Photoelectric conversion device, electronic device, and power module

Abstract

A photoelectric conversion device, an electronic device, and a power module are disclosed. The photoelectric conversion device sequentially includes a first electrode, a photoelectric conversion layer, and a second electrode. The photoelectric conversion device includes a sealing member on a non-opposing side of one of the first and second electrodes, the non-opposing side not facing the photoelectric conversion layer. The sealing member sequentially includes an insulating layer, a metal layer, and a substrate, starting from one electrode. At the end of the sealing member in the planar direction, the length of the insulating layer in the planar direction is equal to or longer than the length of the metal layer in the planar direction, and the length of the metal layer in the planar direction is at least 0.1 μm longer than the length of the substrate in the planar direction.

Description

Technical Field

[0001] This invention relates to photoelectric conversion devices, electronic devices, and power modules. Background Technology

[0002] In recent years, people have envisioned an Internet of Things (IoT) society where everything is interconnected, enabling comprehensive control. To achieve this, a vast number of sensors need to be attached to various devices to acquire data; however, this requires power to drive these numerous sensors. Wiring a large number of sensors and using batteries is impractical; more importantly, due to the growing societal need to reduce environmental impact, a power source powered by environmentally friendly generators is required.

[0003] Photovoltaic conversion devices, which generate electricity wherever there is light, have attracted attention. In particular, flexible photovoltaic conversion devices are expected to have high efficiency and adaptability to various conditions; therefore, they are expected to be suitable for wearable devices, etc.

[0004] For example, Applied Physics Letters 108, 253301 (2016) and Japanese Journal of Applied Physics 54, 071602 (2015) reported the results of a feasibility study on photoelectric conversion devices for wearable devices.

[0005] Generally speaking, organic thin-film solar cells are expected to become environmentally friendly power generation devices with high efficiency and flexibility; and a photoelectric conversion device using a transparent base film as a substrate has been proposed in Japanese Unexamined Patent Application Publication No. 2014-220333.

[0006] Such a photoelectric conversion device generally consists of a first electrode, an electron transport layer, a photoelectric conversion layer, a hole transport layer, and a second electrode; these are stacked in this order on a substrate, which serves as a supporting substrate. On the other hand, because the function of this photoelectric conversion device is reduced if water or other substances seep into its interior, a sealing member is also provided to prevent these external substances from intruding into the interior of the photoelectric conversion device. For example, a laminated film of insulating and metal layers is used as the sealing member; and in a photoelectric conversion device with the above structure, the film covers the device from the second electrode side, thereby adhering to the substrate side to act as a sealing member.

[0007] However, in photoelectric conversion devices that use a sealing member having an insulating layer, a metal layer, and a substrate in sequence, when pressure is applied during manufacturing or use, deformation at the ends can cause the metal layer to come into contact with other layers, including electrodes, leading to electrical malfunctions. Summary of the Invention

[0008] According to one aspect of the present invention, a photoelectric conversion device sequentially includes a first electrode, a photoelectric conversion layer, and a second electrode. The photoelectric conversion device includes a sealing member on a non-opposing surface side of one of the first and second electrodes, the non-opposing surface side not facing the photoelectric conversion layer. The sealing member sequentially includes an insulating layer, a metal layer, and a substrate, starting from one electrode. At the planar end of the sealing member, the length of the insulating layer in the planar direction is equal to or longer than the length of the metal layer in the planar direction, and the length of the metal layer in the planar direction is at least 0.1 μm longer than the length of the substrate in the planar direction.

[0009] According to one aspect of the invention, a photoelectric conversion device that suppresses electrical faults can be provided even when pressure is applied during its manufacture or use. Attached Figure Description

[0010] Figure 1 This is a top view schematic diagram showing an example of a photoelectric conversion device;

[0011] Figure 2 This is a cross-sectional schematic diagram showing an example of a photoelectric conversion device;

[0012] Figure 3 yes Figure 2 An enlarged cross-sectional view of the sealed area at the left end of the photoelectric conversion device shown;

[0013] Figure 4 This is an enlarged cross-sectional schematic diagram of the sealing area of ​​the photoelectric conversion device not included in this invention;

[0014] Figure 5 This is an enlarged cross-sectional schematic diagram of the sealing area of ​​the photoelectric conversion device not included in this invention;

[0015] Figure 6A This is a schematic diagram illustrating an example of a method for manufacturing a photoelectric conversion module;

[0016] Figure 6B This is a schematic diagram illustrating an example of a method for manufacturing a photoelectric conversion module;

[0017] Figure 6C This is a schematic diagram illustrating an example of a method for manufacturing a photoelectric conversion module;

[0018] Figure 6D This is a schematic diagram illustrating an example of a method for manufacturing a photoelectric conversion module;

[0019] Figure 6E This is a schematic diagram illustrating an example of a method for manufacturing a photoelectric conversion module;

[0020] Figure 6F This is a schematic diagram illustrating an example of a method for manufacturing a photoelectric conversion module;

[0021] Figure 6G This is a schematic diagram illustrating an example of a method for manufacturing a photoelectric conversion module;

[0022] Figure 6H This is a schematic diagram illustrating an example of a method for manufacturing a photoelectric conversion module;

[0023] Figure 6I This is a schematic diagram illustrating an example of a method for manufacturing a photoelectric conversion module;

[0024] Figure 6J This is a schematic diagram illustrating an example of a method for manufacturing a photoelectric conversion module;

[0025] Figure 6K This is a schematic diagram illustrating an example of a method for manufacturing a photoelectric conversion module;

[0026] Figure 7 This is a schematic diagram illustrating an example of the basic structure of an electronic device;

[0027] Figure 8 This is a schematic diagram illustrating an example of the basic structure of an electronic device;

[0028] Figure 9 This is a schematic diagram illustrating an example of the basic structure of an electronic device;

[0029] Figure 10 This is a schematic diagram illustrating an example of the basic structure of a power module;

[0030] Figure 11 This is a schematic diagram illustrating an example of the basic structure of a power module;

[0031] Figure 12 This is a schematic diagram illustrating an example of the basic structure of a personal computer mouse;

[0032] Figure 13 It is shown Figure 12 A schematic representation of the appearance of an example of a personal computer mouse;

[0033] Figure 14 This is a schematic diagram illustrating an example of the basic structure of a personal computer keyboard;

[0034] Figure 15 It is shown Figure 14 A schematic representation of an example of a personal computer keyboard;

[0035] Figure 16 It is shown Figure 14 A schematic view of another example of a personal computer keyboard;

[0036] Figure 17 This is a schematic diagram illustrating an example of the basic structure of a sensor;

[0037] Figure 18 This is a schematic diagram illustrating an example of wireless communication for transmitting data acquired by a sensor to a personal computer, smartphone, or other device; and

[0038] Figure 19 This is a schematic diagram illustrating an example of the basic configuration of a turntable.

[0039] The accompanying drawings are intended to illustrate exemplary embodiments of the invention and should not be construed as limiting its scope. The same or similar reference numerals denote the same or similar components in the various drawings. Detailed Implementation

[0040] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention.

[0041] As used in this article, the singular forms “one” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0042] In describing the preferred embodiments shown in the accompanying drawings, specific terminology may be used for clarity. However, the disclosure of this patent specification is not intended to be limited to the specific terminology chosen so far, and it should be understood that each specific element includes all technical equivalents that have the same function, operate in a similar manner, and achieve similar results.

[0043] The embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

[0044] Photovoltaic conversion devices related to organic thin-film solar cells

[0045] A "photovoltaic conversion device" is a device that converts light energy into electricity or vice versa. Specifically, examples include devices composed of solar cells and photodiodes. Examples of solar cells include organic thin-film solar cells, dye-sensitized solar cells, and perovskite solar cells. In this disclosure, a photovoltaic conversion device composed of organic thin-film solar cells will be described first, followed by descriptions of dye-sensitized solar cells and perovskite solar cells.

[0046] A photoelectric conversion device has at least a first electrode, a photoelectric conversion layer, and a second electrode arranged sequentially. The term "sequentially" means that the electrodes and layers are arranged as a whole in the above-described order, but other layers may be inserted between the electrodes and layers. Examples of inserting other layers include a photoelectric conversion device having a first electrode, an electron transport layer, a photoelectric conversion layer, a hole transport layer, and a second electrode arranged sequentially. In this case, other layers may be inserted between the electrodes and layers or between layers. The term "sequentially" here indicates that these electrodes and layers can be stacked sequentially from the first electrode side or from the second electrode side. Specifically, when viewed from the incident surface side, the photoelectric conversion device can be stacked sequentially in the order of the first electrode, the photoelectric conversion layer, and the second electrode, or in the order of the second electrode, the photoelectric conversion layer, and the first electrode. When the photoelectric conversion device has an electron transport layer and a hole transport layer, when viewed from the incident surface side, the photoelectric conversion device can have a configuration where the first electrode, the electron transport layer, the photoelectric conversion layer, the hole transport layer, and the second electrode are stacked sequentially, or a configuration where the second electrode, the hole transport layer, the photoelectric conversion layer, the electron transport layer, and the first electrode are stacked sequentially. This application primarily describes the sequential stacking of the first electrode, electron transport layer, photoelectric conversion layer, hole transport layer, and second electrode when viewed from the incident surface side; however, the photoelectric conversion device is not limited to this configuration. Through the above description, those skilled in the art can easily understand embodiments where the second electrode, hole transport layer, photoelectric conversion layer, electron transport layer, and first electrode are stacked sequentially when viewed from the incident surface side.

[0047] The photoelectric conversion device has a sealing member. The sealing member is disposed on the non-opposing side of one electrode selected from the first electrode and the second electrode (hereinafter also referred to as "one electrode"), which is not opposite to the photoelectric conversion layer. In this application, "one electrode" refers to the electrode of the first electrode and the second electrode located at a position far from the incident surface. The other electrode selected from the first electrode and the second electrode (hereinafter also referred to as "another electrode") is the electrode of the first electrode and the second electrode located close to the incident surface. "Non-opposing surface" refers to the surface opposite to the surface that is directly opposite to the photoelectric conversion layer or indirectly opposite to it through other layers. The term "non-opposing surface side" means that the sealing member only needs to be located on the non-opposing surface side of one electrode, and the sealing member and the electrode may be adjacent to each other or not adjacent to each other. When the sealing member and an electrode are not adjacent, other layers, etc., can be inserted between the sealing member and the electrode; therefore, for example, a surface protection portion described later can be inserted. Furthermore, "arranged on the non-opposing surface side" means that at least a portion of the sealing member needs to be located on the non-opposing surface side of one electrode, such that the entire sealing member is not necessarily located on the non-opposing surface side of one electrode. Preferably, a sealing component encapsulates an electrode and a photoelectric conversion layer, and when the photoelectric conversion device has an electron transport layer and a hole transport layer, the electron transport layer and the hole transport layer are preferably further encapsulated.

[0048] The photoelectric conversion device has a surface protection section as required. The surface protection section is arranged adjacent to the non-opposing side of one electrode.

[0049] If necessary, the photoelectric conversion device has a substrate (which is different from the substrate that constitutes the sealing member described later, and is therefore sometimes referred to as the "device substrate"), a UV blocking layer, etc.

[0050] When a substrate is present, the photoelectric conversion device preferably has a configuration in which the substrate, first electrode, electron transport layer, photoelectric conversion layer, hole transport layer, and second electrode are stacked in that order when viewed from the incident surface side, or a configuration in which the substrate, second electrode, hole transport layer, photoelectric conversion layer, electron transport layer, and first electrode are stacked in that order. Furthermore, it is preferable that the substrate is arranged adjacent to another electrode on a side that is not opposite to the photoelectric conversion layer of the other electrode.

[0051] Substrate (device substrate)

[0052] A "substrate (device substrate)" is a component that supports the electrodes, layers, etc., that constitute a photoelectric conversion device. From the viewpoint of improving photoelectric conversion efficiency, a substrate with high light transmittance is preferred, and a transparent substrate is more preferred. Furthermore, from the viewpoint of expanding its applications, a substrate with high flexibility is preferred.

[0053] Examples of transparent and flexible substrates include polyester resin films, such as polyethylene terephthalate (PET), polycarbonate, polyimide, polymethyl methacrylate, polysulfone, polyetheretherketone, and thin glass films (glass with a thickness of 200 μm or less). Among these materials, polyester and polyimide resin films, as well as thin glass films, are preferred from the viewpoint of ease of manufacture and cost. When using a resin film or thin glass film as a substrate, the thickness of the substrate is preferably 200 μm or less. When the substrate thickness is 200 μm or less, its flexibility is enhanced, thus improving its durability even if the photoelectric conversion device is bent. The thickness of the substrate can be measured by known methods, such as using a contact thickness gauge.

[0054] Examples of materials with a transparent but inflexible substrate include inorganic transparent crystalline materials such as glass other than thin glass films (in other words, glass with a thickness exceeding 200 μm). These materials are preferred because they are not flexible but highly flat.

[0055] The substrate preferably has gas barrier properties. Gas barrier properties refer to the function of inhibiting the permeation of water vapor, oxygen, etc. In this application, "a substrate with gas barrier properties" is not limited to a substrate that is gas barrier itself, but also includes a substrate with a gas barrier layer adjacent to the substrate, which is a gas barrier layer. A gas barrier substrate can provide a photoelectric conversion device with high storage durability, wherein even if the device is placed in a high temperature and high humidity environment for a long time, the decrease in photoelectric conversion efficiency can be further suppressed. The gas barrier layer will be described later.

[0056] Typically, the required functions of a gas-barrier substrate are expressed in terms of water vapor permeability, oxygen permeability, etc. According to the JIS K7129 B method, the preferred daily water vapor permeability is, for example, 10 g / m³. 2 The following values ​​are preferred, although lower is better. According to JIS K7126-2, the preferred daily oxygen permeability is, for example, 1 cm³. 3 / m 2 • Below atm, although the lower the better.

[0057] As a thin resin film with gas barrier properties, known films can be appropriately used. Examples include aluminum-coated resin films and silicon oxide-coated resin films.

[0058] First electrode

[0059] The "first electrode" is an electrode that collects electrons generated by photoelectric conversion. When the first electrode is positioned on the incident surface, from the viewpoint of improving photoelectric conversion efficiency, it is preferable that the first electrode has high light transmittance, and more preferably, that it is transparent. However, when the first electrode is positioned on the side opposite to the incident surface, this may reduce light transmittance and transparency.

[0060] For the first electrode to be transparent, a transparent electrode that is transparent to visible light can be used. For example, a transparent electrode is a structure composed of a transparent conductive film, a metal thin film, and another transparent conductive film in sequence. The two transparent conductive films sandwiching the metal thin film can be formed of the same material or different materials.

[0061] Examples of materials used for transparent conductive films include indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), tin oxide (SnO2), silver nanowires, and carbon nanotubes (carbon nanotubes, graphene, etc.). Among these materials, indium tin oxide (ITO), indium zinc oxide (IZO), and aluminum-doped zinc oxide (IZO) are preferred.

[0062] Examples of materials used for metal thin films include thin films formed from metals such as aluminum, copper, silver, gold, platinum, and nickel.

[0063] From the viewpoint of maintaining rigidity, it is preferable to use a first electrode that is transparent and integrated with the aforementioned substrate. Examples include FTO-coated glass, ITO-coated glass, aluminum-coated glass, FTO-coated transparent plastic film, ITO-coated transparent plastic film, and plastic film coated with an ITO / silver / ITO laminate.

[0064] Examples of materials used for the opaque first electrode include metals such as platinum, gold, silver, copper, and aluminum, as well as graphite.

[0065] The average thickness of the first electrode is preferably 5 nm or more and 10 μm or less, more preferably 50 nm or more and 1 μm or less.

[0066] The sheet resistance of the first electrode is preferably 50 Ω / sq or less, more preferably 30 Ω / sq or less, and even more preferably 20 Ω / sq or less.

[0067] When the first electrode is transparent, its transmittance is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more. There is no particular upper limit; therefore, it can be selected according to the purpose.

[0068] The first electrode can be formed by wet coating, dry coating such as vapor deposition and sputtering, and printing.

[0069] Electron transport layer

[0070] An "electron transport layer" is a layer that transports electrons generated in the photoelectric conversion layer and suppresses the entry of holes generated in the photoelectric conversion layer. The electron transport layer can have a structure consisting of one or more layers. As an example, a structure with two electron transport layers will be described below. Specifically, this structure has a first electron transport layer and a second electron transport layer (also called an "intermediate layer") disposed between the first electron transport layer and the photoelectric conversion layer. When the electron transport layer has a single layer, it is preferably identical to the first electron transport layer.

[0071] First electron transport layer

[0072] The first electron transport layer is preferably a layer containing metal oxide particles.

[0073] Examples of metal oxides include oxides of titanium, zinc, lithium, and tin, as well as ITO, FTO, ATO, AZO, and GZO. Zinc oxide is preferred, and zinc oxide doped to improve its conductivity is more preferred. Examples of doped zinc oxide include aluminum-doped zinc oxide, gallium-doped zinc oxide, and lithium-doped zinc oxide. Metal oxides can be made from metal alkoxides or the like, which are used as raw materials.

[0074] The average particle size of the metal oxide particles is preferably 1 nm or more and 50 nm or less, more preferably 5 nm or more and 20 nm or less.

[0075] The average particle size of the metal oxide particles can be determined, for example, by measuring at least 100 randomly selected metal oxide particles using the method described below, and calculating the average of these measurements. First, a dispersion solution containing metal oxide particles is transferred to a glass atomizer using a micropipette. Next, the dispersion is sprayed from the atomizer onto a grid coated with a collodion film for TEM. Using a PVD method, the grid is vapor-deposited with carbon, and images of the metal oxide particles are obtained by electron microscopy. Image processing is performed on the resulting images to measure the particle size of the metal oxide particles. The particle size of the metal oxide particles can also be measured by observing the cross-section of the photoelectric conversion device using scanning transmission electron microscopy (TEM) and then using image processing for particle identification. Particle size distribution can also be measured by laser diffraction and scattering methods. The cross-section of the photoelectric conversion device, TEM observation, and particle size distribution measurement can be performed using known methods.

[0076] The average thickness of the first electron transport layer is preferably 1 nm or more and 300 nm or less, more preferably 10 nm or more and 150 nm or less.

[0077] Examples of methods for manufacturing the first electron transport layer include, for instance, coating a dispersion containing metal oxide particles and a dispersion medium and then drying it. Examples of dispersion media include alcohols such as methanol, ethanol, isopropanol (2-propanol), 1-propanol, 2-methoxyethanol, and 2-ethoxyethanol, and mixtures thereof.

[0078] Second electron transport layer (intermediate layer)

[0079] The second electron transport layer is preferably a layer containing an amine compound. Although there is no particular limitation on the amine compound as long as it is a material that can improve the photoelectric conversion efficiency of the photoelectric conversion element by setting the second electron transport layer, it is preferred to use an amine compound represented by, for example, the following general formula (4).

[0080]

[0081] In general formula (4), R4 and R5 each represent an alkyl group that may have substituents and has 1 or more but less than 4 carbon atoms, or a ring structure bonded to R4 and R5. The alkyl group is an alkyl group that may have substituents and preferably has 1 or more but less than 4 carbon atoms, more preferably an alkyl group that does not have substituents and has 1 or more but less than 4 carbon atoms. Examples of the substituents include methyl, ethyl, and hydroxyl. The ring structure preferably has 3 or more but less than 6 carbon atoms. When R4 and R5 are each alkyl groups that may have substituents and have 1 or more but less than 4 carbon atoms, the alkyl groups in R4 and R5 may be the same or different.

[0082] In the above general formula (4), X represents a divalent aromatic group having 6 or more carbon atoms and 14 or less, or a divalent alkyl group having 1 or more carbon atoms and 4 or less, wherein, preferably, a divalent aromatic group having 6 or more carbon atoms and 14 or less.

[0083] In the above general formula (4), A represents any one of the substituents shown in the following structural formulas (1) to (3), with the substituent shown in structural formula (1) being preferred.

[0084] -COOH…Structural formula (1)

[0085] -P(=O)(OH)2…Structural formula (2)

[0086] -Si(OH)3…Structural formula (3)

[0087] Examples of amine compounds other than general formula (4) include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, trimethoxy[3-(phenylamino)propyl]silane, trimethoxy[3-(methylamino)propyl]silane, bis[3-(trimethoxysilyl)propyl]amine, bis[3-(triethoxysilyl)propyl]amine, and N,N'-bis[3-(trimethoxysilyl)propyl]ethane-1,2-diamine.

[0088] Examples of methods for manufacturing a second electron transport layer include spin coating, in which a solution containing an amine compound is spin-coated, or immersion coating, followed by drying.

[0089] Photoelectric conversion layer

[0090] A photoelectric conversion layer is a layer that generates electrons and holes by absorbing light. The photoelectric conversion layer contains two or more organic materials, specifically a donor organic material (also called a p-type organic semiconductor material) and an acceptor organic material (also called an n-type organic semiconductor material). Each of the donor and acceptor organic materials can be made of multiple organic materials; therefore, it is preferable that the photoelectric conversion layer contains three or more organic materials. In the photoelectric conversion layer, it is preferable to mix the donor and acceptor organic materials to form a bulk heterostructure.

[0091] Donor organic materials

[0092] The donor organic material is preferably a π-electron conjugated compound with a highest occupied molecular orbital (HOMO) energy level of 4.8 eV or higher and 5.7 eV or lower, and more preferably a π-electron conjugated compound with an energy level of 5.1 eV or higher and 5.5 eV or lower, or 5.2 eV or higher and 5.6 eV or lower.

[0093] The highest occupied molecular orbital (HOMO) energy level can be obtained by measurement using photoelectron yield spectroscopy, cyclic voltammetry, or similar methods. Specifically, it can be measured using instruments such as the AC-3 manufactured by Riken Keiki Co., Ltd.

[0094] Examples of donor organic materials include porphyrins and phthalocyanines, which are conjugated polymers or low-molecular-weight conjugated compounds in which various aromatic derivatives (e.g., thiophene, fluorene, carbazole, thienothiophene, benzodithiophene, dithienothiophene, quinoxaline, and benzothiadiazole) are coupled. Donor organic materials can also be donor-acceptor linked materials, etc., having both electron-donating and electron-accepting portions in their molecular structure.

[0095] When the donor organic material has a number-average molecular weight (Mn), it is preferably 10,000 or less, more preferably 5,000 or less. When the material is a polymer, its molecular weight is preferably 10,000 or more.

[0096] In another preferred example of the donor organic material, the highest occupied molecular orbital (HOMO) energy level is above 5.1 eV and below 5.5 eV, and the number average molecular weight (Mn) is below 10,000. Examples of such organic materials include those compounds represented by the following general formula (1).

[0097]

[0098] In general formula (1), R1 represents an alkyl group having 2 or more but less than 8 carbon atoms.

[0099] In general formula (1), n ​​represents an integer greater than 1 and less than 3.

[0100] In general formula (1), Y represents a halogen atom.

[0101] In the above general formula (1), m represents an integer greater than 0 and less than 4.

[0102] In general formula (1), X is represented by general formula (2) or general formula (3) below.

[0103]

[0104]

[0105] In general formula (2), R2 represents a straight-chain or branched alkyl group, preferably a straight-chain or branched alkyl group with 2 or more and 30 or less carbon atoms.

[0106] In general formula (3), R3 represents a straight-chain or branched alkyl group, preferably a straight-chain or branched alkyl group with 2 or more and 30 or less carbon atoms.

[0107] In another preferred example of the donor organic material, the highest occupied molecular orbital (HOMO) energy level is 5.2 eV or higher and 5.6 eV or lower, and the number average molecular weight (Mn) is 10,000 or higher. Note that this organic material is preferably used in combination with the aforementioned organic materials having a highest occupied molecular orbital (HOMO) energy level of 5.1 eV or higher and 5.5 eV or lower, and a number average molecular weight (Mn) of 10,000 or lower.

[0108] Examples of organic materials with a highest occupied molecular orbital (HOMO) energy level of 5.2 eV or higher and 5.6 eV or lower and a number average molecular weight (Mn) of 10,000 or higher include 2,1,3-benzothiadiazole-thiophene copolymers, quinoxaline-thiophene copolymers, thiophene-benzodithiaphene copolymers, and polyfluorene polymers.

[0109] 2,1,3-benzothiadiazole-thiophene type copolymers are represented by conjugated copolymers having a thiophene backbone and a 2,1,3-benzothiadiazole backbone in their main chain. Specific examples of 2,1,3-benzothiadiazole-thiophene type copolymers include those represented by the following general formulas (5) to (8). In the following general formulas (5) to (8), n independently represents an integer greater than 1 and less than 1,000.

[0110]

[0111]

[0112] Quinoxaline-thiophene copolymers refer to conjugated copolymers having a thiophene backbone and a quinoxaline backbone in their main chain. Specific examples of quinoxaline-thiophene copolymers include those represented by the following general formula (9). In general formula (9), n represents an integer greater than 1 and less than 1,000.

[0113]

[0114] Thiophene-benzodithiophene type copolymers refer to conjugated copolymers having a thiophene backbone and a benzodithiophene backbone in their main chain. Specific examples of thiophene-benzodithiophene type copolymers include those represented by the following general formulas (10) to (13). In general formulas (10) to (13), n independently represents an integer greater than 1 and less than 1,000.

[0115]

[0116]

[0117] Receptor organic materials

[0118] The acceptor organic material is preferably a π-electron conjugated compound with a lowest unoccupied molecular orbital (LUMO) energy level of 3.5 eV or higher and 4.5 eV or lower.

[0119] Examples of acceptor organic materials include fullerenes or derivatives thereof, naphthalenetetracarboxylic acid imide derivatives, and perylenetetracarboxylic acid imide derivatives. Among these, fullerene derivatives are preferred.

[0120] Examples of fullerene derivatives include C 60 , Phenyl-C61-lactic acid methyl ester (fullerene derivatives are described in published literature as PCBM,

[60] PCBM or PC 61 BM et al.), C 70 , phenyl-C 71 - Methyl lactate (a fullerene derivative described in published literature as PCBM,

[70] PCBM or PC 71 BM et al.) and fullerene derivatives of the fullerpyrrolidine type represented by the following general formula (14).

[0121]

[0122] In general formula (14), Y1 and Y2 each independently represent a hydrogen atom, alkyl, alkenyl, alkynyl, aryl, or aralkyl group. However, Y1 and Y2 are not both hydrogen atoms. The aforementioned alkyl, alkenyl, alkynyl, aryl, and aralkyl groups may or may not have substituents.

[0123] In general formula (14), Ar represents aryl. Aryl groups may or may not have substituents.

[0124] Average thickness of photoelectric conversion layer

[0125] The average thickness of the photoelectric conversion layer is preferably 50 nm or more and 400 nm or less, more preferably 60 nm or more and 250 nm or less. When the average thickness is 50 nm or more, the amount of charge carriers generated due to light absorption in the photoelectric conversion layer is sufficient. When the average thickness is 400 nm or less, the decrease in carrier transport efficiency caused by light absorption is suppressed.

[0126] The average thickness of the photoelectric conversion layer can be calculated, for example, by measuring the thickness of the photoelectric conversion layer at nine randomly selected points and averaging these measurements. First, a liquid containing the material constituting the photoelectric conversion layer is applied to a substrate, dried, and then wiped away with solvent at random locations. Then, the height of the stage at the wiped area is measured using a DEKTAK microscope manufactured by Bruker to obtain a measurement value as the thickness. The average thickness of the photoelectric conversion layer can also be measured by observing the cross-section of the photoelectric conversion device using a scanning electron microscope (SEM) or a transmission electron microscope (TEM).

[0127] Methods for forming bulk heterostructures in photoelectric conversion layers

[0128] The photoelectric conversion layer can be a layer with a planar junction interface formed by sequentially stacking the aforementioned organic materials. However, to increase the area of ​​the junction interface, it is preferable to form a bulk heterojunction with a three-dimensional hybrid structure of these organic materials. A bulk heterojunction is formed, for example, as follows.

[0129] When each organic material is highly soluble, it is dissolved in a solvent to obtain a solution in which these organic materials are mixed in a molecular state; then, after coating the mixture, it is dried to remove the solvent. In this case, the aggregation state of each organic material can be optimized by further heat treatment.

[0130] On the other hand, when using organic materials with low solubility, the organic materials are prepared by dispersing them in a liquid solution containing other organic materials; then, after coating the liquid, they are dried to remove the solvent. In this case, the aggregation state of each organic material can be optimized by further heat treatment.

[0131] Methods for forming photoelectric conversion layers

[0132] Methods for forming the photoelectric conversion layer include processes involving providing a liquid containing the aforementioned organic material. Examples of such methods include spin coating, blade coating, slot die coating, screen printing, rod coating, casting, print transfer, dip coating, ink-jet coating, spray coating, and vacuum phase deposition. Among these, the method is appropriately selected based on the characteristics of the photoelectric conversion layer to be formed, such as thickness control and orientation control.

[0133] For example, when using spin coating, it is preferable to use a solution containing the aforementioned organic materials at a concentration of 5 mg / mL or more and 40 mg / mL or less. The concentration is the total mass of these organic materials relative to the volume of the solution containing them. By setting the concentration to the above levels, a homogeneous photoelectric conversion layer can be easily prepared.

[0134] Annealing can be performed under reduced pressure or in an inert atmosphere (nitrogen or argon) to remove the solvent or dispersion medium from the liquid containing the coated organic material. The annealing temperature is preferably 40°C or higher and 300°C or lower, more preferably 50°C or higher and 150°C or lower. Annealing is necessary because it can lead to an increase in the contact area at the interfaces between the layers by allowing the materials constituting each layer to interpenetrate, thereby increasing the short-circuit current.

[0135] Examples of solvents used to dissolve or disperse organic materials include methanol, ethanol, butanol, toluene, xylene, o-chlorophenol, acetone, ethyl acetate, ethylene glycol, tetrahydrofuran, dichloromethane, chloroform, dichloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, o-dichlorobenzene, chloronaphthalene, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and γ-butyrolactone. These can be used alone or in combination of two or more. Chlorobenzene, chloroform, and o-dichlorobenzene are particularly preferred.

[0136] The solvents or dispersion media described above may contain various additives. Examples of additives include diiodooctane and octane dithiol.

[0137] Hole transport layer

[0138] A "hole transport layer" is a layer that transports holes generated in the photoelectric conversion layer and suppresses the penetration of electrons generated in the photoelectric conversion layer. A hole transport layer can have a structure consisting of one or more layers. Below, as an example, a structure with a single hole transport layer will be described.

[0139] The hole transport layer is preferably a layer containing at least one compound selected from organic and inorganic compounds with hole transport properties. Examples of organic compounds with hole transport properties include conductive polymers such as PEDOT:PSS (polyvinyl dioxythiophene: polystyrene sulfonic acid) and aromatic amine derivatives. Examples of inorganic compounds with hole transport properties include molybdenum oxide, tungsten oxide, vanadium oxide, nickel oxide, and copper oxide (I). Among these compounds with hole transport properties, molybdenum oxide, tungsten oxide, and vanadium oxide are preferred.

[0140] The average thickness of the hole transport layer is preferably less than 200 nm, and more preferably more than 1 nm and less than 50 nm.

[0141] Examples of methods for manufacturing hole transport layers include coating a liquid containing a compound with hole transport properties and a solvent or dispersion medium, and then drying the liquid. Examples of coating methods include spin coating, sol-gel coating, slot die coating, and sputtering.

[0142] Second electrode

[0143] The "second electrode" is an electrode that collects holes generated by photoelectric conversion. When the second electrode is positioned on the incident surface, from the viewpoint of improving photoelectric conversion efficiency, it is preferable that the second electrode has high light transmittance, and more preferably, that it is transparent. However, when the second electrode is positioned on the side opposite to the incident surface, this may reduce light transmittance and transparency.

[0144] The second electrode can be the same as the first electrode described above; therefore, the description of this electrode is omitted.

[0145] Surface protection

[0146] The "surface protection layer (also called the "passivation layer" when laminated)" is a component disposed between an electrode and a sealing member to prevent direct contact between the sealing member and the electrodes of the first and second electrodes located away from the incident point. The shape of the surface protection layer is not particularly limited, but lamination is preferred. When the surface protection layer is disposed on an electrode (specifically, when it is disposed adjacent to a non-opposing surface of an electrode that is not aligned with the photoelectric conversion layer), it can suppress the contact of water or oxygen that has seeped in from the outside with the electrode; it can also suppress corrosion and deterioration of the electrode over time, thereby improving storage durability. Furthermore, in the photoelectric conversion device, the adhesive member constituting the sealing member does not directly contact an electrode, thereby suppressing the problem of peeling caused by the transfer of material constituting an electrode to the adhesive member side.

[0147] Preferably, the surface protection portion covers the entire exposed surface of an electrode. Covering the entire exposed surface of an electrode further enhances the function of the surface protection portion. The exposed surface of an electrode specifically refers to the non-opposing surface, side surface, etc., of an electrode.

[0148] Examples of materials constituting the surface protection layer include metal oxides (e.g., SiOx, SiOxNy, and Al2O3), as well as polyethylene, fluorinated coatings, and polymers (such as parylene). These can be used alone or in combination of two or more. Fluorinated coatings are preferred.

[0149] In the case of using fluorine-based coatings, examples of materials constituting the surface protective layer include compounds derived from fluorine-based silane compounds (also known as "fluorinated silane compounds"). In other words, this means using fluorine-based silane compounds as the material forming the surface protective layer. Fluorine-based silane compounds are highly reactive with various metals or metal oxides that can form an electrode, thus allowing the formation of a thin and uniformly flat surface protective layer on an electrode. Since a thin film surface protective layer can be formed, the flexibility of the surface protective layer is improved. Therefore, even when the photoelectric conversion device is bent, damage to the surface protective layer can be suppressed, thereby suppressing electrode peeling of the first electrode of the photoelectric conversion device and a decrease in storage durability. Furthermore, surface protective layers containing compounds derived from fluorine-based silane compounds have high water repellency, stain resistance, weather resistance, and abrasion resistance. Additionally, since fluorine-based silane compounds can be dissolved in non-fluorine organic solvents rather than fluorine organic solvents for use, they are easy to handle.

[0150] Here, fluorosilane compounds are fluorinated compounds having an alkoxysilane group. The alkoxysilane group is not particularly limited as long as it has one to three alkoxy groups bonded to silicon atoms; examples of alkoxy groups include methoxy, ethoxy, and propoxy. As described above, compounds derived from fluorosilane compounds constituting the surface protection portion can be chemically bonded to an electrode by reacting the fluorosilane compound with an electrode. In other words, the surface protection portion is not limited to a separate component not chemically bonded to an electrode, but can also be chemically bonded to an electrode even if its function differs from that of the electrode.

[0151] As a fluorinated silane compound, a compound represented by the following general formula (A) is preferred, for example. By using a compound represented by general formula (A), electrode stripping and degradation of storage durability in the photoelectric conversion device are further suppressed.

[0152] CF3 (CF2) q -O(CF2CF2O) m (CF2) p (CH2) n SiR 1 (3-a) (OR 2 ) a

[0153] …General Formula (A)

[0154] In general formula (A), R 1 and R 2 Each of these groups independently represents a monovalent hydrocarbon group with 1 or more carbon atoms and 4 or less. a represents an integer with 2 or more carbon atoms and 3 or less, p represents an integer with 1 or more carbon atoms and 2 or less, q represents an integer with 0 or more carbon atoms and 5 or less, m represents an integer with 1 or more carbon atoms and 3 or less, n represents an integer with 2 or more carbon atoms and 4 or less, and p+q+2m+n is an integer with 5 or more carbon atoms and 14 or less.

[0155] The average thickness of the surface protection portion is preferably 1 μm or less. When the thickness is 1 μm or less, the flexibility of the surface protection portion is enhanced. Therefore, even when the photoelectric conversion device is bent, damage to the surface protection portion can be suppressed, thereby suppressing electrode peeling of the first electrode of the photoelectric conversion device and the reduction in storage durability. There are no particular limitations on the method for measuring the average thickness of the surface protection portion, and known measurement methods can be used. For example, a stylus-type thin-film profilometer, a white light interference microscope, and an atomic force microscope can be used to measure the thickness. The thickness is measured at five or more different locations on the surface protection portion, and the average value of these measurements is taken.

[0156] Traditionally, metal oxides such as SiOx, SiOxNy, and Al2O3, as well as polymers such as polyethylene, fluorinated coatings, and parylene, have been used as materials for the surface protection layer. However, these conventional materials are difficult to form thin surface protection layers; specifically, it is particularly difficult to reduce their thickness to below 1 μm, resulting in insufficient flexibility. Consequently, when a photoelectric conversion device with a surface protection layer formed from conventional materials is bent, bending stress induces cracks in the surface protection layer, allowing water and oxygen to penetrate and thus deteriorating storage durability. In contrast, when compounds derived from fluorosilanes are used as materials for the surface protection layer, it is easier to reduce the average thickness of the surface protection layer to below 1 μm, thereby improving the flexibility of the surface protection layer and thus improving storage durability.

[0157] Examples of methods for manufacturing surface protective parts include manual coating, nozzle flow coating, dip coating, spray coating, reverse coating, flow coating, spin coating, and roll coating.

[0158] Sealing components

[0159] A "sealing member" is a component that prevents external substances such as water and oxygen from entering the photoelectric conversion device and contacting the layers. Preferably, the sealing member, from one electrode side, sequentially comprises an adhesive member that enables the sealing member to bond with other components and a gas barrier member that prevents external substances from entering the photoelectric conversion device; more preferably, these components are integrated into a thin-film type component. The term "sequentially" means that these components can be arranged as a whole in the above-described order; therefore, other components or layers can be inserted between the adhesive member and the gas barrier member. When the sealing member is located on the side opposite to the incident surface, the sealing member does not need to be light-transmitting or transparent. The sealing member is preferably the outermost component constituting the photoelectric conversion device; in this case, the components constituting the sealing member (adhesive member, gas barrier member, etc.) are also at least partially exposed to the outside.

[0160] The required properties of gas barrier materials are generally expressed in terms of water vapor permeability and oxygen permeability. According to the JIS K7129B method, the preferred daily water vapor permeability is, for example, 10 g / m³. 2 The following values ​​are preferred, although lower is better. According to JIS K7126-2, the preferred daily oxygen permeability is, for example, 1 cm³ / min. 3 / m 2 • Below atm, although the lower the better.

[0161] The gas-barrier member has a metal layer and a substrate arranged sequentially from one electrode side (this differs from the substrate constituting the photoelectric conversion device described above; therefore, it can be referred to as a "sealing substrate"). As will be described later, gas-barrier members with metal layers can sometimes cause electrical faults in manufactured photoelectric conversion devices, but these faults can be suppressed by using the structure of the present invention. The term "sequentially" means that the metal layer and the substrate can be arranged in the order described above; therefore, other components or layers can be inserted between the metal layer and the substrate.

[0162] A metal layer refers to a thin metal film. Examples include films formed of metals such as aluminum, copper, silver, gold, platinum, and nickel, with films formed of aluminum being preferred.

[0163] The substrate is a component that supports the various layers (metal layers, insulating layers, etc.) constituting the sealing member. Furthermore, from the viewpoint of expanding its applications, a substrate with high flexibility is preferred. Examples of substrates include polyester resin films, such as polyethylene terephthalate (PET), polycarbonate, polyimide, polymethyl methacrylate, polysulfone, polyetheretherketone, and thin glass films (glass with a thickness of 200 μm or less). Among these materials, polyester and polyimide resin films, as well as thin glass films, are preferred from the viewpoints of ease of manufacture and cost. When using a resin film or thin glass film as the substrate, the thickness of the substrate is preferably 200 μm or less. When the substrate thickness is 200 μm or less, its flexibility is enhanced, thus improving its durability even if the photoelectric conversion device is bent. The thickness of the substrate can be measured by known methods, such as using a contact thickness gauge.

[0164] As described above, the adhesive member functions to bond the sealing member to other components; it also functions as an insulating layer that prevents electrical connection between an electrode and a metal layer in the gas barrier layer. Therefore, in the description of this disclosure, the adhesive member is also referred to as an insulating layer. However, this does not preclude the use of the adhesive member and the insulating layer as separate components.

[0165] In the adhesive component (insulating layer), for example, general materials used for sealing organic electroluminescent devices, organic transistors, etc., can be used as the material. Specifically, examples include pressure-sensitive adhesive resins, thermosetting resins, thermoplastic resins, and photocurable resins. Among these, pressure-sensitive adhesive resins that do not require heating during the sealing process are preferred. On the other hand, when using pressure-sensitive adhesive resins, as described later, electrical faults may occur in the manufactured photoelectric conversion device because the sealing component needs to be pressure-bonded with other components during the formation of the photoelectric conversion device; however, this fault can be suppressed by using the composition of the present invention. Specific examples of materials used for the adhesive component include ethylene-vinyl acetate copolymer resins, styrene-isobutylene resins, hydrocarbon resins, epoxy resins, polyester resins, acrylic resins, polyurethane resins, and silicone resins. Various adhesive properties can be obtained by chemically modifying the main chain, branches, and ends of these resins and by adjusting their molecular weight, etc.

[0166] UV blocking layer

[0167] A "UV cutoff layer" is a layer disposed on the incident surface side to suppress the degradation of the photoelectric conversion device due to UV light. Preferably, the UV cutoff layer is a film-like component that absorbs UV light. The UV cutoff layer is preferably disposed on a substrate located on the incident surface side.

[0168] Typically, the required functionality of a UV-blocking layer is expressed in terms of light transmittance, etc. For example, light transmittance below 370 nm is preferably less than 1%. Additionally, light transmittance below 410 nm is preferably less than 1%.

[0169] Gas barrier

[0170] A "gas barrier layer" is a layer that prevents external substances such as water and oxygen from entering the photoelectric conversion device. The gas barrier layer is preferably a continuous film. It is preferably disposed adjacent to the substrate (device substrate), and more preferably disposed between another electrode and the substrate. Note that when the gas barrier layer is disposed adjacent to the substrate, the gas barrier layer is considered to be a component constituting the substrate (device substrate) in this disclosure.

[0171] The required functions of a gas barrier layer are generally expressed in terms of water vapor permeability and oxygen permeability. According to JIS K7129 B method, the preferred daily water vapor permeability is, for example, 10 g / m³. 2 The following values ​​are preferred, although lower is better. According to JIS K7126-2, the preferred daily oxygen permeability is, for example, 1 cm³ / min. 3 / m 2 • Below atm, although the lower the better.

[0172] Examples of materials used for gas barrier layers include materials of SiO2, SiNx, Al2O3, SiC, SiCN, SiOC, and SiOAl, as well as siloxane-based materials.

[0173] Other layers

[0174] The photoelectric conversion device may also have other layers as needed, such as insulating porous layers, anti-deterioration layers, and protective layers.

[0175] Configuration of photoelectric conversion devices related to organic thin-film solar cells

[0176] Reference Figures 1 to 3 This describes a configuration example of a photoelectric conversion device. Figure 1 This is a top view schematic diagram showing an example of a photoelectric conversion device. Figure 2 This is a cross-sectional schematic diagram showing an example of a photoelectric conversion device. Figure 3 yes Figure 2 An enlarged cross-sectional view of the sealed area at the left end of the photoelectric conversion device shown.

[0177] like Figure 1 As shown in the top view, the photoelectric conversion device 1 has a photoelectric conversion area 2 (i.e., the area capable of photoelectric conversion), a sealing area 3 surrounding the photoelectric conversion area 2, and other areas 4 (where terminals and other components are provided).

[0178] like Figure 2 As shown in the cross-sectional schematic diagram, in the photoelectric conversion region 2, the photoelectric conversion device 1 has a stacked structure consisting of a UV cutoff layer 11, a substrate (device substrate) 12, a first electrode 13, a first electron transport layer 14, a second electron transport layer (intermediate layer) 15, a photoelectric conversion layer 16, a hole transport layer 17, a second electrode 18, a surface protection portion (passivation layer) 19, and a sealing member 20 arranged sequentially from the incident surface side along the stacking direction z. (Hereinafter, this structure is also referred to as "structure A"). In the sealing region 3, the photoelectric conversion device 1 has a UV cutoff layer 11, a substrate (device substrate) 12, a first electrode 13, and a sealing member 20 arranged sequentially from the incident surface side along the stacking direction z. At this time, the sealing member 20 has an adhesive member (insulating layer) 21 and a gas barrier member 22, and the gas barrier member 22 has a metal layer 23 and a substrate (sealing substrate) 24. The sealing member 20 encapsulates the first electron transport layer 14, the second electron transport layer (intermediate layer) 15, the photoelectric conversion layer 16, the hole transport layer 17, the second electrode 18, and the surface protection portion (passivation layer) 19, and is joined with the surface protection portion (passivation layer) 19 and the sealing region 3 in the first electrode 13. Note that in the photoelectric conversion device 1, the first electrode 13 corresponds to the aforementioned "other electrode," and the second electrode 18 corresponds to the aforementioned "one electrode." The photoelectric conversion device 1 may also have a connection portion that is electrically connected in series or in parallel with other photoelectric conversion devices. The stacking direction z represents the direction perpendicular to the surface (xy surface) of each layer in the photoelectric conversion device. The direction contained in the surface (xy surface) of each layer of the photoelectric conversion device represents the surface direction.

[0179] The stacking order of the first electrode 13 to the second electrode 18 in the photoelectric conversion region 2 of the photoelectric conversion device 1 having structure A is not limited to the above order. Specifically, in the photoelectric conversion region 2, the photoelectric conversion device 1 may have a stacked structure in which, from the incident surface side along the stacking direction z, the layers are: UV cut-off layer 11, substrate (device substrate) 12, second electrode 13, hole transport layer 14, photoelectric conversion layer 15, second electron transport layer (intermediate layer) 16, first electron transport layer 17, first electrode 18, surface protection part (passivation layer) 19, and sealing member 20 (hereinafter, this structure is also referred to as "structure B"). In this case, the sealing member 20 encapsulates the hole transport layer 14, photoelectric conversion layer 15, second electron transport layer (intermediate layer) 16, first electron transport layer 17, first electrode 18, and surface protection part (passivation layer) 19, and is bonded to the surface protection part (passivation layer) 19 in the second electrode 13 and the sealing region 3. Note that in the photoelectric conversion device 1, the second electrode 13 corresponds to the aforementioned "other electrode", while the first electrode 18 corresponds to the aforementioned "one electrode".

[0180] In this disclosure, such as Figure 1 and Figure 2 As shown, the photoelectric conversion device with structure A is described as an example, but those skilled in the art can easily understand the photoelectric conversion device with structure B from this description.

[0181] Next, use Figure 3 The cross-sectional schematic diagram illustrates the relationship between the adhesive component (insulating layer) 21, the metal layer 23, and the substrate (sealing substrate) 24. Figure 3 yes Figure 2 The diagram shows an enlarged cross-sectional view of the sealed area at the left end of the photoelectric conversion device 1. The photoelectric conversion area 2 is omitted from the diagram. Figure 3 As shown, the end of the photoelectric conversion device in the surface direction is composed of, sequentially from the incident surface side along the stacking direction z, a UV cutoff layer 11, a substrate (device substrate) 12, a first electrode 13 serving as another electrode, an adhesive member (insulating layer) 21, a metal layer 23, and a substrate (sealing substrate) 24. Furthermore, as... Figure 3 As shown, at the end of the sealing member 20 in the planar direction, the length of the adhesive member (insulating layer) 21 in the planar direction is equal to or longer than the length of the metal layer 23 in the planar direction, and the length of the metal layer 23 in the planar direction is longer than the length of the substrate (sealing substrate) 24 in the planar direction.

[0182] At the end of the sealing member 20 in the planar direction, for example, it can be determined that the length of the adhesive member (insulating layer) 21 in the planar direction is equal to or longer than the length of the metal layer 23 in the channel direction, and the length of the metal layer 23 in the planar direction is longer than the length of the substrate (sealing substrate) 24 in the planar direction. First, with... Figure 3 Similarly, in the photoelectric conversion device, a cross-section including the stacking direction z is formed. Next, in the adhesive member (insulating layer) 21, metal layer 23, and substrate (sealing substrate) 24, starting from the most protruding end of the sealing member 20 in the planar direction, an inner position approximately 3 to 5 times the sum of the thicknesses of the adhesive member (insulating layer) 21, metal layer 23, and substrate (sealing substrate) 24 is determined. Then, a reference line L0 passing through this position and parallel to the stacking direction z is determined (assuming that in the adhesive member (insulating layer) 21, metal layer 23, and substrate (sealing substrate) 24, the reference line L0 needs to be located inside the end of the sealing member 20 with the least protruding surface in the planar direction). Next, the maximum length L in the planar direction between the reference line L0 and the end of the adhesive member (insulating layer) 21 is measured. 21 The maximum length L in the planar direction between the baseline L0 and the end of the metal layer 23 23 and the maximum length L in the planar direction between the baseline L0 and the end of the base (sealing base) 24. 24 Next, the measurement position is changed by forming another cross-section, etc.; then, the length L is... 21 L 23 L 24 Measure at least three times and take the average value. When the length L... 21 Equal to length L 23 When, or when the length L 21 Length L 23 For an extended period, the length of the adhesive member (insulating layer) 21 in the planar direction is determined to be equal to or longer than the length of the metal layer 23 in the planar direction at the end of the sealing member 20. Similarly, when the length L 23 Length L 24 For an extended period, the length of the metal layer 23 in the planar direction is determined to be longer than the length of the base (sealing base) 24 in the planar direction at the end of the sealing member 20 at the planar direction. In this disclosure, the length L is... 21 With length L 23 The difference is denoted as Δ1, and the length L is... 23 With length L 24 The difference is denoted as Δ2. This cross-section can be observed using an electron microscope or similar instrument.

[0183] Next, the reasons for the preferred configuration (i.e., the length of the adhesive member (insulating layer) 21 in the surface direction is preferably equal to or longer than the length of the metal layer 23 in the surface direction and the length of the metal layer 23 in the surface direction is preferably longer than the length of the substrate (sealing substrate) 24 in the surface direction) will be explained by using the information included in this application. Figure 3 The configurations shown and those not included in this application Figure 4 and Figure 5 The configuration shown will be used for explanation. Figure 4 This is an enlarged cross-sectional schematic diagram of the sealing area of ​​the photoelectric conversion device not included in this application. Figure 5 This is an enlarged cross-sectional schematic diagram of the sealing area of ​​the photoelectric conversion device not included in this application.

[0184] like Figure 4 As shown, when the length of the metal layer 23 in the surface direction of the sealing member 20 is longer than the length of the adhesive member (insulating layer) 21 in the surface direction, pressure can be applied to the photoelectric conversion device during its manufacturing, use, etc. At this time, as... Figure 4 As shown, when a pressure F is applied to the left end of the metal layer 23, the metal layer 23 deforms in the direction of the other electrode, namely the first electrode 13 (the negative direction of the stacking direction z), so that the metal layer 23 and the other electrode, namely the first electrode 13, can approach or contact each other. When the metal layer 23 and the other electrode, namely the first electrode 13, approach or contact each other, an electrical fault (e.g., a short circuit) will occur in the photoelectric conversion device.

[0185] In addition, such as Figure 5 As shown, when the length of the substrate (sealing substrate) 24 in the planar direction of the sealing member 20 is longer than the length of the metal layer 23 in the planar direction, pressure can be applied to the photoelectric conversion device during its manufacturing, use, etc. At this time, as... Figure 5 As shown, when pressure F is applied to the left end of the substrate (sealing substrate) 24, the pressure applied to the substrate (sealing substrate) 24 is also applied to the left end of the metal layer 23. Then, the left end of the metal layer 23 deforms in the direction of the other electrode, i.e., the first electrode 13 (the negative direction of the lamination direction z), such that the metal layer 23 and the other electrode, i.e., the first electrode 13, can approach or contact each other. When the metal layer 23 and the other electrode, i.e., the first electrode 13, approach or contact each other, an electrical fault (e.g., a short circuit) occurs in the photoelectric conversion device.

[0186] On the contrary, such as Figure 3As shown, the length of the adhesive member (insulating layer) 21 in the planar direction of the sealing member 20 is equal to or longer than the length of the metal layer 23 in the planar direction, such that even when pressure is applied during the fabrication or use of the photoelectric conversion device, deformation of the metal layer 23 toward the other electrode, namely the first electrode 13 (the negative direction of the lamination direction z), is suppressed; as a result, a photoelectric conversion device that suppresses the occurrence of electrical faults can be provided. Furthermore, as... Figure 3 As shown, the length of the metal layer 23 in the planar direction of the sealing member 20 is longer than the length of the substrate (sealing substrate) 24 in the planar direction, so that even when pressure is applied to the substrate (sealing substrate) 24 during the fabrication or use of the photoelectric conversion device, the transmission of pressure applied to the substrate (sealing substrate) 24 to the left end of the metal layer 23 is suppressed. Therefore, deformation of the left end of the metal layer 23, which is immersed in the adhesive member (insulating layer) 21, toward the other electrode, namely the first electrode 13 (the negative direction of the lamination direction z), is suppressed; as a result, a photoelectric conversion device that suppresses the occurrence of electrical faults can be provided.

[0187] As an example of applying pressure in the fabrication process of the aforementioned photoelectric conversion device, when the material constituting the adhesive member (insulating layer) 21 is a pressure-sensitive adhesive resin, pressure is required during bonding to connect the sealing member 20 to other members to form the photoelectric conversion device.

[0188] Note that, as described above, electrical faults (e.g., short circuits) in the photoelectric conversion device are caused by proximity or contact between the metal layer 23 and the other electrode, namely the first electrode 13. In other words, the closer the metal layer 23 is to the other electrode, namely the first electrode 13, the more likely an electrical fault (e.g., a short circuit) will occur. Therefore, the structure of the present invention is more effective when the photoelectric conversion device has such a structure.

[0189] An example of a situation where the metal layer 23 and the other electrode, namely the first electrode 13, are in close proximity is shown in Figure 3 In the photoelectric conversion device, at the end in the face direction, along the stacking direction z, it is composed of a first electrode 13 (i.e., another electrode), an adhesive member (insulating layer) 21, a metal layer 23, and a substrate (sealing substrate) 24 in sequence. In other words, the other electrode (i.e., the first electrode 13) and the metal layer 23 are adjacent to each other through the adhesive member (insulating layer) 21.

[0190] Another example of a situation where the metal layer 23 and the other electrode, namely the first electrode 13, are in close proximity is the layer thickness, which is approximately the same as that of the adhesive member (insulating layer) 21. Figure 3 T in 21 In the case where the end of the sealing member 20 is very small in the face direction. Adhesive member (insulating layer) 21 (T 21 The layer thickness can be set to less than 50.0 μm, for example.

[0191] In this embodiment, as described above, the length of the adhesive member (insulating layer) 21 in the planar direction of the sealing member 20 is equal to or longer than the length of the metal layer 23 in the planar direction (length L). 21 For is equal to or longer than length L 23 Specifically, it indicates the degree of prominence (length L). 21 With length L 23 The difference (Δ1) is preferably 0 μm or more and 20 μm or less, more preferably 0 μm or more and 10 μm or less, even more preferably 0 μm or more and 10 μm or less, and even more preferably 0 μm or more and 5 μm or less. The above range provides a photoelectric conversion device that further suppresses the occurrence of electrical faults.

[0192] In this embodiment, as described above, in the planar direction of the sealing member 20, the length of the metal layer 23 in the planar direction is longer than the length of the substrate (sealing substrate) 24 in the planar direction (length L). 23 Length L 24 (Length); specifically, Δ2 (length L) represents the degree of prominence. 23 With length L 24 The difference (Δ2) is preferably 0.1 μm or more, more preferably 0.5 μm or more, even more preferably 0.9 μm or more, and particularly preferably 1.0 μm or more. Furthermore, Δ2 is preferably 20 μm or less, more preferably 10 μm or less. The above range provides a photoelectric conversion device that further suppresses the occurrence of electrical faults.

[0193] Photovoltaic conversion modules related to organic thin-film solar cells

[0194] A "photoelectric conversion module" is a module with multiple photoelectric conversion devices electrically connected. These devices can be electrically connected in series or in parallel. A photoelectric conversion module can have multiple photoelectric conversion devices connected in series or in parallel. All "connections" in this disclosure are not limited to physical connections but also include electrical connections.

[0195] A photoelectric conversion module has multiple photoelectric conversion devices, a connection portion electrically connecting the photoelectric conversion devices, and other components as needed. In other words, a photoelectric conversion module has at least a first photoelectric conversion device, a second photoelectric conversion device adjacent to the first photoelectric conversion device, a connection portion electrically connecting the first and second photoelectric conversion devices, and other components as needed. The photoelectric conversion devices and the connection portion may differ only in function; therefore, the photoelectric conversion devices and the connection portion may be independent components, or they may be continuous components or integral components. For example, an electrode and a connection portion, which are components of a photoelectric conversion device, may be independent components, or they may be continuous components or integral components.

[0196] Manufacturing method of photoelectric conversion device and photoelectric conversion module of organic thin film solar cell

[0197] The following description will present an example of a method for manufacturing a photoelectric conversion module, which also implies that an example of a method for fabricating a photoelectric conversion device will be described simultaneously. In this disclosure, a method having, as... Figure 2 This is an example of a method for fabricating a photoelectric conversion device with structure A shown. However, through this description, those skilled in the art can readily understand an example of a method for fabricating a photoelectric conversion device with structure B.

[0198] A method for manufacturing a photoelectric conversion module having a photoelectric conversion device includes, for example, a process for forming a barrier layer on a substrate, a process for forming a first electrode on a substrate having a barrier layer, a process for forming an electron transport layer on the first electrode, a process for forming a photoelectric conversion layer on the electron transport layer, a process for forming a through portion through which the electron transport layer and the photoelectric conversion layer are formed, a process for forming a hole transport layer on the photoelectric conversion layer and covering the exposed surfaces of the first electrode, the electron transport layer, and the photoelectric conversion layer with a material of the hole transport layer, and a process for forming a second electrode on the hole transport layer. The process includes: a second electrode forming process in which the material of the second electrode is filled in the through portion to form a through structure; a surface protection forming process in which a surface protection portion is formed on the second electrode; a sealing region forming process in which a sealing region is formed on the first electrode by removing the outer periphery of the laminated material from the electron transport layer to the surface protection portion; a sealing member forming process in which the sealing member encapsulates the laminated material from the electron transport layer to the surface protection portion, thereby bonding the surface protection portion to the sealing region; a sealing member forming process in which the insulating layer, the metal layer, and the substrate (sealing substrate) are formed into the above-described shape at the end of the sealing member in the face direction; and other processes as needed, such as a UV cut-off layer forming process.

[0199] Gas barrier layer formation process

[0200] The preferred method for manufacturing a photoelectric conversion module with a photoelectric conversion device includes a gas barrier layer forming process on a substrate. When the substrate itself is gas barrier, it is not necessary to form a gas barrier layer.

[0201] First electrode formation process

[0202] The preferred method for manufacturing a photoelectric conversion module having a photoelectric conversion device includes a first electrode forming process in which a first electrode is formed on a substrate having a barrier layer. When the substrate does not have a barrier layer, the first electrode can be formed on the substrate.

[0203] The method for forming the first electrode has been described in the description of the first electrode.

[0204] Electron transport layer formation process

[0205] The manufacturing method of a photoelectric conversion module having a photoelectric conversion device preferably includes an electron transport layer forming process for forming an electron transport layer on a first electrode. When the electron transport layer has a first electron transport layer and a second electron transport layer (intermediate layer) as electron transport layers, the electron transport layer forming process preferably includes a first electron transport layer forming process for forming the first electron transport layer on the first electrode and a second electron transport layer forming process for forming the second electron transport layer on the first electron transport layer.

[0206] The method for forming the electron transport layer has been described in the description of the electron transport layer.

[0207] Photoelectric conversion layer formation process

[0208] The preferred method for manufacturing a photoelectric conversion module having a photoelectric conversion device is a photoelectric conversion layer forming process that forms a photoelectric conversion layer on an electron transport layer.

[0209] The method for forming the photoelectric conversion layer has been described in the description of the photoelectric conversion layer.

[0210] Through-section Formation Process

[0211] A preferred method for manufacturing a photoelectric conversion module with a photoelectric conversion device is a through-hole forming process in which a through-hole is formed through the electron transport layer and the photoelectric conversion layer. In this disclosure, the through-hole refers to a hollow hole. Figure 2 In the case of the photoelectric conversion device with structure A shown, a hole is indicated that penetrates the electron transport layer and the photoelectric conversion layer. The shape and size of the through-hole are not limited as long as electrical connection between the photoelectric conversion devices is possible; therefore, it can be linear or circular when viewed from the second electrode side of the photoelectric conversion module, and rectangular or square when observing the cross-section of the photoelectric conversion device. Each layer is divided by this through-hole to form multiple photoelectric conversion devices.

[0212] Examples of methods for forming through sections include laser removal and mechanical scribing.

[0213] Hole transport layer formation process

[0214] The preferred method for manufacturing a photoelectric conversion module having a photoelectric conversion device is a hole transport layer forming process in which a hole transport layer is formed on the photoelectric conversion layer and the exposed surfaces of the first electrode, the electron transport layer, and the photoelectric conversion layer in the through-section are covered by the material of the hole transport layer.

[0215] The method for forming the hole transport layer has been described in the description of the hole transport layer.

[0216] Second electrode formation process

[0217] A preferred method for manufacturing a photoelectric conversion module with a photoelectric conversion device includes a second electrode formation process in which a second electrode is formed on a hole transport layer and the material of the second electrode is filled into a through-hole portion to form a through-hole structure. In this disclosure, the through-hole structure represents a structure that fills the interior of the through-hole portion, and... Figure 2 In the case of the photoelectric conversion module with structure A shown, this represents a structure formed from the material of the hole transport layer and the material of the second electrode. The through-section serves as a connection between photoelectric conversion devices.

[0218] The method for forming the second electrode has been described in the description of the second electrode.

[0219] Surface protection part formation process

[0220] The preferred method for manufacturing a photoelectric conversion module having a photoelectric conversion device is a surface protection part forming process that forms a surface protection part on a second electrode.

[0221] The method for forming the surface protective part has been described in the description of the surface protective part.

[0222] Sealing area formation process

[0223] The manufacturing method of a photoelectric conversion module having a photoelectric conversion device preferably includes a sealing region forming process that forms a sealing region on a first electrode by removing the outer periphery of the laminated material from the electron transport layer to the surface protection portion (electron transport layer, photoelectric conversion layer, hole transport layer, second electrode and surface protection portion), thereby exposing the first electrode.

[0224] Examples of methods used for peripheral removal include laser removal and mechanical scribing.

[0225] Sealing component forming process

[0226] A method for manufacturing a photoelectric conversion module with a photoelectric conversion device can include a sealing member forming process in which various laminated materials (electron transport layer, photoelectric conversion layer, hole transport layer, second electrode, and surface protection layer) are encapsulated in a sealing member, and the surface protection portion contacts the sealing area to adhere to each other. The sealing member forming process can also be performed by attaching a gas barrier member to the adhesive member after coating it, or by attaching an adhesive member pre-coated onto the gas barrier member.

[0227] Although, as described in this manufacturing method, the sealing member encapsulates the stacked layers in the photoelectric conversion device, the embodiment can also encapsulate the photoelectric conversion module; therefore, the result is that the stacked layers in the photoelectric conversion device are encapsulated. In other words, the process is not limited to the embodiment of encapsulating the stacked layers in each photoelectric conversion device.

[0228] Sealing component forming process

[0229] In a method for manufacturing a photoelectric conversion module having a photoelectric conversion device, the insulating member is formed such that at the end of the sealing member in the planar direction, the length of the insulating layer in the planar direction is equal to or longer than the length of the metal layer in the planar direction, and the length of the metal layer in the planar direction is more than 0.1 μm longer than the length of the substrate (sealing substrate) in the planar direction.

[0230] Examples of methods for shaping a sealing member into the aforementioned shape include laser removal and mechanical scribing. This shaping can be performed before or after the sealing member is bonded to other components.

[0231] UV cutoff layer formation process

[0232] The manufacturing method of a photoelectric conversion module with a photoelectric conversion device can include a UV cut-off layer forming process as needed to form a UV cut-off layer on the incident surface side.

[0233] Other processes

[0234] The manufacturing method of a photoelectric conversion module with a photoelectric conversion device can include, as needed, processes for forming an insulating porous layer, a degradation prevention layer, and a protective layer.

[0235] Specific examples related to the manufacturing methods of photoelectric conversion devices and photoelectric conversion modules for organic thin-film solar cells.

[0236] Figures 6A to 6K An example illustrating a method for manufacturing a photoelectric conversion module having a photoelectric conversion device. Figures 6A to 6K This is a schematic diagram illustrating an example of a method for manufacturing a photoelectric conversion module.

[0237] like Figure 6AAs shown, firstly, a first electrode 13 (another electrode) is formed on a substrate 12 with gas barrier properties. When multiple photoelectric conversion devices are formed on a substrate 12, such as Figure 6B As shown, a portion of the first electrode 13 is removed to form a first partition 13'. The photoelectric conversion device to be formed on the left side of the partition 13' is called the first photoelectric conversion device, and the photoelectric conversion device to be formed on the right side of the partition 13' is called the second photoelectric conversion device. Next, as... Figure 6C and Figure 6D As shown, a first electron transport layer 14 and a second electron transport layer (intermediate layer) 15 are formed on the substrate 12 and the first electrode 13. Next, as... Figure 6E As shown, a photoelectric conversion layer 16 is formed on the second electron transport layer 15 thus formed. After the photoelectric conversion layer 16 is formed, as... Figure 6F As shown, a predetermined area of ​​the first electron transport layer 14, the second electron transport layer 15, and the photoelectric conversion layer 16 formed on the first electrode 13 is removed to form a through-hole 16'. After forming the through-hole 16', as... Figure 6G and Figure 6H As shown, a hole transport layer 17 and a second electrode 18 are formed. With the formation of the hole transport layer 17 and the second electrode 18, a connecting portion 18' is formed in the through portion 16', which is a structure made of the material of the hole transport layer and the material of the second electrode. When multiple photoelectric conversion devices are formed on a substrate 12, such as... Figure 6I As shown, a predetermined region between the second electrode 18 (one electrode) in the first photoelectric conversion device and the second electrode 18 (one electrode) in the second photoelectric conversion device is removed by penetrating the second electrode 18 and the hole transport layer 17 to form a second partition 13.” Then, as… Figure 6J As shown, a surface protection portion 19 is formed on the second electrode 18. At this time, along with the formation of the surface protection portion 19, a structure containing the material constituting the surface protection portion (assuming this structure is also part of the partition) is formed in the second partition 13”. Figure 6J As shown, this structure (separator) is continuous with each surface protection portion 19 in the first and second photoelectric conversion devices. Figure 6JAs shown, the aforementioned structure (separator) contacts the side surface of each second electrode 18 (one electrode) in the first and second photoelectric conversion devices, the side surface of each hole transport layer 17 in the first and second photoelectric conversion devices, and the photoelectric conversion layer 16. Since the structure (separator) has the same material as the material constituting the surface protection portion, it contacts and covers the photoelectric conversion layer and the side surface, thus suppressing the contact between water or oxygen penetrating from the outside and the layers of the photoelectric conversion layer; therefore, it can suppress corrosion and deterioration of the layers of the photoelectric conversion layer over time, thereby improving its storage durability. Next, as... Figure 6K As shown, the outer periphery of the laminated layer from electron transport layer 14 to surface protection portion 19 is removed to expose the first electrode 13, thereby forming a sealing region on the first electrode 13; and the laminated layer from electron transport layer to surface protection portion is encapsulated by sealing member 20, and the surface protection portion and sealing region are bonded together by bringing them into contact with each other. Next, the sealing member is shaped such that the insulating layer, metal layer, and substrate have the aforementioned shape at the upper end of the sealing member 20 in the planar direction.

[0238] Photovoltaic conversion devices related to dye-sensitized solar cells

[0239] As an example other than the photoelectric conversion device related to the above-mentioned organic thin-film solar cells, a photoelectric conversion device for dye-sensitized solar cells will be described.

[0240] The photoelectric conversion device includes at least a first electrode, a photoelectric conversion layer, and a second electrode in sequence. Furthermore, the photoelectric conversion layer includes an electron transport section, a photosensitive compound, and a hole transport section. Additionally, the photoelectric conversion device may include a surface protection section. The surface protection section is arranged adjacent to the surface of one of the electrodes selected from the first and second electrodes and not facing the photoelectric conversion layer.

[0241] Furthermore, the photoelectric conversion device has a sealing member. The sealing member is preferably arranged adjacent to the surface protection portion and encapsulates the surface protection portion, an electrode, and the photoelectric conversion layer.

[0242] In addition, the photoelectric conversion device may have a substrate (device substrate) as needed. The substrate (device substrate) is preferably arranged adjacent to another electrode on the side opposite to the photoelectric conversion layer of the other electrode.

[0243] In other words, as an example, the photoelectric conversion device has a configuration of a substrate (device substrate), a first electrode, a photoelectric conversion layer, a second electrode, a surface protection portion, and a sealing member stacked sequentially. Each component will be described below. However, descriptions of the substrate (device substrate), the first electrode, the second electrode, the surface protection portion, and the sealing member will be omitted because these components can be the same as those in the photoelectric conversion device of the aforementioned organic thin-film solar cell.

[0244] Photoelectric conversion layer

[0245] The photoelectric conversion layer has an electron transport section for transmitting electrons, a photosensitive compound for absorbing light and generating charge, and a hole transport section for transmitting holes.

[0246] Electronic transmission department

[0247] The electron transport section transports electrons generated by the photosensitive compound.

[0248] Depending on the requirements, the electron transport section includes electron transport materials and other materials. There are no particular limitations on the electron transport materials; they can be appropriately selected according to the purpose, with semiconductor materials being preferred. The semiconductor materials have a particulate shape and are preferably formed into a porous film by bonding together. A photosensitive compound is chemically or physically adsorbed onto the surface of the semiconductor particles constituting the porous electron transport section.

[0249] There are no particular restrictions on semiconductor materials; therefore, any known materials can be used, such as single semiconductors, compound semiconductors, and compounds with perovskite structures.

[0250] Examples of single semiconductors include silicon and germanium.

[0251] Examples of compound semiconductors include metal chalcogenides, specifically oxides of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, and tantalum; sulfides of cadmium, zinc, lead, silver, antimony, and bismuth; selenides of cadmium and lead; and cadmium telluride. Other examples of compound semiconductors include phosphides of metals such as zinc, gallium, indium, and cadmium, as well as gallium arsenide, copper indium selenide, and copper indium sulfide.

[0252] Examples of compounds with a perovskite structure include strontium titanate, calcium titanate, sodium titanate, barium titanate, and potassium niobate.

[0253] Among these, oxide semiconductors are preferred, and titanium dioxide, zinc oxide, tin oxide, and niobium oxide are more preferred. When titanium dioxide is used as the electron transport material in the electron transport section, it has a high conduction band, thus enabling a high open-circuit voltage. Furthermore, its refractive index is so high that a high short-circuit current can be obtained due to the light confinement effect. In addition, the improved dielectric constant and mobility bring the advantage of obtaining a high fill factor.

[0254] These can be used individually or in combination of two or more. There are no particular restrictions on the crystal type of semiconductor materials; therefore, the choice can be made according to the application. This can be any of single crystal, polycrystalline, or amorphous.

[0255] There is no particular limitation on the number-average particle size of the primary particles in the semiconductor material, so it can be selected according to the purpose. However, the diameter is preferably 1 nm or more and 100 nm or less, more preferably 5 nm or more and 50 nm or less. Furthermore, semiconductor materials with particle sizes larger than the number-average particle size can be mixed or stacked. Due to the scattering effect of the incident light caused by this, the conversion efficiency can be easily improved. In this case, the number-average particle size is preferably 50 nm or more and 500 nm or less.

[0256] There is no particular limitation on the average thickness of the electron transport section; therefore, it can be selected according to the purpose. However, the thickness is preferably 50 nm or more and 100 μm or less, more preferably 100 nm or more and 50 μm or less, and even more preferably 120 nm or more and 10 μm or less. When the average thickness of the electron transport section is within the preferred range, the amount of photosensitive compound per unit projected area is sufficiently ensured to maintain a high light capture rate, and the diffusion distance of the injected electrons is not easily increased, thereby reducing losses due to charge recombination.

[0257] Photosensitive compounds

[0258] Photosensitive compounds are adsorbed onto the surface of the semiconductor material constituting the electron transport section to further improve output and photoelectric conversion efficiency.

[0259] There are no particular restrictions on photosensitive compounds, as long as they can be photoexcited by light irradiating a photoelectric conversion device; therefore, selection can be made according to the purpose. Examples include metal complex compounds, coumarin compounds, polyene compounds, dihydroindole compounds, and thiophene compounds, which are known photosensitive compounds.

[0260] As a photosensitive compound, it is preferred to use at least one compound selected from the compounds represented by the following general formula (15) and the following general formula (16).

[0261]

[0262] In general formula (15), Ar1 and Ar2 each represent an aryl group that may have substituents. R1 and R2 each represent a straight-chain or branched alkyl group having 4 to 10 carbon atoms. X represents any substituent represented by the following structural formula.

[0263]

[0264] In general formula (16), n represents an integer of 0 or 1. R3 represents an aryl group that may have substituents, or any substituent represented by the following structural formula.

[0265]

[0266] Among the photosensitive compounds represented by general formula (15), compounds represented by the following general formula (17) are more preferred because high output can be obtained even under low brightness light.

[0267]

[0268] In general formula (17), Ar4 and Ar5 each represent a phenyl group that may have substituents or a naphthyl group that may have substituents. Ar6 represents a phenyl group that may have substituents or a thiophene group that may have substituents.

[0269] Hole transport unit

[0270] There are no particular limitations on the hole transport section; therefore, known materials can be used, as long as they have the function of transporting holes. Examples include an electrolyte solution containing redox pairs dissolved in an organic solvent, a gel electrolyte impregnated with a polymer containing a liquid containing redox pairs dissolved in an organic solvent, a molten salt containing redox pairs, a solid electrolyte, inorganic hole transport materials, and organic hole transport materials. Among these, while electrolytes and gel electrolytes can be used, solid electrolytes are preferred, and organic hole transport materials are more preferred.

[0271] Examples of organic hole transport materials include oxadiazole compounds, triphenylmethane compounds, pyrazoline compounds, hydrazone compounds, oxadiazole compounds, tetraarylbenzidine compounds, stilbene compounds, and spiro compounds. Spiro compounds are preferred among these.

[0272] For spiro compounds, for example, compounds represented by the following general formula (18) are preferred.

[0273]

[0274] In general formula (18), R 31 To R 34 Each can be used independently to represent substituted amino groups such as dimethylamino, diphenylamino, and naphthyl-4-tolylamino.

[0275] In addition, the hole transport layer preferably contains a lithium salt represented by the following general formula (19).

[0276]

[0277] In general formula (3), A and B each represent any one of the substituents F, CF3, C2F5, C3F7 and C4F9, where substituents A and B are different.

[0278] Examples of lithium salts include lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide (Li-FTFSI), lithium (fluorosulfonyl)(pentafluoroethanesulfonyl)imide (Li-FPFSI), lithium (fluorosulfonyl)(nonafluorobutyryl)imide (Li-FNFSI), lithium (nonafluorobutyryl)(trifluoromethanesulfonyl)imide (Li-NFTFSI), and lithium (pentafluoroethanesulfonyl)(trifluoromethanesulfonyl)imide (Li-PFTFSI). Of these, lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide (Li-FTFSI) is particularly preferred.

[0279] Photovoltaic conversion devices related to perovskite solar cells

[0280] As an example other than the photoelectric conversion devices related to the aforementioned organic thin-film solar cells, a photoelectric conversion device related to perovskite solar cells will be described.

[0281] A photoelectric conversion device has at least a first electrode, a photoelectric conversion layer, and a second electrode in sequence. When other layers are inserted between the electrodes and layers, an example may be a photoelectric conversion device having a first electrode, an electron transport layer, a photoelectric conversion layer, a hole transport layer, and a second electrode in sequence.

[0282] Additionally, the photoelectric conversion device may have a surface protection portion. The surface protection portion is arranged adjacent to the surface of an electrode selected from the first electrode and the second electrode, and which is not aligned with the photoelectric conversion layer.

[0283] In addition, the photoelectric conversion device has a sealing member. The sealing member is preferably adjacent to the surface protection portion and encapsulates the surface protection portion, an electrode, and the photoelectric conversion layer.

[0284] In addition, the photoelectric conversion device may have a substrate (device substrate) as needed. The substrate (device substrate) is preferably arranged adjacent to another electrode on the side that is not opposite to the photoelectric conversion layer of the other electrode.

[0285] In other words, as an example, the photoelectric conversion device has a configuration in which a substrate (device substrate), a first electrode, an electron transport layer, a photoelectric conversion layer, a hole transport layer, a second electrode, a surface protection portion, and a sealing member are stacked in sequence. Each component will be described below. However, descriptions of the substrate (device substrate), the first electrode, the second electrode, the surface protection portion, and the sealing member will be omitted because these components can be the same as those in the photoelectric conversion device of the aforementioned organic thin-film solar cell.

[0286] Electron transport layer

[0287] The electron transport layer transports electrons generated in the photoelectric conversion layer.

[0288] The electron transport layer contains an electron transport material. There are no particular restrictions on the electron transport material; therefore, it can be appropriately selected according to the purpose, with semiconductor materials being preferred. There are also no particular restrictions on the semiconductor material; therefore, any known material can be used, such as a single semiconductor and compounds having a compound semiconductor structure.

[0289] Examples of single semiconductors include silicon and germanium.

[0290] Examples of semiconductors include metal chalcogenides. Examples of metal chalcogenides include metal oxides (oxide semiconductors), metal sulfides, metal selenides, and metal tellurides. Examples of metal oxides (oxide semiconductors) include oxides of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, and tantalum. Examples of metal sulfides include sulfides of cadmium, zinc, lead, silver, antimony, and bismuth. Examples of metal selenides include selenides of cadmium and lead. Examples of metal tellurides include cadmium telluride. Examples of other compound semiconductors include phosphides of metals such as zinc, gallium, indium, and cadmium, as well as gallium arsenide, copper indium selenide, and copper indium sulfide.

[0291] Preferably, metal oxides (oxide semiconductors) are used, more preferably materials containing at least one of titanium oxide, zinc oxide, tin oxide, and niobium oxide, and particularly preferably tin oxide. These can be used alone or in combination of two or more. There are no particular restrictions on the crystal type of the semiconductor material; therefore, it can be selected as appropriate depending on the application. This can be any of single crystal, polycrystalline, or amorphous.

[0292] Photoelectric conversion layer

[0293] A photoelectric conversion layer is a layer that performs photoelectric conversion and has a perovskite layer containing perovskite compounds.

[0294] Perovskite compounds are composite materials of organic and inorganic compounds, and can be represented by the following general formula (20).

[0295] X α Y β M γ …General formula (20)

[0296] In general formula (20), the ratio of α:β:γ is 3:1:1, where β and γ are integers greater than 1. For example, X can be a halide ion, Y can be an ion of an organic compound with an amino group, and M can be a metal ion.

[0297] X in the above general formula (20) is not particularly limited and can be selected according to the purpose; for example, halide ions such as chlorine, bromine and iodine can be used. These can be used alone or in combination of two or more.

[0298] In the above general formula (20), Y can be: an organic cation, such as the ion of alkylamine compounds including methylamine, ethylamine, n-butylamine and formamidinium, or an inorganic alkali metal cation, such as cesium ion, potassium ion and rubidium ion. These can be used alone or in combination of two or more, and inorganic alkali metal cations can be used in combination with organic cations.

[0299] M in the above general formula (20) is not particularly limited and can be selected according to the purpose. For example, metal ions such as lead, indium, antimony, tin, copper and bismuth can be used. These can be used alone or in combination of two or more.

[0300] The preferred perovskite layer has a layered perovskite structure, in which layers of metal halide and organic cation molecules are alternately stacked.

[0301] Hole transport layer

[0302] The hole transport layer transports holes generated in the photoelectric conversion layer.

[0303] The hole transport layer contains hole transport material. There are no particular limitations on the hole transport material; therefore, it can be appropriately selected according to the purpose, preferably including compounds having repeating structures represented by the following general formula (21) and compounds represented by the following general formula (22).

[0304]

[0305] In general formula (21), Ar1 represents an aryl group. Examples of aryl groups include phenyl, 1-naphthyl, and 9-anthrayl. Aryl groups may have substituents. Examples of substituents include alkyl, alkoxy, and aryl groups. Ar2, Ar3, and Ar4 each independently represent an arylene and a divalent heterocyclic group. Examples of arylene groups include 1,4-phenylene, 1,1'-biphenylene, and 9,9'-di-n-hexylfluorene. A divalent heterocyclic group may be, for example, 2,5-thiophene. R1 through R4 each independently represent a hydrogen atom, an alkyl group, and an aryl group. Examples of alkyl groups include methyl and ethyl. Examples of aryl groups include phenyl and 2-naphthyl. Alkyl and aryl groups may have substituents.

[0306]

[0307] In general formula (22), R1 to R5 represent hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, or aryl groups, which may be the same or different. X represents a cation. R1 and R2, or R2 and R3, may form a ring structure together.

[0308] Examples of halogen atoms include chlorine, bromine, and iodine atoms.

[0309] Alkyl groups include, for example, alkyl groups having 1 to 6 carbon atoms. Alkyl groups can be substituted with halogen atoms.

[0310] The alkoxy group can be, for example, an alkoxy group having 1 to 6 carbon atoms.

[0311] The aryl group can be, for example, phenyl.

[0312] There are no particular restrictions on the cations; therefore, selection can be made according to the purpose. Examples include alkali metal cations, phosphonium cations, iodonium cations, nitrogen-containing cations, and sulfonium cations. Nitrogen-containing cations here refer to ions with a positive charge on the nitrogen atom, such as ammonium cations, pyridinium cations, and imidazolium cations.

[0313] Apart from compounds having repeating structures represented by general formula (21) and compounds represented by general formula (22), there are no particular restrictions on hole-transporting materials as long as they are hole-transporting materials; therefore, selection can be made according to the purpose. Here, organic compounds are preferred, including polymeric materials and low molecular weight materials as described below.

[0314] There are no particular restrictions on the polymer materials used in the hole transport layer; therefore, they can be selected depending on the purpose. Examples include polythiophene compounds, polyphenylene vinylidene compounds, polyfluorene compounds, polyphenylene compounds, and polythiadiazole compounds.

[0315] Examples of polythiophene compounds include poly(3-n-hexylthiophene), poly(3-n-octylthiophene), poly(9,9'-dioctyl-fluorene-co-bithiophene), poly(3,3”'-eicosyltetrathiophene), poly(3,6-dioctylthiopheneno[3,2-b]thiophene), poly(2,5-bis(3-decylthiophene-2-yl)thiopheneno[3,2-b]thiophene), poly(3,4-didecylthiophene-co-thiopheneno[3,2-b]thiophene), poly(3,6-dioctylthiophene[3,2-b]thiophene-co-thiopheneno[3,2-b]thiophene), poly(3,6-dioctylthiophene[3,2-b]thiophene-co-thiophene), and poly(3,6-dioctylthiophene[3,2-b]thiophene-co-bithiophene).

[0316] Examples of polyphenylene vinylidene compounds include poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylidene], poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylene vinylidene] and poly[(2-methoxy-5-(2-ethylphenylhexyloxy)-1,4-phenylene vinylidene)-co-(4,4'-phenylene vinylidene)].

[0317] Examples of polyfluorene compounds include poly(9,9'-eicosylfluorene-2,7-diyl), poly[(9,9-dioctyl-2,7-divinylfluorene)-alt-co-(9,10-anthracene)], poly[(9,9-dioctyl-2,7-divinylfluorene)-alt-co-(4,4'-biphenyl)], poly[(9,9-dioctyl-2,7-divinylfluorene)-alt-co-(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene)], and poly[(9,9-dioctyl-2,7-diyl)-co-(1,4-(2,5-dihexyloxy)benzene)].

[0318] Examples of polyphenylene compounds include poly[2,5-dioctyloxy-1,4-phenylene] and poly[2,5-di(2-ethylhexyloxy)-1,4-phenylene].

[0319] Examples of polythiadiazole compounds include poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(1,4-benzo(2,1',3)thiadiazole)] and poly(3,4-decylthiophene-co-(1,4-benzo(2,1',3)thiadiazole).

[0320] There are no particular restrictions on the low molecular weight materials used in the hole transport layer; therefore, selection can be made according to the purpose. Examples include oxadiazole compounds, triphenylmethane compounds, pyrazoline compounds, hydrazone compounds, tetraarylbenzidine compounds, stilbene compounds, spirodifluorene compounds, and thiophene oligomers.

[0321] Electronic devices

[0322] The electronic device includes at least the aforementioned photoelectric conversion device (or a photoelectric conversion module having multiple photoelectric conversion devices) and a device electrically connected to the photoelectric conversion device. The device electrically connected to the photoelectric conversion device is a device capable of operating by the electricity generated by the photoelectric conversion performed by the photoelectric conversion device. Depending on its application, the electronic device can have multiple embodiments, including the first and second embodiments described below.

[0323] The first embodiment is an electronic device having a photoelectric conversion device, a device electrically connected to the photoelectric conversion device, and other devices as needed.

[0324] The second embodiment is an electronic device having a photoelectric conversion device, a battery electrically connected to the photoelectric conversion device, a device electrically connected to the photoelectric conversion device and the battery, and other devices as needed.

[0325] Power module

[0326] The power module has at least a photoelectric conversion device, a power IC (integrated circuit) electrically connected to the photoelectric conversion device, and other devices as needed.

[0327] usage

[0328] Photovoltaic conversion devices can be used as independent power sources, where the electricity generated by photoelectric conversion can power the device. Since the photovoltaic conversion device generates electricity upon exposure to light, there is no need to connect the electronic device to an external power source or replace batteries. This allows the electronic device to be carried around and operated in places without a power source, and to operate in locations where battery replacement is difficult or necessary. Furthermore, when using dry cell batteries in electronic devices, the device's weight and size increase, making it difficult to install on walls or ceilings or carry around. However, due to its slim and lightweight design, the photovoltaic conversion device offers greater freedom in choosing installation locations and also provides advantages in terms of wearing and carrying.

[0329] Therefore, since photoelectric conversion devices can be used as independent power sources, electronic devices equipped with photoelectric conversion devices can be used in a wide variety of applications. Examples of applications for electronic devices with photoelectric conversion devices include display devices (such as desktop calculators, watches, mobile phones, electronic notebooks, and electronic paper), personal computer accessories (such as personal computer mice and personal computer keyboards), various sensing devices (such as temperature / humidity sensors and human body sensors), transmitters (such as beacons and Global Positioning System (GPS), auxiliary lights, and remote controls).

[0330] The photoelectric conversion device of this invention can generate electricity even under low illumination conditions. Low illumination refers to, for example, the illuminance of indoor lighting. Specifically, this illuminance is between 20 lux and 1000 lux, which is very low compared to direct sunlight (approximately 100,000 lux). In other words, it can generate electricity indoors even in dim shadows, making it suitable for a wide range of applications. It is also safe because there is no leakage like with dry cell batteries, and it cannot be accidentally swallowed like with button batteries. Furthermore, it can be used as an auxiliary power source to extend the continuous use time of rechargeable or dry cell battery-powered appliances. Therefore, by combining the photoelectric conversion device with a device that utilizes the electricity generated by photoelectric conversion, a lightweight, easy-to-use, flexible installation location, replacement-free, highly safe electronic device that effectively reduces environmental impact can be obtained. Therefore, electronic devices equipped with photoelectric conversion devices can be used for a variety of purposes.

[0331] Figure 7 This is a schematic diagram illustrating an example of the basic configuration of an electronic device that combines a photoelectric conversion device with a circuitry that operates by the power generated by the photoelectric conversion of the photoelectric conversion device; when the photoelectric conversion device is illuminated with light, this generates power, which can be extracted and used to operate the circuitry.

[0332] However, because the output of the photoelectric conversion device varies with ambient light, Figure 7 The electronic device shown does not always operate stably. Therefore, in order to provide a stable voltage to the device circuitry, it is preferable to install a power supply IC between the photoelectric conversion device and the device circuitry, such as... Figure 8 A schematic diagram of an example of the basic configuration of an electronic device is shown.

[0333] Photovoltaic conversion devices can generate electricity under sufficient sunlight. However, when the illuminance is insufficient, the expected power cannot be obtained, which is a drawback of photovoltaic conversion devices. In such cases, such as... Figure 9 A schematic diagram illustrating a basic configuration of an electronic device shows that, by installing a storage device such as a capacitor between the power supply IC and the device circuitry, excess power can be transferred from the photoelectric conversion device to the storage device. Therefore, even in low illumination conditions or when the photoelectric conversion device is not illuminated, the power stored in the storage device can be supplied to the device circuitry, enabling the device circuitry to operate stably.

[0334] Thus, in electronic devices that combine photoelectric conversion devices with device circuitry, by combining a power IC with an energy storage device, the device can operate even in environments without power, and can be driven stably without battery replacement, making electronic devices equipped with photoelectric conversion devices usable in a variety of applications.

[0335] In addition, photoelectric conversion devices can also be used as power modules. For example, such as Figure 10 The diagram illustrates an example of a basic configuration of a power module. When the photoelectric conversion device is connected to the power IC, a DC power module can be constructed that can supply the power generated by the photoelectric conversion device to the power IC at a constant voltage level.

[0336] In addition, such as Figure 11 A schematic diagram illustrating an example of the basic structure of a power module shows how, by adding a storage device to the power IC, the power generated by the photoelectric conversion device can be charged into the storage device. Therefore, a power module capable of supplying power can be constructed even in very low illumination conditions or when the photoelectric conversion device has no light.

[0337] Figure 10 and Figure 11 The power module shown can be used as a power module that does not require battery replacement, unlike traditional primary batteries. Therefore, power modules with photoelectric conversion devices can be used in a variety of applications.

[0338] The following section will describe specific applications of electronic devices with photoelectric conversion devices and devices that can be operated by electricity.

[0339] Applications of personal computer mice

[0340] Figure 12 This is a schematic diagram illustrating an example of the basic structure of a personal computer mouse (hereinafter also referred to as "mouse"), an example of an electronic device. For example... Figure 12 As shown, the mouse includes a photoelectric conversion device, a power supply IC, a power storage device, and a mouse control circuit. The power for the mouse control circuit is supplied by the connected photoelectric conversion device or power storage device. This allows the power storage device to be charged when the mouse is not in use, enabling the mouse to operate on that charge; thus, a mouse that eliminates the need for wiring or battery replacements can be obtained. Furthermore, because no battery is required, the weight of the device can be reduced, making it suitable for mouse applications.

[0341] Figure 13 yes Figure 12 The illustration shows the appearance of an example of a personal computer mouse. Figure 13 As shown, the photoelectric conversion device, power IC, power storage device, and mouse control circuit are installed inside the mouse. The top of the photoelectric conversion device is covered by a transparent shell to allow light to reach it. The entire mouse shell can also be molded from transparent resin. The placement of the photoelectric conversion device is not limited to this; for example, even if the mouse is covered by a hand, it can be placed in a position where light can reach the photoelectric conversion device.

[0342] PC keyboard applications

[0343] Figure 14 This is a schematic diagram illustrating an example of the basic structure of a personal computer keyboard (hereinafter also referred to as "keyboard"), which is an example of an electronic device. For example... Figure 14 As shown, the keyboard includes a photoelectric conversion device, a power supply IC, a power storage device, and a keyboard control circuit. The power for the keyboard control circuit is supplied by the connected photoelectric conversion device or power storage device. This allows the power storage device to be charged when the keyboard is not in use, enabling the keyboard to operate with that power; thus, a keyboard that eliminates the need for wiring or battery replacements can be obtained. Furthermore, because no battery is required, the weight of the device can be reduced, making it suitable for keyboard applications.

[0344] Figure 15 yes Figure 14 The image shows a schematic of a personal computer keyboard. Figure 15 As shown, the photoelectric conversion device, power IC, energy storage device, and keyboard control circuit are installed inside the keyboard. The top of the photoelectric conversion device is covered by a transparent shell to allow light to reach it. The entire keyboard shell can also be molded from transparent resin. The placement of the photoelectric conversion device is not limited to this. For example, when the space in the keyboard to accommodate the photoelectric conversion device is small, a small photoelectric conversion device can be embedded in some of the keys, such as... Figure 16 A schematic view of another example of a personal computer keyboard is shown.

[0345] Sensor Applications

[0346] Figure 17 This is a schematic diagram illustrating an example of the basic structure of a sensor, which is an example of an electronic device. For example... Figure 17 As shown, the sensor comprises a photoelectric conversion device, a power supply IC, a power storage device, and a sensor circuit. Power for the sensor circuit is supplied by the connected photoelectric conversion device or power storage device. This allows the sensor to be configured without connecting to an external power source or replacing batteries. The sensor's sensing targets can include temperature, humidity, illuminance, human presence, CO2, acceleration, UV radiation, noise, geomagnetism, and air pressure. Figure 18 As shown in A, the sensor preferably senses the target periodically and transmits the acquired data to a personal computer (PC) or smartphone via wireless communication.

[0347] With the advent of the Internet of Things (IoT) society, sensors are expected to rapidly become ubiquitous. However, replacing the battery in each of these countless sensors would be cumbersome and impractical. Furthermore, sensor operability is reduced if placed in locations where battery replacement is difficult, such as ceilings and walls. Therefore, sensors powered by photoelectric conversion devices offer significant advantages. The photoelectric conversion device according to the invention also boasts high output even under low illumination and low dependence on the angle of light incidence, resulting in a high degree of freedom in choosing its installation location.

[0348] Turntable Applications

[0349] Figure 19 This is a schematic diagram illustrating an example of the basic structure of a turntable, which is an example of an electronic device. For example... Figure 19 As shown, the turntable includes a photoelectric conversion device, a power supply IC, a power storage device, and a turntable control circuit. The power for the turntable control circuit is supplied by the connected photoelectric conversion device or power storage device. This allows the turntable to be configured without connecting to an external power source or replacing batteries. For example, a turntable used in a display case showcasing merchandise would be unattractive if power wiring were required. Furthermore, replacing batteries necessitates removing the displayed items, a cumbersome process. Therefore, a turntable powered by a photoelectric conversion device offers significant advantages.

[0350] Example

[0351] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments at all.

[0352] Example 1

[0353] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0354] Substrate with first electrode

[0355] First, a polyethylene terephthalate (PET) substrate (50 mm x 50 mm) with an indium-doped tin oxide (ITO) patterned barrier layer was purchased from Geomatics Ltd. For example... Figure 6B As shown, the first partition is formed in the first electrode.

[0356] Formation of the first electron transport layer

[0357] Next, a solution of zinc oxide nanoparticles (average particle size of 12 nm, manufactured by Aldrich) was spin-coated onto an ITO barrier PET film (15 Ω / sq) at 3000 rpm and dried at 100 °C for 10 minutes to form the first electron transport layer.

[0358] Formation of the second electron transport layer (intermediate layer)

[0359] Next, dimethylaminobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in ethanol to prepare a 1 mg / ml solution, which was then spin-coated onto the first electron transport layer at a speed of 3000 rpm to form a second electron transport layer with an average thickness of less than 10 nm.

[0360] Formation of photoelectric conversion layer

[0361] Next, 16 mg of the following example compound 1 (number-average molecular weight (Mn) of 1,463 and highest occupied molecular orbital (HOMO) energy level of 5.27 eV), 1 mg of the following example compound 2 (number-average molecular weight (Mn) of 15,000 and highest occupied molecular orbital (HOMO) energy level of 5.33 eV) and 10 mg of the following example compound 3 were dissolved in 1 mL of chloroform to obtain photoelectric conversion layer coating solution A.

[0362]

[0363]

[0364] Next, photoelectric conversion layer coating solution A is spin-coated onto the intermediate layer at 600 rpm to form a photoelectric conversion layer with an average thickness of 220 nm.

[0365] Formation of the through section

[0366] Next, as a preliminary step, a through-section is formed to create a connection that links the photoelectric conversion devices in series. The through-section is formed (deleted) using a laser. In the plan view of the photoelectric conversion device viewed from the second electrode side, the through-section is rectangular in shape.

[0367] Formation of hole transport layer, second electrode and connector

[0368] Next, a hole transport layer material composed of molybdenum oxide (manufactured by Japan Pure Chemical Co., Ltd.) with an average thickness of 50 nm and a second electrode material composed of silver with an average thickness of 100 nm are sequentially deposited on the photoelectric conversion layer and the through-hole portion by vacuum phase deposition to form the hole transport layer, the second electrode, and the connection portion. Figure 6I As shown, the second partition is formed on the second electrode.

[0369] Formation of surface protective layer

[0370] Next, a material for surface protection, consisting of a fluorinated silane compound (DURASURF DS-5935F130, a compound satisfying general formula (A), manufactured by Harves Ltd.), is spin-coated onto the second electrode at 1000 rpm.

[0371] Formation of the sealing area

[0372] Next, a laser processing machine (manufactured by TOWA Laserfront) is used to remove the outer periphery (3 mm wide) of the stack from the formed electron transport layer to the surface protective layer to expose the first electrode, thereby forming a sealing area on the first electrode.

[0373] Formation of sealing components

[0374] Next, a sealing member formed by sequentially laminating a polyolefin resin adhesive component (pressure-sensitive adhesive resin, manufactured by MORESCO) and an Al / PET laminated gas barrier component (manufactured by Toyo Aluminium KK) is arranged to encapsulate from the electron transport layer to the surface protective layer and to contact the sealing area on the first electrode; then, they are bonded together using a vacuum laminator (manufactured by Joyo Engineering Ltd.) with an applied pressure of 0.2 MPa.

[0375] Formation of the end shape of the sealing component

[0376] Next, by using a laser marking machine (manufactured by Seishin Trading Ltd.), the end of the sealing member in the face direction is processed so that the length of the insulating layer in the face direction is equal to or longer than the length of the metal layer in the face direction, and the length of the metal layer in the face direction is longer than the length of the substrate in the face direction, so as to obtain a photoelectric conversion device.

[0377] Calculation of short-circuit occurrence rate after surface load test

[0378] First, the current-voltage characteristics of the manufactured photoelectric conversion device were measured under illumination from a white LED (color temperature 5000K, illuminance 200 lx). Measurements were performed using a bulb-type LED lamp (LDA11N-G / 40W, manufactured by Toshiba Lighting Technology Co., Ltd.) with white LED illumination and a KETSIGHT B2902A evaluation instrument (light source meter). The output of the LED light source was measured using a Sekonic C-7000 spectrometer.

[0379] Next, a surface load test was conducted as follows. Specifically, the photoelectric conversion device, whose photoelectric conversion efficiency had been measured, was placed between two smooth glass plates, each 0.7 mm thick; then, after placing it on a horizontal platform, a weight of approximately 1,422 N / m was placed on it according to JIS 8938-1995. 2 The stress is applied for about 1 minute.

[0380] Next, the photoelectric conversion devices were removed after the surface load test, and their current-voltage characteristics were measured in the same manner as in the surface load test. A short circuit was considered to have occurred when the open-circuit voltage after the surface load test was less than 10% of the open-circuit voltage before the test; this was counted as the number of short circuits. However, as a result of optical microscopic observation of the short-circuited devices, factors other than conductivity at the end of the sealing member (such as film defects in the photoelectric conversion area) were excluded from the count when considered as the cause of the short circuit. This measurement was performed on 50 photoelectric conversion devices. The result was that the short circuit rate, the ratio of the number of short circuits to the total number of measurements, was calculated as 0%.

[0381] Measurement of the end shapes (Δ1 and Δ2) of the sealing component

[0382] Another photoelectric conversion device was manufactured under the same manufacturing conditions as the photoelectric conversion device used in the measurement of short-circuit occurrence rate after the surface load test described above. The cross-section of the photoelectric conversion device in the surface at three locations, including the lamination direction, was exposed using an Ion Milling microscope (manufactured by Hitachi High-Tech). The end of the sealing member in the planar direction was then observed using a scanning electron microscope (SEM, manufactured by Carl Zeiss Ag). Next, in the observed images, a position approximately 500 μm away in the planar direction from the end of the most protruding portion of the sealing member in the adhesive member (insulating layer), metal layer (Al), and substrate (PET) was determined. Then, a reference line L0 parallel to the lamination direction and passing through this position was established. Next, the maximum length L between the reference line L0 and the end of the adhesive member (insulating layer) in the planar direction was measured. 21 The maximum length L between the baseline L0 and the end of the metal layer in the surface direction 23 The maximum length L of the baseline L0 and the end of the substrate (PET) in the planar direction 24 Then, by length L 21 L 23 and L 24 Determine Δ1(L) 21 -L 23 ) and Δ2(L 23 -L 24 The average values ​​of Δ1 and Δ2 at the three locations were calculated to obtain Δ1 of 5.0 μm and Δ2 of 10.0 μm. These values ​​differ from the target values ​​during process execution by less than ±50 nm.

[0383] Example 2

[0384] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0385] In the preparation of the photoelectric conversion device in Example 1, the photoelectric conversion device was prepared in the same manner as in Example 1, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 10.0 μm.

[0386] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0387] Example 3

[0388] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0389] In the preparation of the photoelectric conversion device in Example 1, the photoelectric conversion device was prepared in the same manner as in Example 1, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 2.0 μm.

[0390] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0391] Example 4

[0392] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0393] In the preparation of the photoelectric conversion device in Example 1, the photoelectric conversion device was prepared in the same manner as in Example 1, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 1.0 μm.

[0394] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0395] Example 5

[0396] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0397] In the preparation of the photoelectric conversion device in Example 1, the photoelectric conversion device was prepared in the same manner as in Example 1, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 0.9 μm.

[0398] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0399] Example 6

[0400] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0401] In the preparation of the photoelectric conversion device in Example 1, the photoelectric conversion device was prepared in the same manner as in Example 1, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 0.5 μm.

[0402] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0403] Example 7

[0404] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0405] In the preparation of the photoelectric conversion device in Example 1, the photoelectric conversion device was prepared in the same manner as in Example 1, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 0.1 μm.

[0406] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0407] Example 8

[0408] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0409] In the preparation of the photoelectric conversion device in Example 7, the photoelectric conversion device was prepared in the same manner as in Example 7, except that the photoelectric conversion layer coating liquid A was changed to the photoelectric conversion layer coating liquid B described later.

[0410] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0411] Photoelectric conversion layer coating liquid B

[0412] Preparation of photoelectric conversion layer coating solution B: 16 mg of the following example compound 4 (number average molecular weight (Mn) of 1554 and highest occupied molecular orbital (HOMO) energy level of 5.13 eV), 1 mg of the following example compound 5 (number average molecular weight (Mn) of 58737 and highest occupied molecular orbital (HOMO) energy level of 5.33 eV, manufactured by Ossila Ltd.) and 10 mg of PC61BM (E100H, manufactured by Frontier Carbon Ltd.) were dissolved in 1 mL of chloroform.

[0413]

[0414] Example 9

[0415] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0416] In the preparation of the photoelectric conversion device in Example 7, the photoelectric conversion device was prepared in the same manner as in Example 7, except that the photoelectric conversion layer coating liquid A was changed to the photoelectric conversion layer coating liquid C described later.

[0417] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0418] Photoelectric conversion layer coating liquid C

[0419] Preparation of photoelectric conversion layer coating solution C: 16 mg of the following example compound 6 (number average molecular weight (Mn) of 1886 and highest occupied molecular orbital (HOMO) energy level of 5.00 eV) and 10 mg of PC61BM (E100H, manufactured by Frontier Carbon) were dissolved in 1 mL of chloroform.

[0420]

[0421] Example 10

[0422] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0423] In the preparation of the photoelectric conversion device in Example 7, the photoelectric conversion device was prepared in the same manner as in Example 7, except that the photoelectric conversion layer coating liquid A was changed to the photoelectric conversion layer coating liquid D described later.

[0424] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0425] Photoelectric conversion layer coating liquid D

[0426] Preparation of photoelectric conversion layer coating solution D: 16 mg of the above-mentioned example compound 1 (number average molecular weight (Mn) of 1463 and highest occupied molecular orbital (HOMO) energy level of 5.27 eV), 1 mg of the above-mentioned example compound 2 (number average molecular weight (Mn) of 15000 and highest occupied molecular orbital (HOMO) energy level of 5.33 eV) and 10 mg of the following example compound 7 (ITIC-F, manufactured by Merck) were dissolved in 1 mL of chloroform.

[0427]

[0428] Example 11

[0429] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0430] In the fabrication of the photoelectric conversion device in Example 7, the photoelectric conversion device was fabricated in the same manner as in Example 7, except that a second electron transport layer (intermediate layer) was not formed.

[0431] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are summarized in Table 1.

[0432] Example 12

[0433] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0434] In the fabrication of the photoelectric conversion device in Example 7, the photoelectric conversion device was fabricated in the same manner as in Example 7, except that the first electron transport layer was not formed.

[0435] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0436] Example 13

[0437] Fabrication of photoelectric conversion devices (fabrication of dye-sensitized solar cells)

[0438] An ITO conductive film, serving as the first electrode, is sputtered onto a glass substrate to form an ITO-coated glass. On this ITO-coated glass, a dense layer composed of titanium oxide is formed by oxygen reaction sputtering as a hole-blocking layer.

[0439] Next, 3 g of titanium dioxide (trade name: P90, manufactured by AEROSIL JAPAN Co., Ltd.), 0.2 g of acetylacetone, 0.3 g of polyoxyethylene octylphenyl ether (manufactured by Wako Pure Chemical Industries Co., Ltd.) as a surfactant, were mixed with 5.5 g of water and 1.0 g of ethanol for 12 hours using a bead mill to obtain a titanium dioxide dispersion. 1.2 g of polyethylene glycol (trade name: polyethylene glycol 20000, manufactured by Wako Pure Chemical Industries Co., Ltd.) was added to the obtained titanium dioxide dispersion to prepare a paste. The paste thus prepared was coated onto a hole-blocking layer (average thickness 1.5 μm), dried at 50 °C, and calcined in air at 500 °C for 30 minutes to form a porous electron transport layer.

[0440] Next, the glass substrate on which the electron transport layer is formed is immersed in an acetonitrile / tert-butanol solution (volume ratio 1:1) of the photosensitive compound represented by the following example compound 8 (trade name: D358, Mitsubishi Paper Mills Ltd.); then, it is left to stand in the dark for 1 hour to allow the photosensitive compound to be adsorbed onto the surface of the electron transport layer.

[0441] Next, 19.0 mg of an alkali metal salt (Kanto Chemical Co., Ltd.) represented by Example Compound 10, 37.5 mg of an alkaline compound (Merck Co., Ltd.) represented by Example Compound 11, and 12.5 mg of an oxidant (trade name: FK269, Sigma-Aldrich Japan KK) represented by Example Compound 12 were dissolved in 1 mL of a chlorobenzene solution containing 186.5 mg of a hole transport material (Merck Co., Ltd.) represented by Example Compound 9 to prepare a hole transport layer coating solution. Then, the hole transport layer coating solution was spin-coated onto an electron transport layer on which the photosensitive compound was adsorbed to form a hole transport layer (average thickness of 600 nm).

[0442] Next, silver is vacuum-deposited onto the hole transport layer to form a second electrode (average thickness 100 nm).

[0443] Next, a material for surface protection, consisting of a fluorinated silane compound (DURASURF DS-5935F130, a compound satisfying general formula (A), manufactured by Harves Ltd.), is spin-coated onto the second electrode at 1000 rpm.

[0444] Next, in a plane parallel to the light-receiving surface, a laser processing machine (manufactured by TOWA Laserfront) is used to remove the hole transport layer on the periphery where no electron transport layer has been formed, so as to expose the first electrode and thereby form a sealing area on the first electrode.

[0445] Next, sealing components formed by sequentially layering polyolefin resin adhesive components (pressure-sensitive adhesive resin, manufactured by MORESCO) and Al / PET laminated gas barrier components (manufactured by Toyo Aluminium KK) are arranged to encapsulate the entire device except for the terminal portion; then, they are bonded together using a vacuum laminator (manufactured by Joyo Engineering Ltd.) with an applied pressure of 0.2 MPa.

[0446] Next, the end face of the sealing member is processed using a laser marking machine (manufactured by Seishin Trading Ltd.) so that the length of the insulating layer in the face direction is equal to or longer than the length of the metal layer in the face direction, and the length of the metal layer in the face direction is longer than the length of the substrate in the face direction, to obtain a photoelectric conversion device. Specifically, the end shape of the sealing member is processed to have Δ1 of 0 μm and Δ2 of 0.1 μm.

[0447] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0448]

[0449] Example 14

[0450] Fabrication of photoelectric conversion devices (fabrication of dye-sensitized solar cells)

[0451] In the preparation of the photoelectric conversion device in Example 13, the photoelectric conversion device was prepared in the same manner as in Example 13, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 1.0 μm.

[0452] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0453] Example 15

[0454] Fabrication of photoelectric conversion devices (fabrication of perovskite solar cells)

[0455] First, a solution obtained by dissolving 0.36 g of a 75% di(acetylacetonate) diisopropyl titanate solution in 10 ml of isopropanol was coated onto an FTO glass substrate using spin coating. The solution was dried at 120°C for 3 minutes and then calcined at 450°C for 30 minutes to form a first electrode and a dense electron transport layer (dense layer) on the substrate. The average thickness of the dense layer was 10 to 40 μm.

[0456] Next, a dispersion of titanium dioxide paste diluted with α-terpineol (trade name: MPT-20, manufactured by GreatCell Solar Ltd.) was applied to the dense layer using spin coating, dried at 120°C for 3 minutes, and then fired at 550°C for 30 minutes.

[0457] Next, spin coating was used to apply a solution containing 0.1 M (where M represents mol / dm³). 3An acetonitrile solution of lithium bis(trifluoromethanesulfonyl)imide (trade number: 38103, manufactured by Kanto Chemical Co., Ltd.) was coated onto the above-mentioned film, and then calcined at 450°C for 30 minutes to obtain a porous electron transport layer (porous layer). The average thickness of the porous layer is 150 nm.

[0458] Next, lead(II) iodide (0.5306 g), lead(II) bromide (0.0736 g), methylamine bromide (0.0224 g), and formamidinium iodide (0.1876 g) were added to N,N-dimethylformamide (0.8 ml) and dimethyl sulfoxide (0.2 ml); then, they were heated and stirred at 60 °C. Simultaneously with the addition of chloroform (0.3 ml), the resulting solution was spin-coated onto a porous layer to form a perovskite film; it was then dried at 150 °C for 30 minutes to obtain the perovskite layer. The average thickness of the perovskite layer was 200 to 350 nm. Furthermore, an isopropanol solution containing 1 mM 2-phenylethylammonium bromide was spin-coated onto the formed perovskite layer.

[0459] Next, 73.6 mg of the polymer described in Example Compound 13 and 7.4 mg of the additive described in Example Compound 14 were weighed and dissolved in 3.0 ml of chlorobenzene. The resulting solution was spin-coated onto the laminate obtained by the above process to obtain a hole transport layer. The average thickness of the hole transport layer (the portion on the perovskite layer) was 50 to 120 nm.

[0460] Next, a 100 nm layer of gold is deposited on the stack via vacuum phase deposition to form the second electrode.

[0461] Next, a material for surface protection, consisting of a fluorinated silane compound (DURASURF DS-5935F130, a compound satisfying general formula (A), manufactured by Harves Ltd.), is spin-coated onto the second electrode at 1000 rpm.

[0462] Next, in the area where no gold has been deposited, on the surface parallel to the light-receiving surface, the layers formed on the outer periphery are removed using a laser processing machine (TOWA Laserfront) to expose the first electrode, thereby forming a region that seals the first electrode.

[0463] Next, sealing components formed by sequentially layering polyolefin resin adhesive components (pressure-sensitive adhesive resin, manufactured by MORESCO) and Al / PET laminated gas barrier components (manufactured by Toyo Aluminium KK) are arranged to encapsulate the entire device except for the terminal portion; then, they are bonded together using a vacuum laminator (manufactured by Joyo Engineering Ltd.) with an applied pressure of 0.2 MPa.

[0464] Next, the end face of the sealing member is processed using a laser marking machine (manufactured by Seishin Trading Ltd.) so that the length of the insulating layer in the face direction is equal to or longer than the length of the metal layer in the face direction, and the length of the metal layer in the face direction is longer than the length of the substrate in the face direction, to obtain a photoelectric conversion device. Specifically, the end shape of the sealing member is processed to have Δ1 of 0 μm and Δ2 of 0.1 μm.

[0465] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0466]

[0467] Example 16

[0468] Fabrication of photoelectric conversion devices (fabrication of perovskite solar cells)

[0469] In the preparation of the photoelectric conversion device in Example 15, the photoelectric conversion device was prepared in the same manner as in Example 15, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 1.0 μm.

[0470] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0471] Comparative Example 1

[0472] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0473] In the preparation of the photoelectric conversion device in Example 1, the photoelectric conversion device was prepared in the same manner as in Example 1, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 0 μm.

[0474] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0475] Comparative Example 2

[0476] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0477] In the preparation of the photoelectric conversion device in Example 1, the photoelectric conversion device was prepared in the same manner as in Example 1, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = -0.5 μm.

[0478] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0479] Comparative Example 3

[0480] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0481] In the preparation of the photoelectric conversion device in Example 1, the photoelectric conversion device was prepared in the same manner as in Example 1, except that the end shape of the sealing member was processed to be Δ1 = -0.1 μm and Δ2 = 2.0 μm.

[0482] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0483] Comparative Example 4

[0484] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0485] In the preparation of the photoelectric conversion device in Example 8, the photoelectric conversion device was prepared in the same manner as in Example 8, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 0 μm.

[0486] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0487] Comparative Example 5

[0488] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0489] In the preparation of the photoelectric conversion device in Example 9, the photoelectric conversion device was prepared in the same manner as in Example 9, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 0 μm.

[0490] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0491] Comparative Example 6

[0492] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0493] In the preparation of the photoelectric conversion device in Example 10, the photoelectric conversion device was prepared in the same manner as in Example 10, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 0 μm.

[0494] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0495] Comparative Example 7

[0496] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0497] In the preparation of the photoelectric conversion device in Example 11, the photoelectric conversion device was prepared in the same manner as in Example 11, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 0 μm.

[0498] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0499] Comparative Example 8

[0500] Fabrication of photoelectric conversion devices (fabrication of organic thin-film solar cells)

[0501] In the preparation of the photoelectric conversion device in Example 12, the photoelectric conversion device was prepared in the same manner as in Example 12, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 0 μm.

[0502] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0503] Comparative Example 9

[0504] Fabrication of photoelectric conversion devices (fabrication of dye-sensitized solar cells)

[0505] In the preparation of the photoelectric conversion device in Example 13, the photoelectric conversion device was prepared in the same manner as in Example 13, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 0 μm.

[0506] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0507] Comparative Example 10

[0508] Fabrication of photoelectric conversion devices (fabrication of dye-sensitized solar cells)

[0509] In the preparation of the photoelectric conversion device in Example 13, the photoelectric conversion device was prepared in the same manner as in Example 13, except that the end shape of the sealing member was processed to be Δ1 = -0.1 μm and Δ2 = 2.0 μm.

[0510] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0511] Comparative Example 11

[0512] Fabrication of photoelectric conversion devices (fabrication of perovskite solar cells)

[0513] In the preparation of the photoelectric conversion device in Example 15, the photoelectric conversion device was prepared in the same manner as in Example 15, except that the end shape of the sealing member was processed to be Δ1 = 0 μm and Δ2 = 0 μm.

[0514] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0515] Comparative Example 12

[0516] Fabrication of photoelectric conversion devices (fabrication of perovskite solar cells)

[0517] In the preparation of the photoelectric conversion device in Example 15, the photoelectric conversion device was prepared in the same manner as in Example 15, except that the end shape of the sealing member was processed to be Δ1 = -0.1 μm and Δ2 = 2.0 μm.

[0518] The short-circuit incidence rate and the end shapes (Δ1, Δ2) of the sealing components were calculated after the surface load test in the same manner as in Example 1. The results are listed in Table 1.

[0519] Table 1

[0520]

[0521] The results in Table 1 show that the photoelectric conversion device according to the present invention has Δ1 greater than 0 μm and Δ2 greater than 0.1 μm, thus it can be seen that this can suppress the increase in short-circuit incidence after surface load test.

[0522] The above embodiments are illustrative and do not limit the invention. Therefore, many additional modifications and variations are possible based on the above teachings. For example, within the scope of this disclosure and the appended claims, at least one element of the different illustrative and exemplary embodiments herein may be combined with or substituted for each other. Furthermore, the number, position, shape, etc., of the constituent elements of the embodiments are not limited to any particular embodiment and may be preferably set. Therefore, it should be understood that within the scope of the appended claims, the disclosure of this invention may be practiced in ways different from those specifically described herein.

Claims

1. A photoelectric conversion device, comprising, in sequence, a device substrate, a first electrode, a photoelectric conversion layer, and a second electrode, wherein, The photoelectric conversion device includes a sealing member on the non-opposing side of the second electrode, wherein the non-opposing side is not opposite to the photoelectric conversion layer. The sealing component, starting from the second electrode, sequentially comprises an insulating layer, a metal layer, and a sealing substrate. The insulating layer includes a pressure-sensitive adhesive resin. The sealing substrate includes at least one of a resin film and a thin glass film. The photoelectric conversion device further includes a surface protection portion between the second electrode and the insulating layer, and At the end of the sealing member in the face direction, the length of the insulating layer in the face direction is equal to or longer than the length of the metal layer in the face direction, and the length of the metal layer in the face direction is more than 0.1 μm longer than the length of the sealing substrate in the face direction.

2. The photoelectric conversion device according to claim 1, wherein At the end, the length of the metal layer in the surface direction is more than 1.0 μm longer than the length of the sealing substrate in the surface direction.

3. The photoelectric conversion device according to claim 1 or 2, wherein, At the end, the thickness of the insulating layer is less than 50.0 μm.

4. The photoelectric conversion device according to claim 1 or 2, wherein, The photoelectric conversion device comprises, in sequence, the first electrode, the insulating layer, the metal layer, and the substrate at its end in the planar direction.

5. The photoelectric conversion device according to claim 1 or 2, wherein, It includes, in sequence, the first electrode, the electron transport layer, the photoelectric conversion layer, the hole transport layer, and the second electrode.

6. The photoelectric conversion device according to claim 1 or 2, wherein, The photoelectric conversion layer comprises organic materials with a highest occupied molecular orbital (HOMO) energy level of 5.1 eV or higher and 5.5 eV or lower, and a number-average molecular weight (Mn) of 10,000 or lower.

7. The photoelectric conversion device according to claim 6, wherein, The photoelectric conversion layer also includes organic materials with a highest occupied molecular orbital (HOMO) energy level of 5.2 eV or higher and 5.6 eV or lower, and a number-average molecular weight (Mn) of 10,000 or higher.

8. The photoelectric conversion device according to claim 1 or 2, wherein, The photoelectric conversion layer contains a compound represented by the following general formula (1): …General formula (1) In the general formula (1), R1 represents an alkyl group having 2 or more and 8 or fewer carbon atoms, n represents an integer of 1 or more and 3 or fewer, X is represented by the following general formula (2) or general formula (3), Y represents a halogen atom, and m represents an integer of 0 or more and 4 or fewer. …General formula (2) In the general formula (2), R2 represents a straight-chain or branched alkyl group. …General formula (3) In the general formula (3), R3 represents a straight-chain or branched alkyl group.

9. The photoelectric conversion device according to claim 1 or 2, wherein, The photoelectric conversion layer comprises an organic material containing fullerene derivatives.

10. The photoelectric conversion device according to claim 5, wherein, The electron transport layer includes a first electron transport layer and a second electron transport layer disposed between the first electron transport layer and the photoelectric conversion layer. The first electron transport layer contains metal oxide particles, and The second electron transport layer contains an amine compound represented by the following general formula (4). …General formula (4) In the general formula (4), R4 and R5 each represent an alkyl group having a substituent and having 1 or more but less than 4 carbon atoms, or a ring structure bonded to R4 and R5; X represents a divalent aromatic group having 6 or more but less than 14 carbon atoms, or a divalent alkyl group having 1 or more but less than 4 carbon atoms; and A represents one of the substituents represented by the following structural formulas (1) to (3). …Structural formula (1) …Structural formula (2) …Structure (3).

11. An electronic device comprising a photoelectric conversion device according to any one of claims 1 to 10 and a means electrically connected to said photoelectric conversion device.

12. An electronic device comprising a photoelectric conversion device according to any one of claims 1 to 10, a battery electrically connected to the photoelectric conversion device, and a means electrically connected to the photoelectric conversion device and the battery.

13. A power module comprising a photoelectric conversion device according to any one of claims 1 to 10 and a power supply IC electrically connected to the photoelectric conversion device.

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