JPWO2013002246A1 - Dye-sensitized solar cell and method for producing the same - Google Patents

Abstract

The present invention includes a first electrode having a conductive layer and a porous oxide semiconductor layer, a second electrode provided to face the porous oxide semiconductor layer of the first electrode, and a porous oxide semiconductor of the first electrode A dye-sensitized solar cell comprising a photosensitizing dye supported on a layer and an electrolyte disposed between the first electrode and the second electrode, wherein the first electrode has a granular body, and the granular body Has at least a first granular material adhering to the conductive layer, and in the granular material, the ratio of the maximum length to the minimum length when observed two-dimensionally with a scanning electron microscope is 1 to 3, The body is a dye-sensitized solar cell made of titanium oxide having an average particle size of 5 nm or less.

Description

  The present invention relates to a dye-sensitized solar cell and a method for producing the same.

  In recent years, a dye-sensitized solar cell has attracted attention as a photoelectric conversion element because it is inexpensive and can provide high photoelectric conversion efficiency.

  A dye-sensitized solar cell generally includes a working electrode, a counter electrode, a photosensitizing dye supported on the oxide semiconductor layer of the working electrode, and an electrolyte disposed between the working electrode and the counter electrode.

  For such a dye-sensitized solar cell, further improvement in photoelectric conversion efficiency is required, and various studies have been conducted for that purpose.

  For example, in Patent Document 1 below, a dye is formed by using an optical semiconductor electrode in which an alkoxide of the same metal as the metal oxide semiconductor material is applied to the surface of the metal oxide semiconductor material and baked, and then a sensitizing dye is attached. It has been proposed to improve the photoelectric conversion efficiency of sensitized solar cells.

  In Patent Document 2 below, a coating liquid formed through processes such as hydrolysis and polycondensation using a titanium oxide precursor as a starting material is applied onto a transparent conductive film, and steps such as drying and baking of the coating liquid are performed. Proposed to improve the electron conductivity between the transparent conductive film and the semiconductor electrode film by forming an intermediate film having a predetermined surface roughness and forming a semiconductor electrode film on the intermediate film. Has been.

JP 2000-294814 A JP 2004-281288 A

  However, in the dye-sensitized solar cell having the photo semiconductor electrode or the semiconductor electrode film obtained by the method described in Patent Documents 1 and 2 described above, the photoelectric conversion efficiency is still not sufficient.

  This invention is made | formed in view of the said situation, and it aims at providing the dye-sensitized solar cell which has the outstanding photoelectric conversion efficiency, and its manufacturing method.

  As a result of studying the cause of the above problem, the present inventor has found that when the methods described in Patent Documents 1 and 2 are used, a smaller needle is formed on the surface of the particles constituting the porous oxide semiconductor layer of the working electrode. It has been found that a sticky body adheres or a coarse granular body is formed instead of a needle-like body, and this is considered to be the cause of the above problem. In view of this, the present inventor has conducted further research with a particular focus on the shape and size of the adherent adhering to the surface of the particles constituting the conductive layer of the working electrode or the porous oxide semiconductor layer provided thereon. As a result, the adhering body becomes a granular body having a predetermined average particle diameter and a predetermined minimum length / maximum length ratio, and the above problem can be solved by adhering the granular body to at least the conductive layer. The headline and the present invention were completed.

  That is, the present invention provides a first electrode having a conductive layer and a porous oxide semiconductor layer, a second electrode provided opposite to the porous oxide semiconductor layer of the first electrode, and the first electrode. A dye-sensitized solar cell comprising a photosensitizing dye supported on a porous oxide semiconductor layer and an electrolyte disposed between the first electrode and the second electrode, wherein the first electrode is granular The granular body has at least a first granular body adhering to the conductive layer, and the granular body has a maximum length with respect to a minimum length when two-dimensionally observed with a scanning electron microscope. Is a dye-sensitized solar cell made of titanium oxide having an average particle size of 5 nm or less.

  According to the present invention, a dye-sensitized solar cell having excellent photoelectric conversion efficiency is provided.

  The reason why the dye-sensitized solar cell of the present invention has excellent photoelectric conversion efficiency is not yet clear, but the present inventor presumes that the reason is as follows.

  That is, in the dye-sensitized solar cell of the present invention, the first electrode has a granular material, and the granular material has at least a first granular material that adheres to the conductive layer. Moreover, the ratio of the maximum length to the minimum length of the granular material (maximum length / minimum length) is 1 to 3, and this ratio (hereinafter referred to as “aspect ratio”) exceeds 3 as compared with the case where Thus, the granular material has a shape close to a sphere. For this reason, the granular material adhering to a conductive layer among the said granular materials can be provided in the outer side of the area | region in which the porous oxide semiconductor layer is formed at least among the surfaces of a conductive layer without gap. Therefore, the reverse electron movement in which the electrons that have reached the conductive layer from the photosensitizing dye through the porous oxide semiconductor layer move to the electrolyte is sufficiently suppressed by the first granular material attached to the conductive layer. Furthermore, since the average particle size of the granular material is as small as 5 nm or less, it is considered that the decrease in light transmittance can be sufficiently prevented. From the above, the inventor presumes that the dye-sensitized solar cell of the present invention has excellent photoelectric conversion efficiency.

  In the dye-sensitized solar cell of the present invention, the granular material is preferably made of titanium oxide having an average particle diameter of 1 nm or more.

  In this case, it becomes easier to maintain the crystallinity of titanium oxide as compared with the case where the granular material is made of titanium oxide having an average particle size of less than 1 nm.

  In the dye-sensitized solar cell of the present invention, the porous oxide semiconductor layer is in direct contact with the conductive layer, and the granular material is spaced apart from the first granular material and the conductive layer, and the porous It is preferable to have the 2nd granule adhering to an oxide semiconductor layer.

  In this case, the granule that is an oxide semiconductor also has a second granule that is separated from the conductive layer and adheres to the porous oxide semiconductor layer. For this reason, the surface area of an oxide semiconductor increases more. In addition, when the electrons move from the particles constituting the porous oxide semiconductor layer to the particles, the movement of the electrons is promoted by the second granular material. For this reason, the electron transfer from a photosensitizing dye to an oxide semiconductor is performed efficiently. Further, reverse electron transfer in which electrons move from the porous oxide semiconductor layer to the electrolyte can be suppressed.

  In the dye-sensitized solar cell of the present invention, the porous oxide semiconductor layer is preferably composed of oxide semiconductor particles, and the second granular material preferably has an average particle size smaller than that of the oxide semiconductor particles. .

  In this case, it is possible for the second granular material to be present densely in the gap between the oxide semiconductor particles as compared with the case where the oxide semiconductor particle has an average particle size equal to or smaller than the average particle size of the second granular material. Thus, the leakage current from the oxide semiconductor particles can be more sufficiently reduced while allowing electrons to easily flow between the oxide semiconductor particles.

  In the dye-sensitized solar cell of the present invention, it is preferable that at least a part of the first granular material is attached to the porous oxide semiconductor layer.

  In this case, when the electrons move from the porous oxide semiconductor layer to the conductive layer, the movement of the electrons is promoted by the first granular material as an intermediary. In addition, the adhesion between the porous oxide semiconductor layer and the conductive layer is enhanced by the first granular material.

  Here, it is preferable that the 1st granule adhering to the said porous oxide semiconductor layer is arrange | positioned among the said 1st granule on the inner side and the outer side of the said porous oxide semiconductor layer.

  In this case, since the 1st granule adhering to a porous oxide semiconductor layer is arrange | positioned inside and outside the porous oxide semiconductor layer, the 1st granule is inside the porous oxide semiconductor layer. As compared with the case where the electrode is disposed only on either the outer side or the outer side, the electron transfer from the porous oxide semiconductor layer to the conductive layer is performed more efficiently.

  Further, the first granular material attached to the porous oxide semiconductor layer is attached to the porous oxide semiconductor layer not only inside but also outside the porous oxide semiconductor layer. Therefore, the time (length) during which electrons pass through the granular material is shortened, and the movement of electrons can be more efficiently promoted.

  Furthermore, the first granular material attached to the porous oxide semiconductor layer is attached to the porous oxide semiconductor layer not only inside but also outside the porous oxide semiconductor layer. For this reason, the adhesiveness of a porous oxide semiconductor layer and a conductive layer is further improved.

  In the dye-sensitized solar cell of the present invention, the first electrode further includes a wiring part provided on the conductive layer around the porous oxide semiconductor layer, and the granular material is a surface of the wiring part. It is preferable to further have the 3rd granule provided in at least one part.

  In this case, since at least a part of the surface of the wiring part is protected by the third granular material, corrosion of the wiring part due to the electrolyte can be sufficiently suppressed.

  In the dye-sensitized solar cell of the present invention, the porous oxide semiconductor layer is preferably composed of titanium oxide.

  In this case, since the granular material and the porous oxide semiconductor layer are composed of titanium oxide, the resistance between the porous oxide semiconductor layer and the granular material is sufficiently reduced, and electron transfer can be performed more efficiently. Can do.

  Further, the present invention provides a first electrode having a conductive layer and a porous oxide semiconductor layer, a second electrode provided facing the porous oxide semiconductor layer side of the first electrode, and the first electrode A method for producing a dye-sensitized solar cell, comprising: a photosensitizing dye supported on the porous oxide semiconductor layer; and an electrolyte disposed between the first electrode and the second electrode. A first electrode forming step for forming one electrode, a dye carrying step for carrying a photosensitizing dye on the first electrode, and a bonding step for bonding the first electrode and the second electrode. The one-electrode forming step includes a surface treatment step in which a surface treatment solution containing at least a titanium alkoxide and a diketone-containing solvent is applied on the conductive layer, and then the surface treatment solution is baked. It is a manufacturing method of a battery.

  According to the production method of the present invention, the above-described dye-sensitized solar cell can be produced. That is, it has a granule having at least a first granule adhering to the conductive layer, and the ratio of the maximum length to the minimum length when observed two-dimensionally with a scanning electron microscope is 1 to 3 in the granule. And a dye-sensitized solar cell having a first electrode made of titanium oxide having an average particle diameter of 5 nm or less is obtained.

  In the manufacturing method, the first electrode forming step includes a porous oxide semiconductor layer forming step of forming the porous oxide semiconductor layer on the conductive layer before the surface treatment step, and the surface treatment In the step, it is preferable to apply the surface treatment solution on at least the conductive layer and the porous oxide semiconductor layer.

  In this case, since the porous oxide semiconductor layer is formed on the conductive layer before the surface treatment step, the granular material can be attached to the porous oxide semiconductor layer. For this reason, the surface area of an oxide semiconductor increases and it becomes possible to carry more photosensitizing dyes. For this reason, the dye-sensitized solar cell in which the electron transfer from a photosensitizing dye to an oxide semiconductor is performed efficiently can be obtained.

  In the manufacturing method, the first electrode forming step further includes a wiring portion forming step of forming a wiring portion on the conductive layer before the surface treatment step, and in the surface treatment step, at least the conductive layer and It is preferable to apply the surface treatment solution onto the wiring part.

  In this case, a granular material made of titanium oxide having a ratio of the maximum length to the minimum length of 1 to 3 when observed two-dimensionally with a scanning electron microscope and having an average particle diameter of 5 nm or less is used as a conductive layer. It is possible to adhere not only to the top but also to the wiring portion. For this reason, in the dye-sensitized solar cell obtained, the surface of the wiring part is protected by the granular material, and corrosion of the wiring part due to the electrolyte can be sufficiently suppressed.

  Moreover, in the said solvent, it is preferable that the molar ratio of the said titanium alkoxide with respect to the said diketone is 0.5-2.0.

  In this case, the granular material can be formed more efficiently than when the molar ratio is outside the above range.

  Furthermore, in the said solvent, it is preferable that the molar ratio of the said titanium alkoxide with respect to the said diketone is 1.0-2.0.

  In this case, the granular material can be formed more efficiently than when the molar ratio is outside the above range.

  In the manufacturing method, the porous oxide semiconductor layer is preferably made of titanium oxide.

  In this case, since the granular material and the porous oxide semiconductor layer are composed of titanium oxide, the resistance between the porous oxide semiconductor layer and the granular material is sufficiently reduced, and the electron transfer is efficiently performed. A dye-sensitized solar cell can be obtained.

  In the present invention, the “average particle diameter” means an average value of the maximum lengths of 50 granular bodies observed two-dimensionally with a scanning electron microscope (hereinafter referred to as “SEM”). And

  The “aspect ratio” refers to an average value of 50 granular materials having a ratio of the maximum length to the minimum length observed two-dimensionally by SEM.

  Further, “inside the porous oxide semiconductor layer” refers to a region of the conductive layer covered with the porous oxide semiconductor layer.

  ADVANTAGE OF THE INVENTION According to this invention, the dye-sensitized solar cell which has the outstanding photoelectric conversion efficiency, and its manufacturing method are provided.

It is sectional drawing which shows one Embodiment of the dye-sensitized solar cell of this invention. It is a partial expanded sectional view which shows the working electrode of FIG. It is sectional drawing which shows the granular material of FIG. It is a partial expanded sectional view which shows the modification of the working electrode of FIG. It is a partial expanded sectional view which shows the other modification of the working electrode of FIG. 2 is a view showing an SEM photograph near the surface of a porous oxide semiconductor layer of Example 1. FIG. 2 is a view showing an SEM photograph near the surface of a transparent conductive film of Example 1. FIG. It is a figure which shows the SEM photograph of interface surface vicinity of the porous oxide semiconductor layer of the comparative example 1, and a transparent conductive film.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In all the drawings, the same or equivalent components are denoted by the same reference numerals, and redundant description is omitted.

  FIG. 1 is a cross-sectional view showing a preferred embodiment of a dye-sensitized solar cell according to the present invention, and FIG. 2 is a partially enlarged cross-sectional view showing a working electrode of FIG.

  As shown in FIG. 1, the dye-sensitized solar cell 100 includes a working electrode 1 and a counter electrode 2 disposed so as to face the working electrode 1. Between the working electrode 1 and the counter electrode 2, a sealing portion 4 that connects the working electrode 1 and the counter electrode 2 is provided. The cell space surrounded by the working electrode 1, the counter electrode 2, and the sealing portion 4 is filled with an electrolyte 3.

  The working electrode 1 includes a transparent substrate 6, a transparent conductive film 7 provided on the counter electrode 2 side of the transparent substrate 6, and a porous oxide semiconductor layer provided on the transparent conductive film 7 so as to face the counter electrode 2 directly. 8 and a wiring portion 11 provided on the transparent conductive film 7. The porous oxide semiconductor layer 8 is in contact with the electrolyte 3, and a photosensitizing dye is supported on the porous oxide semiconductor layer 8 in the working electrode 1. In addition, the wiring portion 11 includes a current collecting wiring 12 provided on the transparent conductive film 7 and a wiring protective layer 13 that covers and protects the current collecting wiring 12. The outermost part of the wiring part 11 is connected to the sealing part 4.

  As shown in FIG. 2, the working electrode 1 has a granular body 90 that exists on the counter electrode 2 side with respect to the transparent conductive film (conductive layer) 7, and the granular body 90 includes a plurality of granular bodies 9 a, 9 b, 9 c. , 9d, 9e. The granular materials 9a to 9e are made of titanium oxide having an average particle size of 5 nm or less.

  The granular material 9 a as the first granular material provided on the transparent conductive film 7 is also attached to the porous oxide semiconductor layer 8. In the present embodiment, the granular material 9 a does not exist inside the porous oxide semiconductor layer 8.

  The granular material 9 b as the second granular material is attached to the porous oxide semiconductor layer 8 at a position spaced from the surface of the transparent conductive film 7. That is, the granular material 9 b is not in contact with the transparent conductive film 7.

  The granular material 9 c as the first granular material adheres only to the surface of the transparent conductive film 7 and does not adhere to the oxide semiconductor particles 8 a of the porous oxide semiconductor layer 8. The granular material 9d as the second granular material joins the granular materials 9b and adheres to the oxide semiconductor particles 8a via the granular material 9b. The granular material 9e as the third granular material adheres only on the surface 11a of the wiring part 11, and does not adhere to the transparent conductive film 7 or the porous oxide semiconductor layer 8.

  The shape of the granular material 90 is, for example, a circular shape or a semicircular shape, but may be other shapes. In addition, the shape said here means the shape observed two-dimensionally by SEM. The aspect ratio of the granular material 90 is 1 to 3. Here, the aspect ratio of the granular material 90 is an average value of 50 granular materials 90 having a ratio of the maximum length Lmax to the minimum length Lmin observed two-dimensionally by SEM, as shown in FIG. .

  According to the dye-sensitized solar cell 100 described above, it is possible to have excellent photoelectric conversion efficiency.

  The reason why the dye-sensitized solar cell 100 has excellent photoelectric conversion efficiency is not yet clear, but the inventor presumes that the reason is as follows.

  That is, in the dye-sensitized solar cell 100, the working electrode 1 has a granular body 90, and the granular body 90 has granular bodies 9 a and 9 c that adhere to the transparent conductive film 7. Moreover, the aspect ratios of the granular bodies 9a and 9c are 1 to 3, and the granular bodies 9a and 9c have a shape close to a sphere as compared with the case where the aspect ratio exceeds 3. For this reason, it becomes possible to provide the said granular material 9a, 9c without a gap | interval in the outer side of the area | region in which the porous oxide semiconductor layer 8 on the transparent conductive film 7 is formed. For this reason, the reverse electron movement in which the electrons that have reached the transparent conductive film 7 from the photosensitizing dye through the porous oxide semiconductor layer 8 move to the electrolyte 3 is sufficiently suppressed by the granular materials 9a and 9c. Furthermore, since the average particle diameter of the granular materials 9a and 9c is as small as 5 nm or less, it is possible to sufficiently prevent a decrease in light transmittance. From the above, the inventor presumes that the dye-sensitized solar cell 100 has excellent photoelectric conversion efficiency.

  In the dye-sensitized solar cell 100, the granular material 9 a on the transparent conductive film 7 is also attached to the porous oxide semiconductor layer 8.

  In this case, it is considered that when the electrons move from the porous oxide semiconductor layer 8 to the transparent conductive film 7, the granular material 9a acts as an intermediary to promote the movement of the electrons. In addition, the adhesion between the porous oxide semiconductor layer 8 and the transparent conductive film 7 is enhanced by the granular material 9a.

  In the dye-sensitized solar cell 100, the granular materials 9 b and 9 d that are oxide semiconductors are attached to the porous oxide semiconductor layer 8. For this reason, the surface area of an oxide semiconductor increases more. In addition, when the electrons move from the particles of the porous oxide semiconductor layer 8 to the particles, the particles 9b and 9d are considered to promote the movement of the electrons through the mediation. Therefore, electron transfer from the photosensitizing dye to the oxide semiconductor is efficiently performed. In addition, reverse electron transfer in which electrons move from the porous oxide semiconductor layer 8 to the electrolyte 3 can be suppressed.

  Next, the working electrode 1, the wiring part 11, the photosensitizing dye, the counter electrode 2, the electrolyte 3, and the sealing part 4 will be described in detail.

(Working electrode)
The material which comprises the transparent substrate 6 should just be a transparent material, for example, As such a transparent material, glass, such as borosilicate glass, soda lime glass, white plate glass, quartz glass, polyethylene terephthalate (PET), for example , Polyethylene naphthalate (PEN), polycarbonate (PC), polyethersulfone (PES) and the like. The thickness of the transparent substrate 6 is appropriately determined according to the size of the dye-sensitized solar cell 100 and is not particularly limited, but may be in the range of 50 to 10,000 μm, for example.

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

The porous oxide semiconductor layer 8 is composed of a porous oxide semiconductor. As shown in FIG. 2, the porous oxide semiconductor includes, for example, titanium oxide (TiO ₂ ), zinc oxide (ZnO), tungsten oxide (WO ₅ ), niobium oxide (Nb ₂ O ₅ ), strontium titanate (SrTiO _5). ), 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 an oxide semiconductor particle 8a composed of two or more thereof Consists of. The average particle diameter of these oxide semiconductor particles 8a is 1 to 1000 nm, which increases the surface area of the oxide semiconductor covered with the photosensitizing dye, that is, widens the field for photoelectric conversion and increases the number of electrons. Is preferable because it can be generated. Here, it is preferable that the porous oxide semiconductor layer 8 is composed of a stacked body in which oxide semiconductor particles 8a having different particle size distributions are stacked. In this case, it becomes possible to cause reflection of light repeatedly in the laminated body, and light can be efficiently converted into electrons without escaping incident light to the outside of the laminated body. The thickness of the porous oxide semiconductor layer 8 may be, for example, 0.5 to 50 μm. In addition, the porous oxide semiconductor layer 8 can also be comprised with the laminated body of the several semiconductor layer which consists of a different material.

  It is preferable that the oxide semiconductor particles 8a constituting the porous oxide semiconductor layer 8 have an average particle size larger than the granular materials 9b and 9d. In this case, compared with the case where the oxide semiconductor particles 8a have an average particle size equal to or less than the average particle size of the granular materials 9b and 9d, the granular materials 9b and 9d are densely present in the gaps between the oxide semiconductor particles 8a. Thus, the leakage current from the oxide semiconductor particles 8a can be more sufficiently reduced while allowing electrons to easily flow between the oxide semiconductor particles 8a.

  The average particle diameter of the granular materials 9a to 9e is preferably 1 nm or more. In this case, it becomes easier to maintain the crystallinity of the titanium oxide as compared with the case where the granules 9a to 9e are made of titanium oxide having an average particle diameter of less than 1 nm.

  The average particle size of the granules 9a to 9e is more preferably 2 to 4 nm.

  The aspect ratio of the granular materials 9a to 9e is preferably 1.5 to 2.5. In this case, the leakage current can be more sufficiently reduced as compared with the case where the aspect ratio of the granular materials 9a to 9e is out of the above range.

(Wiring section)
The current collection wiring 12 should just be a material which has resistance lower than the transparent conductive film 7, As such a material, metals, such as gold | metal | money, silver, copper, platinum, aluminum, titanium, and nickel, are mentioned, for example.

  Examples of the material constituting the wiring protective layer 13 include a material capable of transmitting light, such as a non-lead low-melting glass frit, and a lead oxide glass frit that cannot transmit light. Materials. Here, the softening point of the low melting point glass frit is preferably 550 ° C. or less.

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

(Counter electrode)
As shown in FIG. 1, the counter electrode 2 includes a counter electrode substrate 9, and a conductive catalyst layer (conductive layer) 10 that is provided on the working electrode 1 side of the counter electrode substrate 9 and promotes a reduction reaction on the surface of the counter electrode 2. It has.

  The counter electrode substrate 9 is made of, for example, a corrosion-resistant metal material such as titanium, nickel, platinum, molybdenum, or tungsten, a glass substrate, or the above-described transparent substrate 6 formed with a conductive oxide such as ITO or FTO, carbon, Consists of conductive polymer. The thickness of the counter electrode substrate 9 is appropriately determined according to the size of the dye-sensitized solar cell 100 and is not particularly limited, but may be, for example, 0.005 to 0.1 mm.

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

(Electrolytes)
The electrolyte 3 is usually composed of an electrolytic solution, and this electrolytic solution contains a redox couple such as I ⁻ / I ₃ ⁻ and an organic solvent. As an organic solvent, acetonitrile, methoxyacetonitrile, methoxypropionitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, γ-butyrolactone, valeronitrile, pivalonitrile, glutaronitrile, methacrylonitrile, isobutyronitrile, Phenylacetonitrile, acrylonitrile, succinonitrile, oxalonitrile, pentanitrile, adiponitrile and the like can be used. Examples of the redox pair include I ⁻ / I ₃ ⁻ and other pairs such as redox pairs such as bromine / bromide ions, zinc complexes, iron complexes, and cobalt complexes.

The electrolyte 3 may include an ionic liquid electrolyte made of a mixture of the ionic liquid and the organic solvent as a volatile component, instead of the organic solvent. The electrolyte 3 may include 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-methyl-3-methylimidazolium iodide, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-hexyl-3-methylimidazolium iodide. Id, 1-ethyl-3-propylimidazolium iodide, dimethylimidazolium iodide, ethylmethylimidazolium iodide, dimethylpropylimidazolium iodide, butylmethylimidazolium iodide, or methylpropylimidazolium iodide Preferably used. The electrolyte 40 may further contain an additive. As the _{additive, LiI, I 2, 4-} t- butylpyridine, guanidinium thiocyanate, 1-methylbenzimidazole, 1-butyl-benzimidazole and the like. Further, the electrolyte 3 may be 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 electrolyte, and may be 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.

(Sealing part)
Examples of the material constituting the sealing portion 4 include inorganic insulating materials such as lead-free transparent low melting point glass frit, ionomers, ethylene-vinyl acetic anhydride copolymers, ethylene-methacrylic acid copolymers, ethylene -Various modified polyolefin resin containing a vinyl alcohol copolymer etc., ultraviolet curable resin, and resin, such as a vinyl alcohol polymer, are mentioned. In addition, the sealing part 4 may be comprised only with resin, and may be comprised with resin and an inorganic filler.

  Furthermore, in the dye-sensitized solar cell 100, when both the porous oxide semiconductor layer 8 and the granular materials 9a and 9b are made of titanium oxide, the porous oxide semiconductor layer 8 and the granular materials 9a and 9b The resistance between them is sufficiently reduced, and electron transfer can be performed more efficiently. Furthermore, the granular material 9d couples the granular materials 9b to form a large number of conductive paths. This is considered to contribute to the dye-sensitized solar cell 100 having better photoelectric conversion efficiency.

  Furthermore, in the dye-sensitized solar cell 100, the granular material 9 e is provided on the surface 11 a of the wiring part 11. For this reason, the surface 11a of the wiring part 11 is protected by the granular material 9e. Therefore, corrosion of the wiring part 11 by the electrolyte 3 can be sufficiently suppressed by the granular material 9e.

  Next, the manufacturing method of the dye-sensitized solar cell 100 is demonstrated.

<First electrode forming step>
First, the working electrode 1 is prepared as follows.

  First, the transparent conductive film 7 is formed on the transparent substrate 6. As a method for forming the transparent conductive film 7, a sputtering method, a vapor deposition method, a spray pyrolysis (SPD) method, a CVD method, or the like is used.

(Porous oxide semiconductor layer forming step)
Next, a paste for forming a porous oxide semiconductor layer is printed on the transparent conductive film 7. The porous oxide semiconductor layer forming paste includes a resin such as polyethylene glycol and a solvent such as terpineol in addition to the oxide semiconductor particles 8a described above. As a printing method of the paste for forming the porous oxide semiconductor layer, for example, a screen printing method, a doctor blade method, a bar coating method, or the like can be used.

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

(Wiring section forming process)
Next, the current collector wiring 12 is formed on the transparent conductive film 7. The current collector wiring 12 can be formed, for example, by applying and baking a metal paste around the porous oxide semiconductor layer 8 so as to be separated from the porous oxide semiconductor layer 8.

  Subsequently, a wiring protective layer 13 is formed so as to cover the current collecting wiring 12 and to be in contact with the transparent conductive film 7. The wiring protective layer 13 can be formed by, for example, applying and drying a paste containing a low melting point glass frit so as to cover the current collecting wiring 12, and then baking. In this way, the wiring part 11 is obtained.

(Surface treatment process)
Next, after applying a surface treatment solution containing a titanium alkoxide and a solvent containing diketone on the exposed region of the transparent conductive film 7, the porous oxide semiconductor layer 8, and the surface 11a of the wiring portion 11, This surface treatment solution is fired. Thereby, the granular material 90 is obtained. That is, the granules 9 a and 9 c are formed on the transparent conductive film 7, and the granules 9 b and 9 d are formed on the porous oxide semiconductor layer 8. Further, a granular material 9e is formed on the surface 11a of the wiring part 11.

  Here, the application includes application by dipping as well as application by ink jet, printing and spraying.

  Examples of the titanium alkoxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetraisobutoxide, titanium tetra n-butoxide, titanium tetra-tert-butoxide, titanium tetra 2-ethyl hexad, titanium tetraisoocta. Examples thereof include xoxide, titanium tetra-n-propoxide, and tetratitadex orthotitanate.

  The solvent contained in the surface treatment solution only needs to contain a diketone. Therefore, the solvent may be composed only of a diketone, or may be a mixed solvent of a diketone and a solvent other than the diketone.

  Examples of the diketone include 1,3-diketone (acetylacetone), 1,2-diketone (diacetyl), 1,4-diketone (2,5-hexanedione), dimedone, and the like. As a solvent other than diketone, for example, an organic solvent such as alcohol such as methanol, ethanol, and propanol can be used.

  In the surface treatment solution, the molar ratio of titanium alkoxide to diketone is preferably 0.5 to 3.0. When the molar ratio is in the above range, the diketone is not excessive as compared with the case where the molar ratio is less than 0.5. Therefore, the exposed region of the transparent conductive film 7, the porous oxide semiconductor layer 8 and on the surface 11 a of the wiring portion 11, the granular materials 9 a to 9 e are uniformly formed. Moreover, since titanium alkoxide does not remain excessively compared with the case where the said molar ratio exceeds 3, the granular materials 9a-9e can be formed efficiently. The molar ratio is preferably 0.5 to 2.0. In this case, the granular materials 9a to 9e can be formed more efficiently than when the molar ratio is outside the range of 0.5 to 2.0. Further, the molar ratio is more preferably 1.0 to 2.0. In this case, the granular materials 9a to 9e can be formed more efficiently than when the molar ratio is outside the range of 1.0 to 2.0.

  The concentration of titanium alkoxide in the surface treatment solution is preferably 40 to 2000 mM, more preferably 300 to 1500 mM.

  The firing temperature is usually 100 to 650 ° C, preferably 350 to 550 ° C.

  In order to prevent the particles 9a on the transparent conductive film 7 to which the porous oxide semiconductor layer 8 adheres from being present inside the porous oxide semiconductor layer 8, for example, the average particle diameter of the oxide semiconductor particles 8a is set to 10 nm. By preventing the granular material 9a from entering the inside of the porous oxide semiconductor layer 8 or by increasing the thickness of the porous oxide semiconductor layer 8, the granular material 9a can reach the transparent conductive film 7. You can prevent it from reaching. The working electrode 1 is obtained as described above.

<Dye supporting step>
Next, a photosensitizing dye is supported on the porous oxide semiconductor layer 8 of the working electrode 1. For this purpose, the working electrode 1 is immersed in a dye-containing solution containing a photosensitizing dye, and the photosensitizing dye is adsorbed on the porous oxide semiconductor layer 8 and then the solvent component of the dye-containing solution. The excess photosensitizing dye may be washed away and dried to adsorb the photosensitizing dye to the porous oxide semiconductor layer 8. However, even if the photosensitizing dye is adsorbed to the porous oxide semiconductor porous layer 8 by applying a dye-containing solution containing the photosensitizing dye to the porous oxide semiconductor layer 8 and then drying it, the photosensitizing dye can be absorbed. The dye-sensitive material can be supported on the porous oxide semiconductor layer 8.

<Counterelectrode preparation process>
On the other hand, the counter electrode 2 is prepared as follows.

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

  Next, an electrolyte 3 is prepared and placed, for example, on the working electrode 1.

<Lamination process>
Next, for example, an annular sheet made of a thermoplastic resin is prepared. Then, the working electrode 1 having the porous oxide semiconductor layer 8 carrying the photosensitizing dye and the counter electrode 2 are sandwiched between the sheet and the electrolyte 3, the sheet is heated and melted, and the working electrode 1 and the counter electrode 2 are bonded together. . At this time, the porous oxide semiconductor layer 8 is arranged inside the annular sheet. In this way, the sealing part 4 is formed between the working electrode 1 and the counter electrode 2, and the dye-sensitized solar cell 100 is obtained, and the manufacture of the dye-sensitized solar cell 100 is completed.

  Before the electrolyte 3 is placed on the working electrode 1, the sealing portion 4 is formed on the working electrode 1 by fixing the sheet on the working electrode 1 by heating and melting, and the electrolyte 3 is placed on the working electrode 1. The dye-sensitized solar cell 100 can be obtained even if the working electrode 1 and the counter electrode 2 are bonded together after being disposed inside the sealing portion 4 formed above. At this time, after forming the sealing part 4 on the counter electrode 2 and disposing the electrolyte 3 inside the sealing part 4, the working electrode 1 and the counter electrode 2 may be bonded together, or the working electrode 1 and the counter electrode 2. The working electrode 1 and the counter electrode 2 may be bonded together after the sealing portion 4 is formed in each of the electrodes and the electrolyte 3 is disposed inside one of the working electrode 1 and the counter electrode 2. The counter electrode 2 may be prepared after the electrolyte 3 is disposed on the working electrode 1.

  When the dye-sensitized solar cell 100 is manufactured as described above, the following effects are obtained.

That is, in the method for manufacturing the dye-sensitized solar cell 100 described above, after forming the porous oxide semiconductor layer 8 and the wiring portion 11 on the transparent conductive film 7, the exposed region of the transparent conductive film 7, the porous oxidation A surface treatment solution containing a titanium alkoxide and a solvent containing diketone is applied to the physical semiconductor layer 8 and the surface 11a of the wiring portion 11, and the surface treatment solution is baked. Here, when the titanium alkoxide reacts with the diketone, it is considered that the compound A shown in the following reaction formula is generated from the application of the assertion treatment solution to the baking. In the structural formulas representing the following titanium alkoxides, R represents an organic group.

  Since this compound A is delocalized and stabilized, even if water or the like enters the surface treatment solution, it does not react with water. For this reason, when applying the surface treatment solution onto the exposed region of the transparent conductive film 7, the porous oxide semiconductor layer 8 and the surface 11a of the wiring portion 11, a small amount of water or the like enters the surface treatment solution. Even so, the compound A is considered not to change to a different compound. As a result, it becomes possible to form the granular materials 9a to 9e stably.

  In addition, when a surface treatment solution containing a titanium alkoxide and a solvent containing a diketone is used, granules (aspect ratios 1 to 3) 9a to 9e having an average particle size of 5 nm or less can be stably formed. The reason for this is not clear, but when the surface treatment solution is baked, in the compound A, the diketone portion is cut to be pure titanium, and both the titanium alkoxide and the diketone are neutral. It is thought that.

  Furthermore, the compound A is considered to be neutral. For this reason, even if the surface treatment solution is applied onto the surface 11 a of the wiring part 11 after the wiring part 11 is formed, the wiring part 11 does not melt.

In general, titanium tetrachloride may be used as the surface treatment solution, and titanium tetrachloride is used by mixing an appropriate amount of water. However, in this case, titanium tetrachloride reacts with water with the passage of time to produce Ti (OH) ₄ . Even when water is not mixed, titanium tetrachloride immediately reacts with water in a water-containing environment to produce Ti (OH) ₄ . Then, when the surface treatment solution is baked with Ti (OH) ₄ being generated in this way, even if particles with a small particle diameter are to be produced, the particles are aggregated to control the particle diameter. Becomes difficult. Alternatively, even if the titanium tetrachloride solution is applied and fired to obtain uniform particle sizes, needle-like particles are formed. Although this reason is not certain, it is thought that it originates from titanium tetrachloride being acidic. The fact that the titanium tetrachloride is acidic is apparent from the fact that the silver or glass frit forming the wiring portion 11 is melted even if the surface treatment is performed with the titanium tetrachloride solution after the wiring portion 11 is formed.

  The present invention is not limited to the above embodiment. For example, in the above-described embodiment, there is no granular material on the transparent conductive film 7 and attached to the porous oxide semiconductor layer 8 inside the porous oxide semiconductor layer 8. As in the working electrode 201 shown in FIG. 4, with respect to the working electrode 1, granular particles that are on the transparent conductive film 7 and are also attached to the porous oxide semiconductor layer 8 inside the porous oxide semiconductor layer 8. The body 9a may exist. In this case, in the working electrode 201, the granular material 9 a that is on the transparent conductive film 7 and also adhered to the porous oxide semiconductor layer 8 is provided inside and outside the porous oxide semiconductor layer 8. become. According to such a dye-sensitized solar cell using the working electrode 201, the granular material 9 a on the transparent conductive film 7 attached to the porous oxide semiconductor layer 8 is inside and outside of the porous oxide semiconductor layer 8. Therefore, compared with the case where the granular material 9 a is disposed only on either the inside or the outside of the porous oxide semiconductor layer 8, the transparent conductive film 7 is formed from the porous oxide semiconductor layer 8. Electron transfer to is performed more efficiently.

  Further, the granular material 9 a on the transparent conductive film 7 attached to the porous oxide semiconductor layer 8 is attached to the porous oxide semiconductor layer 8 not only inside but also outside the porous oxide semiconductor layer 8. . Therefore, the time (length) for electrons to pass through the granular material 9a is shortened, and the movement of electrons can be more efficiently promoted.

  Furthermore, the granular material 9 a on the transparent conductive film 7 is attached to the porous oxide semiconductor layer 8 not only inside but also outside the porous oxide semiconductor layer 8. For this reason, the adhesiveness of the porous oxide semiconductor layer 8 and the transparent conductive film 7 is further improved.

  In order to attach a granular material like the working electrode 201 to the porous oxide semiconductor layer 8, specifically, after attaching the granular material 9c on the transparent conductive film 7, at least one of the granular material 9c. The porous oxide semiconductor layer 8 may be formed so as to cover the portion, and then the granular materials 9b and 9d may be attached to the porous oxide semiconductor layer 8. In addition, the granular material 9c which adhered to the porous oxide semiconductor layer 8 among the granular materials 9c turns into the granular material 9a.

  Further, as the working electrode 301 shown in FIG. 5, the granular material 9 a on the transparent conductive film 7 adhered to the porous oxide semiconductor layer 8 on the inner side and the outer side of the porous oxide semiconductor layer 8 as a granular material, porous Only the granular material 9c which does not adhere to the oxide semiconductor layer 8 but adheres only to the transparent conductive film 7 and the granular material 9e on the surface 11a of the wiring part 11 may be provided. That is, the granular materials 9b and 9d may not be provided. In order to form such a working electrode 301, the granular material 9 c is adhered on the transparent conductive film 7, and after the granular material 9 e is adhered on the surface 11 a of the wiring portion 11, at least the granular material 9 c is formed. The porous oxide semiconductor layer 8 may be formed so as to cover a part. In this case, the granular material 9 c becomes the granular material 9 a when it adheres to the porous oxide semiconductor layer 8.

  Further, in the above-described working electrodes 1, 201, 301, the granular material 9e is disposed on the surface 11a of the wiring portion 11. However, the granular material 9e does not necessarily have to be disposed on the surface 11a of the wiring portion 11. . Moreover, the wiring part 11 is not necessarily required and can be omitted.

  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)
(Production of working electrode)
First, an FTO / glass substrate having an FTO film formed on a glass substrate was prepared. Then, this FTO / glass substrate is cleaned, this substrate is subjected to UV-O ₃ treatment, and a titanium oxide nanoparticle paste containing titanium oxide nanoparticles having an average particle diameter of 20 nm is produced on the substrate by screen printing (manufactured by Solaronix) , Ti nanoixide T / sp) was applied to prepare a 50 × 50 mm × 12 μm film. Then, this board | substrate with a film | membrane was put into hot-air circulation type oven, and baked at 500 degreeC for 1 hour, the porous oxide semiconductor layer was formed on the FTO film | membrane, and the laminated body was obtained.

  On the other hand, titanium tetraisopropoxide and acetylacetone as a diketone were prepared, these were mixed at a molar ratio of 1: 1, and this mixed solution was added to ethanol to obtain a surface treatment solution. The molar concentration of titanium tetraisopropoxide and acetylacetone in the surface treatment solution was 40 mM.

  Next, the laminate was immersed in the surface treatment solution obtained as described above for 24 hours, and then baked at 450 ° C. for 30 minutes. Thus, a working electrode was obtained. About this working electrode, the surface of the porous oxide semiconductor layer was observed using SEM. The results are shown in FIG. As shown in FIG. 5, it was confirmed that the granular material with an average particle diameter of 3 nm adhered on the surface of the porous oxide semiconductor layer. The vicinity of the surface of the FTO film, which is a transparent conductive film, was observed with an SEM. The results are shown in FIG. As shown in FIG. 6, it was confirmed that the granular material with an average particle diameter of 3 nm was adhered also on the FTO film. The aspect ratio of the granular material adhering to the porous oxide semiconductor layer and the granular material adhering to the FTO film were both 1.5.

(Supporting photosensitizing dye)
Next, N719 dye, which is a photosensitizing dye, was dissolved in a mixed solvent in which acetonitrile and t-butyl alcohol were mixed at 1: 1 (volume ratio) to prepare a dye solution. Then, the working electrode was immersed in this dye solution for 24 hours, and the photosensitizing dye was supported on the porous oxide semiconductor layer.

(Production of counter electrode)
On the other hand, the same FTO / glass substrate as used in the production of the working electrode was prepared, and Pt was deposited on the FTO film of this substrate by sputtering. Thus, a counter electrode was produced.

(Electrolytes)
On the other hand, an ionic liquid (hexylmethylimidazolium iodide) containing an iodine / iodide ion redox pair is prepared as an electrolyte, and this is converted into a porous oxide semiconductor carrying a photosensitizing dye by screen printing. It apply | coated so that the porous oxide semiconductor layer might be covered on the working electrode which has a layer.

(Sealing)
Between the working electrode and the counter electrode, a cyclic thermoplastic resin sheet made of high Milan (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.) as an ionomer was sandwiched as a separator. At this time, the electrolyte was arranged inside the thermoplastic resin sheet. Then, the thermoplastic resin sheet was heated and melted at 180 ° C. for 5 minutes to bond the working electrode and the counter electrode. Thus, a dye-sensitized solar cell was obtained.

(Example 2)
A dye-sensitized solar cell was produced in the same manner as in Example 1 except that the solute concentration in the surface treatment solution was changed from 40 mM to 500 mM as shown in Table 1.

  In addition, when the working electrode of the dye-sensitized solar cell of Example 2 was also observed using SEM, as in Example 1, particles having an average particle diameter of 3 nm adhered to the porous oxide semiconductor layer. It was confirmed that particles having an average particle diameter of 3 nm were adhered to the FTO film. The aspect ratio of the granular material adhering to the porous oxide semiconductor layer and the granular material adhering to the FTO film were both 1.5.

Example 3
A dye-sensitized solar cell was produced in the same manner as in Example 1 except that the concentration of the solute in the surface treatment solution was changed from 40 mM to 2000 mM as shown in Table 1.

  In addition, when the working electrode of the dye-sensitized solar cell of Example 3 was also observed using SEM in the same manner as in Example 1, particles having an average particle diameter of 3 nm adhered to the porous oxide semiconductor layer. It was confirmed that particles having an average particle diameter of 3 nm were adhered to the FTO film. The aspect ratio of the granular material adhering to the porous oxide semiconductor layer and the granular material adhering to the FTO film were both 1.5.

Example 4
After forming the porous oxide semiconductor layer on the FTO film, a wiring part is produced on the FTO film as follows, and then the surface treatment solution is formed on the porous oxide semiconductor layer, the FTO film and the wiring part. A dye-sensitized solar cell was produced in the same manner as in Example 1 except that the surface treatment was conducted at

That is, a paste containing Ag was applied onto a FTO / glass substrate treated with UV-O ₃ by a screen printing method and baked to produce a silver wiring. Thereafter, the silver wiring was covered with a glass protective film made of glass frit. In this way, a wiring part composed of the silver wiring and the glass protective film was produced.

  Note that the working electrode of the dye-sensitized solar cell of Example 4 was also observed using SEM in the same manner as in Example 1. As a result, particles with an average particle diameter of 3 nm adhered to the porous oxide semiconductor layer. It was confirmed that particles having an average particle diameter of 3 nm were adhered to the FTO film. Furthermore, it was confirmed that the granular material with an average particle diameter of 3 nm was adhered also to the wiring part. The aspect ratio of the granular material adhering to each of the porous oxide semiconductor layer, the FTO film, and the wiring portion was 1.5.

  Moreover, when the glass protective film in the wiring part was observed, no change was seen in the appearance of the glass, and no change was seen in the appearance of the silver wiring below it.

(Example 5)
The concentration of the solute in the surface treatment solution was changed from 40 mM to 500 mM as shown in Table 1, and the solute / solvent (molar ratio) was changed from 1/1 to 1/2 as shown in Table 1. Prepared a dye-sensitized solar cell in the same manner as in Example 1.

  Note that the working electrode of the dye-sensitized solar cell of Example 5 was also observed using SEM in the same manner as in Example 1. As a result, particles with an average particle diameter of 3 nm adhered to the porous oxide semiconductor layer. It was confirmed that particles having an average particle diameter of 3 nm were adhered to the FTO film. Moreover, the aspect ratio of the granular material adhering to the porous oxide semiconductor layer and the granular material adhering to the FTO film | membrane were all 1.

(Example 6)
The concentration of the solute in the surface treatment solution was changed from 40 mM to 500 mM as shown in Table 1, and the solute / solvent (molar ratio) was changed from 1/1 to 2/1 as shown in Table 1. Prepared a dye-sensitized solar cell in the same manner as in Example 1.

  In addition, when the working electrode of the dye-sensitized solar cell of Example 6 was also observed using SEM in the same manner as in Example 1, particles having an average particle diameter of 3 nm adhered to the porous oxide semiconductor layer. It was confirmed that particles having an average particle diameter of 3 nm were adhered to the FTO film. Moreover, the aspect ratio of the granular material adhering to the porous oxide semiconductor layer and the granular material adhering to the FTO film | membrane were all 3.

(Example 7)
The concentration of the solute in the surface treatment solution was changed from 40 mM to 500 mM as shown in Table 1, and the solute / solvent (molar ratio) was changed from 1/1 to 1/3 as shown in Table 1. Prepared a dye-sensitized solar cell in the same manner as in Example 1.

  In addition, when the working electrode of the dye-sensitized solar cell of Example 7 was also observed using SEM in the same manner as in Example 1, particles having an average particle diameter of 1 nm adhered to the porous oxide semiconductor layer. It was confirmed that particles having an average particle diameter of 1 nm were adhered to the FTO film. The aspect ratio of the granular material adhering to the porous oxide semiconductor layer and the granular material adhering to the FTO film were both 1.5.

(Example 8)
The concentration of the solute in the surface treatment solution was changed from 40 mM to 500 mM as shown in Table 1, and the solute / solvent (molar ratio) was changed from 1/1 to 3/2 as shown in Table 1. Prepared a dye-sensitized solar cell in the same manner as in Example 1.

  In addition, when the working electrode of the dye-sensitized solar cell of Example 8 was also observed using SEM in the same manner as in Example 1, particles having an average particle diameter of 5 nm adhered to the porous oxide semiconductor layer. It was confirmed that particles having an average particle diameter of 5 nm were adhered to the FTO film. The aspect ratio of the granular material adhering to the porous oxide semiconductor layer and the granular material adhering to the FTO film were both 1.5.

(Comparative Example 1)
As a surface treatment solution, a dye was prepared in the same manner as in Example 4 except that a surface treatment solution obtained by adding a titanium tetrachloride solution (manufactured by Aldrich) to pure water to a concentration of 40 mM was used. A sensitized solar cell was produced.

  In addition, when the working electrode of the dye-sensitized solar cell of Comparative Example 1 was also observed using the SEM as in Example 1, as shown in FIG. 7, the acicular body adhered to the FTO film. It was confirmed that Moreover, when the surface vicinity of the porous oxide semiconductor layer of the working electrode of a dye-sensitized solar cell was observed using SEM similarly to Example 1, the acicular body had adhered to the porous oxide semiconductor layer. Was confirmed. These needles had an average particle size of 7 nm and an aspect ratio of 4. No granular material having an average particle diameter of 3 nm was observed on the FTO film or the porous oxide semiconductor layer.

(Comparative Example 2)
A dye-sensitized solar cell was produced in the same manner as in Example 1 except that the laminate formed by forming the porous oxide semiconductor layer on the FTO film was not immersed in the surface treatment solution.

  In addition, when the working electrode of the dye-sensitized solar cell of Comparative Example 2 was also observed using SEM in the same manner as in Example 1, particles were confirmed both on the FTO film and on the porous oxide semiconductor layer. could not.

(Comparative Example 3)
A dye-sensitized solar cell was produced in the same manner as in Example 1 except that a surface treatment solution prepared without using acetylacetone was used as the surface treatment solution.

  In addition, when the working electrode of the dye-sensitized solar cell of Comparative Example 3 was also observed using SEM in the same manner as in Example 1, aggregates of titanium oxide were confirmed. The average particle diameter of this aggregate was 20 nm, and the average particle diameter of titanium oxide constituting the aggregate was 8 nm.

(Comparative Example 4)
A dye-sensitized solar cell was produced in the same manner as in Example 1 except that a surface treatment solution prepared without using titanium tetraisopropoxide was used as the surface treatment solution.

  In addition, when the working electrode of the dye-sensitized solar cell of Comparative Example 4 was also observed using SEM in the same manner as in Example 1, particles were confirmed both on the FTO film and on the porous oxide semiconductor layer. could not.

(Comparative Example 5)
A dye-sensitized solar cell was produced in the same manner as in Example 4 except that the surface treatment was not performed on the laminate formed by forming the porous oxide semiconductor layer on the FTO film.

  In addition, when the working electrode of the dye-sensitized solar cell of Comparative Example 5 was also observed using SEM in the same manner as in Example 1, particles were confirmed both on the FTO film and on the porous oxide semiconductor layer. could not.

(Comparative Example 6)
As a surface treatment solution, a dye was prepared in the same manner as in Example 4 except that a surface treatment solution obtained by adding a titanium tetrachloride solution (manufactured by Aldrich) to pure water to a concentration of 40 mM was used. A sensitized solar cell was produced.

  In addition, when the working electrode of the dye-sensitized solar cell of Comparative Example 6 was also observed using SEM in the same manner as in Example 1, it was confirmed that the acicular body was adhered on the FTO film. Moreover, when the surface vicinity of the porous oxide semiconductor layer of the working electrode of a dye-sensitized solar cell was observed using SEM similarly to Example 1, the acicular body had adhered to the porous oxide semiconductor layer. Was also confirmed. The needles had an average particle size of 7 nm and an aspect ratio of 4. No granular material having an average particle diameter of 3 nm was observed on the FTO film or the porous oxide semiconductor layer.

  Furthermore, when the glass protective film in a wiring part was observed, it was confirmed that glass melt | dissolved, the hole has opened in glass, and also the silver wiring under it has melted.

(Comparative Example 7)
The concentration of the solute in the surface treatment solution was changed from 40 mM to 500 mM as shown in Table 1, and the solute / solvent (molar ratio) was changed from 1/1 to 4/1 as shown in Table 1. Prepared a dye-sensitized solar cell in the same manner as in Example 1.

  Note that the working electrode of the dye-sensitized solar cell of Comparative Example 7 was also observed using SEM in the same manner as in Example 1. As a result, particles with an average particle diameter of 3 nm adhered to the porous oxide semiconductor layer. It was confirmed that particles having an average particle diameter of 3 nm were adhered to the FTO film. Moreover, the aspect ratio of the granular material adhering to the porous oxide semiconductor layer and the granular material adhering to the FTO film | membrane were all 6.

(Comparative Example 8)
The concentration of the solute in the surface treatment solution was changed from 40 mM to 500 mM as shown in Table 1, and the solute / solvent (molar ratio) was changed from 1/1 to 2/3 as shown in Table 1. Prepared a dye-sensitized solar cell in the same manner as in Example 1.

  Note that the working electrode of the dye-sensitized solar cell of Comparative Example 8 was also observed using SEM in the same manner as in Example 1. As a result, particles with an average particle diameter of 4 nm adhered to the porous oxide semiconductor layer. It was confirmed that particles having an average particle diameter of 4 nm were adhered to the FTO film. Moreover, the aspect ratio of the granular material adhering to the porous oxide semiconductor layer and the granular material adhering to the FTO film | membrane were all 3.

For the dye-sensitized solar cells of Examples 1 to 8 and Comparative Examples 1 to 8 obtained as described above, the photoelectric conversion efficiency η (%) was measured. The results are shown in Table 1.

  From the result shown in Table 1, it turned out that the dye-sensitized solar cell of Examples 1-8 has the photoelectric conversion efficiency superior to the dye-sensitized solar cell of Comparative Examples 1-8.

  Therefore, according to this invention, it was confirmed that the dye-sensitized solar cell which has the outstanding photoelectric conversion efficiency is provided.

1, 201, 301 ... Working electrode (first electrode)
2 ... Counter electrode (second electrode)
3 ... electrolyte 7 ... transparent conductive film (conductive layer)
8 ... Porous oxide semiconductor layer 8a ... Oxide semiconductor particles 9a, 9c ... Granules (first granule)
9b, 9d ... granular material (second granular material)
9e Granule (third granule)
90 ... Granules 100 ... Dye-sensitized solar cell Lmax ... Maximum length Lmin ... Minimum length

Claims (14)

A first electrode having a conductive layer and a porous oxide semiconductor layer;
A second electrode provided opposite to the porous oxide semiconductor layer of the first electrode;
A photosensitizing dye carried on the porous oxide semiconductor layer of the first electrode;
A dye-sensitized solar cell comprising an electrolyte disposed between the first electrode and the second electrode,
The first electrode has a granular material, and the granular material has at least a first granular material attached to the conductive layer;
In the granular material, the ratio of the maximum length to the minimum length when observed two-dimensionally with a scanning electron microscope is 1 to 3,
The granular material is a dye-sensitized solar cell made of titanium oxide having an average particle diameter of 5 nm or less.   The dye-sensitized solar cell according to claim 1, wherein the granular material is made of titanium oxide having an average particle diameter of 1 nm or more. The porous oxide semiconductor layer is in direct contact with the conductive layer;
The dye-sensitized solar cell according to claim 1 or 2, wherein the granular material includes the first granular material and a second granular material that is separated from the conductive layer and adheres to the porous oxide semiconductor layer. The porous oxide semiconductor layer is composed of oxide semiconductor particles;
The dye-sensitized solar cell according to claim 3, wherein the second granular material has an average particle size smaller than that of the oxide semiconductor particles.   The dye-sensitized solar cell according to any one of claims 1 to 4, wherein at least a part of the first granular material is attached to the porous oxide semiconductor layer.   The pigment according to claim 5, wherein the first granular material attached to the porous oxide semiconductor layer among the first granular materials is disposed inside and outside the porous oxide semiconductor layer. Sensitized solar cell. The first electrode further includes a wiring portion provided on the conductive layer around the oxide semiconductor layer,
The dye-sensitized solar cell according to any one of claims 1 to 6, wherein the granular body further includes a third granular body provided on at least a part of the surface of the wiring portion.   The dye-sensitized solar cell according to any one of claims 1 to 7, wherein the porous oxide semiconductor layer is made of titanium oxide. A first electrode having a conductive layer and a porous oxide semiconductor layer;
A second electrode provided facing the porous oxide semiconductor layer side of the first electrode;
A photosensitizing dye carried on the porous oxide semiconductor layer of the first electrode;
A method for producing a dye-sensitized solar cell comprising an electrolyte disposed between the first electrode and the second electrode,
A first electrode forming step of forming the first electrode;
A dye carrying step of carrying a photosensitizing dye on the first electrode;
A laminating step of laminating the first electrode and the second electrode,
The first electrode forming step includes a surface treatment step of applying a surface treatment solution containing at least a titanium alkoxide and a diketone-containing solvent on the conductive layer and then baking the surface treatment solution. A method for producing a solar cell.   The first electrode forming step includes a porous oxide semiconductor layer forming step of forming the porous oxide semiconductor layer on the conductive layer before the surface treatment step, and in the surface treatment step, at least the The method for producing a dye-sensitized solar cell according to claim 9, wherein the surface treatment solution is applied on the conductive layer and the porous oxide semiconductor layer.   The first electrode forming step further includes a wiring portion forming step of forming a wiring portion on the conductive layer before the surface treatment step, and in the surface treatment step, at least on the conductive layer and the wiring portion. The method for producing a dye-sensitized solar cell according to claim 9 or 10, wherein the surface treatment solution is applied.   The method for producing a dye-sensitized solar cell according to any one of claims 9 to 11, wherein in the solvent, a molar ratio of the titanium alkoxide to the diketone is 0.5 to 3.   The method for producing a dye-sensitized solar cell according to claim 12, wherein in the solvent, the molar ratio of the titanium alkoxide to the diketone is 1-2. The method for producing a dye-sensitized solar cell according to any one of claims 9 to 13, wherein the porous oxide semiconductor layer is made of titanium oxide.

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