Method for producing photoelectric conversion element, and photoelectric conversion element

Abstract

A method for producing a photoelectric conversion element according to the present disclosure comprises: (A) forming a first electrode layer on a gas barrier layer; (B) removing a portion of the first electrode layer using a pulsed laser to form through holes that penetrate the first electrode layer and partially overlap each other; (C) forming a light absorption layer on the first electrode layer and the gas barrier layer exposed by the through holes; and (D) forming a second electrode layer on the light absorption layer.

Description

Photoelectric conversion element manufacturing method and photoelectric conversion element

[0001] The present disclosure relates to a method for manufacturing a photoelectric conversion element and the photoelectric conversion element.

[0002] In recent years, solar cells have become increasingly important as a renewable energy source. Solar cells consist of a photoelectric conversion element that converts light energy into electrical energy. Furthermore, as described in Non-Patent Document 1, research and development of flexible photoelectric conversion elements in which photoelectric conversion elements are formed on flexible substrates has been actively conducted.

[0003] Japanese Unexamined Patent Publication No. 2022-34875 Patent No. 5734437 H. S. Jung et al. Joule 3, 1850 (2019) J. Dagar et al. Nano Research 11(5), 2669 (2018)

[0004] The present disclosure provides a method for manufacturing a photoelectric conversion element that produces a photoelectric conversion element that has both high durability and uniform appearance.

[0005] The method for manufacturing a photoelectric conversion element according to the present disclosure includes: (A) forming a first electrode layer on a gas barrier layer; (B) removing a portion of the first electrode layer using a pulsed laser to form through-holes that penetrate the first electrode layer and overlap a portion of a plurality of holes; (C) forming a light absorbing layer on the first electrode layer and on the gas barrier layer exposed by the through-holes; and (D) forming a second electrode layer on the light absorbing layer.

[0006] The present disclosure provides a method for manufacturing a photoelectric conversion element that produces a photoelectric conversion element that has both high durability and uniform appearance.

[0007] 1 is a schematic cross-sectional view illustrating a method for manufacturing a photoelectric conversion element according to a first embodiment of the present disclosure. ave 3 is an explanatory diagram for explaining a method for determining the overlap of pulses irradiated to continuously form circular through-holes and the minimum value L of the line width L of the linear through-holes to be formed. min and the ratio L min / L ave 4A is an explanatory diagram for explaining the relationship between the ratio Lmin / L ave 4B is a schematic diagram showing a linear through hole formed by successively forming circular through holes formed by irradiation of one pulse for a linear through hole having a ratio L of 0.57. min / L ave FIG. 5 is a schematic diagram showing linear through holes formed by continuously forming circular through holes formed by irradiating one pulse with respect to linear through holes having a refractive index of 0.91. FIG. 5 is a schematic cross-sectional view showing an example of a photoelectric conversion element according to a first embodiment of the present disclosure. FIG. 6 is a schematic cross-sectional view showing a modified example of the photoelectric conversion element according to the first embodiment of the present disclosure. FIG. 7 is a schematic cross-sectional view showing a photoelectric conversion module, which is a photoelectric conversion element according to a second embodiment of the present disclosure. FIG. 8A is a scanning electron microscope (SEM) image of a partial cross section of the photoelectric conversion element of Example 1. FIG. 8B is a partial top-view SEM image taken from the top of a portion of the first electrode layer in which through holes are formed in Example 1. FIG. 8C is a cross-sectional SEM image of the photoelectric conversion element of Example 1.

[0008] [Knowledge forming the basis of the present disclosure] When a flexible substrate is used for a photoelectric conversion element, a base material containing an organic material, such as a transparent organic material film, is used as the substrate in consideration of light transmittance. Furthermore, to improve the durability of the photoelectric conversion element, it is necessary to prevent gas from entering the element. In particular, in organic solar cells and perovskite solar cells, it is necessary to prevent water vapor from entering. Note that "perovskite solar cell" refers to a solar cell containing a perovskite compound.

[0009] Therefore, as shown in Patent Document 1, a method of forming a thin-film gas barrier layer on a base material containing an organic material, such as an organic film, is commonly used to ensure the gas barrier properties of the substrate. Meanwhile, when fabricating a photoelectric conversion element, it is common to pattern electrodes for the purpose of preventing short circuits and leakage currents, or for the purpose of properly operating the photoelectric conversion element, such as fabricating an integrated module in which multiple cells are integrated. Therefore, when a base material containing an organic material provided with a gas barrier layer is used as the substrate, it is necessary to form patterned electrodes on the gas barrier layer when fabricating the photoelectric conversion element.

[0010] Methods for forming patterned electrodes include a formation method using a mask and a formation method using etching. However, these methods have the problem that the width of the electrode removal portion for patterning cannot be reduced, resulting in non-uniform appearance. Furthermore, as disclosed in Patent Document 2 and Non-Patent Documents 1 and 2, a laser scribing method is also known in which a patterned electrode is formed by removing the electrode using a nanosecond pulse laser. However, when using a laser scribing method to pattern an electrode provided on a gas barrier layer, not only the electrode but also the gas barrier layer is removed or damaged, resulting in a problem of reduced durability as an element.

[0011] The present inventors have conducted extensive research to obtain a photoelectric conversion element that combines high durability with uniformity in appearance, and have created the manufacturing method for the photoelectric conversion element of the present disclosure and the photoelectric conversion element of the present disclosure.

[0012] [Embodiments of the Present Disclosure] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings.

[0013] 1 is a schematic cross-sectional view illustrating a method for manufacturing a photoelectric conversion element according to a first embodiment of the present disclosure. The method for manufacturing a photoelectric conversion element according to the first embodiment includes: (A) forming a first electrode layer 3 on the gas barrier layer 2 of a gas barrier layer-attached substrate including a substrate 1 containing an organic material and a gas barrier layer 2 provided on a first main surface 1a of the substrate 1 (see FIG. 1( a)); (B) removing a portion of the first electrode layer 3 using a pulsed laser having a pulse width of less than 1 ns to form linear through-holes 6 penetrating the first electrode layer 3 (see FIG. 1( b)); (C) forming a light absorbing layer 4 on the first electrode layer 3 and on the gas barrier layer 2 exposed by the through-holes 6 (see FIG. 1( c)); and (D) forming a second electrode layer 5 on the light absorbing layer 4 (see FIG. 1( d)).

[0014] Average value L of the line width L of the through holes 6 ave is preferably less than 100 μm, more preferably 50 μm or less.ave is obtained using an image (e.g., an SEM image) of the first electrode layer 3 having the through-holes 6 formed therein photographed from above. Specifically, in the image of the first electrode layer 3 having the through-holes 6 photographed from above, the area and length (i.e., the length along the linear extension direction of the through-holes 6) of the portion where the first electrode layer 3 has been removed are obtained. Next, a rectangle having the same area as the obtained area and the same length as the obtained length of the linear through-holes 6 is determined. The width (length of the short side) of the rectangle is multiplied by the average value L of the linear width L of the through-holes 6. ave Let's say.

[0015] FIG. 2 shows the average value L of the line width L of the through-holes 6. ave 2( a ) is an explanatory diagram illustrating a method for calculating the length Lx of the through hole 6. FIG. 2( a ) is a schematic diagram illustrating the shape of the through hole 6 when the first electrode layer 3 having the through hole 6 formed therein is viewed from above. Hereinafter, the shape of the through hole 6 when the first electrode layer 3 having the through hole 6 formed therein is viewed from above will be referred to as the “shape of the through hole 6.” As described above, the through hole 6 is formed by removing a portion of the first electrode layer 3 using a pulsed laser having a pulse width of less than 1 ns. Therefore, as shown in FIG. 2( a ), the shape of the through hole 6 is linear overall, with multiple circular holes arranged in one direction so as to overlap each other. For such a through hole 6, the length Lx of the through hole 6 in the linear extension direction and the area of ​​the through hole 6 are calculated. Lx and the area of ​​the through hole 6 can be calculated, for example, by analyzing an SEM image of the through hole 6. Next, a rectangle 61 is determined, as shown in FIG. 2( b ), having the same area as the area of ​​the through hole 6 and the same length Lx as the length Lx of the linear through hole 6. The width Ly of this rectangle 61 is the average value L of the line width L of the through-hole 6 ave It is identified as follows.

[0016] According to the manufacturing method of the first embodiment, the through-holes 6 are formed using a pulse laser having a pulse width of less than 1 ns. Therefore, the electrode removal portion for patterning the first electrode layer 3 is formed by forming the through-holes 6 with an average line width L of the through-holes 6. aveHowever, the through-holes 6 can be formed with a narrow width, preferably less than 100 μm, more preferably 50 μm or less. As a result, in the photoelectric conversion element obtained by the manufacturing method according to the first embodiment, the portions where the first electrode layer 3 has been removed by patterning are thin and therefore inconspicuous. Therefore, there is little difference in appearance between the portions where the first electrode layer 3 has not been removed and the portions where the first electrode layer 3 has been removed, thereby achieving uniformity in the appearance of the photoelectric conversion element. Furthermore, because the through-holes 6 are formed using a pulsed laser with a pulse width of less than 1 ns, damage to the gas barrier layer due to pulsed laser irradiation can be reduced. Therefore, the gas barrier properties of the gas barrier layer 2 can be maintained in a good state, and the gas barrier layer 2 effectively suppresses the intrusion of gases such as water vapor into the photoelectric conversion element. As a result, the photoelectric conversion element obtained by the manufacturing method according to the first embodiment can have high durability. Furthermore, because the manufacturing method according to the first embodiment uses a substrate containing an organic material, a flexible photoelectric conversion element can be obtained. The manufacturing method according to the first embodiment may also use a glass substrate or a metal substrate. In the manufacturing method according to the first embodiment, a second photoelectric conversion element may be further formed above the base material, and the gas barrier layer may be disposed above the second photoelectric conversion element, forming a tandem structure.

[0017] As described above, the manufacturing method according to the first embodiment makes it possible to manufacture a flexible photoelectric conversion element that has both high durability and uniformity in appearance.

[0018] In the above (B) of the manufacturing method according to the first embodiment, the average value L of the line width L ave The minimum value of the line width L for min The ratio L min / L ave However, 0.57<L min / L ave It is desirable to form through-holes 6 whose line width L changes continuously by irradiating the first electrode layer 3 with a pulse laser so that the minimum value L of the line width L satisfies the relationship L<0.91. minis obtained using an image (for example, an SEM image) of the first electrode layer 3 in which the through-holes 6 are formed, taken from above. Specifically, in the image of the first electrode layer 3 in which the through-holes 6 are formed, taken from above, the smallest value of the line width of the portion where the first electrode layer 3 has been removed (i.e., the portion of the linear through-holes 6) is identified, and this is taken as the minimum value L of the line width L. min Let's say.

[0019] In processing using a pulsed laser, a circular through-hole is usually formed with each pulse. To form linear through-holes in the first electrode layer with a pulsed laser, circular through-holes are formed continuously with each pulse. In this case, by reducing the overlap between pulses, damage to the gas barrier layer 2 caused by irradiation with the pulsed laser can be reduced.

[0020] FIG. 3 shows the overlap of pulses irradiated to continuously form circular through-holes and the minimum value L of the line width L of the linear through-holes 6 to be formed. min and the ratio L min / L ave 3A is an explanatory diagram for explaining the relationship between the pulses 100 and the first electrode layer 3. Note that FIG. 3 shows pulses 100 irradiated to form the through-holes 6. In FIG. 3, overlapping portions of the pulses 100 are hatched. The shape of the pulses 100 substantially matches the shape of the portions of the first electrode layer 3 removed by the irradiation of the pulses 100. In the example shown in FIG. 3A, although the outer shape of the linear through-holes 6 formed is affected by the arc, the circular through-holes formed by each pulse are connected to each other, thereby realizing an overall linear shape, and the overlap of the pulses 100 can be reduced. In this case, the minimum value L of the through-holes 6 formed is min is small, so the ratio L min / L ave 3(a) , the overlap of the pulses 100 when forming the through-holes is slightly larger than that in the example of FIG. 3(a), and the minimum value L min and the ratio L min / L ave3(a) is also larger than the example in FIG. 3(a). However, in the example in FIG. 3(b), the influence of the arc remaining in the outer shape of the linear through-hole 6 formed is reduced, and the outer shape of the linear through-hole 6 formed can be made closer to a straight line. In the example in FIG. 3(b), the pulses 100 overlap once in the overlapping portion of the pulses 100, i.e., the number of pulses irradiated to the overlapping portion is two, so damage to the gas barrier layer 2 by the pulse laser can be sufficiently suppressed. In the example shown in FIG. 3(c), the overlap of the pulses 100 when forming the through-hole is larger than the example in FIG. 3(b), and the minimum value L min and the ratio L min / L ave 3(b). However, in the example of FIG. 3(c), the influence of the arc remaining on the outer shape of the linear through-hole 6 formed is greatly reduced, and the outer shape of the linear through-hole 6 formed can be made closer to a straight line. Furthermore, because there is a portion where the pulses 100 overlap twice, there is more damage to the gas barrier layer 2 by the pulsed laser than in the examples of FIGS. 3(a) and 3(b), but compared to the conventional method using a pulsed laser, damage to the gas barrier layer 2 can be sufficiently reduced.

[0021] In the above (B) of the manufacturing method according to the first embodiment, the ratio L min / L ave is 0.57<L min / L ave By irradiating the first electrode layer 3 with a pulsed laser so that the ratio L<0.91 is satisfied, linear through-holes can be formed while further reducing damage to the gas barrier layer 2 caused by the pulsed laser. min / L ave 4B is a schematic diagram showing a linear through-hole 6 formed by successively forming circular through-holes 62 formed by irradiation of one pulse for a linear through-hole 6 having a ratio L of 0.57. min / L ave 1 is a schematic diagram showing a linear through-hole 6 formed by successively forming circular through-holes 62 formed by irradiation with one pulse for a linear through-hole 6 having a ratio L of 0.91. min / L ave4A , the circular through-holes 62 formed by irradiation with one pulse can be more reliably made continuous and linear, so that linear through-holes 6 can be efficiently formed while suppressing damage to the gas barrier layer 2. min / L ave The state where the ratio L is 0.91 is a state where the pulse overlap is maximized within a range where there is no overlap of two or more pulses (i.e., the same region is not irradiated with three or more pulses). min / L ave By making the ratio less than 0.91, damage to the gas barrier layer 2 by the pulse laser can be suppressed, and linear through holes 6 with excellent appearance can be formed.

[0022] 5 is a schematic cross-sectional view showing an example of a photoelectric conversion element according to the first embodiment of the present disclosure. The photoelectric conversion element 10 according to the first embodiment shown in FIG. 5 can be manufactured, for example, by the manufacturing method of the photoelectric conversion element according to the first embodiment described above. The photoelectric conversion element 10 according to the first embodiment includes a substrate 1 containing an organic material, a gas barrier layer 2 disposed on the substrate 1, a first electrode layer 3 disposed on the gas barrier layer 2 and having linear through-holes 6, a light absorbing layer 4 disposed on the first electrode layer 3 and on the gas barrier layer 2 exposed by the through-holes 6, and a second electrode layer 5 disposed on the light absorbing layer 4. The average value L of the line width L of the through-holes 6 ave In the photoelectric conversion element 10 according to the first embodiment, the layered structure formed of the substrate 1, the gas barrier layer 2, and the first electrode layer 3 having the through-holes 6 has a water vapor permeability of 1×10 or less when measured under conditions of a temperature of 85° C. and a relative humidity of 85%. 0 (g / m 2 / day).

[0023] Specifically, the water vapor transmission rate of the laminate is measured using a calcium corrosion method. A specimen for evaluation is prepared as follows: The laminate to be measured is placed on a glass substrate on which a metal calcium thin film and electrodes are formed, covering the metal calcium. Butyl rubber is placed between the laminate and the glass substrate along the periphery of the laminate, thereby bonding the laminate and the glass substrate. The specimen thus prepared is left to stand for a certain period of time under conditions of 85°C and 85% relative humidity, and the water vapor transmission rate is measured by measuring the change in the resistance value of the metal calcium thin film.

[0024] Hereinafter, in order to distinguish the through holes 6 provided in the first electrode layer 3 from the through holes that may be provided in the light absorbing layer 4 in the second embodiment described later, the through holes 6 provided in the first electrode layer 3 will be referred to as first through holes 6. Furthermore, the through holes provided in the light absorbing layer 4 will be referred to as second through holes.

[0025] In the photoelectric conversion element 10 according to the first embodiment, the average value L of the line width L of the first through holes 6 provided in the first electrode layer 3 ave is preferably less than 100 μm, more preferably 50 μm or less. Therefore, the photoelectric conversion element 10 can have a uniform appearance because the width of the electrode removal portion for patterning the first electrode layer 3 can be made small. Furthermore, the photoelectric conversion element 10 has a thickness of 1×10 0 (g / m 2 Since the photoelectric conversion element 10 has a low water vapor permeability of less than 1 / day, the gas barrier layer provides excellent gas barrier properties. Therefore, the photoelectric conversion element 10 can prevent gases such as water vapor from penetrating into the element, and therefore has high durability. In this way, the photoelectric conversion element 10 according to the first embodiment is a flexible photoelectric conversion element that has both high durability and uniform appearance.

[0026] In order to further improve durability, the water vapor permeability of the laminate is set to 1×10 -1 (g / m 2 / day) or less, or 1 × 10 -2 (g / m 2 / day) or less.

[0027] Each component of the photoelectric conversion element 10 will be specifically described below.

[0028] <Substrate> The substrate 1 containing an organic material plays a role in supporting each layer of the photoelectric conversion element 10. Furthermore, in order to realize a lightweight and flexible photoelectric conversion element 10, the substrate 1 is made of, for example, an organic film. When the substrate 1 is on the light incident side, the substrate 1 is made of a light-transmitting material.

[0029] Examples of materials for the organic film that serves as the substrate 1 include polyester, polyamide, polyimide, polyamideimide, polystyrene, polyolefin, polycarbonate, polysulfone, polyurethane, polyarylate, polyether ether ketone, polyethersulfone, acrylic resin, fluororesin, cellulose acylate resin, cycloolefin polymer, etc. Among these, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polypropylene (PP), polyphenylene sulfide (PPS), polyetherimide (PEI), polytetrafluoroethylene (PTFE), etc.

[0030] <Gas Barrier Layer> The gas barrier layer 2 serves to prevent the intrusion of gas from the outside into the light absorbing layer 4. In particular, it serves to prevent the intrusion of water vapor. The gas barrier layer 2 is generally made of an inorganic oxide, but is not limited to this as long as it is a substance with high water vapor barrier properties. The water vapor transmission rate WVTR of the gas barrier layer 2 is, for example, 1×10 0 (g / m 2 / day) and is less than 1 × 10 -1 (g / m 2 / day) or less, and may be 1×10 -2 (g / m 2 / day) or less. The WVTR here is a value measured under conditions of a temperature of 85°C and a relative humidity of 85%.

[0031] <First Electrode Layer> The first electrode layer 3 is conductive. It may also be translucent. For example, it may be formed using a metal oxide and / or metal nitride that transmits light from the visible region to the near-infrared region and is conductive. Examples of such materials include titanium oxide doped with at least one element selected from the group consisting of lithium, magnesium, niobium, and fluorine; gallium oxide doped with at least one element selected from the group consisting of tin and silicon; gallium nitride doped with at least one element selected from the group consisting of silicon and oxygen; tin oxide doped with at least one element selected from the group consisting of antimony and fluorine; zinc oxide doped with at least one element selected from the group consisting of boron, aluminum, gallium, and indium; indium-tin composite oxide; or a composite thereof. The thickness of the first electrode layer 3 is, for example, 1 nm or more and 1000 nm or less.

[0032] The first electrode layer 3 is provided with linear first through holes 6. By providing the first through holes 6, the first electrode layer 3 is made up of, for example, a plurality of parts that are electrically isolated within the plane. The first through holes 6 penetrate only the first electrode layer 3 and do not penetrate the gas barrier layer 2.

[0033] As described above, the first through holes 6 provided in the first electrode layer 3 are formed by removing a portion of the first electrode layer 3 using a pulsed laser in the above-described (B) of the manufacturing method according to the first embodiment. The pulse width of the pulsed laser is less than 1 ns. Because the pulse width is small, thermal damage caused by laser processing can be locally inflicted on the first electrode layer 3, and only the first electrode layer 3 can be removed without affecting the underlying gas barrier layer 2. The wavelength of the pulsed laser can be 1064 nm, 532 nm, or 355 nm, but is not particularly limited to these, as long as it is a wavelength that can process the first electrode layer 3.

[0034] As described above, the line width L of the first through holes 6 formed in the first electrode layer 3 is an average value L aveHowever, it is preferably less than 100 μm, and more preferably 50 μm or less. In processing using a pulsed laser, a circular through-hole is usually formed for each pulse. In order to form the first through-holes 6 that electrically separate the first electrode layer 3 into a plurality of parts, these circular through-holes are formed continuously. In this case, by reducing the overlap between pulses, damage to the gas barrier layer 2 can be reduced. For this reason, it is desirable that the line width of the through-holes 6 changes continuously. The average value L of the line width L ave The minimum value of the line width L for min The ratio L min / L ave is 0.57<L min / L ave As described above, it is desirable that the ratio L min / L ave By satisfying the above range, damage to the gas barrier layer during production can be reduced, thereby realizing the photoelectric conversion element 10 having high gas barrier properties. Therefore, the durability of the photoelectric conversion element 10 can be further improved.

[0035] High gas barrier properties can be maintained by suppressing the effect of forming the first through holes 6 on the gas barrier layer 2. For example, it is desirable that the ratio t1 / t0 of the thickness t1 of the gas barrier layer 2 at the portion exposed from the first electrode layer 3 by the first through holes 6 to the thickness t0 of the gas barrier layer 2 at the portion covered by the first electrode layer 3 satisfies 0.8≦t1 / t0≦1. When the thickness ratio t1 / t0 of the gas barrier layer 2 satisfies the above range, the gas barrier properties of the gas barrier layer 2 are sufficiently maintained. Therefore, when the thickness ratio t1 / t0 of the gas barrier layer 2 satisfies the above range, high gas barrier properties can be achieved, and the durability of the photoelectric conversion element 10 can be further improved.

[0036] The film thickness t0 and film thickness t1 of the gas barrier layer 2 can be determined from a cross-sectional SEM image of the photoelectric conversion element 10. Specifically, for a portion of the gas barrier layer 2 that is covered with the first electrode layer 3, the film thickness of the gas barrier layer 2 is measured at any five locations within a range of 1 μm, and the average value is defined as film thickness t0. Furthermore, for a portion of the gas barrier layer 2 that is not covered with the first electrode layer 3, the film thickness of the gas barrier layer 2 is measured at any five locations within a range of 1 μm, and the average value is defined as film thickness t1. However, if damage such as through holes or peeling is confirmed in the gas barrier layer 2 in the portion that is not covered with the first electrode layer 3, the function as a gas barrier layer will be significantly reduced, and therefore film thickness t1 is considered to be 0.

[0037] <Light Absorbing Layer> The light absorbing layer 4 is present so as to fill the first through-holes 6 and is disposed so as to be in contact with the first electrode layer 3 and the gas barrier layer 2 .

[0038] The light absorbing layer 4 contains, for example, a perovskite compound. From the viewpoint of durability, a photoelectric conversion element containing a perovskite compound needs to further reduce the amount of gases such as water vapor that penetrates into the element. As described above, the photoelectric conversion element 10 according to the first embodiment can prevent gases such as water vapor from penetrating into the element, and therefore can achieve excellent durability even when the light absorbing layer 4 contains a perovskite compound. Therefore, a flexible photoelectric conversion element 10 can be realized that contains a perovskite compound and achieves both high durability and uniformity in appearance.

[0039] 6 is a schematic cross-sectional view showing a modified example of the photoelectric conversion element according to the first embodiment of the present disclosure. As shown in FIG. 6, in the modified photoelectric conversion element 20, the light absorption layer 4 includes a photoelectric conversion layer 40. In this case, the photoelectric conversion layer 40 may include a perovskite compound. When producing such a photoelectric conversion element 20, in the production method according to the first embodiment, the step (C) above includes forming the photoelectric conversion layer 40.

[0040] Perovskite compounds can be represented by the chemical formula ABX3, where A is a monovalent cation. Examples of monovalent cations include monovalent cations such as alkali metal cations and organic cations. More specifically, methylammonium cation (CH3NH3 + ), formamidinium cation (HC(NH2)2 + ), ethylammonium cation (CH3CH2NH3 + ), guanidinium cation (CH6N3 + ), potassium cation (K + ), cesium cation (Cs + ), and rubidium cation (Rb + B is a divalent cation, for example, a lead cation (Pb 2+ ) and tin cations (Sn 2+ ) X is a monovalent anion such as a halogen anion. Each of the A, B, and X sites may be occupied by multiple types of ions.

[0041] The thickness of the photoelectric conversion layer 40 is, for example, 50 nm or more and 10 μm or less. The photoelectric conversion layer 40 can be formed by using a solution coating method, a printing method, a vapor deposition method, or the like. The photoelectric conversion layer 40 may also be formed by cutting out a perovskite compound.

[0042] The photoelectric conversion layer 40 may primarily contain a perovskite compound represented by the chemical formula ABX3. Here, "the photoelectric conversion layer 40 primarily contains a perovskite compound represented by the chemical formula ABX3" means that the photoelectric conversion layer 40 contains 90 mass% or more of a perovskite compound represented by the chemical formula ABX3. The photoelectric conversion layer 40 may also contain 95 mass% or more of a perovskite compound represented by the chemical formula ABX3. The photoelectric conversion layer 40 may be made of a perovskite compound represented by the chemical formula ABX3. The photoelectric conversion layer 40 may contain defects or impurities as long as it contains a perovskite compound represented by the chemical formula ABX3.

[0043] The photoelectric conversion layer 40 may further contain a compound other than the perovskite compound represented by the chemical formula ABX3. Examples of the other compound include a compound having a Ruddlesden-Popper type layered perovskite structure.

[0044] As shown in Fig. 6 , the light absorbing layer 4 may include an electron transport layer 41. In this case, the electron transport layer 41 is located between the photoelectric conversion layer 40 and the first electrode layer 3, or between the photoelectric conversion layer 40 and the second electrode layer 5. Note that Fig. 6 shows an example in which the electron transport layer 41 is located between the photoelectric conversion layer 40 and the first electrode layer 3.

[0045] The electron transport layer 41 includes a semiconductor. The electron transport layer 41 may be a semiconductor having a band gap of 3.0 eV or more. By forming the electron transport layer 41 from a semiconductor having a band gap of 3.0 eV or more, visible light and infrared light can be transmitted to the photoelectric conversion layer 40. An example of the semiconductor is an inorganic n-type semiconductor.

[0046] Examples of inorganic n-type semiconductors that can be used include oxides of metal elements, nitrides of metal elements, and perovskite oxides. Examples of oxides of metal elements that can be used include oxides of Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, Si, and Cr. More specific examples include TiO2 and SnO2. Examples of nitrides of metal elements include GaN. Examples of perovskite oxides include SrTiO3 and CaTiO3. The electron transport layer 41 may also include multiple layers made of different materials.

[0047] As shown in Fig. 6 , the light absorption layer 4 may include a hole transport layer 42. In this case, the hole transport layer 42 is located between the photoelectric conversion layer 40 and the first electrode layer 3, or between the photoelectric conversion layer 40 and the second electrode layer 5. Note that Fig. 6 shows an example in which the hole transport layer 42 is disposed between the photoelectric conversion layer 40 and the second electrode layer 5.

[0048] The hole transport layer 42 includes a hole transport material, which is a material that transports holes. The hole transport layer 42 is made of a hole transport material such as an organic material or an inorganic semiconductor.

[0049] Representative examples of organic compounds used as hole transport materials include 2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)9,9'-spirobifluorene, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (hereinafter sometimes abbreviated as "PTAA"), poly(3-hexylthiophene-2,5-diyl), poly(3,4-ethylenedioxythiophene), and copper phthalocyanine.

[0050] The inorganic semiconductor used as the hole transport material is a p-type semiconductor. Examples of inorganic semiconductors include CuO, CuGaO, CuSCN, CuI, and NiO. x , MoO x , VO, or a carbon material such as graphene oxide. The hole transport layer 42 may also include multiple layers made of different materials.

[0051] 6 , the light absorption layer 4 may include an electron transport layer 41, a photoelectric conversion layer 40 containing a perovskite compound, and a hole transport layer 42. According to this configuration, the photoelectric conversion element 20 is a flexible photoelectric conversion element that contains a perovskite compound and combines high durability with a uniform appearance, and can further be a photoelectric conversion element that can improve photoelectric conversion efficiency. When manufacturing a photoelectric conversion element 20 having such a configuration, in the manufacturing method according to the first embodiment, the above (C) includes forming the electron transport layer 41, forming the photoelectric conversion layer 40, and forming the hole transport layer 42.

[0052] <Second Electrode Layer> The second electrode layer 5 is conductive. The second electrode layer 5 may be made of the same material as the first electrode layer 3. Alternatively, the second electrode layer 5 may be made of a metal material. The thickness of the second electrode layer 5 is, for example, 1 nm or more and 1000 nm or less.

[0053] Second Embodiment FIG. 7 is a schematic cross-sectional view showing a photoelectric conversion module, which is a photoelectric conversion element according to a second embodiment of the present disclosure.

[0054] The photoelectric conversion element according to the second embodiment is a photoelectric conversion module 30 in which multiple cells are connected. FIG. 7 shows an example of a structure in which three cells are connected in series. In the photoelectric conversion module 30 shown in FIG. 7 , the light absorption layer 4 and the second electrode layer 5 are divided into three cells at positions different from the first through-holes 6, and each cell of the light absorption layers 4a, 4b, and 4c has second through-holes 9a, 9b, and 9c, which are respectively located differently from the first through-holes 6a, 6b, and 6c. The second electrode layers 5a, 5b, and 5c are connected to the first electrode layers of adjacent cells through the second through-holes 9a, 9b, and 9c, respectively. This results in multiple cells being connected in series. Here, the formation of the second through-holes 9a, 9b, and 9c and the division of the cells can be achieved by, but is not limited to, a pulsed laser processing technique.

[0055] The photoelectric conversion element according to the second embodiment can provide a photoelectric conversion module 30 that has both high durability and uniform appearance.

[0056] [Other Embodiments] (Additional Notes) The above description of the embodiments discloses the following techniques.

[0057] (Technology 1) A method for manufacturing a photoelectric conversion element, comprising: (A) forming a first electrode layer on a gas barrier layer; (B) removing parts of the first electrode layer using a pulsed laser to form through-holes that penetrate the first electrode layer and overlap a plurality of holes; (C) forming a light absorbing layer on the first electrode layer and on the gas barrier layer exposed by the through-holes; and (D) forming a second electrode layer on the light absorbing layer. According to the manufacturing method of Technology 1, a photoelectric conversion element that combines high durability and uniformity in appearance can be manufactured.

[0058] (Technology 2) The method for manufacturing a photoelectric conversion element according to Technology 1, wherein the pulse laser has a pulse width of less than 1 ns.

[0059] (Technology 3) The method for manufacturing a photoelectric conversion element according to Technology 1 or 2, wherein a ratio t1 / t0 of a thickness t1 of the gas barrier layer at a portion exposed from the first electrode layer by the through hole to a thickness t0 of the gas barrier layer at a portion covered by the first electrode layer satisfies 0.8≦t1 / t0≦1.

[0060] (Technology 4) The line width L of the through hole is an average value L of the line width L ａｖｅ The method for producing a photoelectric conversion element according to Technology 1 or 2, wherein the thickness of the first and second electrodes is less than 100 μm.

[0061] (Technology 5) In (B), the average value L of the line width L of the through holes ａｖｅ The minimum value L of the line width L for ｍｉｎ The ratio L ｍｉｎ / L ａｖｅ However, 0.57<L ｍｉｎ / L ａｖｅ 3. The method for manufacturing a photoelectric conversion element according to claim 1, wherein the pulsed laser is irradiated onto the first electrode layer so as to satisfy a ratio of 1 / (f) to 1 / f<0.91, thereby forming the through-holes whose line width L changes continuously.

[0062] In processing using a pulsed laser, a circular through-hole is usually formed for each pulse. In order to form linear through-holes in the first electrode layer using a pulsed laser, circular through-holes are formed for each pulse in succession. In this case, by reducing the overlap between pulses, damage to the gas barrier layer caused by irradiation with the pulsed laser can be reduced. According to the manufacturing method of Technology 2, the ratio L min / L ave is 0.57<L min / L ave By irradiating the first electrode layer with a pulsed laser so that the ratio <0.91 is satisfied, linear through holes can be formed while further reducing damage to the gas barrier layer.

[0063] (Technology 6) The method for manufacturing a photoelectric conversion element according to Technology 1 or 2, wherein in (A), the gas barrier layer is provided on a first main surface of a substrate containing an organic material.

[0064] (Technology 7) The method for producing a photoelectric conversion element according to Technology 1 or 2, wherein in (A), the gas barrier layer is formed above a second photoelectric conversion element.

[0065] (Technology 8) The method for producing a photoelectric conversion element according to Technology 1 or 2, wherein the light absorption layer includes a photoelectric conversion layer containing a perovskite compound, and (C) includes forming the photoelectric conversion layer.

[0066] From the viewpoint of durability, it is necessary to further reduce the intrusion of gases such as water vapor into a photoelectric conversion element containing a perovskite compound. The photoelectric conversion element manufactured by the manufacturing method according to Technique 8 has a configuration in which the light absorption layer contains a perovskite compound, but can prevent gases such as water vapor from intruding into the element, thereby achieving excellent durability.

[0067] (Technology 9) The method for manufacturing a photoelectric conversion element according to Technology 1 or 2, wherein the light absorption layer includes an electron transport layer, a photoelectric conversion layer including a perovskite compound, and a hole transport layer, and (C) includes forming the electron transport layer, forming the photoelectric conversion layer, and forming the hole transport layer.

[0068] According to the manufacturing method of Technology 9, it is possible to manufacture a photoelectric conversion element containing a perovskite compound that has both high durability and uniform appearance and can further improve photoelectric conversion efficiency.

[0069] (Technology 10) A photoelectric conversion element comprising: a gas barrier layer; a first electrode layer disposed on the gas barrier layer and having first through holes arranged so that a portion of a plurality of holes overlaps one another; a light absorbing layer disposed on the first electrode layer and on the gas barrier layer exposed by the first through holes; and a second electrode layer disposed on the light absorbing layer.

[0070] (Technology 11) The photoelectric conversion element according to Technology 10, wherein a ratio t1 / t0 of a thickness t1 of the gas barrier layer at a portion exposed from the first electrode layer by the first through hole to a thickness t0 of the gas barrier layer at a portion covered by the first electrode layer satisfies 0.8≦t1 / t0≦1.

[0071] This configuration makes it possible to achieve high gas barrier properties, thereby further increasing the durability of the photoelectric conversion element.

[0072] (Technology 12) The line width L of the first through hole is an average value L of the line width L ａｖｅ The photoelectric conversion element according to claim 10, wherein the thickness of the first electrode is less than 100 μm.

[0073] (Technology 13) The line width L of the first through hole changes continuously, and the average value L of the line width L ａｖｅ The minimum value L of the line width L for ｍｉｎ The ratio L ｍｉｎ / L ａｖｅ However, 0.57<L ｍｉｎ / L ａｖｅ The photoelectric conversion element according to claim 10, wherein the photoelectric conversion element satisfies <0.91.

[0074] This configuration reduces damage to the gas barrier layer during manufacturing, thereby realizing a photoelectric conversion element with high gas barrier properties, thereby further improving the durability of the photoelectric conversion element.

[0075] (Technology 14) The photoelectric conversion element according to Technology 10, wherein the gas barrier layer is a gas barrier layer provided on a first main surface of a substrate containing an organic material.

[0076] (Technology 15) The photoelectric conversion element according to claim 10, further comprising a second photoelectric conversion element, wherein the gas barrier layer is a gas barrier layer disposed above the second photoelectric conversion element.

[0077] (Technology 16) A laminate formed of the substrate, the gas barrier layer, and the first electrode layer has a water vapor permeability of 1×10 or less when measured under conditions of a temperature of 85° C. and a relative humidity of 85%. 0 (g / m ２ / day).

[0078] This configuration makes it possible to provide a photoelectric conversion element that is both highly durable and has a uniform appearance.

[0079] (Technology 17) The photoelectric conversion element according to Technology 10, wherein the light absorption layer contains a perovskite compound.

[0080] This configuration makes it possible to provide a photoelectric conversion element that contains a perovskite compound and that has both high durability and uniform appearance.

[0081] (Technology 18) The photoelectric conversion element according to Technology 10, wherein the light absorption layer includes an electron transport layer, a photoelectric conversion layer containing a perovskite compound, and a hole transport layer.

[0082] This configuration makes it possible to provide a photoelectric conversion element that contains a perovskite compound, has high durability and a uniform appearance, and is capable of further improving photoelectric conversion efficiency.

[0083] (Technology 19) The photoelectric conversion element according to Technology 10, wherein the light absorption layer and the second electrode layer are divided into a plurality of cells at positions different from the first through holes, the light absorption layer of each of the plurality of cells has a second through hole provided at a position different from the first through hole, the second electrode layer is connected to the first electrode layer of an adjacent cell via the second through hole, and the plurality of cells are connected in series with each other.

[0084] This configuration makes it possible to provide a photovoltaic conversion module in which a plurality of cells are integrated, and which has both high durability and uniform appearance.

[0085] Examples of the present disclosure are shown below, but the present disclosure is not limited to the following examples.

[0086] Example 1 First, a PET film was prepared, the main surface of which was provided with an indium-tin composite oxide layer as the gas barrier layer 2 and the first electrode layer 3. In this example, a PET film having a thickness of 75 μm was used as the substrate 1.

[0087] Next, the first electrode layer 3 was removed using a picosecond pulse laser with a pulse width of 2 ps, a repetition frequency of 50 kHz, and a wavelength of 532 nm to form the first through holes 6. The laser power was 80 mW. The average line width L of the first through holes 6 was L ave The average line width L of the first through-holes 6 was 10 μm. FIG. 8A is an SEM image of a partial cross section of the photoelectric conversion element of Example 1. FIG. 8B is a partial top-view SEM image of a part of the first electrode layer 3 in which the through-holes 6 are formed, taken from the top. In the part in which the through-holes 6 are formed in the first electrode layer 3, the gas barrier layer 2 below the removed part is exposed and can be seen. The average line width L of the first through-holes 6 is 10 μm. ave was determined using FIG. 8B.

[0088] Next, a SnO2 layer was formed as the electron transport layer 41 by spin coating on the first electrode layer 3. The thickness of the SnO2 layer was 30 nm.

[0089] Next, a source solution of a photoelectric conversion material was applied by spin coating to form a photoelectric conversion layer 40 containing a perovskite compound. The source solution used contained lead(II) iodide (manufactured by Tokyo Chemical Industry Co., Ltd.), lead(II) bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), formamidinium iodide (manufactured by GreatCell Solar), and methylammonium iodide (manufactured by GreatCell Solar). The solvent used for the solution was a mixture of dimethyl sulfoxide (manufactured by Acros) and N,N-dimethylformamide (manufactured by Acros). The mixture ratio of dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) in the source solution (DMSO:DMF) was 1:8 by volume.

[0090] Next, a raw material solution of a hole transport material was applied by spin coating onto the photoelectric conversion layer 40 to form a hole transport layer 42 containing PTAA. The solvent for the raw material solution was toluene (manufactured by Acros), and the solution contained 10 g / L of PTAA.

[0091] Next, an indium-tin composite oxide film was formed on the hole transport layer 42 by sputtering, thereby forming a second electrode layer 5. In this manner, the photoelectric conversion element of Example 1 was obtained. FIG. 8C is a cross-sectional SEM image of the photoelectric conversion element of Example 1. As shown in FIG. 8C, the photoelectric conversion element produced in Example 1 had the same structure as the photoelectric conversion element 20 described in the first embodiment. More specifically, in the SEM image shown in FIG. 8C, the right-hand region of the SEM image is the portion in which the first through hole 6 was formed in the photoelectric conversion element of Example 1. As can be seen from the SEM image, the portion in which the first through hole 6 was formed in the photoelectric conversion element of Example 1 includes the substrate 1, the gas barrier layer 2, the electron transport layer 41, the photoelectric conversion layer 40, the hole transport layer 42, and the second electrode layer 5 stacked in this order. On the other hand, in the portion of the photoelectric conversion element of Example 1 where the first through hole 6 is not formed (i.e., the left region of the SEM image), a substrate 1, a gas barrier layer 2, a first electrode layer 3, an electron transport layer 41, a photoelectric conversion layer 40, a hole transport layer 42, and a second electrode layer 5 are stacked in this order.

[0092] In Example 2, the laser power for forming the first through-holes 6 was set to 80 mW, and the same location was irradiated with the laser twice to form the first through-holes 6. Otherwise, the photoelectric conversion element of Example 2 was obtained in the same manner as in Example 1.

[0093] In Comparative Example 1, a nanosecond laser was used as the laser for forming the first through holes 6. The pulse width was 10 ns and the wavelength was 355 nm. Otherwise, the photoelectric conversion element of Comparative Example 1 was obtained in the same manner as in Example 1.

[0094] In Comparative Example 2, a mask sputtering method was used to form the first through holes 6. When forming the first electrode layer on the gas barrier layer, a mask was used to sputter indium-tin composite oxide, thereby forming the first electrode layer 3 having the first through holes 6. Otherwise, the photoelectric conversion element of Comparative Example 2 was obtained in the same manner as in Example 1.

[0095] <Evaluation of Fabricated Photoelectric Conversion Elements> (Water Vapor Transmission Rate (WVTR)) The water vapor transmission rate of a laminate formed of a substrate 1, a gas barrier layer 2, and a first electrode layer 3 having through-holes 6 was measured under conditions of a temperature of 85°C and a relative humidity of 85%. Specifically, the water vapor transmission rate was obtained using the calcium corrosion method described above. The results are shown in Table 1. Furthermore, a durability test of the perovskite solar cell was conducted using the laminates of Examples 1, 2, and Comparative Example 1, whose water vapor transmission rates had been measured. A perovskite solar cell was placed on a glass substrate and covered with a laminate formed of a substrate 1, a gas barrier layer 2, and a first electrode layer 3 having through-holes 6. After 200 hours had elapsed under conditions of a temperature of 85°C and a relative humidity of 85%, the appearance of the perovskite solar cell was visually observed. When the water vapor transmission rate of the laminate was 1×10 0 (g / m 2 When the laminates of Examples 1 and 2, which satisfied the water vapor transmission rate of less than 1×10 / day, were used, the appearance was maintained. 0 (g / m 2 When the laminate of Comparative Example 1, which did not satisfy the condition of less than 1000 kJ / day, was used, discoloration of the perovskite solar cell was confirmed.

[0096] (Average value L of the line width L of the first through hole ave ) Average value L of the line width L of the first through holes 6 ave was obtained using an SEM image of the first electrode layer 3 having the first through holes 6 formed therein photographed from above. Specifically, in the SEM image of the first electrode layer 3 having the first through holes 6 formed therein photographed from above, the area and length (i.e., the length along the linear extension direction of the through holes 6) of the portion where the first electrode layer 3 had been removed were obtained. Next, a rectangle having the same area as the obtained area and the same length as the obtained length of the linear first through holes 6 was determined. The width (length of the short side) of the rectangle was calculated by multiplying the average value L of the linear width L of the first through holes 6 by 1 / 2. ave The results are shown in Table 1.

[0097] (Appearance) The uniformity of the appearance of the fabricated photoelectric conversion element was visually confirmed. In Table 1, A is recorded when uniformity was maintained, and B is recorded when uniformity was not maintained.

[0098] (Evaluation of Gas Barrier Property) The gas barrier property was evaluated based on the WVTR value. 0 (g / m 2 / day), the gas barrier property was deemed to be sufficient, and in Table 1, A was recorded when the gas barrier property was sufficient, and B was recorded when the gas barrier property was insufficient.

[0099]

[0100] As is clear from Table 1, the gas barrier properties were reduced in Comparative Example 1. This is thought to be because the barrier layer was not present in at least a portion of the through-hole portion, resulting in a higher WVTR value compared to Examples 1 and 2. Comparative Example 2 further showed a higher average value L of the line width L of the first through-holes 6. ave In contrast, in Examples 1 and 2, the first through holes were formed using a laser with a short pulse width of less than 1 ns, thereby achieving both gas barrier properties and uniformity in appearance.

[0101] In the manufacturing methods according to the first embodiment, the second embodiment, and other embodiments, a second photoelectric conversion element may be further formed above the substrate, and the gas barrier layer may be disposed above the second photoelectric conversion element, forming a tandem structure.

[0102] When the second photoelectric conversion element is included, the second photoelectric conversion element may include a light absorbing layer, the light absorbing layer may include a photoelectric conversion layer, and the photoelectric conversion layer may include a perovskite compound.

[0103] The photoelectric conversion element of the present disclosure can achieve both high durability and uniformity in appearance, and therefore can be said to have extremely high industrial applicability.

[0104] DESCRIPTION OF SYMBOLS 1 Substrate 2 Gas barrier layer 3, 3a, 3b, 3d First electrode layer 4, 4a, 4b, 4c Light absorption layer 40 Photoelectric conversion layer 41 Electron transport layer 42 Hole transport layer 5, 5a, 5b, 5c Second electrode layer 6, 6a, 6b, 6c First through-hole 61 Rectangular 62 Circular through-hole 9a, 9b, 9c Second through-hole 10, 20 Photoelectric conversion element 30 Photoelectric conversion module

Claims

1. A method for manufacturing a photoelectric conversion element, comprising: (A) forming a first electrode layer on a gas barrier layer; (B) removing portions of the first electrode layer using a pulsed laser to form through-holes that penetrate the first electrode layer and overlap a portion of a plurality of holes; (C) forming a light absorbing layer on the first electrode layer and on the gas barrier layer exposed by the through-holes; and (D) forming a second electrode layer on the light absorbing layer.

2. The method for producing a photoelectric conversion element according to claim 1, wherein the pulse laser has a pulse width of less than 1 ns.

3. The method for manufacturing a photoelectric conversion element described in claim 1 or 2, wherein a ratio t1 / t0 of a thickness t0 of the gas barrier layer at a portion covered by the first electrode layer to a thickness t1 of the gas barrier layer at a portion exposed from the first electrode layer by the through hole satisfies 0.8≦t1 / t0≦1.

4. The line width L of the through hole is the average value L of the line width L ａｖｅ The method for producing a photoelectric conversion element according to claim 1 or 2, wherein the thickness of the first insulating film is less than 100 μm.

5. In the above (B), the average value L of the line width L of the through hole ａｖｅ The minimum value L of the line width L for ｍｉｎ The ratio of L ｍｉｎ / L ａｖｅ However, 0.57<L ｍｉｎ / L ａｖｅ The method for producing a photoelectric conversion element according to claim 1 , further comprising the step of irradiating the first electrode layer with the pulsed laser to form the through hole in which the line width L changes continuously so as to satisfy a relationship between the line width L and the surface roughness R and the surface roughness R of the first electrode layer and the surface roughness R of the second electrode layer.

6. The method for producing a photoelectric conversion element according to claim 1 or 2, wherein in (A), the gas barrier layer is provided on a first main surface of a substrate containing an organic material.

7. The method for producing a photoelectric conversion element according to claim 1 or 2, wherein in (A), the gas barrier layer is formed above a second photoelectric conversion element.

8. The method for producing a photoelectric conversion element according to claim 1 or 2, wherein the light absorption layer includes a photoelectric conversion layer containing a perovskite compound, and (C) includes forming the photoelectric conversion layer.

9. The method for producing a photoelectric conversion element according to claim 1 or 2, wherein the light absorption layer includes an electron transport layer, a photoelectric conversion layer including a perovskite compound, and a hole transport layer, and (C) includes forming the electron transport layer, forming the photoelectric conversion layer, and forming the hole transport layer.

10. A photoelectric conversion element comprising: a gas barrier layer; a first electrode layer disposed on the gas barrier layer and having first through holes arranged so that a portion of a plurality of holes overlap one another; a light absorbing layer disposed on the first electrode layer and on a portion of the gas barrier layer exposed by the first through holes; and a second electrode layer disposed on the light absorbing layer.

11. The photoelectric conversion element described in claim 10, wherein a ratio t1 / t0 of a thickness t0 of the gas barrier layer at a portion covered by the first electrode layer to a thickness t1 of the gas barrier layer at a portion exposed from the first electrode layer by the first through hole satisfies 0.8≦t1 / t0≦1.

12. The line width L of the first through hole is the average value L of the line width L ａｖｅ The photoelectric conversion element according to claim 10 , wherein the thickness of the first insulating film is less than 100 μm.

13. The line width L of the first through hole changes continuously, and the average value L of the line width L ａｖｅ The minimum value L of the line width L for ｍｉｎ The ratio of L ｍｉｎ / L ａｖｅ However, 0.57<L ｍｉｎ / L ａｖｅ The photoelectric conversion element according to claim 10 , wherein the photoelectric conversion element satisfies a refractive index of 0.75 or less.

14. The photoelectric conversion element according to claim 10, wherein the gas barrier layer is a gas barrier layer provided on a first main surface of a substrate containing an organic material.

15. The photoelectric conversion element according to claim 10, further comprising a second photoelectric conversion element, wherein the gas barrier layer is a gas barrier layer disposed above the second photoelectric conversion element.

16. The laminate formed of the substrate, the gas barrier layer, and the first electrode layer has a water vapor permeability of 1×10 or less when measured under conditions of a temperature of 85° C. and a relative humidity of 85%. 0 (g / m ２ The photoelectric conversion element according to claim 14 , wherein the photoelectric conversion efficiency is less than 100%. / day.

17. The photoelectric conversion element according to claim 10, wherein the light absorbing layer contains a perovskite compound.

18. The photoelectric conversion element according to claim 10, wherein the light absorbing layer includes an electron transport layer, a photoelectric conversion layer containing a perovskite compound, and a hole transport layer.

19. A photoelectric conversion element as described in claim 10, wherein the light absorption layer and the second electrode layer are divided into a plurality of cells at a position different from the first through hole, the light absorption layer of each of the plurality of cells has a second through hole provided at a position different from the first through hole, the second electrode layer is connected to the first electrode layer of an adjacent cell via the second through hole, and the plurality of cells are connected in series with each other.

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