JP2011029131A - Photoelectric conversion device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric conversion device having high reliability by maintaining airtightness for a long time. <P>SOLUTION: The photoelectric conversion device X1 includes a translucent substrate 1 having a first principal surface, a support substrate 9 having a second principal surface countering the first principal surface, an electrolyte 4 arranged in a gap formed between the translucent substrate 1 and the support substrate 9, a first sealing member 5 made of a corrosion resistant material and bonding the translucent substrate 1 with the support substrate 9, and a second sealing member 7 containing an inorganic material, arranged on the outside of the first sealing member 5 separately from it and bonding the translucent substrate 1 with the support substrate 9. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photoelectric conversion device, and more particularly to a dye-sensitized solar cell.

  There are various types of solar cells, such as bulk crystal silicon solar cells and thin film amorphous silicon solar cells using an amorphous silicon thin film. Further, for the purpose of reducing silicon raw materials, a dye-sensitized solar cell has attracted attention as a next-generation solar cell that does not use silicon.

  As such a dye-sensitized solar cell, a first electrode having a semiconductor layer carrying a sensitizing dye as in Patent Document 1, and a first electrode disposed so as to face the first electrode. 2 electrodes and an electrolyte injected between the pair of electrodes. This electrolyte is accommodated in an electrolyte chamber constituted by a pair of electrodes and a sealing portion for joining them so as not to leak outside.

  In order to stably operate the dye-sensitized solar cell for a long period of time, it is necessary to stably and hermetically seal the electrolyte chamber for a long period of time. In Patent Document 1, the electrolyte chamber is sealed by double sealing with a first sealing portion 13a and a second sealing portion 15a provided to cover the outer surface of the first sealing portion 13a. It is tightly sealed.

JP 2004-119149 A

  In the dye-sensitized solar cell disclosed in Patent Literature 1, it is effective to configure the first sealing portion and the second sealing portion with different materials according to their functions. However, when different materials are used, the sealing conditions are different between the first sealing portion and the second sealing portion. After sealing one sealing part, when trying to seal the other sealing part, one sealing part may be deteriorated or damaged by heat treatment during sealing of the other sealing part. To do. As a result, there is a problem that the reliability of hermetic sealing cannot be increased.

  The present invention has been completed in view of the above-described conventional problems, and an object thereof is to obtain a photoelectric conversion device with high operation reliability by maintaining airtightness for a long period of time.

  In one embodiment of the photoelectric conversion device of the present invention, a translucent substrate having a first main surface, a support substrate having a second main surface opposite to the first main surface, and the translucency. An electrolyte disposed in a gap formed between the substrate and the support substrate; a first sealing member made of a corrosion-resistant material that joins the translucent substrate and the support substrate; and the first seal A second sealing member including an inorganic material, which is disposed outside the member and spaced apart from the first sealing member, and which joins the translucent substrate and the support substrate.

  With such a configuration, the first sealing member made of a corrosion-resistant material can increase the resistance against sealing electrolyte. Moreover, airtightness can be improved by the 2nd sealing member containing an inorganic material. Furthermore, since the first sealing member and the second sealing member are arranged apart from each other, the influence of heat or the like on the other sealing member is suppressed when sealing one sealing member. Can do. As a result, a photoelectric conversion device that maintains hermeticity for a long time and has high operational reliability can be obtained.

  In the photoelectric conversion device of the present invention, preferably, since the corrosion-resistant material includes a resin, the resistance to the sealing electrolyte can be increased by using a resin that does not corrode by the electrolyte. Moreover, since the thermal expansion of the electrolyte can be relaxed, the mechanical strength can be improved.

  Preferably, in the photoelectric conversion device of the present invention, a base is provided on at least one of the space between the translucent substrate and the second sealing member and the support substrate and the second sealing member. And the second sealing member has an absorption coefficient larger than that of the base portion with respect to any wavelength in the region of 400 to 2400 nm. By providing the pedestal, the volume of the second sealing member can be reduced, the thermal strain and thermal stress during sealing can be reduced, and the sealing reliability can be improved. In addition, since the light in the wavelength range can pass through the light-transmitting substrate, the second sealing member having a larger absorption coefficient in the wavelength range than the base can be selectively heated, and thermal strain during sealing The thermal stress can be reduced and the sealing reliability can be improved.

  In the photoelectric conversion device of the present invention, preferably, the base portion is provided on each of the translucent substrate and the support substrate. By placing the pedestal symmetrically on the substrate and sealing with the second sealing portion, it is possible to reduce thermal strain or thermal stress on the substrate and improve sealing reliability. it can.

  In the photoelectric conversion device of the present invention, preferably, the softening point of the second sealing member is lower than the softening point of the base portion. By selectively softening and sealing the second sealing member, thermal strain or thermal stress on the substrate can be reduced, and sealing reliability can be improved. Moreover, the distance between the said translucent board | substrate and the said support substrate can be adjusted with the said base part.

  Preferably, in the photoelectric conversion device of the present invention, the softening point of the base portion is lower than the softening point of the translucent substrate provided with the base portion or the softening point of the support substrate provided with the base portion. . Thereby, a base part can be softened on the said translucent board | substrate and the said support substrate, and a highly airtight base part can be formed.

  In the photoelectric conversion device of the present invention, preferably, the base is provided on the translucent substrate, an electrode is formed on the first main surface, and the electrode is connected to the base and the translucent. It extends to the interface with the substrate. Thereby, an electrode can be pulled out to the outer side of a base part, and the electric power of a photoelectric conversion apparatus can be input / output.

  In the photoelectric conversion device of the present invention, preferably, the base is provided on the support substrate, an electrode is formed on the second main surface, and the electrode is an interface between the base and the support substrate. It extends to. Thereby, an electrode can be pulled out to the outer side of a base part, and the electric power of a photoelectric conversion apparatus can be input / output.

  In the photoelectric conversion device of the present invention, preferably, the second sealing member includes a light absorber. Thereby, the heating state at the time of optical heating sealing can be adjusted with the density | concentration of a light absorber, and the reliability of sealing can be improved.

  In the photoelectric conversion device of the present invention, preferably, the inorganic material includes a metal. Thereby, the translucent substrate and the support substrate can be bonded at a temperature lower than the strain point of the translucent substrate or the support substrate by electric heating, combined use of ultrasonic wave and electric heating, laser heating, or the like. Therefore, it is possible to reduce the occurrence of thermal strain or thermal stress on the light-transmitting substrate or the support substrate, and to improve the sealing reliability.

  In the photoelectric conversion device of the present invention, it is preferable that at least one of the transparent substrate and the second sealing member and the support substrate and the second sealing member be insulative. It has a base. Thereby, the electrode can be pulled out satisfactorily.

  In the photoelectric conversion device of the present invention, preferably, the base portion includes glass, so that insulating properties, air tightness, and mechanical strength can be maintained for a long period of time.

  In the photoelectric conversion device of the present invention, preferably, a substance having lower thermal conductivity than that of the second sealing member is filled between the first sealing member and the second sealing member. Thereby, the 2nd sealing member containing an inorganic material can be formed by the optical heating sealing method etc., reducing deterioration of the 1st sealing member.

  In the photoelectric conversion device of the present invention, preferably, the first sealing member covers an outer peripheral portion of a semiconductor layer provided on the translucent substrate. Thereby, the leakage current between the electrodes formed on the surface of the electrolyte and the translucent substrate can be suppressed, and the conversion efficiency can be improved.

  According to the present invention, it is possible to obtain a photoelectric conversion device that maintains hermeticity for a long time and has high operational reliability.

It is sectional drawing which shows 1st Embodiment of the photoelectric conversion apparatus which concerns on this invention. It is sectional drawing which shows 2nd Embodiment of the photoelectric conversion apparatus which concerns on this invention. It is sectional drawing which shows 3rd Embodiment of the photoelectric conversion apparatus which concerns on this invention. It is sectional drawing which shows 4th Embodiment of the photoelectric conversion apparatus which concerns on this invention. It is sectional drawing which shows 5th Embodiment of the photoelectric conversion apparatus which concerns on this invention. It is sectional drawing which shows 6th Embodiment of the photoelectric conversion apparatus which concerns on this invention. It is sectional drawing which shows 7th Embodiment of the photoelectric conversion apparatus which concerns on this invention. It is a plane perspective view which shows 7th Embodiment of the photoelectric conversion apparatus which concerns on this invention.

  Embodiments according to the photoelectric conversion device of the present invention will be described below in detail with reference to the drawings schematically shown.

  FIG. 1 is a cross-sectional view showing a first embodiment of the photoelectric conversion device of the present invention. The photoelectric conversion device X1 includes a pair of substrates (hereinafter, referred to as a first substrate 1 and a second substrate 9) that are disposed so that their principal surfaces face each other, and the first substrate 1 and the second substrate. A first electrode 2 and a second electrode 8 are respectively formed on one main surface of 9. On the first electrode 2, a semiconductor layer 3 carrying a pigment (not shown) is formed.

  In the photoelectric conversion device X 1, the electrolyte 4 is disposed in a gap between one main surface of the first substrate 1 and the second substrate 9. In other words, the electrolyte 4 is disposed so as to be sandwiched between the first electrode 2 and the second electrode 8. The periphery of the electrolyte 4 is covered with a first sealing member 5 in order to suppress leakage to the outside. Further, the second sealing member 7 that prevents leakage of the electrolyte 4 to the outside and prevents intrusion of moisture and oxygen from the outside is provided outside the first sealing member 5. (Hereinafter, a region between the first sealing member 5 and the second sealing member 7 is referred to as a gap 6). By providing the gap 6, it is possible to form the second sealing member 7 that requires higher temperature treatment than the first sealing member 5 without deteriorating the first sealing member 5. Moreover, even if a crack occurs in the second sealing member 7, the crack does not extend to the first sealing member 5, and leakage of the electrolyte 4 and external moisture and oxygen intrusion into the electrolyte 4 are suppressed. Can do.

  From the viewpoint of more effectively suppressing the heat generated when the gap 6 is sealed by the second sealing member 7 from being transmitted to the first sealing member 5, the second sealing member 7. It is filled with a substance having a lower thermal conductivity than the vacuum or is in a vacuum. The material having a lower thermal conductivity than the second sealing member 7 includes any of a solid material, a liquid material, and a gas material. In the case where a crack occurs in the second sealing member 7, from the viewpoint of suppressing the crack from extending to the first sealing member 5 or growing the crack, the gap 6 is It should be filled with gas. In particular, the gap 6 is preferably filled with at least one selected from the group consisting of air, nitrogen, oxygen, a solvent contained in the electrolyte, and a solute vapor. In this case, even if a substance filling the gap 6 enters the electrolyte 4 through a crack generated in the first sealing member 5 or permeates the first sealing member 5, the characteristic deterioration of the electrolyte 4 is deteriorated. Can be reduced.

  Below, the detail of the member which comprises the photoelectric conversion apparatus which concerns on embodiment of this invention mentioned above is shown.

<First and second substrates>
The first substrate 1 supports the first electrode 2 and the semiconductor layer 3 disposed on the first electrode 2 on one main surface. The first substrate 1 is a translucent substrate having translucency because it is mainly provided on the light incident side.

  Examples of the material of the first substrate 1 include glass materials such as blue plate glass, white plate glass, and non-alkali glass that are transparent to visible light, or PET (polyethylene terephthalate) and PEN (polyethylene naphthalate). And other resin materials.

  The second substrate 9 is a support substrate for supporting the second electrode 8 on one main surface. The second substrate 9 is a glass material such as blue plate glass, white plate glass, non-alkali glass or the like, which is a material having translucency like the first substrate 1, or PET (polyethylene terephthalate), PEN (polyethylene naphthalate). If it is comprised with resin materials, such as), the incident surface (light-receiving surface) of light can be expanded more and photoelectric conversion efficiency can be improved. Further, since the second substrate 9 does not have to be located on the light incident side, the second substrate 9 may have a small translucency. Examples of such a material having low translucency include metal materials such as titanium, tantalum, niobium, nickel, tungsten, stainless steel, and aluminum alloy. With such a conductive metal material, since the first substrate 1 itself acts as an electrode, the second electrode 8 is not necessary, and the number of components can be reduced. The second substrate 9 is preferably made of titanium, nickel, tungsten, or aluminum from the viewpoint of improving the corrosion resistance against the electrolyte 4.

  The first substrate 1 or the second substrate 9 may be formed with an injection hole (not shown) for injecting the electrolyte 4 from the outside. The shape of the injection hole is not particularly limited as long as the electrolyte 4 can be injected between the first and second substrates. For example, the cross-sectional shape is circular, elliptical, or It may be a polygon such as a rectangle. As the size of the injection hole, for example, if the cross-sectional shape is circular, the diameter is preferably about 0.1 to 3 mm.

<First and second electrodes>
The first electrode 2 has a function of extracting a current generated by the semiconductor layer 3 and is provided on one main surface of the first substrate 1. The first electrode 2 preferably has a light-transmitting property with respect to visible light because light is incident from the other main surface side of the first substrate 1.

  The material of the first electrode 2 is, for example, selected from the group consisting of an ITO (tin-doped indium oxide: indium tin oxide) layer, an FTO (fluorine-doped tin oxide) layer, a doped tin oxide layer, and a tin oxide layer. And at least one kind. In addition, the thickness of the first electrode 2 is preferably about 0.3 to 2 μm from the viewpoint of easy manufacturing and appropriate sheet resistance. Such a 1st electrode 2 is formed in layered form by CVD method, sputtering method, spray method etc., for example.

  The second electrode 8 is for passing electric charge to the electrolyte 4, and is provided on one main surface of the second substrate 9. As the material of the second electrode 8, if the second substrate 9 is also used as a light receiving portion, the same material as the first electrode 2, that is, the above-described light-transmitting material may be used. On the other hand, as long as light is not received from the second substrate 9, the second electrode 8 may not be made of a light-transmitting material, such as titanium, nickel, stainless steel, aluminum, aluminum alloy, or tungsten. You may comprise by the metal material of.

  The second electrode 8 is made of platinum, palladium, ruthenium, osmium, rhodium, iridium, carbon, PEDOT: TsO (polyethylenedioxythiophene-toluenesulfonate), etc. on the contact surface with the electrolyte 4. If a catalyst layer not shown is formed, charge transfer to the electrolyte 4 can be performed efficiently.

<Electrolyte>
The electrolyte 4 has a function of passing the charge received from the second electrode 8 to the dye supported on the semiconductor layer 3. The electrolyte 4 only needs to be in a state that can be injected from an injection hole formed in the substrate. For example, a liquid (electrolytic solution) or a gel can be used, and the electrolyte 4 becomes a solid after injection. Also good. Alternatively, the electrolyte 4 may be applied to the first electrode 2 or the second electrode 8 on which the semiconductor layer 3 supporting the dye is formed by screen printing, a dispenser, a doctor blade, or the like.

  When the electrolyte 4 is an electrolytic solution, examples thereof include iodine / iodide salts, bromine / bromide salts, cobalt complexes, and potassium ferrocyanide. The notation “iodine / iodide salt” means that the content of iodine and iodide salt changes due to the chemical reaction of the electrolyte. When the electrolyte 4 is liquid or gel at the time of injection and becomes solid after injection, the electrolyte 4 is a solid electrolyte such as a gel electrolyte, a talc gel electrolyte, or a polymer electrolyte, a conductive polymer such as polythiophene / polypyrrole or polyphenylene vinylene, or fullerene. And organic molecular electron transport agents such as derivatives, pentacene derivatives, perylene derivatives, and triphenyldiamine derivatives. The thickness of the electrolyte 4, that is, the distance between one main surface of the first substrate 1 and one main surface of the second substrate 9 is preferably about 1 to 500 μm.

  When a gel electrolyte is used as the electrolyte 4, the gel electrolyte can be applied by screen printing, metal mask printing, doctor blade application, dispenser application, spray application, roller application, calendar application, ink jet application, die coater, etc. As shown in FIG. 5, the electrolyte 4 can be formed by disposing the first sealing member 5 and the gap 11 as shown in FIG. Thereby, since the highly corrosive electrolyte 4 and the 1st sealing member 5 are spaced apart from the clearance gap 11, degradation of the 1st sealing member 5 can be suppressed and long-term sealing can be performed. .

<First and second sealing members>
The first sealing member 5 is disposed around the electrolyte 4 so as to confine the electrolyte 4 between the first substrate 1 and the second substrate 9, and is a member for reducing leakage of the electrolyte 4 to the outside. It is. The first sealing member 5 is made of a corrosion-resistant material in order to suppress elution of the sealing member by an electrolyte that increases the resistance to sealing electrolyte 4 or reduces the conversion efficiency. Here, the corrosion-resistant material is a material that is stable with respect to the electrolyte and that does not substantially dissolve even when left in contact with the electrolyte for one day. Examples of the corrosion resistant material include resin and glass. Preferably, the corrosion resistant material includes a resin. Accordingly, the corrosion resistance can be improved, and the first substrate 1 and the second substrate 9 can be easily primary-sealed with the first sealing member 5, and the sealing process can be easily performed. can do.

  The first sealing member 5 containing a resin is, for example, polyethylene, modified polyethylene, maleic acid modified polyethylene, polypropylene, modified polypropylene, maleic acid modified polypropylene, ionomer resin, fluorine resin, epoxy resin, polyisobutylene resin, silicone resin or Examples thereof include resin materials such as acrylate resins, thermoplastic resins, thermosetting resins, photocuring resins, photothermosetting resins, moisture curing resins, and two-component mixed curing resins. Polyethylene, modified polyethylene, maleic acid modified polyethylene, polypropylene, modified polypropylene, maleic acid modified polypropylene, ionomer resin, fluororesin, epoxy resin, polyisobutylene resin, silicone resin due to sealing temperature of 300 ° C. or less and corrosion resistance with electrolyte 4 Alternatively, a resin material such as an acrylate resin or a thermoplastic resin, a thermosetting resin, a photocuring resin, a photothermosetting resin, a moisture curing resin, or a two-component mixed curing resin is preferable.

  Moreover, these 1st sealing members 5 may contain a filler etc. as needed from a viewpoint of raising mechanical strength. As such a filler, a filler having corrosion resistance with the electrolyte 4 is preferable. Further, the first sealing member 5 may be a liquid, a solid, a film, or a liquid containing a solid filler. Further, the first sealing member 5 of the film may control the gap between the first substrate 1 and the second substrate 9 depending on the film thickness of the first sealing member 5. You may control the gap between the 1st board | substrate 1 and the 2nd board | substrate 9 with the filler size of the liquid 1st sealing member 5 containing the solid filler.

  The gap 6 formed on the outer periphery of the first sealing member 5 is formed of at least one selected from the group consisting of air, nitrogen, oxygen, vapor of a solvent contained in the electrolyte 4, and an electrolyte volatile component. Is good. Even if such a gap 6 is cracked in the second sealing member 7, the crack does not extend to the first sealing member 5, and leakage of the electrolyte 4 and intrusion of moisture and oxygen from the outside to the electrolyte 4. Can be suppressed. In addition, the gap 6 can form the second sealing member 7 that requires higher temperature treatment than the first sealing member 5 without deteriorating the first sealing member 5.

  The second sealing member 7 is disposed around the gap 6 so as to airtightly confine the electrolyte 4 between the first substrate 1 and the second substrate 9, and suppresses leakage of the electrolyte 4 to the outside. It is a member. The second sealing member 7 includes an inorganic material that is a highly airtight material. In particular, from the viewpoint of high airtightness and easy handling, the second sealing member 7 is preferably formed of at least one selected from the group consisting of glass, glass frit, and metal. . For example, even if the second sealing member 7 controls the gap between the first substrate 1 and the second substrate 9 by the film thickness after temporary baking (heat treatment before bonding the substrates). Good.

  Adhesion between the first substrate 1 and the second substrate 9 by the second sealing member 7 includes pressure bonding, moisture curing sealing, heat sealing, UV sealing, laser sealing, light sealing, and ultrasonic sealing. Or microwave sealing. The second sealing member 7 preferably has a softening point lower than the softening points of the first substrate 1 and the second substrate 9. Thereby, for example, the second sealing member 7 can be selectively melted by microwave heating or laser heating, and the first substrate 1 and the second substrate 9 can be suppressed while suppressing thermal distortion. The second substrate 9 can be bonded and sealed satisfactorily. When the second sealing member 7 is heated by microwaves, it is better to include a microwave absorber that selectively absorbs microwaves in the second sealing member 7. Moreover, when the 2nd sealing member 7 is laser-heated, it is better to include the light absorber which absorbs a laser beam in the 2nd sealing member 7. FIG.

  Moreover, it is preferable that the 2nd sealing member 7 is larger than the 1st board | substrate 1 which is a translucent board | substrate with the absorption coefficient with respect to the any wavelength of 400-2400 nm. In the case of a solar cell, it is necessary to use sunlight of 400 to 2400 nm, and the translucent substrate can transmit light of 400 to 2400 nm. With such a configuration, it is possible to selectively heat the second sealing member 7 by irradiating light of 400 to 2400 nm, and the second sealing member 5 while suppressing heat conduction to the first sealing member 5. Sealing by the sealing member 7 can be performed satisfactorily.

  Such a 2nd sealing member 7 can be comprised by containing light absorbers, such as a laser absorption component, in matrix materials, such as glass. The light absorption coefficient of the second sealing member 7 can be easily controlled by adjusting the type and content of the light absorber. Therefore, it is possible to easily control the amount of heat and light energy with respect to the film thickness necessary for melting and sealing the second sealing member 7 and enabling highly reliable sealing.

The material of the second sealing member 7 is preferably a glass frit containing a laser absorption component and a glass component. This laser absorbing component plays a role of efficiently melting and sintering the glass frit by selectively absorbing laser light and converting the energy into heat. The laser absorbing component is preferably melted as part of the matrix forming the glass frit, but may be segregated in the matrix. Further, if the thermal expansion coefficient of the glass frit is close to the thermal expansion coefficient of the second substrate 9, the occurrence of defects such as cracks can be reduced. Examples of the glass component forming the glass frit include SiO ₂ —Bi ₂ O ₃ —MO _X , B ₂ O ₃ —Bi ₂ O ₃ —MO _X , and SiO ₂ —CaO—Na (K) ₂ O—MO. _X- type, P ₂ O ₅ —MgO—MO _X- type (M is one or more metal elements, and X is an integer). Moreover, as a laser absorption component, chromium, iron, nickel, cobalt, manganese, copper, or the simple substance or oxide of carbon, or these 2 or more types of compounds is mentioned, for example.

  It is preferable that the 2nd sealing member 7 contains a metal. In this case, in order to prevent a short circuit between the first electrode 2 and the second electrode 8, it is preferable to provide an insulating base 10 (referred to as a base 10 used in FIG. 2 and the like described later). Thereby, mechanical strength can be improved and the reliability of sealing can be improved. In addition, the first substrate 1 and the second substrate are heated at a temperature lower than the strain point of the first substrate 1 or the second substrate 9 by electric heating, combined use of ultrasonic waves and electric heating, laser heating, or the like. 9 can be bonded to each other, so that the occurrence of thermal strain or thermal stress in the first substrate 1 or the second substrate 9 can be reduced, and the sealing reliability can be further improved.

<Semiconductor layer>
The semiconductor layer 3 is composed of a porous body having a function of supporting a dye. Thus, since the porous semiconductor layer 3 has a large surface area and can carry (adsorb) more dye, it absorbs light efficiently and contributes to improvement in photoelectric conversion efficiency.

  Examples of the material of the porous semiconductor layer 3 include titanium (Ti), zinc (Zn), tin (Sn), niobium (Nb), indium (In), yttrium (Y), and lanthanum (La). At least one metal oxide of metals such as zirconium (Zr), tantalum (Ta), hafnium (Hf), strontium (Sr), barium (Ba), calcium (Ca), vanadium (V), tungsten (W) Even if the semiconductor is good and contains one or more of non-metallic elements such as nitrogen (N), carbon (C), fluorine (F), sulfur (S), chlorine (Cl), phosphorus (P), etc. Good. In particular, titanium oxide is preferable because the electron energy band gap is in the range of 2 to 5 eV, which is larger than the energy of visible light. The porous semiconductor layer is preferably an n-type semiconductor whose conduction band is lower than that of the dye at the electron energy level.

  Moreover, since the semiconductor layer 3 is a porous body, it has a large number of fine pores (having a pore diameter of preferably about 10 to 40 nm) inside. Moreover, the thickness of the semiconductor layer 3 is 1-50 micrometers from a viewpoint of optimizing a photoelectric conversion effect | action, More preferably, 10-30 micrometers is good. In addition, an ultrathin (thickness: about 200 nm) dense layer of an n-type oxide semiconductor such as titanium oxide or niobium oxide may be inserted between the semiconductor layer 3 and the first electrode 2, and the effect of suppressing reverse current. Therefore, the conversion efficiency can be improved.

  Examples of the dye include ruthenium-tris, ruthenium-bis, osmium-tris, osmium-bis type transition metal complexes, polynuclear complexes, or ruthenium-cis-diaqua-bipyridyl complexes, or phthalocyanines, porphyrins, polycyclic aromatic compounds, It is preferable to use a xanthene group such as rhodamine B.

  In order to adsorb the dye to the porous semiconductor layer 3, it is effective that the dye has at least one carboxyl group, sulfonyl group, hydroxamic acid group, alkoxy group, aryl group, phosphoryl group, etc. as a substituent. is there. Here, the substituent is not particularly limited as long as it can strongly adsorb the dye itself to the porous semiconductor layer 3 and can easily transfer charges from the excited sensitizing dye to the porous semiconductor layer 3.

Examples of the method for adsorbing the dye on the semiconductor layer 3 include a method of immersing the semiconductor layer 3 formed on the first substrate 1 in a solution in which the dye is dissolved. As the solvent of the solution for dissolving the dye when the dye is adsorbed on the semiconductor layer 3, for example, alcohols such as ethanol, ketones such as acetone, ethers such as diethyl ether, nitrogen compounds such as acetonitrile, etc. Or what mixed 2 or more types is mentioned. The concentration of the dye in the solution is preferably about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol / l (l (liter): 1000 cm ³ ).

  Next, another embodiment of the present invention will be described.

  FIG. 2 is a cross-sectional view showing a second embodiment according to the photoelectric conversion device of the present invention. The photoelectric conversion device X2 is different from the photoelectric conversion device X1 in that the second sealing member 7 is formed on the base portion 10. The pedestal 10 is a trapezoidal part protruding from the main surface of the first substrate 1 or the main surface of the second substrate 9. The base 10 includes a thin film having a thickness of about several μm.

  In the photoelectric conversion device X2, the thickness of the second sealing member 7 can be reduced by providing the pedestal 10. As a result, the amount of heat for melting the second sealing member 7 by microwaves or laser light can be reduced, and the sealing between the first substrate 1 and the base portion 10 by the second sealing member 7 in a state where the thermal strain is small. It is possible to improve the reliability of hermetic sealing.

  The platform 10 can be formed on at least one of the first substrate 1 and the second substrate 9. The base 10 is preferably formed of at least one selected from the group consisting of glass, glass frit, and metal in order to improve the reliability of hermetic sealing.

  The softening point of the base part 10 is preferably lower than the softening point of the first substrate 1 on which the base part 10 is provided or the softening point of the second substrate 9 on which the base part 10 is provided. That is, when the pedestal 10 is provided on the first substrate 1, the softening point of the pedestal 10 is preferably lower than the softening point of the first substrate 1. Further, when the pedestal 10 is provided on the second substrate 9, the softening point of the pedestal 10 is preferably lower than the softening point of the second substrate 9. Thereby, when the base part 10 is heated and melted and the base part 10 is joined to the first substrate 1 or the second substrate 9, the first substrate 1 or the second substrate 9 is distorted. It can suppress and can improve the reliability of airtight sealing.

  The softening point of the second sealing member 7 is preferably lower than that of the base part 10. Thereby, the 2nd sealing member 7 can be selectively melted, it can suppress that a thermal strain arises in the base part 10, and can suppress that a stress arises in a junction part.

  In addition, the second sealing member 7 preferably has an absorption coefficient larger than that of the base 10 for any wavelength in the region of 400 to 2400 nm. Accordingly, the second sealing member 7 can be selectively heated by irradiating a laser beam of 400 to 2400 nm, and the second sealing is performed while suppressing heat conduction to the first sealing member 5. Sealing with the member 7 can be performed.

  When the pedestal 10 is provided on the first substrate 1, the first electrode 2 formed on the main surface of the first substrate 1 extends to the interface between the pedestal 10 and the first substrate 1. It is preferable to take out. Thereby, the output of photoelectric conversion can be taken out easily. From the same viewpoint, when the pedestal 10 is provided on the second substrate 9, the second electrode 8 formed on the main surface of the second substrate 9 is connected to the pedestal 10 and the second substrate 9. It is preferable to extend to the interface with the substrate 9.

  When the second sealing member 7 contains a metal, the material of the second sealing member 7 is indium, lead, bismuth, silver, tin-based alloy, indium-based alloy, bismuth-based alloy, silver-based alloy, tin- Bismuth alloy, tin-lead alloy, tin-silver alloy, tin-copper alloy, tin-silver-copper alloy, indium-silver alloy, gold-tin alloy, Cerasolza (Kuroda Techno Co., Ltd.) ) And the like. Furthermore, in order to suppress corrosion from the outside of the second sealing member 7, a protective material may be coated on the outside.

When the 2nd sealing member 7 contains a metal, it is preferable that the base part 10 is insulating. Thereby, the 1st electrode 2 or the 2nd electrode 8 can be favorably extracted to the outer surface of the photoelectric conversion device. That is, it is possible to prevent the first electrode 2 or the second electrode 8 from coming into contact with the second sealing member 7 and causing a defect such as a short circuit. Such an insulating base 10 preferably contains glass from the viewpoint of enhancing both insulation and sealing properties. The pedestal 10 is arranged to insulate the first electrode 2 or the second electrode 8 from the sealing member 7. The base 10 is preferably made of a material having a melting point lower than the strain point of the first substrate 1 or the second substrate 9. Furthermore, the base 10 is preferably made of a material having a melting point lower than the temperature at which the first electrode 2 and the second electrode 8 irreversibly increase in resistance. Further, the base 10 is preferably made of a material having not only insulating properties but also sealing properties. As the base part 10, a metal oxide thin film, metal oxide nanoparticles, a low melting glass, and a low melting glass frit are preferable. The pedestal 10 has a low melting point glass frit, such as a lead glass frit (PbO—B ₂ O ₃ system, etc.), a bismuth glass frit (SiO ₂ —Bi ₂ O ₃ —MO _X system, B ₂ O ₃ —Bi ₂ O). _3- MO _X system (M is one or more metal elements, X is an integer), Bi ₂ O ₃ —SnO system, Bi ₂ O ₃ —B ₂ O ₃ system, Bi ₂ O ₃ —B ₂ O ₃ -BaO _{based, Bi 2 O 3 -ZnO-SiO} 2 -B 2 O 3 system, etc.), vanadium-based glass frit _{(V 2} O 5 -ZnO-BaO series, etc.), phosphoric acid-based glass frit _(P 2 _{O 5} - SnO system, P ₂ O ₅ —CuO system, P ₂ O ₅ —MgO—MO _X system (M is one or more metal elements, X is an integer), borosilicate glass frit (B ₂ O ₃ -SiO ₂ system, etc.), zinc-based glass frit (ZnO SiO ₂ -B ₂ O ₃ -RO system, etc.) and the like are good. Moreover, the base part 10 may contain fillers, such as a gap material for gap control, etc., such as a pigment for coloring, such as an alumina, a zirconium silicate, etc. for thermal expansion adjustment.

  Next, another embodiment of the present invention will be described.

  FIG. 3 is a cross-sectional view showing a third embodiment of the photoelectric conversion device of the present invention. The photoelectric conversion device X <b> 3 is photoelectric in that the base 10 is provided on each of the first substrate 1 and the second substrate 9, and the second sealing member 7 is formed between the bases 10. This is different from the conversion device X2.

  In the photoelectric conversion device X3, since the second sealing member 7 is formed between the base portions 10, the thickness of the second sealing member 7 can be reduced. Further, the amount of heat for melting the second sealing member 7 can be reduced, and the first substrate 1 and the second substrate 9 can be sealed by the second sealing member 7 in a state where the thermal strain is small. The reliability of hermetic sealing can be increased. Furthermore, since the second sealing member 7 can be assembled with a symmetrical member structure, the sealing yield can be improved and the sealing strength can be increased.

  Next, another embodiment of the present invention will be described.

  FIG. 4 is a sectional view showing a fourth embodiment according to the photoelectric conversion device of the present invention. In the photoelectric conversion device X4, the base portion 10 has a width wider than the width of the second sealing member 7 (the thickness between the side surface on the electrolyte 4 side and the side surface on the opposite side in FIG. 4). This is different from the photoelectric conversion device X3. Thereby, when the 2nd sealing member 7 contains a metal, it can suppress effectively that the 2nd sealing member 7 spreads and contacts the 1st electrode 2 or the 2nd electrode 8. FIG.

  Next, another embodiment of the present invention will be described.

  FIG. 5 is a cross-sectional view showing a fifth embodiment of the photoelectric conversion device of the present invention. The photoelectric conversion device X5 is different from the photoelectric conversion device X1 in that the electrolyte 4 is separated from the first sealing member 5 by the gap 11.

  In the photoelectric conversion device X5, since the highly corrosive electrolyte 4 is separated from the first sealing member 5 by the gap 11, the deterioration of the first sealing member 5 can be suppressed, and the long-term Can be sealed.

  Next, another embodiment of the present invention will be described.

  FIG. 6 is a sectional view showing a sixth embodiment according to the photoelectric conversion device of the present invention. The photoelectric conversion device X6 is different from the photoelectric conversion device X1 in that a part of the first sealing member 5 covers the outer peripheral portion of the semiconductor layer 3.

  In the photoelectric conversion device X6, the area where the first electrode 2 directly contacts the electrolyte 4 can be reduced by partially covering the outer periphery of the semiconductor layer 3 with a part of the first sealing member 5, so that the first electrode 2 and the electrolyte 4 can be suppressed, and the conversion efficiency can be improved.

  Next, another embodiment of the present invention will be described.

  FIG. 7 is a sectional view showing a seventh embodiment according to the photoelectric conversion device of the present invention. FIG. 8 is a plan perspective view thereof. In FIG. 8, the protective material 12 is omitted for easy viewing. In the photoelectric conversion device X7, the second sealing member 7 protrudes from at least one of the first substrate 1 and the second substrate 9 (extrudes from both in FIG. 7), the side surface of the first substrate 1, or the first 2 is different from the photoelectric conversion device X1 in that it is bonded to the side surface of the substrate 9.

  Here, an embodiment of the inlet 13 for injecting the liquid electrolyte 4 is also shown. In addition, the dye solution is circulated from the main inlet 13 into the cell formed from the first electrode 2, the second electrode 8, and the first sealing member 5, thereby forming the semiconductor layer 3 such as porous titanium oxide. A dye can also be adsorbed. After the dye is adsorbed to the semiconductor layer 3 such as porous titanium oxide, the electrolyte 4 is injected from the main inlet 13 into the cell and partway through the inlet 13 to form the first gap 15 and the second gap 16. After injecting the sealing material 14 such as an acrylate UV curing adhesive as described above, the sealing material 14 is UV cured by irradiating with UV light. Here, the second gap 16 may be omitted. Next, a sealing member 17 such as a thermoplastic film is attached on the injection port 13, and a lid member 19 is further attached on the sealing member 17. Here, the injection hole 13 may be sealed by attaching a lid member 19 to which the sealing member 17 is attached. Next, a gap 18 is provided, and a base 20 such as Cerasolza (manufactured by Kuroda Techno Co., Ltd.) or glass frit is installed, and this is subjected to an ultrasonic heating method or laser heating to cover the cover 19 and the second substrate 9. And the injection hole 13 can be sealed.

  Here, by providing the first gap 15 or the second gap 16 in the middle of the injection port 13, when the photoelectric conversion device X6 receives a temperature load, the capacitance change due to the thermal expansion of the liquid electrolyte 4 occurs. The internal pressure change accompanying this can be absorbed, and the destruction of the first sealing member 5, the second sealing member 7, the sealing material 14, the sealing member 17 or the base body 20 is suppressed, and long-term reliability is achieved. Can be secured. Further, by providing a gap 18 such as air between the sealing member 17 and the base body 20, when the base body 20 is formed at a high temperature, thermal deterioration of the sealing member 17 such as resin can be suppressed. Further, by using Cerasolzer (manufactured by Kuroda Techno) or glass frit for the base 20, the base 20 is melted below the strain point of the lid 19 and the second substrate 9, and the lid 19 or the second Since the second substrate 9 can be bonded by the dense base 20, the long-term reliability of the photoelectric conversion device can be secured by hermetic sealing.

  In the photoelectric conversion device X7, the second sealing member 7 protrudes from at least one of the first substrate 1 and the second substrate 9, and is bonded to the side surface of the first substrate 1 or the side surface of the second substrate 9. Since the second sealing member 7 can be melted by ultrasonic heating or the like directly from the side surface of the first substrate 1 or the side surface of the second substrate 9, the periphery of the second sealing member 7 Since the heating of the member can be reduced and the thermal strain on the joint can be reduced, the first substrate 1 and the second substrate 9 can be cracked, the second sealing member 7 can be sealed such as cracks and peeling. The yield can be improved, and the long-term reliability can be improved. The gap between the first electrode 2 or the second electrode 8 can be controlled by the thickness of the first sealing member 5 and the filler size included in the first sealing member 5.

  A protective material 12 such as an organic resin may be disposed on the outer periphery of the second sealing member 7 for reinforcement. In this case, the sealing strength can be increased and the corrosion of the second sealing member 7 from the outside can be suppressed. This organic resin is a resin material such as polyethylene, modified polyethylene, maleic acid modified polyethylene, polypropylene, modified polypropylene, maleic acid modified polypropylene, ionomer resin, fluororesin, epoxy resin, polyisobutylene resin, silicone resin or acrylate resin, or thermoplastic resin. A thermosetting resin, a photocurable resin, a photothermosetting resin, a moisture curable resin, and a two-component mixed curable resin are preferable. Moreover, this organic resin may contain a filler etc. as needed from a viewpoint of raising mechanical strength.

  Further, for example, as shown in FIG. 7, the first electrode 2 on the first substrate 1 or a part of the second electrode 7 on the second substrate is removed, and an insulating portion is provided on the substrate. When the 2 sealing member 7 contains a metal, the short circuit with the 1st electrode 2 and the 2nd electrode 7 by the 2nd sealing member 7 can be suppressed.

  It should be noted that the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the scope of the present invention. For example, in the photoelectric conversion devices X1 to X7, the semiconductor layer 3 may be provided not on the first substrate 1 side that is a light-transmitting substrate but on the second substrate 9 side that is a support substrate. It may be provided on both the side and the second substrate 9 side. In the photoelectric conversion devices X1 to X6, an organic resin may be disposed on the outer peripheral portion of the second sealing member 7 for reinforcement. In this case, the sealing strength can be increased. This organic resin is a resin material such as polyethylene, modified polyethylene, maleic acid modified polyethylene, polypropylene, modified polypropylene, maleic acid modified polypropylene, ionomer resin, fluororesin, epoxy resin, polyisobutylene resin, silicone resin or acrylate resin, or thermoplastic resin. A thermosetting resin, a photocurable resin, a photothermosetting resin, a moisture curable resin, and a two-component mixed curable resin are preferable. Moreover, this organic resin may contain a filler etc. as needed from a viewpoint of raising mechanical strength. Moreover, the base part 10 in the photoelectric conversion devices X2 to X4 and X7 may be formed in a frame shape along the entire circumference of the second sealing member 7, and, for example, as shown in FIG. Alternatively, it may be partially formed only in a portion overlapping with the electrode 2 or the second electrode 8.

X1, X2, X3, X4, X5, X6, X7: photoelectric conversion device 1: first substrate (translucent substrate)
2: First electrode 3: Semiconductor layer 4: Electrolyte 5: First sealing member 6: Gap 7: Second sealing member 8: Second electrode 9: Second substrate (support substrate)
10: base part 11: gap 12: protective material 13: injection port 14: sealing material 15: first gap 16: second gap 17: sealing member 18: gap 19: lid material 20: base body

Claims (14)

A translucent substrate having a first major surface;
A support substrate having a second main surface opposite to the first main surface;
An electrolyte disposed in a gap formed between the translucent substrate and the support substrate;
A first sealing member made of a corrosion-resistant material that joins the translucent substrate and the support substrate;
A second sealing member including an inorganic material, disposed outside the first sealing member and spaced apart from the first sealing member, and joining the translucent substrate and the support substrate; A photoelectric conversion device comprising the photoelectric conversion device.   The photoelectric conversion device according to claim 1, wherein the corrosion-resistant material includes a resin.   At least one of the light-transmitting substrate and the second sealing member and between the support substrate and the second sealing member is provided with a pedestal, and the second seal 3. The photoelectric conversion device according to claim 1, wherein the stop member has an absorption coefficient larger than that of the base portion with respect to any wavelength in a range of 400 to 2400 nm.   The photoelectric conversion device according to claim 3, wherein the base portion is provided on each of the translucent substrate and the support substrate.   5. The photoelectric conversion device according to claim 3, wherein a softening point of the second sealing member is lower than a softening point of the base portion.   6. The softening point of the pedestal portion is lower than a softening point of the translucent substrate provided with the pedestal portion or a softening point of the support substrate provided with the pedestal portion. The photoelectric conversion apparatus in any one of.   The base portion is provided on the translucent substrate, an electrode is formed on the first main surface, and the electrode extends to an interface between the base portion and the translucent substrate. The photoelectric conversion device according to claim 3, wherein:   The platform is provided on the support substrate, and an electrode is formed on the second main surface, and the electrode extends to an interface between the platform and the support substrate. The photoelectric conversion device according to claim 3.   The photoelectric conversion device according to claim 1, wherein the second sealing member includes a light absorber.   The photoelectric conversion device according to claim 1, wherein the inorganic material contains a metal.   An insulating base is provided on at least one of the space between the translucent substrate and the second sealing member and between the support substrate and the second sealing member. The photoelectric conversion device according to claim 10.   The photoelectric conversion device according to claim 11, wherein the base portion includes glass.   13. The material according to claim 1, wherein a substance having a lower thermal conductivity than that of the second sealing member is filled between the first sealing member and the second sealing member. The photoelectric conversion apparatus of crab.   The photoelectric conversion device according to claim 1, wherein the first sealing member covers an outer peripheral portion of a semiconductor layer provided on the translucent substrate.