JP2016086032A - Manufacturing method of dye-sensitized photoelectric conversion element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a dye-sensitized photoelectric conversion element capable of sufficiently improving durability.SOLUTION: A dye-sensitized photoelectric conversion element 100 includes a cell comprising: a first base material 1 with an electrode 7; a second base material 2 facing to the first base material 1; an annular sealing part 4 bounding the first base material 1 and the second base material 2; an oxide semiconductor layer 3 that is arranged between the first base material 1 and the second base material 2; an electrolyte 5 that is arranged between the first base material 1 and the second base material 2. A manufacturing method of the dye-sensitized photoelectric conversion element comprises: a preparation step for a first base substrate including the first base material 1 and a second base substrate of the second base material 2; a step for preparing a laminating member by contacting through an annular sealing member for forming the sealing part 4 by facing the first base substrate to the second base substrate; a step for bounding the first base substrate to the second base substrate through the sealing member by arranging the laminating member into a chamber inner part and reducing a voltage in the chamber inner space. In the preparation step for the substrate member, at least one of the first substrate member and the second substrate member has the oxide semiconductor layer 3, and one of the first substrate member and the second substrate member has the electrolyte 5. In the bounding step, the sealing member is bounded to the first substrate member and the second substrate member by heating the sealing member.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a dye-sensitized photoelectric conversion element.

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

  The dye-sensitized photoelectric conversion element generally includes at least one dye-sensitized photoelectric conversion cell, and the dye-sensitized photoelectric conversion cell is an oxide provided between the conductive substrate, the counter electrode, and the conductive substrate and the counter electrode. A semiconductor layer, a photosensitizing dye supported on the oxide semiconductor layer, a sealing portion connecting the conductive substrate and the counter electrode, and an electrolyte impregnated in the oxide semiconductor layer are provided.

  As a method for producing such a dye-sensitized photoelectric conversion element, a sealing material made of an adhesive resin is formed on either the working electrode or the counter electrode, and an electrolyte is injected inside the sealing material under reduced pressure. A method of manufacturing a dye-sensitized photoelectric conversion element by forming an electrolyte layer and subsequently bonding the working electrode and the counter electrode while heating and pressing under reduced pressure is known (for example, see Patent Document 1 below).

JP 2007-220608 A

  However, the above-described method for producing a dye-sensitized photoelectric conversion element described in Patent Document 1 has room for improvement in terms of improving the durability of the obtained dye-sensitized photoelectric conversion element.

  The present invention has been made in view of the above circumstances, and aims to provide a method for producing a dye-sensitized photoelectric conversion element capable of producing a dye-sensitized photoelectric conversion element capable of sufficiently improving durability. To do.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, in the method for producing a dye-sensitized photoelectric conversion element described in Patent Document 1 described above, the formation of the electrolyte layer is performed under reduced pressure, and then the working electrode and the counter electrode are bonded together. The present inventors thought that this may be a cause of problems. The reason is as follows. That is, when the working electrode and the counter electrode are brought into contact with each other, the electrolyte is volatilized from the electrolyte layer formed inside the sealing material, and an electrolyte vapor layer is formed between the sealing material and the working electrode or the counter electrode. The As a result, the present inventors have thought that the sealing material and the working electrode or the counter electrode cannot be sufficiently bonded, and there is room for improvement in terms of improvement in durability. For this reason, as a result of intensive studies to suppress the formation of an electrolyte vapor layer between the sealing material and the working electrode or the counter electrode, it was found that the above-described problems can be solved by the following invention. The invention has been completed.

  That is, the present invention includes a first base material including an electrode, a second base material facing the first base material, an annular sealing portion for bonding the first base material and the second base material, A dye-sensitized photoelectric conversion cell comprising an oxide semiconductor layer provided between a first base material and the second base material, and an electrolyte disposed between the first base material and the second base material. A method of manufacturing a dye-sensitized photoelectric conversion element for manufacturing a dye-sensitized photoelectric conversion element having a first base including the first base and a second base including the second base A preparation step, a laminate preparation step of preparing a laminate by bringing the first substrate and the second substrate into contact with each other through an annular sealing material that forms the sealing portion in a state of facing each other, and In a state where the laminate is disposed inside the chamber, the internal space of the chamber is depressurized and then inserted through the sealing material. A bonding step of bonding the first substrate and the second substrate, and in the substrate preparation step, either one of the first substrate and the second substrate is the oxide semiconductor layer. Any one of the first substrate and the second substrate has the electrolyte, and the sealing material is heated by heating the sealing material in the bonding step. A method for producing a dye-sensitized photoelectric conversion element bonded to a first substrate and the second substrate.

  According to the manufacturing method, after the first base and the second base are brought into contact with each other via the annular sealing material that forms the sealing portion in a state of being opposed to each other, the stacked body is prepared. In a vacuum. For this reason, even when the electrolyte evaporates when the encapsulant is heated and melted, the formation of an electrolyte vapor layer between the encapsulant and the first or second substrate is sufficiently suppressed. Is done. As a result, the sealing material and the first base or the second base can be sufficiently bonded. Even if the electrolyte evaporates, the electrolyte is confined in the laminated body and is difficult to leak to the outside. For this reason, durability of the dye-sensitized photoelectric conversion element obtained can be improved.

  In the manufacturing method, it is preferable that the sealing material is fixed to at least one of the first base and the second base in the base preparation step.

  In this case, the following effects can be obtained as compared with the case where the sealing material is not fixed to either the first base or the second base. That is, compared with the case where the sealing material is not fixed to both bases, in the subsequent bonding step, the formation of a vapor layer of the electrolyte between the sealing material and the base is further suppressed. It becomes possible to adhere the sealing material and the substrate more sufficiently.

  In the manufacturing method, in the base preparation step, the sealing material is fixed only to one of the first base and the second base, and the sealing is fixed to the other base. Preferably not.

  In this case, the following effects can be obtained as compared with the case where the sealing material is fixed to both the first base and the second base. That is, since the sealing material only needs to be fixed to one of the first base and the second base, the sealing material is applied to one base as compared with the case where the sealing material is fixed to both bases. Since it does not need to be fixed, the time required for preparing the laminate is shortened. Moreover, when preparing a laminated body, it becomes unnecessary to align the sealing materials fixed to a 1st base | substrate and a 2nd base | substrate. Therefore, a dye-sensitized photoelectric conversion element can be produced efficiently. Moreover, since it becomes unnecessary to align the sealing materials fixed to the 1st base | substrate and the 2nd base | substrate, when heating a sealing material in a bonding process, the alignment of sealing materials is inadequate. Compared to the case where heating is performed as it is, it becomes possible to form a sealing portion with a desired thickness, and between the sealing portion and the first base, and between the sealing portion and the second base, High adhesiveness can be ensured. For this reason, durability of the dye-sensitized photoelectric conversion element obtained can be improved. Further, by not fixing the sealing material to one substrate, it is possible to sufficiently prevent impurities generated when the sealing material is fixed to the one substrate from adhering to the surface of the substrate.

  In the manufacturing method, in the base preparation step, it is preferable that a base on which the sealing material is not fixed has the oxide semiconductor layer among the first base and the second base.

  In this case, in the first substrate and the second substrate where the sealing material is not fixed, contamination of the oxide semiconductor layer due to impurities generated in the step of fixing the sealing material to the substrate is sufficiently suppressed. For this reason, the photoelectric conversion in the oxide semiconductor layer is more sufficiently suppressed from being inhibited by impurities, and the photoelectric conversion characteristics of the obtained dye-sensitized photoelectric conversion element can be more sufficiently improved.

In the manufacturing method, the base preparation step includes a step of dripping the electrolyte into the oxide semiconductor layer when preparing the base having the oxide semiconductor layer among the first base and the second base. In addition, the dropping amount of the electrolyte per 1 mm ³ of the volume of the oxide semiconductor layer is preferably 0.5 to 4.0 μL.

In this case, the oxide is sufficiently impregnated in the oxide semiconductor layer and the photoelectric conversion of the dye-sensitized photoelectric conversion element as compared with the case where the drop amount of the electrolyte per 1 mm ³ volume of the oxide semiconductor layer is less than 0.5 μL. The characteristics can be further improved. Further, when the amount of electrolyte dropped per 1 mm ³ of the oxide semiconductor layer is 0.5 to 4.0 μL, the electrolyte overflows from the oxide semiconductor layer as compared with the case where the amount of electrolyte dropped exceeds 4.0 μL. It becomes difficult to take out, and when preparing a laminated body or forming a sealing part, it is more fully suppressed that electrolyte enters between a sealing material and a 1st base | substrate or a 2nd base | substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the dye-sensitized photoelectric conversion element which can manufacture the dye-sensitized photoelectric conversion element which can fully improve durability is provided.

It is sectional drawing which shows the dye-sensitized photoelectric conversion element obtained by one Embodiment of the manufacturing method of the dye-sensitized photoelectric conversion element which concerns on this invention. It is sectional drawing which shows the state which fixed the sealing material to the 2nd base | substrate used for one Embodiment of the manufacturing method of the dye-sensitized photoelectric conversion element which concerns on this invention. It is sectional drawing which shows the 1st base | substrate used for one Embodiment of the manufacturing method of the dye-sensitized photoelectric conversion element which concerns on this invention. FIG. 4 is a cross-sectional view illustrating a state in which a sealing member is fixed to the second base body of FIG. 2 and the first base body of FIG. 3 is opposed to each other. It is sectional drawing which shows the laminated body formed by laminating | stacking the 2nd base | substrate of FIG. 2 and the 1st base | substrate of FIG. 3 through the sealing material. It is sectional drawing which shows the state which has bonded the 1st base | substrate and the 2nd base | substrate through the sealing material in the laminated body of FIG. It is sectional drawing which shows 1 process of other embodiment of the manufacturing method of the dye-sensitized photoelectric conversion element which concerns on this invention. It is sectional drawing which shows 1 process of further another embodiment of the manufacturing method of the dye-sensitized photoelectric conversion element which concerns on this invention.

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

  First, an embodiment of a method for producing a dye-sensitized photoelectric conversion element according to the present invention will be described with reference to the drawings.

  First, prior to description of a method for manufacturing a dye-sensitized photoelectric conversion element, a dye-sensitized photoelectric conversion element 100 obtained by this manufacturing method will be described with reference to FIG. FIG. 1 is a sectional view showing a dye-sensitized photoelectric conversion element obtained by an embodiment of a method for producing a dye-sensitized photoelectric conversion element according to the present invention.

  As shown in FIG. 1, the dye-sensitized photoelectric conversion element 100 includes one dye-sensitized photoelectric conversion cell 50, and the dye-sensitized photoelectric conversion cell 50 includes the first base material 1 including the electrode 7, 1 It has the 2nd base material 2 which opposes the base material 1. FIG. In this embodiment, the 2nd base material 2 is comprised by the counter electrode. Further, the oxide semiconductor layer 3 is fixed on the electrode 7 of the first substrate 1, and the photosensitizing dye is supported on the oxide semiconductor layer 3. The first base material 1 and the second base material 2 are bonded to each other via an annular sealing portion 4. An electrolyte 5 is disposed between the first substrate 1 and the second substrate 2. Here, the electrolyte 5 is impregnated in the oxide semiconductor layer 3.

  The first base material 1 includes an electrode 7 and a transparent substrate 6 provided on the opposite side of the electrode 7 from the second base material 2. Here, the electrode 7 is made of a transparent conductive layer.

  The second base material 2 includes a counter electrode substrate 8 and a conductive catalyst layer 9 that is provided on the first base material 1 side of the counter electrode substrate 8 and promotes a reduction reaction on the surface of the second base material 2. Yes.

  Next, the said 1st base material 1, the 2nd base material 2, the oxide semiconductor layer 3, the sealing part 4, the electrolyte 5, and a photosensitizing dye are demonstrated in detail.

(First base material)
As described above, the first base material 1 includes the electrode 7 made of a transparent conductive layer, and the transparent substrate 6 provided on the opposite side of the second base material 2 with respect to the electrode 7.

  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), and polyethersulfone (PES). The thickness of the transparent substrate 6 is appropriately determined according to the size of the dye-sensitized photoelectric conversion element 100 and is not particularly limited, but may be, for example, in the range of 50 to 40,000 μm.

Examples of the material constituting the electrode 7 include conductive metal oxides such as tin-added indium oxide (ITO), tin oxide (SnO ₂ ), and fluorine-added tin oxide (FTO). The electrode 7 may be a single layer or a laminate of a plurality of layers made of different conductive metal oxides. When the electrode 7 is composed of a single layer, the electrode 7 is preferably composed of FTO because it has high heat resistance and chemical resistance. The thickness of the electrode 7 may be in the range of 0.01 to 2 μm, for example.

(Second base material)
The second base material 2 includes the counter electrode substrate 8 and the catalyst layer 9 as described above.

  The counter electrode substrate 8 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 8 is appropriately determined according to the size of the dye-sensitized photoelectric conversion element 100 and is not particularly limited, but may be, for example, 0.005 mm to 0.1 mm.

  The catalyst layer 9 is composed of platinum, a carbon-based material, a conductive polymer, or the like.

(Oxide semiconductor layer)
The oxide semiconductor layer 3 is composed of oxide semiconductor particles. 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 ), and tin oxide (SnO ₂ ). , Indium oxide (In ₃ O ₃ ), zirconium oxide (ZrO ₂ ), thallium oxide (Ta ₂ O ₅ ), lanthanum oxide (La ₂ O ₃ ), yttrium oxide (Y ₂ O ₃ ), holmium oxide (Ho ₂ O) ₃ ), bismuth oxide (Bi ₂ O ₃ ), cerium oxide (CeO ₂ ), aluminum oxide (Al ₂ O ₃ ), or two or more thereof. The thickness of the oxide semiconductor layer 3 may be, for example, 0.1 to 100 μm.

(Sealing part)
Examples of the sealing portion 4 include thermoplastic resins such as modified polyolefin resins and vinyl alcohol polymers. Examples of modified polyolefin resins include ionomers, ethylene-vinyl acetic anhydride copolymers, ethylene-methacrylic acid copolymers, and ethylene-vinyl alcohol copolymers. These resins can be used alone or in combination of two or more.

(Electrolytes)
The electrolyte 5 includes a redox couple such as I ⁻ / I ₃ ^— and an organic solvent. As an organic solvent, acetonitrile, methoxyacetonitrile, methoxypropionitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, γ-butyrolactone, valeronitrile, pivalonitrile, glutaronitrile, methacrylonitrile, isobutyronitrile, Phenylacetonitrile, acrylonitrile, succinonitrile, oxalonitrile, pentanitrile, adiponitrile and the like can be used. Examples of the redox pair include I ⁻ / I ₃ ^— and redox pairs such as bromine / bromide ions, zinc complexes, iron complexes, and cobalt complexes. The electrolyte 5 may use an ionic liquid instead of the organic solvent. As the ionic liquid, for example, a known iodine salt such as a pyridinium salt, an imidazolium salt, or a triazolium salt, and a room temperature molten salt that is in a molten state near room temperature is used. Examples of such room temperature molten salts include 1-hexyl-3-methylimidazolium iodide, 1-ethyl-3-propylimidazolium iodide, dimethylimidazolium iodide, ethylmethylimidazolium iodide, and dimethylpropyl. Imidazolium iodide, butylmethylimidazolium iodide, or methylpropyl imidazolium iodide is preferably used.

  The electrolyte 5 may be a mixture of the ionic liquid and the organic solvent instead of the organic solvent.

An additive can be added to the electrolyte 5. As the _{additive, LiI, I 2, 4-} t- butylpyridine, guanidinium thiocyanate, 1-methylbenzimidazole, 1-butyl-benzimidazole and the like.

Further, as the electrolyte 5, a nanocomposite gel electrolyte, which is a pseudo-solid electrolyte formed by kneading nanoparticles such as SiO ₂ , TiO ₂ , and carbon nanotubes with the above electrolyte, may be used, or polyvinylidene fluoride. Alternatively, an electrolyte gelled with an organic gelling agent such as a polyethylene oxide derivative or an amino acid derivative may be used.

(Photosensitizing dye)
Examples of the photosensitizing dye include a ruthenium complex having a ligand containing a bipyridine structure, a terpyridine structure, and the like, and organic dyes such as porphyrin, eosin, rhodamine, and merocyanine. Among these, a ruthenium complex having a ligand containing a terpyridine structure is preferable. In this case, the photoelectric conversion characteristics of the dye-sensitized photoelectric conversion element 100 can be further improved.

  Next, a manufacturing method of the above-described dye-sensitized photoelectric conversion element 100 will be described with reference to FIGS. FIG. 2 is a cross-sectional view showing a state in which a sealing material is fixed to a second substrate used in an embodiment of a method for producing a dye-sensitized photoelectric conversion device according to the present invention, and FIG. FIG. 4 is a cross-sectional view showing a first substrate used in an embodiment of a method for manufacturing a photoelectric conversion element, and FIG. 4 is a diagram in which a sealing member is fixed to the second substrate in FIG. 2 and the first substrate in FIG. FIG. 5 is a cross-sectional view showing a laminated body formed by laminating the second base body of FIG. 2 and the first base body of FIG. 3 through a sealing material, and FIG. It is sectional drawing which shows the state which has bonded the 1st base | substrate and the 2nd base | substrate through the sealing material in the laminated body of.

<Base preparation process>
First, as shown in FIG. 2, a second base 20 is prepared. In the second substrate 20, the sealing material 4A is fixed to the surface on the catalyst layer 9 side.

  On the other hand, as shown in FIG. 3, the first base 1, the oxide semiconductor layer 3 provided on the first base 1, and the oxide semiconductor layer 3 provided on the first base 1 are impregnated. A first substrate 10 having an electrolyte 5 is prepared. In the present embodiment, the annular sealing material 4 </ b> A that forms the sealing portion 4 is not fixed to the first base 10. Therefore, the oxide semiconductor layer 3 is included in the first base body 10 to which the sealing material 4A is not fixed.

<Laminated body preparation process>
Next, as shown in FIG. 4, the first base 10 and the second base 20 with the sealing material 4 </ b> A are made to face each other and then brought into contact with each other as shown in FIG. 5. At this time, the sealing material 4A is brought into contact with the electrode 7 of the first base material 1, and the oxide semiconductor layer 3 is disposed inside the sealing material 4A. At this time, the sealing material 4A is not yet melted. In other words, the sealing material 4 </ b> A is not bonded to the electrode 7 of the first base material 1.

  In this way, the laminated body 50A is prepared.

<Lamination process>
Next, the stacked body 50A is placed inside a chamber (not shown). In this state, the internal space of the chamber is decompressed. Thereafter, as shown in FIG. 6, the heating member 40 is brought into contact with the second base material 2, and the sealing material 4 </ b> A is heated and melted through the second base material 2 while being pressurized.

  Thus, the sealing material 4A is adhered to the first base material 1 to form the sealing portion 4, and the first base body 10 and the second base body 20 are bonded to each other. Thereafter, the decompression operation of the internal space of the chamber is stopped, and the internal space of the chamber is opened to the atmosphere.

  As described above, the dye-sensitized photoelectric conversion element 100 including one dye-sensitized photoelectric conversion cell 50 is obtained.

  According to the manufacturing method, after the first base body 10 and the second base body 20 are brought into contact with each other through the sealing material 4A in a state of facing each other, the stacked body 50A is prepared, and then the stacked body 50A is decompressed in the chamber. Placed below. At this time, the stacked body 50 </ b> A is prepared such that the sealing material 4 </ b> A contacts the first base material 1 of the first base 10. For this reason, even if the electrolyte 5 evaporates when the sealing material 4A is melted, the formation of a vapor layer of the electrolyte 5 between the sealing material 4A and the first base 10 is sufficiently suppressed. The As a result, the sealing material 4A and the first base 10 can be sufficiently bonded. Further, even when the electrolyte 5 evaporates, the electrolyte 5 is confined in the stacked body 50A and is difficult to leak to the outside. For this reason, durability of the dye-sensitized photoelectric conversion element 100 obtained can be improved.

  Further, in the manufacturing method, when preparing the stacked body 50A in the stacked body preparation step, the sealing material 4A is fixed only to the second base body 20, and the sealing material 4A is not fixed to the first base body 10. . In this case, the following effects can be obtained as compared with the case where the sealing material 4A is fixed to both the first base 10 and the second base 20. That is, since the sealing material 4A only needs to be fixed to the second base body 20 of the first base body 10 and the second base body 20, the sealing material 4A is fixed to both the first base body 10 and the second base body 20. Compared with the case where the first base 10 is not fixed to the first base material 1, the time required for preparing the stacked body 50A is shortened. Further, when preparing the stacked body 50A, it is not necessary to align the sealing materials 4A fixed to the first base 10 and the second base 20. Therefore, the dye-sensitized photoelectric conversion element 100 can be manufactured efficiently. Further, since it is not necessary to align the sealing materials 4A fixed to the first base 10 and the second base 20, the sealing materials 4A are bonded together when the sealing material 4A is heated and melted in the bonding step. As compared with the case where the resin is heated and melted with insufficient alignment, it is possible to form the sealing portion 4 having a desired thickness. High adhesiveness can be ensured between the material 1 and between the sealing portion 4 and the second base material 2. For this reason, the durability of the dye-sensitized photoelectric conversion element 100 can be further improved. Furthermore, by not fixing the sealing material 4A to the first base body 10, it is possible to sufficiently prevent impurities generated when the sealing material 4A is fixed to the first base body 10 from adhering to the surface of the first base body 10. . Further, since the sealing material 4A is fixed only to the second base body 20 and the sealing material 4A is not fixed to the first base body 10, the sealing material 4A is applied to both the first base body 10 and the second base body 20. Compared to the case where is not fixed, the following effects can be obtained. That is, compared with the case where the sealing material 4A is not fixed to both the first base 10 and the second base 20, the electrolyte is interposed between the sealing material 4A and the second base 20 in the subsequent bonding step. The formation of 40 vapor layers is further suppressed, and in particular, the sealing material 4A and the second substrate 20 can be more sufficiently bonded.

  Further, in the above manufacturing method, in the first base 10 in which the sealing material 4A is not fixed among the first base 10 and the second base 20, oxidation due to impurities generated in the step of fixing the sealing material 4A to the first base 10 is performed. Contamination of the physical semiconductor layer 3 is sufficiently suppressed. For this reason, the photoelectric conversion in the oxide semiconductor layer 3 is more sufficiently suppressed from being impeded by impurities, and the photoelectric conversion characteristics of the resulting dye-sensitized photoelectric conversion element 100 can be more sufficiently improved. For example, transfer of the component of the carrier film used when forming the sealing material 4 </ b> A to the first base 10 to the oxide semiconductor layer 3 is sufficiently suppressed. As a result, inhibition of dye adsorption in the subsequent process is sufficiently suppressed, and the power generation efficiency of the resulting dye-sensitized photoelectric conversion element 100 can be further improved.

  Next, the base material preparation process, the laminate preparation process, and the bonding process described above will be described in detail.

<Base preparation process>
As described above, first, the first base 10 and the second base 20 with the sealing material 4A are prepared.

  The second substrate 20 can be obtained as follows.

  That is, first, the counter electrode substrate 8 is prepared. Then, the catalyst layer 9 is formed on the counter electrode substrate 8. As a method for forming the catalyst layer 9, a sputtering method, a vapor deposition method, or the like is used. Of these, sputtering is preferred from the viewpoint of film uniformity.

  An annular sealing material 4A is fixed to the second base 20. In order to fix the annular sealing material 4A on the second base body 20, the annular sealing material 4A is disposed on the second base body 20, and the annular sealing material 4A is melted by heating. The two substrates 20 may be adhered. Thus, the second base body 20 with the sealing material 4A is obtained.

  On the other hand, the first substrate 10 can be obtained as follows.

  First, the first substrate 1 is prepared. The first base material 1 can be formed by forming the electrode 7 on the transparent substrate 6.

  As a method for forming the electrode 7, a sputtering method, a vapor deposition method, a spray pyrolysis method, a CVD method, or the like is used.

  Next, the oxide semiconductor layer 3 is formed on the first substrate 1. The oxide semiconductor layer 3 may be formed on the first substrate 1 as follows. That is, the oxide semiconductor layer 3 is formed by printing the oxide semiconductor layer forming paste on the electrode 7 of the first base material 1 and then baking the paste.

  The oxide semiconductor layer forming paste includes a resin such as polyethylene glycol and a solvent such as terpineol in addition to the oxide semiconductor particles described above. As a method for printing the oxide semiconductor layer forming paste, for example, a screen printing method, a doctor blade method, a bar coating method, or the like can be used.

  Although the firing temperature of the oxide semiconductor layer forming paste varies depending on the oxide semiconductor particles, it is usually 350 to 600 ° C., and the firing time also varies depending on the oxide semiconductor particles, but is usually 1 to 5 hours.

  In order to adsorb the photosensitizing dye on the surface of the oxide semiconductor layer 3, the oxide semiconductor layer 3 is immersed in a solution containing the photosensitizing dye, and the photosensitizing dye is used as the oxide semiconductor layer. After the photosensitizing dye is adsorbed onto the oxide semiconductor layer 3, the photosensitizing dye may be adsorbed onto the oxide semiconductor layer 3 by washing away excess photosensitizing dye with the solvent component of the solution and drying it. However, the photosensitizing dye may be adsorbed to the oxide semiconductor layer 3 by applying a solution containing the photosensitizing dye to the oxide semiconductor layer 3 and then drying the solution.

In order to impregnate the oxide semiconductor layer 3 with the electrolyte 5, the electrolyte 5 may be dropped. Here, the dropping amount of the electrolyte 5 is not particularly limited, but is preferably 0.5 to 4.0 μL per 1 mm ³ of the volume of the oxide semiconductor layer 3. In this case, as compared with the case dropping amount of the electrolyte 5 per volume 1 mm ³ of the oxide semiconductor layer 3 is less than 0.5 [mu] L, will be the electrolyte 5 is impregnated sufficiently oxide semiconductor layer 3, the dye The photoelectric conversion characteristics of the sensitized photoelectric conversion element 100 can be further improved. In the case dropping amount of the electrolyte 5 per volume 1 mm ³ of the oxide semiconductor layer 3 is 0.5~4.0μL, compared to when dropping amount of the electrolyte 5 exceeds 4.0MyuL, first substrate 10, the electrolyte 5 is less likely to overflow from the oxide semiconductor layer 3, and the electrolyte 5 is more sufficiently suppressed from entering between the sealing material 4 </ b> A and the first substrate 1 when preparing the stacked body 50 </ b> A. Is done. Note that the volume of the oxide semiconductor layer 3 refers to a volume including internal vacancies.

Dropping amount of the electrolyte 5 per volume 1 mm ³ of the oxide semiconductor layer 3 is more preferably 1.4～3.0MyuL, particularly preferably 2.3～2.8MyuL.

<Laminated body preparation process>
The laminated body 50A is prepared under atmospheric pressure. Here, the atmospheric pressure refers to a pressure of 101325 Pa when converted to 0 ° C.

<Lamination process>
In the bonding step, the space inside the chamber in which the stacked body 50A is arranged is decompressed. In this case, this space is normally depressurized to a pressure in the range of 50 Pa or more and less than 1013 hPa. Here, this pressure is preferably 50 to 800 Pa, and more preferably 300 to 800 Pa.

  Moreover, when decompressing the internal space of the chamber as described above, it is preferable that at least one of the first base material 1 and the second base material 2 has flexibility.

  In this case, when the dye-sensitized photoelectric conversion element 100 is placed under atmospheric pressure as compared with the case where neither the first base material 1 nor the second base material 2 has flexibility, the first base material. The flexible electrode of the first and second substrates 2 bends due to atmospheric pressure, and the distance between the first substrate 1 and the second substrate 2 can be reduced. As a result, compared with the case where neither the 1st base material 1 nor the 2nd base material 2 has flexibility, a photoelectric conversion characteristic improves more.

  Further, as described above, the bonding of the first base 10 and the second base 20 is performed by heating the sealing material 4A while applying pressure.

  At this time, although the pressure at the time of pressurization of 4 A of sealing materials is not restrict | limited, Usually, it is 1-50 MPa, Preferably it is 2-30 MPa, More preferably, it is 3-20 MPa.

  Moreover, the temperature at which the sealing material 4A is melted may be equal to or higher than the melting point of the material constituting the sealing material 4A. The temperature at which the sealing material 4A is melted is preferably (melting point of the sealing material 4A + 200 ° C.) or less. If the temperature exceeds (the melting point of the sealing material 4A + 200 ° C.), the sealing material 4A may be decomposed by heat.

  The present invention is not limited to the above embodiment. For example, in the above embodiment, the sealing material 4A is not fixed to the first base body 10, but as shown in FIG. 7, even if the annular sealing material 4A is fixed to the first base body 10A. Good. In this case, the sealing material 4A is fixed on the first base material 1 of the first base 10 so as to surround the oxide semiconductor layer 3. Further, in a laminated body in which the first base body 10A and the second base body 20 are laminated via the sealing material 4A, the sealing material 4A fixed to the first base body 10A and the sealing fixed to the second base body 20 are used. It overlaps in the state which the stop material 4A contacted. Further, since the sealing material 4A is fixed to both the first base body 10 and the second base body 20, compared with the case where the sealing material 4A is not fixed to either the first base body 10 or the second base body 20. Thus, the following effects can be obtained. That is, compared with the case where the sealing material 4A is not fixed to both the first base body 10 and the second base body 20, in the subsequent bonding step, between the sealing material 4A and the first base body 10, and The formation of a vapor layer of the electrolyte 40 between the sealing material 4A and the second base 20 is further suppressed, and the sealing material 4A and the second base 20 can be more sufficiently bonded. In addition, the sealing material 4A and the first base 10 can be more sufficiently bonded.

  In the above embodiment, the sealing material 4A is not fixed to the first base body 10 and the sealing material 4A is fixed to the second base body 20, but the sealing material 4A is fixed to the first base body 10. The sealing material 4A may not be fixed to the second base 20. In this case, the sealing material 4 </ b> A is fixed to the first base 10 so as to surround the oxide semiconductor layer 3 on the first base material 1. Further, since the sealing material 4A is fixed only to the first base body 10 and the sealing material 4A is not fixed to the second base body 20, the sealing material 4A is applied to both the first base body 10 and the second base body 20. Compared to the case where is not fixed, the following effects can be obtained. That is, as compared with the case where the sealing material 4A is not fixed to both the first base 10 and the second base 20, the electrolyte is interposed between the sealing material 4A and the first base 10 in the subsequent bonding step. The formation of 40 vapor layers is further suppressed, and in particular, the sealing material 4A and the first base 10 can be more sufficiently bonded.

  In the above embodiment, the sealing material 4A is fixed to the second base 20 and the sealing material 4A is not fixed to the first base 210. However, the sealing material 4A is sealed to either the first base 10 or the second base 20. Stop material 4A does not need to be fixed. However, in this case, when preparing the laminated body, the sealing material 4A is disposed between the first base 10 and the second base 20, and this sealing material 4A is used in the bonding step. 10 and the second base 10 are fixed.

  Furthermore, in the above-described embodiment, the stacked body 50A is prepared under atmospheric pressure, and then the stacked body 50A is disposed inside the chamber. However, as long as the pressure in the internal space of the chamber is not reduced, the stacked body 50A is May be prepared in the chamber.

  In the above embodiment, a thermoplastic resin is used as the sealing material 4A. However, as the sealing material 4A, a thermosetting resin, an ultraviolet curable resin, or the like may be used. In this case, when a thermosetting resin is used as the sealing material 4A, the sealing material is heated to the first base 10 and the second base 20 by heating the sealing material 4A without melting in the bonding step. It will be glued. In the case where an ultraviolet curable resin is used as the sealing material 4A, the sealing material is irradiated with ultraviolet rays while heating the sealing material 4A without melting it in the laminating step, so that the sealing material becomes the first base 10 and the first substrate. The two substrates 20 are bonded.

  Furthermore, in the above-described embodiment, the second base 20 in which the second base 2 is configured as a counter electrode is used. However, as shown in FIG. 8, a base made of an insulating substrate is used instead of the second base 20. A second substrate 220 using the material 202 may be used. Here, the sealing material 4 </ b> A is fixed to the second base body 220. In this case, the first base 210 has a structure 211 provided on the first base 1. The structure 211 is provided on the electrode 7 in the first base material 1. The structure 211 includes the oxide semiconductor layer 3, the porous insulating layer 212, and the counter electrode 214 in this order from the first base material 1 side. The oxide semiconductor layer 3 and the porous insulating layer 212 are impregnated with the electrolyte 5. Further, the sealing material 4A is not fixed to the first base 210. Here, as the second base material 202, for example, a glass substrate or a resin film can be used. Moreover, as the counter electrode 214, the thing similar to the 2nd base material 2 can be used. Alternatively, the counter electrode 214 may be formed of a single porous layer containing, for example, carbon. The porous insulating layer 212 is mainly for preventing physical contact between the oxide semiconductor layer 3 and the counter electrode 214 and impregnating the electrolyte 5 therein. As such a porous insulating layer 212, for example, a fired body of an oxide can be used. Note that the first base 210 illustrated in FIG. 8 includes only one structure 211, but may include a plurality of structures 211. The porous insulating layer 212 is provided between the oxide semiconductor layer 3 and the counter electrode 214, but is provided between the first base material 1 and the counter electrode 214 so as to surround the oxide semiconductor layer 3. May be. Even in this configuration, physical contact between the oxide semiconductor layer 3 and the counter electrode 214 can be prevented. In FIG. 8, the sealing material 4A is fixed to the second base 220, and the sealing material 4A is not fixed to the first base 210, but the sealing material 4A is fixed to the second base 220. Alternatively, the sealing material 4A may be fixed only to the first base 210, the sealing material 4A may be fixed to the second base 220, and the sealing material 4A may be fixed to the first base 210. Also good. Further, the sealing material 4A may not be fixed to either the first base 210 or the second base 220. However, in this case, when preparing the laminated body, the sealing material 4A is disposed between the first base 210 and the second base 220, and this sealing material 4A is used in the bonding step. 210 and the second base 210 are fixed.

  Further, in the above embodiment, the electrolyte 5 is impregnated in the oxide semiconductor layer 3, but the electrolyte 5 is not necessarily impregnated in the oxide semiconductor layer 3.

  In the above embodiment, the dye-sensitized photoelectric conversion element is configured by one dye-sensitized photoelectric conversion cell 50. However, the dye-sensitized photoelectric conversion element may include a plurality of dye-sensitized photoelectric conversion cells 50. Good.

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

Example 1
First, a substrate made of titanium having a size of 6.0 cm × 6.0 cm × 0.05 mm was prepared as a counter electrode substrate. And the platinum catalyst layer of thickness 10nm was formed on the counter electrode board | substrate by sputtering method, and the counter electrode as a 2nd base material was obtained. In this way, the 2nd base | substrate which consists of a 2nd base material was obtained.

  Next, 5.0 cm × 5.0 cm × 50 μm is placed in the center of a 6.0 cm × 6.0 cm × 50 μm sheet made of Himiran (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd., melting point: 98 ° C.) as an ionomer. A square annular resin sheet having an opening was prepared. And this resin sheet was arrange | positioned in the cyclic | annular site | part on the counter electrode which is a 2nd base | substrate. The resin sheet was heated and melted at 150 ° C. for 1 minute to adhere to the annular portion, and the second sealing material was fixed to the annular portion on the counter electrode. In this way, the 2nd base | substrate with a 2nd sealing material was obtained.

  On the other hand, an FTO substrate of 8.0 cm × 8.0 cm × 4.0 mm was prepared as an electrode. Subsequently, a titanium oxide paste (Solaronix, Ti nanoixide T / sp) is applied on the FTO substrate by a doctor blade method so that the thickness becomes 15 μm, and then the FTO substrate to which this paste is applied is applied. Then, it was placed in a hot air circulation type oven and baked at 500 ° C. for 0.5 hour to form an oxide semiconductor layer having a thickness of 15 μm on the FTO substrate to obtain a structure.

  Next, this structure was oxidized by being immersed overnight in a dye solution in which 0.2719 of N719 as a photosensitizing dye was dissolved in a mixed solvent in which acetonitrile and t-butanol were mixed at a volume ratio of 1: 1. A photosensitizing dye was supported on the physical semiconductor layer. Thus, a working electrode was obtained.

  Next, a square annular resin sheet was prepared in which an opening of 5.0 cm × 5.0 cm × 50 μm was formed in the center of a 6.0 cm × 6.0 cm × 50 μm sheet made of high Milan as an ionomer. This resin sheet was disposed in an annular portion surrounding the oxide semiconductor layer of the working electrode. The resin sheet was heated and melted at 150 ° C. for 1 minute to adhere to the annular portion, and the first sealing material was fixed to the annular portion on the FTO substrate.

Next, the working electrode to which the first sealing material is fixed is arranged so that the surface of the FTO substrate on the oxide semiconductor layer side is horizontal, a volatile solvent made of methoxyacetonitrile is the main solvent, and lithium iodide is 0 A volatile electrolyte containing 0.1 M, 0.05 M iodine and 0.5 M 4-tert-butylpyridine was dropped into the oxide semiconductor layer and impregnated. At this time, the dropping amount of the electrolyte per 1 mm ³ of the volume of the oxide semiconductor layer was 2.4 μL.

  In this way, the 1st base | substrate with a 1st sealing material was obtained.

  Next, the first substrate with the first sealing material and the second substrate with the second sealing material are opposed to each other, and the first sealing material and the second sealing material are overlapped at atmospheric pressure. To obtain a laminate.

  And the laminated body was arrange | positioned in the glove box and the internal space of the glove box was pressure-reduced. Then, the brass frame of the same size as the second sealing material is heated, the brass frame is placed on the counter electrode so as to sandwich the second sealing material and the counter electrode, and using a press machine at 5 MPa The first sealing material and the second sealing material were heated and melted at 200 ° C. while pressurizing to form a sealing portion. Thus, a dye-sensitized photoelectric conversion element comprising one dye-sensitized photoelectric conversion cell was obtained.

(Example 2)
The first sealing material is not formed in the annular portion on the FTO substrate of the first base, and the second sealing material is used as the oxide semiconductor in the FTO substrate of the working electrode of the first base when the laminate is prepared. A dye-sensitized photoelectric conversion element composed of a dye-sensitized photoelectric conversion cell was obtained in the same manner as in Example 1 except that the ring-shaped portion surrounding the layer was directly contacted.

(Comparative Example 1)
After putting the first base body and the second base body with the second sealing material inside the glove box, the internal space of the glove box is depressurized, and the first base body and the second base material with the second sealing material are decompressed. Dye sensitization comprising a dye sensitized photoelectric conversion cell in the same manner as in Example 2 except that the substrate was opposed to each other and the second sealing material and the first substrate were overlapped and contacted to obtain a laminate. A photoelectric conversion element was obtained.

[Characteristic evaluation]
(1) Photoelectric conversion characteristics The initial conversion efficiency (η ₀ ) of the dye-sensitized photoelectric conversion elements obtained in Examples 1-2 and Comparative Example 1 was measured. The results are shown in Table 1. Table 1 shows the relative value of the initial photoelectric conversion efficiency η ₀ with Example 1 as 100.

(2) Durability Durability can be evaluated by the retention rate of photoelectric conversion efficiency of the dye-sensitized photoelectric conversion element. The durability was specifically evaluated as follows. That is, first, the dye-sensitized photoelectric conversion elements obtained in Examples 1 and 2 and Comparative Example 1 were allowed to stand for 1000 hours in a high-temperature environment at 85 ° C. immediately after their production, and the photoelectric conversion efficiency (η) was measured. And based on the photoelectric conversion efficiency ((eta)) measured in this way and the initial conversion efficiency ((eta) ₀ ) measured as mentioned above, the retention rate of the photoelectric conversion efficiency was computed based on the following formula. The results are shown in Table 1. Table 1 shows the relative value of the retention rate of photoelectric conversion efficiency with Example 1 as 100.

Retention rate of photoelectric conversion efficiency = 100 × η / η ₀

  From the results shown in Table 1, it was found that the dye-sensitized photoelectric conversion elements of Examples 1 and 2 were superior to the dye-sensitized photoelectric conversion element of Comparative Example 1 in terms of durability. Therefore, according to the method for producing a dye-sensitized photoelectric conversion element of the present invention, it was confirmed that a dye-sensitized photoelectric conversion element capable of sufficiently improving durability can be produced.

DESCRIPTION OF SYMBOLS 1 ... 1st base material 2,202 ... 2nd base material 3 ... Oxide semiconductor layer 4 ... Sealing part 4A ... Sealing material 5 ... Electrolyte 7 ... Electrode 10, 10A, 210 ... 1st base | substrate 20, 220 ... 1st Two substrates 50 ... Dye-sensitized photoelectric conversion cell 50A ... Laminate 100 ... Dye-sensitized photoelectric conversion element

Claims (5)

A first base material including an electrode; a second base material facing the first base material; an annular sealing portion for bonding the first base material and the second base material; the first base material; A dye-sensitized photoelectric conversion device having a dye-sensitized photoelectric conversion cell comprising an oxide semiconductor layer provided between the second substrate and an electrolyte disposed between the first substrate and the second substrate. A method for producing a dye-sensitized photoelectric conversion element for producing a conversion element,
A substrate preparing step of preparing a first substrate including the first substrate and a second substrate including the second substrate;
A laminate preparation step of preparing a laminate by bringing the first substrate and the second substrate into contact with each other through an annular sealing material that forms the sealing portion in a state of facing each other;
A bonding step of bonding the first base and the second base through the sealing material after decompressing the internal space of the chamber in a state where the laminate is disposed inside the chamber. ,
In the base preparation step, any one of the first base and the second base has the oxide semiconductor layer, and one of the first base and the second base A substrate has the electrolyte;
The manufacturing method of the dye-sensitized photoelectric conversion element by which the said sealing material is adhere | attached on a 1st base | substrate and a said 2nd base | substrate by heating the said sealing material in the said bonding process.   The method for producing a dye-sensitized photoelectric conversion element according to claim 1, wherein the sealing material is fixed to at least one of the first base and the second base in the base preparation step.   The said base | substrate preparation process WHEREIN: The said sealing material is fixed only to one base | substrate among the said 1st base | substrate and the said 2nd base | substrate, The said sealing material is not fixed to the other base | substrate. The manufacturing method of the dye-sensitized photoelectric conversion element of description.   In the base preparation step, a base of the first base and the second base that is not fixed with the sealing material has the oxide semiconductor layer, and the oxide semiconductor layer is impregnated with the electrolyte. The method for producing a dye-sensitized photoelectric conversion element according to claim 3. The base preparation step includes a step of dropping the electrolyte onto the oxide semiconductor layer when preparing the base having the oxide semiconductor layer among the first base and the second base;
The manufacturing method of the dye-sensitized photoelectric conversion element of Claim 4 whose dripping amount of the said electrolyte per volume 1mm < ³ > of the said oxide semiconductor layer is 0.5-4.0 microliters.

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