WO2023234118A1 - 光電変換素子及びその製造方法 - Google Patents

光電変換素子及びその製造方法 Download PDF

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WO2023234118A1
WO2023234118A1 PCT/JP2023/019144 JP2023019144W WO2023234118A1 WO 2023234118 A1 WO2023234118 A1 WO 2023234118A1 JP 2023019144 W JP2023019144 W JP 2023019144W WO 2023234118 A1 WO2023234118 A1 WO 2023234118A1
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layer
electrode layer
upper electrode
thickness
photoelectric conversion
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French (fr)
Japanese (ja)
Inventor
奈織美 瀧本
哲雄 奥山
啓介 松尾
桂也 ▲徳▼田
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Toyobo Co Ltd
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Toyobo Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/10—Organic photovoltaic [PV] modules; Arrays of single organic PV cells
    • H10K39/12—Electrical configurations of PV cells, e.g. series connections or parallel connections
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes

Definitions

  • the present invention relates to a photoelectric conversion element and a method for manufacturing the same.
  • a photoelectric conversion element is generally laminated in this order: a substrate, a lower electrode layer, a functional layer, and an upper electrode layer.
  • a substrate As methods for forming the upper electrode layer, bar coating methods, spin coating methods, and the like are conventionally known.
  • Patent Document 1 An example of a manufacturing method that suppresses the surface roughness of the upper electrode layer is disclosed in Patent Document 1.
  • a method for manufacturing a back electrode layer (upper electrode layer) a dispersion liquid containing metal nanoparticles and a dispersion medium is sprayed onto an organic semiconductor layer (functional layer) as droplets, and the dispersion medium is also applied.
  • a method of dry removal is disclosed.
  • the upper electrode layer is laminated not only on the upper surface of the functional layer but also on the side surface formed at the end of the functional layer.
  • the upper electrode layer since the coating is sprayed using an air gun spray, the upper electrode layer is not laminated on the side surface.
  • the thickness of the upper electrode layer is considerably thinner than the thickness of the upper electrode layer laminated on the upper surface of the functional layer.
  • the upper electrode layer stacked on the side surface can serve as a current path. In such a current path, if the thickness of the upper electrode layer laminated on the side surface is considerably thinner than the thickness of the upper electrode layer laminated on the top surface of the functional layer, the resistance will increase, and the photoelectric conversion element of Patent Document 1 Conversion efficiency was insufficient.
  • An object of the present invention is to provide a photoelectric conversion element in which the thickness of the upper electrode layer laminated on the end (side surface) of the functional layer is approximately the same as that of the upper electrode layer laminated on the upper surface of the functional layer.
  • the present inventors generated a mist containing metal particles from a solution containing metal particles, and attached the mist to the surface of the functional layer to form an upper electrode layer. It has been found that by forming the upper electrode layer, the thickness of the upper electrode layer laminated on the end (side surface) of the functional layer becomes approximately the same as the thickness of the upper electrode layer laminated on the upper surface of the functional layer.
  • a photoelectric conversion element comprising a substrate, a lower electrode layer, a functional layer, and an upper electrode layer, in which at least a portion of the photoelectric conversion element includes the substrate, the lower electrode layer, the functional layer, and the upper electrode layer.
  • the electrode layers are laminated in this order, and the functional layer includes an electron transport layer, an active layer, and a hole transport layer, and has an upper surface and a side surface formed at an end of the functional layer.
  • the upper electrode layer is provided on at least a part of the upper surface and at least a part of the side surface, and when the thickness of the laminated part of the lower electrode layer and the functional layer is H, the thickness of the laminated part on the substrate side is At a height of H/2 from the surface to the upper surface side, the thickness of the upper electrode layer provided on the side surface is 80% to 120% of the thickness of the upper electrode layer provided on the upper surface.
  • a photoelectric conversion element characterized by: [2] A photoelectric conversion element comprising a substrate, a lower electrode layer, a functional layer, and an upper electrode layer, in which at least a portion of the photoelectric conversion element includes the substrate, the lower electrode layer, the functional layer, and the upper electrode layer.
  • the electrode layers are laminated in this order, and the functional layer includes an electron transport layer, an active layer, and a hole transport layer, and has an upper surface and a side surface formed at an end of the functional layer.
  • the upper electrode layer is provided on at least a portion of the upper surface and at least a portion of the side surface, and when the thickness of the active layer is H', the upper electrode layer has a thickness H' from the substrate-side surface of the active layer to the upper surface side. /2 height position, the thickness of the upper electrode layer provided on the side surface is 80% to 120% of the thickness of the upper electrode layer provided on the upper surface. element.
  • a photoelectric conversion element comprising a substrate, a lower electrode layer, a functional layer, and an upper electrode layer, in which at least a portion of the photoelectric conversion element includes the substrate, the lower electrode layer, the functional layer, and the upper electrode layer.
  • the electrode layers are laminated in this order, and the functional layer includes an active layer and has an upper surface and a side surface formed at an end of the functional layer, and the upper electrode layer covers at least one part of the upper surface. and at least a part of the side surface, and when the thickness of the active layer is H', at a position at a height of H'/2 from the substrate side surface of the active layer to the upper surface side.
  • a photoelectric conversion element characterized in that the thickness of the upper electrode layer provided on the side surface is 80% to 120% of the thickness of the upper electrode layer provided on the upper surface.
  • the photoelectric conversion element according to any one of [1] to [3] above, wherein the upper electrode layer contains silver, gold, copper, or platinum.
  • a method for manufacturing a photoelectric conversion element comprising a substrate, a lower electrode layer, a functional layer, and an upper electrode layer, comprising the steps of generating a mist containing metal particles from a solution containing metal particles, and generating the mist. forming the upper electrode layer by adhering it to the surface of the functional layer, the functional layer including an active layer.
  • step of generating the mist includes a step of applying ultrasonic waves to the solution.
  • the metal particles contain silver, gold, copper, or platinum.
  • step of forming the functional layer using a mist containing a functional layer forming material further comprising the step of forming the functional layer using a mist containing a functional layer forming material.
  • a method for manufacturing a photoelectric conversion element comprising a substrate, a lower electrode layer, a functional layer, and an upper electrode layer, the method comprising: generating a mist containing metal particles from a solution containing metal particles; forming the upper electrode layer by adhering it to the surface of the functional layer, the functional layer comprising an electron transport layer, an active layer, and a hole transport layer.
  • the thickness of the upper electrode layer laminated on the edge (side surface) of the functional layer is approximately the same as the thickness of the upper electrode layer laminated on the upper surface of the functional layer parallel to the surface of the substrate, resulting in a photoelectric converter with excellent conversion efficiency. A conversion element can be obtained.
  • FIG. 1 is a cross-sectional view of a plane perpendicular to a substrate in an example of a photoelectric conversion element of the present invention.
  • FIG. 3 is a cross-sectional view of the active layer in a plane parallel to the substrate in another example of the photoelectric conversion element of the present invention.
  • the photoelectric conversion element of the present invention includes a substrate, a lower electrode layer, a functional layer, and an upper electrode layer, and in at least a part of the photoelectric conversion element of the present invention, the substrate, the lower electrode layer, the functional layer, The upper electrode layers are laminated in this order.
  • upper (part) and lower (part) do not mean top and bottom; for example, with respect to an upper electrode layer and a lower electrode layer, it refers to one of a pair of electrode layers provided with a functional layer in between.
  • the electrode layer disposed on the substrate side is defined as a lower electrode layer
  • the electrode layer provided on the opposite side to the substrate is defined as an upper electrode layer, thereby simply defining an upper (part) and a lower (part).
  • the term "surface” refers to the surface closer to the upper electrode layer unless otherwise specified.
  • the substrate, the lower electrode layer, the functional layer, and the upper electrode layer will be explained in this order.
  • the substrate is not particularly limited, and examples thereof include a glass substrate, a plastic substrate, a polymer film, and the like. When light is taken in from the substrate side, it is preferable to use a substrate with high light transmittance.
  • the lower electrode layer is not particularly limited as long as it contains a known lower electrode layer forming material.
  • the materials for forming the lower electrode layer include aluminum (Al), gold (Au), platinum (Pt), iridium (Ir), ruthenium (Ru), titanium (Ti), molybdenum (Mo), tantalum (Ta), and copper ( Cu), silver (Ag), and other metals; metal oxides such as indium tin oxide (ITO), iridium oxide (IrO 2 ), ruthenium oxide (RuO 2 ), LaNiO 3 , and SrRuO 3 ; .
  • the lower electrode layer forming material may be used alone or in combination of two or more selected materials. Moreover, the lower electrode layer may be an anode and the upper electrode layer may be a cathode, or the lower electrode layer may be a cathode and the upper electrode layer may be an anode. When light is taken in from the substrate side, the lower electrode layer is preferably transparent.
  • the thickness of the lower electrode layer is not particularly limited, and is, for example, 30 nm or more, preferably 50 nm or more, and, for example, 200 nm or less, preferably 150 nm or less.
  • the method for manufacturing the lower electrode layer is not particularly limited, and the lower electrode layer is formed by generating a mist from a solution containing the lower electrode layer forming material, and depositing the misted raw material on the surface of the substrate to form a film. can do.
  • the method for manufacturing the lower electrode layer is preferably the above-mentioned misting method, but other methods include vapor deposition methods such as vacuum evaporation and sputtering, spray methods, spin coating methods, dip coating methods, slot die coating methods, It may be formed by a coating method such as a doctor blade method, a bar coating method, an inkjet method, a screen printing method, or a gravure printing method.
  • vapor deposition methods such as vacuum evaporation and sputtering
  • spray methods spin coating methods
  • dip coating methods dip coating methods
  • slot die coating methods It may be formed by a coating method such as a doctor blade method, a bar coating method, an inkjet method, a screen printing method, or a gravure printing method.
  • the functional layer includes an active layer, and preferably includes an electron transport layer, an active layer, and a hole transport layer.
  • an inverted structure may be used, in which an electron transport layer, an active layer, and a hole transport layer are laminated in this order on a lower electrode layer (cathode), or a hole transport layer, an active layer, and an electron transport layer are laminated on a lower electrode layer (anode).
  • a regular structure in which the layers are stacked in order may be used, and the stacking order within the functional layer differs depending on whether the lower electrode layer plays the role of a cathode or an anode.
  • the functional layer has an upper surface and a side surface formed at the end of the functional layer.
  • an upper electrode layer is provided on at least a portion of the upper surface of the functional layer, and an upper electrode layer is also provided on at least a portion of the side surface of the functional layer.
  • the upper surface of the functional layer may be a flat surface or a curved surface, but is preferably a flat surface, and preferably a flat surface parallel to the surface of the substrate. Note that in this specification, "parallel” refers to a plane that is inclined at 0 to 10 degrees with respect to the surface of the substrate.
  • the side surfaces of the functional layer may be flat or curved, but are preferably flat.
  • the electron transport layer is not particularly limited, and may contain a known electron transport material.
  • electron-transporting materials include zinc oxide, titanium oxide, zirconium oxide, tin oxide, indium oxide, ITO (indium tin oxide), FTO (fluorine-doped tin oxide), GZO (gallium-doped zinc oxide), and ATO (antimony).
  • Examples include doped tin oxide), AZO (aluminum doped zinc oxide), PEIE (polyethyleneimine ethoxylate), and PEI (polyethyleneimine).
  • the electron transport layer contain an electron transport material, we can increase the efficiency of electron injection into the cathode, prevent the injection of holes from the active layer, increase the electron transport ability, and suppress the deterioration of the active layer. You can do it.
  • an electron transport layer between the active layer and the electrode layer which becomes the cathode.
  • the electron transport layer is more preferably in contact with at least one of the active layer and the electrode layer that serves as the cathode, and even more preferably in contact with the active layer and the electrode layer that serves as the cathode.
  • the thickness of the electron transport layer is not particularly limited, and is, for example, 20 nm or more, preferably 40 nm or more, and, for example, 100 nm or less, preferably 70 nm or less.
  • the method for manufacturing the electron transport layer is not particularly limited, and the electron transport layer may be formed by generating a mist from a solution containing an electron transport material and depositing the mist-formed raw material on the outermost surface to form a film. I can do it.
  • the outermost surface refers to the surface of the laminate immediately before forming the corresponding layer.
  • the electron transport layer can be formed by depositing a misted raw material on the outermost surface including the surface of the lower electrode layer to form a film. Even in the case of a normal structure, the electron transport layer can be formed by depositing a misted raw material on the outermost surface including the surface of the active layer to form a film.
  • the method for manufacturing the electron transport layer is preferably the above-mentioned misting method, but other methods include vapor deposition methods such as vacuum evaporation and sputtering, spray methods, spin coating methods, dip coating methods, slot die coating methods, It may be formed by a coating method such as a doctor blade method, a bar coating method, an inkjet method, a screen printing method, or a gravure printing method.
  • vapor deposition methods such as vacuum evaporation and sputtering
  • spray methods spin coating methods
  • dip coating methods dip coating methods
  • slot die coating methods It may be formed by a coating method such as a doctor blade method, a bar coating method, an inkjet method, a screen printing method, or a gravure printing method.
  • the active layer is not particularly limited and may contain a known active layer forming material.
  • the active layer forming material includes at least a p-type semiconductor material (electron-donating compound) and an n-type semiconductor material (electron-accepting compound).
  • p-type semiconductor materials include, for example, polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives containing an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives. , polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyfluorene and its derivatives, polybenzobisthiazole and its derivatives, and the like.
  • the n-type semiconductor material may be a low-molecular compound or a high-molecular compound.
  • n-type semiconductor materials that are low molecular weight compounds include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives.
  • n-type semiconductor materials that are polymeric compounds include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives.
  • polypyrrole and its derivatives polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, and the like.
  • the thickness of the active layer is not particularly limited, and is, for example, 80 nm or more, preferably 100 nm or more, and, for example, 400 nm or less, preferably 300 nm or less.
  • the method for producing the active layer is not particularly limited, and the active layer can be formed by generating a mist from a solution containing the active layer forming material and depositing the mist-formed raw material on the outermost surface to form a film. .
  • the active layer can be formed by depositing a misted raw material on the outermost surface including the surface of the electron transport layer to form a film.
  • the active layer can be formed by depositing a misted raw material on the outermost surface including the surface of the hole transport layer to form a film.
  • the active layer is preferably provided between an electron transport layer and a hole transport layer, and is preferably in contact with at least one of the electron transport layer or the hole transport layer. More preferably, it is in contact with the electron transport layer and the hole transport layer.
  • the method for manufacturing the active layer is preferably the above-mentioned mist method, but other methods include vapor deposition methods such as vacuum evaporation and sputtering, spray methods, spin coating methods, dip coating methods, slot die coating methods, and doctor coating methods. It may be formed by a coating method such as a blade method, bar coating method, inkjet method, screen printing method, or gravure printing method.
  • the material contained in the hole transport layer is not particularly limited, and may include known hole transport materials.
  • hole-transporting materials include conductive polymers such as polyvinylcarbazole, polysilane, polythiophene, polyethylenedioxythiophene, and polystyrene sulfonate, and metal oxides such as molybdenum trioxide and tungsten trioxide.
  • the hole transport layer contains a hole transporting material, it is possible to increase the efficiency of hole injection into the anode, prevent the injection of electrons from the active layer, increase the hole transport ability, and suppress the deterioration of the active layer. You can do it.
  • a hole transport layer between the active layer and the electrode layer that becomes the anode it is possible to prevent the anode from peeling off and to remove the anode from the active layer. Hole extraction efficiency can be increased.
  • the hole transport layer is more preferably in contact with at least one of the active layer or the electrode layer that will become the anode, and even more preferably the hole transport layer is in contact with the active layer and the electrode layer that will be the anode. By providing such a hole transport layer, a photoelectric conversion element with high reliability and higher photoelectric conversion efficiency can be obtained.
  • the thickness of the hole transport layer is not particularly limited, and is, for example, 5 nm or more, preferably 10 nm or more, and, for example, 200 nm or less, preferably 100 nm or less.
  • the method for manufacturing the hole transport layer is not particularly limited, and the hole transport layer may be formed by generating a mist from a solution containing a hole transporting material and depositing the mist-formed raw material on the outermost surface to form a film. I can do it.
  • the hole transport layer can be formed by depositing a misted raw material on the outermost surface including the surface of the active layer to form a film.
  • the hole transport layer can be formed by depositing a misted raw material on the surface of the lower electrode layer to form a film.
  • the method for manufacturing the hole transport layer is preferably the above-mentioned mist method, but other methods include vapor deposition methods such as vacuum evaporation and sputtering, spray methods, spin coating methods, dip coating methods, slot die coating methods, It may be formed by a coating method such as a doctor blade method, a bar coating method, an inkjet method, a screen printing method, or a gravure printing method.
  • vapor deposition methods such as vacuum evaporation and sputtering
  • spray methods spin coating methods
  • dip coating methods dip coating methods
  • slot die coating methods It may be formed by a coating method such as a doctor blade method, a bar coating method, an inkjet method, a screen printing method, or a gravure printing method.
  • the substrate, lower electrode layer, and functional layers have been described above, the composition, thickness, and manufacturing method of these layers are not limited to the above description. Further, the lower electrode layer, electron transport layer, active layer, and hole transport layer may be formed continuously on the outermost surface when forming each layer, or may be formed discontinuously (for example, in the lower electrode layer). (The lower electrode layer, electron transport layer, active layer, and holes may be formed on a part of the surface of the substrate. It is sufficient if the transport layers are laminated. Furthermore, as mentioned above, it is preferable that the lower electrode layer and the functional layers (electron transport layer, active layer, hole transport layer) are formed by depositing mist-formed raw materials on the outermost surface.
  • the functional layer using a mist containing.
  • only one layer among the lower electrode layer, electron transport layer, active layer, and hole transport layer may be formed by attaching a mist-formed raw material, or two or more layers may be formed by attaching a mist-formed raw material.
  • the film may be formed by
  • the functional layer includes an electron transport layer, an active layer, and a hole transport layer.
  • the upper electrode layer is not particularly limited as long as it contains a known upper electrode layer forming material.
  • the material for forming the upper electrode layer the same material as the above-mentioned material for forming the lower electrode layer may be used, and the upper electrode layer contains metal, preferably silver, gold, copper, or platinum. It is more preferable to include.
  • the upper electrode layer forming material may be a single type of material, or a combination of two or more selected types of materials.
  • the thickness of the upper electrode layer provided on the upper surface of the functional layer is not particularly limited, and is, for example, 50 nm or more, preferably 80 nm or more, and, for example, 300 nm or less, preferably 200 nm or less.
  • the upper electrode layer is provided on at least a portion of the upper surface of the functional layer and at least a portion of the side surface of the functional layer, and the thickness of the upper electrode layer provided on the side surface of the functional layer (hereinafter referred to as the thickness in the lateral direction) is The thickness of the upper electrode layer provided on the upper surface of the functional layer (hereinafter sometimes referred to as the thickness in the upper surface direction) is approximately the same as the thickness of the upper electrode layer provided on the upper surface of the functional layer. Specifically, the following (1) or (2) is satisfied, and it is preferable that the following (1) and (2) are satisfied.
  • the thickness of the upper electrode layer in the side direction is approximately the same as the thickness of the upper electrode layer in the upper surface direction.
  • the upper limit of the thickness for both (1) and (2) below is preferably 100%.
  • the upper electrode layer is provided on the side surface of the functional layer at a height of H'/2 from the substrate side surface of the active layer to the upper surface side of the functional layer.
  • the thickness is 80% to 120% of the thickness of the upper electrode layer provided on the upper surface of the functional layer.
  • the thickness of the laminated portion of the lower electrode layer and the functional layer refers to the thickness of the layer farthest from the substrate among the electron transport layer, active layer, and hole transport layer from the substrate side surface of the lower electrode layer. This refers to the thickness of the layer to the surface on the side opposite to the substrate (top side of the functional layer).
  • the thickness of the thinnest upper electrode layer in a cross section parallel to the surface of the substrate at "a height of H/2 from the substrate side surface of the laminated part to the upper surface side of the functional layer” is defined as "the side surface of the functional layer”.
  • the active layer is thicker than other layers provided in the functional layer, so the layer located at a height of H/2 from the substrate side surface of the laminated part to the upper surface of the functional layer is usually an active layer. be.
  • the position at a height of H'/2 from the substrate side surface of the active layer to the upper surface side of the functional layer is the intermediate height between both surfaces of the active layer, that is, from the substrate side surface of the active layer to the opposite substrate side. (on the side opposite to the substrate) means a point that is higher by H'/2, and the thickness of the upper electrode layer provided on the side surface of the functional layer at the height of H'/2 is also H'/2.
  • the measurement is performed in the same manner as the method for measuring the thickness of the upper electrode layer provided on the side surface of the functional layer at a height of /2.
  • the thickness of the upper electrode layer provided on the side surface of the functional layer at the height of H/2 is referred to as “thickness of the upper electrode layer at the height of H/2”
  • the thickness of the upper electrode layer provided on the side surface of the functional layer at the height of H'/2 is referred to as “thickness of the upper electrode layer at the height of H/2”.
  • the thickness of the upper electrode layer provided on the side surface of the functional layer at the height is referred to as "thickness of the upper electrode layer at the height of H'/2”.
  • FIG. 1 is a cross-sectional view of a plane perpendicular to a substrate showing an example of the photoelectric conversion element of the present invention.
  • the upper electrode layer is laminated only on one side of the functional layer.
  • two stacked bodies are connected in series, and the upper electrode layer is electrically connected to the adjacent lower electrode layer. Note that H, H', and H'/2 are illustrated in FIG.
  • FIG. 2 shows an example of a photoelectric conversion element in which upper electrode layers are laminated on all sides of the functional layer.
  • FIG. 2 shows a cross-sectional view parallel to the surface of the substrate at a height of H/2.
  • L1 ⁇ L2 ⁇ L3 ⁇ L4 as shown in FIG. 2 the thickness of the upper electrode layer at the height of H/2 is L1.
  • the thickness in the side direction is preferably 80% to 120% of the thickness in the top surface direction at a height of H''/2 from the substrate side surface of the layer to the top surface side of the functional layer, and preferably 80 to 100%. % is more preferable.
  • the layer farthest from the substrate is the hole transport layer in the inverted structure, and the electron transport layer in the forward structure.
  • the “thickness of the upper electrode layer provided on the side surface of the functional layer” at the height of H''/2 above is also Measurement is carried out in the same manner as for "thickness”. Note that hereinafter, the thickness of the upper electrode layer provided on the side surface of the functional layer at the height of H''/2 will be referred to as “thickness of the upper electrode layer at the height of H''/2.
  • the thickness of the upper electrode layer provided on the side surface of the functional layer is such that the thickness of the upper electrode layer at a height of H/2 is 70 to 120% of the thickness of the upper electrode layer at a height of H''/2. It is preferably 90% to 110%, more preferably 90% to 110%.
  • the thickness of the upper electrode layer provided on the side surface of the functional layer is such that the thickness of the upper electrode layer at a height of H'/2 is 70 to 120% of the thickness of the upper electrode layer at a height of H''/2. It is preferably 90% to 110%, more preferably 90% to 110%.
  • the method for measuring the thickness of the upper electrode layer at four locations in terms of height is as follows. A cross-sectional view perpendicular to the substrate as shown in Fig. 1 is prepared using a focused ion beam processing and observation device (FIB), and a cross-sectional view perpendicular to the substrate is prepared using a field emission scanning electron microscope (FE-SEM) or a transmission electron microscope (TEM). The thickness of the upper electrode layer at the four locations is measured. Note that portions with a thickness of approximately 80 nm or more are measured using SEM, and portions with a thickness of less than 80 nm are measured using TEM.
  • FIB focused ion beam processing and observation device
  • FE-SEM field emission scanning electron microscope
  • TEM transmission electron microscope
  • the thickness of the upper electrode layer at the four locations mentioned above should be measured using only FE-SEM or TEM without using FIB. Good too.
  • an FIB is used to measure the thickness of the upper electrode layer perpendicular to the substrate. A cross section is prepared and the thickness of the upper electrode layer is measured.
  • the method for manufacturing the upper electrode layer includes a step of generating a mist containing metal particles from a solution containing metal particles, and adhering the mist to the surface (upper surface and side surface) of the functional layer to form the upper electrode layer. and a step of doing so.
  • the misting method for generating mist is not particularly limited, but examples include a method of applying ultrasonic waves to a solution containing metal particles using an ultrasonic atomizer or the like to atomize the solution, and a method of atomizing the solution.
  • a method of atomizing a solution containing metal particles by applying pressure to a solution containing metal particles and ejecting it from a small hole using a device equipped with a liquid pressurizing means that pressurizes the liquid and a method that uses a discharge electrode and a high voltage application means.
  • Examples of methods include electrostatic atomization by applying high voltage to a solution containing metal particles using a device equipped with the device, and a method of atomizing the solution by applying ultrasonic waves to a solution containing metal particles. preferable.
  • the upper electrode layer is provided not only on the top surface of the functional layer but also on the side surfaces of the functional layer, and the thickness in the side direction is approximately the same as the thickness in the top surface direction, resulting in photoelectric conversion with excellent conversion efficiency. It can be an element.
  • the upper electrode layer By forming the upper electrode layer using the above manufacturing method, it is possible to form the upper electrode layer in a short time and at atmospheric pressure. Furthermore, even if the upper electrode layer has to be formed over a wide area, it is possible to form the upper electrode layer with a uniform thickness. When all layers other than the upper electrode layer are formed using mist as described above, it is possible to manufacture a photoelectric conversion element with less equipment.
  • the photoelectric conversion element of the present invention can be used as a solar cell. Moreover, the photoelectric conversion element of the present invention can also be used as a photodetector by providing an output detection means for detecting an output signal output from the photoelectric conversion element.

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PCT/JP2023/019144 2022-06-03 2023-05-23 光電変換素子及びその製造方法 Ceased WO2023234118A1 (ja)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57211280A (en) * 1981-06-22 1982-12-25 Mitsubishi Electric Corp Assembling structure of solar cell
JP2009289817A (ja) * 2008-05-27 2009-12-10 Mitsubishi Electric Corp 光電変換装置およびその製造方法
JP2012114424A (ja) * 2010-11-02 2012-06-14 Susumu Yoshikawa 太陽電池および太陽電池の製造方法
WO2013176222A1 (ja) * 2012-05-24 2013-11-28 株式会社ニコン 基板処理装置、及びデバイス製造方法
US20150171229A1 (en) * 2012-07-31 2015-06-18 Lg Innotek Co., Ltd. Solar cell apparatus and method of fabricating the same
JP2016181625A (ja) * 2015-03-24 2016-10-13 株式会社東芝 光電変換素子および光電変換素子の製造方法
JP2017119907A (ja) * 2015-12-24 2017-07-06 株式会社Flosfia ペロブスカイト膜の製造方法
WO2017154937A1 (ja) * 2016-03-11 2017-09-14 株式会社ニコン ミスト発生装置、成膜装置、ミスト発生方法、成膜方法、および、デバイス製造方法
JP2020114943A (ja) * 2015-02-18 2020-07-30 株式会社ニコン 薄膜製造装置、及び薄膜製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57211280A (en) * 1981-06-22 1982-12-25 Mitsubishi Electric Corp Assembling structure of solar cell
JP2009289817A (ja) * 2008-05-27 2009-12-10 Mitsubishi Electric Corp 光電変換装置およびその製造方法
JP2012114424A (ja) * 2010-11-02 2012-06-14 Susumu Yoshikawa 太陽電池および太陽電池の製造方法
WO2013176222A1 (ja) * 2012-05-24 2013-11-28 株式会社ニコン 基板処理装置、及びデバイス製造方法
US20150171229A1 (en) * 2012-07-31 2015-06-18 Lg Innotek Co., Ltd. Solar cell apparatus and method of fabricating the same
JP2020114943A (ja) * 2015-02-18 2020-07-30 株式会社ニコン 薄膜製造装置、及び薄膜製造方法
JP2016181625A (ja) * 2015-03-24 2016-10-13 株式会社東芝 光電変換素子および光電変換素子の製造方法
JP2017119907A (ja) * 2015-12-24 2017-07-06 株式会社Flosfia ペロブスカイト膜の製造方法
WO2017154937A1 (ja) * 2016-03-11 2017-09-14 株式会社ニコン ミスト発生装置、成膜装置、ミスト発生方法、成膜方法、および、デバイス製造方法

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