentle. Therefore, an effect can be obtained in that it is possible to prevent the transparent conductive film 3 from being damaged or broken due to bending a substrate 2 at a steep angle, so that a high-quality photoelectric conversion element 1D can be manufactured. In addition, it is possible to prevent the transparent conductive film 3 from being damaged by the corner portion 50 of the sealing material 10 during press processing, and may also cause damage to both ends of the oxide semiconductor 4 and the catalyst layer 18 due to circumstances. Reduced power generation area.

In addition, since the side wall portion 15 of a substrate 2 can be arranged along the inclined surface 51 after the chamfering of the sealing material 10, when an external force is applied to the side wall portion 15 of a substrate 2, the inclined surface of the sealing material 10 can be used. 51Supporting the side wall portion 15. Therefore, the photoelectric conversion element 1D can obtain an effect that the transparent conductive film 3 can be prevented from being damaged by the inclined surface 51 when a substrate 2 is subjected to an external force.

Furthermore, when the photoelectric conversion element 1D is manufactured, a substrate 2 can be press-processed on the inclined surface 51 of the sealing material 10. In other words, since the photoelectric conversion element 1D can be press-processed by using the chamfered sealing material 10 as a support table, the following effects can be obtained: an excessive bending of a substrate 2 can be prevented, and a transparent conductive film 3 can be prevented. damaged.

In particular, as shown in FIG. 13, when a plurality of photoelectric conversion elements 1D are connected, that is, the electrical module 80 is continuously produced in a roll-to-roll manner, the density that can be chamfered can be obtained. The sealing material 10 has the effect of easily and pressurizing one substrate 2 as a support table with high production efficiency. 13 shows a case where the transparent conductive film 3 and the opposite conductive film 7 are formed with grooves 75 to insulate them from each other, and the photoelectric conversion elements 1D and 1D are connected in series to each other through the conductive material 70 as an electrical module. Figure of an example of 80.

The third embodiment of the present invention has been described above, but the sealing material 10 of the present invention may be chamfered so as to be smoothly curved as long as the inclination angle of the side wall portion 15 can be set to be gentle. In addition, the corner portion 60 generated by chamfering the sealing material 10 may not be sharpened.

In this embodiment, the case where only one substrate 2 is bent is described as an example. However, when the other substrate 6 is bent so as to protrude toward the internal space S, the sealing material 10 is another The corners of one substrate 6 side and the internal space S side may also be chamfered. As shown in FIG. 10 (b), when both the one substrate 2 and the other substrate 6 are bent toward the internal space S, two of one of the substrate 2 side of the sealing material 10 and the other substrate 6 side It can also be chamfered.

Hereinafter, the present invention will be specifically described using examples.

[Example] [Example 1]

A solar cell similar to the solar cell 1A was produced according to the following specifications schematically shown in FIG. 10 (a).

<First electrode 5>

The PEN film having a thickness of 125 μm was embossed to form a convex portion 17 having a height dimension L1 of 30 μm as shown in FIG. 10 (a). Indium tin oxide (ITO) was formed as a transparent conductive film on the plate surface on the side of the convex portion 17 where the PEN film was formed by a sputtering method, and the film was cut so as to be 16 × 54 mm. The TiO ₂ slurry was applied onto the ITO with an applicator so as to be 10 × 50 mm square, and heated at 120 ° C. to harden it. Thereafter, the organic pigment was dissolved in a solvent so that the pigment concentration became 0.02 to 0.5 mM, and the substrate was immersed in the solution for 10 minutes. The substrate taken out of the solution was washed with ethanol and dried.

<Second electrode 8>

Indium tin oxide (ITO) was formed on the PEN film with a thickness of 125 μm as a conductive film by sputtering. The PEN film was cut so as to be 16 × 54 mm. Carbon was coated on ITO to 10 × 50 mm and heated at 120 ° C. to harden it.

<Sealing material 10>

An opening is formed in the hot-melt resin so that the hot-melt resin does not contact the semiconductor layer 4. The dimensions were set to be 60 μm and 14 × 54 mm so that the internal space S could be sealed.

<Divider 9>

Regarding the separator 9 (manufactured by Hirose Paper Co., Ltd.), the area other than the current extraction wiring portion is set to a size that covers ITO or more, and the thickness is 20 μm and 15 × 55 mm.

The first electrode 5 and the second electrode 8 obtained in the above manner are arranged so that the TiO ₂ layer 4 and the carbon layer 18 face each other, and the first electrode 5-the hot-melt resin 10-the separator 9- The molten resin 10-the mold-releasing resin sheet (Naflon sheet)-the second electrode 8 was hot-pressed and bonded at 120 ° C while applying pressure.

The release resin sheet disposed between the first electrode 5 and the second electrode 8 is drawn out to form a liquid injection hole 21 (see FIG. 7), and the first electrode 5 and the second electrode 8 after bonding are mounted and Fix it in a folding machine, immerse the injection hole 21 in the electrolyte 11 and vacuum the dryer. After the pumping pressure reaches 100 Pa, the atmosphere is opened to inject the electrolyte 11 into the first electrode 5 and the second electrode 8 between. Since the electrolytic solution 11 adheres to the periphery of the injection hole 21, it is wiped and washed with a solvent (ethanol).

Thereafter, the liquid injection hole 21 is sealed by hot pressing. In this way, a solar cell 1A was produced.

For the above-mentioned solar cell 1A, a micrometer was used to measure the thickness of the convex portion 17 shown in FIG. 10 (a) (that is, the size between the plate surfaces on the outside of the PEN film facing each other in the area where the convex portion 17 is formed). ) The thickness dimension of M1 and the sealing material 10 (that is, the dimension between the plate surfaces on the outside of the PEN film facing each other at the portion where the sealing material 10 is arranged) N1 was measured, and the results are shown in Table 1. The power generation performance of the solar cell 1A was confirmed using simulated sunlight. The results are shown in Table 2.

[Example 2]

A solar cell 1C was produced according to the following specifications schematically shown in FIG. 10 (b).

<First electrode 5>

A first electrode 5 similar to that of the first embodiment is formed.

<Second electrode 8>

On the PEN film, a convex portion 17 protruding with the same height dimension as that of the first electrode 5 is formed, and indium tin oxide (ITO) is formed on the plate surface on the side where the convex portion 17 is formed as a counter conductive film by sputtering. Otherwise, a second electrode 8 similar to that of the first embodiment is formed.

<Sealing material 10>

The same sealing material 10 as in Example 1 was prepared.

<Divider 9>

A spacer 9 similar to that in Example 1 was prepared.

The first electrode 5 and the second electrode 8 obtained in the above manner are arranged so that the TiO ₂ layer 4 and the carbon layer 18 face each other, and the first electrode 5-the hot-melt resin 10-the separator 9-are sequentially laminated. Hot-melt resin 10-Releasable resin sheet (Naflon sheet) -Second electrode 8 was hot-pressed while applying pressure at 120 ° C.

The release resin sheet located between the first electrode 5 and the second electrode 8 is drawn out to form a liquid injection hole 21 (see FIG. 7), and the first electrode 5 and the second electrode 8 are bonded to each other and joined. The body 1a is installed and fixed to a folding machine, and the dryer is evacuated under the state that the injection hole 21 is immersed in the electrolyte 11 and the atmosphere is opened to inject the electrolyte 11 into the internal space S after being evacuated to 100 Pa. Thereafter, sealing is performed by hot-pressing the liquid injection hole 21.

Since the electrolytic solution adheres to the periphery of the injection hole 21, it is wiped with a solvent (ethanol) and washed. In this way, a solar cell 1C was produced.

For the above-mentioned solar cell 1C, the thickness dimension M2 of the convex portion 17 and the thickness dimension N2 of the sealing material 10 shown in FIG. 10 (b) were measured with a micrometer, and the results are shown in Table 1. Moreover, the power generation performance of the above-mentioned solar cells was confirmed using simulated sunlight, and the results are shown in Table 2.

[Example 3]

A solar cell 1B was produced according to the following specifications schematically shown in FIG. 10 (c).

<First electrode 5>

The fine particles made of the oxide semiconductor are dispersed in nitrogen, and the fine particles made of the oxide semiconductor are sprayed from the nozzle at a high speed toward the surface of the PEN film to form a film. At this time, tension is applied to the PEN film to extend it, and the tension is released after the oxide semiconductor particles are formed, thereby shrinking and bending the plate surface on the side opposite to the side where the fine particles composed of the oxide semiconductor are formed. Thus, the PEN film is bent so as to protrude toward the plate surface side on which the fine particles composed of the oxide semiconductor are formed. Thereafter, it was cut into a size of 16 × 54 mm to obtain a first electrode 5.

<Second electrode 8>

PEDOT was formed on ITO to a thickness of 35 nm as a counter electrode. The ITO-PEN film was cut into a film of 16 × 54 mm to obtain a second electrode 8.

<Sealing material 10>

The thermosetting resin was cut into short strips to obtain two types of thickness: 100 μm, 3 × 14 mm and thickness: 100 μm, 3 × 54 mm. The two types of thermosetting resins are arranged in a rectangular shape on the outer periphery of the first electrode 5, and the thermosetting resins are arranged so that the distance between the semiconductor layer 4 and the sealing material 10 becomes 1 mm or less.

Moreover, in this embodiment, a separator is not used, but even if the PEDOT layer is in contact with the TiO ₂ layer, the catalyst layer 18 and the transparent conductive film 3 are difficult to contact, so there is no short circuit.

After the electrolytic solution 11 was dropped on the film formation of the first electrode 5 obtained in the above manner, the first electrode 5 and the second electrode 8 were arranged so that the TiO ₂ layer and the PEDOT layer faced each other, and The first electrode 5 and the second electrode 8 are laminated with each other and then thermally laminated. In this way, the solar cell 1B was produced.

For the above-mentioned solar cell 1B, the thickness dimension M3 of the convex portion 17 and the thickness dimension N3 of the sealing material 10 shown in FIG. 10 (c) were measured with a micrometer, and the results are shown in Table 1.

The power generation performance of the solar cell 1B was confirmed using simulated sunlight. The results are shown in Table 2.

[Comparative Example 1]

The solar cell 100 was manufactured according to the following specifications schematically shown in FIG. 11.

<First electrode>

A first electrode was formed in the same manner as in Example 1 except that a flat surface was formed on the PEN film cut to a size of 16 × 54 mm without forming unevenness.

<Second electrode>

A second electrode was formed in the same manner as in Example 1.

<Sealing material>

The same sealing material as in Example 1 was prepared.

<Divider 9>

The same spacer as in Example 1 was prepared.

The first electrode 5 and the second electrode 8 obtained in the above manner are arranged so that the TiO ₂ layer 4 and the carbon layer 18 face each other, and the first electrode 5-the hot-melt resin 10-the separator 9- Molten resin 10-Releasable resin sheet (Naflon sheet) -Second electrode 8 was hot-pressed while applying pressure at 120 ° C.

The mold release resin sheet placed between the first electrode 5 and the second electrode 8 is pulled out, and the first electrode 5 and the second electrode 8 after bonding are mounted and fixed to a folding machine, and the liquid injection hole is immersed The electrolytic solution 11 was evacuated, and the atmosphere was opened after 100 Pa was evacuated to inject the electrolytic solution 11 between the first electrode 5 and the second electrode 8. Thereafter, sealing is performed by hot-pressing the injection hole. In this way, the solar cell 100 was manufactured.

For the above-mentioned solar mine 100, a micrometer was used to measure the thickness dimension M4 inside the sealing material 10 and the thickness dimension N4 of the sealing material 10, and the results are shown in Table 1. In addition, the simulated solar light was used to confirm the power generation performance of solar cells. The results are shown in Table 2.

[Evaluation results]

The thickness dimensions M1 to M3 of Examples 1, 2, and 3 show values that are lower than the thickness dimension M4 of Comparative Example 1, respectively. In addition, the power generation performance of Examples 1, 2, and 3 showed higher values than the power generation performance of Comparative Example 1. Based on this, it was confirmed that, by reducing the thickness of the convex portion 17, the power generation performance of the solar cells 1A to 1C can be improved compared with the conventional solar cell 100.

In addition, the solar cells of the respective specifications of Examples 1, 2, 3, and Comparative Example 1 were produced 10 times. As a result, the thickness dimensions M1 to M3 and the power generation performance of Examples 1, 2, and 3 all had deviations of ± 5% or less. Here, both the thickness dimension M4 and the power generation performance of Comparative Example 1 have a deviation of ± 10% or more.

From this, it can be seen that the thicknesses M1 to M3 after the electrolyte solution 11 is filled are more uniform in the case of the structures of Examples 1, 2, and 3 than in the case of the structure of Comparative Example 1.

That is, according to the present invention, it can be seen that the distance between the second electrode 8 to the first electrode 5 which has been a problem in the production of the solar cell 100 can be fixed as much as possible. In addition, it was found that by making the distance between the second electrode 8 to the first electrode 5 as constant as possible, the power generation performance of the solar cells 1A to 1C can be stabilized.

Claims (11)

A photoelectric conversion element includes a first electrode having a transparent conductive film formed on a surface of a substrate, a semiconductor layer formed on the surface of the transparent conductive film, and a second electrode spaced apart from the one substrate. An opposing conductive film is formed on the plate surface of the other substrate disposed opposite to the transparent conductive film, and an electrolyte is sealed between the first electrode and the second electrode; at least the A substrate is bent inside the outer peripheral wall portion that seals the electrolyte and protrudes toward the other substrate disposed oppositely; the curvature of the curved surface of the one substrate is formed in a range of 0.01 to 0.1. For example, the photoelectric conversion element according to the first patent application scope, wherein at least one of the one substrate or the other substrate is formed of a resin film. For example, the photoelectric conversion element of the scope of application for a patent, wherein the peripheral wall portion of the one substrate and the peripheral wall portion of the other substrate are connected by a sealing material, and the sealing material and the curved portion Corner portions facing the inside of the outer peripheral wall portion are chamfered. For example, in the photoelectric conversion element according to claim 3, the sealing material is chamfered along a curved shape inside the outer peripheral wall portion. An electrical module includes a plurality of photoelectric conversion elements according to any one of claims 1 to 4 of a patent application. A method for manufacturing a photoelectric conversion element is as follows. The photoelectric conversion element includes: a first electrode: a transparent conductive film is formed on a surface of a substrate; and a semiconductor is formed on the surface of the transparent conductive film. Layer, second electrode: an opposite conductive film is formed on a surface of another substrate disposed opposite to the one substrate at a distance from the first substrate, and an opposite conductive film is formed so as to oppose the transparent conductive film, and an electrolyte is sealed in Between the first electrodes and the second electrodes; at least the one substrate is bent inside the outer peripheral wall portion sealing the electrolyte, and protrudes toward the other substrate arranged oppositely; wherein the semiconductor layer is formed and the A substrate imparts compressive internal stress to bend the substrate. For example, the method for manufacturing a photoelectric conversion element according to item 6 of the application, wherein the semiconductor layer is formed by an aerosol deposition method. A photoelectric conversion element includes: a first electrode: a transparent conductive film is formed on a surface of a substrate; a semiconductor layer is formed on the surface of the transparent conductive film; and a second electrode: is opposed to the substrate with a space therebetween. An opposite conductive film is formed on the plate surface of the other substrate, and an opposite conductive film is formed, and an electrolyte is sealed between the first electrode and the second electrode; at least the one substrate, It is bent inside the outer peripheral wall part that seals the electrolyte, and protrudes toward the other substrate disposed oppositely. For example, the photoelectric conversion element in the eighth aspect of the patent application, wherein at least one of the substrates includes: a side wall portion: inside the peripheral wall portion that seals the electrolyte, is bent toward the other substrate disposed in the opposite direction and is bent along the outer periphery; A wall portion is formed, and an inner side wall portion is formed inside the front end of the side wall portion; the side wall portion is inclined with respect to the outer peripheral wall portion. For example, the photoelectric conversion element according to the first scope of the patent application, wherein a separator is provided between the first electrode and the second electrode. For example, the photoelectric conversion element in the eighth aspect of the patent application, wherein a separator is provided between the first electrode and the second electrode.