JP2014203539A - Dye-sensitized solar cell and method of manufacturing the same, and electronic equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell improved in low cost property as a monolithic structure, a method of manufacturing the same, and electronic equipment.SOLUTION: A dye-sensitized solar cell comprises: a first substrate 20M; a counter electrode 19 arranged on the first substrate; a separator 24 formed of an insulation porous body formed so as to cover the counter electrode; a current extraction electrode 10 arranged on the separator; a porous semiconductor layer 130 arranged on the current extraction electrode and having a semiconductor fine particle and a dye molecule; an electrolyte 14 obtained by dissolving a redox electrolyte for immersing the separator, the current extraction electrode, and the porous semiconductor layer; a second substrate 22 arranged above the porous semiconductor layer via a predetermined gap; and a sealing material 16 arranged between the first substrate and the second substrate and sealing the electrolyte.

Description

  The present invention relates to a dye-sensitized solar cell (DSC), and more particularly to a dye-sensitized solar cell capable of improving low cost as a monolithic structure, a method for manufacturing the same, and an electronic device.

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

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

JP-A-11-135817

  However, since the conventional DSC uses a glass substrate in which a transparent conductive film or a conductive film is provided on the first substrate and the second substrate, there is a problem that the component cost increases.

  The objective of this invention is providing the dye-sensitized solar cell which can improve low cost as a monolithic structure, its manufacturing method, and an electronic device.

  According to one aspect of the present invention for achieving the above object, the first substrate, a counter electrode disposed on the first substrate, and an insulating porous body formed to cover the counter electrode. A separator, a current extraction electrode disposed on the separator, a porous semiconductor layer disposed on the current extraction electrode and including semiconductor fine particles and dye molecules, the separator, the current extraction electrode, and the porous semiconductor layer An electrolyte solution in which a redox electrolyte is immersed, a second substrate disposed above the porous semiconductor layer with a predetermined gap interposed therebetween, and disposed between the first substrate and the second substrate. A dye-sensitized solar cell comprising a sealing material for sealing the electrolytic solution is provided.

  According to another aspect of the present invention, a first substrate, a porous semiconductor layer disposed on the first substrate and comprising semiconductor fine particles and dye molecules, on the first substrate and on the porous semiconductor layer A current extraction electrode disposed; a separator made of an insulating porous body formed so as to cover an end portion of the current extraction electrode and the porous semiconductor layer; a counter electrode disposed on the separator; An electrolytic solution in which a redox electrolyte for immersing the porous semiconductor layer, the separator, and the counter electrode is dissolved, a second substrate disposed above the counter electrode with a predetermined gap therebetween, the first substrate, and the second substrate Provided is a dye-sensitized solar cell that is disposed between a substrate and a sealing material that seals the electrolytic solution.

  According to another aspect of the present invention, a first substrate, a current extraction electrode disposed on the first substrate, a porous semiconductor layer disposed on the current extraction electrode and comprising semiconductor fine particles and dye molecules, A separator made of an insulating porous body formed so as to cover all or part of the porous semiconductor layer, a counter electrode disposed on the separator, the porous semiconductor layer, the separator, and the counter electrode An electrolytic solution in which a redox electrolyte is immersed, a second substrate disposed above the counter electrode with a predetermined gap therebetween, and disposed between the first substrate and the second substrate. There is provided a dye-sensitized solar cell including a sealing material for sealing a liquid.

According to another aspect of the present invention, after the first substrate is pretreated by a cleaning process, a step of forming a counter electrode on the first substrate, and a porous material made of an insulating ceramic so as to cover the counter electrode A step of forming a separator by sintering, a step of forming a current extraction electrode on the separator, a step of forming a porous semiconductor layer on the current extraction electrode, and immersing the entire device in a dye solution A step of immersing a dye in the porous semiconductor layer, a step of making the first substrate and the second substrate face each other, and bonding them using a sealing material, and the first substrate and the second substrate A method for producing a dye-sensitized solar cell having a step of injecting an electrolytic solution is provided.

  According to another aspect of the present invention, after the first substrate is pretreated by a cleaning process, a step of forming a porous semiconductor layer including semiconductor fine particles on the first substrate, the first substrate and the porous substrate are formed. Forming a current extraction electrode on the porous semiconductor layer, and sintering and forming a porous separator made of an insulating ceramic so as to cover the current extraction electrode and the end of the porous semiconductor layer And forming a counter electrode on the separator; immersing the entire device in a dye solution; immersing the dye in the porous semiconductor layer; and causing the first substrate and the second substrate to face each other. There is provided a method for producing a dye-sensitized solar cell, which includes a step of bonding using a sealing material, and a step of injecting an electrolytic solution between the first substrate and the second substrate.

  According to another aspect of the present invention, after the first substrate is pretreated by a cleaning process, a step of forming a current extraction electrode made of a transparent conductive film on the first substrate is disposed on the current extraction electrode. A step of forming a porous semiconductor layer comprising semiconductor fine particles, and a step of sintering and forming a porous separator made of an insulating ceramic so as to cover all or part of the porous semiconductor layer; Forming a counter electrode on the separator; immersing the entire device in a dye solution; immersing the dye in the porous semiconductor layer; and causing the first substrate and the second substrate to face each other and sealing. Provided is a method for manufacturing a dye-sensitized solar cell, which includes a step of bonding using a stopper and a step of injecting an electrolyte between the first substrate and the second substrate.

  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 low cost as a monolithic structure, its manufacturing method, and an electronic device can be provided.

The typical plane pattern block diagram of DSC which concerns on 1st Embodiment. 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. The typical cross-section figure of DSC which concerns on a comparative example. The typical cross-section figure which shows the semiconductor fine particle layer sintered about DSC which concerns on 1st Embodiment. The typical cross-section figure which shows the state which sintered the semiconductor fine particle layer on the metal film about DSC which concerns on 1st Embodiment. The typical cross-section figure which shows the state which sintered the semiconductor fine particle layer on the glass substrate through the electrically conductive film about DSC which concerns on 1st Embodiment. The typical cross-section figure of DSC which concerns on 1st Embodiment. It is a manufacturing method of DSC which concerns on 1st Embodiment, Comprising: (a) Process drawing which pre-processes a metal film, (b) Process drawing which forms an insulating film on a metal film, (c) Insulating film Process drawing to pattern, (d) Process drawing which forms the counter electrode which consists of ITO and a catalyst layer on a metal film. It is a manufacturing method of DSC which concerns on 1st Embodiment, Comprising: (a) Process drawing which forms a porous separator by baking so that a counter electrode may be covered, (b) Process which forms an electric current extraction electrode on a separator FIG. 4C is a process chart in which a porous semiconductor layer is formed on a current extraction electrode and a dye is supported. It is a manufacturing method of DSC which concerns on 1st Embodiment, Comprising: A metal film and a 2nd board | substrate are bonded together through a sealing material, electrolyte solution is inject | poured, and DSC is completed. The typical plane pattern block diagram of DSC which concerns on 2nd Embodiment. FIG. 14 is a schematic cross-sectional structure diagram taken along line IV-IV in FIG. 13. FIG. 14 is a schematic cross-sectional structure diagram taken along line VV in FIG. 13. FIG. 14 is a schematic cross-sectional structure diagram taken along line VI-VI in FIG. 13. The typical cross-section figure of DSC using the counterbore glass substrate as the 2nd substrate. The typical cross-section figure of DSC using the counterbore plastic substrate as the 2nd substrate. It is a manufacturing method of DSC which concerns on 2nd Embodiment, Comprising: (a) Process drawing which pre-processes a glass substrate, (b) Process drawing which forms a porous semiconductor layer on a glass substrate, (c) Glass substrate and FIG. 5 is a process diagram for forming a current extraction electrode on a porous semiconductor layer. It is a DSC manufacturing method according to the second embodiment, (a) a process diagram for firing and forming a porous separator on a current extraction electrode, (b) a process diagram for forming a counter electrode on the separator, (C) After the step of FIG. 20B, the entire device is immersed in a dye solution, and the dye is adsorbed to the porous semiconductor layer. It is a manufacturing method of DSC which concerns on 2nd Embodiment, Comprising: Process drawing which shows the case where a counter electrode is formed with carbon particulates. It is a manufacturing method of DSC which concerns on 2nd Embodiment, Comprising: Process drawing which shows the case where a counter electrode is formed with the sintered compact of electroconductive fine particles and the fine particle of a catalyst substance. It is a manufacturing method of DSC which concerns on 2nd Embodiment, Comprising: The process drawing which bonds a 1st board | substrate and a 2nd board | substrate through a sealing material. The typical cross-section figure of DSC which concerns on 3rd Embodiment. The typical cross-section figure of DSC using the counterbore glass substrate as the 2nd substrate. The typical cross-section figure of DSC using the counterbore plastic substrate as the 2nd substrate. It is a manufacturing method of DSC which concerns on 3rd Embodiment, Comprising: (a) Process drawing which forms the current extraction electrode which consists of a transparent conductive film on a glass substrate, (b) Process drawing which patterns a current extraction electrode, c) Process drawing for forming a porous semiconductor layer on the current extraction electrode, (d) Process drawing for forming a porous separator on the porous semiconductor layer by firing. It is a manufacturing method of DSC which concerns on 3rd Embodiment, Comprising: (a) Process drawing which forms a counter electrode on a separator, (b) After the process of FIG. 28 (a), the whole device is immersed in the dye solution. The process figure which makes a porous semiconductor layer adsorb | suck a pigment | dye, (c) The process figure which bonds a 1st board | substrate and a 2nd board | substrate through a sealing material. 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 (12) / dye 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 the J section of FIG. Explanatory drawing which shows the energy level and electric power generation cycle of each component material of DSC which concern on embodiment. 2 is a chemical structural formula showing a dye used in the DSC according to the embodiment, (a) a chemical structural formula showing an indoleine dye (D149), (b) a chemical structural formula showing N719, and (c) showing a D131. Chemical structural formula. (A) In DSC which concerns on embodiment, the typical cross-section figure which has arrange | positioned two basic cells in series structure, (b) The typical circuit representation of Fig.36 (a). (A) In DSC which concerns on embodiment, the typical cross-section figure which has arrange | positioned two basic cells in parallel structure, (b) The typical circuit expression of Fig.37 (a). The top view which is 1 process of the manufacturing method of DSC which concerns on embodiment, Comprising: The state in which the some internal 1st electrode was formed on the 1st board | substrate. The top view which is 1 process of the manufacturing method of DSC which concerns on embodiment, Comprising: The several internal 2nd electrode was formed on the 2nd board | substrate. The top view which is 1 process of the manufacturing method of DSC which concerns on embodiment, and shows the state which bonded together the 1st board | substrate and the 2nd board | substrate through the sealing material. FIG. 41 is a schematic cross-sectional structure diagram illustrating one step of the DSC manufacturing method according to the embodiment and taken along line VII-VII in FIG. 40. 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 concerning the 1st-3rd embodiment, (b) The explanatory view which shows the state which connected three cells in series. (A) A schematic diagram showing a state in which five DSC cells according to the first to third embodiments are connected in series, (b) an explanatory view of FIG. 45 (a), and (c) FIG. 45 (a). FIG. (A) Schematic diagram showing a state in which n DSC cells according to the first to third embodiments are stacked in a tandem configuration, and (b) an explanatory diagram of FIG. (A) A schematic diagram showing a state in which n DSC cells according to the first to third embodiments stacked in a tandem configuration are connected in parallel, and (b) an explanatory diagram of FIG. 47 (a). 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-3rd embodiment. The side view of the remote control device carrying DSC which concerns on the 1st-3rd embodiment. The side view which shows the other structural example of the remote control device carrying DSC which concerns on the 1st-3rd embodiment. The bird's-eye view which shows the structural example of the desktop digital timepiece carrying DSC which concerns on the 1st-3rd embodiment. (A) The bird's-eye view which shows the state which opened the electronic notebook carrying DSC which concerns on 1st-3rd 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-3rd embodiment. The typical block block diagram of the DSC drive sensor module carrying DSC which concerns on the 1st-3rd embodiment. The typical block block diagram of another DSC drive sensor module carrying DSC which concerns on the 1st-3rd 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 third 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]
A schematic planar pattern configuration of the DSC 200 according to the first embodiment is expressed as shown in FIG. 1A, and a schematic cross-sectional structure along the line II is shown in FIG. 1B. It is expressed in Further, a schematic cross-sectional structure diagram along the line II-II is represented as shown in FIG. 3, and a schematic cross-sectional structure diagram along the line III-III is represented as shown in FIG.

  The DSC 200 according to the present embodiment covers the first substrate 20M made of a metal film, the ITO 18 disposed on the first substrate 20M, and the ITO 18 (counter electrode 19), as shown in FIGS. Separator 24 made of an insulating porous body formed in this way, current extraction electrode 10 disposed on separator 24, a porous structure including semiconductor fine particle layer 120 and dye molecule Dye disposed on current extraction electrode 10. The porous semiconductor layer 130, the separator 24, the current extraction electrode 10, and the electrolytic solution 14 in which the redox electrolyte for immersing the porous semiconductor layer 130 is dissolved, and the porous semiconductor layer 130 is disposed with a predetermined gap therebetween. A second substrate 22 and a sealing material 16 that is disposed between the first substrate 20M and the second substrate 22 and seals the electrolytic solution 14 are provided.

  Here, the ITO 18 is mixed with a catalyst material. As a result, the counter electrode 19 is formed by the mixed layer of the ITO 18 and the catalyst material.

As shown in FIG. 2, an insulating film 23 made of SiO ₂ or the like is formed between the first substrate 20M and the current extraction electrode 10 on the right side of the drawing. This is because it is necessary to insulate between the current extraction electrode 10 and the first substrate 20M in order to use the conductive metal film as the first substrate 20M.

  As the sealing material 16, a resin such as an ultraviolet curable resin is used.

  Moreover, the opening part sealing material 3b which seals the opening part which inject | poured the electrolyte solution 14, 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. I have. Both the cap sealing material 3a and the opening sealing material 3b are made of a resin such as an ultraviolet curable resin.

  In the example shown in FIGS. 1 to 4, the first substrate 20 </ b> M is formed of a metal film having a predetermined thickness (for example, about 0.05 to 0.1 mm). The metal film 20M is made of, for example, stainless steel or Ti. Thereby, since the comparatively high cost glass substrate in which the transparent conductive film was formed is not used as the first substrate, the cost can be reduced. Moreover, it can be set as DSC200 provided with durability strong against rust etc.

The current extraction electrode 10 is formed of a transparent conductive film, a metal vapor deposition film, or a film made of conductive fine particles. The transparent conductive film, ITO, FTO, ZnO, is formed in one of SnO _2.

  The separator 24 can be made of a porous ceramic. Thereby, the electrolyte solution 14 is immersed into the separator 24, and the counter electrode 19, the current extraction electrode 10, and the porous semiconductor layer 130 can be electrochemically connected via the electrolyte solution 14.

  The porous ceramic is composed of a sintered body containing fine particles of aluminum oxide or silicon dioxide.

  Further, the counter electrode 19 (indicated by ITO 18: a mixed layer of ITO and a catalyst substance) can be a porous electrode. Thereby, the electrolytic solution 14 is immersed in the counter electrode 19, and the electrochemical connection between the current extraction electrode 10 and the porous semiconductor layer 130 can be improved.

The porous electrode is formed of a sintered body of conductive fine particles and catalytic fine particles. The fine particles of the conductor are made of, for example, ITO or SnO ₂ or metal fine particles, and the fine particles of the catalyst material are made of Pt or carbon.

  In addition, a conductive auxiliary layer that increases conductivity may be formed on the counter electrode 19. The conductive auxiliary layer can be formed of, for example, a carbon fine particle layer or a metal vapor deposition layer (for example, a vapor deposition layer of Ti, Au, or the like). Thereby, the efficiency of current extraction can be improved.

  The second substrate 22 is made of a glass substrate or a plastic film. The plastic film is formed of PET resin or PEN resin. Thereby, since the comparatively high cost glass substrate in which the transparent conductive film was formed is not used as the second substrate, the cost can be reduced.

  The dye Dye is formed of any one of a red dye (N719), a black dye (N749), D131 and D205, a phthalocyanine dye, a porphyrin dye, and an indoline dye (D149).

The semiconductor fine particles constituting the porous semiconductor layer 130 can be any of TiO ₂ , ZnO, WO ₃ , InO ₃ , Nb ₂ O ₃ , and SnO ₂ .

(Comparative example)
FIG. 5 shows a schematic sectional view of a DSC 200A according to a comparative example.

  In addition, about the structure similar to DSC200 which concerns on this Embodiment, the same code | symbol is attached | subjected and the overlapping description is abbreviate | omitted.

  In the DSC 200A according to the comparative example, as the first substrate 20 and the second substrate 22, a glass substrate in which conductive films (such as TCO) constituting the first electrode 10 and the second electrode 18 are formed in advance is used, and the cost is low. It was bulky.

In consideration of low cost, even if low cost plastic films are applied as the first substrate 20 and the second substrate 22, the heat resistance temperature of these films (for example, PET resin is about 150 ° C., PEN resin) Was about 200 ° C.) much lower than the sintering temperature of TiO ₂ (about 500 ° C.), and could not be realized.

(About porous semiconductor layers)
Configuration examples of the semiconductor fine particle layer 120 constituting the porous semiconductor layer 130 applied to the DSC according to the first embodiment are shown in FIGS.

A schematic cross-sectional structure diagram of the semiconductor fine particle layer 120 is shown in FIG. The semiconductor fine particle layer 120 is formed by using, for example, a printing apparatus or a dispenser as a conductive paste material including a paste containing nano-sized metal fine particles (for example, Ag particles) 124 and TiO ₂ fine particles (for example, several nm to several hundred nm). It is used by applying on a substrate (for example, metal film 20M) and sintering at a high temperature of about 500 ° C.

  FIG. 7 shows a state in which the semiconductor fine particle layer 120 is sintered on the metal film 20M in the DSC 200 according to the first embodiment. FIG. 8 shows a state in which the semiconductor fine particle layer 120 is sintered on the glass substrate 20G via the conductive film 10 in the DSC 200 according to the first embodiment.

(DSC manufacturing method according to the first embodiment)
Next, a DSC manufacturing method according to the first embodiment will be described.

The DSC manufacturing method according to the first embodiment includes the following steps:
(1) After pre-processing the first substrate 20M made of a metal film by a cleaning process, forming a counter electrode 19 (indicated by ITO 18: mixed layer of ITO and a catalyst material) on the first substrate 20M;
(2) a step of sintering and forming a porous separator 24 made of an insulating ceramic so as to cover the counter electrode 19;
(3) forming the current extraction electrode 10 on the separator 24;
(4) forming a porous semiconductor layer 120 on the current extraction electrode 10;
(5) a step of immersing the entire device in a dye solution, adsorbing the dye Dye to the porous semiconductor layer 120, and forming a porous semiconductor layer 130 (120 + Dye);
(6) a step of causing the first substrate 20M and the second substrate 22 to face each other and bonding using the sealing material 16;
(7) Injecting the electrolytic solution 14 between the first substrate 20M and the second substrate 22.

  A specific example of the DSC manufacturing method according to the first embodiment will be described with reference to FIGS.

(A) First, the metal film 20M formed of stainless steel or Ti is pretreated (FIG. 10A).

(B) An insulating film 23 made of SiO ₂ or the like is formed on the metal film 20M (FIG. 10B).

(C) The insulating film 23 is patterned by etching (FIG. 10C).

(D) A counter electrode 19 (indicated by ITO 18: mixed layer of ITO and a catalyst substance) is formed on the metal film 20M (FIG. 10 (d)).

(E) A porous separator 24 is baked to cover the counter electrode 19 (FIG. 11A).

(F) The current extraction electrode 10 is formed on the separator 24 (FIG. 11B).

(G) After forming the porous semiconductor layer 120 on the current extraction electrode 10, the entire device is immersed in the dye solution, and the dye Dye is adsorbed on the porous semiconductor layer 120, and the porous semiconductor layer 130 (120 + Dye). Is formed (FIG. 11C).

(H) The metal film 20M and the second substrate 22 are bonded together through the sealing material 16, and the electrolytic solution 14 is injected to complete the DSC (FIGS. 12 and 9).

  Here, the separator 24 can be made of a porous ceramic. Thereby, the electrolyte solution 14 is immersed into the separator 24, and the counter electrode 19, the current extraction electrode 10, and the porous semiconductor layer 130 can be electrochemically connected via the electrolyte solution 14.

  The porous ceramic is composed of a sintered body containing fine particles of aluminum oxide or silicon dioxide.

  Further, the counter electrode 19 (indicated by ITO 18: a mixed layer of ITO and a catalyst substance) can be a porous electrode. Thereby, the electrolytic solution 14 is immersed in the counter electrode 19, and the electrochemical connection between the current extraction electrode 10 and the porous semiconductor layer 130 can be improved.

The porous electrode may be formed of a sintered body of conductive fine particles and catalytic fine particles. The fine particles of the conductor are made of, for example, ITO or SnO ₂ or metal fine particles, and the fine particles of the catalyst material are made of Pt or carbon. In addition, a conductive auxiliary layer that increases conductivity may be formed on the counter electrode 19. The conductive auxiliary layer is formed of, for example, a carbon fine particle layer or a metal vapor deposition layer (for example, a vapor deposition layer of Ti, Au, or the like). Thereby, the efficiency of current extraction can be improved.

  Moreover, the 2nd board | substrate 22 is comprised with plastic films, such as a glass substrate or PET resin, or PEN resin. Thereby, cost can be reduced compared with the case where the comparatively high cost glass substrate in which the transparent conductive film is formed is used as the second substrate.

[Second Embodiment]
A schematic planar pattern configuration of the DSC 200 according to the second embodiment is expressed as shown in FIG. 13, and a schematic cross-sectional structure taken along the line IV-IV is expressed as shown in FIG. Further, a schematic cross-sectional structure diagram along the VV line is expressed as shown in FIG. 15, and a schematic cross-sectional structure diagram along the VI-VI line is expressed as shown in FIG.

  As shown in FIGS. 13 to 16, DSC 200 according to the present embodiment includes first substrate 20 </ b> G formed of a glass substrate, semiconductor fine particle layer 120 and dye molecule Dye arranged on first substrate 20 </ b> G. Porous semiconductor layer 130, current extraction electrode 10 disposed on first substrate 20G and porous semiconductor layer 130, and insulation formed so as to cover the ends of current extraction electrode 10 and porous semiconductor layer 130 A separator 24 made of a porous material, a counter electrode 19 disposed on the separator 24, an electrolytic solution 14 in which a redox electrolyte for immersing the porous semiconductor layer 130, the separator 24, and the counter electrode 19 is dissolved; It is disposed between a second substrate 22G composed of a glass substrate disposed above with a predetermined gap and between the first substrate 20G and the second substrate 22G. 14 and a sealant 16 for sealing.

  As shown in FIG. 14, a conductive film 18 serving as a current extraction electrode is formed between the first substrate 20 </ b> G and the sealing material 16 on the right side of the figure, and is connected to the counter electrode 19.

  As the sealing material 16, a resin such as an ultraviolet curable resin is used.

  Moreover, the opening part sealing material 3b which seals the opening part which inject | poured the electrolyte solution 14, 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. Prepare. Both the cap sealing material 3a and the opening sealing material 3b are made of a resin such as an ultraviolet curable resin.

  As the first substrate 20G and the second substrate 22G, ordinary glass substrates (elementary glass) on which a transparent conductive film is not formed in advance are used, so that the cost can be reduced.

The current extraction electrodes 10 and 18 are formed of a transparent conductive film, a metal vapor deposition film, or a film made of conductive fine particles. The transparent conductive film, ITO, FTO, ZnO, is formed in one of SnO _2.

  The separator 24 is made of a porous ceramic. Thereby, the electrolyte solution 14 is immersed into the separator 24, and the counter electrode 19, the current extraction electrode 10, and the porous semiconductor layer 130 can be electrochemically connected via the electrolyte solution 14.

  The porous ceramic can be composed of a sintered body containing fine particles of aluminum oxide or silicon dioxide.

  The counter electrode 19 can be a porous electrode. Thereby, the electrolytic solution 14 is immersed in the counter electrode 19, and the electrochemical connection between the current extraction electrodes 10 and 18 and the porous semiconductor layer 130 can be improved.

The porous electrode is formed of a sintered body of conductive fine particles and catalytic fine particles. The fine particles of the conductor are made of, for example, ITO or SnO ₂ or metal fine particles, and the fine particles of the catalyst material are made of Pt or carbon.

  In addition, a conductive auxiliary layer that increases conductivity may be formed on the counter electrode 19. The conductive auxiliary layer is formed of, for example, a carbon fine particle layer or a metal vapor deposition layer (for example, a vapor deposition layer of Ti, Au, or the like). Thereby, the efficiency of current extraction can be improved.

  The dye Dye is formed of any one of a red dye (N719), a black dye (N749), D131 and D205, a phthalocyanine dye, a porphyrin dye, and an indoline dye (D149).

The semiconductor fine particles constituting the porous semiconductor layer 130 can be any of TiO ₂ , ZnO, WO ₃ , InO ₃ , Nb ₂ O ₃ , and SnO ₂ .

  FIG. 17 is a schematic cross-sectional view of a DSC using a counterbore glass substrate 22GZ as the second substrate.

  The counterbore part of the counterbore glass substrate 22GZ was soaked in hydrofluoric acid (hydrofluoric acid) that was patterned on the glass substrate by applying a photoresist used in a semiconductor process or the like, exposing it to ultraviolet light, and developing it. Thereafter, the photoresist and the like are formed by washing and removing with an organic solvent.

  The photoresist is resistant to hydrofluoric acid, and the glass under the photoresist is not eroded by hydrofluoric acid, so that a spot can be formed. Instead of the photoresist, a resist for printing resistant to hydrofluoric acid may be formed by printing.

  Further, after cleaning the photoresist or the like with an organic solvent, an oxygen plasma treatment or an immersion treatment in sulfuric acid is performed to completely remove the organic residue remaining in the spotted portion, so that the spotted glass substrate 22GZ and the first substrate 20G The adhesive strength at the time of adhering through the sealant 16U is improved.

  The counterbore glass substrate 22GZ is bonded to the first substrate 20G via the sealing material 16U.

  By using the counterbore glass substrate 22GZ, the sealing performance is improved and the reliability can be improved.

  FIG. 18 is a schematic sectional view of a DSC using a counterbore plastic substrate 22P as the second substrate.

  The counterbore plastic substrate 22P is formed by extrusion molding of a transparent resin or the like.

  By using the counterbore plastic substrate 22P, the sealing performance is improved, the reliability is improved, and the cost can be reduced.

(DSC manufacturing method according to the second embodiment)
Next, a DSC manufacturing method according to the second embodiment will be described.

The DSC manufacturing method according to the second embodiment includes the following steps:
(1) forming a porous semiconductor layer 120 on the first substrate 20G after pre-processing the first substrate 20G formed of a glass substrate by a cleaning process;
(2) forming the current extraction electrodes 10 and 18 on the first substrate 20G and the porous semiconductor layer 120;
(3) a step of sintering and forming a porous separator 24 made of an insulating ceramic so as to cover the current extraction electrode 10 and the end of the porous semiconductor layer 120;
(4) forming the counter electrode 19 on the separator 24;
(5) a step of immersing the entire device in a dye solution and adsorbing the dye Dye to the porous semiconductor layer 120;
(6) a step of causing the first substrate 20G and the second substrate 22 to face each other and bonding using the sealing material 16;
(7) Injecting the electrolytic solution 14 between the first substrate 20G and the second substrate 22.

  A specific example of the DSC manufacturing method according to the second embodiment will be described with reference to FIGS.

(A) First, the first substrate 20G made of a glass substrate is pretreated (FIG. 19A).

(B) The porous semiconductor layer 120 is formed on the glass substrate 20G (FIG. 19B).

(C) The current extraction electrodes 10 and 18 are formed on the glass substrate 20G and the porous semiconductor layer 120 (FIG. 19C).

(D) A porous separator 24 is baked and formed on the current extraction electrode 10 (FIG. 20A).

(E) The counter electrode 19 is formed on the separator 24 (FIG. 20B).

(F) The entire device is immersed in the dye solution, and the dye Dye is adsorbed to the porous semiconductor layer 120. As a result, a porous semiconductor layer 130 (120 + Dye) is obtained (FIG. 20C).

(G) The first substrate 20G and the second substrate 22 are bonded together through a sealing material (FIG. 23).

(H) The electrolytic solution 14 is injected to complete the DSC 200 (FIG. 14).

  FIG. 21 shows a case where the counter electrode 19 is formed of carbon fine particles 19O. FIG. 22 shows a case where the counter electrode 19P is formed of a sintered body of conductive fine particles and catalyst material fine particles.

  Here, the separator 24 is made of a porous ceramic. Thereby, the electrolyte solution 14 is immersed to the inside of the separator 24, and the counter electrode 19P, the current extraction electrode 10, and the porous semiconductor layer 130 can be electrochemically connected via the electrolyte solution 14.

  The porous ceramic is made of, for example, a sintered body containing fine particles of aluminum oxide or silicon dioxide.

  The counter electrode 19P can be a porous electrode. Thereby, the electrolytic solution 14 can be immersed into the counter electrode 19P, and the electrochemical connection between the current extraction electrode 10 and the porous semiconductor layer 130 can be improved.

The porous electrode is formed of a sintered body of conductive fine particles and catalytic fine particles. The fine particles of the conductor are made of, for example, ITO or SnO ₂ or metal fine particles, and the fine particles of the catalyst material are made of Pt or carbon. In addition, a conductive auxiliary layer that increases conductivity may be formed on the counter electrode 19. The conductive auxiliary layer is formed of, for example, a carbon fine particle layer or a metal vapor deposition layer (for example, a vapor deposition layer of Ti, Au, or the like). Thereby, the efficiency of current extraction can be improved.

  Moreover, the 2nd board | substrate 22 is comprised with plastic films, such as a glass substrate or PET resin, or PEN resin. Thereby, cost can be reduced compared with the case where a relatively high-cost glass substrate on which a transparent conductive film is formed is used as the second substrate.

[Third embodiment]
A schematic cross-sectional structure diagram of the DSC 200 according to the third embodiment is as shown in FIG.

  As shown in FIG. 24, the DSC 200 according to the present embodiment includes a first substrate 20G formed of a glass substrate, current extraction electrodes 10 and 18 disposed on the first substrate 20G, and the current extraction electrode 10 And a separator 24 made of an insulating porous body formed so as to cover all or part of the porous semiconductor layer 130, the semiconductor fine particle layer 120 and the dye molecule Dye. The counter electrode 19 disposed on the separator 24, the electrolyte solution 14 in which the redox electrolyte for immersing the porous semiconductor layer 130, the separator 24 and the counter electrode 19, and the counter electrode 19 are disposed with a predetermined gap therebetween. A second substrate 22 and a sealing material 16 that is disposed between the first substrate 20G and the second substrate 22 and seals the electrolytic solution 14 are provided.

  As shown in FIG. 24, on the right side of the figure, a conductive film 18 serving as a current extraction electrode is formed between the first substrate 20 </ b> G and the sealing material 16, and connected to the counter electrode 19.

  As the sealing material 16, a resin such as an ultraviolet curable resin is used.

  In the present embodiment, since a normal glass substrate (raw glass) on which a transparent conductive film is not formed in advance is used as the first substrate 20G, the cost can be reduced.

The current extraction electrodes 10 and 18 are formed of a transparent conductive film, a metal vapor deposition film, or a film made of conductive fine particles. The transparent conductive film, ITO, FTO, ZnO, is formed in one of SnO _2.

  The separator 24 is made of a porous ceramic. Thereby, the electrolyte solution 14 is immersed into the separator 24, and the counter electrode 19, the current extraction electrode 10, and the porous semiconductor layer 130 can be electrochemically connected via the electrolyte solution 14.

  The porous ceramic is composed of a sintered body containing fine particles of aluminum oxide or silicon dioxide.

  The counter electrode 19 can be a porous electrode. Thereby, the electrolytic solution 14 is immersed in the counter electrode 19, and the electrochemical connection between the current extraction electrodes 10 and 18 and the porous semiconductor layer 130 can be improved.

The porous electrode is formed of a sintered body of conductive fine particles and catalytic fine particles. The fine particles of the conductor are made of, for example, ITO or SnO ₂ , metal fine particles, and the like, and the fine particles of the catalyst material are made of Pt or carbon.

  In addition, a conductive auxiliary layer that increases conductivity may be formed on the counter electrode 19. The conductive auxiliary layer is formed of, for example, a carbon fine particle layer or a metal vapor deposition layer (for example, a vapor deposition layer of Ti, Au, or the like). Thereby, the efficiency of current extraction can be improved.

  The dye Dye is formed of any one of a red dye (N719), a black dye (N749), D131 and D205, a phthalocyanine dye, a porphyrin dye, and an indoline dye (D149).

The semiconductor fine particles constituting the porous semiconductor layer 130 can be any of TiO ₂ , ZnO, WO ₃ , InO ₃ , Nb ₂ O ₃ , and SnO ₂ .

  FIG. 25 is a schematic cross-sectional structure diagram of a DSC using a counterbore glass substrate 22GZ as the second substrate.

  The counterbore part of the counterbore glass substrate 22GZ is formed by immersing a glass plate in hydrogen fluoride or the like.

  The counterbore glass substrate 22GZ is bonded to the first substrate 20G via the sealing material 16U.

  By using the counterbore glass substrate 22GZ, the sealing performance is improved and the reliability can be improved.

  FIG. 26 is a schematic sectional view of a DSC using a counterbore plastic substrate 22P as the second substrate.

  The counterbore plastic substrate 22P is formed by extrusion molding of a transparent resin or the like.

  By using the counterbore plastic substrate 22P, the sealing performance is improved, the reliability is improved, and the cost can be reduced.

(DSC manufacturing method according to the third embodiment)
Next, a DSC manufacturing method according to the third embodiment will be described.

The DSC manufacturing method according to the third embodiment includes the following steps:
(1) forming the current extraction electrodes 10 and 18 made of a transparent conductive film on the first substrate 20G after pre-processing the first substrate 20G made of a glass substrate by a cleaning process;
(2) forming a porous semiconductor layer 120 on the current extraction electrode 10;
(3) a step of sintering and forming a porous separator 24 made of an insulating ceramic so as to cover all or part of the porous semiconductor layer 120;
(4) forming the counter electrode 19 on the separator 24;
(5) a step of immersing the entire device in a dye solution, adsorbing the dye Dye to the porous semiconductor layer 120, and forming a porous semiconductor layer 130 (120 + Dye);
(6) a step of causing the first substrate 20G and the second substrate 22G made of a glass substrate to face each other and bonding together using the sealing material 16;
(7) Injecting the electrolytic solution 14 between the first substrate 20G and the second substrate 22G.

  With reference to FIG. 27 and FIG. 28, a specific example of the manufacturing method of the DSC 200 according to the third embodiment will be described.

(A) First, the first substrate 20G made of a glass substrate is pretreated, and the current extraction electrode 10 (18) made of a transparent conductive film is formed on the first substrate 20G (FIG. 27A).

(B) The current extraction electrodes 10 and 18 are etched and patterned (FIG. 27B).

(C) A porous semiconductor layer 120 is formed on the current extraction electrode 10 (FIG. 27C).

(D) A porous separator 24 is baked and formed on the porous semiconductor layer 120 (FIG. 27D).

(E) The counter electrode 19 is formed on the separator 24 (FIG. 28A).

(F) The entire device is immersed in the dye solution, and the dye Dye is adsorbed to the porous semiconductor layer 120 to form the porous semiconductor layer 130 (120 + Dye) (FIG. 28B).

(G) The first substrate 20G and the second substrate 22G made of a glass substrate are bonded to each other through the sealing material 16 (FIG. 28C).

(H) The electrolytic solution 14 is injected to complete the DSC 200 (FIG. 26).

  Here, the separator 24 is made of a porous ceramic. Thereby, the electrolyte solution 14 is immersed into the separator 24, and the counter electrode 19, the current extraction electrode 10, and the porous semiconductor layer 130 can be electrochemically connected via the electrolyte solution 14.

  The porous ceramic is composed of a sintered body containing fine particles of aluminum oxide or silicon dioxide.

  The counter electrode 19 can be a porous electrode. Thereby, the electrolytic solution 14 is immersed in the counter electrode 19, and the electrochemical connection between the current extraction electrode 10 and the porous semiconductor layer 130 can be improved.

The porous electrode is formed of a sintered body of conductive fine particles and catalytic fine particles. The fine particles of the conductor are made of, for example, ITO or SnO ₂ or metal fine particles, and the fine particles of the catalyst material are made of Pt or carbon. In addition, a conductive auxiliary layer that increases conductivity may be formed on the counter electrode 19. The conductive auxiliary layer is formed of, for example, a carbon fine particle layer or a metal vapor deposition layer (for example, a vapor deposition layer of Ti, Au, or the like). Thereby, the efficiency of current extraction can be improved.

  As in the first and second embodiments, the second substrate may be a counterbore glass substrate 22GZ or a counterbore plastic substrate 22P to improve reliability.

  The second substrate 22 is made of a plastic film such as PET resin or PEN resin. Thereby, cost can be reduced compared with the case where a relatively high-cost glass substrate on which a transparent conductive film is formed is used as the second substrate.

A schematic structure of the semiconductor fine particles 2 of the porous semiconductor layer 130 of the DSC 200 according to the third embodiment is expressed as shown in FIG. As shown in FIG. 29, in the porous semiconductor layer 130, 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 130.

(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 240.

(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 130 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 counter electrode 19 and is supplied with electrons from the counter electrode 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 130.

  Moreover, the principle of operation 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 130 made of TiO ₂ . The electrons (e ⁻ ) conducted in the porous semiconductor layer 130 conduct the load 240 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 (130) / 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. 32 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 130 made of TiO ₂ . The electrons (e ⁻ ) conducted in the porous semiconductor layer 130 conduct the load 240 of the external circuit from the first electrode 10A and move to the second electrode 18A. Electrons (e ⁻ ) injected from the counter electrode 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 redox level E _RO of the electrolytic solution 14 and the Fermi level E _f of the porous semiconductor layer 130 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. 30, 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. 34, when light is irradiated from the outside, the electrons existing in the full band S ⁰ / S ⁺ of the dye (Dye) are excited by the conduction band S ^* by the photons (hν), and the porous semiconductor layer 130 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 in the porous semiconductor layer 130 conduct the load 240 of the external circuit from the first electrode 10A and move to the second electrode 18A. Electrons (e ⁻ ) injected from the counter electrode 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 130 is the maximum electromotive force V _MAX .

  The chemical structural formula showing the dye used in the DSC 200 according to the embodiment, the chemical structural formula showing the indoline dye (D149) is expressed as shown in FIG. 35 (a), and the chemical structural formula showing N719 Is represented as shown in FIG. 35 (b), and the chemical structural formula representing D131 is represented as shown in FIG. 35 (c).

-Series configuration-
In DSC 200 according to the embodiment, a schematic cross-sectional structure in which two basic cells are arranged in series is represented as shown in FIG. The schematic circuit representation of FIG. 36A is expressed as shown in FIG.

The basic cell has a configuration in which two DSCs 200 shown in FIG. 14 are connected. That is, drawing, the conductive film 18 ₁ which extends from the left side of the DSC, and has a conductive film 10 ₂ of the right side of the DSC. Thereby, as shown in FIG.30 (b), two basic cells are arrange | positioned in a serial structure.

―Parallel configuration―
In DSC 200 according to the embodiment, a schematic cross-sectional structure in which two basic cells are arranged in a parallel configuration is expressed as shown in FIG. Also, the schematic circuit representation of FIG. 37A is expressed as shown in FIG. As shown in FIG. 37 (b), the two basic cells are arranged in a parallel configuration.

(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. ... 18 A plan view showing a state in which _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 _,.

  It is one 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 which consist of a plastic film are bonded together through the sealing material 16 A plan view showing the state is represented as shown in FIG. 40, and a schematic cross-sectional structure taken along line VII-VII in FIG. 40 is represented as shown in FIG. In FIG. 41, the first substrate (working electrode side) 20 is arranged upward, and the second substrate (counter electrode side) is arranged downward.

  FIG. 42 is a plan view showing a state in which the horizontal scribe line SL1 is formed, which is a process of the DSC 200 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. 41, 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 in which a total of m × n DSCs are bonded as shown in FIG. 41, 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. 43, 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 is broken along the scribe line SL1 and the scribe line SL2 and separated into each element due to the cleavage property of the glass material.

  Although not shown in the drawings, after being separated into each element, an electrolyte solution is injected, sealed by adhesion of a glass plate, filling with resin, or the like, and by closing an opening into which the electrolyte solution is injected, moisture or the like DSC 200 is built in such a way that it does not enter.

  According to the embodiment, it is possible to provide a dye-sensitized solar cell capable of improving the low cost and a manufacturing method thereof.

(Application example)
-Battery cell-
Next, with reference to FIGS. 44 to 47, application examples of a battery cell (hereinafter, simply referred to as “cell”) configured by the DSC 200 according to the first to third embodiments will be described.

  FIG. 44A shows a state in which three cells B1 to B3 are formed. In the example of FIG. 44A, 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. 45 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. 46 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. 47 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. 48 shows the wavelength region of ultraviolet light L1 (wavelength of 10 to 400 nm), the wavelength region of white light L2 (wavelength of 400 to 800 nm), and the wavelength region of infrared light L3 (wavelength of 600 to 1000 nm). The DSC 200 according to the first to third embodiments can exhibit a power generation function by using light rays in at least one region of L1 to L3.

  In particular, the DSC 200 according to the first to third embodiments is excellent in low cost and can contribute to cost reduction.

-Electronics-
The DSC 200 according to the first to third 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. 49 to 51, a configuration example of a remote control device 330 equipped with the DSC 200 according to the first to third embodiments will be described.

  As shown in FIG. 49 and FIG. 50, 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. 50, the transparent member 40 that protects the DSC 200 is fitted into the opening 41 so as to be flush with the front and back surfaces of the housing 38. This prevents dust from being attached to or damaged from the front and back surfaces of the DSC 200.

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

  As a result, external light such as sunlight and room light enters from the front surface side, back surface side, and side surface side of the remote control device 330 via the transparent member 40, so that incident light from the first substrate 20 side of the DSC 200 and Any of the incident light from the two substrates 22 side reaches the porous semiconductor layer 130. 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 third 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.

  48, 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. 51, 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. 52, a configuration example of a desktop digital timepiece 50 equipped with the DSC 200 according to the first to third 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. 52, 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. 52, the DSC 200 included 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. 53, the structural example of the electronic notebook 80 carrying DSC200 which concerns on embodiment is demonstrated.

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

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

  As shown in FIG. 53 (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 portion 80a is closed as shown in FIG. 53 (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 to third embodiments, 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 first to third 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. 54, a configuration example of electronic dictionary 90 equipped with DSC 200 according to the first to third 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. 54, in the state where the lid 90a is opened, the DSC 200 on the lid 90a side exhibits a power generation function by any light incident from both the front and back surfaces, and the DSC 200 on the main body 90b side The power generation function is demonstrated by the incident light. Therefore, stable power can be supplied to the arithmetic unit and the like included in the liquid crystal unit 34 and the main body 90b.

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

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

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

  Further, for example, the electronic dictionary 90 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 the manufacturing cost can be reduced because one DSC 200 is sufficient. .

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

  In particular, the DSC 200 according to the first to third embodiments is superior in cost effectiveness to the DSC 200 according to the first to third embodiments, and contributes to the reduction in cost of various electronic devices such as the electronic dictionary 90. be able to.

(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. 55, a DSC drive sensor module 800 equipped with the DSC 200 according to the first to third 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. 56, a schematic block configuration of another DSC drive sensor module 807 equipped with the DSC 200 according to the first to third 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 200 according to the first to third 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 200 according to the first to third embodiments is applied, the power supply can be controlled in accordance with the indoor environment of the entire building 910.

  In particular, the DSC 200 according to the first to third embodiments is superior in cost effectiveness to the DSC 200 according to the first to third embodiments, and contributes to a reduction in the cost of the DSC drive sensor module 807 and the like. it can.

  As described above, according to the present invention, it is possible to provide a dye-sensitized solar cell, a method for manufacturing the same, and an electronic apparatus that can improve the low cost.

[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 improve the low cost, and can be applied to various electronic devices, wireless sensor network systems, and the like by being applied as a small, light and highly efficient power source.

3a ... Cap sealing material 3b ... Opening sealing material 2 ... Semiconductor fine particles 4, 30, 32 ... Dye molecule 10 ... Current extraction electrode (first electrode, conductive film)
10A, 10 ₁ A, 10 ₂ A, 10 ₃ A, 10 ₄ A ... first internal electrode 10B, 10 ₁ B, 10 ₂ B, 10 ₃ B, 10 ₄ B, external first electrode 14 ... electrolyte (charge) Transport layer)
16, 16U ... Sealing material 18 ... Conductive film (second electrode)
18A: Internal second electrodes 18B, 18 ₁ B, 18 ₂ B, 18 ₃ B, 18 ₄ B ... External second electrodes 19, 19P ... Counter electrode 19O ... Carbon fine particles 20, 20G, 20M ... First substrates 22, 22G ... Second substrate 22GZ ... Spot glass substrate 22P ... Spot plastic substrate 23 ... Insulating film 24 ... Separator 26, 28 ... Redox electrolyte 30, 32 ... Dye molecule 31, 311 ... Cell 120 ... Porous semiconductor layer (semiconductor fine particle layer, TiO2) ₂ membranes)
122 ... Semiconductor fine particles (TiO ₂ particles)
124 ... Metal fine particles (Ag particles)
130 - 130 ₁ - 130 ₂ - 130 ₃ - 130 ₄ ... porous semiconductor layer (120 + Dye)
200, 200A ... Dye-sensitized solar cell (DSC)
240 ... Load Dye ... Dye

Claims (27)

A first substrate;
A counter electrode disposed on the first substrate;
A separator made of an insulating porous body formed so as to cover the counter electrode;
A current extraction electrode disposed on the separator;
A porous semiconductor layer disposed on the current extraction electrode and comprising semiconductor fine particles and dye molecules;
An electrolytic solution in which a redox electrolyte for immersing the separator, the current extraction electrode, and the porous semiconductor layer is dissolved;
A second substrate disposed above the porous semiconductor layer with a predetermined gap therebetween;
A dye-sensitized solar cell, comprising: a sealing material disposed between the first substrate and the second substrate and sealing the electrolytic solution. A first substrate;
A porous semiconductor layer disposed on the first substrate and comprising semiconductor fine particles and dye molecules;
A current extraction electrode disposed on the first substrate and on the porous semiconductor layer;
A separator made of an insulating porous body formed so as to cover an end portion of the current extraction electrode and the porous semiconductor layer;
A counter electrode disposed on the separator;
An electrolytic solution in which a redox electrolyte for immersing the porous semiconductor layer, the separator and the counter electrode is dissolved;
A second substrate disposed above the counter electrode with a predetermined gap therebetween;
A dye-sensitized solar cell, comprising: a sealing material disposed between the first substrate and the second substrate and sealing the electrolytic solution. A first substrate;
A current extraction electrode disposed on the first substrate;
A porous semiconductor layer disposed on the current extraction electrode and comprising semiconductor fine particles and dye molecules;
A separator made of an insulating porous body formed so as to cover all or part of the porous semiconductor layer;
A counter electrode disposed on the separator;
An electrolytic solution in which a redox electrolyte for immersing the porous semiconductor layer, the separator and the counter electrode is dissolved;
A second substrate disposed above the counter electrode with a predetermined gap therebetween;
A dye-sensitized solar cell, comprising: a sealing material disposed between the first substrate and the second substrate and sealing the electrolytic solution.   The said 1st board | substrate is comprised with a glass substrate, The dye-sensitized solar cell of Claim 2 or Claim 3 characterized by the above-mentioned.   The dye-sensitized solar cell according to claim 1, wherein the first substrate is made of a metal film having a predetermined thickness.   The dye-sensitized solar cell according to claim 5, wherein the metal film is made of stainless steel or Ti.   The dye-sensitized solar cell according to any one of claims 1 to 3, wherein the current extraction electrode includes a transparent conductive film, a metal vapor deposition film, or a film made of conductive fine particles. The transparent conductive film, ITO, FTO, ZnO, dye-sensitized solar cell according to claim 7, characterized in that formed in one of SnO _2.   The dye-sensitized solar cell according to any one of claims 1 to 8, wherein the separator is made of a porous ceramic.   The dye-sensitized solar cell according to claim 9, wherein the porous ceramic is a sintered body containing fine particles of aluminum oxide or silicon dioxide.   The dye-sensitized solar cell according to any one of claims 1 to 10, wherein the counter electrode is a porous electrode.   The dye-sensitized solar cell according to claim 11, wherein the porous electrode is formed of a sintered body of conductive fine particles and catalytic fine particles. The fine particles of the conductor is composed of ITO or SnO _2, fine particles of the catalyst material the dye-sensitized solar cell according to claim 12, characterized in that it is composed of Pt or carbon.   The dye-sensitized solar cell according to any one of claims 1 to 13, wherein a conductive auxiliary layer for increasing conductivity is formed on the counter electrode.   The dye-sensitized solar cell according to claim 14, wherein the conductive auxiliary layer is formed of a carbon fine particle layer or a metal vapor deposition layer.   The said 2nd board | substrate is comprised with a glass substrate or a plastic film, The dye-sensitized solar cell of any one of Claims 1-15 characterized by the above-mentioned.   The dye-sensitized solar cell according to any one of claims 1 to 16, wherein the second substrate has a counterbore structure.   The dye-sensitized solar cell according to claim 16, wherein the plastic film is formed of PET resin or PEN resin.   The dye is formed of any one of a red dye (N719), a black dye (N749), D131, D205, a phthalocyanine dye, a porphyrin dye, and an indoline dye (D149). The dye-sensitized solar cell of any one of these. The dye enhancement according to claim 1, wherein the semiconductor fine particles are formed of any one of TiO ₂ , ZnO, WO ₃ , InO ₃ , Nb ₂ O ₃ , and SnO _2. Sensitive solar cell. 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 20, further comprising an external second electrode disposed on the second substrate outside the sealing material. 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 claim 21, 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 claim 21, wherein a plurality of cells of the dye-sensitized solar cell are connected in parallel via the insulating layer. Forming a counter electrode on the first substrate after pre-processing the first substrate by a cleaning step;
A step of sintering and forming a porous separator made of an insulating ceramic so as to cover the counter electrode;
Forming a current extraction electrode on the separator;
Forming a porous semiconductor layer on the current extraction electrode;
Immersing the entire device in a dye solution, immersing the dye in the porous semiconductor layer; and
A step of causing the first substrate and the second substrate to face each other and bonding using a sealing material;
Injecting electrolyte solution between said 1st board | substrate and said 2nd board | substrate, The manufacturing method of the dye-sensitized solar cell characterized by the above-mentioned. Forming a porous semiconductor layer comprising semiconductor fine particles on the first substrate after pre-processing the first substrate by a cleaning step;
Forming a current extraction electrode on the first substrate and the porous semiconductor layer;
A step of sintering and forming a porous separator made of an insulating ceramic so as to cover the ends of the current extraction electrode and the porous semiconductor layer;
Forming a counter electrode on the separator;
Immersing the entire device in a dye solution, immersing the dye in the porous semiconductor layer; and
A step of causing the first substrate and the second substrate to face each other and bonding using a sealing material;
Injecting electrolyte solution between said 1st board | substrate and said 2nd board | substrate, The manufacturing method of the dye-sensitized solar cell characterized by the above-mentioned. Forming a current extraction electrode made of a transparent conductive film on the first substrate after pre-processing the first substrate by a cleaning step;
Forming a porous semiconductor layer provided on the current extraction electrode and comprising semiconductor fine particles; and
A step of sintering and forming a porous separator made of an insulating ceramic so as to cover all or part of the porous semiconductor layer;
Forming a counter electrode on the separator;
Immersing the entire device in a dye solution, immersing the dye in the porous semiconductor layer; and
A step of causing the first substrate and the second substrate to face each other and bonding using a sealing material;
Injecting electrolyte solution between said 1st board | substrate and said 2nd board | substrate, The manufacturing method of the dye-sensitized solar cell characterized by the above-mentioned.   An electronic apparatus comprising the dye-sensitized solar cell according to any one of claims 1 to 23.

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