Method for manufacturing organic photoelectric conversion element

Abstract

The present invention enables on-demand production of organic photoelectric conversion elements, independent of the timing of material synthesis. A method for producing an organic photoelectric conversion element comprises a pair of electrodes, including an anode and a cathode, and an active layer disposed between the pair of electrodes and containing a π-conjugated polymer. The method comprises: a storage step of storing the π-conjugated polymer in a sealed container, wherein the interior of the sealed container is an atmosphere that suppresses an increase in the electron spin concentration of the π-conjugated polymer; and a step of forming the active layer using the stored π-conjugated polymer.

Description

Technical Field

[0001] The present invention relates to a method for producing an organic photoelectric conversion element, and further relates to a method for storing an organic semiconductor material used in the production method, and a reagent package that can be used in the production method and the storage method. Background Art

[0002] Organic photoelectric conversion elements are extremely useful devices from the viewpoints of, for example, energy conservation and reduction of carbon dioxide emissions, and have attracted attention.

[0003] An organic photoelectric converter is an electronic device that comprises at least a pair of electrodes, consisting of an anode and a cathode, and an active layer comprising an organic semiconductor material disposed between the electrodes. In an organic photoelectric converter, one of the electrodes is made of a light-transmitting material, allowing light to enter the active layer from the light-transmitting electrode. The energy (hν) of the light incident on the active layer generates charges (holes and electrons) in the active layer. The generated holes move toward the anode, and the electrons move toward the cathode. The charges that have reached the anode and cathode are then extracted outside the organic photoelectric converter.

[0004] Organic semiconductor materials used as functional materials in the active layer of organic photoelectric conversion elements are known to be difficult to store for long periods of time, particularly in atmospheric conditions. For example, Patent Document 1 discloses that when storing the organic layer material (organic light-emitting material) of an organic electroluminescent element, the organic light-emitting material should be quickly stored in a light-shielding container after synthesis, kept within a temperature range of -100°C to 100°C, and stored in an atmosphere of an inert gas such as nitrogen, carbon dioxide, or argon.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2009-027091 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] However, the mechanism of organic semiconductor material degradation, including not only degradation of the physical properties of organic semiconductor materials but also degradation of the electrical characteristics of organic photoelectric conversion devices manufactured using these materials, remains unclear. Consequently, conventional methods, such as those disclosed in Patent Document 1, which require complex handling and large-scale storage equipment, have been employed to comprehensively address the various factors assumed to contribute to organic semiconductor material degradation.

[0010] Furthermore, in the current situation where long-term storage of organic semiconductor materials is not recommended, after the manufacture of the organic semiconductor materials, the storage period of the manufactured organic semiconductor materials must be shortened as much as possible to manufacture devices using the organic semiconductor materials. Therefore, it is necessary to adjust the timing so that the manufacture of the devices and the manufacture of the organic semiconductor materials are close to each other.

[0011] Therefore, there is a great demand for a technology that can achieve longer-term storage of organic semiconductor materials.

[0012] Means for solving problems

[0013] The present inventors conducted intensive studies to solve the above-mentioned problems and found that the progression of temporal degradation of organic semiconductor materials is related to the electron spin concentration of the organic semiconductor material and the oxygen concentration of the storage atmosphere, thereby completing the present invention.

[0014] Therefore, the present invention provides the following [1] to

[20] .

[0015] [1] A method for manufacturing an organic photoelectric conversion element comprising a pair of electrodes including an anode and a cathode, and an active layer disposed between the pair of electrodes and comprising a π-conjugated polymer, the method comprising:

[0016] a step of storing the π-conjugated polymer in a sealed container, wherein the interior of the sealed container is an atmosphere that suppresses an increase in the electron spin concentration of the π-conjugated polymer; and

[0017] A step of forming the active layer using the stored π-conjugated polymer.

[0018] [2] The method for producing an organic photoelectric conversion element according to [1], wherein the atmosphere in the storage step has an oxygen concentration of 1% or less.

[0019] [3] The method for producing an organic photoelectric conversion element according to [1] or [2], wherein a deoxidizing agent is provided in the sealing container in the storage step.

[0020] [4] The method for producing an organic photoelectric conversion element according to any one of [1] to [3], wherein the electron spin concentration per 1 g of the π-conjugated polymer after storage is 10×10 16 the following.

[0021] [5] The method for producing an organic photoelectric conversion element according to any one of [1] to [4], wherein the maximum absorption wavelength of the π-conjugated polymer after storage is 500 nm or longer.

[0022] [6] The method for producing an organic photoelectric conversion element according to any one of [1] to [5], wherein the electron spin concentration per 1 g of the π-conjugated polymer after storage is less than 2.4 times the electron spin concentration per 1 g of the π-conjugated polymer before storage.

[0023] [7] The method for producing an organic photoelectric conversion element according to any one of [1] to [6], wherein

[0024] The method further includes a step of preparing a coating solution containing the stored π-conjugated polymer.

[0025] The step of forming the active layer is a step of forming the active layer by applying the coating liquid obtained in the preparation step.

[0026] [8] A reagent package comprising:

[0027] π-conjugated polymers, which are used to form active layers of organic photoelectric conversion elements;

[0028] a sealing container capable of sealing and removing the π-conjugated polymer and having gas barrier properties, wherein the π-conjugated polymer is sealed in the sealing container in an airtight state; and

[0029] a deoxidizer, which is arranged to be in contact with the atmosphere in the airtight sealed container;

[0030] The atmosphere has an oxygen concentration of 1% or less.

[0031] [9] The reagent package according to [8], wherein the electron spin concentration per 1g of the π-conjugated polymer after storage is 10×10 16 the following.

[0032]

[10] The reagent package according to [8] or [9], wherein the maximum absorption wavelength of the π-conjugated polymer after storage is 500 nm or longer.

[0033]

[11] The reagent package according to any one of [8] to

[10] , wherein the deoxidizing agent contains at least one material selected from the group consisting of iron, sugar, and reducing ketone.

[0034]

[12] The reagent package according to

[11] , wherein the material is a material containing iron.

[0035]

[13] The reagent package according to any one of [8] to

[12] , wherein

[0036] The above-mentioned enclosed containers include:

[0037] a main body having an opening for housing the π-conjugated polymer;

[0038] an inner cover detachably fitted to the inner wall of the opening, defining a recess in which the deoxidizer can be placed while the deoxidizer is separated from the π-conjugated polymer, and having a hole for allowing the deoxidizer to contact the atmosphere with which the π-conjugated polymer is in contact; and

[0039] The outer cover is detachably fitted to the outer wall of the opening when the inner cover is attached, thereby making the interior of the main body airtight.

[0040]

[14] A storage method comprising the step of storing a π-conjugated polymer in a sealed container, wherein the interior of the sealed container is an atmosphere that suppresses an increase in the electron spin concentration of the π-conjugated polymer.

[0041]

[15] The storage method as described in

[14] , wherein the atmosphere in the storage step is an atmosphere with an oxygen concentration of 1% or less.

[0042]

[16] The storage method according to

[14] or

[15] , wherein the electron spin concentration per 1g of the π-conjugated polymer after storage is 10×10 16 the following.

[0043]

[17] The storage method according to any one of

[14] to

[16] , wherein the maximum absorption wavelength of the π-conjugated polymer after storage is 500 nm or more.

[0044]

[18] The storage method according to any one of

[14] to

[17] , wherein the deoxidizer contains at least one material selected from the group consisting of iron, sugar, and reducing ketone.

[0045]

[19] The storage method as described in

[18] , wherein the above-mentioned deoxidizer contains iron.

[0046]

[20] The storage method according to any one of

[14] to

[19] , wherein

[0047] The above-mentioned enclosed containers include:

[0048] a main body having an opening for housing the π-conjugated polymer;

[0049] an inner cover detachably fitted to the inner wall of the opening, defining a recess in which the deoxidizer can be placed while the deoxidizer is separated from the π-conjugated polymer, and having a hole for allowing the deoxidizer to contact the atmosphere with which the π-conjugated polymer is in contact; and

[0050] The outer cover is detachably fitted to the outer wall of the opening when the inner cover is attached, thereby making the interior of the main body airtight.

[0051] Effects of the Invention

[0052] According to the present invention, it is possible to produce an organic photoelectric conversion element as needed using the stored π-conjugated polymer without adjusting the synthesis timing of the π-conjugated polymer as a material for the active layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 It is a schematic diagram showing a reagent package in a perspective manner. DETAILED DESCRIPTION

[0054] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. It should be noted that the accompanying drawings merely schematically illustrate the shapes, sizes, and configurations of the constituent elements to the extent that the invention can be understood. The present invention is not limited to the following description, and each constituent element may be appropriately changed without departing from the scope of the present invention. In the drawings used in the following description, the same constituent elements are sometimes represented by the same symbols, and repeated descriptions are omitted. In addition, the configuration of the embodiments of the present invention is not necessarily limited to the configurations shown in the drawings.

[0055] 1. Method for producing an organic photoelectric conversion element and method for storing a π-conjugated polymer

[0056] The method for manufacturing an organic photoelectric conversion element of the present embodiment is a method for manufacturing an organic photoelectric conversion element comprising a pair of electrodes including an anode and a cathode, and an active layer disposed between the pair of electrodes and containing a π-conjugated polymer, wherein the method comprises: a storage step (hereinafter referred to as step (1)) of storing the π-conjugated polymer in a sealed container, wherein the interior of the sealed container is an atmosphere that suppresses an increase in the electron spin concentration of the π-conjugated polymer; and a step of forming the active layer using the stored π-conjugated polymer (hereinafter referred to as step (2)).

[0057] The method for producing an organic photoelectric conversion device according to this embodiment includes a method for storing a π-conjugated polymer. The method for storing a π-conjugated polymer includes the above-mentioned step (1).

[0058] The organic photoelectric conversion element of this embodiment can be produced by appropriately combining methods suitable for the materials selected when forming each component. The following describes in detail the method for producing the organic photoelectric conversion element of this embodiment and the method for storing the π-conjugated polymer.

[0059] <Process (1)>

[0060] (i) Enclosed in container

[0061] like Figure 1 As shown, the sealing container 20 is a sealing container that can freely seal and remove the π-conjugated polymer 60 and has gas barrier properties. It is a sealing container that can seal the π-conjugated polymer 60 in an airtight state.

[0062] The shape and storage capacity of the sealing container 20 are not particularly limited as long as the desired amount of the π-conjugated polymer 60 can be freely stored and removed. The sealing container 20 is not particularly limited as long as it can maintain an airtight state within the sealing container 20 and, further, can be adjusted to reduce the composition of the atmosphere within the airtight sealing container 20, particularly the oxygen concentration, to a predetermined concentration and maintain the reduced oxygen concentration, thereby suppressing the increase in the electron spin concentration of the π-conjugated polymer 60 over time.

[0063] Examples of the sealing container 20 include a bag-shaped container 40 that satisfies the aforementioned conditions, a bottle-shaped container 30 such as a reagent bottle, and a combination thereof.

[0064] The material constituting the sealing container 20 is not particularly limited as long as the purpose and effects of the present invention are not impaired. Examples of such materials include resin materials such as polyethylene and polyethylene terephthalate; metals such as ceramics, glass, alloys, and combinations thereof.

[0065] As preferred specific examples of the sealing container 20, there can be cited an aluminum bag with a clamp (for example, Lamizip (registered trademark) aluminum mold, manufactured by Japan Co., Ltd.) which is a bag-shaped body having a freely openable and closable opening mechanism at the opening (a bag-shaped body having a freely openable and closable clamp at the opening of a bag-shaped aluminum foil, a bag-shaped body obtained by coating the surface of a polymer film with a metal such as aluminum or by laminating a metal foil such as aluminum foil) and a plastic reagent bottle (for example, trade name: Clean Bottle, manufactured by Aicello Co., Ltd.).

[0066] It is also possible to use a combination of multiple or more sealing containers 20 selected from the above-exemplified sealing containers 20. In this case, the deoxidizer 50 may be provided in only one of the multiple or more sealing containers 20, or in two or more selected sealing containers 20, or in all of the selected sealing containers 20.

[0067] Specifically, if Figure 1 As shown, for example, a mode can be exemplified in which a plastic reagent bottle containing both the π-conjugated polymer 60 and the deoxidizer 50 is sealed in a bag-shaped container 40 containing one or more deoxidizers (packages) described later.

[0068] By using a plurality of or a combination of different sealing containers in this manner, it is possible to more effectively maintain a reduced oxygen concentration in the atmosphere in contact with the π-conjugated polymer, and as a result, it is possible to more effectively suppress degradation of the π-conjugated polymer.

[0069] Furthermore, the encapsulating container 20 exemplified above may be used in combination with a container that cannot enclose the deoxidizer 50, or a container that has insufficient gas barrier properties or insufficient airtightness (referred to as a non-encapsulating container). In this case, for example, only the π-conjugated polymer 60 may be contained in the non-encapsulating container, and the non-encapsulating container containing only the π-conjugated polymer and the deoxidizer 50 may be enclosed in the encapsulating container 20 exemplified above.

[0070] Specifically, for example, a method can be used in which a reagent bottle, serving as a non-sealed container containing the π-conjugated polymer 60, is sealed together with the deoxidizer 50 in the bag-shaped container 40, serving as the sealed container 20. In this case, the non-sealed container is sealed so that the internal atmosphere is an atmosphere that suppresses an increase in the electron spin concentration of the π-conjugated polymer 60. In this manner, the π-conjugated polymer 60 can be stored while maintaining the internal atmosphere of the sealed container 20 in an atmosphere that suppresses an increase in the electron spin concentration of the π-conjugated polymer 60.

[0071] The sealing container 20 of the present embodiment can be configured as follows, for example, from the perspective of arranging the π-conjugated polymer 60 and the deoxidizer 50 separately during storage: a bottle-shaped container 30 comprising: a main body 32 having an opening 32a for accommodating the π-conjugated polymer 60; an inner lid 36 detachably fitted to the inner wall of the main body 32, defining a recess 36a for placing the deoxidizer 50 while the deoxidizer 50 is separated from the π-conjugated polymer 60, and having a hole 36b for allowing the deoxidizer 50 to contact the atmosphere with which the π-conjugated polymer 60 is in contact; and an outer lid 38 detachably fitted to the outer wall of the opening 32a when the inner lid 36 is attached, thereby making the interior of the main body 32 airtight.

[0072] As a specific example of this method, the following method can be cited: in a plastic reagent bottle (bottle-shaped container 30) having an inner cap 36 and an outer cap 38 capable of carrying a deoxidizer 50, one or more through holes (hole portions 36b) of a size (diameter) that prevents the deoxidizer 50 from falling into the main body portion 32 that accommodates the π-conjugated polymer 60 are provided in the inner cap 36.

[0073] (ii) Deoxidizer

[0074] The deoxidizer 50 of this embodiment is arranged in the sealed container 20 which is filled with the π-conjugated polymer 60 and is in an airtight state so as to be in contact with the atmosphere in the sealed container 20. It has the function of making the atmosphere in the sealed container 20 an atmosphere that suppresses the increase in the electron spin concentration of the π-conjugated polymer. Specifically, it has the function of making the atmosphere in the sealed container 20 an atmosphere with an oxygen concentration of less than 1%.

[0075] The dosage form and active ingredient of the deoxidizer 50 of this embodiment are not particularly limited. Examples of the dosage form of the deoxidizer 50 include various dosage forms such as tablets and pouch-type packages in which the active ingredient is packaged to function.

[0076] The formulation, active ingredient, and dosage of the deoxidizer 50 can be appropriately selected in consideration of the shape of the selected sealing container 20, the type, properties, and amount of the π-conjugated polymer 60, the volume of the atmosphere in the sealing container 20, the expected storage period, and the like.

[0077] As the effective components of the deoxidizer 50 of this embodiment, in particular from the perspective of making the atmosphere an atmosphere with an oxygen concentration of less than 1% and maintaining the oxygen concentration of less than 1% for at least a specified period, examples include iron (iron powder); sugars (such as glucose, maltooligosaccharides), and organic compounds such as reducing ketones.

[0078] From the perspective of availability and adjustment of the oxygen concentration in the sealed container 20, the deoxidizer 50 preferably contains at least one material selected from the group consisting of iron, sugar and reducing ketone; from the perspective of adsorbing oxidizing substances in the atmosphere other than oxygen, it more preferably contains iron.

[0079] Regarding the properties of the deoxidizer 50 , powder or granular form is preferred from the viewpoint of availability, and powder is more preferred from the viewpoint of adjusting the oxygen concentration in the sealed container 20 .

[0080] Examples of the deoxidizer 50 of this embodiment include Ageless (registered trademark, manufactured by Mitsubishi Gas Chemical Co., Ltd.), Sequl (registered trademark, manufactured by Nissofine Co., Ltd.), and WonderKeep (registered trademark, manufactured by Powdertech Co., Ltd.), which are commercially available small bag-sealed packages.

[0081] The amount of the deoxidizer 50 (active ingredient) used may be determined in consideration of the type, properties, and amount of the π-conjugated polymer 60 , the volume of the atmosphere sealed in the container 20 , the expected storage period, and the like.

[0082] For example, when the volume of the atmosphere sealed in the container 20 is 50 mL and the assumed storage period is 1 year, one deoxidizer 50 capable of absorbing 50 mL of oxygen may be used.

[0083] The arrangement of the deoxidizer 50 within the sealed container 20 is not particularly limited, provided the aforementioned conditions are met. For example, when a pouch-type package is used as the deoxidizer 50, the package may be arranged so that the package is in direct contact with the π-conjugated polymer 60 within the sealed container 20, or so that the package is in contact with at least the atmosphere within the sealed container 20. In other words, the conjugated polymer 60 and the package may be separated from each other but both may be in contact with the atmosphere within the sealed container 20.

[0084] (iii) π-conjugated polymers

[0085] Next, the π-conjugated polymer 60 of this embodiment will be described. The π-conjugated polymer 60 of this embodiment is a π-conjugated polymer that can function as a p-type semiconductor material for forming an active layer of an organic photoelectric conversion element.

[0086] The π-conjugated polymer 60 of this embodiment is a polymer compound having a molecular weight distribution and a π-conjugated system in which multiple bonds and single bonds are alternately and repeatedly connected in the main chain through bonds between carbon atoms or bonds between carbon atoms and heteroatoms.

[0087] The π-conjugated polymer 60 may be any type of copolymer, for example, a block copolymer, a random copolymer, an alternating copolymer, a graft copolymer, or the like.

[0088] The π-conjugated polymer 60 of the present embodiment has a predetermined polystyrene-equivalent weight average molecular weight.

[0089] The polystyrene-equivalent weight average molecular weight refers to a weight average molecular weight calculated by gel permeation chromatography (GPC) using a polystyrene standard sample.

[0090] The polystyrene-equivalent weight average molecular weight of the π-conjugated polymer 60 of this embodiment is not particularly limited. In particular, from the perspective of effective storage effects, it is preferred to use a π-conjugated polymer having a polystyrene-equivalent weight average molecular weight of 40,000 to 200,000, more preferably 40,000 to 150,000, and even more preferably 45,000 to 150,000.

[0091] The method for producing and storing an organic photoelectric conversion element of the present embodiment can be suitably used for an organic photoelectric conversion element having an initial electron spin concentration of 0.3×10 16 (Spin / g) or more π-conjugated polymer 60.

[0092] The π-conjugated polymer 60 having a high electron spin concentration is considered to be particularly susceptible to degradation (radicalization) by oxygen in the storage atmosphere, and therefore can be suitably applied to the organic photoelectric conversion element manufacturing method, reagent package 10, and storage method of the present invention.

[0093] The electron spin concentration per 1 g of the π-conjugated polymer 60 before storage treatment in this embodiment is preferably 0.3×10 16 (Spin / g) or more; from the perspective of more effectively suppressing the increase in electron spin concentration, that is, the degradation of the π conjugated polymer 60, more preferably 0.8 × 10 16 More preferably, 1.0×10 16 More than 2.0×10 16 From the perspective of external quantum yield, it is preferably 10×10 16 Below, more preferably 7.0×10 16 the following.

[0094] From the viewpoint of the film quality of the active layer, the electron spin concentration per 1 g of the π-conjugated polymer 60 obtained through the above step (1) after storage is more preferably 10.0×10 16 Below, more preferably 8.0×10 16 Below, more preferably 7.0×10 16 the following.

[0095] From the perspective of device characteristics, the electron spin concentration per 1g of the π-conjugated polymer 60 obtained after storage through the above-mentioned step (1) is preferably less than 2.4 times the electron spin concentration per 1g of the π-conjugated polymer 60 before storage treatment, more preferably less than 2.0 times, further preferably less than 1.5 times, and further preferably less than 1.3 times.

[0096] Here, the electron spin concentration is a parameter obtained from an ESR spectrum measured by an electron spin resonance (ESR) method. The ESR spectrum can be obtained using, for example, an X-band ESR device.

[0097] Specifically, first, an ESR method using an ESR device is used to obtain an ESR spectrum reflecting the electron spin characteristics of the π-conjugated polymer 60. The area of ​​the ESR spectrum is correlated with the electron spin amount, and thus the electron spin amount can be calculated from the area of ​​the ESR spectrum.

[0098] The area of ​​the ESR spectrum can be calculated using any suitable calculation method known in the art or commercially available software.

[0099] As a method for calculating the electron spin amount from the obtained ESR spectrum area, any conventionally known appropriate method can be used. As a method for calculating the electron spin amount from the ESR spectrum area, for example, the method described in Practical ESR Primer (Kodansha Scientific Co., Ltd.) can be cited.

[0100] The electron spin concentration (Spin / g) can be calculated by dividing the calculated electron spin amount by the weighed value of the π-conjugated polymer 60 to be measured.

[0101] Furthermore, the method for manufacturing an organic photoelectric conversion element, the reagent package 10, and the storage method of this embodiment are suitable for use with a π-conjugated polymer 60 having a maximum absorption wavelength of 500 nm or greater, in other words, a wavelength within a wavelength range including the near-infrared region, before or after storage. In this embodiment, the maximum absorption wavelength is more preferably 600 nm or greater, further preferably 670 nm or greater, even more preferably 700 nm or greater, and even more preferably 750 nm or greater. Furthermore, from the perspective of the polymer's atmospheric stability, the maximum absorption wavelength is more preferably 2000 nm or less, and even more preferably 1800 nm or less.

[0102] Furthermore, the organic photoelectric conversion device manufacturing method, reagent package 10, and storage method of the present invention are suitable for use with π-conjugated polymers having a band gap (i.e., a difference between the energy levels of the LUMO (Lowest Unocupied Molecular Orbital) and the HOMO (Highest Occupied Molecular Orbital)) of 2.0 eV or less. In this embodiment, the band gap of the π-conjugated polymer is more preferably 1.8 eV or less, further preferably 1.6 eV or less, and even more preferably 1.4 eV or less.

[0103] Hereinafter, terms commonly used in more specifically describing the π-conjugated polymer 60 of this embodiment will be described.

[0104] In this specification, a "structural unit" refers to a unit structure existing in one or more units in the π-conjugated polymer 60. The "structural unit" is preferably contained as a "repeating unit" (a unit structure existing in two or more units in the π-conjugated polymer 60).

[0105] The "hydrogen atom" may be a protium atom or a deuterium atom.

[0106] The "halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0107] The phrase “having or not having a substituent” includes both the case where all hydrogen atoms constituting the compound or group are unsubstituted and the case where part or all of one or more hydrogen atoms are substituted with a substituent.

[0108] Unless otherwise specified, an "alkyl group" may be linear, branched, or cyclic. A linear alkyl group generally has 1 to 50 carbon atoms, excluding the number of carbon atoms in substituents, preferably 1 to 30, and more preferably 1 to 20 carbon atoms. A branched or cyclic alkyl group generally has 3 to 50 carbon atoms, excluding the number of carbon atoms in substituents, preferably 3 to 30, and more preferably 4 to 20 carbon atoms.

[0109] The alkyl group may be substituted. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-ethylbutyl, n-hexyl, cyclohexyl, n-heptyl, cyclohexylmethyl, cyclohexylethyl, n-octyl, 2-ethylhexyl, 3-n-propylheptyl, adamantyl, n-decyl, 3,7-dimethyloctyl, 2-ethyloctyl, 2-n-hexyldecyl, n-dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl groups; and alkyl groups having substituents such as trifluoromethyl, pentafluoroethyl, perfluorobutyl, perfluorohexyl, perfluorooctyl, 3-phenylpropyl, 3-(4-methylphenyl)propyl, 3-(3,5-di-n-hexylphenyl)propyl, and 6-ethoxyhexyl groups.

[0110] The "aryl group" refers to an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon which may have a substituent.

[0111] The aryl group may have a substituent. Specific examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 2-phenylphenyl, 3-phenylphenyl, 4-phenylphenyl, and groups having a substituent such as an alkyl group, an alkoxy group, an aryl group, or a fluorine atom.

[0112] An "alkoxy group" may be linear, branched, or cyclic. A linear alkoxy group generally has 1 to 40 carbon atoms, preferably 1 to 10 carbon atoms, excluding the carbon atoms in the substituent. A branched or cyclic alkoxy group generally has 3 to 40 carbon atoms, preferably 4 to 10 carbon atoms, excluding the carbon atoms in the substituent.

[0113] The alkoxy group may be substituted. Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy, cyclohexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, 3,7-dimethyloctyloxy, and lauryloxy.

[0114] The number of carbon atoms in the "aryloxy group" is usually 6 to 60, preferably 6 to 48, not including the number of carbon atoms in the substituent.

[0115] The aryloxy group may be substituted. Specific examples of the aryloxy group include phenoxy, 1-naphthyloxy, 2-naphthyloxy, 1-anthryloxy, 9-anthryloxy, 1-pyreneoxy, and groups having a substituent such as an alkyl group, an alkoxy group, or a fluorine atom.

[0116] An "alkylthio group" may be linear, branched, or cyclic. A linear alkylthio group generally has 1 to 40 carbon atoms, preferably 1 to 10 carbon atoms, excluding the carbon atoms of the substituent. A branched or cyclic alkylthio group generally has 3 to 40 carbon atoms, preferably 4 to 10 carbon atoms, excluding the carbon atoms of the substituent.

[0117] The alkylthio group may be substituted. Specific examples of the alkylthio group include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, tert-butylthio, pentylthio, hexylthio, cyclohexylthio, heptylthio, octylthio, 2-ethylhexylthio, nonylthio, decylthio, 3,7-dimethyloctylthio, laurylthio, and trifluoromethylthio.

[0118] The number of carbon atoms in the "arylthio group" is usually 6 to 60, preferably 6 to 48, not including the carbon atoms in the substituent.

[0119] The arylthio group may be substituted. Examples of the arylthio group include a phenylthio group, a C1-C12 alkoxyphenylthio group (where "C1-C12" indicates that the group immediately following it has 1 to 12 carbon atoms. The same applies hereinafter), a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

[0120] A "p-valent heterocyclic group" (p represents an integer greater than or equal to 1) refers to an atomic group remaining after removing p hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring from a heterocyclic compound that may or may not have a substituent. Among p-valent heterocyclic groups, a "p-valent aromatic heterocyclic group" is preferred. A "p-valent aromatic heterocyclic group" refers to an atomic group remaining after removing p hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring from an aromatic heterocyclic compound that may or may not have a substituent.

[0121] Here, examples of the substituent that the heterocyclic compound may have include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imide residue, an amide group, an imide group, a substituted oxycarbonyl group, an alkenyl group, an alkynyl group, a cyano group, and a nitro group.

[0122] The aromatic heterocyclic compound includes not only compounds in which the heterocyclic ring itself exhibits aromaticity but also compounds in which an aromatic ring is fused to a heterocyclic ring that does not exhibit aromaticity.

[0123] Specific examples of aromatic heterocyclic compounds in which the heterocycle itself exhibits aromaticity include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole.

[0124] Specific examples of aromatic heterocyclic compounds in which an aromatic ring is fused to a non-aromatic heterocyclic ring include phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, and benzopyran.

[0125] The monovalent heterocyclic group has usually 2 to 60 carbon atoms, and preferably 4 to 20 carbon atoms, not including the carbon atoms of the substituent.

[0126] The monovalent heterocyclic group may have a substituent. Specific examples of the monovalent heterocyclic group include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidyl group, a quinolyl group, an isoquinolyl group, a pyrimidyl group, a triazinyl group, and groups in which these groups have a substituent such as an alkyl group or an alkoxy group.

[0127] "Substituted amino" refers to an amino group having a substituent. Examples of substituents that a substituted amino group may have include an alkyl group, an aryl group, and a monovalent heterocyclic group. Preferred substituents are alkyl groups, aryl groups, and monovalent heterocyclic groups. Substituted amino groups generally have 2 to 30 carbon atoms.

[0128] Examples of the substituted amino group include dialkylamino groups such as dimethylamino and diethylamino, and diarylamino groups such as diphenylamino, bis(4-methylphenyl)amino, bis(4-tert-butylphenyl)amino, and bis(3,5-di-tert-butylphenyl)amino.

[0129] The number of carbon atoms in the "acyl group" is usually 2 to 20, preferably 2 to 18. Specific examples of the acyl group include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, benzoyl, trifluoroacetyl, and pentafluorobenzoyl.

[0130] An "imine residue" refers to an atomic group remaining after removing a hydrogen atom directly bonded to a carbon atom or nitrogen atom constituting a carbon-nitrogen double bond from an imine compound. An "imine compound" refers to an organic compound having a carbon-nitrogen double bond within the molecule. Examples of imine compounds include aldimines, ketimines, and compounds in which the hydrogen atom bonded to the nitrogen atom constituting a carbon-nitrogen double bond in aldimines is substituted with an alkyl group or the like.

[0131] The imine residue generally has 2 to 20 carbon atoms, and preferably has 2 to 18 carbon atoms. Examples of the imine residue include groups represented by the following structural formulas.

[0132] [Chemistry 1]

[0133]

[0134] An "amide group" refers to the remaining atomic group after removing one hydrogen atom bonded to a nitrogen atom from an amide. The number of carbon atoms in an amide group is generally 1 to 20, preferably 1 to 18. Specific examples of amide groups include formamide, acetamide, propionamide, butyramide, benzamide, trifluoroacetamide, pentafluorobenzamide, diformamide, diacetamide, dipropionamide, dibutyramide, dibenzamide, bis(trifluoroacetamide), and bis(pentafluorobenzamide).

[0135] An "imido group" refers to an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an imide group. An imide group generally has 4 to 20 carbon atoms. Specific examples of imide groups include those represented by the following structural formulas.

[0136] [Chemistry 2]

[0137]

[0138] The "substituted oxycarbonyl group" refers to a group represented by R'-O-(C=O)-, where R' represents an alkyl group, an aryl group, an aralkyl group, or a monovalent heterocyclic group.

[0139] The substituted oxycarbonyl group usually has 2 to 60 carbon atoms, and preferably has 2 to 48 carbon atoms.

[0140] Specific examples of the substituted oxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, 3,7-dimethyloctyloxycarbonyl, dodecyloxycarbonyl, trifluoromethoxycarbonyl, pentafluoroethoxycarbonyl, perfluorobutoxycarbonyl, perfluorohexyloxycarbonyl, perfluorooctyloxycarbonyl, phenoxycarbonyl, naphthyloxycarbonyl and pyridyloxycarbonyl.

[0141] An "alkenyl group" may be linear, branched, or cyclic. A linear alkenyl group generally has 2 to 30 carbon atoms, excluding the number of carbon atoms in substituents, and preferably 3 to 20 carbon atoms. A branched or cyclic alkenyl group generally has 3 to 30 carbon atoms, excluding the number of carbon atoms in substituents, and preferably 4 to 20 carbon atoms.

[0142] The alkenyl group may have a substituent. Specific examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 5-hexenyl, 7-octenyl, and groups in which these groups have a substituent such as an alkyl group or an alkoxy group.

[0143] An "alkynyl group" may be linear, branched, or cyclic. A linear alkynyl group generally has 2 to 20 carbon atoms, excluding the number of carbon atoms in substituents, and preferably 3 to 20 carbon atoms. A branched or cyclic alkynyl group generally has 4 to 30 carbon atoms, excluding the number of carbon atoms in substituents, and preferably 4 to 20 carbon atoms.

[0144] The alkynyl group may have a substituent. Specific examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 5-hexynyl, and groups in which these groups have a substituent such as an alkyl group or an alkoxy group.

[0145] As the π-conjugated polymer 60 of this embodiment, 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, polythiophenylene vinylene and its derivatives, polyfluorene and its derivatives, etc.

[0146] More specifically, examples of the π-conjugated polymer 60 of the present embodiment include polymer compounds containing a structural unit represented by the following formula (I) and / or a structural unit represented by the following formula (II).

[0147] [Chemistry 3]

[0148]

[0149] In formula (I), Ar 1 and Ar 2 represents a trivalent aromatic heterocyclic group, and Z represents a group represented by the following formulae (Z-1) to (Z-7).

[0150] [Chemistry 4]

[0151]

[0152] In formula (II), Ar 3 represents a divalent aromatic heterocyclic group.

[0153] [Chemistry 5]

[0154]

[0155] In formulas (Z-1) to (Z-7), R represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imide residue, an amide group, an imide group, a substituted oxycarbonyl group, an alkenyl group, an alkynyl group, a cyano group, or a nitro group. In each of formulas (Z-1) to (Z-7), when there are two R groups, the two R groups may be the same or different.

[0156] Examples of the structural unit represented by formula (I) include the structural unit represented by the following formula (I-1).

[0157] [Chemistry 6]

[0158]

[0159] In formula (I-1), Z has the same meaning as above.

[0160] Examples of the structural unit represented by formula (I-1) include structural units represented by the following formulae (501) to (505).

[0161] [Chemistry 7]

[0162]

[0163] In formulae (501) to (505), R has the same meaning as above. When there are two or more Rs, the two Rs may be the same or different from each other.

[0164] Ar 3 The number of carbon atoms in the divalent aromatic heterocyclic group represented by is usually 2 to 60, preferably 4 to 60, and more preferably 4 to 20. 3The divalent aromatic heterocyclic group represented by may have a substituent. 3 Examples of substituents that the divalent aromatic heterocyclic group represented may have include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imide residue, an amide group, an imide group, a substituted oxycarbonyl group, an alkenyl group, an alkynyl group, a cyano group, and a nitro group.

[0165] As Ar 3 Examples of the divalent aromatic heterocyclic group include groups represented by the following formulae (101) to (185).

[0166] [Chemistry 8]

[0167]

[0168]

[0169] [Chemistry 9]

[0170]

[0171]

[0172] [Chemistry 10]

[0173]

[0174]

[0175] [Chemistry 11]

[0176]

[0177] In formulae (101) to (185), R has the same meaning as above. When there are two or more Rs, the two or more Rs may be the same or different from each other.

[0178] Examples of the structural unit represented by the above formula (II) include structural units represented by the following formulae (II-1) to (II-6).

[0179] [Chemistry 12]

[0180]

[0181] In formulas (II-1) to (II-6), X 1 and X 2 Each independently represents an oxygen atom or a sulfur atom, and R has the same meaning as above. When there are two or more Rs, the two or more Rs may be the same or different from each other.

[0182] From the viewpoint of the availability of the raw material compounds, X in formula (II-1) to formula (II-6) 1 and X 2 Preferably, they are all sulfur atoms.

[0183] The π-conjugated polymer 60 of the present embodiment may be a polymer compound including a structural unit having a thiophene skeleton.

[0184] The π-conjugated polymer 60 of this embodiment may include two or more structural units represented by formula (I), or may include two or more structural units represented by formula (II).

[0185] The π-conjugated polymer 60 of this embodiment may also include a structural unit represented by the following formula (III).

[0186] [Chemistry 13]

[0187]

[0188] In formula (III), Ar 4 represents an arylene group.

[0189] Ar 4 The arylene group represented herein refers to the atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon, which may or may not have a substituent. Aromatic hydrocarbons also include compounds having fused rings, and compounds in which two or more rings selected from the group consisting of independent benzene rings and fused rings are bonded directly or through a divalent group such as a vinylene group.

[0190] Examples of the substituent that the aromatic hydrocarbon may have include the same substituents as exemplified as the substituent that the heterocyclic compound may have.

[0191] The number of carbon atoms in the arylene group excluding the substituent is usually 6 to 60, preferably 6 to 20. The upper limit of the number of carbon atoms in the arylene group including the substituent is 100.

[0192] Examples of arylene groups include phenylene groups (for example, formulas 1 to 3 below), naphthalene diyl groups (for example, formulas 4 to 13 below), anthracene diyl groups (for example, formulas 14 to 19 below), biphenyl diyl groups (for example, formulas 20 to 25 below), terphenyl diyl groups (for example, formulas 26 to 28 below), condensed ring compound groups (for example, formulas 29 to 35 below), fluorene diyl groups (for example, formulas 36 to 38 below), and benzofluorene diyl groups (for example, formulas 39 to 46 below).

[0193] [Chemistry 14]

[0194]

[0195] [Chemistry 15]

[0196]

[0197] [Chemistry 16]

[0198]

[0199] [Chemistry 17]

[0200]

[0201] [Chemistry 18]

[0202]

[0203] [Chemistry 19]

[0204]

[0205] [Chemistry 20]

[0206]

[0207] [Chemistry 21]

[0208]

[0209] In Formulae 1 to 46, R as a substituent has the same meaning as above. When there are two or more Rs, the two or more Rs may be the same as or different from each other.

[0210] The structural unit constituting the π-conjugated polymer 60 of this embodiment may be a structural unit formed by combining and linking two or more structural units selected from the structural unit represented by formula (I), the structural unit represented by formula (II), and the structural unit represented by formula (III).

[0211] When the π-conjugated polymer 60 of the present embodiment contains a structural unit represented by formula (I) and / or a structural unit represented by formula (II), if the amount of all structural units contained in the polymer compound is set to 100 mol%, the total amount of the structural unit represented by formula (I) and the structural unit represented by formula (II) is usually 20 to 100 mol%, and from the viewpoint of improving charge transport properties, it can be 40 to 100 mol% or 50 to 100 mol%.

[0212] Specific examples of the π-conjugated polymer 60 of the present embodiment include polymer compounds represented by the following formulae P-1 to P-4.

[0213] [Chemistry 22]

[0214]

[0215] In the above step (1), a predetermined amount of the π-conjugated polymer 60 is contained in the sealing container 20, and a deoxidizing agent 50 containing an effective amount of an effective ingredient relative to the predetermined amount of the π-conjugated polymer 60 is arranged. The sealing container 20 is made airtight using means and methods suitable for the selected sealing container 20, thereby sealing the π-conjugated polymer 60 and the deoxidizing agent 50 in the sealing container 20.

[0216] This step makes the atmosphere in the sealed container 20 have an oxygen concentration of 1% or less. From the viewpoint of more effectively suppressing an increase in electron spin concentration, the oxygen concentration is more preferably 1% or less, and even more preferably 0.5% or less.

[0217] <Process (2)>

[0218] The active layer of the organic photoelectric conversion element of this embodiment includes a p-type semiconductor material (electron-donating compound) and an n-type semiconductor material (electron-accepting compound). The type of the selected organic semiconductor material can be determined based on its HOMO or LUMO energy level.

[0219] The thickness of the active layer is generally preferably 1 nm to 100 μm, more preferably 2 nm to 1000 nm, further preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm. When the organic photoelectric conversion element is used in, for example, a solar cell, the thickness of the active layer is preferably 500 nm to 1000 nm. Furthermore, when the organic photoelectric conversion element is used in, for example, a light detection element, the thickness of the active layer is preferably 500 nm to 1000 nm.

[0220] The active layer can be produced by, for example, a coating method using an ink composition (coating liquid).

[0221] Here, an example of forming an active layer, which is a main component of an organic photoelectric conversion element, by a coating method will be described. The process of forming the active layer includes the following steps (i) and (ii).

[0222] Process (i)

[0223] Any suitable coating method can be used to apply the ink composition to the object to be coated. Preferred coating methods include slit coating, blade coating, spin coating, micro-gravure coating, gravure printing, rod coating, inkjet printing, nozzle coating, and capillary coating. Slit coating, spin coating, capillary coating, and rod coating are more preferred, and slit coating and spin coating are even more preferred.

[0224] The ink composition for forming the active layer is applied to a coating object selected according to the photoelectric conversion element and its manufacturing method. In the manufacturing method of the organic photoelectric conversion element, the ink composition for forming the active layer is applied to a functional layer that is adjacent to the active layer and that is possessed by the organic photoelectric conversion element. Therefore, the coating object of the ink composition for forming the active layer varies depending on the layer structure of the organic photoelectric conversion element being manufactured and the order in which the layers are formed. For example, when the organic photoelectric conversion element has a layer structure of substrate / anode / hole transport layer / active layer / electron transport layer / cathode, and the layer recorded further to the left is formed first, the coating object of the ink composition is the hole transport layer. In addition, for example, when the organic photoelectric conversion element has a layer structure of substrate / cathode / electron transport layer / active layer / hole transport layer / anode, and the layer recorded further to the left is formed first, the coating object of the ink composition is the electron transport layer.

[0225] Step (ii)

[0226] As a method for removing the solvent from the coating film of the ink composition, that is, a method for drying the coating film to remove the solvent and solidify it, any appropriate method can be used. Examples of the method for removing the solvent include drying treatments such as direct heating using a hot plate, hot air drying, infrared heating drying, flash lamp annealing drying, and reduced pressure drying.

[0227] The process of forming the active layer may include other steps in addition to step (i) and step (ii) as long as the object and effect of the present invention are not impaired.

[0228] The method for producing an organic photoelectric conversion element of this embodiment may be a method for producing an organic photoelectric conversion element including a plurality of active layers, or may be a method for producing an organic photoelectric conversion element by repeating step (i) and step (ii) a plurality of times.

[0229] (Ink composition)

[0230] The ink composition used in step (i) above may be a solution, a dispersion, an emulsion, a suspension, or other dispersion. The ink composition of this embodiment is an ink composition for forming an active layer, and includes a π-conjugated polymer as a p-type semiconductor material, an n-type semiconductor material, a first solvent, and optionally a second solvent.

[0231] The ink composition may contain only one p-type semiconductor material (π-conjugated polymer 60 ), or may contain two or more p-type semiconductor materials in combination at any ratio.

[0232] (n-type semiconductor material)

[0233] The n-type semiconductor material (electron-accepting compound) may be a low-molecular compound or a high-molecular compound.

[0234] Examples of n-type semiconductor materials of low molecular weight compounds include oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, fullerenes such as C60 fullerene and their derivatives, and phenanthrene derivatives such as bathocuproin.

[0235] Examples of n-type semiconductor materials of polymer 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, and polyfluorene and its derivatives.

[0236] The n-type semiconductor material is preferably at least one selected from fullerenes and fullerene derivatives, and more preferably a fullerene derivative.

[0237] As an example of fullerene, C 60 Fullerene, C 70 Fullerene, C 76 Fullerene, C 78 Fullerenes and C 84 Fullerene. Examples of fullerene derivatives include derivatives of these fullerenes. Fullerene derivatives refer to compounds in which at least a portion of fullerene is modified.

[0238] Examples of fullerene derivatives include compounds represented by the following formulae (N-1) to (N-4).

[0239] [Chemistry 23]

[0240]

[0241] In formula (N-1) to formula (N-4), R a represents an alkyl group, an aryl group, a monovalent heterocyclic group or a group having an ester structure. a They may be the same as or different from each other.

[0242] In formula (N-1) to formula (N-4), R b represents an alkyl group or an aryl group. b They may be the same as or different from each other.

[0243] As R a Examples of the group having an ester structure include a group represented by the following formula (19).

[0244] [Chemistry 24]

[0245]

[0246] In formula (19), u1 represents an integer from 1 to 6. u2 represents an integer from 0 to 6. R c represents an alkyl group, an aryl group or a monovalent heterocyclic group.

[0247] As C 60 Examples of fullerene derivatives include the following compounds.

[0248] [Chemistry 25]

[0249]

[0250] As C 70 Examples of fullerene derivatives include the following compounds.

[0251] [Chemistry 26]

[0252]

[0253] Specific examples of fullerene derivatives include [6,6]-phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6]-Phenyl C61 butyric acid methyl ester), [6,6]-phenyl-C71 butyric acid methyl ester (C70PCBM, [6,6]-Phenyl C71 butyric acid methyl ester), [6,6]-phenyl-C85 butyric acid methyl ester (C84PCBM, [6,6]-Phenyl C85 butyric acid methyl ester), and [6,6]-thienyl-C61 butyric acid methyl ester.

[0254] The ink composition may contain only one n-type semiconductor material, or may contain a combination of two or more n-type semiconductor materials in any ratio.

[0255] (First solvent)

[0256] The solvent may be selected in consideration of its solubility in the selected p-type semiconductor material and n-type semiconductor material and its characteristics (such as boiling point) depending on the drying conditions when forming the active layer.

[0257] The first solvent as the main solvent is an aromatic hydrocarbon (hereinafter referred to as an aromatic hydrocarbon) which may have a substituent (eg, an alkyl group or a halogen atom). The first solvent is preferably selected in consideration of the solubility of the selected p-type semiconductor material and n-type semiconductor material.

[0258] Examples of such aromatic hydrocarbons include toluene, xylenes (e.g., o-xylene, m-xylene, p-xylene), trimethylbenzenes (e.g., mesitylene, 1,2,4-trimethylbenzene (pseudocumene)), butylbenzenes (e.g., n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (e.g., 1-methylnaphthalene), tetralin, indane, chlorobenzene, and dichlorobenzene (o-dichlorobenzene).

[0259] The first solvent may be composed of only one type of aromatic hydrocarbon or may be composed of two or more types of aromatic hydrocarbons. The first solvent is preferably composed of only one type of aromatic hydrocarbon.

[0260] The first solvent preferably contains one or more selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, mesitylene, pseudocumene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetralin, indane, chlorobenzene and o-dichlorobenzene, more preferably o-xylene, pseudocumene, tetralin, chlorobenzene or o-dichlorobenzene.

[0261] (Second solvent)

[0262] The second solvent is preferably a solvent selected from the perspective of improving the solubility of the n-type semiconductor material. Examples of the second solvent include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, and propiophenone; and ester solvents such as ethyl acetate, butyl acetate, phenyl acetate, ethyl cellosolve acetate, methyl benzoate, butyl benzoate, and benzyl benzoate.

[0263] From the viewpoint of reducing dark current, the second solvent is preferably acetophenone, propiophenone, or benzyl benzoate.

[0264] (Combination of the first solvent and the second solvent)

[0265] Examples of the combination of the first solvent and the second solvent include the combinations shown in Table 1 below.

[0266] [Table 1]

[0267] 1st solvent Second solvent Pseudocumene Phenylacetone Pseudocumene Benzyl benzoate Tetralin Phenylacetone o-Xylene acetophenone

[0268] (Weight ratio of the first solvent to the second solvent)

[0269] From the perspective of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material, the weight ratio of the first solvent as the main solvent to the second solvent as the additional solvent (first solvent / second solvent) is preferably in the range of 85 / 15 to 95 / 5.

[0270] (Total weight percentage of the first solvent and the second solvent in the ink composition)

[0271] When the total weight of the ink composition is 100 weight %, from the perspective of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material, the total weight of the first solvent and the second solvent contained in the ink composition is preferably 90 weight % or more, more preferably 92 weight % or more, and even more preferably 95 weight % or more. From the perspective of further increasing the content of the p-type semiconductor material and the n-type semiconductor material in the ink composition and facilitating the formation of a film with a certain thickness or greater, the above total weight is preferably 99 weight % or less, more preferably 98 weight % or less, and even more preferably 97.5 weight % or less.

[0272] (Optional solvent)

[0273] The ink composition may contain an optional solvent in addition to the first and second solvents. When the total weight of all solvents in the ink composition is taken as 100% by weight, the content of the optional solvent is preferably 5% by weight or less, more preferably 3% by weight or less, and even more preferably 1% by weight or less. The optional solvent is preferably one having a higher boiling point than the second solvent.

[0274] (Optional Ingredients)

[0275] The ink composition may contain, in addition to the first solvent, the second solvent, the p-type semiconductor material, and the n-type semiconductor material, optional components such as a UV absorber, an antioxidant, a sensitizer for sensitizing the function of generating charge using absorbed light, and a light stabilizer for increasing stability against ultraviolet light, within the limits that do not impair the purpose and effects of the present invention.

[0276] (Concentrations of p-type semiconductor material and n-type semiconductor material in ink composition)

[0277] The combined concentration of the p-type semiconductor material and the n-type semiconductor material in the ink composition is preferably from 0.01% to 20% by weight, more preferably from 0.01% to 10% by weight, even more preferably from 0.01% to 5% by weight, and particularly preferably from 0.1% to 5% by weight. The p-type semiconductor material and the n-type semiconductor material may be dissolved or dispersed in the ink composition. The p-type semiconductor material and the n-type semiconductor material are preferably at least partially dissolved, and more preferably completely dissolved.

[0278] (Preparation of ink composition)

[0279] The ink composition can be prepared using known methods. For example, the ink composition can be prepared by mixing a first solvent and a second solvent to prepare a mixed solvent, and then adding a p-type semiconductor material and an n-type semiconductor material to the mixed solvent; adding a p-type semiconductor material to the first solvent, adding an n-type semiconductor material to the second solvent, and then mixing the first and second solvents containing the added materials; and the like.

[0280] Alternatively, the first solvent, the second solvent, the p-type semiconductor material, and the n-type semiconductor material may be mixed by heating at a temperature below the boiling point of the solvent.

[0281] After mixing the first and second solvents, the p-type semiconductor material, and the n-type semiconductor material, the resulting mixture can be filtered through a filter, and the resulting filtrate can be used as an ink composition. The filter can be made of a fluororesin such as polytetrafluoroethylene (PTFE), for example.

[0282] According to the manufacturing method of the organic photoelectric conversion element of this embodiment, the π-conjugated polymer 60 serving as the material of the active layer can be stored while effectively suppressing the increase in the electron spin concentration, that is, the time-dependent degradation of the π-conjugated polymer 60. Therefore, the organic photoelectric conversion element can be manufactured on demand using the stored π-conjugated polymer 6 without specially coordinating the synthesis timing of the π-conjugated polymer 60.

[0283] Furthermore, the storage method of this embodiment allows the π-conjugated polymer 60 to be stably stored for a longer period of time while effectively suppressing an increase in the electron spin concentration of the π-conjugated polymer 60 , that is, temporal degradation of the π-conjugated polymer 60 , through a simple process.

[0284] 2. Organic photoelectric conversion elements

[0285] The organic photoelectric conversion element of this embodiment includes: a pair of electrodes including an anode and a cathode; and an active layer provided between the pair of electrodes and containing a π-conjugated polymer 60 as an organic semiconductor material.

[0286] Hereinafter, the configuration other than the active layer already described, which may be included in the organic photoelectric conversion element of this embodiment, and the steps for forming the same will be described.

[0287] (Substrate)

[0288] Organic photoelectric conversion elements are usually formed on a substrate. Electrodes including a cathode and an anode are usually formed on the substrate. The material of the substrate is not particularly limited as long as it is a material that does not undergo chemical changes when forming a layer, especially a layer containing an organic compound. Examples of the material of the substrate include glass, plastic, polymer film, and silicon. As the substrate, a substrate can be prepared that is formed with the electrodes described later, or provided with a layer of conductive material that can function as an electrode by patterning. As an example of a substrate provided with a layer of conductive material, a glass substrate formed with a layer of indium tin oxide (ITO) can be mentioned.

[0289] (electrode)

[0290] As the material of the transparent or translucent electrode, for example, conductive metal oxide films, translucent metal films, etc. can be cited. Specifically, conductive materials such as ITO, indium zinc oxide (IZO), NESA, gold, platinum, silver, and copper as their composites can be cited. As the material of the transparent or translucent electrode, ITO, IZO, and tin oxide are preferred. In addition, as the electrode, a transparent conductive film using organic compounds such as polyaniline and derivatives thereof, polythiophene and derivatives thereof as the material can be adopted. The transparent or translucent electrode can be an anode or a cathode. When the substrate is opaque, it is preferred that the electrode on the opposite side of the electrode arranged on the opaque substrate side (i.e., the electrode away from the substrate side) is a transparent or translucent electrode.

[0291] As long as one of the electrodes in a pair is transparent or translucent, the other electrode can be an electrode with low light transmittance. Examples of materials for electrodes with low light transmittance include metals and conductive polymers. Specific examples of materials for electrodes with low light transmittance include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, and ytterbium, as well as alloys of two or more of these metals; or alloys of one or more of these metals with one or more metals selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin; graphite, graphite intercalation compounds, polyaniline and its derivatives, and polythiophene and its derivatives. Examples of alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.

[0292] As a method for forming the electrode, any conventionally known appropriate method can be used. Examples of the method for forming the electrode include vacuum deposition, sputtering, ion plating, and plating.

[0293] (Middle layer)

[0294] The organic photoelectric conversion element of this embodiment may include an additional intermediate layer such as a charge transport layer (electron transport layer, hole transport layer, electron injection layer, hole injection layer) as a further component for improving properties such as photoelectric conversion efficiency.

[0295] As the material used for such an intermediate layer, any conventionally known appropriate material can be used. Examples of the material for the intermediate layer include halides and oxides of alkali metals or alkaline earth metals such as lithium fluoride.

[0296] Examples of materials used in the intermediate layer include fine particles of inorganic semiconductors such as titanium oxide, and a mixture of PEDOT (poly(3,4-ethylenedioxythiophene)) and PSS (poly(4-styrenesulfonate)) (PEDOT:PSS).

[0297] The organic photoelectric conversion element may include a hole transport layer between the anode and the active layer. The hole transport layer has the function of transporting holes from the active layer to the electrode.

[0298] The hole transport layer (hole injection layer) that is disposed in contact with the anode is sometimes specifically referred to as a hole injection layer. The hole transport layer (hole injection layer) disposed in contact with the anode has the function of promoting the injection of holes into the anode. The hole transport layer (hole injection layer) may be in contact with the active layer.

[0299] The hole transport layer contains a hole transport material. Examples of hole transport materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing a structural unit having an aromatic amine residue, CuSCN, CuI, NiO, and molybdenum oxide (MoO 3 ).

[0300] An organic photoelectric conversion element may include an electron transport layer between the cathode and the active layer. The electron transport layer has the function of transporting electrons from the active layer to the cathode. The electron transport layer may be in contact with the cathode or the active layer.

[0301] The electron transport layer contains an electron transport material. Examples of the electron transport material include zinc oxide nanoparticles, gallium-doped zinc oxide nanoparticles, aluminum-doped zinc oxide nanoparticles, polyethyleneimine, epoxidized polyethyleneimine, and PFN-P2.

[0302] The intermediate layer can be formed by the same coating method as the method for producing the active layer described above.

[0303] (Sealing layer)

[0304] The organic photoelectric conversion element of this embodiment may further include a sealing layer. The sealing layer may be provided, for example, on the side of the electrode farther from the substrate. The sealing layer may be formed using a material having water barrier properties (water vapor barrier properties) or oxygen barrier properties (oxygen barrier properties) using a method appropriate for the selected material.

[0305] (Applications of organic photoelectric conversion elements)

[0306] The organic photoelectric conversion element of this embodiment can generate a photoelectromotive force between electrodes by irradiating light, and can function as a solar cell. Alternatively, a thin-film solar cell module can be fabricated by integrating multiple solar cells.

[0307] Furthermore, in the organic photoelectric conversion element of this embodiment, light can flow from the transparent or translucent electrode side while a voltage is applied between the electrodes, allowing photocurrent to flow, thereby enabling it to function as a light detection element (photosensor). Furthermore, multiple photosensors can be integrated to form an image sensor.

[0308] 3. Reagent package

[0309] The reagent package 10 of the present embodiment can be suitably applied to the method for manufacturing an organic photoelectric conversion element and the method for storing the π-conjugated polymer 60 described above.

[0310] like Figure 1 As shown, the reagent package 10 of this embodiment includes: a π-conjugated polymer 60, which is used to form an active layer of an organic photoelectric conversion element; a sealing container 20, which can freely seal and remove the π-conjugated polymer 60 and has gas barrier properties, and the π-conjugated polymer 60 is sealed in the sealing container 20 in an airtight state; and a deoxidizer 50, which is arranged to be in contact with the atmosphere in the airtight sealing container 20, and the oxygen concentration of the atmosphere is less than 1%.

[0311] exist Figure 1 In the illustrated configuration, the deoxidizer 50 is provided in both the bottle container 30 and the bag container 40 serving as the sealing container 20. Specifically, one deoxidizer 50 is placed in the recess 36a of the inner lid 36 of the bottle container 30, and three more deoxidizers 50 are enclosed outside the bottle container 30 and within the bag container 40.

[0312] The form, material, and manufacturing method of the organic photoelectric conversion element, the π-conjugated polymer 60 , the sealing container 20 , and the deoxidizer 50 of the reagent package 10 of this embodiment are as described above.

[0313] According to the reagent package 10 of this embodiment, the π-conjugated polymer 60 can be stably stored for a longer period of time while effectively suppressing an increase in the electron spin concentration of the π-conjugated polymer 60 , that is, temporal degradation of the π-conjugated polymer 60 , with a simple configuration.

[0314] Example

[0315] Hereinafter, in order to further explain the present invention in detail, examples are given, but the present invention is not limited to the examples.

[0316] In this embodiment, a polymer compound and a compound having the structural units and compositions shown in Table 2 below were used as the p-type semiconductor material and the n-type semiconductor material.

[0317] [Table 2]

[0318]

[0319] Polymer compound P-1 was synthesized by referring to the method described in International Publication No. 2013051676 (band gap: 1.38 eV, maximum absorption wavelength: 780 nm).

[0320] As the polymer compound P-2, PCE10 (trade name, manufactured by 1-material Co., Ltd.) was obtained and used (band gap: 1.59 eV, maximum absorption wavelength: 680 nm).

[0321] As the polymer compound P-3, PDPP3T (trade name, manufactured by Lumtec Corporation) was obtained and used (band gap: 1.24 eV, maximum absorption wavelength: 850 nm).

[0322] As the polymer compound P-4, Poly(3-hexylthiophene-2,5-diyl) (trade name, manufactured by Sigma-Aldrich) was obtained and used (band gap: 2.00 eV, maximum absorption wavelength: 500 nm).

[0323] As compound C-1, DTS(FBTTh2)2 (trade name, manufactured by 1-material) was obtained and used.

[0324] As compound N-1 (C60PCBM), E100 (trade name, manufactured by Frontier Carbon Co., Ltd.) was obtained and used.

[0325] (Preparation of ink composition)

[0326] The above-mentioned polymer compound or compounds and solvent were used to prepare an ink composition for forming an active layer as follows. The solvents used and their boiling points (bp) are shown in Table 3 below.

[0327] [Table 3]

[0328] solvent bp(℃) Pseudocumene 169 Benzyl benzoate 323

[0329] <Preparation Example 1>

[0330] A mixed solvent was prepared using pseudocumene as the first solvent and benzyl benzoate as the second solvent, with the weight ratio of the first solvent to the second solvent being 90:10. The prepared mixed solvent was mixed with 1.44% by weight of polymer compound P-1 (weight-average molecular weight: 62,200) as a p-type semiconductor material and 1.5% by weight of compound N-1 as an n-type semiconductor material (p / n ratio = 1 / 1.5) relative to the total weight of the ink composition. After stirring at 60°C for 12 hours, the mixture was filtered through a 5 μm pore size PTFE filter to obtain ink composition (I-1). Table 4 below shows the p-type semiconductor materials used in ink composition (I-1), the weight-average molecular weight of the p-type semiconductor materials, and the p / n ratio.

[0331] <Preparation Examples 2 to 4>

[0332] Ink compositions (I-2) to (I-4) were prepared using the same solvent and n-type semiconductor material as in Preparation Example 1, except that the ink compositions each contained the polymer compound shown in Table 3 below as the p-type semiconductor material. Table 4 below shows the p-type semiconductor materials used in ink compositions (I-2) to (I-4), the weight-average molecular weight of the p-type semiconductor materials, and the p / n ratio.

[0333] [Table 4]

[0334] Preparation Example Ink composition polymer compounds Weight average molecular weight (Mw) p / n ratio 1 (I-1) P-1 62,200 1 / 1.5 2 (I-2) P-2 144,000 1 / 1.5 3 (I-3) P-3 59,400 1 / 1.5 4 (I-4) P-4 110,000 1 / 1.5

[0335] (Creation of standard curve)

[0336] The preparation of a calibration curve showing the correlation between the electron spin amount and the area value of the ESR spectrum was carried out using TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl, 2,2,6,6-tetramethylpiperidine-1-oxide) as a standard substance.

[0337] First, 1.02 mg of TEMPO was dissolved in 10 mL of toluene to prepare a 0.65 mM TEMPO solution (standard solution 1). 1 mL of the resulting solution was measured in a 10 mL volumetric flask and the volume was adjusted with toluene to prepare a 0.065 mM solution (standard solution 2).

[0338] The same operation was performed to prepare 0.0065 mM (standard solution 3) and 0.00065 mM (standard solution 4). ESR measurements were performed on each of the obtained standard solutions 1 to 4, and the area values ​​of the obtained ESR spectra were determined. A calibration curve was prepared based on the obtained area values.

[0339] <Example 1>

[0340] 50 mg of polymer compound P-1, a π-conjugated polymer, was prepared and placed in a glass container A (10 mL screw-cap vial) under atmospheric pressure. The cap was loosened to prevent the container from becoming airtight, ensuring that the atmosphere inside the container A was an atmosphere that suppressed an increase in the electron spin concentration of polymer compound P-1. The container A and Sequl AP-250 (manufactured by Nissofine) as a deoxidizer were then placed in an aluminum bag with a clamp (aluminum foil ziplock bag, manufactured by Seisan Nipponsha Co., Ltd., AL-10) serving as a sealing container. The opening of the aluminum foil ziplock bag was sealed by heat lamination, and container A and the deoxidizer were sealed within the aluminum foil ziplock bag. This maintained the oxygen concentration of the atmosphere in contact with polymer compound P-1 at 1% or less.

[0341] The aluminum foil ziplock bag containing container A containing polymer compound P-1 and the deoxidizer was placed in a thermostatic chamber set at 60°C and 75% RH and stored for two weeks. After two weeks, the external quantum efficiency (EQE) and electron spin concentration of polymer compound P-1 after storage were measured and evaluated using the methods described below. The methods for measuring EQE and electron spin concentration are described below.

[0342] The results are shown together with the EQE and electron spin concentration before storage treatment in the following Table 5. EQE is shown as a relative value based on the EQE of the organic photoelectric conversion element produced using the polymer compound P-1 before storage treatment.

[0343] <Example 2>

[0344] EQE and electron spin concentration were measured and evaluated in the same manner as in Example 1, except that the polymer compound P-2, which is a π-conjugated polymer, was used instead of the polymer compound P-1. The results are shown in Table 5 below.

[0345] <Example 3>

[0346] EQE and electron spin concentration were measured in the same manner as in Example 1, except that the polymer compound P-3, which is a π-conjugated polymer, was used instead of the polymer compound P-1. The results are shown in Table 5 below.

[0347] <Example 4>

[0348] The EQE and electron spin concentration were measured and evaluated in the same manner as in Example 1, except that the polymer compound P-4, which is a π-conjugated polymer, was used instead of the polymer compound P-1. The results are shown in Table 5 below.

[0349] <Comparative Example 1>

[0350] Except that the deoxidizer was not sealed in the aluminum foil ziplock bag, the EQE and electron spin concentration were measured and evaluated in the same manner as in Example 1. The results are shown in Table 5 below.

[0351] <Comparative Example 2>

[0352] Except that the deoxidizer was not sealed in the aluminum foil ziplock bag, the EQE and electron spin concentration were measured and evaluated in the same manner as in Example 2. The results are shown in Table 5 below.

[0353] <Comparative Example 3>

[0354] Except that the deoxidizer was not sealed in the aluminum foil ziplock bag, the EQE and electron spin concentration were measured and evaluated in the same manner as in Example 3. The results are shown in Table 5 below.

[0355] <Comparative Example 4>

[0356] Except that the deoxidizer was not sealed in the aluminum foil ziplock bag, the EQE and electron spin concentration were measured and evaluated in the same manner as in Example 4. The results are shown in Table 5 below.

[0357] (Measurement of Electron Spin Concentration)

[0358] The electron spin concentration per 1 g of the polymer compound (p-type semiconductor material) of Examples 1 to 4 and Comparative Examples 1 to 4 was measured by ESR measurement using an X-band ESR device (manufactured by JEOL).

[0359] 5 mg of the polymer compound before and after storage were measured and placed in ESR tubes. ESR measurement is performed. The electron spin amount is quantified from the area value of the obtained ESR spectrum using the previously described calibration curve. The obtained electron spin amount is divided by the weighed value of the p-type semiconductor material, and the resulting value is defined as the electron spin concentration per 1g of the polymer compound (Spin / g).

[0360] (Manufacturing of an Organic Photoelectric Conversion Element for EQE Measurement and Measurement of EQE)

[0361] A glass substrate on which an ITO layer was formed in a thickness of 150 nm by sputtering was subjected to surface treatment using ozone UV treatment to prepare a cathode.

[0362] A coating liquid was prepared by diluting a 45 wt% isopropyl alcohol dispersion (HTD-711Z, manufactured by TAYCA) of zinc oxide nanoparticles (particle diameter 20 to 30 nm) with 3-pentanol in an amount 10 times the weight of the dispersion.

[0363] The obtained coating liquid was applied on the ITO layer by spin coating to a thickness of 40 nm, and then subjected to a heat drying treatment at 200° C. for 10 minutes in a nitrogen atmosphere to form an electron transport layer.

[0364] Next, an ink composition containing the polymer compound described before and after storage treatment was applied to the formed electron transport layer by spin coating. After forming a coating film, the resulting coating film was dried for 5 minutes on a hot plate heated to 100°C, thereby forming an active layer. The dried active layer was heat-treated (baked) for 10 minutes in a glove box using a hot plate heated to 130°C. The thickness of the active layer after heat treatment was approximately 250nm.

[0365] Then, in a resistance heating evaporation device, a MoO 3 layer was formed with a thickness of about 30 nm on the active layer, and then an Ag layer was formed with a thickness of about 80 nm on the MoO 3 layer, thereby manufacturing an anode.

[0366] Next, a UV-curable sealant was applied around the periphery of the organic photovoltaic cell, which was a laminated structure formed up to the cathode as described above, and after laminating a glass substrate, UV light was irradiated to seal the cell. The resulting package for the organic photovoltaic cell was a 1 cm x 1 cm square.

[0367] The EQE of the manufactured organic photoelectric conversion element was measured using a solar simulator (CEP-2000, manufactured by Spectrometer Corporation).

[0368] [Table 5]

[0369]

[0370] From Examples 1 to 4 and Comparative Examples 1 to 4, it is understood that in the polymer compound (p-type semiconductor material) which is a π-conjugated polymer after the storage treatment, the increase in the spin concentration after the storage treatment is significantly suppressed.

[0371] Furthermore, in the organic photoelectric conversion element manufactured using the p-type semiconductor material after the storage treatment, the decrease in EQE was significantly suppressed, and the electrical characteristics of the organic photoelectric conversion element were equivalent to those of the organic photoelectric conversion element manufactured using the polymer compound before the storage treatment.

[0372] It can be seen from this that according to this embodiment, the π-conjugated polymer can be stored while effectively suppressing the increase in the electron spin concentration of the π-conjugated polymer, that is, the time-dependent degradation of the π-conjugated polymer, through a simple process. Even if the p-type semiconductor material after the storage treatment is used, the impact on the characteristics of the organic photoelectric conversion element, that is, the external quantum efficiency, is small.

[0373] <Comparative Example 5>

[0374] The electron spin concentration was measured in the same manner as in Example 1 (with a deoxidizing agent) and Comparative Example 1 (without a deoxidizing agent), except that Compound C-1 was used instead of Polymer Compound P-1. The results are shown in Table 6 below.

[0375] [Table 6]

[0376]

[0377] For Compound C-1, a low molecular weight compound that is not a π-conjugated polymer, no change in spin concentration was detected before and after storage. This indicates that the organic photoelectric conversion device manufacturing method, storage method, and reagent package of the present invention are particularly suitable for π-conjugated polymers.

[0378] <Example 5>

[0379] Under atmospheric pressure, 1.6 g of polymer compound P-1, a π-conjugated polymer, was placed in a container with an inner lid (Hi-Resist BRS-150, manufactured by Kinki Container Co., Ltd.). The inner lid, which had a 1 cm square hole, was fitted into the opening of the container body. One deoxidizer, Sequl AP-250 (manufactured by Nissofine), was placed on the inner lid, and the container was sealed. The sealed container containing polymer compound P-1 and four deoxidizers (Sequl AP-250 (manufactured by Nissofine)) were placed in an aluminum foil ziplock bag and sealed by heat lamination to maintain the oxygen concentration of the atmosphere with which polymer compound P-1 came into contact at 1% or less.

[0380] The container (containing polymer compound P-1 and a deoxidizer) and the aluminum foil ziplock bag containing the deoxidizer were placed in a thermostatic chamber set at 60°C / 75% RH and stored for three months. After three months, the electron spin concentration of polymer compound P-1 after storage was measured using the same method as in Example 1. The results are shown in Table 7 below, along with the electron spin concentration before storage.

[0381] <Comparative Example 6>

[0382] The electron spin concentration was measured and evaluated in the same manner as in Example 5, except that the deoxidizer was not enclosed in the container and the aluminum foil ziplock bag. The results are shown in Table 7 below.

[0383] [Table 7]

[0384]

[0385] In Example 5, in which the deoxidizer was placed in both the container and the aluminum foil ziplock bag, compared to Comparative Example 5 in which no deoxidizer was placed in either the container or the aluminum foil ziplock bag, the π-conjugated polymer could be stored while the increase in the electron spin concentration of the π-conjugated polymer, that is, the time-dependent degradation of the π-conjugated polymer, was extremely effectively suppressed.

[0386] Explanation of symbols

[0387] 10 Reagent package

[0388] 20 sealed in container

[0389] 30 bottle containers

[0390] 32 Main body

[0391] 32a Opening

[0392] 36 inner cover

[0393] 36a recess

[0394] 36b hole

[0395] 38 outer cover

[0396] 40 Bag Containers

[0397] 50 deoxidizer

[0398] 60π conjugated polymer

Claims

1. A method for manufacturing an organic photoelectric conversion element, the organic photoelectric conversion element comprising a pair of electrodes including an anode and a cathode, and an active layer provided between the pair of electrodes and comprising a π-conjugated polymer, wherein: The manufacturing method comprises: a step of storing the π-conjugated polymer in a sealed container, wherein the interior of the sealed container is an atmosphere that suppresses an increase in the electron spin concentration of the π-conjugated polymer; and a step of forming the active layer using the stored π-conjugated polymer, In the storage step, a deoxidizer is provided in the sealing container. The π-conjugated polymer is a polymer compound comprising a structural unit represented by the following formula (I) and / or a structural unit represented by the following formula (II). In formula (I), Ar 1 and Ar 2 represents a trivalent aromatic heterocyclic group, Z represents a group represented by the following formula (Z-1) to formula (Z-7), -And 3 -(II) In formula (II), Ar 3 represents a divalent aromatic heterocyclic group, In formulas (Z-1) to (Z-7), R represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an imide group, a substituted oxycarbonyl group, an alkenyl group, an alkynyl group, a cyano group or a nitro group. In each of formulas (Z-1) to (Z-7), when there are two Rs, the two Rs are the same or different from each other.

2. The method for manufacturing an organic photoelectric conversion element according to claim 1, wherein: The atmosphere in the storage step is an atmosphere having an oxygen concentration of 1% or less.

3. The method for producing an organic photoelectric conversion element according to claim 1 or 2, wherein: The electron spin concentration of the π-conjugated polymer per 1 g after storage is 10×10 16 the following.

4. The method for producing an organic photoelectric conversion element according to claim 1 or 2, wherein: The maximum absorption wavelength of the π-conjugated polymer after storage is 500 nm or longer.

5. The method for producing an organic photoelectric conversion element according to claim 1 or 2, wherein: The electron spin concentration per 1 g of the π-conjugated polymer after storage is less than 2.4 times the electron spin concentration per 1 g of the π-conjugated polymer before storage.

6. The method for producing an organic photoelectric conversion element according to claim 1 or 2, wherein: The method further includes a step of preparing a coating solution containing the stored π-conjugated polymer. The step of forming the active layer is a step of forming the active layer by applying the coating liquid obtained in the preparation step.

7. A reagent package, comprising: π-conjugated polymers, which are used to form active layers of organic photoelectric conversion elements; a sealing container capable of sealing and removing the π-conjugated polymer and having gas barrier properties, wherein the π-conjugated polymer is sealed in the sealing container in an airtight state; and a deoxidizer arranged to be in contact with the atmosphere in the airtight sealed container, The atmosphere has an oxygen concentration of 1% or less. The π-conjugated polymer is a polymer compound comprising a structural unit represented by the following formula (I) and / or a structural unit represented by the following formula (II). In formula (I), Ar 1 and Ar 2 represents a trivalent aromatic heterocyclic group, Z represents a group represented by the following formula (Z-1) to formula (Z-7), -And 3 -(II) In formula (II), Ar 3 represents a divalent aromatic heterocyclic group, In formulas (Z-1) to (Z-7), R represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an imide group, a substituted oxycarbonyl group, an alkenyl group, an alkynyl group, a cyano group or a nitro group. In each of formulas (Z-1) to (Z-7), when there are two Rs, the two Rs are the same or different from each other.

8. The reagent package according to claim 7, wherein: The electron spin concentration of the π-conjugated polymer per 1 g after storage is 10×10 16 the following.

9. The reagent package according to claim 7 or 8, wherein: The maximum absorption wavelength of the π-conjugated polymer after storage is 500 nm or longer.

10. The reagent package according to claim 7 or 8, wherein: The deoxidizer contains at least one material selected from the group consisting of iron, sugar, and reducing ketone.

11. The reagent package according to claim 10, wherein: The material is a material containing iron.

12. The reagent package according to claim 7 or 8, wherein: The enclosed container includes: a main body having an opening for accommodating the π-conjugated polymer; an inner cover detachably fitted into the inner wall of the opening, defining a recess in which the deoxidizer can be placed while the deoxidizer is separated from the π-conjugated polymer, and having a hole for allowing the deoxidizer to contact the atmosphere with which the π-conjugated polymer is in contact; and The outer cover is detachably fitted to the outer wall of the opening when the inner cover is attached, thereby making the interior of the main body airtight.

13. A storage method comprising the step of storing a π-conjugated polymer in a sealed container, wherein the interior of the sealed container is an atmosphere that suppresses an increase in the electron spin concentration of the π-conjugated polymer, wherein a deoxidizing agent is provided in the sealed container during the storage step. The π-conjugated polymer is a polymer compound comprising a structural unit represented by the following formula (I) and / or a structural unit represented by the following formula (II). In formula (I), Ar 1 and Ar 2 represents a trivalent aromatic heterocyclic group, Z represents a group represented by the following formula (Z-1) to formula (Z-7), -And 3 -(II) In formula (II), Ar 3 represents a divalent aromatic heterocyclic group, In formulas (Z-1) to (Z-7), R represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an imide group, a substituted oxycarbonyl group, an alkenyl group, an alkynyl group, a cyano group or a nitro group. In each of formulas (Z-1) to (Z-7), when there are two Rs, the two Rs are the same or different from each other.

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