JP2007059181A - Optical device and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical device having sealing structure of high barrier characteristic, keeping high stable optical characteristics over a long time, and is suitable for a dye-sensitized solar cell or the like. <P>SOLUTION: The optical device is equipped with a plurality of substrates 210, 240 facing each other, and houses an electrolyte 230 in an inside space between the substrates. A through hole 254, communicating with the outside, is installed in either substrate of the plurality of substrates, and the through hole comprises a recessed part 250 which open to the outside and a communicating hole 252 communicating with the recessed part and opened to the inside space; the communicating hole 252 is present in a region of the recessed part 250; and when the maximum opening area of the recessed part 250 is represented by S2 and an opening area in the communicating position with the recessed part 250 out of the communicating hole 252 is represented by S1, relation of S1<S2 is satisfied. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an optical device configured as a dye-sensitized solar cell, a liquid crystal display device, a display device, and the like and a manufacturing method thereof, and particularly relates to a sealing technique for an optical device.

  As a characteristic required for a solar cell, it is mentioned to show the stable photoelectric conversion characteristic over a long period of time. In particular, in the case of a dye-sensitized solar cell using a semiconductor carrying a sensitizing dye, it contains a liquid or gel-like electrolyte component as a constituent element thereof, so that the electrolyte component volatilizes or leaks from the battery, or in the atmosphere. Therefore, it has been a challenge to avoid performance degradation due to the intrusion of moisture, oxygen, and other components into the electrolyte.

  As a method for solving this problem, a method using a non-volatile molten salt electrolyte as an electrolyte (for example, JP 2001-196105 A), a method using a gel electrolyte (for example, JP 2001-536513 A). ) Etc. have been studied. In addition, a method of sealing (end sealing) an electrolyte using a sealing material is described (for example, refer to Patent Document 1 described later).

  In Example 1 described in Patent Document 1, an electrolytic solution is injected between a titanium oxide film and a counter electrode from an electrolytic solution inlet provided in a film on which a counter electrode is deposited, and around the electrolytic solution inlet. After the attached electrolyte solution is wiped off and the electrolyte solution injection port is sealed with a silicone adhesive tape, the silicone adhesive tape is attached with a one-component ultraviolet curable resin.

  Moreover, in Example 2 described in Patent Document 1, an electrolytic solution is injected between an electrode carrying a sensitizing dye and a counter electrode from an electrolytic solution injection port provided in a film on which the counter electrode is deposited, and electrolysis is performed. Remove the electrolyte at the liquid inlet, create a void at the electrolyte inlet, wipe the electrolyte around the electrolyte inlet, and then wipe the electrolyte with polyimide tape with silicone adhesive After sealing, it is reinforced and sealed with epoxy resin. In addition, the description regarding the specific shape of the electrolytic injection port is not described regarding Example 1 and 2 of patent document 1. FIG.

JP 2004-119306 A (paragraphs 0049, 0051, 0057)

  In an optical apparatus typified by a dye-sensitized solar cell configured as a wet device, the greatest point that determines the lifetime of an element is a sealing technique. Many optical devices configured as wet devices that inject liquid into the gap between the substrates facing each other seal the outer periphery of the element (main seal) before injecting the liquid, and then supply the liquid from a separate injection port It is common to inject. At this time, sealing of the outer periphery of the element may be performed before injecting the liquid into the gap, and since the liquid and the sealant are cured without being in direct contact, the sealing performance is relatively high. On the other hand, the final injection port sealing (so-called end seal) after injecting the liquid into the gap is caused by the liquid injected into the interior and the sealant before curing touching in the vicinity of the injection port. There is a problem that the adhesive strength is significantly reduced.

  In addition, a method of placing a sealant on a smooth substrate and curing it is common, but when the sealant after curing peels off due to physical contact, liquid leakage from the interface between the substrate and the resin There is a problem that will occur. In addition, in order to improve sealing performance, a base material with a high barrier property may be attached to the injection port and sealed, but the thickness of this base material is a problem when incorporating elements into small portable devices. There is a case.

  FIG. 9 is a diagram illustrating the configuration of a dye-sensitized solar cell configured as a wet device, which is assumed from the description in Patent Document 1 of the prior art, and FIG. 9A is a dye-sensitized solar cell. FIG. 9B is a schematic sectional view of the AA portion, and FIG. 9C is a schematic partial sectional view of the BB portion.

  The structure of the dye-sensitized solar cell 300 described in Patent Document 1 is assumed to be configured as shown in FIG. That is, a metal oxide semiconductor layer is provided between a transparent substrate 312 provided with a transparent conductive film (transparent electrode) 314 and a substrate 346 having a conductive film (counter electrode) 342 and a current collector 344 that are opposite to the transparent electrode 314. 316 and an electrolyte layer (electrolytic solution) 330 are provided. The semiconductor layer 316 includes an oxide semiconductor material and a sensitizing dye. Further, the transparent conductive film 314 and the conductive film 342 are connected by a conductive wire, and a current circuit 358 having an ammeter (ammeter) 357 is formed. On the side of the surface other than the light receiving surface 359, a second gap is formed between the light receiving substrate 310 (configured with the transparent substrate 312 and the transparent electrode 314) and the counter substrate 340 (configured with the substrate 346, the current collector 344, and the conductive film 342). 1 sealing material 320 is provided, and the semiconductor layer 316 and the electrolyte layer 316 are sealed.

  In the embodiment described in Patent Document 1, as shown in FIG. 9C, the electrolytic solution 330 is inserted between the light receiving substrate 310 and the counter substrate 340, and the electrolyte injection port 352 penetrating the counter substrate 340 (FIG. 9). In the example shown in Fig. 4, after injection from four places, the electrolyte injection port 352 is sealed with tape 353 (silicone adhesive tape or polyimide tape with silicone adhesive), and then resin 354 (one-component ultraviolet curing) A tape 353 is attached with resin or epoxy resin, and is reinforced and sealed.

  However, in the electrolyte sealing technique described in Patent Document 1, the resin 354 that reinforces and seals the tape 353 becomes convex on the outer surface of the counter substrate 340. Due to this convex reinforcement / sealing site, there is a problem that the thickness of the solar cell increases. In addition, when a solar cell shown in FIG. 9 is stacked as a battery cell to produce a stacked solar cell, the battery cells can be stacked in close contact because there is a convex reinforcing / sealing site. However, there is a problem that it is difficult to realize a small stacked solar cell with good photoelectric conversion efficiency.

  Furthermore, in the sealing technique described in Patent Document 1, after injecting the electrolytic solution 330 from the electrolytic solution inlet 352, before the end sealing of the electrolytic inlet 352, the electrolytic solution attached to the periphery of the electrolytic solution inlet 352 is removed. When wiping off, the electrolytic solution in the electrolytic solution injection port 352 disappears once, but then, the electrolytic solution 330 enters the electrolytic solution injection port 352 by capillary action, so that the tape 353 that seals the electrolytic solution injection port 352 is used. In addition, there is a problem that the resin 353 enters the interface between the counter substrate 340, the adhesive strength is reduced, and the convex reinforcement / sealing site is easily peeled off by mechanical contact from the outside. Therefore, the volatilization or leakage of the electrolyte from the inside of the solar cell or the intrusion of moisture, oxygen, and other components from the atmosphere into the inside of the solar cell occurs, and thus high barrier characteristics must be maintained for a long time. There is a problem that the characteristics of a highly stable solar cell cannot be maintained for a long time.

  Even when the electrolyte injection port 352 is end-sealed with only the resin 354 without using the tape 353, the same problem is caused, and further, the degree of deterioration is considered to increase because the resin 354 directly contacts the electrolyte. . Furthermore, in the case of a liquid crystal display device and an electrochromic display device configured as a wet device, it is necessary to inject and seal a functional material that contributes to display inside the device. Clearly there are similar problems.

  The present invention has been made to solve the above-described problems, and its object is to provide a dye-sensitized solar cell and a liquid crystal that have high barrier characteristics and can maintain highly stable optical characteristics for a long period of time. An object of the present invention is to provide an optical device configured as a display device, an electrochromic display device, and the like, and a manufacturing method thereof.

  That is, the present invention provides an optical device including a plurality of substrates facing each other, and a functional substance such as an electrolyte solution accommodated in an internal space between these substrates. A through hole that communicates with the outside is formed, and the through hole includes a recess that opens to the outside, and a communication hole that is connected to the recess and opens into the internal space, and the communication hole is formed in the region of the recess. And at least the bottom of the recess is closed by a sealing material, where S2 is the maximum opening area of the recess and S1 is the opening area of the communication hole at the connection position with the recess. The present invention relates to an optical device characterized by satisfying the relationship.

  Further, in the first manufacturing method of the optical device, the step of bonding the plurality of bases to each other, the step of injecting the functional substance into the internal space from the opening of the recess, and at least the inside of the recess And a step of filling the bottom portion with a sealing material.

  Furthermore, in the second manufacturing method of the optical device, the step of forming a solid electrolyte layer on any one of the plurality of substrates, the step of bonding the plurality of substrates to each other, The present invention relates to a method for manufacturing an optical device, which includes a step of exhausting the internal space through a through hole and a step of filling a sealing material in at least the bottom of the recess.

  According to the optical device of the present invention, since the through hole is constituted by the communication hole and the concave portion having a relationship of S1 <S2, the contact of the functional substance with the sealing material in the concave portion can be reduced, and the sealing is performed. High performance can be maintained. Therefore, it is possible to effectively prevent the volatilization or leakage of the functional substance or its component inside the optical apparatus or the entry of moisture, oxygen or other components from the atmosphere into the functional substance or its component. The barrier characteristics can be maintained for a long time, the characteristics of the highly stable optical device can be maintained for a long time, and the thickness of the element does not increase.

  According to the first manufacturing method of the optical device of the present invention, the thickness of the element is increased by improving the shape of the through hole (injection port) used for injecting the functional substance into the inside as described above. In addition, it is possible to provide a method for manufacturing an optical apparatus including a wet device having high sealing performance and durability.

  According to the second manufacturing method of the optical device of the present invention, the shape of the through hole (exhaust port) that functions to exhaust the inside is improved as described above, so that the thickness of the element is not increased and sealing is performed. It is possible to provide a method for manufacturing an optical apparatus including a dry device having high performance and durability.

  In the optical device of the present invention, when the maximum opening area of the recess is S2, and the opening area of the communication hole at the connection position with the recess is S1, S2> S1, and (S2 / S1) is 1. 5 or more is preferable. S2 is set to a size that allows the tip of the injection nozzle or the exhaust nozzle to be inserted, and S1 is set to a size that prevents leaching of the functional substance inside and prevents liquid from entering from the injection nozzle. S1, and (S2 / S1) is 1.5 or more. Thereby, a stable liquid injection operation or exhaust operation can be performed. More preferably, (S2 / S1) is set to 2 or more. Thereby, it is possible to further improve the liquid injection operation or the exhaust operation.

  In the optical device of the present invention, it is preferable that the concave portion or the communication hole has a columnar shape or a truncated cone shape. Thereby, it becomes possible to form the said recessed part and the said communicating hole easily.

  In the optical device according to the aspect of the invention, it is preferable that the maximum diameter of the opening of the recess is φ0.5 mm to φ50 mm, and the diameter of the opening of the communication hole at the connection position is φ0.1 mm to φ10 mm. Generally speaking, in order that the tip of the liquid injection nozzle or the exhaust nozzle can be inserted into the opening of the recess, the maximum diameter of the opening of the recess is φ0.5 mm to φ50 mm. Well, in order to sufficiently inject the functional substance into the inside at the connection position and reduce the leaching after the injection, the diameter of the opening of the communication hole at the connection position is φ0. .1 mm to φ10 mm may be used.

  Depending on the amount of liquid to be injected or the amount of exhaust to be exhausted by the injection nozzle or the exhaust nozzle, that is, the volume of the target space to be injected or the volume of the target space to be exhausted, By setting the diameter of the opening of the communication hole at the connection position, it is possible to perform the liquid injection operation or the exhaust operation efficiently and with good workability. When the volume is large, the opening is large, and when the volume is small, the opening is small, and the maximum of the opening of the recess corresponds to the volume of the target space to be injected or the volume of the target space to be evacuated. What is necessary is just to change a diameter and the diameter of the opening of the said communicating hole in the said connection position.

  More preferably, the maximum diameter of the opening of the recess is φ1 mm or more, and the diameter of the opening of the communication hole at the connecting position is φ0.3 mm to φ0.5 mm. In order to inject sealing resin into the recess, the maximum diameter of the opening of the recess needs to be 1 mm or more. By using an injection nozzle having a tip outer diameter of φ1 mm or more, the tip of the injection nozzle can be inserted into the recess, and the sealing resin to be injected only into the recess can hardly enter the communication hole.

  The plurality of bases include a first base and a transparent second base, and the first base and the second base are bonded to each other with a sealing material for main seal, and the first base The through-hole is preferably formed in any part of the base and the second base, and the through-hole is formed in a place where work is easy according to the purpose and configuration of the optical device.

  In addition, the optical device of the present invention is configured as a wet (or dry) device, has high sealing performance and can maintain high barrier characteristics for a long period of time, and can maintain the characteristics of a highly stable optical apparatus for a long period of time. It is possible to maintain high reliability. Typical examples of such an optical device are a dye-sensitized solar cell, a liquid crystal display device or an electrochromic display device.

  In the first manufacturing method of the optical device of the present invention, it is preferable that the sealing material filled in the concave portion is a liquid resin precursor, thereby improving workability.

  Furthermore, it is preferable that the liquid resin precursor is a photo-curing type, whereby it becomes possible to remove the sealing material before curing existing in a portion where it is not desired to leave the cured resin by wiping or the like. .

  Moreover, after filling with the resin precursor, it is preferable to cover the resin precursor with a plate and further cure the resin precursor. Accordingly, it is possible to provide a highly reliable optical device that can further improve the barrier characteristics of the optical device and a method for manufacturing the same.

  Furthermore, it is preferable that the surface of the sealing material or the plate in the recess is on the same plane as the surface of the base. As a result, the element thickness of the optical device is reduced, and for example, even when a dye-sensitized solar cell is stacked as a battery cell to produce a stacked solar cell, a convex reinforcement / sealing is performed. Since there is no portion, a plurality of battery cells can be stacked in close contact with each other, and an optical device capable of realizing a small stacked solar cell with excellent barrier properties and a method for manufacturing the same can be provided.

  In the second method for producing an optical device of the present invention, the second sealing material is preferably a liquid resin precursor. Thereby, workability | operativity can be made favorable like the 1st manufacturing method of the optical apparatus of this invention.

  More preferably, the liquid resin precursor is a photo-curing type, and as in the first manufacturing method of the optical device of the present invention, the pre-curing resin is present at a site where the resin after curing is not desired to remain. The sealing material can be removed by wiping or the like.

  Moreover, it is more preferable to cover the resin precursor with a plate after the resin precursor is filled, and to further cure the resin precursor. Thereby, similarly to the first manufacturing method of the optical device of the present invention, it is possible to provide a highly reliable optical device capable of further improving the barrier characteristics of the optical device and a manufacturing method thereof.

  Furthermore, it is more preferable that the surface of the sealing material or the plate in the recess is on the same plane as the surface of the base. As a result, the element thickness of the optical device can be reduced as in the first manufacturing method of the optical device of the present invention, and for example, a dye-sensitized solar cell is stacked as a battery cell, and a stacked solar cell is manufactured. Even when trying to fabricate, since there is no convex reinforcement / sealing part, it is possible to stack multiple battery cells in close contact, realizing a compact stacked solar cell with excellent barrier properties It is possible to provide a method of manufacturing an optical device that can be used.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. In each drawing, each part is exaggerated as necessary to clarify the configuration.

First Embodiment Hereinafter, a dye-sensitized solar cell will be described in detail as an example of an optical apparatus configured as a wet device based on the present invention.

  A general dye-sensitized solar cell has a transparent substrate, a porous dye-sensitized semiconductor layer, an electrolyte layer, and a counter electrode (conductive film) on which a transparent electrode (transparent conductive film) is formed from the light incident side. A structure is formed in which the formed counter substrates are sequentially stacked. The porous dye-sensitized semiconductor layer and the counter electrode face each other, and the transparent substrate and the counter substrate are bonded together with a sealing material with a gap, and the electrolyte layer (electrolytic solution) is a through-hole (opened in the counter substrate ( The liquid filling port is filled into the gap between the transparent substrate and the counter substrate.

  Here, the opening area of the through hole (liquid injection port) opened in the counter substrate is different between the inner surface side and the outer surface side of the substrate, and the area of each opening is not limited, but the inner surface side of the substrate <the outer surface side of the substrate. . Although there is no restriction | limiting also in the shape of each opening part, It is preferable from a point with easy manufacture if it is set as the shape which combined the several cylindrical shape or circular frustum-shaped circular hole from which size differs. There is no limit to the diameter of the opening on the substrate inner surface side of the through-hole (injection port), but considering the sealing performance, a smaller one is preferable. Exists. Specifically, φ0.1 mm to 10 mm is particularly preferable. Similarly, the diameter of the opening on the outer surface side of the substrate is not limited, but it is preferable that the sealing performance is small. On the other hand, an appropriate opening area is required to fill the sealing agent. Specifically, φ0.5 mm to 50 mm is particularly preferable, and the area of the opening needs to satisfy the substrate inner surface side <substrate outer surface side.

  It is preferable to perform sealing by injecting an electrolytic solution from a through-hole (injection port) on the substrate outer surface side, and then filling a liquid resin precursor into a recess in the opening on the substrate outer surface side and curing it. If necessary, the sealing agent can be coated with a base material (low-permeability base material) that has a high barrier property against gas and / or liquid and low permeability to gas and / or liquid. . Further, in consideration of physical strength, it is preferable that the sealing agent filled in the recess and the coated base material are not more convex than the outer surface of the substrate. For this purpose, the outer surface of the substrate may be squeezed. In this manner, the cured sealant and the low-permeability base material are prevented from coming out of the recess so as to exist only inside the recess. Although there is no restriction | limiting in the sealing agent which seals the liquid injection port of this invention, It is preferable to use a photocurable sealing agent from the point that sealing is easy.

  FIG. 1 is a diagram for explaining a dye-sensitized solar cell according to this embodiment. FIG. 1 (A) is a schematic plan view of the dye-sensitized solar cell, and FIG. FIG. 1C is a schematic cross-sectional view of the BB part.

  FIG. 1C shows a through hole (liquid injection port) 254 formed from the communication hole 252 and the recess 250. The through hole 254 may be single or plural. In the example shown in FIG. 1, four through holes 254 are provided. The through hole 254 is formed from the communication hole 252 and the recess 250, but the shape of the recess 250 can be various as described later.

  As shown in FIG. 1, the dye-sensitized solar cell 200 includes a transparent substrate 212 provided with a transparent conductive film (transparent electrode) 214, a conductive film (counter electrode) 242 that forms a counter electrode of the transparent electrode 214, and a current collector 244. A metal oxide semiconductor layer 216 and an electrolyte layer (electrolytic solution) 230 are provided between the substrate 246 and the substrate. The semiconductor layer 216 includes an oxide semiconductor material and a sensitizing dye. A striped or mesh-like wiring pattern is held on the surface opposite to the transparent substrate 212 of the transparent electrode 214 by a metal 218 such as Ni or Ti so as to reduce the electric resistance so that the aperture ratio is about 80% or more. Is formed.

  Further, the transparent electrode 214 and the conductive film 242 are connected by a conductive wire, and a current circuit 258 having an ammeter (ammeter) 257 is formed. On the side of the surface other than the light-receiving surface 259, the second surface is formed between the light-receiving substrate 210 (configured by the transparent substrate 212 and the transparent electrode 214) and the counter substrate 240 (configured by the substrate 246, the current collector 244, and the conductive film 242). 1 sealing material (main seal) 220 is provided, and the semiconductor layer 216 and the electrolyte layer 230 are sealed. The recess 250 is sealed by the second sealing material (end seal) 270 and the glass plate 260.

  2A and 2B are schematic cross-sectional views illustrating sealing of the through hole in FIG. 1C, FIG. 2A is a configuration of Example 1 described later, and FIG. 2B is a diagram of FIG. The structure of the structure of a modification is shown.

  After injecting the electrolytic solution 230 from the glass plate 260 into the inside through the communication hole 252, the electrolytic solution attached to the inner surface of the recess 250 and the periphery of the recess 250 is wiped off. Next, as shown in FIG. 2A, in the through hole 254 formed from the communication hole 252 and the recess 250, the portion of the communication hole 252 connected to the bottom surface of the recess 250 is a second sealing material such as a resin. The second sealing material 270 is covered with a glass plate 260, and the inner surface of the recess 250, the second sealing material 270, and the glass plate 260 are integrated by a resin or the like. The glass plate 260 and the resin or the like that fixes the glass plate 260 are prevented from protruding outside the surface of the counter substrate 240. That is, the resin or the like protruding outside the surface of the counter substrate 240 is squeezed to be flush with the surface of the counter substrate 240 and flattened. As a result, no convex portion is formed on the outer surface of the counter substrate 240 near the concave portion 250.

  Further, as shown in FIG. 2B, the portion of the communication hole 252 connected to the bottom surface of the recess 250 is sealed with a second sealing material 270 such as a resin, and the second sealing material 270 is By squeezing the second sealing material 270 that fills the entire inside of the recess 250 and protrudes outside the surface of the counter substrate 240, the second sealing material 270 is flush with the surface of the counter substrate 240. Alternatively, the structure may be flattened.

  FIG. 3 is a schematic cross-sectional view for explaining a shape example of the through hole in the present embodiment. Here, the inner diameter of the recess 250 on the outer surface of the counter substrate 240 is W2, and the inner diameter of the communication hole 252 on the inner surface of the counter substrate 240 is W1.

  The shape of the through hole shown in FIG. 3 (A) is the same as that of FIG. 2 (A), and the recess 250 has a cylindrical or prismatic shape. A triangular prism, a quadrangular prism, etc. are possible as a prism.

  The recess 250 shown in FIG. 3B has a truncated cone or truncated pyramid shape.

  The recess 250 in FIG. 3C has a semispherical shape.

  A recess 250 illustrated in FIG. 3D is formed by digging a plurality of columns with different diameters or a plurality of prisms with different side lengths into the counter substrate 240 in a plurality of stages. A triangular prism, a quadrangular prism, etc. are possible as a prism. The heights of these cylinders or prisms may be the same or different.

  The recess 250 shown in FIG. 3E is formed by digging a plurality of truncated cones having different diameters on the upper and lower surfaces or a plurality of truncated pyramids having different side lengths on the upper and lower surfaces in the counter substrate 240 in a plurality of stages. . A triangular frustum, a quadrangular frustum, etc. are possible as a pyramid. The height of each of these truncated cones or each truncated pyramid may be the same or different.

  Hereinafter, the relationship between the diameter W2 on the outer surface of the counter substrate 240 and the inner diameter W1 of the communication hole 252 on the inner surface of the counter substrate 240 will be described.

  The inner diameter W2 has such a size that the tip of the liquid injection nozzle for injecting the second sealing material 270 into the concave portion 250 can be inserted, so that the liquid from the liquid injection nozzle does not enter the communication hole 252. It is assumed that the relationship of W1 <W2 is satisfied. Therefore, assuming that the opening area of the recess 250 on the outer surface of the counter substrate 240 is S2, and the opening area of the communication hole 252 on the inner surface of the counter substrate 240 is S1, the relationship of S1 <S2 is satisfied. Here, (S2 / S1) is 1.5 or more, more preferably 2 or more, W2 is 0.5 to 50 mm (especially 1 mm or more), and W1 is 0.1 to 10 mm (especially 0.3 to 0.00). 5 mm).

  By inserting the tip of the liquid injection nozzle into the recess 250 and filling the recess with the sealing material before curing, the sealing material is hardened, so that the sealing material is difficult to peel off from the counter substrate 240 and is durable. The characteristics are greatly improved.

  FIG. 4 is a diagram for explaining an example of a manufacturing process of the dye-sensitized solar cell according to the present embodiment.

  As shown in FIG. 4A, a light receiving substrate 210 in which a semiconductor layer 216 is formed, and a counter substrate 240 in which a recess 250 and a communication hole 252 are formed are manufactured. Next, as illustrated in FIG. 4B, the light receiving substrate 210 and the counter substrate 240 are opposed to each other, and the light receiving substrate 210 and the counter substrate 240 are integrated by the first sealing material 220. As a result, an internal space is formed by the three members of the light receiving substrate 210, the counter substrate 240, and the first sealing material 220. Next, the tip of a liquid injection nozzle for injecting the electrolytic solution is inserted into the concave portion 250, and as shown in FIG. 4C, the electrolytic solution 230 is injected so that bubbles are not mixed into the internal space. Next, according to the procedure described in FIG. 2, the recess 250 is sealed with the second sealing material 270 and the glass plate 260 as shown in FIG.

  The transparent substrate 212 is not particularly limited, and various base materials can be used as long as they are transparent. In addition, a material excellent in moisture and gas barrier properties, solvent resistance, and weather resistance entering from the outside of the solar cell configured as a wet device is preferable. Specifically, a transparent inorganic substrate such as quartz, sapphire, glass, etc. , Polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, tetraacetylcellulose, brominated phenoxy, aramids, polyimides, polystyrenes, polyarylates, polysulfones, polyolefins Although not limited to these, it is preferable to use a substrate having a particularly high transmittance in the visible light region. Here, since the hydrothermal treatment is performed in an alkaline aqueous solution, a substrate having high alkali resistance is particularly preferable as the support. The thickness of these supports is not particularly limited, and can be freely selected depending on the light transmittance and the shielding property between the inside and outside of the solar cell configured as a wet device.

The transparent conductive film (transparent electrode) 214 formed on the transparent substrate 212 is preferably as low as possible. Specifically, 500Ω / □ or less is preferable, and 100Ω / □ or less is more preferable. As the material for forming the transparent conductive film 214, a known material can be used, in particular indium - tin oxide (ITO), fluorine-doped SnO ₂ (FTO), antimony-doped SnO ₂ (ATO), Examples thereof include, but are not limited to, SnO _{2 and the} like, and two or more types can be used in combination. In addition, for the purpose of reducing the surface resistance and improving the current collection efficiency, it is possible to form a highly conductive metal (Ni, Ti) 218 or carbon wiring. This wiring is patterned to increase the aperture ratio so as to ensure a sufficient light collection area.

As the semiconductor fine particles constituting the semiconductor layer 216, a compound semiconductor or a compound having a perovskite structure can be used in addition to a single semiconductor typified by silicon. These semiconductors are preferably n-type semiconductors in which conduction band electrons become carriers under photoexcitation and give an anode current. Specific examples include TiO ₂ , ZnO, WO ₃ , Nb ₂ O ₅ , TiSrO ₃ and SnO ₂ , particularly preferably anatase TiO ₂ . Moreover, the kind of semiconductor is not limited to these, It can use individually or in mixture of 2 or more types or compounded. Further, the semiconductor fine particles can take various forms such as particles, tubes, and rods as required.

  There are no particular restrictions on the method for forming the semiconductor layer 216 to form the semiconductor layer 216. However, in consideration of physical properties, convenience, manufacturing cost, etc., the wet film forming method of the semiconductor fine particles is preferable. A method in which a paste in which water is uniformly dispersed in a solvent such as water is prepared and applied onto a substrate on which a transparent conductive film is formed is preferable. The coating method is not particularly limited and can be performed according to a known method. For example, a dipping method, a spray method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, a gravure coating method, or a wet printing method. Can be performed by various methods such as letterpress, offset, gravure, intaglio, rubber plate, screen printing and the like.

  The crystal form of crystalline titanium oxide is preferably anatase type from the viewpoint of photocatalytic activity. The anatase-type titanium oxide may be a commercially available powder, sol, or slurry, or may have a predetermined particle size by a known method such as hydrolysis of titanium oxide alkoxide. When using a commercially available powder, it is preferable to eliminate secondary aggregation of the particles, and it is preferable to pulverize the particles using a mortar, ball mill or the like when preparing the coating solution. At this time, acetylacetone, hydrochloric acid, nitric acid, a surfactant, a chelating agent, or the like can be added in order to prevent the particles whose secondary aggregation has been released from aggregating again. For the purpose of thickening, various thickeners such as polymers such as polyethylene oxide and polyvinyl alcohol, and cellulose-based thickeners can be added.

  Although there is no restriction | limiting in particular in the particle size of these semiconductor fine particles, 1-200 nm is preferable at the average particle diameter of a primary particle, Most preferably, it is 5-100 nm. It is also possible to improve the quantum yield by mixing two or more kinds of particles having a size larger than the semiconductor fine particles to scatter incident light. In this case, the average size of the particles to be mixed separately is preferably 20 to 500 nm.

  The semiconductor layer 216 preferably has a large surface area so that a large amount of dye can be adsorbed. For this reason, the surface area of the semiconductor fine particle layer coated on the support is preferably 10 times or more, more preferably 100 times or more the projected area. The upper limit is not particularly limited, but is usually about 1000 times. In general, as the thickness of the semiconductor fine particle-containing layer increases, the amount of the supported dye increases per unit projected area and the light capture rate increases. However, the diffusion distance of injected electrons increases and the loss due to charge recombination also increases.

  Accordingly, the semiconductor fine particle layer has a preferable thickness, but is generally 0.1 to 100 μm, more preferably 1 to 50 μm, and particularly preferably 3 to 30 μm. The semiconductor fine particles are preferably fired in order to make the particles contact electronically after being applied to the support and to improve the film strength and the adhesion to the substrate. Although there is no restriction | limiting in particular in the range of a calcination temperature, When a temperature is raised too much, since resistance of a base | substrate will become high and it may melt | fuse, Usually, it is 40 to 700 degreeC, More preferably, it is 40 to 650 degreeC. It is. Moreover, although there is no restriction | limiting in particular in baking time, Usually, it is about 10 minutes-10 hours.

  For the purpose of increasing the surface area of semiconductor particles and increasing necking between semiconductor particles after firing, for example, chemical plating using a titanium tetrachloride aqueous solution, necking treatment using a titanium trichloride aqueous solution, semiconductor ultrafine particle sol having a diameter of 10 nm or less The dipping process may be performed. In the case where a plastic substrate is used as the support for the transparent conductive substrate, a paste containing a binder can be formed on the substrate, and pressure bonding to the substrate by a hot press is also possible.

  The dye to be carried on the semiconductor layer 216 is not particularly limited as long as it exhibits a sensitizing action, but examples thereof include xanthene dyes such as rhodamine B, rose bengal, eosin, erythrosine, merocyanine quinocyanine, cryptocyanine and the like. Basic dyes such as cyanine dyes, phenosafranine, fog blue, thiocin, methylene blue, porphyrin compounds such as chlorophyll, zinc porphyrin, magnesium porphyrin, other azo dyes, phthalocyanine compounds, coumarin compounds, rubipyridine complex compounds, anthraquinone compounds Examples thereof include dyes and polycyclic quinone dyes. Among these, the Ru bipyridine complex compound is particularly preferable because of its high quantum yield, but is not limited thereto, and can be used alone or in combination of two or more.

  The method for adsorbing the dye to the semiconductor layer 216 is not particularly limited. For example, the dye may be an alcohol, nitrile, nitromethane, halogenated hydrocarbon, ether, dimethyl sulfoxide, amide, N-methylpyrrolidone, 1, Dissolve in 3-dimethylimidazolidinone, 3-methyloxazolidinone, esters, carbonates, ketones, hydrocarbons, water, and other solvents, immerse the electrode with a semiconductor layer, or apply a dye solution to the semiconductor electrode layer can do. In addition, deoxycholic acid or the like may be added for the purpose of reducing association between the dyes. An ultraviolet absorber can also be used in combination. After adsorbing the dye, the surface of the semiconductor fine particles may be treated with amines. Examples of amines include pyridine, 4-tert-butylpyridine, polyvinylpyridine and the like. When these amines are liquid, they may be used as they are, or may be used after being dissolved in an organic solvent.

  Any material can be used for the counter electrode 242 as long as it is a conductive material, but an insulating material can also be used as long as a conductive layer is provided on the side facing the semiconductor layer 216. . However, an electrochemically stable material is preferably used as the electrode, and specifically, platinum, gold, carbon, conductive polymer, and the like are preferably used.

  For the purpose of improving the catalytic effect of redox, it is preferable that the side facing the semiconductor layer 216 has a fine structure and an increased surface area. In this case, it is desired to be in a porous state. The platinum black state can be formed by anodization of platinum, chloroplatinic acid treatment, and the like, and the porous carbon can be formed by a method such as sintering of carbon fine particles or firing of an organic polymer. Moreover, it can also be used as a transparent counter electrode by wiring a metal having a high redox catalytic effect such as platinum on a transparent conductive substrate or treating the surface with chloroplatinic acid.

The electrolyte of the electrolyte layer 230 is a combination of I ₂ and metal iodide or organic iodide, Br ₂ and metal bromide or organic bromide, ferrocyanate / ferricyanate, ferrocene / ferricinium ion, etc. Metal complexes, polysulfide sodium, sulfur compounds such as alkyl thiol / alkyl disulfide, viologen dyes, hydroquinone / quinone, and the like can be used. As the cation of the metal compound, Li, Na, K, Mg, Ca, Cs and the like, and as the cation of the organic compound, a quaternary ammonium compound such as tetraalkylammonium, pyridinium, and imidazolium is preferable. However, it is not limited to these, and can be used alone or in combination of two or more. Among these, an electrolyte in which I ₂ and a quaternary ammonium compound such as LiI, NaI or imidazolium iodide are combined is preferable.

The concentration of the electrolyte salt is preferably 0.05M to 5M, more preferably 0.2M to 1M with respect to the solvent. The concentration of I ₂ or Br ₂ is preferably 0.0005M to 1M, more preferably 0.001M to 0.1M. Various additives such as 4-tert-butylpyridine and carboxylic acid can be added for the purpose of improving the open circuit voltage and the short circuit current.

  As a solvent for the electrolyte layer 230, water, alcohols, ethers, esters, carbonate esters, lactones, carboxylic acid esters, phosphate triesters, heterocyclic compounds, nitriles, ketones, amides, nitromethane , Halogenated hydrocarbons, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, hydrocarbons, and the like, but are not limited to these. A mixture of two or more types can be used. In addition, an ionic liquid of tetraalkyl, pyridinium, or imidazolium quaternary ammonium salt can be used as the solvent.

  In order to reduce leakage from the inside of a solar cell configured as a wet device and volatilization of the electrolyte, a gelling agent, a polymer, a crosslinking monomer, etc. were dissolved as a gel matrix into the electrolyte solution and injected into the solar cell. It is also possible to use an electrolyte layer 230 that is later gelled to form a gel electrolyte. As for the ratio between the gel matrix and the electrolyte, the more the electrolyte, the higher the ionic conductivity, but the lower the mechanical strength. On the other hand, if the electrolyte is too small, the mechanical strength is high but the ionic conductivity is lowered. Therefore, the electrolyte is preferably 50 wt% to 99 wt% of the gel electrolyte, and more preferably 80 wt% to 97%. Further, as will be described later, it is possible to realize an all-solid-type solar cell configured as a dry vice by dissolving in a polymer using the electrolyte and the plasticizer and volatilizing and removing the plasticizer.

  Although the manufacturing method of the solar cell comprised as a wet device is not specifically limited, For example, the composition of the electrolyte layer 230 is a liquid or it can be made to gelatinize inside a solar cell, and the composition of the electrolyte layer 230 is an inside. In the liquid state before introduction into the semiconductor layer 216, the semiconductor layer 216 carrying the dye and the counter electrode 242 face each other, and the semiconductor layer 216 and the counter electrode 242 are not in contact with each other so that the semiconductor layer 216 and the counter electrode 242 do not contact each other. The light-receiving substrate 210 and the counter substrate are integrated by sealing with the first sealing material 220 at the peripheral portion of the substrate 210. At this time, although there is no restriction | limiting in particular in the distance of the clearance gap between the semiconductor layer 216 and the counter electrode 242, This distance is 1-100 micrometers normally, More preferably, it is 1-50 micrometers. If the distance between the gaps is too long, the photocurrent decreases due to the decrease in conductivity.

  The material of the first sealing material 220 is not particularly limited, but a material having light resistance, insulation, and moisture resistance is preferable. Various welding methods, epoxy resins, ultraviolet curable resins, acrylic adhesives, EVA (ethylene Vinyl acetate), ionomer resin, ceramic, modified polyethylene (propylene), various heat-sealing materials, and the like can be used.

  In addition, a through-hole 254 (consisting of a concave portion 250 and a communication hole 252) that serves as an injection port for injecting an electrolyte solution is required. However, the semiconductor layer 216 carrying a dye and a counter substrate 240 at a portion facing the semiconductor layer 216 are provided. The location of the through hole 254 is not particularly limited as long as it is not a portion. That is, the through-hole 254 serving as an injection port is a portion of the light receiving substrate 210 where the semiconductor layer 216 is not formed, a portion other than the projected portion of the portion where the semiconductor layer 216 is formed on the counter substrate 240, and the first sealing material 220. Provided at any of the sites.

  Although there is no particular limitation on the liquid injection method, the light receiving substrate 210 and the counter substrate 240 are sealed in advance by the first sealing material 220 in the vicinity of the outer periphery of both substrates, and the electrolyte solution is passed through the through-hole 254. A method of injecting the liquid into the inside is preferable. In this case, a method of dropping a few drops of the electrolyte solution into the recess 250 of the through hole 254 and injecting the solution by a capillary phenomenon or a method of injecting using a pressurizing device such as a pump is simple. In addition, the liquid injection operation can be performed under reduced pressure or under pressure as necessary.

  After the electrolyte solution is completely injected into the cell, the solution remaining in the recess 250 and the communication hole 252 of the through hole 254 is removed, and the recess 250 of the through hole 254 is sealed as described above. The sealing method is not particularly limited, but if necessary, a glass plate or a plastic substrate (plate body) may be attached to the inside of the recess 250 with a sealing agent and sealed as described above. it can. At this time, the pasted base material (plate body) is made not to protrude from the outer surface of the counter substrate 240. When the through hole 254 is formed in the light receiving substrate 210, the pasted base material (plate body) is made not to protrude from the outer surface of the light receiving substrate 210.

  As described above, in the dye-sensitized solar cell according to the present embodiment, the through hole 254 is composed of the communication hole 252 and the recess 250 having a relationship of S1 <S2. The contact of the electrolyte 230 with the material 270 can be reduced, and the sealing performance can be kept high. As a result, even if the electrolyte 230 oozes out from the communication hole 252 to the interface between the substrate 240 and the sealing material 270, the bonding area of the sealing material 270 with respect to the substrate 246 is sufficient, so that the bonding strength is kept high. can do.

  In addition, since there is no protrusion on the outer surface of the counter substrate 240, the adhesive strength between the second sealing material 270 and the glass plate 260 and the recess 250 is improved, and the second sealing is achieved by mechanical contact from the outside. The material 270 and the glass plate 260 are difficult to peel off.

  Accordingly, volatilization or leakage of the electrolyte from the inside of the solar cell is difficult to occur, and further, moisture, oxygen, and other components do not easily enter from the atmosphere to the inside of the solar cell. It is possible to maintain the characteristics of a highly stable solar cell for a long period of time. As a result, the reliability of the solar cell can be further improved.

Second Embodiment In the present embodiment, an all-solid solar cell is realized by preparing a solution comprising an electrolyte, a plasticizer, and a polymer, and volatilizing and removing the plasticizer after coating.

  FIG. 5 is a diagram for explaining a dry-type dye-sensitized solar cell according to this embodiment. FIG. 5 (A) is a schematic plan view of the dye-sensitized solar cell, and FIG. FIG. 5C is a schematic partial cross-sectional view of the BB portion. In addition, the through-hole 254 formed from the communication hole 252 and the recessed part 250 may be single or plural. In FIG. 5, four through holes 254 are provided.

  The dye-sensitized solar cell described with reference to FIGS. 1 to 4 is a wet device, but the dye-sensitized solar cell configured as a dry device according to the present embodiment as compared with this device has a solid electrolyte layer 235. Is different from the electrolyte layer. Other configurations are basically the same as those of the first embodiment described above, and thus common portions may be denoted by common reference numerals and description thereof may be omitted. Prior to the integration of the light receiving substrate 210 and the counter substrate 240 by the first sealing material 220, the solid electrolyte layer 235 is formed in the following manner.

  When a gel electrolyte using a polymer or the like or an all solid electrolyte is used, an electrolyte and a plasticizer are included on a semiconductor layer (formed by being applied and dried on the transparent electrode 214) 216 supporting a dye. A polymer solution is applied and formed into a film by a casting method. That is, an all-solid electrolyte layer is formed by applying a polymer solution containing an electrolyte and a plasticizer and then drying. After completely removing the plasticizer, the substrates 210 and 240 are bonded to each other by the sealing material 220 while degassing the internal space through the through hole 254.

  Further, the recess 250 is sealed with the second sealing material 270 and the glass plate 260 in the same manner as described above. This sealing is preferably performed using a vacuum sealer or the like under an inert gas atmosphere or under reduced pressure. The concave portion 250 of the through hole 254 is sealed by the same method as the sealing shown in FIG. The shape of the recess 250 and the communication hole 252 of the through hole 254 can be the same as the shape of the recess 250 and the communication hole 252 of the through hole 254 shown in FIG. After sealing, in order to sufficiently impregnate the electrolyte into the semiconductor fine particle layer, it is possible to perform heating and pressurizing operations as necessary.

  In the through hole 254, the inner diameter W2 of the recess 250 satisfies the relationship W1 <W2 so that the tip of the exhaust nozzle can be inserted into the recess 250. Therefore, as in the case of using the liquid injection nozzle, assuming that the opening area of the recess 250 on the outer surface of the counter substrate 240 is S2, and the opening area of the communication hole 252 on the inner surface of the counter substrate 240 is S1, S1 <S2. Satisfy the relationship.

  FIG. 6 is a diagram for explaining an example of a manufacturing process of the dye-sensitized solar cell according to the present embodiment.

  As shown in FIG. 6A, a light receiving substrate 210 having a semiconductor layer 216 and a solid electrolyte layer 235 formed thereon, and a counter substrate 240 having a recess 250 and a communication hole 252 are manufactured. Next, as shown in FIG. 6B, the light receiving substrate 210 and the counter substrate 240 are opposed to each other, and the light receiving substrate 210 and the counter substrate 240 are integrated with the first sealing material 220 under reduced pressure (exhaust). Make it. As a result, an internal space is formed by the three members of the light receiving substrate 210, the counter substrate 240, and the first sealing material 220, and gas is vented from the internal space through the through hole 254. Next, as in the case of the dye-sensitized solar cell described with reference to FIGS. 1 to 5, as shown in FIG. 6C, the recess 250 is sealed with the second sealing material 270 and the glass plate 260. Then, the semiconductor layer 216 and the solid electrolyte layer 235 are encapsulated.

  According to the present embodiment described above, since the sealing material 270 and the glass plate 260 are filled and sealed in the concave portion 250 of the through hole 254 as described above, the second sealing material 270 is sealed. And the adhesive strength of the glass plate 260 and the recessed part 250 improves, and it becomes difficult to peel the 2nd sealing material 270 and the glass plate 260 by the mechanical contact from the outside. Therefore, it is difficult for moisture, oxygen, and other components to enter the solar cell from the atmosphere. Therefore, high barrier characteristics can be maintained for a long time, and highly stable solar cell characteristics can be maintained for a long time. it can.

  However, unlike the first embodiment described above, the problem of contact between the liquid electrolyte and the sealing material 270 does not occur. However, the through hole 254 is not described before being sealed (end-sealed). It is also advantageous to have a degassing function.

Third Embodiment FIG. 7 is a diagram for explaining a thin film transistor wet device configured as a liquid crystal display device according to the present embodiment, which is a liquid crystal display device using a bottom gate type organic thin film transistor (TFT) as a drive transistor. It is a fragmentary sectional view corresponding to a pixel.

  The liquid crystal display device 100 includes a drive circuit substrate 118, a counter substrate 119, and a liquid crystal layer 112 sealed between the two substrates. Polarizing plates 101 and 116 are disposed on the outer surfaces of the substrates, respectively. Is pasted in the crossed Nicols method.

  In the drive circuit substrate 118, a gate electrode 104 formed on the substrate 102, a gate insulating film 105 formed to cover the gate electrode, a source electrode 108 and a drain electrode 109 formed on the gate insulating film. The bottom gate type insulated gate organic TFT 117 is constituted by the organic semiconductor layer (channel portion) 107, and the interlayer insulating film 110 and the liquid crystal alignment film 111 are laminated on the organic TFT 117.

  Further, in this drive circuit substrate 118, the auxiliary capacitance electrode 103 formed on the same substrate 102, the gate insulating film 105 formed so as to cover the auxiliary capacitance electrode, and the drain electrode on the gate insulating film 105 A storage capacitor portion 120 is constituted by the pixel electrode 106 formed in connection with 109, and an interlayer insulating film 110 is laminated on the pixel electrode 106 of the storage capacitor portion. Note that the auxiliary capacitance electrode 103 is illustrated in a state where it partially overlaps with the pixel region for explanation. On the other hand, in the counter substrate 119, the counter electrode 114 formed on the substrate 115 and the liquid crystal alignment film 113 are laminated.

  The liquid crystal display device 100 is a transmissive liquid crystal display device in which a backlight 123 is irradiated from the back. For this purpose, each of the electrodes described above is formed of a transparent conductive material, and the gate insulating film 105 ( More preferably, the organic semiconductor layer 107, the interlayer insulating film 110, and the substrates 102 and 115) are also formed of a transparent material. The substrates 102 and 115 may be glass or plastic substrates. In the latter case, the advantage of being flexible can be utilized.

  Although the configuration of the liquid crystal display device using the bottom gate type organic TFT as the drive transistor has been described above, TFTs other than the bottom gate type organic TFT can be used as the drive transistor.

  Although not shown in the liquid crystal display device 100, the counter substrate 119 and the drive circuit board 118 are integrated by the first sealing material 220 with the counter substrate 119 and the drive circuit board 118 facing each other. As a result, an internal space is formed by the three members of the counter substrate 119, the drive circuit substrate 118, and the first sealing material 220. Next, liquid crystal is injected so that bubbles do not enter the internal space. Next, in the same manner as in the first embodiment described above, the concave portion 250 of the through hole 254 is sealed so as not to have a convex portion by the second sealing material 270 and the glass plate 260. In FIG. 7, the first sealing material 220, the through hole 254 (recess 250, the communication hole 252), the second sealing material 270, and the glass plate 260 are not illustrated, but these components are not illustrated. 1 to 5 are basically the same as those shown in FIG.

  Also in the liquid crystal display device according to the present embodiment described above, the same effects as those of the first embodiment described above can be obtained.

  Note that, similarly to the liquid crystal display device according to this embodiment, the optical device according to the present invention can be configured as an electrochromic display device or the like. In this case, since the electrochromic material is liquid, it is injected into the display device in the same manner as the liquid crystal.

  Hereinafter, although the specific Example of this invention is described, this invention is not limited to this Example.

  The dye-sensitized solar cell configured as a wet device in each of the following examples was produced as follows.

Example 1
The TiO ₂ paste was prepared with reference to “the latest technology of dye-sensitized solar cells” (CMC). 125 ml of titanium isopropoxide was slowly added dropwise to 750 ml of 0.1 M nitric acid aqueous solution with stirring at room temperature. When the dropping was completed, the mixture was transferred to a constant temperature bath at 80 ° C. and stirred for 8 hours to obtain a cloudy translucent sol solution. The sol solution was allowed to cool to room temperature, filtered through a glass filter, and then made up to 700 ml. The obtained sol solution was transferred to an autoclave, hydrothermally treated at 220 ° C. for 12 hours, and then dispersed by ultrasonic treatment for 1 hour. Next, this solution was concentrated by an evaporator at 40 ° C. to prepare a TiO ₂ content of 20 wt%. The concentrated sol solution 20 wt% · vs · TiO ₂ polyethylene glycol (molecular weight 500,000) was added anatase TiO ₂ particles diameter 200mm of 30 wt% · vs · TiO _2, uniformly mixed stirred deaerator to obtain a TiO ₂ paste thickened.

The above-mentioned TiO ₂ paste is applied to a conductive glass substrate with a transparent conductive film by a blade coating method at 5 mm × 5 mm and a gap of 200 μm, and then held at 500 ° C. for 30 minutes, and TiO ₂ is baked on the conductive glass. I concluded. The sintered TiO ₂ film was immersed in a 0.05 M TiCl ₄ aqueous solution, held at 70 ° C. for 30 minutes, and then fired again at 500 ° C. for 30 minutes. Impurities were removed from the produced TiO ₂ sintered body, and ultraviolet rays were exposed for 30 minutes with a UV irradiation device in order to enhance the activity.

  Then, 0.3 mM cis-bis (isothiocyanate) -N, N-bis (2,2′-dipyridyl-4,4′-dicarboxylic acid) -ruthenium (II) ditetrabutylammonium salt was dissolved. A dye was supported by immersing in a mixed solvent of butyl alcohol / acetonitrile (volume ratio 1: 1) at room temperature for 24 hours. This electrode was washed in turn with an acetonitrile solution of 4-tert-butylpyridine and acetonitrile, and dried in the dark.

  As shown in FIG. 3A, the counter substrate 240 is formed with a through hole (liquid injection port) 254 including a recess 250 and a communication hole 252. The opening of the recess 250 was φ2.0 mm on the outer surface of the counter substrate 240, and the opening of the communication hole 252 was φ0.3 mm on the inner surface side of the counter substrate 240. As illustrated in FIG. 1, the counter substrate 240 is formed of a transparent substrate 246, a current collector 244, and a conductive film (counter electrode) 242. On the surface of the transparent substrate 246, FTO (fluorine-containing tin oxide) as the current collector 244, then chromium (thickness: 500 mm) as the conductive film (counter electrode) 242, and then platinum (thickness: 1000 mm) are sequentially sputtered. The solution was spray-coated with an isopropyl alcohol solution of chloroplatinic acid and heated at 385 ° C. for 15 minutes.

  The light-receiving substrate 210 having the dye-sensitized semiconductor layer and the counter substrate 240 manufactured as described above are opposed to each other, and the first sealing material 220 is formed in the vicinity of the outer periphery of both the light-receiving substrate 210 and the counter substrate 240. Both substrates were bonded together using an acrylic UV curable resin as a dye-sensitized solar cell having an internal space.

On the other hand, 3 g of methoxyacetonitrile, 0.045 g of sodium iodide (NaI), 1.52 g of 1-propyl-2,3-dimethylimidazolium iodide, 0.152 g of iodine (I ₂ ), 0. 4-tert-butylpyridine. 081 g was dissolved to prepare an electrolyte composition solution.

  This electrolyte solution was injected into the internal space from the concave portion 250 of the through hole (injection port) 254 using a liquid feed pump, and the bubbles existing in the internal space were expelled by reducing the pressure. Next, an acrylic UV curable resin as a second sealing material is dropped on the concave portion 250 formed on the outer surface side of the counter substrate 240, and a glass substrate having a diameter of 1.9 mm is formed as the glass plate 260 of the plate body. Inside, after covering the acrylic UV curable resin dropped on the concave portion 250, the acrylic UV curable resin was cured with ultraviolet rays to integrate the glass plate 260 in the concave portion 250, and as shown in FIG. 2 (A). Thus, the recessed part 250 was sealed with the 2nd sealing material 270 and the glass plate 260, and the dye-sensitized solar cell was obtained.

Example 2
In Example 1, a dye-sensitized solar cell having a configuration in which the glass plate 260 was not used was produced. That is, an element of a dye-sensitized solar cell in which the concave portion 250 was sealed as shown in FIG. 2B using only an acrylic UV curable resin as the second sealing material was prepared.

Comparative Example 1
A dye-sensitized solar cell was formed in the same manner as in Example 1 except that the shape of the through hole (injection port) formed in the counter substrate was the same as that of the electrolyte injection port 352 shown in FIG. Produced. That is, an acrylic UV curable resin as a second sealing material was dropped onto the opening (φ0.3 mm) of the injection port 352 on the outer surface of the counter substrate 340 and cured with ultraviolet rays (however, the tape 353 was used) Not).

Using wet devices (dye-sensitized solar cells) of Example 1, Example 2, and Comparative Example 1 produced as described above, at the time of irradiation with pseudo sunlight (AM1.5, 100 mW / cm ² ). Photoelectric conversion efficiency was measured every 10 days.

  FIG. 8 is a graph showing the relationship between the photoelectric conversion efficiency and the elapsed days of the dye-sensitized solar cell according to each example. The photoelectric conversion efficiency in the elapsed days when the conversion efficiency measured on the first day is 100%. The maintenance rate is shown.

  In Comparative Example 1, the maintenance rate of the photoelectric conversion efficiency decreases with the number of days elapsed from the start of the experiment. In particular, the decrease in the maintenance rate of the photoelectric conversion efficiency is drastically decreased after about 40 days (elapsed days) from the start of the experiment. This rapid decrease in the maintenance factor is because the recess 250 does not exist in the injection port, so that the sealing is not good, the barrier characteristics are insufficient, the leakage of the electrolyte from the inside proceeds, and the internal space It is thought that bubbles are generated in

  In Example 1, from the start of the experiment to about 20 days (elapsed days), there are an initial stage in which the maintenance rate decreases relatively slowly and a later stage in which the maintenance rate decreases more gradually thereafter. It is done. That is, the slope of the maintenance rate decrease in the late stage is much smaller than the slope of the maintenance rate reduction in the early stage. In Example 1, since the through hole 254 is well sealed using resin and glass having excellent barrier properties using the recess 250, good long-term barrier properties are realized.

  In Example 2, the maintenance rate of photoelectric conversion efficiency is substantially the same as that of Comparative Example 1 from the start of the experiment to about 40 days (elapsed days), but even if the elapsed days exceed about 40 days, the maintenance rate of photoelectric conversion efficiency No drastic decrease was observed, and the maintenance rate decreased almost linearly from the start of the experiment. Since the through-hole 254 is well sealed using the recess 250, the barrier property for a relatively long period is good.

  In practical terms, the maintenance rate of the photoelectric conversion efficiency is desirably 60% or more, and more desirably 80% or more. The period during which the maintenance rate of photoelectric conversion efficiency is maintained at 60% or more is about 65 days in Comparative Example 1, but in Example 1 and Example 2, the maintenance rate is maintained at 60% or more after 90 days. The period during which the photoelectric conversion efficiency maintenance rate is maintained at 80% or more is about 40 days in Comparative Example 1, 90 days or more in Example 1, and about 55 days in Example 2. Further, in Example 1, a maintenance rate exceeding 90% was realized even after 90 days had elapsed, and the slope of decrease in the maintenance rate was much smaller than in Example 2 and Comparative Example 1, and from a practical standpoint. It shows a very desirable trend.

  As is apparent from FIG. 8, it can be seen that the dye-sensitized solar cells of Examples 1 and 2 of the present invention have a high photoelectric conversion efficiency maintenance rate and a high barrier property. In particular, Example 1 exhibits highly stable photoelectric conversion characteristics over a long period of time. This is because in Example 1, the constituent components of the electrolyte layer are less likely to volatilize or leak from the inside of the solar cell element, or moisture, oxygen, and other components are less likely to enter the electrolyte layer from the atmosphere. It is.

  While the present invention has been described with reference to the embodiments and examples, the above examples can be variously modified based on the technical idea of the present invention.

  For example, it goes without saying that the form, size, number, and position of the through-hole 254, such as the form, structure, and materials used, of the dye-sensitized solar cell can be selected as appropriate without departing from the spirit of the present invention. Yes. A material having a high barrier property against gas and / or liquid and a low permeability to gas and / or liquid can be appropriately selected and used.

  When using a gel electrolyte, the electrolyte precursor solution may be gelled after being injected from the through hole in the same manner as in the first embodiment. It can be sealed after going.

  Although FIGS. 1 and 5 have been described with reference to an example of a single solar battery cell, a plurality of solar battery cells may be arranged in parallel to form a stack structure (tandem type). However, in the case of the stack structure, if the entire cell is covered with a covering material and a resin layer, the amount of light incident on the next cell decreases, so the covering material and the resin layer are formed at the joint surface between the cells together with the light receiving surface. It is preferable that the light transmittance is controlled to be high or that the covering material and the resin layer are not provided on the joint surface.

  Furthermore, although the dye-sensitized solar cell has been described as an example, the present invention can be applied to solar cells other than the dye-sensitized solar cell. In addition, the shape and form of the optical apparatus configured as a wet or dry device of the present invention may be variously changed according to the application.

  As described above, the optical apparatus according to the present invention is extremely useful as a wet device such as a dye-sensitized solar cell having excellent durability and reliability.

BRIEF DESCRIPTION OF THE DRAWINGS (A) Schematic top view of the dye-sensitized solar cell by the 1st Embodiment of this invention, (B) The AA line schematic sectional drawing, (C) The BB line schematic partial sectional drawing. . It is a schematic sectional drawing explaining the sealing state of the through-hole in FIG. It is a schematic sectional drawing explaining the example of a shape of a through-hole similarly. It is a figure explaining an example of the manufacturing process of a dye-sensitized solar cell. It is (A) schematic plan view of the dye-sensitized solar cell by the 2nd Embodiment of this invention, (B) Its AA line schematic sectional drawing, (C) Its BB line schematic partial sectional drawing. . It is a figure explaining an example of the manufacturing process of a dye-sensitized solar cell. It is a fragmentary sectional view corresponding to one pixel of a liquid crystal display by a 3rd embodiment of the present invention. It is a graph which shows the relationship between the photoelectric conversion efficiency of the dye-sensitized solar cell by the Example of this invention, and elapsed days. It is the (A) schematic plan view of the dye-sensitized solar cell in a prior art, (B) The AA line schematic sectional drawing, (C) The BB line schematic partial sectional drawing.

Explanation of symbols

200, 205 ... Dye-sensitized solar cell, 210 ... Light receiving substrate,
212, 246 ... transparent substrate, 214 ... transparent conductive film (transparent electrode), 216 ... semiconductor layer,
218 ... metal, 220 ... first sealing material, 230 ... electrolyte layer (electrolytic solution),
235 ... Solid electrolyte layer, 240 ... Counter substrate, 242 ... Conductive film (counter electrode),
244 ... Current collector, 250 ... Recess, 252 ... Communication hole, 254 ... Through hole,
257 ... ammeter, 258 ... current circuit, 259 ... light receiving surface, 260 ... glass plate,
270 ... Second sealing material

Claims (21)

  In an optical device including a plurality of substrates facing each other and having a functional substance housed in an internal space between these substrates, a through-hole communicating with the outside is formed in any one of the plurality of substrates. The through-hole is composed of a recess opening to the outside and a communication hole connected to the recess and opening to the internal space. The communication hole exists in the region of the recess and at least the bottom of the recess is The optical device satisfies the relationship of S1 <S2, where S2 is a maximum opening area of the recess, and S1 is an opening area of the communication hole at a connection position with the recess. .   The optical device according to claim 1, wherein (S2 / S1) is 1.5 or more.   The optical device according to claim 2, wherein (S2 / S1) is 2 or more.   The optical device according to claim 1, wherein the recess or the communication hole has a cylindrical shape or a truncated cone shape.   The optical device according to claim 1, wherein a maximum diameter of the opening of the concave portion is 0.5 mm to 50 mm, and a diameter of the opening of the communication hole at the connection position is 0.1 mm to 10 mm.   The optical device according to claim 5, wherein a maximum diameter of the opening of the concave portion is 1 mm or more, and a diameter of the opening portion of the communication hole at the connection position is 0.3 mm to 0.5 mm.   The plurality of bases include a first base and a transparent second base, and the first base and the second base are bonded to each other, and the first base and the second base The optical device according to claim 1, wherein the through hole is formed in any part.   The optical device according to claim 1, wherein the sealing material is covered with a plate.   9. The optical device according to claim 1, wherein a surface of the sealing material or the plate in the concave portion is on the same plane as the surface of the base.   The optical apparatus according to claim 1 configured as a wet device.   The optical device according to claim 10, which is a dye-sensitized solar cell, a liquid crystal display device or an electrochromic display device. A method of manufacturing an optical device according to any one of claims 1 to 11,
Bonding the plurality of substrates together;
Injecting the functional substance into the internal space from the opening of the recess;
And a step of filling a sealing material in at least the bottom of the recess.   The method for manufacturing an optical device according to claim 12, wherein the sealing material is a liquid resin precursor.   The method of manufacturing an optical device according to claim 13, wherein the liquid resin precursor is a photocurable type.   The method for manufacturing an optical device according to claim 13, wherein after filling the resin precursor, the resin precursor is covered with a plate body, and the resin precursor is further cured.   The method for manufacturing an optical device according to claim 14, wherein a surface of the sealing material or the plate in the recess is on the same plane as the surface of the base. A method of manufacturing an optical device according to any one of claims 1 to 11,
Forming a solid electrolyte layer on any of the plurality of substrates;
Adhering the plurality of substrates together;
Exhausting the internal space through the through hole;
And a step of filling a sealing material in at least the bottom of the recess.   The method for manufacturing an optical device according to claim 17, wherein the sealing material is a liquid resin precursor.   The method of manufacturing an optical device according to claim 18, wherein the liquid resin precursor is a photo-curing type.   The method of manufacturing an optical device according to claim 18, wherein after filling the resin precursor, the resin precursor is covered with a plate and further cured.   21. The method of manufacturing an optical device according to claim 19, wherein a surface of the sealing material or the plate in the recess is on the same plane as the surface of the base.

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