JP2014165064A - Dye-sensitized solar cell, manufacturing method of the same and electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell which is suitable when a complicated and minute seal pattern having crossing parts is formed; and provide a manufacturing method of the dye-sensitized solar cell and an electronic apparatus.SOLUTION: A dye-sensitized solar cell comprises: a first substrate 20; a first electrode 10 arranged on the first substrate 20; a porous semiconductor layer 12 which is arranged on the first electrode 10 and includes semiconductor fine particles and dye molecules; an electrolysis solution which contacts the porous semiconductor layer 12 and in which an oxidation-reduction electrolyte is soluble in a solvent; a catalysis layer 19 which contacts the electrolysis solution; a second electrode 18 arranged on the catalyst layer 19; a second substrate 22 arranged on the second electrode 18; and a seal material 16 arranged between the first substrate 20 and the second substrate 22, for sealing the electrolysis solution. By burning the seal material 16, the first substrate 20 and the second substrate 22 are bonded.

Description

  The present invention relates to a dye-sensitized solar cell (DSC), a method for producing the same, and an electronic apparatus, and particularly, a dye suitable for forming a fine and complicated sealing pattern having an intersection. The present invention relates to a sensitized solar cell, a manufacturing method thereof, and an electronic device.

  In recent years, DSC has attracted attention as an inexpensive and high-performance solar cell. DSC was developed by Grezell of Lausanne University of Technology in Switzerland, and has the advantages of high photoelectric conversion efficiency and low manufacturing cost by using titanium oxide carrying a sensitizing dye on the surface. It is expected as a solar cell of the next generation. This solar cell is also called a wet solar cell because an electrolyte is sealed inside.

  DSC is packed between a working electrode having a porous titanium oxide layer carrying a sensitizing dye on its surface, a counter electrode disposed opposite the titanium oxide layer of the working electrode, and the working electrode and the counter electrode. An electrolyte solution (see, for example, Patent Document 1).

  Further, as a sealing material that is between the working electrode and the counter electrode and seals the electrolyte solution, an ultraviolet curable resin that is cured by ultraviolet irradiation is widely used.

  For example, Patent Document 2 describes DSC using an ultraviolet curable epoxy resin as a sealing material.

JP-A-11-135817 JP 2000-30767

  By the way, when the shape of the DSC cell becomes complicated, the pattern of the sealing material (sealing pattern) also becomes complicated. That is, instead of a one-stroke-shaped sealing pattern, a sealing pattern in which the sealing materials intersect with each other in a cross road shape or a sealing pattern overlapping with a T-shaped road shape is also required.

  Furthermore, in addition to the complicated pattern as described above, the sealing line width may be considerably fine depending on the application application. In such a case, when a sealing material made of a conventional ultraviolet curable resin is selected, the curing failure and the adhesion to the substrate may be significantly weakened, and it becomes very difficult to obtain long-term stability in DSC.

  An object of the present invention is to provide a dye-sensitized solar cell suitable for forming a fine and complicated sealing pattern having an intersecting portion, a manufacturing method thereof, and an electronic apparatus.

  According to one aspect of the present invention for achieving the above object, a first substrate, a first electrode disposed on the first substrate, a semiconductor fine particle and a dye molecule disposed on the first electrode, A porous semiconductor layer comprising: an electrolyte solution in contact with the porous semiconductor layer and having a redox electrolyte dissolved in a solvent; a catalyst layer in contact with the electrolyte solution; a second electrode disposed on the catalyst layer; A second substrate disposed on the second electrode; and a sealing material that is disposed between the first substrate and the second substrate and seals the electrolytic solution, and firing the sealing material. Thus, a dye-sensitized solar cell in which the first substrate and the second substrate are bonded together is provided.

  According to another aspect of the present invention, a step of patterning a first electrode on a first substrate, a step of forming a porous semiconductor layer on the first electrode, and a second electrode on a second substrate A step of forming a pattern, a step of forming a catalyst layer on the second electrode, a step of forming a sealing material on at least one of the first substrate and the second substrate, and the sealing A step of bonding the first substrate and the second substrate by firing a material, and a step of adsorbing a dye to the porous semiconductor layer after bonding the first substrate and the second substrate; There is provided a method for producing a dye-sensitized solar cell, which comprises a step of adsorbing the dye and then encapsulating an electrolyte in the DSC cell.

  According to another aspect of the present invention, an electronic apparatus equipped with the dye-sensitized solar cell is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the dye-sensitized solar cell suitable for the case where the fine and complicated sealing pattern which has an intersection part is formed, its manufacturing method, and an electronic device can be provided.

The typical bird's-eye view of DSC which concerns on embodiment. FIG. 2 is a schematic bird's-eye view showing a state in which the DSC is housed in a vacuum chamber, which is a process of the DSC shown in FIG. 1. FIG. 2 is a schematic cross-sectional structure diagram taken along line II-II in FIG. 1. The typical bird's-eye view of DSC which concerns on a comparative example. The typical bird's-eye view of another DSC which concerns on a comparative example. FIG. 5 is a schematic cross-sectional structure diagram taken along line II in FIG. 4. In the DSC manufacturing method according to the comparative example, (a) a process diagram for forming a first electrode on a first substrate, (b) a porous semiconductor layer on the first electrode after the process of FIG. (C) Process diagram for forming the second electrode on the second substrate, (d) Process chart for forming the catalyst layer on the second electrode after the process of FIG. 7 (c). It is a manufacturing method of DSC which concerns on a comparative example, Comprising: (a) Process drawing which forms a sealing material on the 1st board | substrate after the process of FIG.7 (b), (b) After the process of FIG.7 (d) Process drawing which forms a sealing material on a 2nd board | substrate. It is a DSC manufacturing method according to a comparative example, (a) a process diagram for adsorbing a dye to the porous semiconductor layer after the process of FIG. 8 (a), (b) a first process after the process of FIG. 9 (a). FIG. 8B is a process diagram in which the substrate and the second substrate after the process of FIG. 8B are opposed to each other and bonded together by laser irradiation. FIG. 9C is a process of encapsulating an electrolyte in the DSC cell after the process of FIG. Figure. It is a manufacturing method of DSC which concerns on embodiment, Comprising: (a) Process drawing which forms 1st electrode on 1st board | substrate, (b) Porous semiconductor on 1st electrode after process of Fig.10 (a) FIG. 11 is a process chart for forming a layer, (c) a process chart for forming a second electrode on the second substrate, and (d) a process chart for forming a catalyst layer on the second electrode after the process of FIG. It is a manufacturing method of DSC which concerns on embodiment, Comprising: (a) Process drawing which forms a sealing material on the 1st board | substrate after the process of FIG.10 (b), (b) After the process of FIG.10 (d) Process drawing which forms a sealing material on the second substrate. It is a manufacturing method of DSC which concerns on embodiment, Comprising: (a) Process drawing to adsorb | suck pigment | dye to the porous semiconductor layer after the process of FIG.10 (b), (b) The process after the process of FIG.11 (a) FIG. 12 is a process diagram in which one substrate and a second substrate after the process of FIG. It is a manufacturing method of DSC which concerns on embodiment, Comprising: (a) Process drawing which bonds a 1st board | substrate and a 2nd board | substrate by baking the sealing material after the process of FIG.12 (b), (b). FIG. 14 is a process diagram for adsorbing a dye to the porous semiconductor layer after the process of FIG. It is a DSC manufacturing method according to the embodiment, (a) a process diagram in which an electrolytic solution is sealed in the DSC cell after the process of FIG. 13 (b), and (b) a modification of the process of FIG. 12 (b). FIG. It is a typical plane pattern block diagram of the sealing pattern formed in DSC which concerns on embodiment, Comprising: (a) Rectangular sealing pattern, (b) Flower-shaped sealing pattern, (c) Circular sealing pattern (D) A butterfly-shaped sealing pattern. The typical plane pattern block diagram of another sealing pattern formed in DSC which concerns on embodiment. The typical plane pattern block diagram of DSC which concerns on embodiment. FIG. 18 is a schematic cross-sectional structure diagram taken along line III-III in FIG. 17. FIG. 18 is a schematic cross-sectional structure diagram taken along line IV-IV in FIG. 17. FIG. 18 is a schematic sectional view taken along line VV in FIG. 17. FIG. 18 is an enlarged schematic plane pattern configuration diagram of an A part in FIG. 17. The typical structure figure of the semiconductor fine particle of the porous semiconductor layer of DSC which concerns on embodiment. Explanatory drawing of the principle of operation of the DSC according to the embodiment. The operation principle explanatory drawing based on the charge exchange reaction in the electrolyte solution of DSC which concerns on embodiment. In DSC which concerns on embodiment, the energy potential diagram between a porous semiconductor layer (13) / pigment molecule | numerator (32) / electrolyte solution (14). In DSC which concerns on embodiment, it is an energy potential diagram between dye molecule (32) / electrolyte (14), Comprising: The enlarged view of the J section of FIG. Explanatory drawing which shows the energy level and electric power generation cycle of each component material of DSC which concern on embodiment. The chemical structural formula which shows the pigment | dye used for DSC which concerns on embodiment, Comprising: (a) Chemical structural formula which shows D149, (b) Chemical structural formula which shows N719, (c) Chemical structural formula which shows D131. The chemical structural formula which shows another pigment | dye used for DSC which concerns on embodiment, Comprising: (a) Chemical structural formula which shows a phthalocyanine type pigment | dye, (b) Chemical structural formula which shows a porphyrin pigment | dye. (A) In DSC which concerns on embodiment, the schematic cross-section figure which has arrange | positioned four basic cells in series structure, (b) The schematic circuit representation of Fig.30 (a). (A) In DSC which concerns on embodiment, the typical cross-section figure which has arrange | positioned four basic cells in parallel structure, (b) The typical circuit expression of Fig.31 (a). The top view which is 1 process of the manufacturing method of DSC which concerns on embodiment, Comprising: The state in which the some internal 1st electrode was formed on the 1st board | substrate. The top view which is 1 process of the manufacturing method of DSC which concerns on embodiment, Comprising: The several internal 2nd electrode was formed on the 2nd board | substrate. The top view which is 1 process of the manufacturing method of DSC which concerns on embodiment, and shows the state which bonded together the 1st board | substrate and the 2nd board | substrate through the sealing material. FIG. 35 is a schematic cross-sectional structure diagram taken along the line VI-VI in FIG. 34, which is one step of the DSC manufacturing method according to the embodiment. The top view which shows 1 step of the manufacturing method of DSC which concerns on embodiment, Comprising: The state which formed the scribe line of the horizontal direction. The top view which is 1 process of the manufacturing method of DSC which concerns on embodiment, and shows the state which formed the scribe line of the vertical direction further. (A) The top view which shows the structure which formed three cells of DSC which concern on embodiment, (b) The explanatory view which shows the state which connected the three cells in series. (A) Schematic diagram showing a state in which five DSC cells according to the embodiment are connected in series, (b) an explanatory diagram of FIG. 39 (a), (c) a plane showing an example of the configuration of FIG. 39 (a) Figure. (A) The schematic diagram which shows the state which laminated | stacked the cell of n of DSC which concerns on embodiment, and the tandem structure, (b) Explanatory drawing of Fig.40 (a). (A) The schematic diagram which shows the state which connected the thing which laminated | stacked the cell of n DSC which concerns on embodiment, and the tandem structure in parallel, (b) Explanatory drawing of Fig.41 (a). The top view which shows the structural example of the remote control device carrying DSC which concerns on embodiment. The side view of the remote control device carrying DSC which concerns on embodiment. The side view which shows the other structural example of the remote control device carrying DSC which concerns on embodiment. The bird's-eye view which shows the structural example of the desktop digital timepiece carrying DSC which concerns on embodiment. (A) Bird's-eye view which shows the state which opened the electronic notebook which mounts DSC which concerns on embodiment, (b) The bird's-eye view which shows the closed state. The bird's-eye view which shows the state which opened the electronic dictionary carrying DSC which concerns on embodiment.

  Next, embodiments will be described with reference to the drawings. In the following description of the drawings, the same or similar parts are denoted by the same or similar reference numerals. However, it should be noted that the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. Therefore, specific thicknesses and dimensions should be determined in consideration of the following description. Moreover, it is a matter of course that portions having different dimensional relationships and ratios are included between the drawings.

  Further, the embodiments described below exemplify apparatuses and methods for embodying the technical idea of the present invention, and the embodiments of the present invention include the material, shape, structure, The layout is not specified as follows. Various modifications can be made to the embodiment of the present invention within the scope of the claims.

  In the DSC according to the following embodiment, “transparent” is defined as a transmittance of about 50% or more. In addition, “transparent” is also used to mean colorless and transparent to visible light in the DSC according to the embodiment. Visible light corresponds to a wavelength of about 360 nm to 830 nm and an energy of about 3.45 eV to 1.49 eV, and is transparent if the transmittance is 50% or more in this region.

[Embodiment]
(DSC: embodiment)
A schematic bird's-eye view configuration of the DSC 200 according to the embodiment is expressed as shown in FIG. A schematic bird's-eye view configuration, which is a process of manufacturing the DSC 200 shown in FIG. 1 and shows the state in which the DSC 200 is housed in the vacuum chamber 500, is expressed as shown in FIG. Moreover, the schematic cross-sectional structure along the II-II line of FIG. 1 is represented as shown in FIG.

  As shown in FIGS. 1 to 3, the DSC 200 according to the embodiment includes a first substrate 20, a first electrode 10 disposed on the first substrate 20, and a porous disposed on the first electrode 10. An electrolyte solution 14 (not shown) in contact with the semiconductor layer 12, the porous semiconductor layer 12, and a redox electrolyte dissolved in a solvent, a catalyst layer 19 in contact with the electrolyte solution 14, and a first electrode disposed on the catalyst layer 19. Two electrodes 18, a second substrate 22 disposed on the second electrode 18, and a sealing material 16 disposed between the first substrate 20 and the second substrate 22 and sealing the electrolytic solution 14. . The first substrate 20 and the second substrate 22 are bonded together by baking the sealing material 16. Specifically, as shown in FIG. 3, the contact portions 16H of the sealing materials 16A and 16B are thermally welded and cured. Thereafter, the dye Dye is adsorbed on the porous semiconductor layer 12. Specifically, as shown in FIG. 2, a high-boiling organic solvent 600 mixed with the dye Dye is housed in a vacuum chamber 500, and a DSC cell is immersed in the organic solvent 600 (described later). After the dye Dye is adsorbed in this way, the electrolytic solution 14 is sealed inside the DSC cell. Hereinafter, the porous semiconductor layer 12 after the dye Dye is adsorbed may be referred to as “porous semiconductor layer 13”.

  The sealing materials 16, 16 A, and 16 B can be configured by glass frit, thermosetting resin, or a structural combination thereof. Hereinafter, the case where a glass frit is used as the sealing material 16, 16A, 16B will be exemplified, and the same reference numerals 16, 16A, 16B are also used for the glass frit.

  Moreover, the 1st board | substrate 20 or the 2nd board | substrate 22 can be formed with a glass substrate etc., for example. In order to irradiate light, it is desirable that the first substrate 20 and the second substrate 22 are transparent to the irradiation light (white light). An antireflection film or the like may be coated on the light incident side of the first substrate 20 and the second substrate 22.

The first electrode 10 and second electrode 18, for example, ITO, FTO, ZnO, is formed of a transparent electrode such as SnO _2. Electrodes may be processed on the first substrate 10 and the second electrode 18 to form a substrate with FTO, a substrate with a grid such as metal, or the composite substrate described above.

The porous semiconductor layer 12 may be formed using a material such as TiO ₂ , ZnO, WO ₃ , InO ₃ , Nb ₂ O ₃ , SnO ₂ . In particular, TiO ₂ (anatase type, rutile type) which is inexpensive from the viewpoint of efficiency is mainly used. The porous semiconductor layer 12 can be formed using, for example, screen printing technology, spin coating technology, dipping, spray coating technology, or the like.

  Further, the catalyst layer 19 may be made of, for example, Pt, carbon, or a conductive polymer. The conductive polymer may be made of, for example, PEDOT: PSS.

  Further, as the electrolytic solution 14, γ-butyrolactone, propylene carbonate, ethylene carbonate, propylene carbonate, or the like can be used. In some cases, acetonitrile, methoxyacetonitrile, propionitrile, or the like may be used.

  As the dye Dye, red dye (N719), black dye (N749), D131, phthalocyanine dye, porphyrin dye, and the like can be applied.

(DSC: comparative example)
A schematic bird's-eye view configuration of the DSC 200A according to the comparative example is expressed as shown in FIG. A schematic bird's-eye view configuration of another DSC 200B according to the comparative example is expressed as shown in FIG. Further, a schematic cross-sectional structure taken along line II in FIG. 4 is expressed as shown in FIG.

  As shown in FIGS. 4 to 6, the DSCs 200 </ b> A and 200 </ b> B according to the comparative example are disposed on the first substrate 20, the first electrode 10 disposed on the first substrate 20, and the first electrode 10. A porous semiconductor layer 13 comprising fine particles and dye molecules; an electrolyte solution 14 (not shown) in contact with the porous semiconductor layer 13 and having a redox electrolyte dissolved in a solvent; a catalyst layer 19 in contact with the electrolyte solution 14; The second electrode 18 disposed on the layer 19, the second substrate 22 disposed on the second electrode 18, and disposed between the first substrate 20 and the second substrate 22 to seal the electrolytic solution 14. Sealing material 16 to be provided. As shown in FIGS. 4 and 6, the glass frits 16A and 16B are opposed to each other and irradiated with a laser beam hν. Thereby, the glass frit 16A * 16B can be thermally welded and cured, and the first substrate 20 and the second substrate 22 can be bonded together.

  In FIG. 4, a one-stroke writing sealing pattern is illustrated, but in an actual application, as shown in FIG. 5, the sealing pattern usually overlaps (intersects) and becomes a complicated sealing pattern. is there. In such a case, when the glass frit 16 is irradiated with the laser beam hν, heat concentrates at a portion where the glass frit 16 overlaps to generate a “heat pool”, and the first substrate 20 disposed under the glass frit 16. -Damage to the second substrate 22. In addition, there is a possibility that cracks such as microcracks due to “heat accumulation” may occur on the glass frit itself.

In addition, when the laser beam hν is irradiated in this way, there is a limit to miniaturization because the interval between the sealing patterns is determined based on an error in irradiation.

(Manufacturing method: Comparative example)
The manufacturing method of DSC 200A / 200B according to the comparative example is expressed as shown in FIGS. 7 (a) to 9 (c).

First, as shown in FIG. 7A, the first electrode 10 is pattern-formed on the first substrate 20. The 1st board | substrate 20 can be comprised with a glass substrate, and can also use the glass substrate with a transparent electrode in which the transparent electrode was formed in the whole surface. The first electrode 10 can be formed by subjecting an ITO fine particle-containing film to be applied by screen printing to air sintering and heat treatment in an N ₂ atmosphere. If the glass substrate has a transparent electrode, it can be formed by various etching methods. A pattern can also be formed.

  Next, as shown in FIG. 7B, the porous semiconductor layer 12 is formed on the first electrode 10 after the step of FIG. The porous semiconductor layer 12 can be formed by applying screen printing or the like.

On the other hand, as shown in FIG. 7C, the second electrode 18 is patterned on the second substrate 22. Similar to the first substrate 20, the second substrate 22 can be composed of a glass substrate or the like. Similar to the first electrode 10, the second electrode 18 can be formed by subjecting an ITO fine particle-containing film applied by screen printing to air sintering and heat treatment in an N ₂ atmosphere.

  Next, as shown in FIG. 7D, a catalyst layer 19 is formed on the second electrode 18 after the step of FIG. The catalyst layer 19 can be formed by screen printing or the like.

  Next, as shown in FIG. 8A, a glass frit 16A is formed on the first substrate 20 after the step of FIG. 7B. Similarly, as shown in FIG. 8B, a glass frit 16B is formed on the second substrate 22 after the step of FIG.

  Next, as shown in FIG. 9A, the dye Dye is adsorbed to the porous semiconductor layer 12 formed on the first substrate 20 after the step of FIG. 8A.

  Next, as shown in FIG. 9B, the first substrate 20 after the step of FIG. 9A and the second substrate 22 after the step of FIG. 16B is irradiated with a laser beam hν. Thereby, the glass frit 16A * 16B can be thermally welded and cured, and the first substrate 20 and the second substrate 22 can be bonded together.

  Finally, as shown in FIG. 9C, the electrolytic solution 14 is sealed inside the opening (described later), the opening is sealed, and a DSC cell is formed.

(Manufacturing method: embodiment)
The DSC 200 manufacturing method according to the embodiment includes a step of patterning the first electrode 10 on the first substrate 20, a step of forming the porous semiconductor layer 12 on the first electrode 10, and the second substrate 22. The step of patterning the second electrode 18, the step of forming the catalyst layer 19 on the second electrode 18, and the sealing material 16 on at least one of the first substrate 20 and the second substrate 22 A step of forming, a step of bonding the first substrate 20 and the second substrate 22 by baking the sealing material 16, a step of bonding the first substrate 20 and the second substrate 22, and a porous semiconductor layer 12 has a step of adsorbing the dye Dye and a step of encapsulating the electrolyte solution 14 inside the DSC cell after adsorbing the dye Dye.

  For example, the step of adsorbing the dye Dye is performed by immersing the DSC cell in the high boiling point organic solvent 600 mixed with the dye Dye.

  The organic solvent 600 is preferably an organic solvent having a boiling point higher than 60 ° C. Specifically, γ-butyrolactone, propylene carbonate, ethylene carbonate, propylene carbonate, or the like can be used. In some cases, acetonitrile, methoxyacetonitrile, propionitrile, or the like may be used.

  The organic solvent 600 may be heated to 40 ° C to 50 ° C.

  The organic solvent 600 may be formed by dissolving the dye Dye in the organic solvent used when the electrolytic solution 14 is manufactured.

  Further, the organic solvent 600 may be vacuum-injected through an opening for injecting the electrolytic solution 14.

  In addition, the step of bonding the first substrate 20 and the second substrate 22 is performed by heating the sealing material 16 to a temperature (for example, about 200 ° C. to about 600 ° C.) at which the sealing material 16 is dissolved. Also good.

  Hereinafter, a method for manufacturing the DSC 200 according to the embodiment will be described in detail with reference to the drawings. The manufacturing method of DSC 200 according to the embodiment is expressed as shown in FIGS.

First, as shown in FIG. 10A, the first electrode 10 is pattern-formed on the first substrate 20. The 1st board | substrate 20 can be comprised with a glass substrate etc., and can also use the glass substrate with a transparent electrode in which the transparent electrode was formed in the whole surface. The first electrode 10 can be formed by subjecting an ITO fine particle-containing film to be applied by screen printing to air sintering and heat treatment in an N ₂ atmosphere. If the glass substrate has a transparent electrode, it can be formed by various etching methods. A pattern can also be formed.

  Next, as shown in FIG. 10B, the porous semiconductor layer 12 is formed on the first electrode 10 after the step of FIG. The porous semiconductor layer 12 can be formed by applying screen printing or the like.

On the other hand, as shown in FIG. 10C, the second electrode 18 is patterned on the second substrate 22. Similar to the first substrate 20, the second substrate 22 can be composed of a glass substrate or the like. Similar to the first electrode 10, the second electrode 18 can be formed by subjecting an ITO fine particle-containing film applied by screen printing to air sintering and heat treatment in an N ₂ atmosphere.

  Next, as shown in FIG. 10D, a catalyst layer 19 is formed on the second electrode 18 after the step of FIG. The catalyst layer 19 can be formed by screen printing or the like.

  Next, as shown in FIG. 11A, a glass frit 16A is formed on the first substrate 20 after the step of FIG. Similarly, as shown in FIG. 11B, a glass frit 16B is formed on the second substrate 22 after the step of FIG.

  In addition, as shown to Fig.12 (a), you may make the pigment | dye Dye adsorb | suck to the porous semiconductor layer 12 formed in the 1st board | substrate 20 after the process of FIG.10 (b). Thereafter, similarly to FIG. 11A, a glass frit 16A is formed on the first substrate 20 after the step of FIG. However, in this case, there is a possibility that the dye Dye is denatured by heat during heating in a later step (described later).

  Next, as shown in FIG. 12B, the first substrate 20 after the step of FIG. 11A and the second substrate 22 after the step of FIG. Or it heats from the one side of the 2nd board | substrate 22 to the temperature (for example, about 200 degreeC-about 600 degreeC) which the sealing material 16A and the sealing material 16B melt | dissolve using heating apparatuses, such as the hotplate 21. FIG. The DSC 200 may be housed in a heating device such as an oven and heated so that the atmosphere inside the oven reaches a temperature (for example, about 200 ° C. to about 600 ° C.) at which the sealing material 16A and the sealing material 16B are dissolved. . Accordingly, as shown in FIG. 13A, the glass frit 16A / 16B is thermally welded and cured, and the first substrate 20 and the second substrate 22 can be bonded together.

  Next, as shown in FIG. 13B, the dye Dye is adsorbed to the porous semiconductor layer 12 after the step of FIG. A method for adsorbing the dye Dye to the porous semiconductor layer 12 will be described in detail later.

  Finally, as shown in FIG. 14A, the electrolytic solution 14 is sealed inside the opening, the opening is sealed, and a DSC cell is formed.

  FIG. 12B illustrates a configuration in which the glass frit 16A is formed on the first substrate 20 and the glass frit 16B is formed on the second substrate 22, but this embodiment is not limited thereto. It is not something. That is, when the second substrate 22 is a glass substrate, the glass frit 16B may not be provided as shown in FIG. Even without the glass frit 16B, the glass frit 16A on the first substrate 20 side and the second substrate 22 are made of the same material, and therefore can be easily heat-welded using a heating device such as the hot plate 21. Conversely, when the first substrate 20 is a glass substrate, it is needless to say that the glass frit 16A is not necessary. Subsequent steps proceed in the order of FIG. 13A, FIG. 13B, and FIG.

(Dye adsorption)
Hereinafter, a method for adsorbing the dye Dye to the porous semiconductor layer 12 will be described in more detail.

  First, as shown in FIG. 2, the organic solvent 600 mixed with the dye Dye is accommodated in the vacuum chamber 500, and the DSC 200 is accommodated therein. A vacuum valve 500 a connected to a vacuum pump (not shown) is formed in the housing of the vacuum chamber 500. The vacuum valve 500a is opened to operate the vacuum pump, the inside of the vacuum chamber 500 is reduced to a pressure lower than the atmospheric pressure, and the organic solvent 600 is circulated. Subsequently, when the inside of the vacuum chamber 500 is returned to the atmospheric pressure, the organic solvent 600 is exposed to the atmospheric pressure while the reduced pressure state between the first substrate 20 and the second substrate 22 of the DSC 200 is maintained. Due to this pressure difference, the organic solvent 600 is pushed to atmospheric pressure, the organic solvent 600 is injected from the opening of the DSC 200, and the dye Dye is adsorbed on the porous semiconductor layer 12. At this time, when the organic solvent 600 is heated to about 50 ° C. to 60 ° C., the adsorption rate of the dye Dye can be increased. Thereafter, the organic solvent 600 in the vacuum chamber 500 is replaced with the electrolytic solution 14, and the electrolytic solution 14 is injected into the DSC cell from the opening of the DSC 200 in the same manner.

  The organic solvent 600 is a high boiling point organic solvent in which the dye Dye is mixed. The high boiling point type organic solvent here is an organic solvent having a boiling point higher than 60 ° C. Specifically, γ-butyrolactone, propylene carbonate, ethylene carbonate, propylene carbonate, or the like can be used. In some cases, it may be composed of acetonitrile, methoxyacetonitrile, propionitrile, or the like.

  If the high boiling point type organic solvent 600 is used, the organic solvent 600 can be heated to about 50 ° C. to 60 ° C. to increase the adsorption rate of the dye Dye. Such an organic solvent 600 may be formed by dissolving the dye Dye in an organic solvent used when the electrolytic solution 14 is manufactured.

  Here, the description is made on the assumption that the organic solvent 600 is completely removed from the vacuum chamber 500 and then the electrolytic solution 14 is injected, but the present embodiment is not limited to this. That is, the electrolytic solution 14 may be injected while removing the organic solvent 600 from the vacuum chamber 500. Alternatively, if the organic solvent 600 that also serves as the electrolytic solution 14 is used, the organic solvent 600 can be continuously used without removing the organic solvent 600 from the vacuum chamber 500.

(Sealing pattern)
A schematic planar pattern configuration of the sealing pattern formed in the DSC 200 according to the embodiment is expressed as shown in FIG. For example, FIG. 15A is a schematic plane pattern configuration diagram of a rectangular sealing pattern. As shown in FIG. 15A, in a rectangular part B, two linear sealing materials 16 overlap the T-junction shape to form an overlapping portion 16C. FIG. 15B is a schematic plane pattern configuration diagram of a flower-shaped sealing pattern. As shown in FIG.15 (b), the lower end of the sealing material 16 which forms five petals, and the upper end of the sealing material 16 which forms a stem overlap. FIG. 15C is a schematic plane pattern configuration diagram of a circular sealing pattern. As shown in FIG. 15C, the sealing materials 16 forming four circles having different sizes are overlapped at the respective lower ends. FIG. 15D is a schematic plane pattern configuration diagram of a butterfly-shaped sealing pattern. As shown in FIG. 15 (d), the sealing material 16 forming one wing overlaps with the sealing material 16 forming the other wing in a cross-road shape.

  DSC 200 according to the embodiment may include a plurality of DSC cells. Here, the plurality of DSC cells are in contact with the first substrate 20 and the second substrate 22, and the first substrate 20 and the second substrate 22, and are partitioned by the sealing material 16 in a plan view and intersecting each other. It may be sealed with the sealing material 16 provided. Moreover, the intersection may include any of a three-way intersection, a crossroad, or a plurality of overlapping portions. For example, the intersection of the pattern of the sealing material 16 shown in FIGS. 15A and 15D has a three-way. Moreover, the intersection part of the pattern of the sealing material 16 shown in FIG. 15B and FIG. 15C has a plurality of overlapping portions in which a plurality of patterns overlap.

  Even when a complicated sealing pattern having such an intersection is formed, according to the method of firing the sealing material 16, heat accumulation is caused by the overlapping portion 16C of the sealing material 16 as in the case of laser irradiation. It does not occur and can cope with sealing patterns with a narrow pitch.

  A schematic planar pattern configuration of another sealing pattern formed in the DSC 200 according to the embodiment is expressed as shown in FIG. As shown in FIG. 16, a sealing pattern in which five rings 30 </ b> A to 30 </ b> E are connected is formed by connecting a circular sealing material 16 to another circular sealing material 16. In each cell region partitioned by the five rings 30A to 30E, the porous semiconductor layer 13 to which the dye Dye is adsorbed is disposed. These dyes Dye may be the same in all cell regions, or may be different for each cell region. The intersection of the pattern of the sealing material 16 shown in FIG. 16 has a cross.

  As described above, according to the embodiment, it is possible to provide a dye-sensitized solar cell suitable for forming a complicated sealing pattern having an intersection and a method for manufacturing the same. That is, since the first substrate 20 and the second substrate 22 are bonded together by firing the sealing material 16, heat accumulation does not occur in the overlapping portion 16 </ b> C of the sealing material 16, and sealing with a narrow pitch is performed. It is also possible to handle stop patterns. In addition, since the dye Dye is adsorbed to the porous semiconductor layer 12 after the sealing material 16 is baked, the dye Dye is not altered by heat during heating. In addition, the method of firing the sealing material 16 as described above can shorten the process time as compared with the laser irradiation method, and has an effect that it is suitable for mass production of the DSC 200.

〔Concrete example〕
Hereinafter, a specific example of the DSC 200 according to the embodiment will be described in detail. Of course, also in the DSC 200 illustrated below, the first substrate 20 and the second substrate 22 can be bonded together by baking the sealing material 16.

(DSC: embodiment)
A schematic planar pattern configuration of the DSC 200 according to the embodiment is expressed as shown in FIG. 17, and a schematic cross-sectional structure taken along line III-III in FIG. 17 is expressed as shown in FIG. A schematic cross-sectional structure along line IV-IV is represented as shown in FIG. 19, and a schematic cross-sectional structure along line VV in FIG. 17 is represented as shown in FIG. An enlarged schematic plane pattern configuration is expressed as shown in FIG.

  As shown in FIGS. 17 to 21, the DSC 200 according to the embodiment is disposed on the first substrate 20, the internal first electrode 10 </ b> A disposed on the first substrate 20, and the internal first electrode 10 </ b> A. On the porous semiconductor layer 13, an electrolytic solution 14 in contact with the porous semiconductor layer 13, a redox electrolyte dissolved in a solvent, an internal second electrode (counter electrode) 18 A in contact with the electrolytic solution 14, and the internal second electrode 18 The second substrate 22 is disposed, and the sealing material 16 is disposed between the first substrate 20 and the second substrate 22 and seals the electrolytic solution 14.

  In addition, as shown in FIGS. 17 to 21, the DSC 200 according to the embodiment includes an external first electrode 10 </ b> B disposed on the first substrate 20 outside the sealing material 16, and an outside of the sealing material 16. An external second electrode 18B disposed on the second substrate 22 may be provided.

  Moreover, as shown in FIGS. 17 to 21, the DSC 200 according to the embodiment injects the electrolytic solution 14 into the cell region sandwiched between the first substrate 20 and the second substrate 22 and surrounded by the sealing material 16. The internal first electrode 10A and the external first electrode 10B may be patterned on the first substrate 20 and connected to each other at the opening.

  The internal second electrode 18A and the external second electrode 18B may be patterned on the second substrate 22 and connected to each other at the opening.

  Moreover, you may provide the opening part sealing material 3b which seals an opening part, and the cap sealing material 3a which is arrange | positioned at an opening part and couple | bonds the sealing material 16 and the opening part sealing material 3b.

  In the DSC 200 according to the embodiment, the sealing material 16 is in contact with the first substrate 20 and the second substrate 22 as shown in FIGS.

  The inner first electrode 10A and the outer first electrode 10B are electrically connected in the vicinity of the opening for injecting the electrolyte solution 14, as shown in FIGS.

  As shown in FIGS. 17 and 19 to 21, the internal second electrode 18 </ b> A and the external second electrode 18 </ b> B are in the vicinity of the opening for injecting the electrolytic solution 14 and in the vicinity of the opening for injecting the electrolytic solution 14. Electrically connected.

  Moreover, the sealing material 16 is not in contact with the internal first electrode 10A and the internal second electrode 18A, as shown in FIGS. On the other hand, as shown in FIGS. 17 to 21, the sealing material 16 is in contact with the external first electrode 10 </ b> B and the external second electrode 18 </ b> B in the vicinity of the opening for injecting the electrolytic solution 14.

  Further, as shown in FIGS. 17 and 19 to 21, the cap sealing material 3 a and the opening sealing material 3 b are connected to the first electrode 10 </ b> B and the second electrode 18 </ b> B in the opening for injecting the electrolytic solution 14. It may be in contact with the first electrode 10A and the second electrode 18A.

  Further, in the DSC 200 according to the embodiment, as shown in FIGS. 17 to 21, the surface of the internal second electrode 18 </ b> A may be provided with a catalyst layer 19 in contact with the electrolytic solution 14.

A schematic structure of the semiconductor fine particles 2 of the porous semiconductor layer 12 of the DSC 200 according to the embodiment is expressed as shown in FIG. As shown in FIG. 22, in the porous semiconductor layer 12, semiconductor fine particles 2 made of TiO ₂ or the like are bonded to each other to form a complex network. The dye molecules 4 are adsorbed on the surface of the semiconductor fine particles 2. A large number of pores having a size of about 100 nm or less exist in the porous semiconductor layer 12.

(Operating principle)
The operation principle of the DSC 200 according to the embodiment is expressed as shown in FIG.

  When the following reactions (a) to (d) occur continuously, an electromotive force is generated, and a current is conducted to the load 24.

(A) The dye molecule 32 absorbs a photon (hν), emits an electron (e ⁻ ), and the dye molecule 32 becomes an oxidized DO.

(B) The reduced redox electrolyte 26 represented by Re diffuses in the porous semiconductor layer 13 and approaches the oxidized dye molecule 32 represented by DO.

(C) Electrons (e ⁻ ) are supplied from the redox electrolyte 26 to the dye molecules 32. The redox electrolyte 26 becomes an oxidized redox electrolyte 28 represented by Ox, and the dye molecule 32 becomes a reduced dye molecule 30 represented by DR.

(D) The redox electrolyte 28 diffuses in the direction of the catalyst layer 19 and is supplied with electrons from the catalyst layer 19 to become a redox electrolyte 26 of a reductant represented by Re.

  The redox electrolyte 26 needs to approach the vicinity of the dye molecule 32 while diffusing in the complicated space in the porous semiconductor layer 13.

  The operation principle based on the charge exchange reaction in the electrolyte solution 14 of the DSC 200 according to the embodiment is expressed as shown in FIG.

First, when light is irradiated from the outside, photons (hν) react with the dye molecules 32, and the dye molecules 32 transition from the ground state to the excited state. The excited electrons (e ⁻ ) generated at this time are injected into the conduction band of the porous semiconductor layer 13 made of TiO ₂ . The electrons (e ⁻ ) conducted through the porous semiconductor layer 13 conduct the load 24 of the external circuit from the first electrode 10A and move to the second electrode 18A. Electrons (e ⁻ ) injected from the second electrode 18 </ b> A into the electrolytic solution 14 are charge-exchanged with the iodine redox electrolyte (I ⁻ / I ₃ ⁻ ) in the electrolytic solution 14. The iodine redox electrolyte (I ⁻ / I ₃ ⁻ ) diffuses in the electrolytic solution 14 and reacts with the dye molecules 32 again. Here, the charge exchange reaction proceeds according to 3I ⁻ → I ₃ ⁻ + 2e ^{− on the} surface of the dye molecule, and proceeds according to I ₃ ⁻ + 2e ⁻ → 3I ^{− on} the second electrode 18A.

The electrolytic solution 14 uses, for example, acetonitrile as a solvent, and as an electrolyte in this case, for example, iodine exists as an iodine redox electrolyte I ₃ ⁻ in the electrolytic solution 14. Further, as an electrolyte, for example, an iodide salt (lithium iodide, potassium iodide, etc.) exists as an iodine redox electrolyte I ⁻ in the electrolytic solution 14. Further, an additive (for example, TBP: tertiary butyl pyridine) may be applied to the electrolytic solution 14 as a reverse electron transfer inhibiting solution.

  The electrolytic solution 14 can be constituted by dissolving the above solute and additive in a solvent (acetonitrile). In addition, said material is applicable to DSC200 etc., Comprising material differs when using normal temperature molten salt (ionic liquid) and a solid electrolyte.

  In DSC 200 according to the embodiment, an energy potential diagram between the porous semiconductor layer (13) / the dye molecule (32) / the electrolyte solution (14) is expressed as shown in FIG. Moreover, it is an energy potential diagram between a dye molecule (32) / electrolyte solution (14), Comprising: The enlarged view of J part of FIG. 25 is represented as shown in FIG.

When irradiated with light from the outside, the dye molecule 32 changes from the ground state HOMO to the excited state LUMO by photons (hν). The excited electrons (e ⁻ ) generated at this time are injected into the conduction band of the porous semiconductor layer 13 made of TiO ₂ . The electrons (e ⁻ ) conducted through the porous semiconductor layer 13 conduct the load 24 of the external circuit from the first electrode 10A and move to the second electrode 18A. Electrons (e ⁻ ) injected from the catalyst layer 19 into the electrolytic solution 14 are exchanged with the redox electrolyte in the electrolytic solution 14. The redox electrolyte diffuses in the electrolytic solution 14 and reduces the dye molecules 32.

The potential difference between the oxidation-reduction level E _RO of the electrolytic solution 14 and the Fermi level E _f of the porous semiconductor layer 13 is the maximum electromotive force V _MAX . The value of the maximum electromotive force V _MAX varies depending on the redox electrolyte of the electrolytic solution 14. In the case of a single redox electrolyte system (iodine redox electrolyte), for example, 0.9 V (I, N719). When the electrolytic solution 14 contains a mixed redox electrolyte of iodine and bromine, as shown in FIG. 26, the redox potential of the mixed redox electrolyte is adjusted by adjusting the mixing ratio to oxidize the iodine redox electrolyte. It can be adjusted to any value between the reduction potential and the redox potential of the bromine redox electrolyte.

The energy level and power generation cycle of each constituent material of the DSC 200 according to the embodiment are expressed as shown in FIG. In FIG. 27, when irradiated with light from the outside, the electrons existing in the full band S ⁰ / S ⁺ of the dye (Dye) are excited by the conduction band S ^* by photons (hν), and the porous semiconductor layer 13 Electrons are injected into the conduction band E _C. Some of the electrons injected into the conduction band E _C are recombined and transition to the Dye full band S ⁰ / S ⁺ . The electrons (e ⁻ ) conducted through the porous semiconductor layer 13 conduct the load 24 of the external circuit from the first electrode 10A and move to the second electrode 18A. Electrons (e ⁻ ) injected from the catalyst layer 19 into the electrolytic solution 14 are exchanged with the redox electrolyte in the electrolytic solution 14. The redox electrolyte diffuses in the electrolyte solution 14 and reduces the dye molecules 32 in the Dye full zone S ⁰ / S ⁺ by electron injection. The potential difference V _OC between the oxidation-reduction level E _RO of the electrolytic solution 14 and the Fermi level E _f of the porous semiconductor layer 13 is the maximum electromotive force V _MAX .

  A chemical structural formula showing a dye used in the DSC 200 according to the embodiment, the chemical structural formula showing D149 is expressed as shown in FIG. 28A, and the chemical structural formula showing N719 is shown in FIG. The chemical structural formula represented as shown in b) and D131 is represented as shown in FIG.

  29 is a chemical structural formula showing another dye used in the DSC 200 according to the embodiment, and the chemical structural formula showing the purple dye is expressed as shown in FIG. 29A and shows a green dye (porphyrin dye). The chemical structural formula is represented as shown in FIG. Further, phthalocyanine dyes are known as general blue dyes. Of course, the dye Dye used in the DSC 200 according to the embodiment is not limited to these, and various dyes Dye can be appropriately selected.

-Series configuration-
In DSC 200 according to the embodiment, a schematic cross-sectional structure in which four basic cells are arranged in series is represented as shown in FIG. The schematic circuit representation of FIG. 30A is expressed as shown in FIG.

As shown in FIG. 30 (a), the basic cell includes a first substrate 20, internal first electrodes 10 ₁ A, 10 ₂ A, 10 ₃ A, and 10 ₄ A arranged on the first substrate 20, Porous semiconductor layers 13 ₁ , 13 ₂ , 13 _3, and 13 ₄ disposed on internal first electrodes 10 ₁ A, 10 ₂ A, 10 ₃ A, 10 ₄ A, and porous semiconductor layers 13 ₁ , 13 ₂ · 13 ₃ · 13 ₄ and in contact, with the electrolyte 14 _1, 14 _2, 14 _3, 14 ₄ dissolved redox electrolyte in a solvent, the electrolyte solution 14 _1, 14 _2, 14 _3, 14 inner contact with the ₄ second The electrode (counter electrode) 18 ₁ A, 18 ₂ A, 18 ₃ A, 18 ₄ A, and the second substrate 22 disposed on the internal second electrode 18 ₁ A, 18 ₂ A, 18 ₃ A, 18 ₄ A, And a sealing material 16 which is disposed between the first substrate 20 and the second substrate 22 and seals the electrolytes 14 ₁ , 14 ₂ , 14 ₃ and 14 ₄ .

In addition, as shown in FIG. 30A, the basic cell has external first electrodes 10 ₁ B · 10 ₂ B · 10 ₃ B · 10 ₄ arranged on the first substrate 20 outside the sealing material 16. B and external second electrodes 18 ₁ B, 18 ₂ B, 18 ₃ B, and 18 ₄ B disposed on the second substrate 22 outside the sealing material 16 may be provided.

Furthermore, the external first electrode 10 ₂ B and the external second electrode 18 ₁ B are formed between the first substrate 20 and the second substrate 22 along the external side wall of the sealing material 16 as shown in FIG. Are connected via a connection electrode 3A. Similarly, the external first electrode 10 ₃ B / external second electrode 18 ₂ B and the external first electrode 10 ₄ B / external second electrode 18 ₃ B are also connected via the connection electrode 3A.

As a result, as shown in FIG. 30 (b), the four basic cells are arranged in a series configuration.

Also in each basic cell shown in FIG. 30, the electrolytes 14 ₁ , 14 ₂ , 14 ₃ , 14 are sandwiched between the first substrate 20 and the second substrate 22 and surrounded by the sealing material 16. ₄ with an opening for injecting ₄ and the internal first electrodes 10 ₁ A, 10 ₂ A, 10 ₃ A, 10 ₄ A and the external first electrodes 10 ₁ B, 10 ₂ B, 10 ₃ B, 10 ₄ B A pattern is formed on the first substrate 20 and connected to each other at the opening.

The internal second electrodes 18 ₁ A, 18 ₂ A, 18 ₃ A, 18 ₄ A and the external second electrodes 18 ₁ B, 18 ₂ B, 18 ₃ B, 18 ₄ B are patterned on the second substrate 22. And are connected to each other at the opening.

In each basic cell shown in FIG. 30, the electrolytic solution 14 ₁ , 14 ₂ , 14 ₃ , 14 ₄ is formed on the surface of the internal second electrode 18 ₁ A, 18 ₂ A, 18 ₃ A, 18 ₄ A. The catalyst layers 19 ₁ , 19 ₂ , 19 _3, and 19 ₄ may be provided in contact therewith. Other configurations are the same as those of the DSC 200 according to the embodiment shown in FIGS.

―Parallel configuration―
In DSC 200 according to the embodiment, a schematic cross-sectional structure in which four basic cells are arranged in a parallel configuration is expressed as shown in FIG. The schematic circuit representation of FIG. 31A is expressed as shown in FIG.

The external first electrode 10 ₂ B and the external second electrode 18 ₁ B are arranged between the first substrate 20 and the second substrate 22 along the outer side wall of the sealing material 16 as shown in FIG. The insulating layer 3B is insulated. Similarly, the external first electrode 10 ₃ B / external second electrode 18 ₂ B and the external first electrode 10 ₄ B / external second electrode 18 ₃ B are also insulated via the insulating layer 3B. As a result, as shown in FIG. 31 (b), the four basic cells are arranged in a parallel configuration. Other configurations are the same as those of the DSC 200 according to the embodiment shown in FIGS.

(Manufacturing method of a plurality of DSCs)
In the DSC according to the embodiment, a method for manufacturing a plurality of DSC cells is a manufacturing method in which a plurality of (m × n: where m and n are integers) cells are formed and separated to obtain a plurality of DSCs 200. is there.

A step in the method of manufacturing the DSC according to the embodiment, the internal plurality of the first substrate 20 on the first electrode _{10 11 · 10 12 · ... ·} 10 1n · ... · 10 m1 · 10 m2 · ... · 10 A plan view showing a state where _mn is formed is expressed as shown in FIG. Here, the external first electrodes 10 ₁₁ , 10 ₁₂ ,..., 10 _1n ,..., 10 _m1 , 10 _{m2 ,.}

In the DSC manufacturing method according to the embodiment, a plurality of second electrodes 18 ₁₁ , 18 ₁₂ ,..., 18 _1n ,..., 18 _m1 , 18 _{m2 ,.} A plan view showing a state in which is formed is expressed as shown in FIG. Here, the external second electrodes 18 ₁₁ , 18 ₁₂ ,..., 18 _1n ,..., 18 _m1 , 18 _{m2 ,.}

  The top view which is 1 process of the manufacturing method of DSC which concerns on embodiment, Comprising: The 1st board | substrate (working electrode side) 20 and the 2nd board | substrate (counter electrode side) 22 bonded together through the sealing material 16 Is represented as shown in FIG. 34, and a schematic cross-sectional structure taken along line VI-VI in FIG. 34 is represented as shown in FIG. 34 and 35, the first substrate (working electrode side) 20 is arranged in the upward direction, and the second substrate (counter electrode side) is arranged in the downward direction.

  FIG. 36 is a plan view showing a state where the horizontal scribe line SL1 is formed, which is one step of the DSC manufacturing method according to the embodiment, and further forms the vertical scribe line SL2. A plan view showing this state is represented as shown in FIG.

  As shown in FIG. 35, there is a portion where only the substrate remains between the sealing materials 16, but this becomes a scribe line SL2, which is separated into each element by a break such as hitting.

  Next, in a state where a total of m × n DSCs are bonded as shown in FIG. 35, a horizontal scribe line SL1 is formed as shown in FIG.

  Specifically, each scribing line SL1 is formed by accurately aligning the scribing wheel of the scribing device at the position where the sealing material 16 is provided.

  Subsequently, as shown in FIG. 37, a vertical scribe line SL2 is formed.

  Then, when an impact is given along the scribe line SL1 and the scribe line SL2, etc., the glass material breaks along the scribe line SL1 and the scribe line SL2 and is separated into each element due to the wall opening property of the glass material.

  Although not shown in the figure, after being separated into each element, the electrolyte solution is injected, sealed by bonding of a glass plate, filling with resin, etc., and the DSC is treated by preventing the electrolyte solution from leaking out. Built.

  According to the embodiment, it is possible to provide a dye-sensitized solar cell with improved sealing adhesion and good sealing performance and a method for manufacturing the same.

(Application example)
-Battery cell-
Next, with reference to FIGS. 38 to 41, application examples of a battery cell (hereinafter simply referred to as “cell”) configured by the DSC 200 according to the embodiment will be described.

  FIG. 38A shows a state in which three cells B1 to B3 are formed. In the example of FIG. 38A, three cells B1, B2, and B3 having the same area are provided in the same substrate.

  The three cells B1 to B3 are connected in series by wiring (not shown) as shown in FIG. The total voltage V of the cells B1 to B3 is V = V1 + V2 + V3, and the total current amount I is I = I1 = I2 = I3.

  FIG. 39 shows a state in which five cells B1 to B5 are arranged in parallel.

  The five cells B1 to B5 are connected in series by wiring as shown in FIG. The total voltage V of the cells B1 to B5 is the sum 5E of the voltages of the cells B1 to B5.

  FIG. 40 schematically shows a state in which n cells are stacked in a tandem configuration. The n cells are connected in series as shown in FIG. The total cell voltage V is the total voltage nE of the cells.

  FIG. 41 schematically shows a state in which n cells stacked in a tandem configuration are connected in parallel. The total cell voltage V is the sum nE of the voltages of the cells connected in series.

-Electronics-
The DSC according to the embodiment can be mounted on various electronic devices. For example, a remote control device, a desktop digital clock, an electronic notebook, an electronic dictionary, a DSC drive sensor module, etc. can be applied.

  With reference to FIGS. 42 to 44, a configuration example of remote control device 330 equipped with DSC 200 according to the embodiment will be described.

  As shown in FIGS. 42 and 43, the remote control device 330 has an opening 41 penetrating the front and back in a casing 38 made of plastic or the like, and is provided so that the DSC 200 faces the opening 41. A solar cell unit 39 is configured.

  In addition, the remote control device 330 is driven by the solar cell unit 39 as a power source, and includes a liquid crystal unit 34 that displays, for example, date and time, a TV channel number, and an operation button 36 that performs operations such as selecting a TV channel. Is provided.

  The DSC 200 is provided in a horizontal state at a substantially central portion in the thickness direction of the remote control device 330. It should be noted that which of the first substrate 20 side and the second substrate 22 side of the DSC 200 is the front side or the back side of the remote control device 330 may be arbitrary.

  In the configuration example shown in FIG. 43, a transparent member 40 that protects the DSC 200 is fitted into the opening 41 so as to be flush with the front and back surfaces of the housing 38. This prevents dust from being attached to or damaged from the front and back surfaces of the DSC 200.

  A transparent member may be provided on the side surface of the opening 41.

  As a result, external light such as sunlight and room light enters from the front surface side, back surface side, and side surface side of the remote control device 330 via the transparent member 40, so that incident light from the first substrate 20 side of the DSC 200 and Any incident light from the two substrates 22 side reaches the porous semiconductor layer 13. Therefore, the DSC 200 can stably supply power to the remote control device 330 by generating power efficiently using external light.

  In particular, the remote control device 330 such as a television or a video device may be in a state in which the front side provided with the operation buttons 36 or the like faces, for example, a table top plate or the like (inverted state). .

  In remote control device 330 equipped with DSC 200 according to the embodiment, external light such as sunlight or room light is incident from the front surface side, back surface side, and side surface side of remote control device 330 via transparent member 40. If a light beam enters from the front surface or the back surface, the DSC 200 exhibits a power generation function. Therefore, even when the remote control device 330 is placed in an upside down state, power can be stably supplied, and convenience for the user can be improved.

  The electric power generated by the DSC 200 is not directly supplied to the liquid crystal unit 34, but can be supplied from the battery after being stored in the battery.

  In the modification of the remote control device 330 shown in FIG. 44, the transparent member 40 is omitted and the DSC 200 is supported by the support portions 38a and 38b. In addition, the side part of the solar cell part 39 is covered with a part of the housing 38.

  In the remote control device 330 shown in FIG. 44, the DSC 200 exhibits a power generation function by rays (hνf) and (hνr) incident from the front and back of the solar cell unit 39. Two or more DSCs 200 may be overlapped and connected in series by wiring.

  With reference to FIG. 45, a configuration example of a desktop digital timepiece 50 equipped with the DSC 200 according to the embodiment will be described.

  The desktop digital timepiece 50 is provided with a timepiece unit 52 for performing digital timepiece display and a DSC 200 on one plane of a case 54 having a triangular side surface formed of a transparent acrylic plate or the like.

  The DSC 200 is provided with two openings 43 formed in the housing 54 so that the DSC 200 faces the openings 43.

  In the configuration example shown in FIG. 45, the DSC 200 attached to each opening 43 has two cells arranged in parallel via a frame 56. Although not particularly limited, each cell of the DSC 200 can be connected in series by wiring to gain voltage and current.

  As shown in FIG. 45, the DSC 200 included in the tabletop digital timepiece 50 has a power generation function by using either a light beam (hνf) incident from the front side or a light beam (hνr) incident from the back side through the transparent casing 54. It can be demonstrated.

  Accordingly, the degree of freedom of the place where the desktop digital timepiece 50 is placed is increased, and power can be stably supplied to the timepiece unit 52 by effectively using the external light.

  With reference to FIG. 46, a configuration example of an electronic notebook 80 equipped with the DSC 200 according to the embodiment will be described.

  The electronic notebook 80 includes an operation button 36 for performing various inputs and a main body 80b having a liquid crystal unit 34 for displaying various information, and a lid 80a having a DSC 200 that can be freely opened and closed via the main body 80b and the hinge 80c. It consists of and.

  The lid portion 80a is formed with an opening 45 penetrating the lid portion 80a itself on the front and back sides so that the DSC 200 faces the opening portion 45. The DSC 200 may be configured by connecting a plurality of cells.

  The DSC 200 included in the electronic notebook 80 exhibits a power generation function by any of the light rays incident from both the front and back surfaces when the lid 80a is opened as shown in FIG. 46 (a), and stable power is supplied to the main body 80b. Can be supplied.

  On the other hand, as shown in FIG. 46B, even when the lid 80a is closed, the DSC 200 exhibits a power generation function by incident light from the surface side. For example, a secondary battery such as a lithium ion battery provided on the main body 80b side The battery can be charged.

  Thus, according to the electronic notebook 80 equipped with the DSC 200 according to the embodiment, the external light can be used efficiently, and the convenience for the user can be improved.

  In addition, for example, the electronic notebook 80 equipped with the DSC 200 according to the embodiment does not increase in size as compared with the case where conventional solar cells are arranged on both sides of the lid, and is manufactured because only one DSC 200 is sufficient. Cost can be reduced.

  With reference to FIG. 47, a configuration example of electronic dictionary 90 equipped with DSC 200 according to the embodiment will be described.

  The electronic dictionary 90 includes an operation button 36a for performing various inputs and a main body 90b including the DSC 200, a liquid crystal unit 34 for displaying various information that can be freely opened and closed via the main body 90b and the hinge 90c, and a lid including the DSC 200. Part 90a.

  The lid portion 90a and the main body portion 90b are formed with openings 46 penetrating the front and back surfaces so that the DSC 200 faces each opening portion 46. The DSC 200 may be configured by connecting a plurality of cells.

  As shown in FIG. 47, when the lid 90a is opened, the DSC 200 on the lid 90a side exhibits a power generation function by any light incident from both the front and back surfaces, and the DSC 200 on the main body 90b side The power generation function is demonstrated by the incident light. Therefore, stable power can be supplied to the arithmetic unit and the like included in the liquid crystal unit 34 and the main body 90b.

  On the other hand, even when the lid 90a is closed, the DSC 200 on the lid 90a side exhibits a power generation function by incident light from the front side, and can charge, for example, a secondary battery provided on the main body 90b side.

  For example, even when the electronic dictionary 90 is placed with the lid 90a side down, the DSC 200 of the main body 90b exhibits a power generation function by incident light from the front side. The secondary battery provided on the 90b side can be charged.

  As described above, according to the electronic dictionary 90 equipped with the DSC 200 according to the embodiment, external light can be used efficiently, and user convenience can be improved.

  In addition, for example, the electronic dictionary 90 according to the embodiment does not increase in size as compared with the case where conventional solar cells are arranged on both sides of the lid and the main body, and a single DSC 200 is sufficient. Can be reduced.

  Note that the arrangement of the DSC 200 in the electronic dictionary 90 on which the DSC 200 according to the embodiment is mounted can be applied to various electronic devices such as game machines and notebook personal computers having the same structure.

  As described above, according to the present invention, it is possible to provide a dye-sensitized solar cell, a manufacturing method thereof, and an electronic apparatus suitable for forming a fine and complicated sealing pattern having an intersection.

[Other embodiments]
As described above, the embodiments have been described. However, it should be understood that the descriptions and drawings constituting a part of this disclosure are illustrative and do not limit the present invention. From this disclosure, various alternative embodiments, examples and operational techniques will be apparent to those skilled in the art.

  As described above, the present invention includes various embodiments not described herein.

  The dye-sensitized solar cell of the present invention can be applied to various electronic devices by being applied as a small, light and highly efficient power source.

2 ... Semiconductor fine particles 4, 30, 32 ... Dye molecules 10 ... First electrodes 12, 13, 13 ₁ , 13 ₂ , 13 ₃ , 13 ₄ ... Porous semiconductor layers 14, 14 ₁ , 14 ₂ , 14 ₃ , 14 ₄ ... Electrolytic solution 16, 16A, 16B ... Sealing material (glass frit)
18 ... second electrode 19, 19 _1, 19 _2, 19 _3, 19 ₄ ... catalyst layer 20 ... first substrate 22: second substrate 200, 200A, 200B ... dye-sensitized solar cell (DSC)
600 ... Organic solvent

Claims (26)

A first substrate;
A first electrode disposed on the first substrate;
A porous semiconductor layer disposed on the first electrode;
An electrolyte solution in contact with the porous semiconductor layer and having a redox electrolyte dissolved in a solvent;
A catalyst layer in contact with the electrolyte;
A second electrode disposed on the catalyst layer;
A second substrate disposed on the second electrode;
A sealing material disposed between the first substrate and the second substrate and sealing the electrolytic solution;
A dye-sensitized solar cell, wherein the first substrate and the second substrate are bonded together by firing the sealing material. A plurality of DSC cells comprising the dye-sensitized solar cell;
The plurality of DSC cells include the first substrate and the second substrate, the first substrate and the second substrate, and the intersection of the plurality of DSC cells defined by the sealing material in a plan view and intersecting each other. The dye-sensitized solar cell according to claim 1, wherein the dye-sensitized solar cell is sealed with a sealing material.   3. The dye-sensitized solar cell according to claim 2, wherein the intersecting portion includes any of a three-way intersection, a crossroad, or a plurality of overlapping portions.   The dye-sensitized solar cell according to any one of claims 1 to 3, wherein the sealing material includes glass frit, thermosetting resin, or a combination thereof.   The dye-sensitized solar cell according to any one of claims 1 to 4, wherein the first substrate or the second substrate is formed of a glass substrate. The first electrode and the second electrode, ITO, FTO, ZnO, dye-sensitized solar cell according to any one of claims 1 to 5, characterized in that it is formed in one of SnO _2. 7. The porous semiconductor layer according to claim 1, wherein the porous semiconductor layer is formed of any one of TiO ₂ , ZnO, WO ₃ , InO ₃ , Nb ₂ O ₃ , and SnO ₂ . Dye-sensitized solar cell.   The dye-sensitized solar cell according to any one of claims 1 to 7, wherein the catalyst layer is formed of any one of Pt, carbon, and a conductive polymer.   9. The electrolyte according to claim 1, wherein the electrolytic solution is formed of any one of γ-butyrolactone, propylene carbonate, ethylene carbonate, propylene carbonate, acetonitrile, methoxyacetonitrile, and propionitrile. Dye-sensitized solar cell.   The dye enhancement according to any one of claims 1 to 9, wherein the dye is formed of any one of a red dye (N719), a black dye (N749), D131, a phthalocyanine dye, and a porphyrin dye. Sensitive solar cell. Patterning a first electrode on a first substrate;
Forming a porous semiconductor layer on the first electrode;
Patterning the second electrode on the second substrate;
Forming a catalyst layer on the second electrode;
Forming a sealing material on at least one of the first substrate and the second substrate;
Bonding the first substrate and the second substrate by firing the sealing material;
Adhering a dye to the porous semiconductor layer after bonding the first substrate and the second substrate;
And a step of encapsulating an electrolyte in the DSC cell after adsorbing the dye. A method for producing a dye-sensitized solar cell, comprising:   The method for producing a dye-sensitized solar cell according to claim 11, wherein the step of adsorbing the dye is performed by immersing the DSC cell in a high-boiling organic solvent mixed with the dye.   The method for producing a dye-sensitized solar cell according to claim 12, wherein the organic solvent is an organic solvent having a boiling point higher than 60 ° C.   The dye-sensitized solar cell according to claim 12 or 13, wherein the organic solvent is formed of any one of γ-butyrolactone, propylene carbonate, ethylene carbonate, propylene carbonate, acetonitrile, methoxyacetonitrile, and propionitrile. Manufacturing method.   The said organic solvent is heated at 40 to 50 degreeC, The manufacturing method of the dye-sensitized solar cell of any one of Claims 12-14 characterized by the above-mentioned.   The dye sensitization according to any one of claims 12 to 15, wherein the organic solvent is formed by dissolving the dye in an organic solvent used when the electrolytic solution is produced. A method for manufacturing a solar cell.   The method for producing a dye-sensitized solar cell according to any one of claims 12 to 16, wherein the organic solvent is vacuum-injected from an opening for injecting the electrolytic solution.   The step of bonding the first substrate and the second substrate is performed by heating the sealing material to a temperature at which the sealing material dissolves. The manufacturing method of the dye-sensitized solar cell of description.   The method for producing a dye-sensitized solar cell according to claim 18, wherein the temperature at which the sealing material is dissolved is in the range of 200C to 600C.   The method for producing a dye-sensitized solar cell according to any one of claims 11 to 19, wherein the sealing material includes glass frit, thermosetting resin, or a combination thereof.   The method for manufacturing a dye-sensitized solar cell according to any one of claims 11 to 20, wherein the first substrate or the second substrate is formed of a glass substrate. The first electrode and the second electrode, ITO, FTO, ZnO, of the dye-sensitized solar cell according to any one of claims 11 to 21, characterized in that it is formed by any one of SnO ₂ Production method. The porous semiconductor layer is formed of any one of TiO ₂ , ZnO, WO ₃ , InO ₃ , Nb ₂ O ₃ , and SnO ₂ . A method for producing a dye-sensitized solar cell.   The method for manufacturing a dye-sensitized solar cell according to any one of claims 11 to 23, wherein the catalyst layer is formed of any one of Pt, carbon, and a conductive polymer.   The dye enhancement according to any one of claims 11 to 24, wherein the dye is formed of any one of a red dye (N719), a black dye (N749), D131, a phthalocyanine dye, and a porphyrin dye. A method for producing a solar cell.   An electronic apparatus comprising the dye-sensitized solar cell according to any one of claims 1 to 10.

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