JP5430264B2 - Method for manufacturing photoelectric conversion device - Google Patents

Description

The present invention relates to a method for manufacturing a photoelectric conversion equipment such as 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, the dye-sensitized solar cell disclosed in Patent Document 1 has a problem that the bonding material including the first sealing portion and the second sealing portion is likely to crack due to a change in the external environment. Once a crack has occurred in the bonding material, it can be caused by the thermal stress generated by the thermal cycle, the stress caused by falling objects from the sky, and the penetration of water and other substances into the crack in the environment where the solar cell is used for a long time. Expands.

  When the crack extends, it penetrates the bonding material, and when the crack reaches the interface between the substrate and the bonding material, the bonding material and the substrate are peeled off or a crack is formed so that the entire substrate is peeled off, thereby breaking the sealing of the solar cell. As a result, there has been a problem in that the reliability of the solar cell is deteriorated by intrusion of oxygen and moisture from the outside, leakage of internal components, and volatilization.

  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 capable of maintaining hermeticity and bonding reliability for a long period of time. is there.

  One embodiment of the method for manufacturing a photoelectric conversion device of the present invention includes a step of preparing a base body having a photoelectric conversion body housing portion and a hole portion communicating the housing portion with the outside, and bonding onto the base body A step of placing the lid through the material so as to cover the opening of the hole, and irradiating the bonding material with a laser to bond the lid and the base body with the bonding material, and at the same time, the bonding And a step of forming bubbles in the material.

  According to the present invention, a highly reliable photoelectric conversion device that can maintain hermeticity and bonding reliability for a long period of time can be obtained.

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.

  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 may be a discharge hole for discharging the gas in the housing part.

  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 a hole 8 used for injecting the electrolyte 5 from the outside. In the photoelectric conversion device X, the lid body 10b is bonded to the other main surface side of the second substrate 2 via the bonding material 10a in order to prevent the electrolyte 5 from leaking to the outside. And a bubble 11 is contained in a part of this bonding material 10a. With such a structure having the bubbles 11, crack extension of the bonding material 10 can be suppressed, and a highly reliable photoelectric conversion device capable of maintaining hermeticity for a long period can be obtained.

  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 is provided with a hole 8 used for injecting the electrolyte 5 from the outside. The shape of the 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. As the size of the hole 8, for example, if the cross-sectional shape is circular, the diameter is preferably about 0.1 to 3 mm. In the present embodiment, only one hole 8 is provided, but a plurality of holes 8 may be provided. Further, in the present embodiment, the 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 hole 8 can be used not only for injecting the electrolyte 5 but also for discharging the electrolyte 5, injecting and discharging the dye solution, and the like.

<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, and is made of a metal material such as titanium, nickel, or tungsten, for example. 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 may be in a state where it can be injected from the hole portion 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 addition, when 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 made of, 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.

<Cover body>
The lid 10b is a member for further reducing the leakage of the electrolyte 5 or the entry of oxygen, moisture, etc. from the outside by covering the opening of the hole 8. The lid 10b is bonded to the outer surface of the second substrate 2 via a bonding material 10a. The lid 10b may be made of a material that does not easily transmit the electrolyte 5, oxygen, or moisture, and an inorganic material is particularly preferable. Examples of such an inorganic material include glass materials such as blue plate glass, white plate glass, and non-alkali glass, and metal materials such as titanium, tantalum, niobium, nickel, tungsten, stainless steel, and aluminum alloys.

  The lid body 10b is preferably formed by bonding a member such as a previously formed plate body to the second substrate 2 with a bonding material 10a. Thereby, the lid body 10b does not go through a molten state at the time of joining, and the lid body 10b is less likely to be distorted. As a result, even when stress is applied to the lid 10b, cracks are unlikely to occur in the lid 10b. On the other hand, the bonding material 10a for bonding the lid body 10b to the second substrate 2 is solidified through a molten state. In the present invention, since the bonding material 10a has the bubbles 11, the crack is generated. Also, the progress of cracks can be effectively suppressed by the bubbles 11, and the bonding state can be maintained well.

<Bonding material>
The bonding material 10 a is bonded to the outer surface of the second substrate 2 so as to surround the hole 8. The bonding material 10a partially includes bubbles 11. By doing in this way, even if a crack occurs in the bonding material 10a due to external impact, thermal stress, etc., the extension of the crack can be suppressed.

  The bonding material 10a may be a member different from the lid body 10b, but may be a part of the lid body 10b. When the bonding material 10 a is a part of the lid body 10 b, a part of the lid body 10 b is locally heated with a laser or the like, and this part is melted and bonded to the second substrate 2. At this time, the melted portion corresponds to the bonding material 10a.

  In the bonding material 10a, the bubble 11 is formed with an end portion on the hole 8 side (an end portion on the inner peripheral surface side of the bonding material 10a) and an opposite end portion (an end portion on the outer peripheral surface side of the bonding material 10a). In comparison, it is desirable to have more in the center. That is, in the cross section of the bonding material 10a in a virtual plane orthogonal to the facing surface of the lid 10b and the second substrate 2 and crossing the side surface of the bonding material 10a on the hole 8 side and the side surface on the opposite side, It is desirable that the occupied area is larger at the center than at the end on the hole 8 side and the end on the opposite side. By doing in this way, the expansion | extension of a crack can be suppressed also in the crack generate | occur | produced from the inner side of the joining material 10a, and the crack generated from the outer side.

  Note that the occupied area of the bubbles 11 in the cross section of the bonding material 10a in the virtual plane may be the total area of a plurality of bubbles or the area of one bubble. It is preferable that a plurality of bubbles are formed in the central portion of the bonding material 10a. In this case, since the bonding material 10a has a network structure, the strength can be maintained satisfactorily.

  In addition, in the bonding material 10a, the bubbles 11 are compared with the center portion in the end portion on the hole 8 side (the end portion on the inner peripheral surface side of the bonding material 10a) and the opposite end portion (the outer periphery of the bonding material 10a). Many of them may be present in at least one of the end portions on the surface side. That is, in the cross section of the bonding material 10a in a virtual plane orthogonal to the facing surface of the lid 10b and the second substrate 2 and crossing the side surface of the bonding material 10a on the hole 8 side and the side surface on the opposite side, The occupation area may be such that at least one of the end portion on the hole 8 side and the end portion on the opposite side is larger than the central portion. By doing in this way, the expansion | extension of a crack can be suppressed with the bubble 11 of an edge part, maintaining the joining strength of the joining material 10a firmly in a center part.

  It is preferable that the occupied area of the bubbles 11 in the cross section of the bonding material 10a in the virtual plane is 20 to 80%. With such an occupied area, the extension of cracks can be effectively suppressed and the strength of the bonding material 10a can be maintained well.

  The bubbles 11 are included in the bonding material 10a by adding gas or moisture, and heating the bonding material 10a when bonding the lid 10b and the second substrate 2 via the bonding material 10a. It can be formed by growing the gas or moisture that has been stored as bubbles. Further, a substance that generates gas by heating may be included in the bonding material 10a.

  In particular, when the bonding material 10a is heated by a laser, the bubbles 11 can be locally formed at a desired location of the bonding material 10a. For example, if the lid 10b and the second substrate 2 are bonded to each other by irradiating the central portion of the bonding material 10a with the laser, the bubbles 11 are formed so that the occupied area is larger than the both end portions in the central portion of the bonding material 10a. Can be formed.

  In addition, a pigment or dye that absorbs laser light can be appropriately added to the bonding material 10a so that laser heating can be performed satisfactorily.

  The bonding material 10a is preferably formed on the lid 10b or the second substrate 2 by a screen printing method or a dispensing method. When the bonding material 10a is applied by a screen printing method or a dispensing method, air is likely to be mixed into the bonding material 10a. As a result, when the laser is irradiated, bubbles 11 can be generated well and easily by expanding the mixed air.

In addition, the material of the bonding material 10a may be any material as long as it can bond the lid 10b and the second substrate 2, but is preferably made of glass. When the bonding material 10b is made of glass, since it is a dense material, airtight sealing can be improved. Moreover, it is preferable that the bonding material 10a is locally heated with a laser when the lid 10b and the second substrate 2 are bonded. Thereby, it can suppress effectively that heat is transmitted to the electrolyte 5. The material of the bonding material 10a that can be heated by such a laser is preferably a glass frit containing a laser absorption component and a glass component. The laser absorbing component plays a role of selectively 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 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). Examples of the laser absorbing component include chromium, iron, nickel, cobalt, manganese, copper, or a simple substance or oxide of carbon, or two or more kinds of these compounds. Further, if the second substrate 2 is made of a material containing glass, the bonding material 10a and the second substrate 2 can be easily bonded by laser welding or the like.

  In the bonding material 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, and the second substrate 2 2 is formed by joining. Note that the shape of the bonding material 10a is not particularly limited as long as it surrounds at least the opening of the hole 8 and is circular or polygonal in plan view. However, the upper surface of the bonding material 10a is preferably flat because the lid 10b is bonded.

  As a method for bonding the lid 10b, the bonding material 10a may be formed on the lid 10b and then bonded to the second substrate 2 by laser heating, or the bonding material 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 lid 10b is joined to the second substrate 2 by melting the joining material 10a itself by laser heating, but the invention is not limited thereto. For example, the bonding material 10a may be composed of members having different softening points, and the lid 10b may be bonded to the second substrate 2 by melting only members having a low softening point by laser heating.

<Sealing member>
A sealing member 9 that closes the hole 8 may be formed in the hole 8. 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 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 hole 8. In particular, the hole 8 can be more easily plugged with a photocurable resin or a thermosetting resin. That is, the workability is good by making the sealing member 9 function as a temporary stopper for closing the hole 8 by a simple method and preventing leakage of the electrolyte 5 and performing a strong sealing with the protective member 10. At the same time, the reliability of sealing can be improved.

  Moreover, it is preferable that the bonding material 10a is formed away from the sealing member 9 by a predetermined distance. With such a configuration, even if the bonding material 10 a is bonded to the second substrate 2 by welding using heat or the like, the heat is not easily transmitted to the sealing member 9. 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. In addition, since the bonding material 10a partially includes bubbles, crack extension of the bonding material can be suppressed, and a highly reliable photoelectric conversion device that can maintain hermeticity for a long time can be obtained.

  Even if the gap between the sealing member 9 and the bonding material 10a is filled with a member having a lower thermal conductivity than the sealing member 9 and the bonding material 10a, the above-described effects can be obtained. However, if the bonding material 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 bonding material 10a and the sealing member 9. Since it can be interposed, heat conduction from the bonding material 10a to the sealing member 9 can be further reduced.

  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 bonding material 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 to be supported by the inner wall of the hole 8.

  If the sealing member 9 is supported by the inner wall of the hole 8 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 is reduced. be able to. As a result, the thickness of the bonding material 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 bonding material 10a is increased. If the degree of freedom of shape of the bonding material 10a increases, the bonding material 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 ′, X ″ in that the sealing member 9 is bonded to the inner wall of the hole 8 and the other main surface of the second substrate 2. Is different.

  If the sealing member 9 is bonded to the inner wall of the hole 8 and the other main surface of the second substrate 2 as in the photoelectric conversion device X ′ ″, the sealing member 9 has an adhesive strength due to an increase in the 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. .

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: Hole 9: Sealing member 10 a: Bonding material 10 b: Lid 11: Bubble 20: Substrate 21: Photoelectric converter

Claims (1)

Preparing a base body having a photoelectric conversion body housing portion and a hole portion communicating the housing portion with the outside;
  Placing the lid on the base via a bonding material so as to cover the opening of the hole;
  A method of manufacturing a photoelectric conversion device, comprising: irradiating the bonding material with a laser to bond the lid and the base body with the bonding material, and simultaneously forming bubbles in the bonding material.

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