JP5574657B2 - Photoelectric conversion device - Google Patents

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 joining member for joining them so as not to leak outside.

JP 2002-313443 A

  However, in the dye-sensitized solar cell disclosed in Patent Document 1, the joining member is deteriorated by the electrolyte due to long-term use, the airtightness of the electrolyte chamber is lowered, and the operation reliability may be lowered. It was.

  The present invention has been completed in view of the above-described conventional problems, and an object of the present invention is to obtain a photoelectric conversion device with high operation reliability by maintaining hermeticity 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 electrode formed on the first main surface of the substrate and the second main surface of the support substrate; an electrolyte disposed in a gap formed between the translucent substrate and the support substrate; A bonding member for bonding an electrode formed on the first main surface of the translucent substrate and an electrode formed on the second main surface of the support substrate , which are disposed via a gap; and, the joining member, chromium, iron, nickel, cobalt, manganese, if Ku elemental copper or two or more of these compounds, and with there Nde including a glass, a first main of the transmissive substrate Formed between the electrode formed on the surface and the joining member and on the second main surface of the support substrate Have been between the electrode and the bonding member, the is provided with a base portion of insulating at least one,該台unit is characterized in that it has a width greater than the width of the joining member . The void means a gap filled with gas or a vacuum gap.

With such a configuration, it is possible to increase the resistance of the joining member to the electrolyte by separating the electrolyte and the joining member by a gap. Furthermore, since the electrolyte and the bonding member are spaced apart, the influence of heat or the like on the electrolyte or the like can be suppressed during sealing with the bonding member, and the photoelectric conversion characteristics and reliability can be improved. . And since a base part has a width | variety wider than the width | variety of a joining member, it can suppress effectively that a joining member spreads and contacts an electrode. As a result, a photoelectric conversion device that maintains hermeticity for a long time and has high operational reliability can be obtained.

Moreover , the said joining member contains an inorganic material. Thereby, the leakage of the electrolyte component can be more effectively suppressed.

The inorganic material includes glass. As a result, leakage of the electrolyte component or intrusion of moisture, oxygen, etc. from the outside can be suppressed, and long-term reliability can be obtained.

Preferably, in the photoelectric conversion device of the present invention, prior Symbol junction member, the absorption coefficient for any wavelength in the region of 400~2400nm it is greater than the base part. By providing the pedestal, the volume of the joining member can be reduced, thermal strain and thermal stress during sealing can be reduced, and sealing reliability can be improved. In addition, since the light in the above wavelength range can pass through the translucent substrate, it is possible to selectively heat the bonding member having a larger absorption coefficient in the above wavelength range than the base, and the thermal strain and thermal stress at the time of sealing And the reliability of sealing 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. In this way, by arranging the pedestal symmetrically on the substrate and sealing with the bonding member, thermal strain or thermal stress on the substrate can be reduced, and the sealing reliability can be improved. .

  In the photoelectric conversion device of the present invention, preferably, the softening point of the joining member is lower than the softening point of the base portion. Thereby, by selectively softening and sealing the joining member, thermal strain or thermal stress on the substrate can be reduced, and the reliability of sealing 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.

The joining 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.

Further , insulation is provided between at least one of the electrode formed on the first main surface of the translucent substrate and the bonding member and the electrode formed on the second main surface of the support substrate . It has a pedestal. Thereby, the electrode can be pulled out satisfactorily. The said structure WHEREIN: It is preferable that the said base part contains glass. Thereby, it is dense, has high sealing properties, and can improve long-term reliability.

  In the photoelectric conversion device of the present invention, preferably, the electrolyte is an electrolyte having a viscosity of 0.1 Pa · s or more, or a gel electrolyte, including at least one selected from a volatile organic solvent and an ionic liquid. Thereby, a space | gap can be maintained and formed between electrolyte and a joining member, and long-term reliability can be improved.

  In the photoelectric conversion device of the present invention, preferably, the electrolyte is a solid electrolyte. Thereby, a space | gap can be further maintained and formed between electrolyte and a joining member, and long-term reliability can be improved.

  According to the photoelectric conversion device of the present invention, since the bonding member is separated from the highly corrosive electrolyte, deterioration of the bonding member can be suppressed. As a result, a photoelectric conversion device with high operational reliability can be obtained.

Is a sectional view showing an embodiment of the photoelectric conversion equipment of a reference example. Is a sectional view showing an embodiment of the photoelectric conversion equipment of a reference example. Is a sectional view showing an embodiment of the photoelectric conversion equipment of a reference example. It is sectional drawing which shows 1st Embodiment of the photoelectric conversion apparatus which concerns on this invention. Is a sectional view showing an embodiment of the photoelectric conversion equipment of a reference example. 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.

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

Figure 1 is a sectional view showing an implementation form engagement Ru photoelectric conversion device as a reference example. The photoelectric conversion device X1 includes a pair of substrates (hereinafter, referred to as a first substrate 1 and a second substrate 8) 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 7 are respectively formed on one main surface of 8. 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 8. In other words, the electrolyte 4 is disposed so as to be sandwiched between the first electrode 2 and the second electrode 7. On the first electrode 2, a semiconductor layer 3 carrying a dye (not shown) is formed. Although not shown, the second substrate 8 and the second electrode 7 may be formed with injection holes for injecting the electrolyte 4 from the outside. On the second electrode 7, a catalyst made of an organic material such as a noble metal such as platinum or palladium (not shown), PEDOT: TsO (polyethylenedioxythiophene-toluenesulfonate), or carbon may be formed. .

  Since the electrolyte 4 is made of iodine or the like and has high corrosiveness, the electrolyte 4 is formed away from the joining member 6. A gap 5 is formed by this separation. The gap 5 is a gap filled with gas or a vacuum gap. Since the void 5 has low thermal conductivity, the bonding member 6 is locally heated after the electrolyte 4 containing the organic component is formed, and the first substrate 1 and the second substrate 8 are bonded by the bonding member 6. Even if it joins, the heat conduction to the electrolyte 4 can be effectively suppressed. As a result, it is possible to suppress the electrolyte 4 from being deteriorated or vaporized by heat. Therefore, the bonding member 6 can be bonded with an inorganic material such as glass frit or solder having a relatively higher melting point than an adhesive made of an organic material. An ultrasonic wave, light, laser, microwave, thermal probe, or the like can be used for local heating of the bonding member 6.

  In addition, since the gap 5 exists between the electrolyte 4 and the joining member 6, the thermal expansion stress of the electrolyte 4 can be absorbed and relaxed by the gap 5, and the sealing can be maintained for a long time.

  Furthermore, since the joining member 6 is provided via the electrolyte 4 and the gap 5, the joining member 6 does not come into contact with the highly corrosive electrolyte 4, and deterioration or elution of the joining member 6 due to the electrolyte 4 can be suppressed. On the contrary, since elution of the joining member 6 into the electrolyte 4 can be suppressed, deterioration of the electrolyte 4 can also be suppressed, and the photoelectric conversion characteristics can be maintained for a long time. Further, since the electrolyte 4 does not come into contact with the joining member 6, the surface of the joining member 6 is not soiled by the electrolyte 4, and the electrolyte 4 and the joining member 6 can be sealed at the same time, thereby simplifying the process.

  Whether the void 5 is filled with a substance having a lower thermal conductivity than that of the bonding member 6 from the viewpoint of more effectively suppressing heat transferred to the electrolyte 4 when sealed by the bonding member 6. Or a vacuum. The material having a lower thermal conductivity than the joining member 6 is at least selected from the group consisting of air, nitrogen, oxygen, and a solvent vapor contained in the electrolyte and a solute vapor contained in the electrolyte. It is preferable to be filled with one kind.

Below, the detail of the member which comprises the photoelectric conversion apparatus which concerns on embodiment as a reference example 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 8 is a support substrate for supporting the second electrode 7 on one main surface. The second substrate 8 is made of a glass material such as blue plate glass, white plate glass, and non-alkali glass, which is a light-transmitting material, as in the case of 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 8 does not have to be positioned on the light incident side, the second substrate 8 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, the first substrate 1 itself acts as an electrode, so the second electrode 7 is not necessary and the number of components can be reduced. Moreover, when the 2nd board | substrate 8 is a metal, it is suitable to comprise with titanium, nickel, tungsten, and aluminum from a viewpoint of improving the corrosion resistance with respect to the electrolyte 4. FIG.

<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 7 is for passing charge to the electrolyte 4 and is provided on one main surface of the second substrate 8. As a material of the second electrode 7, if the second substrate 8 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, if no light is received from the second substrate 8, the second electrode 7 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 7 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 electric charge received from the second electrode 7 to the dye carried on the semiconductor layer 3.

  The electrolyte 4 is obtained, for example, by adding a redox material to an organic solvent. Examples of such organic solvents include nitriles such as acetonitrile, methoxyacetonitrile, methoxypopionitrile, and valeronitrile, carbonates such as ethylene carbonate and propylene carbonate, amides such as dimethylformamide, and aprotic polarities such as dimethyl sulfoxide. Solvents may be mentioned, and these solvents may be used alone or in combination of two or more. Preferably, the organic solvent used for the electrolyte 4 may include at least one selected from a volatile organic solvent and an ionic liquid. Thereby, the diffusion constant of redox ions is increased, and the power generation efficiency can be increased. In addition, the volatile organic solvent in this embodiment means the solvent which has a boiling point of 260 degrees C or less. In general, a volatile organic solvent has a small molecule and tends to have a large moment due to polarization, so that an ion diffusion constant tends to increase.

  Examples of the redox material added to the organic solvent include lithium iodide, magnesium iodide, 1,2-dimethyl-3-propylimidazolium iodide, butylmethylimidozolium iodide, and N-methylbenzimidazole. 4-tert-butylpyridine, guanidinium thiocyanate and the like.

The electrolyte 4 is preferably an electrolyte 4 having a viscosity of 0.1 Pa · s (25 ° C., shear rate 26 sec ⁻¹ , B-type viscometer 10 rpm) or more, or a gel electrolyte 4, or a solid electrolyte There should be four. Furthermore, thixotropic index _{TI (TI = η 1 / η} 2) ( viscosity at a η1 has shear rate 1sec ^-1, 10η ₂ viscosity when of shear rate 10 sec ^-1) is better than 5 1 or more. From the viewpoint of suppressing the flow of the electrolyte 4 and forming the voids 5 satisfactorily, the TI is preferably 1 or more. Further, from the viewpoint of satisfactorily coating and forming the electrolyte 4, the TI is preferably 5 or less. Thus, after the electrolyte 4 is formed on either the first substrate 1 or the second substrate 8, the electrolyte 4 can be sandwiched between the first substrate 1 and the second substrate 8 before the electrolyte 4 flows out. . This eliminates the need for an electrolyte injection hole and simplifies members and processes.

  Note that the gel electrolyte or solid electrolyte means a state that does not have fluidity when left standing. The gel electrolyte 4 or the solid electrolyte 4 can be obtained, for example, by adding a gelling agent to an electrolytic solution such as iodine / iodide salt, bromine / bromide salt, cobalt complex, potassium ferrocyanide and the like. The notation “iodine / iodide salt” means that the content of iodine and iodide salt changes due to the chemical reaction of the electrolyte.

  Examples of the gelling agent for the gel electrolyte 4 include inorganic gelling agents such as layered clay minerals, organically modified liquid layered clay minerals, nanoparticles of clay, talc, titanium oxide, and polysaccharides (electrolyte) such as gellan. Organic gelation of polyvinylidene fluoride-co-hexafluoropropylene, polyvinyl pyridine, polyacrylic acid, etc. can be used, and it may be solid after injection. As the layered clay mineral, the organically modified liquid layered clay mineral, clay, and talc, it is preferable to use a phyllosilicate in which a silicate tetrahedron is bound in a two-dimensional sheet shape. Specifically, for example, a smectite clay mineral or a vermiculite type Mention may be made of natural or synthetic clay minerals such as clay minerals and mica.

  The electrolyte 4 having a viscosity of 0.1 Pa · s or more, the gel electrolyte 4, or the solid electrolyte 4 is formed on the first electrode 2 or the second electrode 7 on which the semiconductor layer 3 supporting the dye is formed. Alternatively, the solid electrolyte 4 may be applied by screen printing, metal mask printing, doctor blade application, dispenser application, spray application, roller application, calendar application, ink jet application, die coater, or the like. 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 8 is preferably about 1 to 500 μm.

<Gap and bonding member>
The gap 5 formed along the outer periphery of the electrolyte 4 is filled with a gas or is in a vacuum. Preferably, the gap 5 is formed of at least one selected from the group consisting of air, nitrogen, oxygen, solvent vapor, and electrolyte volatile components. Thereby, the characteristic of the electrolyte 4 can be maintained favorable over a long period of time.

The joining member 6 is disposed around the gap 5 so as to airtightly confine the electrolyte 4 between the first substrate 1 and the second substrate 8, and is a member for suppressing leakage of the electrolyte 4 component to the outside. is there. Bonding member 6, including glass, the inorganic material such as metal. Thereby, airtightness can be improved and leakage of electrolyte components and intrusion of moisture, oxygen, and the like in the outside world can be suppressed. As a result, deterioration of the characteristics of the solar cell can be suppressed. In particular, when the bonding member 6 includes glass, thermal expansion with the substrate made of glass or the like can be matched, and the long-term reliability of sealing can be improved. When a phosphoric acid-based, bismuth-based or vanadium-based glass frit is used as the bonding member 6, for example, sealing can be performed at a temperature of 500 ° C. or lower, which is lower than the strain point of soda lime glass. The long-term reliability can be improved. Moreover, the bonding member 6 containing glass can also control the gap between the first substrate 1 and the second substrate 8 by the film thickness after temporary baking. The gap can also be controlled by the joining member 6 to which a high melting point filler such as alumina is added.

  The bonding between the first substrate 1 and the second substrate 8 by the bonding member 6 is performed by pressure bonding, moisture curing sealing, heat sealing, UV sealing, laser sealing, light sealing, ultrasonic sealing, microwave sealing. You can wear it. The bonding member 6 preferably has a softening point lower than the softening point or strain point of the first substrate 1 and the second substrate 8. Thereby, for example, the joining member 6 can be selectively melted by microwave heating or laser heating, and the first substrate 1 and the second substrate 8 can be bonded and sealed satisfactorily. When the joining member 6 is heated by microwaves, the joining member 6 preferably includes a microwave absorber that selectively absorbs microwaves. In addition, when the joining member 6 is laser-heated, the joining member 6 preferably includes a light absorber that absorbs laser light.

  Moreover, it is preferable that the joining member 6 has a larger absorption coefficient with respect to any wavelength in the region of 400 to 2400 nm than the first substrate 1 which is a light-transmitting substrate. 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 bonding member 6 by irradiating light of 400 to 2400 nm, and to perform good sealing with the bonding member 6 while suppressing heat conduction to the electrolyte 4. it can.

Such a bonding member 6, that make up by the inclusion of light absorbing material, such as a laser absorbing component into the matrix material such as glass. The light absorption coefficient of the joining member 6 can be easily controlled by adjusting the type and content of the light absorber. Therefore, the heat quantity and light energy with respect to the film thickness required for melting and sealing of the joining member 6 can be easily controlled, and highly reliable sealing can be achieved.

The material of the bonding member 6 is preferably a glass frit having a laser over the absorption component and the glass component. The laser over the absorbing component, and selectively absorb laser over beam, the energy of the glass frit efficiently melted by converting into heat, responsible for sintering. The laser over the absorbing component, it is preferable to be melted as part of the matrix forming the glass frit may be segregated in the matrix. Further, if the thermal expansion coefficient of the glass frit of the joining member 6 is made close to the thermal expansion coefficient of the second substrate 8, the occurrence of defects such as cracks can be reduced. Examples of the glass component forming the glass frit include phosphoric acid, bismuth, vanadium, 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 _{based, P 2 O 5 -MgO-MO} X system (M is at least one metallic element, X is an integer.) and the like. As the laser over the absorption component, for example, chromium, iron, nickel, cobalt, manganese, or a single body, or the two or more compounds of copper.

  It is preferable that the joining member 6 contains a metal. The metal is at least selected from the group consisting of a low melting point metal, a low melting point alloy, easy fusion gold, solder, a tin alloy, a bismuth alloy, a lead alloy, a gallium alloy, a cadmium alloy, Cerasolza (manufactured by Kuroda Techno). It is good to be formed from one kind. In addition, the bonding member 6 may contain a filler such as alumina or quartz for controlling the gap between the first electrode 2 and the second electrode 7 for adjusting the coefficient of thermal expansion, such as alumina or zirconium silicate, pigment for coloring, or the like. . Thereby, the reliability of sealing can be improved. Further, at a temperature lower than the strain point of the first substrate 1 or the second substrate 8 by electric heating, ultrasonic heating, microwave heating, combined use of ultrasonic and electric heating, laser heating, light heating, or the like. Since the first substrate 1 and the second substrate 8 can be bonded, it is possible to reduce the occurrence of thermal strain or thermal stress in the first substrate 1 or the second substrate 8, and to seal the sealing. The reliability can be further improved. For example, when the sealing member 7 is a Cerasolzer, an ultrasonic soldering apparatus is used, so that the joining member 6 is made FTO (fluorine-doped oxidation) by ultrasonic vibration energy and heat that removes the air layer at the interface in a short time. The first electrode 2 or the second electrode 7 of tin, the first substrate 1 or the second substrate 8 of soda glass, and a base 9 such as a glass frit (refers to a base 9 used in FIG. 2 or the like described later). ) Can be easily adhered, and a highly reliable sealing can be achieved.

<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. The semiconductor layer 3 is provided on the translucent substrate 1 side in the photoelectric conversion device X1 in FIG. 1, but may be provided on the support substrate 8 side.

  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 as a reference example will be described.

Figure 2 is a sectional view showing an implementation form engagement Ru photoelectric conversion device as a reference example. The photoelectric conversion device X2 is different from the photoelectric conversion device X1 in that the joining member 6 is formed on the base portion 9. The base portion 9 is a trapezoidal portion protruding from the main surface of the first substrate 1 or the main surface of the second substrate 8. The base 9 includes a thin film having a thickness of about several μm.

  In the photoelectric conversion device X <b> 2, the thickness of the bonding member 6 can be reduced by providing the base 9. Thereby, for example, in the case of the bonding member 6, the amount of heat for melting the bonding member 6 by microwaves or laser light can be reduced, and the first substrate 1 and the base portion 9 are sealed by the bonding member 6 in a state where the thermal strain is small. It is possible to improve the reliability of hermetic sealing.

  The platform 9 can be formed on at least one of the first substrate 1 and the second substrate 8. The base 9 is preferably formed from 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 9 is preferably lower than the softening point of the first substrate 1 on which the base 9 is provided or the softening point of the second substrate 8 on which the base 9 is provided. That is, when the pedestal 9 is provided on the first substrate 1, the softening point of the pedestal 9 is preferably lower than the softening point of the first substrate 1. When the base 9 is provided on the second substrate 8, the softening point of the base 9 is preferably lower than the softening point of the second substrate 8. Thereby, when the base part 9 is heated and melted and the base part 9 is joined to the first substrate 1 or the second substrate 8, the first substrate 1 or the second substrate 8 is distorted. It can suppress and can improve the reliability of airtight sealing. The base portion 9 is disposed to insulate the first electrode 2 or the second electrode 7 from the bonding member 6. The base 9 is preferably made of a material having a melting point lower than the strain point of the first substrate 1 or the second substrate 8. Furthermore, the base 9 is preferably made of a material having a melting point lower than the temperature at which the first electrode 2 and the second electrode 7 irreversibly increase in resistance. The base 9 is preferably made of a material having not only insulating properties but also sealing properties. As the pedestal 9, a metal oxide thin film, metal oxide nanoparticles, low melting glass, and low melting glass frit are preferable. The pedestal 9 is composed of lead glass frit (PbO—B ₂ O ₃ system, etc.), bismuth glass frit (SiO ₂ —Bi ₂ O ₃ —MO _X system, B ₂ O ₃ —Bi ₂ O, etc.). _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), etc., borosilicate glass frit (B ₂ O ₃ -SiO ₂ system, etc.), zinc-based glass frit (ZnO- iO ₂ -B ₂ O ₃ -RO system, etc.) and the like are good. The base 9 is made of alumina, zirconium silicate, etc. for adjusting thermal expansion, pigments for coloring, etc., fillers such as alumina, quartz, etc. for controlling the gap between the first electrode 2 and the second electrode 7. May be included.

  Further, the softening point of the joining member 6 is preferably lower than the base portion 9. Thereby, the joining member 6 can be selectively melted, it is possible to suppress the occurrence of thermal strain in the base portion 9, and it is possible to suppress the occurrence of stress in the joint portion.

  Moreover, it is preferable that the joining member 6 has an absorption coefficient larger than that of the base portion 9 for any wavelength in the region of 400 to 2400 nm. Thereby, the laser beam of 400 to 2400 nm can be irradiated to selectively heat the bonding member 6, and the bonding member 6 can be sealed while suppressing the heat conduction of the electrolyte 4.

When the base 9 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 base 9 and the first substrate 1. that has been put out. Thereby, the output of photoelectric conversion can be taken out easily. From the same viewpoint, when the pedestal 9 is provided on the second substrate 8, the second electrode 7 formed on the main surface of the second substrate 8 is connected to the pedestal 9 and the second substrate 8. that not extend to the interface with the substrate 8.

  When the joining member 6 contains a metal, the material of the joining member 6 is indium, lead, bismuth, silver, tin-based alloy, indium-based alloy, bismuth-based alloy, silver-based alloy, tin-bismuth-based alloy, tin-lead-based An alloy, a tin-silver alloy, a tin-copper alloy, a tin-silver-copper alloy, an indium-silver alloy, a gold-tin alloy, Cerasolzer (manufactured by Kuroda Techno Co., Ltd.) and the like can be mentioned. Furthermore, in order to suppress corrosion from the outside of the joining member 6, a protective material may be coated on the outside.

When the bonding member 6 comprises a metal, the base portion 9 Ru insulating der. Thereby, the 1st electrode 2 or the 2nd electrode 7 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 7 from coming into contact with the bonding member 6 and causing a defect such as a short circuit. Such an insulating base 9 preferably contains glass from the viewpoint of enhancing both insulation and sealing properties.

Next, another embodiment as a reference example will be described.

Figure 3 is a sectional view showing an implementation form engagement Ru photoelectric conversion device as a reference example. The photoelectric conversion device X3 is different from the photoelectric conversion device X2 in that the base portion 9 is provided on each of the first substrate 1 and the second substrate 8, and the bonding member 6 is formed between the base portions 9. Is different.

  In the photoelectric conversion device X3, since the bonding member 6 is formed between the base parts 9, the film thickness of the bonding member 6 can be reduced. Further, for example, in the case of the bonding member 6, the amount of heat for melting the bonding member 6 by microwaves or laser light can be reduced, and the first substrate 1 and the base portion 9 are sealed by the bonding member 6 in a state where the thermal strain is small. And the reliability of hermetic sealing can be improved. Furthermore, since it can assemble with a symmetrical member structure centering on the joining member 6, a joining yield can be improved and joining strength can be raised.

Next, a description will be given implementation of the present invention.

FIG. 4 is a cross-sectional view showing the first embodiment according to the photoelectric conversion device of the present invention. The photoelectric conversion device X4 is photoelectrically converted in that the base 9 has a width wider than the width of the bonding member 6 (the thickness between the side surface on the electrolyte 4 side and the side surface on the opposite side in FIG. 4). Different from the device X3. Thereby, when the joining member 6 contains a metal, it can suppress effectively that the joining member 6 spreads and contacts the 1st electrode 2 or the 2nd electrode 7. FIG.

Next, another embodiment as a reference example will be described.

Figure 5 is a sectional view showing an implementation form engagement Ru photoelectric conversion device as a reference example. The photoelectric conversion device X5 is different from the photoelectric conversion device X1 in that the protective material 10 is provided outside the bonding member 6. In the photoelectric conversion device X5, the protective member 10 is provided outside the bonding member 6, so that the bonding member 10 protects the chemical and mechanical stimuli such as water, oxygen, acid, impact, and vibration from the outside. 6 can be protected and long-term reliability can be improved. Such a protective material 10 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. Alternatively, a thermoplastic resin, a thermosetting resin, a photocuring resin, a photothermosetting resin, a moisture curing resin, and a two-component mixed curing resin are preferable. Moreover, this protective material 10 may contain a filler etc. as needed from a viewpoint of raising the mechanical strength of the joining member 6. FIG.

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

FIG. 6 is a cross-sectional view showing a second embodiment of the photoelectric conversion device of the present invention. In the photoelectric conversion device X6, a protective material 10 is provided on the outside of the joining member 6 of the photoelectric conversion device X4. Thereby, the spreading of the joining member 6 can be suppressed, and the joining member 6 can be protected and long-term reliability can be improved.

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

FIG. 7 is a cross-sectional view showing a third embodiment of the photoelectric conversion device of the present invention. In the photoelectric conversion device X7, the bonding member 6 protrudes from at least one of the first substrate 1 and the second substrate 8 (in FIG. 7, it protrudes from both), the side surface of the first substrate 1 or the second substrate 8. The photoelectric conversion device X1 is different from the photoelectric conversion device X1 in that it is bonded to the side surface.

  As a result, since the joining member 6 can be melted directly from the side surface of the first substrate 1 or the side surface of the second substrate 8 using ultrasonic waves, heat heating, or the like, heating of members around the joining member 6 is reduced. Since the thermal strain on the bonding portion can be reduced, the sealing yield such as cracks in the first substrate 1 and the second substrate 8, cracks in the bonding member 6 and peeling can be improved, and long-term Reliability can also be improved. Further, for example, by removing a part of the first electrode 2 on the first substrate 1 or the second electrode 7 on the second substrate 8 and providing the insulating portion 11, the bonding member 6 is made of metal. When it contains, the short circuit with the 1st electrode 2 and the 2nd electrode 7 by the joining member 6 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 8 side that is a support substrate. It may be provided on both the side and the second substrate 8 side. Moreover, you may form the base part 10 in photoelectric conversion apparatus X2-X4, X6, X7 in frame shape along the perimeter of the joining member 6, for example, the 1st electrode 2 and the 2nd electrode 8 You may form partially only in the overlap part.

X1, X2, X3, X4, X5, X6, X7: photoelectric conversion device 1: first substrate (translucent substrate)
2: First electrode 3: Semiconductor layer 4: Electrolyte 5: Gaps 6: Bonding member 7: Second electrode 8: Second substrate (support substrate)
9: Base part 10: Protective material 11: Insulating part

Claims (8)

A translucent substrate having a first major surface;
A support substrate having a second main surface opposite to the first main surface;
Electrodes formed on the first main surface of the translucent substrate and the second main surface of the support substrate;
An electrolyte disposed in a gap formed between the translucent substrate and the support substrate;
A joining member that joins the electrode formed on the first main surface of the translucent substrate and the electrode formed on the second main surface of the support substrate , which is disposed via the electrolyte and the gap; and comprises a, the joining member, chromium, iron, nickel, cobalt, manganese, or elemental copper or two or more of these compounds, and with there Nde including a glass, a first of said light-transmitting substrate An insulating base is provided on at least one of the electrode formed on the main surface of the support substrate and the bonding member and between the electrode formed on the second main surface of the support substrate and the bonding member. And
The base part has a width wider than the width of the joining member . Before SL bonding member, a photoelectric conversion device according to claim 1, the absorption coefficient for any wavelength in the region of 400~2400nm being greater than said platform portion. The photoelectric conversion device according to claim 2 , wherein the base portion is provided on each of the translucent substrate and the support substrate. Softening point of the bonding member, a photoelectric conversion device according to claim 2 or 3, characterized in that below the softening point of the base part. Softening point of the base unit, according to claim 2 to 4, characterized in that lower than the softening point of the supporting substrate softening or the base part of the translucent substrate in which the base part is provided is provided The photoelectric conversion apparatus in any one of. The photoelectric conversion device according to claim 1, wherein the base portion includes glass. The electrolyte includes at least one selected from volatile organic solvents and ionic liquids, one of the claims 1 to 6, wherein the viscosity of 0.1 Pa · s or more electrolytes, or a gel electrolyte The photoelectric conversion apparatus of crab. The electrolyte, a photoelectric conversion device according to any one of claims 1 to 6 characterized in that it is a solid electrolyte.