JP2010103094A - Photoelectric conversion device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To attain a highly-reliable photoelectric conversion device for maintaining airtightness for a long period. <P>SOLUTION: The photoelectric conversion device includes a base body 20 having a storage section and having a hole 8 for communicating between the storage section and the outside, a photoelectric conversion body 21 housed in the storage section, a hole blocking member 9 for blocking the hole 8, and a protection member 10 connected with the base body 20 so as to cover the hole blocking member 9. A connected section between the protection member 10 and the base body 20 is separated from the hole blocking member 9. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photoelectric conversion device such as 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 carrying a sensitizing dye, a second electrode disposed so as to face the first semiconductor electrode, and the pair of electrodes An electrolyte injected therebetween. This electrolyte is accommodated in the electrolyte chamber so as not to leak outside. In order to inject the electrolyte into the electrolyte chamber, an electrolyte injection hole must be formed in a part of the electrolyte chamber. Therefore, in order to prevent the electrolyte from leaking from the injection hole, the electrolyte chamber is sealed from the outside by a sealing portion or the like. Such a sealing part is double sealed like a first sealing part and a second sealing part provided so as to cover the first sealing part in order to sufficiently suppress leakage to the outside. Some have been stopped (see, for example, Patent Document 1).

JP 2004-119149 A

  However, in the dye-sensitized solar cell disclosed in Patent Document 1, since both the first sealing portion and the second sealing portion are made of resin, the resin deteriorates due to long-term use and is airtight. There was a possibility that reliability would be lowered. In the case where the first sealing portion is made of resin and the second sealing portion is made of glass frit, the first sealing portion and the second sealing portion are in contact with each other. There was a possibility that the first sealing portion formed in would deteriorate.

  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 highly reliable photoelectric conversion device that can maintain hermeticity for a long period of time.

  In order to achieve the above object, in the present invention, a base body having a housing portion and a hole portion that communicates the housing portion with the outside, a photoelectric conversion body housed in the housing portion, and the hole portion are closed. A sealing member and a protective member joined to the base so as to cover the sealing member, and a joint between the protective member and the base is separated from the sealing member Features.

  Moreover, in this invention, it is preferable that the said protection member has the frame body joined to the said base | substrate, and the cover body joined on this frame body.

  In the present invention, it is preferable that the frame body is bonded to the base body via the sealing member and a gap.

  In the present invention, it is preferable that the frame body and the lid body are integrally formed.

  In the present invention, it is preferable that the lid body is in contact with the sealing member.

  Moreover, in this invention, it is preferable that the said cover body is spaced apart from the said sealing member through the space | gap.

  According to the photoelectric conversion device of the present invention, since the joint between the protective member and the base is separated from the sealing member, even if the protective member and the base are joined using heat, the heat is sealed. Difficult to be transmitted to members. As a result, deterioration of the sealing member due to the heat can be reduced, and a highly reliable photoelectric conversion device that can maintain hermeticity for a long period of time can be obtained.

  Further, in the present invention, if the frame is separated from the sealing member via the gap and joined to the base, a gas having a low thermal conductivity such as air is passed between the frame and the sealing member. Since it can be interposed, heat conduction from the frame to the sealing member can be further reduced.

  In the present invention, if the frame body and the lid body are integrally formed, the frame body and the lid body can be easily manufactured, and the joining process of the lid body, the frame body, and the substrate is simplified.

  In the present invention, if the lid is brought into contact with the sealing member, the heat remaining in the sealing member can be conducted to the lid, so that the heat dissipation of the sealing member is improved. Can do.

  In the present invention, if the lid is separated from the sealing member via a gap, heat conducted from the frame through the lid is less likely to be transmitted to the sealing member. Deterioration can be reduced.

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 a figure which shows the evaluation result of a photoelectric conversion apparatus.

  The photoelectric conversion device of the present invention includes a substrate having a housing portion. The base has, for example, a housing portion formed of a pair of substrates and a sealing material by facing a pair of substrates and bonding them with a frame-shaped sealing material. However, the present invention is not limited to this, and a substrate having a recess may be bonded to the lid.

  A photoelectric conversion body is accommodated in the accommodating portion. Photoelectric converters include those that receive light to generate electricity, and those that generate light by conduction. The photoelectric converter includes, for example, semiconductor elements having various shapes such as a chip shape and a layer shape. In addition, the photoelectric converter includes a dye-sensitized photoelectric converter including an electrolyte and a semiconductor on which a dye is adsorbed.

  The base has a hole that communicates the accommodating portion with the outside of the base. The hole may be an injection hole for injecting an electrolyte as a part of the photoelectric converter, an insulating material for sealing the photoelectric converter, or the like into the housing. Further, the hole portion may be a discharge hole for discharging the substrate in the housing portion.

  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 X includes a pair of substrates (hereinafter, referred to as a first substrate 1 and a second substrate 2) disposed so that their principal surfaces face each other, and the first substrate 1 and the second substrate. The first electrode 3 and the second electrode 4 are respectively formed on one main surface of the two. In the photoelectric conversion device X, an electrolyte 5 is disposed in a gap between one main surface of the first substrate 1 and the second substrate 2. In other words, the electrolyte 5 is disposed so as to be sandwiched between the first electrode 3 and the second electrode 4. The periphery of the electrolyte 5 is covered with a sealing material 6 in order to prevent leakage to the outside. In addition, a semiconductor layer 7 carrying a pigment is formed on the first electrode 3. The second substrate 2 and the second electrode 4 are formed with injection holes 8 for injecting the electrolyte 5 from the outside. In the photoelectric conversion device X, a sealing member 9 that closes the injection hole 8 is provided on the other main surface side of the second substrate 2 in order to prevent the electrolyte 5 from leaking to the outside. The sealing member 9 is further covered with a protective member 10. The protection member 10 includes a frame body 10a that is directly bonded to the second substrate 4, and a lid body 10b that is bonded onto the frame body 10a.

In the photoelectric conversion device X according to the embodiment of the present invention, since the frame 10a is joined to the second substrate 2 so as to be separated from the sealing member 9, the frame 10a and the second substrate 2 are joined. Even if they are joined using heat, the heat is not easily transmitted to the sealing member 9. As a result, according to the photoelectric conversion device X, deterioration of the sealing member 9 due to the heat can be reduced. In addition, in the photoelectric conversion device X, since the frame body 10a and the sealing member 9 are separated from each other, the above-described heat can be reduced from being transmitted to the electrolyte 5 through the sealing member 9, so that the heat Decomposition / degeneration of the electrolyte 5 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 3 and the semiconductor layer 7 disposed on the first electrode 3 on one main surface. Further, the first substrate 1 is provided mainly on the light incident side, and thus has a light-transmitting property.

  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 2 supports the second electrode 4 on one main surface. If the second substrate 2 is made of a light-transmitting material similar to the first substrate 1, the light incident surface (light receiving surface) can be further enlarged and the photoelectric conversion efficiency can be increased. . Further, since the second substrate 2 does not have to be located on the light incident side, the second substrate 2 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 4 is not necessary and the number of parts can be reduced. The second substrate 2 is preferably made of titanium, nickel, or tungsten from the viewpoint of improving the corrosion resistance with respect to the electrolyte 5.

  The second substrate 2 has an injection hole 8 for injecting the electrolyte 5 from the outside. The shape of the injection hole 8 is not particularly limited as long as the electrolyte 5 can be injected between the first and second substrates. For example, the cross-sectional shape is circular, elliptical, Alternatively, it may be a polygon such as a quadrangle. The size of the injection hole 8 is preferably about 0.1 to 3 mm in diameter if the cross-sectional shape is circular, for example. In the present embodiment, only one injection hole 8 is provided, but a plurality of injection holes may be provided. Further, in the present embodiment, the injection hole 8 is provided in the second substrate 2, but it may be provided only in the first substrate 1, or may be provided in each of the first and second substrates. Good. The injection hole 8 can be used not only for injecting the electrolyte 5 but also for discharging the electrolyte 5 and injecting and discharging the dye solution.

<First and second electrodes>
The first electrode 3 has a function of extracting a current generated by the semiconductor layer 7 and is provided on one main surface of the first substrate 1. Since the first electrode 3 receives light from the other main surface side of the first substrate 1, it is preferable that the first electrode 3 has a light-transmitting property with respect to visible light.

  The material of the first electrode 3 is, for example, an ITO (tin doped indium oxide: indium tin oxide) layer, an FTO (fluorine doped tin oxide) layer, or a tin oxide layer. In addition, the thickness of the first electrode 3 is preferably about 0.3 to 2 μm from the viewpoint of easy manufacturing and appropriate sheet resistance. Such a 1st electrode 3 is formed in layered form by CVD method, sputtering method, spray method etc., for example.

The second electrode 4 is for passing charge to the electrolyte 5, and is provided on one main surface of the second substrate 2. As the material of the second electrode 4, the same material as that of the first electrode 3, that is, the above-described light-transmitting material may be used if the second substrate 4 is also used as a light receiving portion. On the other hand, if no light is received from the second substrate 4, the second electrode 4 does not have to be made of a translucent material. For example, it is made of a metal material such as titanium, nickel, or tungsten. May be.

  Further, the second electrode 4 is made of Pt, Pd, Ru, Os, Rh, Ir, etc., carbon, PEDOT: TsO (polyethylenedioxythiophene-toluenesulfonate), etc. on the contact surface with the electrolyte 5. If a catalyst layer not shown is formed, charge transfer to the electrolyte 5 can be performed efficiently.

<Electrolyte>
The electrolyte 5 has a function of passing the charge received from the second electrode 4 to the dye supported on the semiconductor layer 7. The electrolyte 5 only needs to be in a state where it can be injected from the injection hole 8. For example, a liquid (electrolytic solution) or a gel can be used, and the electrolyte 5 may be solid after injection.

  When the electrolyte 5 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. In the case where the electrolyte 5 is liquid or gel at the time of injection and becomes solid after injection, the electrolyte 5 is a solid electrolyte such as a gel electrolyte or a polymer electrolyte, a conductive polymer such as polythiophene / polypyrrole or polyphenylene vinylene, or a fullerene derivative, pentacene. Examples thereof include organic molecular electron transport agents such as derivatives, perylene derivatives, and triphenyldiamine derivatives. The thickness of the electrolyte 5, that is, the distance between one main surface of the first substrate 1 and one main surface of the second substrate is preferably about 1 to 500 μm.

<Sealing member>
The sealing member 6 is disposed around the electrolyte 5 so as to confine the electrolyte 5 between the first substrate 1 and the second substrate 2, and is a member for reducing leakage of the electrolyte 5 to the outside. . The sealing member 6 is, for example, a glass material such as glass frit, polyethylene, modified polyethylene, maleic acid-modified polyethylene, polypropylene, modified polypropylene, maleic acid-modified polypropylene, ionomer resin, fluorine resin, epoxy resin, or acrylate resin. The resin material is mentioned. Further, when the sealing member 6 is made of a resin material, the organic material described above is disposed in a portion that contacts the electrolyte 5 and the outer peripheral portion of the organic material is further covered with a glass material. Airtightness and mechanical strength can be increased.

  In the first embodiment, the sealing member 6, the first substrate 1, and the second substrate 2 constitute a base body 20 having an accommodating portion.

<Semiconductor layer>
The semiconductor layer 7 is composed of a porous body having a function of supporting the dye in the pores. Thus, since the porous semiconductor layer 7 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 7 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 7 is a porous body, it has fine pores (the pore diameter is preferably 1 inside).
A large number of those having a thickness of about 0 to 40 nm. Moreover, the thickness of the semiconductor layer 7 is 1-50 micrometers from a viewpoint of optimizing a photoelectric conversion effect | action, More preferably, 10-30 micrometers is good. Further, an ultrathin (thickness: about 200 nm) dense layer of an n-type oxide semiconductor may be inserted between the semiconductor layer 7 and the first electrode 3, which has an effect of suppressing reverse current.

  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 7, 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 7 and can easily transfer the charge from the excited sensitizing dye to the porous semiconductor layer 7.

Examples of the method for adsorbing the pigment on the semiconductor layer 7 include a method of immersing the semiconductor layer 7 formed on the first substrate 1 in a solution in which the pigment is dissolved. As the solvent of the solution for dissolving the dye when adsorbing the dye on the semiconductor layer 7, 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 ).

  In the first embodiment, the photoelectric conversion body 21 is composed of the semiconductor layer 7 on which the dye is adsorbed and the electrolyte 5.

<Sealing member>
The sealing member 9 is a member for preventing the electrolyte 5 sealed between the first and second substrates from leaking to the outside. The sealing member 9 is bonded to the other main surface of the second substrate 2 so as to close the injection hole 8.

  The sealing member 9 includes a resin material having high corrosion resistance with respect to the electrolyte 5. Examples of such resin materials include film-shaped polyethylene, modified polyethylene, maleic acid-modified polyethylene, polypropylene, modified polypropylene, maleic acid-modified polypropylene, ionomer resins, and fluororesins or liquid butyl resins, epoxy resins, and acrylates. Examples thereof include resins. Moreover, these resin materials may contain a filler etc. as needed from a viewpoint of improving mechanical strength.

  The sealing member 9 may be an organic material, an inorganic material, or a composite material thereof, but is preferably an organic material from the viewpoint of easily closing the injection hole 8. In particular, the injection hole 8 can be more easily plugged with a photocurable resin or a thermosetting resin. In other words, the sealing member 9 is made to function as a temporary stopper for closing the injection hole 8 by a simple method to prevent leakage of the electrolyte 5, and the protective member 10 is firmly sealed, thereby improving workability. At the same time, the reliability of sealing can be improved.

<Protective member>
The protective member 10 is a member for protecting the sealing member 9 from the outside by covering the outer surface of the sealing member 9 and further reducing leakage of the electrolyte 5 to the outside. The protection member 10 includes a frame body 10a and a lid body 10b. The protective member 10 does not have the frame body 10a, and may be directly welded to the second substrate 2 by laser irradiation or the like.

  The frame body 10a is formed at a predetermined distance so as to surround the sealing member 9. Further, the frame body 10 a is bonded to the second substrate 2. Thus, since the frame 10a is separated without contacting the sealing member 9, even if the frame 10a is joined to the second substrate 2 by welding or the like using heat, the heat is sealed. 9 is difficult to be transmitted. As a result, in such a form, the thermal deterioration of the sealing member 9 can be reduced. In addition, since the above-described heat can be reduced from being transmitted to the electrolyte 5 through the sealing member 9, decomposition / degeneration of the electrolyte 5 due to the heat can be reduced.

  Even if the gap between the sealing member 9 and the frame 10a is filled with a member having a lower thermal conductivity than the sealing member 9 and the frame 10a, the above-described effects can be obtained. However, if the frame body 10a and the sealing member 9 are separated via a gap as in the present embodiment, a gas having a low thermal conductivity such as air is passed between the frame body 10a and the sealing member 9. Since it can be interposed, heat conduction from the frame 10a to the sealing member 9 can be further reduced.

The material of the frame 10a is preferably a glass frit containing a laser absorbing 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 a 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 2, 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. Moreover, if the 2nd board | substrate 2 is comprised with the material containing glass, the frame 10a and the 2nd board | substrate 2 can be easily joined by laser welding etc. FIG.

  In the frame 10a including such a glass frit, after the glass frit is disposed on the second substrate 2, for example, the glass frit is irradiated with a YAG laser to melt the glass frit, thereby causing the second substrate to melt. 2 is formed by joining. The shape of the frame body 10a is not particularly limited as long as it surrounds at least the sealing member 9, and is circular or polygonal in plan view. However, the upper surface of the frame 10a is preferably flat because the lid 10b is joined.

  The lid body 10b is joined onto the frame body 10a and mainly covers the upper part of the sealing member 9. The material of the lid 10b may be any material that can be joined to the frame 10a by heat welding. For example, glass materials such as blue plate glass, white plate glass, and non-alkali glass, titanium, tantalum, niobium, nickel , Metal materials such as tungsten, stainless steel or aluminum alloy.

  As a method for joining the protective member 10, after the frame body 10a is formed on the lid body 10b, the frame body 10a may be joined to the second substrate 2 by laser heating, or the frame body 10a may be formed on the second substrate 2. After that, the lid body 10b may be joined by laser heating.

  In the example described above, the protective member 10 is joined to the second substrate 2 by melting the frame 10a itself by laser heating, but the present invention is not limited to this. For example, the frame member 10a may be composed of members having different softening points, and the protective member 10 may be bonded to the second substrate 2 by melting only members having a low softening point by laser heating.

  In the photoelectric conversion device X, the lid 10 b is in contact with the sealing member 9. According to such a form, since the heat remaining in the sealing member 9 can be conducted to the lid body 10b, the heat dissipation of the sealing member 9 can be enhanced. From the viewpoint of improving such heat dissipation, it is preferable that the lid 10b is made of a metal material having a relatively high thermal conductivity. In addition, according to such a configuration, even if the electrolyte 5 expands in a high-temperature environment, the sealing member 9 is directly suppressed by the lid body 10b. Therefore, the second substrate of the sealing member 9 Peeling from 2 can be reduced.

  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 X ′ is different from the photoelectric conversion device X in that the lid 10 b is separated from the sealing member 9.

  In the photoelectric conversion device X ′, if the lid 10b is separated from the sealing member 9 via the gap, heat conducted from the frame 10a via the lid 10b is not easily transmitted to the sealing member 9, Thermal deterioration of the hole member 9 can be reduced.

  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 ″ is different from the photoelectric conversion device X in that the sealing member 9 is formed so as to be supported by the inner wall of the injection hole.

  If the sealing member 9 is supported by the inner wall of the injection hole as in the photoelectric conversion device X ″, the protrusion of the sealing member 9 to the other main surface side of the second substrate 2 can be reduced. it can. As a result, the thickness of the frame body 10a is less affected by the thickness of the sealing member 9 protruding to the other main surface side of the second substrate 2, and the degree of freedom of shape of the frame body 10a is increased. If the degree of freedom of shape of the frame 10a increases, the frame 10a can be designed with only strength and ease of formation.

  FIG. 4 is a sectional view showing a fourth embodiment according to the photoelectric conversion device of the present invention. The photoelectric conversion device X ′ ″ is different from the photoelectric conversion devices X, X ′, and X ″ in that the sealing member 9 is bonded to the inner wall of the injection hole and the other main surface of the second substrate 2. .

  If the sealing member 9 is bonded to the inner wall of the injection hole and the other main surface of the second substrate 2 as in the photoelectric conversion device X ′ ″, the sealing member 9 has an increased bonding strength due to an increase in bonding area, In particular, the strength against tensile stress toward the electrolyte 5 can be increased.

  In addition, although the sealing member 9 and the cover body 10b are spaced apart in FIG. 4, it is not limited to such a form. When the sealing member 9 and the lid 10b are brought into contact with each other in the configuration of FIG. 4, the strength of the sealing member 9 can be reinforced by the lid 10b, or the strength of the lid 10b can be reinforced by the sealing member 9. .

  In the above-described embodiment, the frame body 10a and the lid body 10b of the protection member 10 are configured separately. However, in the present invention, the frame body 10a is not limited to such a form. The lid body 10b may be integrally formed. If the protective member 10 is integrally formed in this manner, the frame body 10a and the lid body 10b can be easily manufactured, and the joining process of the frame body 10a, the lid body 10b, and the second substrate 2 can be performed. It becomes simple.

  A specific example of the photoelectric conversion device of this embodiment will be described below in detail with reference to FIG.

<First substrate 1, second substrate 2, first electrode 3, second electrode 4>
A soda lime glass substrate (size 33 mm × 50 mm, thickness about 4 mm) was used as the first substrate 1 and the second substrate. As the first electrode 3 and the second electrode 4, a SnO ₂ : F layer (F-doped SnO ₂ layer) having a sheet resistance of 12Ω / □ (square) was used.

  On the second electrode 4, a Pt layer as a catalyst was formed with a thickness of 1 nm by sputtering. At this time, the Pt layer had a thickness of about 1 nm and was very thin, so it was formed in an island shape. In addition, two injection holes 8 were formed in the second substrate 2 and the second electrode 4.

<Electrolyte 5>
The electrolyte 5 was prepared by adding a methoxypropionitrile solution to iodine (I ₂ ), methylpropylimidazolium iodide (DMPImI), and 1-methylmenzimidazole (MBI), which are liquid electrolytes.

<Sealing member 6>
The sealing member 6 was formed by printing a glass frit paste whose viscosity was adjusted so as to be printed on the second substrate 2 and firing at a temperature 10 degrees lower than the softening point. After forming the TiO ₂ layer of the semiconductor layer 7 to be described later, the first substrate 1 and the second substrate 2 are overlapped so that the sealing member 6 is sandwiched between the first electrode 3 and the second electrode 4, It was sufficiently heated in a furnace and fused so that the electrolyte 5 was not leaked.

<Semiconductor layer 7>
For the semiconductor layer 7, a paste whose viscosity is adjusted so that TiO ₂ fine particles (center particle size 20 nm) can be printed is formed on the first electrode 3 by a printing method, and after drying, TiO ₂ fine particles (center particle size 400 nm) are further formed. A paste whose viscosity was adjusted so as to be printed was printed and laminated, dried, and fired at 480 ° C. to form a TiO ₂ layer.

  After sealing and sealing the sealing member 6 described above, a dye solution in which a dye (Ruthenium 620-1H3TBA, manufactured by Solaronics) is dissolved in ethanol is circulated using the injection hole 8 to adsorb the dye to the semiconductor layer 7 I let you.

<Sealing member 9>
Next, the injection hole 8 was filled with an ultraviolet curable resin and cured by irradiating with an ultraviolet ray to form a sealing member 9.

<Protective member 10>
A glass frit paste having a viscosity adjusted so as to be printed is printed on soda lime glass used as the lid body 10b, and fired at a temperature 10 degrees lower than the softening point to form the frame body 10a. The frame member 10a was installed so as to surround the two sealing holes, and the protective member 10 was formed by heating and sealing with a semiconductor laser.

  The cell formed above was designated as cell A, and cells B and C subjected to organic resin sealing were prepared for comparison of sealing properties.

  The cells B and C are formed by thermocompression bonding using an ionomer resin for the sealing member 6 and the frame 10a, and are not shown in FIG. 3, but the outer peripheral portions of the sealing member 6 and the frame 10a. Is a cell reinforced by applying UV curable resin and UV curing. In cell B, the width of the sealing member 6 was 9.5 mm, and in cell C, the width of the sealing member 6 was 3 mm.

  When these cells were used to perform a moisture resistance test at 85 ° C. and 85% RH, in the cells B and C, bubbles were generated and expanded in the electrolyte solution over time. Observation with a microscope, the bubble area was calculated, and the electrolyte occupancy (the amount of decrease in the electrolyte area relative to the initial electrolyte occupancy area) was calculated. As shown in FIG. In contrast, the area occupied by the electrolyte decreased with the passage of time, whereas in Cell A, no bubbles were generated or expanded even after 3000 hours, and no change was observed in the area occupied by the electrolyte.

  In this way, a photoelectric conversion device capable of hermetically sealing the electrolyte 5 made of an organic solvent even in an environment of 85 ° C. and 85% RH for a long time was produced.

X, X ′, X ″, X ′ ″: photoelectric conversion device 1: first substrate 2: second substrate 3: first electrode 4: second electrode 5: electrolyte 6: sealing member 7 : Semiconductor layer 8: Injection hole (hole)
9: Sealing member 10: Protection member 10a: Frame 10b: Lid 20: Base 21: Photoelectric converter

Claims (6)

A base having a housing and a hole communicating the housing with the outside;
A photoelectric converter housed in the housing section;
A sealing member that closes the hole;
A protective member joined to the base so as to cover the sealing member,
A joint portion between the protective member and the substrate is separated from the sealing member.   The photoelectric conversion device according to claim 1, wherein the protection member includes a frame body bonded to the base body and a lid body bonded to the frame body.   The photoelectric conversion device according to claim 2, wherein the frame body is bonded to the base via the sealing member and a gap.   The photoelectric conversion device according to claim 2, wherein the frame body and the lid body are integrally formed.   The photoelectric conversion device according to claim 2, wherein the lid is in contact with the sealing member.   The photoelectric conversion device according to claim 2, wherein the lid body is separated from the sealing member via a gap.

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