JP2017034222A - Photoelectric conversion element and photoelectric conversion device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoelectric conversion element which can sufficiently inhibit positional deviation from a holding member when used by being held by the holding member, and a photoelectric conversion device using the element.SOLUTION: A photoelectric conversion element has: a substrate; at least one photoelectric conversion cell provided on the substrate; a back sheet which is fixed to an outer edge of the substrate via an annular attachment part to allow the at least one photoelectric conversion cell between the back sheet and the substrate; and a hard part which is provided inside the attachment part and between the substrate and the back sheet, and which has a Young's modulus larger than that of the attachment part, for sandwiching the back sheet with the holding member when the photoelectric conversion cell is held by the holding member, in which the photoelectric conversion cell has a conductive layer provided on the substrate, a counter substrate which faces the conductive layer and is arranged between the conductive layer and the back sheet, and an oxide semiconductor layer provided between the conductive layer and the counter substrate.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a photoelectric conversion element and a photoelectric conversion apparatus using the photoelectric conversion element.

  A photoelectric conversion device using a dye such as a dye-sensitized solar cell is a next-generation photoelectric conversion device that has attracted attention because it has advantages such as high photoelectric conversion efficiency and low manufacturing cost.

  A photoelectric conversion device using such a dye includes a photoelectric conversion element. In general, a photoelectric conversion element includes a substrate and at least one photoelectric conversion cell provided on the substrate. In addition, in the photoelectric conversion element, an annular and soft adhesive portion such as butyl rubber is further provided on the periphery of the substrate. Some have a back sheet that is fixed via a substrate and at least one photoelectric conversion cell is disposed between the substrate and the substrate (see Patent Document 1 below).

  On the other hand, what has a housing | casing as a holding member holding a photoelectric conversion element is also known as a photoelectric conversion apparatus. The housing generally includes a housing portion that houses the photoelectric conversion element, and a fixing portion that is provided in the housing portion and holds the photoelectric conversion element to the housing portion by pressing the back sheet. In this case, the fixing part of the casing presses the adhesive part through the back sheet.

Japanese Patent Application Laid-Open No. 2014-192008

  However, as described above, the photoelectric conversion element described in Patent Document 1 has the following problems.

  That is, in the photoelectric conversion device including the photoelectric conversion element described in Patent Document 1, since the fixing portion of the casing presses the adhesive portion via the back sheet, when the photoelectric conversion device is placed in a high temperature environment, the adhesive portion As a result, a gap may be formed between the back sheet and the fixed portion of the casing. In this case, the photoelectric conversion element may be displaced from its original position with respect to the casing.

  The present invention has been made in view of the above circumstances, and provides a photoelectric conversion element capable of sufficiently suppressing a positional shift with respect to a holding member when used by being held by a holding member, and a photoelectric conversion device using the photoelectric conversion element. For the purpose.

  In order to solve the above-described problems, the present invention provides a substrate, at least one photoelectric conversion cell provided on the substrate, and is fixed to a peripheral edge portion of the substrate via an annular adhesive portion, and between the substrate. A backsheet on which the at least one photoelectric conversion cell is disposed; and provided between the substrate and the backsheet inside the adhesion portion, having a Young's modulus larger than the adhesion portion, and by a holding member A photoelectric conversion element having a hard part for sandwiching the back sheet together with the holding member when holding the photoelectric conversion cell, wherein the photoelectric conversion cell includes a conductive layer provided on the substrate, and the conductive A photoelectric conversion element having a counter substrate facing the layer and disposed between the conductive layer and the back sheet, and an oxide semiconductor layer provided between the conductive layer and the counter substrate It is.

  According to this photoelectric conversion element, the hard part has a Young's modulus greater than that of the adhesive part that bonds the back sheet and the substrate. For this reason, when the photoelectric conversion element is used while being held by the holding member, the back sheet is firmly held between the holding member and the hard portion as compared with the case where the back sheet is held between the holding member and the adhesive portion. . That is, when the photoelectric conversion element is used while being held by the holding member, the photoelectric conversion element can be firmly fixed by the holding member. For this reason, according to the photoelectric conversion element of this invention, when hold | maintaining and using by a holding member, the position shift of the photoelectric conversion element with respect to a holding member can fully be suppressed.

  In the said photoelectric conversion element, it is preferable that the said hard part is provided on the surface by the side of the said back sheet among the said opposing substrates.

  In this case, when the hard part is not provided on the surface on the backsheet side of the counter substrate, for example, compared to the case where the hard part is provided on the substrate and in the outer region of the photoelectric conversion cell, It is possible to omit an area for installing the hard part on the substrate. For this reason, the area of a board | substrate can be made small and a photoelectric conversion element can be reduced more in size.

  In the photoelectric conversion element, when the hard portion and the oxide semiconductor layer are viewed along the thickness direction of the oxide semiconductor layer, the hard portion and the oxide semiconductor layer overlap each other. It is preferable.

  In this case, even if the holding member is pressed against the hard portion via the back sheet and the counter substrate is bent toward the oxide semiconductor layer, the oxide semiconductor layer sufficiently suppresses the bending of the counter substrate. For this reason, it becomes possible to pinch | interpose a back seat | sheet firmly with a holding member and a hard part. For this reason, the positional shift of the photoelectric conversion element with respect to the holding member can be more sufficiently suppressed.

  In the said photoelectric conversion element, it is preferable that an oxygen scavenger is provided inside the said adhesion part and between the said board | substrate and the said back sheet | seat.

  In this case, since oxygen that has entered the photoelectric conversion element is absorbed by the oxygen scavenger, it is possible to more sufficiently suppress a decrease in power generation performance due to oxygen.

  In the said photoelectric conversion element, it is preferable that a recessed part is formed around the part which is in contact with the said hard part in the said backsheet.

  In this case, the position of the hard part can be easily grasped through the back sheet, compared to the case where the concave part is not formed around the part in contact with the hard part in the back sheet, so the photoelectric conversion element is held by the holding member. When used, the back sheet can be more firmly sandwiched between the holding member and the hard portion.

  Further, the present invention is a photoelectric conversion device comprising a photoelectric conversion element and a holding member that holds the photoelectric conversion element, wherein the photoelectric conversion element is constituted by the photoelectric conversion element, and the holding member is It is a photoelectric conversion apparatus which has the 1st fixing | fixed part which fixes a board | substrate, and the 2nd fixing | fixed part which pinches | interposes the said back sheet with the said hard part.

  According to the photoelectric conversion device of the present invention, the back sheet is firmly sandwiched between the second fixing portion and the hard portion of the holding member, as compared with the case where the back sheet is sandwiched between the holding member and the adhesive portion. That is, the photoelectric conversion element is firmly fixed by the first fixing portion and the second fixing portion of the holding member. For this reason, according to the photoelectric conversion apparatus of this invention, the shift | offset | difference of the position of the photoelectric conversion element with respect to a holding member can fully be suppressed.

  In the photoelectric conversion device, when the second fixing portion and the hard portion of the holding member are viewed along the thickness direction of the oxide semiconductor layer, the hard portion overlaps with the second fixing portion. It is preferable that it extends to the part which does not become.

  In this case, when the second fixing portion and the hard portion of the holding member are viewed along the thickness direction of the oxide semiconductor layer, even if the second fixing portion of the holding member is misaligned with respect to the hard portion, The state in which the back sheet is sandwiched between the second fixed portion and the hard portion of the holding member can be maintained. Moreover, since the area by the side of the 2nd fixed part increases among hard parts, the force added to a photoelectric conversion cell from a hard part can also be disperse | distributed.

  ADVANTAGE OF THE INVENTION According to this invention, when being hold | maintained and used by a holding member, the photoelectric conversion element which can fully suppress the position shift with respect to a holding member, and a photoelectric conversion apparatus using the same are provided.

It is a top view which shows 1st Embodiment of the photoelectric conversion apparatus of this invention. It is a cut surface end view along the II-II line of FIG. It is a cut surface end view which shows the photoelectric conversion cell used for the photoelectric conversion apparatus of FIG. It is a cut surface end view which shows 1 process of the manufacturing method of the photoelectric conversion apparatus of FIG. It is a cut surface end view which shows 1 process of the manufacturing method of the photoelectric conversion apparatus of FIG. It is a top view which shows 2nd Embodiment of the photoelectric conversion apparatus of this invention. FIG. 7 is a cross-sectional end view taken along line VII-VII in FIG. 6. It is a cut surface end view which shows 1 process of the manufacturing method of the photoelectric conversion apparatus of FIG. It is a cut surface end view which shows 1 process of the manufacturing method of the photoelectric conversion apparatus of FIG. It is a cut surface end view which shows 1 process of the manufacturing method of the photoelectric conversion apparatus of FIG. It is a cut surface end view which shows 3rd Embodiment of the photoelectric conversion apparatus of this invention. It is a cut surface end view which shows 4th Embodiment of the photoelectric conversion apparatus of this invention.

<First Embodiment>
Hereinafter, a first embodiment of the photoelectric conversion device of the present invention will be described in detail with reference to FIGS. 1 and 2. FIG. 1 is a plan view showing a first embodiment of the photoelectric conversion device of the present invention, and FIG. 2 is a cross-sectional end view taken along line II-II in FIG.

  As illustrated in FIGS. 1 and 2, the photoelectric conversion device 100 includes a photoelectric conversion element 110 and a housing 120 as a holding member that holds the photoelectric conversion element 110. The photoelectric conversion element 110 is fixed to a transparent substrate 11, a photoelectric conversion cell 70 provided on the transparent substrate 11, and a peripheral portion of the transparent substrate 11 via an annular adhesive portion 60. A back sheet 90 on which the conversion cell 70 is disposed; and a hard portion 80 that is provided inside the adhesive portion 60 and between the transparent substrate 11 and the back sheet 90 and has a Young's modulus greater than that of the adhesive portion 60. ing.

  The photoelectric conversion cell 70 includes a transparent conductive layer 12 as an electrode provided on the transparent substrate 11, a counter substrate 20 facing the transparent conductive layer 12 and disposed between the transparent conductive layer 12 and the back sheet 90, An oxide semiconductor layer 13 provided between the transparent conductive layer 12 and the counter substrate 20, an annular sealing portion 30 provided between the transparent conductive layer 12 and the counter substrate 20, and connecting them, and a sealing portion 30, an electrolyte 40 provided in a cell space formed by the transparent conductive layer 12 and the counter substrate 20. A dye is supported on the oxide semiconductor layer 13.

  The counter substrate 20 is configured as a counter electrode, and includes a conductive substrate 21 serving as a substrate and an electrode, and a catalyst layer 22 provided on the conductive substrate 21.

  The hard part 80 is for sandwiching the back sheet 90 together with the housing 120, and is provided inside the adhesive part 60 and between the transparent substrate 11 and the back sheet 90. Specifically, the hard portion 80 is provided on the surface of the counter substrate 20 on the back sheet 90 side. More specifically, when the hard portion 80 and the oxide semiconductor layer 13 are viewed along the thickness direction of the oxide semiconductor layer 13, the hard portion 80 and the oxide semiconductor layer 13 overlap each other.

  On the other hand, the housing 120 is provided in the first fixing portion 121 that fixes the transparent substrate 11 of the photoelectric conversion element 110 and the first fixing portion 121, and holds the photoelectric conversion element 110 by holding the back sheet 90 to the first fixing portion 121. And a second fixing portion 122 that is fixed together. The first fixing part 121 includes a bottom part 121 a that is in contact with a surface of the transparent substrate 11 opposite to the photoelectric conversion cell 70, and a side wall part 121 b that surrounds the photoelectric conversion element 110. That is, the first fixing part 121 is configured by a housing part that houses the photoelectric conversion element 110. One end (lower end) of the side wall part 121b is connected to the bottom part 121a, and the second fixing part 122 is provided at the other end (upper end) of the side wall part 121b. The photoelectric conversion element 110 is sandwiched between the second fixing portion 122 and the bottom portion 121a. Note that an opening 121c is formed in the bottom 121a of the first fixing part 121 so that light can enter the transparent substrate 11 of the photoelectric conversion element 110.

  The back sheet 90 is sandwiched between the hard part 80 and the second fixing part 122 of the housing 120.

  Furthermore, in this embodiment, as shown in FIG. 1, when the second fixing portion 122 and the hard portion 80 of the housing 120 are viewed along the thickness direction of the oxide semiconductor layer 13, the hard portion 80 is 2 extends to a portion that does not overlap the fixed portion 122.

  According to this photoelectric conversion device 100, the hard portion 80 has a Young's modulus greater than that of the bonding portion 60 that bonds the back sheet 90 and the transparent substrate 11. For this reason, compared with the case where the back sheet 90 is sandwiched between the second fixing portion 122 and the adhesive portion 60 of the housing 120, the back sheet 90 is firmly sandwiched between the fixing portion 122 and the hard portion 80 of the housing 120. In other words, the photoelectric conversion element 110 is firmly fixed to the first fixing portion 121 of the housing 120 by the second fixing portion 122 of the housing 120. For this reason, according to the photoelectric conversion apparatus 100, the position shift of the photoelectric conversion element 110 with respect to the housing | casing 120 can fully be suppressed.

  In the photoelectric conversion device 100, the hard portion 80 is provided on the surface of the counter substrate 20 on the back sheet 90 side. For this reason, when the hard part 80 is not provided on the surface of the counter substrate 20 on the back sheet 90 side, for example, the hard part 80 is provided on the transparent substrate 11 and in the outer region of the photoelectric conversion cell 70. Compared with the case where it has, the area | region for installing the hard part 80 on the transparent substrate 11 can be omitted. For this reason, the area of the transparent substrate 11 can be reduced, and the photoelectric conversion element 110 can be further downsized. Therefore, the photoelectric conversion device 100 can be further downsized.

  Further, in the photoelectric conversion device 100, when the hard portion 80 and the oxide semiconductor layer 13 are viewed along the thickness direction of the oxide semiconductor layer 13, the hard portion 80 and the oxide semiconductor layer 13 overlap each other. Yes. For this reason, even if the second fixing portion 122 of the casing 120 is pressed against the hard portion 80 via the back sheet 90 and the counter substrate 20 is bent toward the oxide semiconductor layer 13 side, it is opposed by the oxide semiconductor layer 13. The bending of the substrate 20 is sufficiently suppressed. For this reason, the back sheet 90 is firmly sandwiched between the second fixing portion 122 and the hard portion 80 of the housing 120. For this reason, the position shift of the photoelectric conversion element 110 with respect to the housing | casing 120 can be suppressed more fully.

  Furthermore, in the photoelectric conversion device 100, when the second fixing portion 122 and the hard portion 80 of the housing 120 are viewed along the thickness direction of the oxide semiconductor layer 13, the hard portion 80 becomes the second fixing portion 122. It extends to the part that does not overlap. For this reason, when the second fixing portion 122 and the hard portion 80 of the housing 120 are viewed along the thickness direction of the oxide semiconductor layer 13, the second fixing portion 122 of the housing 120 is located with respect to the hard portion 80. The back sheet 90 can be kept sandwiched between the second fixing portion 122 and the hard portion 80 of the housing 120 even if they are misaligned. Moreover, since the area by the side of the 2nd fixing | fixed part 122 among the hard parts 80 increases, the force added to the photoelectric conversion cell 70 from the hard part 80 can also be disperse | distributed.

  Next, the photoelectric conversion element 110 and the housing 120 will be described in detail.

≪Photoelectric conversion element≫
The photoelectric conversion element 110 has a transparent substrate 11, a photoelectric conversion cell 70, an adhesive part 60, a back sheet 90, and a hard part 80. Therefore, these will be described in detail below.

<Transparent substrate>
The material which comprises the transparent substrate 11 should just be a transparent material, for example, As such a transparent material, glass, such as borosilicate glass, soda lime glass, white plate glass, quartz glass, polyethylene terephthalate (PET), for example , Polyethylene naphthalate (PEN), polycarbonate (PC), and polyethersulfone (PES). The thickness of the transparent substrate 11 is appropriately determined according to the size of the photoelectric conversion element 100 and is not particularly limited, but may be in the range of 50 to 10,000 μm, for example.

<Photoelectric conversion cell>
The photoelectric conversion cell 70 includes the transparent conductive layer 12, the counter substrate 20, the oxide semiconductor layer 13, the sealing portion 30, the electrolyte 40, and a dye supported on the oxide semiconductor layer 13. . Hereinafter, these will be described in detail.

(Transparent conductive layer)
Examples of the material constituting the transparent conductive layer 12 include conductive metal oxides such as tin-added indium oxide (ITO), tin oxide (SnO ₂ ), and fluorine-added tin oxide (FTO). The transparent conductive layer 12 may be a single layer or a laminate of a plurality of layers made of different conductive metal oxides. When the transparent conductive layer 12 is composed of a single layer, the transparent conductive layer 12 is preferably composed of FTO because it has high heat resistance and chemical resistance. The thickness of the transparent conductive layer 12 may be in the range of 0.01 to 2 μm, for example.

(Opposite substrate)
As described above, the counter substrate 20 includes the conductive substrate 21 serving as a substrate and an electrode, and the catalyst layer 22.

  The conductive substrate 21 is made of a corrosion-resistant metal material such as titanium, nickel, platinum, molybdenum, tungsten, aluminum, and stainless steel. The conductive substrate 21 may be formed of a laminate in which a substrate and an electrode are separated and a conductive layer made of a conductive oxide such as ITO or FTO is formed on a resin film as an electrode. A laminate in which a conductive layer made of a conductive oxide such as FTO is formed may be used. The thickness of the conductive substrate 21 is appropriately determined according to the size of the photoelectric conversion element 110 and is not particularly limited, but may be, for example, 0.01 to 4 mm.

  The catalyst layer 22 is composed of platinum, a carbon-based material, a conductive polymer, or the like.

(Oxide semiconductor layer)
The oxide semiconductor layer 13 is composed of oxide semiconductor particles. Examples of the oxide semiconductor particles include titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), zinc oxide (ZnO), tungsten oxide (WO ₃ ), niobium oxide (Nb ₂ O ₅ ), and strontium titanate (SrTiO ₃ ). , Tin oxide (SnO ₂ ), or two or more of these. The thickness of the oxide semiconductor layer 13 may be 0.1 to 100 μm, for example.

(Sealing part)
Examples of the sealing portion 30 include thermoplastic resins such as modified polyolefin resins and vinyl alcohol polymers, and resins such as ultraviolet curable resins. Examples of modified polyolefin resins include ionomers, ethylene-vinyl acetic anhydride copolymers, ethylene-methacrylic acid copolymers, and ethylene-vinyl alcohol copolymers. These resins can be used alone or in combination of two or more.

(Electrolytes)
The electrolyte 40 includes a redox couple and an organic solvent. As the organic solvent, acetonitrile, methoxyacetonitrile, methoxypropionitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, γ-butyrolactone, valeronitrile, pivalonitrile, and the like can be used. Examples of the redox pair include a redox pair containing a halogen atom such as iodide ion / polyiodide ion (for example, I ⁻ / I ₃ ⁻ ), bromide ion / polybromide ion, zinc complex, iron complex, cobalt complex, and the like. And redox pairs. The iodide ion / polyiodide ion can be formed by iodine (I ₂ ) and a salt (ionic liquid or solid salt) containing iodide (I ⁻ ) as an anion. When using an ionic liquid having an iodide as an anion, only iodine should be added. When using an ionic liquid other than an organic solvent or an anion as an anion, an anion such as LiI or tetrabutylammonium iodide is used. A salt containing iodide (I ⁻ ) may be added. The electrolyte 40 may use an ionic liquid instead of the organic solvent. As the ionic liquid, for example, known iodine salts such as pyridinium salts, imidazolium salts, triazolium salts, and the like are used. Examples of such iodine salts include 1-hexyl-3-methylimidazolium iodide, 1-ethyl-3-propylimidazolium iodide, 1-ethyl-3-methylimidazolium iodide, 1,2- Dimethyl-3-propylimidazolium iodide, 1-butyl-3-methylimidazolium iodide, or 1-methyl-3-propylimidazolium iodide is preferably used.

  In addition, the electrolyte 40 may use a mixture of the ionic liquid and the organic solvent instead of the organic solvent.

  An additive can be added to the electrolyte 40. Examples of the additive include benzimidazoles such as 1-methylbenzimidazole (NMB) and 1-butylbenzimidazole (NBB), LiI, tetrabutylammonium iodide, 4-t-butylpyridine, and guanidinium thiocyanate. . Among them, benzimidazole is preferable as an additive.

Further, as the electrolyte 40, a nano-composite gel electrolyte, which is a pseudo-solid electrolyte formed by kneading nanoparticles such as SiO ₂ , TiO ₂ , carbon nanotubes, etc. into the electrolyte, may be used, and polyvinylidene fluoride may be used. Alternatively, an electrolyte gelled with an organic gelling agent such as a polyethylene oxide derivative or an amino acid derivative may be used.

(Dye)
Examples of the dye include a photosensitizing dye such as a ruthenium complex having a ligand including a bipyridine structure, a terpyridine structure, etc., an organic dye such as porphyrin, eosin, rhodamine, and merocyanine, and an organic substance such as a lead halide-based perovskite crystal. -An inorganic composite pigment | dye etc. are mentioned. For example, CH ₃ NH ₃ PbX ₃ (X = Cl, Br, I) is used as the lead halide perovskite. Among the above dyes, a ruthenium complex having a ligand containing a bipyridine structure or a terpyridine structure is preferable. In this case, the photoelectric conversion characteristics of the photoelectric conversion device 100 can be further improved. In addition, when using a photosensitizing dye as a pigment | dye, the photoelectric conversion apparatus 100 becomes a dye-sensitized photoelectric conversion apparatus.

<Adhesive part>
The material constituting the bonding part 60 may be any material that can bond the back sheet 90 and the transparent substrate 11. Examples of the material constituting the bonding part 60 include butyl rubber, nitrile rubber, and thermoplastic resin. . These can be used alone or in combination of two or more. Although the thickness of the adhesion part 60 is not specifically limited, For example, what is necessary is just 300-1000 micrometers.

<Back sheet>
The back sheet 90 is formed of a laminate including a weather resistant layer and a metal layer.

  The weather resistant layer may be made of, for example, polyethylene terephthalate or polybutylene terephthalate. The thickness of the weather resistant layer may be, for example, 50 to 300 μm.

  The metal layer should just be comprised with the metal material containing aluminum, for example. The metal material is usually composed of aluminum alone, but may be an alloy of aluminum and another metal. Examples of other metals include copper, manganese, zinc, magnesium, lead, and bismuth. Specifically, 1000 series aluminum obtained by adding a trace amount of other metals to 98% or more pure aluminum is desirable. This is because the 1000 series aluminum is cheaper and more workable than other aluminum alloys. Although the thickness of a metal layer is not specifically limited, For example, what is necessary is just 12-30 micrometers.

  The laminate may further include a resin layer. Examples of the material constituting the resin layer include butyl rubber, nitrile rubber, thermoplastic resin, and the like. These can be used alone or in combination of two or more. The resin layer may be formed on the entire surface of the metal layer opposite to the weather-resistant layer, or may be formed only on the peripheral edge.

<Hard part>
The hard part 80 is preferably bonded to the surface of the counter substrate 20 opposite to the transparent conductive layer 12. In this case, since the hard part 80 is firmly fixed to the surface of the counter substrate 20 opposite to the transparent conductive layer 12, the positional deviation of the hard part 80 with respect to the second fixing part 122 of the housing 120 is sufficiently suppressed. The

  The hard portion 80 may or may not be bonded to the back sheet 90, but is preferably not bonded. In this case, when the photoelectric conversion device 100 is placed at a high temperature and the air between the counter substrate 20 and the back sheet 90 expands and the back sheet 90 is deformed, the bonded hard portion 80 is stressed and peeled off. This is less likely to happen.

  As long as the hard part 80 has a Young's modulus larger than the adhesion part 60, what kind of thing may be sufficient as it. For example, when butyl rubber, nitrile rubber, thermoplastic resin, or the like is used as a material constituting the bonding portion 60, the hard portion 80 may be made of glass, thermosetting resin, ceramics, or the like.

  The ratio (Y2 / Y1) of the Young's modulus Y2 of the hard portion 80 to the Young's modulus Y1 of the bonded portion 60 is not particularly limited as long as it is larger than 1, but is preferably 2 to 50000.

<< Case >>
Next, the housing 120 will be described in detail.

  The housing 120 includes a first fixing part 121 and a second fixing part 122. Hereinafter, these will be described in detail.

<First fixing part>
The 1st fixing | fixed part 121 should just have the shape which can accommodate the photoelectric conversion element 110 by the bottom part 121a and the side wall part 121b.

  As a material constituting the first fixing portion 121, for example, polypropylene, polycarbonate, polyimide, polybutylene terephthalate, phenol resin, epoxy resin, metal such as aluminum, ceramics, or the like can be used.

<Second fixing part>
The second fixing portion 122 can press the hard portion 80 via the back sheet 90. For this reason, when there is only one hard part 80, the second fixing part 122 is also constituted by only one. When there are three or more hard portions 80, the same number of second fixing portions 122 as the hard portions 80, that is, three or more second fixing portions 122 are provided. When three second fixing portions 122 are provided, the second fixing portion 122 is provided at the upper end (the end opposite to the bottom portion 121a) of the three side wall portions 121b among the four side wall portions 121b in FIG. It is done. The second fixing part 122 is usually integrally formed with the first fixing part 121. That is, the second fixing part 122 is usually made of the same material as the first fixing part 121. However, the second fixing part 122 may be made of a material different from that of the first fixing part 121.

  Next, the manufacturing method of the photoelectric conversion apparatus 100 mentioned above is demonstrated, referring FIGS. 3 is a cross-sectional end view of the photoelectric conversion cell used in the photoelectric conversion device of FIG. 2, and FIGS. 4 and 5 are cross-sectional end views showing one step of the method of manufacturing the photoelectric conversion device of FIG.

  First, a photoelectric conversion cell 70 shown in FIG. 3 is prepared. Next, as shown in FIG. 4, the hard part 80 is installed on the counter substrate 20 of the photoelectric conversion cell 70. Next, the back sheet 90 is prepared, and as shown in FIG. 5, the back sheet 90 and the transparent substrate 11 are bonded together in the air, that is, under atmospheric pressure, via the annular bonding portion 60. In this way, the photoelectric conversion element 110 is obtained.

  Next, as shown in FIG. 2, the photoelectric conversion element 110 obtained as described above is accommodated in the first fixing portion 121 of the housing 120, and the back sheet 90 is attached to the second portion of the hard portion 80 and the housing 120. The photoelectric conversion element 110 is fixed to the housing 120 by being sandwiched between the fixing portions 122.

  The photoelectric conversion apparatus 100 is obtained as described above.

Second Embodiment
Next, a second embodiment of the photoelectric conversion device of the present invention will be described in detail with reference to FIGS. FIG. 6 is a plan view showing a second embodiment of the photoelectric conversion device of the present invention, and FIG. 7 is a cross-sectional end view taken along the line VII-VII in FIG.

  As shown in FIGS. 6 and 7, the photoelectric conversion device 200 is different from the photoelectric conversion device 100 of the first embodiment in that the photoelectric conversion element 210 is configured as follows. That is, in the photoelectric conversion element 210, a portion where the oxygen scavenger 250 is further provided between the counter substrate 21 and the back sheet 90 inside the bonding portion 60 and is in contact with the hard portion 80 in the back sheet 90. A recess 92 is formed around 91.

  In the photoelectric conversion device 200 of the present embodiment, the height of the oxygen scavenger 250 is lower than the height of the hard portion 80 as shown in FIG. In this case, when the portion of the second fixing portion 122 that comes into contact with the hard portion 80 has a flat plate shape and the second fixing portion 122 is disposed so as to face the oxygen absorber 250, the height of the oxygen absorber 250 is increased. Can be made closer to the counter substrate 20 side than when the height is equal to or higher than the height of the hard portion 80. For this reason, the photoelectric conversion apparatus 200 can be made thinner. Further, when the portion of the second fixing portion 122 that contacts the hard portion 80 is flat and the second fixing portion 122 is disposed so as to face the oxygen scavenger 250, the oxygen scavenger 250 has a high height. Compared to the case where the height is greater than or equal to the height of the portion 80, the back sheet 90 can be firmly sandwiched between the second fixing portion 122 and the hard portion 80. Can be suppressed.

  According to the photoelectric conversion device 200 of the present embodiment, in the photoelectric conversion element 210, oxygen that has entered between the counter substrate 20 and the back sheet 90 is absorbed by the oxygen scavenger 250, so that the power generation performance is reduced by oxygen. Can be more sufficiently suppressed.

  Next, the oxygen scavenger 250 will be described in detail.

<Oxygen scavenger>
The oxygen scavenger 250 is not particularly limited as long as it absorbs oxygen. For example, a metal powder such as iron powder or zinc powder, or an inorganic compound having oxygen defects subjected to reduction treatment (titanium dioxide, oxide) Zinc, cerium oxide, iron oxide, etc.), easily oxidizable unsaturated organic compounds, or those obtained by kneading them with resins such as polyolefin, polyester, polyurethane and the like. These are comprised individually or in mixture of 2 or more types. Especially, what mixed the inorganic compound which has the oxygen defect which gave the reduction process with polyolefin is preferable. In this case, the oxygen scavenger 250 can be easily molded and high oxygen scavenging performance can be obtained.

  The position where the oxygen scavenger 250 is installed is not particularly limited, but is preferably provided between the two hard portions 80. In this case, the photoelectric conversion device 200 can be firmly fixed by the housing 120 without applying stress to the oxygen scavenger 250.

  Next, a method for manufacturing the above-described photoelectric conversion device 200 will be described with reference to FIGS. 3 and 7 to 10. 8 to 10 are sectional end views showing one step of the method of manufacturing the photoelectric conversion device of FIG.

  First, a photoelectric conversion cell 70 shown in FIG. 3 is prepared. Next, as shown in FIG. 8, the hard portion 80 and the oxygen scavenger 250 are installed on the counter substrate 20 of the photoelectric conversion cell 70. At this time, the height of the oxygen scavenger 250 is set lower than the height of the hard portion 80. Next, a back sheet 90 is prepared, and as shown in FIG. 9, the back sheet 90 and the transparent substrate 11 are bonded together in the air, that is, under atmospheric pressure, via the annular bonding portion 60. Thus, the structure 211 is obtained by sealing the space between the back sheet 90 and the transparent substrate 11.

  Next, by leaving the structure 211 obtained as described above, oxygen in the space between the back sheet 90 and the transparent substrate 11 is absorbed by the oxygen scavenger 250, and the back sheet 90 and the transparent substrate 11 are absorbed. The space between is reduced. As a result, the portion around the hard portion 80 in the backsheet 90 bends toward the counter substrate 20, and as shown in FIG. 10, the recess 92 is formed around the portion 91 in contact with the hard portion 80 in the backsheet 90. It is formed.

  Next, as shown in FIG. 7, the photoelectric conversion element 210 is fixed to the first fixing portion 121 of the housing 120, and the back sheet 90 is sandwiched between the hard portion 80 and the second fixing portion 122 of the housing 120. Thus, the photoelectric conversion element 210 is fixed to the housing 120.

  The photoelectric conversion device 200 is obtained as described above.

  According to the above manufacturing method, since the concave portion 92 is formed around the portion 91 in contact with the hard portion 80 in the backsheet 90, it is easy to grasp the position of the hard portion 80 through the backsheet 90. Therefore, the back sheet 90 can be more firmly sandwiched between the second fixing portion 122 and the hard portion 80 of the housing 120, and the positional deviation of the photoelectric conversion element 210 with respect to the housing 120 can be sufficiently suppressed. Further, when the oxygen scavenger 250 is provided in the middle of the two hard portions 80 when the photoelectric conversion device 200 is manufactured, the concave portions 92 formed around the two hard portions 80 have the same shape, and two hard portions are formed. It becomes easier to grasp the position of the portion 80.

  Moreover, according to the manufacturing method, the height of the oxygen scavenger 250 is lower than the height of the hard portion 80, so that it becomes easier to grasp the position of the hard portion 80 from above the back sheet 90. Therefore, the back sheet 90 can be more firmly sandwiched between the second fixing portion 122 and the hard portion 80 of the housing 120, and the positional deviation of the photoelectric conversion element 210 with respect to the housing 120 can be more sufficiently suppressed. Further, since the height of the oxygen scavenger 250 is lower than the height of the hard portion 80, the oxygen scavenger 250 may become an obstacle when the back sheet 90 is sandwiched between the second fixing portion 122 and the hard portion 80. Absent.

  Furthermore, according to the manufacturing method described above, even when the photoelectric conversion device 200 is manufactured in the air, that is, under atmospheric pressure, oxygen is absorbed by the oxygen scavenger 250, so that a decrease in power generation performance due to oxygen can be suppressed.

  The present invention is not limited to the above embodiment. For example, in the above embodiment, when the hard portion 80 and the oxide semiconductor layer 13 are viewed along the thickness direction of the oxide semiconductor layer 13, the hard portion 80 and the oxide semiconductor layer 13 overlap each other. The hard portion 80 and the oxide semiconductor layer 13 do not necessarily overlap each other. For example, like the photoelectric conversion device 300 shown in FIG. 11, the hard portion 80 may be provided on the transparent substrate 11 and in a region outside the photoelectric conversion cell 70.

  In the above embodiment, when the second fixing portion 122 and the hard portion 80 of the housing 120 are viewed along the thickness direction of the oxide semiconductor layer 13, the hard portion 80 does not overlap the second fixing portion 122. Although it extends to the portion, the hard portion 80 may not extend to a portion that does not overlap the second fixing portion 122. That is, the entire hard portion 80 may overlap the second fixing portion 122.

  Furthermore, in the photoelectric conversion devices 100, 200, and 300 of the above embodiment, the oxide semiconductor layer 13 is provided on the transparent conductive layer 12, but the oxide semiconductor layer 13 may be provided on the counter substrate 20. However, in this case, the catalyst layer 22 is provided on the transparent conductive layer 12.

  Furthermore, in the above embodiment, the counter substrate 20 is configured with a counter electrode, but the counter substrate 20 may be configured with an insulating substrate. However, in this case, the transparent conductive layer 12 and the counter substrate 20 are sequentially formed from the transparent conductive layer 12 side by the oxide semiconductor layer 13, the porous insulating layer impregnated with the electrolyte 40, and the counter electrode. A laminate is provided.

  In the above embodiment, the photoelectric conversion devices 100, 200, and 300 have only one photoelectric conversion cell 70, but the photoelectric conversion device 100 may include a plurality of photoelectric conversion cells 70. Here, the plurality of photoelectric conversion cells 70 may be connected in series or may be connected in parallel.

  Furthermore, in the said embodiment, the 1st fixing | fixed part 121 is comprised by the bottom part 121a contact | abutted to the surface on the opposite side to the photoelectric conversion cell 70 among the transparent substrates 11, and the side wall part 121b surrounding the photoelectric conversion element 110. The first fixing part 121 accommodates the photoelectric conversion elements 110 and 210 by connecting one end (lower end) of the side wall part 121b to the bottom part 121a, but the first fixing part 121 includes the photoelectric conversion element 110, The transparent substrate 11 of 210 may be fixed, and in the first fixing part 121, the side wall part 121 b may not surround the photoelectric conversion elements 110 and 210. That is, the first fixing portion 121 may not be configured by a housing portion that houses the photoelectric conversion elements 110 and 210.

  Furthermore, in the second embodiment, the height of the oxygen scavenger 250 is lower than the height of the hard portion 80, but the height of the oxygen scavenger 250 is equal to or higher than the height of the hard portion 80. Also good.

  In the second embodiment, the hard part 80 and the oxygen scavenger 250 are provided separately. However, when the hard part 80 contains a material that absorbs oxygen, that is, the hard part 80 also serves as the oxygen scavenger 250. In some cases, the oxygen scavenger 250 may be omitted.

  Further, in the second embodiment, a desiccant may be further provided between the transparent substrate 11 and the back sheet 90 inside the adhesive portion 60. Here, when the hard part 80 includes a material that absorbs moisture, that is, when the hard part 80 also serves as a desiccant, the desiccant may be omitted. Furthermore, when the hard part 80 includes a material that absorbs moisture and oxygen, the oxygen scavenger and the desiccant may be omitted.

  Furthermore, in the said 2nd Embodiment, although the photoelectric conversion apparatus 200 is manufactured in the air, ie, atmospheric pressure, the photoelectric conversion apparatus 200 may be manufactured under reduced pressure. In this case, the amount of oxygen inside the photoelectric conversion element 210 can be more sufficiently reduced. Therefore, it is possible to more sufficiently suppress a decrease in power generation performance due to oxygen. In addition, since the space between the back sheet 90 and the transparent substrate 11 has already been reduced in pressure when the back sheet 90 is bonded, the recess 92 is formed before the oxygen scavenger 250 absorbs oxygen. Accordingly, the time required for manufacturing the photoelectric conversion device 200 is shortened.

  Also in the first embodiment, the photoelectric conversion device 100 is manufactured in air, that is, under atmospheric pressure, but may be manufactured under reduced pressure. In this case, as in the photoelectric conversion device 400 shown in FIG. 12, in the photoelectric conversion element 110, the concave portion 92 is formed around the hard portion 80 even without the oxygen scavenger 250, so It becomes easy to grasp the position of the portion 80. Therefore, the back sheet 90 can be more firmly sandwiched between the fixed portion 122 and the hard portion 80 of the housing 120, and the photoelectric conversion device 400 manufactured under reduced pressure can be positioned relative to the housing 120 of the photoelectric conversion element 110. The deviation can be more sufficiently suppressed.

11 ... Transparent substrate (substrate)
12 ... Transparent conductive layer (conductive layer)
DESCRIPTION OF SYMBOLS 13 ... Oxide semiconductor layer 20 ... Opposite substrate 60 ... Adhesion part 70 ... Photoelectric conversion cell 80 ... Hard part 90 ... Back sheet 100,200,300,400 ... Photoelectric conversion apparatus 110,210 ... Photoelectric conversion element 120 ... Case 121 ... 1st fixing | fixed part 122 ... 2nd fixing | fixed part 211 ... Structure 250 ... Oxygen absorber

Claims (7)

A substrate,
At least one photoelectric conversion cell provided on the substrate;
A back sheet that is fixed to a peripheral portion of the substrate via an annular adhesive portion, and the at least one photoelectric conversion cell is disposed between the substrate and the substrate;
It is provided between the substrate and the back sheet inside the adhesion part, has a Young's modulus larger than the adhesion part, and holds the photoelectric conversion cell together with the holding member when the photoelectric conversion cell is held by a holding member. A photoelectric conversion element having a hard part for sandwiching the backsheet,
The photoelectric conversion cell is
A conductive layer provided on the substrate;
A counter substrate disposed opposite the conductive layer and disposed between the conductive layer and the back sheet;
A photoelectric conversion element including the conductive layer and an oxide semiconductor layer provided between the counter substrate.   The photoelectric conversion element according to claim 1, wherein the hard portion is provided on a surface of the counter substrate on the backsheet side.   The hard part and the oxide semiconductor layer overlap each other when the hard part and the oxide semiconductor layer are viewed along the thickness direction of the oxide semiconductor layer. Photoelectric conversion element.   The photoelectric conversion element according to any one of claims 1 to 3, wherein an oxygen scavenger is provided between the substrate and the back sheet inside the adhesion portion.   The photoelectric conversion element as described in any one of Claims 1-4 in which a recessed part is formed around the part which is in contact with the said hard part in the said back sheet. A photoelectric conversion element;
A photoelectric conversion device comprising a holding member for holding the photoelectric conversion element,
The photoelectric conversion element comprises the photoelectric conversion element according to any one of claims 1 to 5,
The holding member is
A first fixing part for fixing the substrate;
A photoelectric conversion device comprising: a second fixing portion that sandwiches the back sheet together with the hard portion.   When the second fixing portion and the hard portion of the holding member are viewed along the thickness direction of the oxide semiconductor layer, the hard portion extends to a portion that does not overlap the second fixing portion. The photoelectric conversion device according to claim 6.

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