WO2012053400A1

WO2012053400A1 - Production method for photoelectric conversion element

Info

Publication number: WO2012053400A1
Application number: PCT/JP2011/073388
Authority: WO
Inventors: 一桑原; 崇広清家
Original assignee: 住友化学株式会社
Priority date: 2010-10-19
Filing date: 2011-10-12
Publication date: 2012-04-26
Also published as: TW201232860A; JP2012089637A

Abstract

A method for producing photoelectric conversion elements capable of forming a flat organic layer using a printing method is provided. The production method is a method for producing photoelectric conversion elements comprising a pair of electrodes and one or more organic layers (73) disposed between the pair of electrodes and comprises: a step for preparing a substrate (60) whereon one of the pair of electrodes is disposed; a step wherein ink that includes the material for the organic layers is applied to a transfer body (10), which has a member comprising silicone rubber disposed on a surface section thereof, to film-form ink films (70, 71) on the transfer body, and the ink films are transferred to the substrate to form the organic layers; and a step for forming the other of the pair electrodes.

Description

Method for manufacturing photoelectric conversion element

The present invention relates to a photoelectric conversion element and a method for producing the same, and a solar cell module and an organic photosensor provided with the photoelectric conversion element.

The photoelectric conversion element includes a pair of electrodes and one or more organic layers provided between the electrodes. There are various methods for forming the organic layer, one of which is a coating method. In the coating method, an ink containing a material for forming an organic layer is applied and formed on a substrate by a predetermined method, and the formed ink is solidified to form an organic layer.

A flexographic printing method has been proposed as a method for coating and forming the ink (see, for example, Patent Document 1). In this conventional technique, an ink is formed on a printing plate made of polycarbonate, and the formed ink is transferred to a predetermined substrate to form an organic layer.

JP 2010-27763 A

When a printing plate made of polycarbonate is used as in the prior art, so-called tearing occurs when the ink film is transferred to the substrate. That is, not all the ink film on the printing plate is transferred to the substrate, but the ink film is separated into the printing plate side and the substrate side, a part remains on the printing plate, and the rest is transferred to the substrate. It will be. When such crying occurs, there is a problem that an organic layer having a flat surface cannot be formed.

Therefore, an object of the present invention is to provide a method for producing a photoelectric conversion element capable of forming a flat organic layer by a printing method.

The present invention provides the following [1] to [12].
[1] A method for producing a photoelectric conversion element comprising a pair of electrodes and one or more organic layers provided between the pair of electrodes,
Preparing a substrate provided with one of the pair of electrodes;
An ink containing the material of the organic layer is applied to a transfer body provided with a member made of silicone rubber on the surface portion, an ink film is formed on the transfer body, and the ink film is transferred to the substrate. Forming the organic layer;
Forming a second electrode of the pair of electrodes. A method for manufacturing a photoelectric conversion element.

[2] The photoelectric conversion according to [1], wherein the step of forming the organic layer further includes a step of drying the ink film before transferring the ink film formed on the transfer body to the substrate. Device manufacturing method.

[3] The method for producing a photoelectric conversion element according to [2], wherein the step of drying the ink film is performed by spraying a gas on the ink film.

[4] The step of forming the organic layer further includes a step of patterning the ink film by removing a predetermined portion of the ink film before transferring the ink film to the substrate. 2] The manufacturing method of the photoelectric conversion element of description.

[5] The method for producing a photoelectric conversion element according to any one of [1] to [4], wherein the ink is applied and formed on a transfer body using a nozzle having a slit-like discharge port.

[6] The method for producing a photoelectric conversion element according to any one of [1] to [4], wherein the ink is applied to a transfer body using an anilox roll to form a film.

[7] In the step of forming the organic layer on the substrate, the photoelectric conversion element has an active layer as the organic layer, and the active layer is formed by the step of forming the organic layer. 6] The manufacturing method of the photoelectric conversion element as described in any one of.

[8] The active layer has a thin film containing an electron donating compound material and a thin film containing an electron accepting compound material,
The method for producing a photoelectric conversion element according to [7], wherein each of the thin films is formed by a step of forming the organic layer.

[9] The photoelectric conversion element has two or more active layers as one or more organic layers, and an intermediate electrode layer provided between the active layers,
Each of the active layers is formed by the step of forming the organic layer, and the intermediate electrode layer is formed between the steps of forming the active layer, according to any one of [1] to [8] The manufacturing method of the photoelectric conversion element of description.

[10] A photoelectric conversion element that can be manufactured by the manufacturing method according to any one of [1] to [9].

[11] A photovoltaic power generation module including the photoelectric conversion element according to [10].

[12] An organic photosensor comprising the photoelectric conversion element according to [10].

According to the present invention, a photoelectric conversion element including an organic layer having a flat surface can be formed.

FIG. 1 is a schematic diagram of a printing apparatus. FIG. 2 is a schematic cross-sectional view of the blanket cylinder and the coating unit.

A method for producing a photoelectric conversion element according to the present invention is a method for producing a photoelectric conversion element comprising a pair of electrodes and one or more organic layers provided between the pair of electrodes, the method comprising: A step of preparing a substrate on which one electrode is provided; and a transfer body provided with a member made of silicone rubber on the surface thereof, an ink containing the material of the organic layer is applied to form a film, and the ink is applied to the transfer body. Forming a film, transferring the ink film to the substrate to form the organic layer, and forming the other electrode of the pair of electrodes.

The photoelectric conversion element includes a pair of electrodes composed of an anode and a cathode, and one or more organic layers provided between the pair of electrodes. A photoelectric conversion element can be manufactured by sequentially laminating each layer constituting these photoelectric conversion elements on a predetermined substrate.

The photoelectric conversion element includes at least one active layer as an organic layer. The photoelectric conversion element may further include a predetermined layer as necessary. Examples of layers provided as necessary include so-called hole transport layers and electron transport layers.

An example of the element structure of a photoelectric conversion element provided with one active layer is shown below.
(1) Anode / active layer / cathode (2) Anode / hole transport layer / active layer / cathode (3) Anode / hole transport layer / active layer / electron transport layer / cathode (4) Anode / active layer / electron Transport layer / cathode (here, the symbol “/” indicates that the layers sandwiching the symbol “/” are stacked adjacent to each other. The same applies hereinafter).
Note that the photoelectric conversion element may include two or more active layers. In this case, an intermediate electrode layer is usually provided between the active layer and the active layer.

An example of an element structure of a photoelectric conversion element including two active layers is shown below.
(5) Anode / (layer structural unit A) / intermediate electrode layer / (layer structural unit A) / cathode Here, (layer structural unit A) is any one of the structures (1) to (4) above. In other words, it means a laminate sandwiched between an anode and a cathode. Note that the layer configuration of the two (layer structural unit A) may be different from each other.

An example of an element structure of a photoelectric conversion element including three or more active layers is shown below.
(6) Anode / (layer structural unit B) x / (layer structural unit A) / cathode Here, (layer structural unit B) means “(layer structural unit A) / intermediate electrode layer” and symbol “x” Represents an integer of 2 or more, and (layer structural unit B) x represents a laminate in which the layer structural unit B is laminated in x stages. Further, a plurality of (layer structural units B) may have different layer configurations.

The material of each layer provided between the electrodes will be described later.

In the present invention, among a plurality of layers provided between electrodes, a layer containing an organic substance is referred to as an organic layer. When the photoelectric conversion element includes a plurality of organic layers, at least one of them is formed by the organic layer forming step of the present invention. That is, an ink containing a material that becomes the organic layer is applied to a transfer body provided with a member made of silicone rubber on the surface portion, an ink film is formed on the transfer body, and the ink film of the transfer body is formed. Is transferred to the substrate to form an organic layer.

The specific aspect of the organic layer forming step of the present invention is not particularly limited as long as the organic layer forming step is performed by a printing method using a transfer body in which a member made of silicone rubber is provided on the surface portion. The organic layer forming step is performed using, for example, a printing apparatus such as a reverse printing apparatus or a relief printing apparatus described below.

Details of each of the above layers will be described later, and hereinafter, an apparatus used in the organic layer forming step will be described first.

(Printer)
A printing apparatus used for manufacturing the photoelectric conversion element of this embodiment will be described. FIG. 1 is a schematic diagram of a printing apparatus. FIG. 2 is a schematic cross-sectional view of the blanket cylinder and the coating unit.

As shown in FIGS. 1 and 2, the printing apparatus 5 is an apparatus for forming an organic layer 73 on a substrate 60. The printing apparatus 5 includes a gantry 1, a blanket cylinder 11, a blanket 10 that is wound around the blanket cylinder 11, and a coating unit 20 that applies ink 28 to the blanket 10 and applies an ink film 70. A drying device 30 that dries the coated ink film 70 to form a dried ink film 71, a plate 50 used for patterning by removing a predetermined portion from the dried ink film 71, and A platen platen 51 that supports the plate 50, a substrate platen 61 that supports a substrate 60 on which the patterned ink film is to be transferred, and the blanket cylinder 11 are supported on the gantry 1 and the blanket cylinder 11 is disposed in the horizontal direction. And a blanket cylinder support portion 40 that moves to the center.

The coating unit 20, the platen surface plate 51, and the substrate surface plate 61 are arranged in a line in this order on the top of the gantry 1 (from right to left in FIG. 1).

In the printing apparatus 5, the coating unit 20, the plate surface plate 51, and the substrate surface plate 61 are fixed to the gantry 1, and the blanket cylinder support unit 40 and the blanket cylinder 11 supported by the same are moved in the horizontal direction. Alternatively, the coating unit 20, the plate surface plate 51, and the substrate surface plate 61 move in the horizontal direction, and the blanket cylinder support portion 40 and the blanket cylinder 11 supported thereby are fixed to the gantry 1. May be.

(Blanket and blanket cylinder)
In this embodiment, the blanket cylinder 11 included in the printing apparatus 5 and the blanket 10 wound around the blanket cylinder 11 correspond to a transfer body in which a member made of silicone rubber is provided on the surface portion. The blanket 10 included in the printing apparatus 5 corresponds to a member made of silicone rubber provided on the surface portion of the transfer body.

The blanket cylinder 11 has a cylindrical shape, and the central shaft 12 is rotatably supported by the blanket cylinder support portion 40. As a result, the blanket cylinder 11 can rotate about the horizontal axis (center axis 12) (in the direction of the white arrow in FIG. 2).

The blanket 10 is wound around the circumferential surface of the blanket cylinder 11. The blanket 10 has a flat peripheral surface and has a predetermined elasticity. The blanket 10 can be formed using any kind of silicone rubber, such as thermosetting millable silicone rubber, addition-type liquid silicone rubber, and condensation-type liquid silicone rubber.

Examples of the thermosetting millable silicone rubber include “KE555U” manufactured by Shin-Etsu Chemical Co., Ltd.

Examples of the addition type liquid silicone rubber include KE1600 and KE1606 manufactured by Shin-Etsu Chemical Co., Ltd.

Examples of the condensation type liquid silicone rubber include KE-17 manufactured by Shin-Etsu Chemical Co., Ltd.

Furthermore, SIM-260 and SIM-360 manufactured by Shin-Etsu Chemical Co., Ltd. can also be used.

It is preferable that the peripheral surface of the blanket 10 is subjected to water repellent treatment.

(Blanket trunk support)
The blanket cylinder support unit 40 supports the blanket cylinder 11 so as to be rotatable about the horizontal axis on the gantry 1 and moves the blanket cylinder 11 in the horizontal direction (left and right direction in FIG. 1). Specifically, the blanket cylinder support unit 40 in FIG. 1 moves the blanket cylinder 11 from above the coating unit 20 to the left to move above the plate 50 and further to the left, thereby moving the substrate 60. Can be passed above. At the time of this movement, the blanket 10 is brought into contact with the surface of the plate 50 with a predetermined pressure to roll the blanket 10, and the blanket 10 is brought into contact with the surface of the substrate 60 with a predetermined pressure. The blanket cylinder 11 can reach the left end of the substrate 60 by rolling. Thereafter, the blanket cylinder 11 can be moved again above the coating unit 20. Moreover, this blanket cylinder support part 40 can rotate the blanket cylinder 11 at a predetermined speed.

(Version)
The plate 50 is fixed and supported on a plate surface plate 51. The plate 50 is made of, for example, glass or metal. Concavities and convexities are formed on the surface portion of the plate 50. The uneven pattern is formed so as to correspond to the pattern of the organic layer 73 to be formed. When the ink film 71 on the blanket 10 comes into contact with the convex portion formed on the plate 50, the portion of the ink film 71 in contact with the convex portion is removed from the blanket 10. As a result, an ink film having a pattern corresponding to the concave portion of the plate 50 is formed on the blanket, and this is further transferred to the substrate 60. The shape and size of the recess (pattern) of the organic layer 73 when viewed from one side in the thickness direction of the substrate 60 (sometimes referred to as a plan view) depends on the pattern of the organic layer 73, but is rectangular, for example. In this case, it is 20 μm × 200 mm to 50 mm × 200 mm.

(Coating unit)
The type of the coating unit 20 for applying and forming the ink 28 containing the material of the organic layer 73 on the transfer body is not particularly limited. For example, an anilox roll may be used as the coating unit 20, and a nozzle having a slit-like discharge port may be used.

FIG. 2 shows a coating unit 20 having a nozzle having a slit-like discharge port as an example of the coating unit. The coating unit 20 shown in FIG. 2 includes a coating die 21, an ink tank 22, a line 23 that connects the ink tank 22 and the coating die 21, a coating die lifting unit 24 that lifts and lowers the coating die 21, and an ink. An ink tank raising / lowering unit 25 for raising and lowering the tank 22 is provided.

The coating die 21 is a so-called capillary coater having a capillary passage 21a. One end 21 b of the capillary passage 21 a of the coating die 21 communicates with the ink tank 22 through a line 23. The ink 28 supplied from the ink tank 22 is supplied to the capillary passage 21a through the line 23, and is further discharged upward from the elongated rectangular slit 21c which is the other end of the capillary passage 21a. To be supplied. The coating die 21 is arranged so that the length direction of the slit 21 c is parallel to the central axis 12 of the blanket cylinder 11. The width of the slit 21c is not particularly limited. The width of the slit 21c is preferably about 0.05 mm to 0.5 mm. The coating unit 20 is not limited to a configuration having a capillary coater like the coating die 21 shown in FIG. The coater provided in the coating unit 20 may be any coater that can coat the blanket 10 with the ink film 70 having a relatively uniform thickness. For example, a wire bar coater, a slit coater, a die coater, or the like may be used. Among these coaters, since the uniformity of the ink film 70 can be improved, a die coater, a capillary coater, and a slit coater are preferable.

When the ink film is formed on the transfer body, the ink 28 is discharged from the slit 21c and the blanket cylinder 11 is rotated (in the direction of the white arrow in FIG. 2). By the rotation of the blanket cylinder, an ink film 70 having a certain thickness is applied to the surface of the blanket 10.

The ink tank 22 is a tank that stores the ink 28. This ink 28 is an ink used for forming an organic layer such as an active layer and a charge transport layer on the substrate 60.

The ink tank lifting / lowering unit 25 moves the ink tank 22 in the vertical direction (the vertical direction in FIGS. 1 and 2). The coating die lifting / lowering unit 24 moves the coating die 21 in the vertical direction (the vertical direction in FIGS. 1 and 2).

The discharge speed of the ink 28 discharged from the slit 21c can be controlled by adjusting the relative position of the ink tank 22 and the blanket 10 in the vertical direction. Further, the thickness of the ink film 70 applied to the blanket 10 can be controlled by adjusting the discharge speed of the ink 28 from the slit 21 c and the rotation speed of the blanket cylinder 11. The thickness of the ink film 70 can be set to 2 μm to 20 μm, for example.

In this embodiment, it is preferable to dry the ink film formed on the blanket. The method for drying the ink film is not particularly limited, but in the present embodiment shown in FIG. 2, the ink film 70 is dried by the drying device 30 to obtain the dried ink film 71.

The drying device 30 can dry the ink film 70 applied to the blanket 10 by spraying a gas 8 having a flow rate of 1 × 10 ⁴ L / min · m ² to 50 × 10 ⁴ L / min · m ^2. Device. The gas 8 sprayed from the drying device 30 onto the ink film 70 can be heated from room temperature to 40 ° C., for example. However, if the temperature of the gas 8 is too high, the temperature of the device rises and adversely affects the transfer accuracy. There is a fear. Therefore, the temperature of the gas 8 is preferably room temperature. On the other hand, if the flow rate of the gas 8 is excessive, peripheral foreign matters are sprayed on the blanket 10 and the ink film 70, and there is a high possibility that the foreign matters are mixed into the ink film 70. Therefore, the flow rate of the gas 8 is preferably 5 × 10 ⁴ L / min · m ² to 20 × 10 ⁴ L / min · m ² . Examples of the gas 8 include air, nitrogen, oxygen and the like. The gas 8 is preferably air.

In the present embodiment, the example in which the gas 8 is sprayed on the ink film 70 in order to make the ink film 70 the dried ink film 71 has been described. For example, by sucking air in the vicinity of the ink film 70, an air flow is generated in the vicinity of the surface of the ink film 70, and the excess solvent in the ink film 70 is removed and dried to obtain the dried ink film 71. In addition, as a method for obtaining the organic layer 73, the ink film 70 formed by coating may be naturally dried for a certain period of time to form a dried ink film 71 and then transferred to the substrate 60. The natural drying time is, for example, 10 seconds to 120 seconds.

By using the printing apparatus 5 described above, an ink containing a material that becomes the organic layer is applied to a transfer body provided with a member made of silicone rubber on the surface portion, and an ink film is formed on the transfer body. And the ink film is transferred to the substrate to form the organic layer.

In the printing apparatus 5 of the present embodiment, by using the blanket 10 made of silicone rubber, it is possible to remove substantially all portions of the dried ink film 71 to be removed. Also, when the dried ink film 71 is transferred to the substrate 60, substantially all the dried ink film 71 is transferred to the substrate 60. Since the dried ink film 71 is transferred to the substrate 60 substantially without crying, the organic layer 73 having a flat surface can be formed.

In the step of forming the organic layer 73 by the printing device 5, the ink film 70 on the transfer body is preferably dried under predetermined conditions. That is, when a predetermined portion of the ink film 70 on the transfer body is removed by bringing the blanket 10 into contact with the surface of the plate 50 with a predetermined pressure, the portion to be removed of the ink film 70 is transferred to the transfer body. It is preferable to dry to such an extent that substantially all can be removed. Further, when transferring the ink film to the substrate 60, it is preferable to dry the ink film to such an extent that substantially all the ink film is transferred from the transfer body.

In this way, by drying the ink film 70 applied and formed on the transfer body under predetermined conditions, so-called tearing can be prevented more reliably, and substantially all the dried ink film 71 is transferred to the substrate 60. be able to. Therefore, the organic layer 73 having a flat surface can be formed.

In the above description, the reverse printing method in which the ink film 70 is transferred to the substrate 60 using the reverse printing device as the printing device 5 has been described. However, not only the reverse printing method but also a relief printing method can be applied. The relief printing apparatus used in the relief printing method removes the plate 50 and the plate surface plate 51 from the printing apparatus 5 shown in FIG. 1, for example, and replaces the blanket 10 with a flat surface wound around the blanket cylinder 11. A configuration using a letterpress wound around the blanket cylinder 11 may be used.

In the case of using the relief printing apparatus as described above, when an ink containing a material that becomes an organic layer is applied to the transfer body, an ink film is formed only on the relief of the relief that is wound around the blanket cylinder. By transferring this ink film to the substrate, an ink film corresponding to the pattern of the convex portions of the relief printing plate is formed on the substrate.

The letterpress wound around the blanket cylinder in the letterpress printing apparatus can be formed of, for example, the same material as the blanket 10 of the printing apparatus 5 already described. The relief printing plate can form a plurality of projections by pouring a silicone rubber material into a mold on which a predetermined pattern is formed and curing the material. Note that the shape and size of each convex portion in plan view depends on the pattern of the organic layer formed on the substrate, but is 20 μm × 200 mm to 50 mm × 200 mm in the case of a rectangular shape, for example. In addition, a stripe-shaped convex part may be formed by arranging these rectangular convex parts in parallel in a plan view. For example, 10 to 100 convex portions are arranged.

Thus, by using a relief printing plate made of silicone rubber, substantially all of the ink film is transferred to the substrate when the ink film is transferred to the substrate. Therefore, substantially all the ink film is transferred to the substrate without causing the ink film to cry, so that an organic layer having a flat surface can be formed.

(ink)
The ink 28 used in the coating unit 20 contains the material of the organic layer 73 to be formed and a solvent. After forming the ink film 70 having a predetermined pattern, the organic layer 73 can be formed by drying.

The viscosity of the ink 28 supplied to the transfer body is preferably 2 mPa · s to 50 mPa · s, and the yield value is preferably 10 mPa or less. By setting the viscosity of the ink 28 within this range, the ink film on the transfer body can be sufficiently flattened by the surface tension of the ink 28 and the uniformity of the thickness of the ink film can be made extremely high. . If the viscosity and yield value of the ink 28 exceed the above ranges, it tends to be difficult to sufficiently increase the uniformity of the thickness of the ink film on the transfer body before the ink film is dried and solidified.

(solvent)
The ink 28 is obtained by dissolving or dispersing the material to be the organic layer 73 in a solvent, and the solvent is not particularly limited as long as the material to be the organic layer 73 is dissolved or dispersed. . Examples of such solvents include monochlorobenzene, p-dichlorobenzene, o-dichlorobenzene, chloroform, toluene, xylene, tetralin; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Ethylene glycol monoalkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; anisole Aromatic ketones such as phenetole and methylanisole; ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone and cyclohexanone; ethanol, propanol, Alcohols such as butanol, hexanol, cyclohexanol, ethylene glycol, glycerin; ethyl 3-ethoxypropionate, 3-methoxypro Methyl propionic acid, ethyl lactate, esters such as methyl 2-hydroxyisobutyrate; cyclic esters γ- butyrolactone. These solvents can be used alone or in combination of two or more.

The content of the solvent in the ink 28 is usually 50% by mass or more and 99% by mass or less, and preferably 80% by mass or more and 98% by mass or less, by mass fraction.

(Other additives)
The ink 28 may further contain other additives. Examples of the additive include a filler, a polymer compound other than the binder polymer, a surfactant, an adhesion promoter, an aggregation inhibitor, an organic acid, and a curing agent.

Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

Next, the manufacturing method of a photoelectric conversion element is demonstrated.
(Board preparation process)
In this step, a substrate provided with one of the pair of electrodes is prepared. In this step, a substrate on which one electrode is provided in advance may be obtained from the market, or one electrode of a pair of electrodes may be formed on the substrate in this step.

Note that a predetermined inorganic layer may be formed on one of the pair of electrodes as necessary after the substrate preparation step.

(Organic layer formation process)
In this step, an organic layer is formed. This step is performed at least once, but is performed a plurality of times as necessary.

When a plurality of organic layers are provided between a pair of electrodes, at least one of the organic layers is formed by the organic layer forming step of the present invention. That is, an ink containing a material that becomes the organic layer is applied to a transfer body provided with a member made of silicone rubber on the surface, and an ink film is formed on the transfer body, and the ink film is applied to the substrate. By transferring and forming the organic layer, at least one organic layer is formed.

This step is performed using, for example, the above-described reverse printing apparatus and letterpress printing apparatus.

In addition, as long as at least one organic layer is formed by the organic layer forming step of the present invention, another organic layer may be formed by a method other than the organic layer forming step of the present invention. For example, spray coating method, spin coating method, casting method, micro gravure coating method, die coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, screen printing method, gravure printing method, flexographic method Another organic layer may be formed by coating by a printing method, an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, a capillary coating method, or the like.

In addition, you may form a predetermined | prescribed inorganic layer on an organic layer as needed after an organic layer formation process.

Further, when an inorganic layer is formed between the organic layer and the organic layer, a step of forming the inorganic layer is performed between the organic layer forming step and the organic layer forming step.

(The other electrode forming step)
In this step, the other electrode of the pair of electrodes is formed. Thereby, a photoelectric conversion element is produced.

In the organic layer forming step described above, it is preferable to dry the ink film on the transfer body. By drying the ink film in this manner, it is possible to more reliably prevent crying separation as described above, and an organic layer having a flat surface can be formed. Furthermore, when performing an organic layer formation process continuously, the following effects are acquired by drying an ink film on a transfer body.

Ink for forming a plurality of organic layers by a coating method, wherein the organic layer formed earlier forms a subsequent organic layer in the step of forming another organic layer on the predetermined organic layer In some cases, the function of the previously formed organic layer may be impaired. Moreover, the composition which comprises the organic layer formed previously may mix in the organic layer formed later, and the function of the organic layer formed later may be impaired. However, in this embodiment, since the ink film dried to some extent is laminated on the substrate, it is possible to prevent the previously formed organic layer from being redissolved in the ink for forming the subsequent organic layer. Thus, the plurality of organic layers can be stacked as intended without impairing the functions of the plurality of organic layers.

As will be described later, the active layer has a single layer structure and a multi-layer structure in which a plurality of thin films are stacked. And the active layer of 1 layer structure can be formed by performing the above-mentioned organic layer formation process once. In addition, an active layer having a multi-layer structure can be formed by repeating the organic layer forming step by the number of layers. For example, one of a thin film containing an electron donating compound material and a thin film containing an electron accepting compound material, which will be described later, is formed in the organic layer forming step, followed by the thin film containing the electron donating compound material and the electron accepting material. An active layer having a multilayer structure can be formed by forming the other thin film among the thin films containing the organic compound material in a separate organic layer forming step. Thus, even if it is an active layer of a multilayer structure, each layer can be laminated | stacked as intended, without impairing the function of each layer by drying an ink film to some extent.

Furthermore, in the method for manufacturing a photoelectric conversion element of this embodiment, a photoelectric conversion element including a plurality of active layers can also be produced. A configuration example of a photoelectric conversion element including a plurality of active layers is as follows.

Photoelectric conversion element comprising two active layers (5) Anode / (layer structural unit A) / intermediate electrode layer / (layer structural unit A) / cathode Photoelectric conversion element comprising three or more active layers (6) Anode / (Layer structural unit B) x / (Layer structural unit A) / Cathode

In the photoelectric conversion element having the configuration of (5) or (6), two or more active layers are formed in the organic layer forming step already described, and between each step of forming two or more photoelectric active layers. It can be produced by forming an intermediate electrode layer. When the intermediate electrode layer is formed by a coating method, as in the organic layer forming step already described, an ink containing a material that becomes the intermediate electrode layer is formed on a transfer body provided with a member made of silicone rubber on the surface portion. May be applied to form an ink film on the transfer body, and the ink film may be transferred to the substrate to form an intermediate electrode layer.

Thus, even if it is a photoelectric conversion element provided with a some active layer, it does not impair the function of each active layer by forming each active layer by the organic layer formation process already explained, but a plurality of as intended An active layer can be laminated.

Hereinafter, the specific configuration of each layer constituting the photoelectric conversion element will be described in more detail.

(substrate)
The photoelectric conversion element of the present invention is usually formed on a substrate. The substrate may be any substrate that does not change chemically when the photoelectric conversion element is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. In the case of a structure in which light is taken into the photoelectric conversion element from the substrate, a substrate that exhibits light transmittance is used.

(A pair of electrodes)
Since a photoelectric conversion element needs to take in light inside, at least one of a pair of electrodes needs to be comprised by the electrode which shows a light transmittance.

Examples of the electrode exhibiting light transmittance include a conductive metal oxide film and a translucent metal thin film. The electrode exhibiting light transmittance is formed using a conductive material such as indium oxide, zinc oxide, tin oxide, indium tin oxide (ITO), indium zinc oxide (IZO), NESA, gold, platinum, silver, copper, and the like. A film made of ITO, IZO, or tin oxide is preferable. Examples of the electrode manufacturing method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode.

As examples of opaque electrode materials, metals, conductive polymers, and the like can be used. Specific examples of the electrode material include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like. And one or more alloys selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin. Examples include alloys with metals, graphite, graphite intercalation compounds, polyaniline and derivatives thereof, and polythiophene and derivatives thereof. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy and the like.

(Predetermined layers other than the active layer)
As described above, in the photoelectric conversion element, for example, a hole transport layer, an electron transport layer, and the like are provided as predetermined layers in order to improve photoelectric conversion efficiency. Examples of the material of these predetermined layers include alkali metal such as lithium fluoride, halide or oxide of alkaline earth metal, fine particles of inorganic semiconductor such as titanium oxide, PEDOT (poly-3,4-ethylenedioxide). Oxythiophene) and the like.

(Active layer)
The active layer contains an electron donating compound and an electron accepting compound, and further contains an ultraviolet absorber, inorganic semiconductor fine particles, an antioxidant for the ultraviolet absorber, and the like as necessary. The electron donating compound and the electron accepting compound are relatively determined from the energy level of the energy level of these compounds.

As described above, the active layer has a single layer structure and a multi-layer structure in which a plurality of thin films are stacked. The active layer having a single layer structure contains an electron donating compound and an electron accepting compound in one active layer. The active layer having a multilayer structure is formed by laminating, for example, a thin film containing an electron donating compound material and a thin film containing an electron accepting compound material.

When the photoelectric conversion element has a plurality of active layers, it is preferable that the photoelectric conversion elements have active layers having different light absorption regions.

(Electron donating compound: p-type semiconductor polymer)
Examples of the electron donating compound include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, and aromatic amines in side chains or main chains. And p-type semiconductor polymers such as polysiloxane derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.

Furthermore, as an example of a suitable p-type semiconductor polymer, an organic polymer compound having at least one structural unit of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2): Can be mentioned.

In formula (2), Ar ¹ and Ar ² each independently represent a trivalent heterocyclic group. X ¹ represents a group represented by —O—, a group represented by —S—, a group represented by —C (═O) —, a group represented by —S (═O) —, —SO A group represented by ₂ —, a group represented by —Si (R ³ ) (R ⁴ ) —, a group represented by —N (R ⁵ ) —, a group represented by —B (R ⁶ ) — , -P (R ⁷ )-or a group represented by -P (= O) (R ⁸ )-. R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, aryl Alkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imino group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group It represents a monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, arylalkenyl group, arylalkynyl group, carboxyl group or cyano group.
R ⁵⁰ is a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide Group, acid imide group, imino group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, aryl An alkenyl group, an arylalkynyl group, a carboxyl group or a cyano group is represented.
R ⁵¹ is an alkyl group having 6 to 20 carbon atoms, an alkyloxy group having 6 to 20 carbon atoms, an alkylthio group having 6 to 60 carbon atoms, an aryl group having 6 to 60 carbon atoms, or 6 to 6 carbon atoms. 60 aryloxy groups, arylthio groups having 6 to 60 carbon atoms, arylalkyl groups having 7 to 60 carbon atoms, arylalkyloxy groups having 7 to 60 carbon atoms, arylalkylthio groups having 7 to 60 carbon atoms, An acyl group having 6 to 60 carbon atoms or an acyloxy group having 6 to 60 carbon atoms is represented. X ¹ and Ar ² are bonded to the adjacent position of the heterocyclic ring contained in Ar ¹ , and C (R ⁵⁰ ) (R ⁵¹ ) and Ar ¹ are bonded to the adjacent position of the heterocyclic ring contained in Ar ^2. ing.

As the organic polymer compound, a compound containing both the structural unit represented by the formula (1) and the structural unit represented by the formula (2) is more preferable.
Examples of suitable p-type semiconductor polymers include organic polymer compounds containing an arylene group as a structural unit from the viewpoint of solubility in an organic solvent and ease of raising the degree of polymerization.

Here, the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and a group having a condensed ring, two or more independent benzene rings or condensed rings are directly or via a group such as vinylene. Group bonded together. The arylene group may have a substituent. Examples of the substituent include linear or branched alkyl groups having 1 to 20 carbon atoms or cycloalkyl groups having 1 to 20 carbon atoms, linear or branched groups having 1 to 20 carbon atoms. Examples thereof include an alkoxy group having an alkyl group or a cycloalkyl group having 1 to 20 carbon atoms in its structure. The number of carbon atoms in the arylene group excluding the substituent is usually about 6 to 60, and preferably 6 to 20. The total number of carbon atoms including the substituent of the arylene group is usually about 6 to 100.

Examples of arylene groups include phenylene groups, naphthalenediyl groups, anthracene-diyl groups, biphenyl-diyl groups, terphenyl-diyl groups, fluorenediyl groups (preferably 9,9'-dialkyl-fluorene-2,7- A diyl group), a benzofluorenediyl group, and the like.

The organic polymer compound containing the arylene group as a structural unit is preferably a copolymer further containing a structural unit other than the arylene group.

Examples of the structural unit other than the arylene group include a structural unit that is a thienylene group that may have a substituent (preferably a 2,5-thienylene group that may have a substituent), in the above formula (1). The structural unit represented and the structural unit which combined these are mentioned. Examples of the substituent that the thienylene group may have include a linear or branched alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 1 to 20 carbon atoms.
As the compound containing the arylene group as a structural unit, for example, polymer compound A represented by the following formula (3) and polymer compound B represented by the following formula (4) are used.

(Electron-accepting compound: n-type semiconductor such as n-type semiconductor polymer)
Examples of the electron-accepting compound include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, fullerenes and derivatives thereof such as C ₆₀ fullerene, bathocuproine And phenanthrene derivatives such as titanium oxide, metal oxides such as titanium oxide, and carbon nanotubes. As the electron-accepting compound, titanium oxide, carbon nanotubes, fullerenes, and fullerene derivatives are preferable, and fullerenes and fullerene derivatives are particularly preferable.

Examples of _{fullerene, C 60} _{fullerene, C 70} _{fullerene, C 76} _{fullerene, C 78} _fullerene, such as _{C 84} fullerene, and the like.

Examples of fullerene and fullerene derivatives include C ₆₀ fullerene, C ₇₀ fullerene, C ₇₆ fullerene, C ₇₈ fullerene, C ₈₄ fullerene and derivatives thereof. Specific examples of the fullerene derivative include the following compounds.

Examples of fullerene derivatives include [6,6] phenyl-C ₆₁ butyric acid methyl ester (C ₆₀ PCBM, [6,6] -Phenyl C ₆₁ butyric acid methyl ester), and [6,6] phenyl-C _71. Butyric acid methyl ester (C ₇₀ PCBM, [6,6] -Phenyl C ₇₁ butyric acid methyl ester), [6,6] Phenyl-C ₈₅ butyric acid methyl ester (C ₈₄ PCBM, [6,6] -Phenyl C ₈₅ butyric acid methyl ester), [6,6] thienyl _{-C 61} butyric acid methyl ester _{([6,6] -Thienyl C 61 butyric} acid methyl ester) and the like.

When a fullerene derivative is used as the electron accepting compound, the ratio of the fullerene derivative is preferably 10 parts by weight to 1000 parts by weight and preferably 20 parts by weight to 500 parts by weight with respect to 100 parts by weight of the electron donating compound. It is more preferable.

The thickness of the active layer is usually preferably 1 nm to 100 μm, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, more preferably 20 nm to 200 nm.

(Other ingredients)
In order to express various functions, the active layer may contain other components as necessary. Examples of other components include ultraviolet absorbers, antioxidants, sensitizers for sensitizing the function of generating charges by absorbed light, and light stabilizers for increasing stability from ultraviolet rays. .

Components other than the electron donating compound and the electron accepting compound constituting the active layer are each usually 5 parts by weight or less with respect to 100 parts by weight of the total amount of the electron donating compound and the electron accepting compound, and 0.01 wt. It is effective to blend in an amount of from 3 to 3 parts by weight.

The active layer may contain a polymer compound other than the electron donating compound and the electron accepting compound of the present invention as a polymer binder in order to enhance mechanical properties. As the polymer binder, those that do not inhibit the electron transport property or hole transport property are preferable, and those that do not strongly absorb visible light are preferably used. Examples of the polymer binder include poly (N-vinylcarbazole), polyaniline and its derivatives, polythiophene and its derivatives, poly (p-phenylene vinylene) and its derivatives, poly (2,5-thienylene vinylene) and its Derivatives, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like can be mentioned.

(Intermediate electrode layer)
When the photoelectric conversion element includes a plurality of active layers, an intermediate electrode layer is provided between the active layers as necessary. As the material for the intermediate electrode layer, metals such as gold, platinum, chromium, nickel, lithium, magnesium, calcium, tin, silver, and aluminum are used. For example, the intermediate electrode layer may be composed of metal particles having an average particle diameter of 50 nm or less. The intermediate electrode layer preferably has a high light transmittance so that the plurality of active layers can absorb light.

The intermediate electrode layer can be formed by a method of coating a film in which metal particles are dispersed or a vacuum deposition method. When the intermediate electrode layer is formed by a coating method, the intermediate electrode layer can also be formed by a printing method similar to the organic layer forming step as described above.

(Application of the element)
The photoelectric conversion element of the present invention can be operated as an organic thin film solar cell by generating a photoelectromotive force between the electrodes by irradiating light such as sunlight from an electrode exhibiting optical transparency. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.

(Organic thin film solar cell module)
The organic thin film solar cell module can basically have the same module structure as a conventional solar cell module. The organic thin film solar cell module generally has a structure in which cells are formed on a support substrate such as metal or ceramic, the cell is covered with a filling resin, protective glass, or the like, and light is taken in from the opposite side of the support substrate. The organic thin film solar cell module may have a structure in which cells are formed on a transparent support substrate using a transparent material such as tempered glass and light is taken in from the transparent support substrate side. As the structure of the organic thin film solar cell module, specifically, a module structure called a super straight type, a substrate type, or a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, or the like is known. Even in the organic thin film solar cell module to which the photoelectric conversion element of the present invention is applied, these module structures can be appropriately selected in consideration of the purpose of use, the place of use and the environment of use.

In a typical super straight type or substrate type organic thin film solar cell module, cells are arranged at regular intervals between support substrates that are transparent on one or both sides and subjected to antireflection treatment, and adjacent cells are metal leads or It is connected by flexible wiring or the like, and a collecting electrode is arranged on the outer edge portion, so that the generated power is taken out to the outside. Various types of plastic materials such as ethylene vinyl acetate (EVA) may be used between the substrate and the cell in the form of a film or a filled resin in order to protect the cell and improve current collection efficiency. In addition, when using the organic thin film solar cell module in a place where it is not necessary to cover the surface with a hard material such as a place where there is little impact from the outside, the surface protective layer is made of a transparent plastic film or the above filling resin is cured. Thus, it is possible to provide a protective function and eliminate the support substrate on one side. The periphery of the support substrate is fixed in a sandwich shape with a metal frame in order to ensure internal sealing and module rigidity, and the support substrate and the frame are hermetically sealed with a sealing material. In addition, when a flexible material is used for the cell itself, the support substrate, the filling material, and the sealing material, a solar cell can be formed on the curved surface.

In the case of a solar cell using a flexible support such as a polymer film, cells are sequentially formed while feeding out a roll-shaped support, cut to a desired size, and then the periphery is sealed with a flexible and moisture-proof material. Thus, the battery body can be produced. Moreover, it can also have a module structure called “SCAF” described in Solar Energy Materials and Solar Cells, 48, p383-391. Furthermore, a solar cell using a flexible support can be used by being bonded and fixed to a curved glass or the like.

(Organic light sensor)
The photoelectric conversion element of the present invention can be operated as an organic photosensor by irradiating light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes, so that a photocurrent flows. Furthermore, the organic photosensor is used as a light receiving unit, a drive circuit unit that detects an output due to a signal current generated by the organic photosensor and reads the signal charge, and a wiring that connects the organic photosensor and the drive circuit are provided. It can be used as an organic image sensor. The organic light sensor can be used with a color filter on the light incident surface side to provide color selectivity of light to be detected, or light absorption with high selectivity for each of the three primary colors of light. A plurality of types of organic photosensors having characteristics can also be used. As the driving circuit, an IC chip formed of a transistor using single crystal silicon, or a thin film transistor using a compound semiconductor such as polycrystalline silicon, amorphous silicon, or cadmium selenide, and a conjugated organic compound semiconductor such as pentacene. Can be used. The organic image sensor has a lower manufacturing cost than an existing image sensor using a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS) as an imaging element for a scanner, digital camera, digital video, etc. Advantages such as a small installation area can be expected. In addition, organic photosensors having various photosensitivity characteristics can be used due to the diversity of conjugated compounds. Therefore, it is possible to provide an organic image sensor having performance according to the application.

Hereinafter, examples of the present invention will be described. The following examples are preferred examples for explaining the present invention, and the present invention is not limited to the following examples.

(Polymer A: Synthesis of pentathienyl-fluorene copolymer)

In a 2 L four-necked flask with the inside atmosphere replaced with argon, the compound represented by the above formula (A) (7.928 g, 16.72 mmol) and the compound represented by the formula (B) (13.00 g, 17.60 mmol) , Methyltrioctylammonium chloride (trade name: aliquat336, manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / mL, 25 ° C., trademark of Henkel Corporation) (4.979 g), and 405 mL of toluene was added, and argon was bubbled through the system for 30 minutes while stirring. Dichlorobis (triphenylphosphine) palladium (II) (0.02 g) was added, the temperature was raised to 105 ° C., and 42.2 mL of a 2 mol / L sodium carbonate aqueous solution was added dropwise with stirring. After completion of the dropwise addition, the mixture was reacted for 5 hours, phenylboronic acid (2.6 g) and 1.8 mL of toluene were added, and the mixture was stirred at 105 ° C. for 16 hours. Thereafter, 700 mL of toluene and 200 mL of an aqueous 7.5% sodium diethyldithiocarbamate trihydrate solution were added, and the mixture was stirred at 85 ° C. for 3 hours. After removing the aqueous layer from the reaction solution, the organic layer was washed twice with 300 mL of ion exchanged water at 60 ° C., once with 300 mL of 3% acetic acid at 60 ° C., and further washed with 300 mL of ion exchanged water at 60 ° C. three times. The organic layer was passed through a column filled with celite, alumina, and silica, and the column was washed with 800 mL of hot toluene. The solution was concentrated to 700 mL, poured into 2 L of methanol, and reprecipitated. The polymer was recovered by filtration and washed with 500 mL of methanol, acetone, and methanol. By vacuum drying overnight at 50 ° C., 12.21 g of pentathienyl-fluorene copolymer (Polymer A) represented by the following formula was obtained. The polystyrene equivalent number average molecular weight of the polymer A was 5.4 × 10 ⁴ , and the weight average molecular weight was 1.1 × 10 ⁵ .

(Preparation of OPV ink (ink for active layer))
Next, the polymer A as an electron donating compound and PCBM as an electron accepting compound were dissolved in orthodichlorobenzene to prepare an OPV ink. The concentration of polymer A in the OPV ink was 0.5% by weight, and the concentration of PCBM in the OPV ink was 1.5% by weight. The viscosity of the OPV ink was 12 cP and the yield value was 1.37 dyn / cm ² .

(Ink application)
A blanket made of silicone rubber having a flat surface was prepared, and a predetermined surface portion of this blanket was cut out to form a plurality of convex portions on the surface portion of the blanket, thereby producing a relief plate. The shape of the convex part in plan view is a rectangle, and the dimension is 10 mm × 180 mm. The produced relief was wound around a blanket cylinder to obtain a transfer body.

While rotating the blanket cylinder at a speed of 2 mm / sec, OPV ink was applied to the relief plate with a CAP coater (capillary coater) to form an ink film on the surface of the projection. Thereafter, the ink film was naturally dried for 60 seconds.

A PET (Polyethylene terephthalate) film was set on the substrate platen, the blanket cylinder was rotated by moving the substrate platen while the relief plate was pressed against the PET film, and the ink film on the relief plate was transferred to the PET film.

After the transfer, the letterpress was visually confirmed. As a result, substantially all of the ink film was transferred from the letterpress to the PET film, and no ink film remained on the letterpress.

The active layer formed on the PET film had a thickness of 170 nm ± 5 nm. As a result, an organic layer (active layer) excellent in flatness was formed.

DESCRIPTION OF SYMBOLS 1 Stand 5 Printing apparatus 10 Blanket 11 Blanket cylinder 12 Central axis 20 Coating unit 21 Coating die 22 Ink tank 23 Line 24 Coating die raising / lowering part 25 Ink tank raising / lowering part 28 Ink 30 Drying device 40 Support part 50 Plate 51 Platen plate 60 Substrate 61

Substrate surface plate

70, 71 Ink film 73 Organic layer 21a Passage (capillary passage)
21b One end of passage 21c Slit

Claims

A method for producing a photoelectric conversion element comprising a pair of electrodes and one or more organic layers provided between the pair of electrodes,
Preparing a substrate provided with one of the pair of electrodes;
An ink containing the material of the organic layer is applied to a transfer body provided with a member made of silicone rubber on the surface portion, an ink film is formed on the transfer body, and the ink film is transferred to the substrate. Forming the organic layer;
Forming a second electrode of the pair of electrodes. A method for manufacturing a photoelectric conversion element.
The process for forming the organic layer further includes the step of drying the ink film before transferring the ink film formed on the transfer body to the substrate. Method.
The method for producing a photoelectric conversion element according to claim 2, wherein the step of drying the ink film is performed by spraying a gas on the ink film.
The photoelectric conversion according to claim 1, wherein the step of forming the organic layer further includes a step of patterning the ink film by removing a predetermined portion of the ink film before transferring the ink film to the substrate. Device manufacturing method.
The method for producing a photoelectric conversion element according to claim 1, wherein the ink is applied and formed on a transfer body using a nozzle having a slit-like discharge port.
The method for producing a photoelectric conversion element according to claim 1, wherein the ink is applied and formed on a transfer body using an anilox roll.
The photoelectric conversion element according to claim 1, wherein in the step of forming the organic layer, the photoelectric conversion element has an active layer as the organic layer, and the active layer is formed by the step of forming the organic layer. Production method.
The active layer has a thin film containing an electron donating compound material and a thin film containing an electron accepting compound material;
The method for producing a photoelectric conversion element according to claim 7, wherein each of the thin films is formed by a step of forming the organic layer.
The photoelectric conversion element has two or more active layers as one or more organic layers, and an intermediate electrode layer provided between the active layers,
Each of the said active layer is formed by the process of forming the said organic layer, The said intermediate electrode layer is a manufacturing method of the photoelectric conversion element of Claim 1 formed between the processes of forming the said active layer.
A photoelectric conversion element that can be manufactured by the manufacturing method according to claim 1.
A solar power generation module comprising the photoelectric conversion element according to claim 10.
An organic optical sensor comprising the photoelectric conversion element according to claim 10.