JP2014143077A - Dye-sensitized solar cell, method for manufacturing the same, and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell capable of suppressing a decrease in power generation efficiency by suppressing moisture permeation into an element.SOLUTION: A dye-sensitized solar cell comprises: a first substrate 20; a first internal electrode 10A arranged on the first substrate 20; a porous semiconductor layer 12 arranged on the first internal electrode 10A and including a semiconductor fine particle 2 and a dye molecule 4; an electrolyte 14 which is in contact with the porous semiconductor layer 12 and in which an oxidation-reduction electrolyte is dissolved in a solvent; a second internal electrode 18A in contact with the electrolyte 14; a second substrate 22 arranged on the second internal electrode 18A; and a sealing material 16 arranged between the first substrate 20 and the second substrate 22 and sealing the electrolyte 14. Water-repellent processing is performed in a sidewall outside the sealing material 16.

Description

  The present invention relates to a dye-sensitized solar cell (DSC), and in particular, a dye-sensitized solar cell capable of suppressing moisture permeation into an element and suppressing a decrease in power generation efficiency and a method for manufacturing the same. And electronic devices.

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

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

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

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

JP-A-11-135817 JP 2000-30767

  An object of the present invention is to provide a dye-sensitized solar cell that can suppress moisture permeation into the device and suppress a decrease in power generation efficiency, a method for manufacturing the same, and an electronic device.

  According to one aspect of the present invention for achieving the above object, a first substrate, an internal first electrode disposed on the first substrate, a semiconductor fine particle and a dye disposed on the internal first electrode A porous semiconductor layer comprising molecules; an electrolyte solution in contact with the porous semiconductor layer; a redox electrolyte dissolved in a solvent; an internal second electrode in contact with the electrolyte solution; and an internal second electrode disposed on the internal second electrode A second substrate, and a sealing material that is disposed between the first substrate and the second substrate and seals the electrolytic solution, and the sealing material performs water-repellent treatment on an external side wall. A dye-sensitized solar cell is provided.

  According to another aspect of the present invention, after the first substrate is pre-processed by a cleaning process, a step of patterning the internal first electrode and the external first electrode on the first substrate, and the internal first electrode After forming the porous semiconductor layer on the substrate, the step of immersing the dye in the porous semiconductor layer, the second substrate is pretreated by the cleaning step, and then the internal second electrode and the external second electrode are formed on the second substrate. A step of forming a pattern, a step of forming a catalyst layer on the internal second electrode, a step of making the first substrate and the second substrate face each other and bonding them together using a sealing material, and the sealing Provided is a method for manufacturing a dye-sensitized solar cell, which includes a step of performing water-repellent treatment on an outer side wall of a material, and a step of sealing an opening by enclosing an electrolyte in a DSC cell from the opening. .

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

  According to the present invention, it is possible to provide a dye-sensitized solar cell that can suppress moisture permeation into the device and suppress a decrease in power generation efficiency, a method for manufacturing the same, and an electronic apparatus.

The schematic plane pattern block diagram of DSC which concerns on a comparative example. FIG. 2 is a schematic cross-sectional structure diagram taken along line II in FIG. 1. FIG. 2 is a schematic cross-sectional structure diagram taken along line II-II in FIG. 1. FIG. 3 is a schematic sectional view taken along line III-III in FIG. 1. An example of an overview photograph of a DSC according to a comparative example that was prototyped. In DSC which concerns on a comparative example, the typical sectional structure figure by which the contact part of a sealing material, a 1st electrode, and a 2nd electrode was expanded. The typical plane pattern block diagram of DSC which concerns on another comparative example. FIG. 8 is an example of a surface optical micrograph of a portion B in FIG. 7. The typical plane pattern block diagram of DSC which concerns on 1st Embodiment. FIG. 10 is a schematic sectional view taken along line IV-IV in FIG. 9. FIG. 10 is a schematic sectional view taken along line VV in FIG. 9. FIG. 10 is a schematic cross-sectional structure diagram taken along line VI-VI in FIG. 9. FIG. 10 is an enlarged schematic plane pattern configuration diagram of a portion A in FIG. 9. 2 is an example of an overview photograph of a DSC according to the first embodiment manufactured as a prototype. (a) In DSC which concerns on a comparative example, the typical cross-section figure explaining a mode that a water | moisture content permeates through a sealing material, (b) In DSC which concerns on 1st Embodiment, by water-repellent treatment (HMDS process). FIG. 3 is a schematic cross-sectional structure diagram illustrating a state in which moisture permeation into the element can be suppressed. The schematic diagram explaining the operation principle of the water-repellent process (HMDS process) in the surface of a sealing material in DSC which concerns on 1st Embodiment. The DSC which concerns on 1st Embodiment WHEREIN: The example of a microscope picture of the water droplet on the surface of the sealing material in case the water-repellent process (HMDS process) is not processed to the sealing material surface. The DSC which concerns on 1st Embodiment WHEREIN: The example of a microscope picture of the water droplet on the surface of the sealing material at the time of implementing water-repellent processing (HMDS processing) on the sealing material surface. In DSC which concerns on 1st Embodiment, the schematic diagram explaining a mode that the HMDS molecule | numerator adjoined to the surface of the sealing material. In DSC which concerns on 1st Embodiment, the schematic diagram explaining a HMDS molecule | numerator adjoining to the surface of a sealing material, and a chemical bond reaction having arisen. The DSC which concerns on 1st Embodiment WHEREIN: It is a 60 degreeC90% RH test result, Comprising: The figure which shows the relationship between the electric power generation initial value ratio by the presence or absence of HMDS process, and time. The typical structure figure of the semiconductor fine particle of the porous semiconductor layer of DSC which concerns on 1st Embodiment. Explanatory drawing of the operation principle of the DSC according to the first embodiment. Explanatory drawing of the operation principle based on the charge exchange reaction in the electrolyte solution of the DSC according to the first embodiment. In DSC which concerns on 1st Embodiment, the energy potential diagram between a porous semiconductor layer (12) / dye molecule (32) / electrolyte solution (14). In DSC which concerns on 1st Embodiment, it is an energy potential diagram between a dye molecule (32) / electrolyte solution (14), Comprising: The enlarged view of the J section of FIG. Explanatory drawing which shows the energy level and electric power generation cycle of each component material of DSC which concern on 1st Embodiment. 1 is a chemical structural formula showing a dye used in the DSC according to the first embodiment, wherein (a) chemical structural formula showing indoline, (b) chemical structural formula showing N719, and (c) chemical structural formula showing D131. formula. (A) In DSC which concerns on 1st Embodiment, the typical cross-section figure which has arrange | positioned four basic cells in series structure, (b) The typical circuit representation of Fig.29 (a). (A) In DSC which concerns on 1st Embodiment, the typical cross-section figure which has arrange | positioned four basic cells in parallel structure, (b) The typical circuit expression of Fig.30 (a). It is a DSC manufacturing method according to the first embodiment, (a) a process diagram for pre-processing a second substrate, (b) a process diagram for forming a second electrode on the second substrate, (c) a first process diagram. A process diagram for forming a catalyst layer on two electrodes, (d) a process diagram for forming a first electrode on the first substrate after pretreatment of the first substrate, and (e) a porous semiconductor layer on the first electrode. Step of immersing the dye in the porous semiconductor layer after formation, (f) The second substrate after the step of FIG. 31 (c) and the first substrate after the step of FIG. A process diagram in which a water repellent treatment is performed on the outer side wall of the sealing material after bonding using a stopper, (g) an electrolytic solution is sealed inside from the opening, the opening is sealed, and the DSC cell is sealed Process drawing to form. The typical plane pattern block diagram which shows the example of arrangement | positioning in the board | substrate of the sample (test cell) of DSC which concerns on 1st Embodiment, and a cut line. The typical plane pattern block diagram which shows another example of arrangement | positioning in the board | substrate of the sample (test cell) of DSC which concerns on 1st Embodiment, and a cut line. The typical plane pattern block diagram which shows another example of arrangement | positioning in the board | substrate of the sample (test cell) of DSC which concerns on 1st Embodiment, and a cut line. The top view which shows one process of the manufacturing method of DSC which concerns on 1st Embodiment, and shows the state in which the some internal 1st electrode was formed on the 1st board | substrate. FIG. 5 is a plan view showing a state in which a plurality of internal second electrodes are formed on a second substrate, which is one step of the DSC manufacturing method according to the first embodiment. The top view which is 1 process of the manufacturing method of DSC which concerns on 1st Embodiment, Comprising: The state which bonded together the 1st board | substrate and the 2nd board | substrate through the sealing material. FIG. 38 is a schematic cross-sectional structure diagram showing a DSC manufacturing method according to the first embodiment, which is taken along line VII-VII in FIG. 37. The top view which is 1 process of the manufacturing method of DSC which concerns on 1st 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 1st Embodiment, Comprising: The state which further formed the scribe line of the vertical direction. The typical cross-section figure of DSC which concerns on 2nd Embodiment. (A) In DSC which concerns on 2nd Embodiment, the typical cross-section figure which has arrange | positioned four basic cells in series structure, (b) The typical circuit expression of Fig.42 (a). (A) In DSC which concerns on 2nd Embodiment, the typical cross-section figure which has arrange | positioned four basic cells in parallel structure, (b) The typical circuit expression of Fig.42 (a). It is a DSC manufacturing method according to the second embodiment, wherein (a) a process diagram for pre-processing a second substrate, (b) a process diagram for forming a second electrode on the second substrate, and (c) a process diagram. Step diagram for forming a catalyst layer on two electrodes, (d) Step diagram for roughening the surface of the second substrate after forming a mask on the second electrode and the catalyst layer, (e) Roughened layer (F) After the first substrate is pre-processed, the first electrode is patterned on the first substrate, and the surface of the first substrate is roughened at the same time. Step diagram of forming a layer, (g) Step diagram of immersing a dye in the porous semiconductor layer after forming a porous semiconductor layer on the first electrode, (h) Second substrate after step of FIG. 44 (e) 44 (g) is a process diagram in which the first substrate after the process of FIG. 44 (g) is opposed to each other and pasted together using a sealing material. (I) An electrolytic solution is sealed inside through an opening. It seals the opening process chart of forming a DSC cell. (A) Schematic plane pattern configuration diagram in the case of not performing the roughening process (corresponding to the first embodiment), (b) Schematic of the DSC according to the second embodiment in which the roughening process is performed FIG. (A) An example of an appearance photograph of a prototype sample when the roughening treatment is not performed (the glass substrate is transparent), (b) An appearance photograph of the DSC prototype sample according to the second embodiment in which the roughening treatment is performed. Example (glass substrate is rubbed and glassy opaque). (A) The top view which shows the structure which formed three cells of DSC concerning the 1st-2nd embodiment, (b) The explanatory view which shows the state which connected the three cells in series. (A) Schematic diagram showing a state in which five DSC cells according to the first and second embodiments are connected in series, (b) an explanatory view of FIG. 48 (a), and (c) FIG. 48 (a). FIG. (A) Schematic diagram showing a state in which n DSC cells according to the first and second embodiments are stacked in a tandem configuration, and (b) an explanatory diagram of FIG. 49 (a). (A) A schematic diagram showing a state in which n DSC cells according to the first and second embodiments are stacked in a tandem configuration and connected in parallel, (b) an explanatory diagram of FIG. The graph which shows the wavelength of the light rays L1, L2, and L3. The top view which shows the structural example of the remote control device carrying DSC which concerns on the 1st-2nd embodiment. The side view of the remote control device carrying DSC which concerns on the 1st-2nd embodiment. The side view which shows the other structural example of the remote control device carrying DSC which concerns on the 1st-2nd embodiment. The bird's-eye view which shows the structural example of the desktop digital timepiece carrying DSC which concerns on the 1st-2nd embodiment. (A) The bird's-eye view which shows the state which opened the electronic notebook carrying DSC which concerns on 1st-2nd 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 the 1st-2nd embodiment. The typical block block diagram of the DSC drive sensor module carrying DSC which concerns on the 1st-2nd embodiment. The typical block block diagram of another DSC drive sensor module carrying DSC which concerns on the 1st-2nd embodiment. The structural example of the home energy management system (HEMS: Home Energy Management System) to which the DSC drive sensor module carrying the DSC according to the first to second embodiments is applied.

  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.

[First embodiment]
(DSC: comparative example)
A schematic planar pattern configuration of the DSC 200A according to the comparative example is expressed as shown in FIG. 1, and a schematic cross-sectional structure taken along line II in FIG. 1 is expressed as shown in FIG. A schematic cross-sectional structure along the line -II is represented as shown in FIG. 3, and a schematic cross-sectional structure along the line III-III in FIG. 1 is represented as shown in FIG.

  1 to 4, the DSC 200A according to the comparative example includes a first substrate 20, a first electrode 10 disposed on the first substrate 20, a semiconductor fine particle disposed on the first electrode 10, and A porous semiconductor layer 12 having a dye molecule, an electrolytic solution 14 in contact with the porous semiconductor layer 12 and having a redox electrolyte dissolved in a solvent, a second electrode (counter electrode) 18 in contact with the electrolytic solution 14, and a second electrode 18 The second substrate 22 disposed above, the catalyst layer 19 disposed on the surface of the second electrode 18 in contact with the electrolytic solution 14, and disposed between the first electrode 10 and the second electrode 18, and the electrolytic solution 14 And a sealing material 16 for sealing. Here, 3a and 3b are sealing materials for the opening for injecting the electrolytic solution.

  In the DSC 200A according to the comparative example, the sealing material 16 is in contact with the first electrode 10 and the second electrode 18 as shown in FIGS.

  An example of an overview photograph of a DSC 200A according to a comparative example manufactured as a prototype is expressed as shown in FIG. As is clear from FIG. 5, the electrolyte solution 14 sealed with the sealing material 16 flows out of the sealing material 16.

  In the DSC 200A according to the comparative example, an enlarged schematic cross-sectional structure of contact portions Lu and Ld between the sealing material 16 and the first electrode 10 and the second electrode 18 is expressed as shown in FIG.

  A schematic planar pattern configuration of a DSC 200B according to another comparative example is expressed as shown in FIG. In a DSC 200B according to another comparative example, as shown in FIG. 7, a part of the first electrode 10 and the second electrode 18 is removed by patterning. For this reason, the sealing material 16 is in direct contact with the first substrate 20 and the second substrate 22 in the region where the first electrode 10 and the second electrode 18 are removed. In FIG. 7, the sealing material 16 is in contact with both the second electrode 18 and the second substrate 22 in the portion B.

  FIG. 8 shows an example of a surface optical micrograph of a portion B of FIG. 7 after 250 hours in a 60 ° C. 90% RH test, which is a prototype example of DSC 200B according to another comparative example.

As is clear from FIG. 8, in the range where the sealing material 16 is in direct contact with the second substrate 22, no floating of the sealing material 16 is observed. On the other hand, in the boundary region where the sealing material 16 is in contact with the second electrode 18, the seal floating state (sealing material 16A) of the sealing material 16 is observed, and this seal floating portion (the sealing material 16 is the second material). The boundary region in contact with the electrode 18) causes the electrolyte solution 14A to flow out (electrolyte solution 14A).

  Thus, in the DSC 200A or 200B according to the comparative example, since the sealing material 16 is in direct contact with the first electrode 10 and the second electrode 18, the first sealing material 16 and the first sealing material 16 shown in FIG. The outflow of the electrolyte solution 14 is observed at the contact portions Lu and Ld between the electrode 10 and the second electrode 18.

(DSC: First Embodiment)
A schematic planar pattern configuration of the DSC according to the first embodiment is expressed as shown in FIG. 9, and a schematic cross-sectional structure taken along line IV-IV in FIG. 9 is expressed as shown in FIG. 9 is represented as shown in FIG. 11, and the schematic cross-sectional structure along line VI-VI in FIG. 9 is represented as shown in FIG. An enlarged schematic plane pattern configuration of the A part of the A is expressed as shown in FIG.

  As shown in FIGS. 9 to 13, the DSC 200 according to the first embodiment includes a first substrate 20, an internal first electrode 10 </ b> A disposed on the first substrate 20, and an internal first electrode 10 </ b> A. The disposed porous semiconductor layer 12, the electrolytic solution 14 in contact with the porous semiconductor layer 12, in which the redox electrolyte is dissolved in the solvent, the internal second electrode (counter electrode) 18A in contact with the electrolytic solution 14, and the internal second electrode The second substrate 22 disposed on the first substrate 18 and the sealing material 16 disposed between the first substrate 20 and the second substrate 22 and sealing the electrolyte solution 14 are provided. Here, the sealing material 16 is subjected to water repellent treatment on the outer side wall.

  The water repellent treatment can be performed by, for example, hexamethyldisilazane (HMDS) (HMDS treatment), but other substances and chemicals having the same effect may be used.

  Moreover, the DSC 200 according to the first embodiment includes an external first electrode 10B disposed on the first substrate 20 outside the sealing material 16 and the sealing material 16 as shown in FIGS. The external second electrode 18B disposed on the external second substrate 22 may be provided.

  Further, as shown in FIGS. 9 to 13, the DSC 200 according to the first embodiment has an electrolyte solution in a 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 in 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 first 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. 9 and 11 to 13, the internal second electrode 18 </ b> A and the external second electrode 18 </ b> B are in the vicinity of the opening for injecting the electrolytic solution 14 and in the vicinity of the opening for injecting the electrolytic solution 14. Electrically connected.

  Moreover, the sealing material 16 is not in contact with the internal first electrode 10A and the internal second electrode 18A, as shown in FIGS. On the other hand, as shown in FIGS. 9 to 13, 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. 9 and 11 to 13, 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 electrolyte solution 14. In contact.

  Moreover, in DSC200 which concerns on 1st Embodiment, as shown in FIGS. 9-13, 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. .

  An example of an overview photograph of the prototype DSC 200 according to the first embodiment is represented as shown in FIG. As shown in FIG. 14, the outflow of the electrolyte solution 14 sealed with the sealing material 16 to the outside of the sealing material 16 is not observed.

  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.

  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.

The 1st board | substrate 20 and the 2nd board | substrate 22 can be formed with a glass substrate etc., for example. A flexible plastic substrate can also be used. In this case, as the TiO ₂ paste constituting the porous semiconductor layer, one that can be fired at 200 ° C. or less is used.

  Moreover, 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 electrodes 10A and 10B are formed of transparent electrodes such as ITO, FTO, ZnO, and SnO ₂ . An electrode may be processed on the first substrate 20 to form a substrate with an FTO, a substrate with a grid such as metal, or the composite substrate described above.

Similarly, the second electrodes 18A and 18B are formed of transparent electrodes such as ITO, FTO, ZnO, and SnO ₂ . An electrode may be processed on the second substrate 22 to form a substrate with FTO, a substrate with a grid such as metal, or the above-described composite substrate.

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 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.

  In the DSC 200 according to the first embodiment, the solvent is a liquid that dissolves the electrolyte and the additive, has a high boiling point, high chemical stability, high dielectric constant (electrolyte dissolves well), and low viscosity. It is desirable. For example, it may be composed of acetonitrile, propylene carbonate, γ-butyrolactone, methoxyacetonitrile, propionitrile, ethylene carbonate, propylene carbonate, and the like.

  Red dye (N719), black dye (N749), D131, etc. can be applied as the dye.

In the DSC 200A according to the comparative example, a schematic cross-sectional structure for explaining how moisture (H ₂ O) enters through the sealing material 16 is expressed as shown in FIG. On the other hand, in the DSC 200 according to the first embodiment, a schematic cross-sectional structure for explaining how water permeation into the element can be suppressed by water repellent treatment (HMDS treatment) is as shown in FIG. expressed. In the DSC 200A according to the comparative example, moisture (H ₂ O) penetrates into the DSC cell through the sealing material 16 and the electrolyte solution 14 may be altered or the pigment may be desorbed, resulting in a decrease in power generation efficiency. On the other hand, in the DSC 200 according to the first embodiment, the water repellent treatment (HMDS treatment) is performed on the outer side wall of the sealing material 16, so that moisture (H ₂ O) is passed through the sealing material 16 through the DSC. Intrusion into the cell can be suppressed.

  In the DSC 200 according to the first embodiment, the operation principle of the water repellent treatment (HMDS treatment) on the surface of the sealing material 16 is expressed as shown in FIG.

In the DSC 200 according to the first embodiment, HMDS molecules (NH (Si (CH ₃ ) ₃ ) ₂ ) and the surface of the sealing material 16 are formed by water repellent treatment (HMDS treatment) on the surface of the sealing material 16. The two OH groups react. That is, the reaction of the formula (1) proceeds.

NH (Si (CH ₃ ) ₃ ) ₂ + 2OH → 2SiO (CH ₃ ) ₃ + NH ₃ ↑ (1)

As a result, as shown in FIG. 16, molecules represented by SiO (CH ₃ ) ₃ are adsorbed on the surface of the sealing material 16, and entry of water (H ₂ O) molecules from the outside can be suppressed. Become.

  An example of a micrograph of the water droplet 17 on the surface of the sealing material 16 when the surface of the sealing material 16 has not been subjected to water repellent treatment (HMDS treatment) is represented as shown in FIG. On the other hand, in the DSC 200 according to the first embodiment, an example of a micrograph of the water droplet 17 on the surface of the sealing material 16 when the surface of the sealing material 16 is subjected to water repellent treatment (HMDS treatment) is shown in FIG. It is expressed as shown in

  In the example of FIG. 17, the adsorption angle of the water droplet 17 is about 60 degrees. On the other hand, in the example of FIG. 18, the adsorption angle of the water droplet 17 is about 90 degrees. Therefore, in the DSC 200 according to the first embodiment, the adsorption angle of the water droplet 17 when the HMDS treatment is performed on the surface of the sealing material 16 is about 90 degrees, and the water repellency is improved.

  In DSC200 which concerns on 1st Embodiment, a mode that the HMDS molecule | numerator adjoined to the surface of the sealing material 16 is typically represented as shown in FIG. The state in which the chemical bonding reaction has occurred is schematically represented as shown in FIG.

In the DSC 200 according to the first embodiment, the HMDS treatment on the surface of the encapsulant 16 causes HMDS molecules (NH (Si (CH ₃ ) ₃ ) ₂ ) and two OH on the surface of the encapsulant 16. The group proceeds according to the reaction formula (1), and the ammonia molecule NH ₃ is dissociated.

As a result, as shown in FIG. 20, molecules represented by SiO (CH ₃ ) ₃ are adsorbed on the surface of the sealing material 16, and entry of water (H ₂ O) molecules from the outside can be suppressed. Become.

  In the DSC 200 according to the first embodiment, the relationship between the initial value ratio of the power generation amount and the time according to the presence or absence of the HMDS process, which is a result of the 60 ° C. and 90% RH test, is expressed as shown in FIG. The power generation initial value ratio is a relative value that changes with time, assuming 1 when the time t = 0. When the HMDS process is performed for about 20 minutes, the power generation initial value ratio can be maintained at 1 even when t = 300h, whereas when the HMDS process is not performed, the power generation initial value ratio is maintained. When t exceeds 250 h, a downward trend is observed.

  According to the DSC according to the first embodiment, by performing the water repellent treatment (HMDS treatment) on the surface of the sealing material, it is possible to suppress a decrease in power generation efficiency even if it exceeds t = 300 h.

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

(Operating principle)
The operation principle of the DSC 200 according to the first 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 12 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 12.

  The operation principle based on the charge exchange reaction in the electrolyte solution 14 of the DSC 200 according to the first 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 12 made of TiO ₂ . The electrons (e ⁻ ) conducted through the porous semiconductor layer 12 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 first embodiment, the energy potential diagram between the porous semiconductor layer (12) / dye molecule (32) / electrolytic solution (14) is expressed as shown in FIG. Moreover, it is an energy potential diagram between a dye molecule (32) / electrolyte solution (14), Comprising: The enlarged view of J part of FIG. 25 is represented as shown in FIG.

When irradiated with light from the outside, the dye molecule 32 changes from the ground state HOMO to the excited state LUMO by photons (hν). The excited electrons (e ⁻ ) generated at this time are injected into the conduction band of the porous semiconductor layer 12 made of TiO ₂ . The electrons (e ⁻ ) conducted through the porous semiconductor layer 12 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 12 is the maximum electromotive force V _MAX . The value of the maximum electromotive force V _MAX varies depending on the redox electrolyte of the electrolytic solution 14. In the case of a single redox electrolyte system (iodine redox electrolyte), for example, 0.9 V (I, N719). When the electrolytic solution 14 contains a mixed redox electrolyte of iodine and bromine, as shown in FIG. 26, the redox potential of the mixed redox electrolyte is adjusted by adjusting the mixing ratio to oxidize the iodine redox electrolyte. It can be adjusted to any value between the reduction potential and the redox potential of the bromine redox electrolyte.

The energy level and power generation cycle of each constituent material of the DSC 200 according to the first embodiment are expressed as shown in FIG. In FIG. 27, 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 the photons (hν), and the porous semiconductor layer 12 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 12 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 12 is the maximum electromotive force V _MAX .

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

-Series configuration-
In the DSC 200 according to the first embodiment, a schematic cross-sectional structure in which four basic cells are arranged in series is expressed as shown in FIG. Also, the schematic circuit representation of FIG. 29A is expressed as shown in FIG.

As shown in FIG. 29A, 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 12 ₁ , 12 ₂ , 12 _3, and 12 ₄ disposed on internal first electrodes 10 ₁ A, 10 ₂ A, 10 ₃ A, 10 ₄ A, and porous semiconductor layers 12 ₁ , 12 ₂ · 12 ₃ · 12 _{4 in contact} with an electrolytic solution 14 ₁ · 14 ₂ · 14 ₃ · 14 _{4 in} which a redox electrolyte is dissolved in a solvent, and an internal second in contact with the electrolytic solution 14 ₁ · 14 ₂ · 14 ₃ · 14 ₄ The electrode (counter electrode) 18 ₁ A, 18 ₂ A, 18 ₃ A, 18 ₄ A, and the second substrate 22 disposed on the internal second electrode 18 ₁ A, 18 ₂ A, 18 ₃ A, 18 ₄ A, And a sealing material 16 which is disposed between the first substrate 20 and the second substrate 22 and seals the electrolytes 14 ₁ , 14 ₂ , 14 ₃ and 14 ₄ .

In addition, as shown in FIG. 29 (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 through a connection electrode 13A. 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 13A.

As a result, as shown in FIG. 29 (b), the four basic cells are arranged in a series configuration.

Also in each basic cell shown in FIG. 29, the electrolytes 14 ₁ , 14 ₂ , 14 ₃ , 14 are located in the cell region sandwiched between the first substrate 20 and the second substrate 22 and surrounded by the sealing material 16. ₄ with an opening for injecting ₄ and the internal first electrodes 10 ₁ A, 10 ₂ A, 10 ₃ A, 10 ₄ A and the external first electrodes 10 ₁ B, 10 ₂ B, 10 ₃ B, 10 ₄ B A pattern is formed on the first substrate 20 and connected to each other at the opening.

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

In each basic cell shown in FIG. 29, the electrolytes 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 first embodiment shown in FIGS.

―Parallel configuration―
In the DSC 200 according to the first embodiment, a schematic cross-sectional structure in which four basic cells are arranged in a parallel configuration is expressed as shown in FIG. The schematic circuit representation of FIG. 30A 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 13B 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 through the insulating layer 13B. As a result, as shown in FIG. 30 (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 first embodiment shown in FIGS.

(Production method)
The DSC manufacturing method according to the first embodiment is expressed as shown in FIGS. 31 (a) to 31 (g).

(A) First, as shown in FIG. 31A, the second substrate 22 is pretreated by a cleaning process. Here, the second substrate 22 can be composed of a glass substrate, a flexible plastic substrate, or the like, and a glass substrate with a transparent electrode having a transparent electrode formed on the entire surface or a flexible plastic substrate can also be used.

(B) Next, as shown in FIG. 31 (b), the internal second electrode 18 </ b> A 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. A substrate or a flexible plastic substrate can be patterned by various etching methods.

(C) Next, as shown in FIG. 31C, 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. 31 (d), similarly to the second substrate 22, after the first substrate 20 is pretreated, the internal first electrode 10 </ b> A is patterned on the first substrate 20. The external first electrode 10B is also formed on the first substrate 20 at the same time. Here, the 1st board | substrate 20 can be comprised with a glass substrate or a flexible plastic substrate. 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. 31 (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. 31 (f), the second substrate 22 after the step of FIG. 31 (c) and the first substrate 20 after the step of FIG. After bonding using the stopper 16, a water repellent treatment is performed on the outer side wall of the sealing member 16. Here, the water repellent treatment can be carried out with, for example, hexamethyldisilazane (HMDS) (HMDS treatment).

(G) Next, as shown in FIG. 31 (g), the electrolytic solution 14 is sealed inside the opening, the opening is sealed, and a DSC cell is formed. In addition, as shown in FIG.31 (g), you may implement the HMDS process after enclosing the electrolyte solution 14. FIG.

(DSC test cell placement example and cut line)
DSC samples (test cells) 200 ₁₁ , 200 ₁₂ ,... 200 _1n ,..., 200 _m1 , 200 _m2 ,..., 200 _mn in the first substrate 20 and cut lines A schematic planar pattern configuration of SL1 and SL2 is expressed as shown in FIG. Further, another exemplary arrangement in the substrate and a schematic plane pattern configuration of the cut line are expressed as shown in FIG. Further, another exemplary arrangement in the substrate and a schematic plane pattern configuration showing a cut line are expressed as shown in FIG.

  On the 1st board | substrate 20, the porous semiconductor layer 12 arrange | positioned on the internal 1st electrode 10A and the external 1st electrode 10B are arrange | positioned at matrix form. Also on the second substrate 22 facing the first substrate 20, the catalyst layer 19 and the external second electrode 18B disposed on the internal second electrode 18A are disposed in a matrix (not shown). The pattern shape of the first external electrode 10B shown in FIG. 32 corresponds to the example shown in FIG.

  The pattern shape of the external first electrode 10B shown in FIGS. 33 and 34 is a modification of the pattern shape of the external first electrode 10B shown in FIG. After the manufacturing process shown in FIG. 31, a plurality of individual DSC cells can be simultaneously formed by cutting along the cut lines SL1 and SL2. Also, a plurality of serial configurations shown in FIG. 29 or a parallel configuration shown in FIG. 30 can be formed simultaneously.

  Even when the pattern shape of the external first electrode 10B shown in FIG. 33 and FIG. 34 is applied, after the manufacturing process shown in FIG. 31, the individual cuts are made at the cut lines SL1 and SL2. A plurality of DSC cells can be formed simultaneously. Also, a plurality of serial configurations shown in FIG. 29 or a parallel configuration shown in FIG. 30 can be formed simultaneously.

(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 first embodiment, which includes a plurality of internal first electrodes 10 ₁₁ A, 10 ₁₂ A,..., 10 _1n A _,. A plan view showing a state where 10 _m2 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 _,.

A step in the method of manufacturing the DSC according to the first embodiment, the second electrode _{18 11 A · 18 12 A ·} ... · 18 more on the second substrate _{22 1n A · ... · 18 m1} A · FIG. 36 is a plan view showing a state in which 18 _m2 A... 18 _mn A is formed. Here, the external second electrodes 18 ₁₁ B, 18 ₁₂ B,..., 18 _1n B,..., 18 _m1 B, 18 _m2 B _,.

  It is a process of the DSC manufacturing method according to the first embodiment, and includes a state in which the first substrate (working electrode side) 20 and the second substrate (counter electrode side) 22 are bonded together via the sealing material 16. The plan view shown is represented as shown in FIG. 37, and the schematic cross-sectional structure taken along line VII-VII in FIG. 37 is represented as shown in FIG. In FIG. 37 and FIG. 38, the first substrate (working electrode side) 20 is arranged upward, and the second substrate (counter electrode side) is arranged downward.

  FIG. 39 is a plan view showing a state in which the horizontal scribe line SL1 is formed, which is a step of the DSC manufacturing method according to the first embodiment, and is further represented by a vertical scribe line. A plan view showing a state in which SL2 is formed is expressed as shown in FIG.

  As shown in FIG. 38, there is a portion where only the substrate remains between the sealing materials 16, but this becomes a scribe line SL2, which is separated into each element by a break such as hitting.

  Next, in a state where a total of m × n DSCs are bonded as shown in FIG. 38, a horizontal scribe line SL1 is formed as shown in FIG.

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

  Subsequently, as shown in FIG. 40, a vertical scribe line SL2 is formed.

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

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

  According to the first embodiment, a water-repellent treatment is performed on the side surface of the sealing material, thereby suppressing moisture permeation into the element and suppressing a decrease in power generation efficiency, and its A manufacturing method can be provided.

[Second Embodiment]
(DSC)
A schematic cross-sectional structure of the DSC according to the second embodiment is expressed as shown in FIG.

  As shown in FIG. 41, the DSC 200 according to the second embodiment is disposed on the first substrate 20, the internal first electrode 10A disposed on the first substrate 20, and the internal first electrode 10A. On the porous semiconductor layer 12, an electrolytic solution 14 in contact with the porous semiconductor layer 12, a redox electrolyte dissolved in a solvent, an internal second electrode (counter electrode) 18 A in contact with the electrolytic solution 14, and the internal second electrode 18 The second substrate 22 is disposed, and the sealing material 16 is disposed between the first substrate 20 and the second substrate 22 and seals the electrolytic solution 14. Here, the 1st board | substrate 20 and the 2nd board | substrate 22 are implementing the roughening process to the surface which opposes, and are provided with the roughening layers 20F * 22F as shown in FIG. Here, the sealing material 16 is subjected to water repellent treatment on the outer side wall. The water repellent treatment can be performed, for example, with hexamethyldisilazane (HMDS) (HMDS treatment).

  The DSC 200 according to the second embodiment includes the roughening layers 20F and 22F on the first substrate 20 and the second substrate 22, so that the sealing material 16 and the first substrate 20 and the second substrate 22 are separated from each other. Adhesion can be improved.

  Furthermore, the second embodiment DSC 200 can suppress water permeation into the element and reduce power generation efficiency by performing water repellent treatment on the side surface of the sealing material.

  In addition, although the DSC 200 according to the second embodiment is not shown in FIG. 41, the external first first electrode disposed on the roughened layer 20 </ b> F of the first substrate 20 outside the sealing material 16. The electrode 10B and the external second electrode 18B disposed on the roughened layer 22F of the second substrate 22 outside the sealing material 16 may be provided. Other configurations are the same as those of the first embodiment.

-Series configuration-
In the DSC according to the second embodiment, a schematic cross-sectional structure in which four basic cells are arranged in a series configuration is represented as shown in FIG. 42A, and the schematic circuit expression of FIG. This is expressed as shown in FIG. Here, the 1st board | substrate 20 and the 2nd board | substrate 22 are implementing the roughening process on the surface which opposes, and as shown to Fig.42 (a), it is provided with the roughening layers 20F and 22F.

42A, the external first electrodes 10 ₁ B, 10 ₂ B, 10 ₃ B, and the like are disposed on the roughened layer 20F of the first substrate 20 outside the sealing material 16. 10 ₄ B and external second electrodes 18 ₁ B, 18 ₂ B, 18 ₃ B, and 18 ₄ B disposed on the roughened layer 22F of the second substrate 22 outside the sealing material 16 are provided. By providing the roughened layers 20F and 22F on the first substrate 20 and the second substrate 22, the adhesion between the sealing material 16 and the first substrate 20 and the second substrate 22 can be improved. Other configurations are the same as those of the first embodiment shown in FIG.

―Parallel configuration―
In the DSC according to the second embodiment, a schematic cross-sectional structure in which four basic cells are arranged in a parallel configuration is expressed as shown in FIG. 43 (a), and the schematic circuit expression of FIG. This is expressed as shown in FIG. Here, the 1st board | substrate 20 and the 2nd board | substrate 22 are implementing the roughening process to the surface which opposes, and are provided with the roughening layers 20F and 22F as shown to Fig.43 (a).

As shown in FIG. 43 (a), the external first electrodes 10 ₁ B, 10 ₂ B, 10 ₃ B, and the like are disposed on the roughened layer 20F of the first substrate 20 outside the sealing material 16. 10 ₄ B and external second electrodes 18 ₁ B, 18 ₂ B, 18 ₃ B, and 18 ₄ B disposed on the roughened layer 22F of the second substrate 22 outside the sealing material 16 are provided. By providing the roughened layers 20F and 22F on the first substrate 20 and the second substrate 22, the adhesion between the sealing material 16 and the first substrate 20 and the second substrate 22 can be improved. Other configurations are the same as those of the first embodiment shown in FIG.

(Production method)
The DSC manufacturing method according to the second embodiment is expressed as shown in FIGS. 44 (a) to 44 (i).

(A) First, as shown in FIG. 44A, the second substrate 22 is preprocessed by a cleaning process. Here, the second substrate 22 can be composed of a glass substrate, a flexible plastic substrate, or the like, and a glass substrate with a transparent electrode having a transparent electrode formed on the entire surface or a flexible plastic substrate can also be used.

(B) Next, as shown in FIG. 44B, 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 as shown in FIG. Here, the internal second electrode 18A and the external second electrode 18B 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, and glass with a transparent electrode. A substrate or a flexible plastic substrate can be patterned by various etching methods.

(C) Next, as shown in FIG. 44C, 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. 44D, a resist layer 21 is formed on the catalyst layer 19, and the surface of the second substrate 22 is roughened using the resist layer 21 as a mask. In the surface roughening treatment, for example, the surface of the second substrate 22 can be easily roughened by treating the second substrate 22 with about 4.5% hydrofluoric acid for about 10 minutes.

(E) Next, as shown in FIG. 44E, after the roughened layer 22F is formed on the surface of the second substrate 22, the resist layer 21 is removed. Since the internal second electrode 18A and the external second electrode 18B can be simultaneously etched by the roughening process, the screen printing processes (b) and (c) are omitted, The pattern formation of the two electrodes 18A and the external second electrode 18B, the pattern formation of the catalyst layer 19, and the formation of the roughened layer 22F may be performed simultaneously.

(F) Next, as shown in FIG. 44 (f), as with the second substrate 22, after the pretreatment of the first substrate 20, the internal first electrode 10 </ b> A is patterned on the first substrate 20 and the first The surface of one substrate 20 is roughened to form a roughened layer 20F. The external first electrode 10B is also formed on the first substrate 20 simultaneously as shown in FIG. Here, the 1st board | substrate 20 can be comprised with a glass substrate or a flexible plastic substrate. 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. In the roughening treatment, the surface of the first substrate 20 can be easily roughened by treating the first substrate 20 with about 4.5% hydrofluoric acid for about 10 minutes, for example. In addition, since the internal first electrode 10A and the external first electrode 10B can be simultaneously etched by the roughening process, the pattern formation and the roughening layer of the internal first electrode 10A and the external first electrode 10B are possible. 20F can be formed at the same time. 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.

(G) Next, as shown in FIG. 44G, 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.

(H) Next, as shown in FIG. 44 (h), the second substrate 22 after the step of FIG. 44 (e) and the first substrate 20 after the step of FIG. 44 (g) are opposed to each other and sealed. After bonding using the stopper 16, a water repellent treatment is performed on the side wall of the sealing member 16 from the outside of the DSC cell. The water repellent treatment can be carried out with, for example, hexamethyldisilazane (HMDS) (HMDS treatment). Moreover, since the sealing material 16 contacts the roughened layers 20F and 22F, the adhesion between the sealing material 16 and the first substrate 20 and the second substrate 22 can be improved.

(I) Next, as shown in FIG. 44 (i), the electrolytic solution 14 is sealed inside the opening, the opening is sealed, and a DSC cell is formed. Note that, as shown in FIG. 44 (i), the HMDS treatment may be performed after the electrolytic solution 14 is sealed.

  A schematic planar pattern configuration (corresponding to the first embodiment) on the second substrate 22 when the roughening process is not performed is expressed as shown in FIG. 45A, and the roughening process is performed. A schematic plane pattern configuration on the second substrate 22 of the DSC according to the second embodiment is expressed as shown in FIG. Although not shown, a schematic planar pattern configuration on the first substrate 20 of the DSC according to the second embodiment in which the roughening process is performed can be expressed in the same manner as in FIG. .

  In the DSC according to the second embodiment, as shown in FIG. 45 (b), a roughening layer 22 </ b> F is formed by performing a roughening process on the second substrate 22.

  An example of an appearance photograph of a prototype sample when the surface roughening process is not performed (corresponding to the first embodiment) is expressed as shown in FIG. An example of an external appearance photograph of the DSC prototype sample according to the form is represented as shown in FIG. In FIG. 46A, the first substrate 20 (second substrate 22) formed of a glass substrate is transparent. On the other hand, in FIG.46 (b), the 1st board | substrate 20 (2nd board | substrate 22) formed with the glass substrate by the roughening process is frosted glass-like opaque.

  According to the DSC according to the second embodiment, the roughening process is performed on the facing surfaces of the first substrate and the second substrate that are in contact with the sealing material, thereby the sealing material, the first substrate, and the second substrate. Adhesion with can be improved.

  Also, in the DSC according to the second embodiment, similarly to the first embodiment, it is possible to suppress a decrease in power generation efficiency by performing water repellent treatment (HMDS treatment) on the surface of the sealing material. It is.

  According to the second embodiment, there is provided a dye-sensitized solar cell capable of suppressing moisture permeation into the element by water-repellent treatment on the side surface of the sealing material and suppressing a decrease in power generation efficiency and a method for manufacturing the same. be able to.

(Application example)
-Battery cell-
Next, with reference to FIGS. 47 to 50, application examples of battery cells (hereinafter simply referred to as “cells”) configured by the DSC 200 according to the first and second embodiments 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.

  FIG. 51 shows the wavelength region of the ultraviolet light L1 (wavelength of 10 to 400 nm), the wavelength region of the white light L2 (wavelength of 400 to 800 nm), and the wavelength region of the infrared light L3 (wavelength of 600 to 1000 nm). The DSC 200 according to the first to second embodiments can exhibit a power generation function by using light rays in at least one region of L1 to L3.

-Electronics-
The DSCs according to the first and second embodiments 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. 52 to 54, a configuration example of a remote control device 330 on which the DSC 200 according to the first to second embodiments is mounted will be described.

  As shown in FIGS. 52 and 53, the remote control device 330 has an opening 41 penetrating the front and back in a casing 38 made of plastic or the like, and is provided so that the DSC 200 faces the opening 41. A solar cell unit 39 is configured.

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

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

  In the configuration example shown in FIG. 53, the transparent member 40 that protects the DSC 200 is fitted in the opening 41 so as to be flush with the front and back surfaces of the housing 38. This prevents dust from being attached to or damaged from the front and back surfaces of the DSC 200.

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

  As a result, external light such as sunlight and room light enters from the front surface side, back surface side, and side surface side of the remote control device 330 via the transparent member 40, so that incident light from the first substrate 20 side of the DSC 200 and All of the incident light from the two substrates 22 side reaches the porous semiconductor layer 12. 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 the remote control device 330 on which the DSC 200 according to the first to second embodiments is mounted, external light such as sunlight and indoor light is transmitted from the front surface side, back surface side, and side surface side of the remote control device 330 via the transparent member 40. Since the light is incident, the DSC 200 exhibits a power generation function when a light beam enters from the front surface or the back surface of the apparatus. 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. 54, the transparent member 40 is omitted and the DSC 200 is supported by the support portions 38a and 38b. In addition, the side part of the solar cell part 39 is covered with a part of the housing 38.

  In the remote control device 330 shown in FIG. 54, 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. 55, a configuration example of a desktop digital timepiece 50 equipped with the DSC 200 according to the first to second embodiments 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. 55, 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. 55, the DSC 200 included in the tabletop digital timepiece 50 has a power generation function by using either a light beam (hνf) incident from the front side or a light beam (hνr) incident from the back side through the transparent casing 54. It can be demonstrated.

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

  With reference to FIG. 56, 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.

  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 80a is opened as shown in FIG. 56 (a), and stable power is supplied to the main body 80b. Can be supplied.

  On the other hand, even when the lid portion 80a is closed as shown in FIG. 56 (b), the DSC 200 exhibits a power generation function by incident light from the front surface side, for example, a secondary battery such as a lithium ion battery provided on the main body portion 80b side. The battery can be charged.

  As described above, according to the electronic notebook 80 equipped with the DSC 200 according to the first and second embodiments, the external light can be used efficiently and the convenience of the user can be improved.

  Further, for example, the electronic notebook 80 equipped with the DSC 200 according to the first and second embodiments is not increased in size as compared with the case where conventional solar cells are arranged on both sides of the lid portion. Since one DSC 200 is sufficient, the manufacturing cost can be reduced.

  With reference to FIG. 57, a configuration example of electronic dictionary 90 equipped with DSC 200 according to the first to second embodiments 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. 57, in the state where the lid 90a is opened, the DSC 200 on the lid 90a side performs a power generation function by any light incident from both the front and back surfaces, and the DSC 200 on the main body 90b side The power generation function is demonstrated by the incident light. Therefore, stable power can be supplied to the arithmetic unit and the like included in the liquid crystal unit 34 and the main body 90b.

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

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

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

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

  The arrangement of the DSC 200 in the electronic dictionary 90 equipped with the DSC 200 according to the first and second embodiments can be applied to various electronic devices such as game machines and notebook computers having the same structure. It is.

(Application to sensor network)
A sensor network combining a wireless communication module, DSC, sensor, and the like can be constructed. If the communication distance is in the range of about 30 m, for example, 315 MHz or 868 MHz can be applied as the wavelength band. Furthermore, if the communication distance is in the range of about 100 m, for example, 920 MHz can be applied as the wavelength band.

  As shown in FIG. 58, a DSC drive sensor module 800 equipped with a DSC according to the first to second embodiments includes a DSC module 801 and a wireless communication module 805. The DSC module 801 includes DSC series or parallel cells DSC1 and DSC2 that can generate electric power with room light, and functions as a sensor driving power source. The wireless communication module 805 is equipped with a wireless sensor node 804 and can perform sensing and wireless communication.

  As shown in FIG. 59, a schematic block configuration of another DSC drive sensor module 807 equipped with the DSC according to the first to second embodiments includes a DSC module 801, a wireless communication module 805, and a power storage unit 806. With. The DSC module 801 includes DSC series or parallel cells DSC1, DSC2, DSC3, and DSC4 that can generate electric power with room light, and functions as a sensor driving power source. The power storage unit 806 is equipped with an electric double layer capacitor (EDLC) 808 and a control IC 809. By accumulating the electric power generated in the DSC module 801 in the power storage unit 806, the electric power can be stably supplied to the wireless communication module 805.

  A configuration example of a home energy management system (HEMS) 900 to which the DSC driving sensor module 800 equipped with the DSC according to the first to second embodiments is applied is expressed as shown in FIG. .

  Each DSC drive sensor module 800 collects sensing information such as a temperature / humidity sensor and an illuminance sensor, and usage statuses of the PC 930, the TV 901, the air conditioner 940 (air conditioner controller 903), the solar battery 902, etc., and receives sensor information by wireless communication. Data is transmitted to the device 920. In the sensor information receiver 920, signal processing for data reception, grasping of energy usage status, and the like is performed.

  According to the home energy management system 900 to which the DSC driving sensor module 800 equipped with the DSC according to the first to second embodiments is applied, the power supply can be controlled in accordance with the indoor environment of the entire building 910.

  As described above, according to the present invention, a dye-sensitized solar cell capable of suppressing moisture permeation into the element and suppressing a decrease in power generation efficiency by water-repellent treatment on the side surface of the sealing material and a method for manufacturing the same And an electronic device can be provided.

[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, wireless sensor network systems, and the like by being applied as a small, lightweight and highly efficient power source.

2 ... Semiconductor fine particle 3a ... Opening sealing material 3b ... Cap sealing material 4, 30, 32 ... Dye molecule 10 ... First electrode 10A, 10 ₁ A, 10 ₂ A, 10 ₃ A, 10 ₄ A, inner part 1 electrode 10B, 10 ₁ B, 10 ₂ B, 10 ₃ B, 10 ₄ B ... external first electrode 12, 12 ₁ , 12 ₂ , 12 ₃ , 12 ₄ ... porous semiconductor layer 13A ... connection electrode 13B ... insulating layer 14 · 14 ₁ · 14 ₂ · 14 ₃ · 14 ₄ ... Electrolyte (charge transport layer)
16, 16A ... Sealing material 17 ... Water droplet 18 ... Second electrode 18A, 18 ₁ A, 18 ₂ A, 18 ₃ A, 18 ₄ A ... Internal second electrode 18B, 18 ₁ B, 18 ₂ B, 18 ₃ B 18 ₄ B: external second electrodes 19, 19 ₁ , 19 ₂ , 19 ₃ , 19 _4, catalyst layer 20, first substrate 20 F, 22 F, roughening layer 21, resist layer 22, second substrates 26, 28. ... Redox electrolyte 200, 200A, 200B ... Dye-sensitized solar cell (DSC)

Claims (27)

A first substrate;
An internal first electrode disposed on the first substrate;
A porous semiconductor layer disposed on the internal first electrode and comprising 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;
An internal second electrode in contact with the electrolyte;
A second substrate disposed on the internal second electrode;
A sealing material disposed between the first substrate and the second substrate and sealing the electrolytic solution;
The dye-sensitized solar cell, wherein the sealing material is subjected to water repellent treatment on an external side wall.   The dye-sensitized solar cell according to claim 1, further comprising a first roughened layer on a surface of the first substrate in contact with the sealing material.   3. The dye-sensitized solar cell according to claim 1, further comprising a second roughened layer on a surface of the second substrate in contact with the sealing material. An external first electrode disposed on the first substrate outside the sealing material;
The dye-sensitized solar cell according to any one of claims 1 to 3, further comprising an external second electrode disposed on the second substrate outside the sealing material. An opening for injecting the electrolyte into a cell region sandwiched between the first substrate and the second substrate and surrounded by the sealing material;
5. The dye-sensitized solar cell according to claim 4, wherein the internal first electrode and the external first electrode are patterned on the first substrate and connected to each other in the opening.   6. The dye-sensitized solar cell according to claim 5, wherein the internal second electrode and the external second electrode are patterned on the second substrate and connected to each other in the opening. An opening sealing material for sealing the opening;
The dye sensitization according to any one of claims 4 to 6, further comprising: a cap sealing material that is disposed in the opening and joins the sealing material and the opening sealing material. Solar cell.   The dye-sensitized solar cell according to any one of claims 1 to 7, wherein the sealing material is not in contact with the first internal electrode and the second internal electrode.   The dye-sensitized solar cell according to any one of claims 1 to 8, wherein the sealing material is in contact with the external first electrode or the external second electrode in the opening.   The said cap sealing material and the said opening part sealing material contact the said external 1st electrode or the said external 2nd electrode in the said opening part, The any one of Claims 1-9 characterized by the above-mentioned. Dye-sensitized solar cell.   The dye-sensitized solar cell according to any one of claims 1 to 10, wherein a catalyst layer is provided on the surface of the internal second electrode in contact with the electrolytic solution.   The said sealing material, the said cap sealing material, and the said opening part sealing material are equipped with a glass frit, an ultraviolet curable resin, a thermosetting resin, or these combination, The any one of Claims 1-11 characterized by the above-mentioned. 2. A dye-sensitized solar cell according to 1.   The dye-sensitized solar cell according to any one of claims 1 to 12, wherein the first substrate and the second substrate are formed of a glass substrate or a plastic substrate. The first electrode and the second electrode, ITO, FTO, ZnO, dye-sensitized solar cell according to any one of claims 1 to 13, characterized in that it is formed in one of SnO _2. 15. The porous semiconductor layer 12 is formed of any one of TiO ₂ , ZnO, WO ₃ , InO ₃ , Nb ₂ O ₃ , and SnO _2. 15. Dye-sensitized solar cell.   The dye-sensitized solar cell according to any one of claims 1 to 15, wherein the catalyst layer is formed of Pt, carbon, or a conductive polymer.   The dye according to any one of claims 1 to 16, wherein the solvent is formed of any one of acetonitrile, propylene carbonate, γ-butyrolactone, methoxyacetonitrile, propionitrile, ethylene carbonate, and propylene carbonate. Sensitized solar cell.   The dye-sensitized solar cell according to any one of claims 1 to 17, wherein the dye is formed of any one of a red die (N719), a black die (N749), and D131.   The dye-sensitized solar cell according to claim 1, wherein the water repellent treatment is HMDS treatment. A connection electrode disposed between the first substrate and the second substrate along the outer side wall of the sealing material, the external first electrode and the external second electrode;
The dye-sensitized solar cell according to any one of claims 4 to 19, wherein a plurality of cells of the dye-sensitized solar cell are connected in series via the connection electrode. An insulating layer disposed between the first substrate and the second substrate along the outer side wall of the sealing material, the external first electrode and the external second electrode;
The dye-sensitized solar cell according to any one of claims 4 to 19, wherein a plurality of cells of the dye-sensitized solar cell are connected in parallel via the insulating layer. After the first substrate is pre-processed by a cleaning step, a step of patterning the internal first electrode and the external first electrode on the first substrate;
A step of immersing a dye in the porous semiconductor layer after forming a porous semiconductor layer on the internal first electrode;
After the second substrate is pre-processed by a cleaning step, a step of patterning an internal second electrode and an external second electrode on the second substrate;
Forming a catalyst layer on the internal second electrode;
A step of causing the first substrate and the second substrate to face each other and bonding using a sealing material;
Performing a water repellent treatment on the outer side wall of the sealing material;
A method of manufacturing a dye-sensitized solar cell, comprising: encapsulating an electrolyte in the DSC cell from the opening, and sealing the opening. Forming the first roughened layer by roughening the surface of the first substrate simultaneously with the step of patterning the internal first electrode and the external first electrode;
Forming a second roughened layer by forming a resist layer on the catalyst layer and roughening the surface of the second substrate using the resist layer as a mask. The manufacturing method of the dye-sensitized solar cell of Claim 22.   The dye-sensitized solar according to claim 22 or 23, wherein the step of forming the first roughened layer and the step of forming the second roughened layer are performed by etching with hydrofluoric acid. Battery manufacturing method.   25. The step of performing HMDS treatment on the outer side wall of the sealing material is performed after the step of encapsulating the electrolytic solution and sealing the opening. The manufacturing method of the dye-sensitized solar cell of description.   The method for producing a dye-sensitized solar cell according to any one of claims 22 to 25, wherein the water repellent treatment is an HMDS treatment.   An electronic apparatus comprising the dye-sensitized solar cell according to any one of claims 1 to 21.