JP2014165069A - 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 can improve adhesion and humidity resistance of a sealing part; 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 13 which is arranged on the first electrode 10 and includes semiconductor fine particles and dye molecules; an electrolysis solution 14 which contacts the porous semiconductor layer 13 and in which an oxidation-reduction electrolyte is soluble in a solvent; a catalyst layer 19 which contacts the electrolysis solution 14; a second electrode 18 arranged on the catalyst layer 19; a second substrate 22 arranged on the second electrode 18; first sealing parts 16A, 16B arranged between the first substrate 20 and the second substrate 22, for sealing the electrolysis solution 14; and a second sealing part 40 formed on an outer circumference of the first sealing parts 16A, 16B, for sealing the electrolysis solution 14.

Description

  The present invention relates to a dye-sensitized solar cell (DSC), a method for producing the same, and an electronic device, and more particularly, a dye-sensitized solar cell capable of improving adhesion and moisture resistance of a sealing portion. The present invention relates to a battery, 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 a glass substrate on which transparent electrodes such as ITO and FTO are formed. A titanium oxide having a thickness of several tens of μm on which a dye such as a red die (N719) or a black die (N749) is adsorbed, and an organic solvent such as acetonitrile. In addition, an electrolyte solution in which an electrolyte such as iodine is added to a glass substrate on which a transparent electrode such as ITO or FTO is formed is sandwiched between substrates obtained by stacking Pt.

  And in order to hold | maintain and protect the titanium oxide and electrolyte solution which adsorb | sucked the pigment | dye, the edge part of two board | substrates which opposes is covered and sealed with resin (for example, refer patent document 1). .

JP 2010-277722 A

  By the way, the line width of the sealing part which seals electrolyte solution may be very narrow, such as 0.1 mm and 0.2 mm. In this case, cracking or peeling may occur in the side surface portion of the sealing portion. When cracking or peeling occurs in this way, moisture and oxygen penetrate into the DSC cell relatively easily and react with the electrolytic solution, causing the power generation performance to deteriorate.

  The objective of this invention is providing the dye-sensitized solar cell which can improve the adhesiveness and moisture resistance of a sealing part, its manufacturing method, and an electronic device.

  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 having 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; a first sealing portion disposed between the first substrate and the second substrate for sealing the electrolyte; and an outer periphery of the first sealing portion A dye-sensitized solar cell is provided that includes a second sealing portion that is formed in the portion and seals the electrolytic solution.

  According to another aspect of the present invention, a step of forming a first electrode on a first substrate, a step of forming a porous semiconductor layer having semiconductor fine particles on the first electrode, and the porous semiconductor layer A step of immersing in a dye solution to adsorb dye molecules; a step of forming a second electrode on the second substrate; a step of forming a catalyst layer on the second electrode; the first substrate and the second substrate; Applying glass frit on the substrate to form a first base part and a second base part having a predetermined height; and applying a photocurable resin on the first base part and the second base part; A step of causing the first substrate and the second substrate to face each other and bringing the first base portion and the second base portion into close contact with each other via the photocurable resin, and the first base portion and the second base. The first base part and the front by applying pressure in the direction in which the part is closely attached A step of causing the photocurable resin to protrude from the side surface portion of the second base portion, a step of irradiating and curing the photocurable resin with light, and a redox electrolyte between the first substrate and the second substrate. And a step of injecting an electrolytic solution dissolved in a solvent.

  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 which can improve the adhesiveness and moisture resistance of a sealing part, its manufacturing method, and an electronic device can be provided.

The typical cross-section block diagram which shows the state before bonding the 1st board | substrate and 2nd board | substrate of DSC which concern on embodiment. The typical cross-section block diagram which shows the state after bonding the 1st board | substrate and 2nd board | substrate of DSC shown by FIG. The typical cross-section block diagram which shows the state before bonding the 1st board | substrate and 2nd board | substrate of DSC which concern on the comparative example 1. FIG. The typical cross-section block diagram which shows the state after bonding the 1st board | substrate and 2nd board | substrate of DSC shown by FIG. The typical cross-section block diagram which expanded the DSC shown by FIG. 1 partially. The typical cross-section block diagram which expanded the DSC shown by FIG. 2 partially. It is a manufacturing method of DSC which concerns on embodiment, Comprising: Process drawing which arrange | positions platemaking on a 1st board | substrate. It is a manufacturing method of DSC which concerns on embodiment, Comprising: Process drawing which arrange | positions another platemaking on a 1st board | substrate. It is a manufacturing method of DSC which concerns on embodiment, Comprising: (a) Process drawing which slides a squeegee on the platemaking after the process of FIG. 7, (b) On the 1st board | substrate after the process of FIG. 9 (a) Process drawing which forms glass frit. It is a manufacturing method of DSC which concerns on embodiment, Comprising: (a) Process drawing which slides a squeegee on the platemaking after the process of FIG.9 (b), (b) Glass frit after the process of FIG.10 (a) Process drawing which apply | coats ultraviolet curing resin on it. It is a manufacturing method of DSC which concerns on embodiment, Comprising: Electrolyte solution is enclosed, an opening part is sealed, and a process drawing which forms a DSC cell. Sectional drawing which shows the structural example of the sealing part of DSC which concerns on the comparative example 2. FIG. (A) Cross-sectional view showing a configuration example of a DSC sealing portion according to the first embodiment, (b) Cross-sectional view showing a configuration example of a DSC sealing portion according to the second embodiment, (c) Third embodiment Sectional drawing which shows the structural example of the sealing part of DSC which concerns on an example, (d) Sectional drawing which shows the structural example of the sealing part of DSC which concerns on 4th Example, (e) Sealing of DSC which concerns on 5th Example Sectional drawing which shows the structural example of a stop part, (f) Sectional drawing which shows the structural example of the sealing part of DSC which concerns on 6th Example. It is a figure which shows the process of forming the sealing part of DSC which concerns on the comparative example 2, Comprising: (a) Sectional drawing which shows the state before hardening a 2nd sealing part, (b) Curing a 2nd sealing part Sectional drawing which shows the state after making it do. It is a figure which shows the process of forming the sealing part of DSC which concerns on 5th Example, Comprising: (a) Sectional drawing which shows the state before hardening a 2nd sealing part, (b) A 2nd sealing part is shown. Sectional drawing which shows the state after making it harden | cure. (A) Cross-sectional view showing a configuration example of a DSC sealing portion according to the seventh embodiment, (b) Cross-sectional view showing a configuration example of a DSC sealing portion according to the eighth embodiment, (c) Fourth embodiment Sectional drawing which shows the state of the sealing part which concerns on an example, (d) The enlarged view of the D section of FIG.16 (c). The top view which shows the structural example of the ventilation part formed in a sealing part. It is process drawing which shows the manufacturing method of DSC which concerns on embodiment, Comprising: The top view and sectional drawing which show the process of forming a transparent electrode in a 1st board | substrate. It is process drawing which shows the manufacturing method of DSC which concerns on embodiment, Comprising: The top view and sectional drawing which show the process of forming a porous semiconductor layer. It is process drawing which shows the manufacturing method of DSC which concerns on embodiment, Comprising: The top view and sectional drawing which show the state which made the porous semiconductor layer adsorb | suck the pigment | dye. It is process drawing which shows the manufacturing method of DSC which concerns on embodiment, Comprising: The top view and sectional drawing which show the process of forming a sealing part. It is process drawing which shows the manufacturing method of DSC which concerns on embodiment, Comprising: The top view and sectional drawing which show the process of bonding a counter electrode board | substrate and a working electrode board | substrate, and irradiating light and hardening a sealing part. It is process drawing which shows the manufacturing method of DSC which concerns on embodiment, Comprising: The top view and sectional drawing which show the state which inject | poured electrolyte solution and sealed the injection hole. The graph which shows the wavelength and intensity distribution of light W1, W2. The typical plane pattern block diagram of DSC which concerns on embodiment. FIG. 26 is a schematic sectional view taken along the line II of FIG. FIG. 26 is a schematic cross-sectional structure diagram taken along the line II-II in FIG. 25. FIG. 26 is a schematic sectional view taken along the line II-III in FIG. 25. FIG. 26 is an enlarged schematic plane pattern configuration diagram of a portion A in FIG. 25. 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 a dye molecule (32) / electrolyte solution (14), Comprising: The enlarged view of J part 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) The chemical structural formula of D205 which exhibits purple, (b) The chemical structural formula which shows the porphyrin pigment which exhibits green. (A) In DSC which concerns on embodiment, the schematic cross-section figure which has arrange | positioned four basic cells in series structure, (b) The typical circuit expression of Fig.38 (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.39 (a). It is a DSC manufacturing method according to the embodiment, (a) a process diagram for pre-processing the second substrate, (b) a process diagram for forming the second electrode on the second substrate, (c) on the second electrode (D) a process diagram for forming the first electrode on the first substrate after pretreatment of the first substrate; (e) a porous semiconductor layer formed on the first electrode; Step of immersing the dye in the porous semiconductor layer, (f) The second substrate after the step of FIG. 40 (c) and the first substrate after the step of FIG. (G) Process drawing in which an electrolytic solution is sealed inside from an opening, the opening is sealed, and a DSC cell is formed. 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. 44 is a schematic cross-sectional structure diagram taken along the line IV-IV in FIG. 43, 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) A schematic diagram showing a state in which five DSC cells according to the embodiment are connected in series, (b) an explanatory view of FIG. 48 (a), and (c) a plan view showing a configuration example of FIG. 48 (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.49 (a). (A) The schematic diagram which shows the state which connected the thing which laminated | stacked the cell of n of DSC which concerns on embodiment, and the tandem structure in parallel, (b) Explanatory drawing of Fig.50 (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)
The DSC 200 according to the embodiment is represented as shown in FIGS. 1 to 2 and FIGS. As shown in FIG. 11, the DSC 200 according to the embodiment includes a first substrate 20, a first electrode 10 disposed on the first substrate 20, a semiconductor fine particle and a dye molecule disposed on the first electrode 10. A porous semiconductor layer 13, an electrolyte solution 14 in contact with the porous semiconductor layer 13, a redox electrolyte dissolved in a solvent, a catalyst layer 19 in contact with the electrolyte solution 14, and a second electrode disposed on the catalyst layer 19. An electrode 18, a second substrate 22 disposed on the second electrode 18, and first sealing portions 16 </ b> A and 16 </ b> B (which are disposed between the first substrate 20 and the second substrate 22 and seal the electrolyte solution 14). 1st sealing part 16) and the 2nd sealing part 40 which is formed in the outer peripheral part of 1st sealing part 16A * 16B and seals the electrolyte solution 14 is provided. That is, the first sealing portion 16 and the second sealing portion 40 form a double-structure sealing portion.

  Specifically, the first sealing portion 16A includes a first base portion having a predetermined height (for example, about 10 μm) formed by applying glass frit on the first substrate 20. Hereinafter, the same reference numeral 16A is used for the first sealing part, the first base part, and the glass frit on the first substrate 20 side.

  Similarly, the first sealing portion 16B includes a second base portion having a predetermined height (for example, about 10 μm) formed by applying glass frit on the second substrate 22. Hereinafter, the same reference numeral 16B is used for the first sealing part, the second base part, and the glass frit on the second substrate 22 side.

  Further, the second sealing portion 40 includes a photo-curing resin formed on a joint portion between the first base portion 16A and the second base portion 16B, and side portions of the first base portion 16A and the second base portion 16B. . As the photocurable resin, for example, an ultraviolet curable resin can be used. Ultraviolet light (UV) for curing the ultraviolet curable resin is an electromagnetic wave having a short wavelength in the range of 10 to 400 nm. Moreover, ultraviolet rays (UV) are UV-A (long wavelength ultraviolet rays: wavelength 315 to 400 nm), UV-B (medium wavelength ultraviolet rays: wavelength 280 to 315 nm), UV-C (short wavelength ultraviolet rays: wavelength around 10 nm to 280 nm) depending on the wavelength. ). As an ultraviolet (UV) irradiation source, a UV lamp (mercury lamp, metal halide lamp) or the like is used. Here, examples of the ultraviolet curable resin include epoxy acrylate, urethane acrylate, polyester acrylate, unsaturated polyester, polyether acrylate, vinyl acrylate, polybutadiene acrylate, and polystyrylethyl methacrylate. In addition, acrylic ultraviolet curable resin is more preferable in terms of electrolytic solution resistance and sealing properties.

  Moreover, the 1st board | substrate 20 or the 2nd board | substrate 22 can be formed with the glass substrate with a transparent electrode in which the transparent substrate and the transparent substrate were formed, 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. The porous semiconductor layer 12 after adsorbing the dye Dye is referred to as “porous semiconductor layer 13”.

  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, D205, a phthalocyanine dye, a porphyrin dye, and the like can be applied.

(Before and after bonding: embodiment)
A schematic cross-sectional configuration showing a state before the first substrate 20 and the second substrate 22 of the DSC 200 according to the embodiment are bonded together is expressed as shown in FIG. As shown in FIG. 1, a first base portion 16A is formed on the first substrate 20, and an ultraviolet curable resin 40A is applied to the tip portion of the first base portion 16A. Similarly, the 2nd base part 16B is formed on the 2nd board | substrate 22, and the ultraviolet curable resin 40B is apply | coated to the front-end | tip part of the 2nd base part 16B. The line width L ₁ of the first base portion 16A and the second base portion 16B is, for example, about 0.1 mm. The first substrate 20 and the second substrate 22 are opposed to each other, and the first base portion 16A and the second base portion 16B are brought into close contact with each other via the ultraviolet curable resins 40A and 40B.

A schematic cross-sectional configuration showing a state after the first substrate 20 and the second substrate 22 of the DSC 200 shown in FIG. 1 are bonded together is expressed as shown in FIG. As shown in FIG. 2, an ultraviolet curable resin 40W is formed on the outer periphery of the first base portion 16A and the second base portion 16B. This ultraviolet curable resin 40W is obtained by integrating the ultraviolet curable resins 40A and 40B. That is, as shown in FIG. 1, the first base portion 16A and the second base portion 16B are brought into close contact with each other through the ultraviolet curable resins 40A and 40B, and further, the first base portion 16A and the second base portion 16B are brought into close contact with each other. Apply pressure in the direction of As a result, the ultraviolet curable resins 40A and 40B protrude from the side surfaces of the first base portion 16A and the second base portion 16B, and the protruding ultraviolet curable resins 40A and 40B are integrated into the ultraviolet curable resin as shown in FIG. 40W is formed. The width 2L ₁ of the ultraviolet curable resin 40W is preferably about twice the line width L ₁ of the first base portion 16A and the second base portion 16B. For example, when the line width L _{1 of} the first base portion 16A and the second base portion 16B is 0.1 mm, the width 2L ₁ of the ultraviolet curable resin 40W is 0.2 mm. The second sealing portion 40 can be formed by irradiating the ultraviolet curable resin 40W with ultraviolet rays (UV) and curing it.

(Before and after bonding: Comparative Example 1)
A schematic cross-sectional configuration showing a state before the first substrate 20 and the second substrate 22 of the DSC 200A according to the comparative example 1 are bonded together is expressed as shown in FIG. As shown in FIG. 3, the first base portion 16A is formed on the first substrate 20, and the ultraviolet curable resin 40A is applied to the tip portion of the first base portion 16A. Similarly, the 2nd base part 16B is formed on the 2nd board | substrate 22, and the ultraviolet curable resin 40B is apply | coated to the front-end | tip part of the 2nd base part 16B. Line width L ₂ of the first base portion 16A and the second base portion 16B is, for example, about 0.2 mm. The first substrate 20 and the second substrate 22 are opposed to each other, and the first base portion 16A and the second base portion 16B are brought into close contact with each other via the ultraviolet curable resins 40A and 40B.

A schematic cross-sectional configuration showing a state after the first substrate 20 and the second substrate 22 of the DSC 200A shown in FIG. 3 are bonded together is expressed as shown in FIG. As shown in FIG. 4, an ultraviolet curable resin 40X in which the ultraviolet curable resins 40A and 40B are integrated is formed at the distal ends of the first base portion 16A and the second base portion 16B. On the other hand, the ultraviolet curable resin 40X is not formed on the side surface portion W of the first base portion 16A and the second base portion 16B, and the glass frit constituting the first base portion 16A and the second base portion 16B is exposed. It has become. Since the glass frit is brittle and has low adhesion, when the line width L _{2 of} the first base portion 16A and the second base portion 16B is extremely narrow, such as 0.1 mm or 0.2 mm, the first base portion 16A and the second base portion There is a possibility that cracking or peeling occurs on the side surface W of 16B. When cracking or peeling occurs in this way, moisture or oxygen enters the DSC cell relatively easily and reacts with the electrolyte solution 14 to cause deterioration in power generation performance.

(Adjustment of protrusion amount)
Next, a method for adjusting the amount by which the UV curable resins 40A and 40B protrude in the DSC 200 according to the embodiment will be described. Any one or a plurality of adjustment methods described below can be combined as appropriate.

First, the amount by which the ultraviolet curable resins 40A and 40B protrude can be adjusted by the pressure applied in the direction in which the first base portion 16A and the second base portion 16B are brought into close contact with each other. That is, as shown in FIG. 5, the UV curable resin 40A applied to the tip of the first base portion 16A and the UV curable resin 40B applied to the tip of the second base portion 16B are brought into close contact with each other. The distance between the first substrate 20 and the second substrate 22 at this time is H ₁ . Here, pressure is applied in the direction in which the first base portion 16A and the second base portion 16B are brought into close contact with each other, and the distance between the first substrate 20 and the second substrate 22 is reduced to H ₂ as shown in FIG. . The smaller the distance H ₂ is relative to the distance H ₁ (that is, the greater the pressure applied in the direction in which the first base portion 16A and the second base portion 16B are brought into close contact with each other), the first base portion 16A and the second base portion 16B. Many UV curable resins 40 </ b> A and 40 </ b> B can be protruded from the side surface portion of each other.

  The amount of the ultraviolet curable resin 40A / 40B protruding may be adjusted by the pressure with which the squeegee slides on the plate for screen printing. That is, the ultraviolet curable resins 40A and 40B can be formed by, for example, screen printing (described later). The stronger the pressure with which the squeegee slides on the screen printing plate making, the more UV curable resin 40A and 40B can protrude from the side surfaces of the first base portion 16A and the second base portion 16B.

  Further, the amount of the ultraviolet curable resin 40A / 40B protruding may be adjusted by the viscosity of the ultraviolet curable resin 40A / 40B. The lower the viscosity of the UV curable resins 40A and 40B, the more UV curable resins 40A and 40B can protrude from the side surfaces of the first base portion 16A and the second base portion 16B.

  Further, the amount of the ultraviolet curable resin 40A / 40B protruding may be adjusted by the interval between the first substrate 20 or the second substrate 22 and the plate for screen printing (described later). The larger the distance between the first substrate 20 or the second substrate 22 and the screen printing plate making, the more UV curing resin 40A / 40B protrudes from the side surfaces of the first base portion 16A and the second base portion 16B. it can.

As shown in FIG. 6, the thickness L _{1/2 of} the portion where the UV curable resins 40A and 40B protrude is not less than ½ of the line width L ₁ of the first base portion 16A or the second base portion 16B. desirable. If it does in this way, it is possible to cover the whole side part of 16 A of 1st base parts and the 2nd base part 16B with the ultraviolet curable resin 40W of appropriate thickness.

(Production method)
The manufacturing method of DSC 200 according to the embodiment is expressed as shown in FIGS. As shown in FIG. 11, the DSC 200 manufacturing method according to the embodiment includes a step of forming the first electrode 10 on the first substrate 20 and a porous semiconductor layer 13 having semiconductor fine particles on the first electrode 10. The step of forming, the step of immersing the porous semiconductor layer 13 in the dye solution to adsorb the dye molecules, the step of forming the second electrode 18 on the second substrate 22, and the catalyst layer 19 on the second electrode 18. Forming a first base portion 16A and a second base portion 16B having a predetermined height by applying glass frits 16A and 16B on the first substrate 20 and the second substrate 22. The step of applying the ultraviolet curable resins 40A and 40B on the base portion 16A and the second base portion 16B, and the first base portion 16A and the second base portion 16B are made to face the first substrate 20 and the second substrate 22. UV curable resin 40 -UV curable resin is applied to the side surfaces of the first base portion 16A and the second base portion 16B by applying pressure in a direction in which the first base portion 16A and the second base portion 16B are in close contact with each other through the step 40B. The redox electrolyte was dissolved in a solvent between the step of protruding 40A and 40B, the step of irradiating and curing the ultraviolet curable resin 40A and 40B with ultraviolet rays (UV), and the first substrate 20 and the second substrate 22. And a step of injecting the electrolytic solution 14.

  Thereby, in the outer peripheral part of 16 A of 1st base parts and the 2nd base part 16B (1st sealing part 16), an ultraviolet curable resin can be hardened and the 2nd sealing part 40 can be formed. Hereinafter, the process of forming such a double-structured sealing portion by screen printing will be described in detail with reference to FIGS.

First, as shown in FIG. 7, a screen printing plate making 21 is disposed on the first substrate 20. In the plate making 21, an opening groove 21 </ b> W is formed in a portion where a sealing portion is formed. Here exemplifies the case where is formed a rectangular opening groove 21W width W _1. Of course, as shown in FIG. 8, the width W ₂ (W ₂ > W ₁ ) and shape of the opening groove 21W can be appropriately adjusted according to the width and shape of the sealing portion.

Next, as shown in FIG. 9A, the glass paste 16Ap is placed on the plate making 21 after the process of FIG. 7, and the squeegee 50S is slid on the plate making 21. Thus, the glass paste 16Ap is filled in opening groove 21W of width W ₁ which is formed in plate-making 21 to eject glass paste 16Ap from the opening groove 21W. As a result, a glass frit 16A having a line width W ₁ can be formed on the first substrate 20 as shown in FIG. 9B.

Next, as shown in FIG. 10A, a paste-like ultraviolet curable resin 40 Wp is placed on the plate making 21 after the step of FIG. 9B, and the squeegee 50 </ b> S is slid on the plate making 21. Thus, a paste of the ultraviolet curing resin 40Wp is filled in opening groove 21W of width W ₁ which is formed in plate-making 21 to eject pasty ultraviolet curable resin 40Wp from the opening groove 21W. As a result, as shown in FIG. 10B, an ultraviolet curable resin 40A having a width W _s can be applied to the tip of the glass frit 16A having a line width W ₁ .

Here, in the process of FIG. 10A, the greater the pressure with which the squeegee 50S slides on the plate making 21, the more UV curable resin 40Wp is discharged from the opening groove 21W, so the width W of the UV curable resin 40A. _s becomes wider. As a result, when the 1st board | substrate 20 and the 2nd board | substrate 22 are bonded together, many ultraviolet curable resin 40A * 40B can protrude from the side part of 16 A of 1st base parts and the 2nd base part 16B. Of course, in the process of FIG. 10A, even when the width of the opening groove in the plate making 21 is set to W _s (W _s > W ₁ ), the width of the discharged UV curable resin 40A is increased.

Further, in the process of FIG. 10A, the wider the distance between the first substrate 20 and the plate making 21, the more UV curable resin 40Wp is discharged from the opening groove 21W, and therefore the width W _s of the UV curable resin 40A is increased. Become wider. As a result, when the 1st board | substrate 20 and the 2nd board | substrate 22 are bonded together, many ultraviolet curable resin 40A * 40B can protrude from the side part of 16 A of 1st base parts and the 2nd base part 16B.

  Thereafter, the ultraviolet curable resins 40A and 40B are irradiated with ultraviolet rays (UV). Thereby, the ultraviolet curable resins 40A and 40B can be cured in a state where the ultraviolet curable resins 40A and 40B are in close contact with the outer peripheral portions of the first base portion 16A and the second base portion 16B. Other steps (for example, a step of encapsulating the electrolytic solution 14) will be described later.

  As described above, in the embodiment, the double sealing portion is formed by forming the second sealing portion 40 on the outer peripheral portion of the first sealing portion 16. And moisture resistance can be improved. As a result, moisture and oxygen can be prevented from entering the DSC cell, and the reliability of the DSC 200 can be improved.

  Specifically, the 1st sealing part 16 is formed with glass frit 16A * 16B, and the 2nd sealing part 40 is formed with ultraviolet curing resin 40A * 40B. The glass frits 16A and 16B are superior in moisture resistance compared to the ultraviolet curable resins 40A and 40B, while the ultraviolet curable resins 40A and 40B are superior in adhesiveness compared to the glass frits 16A and 16B. Therefore, if the glass frit 16A / 16B and the ultraviolet curable resin 40A / 40B have a double structure, it is possible to form a sealing portion excellent in both adhesion and moisture resistance. In addition, since the second sealing portion 40 can be formed by a simple method of protruding the ultraviolet curable resins 40A and 40B when the first substrate 20 and the second substrate 22 are bonded together, There is also an effect that it is suitable for mass production of DSC200.

  In the present embodiment, the ultraviolet curable resin 40A / 40B is applied to both the first base portion 16A and the second base portion 16B, but one of the first base portion 16A and the second base portion 16B is applied. Only an ultraviolet curable resin may be applied. Of course, in order to allow a sufficient amount of the ultraviolet curable resin to protrude from the side surfaces of the first base portion 16A and the second base portion 16B, both the first base portion 16A and the second base portion 16B have the UV curable resin 40A. It is desirable to apply 40B.

〔Concrete example〕
Hereinafter, a specific example of the DSC 200 according to the embodiment will be described in detail. Also in the DSC 200 exemplified below, the second sealing portion 40 is formed on the outer peripheral portion of the first sealing portion 16 to form a double-structure sealing portion. The first sealing portion 16 is preferably formed of glass frit 16A / 16B, and the second sealing portion 40 is preferably formed of ultraviolet curable resin 40A / 40B. It is also possible to form a part.

(Comparative Example 2)
Here, with reference to FIG. 12 and FIG. 14, the structure of the sealing part of DSC200B which concerns on the comparative example 2 is demonstrated.

  That is, the first sealing portion 16 has a predetermined height (for example, about 10 μm) of the first base portion 16A and the second base portion 16B that are formed in advance on the first substrate 20 side and the second substrate 22 side by the photo-curing resin. It consists of. Hereinafter, various types of sealing portions will be exemplified, but the second sealing portion 40 is formed on the outer peripheral portion of the first sealing portion 16 in the same manner.

  Note that the thickness L of the entire sealing portion is, for example, about 30 μm. That is, in the example shown in FIG. 12, the heights of the first base portion 16A, the second base portion 16B, and the second sealing portion 40 constituting the joint portion are each about 10 μm.

  The first base portion 16A, the second base portion 16B, and the second sealing portion 40 are formed by applying an ultraviolet curable resin by a screen printing technique, and the thickness formed in one step of this printing method. However, it is about 10 μm. Of course, the first base portion 16A and the second base portion 16B can be formed of glass frits 16A and 16B.

  Here, the ultraviolet curable resin which comprises the 2nd sealing part 40 is apply | coated to the front-end | tip part of either the 1st base part 16A or the 2nd base part 16B which was formed previously. And the 1st board | substrate 20 and the 2nd board | substrate 22 are made to oppose, and between the 1st base part 16A and the 2nd base part 16B was joined via the 2nd sealing part 40 which consists of ultraviolet curable resin, (See FIG. 14A). In FIG. 14A, reference numeral 40 a indicates a contact portion between the first base portion 16 </ b> A and the second base portion 16 </ b> B and the second sealing portion 40.

  Next, ultraviolet rays (UV) are irradiated from the first substrate 20 side or the second substrate 22 side to cure the ultraviolet curable resin constituting the second sealing portion 40 (see FIG. 14B). In FIG. 14B, reference numeral 40 b denotes a contact portion between the first base portion 16 </ b> A and the second base portion 16 </ b> B and the second sealing portion 40.

  However, in the first sealing portion 16 as the comparative example 2, since the first base portion 16A and the second base portion 16B are made of an ultraviolet curable resin, the first sealing portion 16 itself easily absorbs ultraviolet rays. have.

  Therefore, ultraviolet rays (UV) irradiated from the first substrate 20 side or the second substrate 22 side are absorbed to some extent before reaching the ultraviolet curable resin, and the ultraviolet curable resin is not sufficiently cured.

  When the UV curable resin is not sufficiently cured, moisture and oxygen penetrate into the cell relatively easily and react with the electrolyte solution 14 to deteriorate the power generation performance. Therefore, the DSC 200B has sufficient durability. It cannot be secured.

(Example)
Next, first to sixth embodiments will be described with reference to FIGS.

  In the first to third embodiments shown in FIGS. 13A to 13C, when the pair of first base portion 16A and second base portion 16B makes the first substrate 20 and the second substrate 22 face each other. In addition, this is a configuration example in the case where the tip end portion of the first base portion 16A and the tip end portion of the second base portion 16B are formed to face each other.

  In the first to third embodiments shown in FIGS. 13A to 13C, the first base portion 16A side and the second base portion 16B side are joined to the first base portion 16A and the second base portion 16B. An opening AP through which ultraviolet rays (UV) for curing the ultraviolet curable resin are incident is formed on the portion.

  The width of the opening AP is, for example, about 0.05 to 0.5 mm.

In the first embodiment shown in FIG. 13 (a), the first base portion 16A and the second base portion 16B are formed so that the cross-sectional shape is substantially wedge-shaped. The second embodiment shown in FIG. 13 (b). In the example and the third embodiment shown in FIG. 13C, the first base portion 16 </ b> A and the second base portion 16 </ b> B have a shape in which the cross-sectional area decreases as the distance from the first substrate 20 and the second substrate 22 increases. .

  In the second embodiment shown in FIG. 13 (b), the first base portion 16A and the second base portion 16B have a shape in which both side portions have negative curvature.

  Further, in the third embodiment shown in FIG. 13C, the first base portion 16A and the second base portion 16B have a shape in which both side portions have a positive curvature.

  In the first to third embodiments shown in FIGS. 13A to 13C, ultraviolet rays (UV) are incident from at least one opening AP on the first base portion 16A side and the second base portion 16B side. Thus, the ultraviolet curable resin constituting the second sealing portion 40 can be cured.

  At this time, since ultraviolet rays (UV) are directly incident on the ultraviolet curable resin through the opening AP, it is possible to secure a sufficient amount of light for curing the ultraviolet curable resin as compared with the above-described Comparative Example 2. Thereby, the 2nd sealing part 40 is fully hardened also including a center part, and can join the 1st base part 16A and the 2nd base part 16B reliably.

  Moreover, since the contact area of 16 A of 1st base parts and the 2nd base part 16B, and ultraviolet curable resin (2nd sealing part 40) is large compared with the comparative example 2, joining strength can be raised.

  Therefore, the penetration of moisture and oxygen into the cell is effectively prevented, and the durability of the DSC 200 is improved.

  Three or more first base parts 16A and two second base parts 16B are formed, and an opening AP is formed between the first base parts and between the second base parts. good.

  In the fourth to sixth embodiments shown in FIGS. 13D to 13F, when the first base portion 16A and the second base portion 16B face the first substrate 20 and the second substrate 22, This is a configuration example in the case where the positions of the front end of the first base portion 16A and the front end of the second base portion 16B are staggered.

  In the fourth to sixth embodiments shown in FIGS. 13D to 13F, the first base portion 16A and the second base portion 16B are the front end portion of the first base portion 16A and the front end portion of the second base portion 16B. Are arranged at such a height that the tip portions overlap each other in the arrangement direction.

  In the fourth embodiment shown in FIG. 13D, a first base portion 16A and a second base portion 16B are formed on the first substrate 20 and the second substrate 22, respectively. And each 1st base part 16A and 2nd base part 16B are the clearance gaps in which the ultraviolet curable resin which comprises the 2nd sealing part 40 is interposed when the 1st board | substrate 20 and the 2nd board | substrate 22 are made to oppose. It is arranged so that

  Here, FIG. 15 is a diagram illustrating a process of forming the sealing portion of the DSC 200 according to the fifth embodiment, and FIG. 15A is a cross-sectional view illustrating a state before the second sealing portion 40 is cured. FIG. 15B is a cross-sectional view showing a state after the second sealing portion 40 is cured.

  In FIG. 15A, reference numeral 40 a indicates a contact portion between the first base portion 16 </ b> A and the second base portion 16 </ b> B and the second sealing portion 40. Moreover, the place enclosed with the dashed-dotted lines A, B, and C shows the site | part hardened | cured especially firmly by irradiation of an ultraviolet-ray (UV).

  Further, in FIG. 15B, reference numeral 40b indicates a portion where ultraviolet rays (UV) are not spread and are not sufficiently cured, but the other portions are sufficiently cured to obtain a practically sufficient strength. It is done.

  In the fifth embodiment shown in FIG. 13 (e), one first base portion 16 A is formed on the first substrate 20, and two second base portions 16 B are formed on the second substrate 22. And when the 1st board | substrate 20 and the 2nd board | substrate 22 are made to oppose, it arrange | positions so that the 1st base part 16A may be located between the two 2nd base parts 16B, and the 1st base part 16A and the 1st base part The ultraviolet curable resin which comprises the 2nd sealing part 40 is pinched | interposed with 2 base parts 16B.

  In the sixth embodiment shown in FIG. 13 (f), a pair of first base portions 16 A is formed on the first substrate 20, and a pair of second base portions 16 B is formed on the second substrate 22. And when the 1st board | substrate 20 and the 2nd board | substrate 22 were made to oppose, 16A of 1st base parts and the 2nd base part 16B are arrange | positioned alternately, and each pair of 1st base part 16A and 2nd An ultraviolet curable resin constituting the second sealing portion 40 is sandwiched between the base portion 16B.

In the fourth to sixth embodiments shown in FIGS. 13D to 13F, the first base portion 16A and the second base portion 16B are formed so that the cross-sectional shapes are substantially wedge-shaped and In the fourth to sixth embodiments, ultraviolet rays (UV) are emitted from at least one opening AP on the first base portion 16A side and the second base portion 16B side to the ultraviolet curable resin constituting the second sealing portion 40. It can be incident and cured.

  At this time, ultraviolet rays (UV) are directly incident on the ultraviolet curable resin constituting the second sealing portion 40 through the opening AP, so that the ultraviolet curable resin is sufficiently cured as compared with the comparative example 2 described above. The amount of light to be generated can be secured. As a result, the entire second sealing portion 40 is sufficiently cured, and the first base portion 16A and the second base portion 16B can be firmly joined.

  Moreover, since the contact area of the 1st base part 16A and the 2nd base part 16B, and the 2nd sealing part 40 is large compared with the comparative example 2, joining strength can be raised. In particular, in the case of the fifth embodiment shown in FIG. 13 (e) and the sixth embodiment shown in FIG. 13 (f), the first base portion 16A, the second base portion 16B, and the second sealing portion 40 An anchor effect due to the frictional force acts between them, resulting in stronger joining.

  Therefore, penetration of moisture and oxygen into the cell is more effectively prevented, and the durability of the DSC 200 is further improved.

  In the sixth embodiment, three or more first base portions 16A of the first substrate 20 and three or more second base portions 16B of the second substrate 22 may be formed.

  In the first to sixth embodiments, the ultraviolet curable resin that forms the first base portion 16A and the second base portion 16B and the ultraviolet curable resin that forms the second sealing portion 40 depend on light having different wavelengths. It may be cured.

  That is, for example, as shown in FIG. 24, it is possible to use an ultraviolet curable resin that is cured by ultraviolet light W1 having a wavelength λ1 and an ultraviolet curable resin that is cured by ultraviolet light having a wavelength λ2.

  Specifically, for example, an ultraviolet curable resin that is cured by ultraviolet light having a wavelength of 360 nm is used for the first base portion 16A and the second base portion 16B, and an ultraviolet curable resin that is cured by ultraviolet light having a wavelength of 380 nm is used for the second sealing portion 40. Can be used. Thereby, the 2nd sealing part 40 can be hardened more reliably by the ultraviolet-ray with a wavelength of 380 nm which can inject more deeply.

  Next, a seventh embodiment and an eighth embodiment of the present invention will be described with reference to FIGS. 16 (a) and 16 (b).

  The seventh embodiment shown in FIG. 16A has a configuration in which the first base portion 16A and the second base portion 16B are added one by one with respect to the third embodiment shown in FIG. 13C. .

  Thereby, the contact area of 16 A of 1st base parts, the 2nd base part 16B, and the 2nd sealing part 40 becomes wider, and joining strength is improved further.

  In addition, there are two openings AP on both the first substrate 20 side and the second substrate 22 side, and ultraviolet rays (UV) are more reliably formed into the ultraviolet curable resin constituting the second sealing portion 40 through the opening AP. Incident. Thereby, the 2nd sealing part 40 is fully hardened, and the 1st base part 16A and the 2nd base part 16B, and the 2nd sealing part 40 are joined more firmly.

  The eighth embodiment shown in FIG. 16 (b) is similar to the sixth embodiment shown in FIG. 13 (f), but the first base portion 16A in the form as in the third embodiment shown in FIG. This is an example in which the second base portion 16B is applied. In this case, as shown in FIG. 16B, the first base portion 16A and the second base portion 16B do not overlap in the arrangement direction. Also in this case, a sufficient amount of ultraviolet rays (UV) is incident on the ultraviolet curable resin constituting the second sealing portion 40 through the opening AP. Thereby, the 2nd sealing part 40 is fully hardened, and the 1st base part 16A and the 2nd base part 16B, and the 2nd sealing part 40 are joined firmly.

  FIG. 16C is a cross-sectional view showing a state of the sealing portion of the DSC 200 according to the above-described fourth embodiment, and FIG. 16D is an enlarged view of a D portion in FIG.

  As shown in FIG.16 (d), the contact surface of 16 A of 1st base parts (or 2nd base part 16B) and the 2nd sealing part 40 is predetermined | prescribed roughness (for example, surface roughness Rs = 100- 1000 μm). This is because the ultraviolet curable resin constituting the first base portion 16A, the second base portion 16B and the second sealing portion 40 is applied by screen printing. This is because the cured resin becomes granular.

  As described above, the contact surface between the first base portion 16A (or the second base portion 16B) and the second sealing portion 40 has minute irregularities, so that the frictional force on the contact surface is increased and the contact surface is more firmly joined.

  FIG. 17 shows an example of the configuration of the venting part formed in the sealing part. As shown in FIG. 17, eight slits SL <b> 1 to SL <b> 8 are formed in the first sealing portion 16 and the second sealing portion 40 as venting portions. Reference numeral 16 (40) shown in FIG. 17 and the like means that the second sealing portion 40 is formed on the outer peripheral portion of the first sealing portion 16. Hereinafter, the description will be made mainly focusing on the first sealing portion 16, but the second sealing portion 40 is also provided with the same mechanism (for example, slits SL1 to SL8).

  That is, when forming the second sealing portion 40 by applying an ultraviolet curable resin to at least one of the first base portion 16A and the second base portion 16B constituting the first sealing portion 16, the first base portion is formed. A venting part (slits SL1 to SL8) for venting air between the part 16A and the second base part 16B and the applied ultraviolet curable resin can be formed.

  Thereby, the ultraviolet curing resin which comprises the 2nd sealing part 40 was apply | coated to at least one of the 1st base part 16A and the 2nd base part 16B, and the 1st board | substrate 20 and the 2nd board | substrate 22 were piled up. At that time, the air between the first base portion 16A and the second base portion 16B and the applied ultraviolet curable resin escapes to the outside through the venting portions (slits SL1 to SL8). Accordingly, it is possible to prevent the UV curable resin from smoothly entering between the first base portion 16A and the second base portion 16B and to form a gap, and to improve the adhesion.

(Production method)
With reference to FIGS. 18-23, the manufacturing method of DSC200 which concerns on embodiment is demonstrated. 21 to 23, the configuration of the first sealing portion 16 is schematically shown as a straight structure, but the detailed structure is shown in FIGS. 13 (a) to 13 (f), FIG. 15, and FIG. It has the same configuration as any of the configurations shown in (a) to (c).

  The DSC 200 manufacturing method according to the embodiment includes a step of forming the first electrode 10 on the first substrate 20, a step of forming the porous semiconductor layer 12 having the semiconductor fine particles 2 on the first electrode 10, The step of immersing the porous semiconductor layer 12 in the dye solution to adsorb the dye molecules 4, the step of forming the second electrode 18 on the second substrate 22, the first substrate 20 and the second substrate 22 on the first substrate 20 A step of applying a photocurable resin to form the first base portion 16A and the second base portion 16B having a predetermined height, and a step of irradiating the first photocurable resin with light to cure the first photocurable resin. And applying the second photo-curing resin to the first base portion 16A or the second base portion 16B to form the second sealing portion 40, the first substrate 20 and the second substrate 22 facing each other, The first sealing portion 16A and the second mounting portion 16B are connected to the second sealing portion 40. And the step of causing the second photocurable resin to cure by irradiating the second photocurable resin with the second light through the opening AP of the first base portion 16A or the second base portion 16B. And a step of injecting an electrolytic solution 14 in which a redox electrolyte is dissolved in a solvent between the first substrate 20 and the second substrate 22. Of course, there is a step of causing the second photo-curing resin to protrude from the side surfaces of the first base portion 16A and the second base portion 16B by applying pressure in the direction in which the first base portion 16A and the second base portion 16B are brought into close contact with each other. May be.

(A) First, as shown in FIG. 18, a first electrode (transparent electrode) 10 is formed on a first substrate 20 made of a glass substrate or the like. The first electrode 10 is formed by, for example, sputtering film formation of FTO, ZnO, ITO, SnO ₂ or the like.

(B) Next, as shown in FIG. 19, the porous semiconductor layer 12 is formed on the first electrode. Specifically, for example, a paste containing fine particles such as TiO ₂ , ZnO, WO ₃ , InO ₃ , ZrO ₂ , Ta ₂ O ₃ , Nb ₂ O ₃ , SnO ₂ is applied by screen printing, and paste at a predetermined temperature. By baking the layer, the porous semiconductor layer 12 is formed.

(C) Next, as shown in FIG. 20, the porous semiconductor layer 12 is adsorbed with the dye by immersing the porous semiconductor layer 12 in the dye solution. As the dye, D149, red die (N719), D131, black die (N749) and the like shown in FIG. 8 can be applied. Thereby, as shown in FIG. 20, a working electrode provided with the porous semiconductor layer 12 in which the dye (Dye) is adsorbed is created.

(D) Next, as shown in FIG. 21, the porous semiconductor layer 13 is surrounded and an ultraviolet curable resin is applied to form the first sealing portion 16. Specifically, as shown in FIGS. 13A to 13F and FIGS. 16A and 16B, the first base portion 16A is provided on the first substrate 20, and the second base portion is provided on the second substrate 22. 16B is formed in advance, and an ultraviolet curable resin constituting the second sealing portion 40 is applied on the first base portion 16A by screen printing.

(E) Next, as shown in FIG. 22, the first substrate 20 and the second substrate 22 are opposed to each other through the first sealing portion 16. The second electrode 18 is formed on the second substrate 22 in advance. Further, the second substrate 22 is provided with an inlet 34a and an exhaust hole 34b for the electrolytic solution 14. By bonding the first substrate 20 and the second substrate 22 together, the first sealing portion 16 is in a state as shown in FIGS. 13 (a) to 13 (f) and FIGS. 16 (a) and 16 (b). . Of course, the ultraviolet curable resin can be protruded from the side surface of the first sealing portion 16. Then, ultraviolet rays (UV) are irradiated from either the first substrate 20 side or the second substrate 22 side.

  As shown in FIGS. 13A to 13F and FIGS. 16A and 16B, the ultraviolet rays (UV) are directly incident on the ultraviolet curable resin constituting the second sealing portion 40 from the opening AP. . Thereby, the 2nd sealing part 40 is fully hardened, and the 1st base part 16A and the 2nd base part 16B, and the 2nd sealing part 40 are connected firmly.

(F) Next, as shown in FIG. 23, after the electrolyte solution 14 is injected from the injection port 34a, the glass plate 34c is bonded and sealed to the injection port 34a and the vent hole 34b, respectively.

  The DSC 200 completed through the above steps has a high sealing property because the sealing portion is sufficiently cured, effectively prevents moisture and oxygen from entering the cell, and improves weather resistance and durability.

(DSC: embodiment)
A schematic planar pattern configuration of the DSC according to the embodiment is expressed as shown in FIG. 25, and a schematic cross-sectional structure taken along line II in FIG. 25 is expressed as shown in FIG. A schematic cross-sectional structure along the line II-II is expressed as shown in FIG. 27, and a schematic cross-sectional structure along the line III-III in FIG. 25 is expressed as shown in FIG. The enlarged schematic planar pattern configuration is expressed as shown in FIG.

  As shown in FIGS. 25 to 29, 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 first sealing portion 16 is disposed between the first substrate 20 and the second substrate 22 and seals the electrolytic solution 14. Of course, it is possible to form the second sealing portion 40 on the outer peripheral portion of the first sealing portion 16. In the following description, the first sealing portion 16 may be referred to as the sealing material 16.

  In addition, as shown in FIGS. 25 to 29, 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.

  In addition, as shown in FIGS. 25 to 29, the DSC 200 according to the embodiment injects the electrolyte 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 internal first electrode 10A and the external 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. 25 and 27 to 29, the internal second electrode 18A and the external second electrode 18B are arranged 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.

  Further, as shown in FIGS. 25 to 29, the sealing material 16 is not in contact with the internal first electrode 10 </ b> A and the internal second electrode 18 </ b> A. On the other hand, as shown in FIGS. 25 to 29, 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. 25 and 27 to 29, 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. The first electrode 10A and the second electrode 18A may be in contact with each other.

  Moreover, in DSC200 which concerns on embodiment, as shown in FIGS. 25-29, the surface of internal 2nd electrode 18A may be provided with the catalyst layer 19 in contact with the electrolyte solution 14. As shown in FIG.

  The sealing material 16, the cap sealing material 3 a, and the opening sealing material 3 b can be configured by glass frit, ultraviolet curable resin, thermosetting resin, or a structural combination thereof.

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. 30, 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.

  Moreover, 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 wet DSC etc., Comprising material differs, when normal temperature molten salt (ionic liquid) and a solid electrolyte are used.

  In the 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. 33 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 includes a mixed redox electrolyte of iodine and bromine, as shown in FIG. 34, 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. 35, when light is irradiated from the outside, 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 .

  36 is a chemical structural formula showing a dye used in the DSC according to the embodiment, the chemical structural formula showing indoline is expressed as shown in FIG. 36A, and the chemical structural formula showing N719 is shown in FIG. The chemical structural formula shown as shown in b) and showing D131 is shown as shown in FIG.

  37 is a chemical structural formula showing another dye used in the DSC 200 according to the embodiment, and the chemical structural formula of D205 exhibiting a purple color is represented as shown in FIG. The chemical structural formula shown is expressed 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. Also, the schematic circuit representation of FIG. 38A is expressed as shown in FIG.

As shown in FIG. 38A, the basic cell includes a first substrate 20 and 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 .

Further, as shown in FIG. 38 (a), the basic cell has external first electrodes 10 ₁ B, 10 ₂ B, 10 ₃ B, and 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.

Further, 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 outer 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. 38 (b), the four basic cells are arranged in a series configuration.

Also in each basic cell shown in FIG. 38, 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.

Also in each basic cell shown in FIG. 38, the electrolytic solutions 14 ₁ , 14 ₂ , 14 ₃ , 14 ₄ are formed on the surfaces of the internal second electrodes 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 represented as shown in FIG. Also, the schematic circuit representation of FIG. 39A 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. 39 (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.

(Production method)
The DSC manufacturing method according to the embodiment is expressed as shown in FIGS. 40 (a) to 40 (g).

(A) First, as shown in FIG. 40A, the second substrate 22 is pretreated by a cleaning process. Here, the 2nd board | substrate 22 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.

(B) Next, as shown in FIG. 40B, the internal second electrode 18A is patterned on the second substrate 22. The external second electrode 18B is also formed on the second substrate 22 at the same time. Here, the internal second electrode 18A and the external second electrode 18B 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, and glass with a transparent electrode. If it is a substrate, it is possible to form a pattern by various etching methods.

(C) Next, as shown in FIG. 40C, the catalyst layer 19 is formed on the internal second electrode 18A. The catalyst layer 19 can be formed by screen printing or the like.

(D) Next, as shown in FIG. 40D, after the pretreatment of the first substrate 20, the internal first electrode 10 </ b> A is patterned on the first substrate 20, as with the second substrate 22. The external first electrode 10B is also formed on the first substrate 20 at the same time. Here, the first substrate 20 can be formed of a glass substrate or the like. Here, the internal first electrode 10A and the external first electrode 10B 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.

(E) Next, as shown in FIG. 40 (e), after forming the porous semiconductor layer 12 on the internal first electrode 10 </ b> A, the dye Dye is immersed in the porous semiconductor layer 12. The porous semiconductor layer 12 can be formed by applying screen printing or the like. In the steps so far, the processing step for the second substrate 22 is performed first with respect to the processing step for the first substrate 20, but the processing step for the first substrate 20 is performed for the second substrate 22. May be performed first.

(F) Next, as shown in FIG. 40 (f), the second substrate 22 after the step of FIG. 40 (c) and the first substrate 20 after the step of FIG. 40 (e) are opposed to each other and sealed. Bonding is performed using a stopper 16. Of course, the ultraviolet curable resin can be protruded from the side surface of the sealing material 16.

(G) Next, as shown in FIG. 40G, the electrolytic solution 14 is sealed inside the opening, the opening is sealed, and a DSC cell is formed.

(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 process of manufacturing a DSC according to the embodiment, which includes a plurality of internal first electrodes 10 ₁₁ A, 10 ₁₂ A,..., 10 _1n A, ..., 10 _m1 A, 10 _m2 on the first substrate 20. A plan view showing a state where A... 10 _mn A is formed is expressed as shown in FIG. Here, the external first electrodes 10 ₁₁ B, 10 ₁₂ B,..., 10 _1n B,..., 10 _m1 B, 10 _m2 B _,.

In the DSC manufacturing method according to the embodiment, a plurality of second electrodes 18 ₁₁ A, 18 ₁₂ A,..., 18 _1n A, ..., 18 _m1 A, 18 _m2 A are formed on the second substrate 22. ... A plan view showing a state where 18 _mn A is formed is expressed as shown in FIG. Here, the external second electrodes 18 ₁₁ B, 18 ₁₂ B,..., 18 _1n B,..., 18 _m1 B, 18 _m2 B _,.

  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. 43, and a schematic cross-sectional structure taken along line IV-IV in FIG. 43 is represented as shown in FIG. 43 and 44, 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. 45 is a plan view showing a state in which the horizontal scribe line SL1 is formed, which is a process 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. 44, 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 m × n DSCs are bonded together as shown in FIG. 44, 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, a vertical scribe line SL2 is formed as shown in FIG.

  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. 47 to 50, application examples of the battery cell (hereinafter simply referred to as “cell”) configured by the DSC 200 according to the embodiment will be described.

  FIG. 47A shows a state in which three cells B1 to B3 are formed. In the example of FIG. 47A, 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. 48 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. 49 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. 50 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. 51 to 53, a configuration example of remote control device 330 equipped with DSC 200 according to the embodiment will be described.

  As shown in FIG. 51 and FIG. 52, the remote control device 330 is provided with an opening 41 penetrating the front and back in a casing 38 made of plastic or the like, and provided with the DSC 200 facing 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. 52, a transparent member 210 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 210, 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 and room light is incident from the front surface side, back surface side, and side surface side of remote control device 330 via transparent member 210. 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. 53, the transparent member 210 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. 53, the DSC 200 exhibits a power generation function by light 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. 54, 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. 54, 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. 54, the DSC 200 provided in the tabletop digital timepiece 50 has a power generation function by using either a light ray (hνf) incident from the front side or a light ray (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. 55, a configuration example of electronic notebook 80 equipped with 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.

  An opening 45 is formed in the lid 80a so as to penetrate the lid 80a itself from the front and back, and the DSC 200 is provided so as to face the opening 45. The DSC 200 may be configured by connecting a plurality of cells.

  As shown in FIG. 55 (a), the DSC 200 provided 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 portion 80a is opened, and stable power is supplied to the main body portion 80b. Can be supplied.

  On the other hand, even when the lid 80a is closed as shown in FIG. 55 (b), the DSC 200 exhibits a power generation function by incident light from the front side, and is 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. 56, 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. 56, when the lid 90a is opened, the DSC 200 on the lid 90a side performs a power generation function by any of the light rays 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 that can improve the adhesion and moisture resistance of the sealing portion, a method for manufacturing the same, and an electronic apparatus.

[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 particle 3a ... Cap sealing material 3b ... Opening sealing material 3A ... Connection electrode 3B ... Insulating layer 4, 30, 32 ... Dye molecule 10 ... First electrode 12, 13, 13 ₁ , 13 ₂ , 13 ₃ 13 ₄ ... Porous semiconductor layer 14 · 14 ₁ · 14 ₂ · 14 ₃ · 14 ₄ ... Electrolytic solution 16 ... First sealing part (sealing material)
16A ... 1st sealing part (1st base part, glass frit)
16B ... 1st sealing part (2nd base part, glass frit)
18 ... second electrode 19, 19 _1, 19 _2, 19 _3, 19 ₄ ... catalyst layer 20 ... first substrate 21 ... platemaking 22 ... second substrate 40 ... second sealing portion 40A, 40B, 40W ... photocurable resin (UV curable resin)
50S ... Squeegee 200, 200A, 200B ... Dye-sensitized solar cell (DSC)

Claims (28)

A first substrate;
A first electrode disposed on the first substrate;
A porous semiconductor layer disposed on the first electrode and having semiconductor fine particles and dye molecules;
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 first sealing portion disposed between the first substrate and the second substrate and sealing the electrolytic solution;
A dye-sensitized solar cell, comprising: a second sealing portion that is formed on an outer peripheral portion of the first sealing portion and seals the electrolytic solution. The first sealing portion includes a first base portion and a second base portion having a predetermined height formed by applying glass frit on the first substrate and the second substrate,
The second sealing portion includes a light curable resin formed on a joint portion between the first base portion and the second base portion, and side surfaces of the first base portion and the second base portion. The dye-sensitized solar cell according to claim 1, wherein   The second sealing portion is formed by causing the photocurable resin to protrude from side surfaces of the first base portion and the second base portion when the first substrate and the second substrate are bonded together. The dye-sensitized solar cell according to claim 2.   4. The dye-sensitized solar cell according to claim 3, wherein the thickness of the portion where the photocurable resin protrudes is ½ or more of the line width of the first base portion or the second base portion.   5. The dye-sensitized solar cell according to claim 4, wherein the amount of the photocurable resin protruding is adjusted by a pressure applied in a direction in which the first base portion and the second base portion are brought into close contact with each other.   5. The dye-sensitized solar cell according to claim 4, wherein the amount of the photocuring resin protruding is adjusted by a pressure of sliding a squeegee on screen printing plate making.   5. The dye-sensitized solar cell according to claim 4, wherein the amount of the photo-curing resin protruding is adjusted by the viscosity of the photo-curing resin.   5. The dye-sensitized solar cell according to claim 4, wherein the amount of the photo-curing resin protruding is adjusted by an interval between the first substrate or the second substrate and screen printing plate-making.   The dye-sensitized solar cell according to any one of claims 2 to 8, wherein the photo-curing resin is an ultraviolet-curing resin.   The said 1st board | substrate and the said 2nd board | substrate are formed with the glass substrate or the glass substrate with a transparent electrode in which the transparent electrode was formed in the whole surface, The any one of Claims 1-9 characterized by the above-mentioned. Dye-sensitized solar cell. The first electrode and the second electrode, ITO, FTO, ZnO, dye-sensitized solar cell according to any one of claims 1 to 10, characterized in that it is formed in one of SnO _2. 12. 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 12, wherein the catalyst layer is formed of any one of Pt, carbon, and a conductive polymer.   14. 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 is formed of any one of a red dye (N719), a black dye (N749), D131, D205, a phthalocyanine dye, and a porphyrin dye. Dye-sensitized solar cell. Forming a first electrode on a first substrate;
Forming a porous semiconductor layer having semiconductor fine particles on the first electrode;
Immersing the porous semiconductor layer in a dye solution to adsorb dye molecules;
Forming a second electrode on the second substrate;
Forming a catalyst layer on the second electrode;
Applying glass frit on the first substrate and the second substrate to form a first base portion and a second base portion having a predetermined height;
Applying a photo-curing resin on the first base part and the second base part;
The first substrate and the second substrate are opposed to each other, and the first base portion and the second base portion are brought into close contact with each other via the photocurable resin;
A step of causing the photocurable resin to protrude from the side surfaces of the first base part and the second base part by applying pressure in a direction in which the first base part and the second base part are in close contact with each other; and
Irradiating and curing the light curable resin;
And a step of injecting an electrolytic solution in which a redox electrolyte is dissolved in a solvent between the first substrate and the second substrate.   17. The dye-sensitized solar cell according to claim 16, wherein a thickness of a portion where the photocurable resin protrudes is ½ or more of a line width of the first base portion or the second base portion. Production method.   18. The dye-sensitized solar cell according to claim 17, wherein the amount of the photocurable resin protruding is adjusted by a pressure applied in a direction in which the first base portion and the second base portion are in close contact with each other. Production method.   18. The method for producing a dye-sensitized solar cell according to claim 17, wherein the amount of the photo-curing resin protruding is adjusted by a pressure of sliding a squeegee on a plate for screen printing.   The method for producing a dye-sensitized solar cell according to claim 17, wherein the amount of the photo-curing resin protruding is adjusted by the viscosity of the photo-curing resin.   18. The dye-sensitized solar cell according to claim 17, wherein the amount of the photocuring resin protruding is adjusted by an interval between the first substrate or the second substrate and a plate for screen printing. Method.   The said 1st board | substrate and the said 2nd board | substrate are formed by the glass substrate or the glass substrate with a transparent electrode in which the transparent electrode was formed in the whole surface, The any one of Claims 16-21 characterized by the above-mentioned. A method for producing a dye-sensitized solar cell. The first electrode and the second electrode, ITO, FTO, ZnO, of the dye-sensitized solar cell according to any one of claims 16-22, 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 producing a dye-sensitized solar cell according to any one of claims 16 to 24, wherein the catalyst layer is formed of any one of Pt, carbon, and a conductive polymer.   The electrolyte solution is formed of any one of γ-butyrolactone, propylene carbonate, ethylene carbonate, propylene carbonate, acetonitrile, methoxyacetonitrile, and propionitrile, according to any one of claims 16 to 25. A method for producing a dye-sensitized solar cell.   27. The dye according to any one of claims 16 to 26, wherein the dye is formed of any one of a red dye (N719), a black dye (N749), D131, D295, a phthalocyanine dye, and a porphyrin dye. A method for producing a dye-sensitized solar cell.   An electronic apparatus comprising the dye-sensitized solar cell according to any one of claims 1 to 15.

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