WO2013039020A1 - Method for manufacturing photoelectric conversion device, electrode for photoelectric conversion device, photoelectric conversion device, and light-emitting device - Google Patents

Abstract

This photoelectric conversion device comprises: a photoelectric conversion layer (13) for performing a conversion between light and electrical energy; and a plurality of first conductive wire members (121) and a plurality of second conductive wire members (122) provided on one-surface side of the photoelectric conversion layer (13). The first conductive wire members and the second conductive wire members are arranged alternately. A p-layer organic semiconductor (13A) comprising a hole-transporting material is provided to each of the first conductive wire members (121). An n-layer organic semiconductor (13B) comprising an electron-transporting material is provided to each of the second conductive wire members (122). The first conductive wire members function as p-type electrodes, and the second conductive wire members function as n-type electrodes.

Description

Method for manufacturing photoelectric conversion device, electrode for photoelectric conversion device, photoelectric conversion device, and light emitting device

The present invention relates to a method for producing a photoelectric conversion device, an electrode for a photoelectric conversion device used for the photoelectric conversion device, a photoelectric conversion device using the same, and a light emitting device.

A photoelectric conversion device is a device that converts light into electrical energy and a device that converts electrical energy into light. Examples of the former include solar cells, and examples of the latter include light emitting diodes.

Today, the need for solar power supply as a clean energy is recognized again. There are various types of solar cells, such as Si solar cells, compound solar cells, and organic semiconductor thin film solar cells.

For example, in the case of a single crystal Si solar cell among Si solar cells, the surface layer of the wafer is made an n-type semiconductor by vapor phase diffusion or implantation of n-type impurity ions into a p-type single crystal wafer. A pn junction and a pin junction are formed. A solar cell having a sandwich structure is manufactured by forming a front electrode and a back electrode.

There are various types of compound solar cells, but they have the advantages of high energy conversion efficiency, low light degradation due to secular change, excellent radiation resistance, wide light absorption wavelength range, and large light absorption coefficient. A chalcopyrite solar cell will be described as an example. This is a solar cell provided with a CIGS layer made of a chalcopyrite compound (Cu (In + Ga) Se ₂ ) containing Group I, Group III, and Group VI elements as a p-type light absorption layer (for example, Patent Documents) 1).

This solar cell with a CIGS layer generally has a back electrode 1 layer, which is a positive electrode made of a Mo metal layer, on a glass substrate such as a soda lime glass (SLG) substrate, and Na unevenness caused by the SLG substrate. The multilayer structure includes a Na dip layer for prevention, a CIGS light absorption layer, an n-type buffer layer, and an outermost surface layer formed of a transparent electrode layer serving as a negative electrode. Here, the n-type buffer layer is made of CdS, ZnO, InS or the like, and the transparent electrode layer is made of ZnOAl or the like.

In this multilayer laminated structure, when irradiation light enters from the light receiving portion on the surface, a pair of electrons and holes are generated in the vicinity of the pn junction of the multilayer laminated structure by being excited by the irradiation light having energy greater than the band gap. The excited electrons and holes reach the pn junction by diffusion, and the electrons are collected in the n region and the holes are separated in the p region due to the internal electric field of the junction. As a result, the n region is negatively charged, the p region is positively charged, and a potential difference is generated between the electrodes provided in each region. Using this potential difference as an electromotive force, a photocurrent is obtained when the electrodes are connected by a conductive wire.

The CIGS light absorbing layer is obtained by the following process. That is, the substrate itself provided with the In layer and the Cu—Ga layer as a precursor is accommodated in the annealing chamber and preheated. Thereafter, the precursor is converted into a CIGS layer by raising the temperature of the chamber to a temperature range of 500 to 520 ° C. while introducing H ₂ Se gas through a gas introducing tube inserted into the annealing chamber.

In recent years, an organic thin film solar cell using an organic semiconductor can be formed by a simple film forming method, and thus has attracted attention as a solar cell that is easy to manufacture and suitable for mass production. Various organic thin-film solar cells having so-called bulk heterojunction structures and nanophase separation structures have been proposed. In these structures, since a wide contact interface between the p-type organic semiconductor and the n-type organic semiconductor can be secured, the photoelectric conversion efficiency can be improved.

Such an organic thin film solar cell is prepared, for example, by dissolving a hole transport material and an electron transport material in various solvents to prepare a material-containing liquid, and depositing the material-containing liquid on the surface of the electrode. It is manufactured by forming a photoelectric conversion layer including an organic semiconductor or an n-type organic semiconductor.

For example, Patent Document 2 below proposes an organic thin film solar cell in which an anode, a photoelectric conversion layer having a bulk heterojunction structure, and a cathode are sequentially laminated on one surface of a substrate. In this patent document 1, not only a cathode is formed at a low temperature but also an organic metal by forming a laminated structure in which a cathode made of silver oxide and a reducing agent and an electron transport layer doped with an organic metal are applied in the vicinity of the cathode. It is said that the junction between the doped layer and the cathode is improved.

On the other hand, as an electrode of a photoelectric conversion device that is easy to manufacture and suitable for mass production, one using a conductive wire is known. For example, Patent Document 3 below proposes a method of manufacturing a photovoltaic element or the like by joining a mesh electrode body woven with metal wires onto the surface of a photovoltaic body. In Patent Document 2, by wiring a metal wire, the aspect ratio between the thinness and thickness of the wire can be appropriately adjusted as compared with the wiring using printing, lithography, etc., the cost can be reduced, and the mesh can be woven. It is said that wiring can be speeded up.

Japanese Patent Laid-Open No. 2006-196771 JP 2011-124468 A JP 2006-165149 A

However, in the conventional structure, a pair of electrodes is provided across a region to be a pn junction. Therefore, the electrode on the light irradiation side needs to have good light transmittance and low electric resistance, and the electrode on the light irradiation side has to be formed by vapor deposition or plating of an expensive rare metal. Along with that, the manufacturing process was also complicated.

In a conventional monochromatic or color light emitting device using organic EL (Electro-Luminescence), for example, an organic EL material is confined between an aluminum plate and a glass substrate with ITO, and the outer peripheral edge is sealed, and the aluminum plate and ITO The organic EL was made to emit light by applying a voltage between the two. Moreover, the flexibility was provided to the light-emitting device using the aluminum foil instead of the aluminum plate, and using the transparent resin sheet with ITO instead of the glass substrate with ITO.

Since such a light emitting device emits light uniformly on the surface, it is used as backlight illumination of a liquid crystal display device. The liquid crystal display device is provided with a liquid crystal panel on a backlight illumination unit. The liquid crystal panel is configured by bonding a TFT (Thin Film Transistor) substrate and a CF (Color Filer) substrate together and enclosing liquid crystal molecules therebetween. The TFT substrate is a substrate on which TFT elements are formed in a matrix, and the CF substrate is a substrate on which a color filter is formed.

However, in the conventional light emitting device, there is a limit to bending even when using an aluminum foil and a transparent resin sheet with ITO. This is because the light emitting layer made of the organic EL material is peeled off between the aluminum foil and the ITO, and no voltage is applied to the entire surface of the light emitting layer, resulting in uneven light emission.

Furthermore, in the conventional method for producing a photoelectric conversion device using a material-containing liquid containing a hole transport material or an electron transport material, it is difficult to ensure flexibility of the electrode, such as using a substrate to hold the electrode, A photoelectric conversion device having sufficient flexibility could not be obtained. In addition, by arranging a large number of p-type organic semiconductors and n-type organic semiconductors between the electrodes to widen the contact interface and ensure the performance of photoelectric conversion, the organic semiconductors arranged between the electrodes are insufficient or non-uniform. If it is arranged, the performance of photoelectric conversion is lowered accordingly.

In conventional flexible electrodes using conductive wires having conductivity, when a plurality of wires are arranged, the arrangement of the wires such as misalignment, bending, distortion, and deformation often occurs. When the arrangement of the wires is disturbed, the distance between the electrodes varies, the abundance of the p-type organic semiconductor and the n-type organic semiconductor arranged between the electrodes and the moving distance of the carriers become uneven, and the performance of photoelectric conversion is improved. It was falling.

Therefore, the present invention provides a manufacturing method capable of easily manufacturing a flexible photoelectric conversion device while ensuring the performance of photoelectric conversion, and an electrode structure for producing a photoelectric conversion device that can be suitably used for this manufacturing method. The first purpose is to provide it.

A second object of the present invention is to provide an electrode structure for a photoelectric conversion device that does not require light transmission as an electrode material, and a photoelectric conversion device using the same.

A third object of the present invention is to provide a light-emitting device with a simple structure and less flexibility.

In the method for producing a photoelectric conversion device of the present invention that achieves the first object, a material-containing liquid containing at least one of a hole transport material and an electron transport material in a solvent is attached to an electrode structure. And a method of forming an organic semiconductor in contact with the electrode structure from a material adhered to the electrode structure, and a plurality of conductive wires and an arrangement adjusting wire for adjusting an arrangement interval of the plurality of conductive wires; Are prepared by using a solvent capable of dissolving the arrangement adjusting wire, and bringing the material containing liquid into contact with the electrode structure. The organic semiconductor is formed by dissolving and attaching at least one material to the conductive wire.
In this manufacturing method, it is particularly preferable to manufacture an organic semiconductor thin film solar cell.

In this method of manufacturing a photoelectric conversion device, it is preferable to prepare an electrode structure in which conductive wires are spaced apart from each other by a predetermined interval by interposing an arrangement adjusting wire between conductive wires.
An electrode structure comprising a plurality of vertical wires made of a plurality of conductive wires and arrangement adjusting wires and a plurality of horizontal wires arranged intersecting the plurality of vertical wires can be prepared, and the arrangement adjusting wires can be dissolved. It is preferable to prepare the material-containing liquid using a solvent that cannot dissolve the horizontal wire.

In this manufacturing method, a material-containing liquid containing a hole transport material and an electron transport material is prepared and brought into contact with the electrode structure, and the p-type organic semiconductor is formed in a state of being connected to some conductive wires, and n It is preferable to form the type organic semiconductor in a state where it is connected to the other part of the conductive wire.

In this manufacturing method, the material-containing liquid may be attached to one side of the electrode structure.
Also, an electrode structure having a plurality of electrode portions in which a plurality of conductive wires are integrated together with a placement adjusting wire and having a plurality of electrode portions opposed to each other is prepared, and a placement adjusting wire is prepared. The material-containing liquid may be prepared using a solvent that can dissolve the support wire but cannot dissolve the support wire.

The electrode for producing a photoelectric conversion device used in such a production method is preferably one in which the solubility of the arrangement adjusting wire in the solvent for producing the photoelectric conversion device is larger than that of the conductive material.

In order to achieve the second object, an electrode for a photoelectric conversion device of the present invention is an electrode provided on one side of a photoelectric conversion layer that converts light and electric energy, and includes a plurality of vertical wires and a plurality of vertical wires. The vertical wire and the horizontal wire intersect each other to form a net, and the vertical wire includes a plurality of first conductive wires, a plurality of second conductive wires, and a plurality of The first conductive wire and the second conductive wire are alternately arranged, and the first insulating wire is provided between the first conductive wire and the second conductive wire. The horizontal wire is made of a second insulating wire, wherein the first conductive wire functions as a p-type electrode, and the second conductive wire functions as an n-type electrode.
A plurality of the first insulating wire rods may be provided between the first conductive wire rod and the second conductive wire rod 3 described above.

In order to achieve the second object, a photoelectric conversion device of the present invention includes a photoelectric conversion layer that converts light and electric energy, and a pair of electrodes provided on one side of the photoelectric conversion layer, One electrode and the other electrode are provided side by side, a p-layer organic semiconductor made of a hole transport material is provided on the one electrode, and an electron transport material is provided on the other electrode. An n-layer organic semiconductor is provided, the one electrode functions as a p-type electrode, and the other electrode functions as an n-type electrode.
In the present invention, the p-layer organic semiconductor and the n-layer organic semiconductor are preferably covered with a transparent protective layer.

In this photoelectric conversion device, a p-layer organic semiconductor made of a hole transport material is provided on the first conductive wire with respect to the optoelectronic device electrode, and an electron transport material is provided on the second conductive wire. The p-layer organic semiconductor and the n-layer organic semiconductor may be alternately arranged, for example, alternately formed on the same surface. Here, the same surface may be either a virtual surface or a substrate surface, but when formed on the substrate surface, it may be a flat substrate or a flexible substrate that can be bent.

In order to achieve the third object, the light-emitting device of the present invention is configured by arranging a light-emitting layer made of an organic EL material and the light-emitting layer, and alternately arranging one conductive wire and the other conductive wire. Alternating electrodes.

Preferably, an arrangement adjusting wire extending in the same direction is provided between one conductive wire and the other conductive wire, and the arrangement adjusting wire has an interval between the one conductive wire and the other conductive wire. maintain.

Preferably, a crossing wire extends in a direction crossing one conductive wire and the other conductive wire, and the crossing wire, one conductive wire, and the other conductive wire are knitted.

Preferably, a crossing wire extends in a direction crossing one conductive wire, the other conductive wire, and the arrangement adjusting wire, and the crossing wire, one conductive wire, the other conductive wire, and the arrangement adjustment. Wires for use are knitted.

Preferably, one wiring part in which one end of one conductive wire is connected to each other and the other wiring part in which the other end of the other conductive wire is connected to each other, one wiring part and the other wiring part When a voltage is applied to the light emitting layer, the light emitting layer emits light.

According to the method for manufacturing a photoelectric conversion device of the present invention, since an electrode structure in which a plurality of conductive wires are integrally connected together with a wire for adjusting arrangement is used, even a conductive wire having flexibility can be easily arranged. In addition, the arrangement interval of the plurality of conductive wires can be easily adjusted by the arrangement adjusting wire, and the state can be stably maintained at the time of manufacture. For this reason, it is possible to prevent variation in the arrangement interval of the plurality of conductive wires and to ensure the performance of photoelectric conversion.

Then, since the arrangement adjusting wire is dissolved by bringing the material containing liquid into contact with the electrode structure, in the obtained photoelectric conversion device, the hole transport material of the material containing liquid is disposed at the portion where the arrangement adjusting wire is arranged. And an electron transport material can be arranged. Therefore, many organic semiconductors can be uniformly arranged between the conductive wires, and the performance of photoelectric conversion can be ensured. Therefore, it is possible to easily manufacture a photoelectric conversion device having flexibility while ensuring the performance of photoelectric conversion.

According to the electrode for producing a photoelectric conversion device used in this manufacturing method, a plurality of conductive wires are integrated together with the arrangement adjusting wire, and the solubility of the arrangement adjusting wire in the solvent for producing the photoelectric conversion device is more than the conductive material. Since it is large, it can be suitably used to produce the photoelectric conversion device as described above.

According to the photoelectric conversion device electrode of the present invention, the electrode has an alternately arranged planar electrode structure in which one electrode functioning as a p-type electrode and the other electrode functioning as an n-type electrode are formed on the same plane. Therefore, the transparent electrode material conventionally required as the electrode material becomes unnecessary.
Conventionally, a p-layer organic semiconductor is laminated on one electrode and an n-layer organic semiconductor is laminated thereon to form a pn junction, and the other electrode is transparent on the n-layer organic semiconductor. There is no need to sequentially stack the electrodes to form a photoelectric conversion device.
The electrode structure and photoelectric conversion device of the present invention can be produced on a flexible substrate such as a glass substrate. Since an organic semiconductor can be provided on the electrode by coating, the manufacturing process is not complicated, and the electrode can be manufactured at low cost.

According to the light emitting device of the present invention, the alternately arranged electrodes are provided in the light emitting layer. In the alternating electrode, one and the other conductive wires are alternately arranged, and if necessary, an arrangement adjusting wire is provided between them or another wire intersects with each other. Unlike the resin molded sheet or film itself, it is easily deformable such as curved by an external force. In addition, since the organic EL material is in close contact with the one and the other conductive wires themselves, the light emission performance is hardly affected even if they are curved. In addition, the structure is extremely simple, and the productivity can be improved and the cost can be reduced.

It is sectional drawing of the photoelectric conversion device which concerns on 1st Embodiment of this invention. It is a perspective view which shows the electrode structure in the photoelectric conversion device shown in FIG. It is an enlarged view of the area | region shown with the code | symbol A in FIG. It is a figure which shows typically the light-emitting device which concerns on 2nd Embodiment of this invention. It is a figure which shows typically the cross section of the light emission part among the light-emitting devices which concern on 2nd Embodiment of this invention. It is a figure which shows typically the alternating array electrode of the light emission part shown in FIG. It is a figure which shows typically the cross section of the light emission part among the light-emitting devices which concern on 3rd Embodiment of this invention. It is a figure which shows typically the alternating array electrode of the light emission part shown in FIG. It is a figure which shows typically the cross section of the light emission part among the light-emitting devices which concern on 4th Embodiment of this invention. It is a figure which shows typically the cross section of the light emission part among the light-emitting devices which concern on 5th Embodiment of this invention. It is sectional drawing which shows the photoelectric conversion device manufactured by 6th Embodiment of this invention. It is a perspective view which shows typically the electrode structure for photoelectric conversion device manufacture in 6th Embodiment of this invention. (A)-(d) is a fragmentary sectional view for demonstrating a part of manufacturing process of the photoelectric conversion device in 6th Embodiment of this invention. It is sectional drawing which shows the modification of the photoelectric conversion device of 6th Embodiment of this invention.

Hereinafter, the present invention will be described in detail according to some embodiments with reference to the drawings.
[First Embodiment]
In the first embodiment, the photoelectric conversion device will be described assuming a solar cell as a device that converts light into electric energy, but the present invention can be similarly applied to a device that converts electric energy into light energy. .

FIG. 1 is a cross-sectional view of a photoelectric conversion device 1 according to the first embodiment of the present invention, and FIG. 2 is a perspective view of the photoelectric conversion device.

The photoelectric conversion device 1 includes an insulating substrate 11, an electrode 12 provided on the upper surface of the substrate 11, a photoelectric conversion layer 13 that covers the electrode 12, and a protective layer 14 that covers the upper surface of the photoelectric conversion layer 13. It is configured. In FIG. 2, the display of the photoelectric conversion layer 13 and the protective layer 14 is omitted.

The base material 11 is formed in a sheet shape and has flexibility. For example, what was formed as a flexible substrate by PET etc. is used. In the first embodiment, as shown in FIG. 2, the base material 11 has a rectangular outline. Hereinafter, for convenience of explanation, the short side is referred to as the first side 11A, and the long side is referred to as the second side 11B.

The electrode 12 will be described with reference to FIG. The electrode 12 extends along the first side 11 </ b> A of the base 11, and further has a plurality of vertical wires 12 </ b> A arranged at a predetermined pitch in the extending direction of the second side 11 </ b> B, and the second side 11 </ b> B of the base 11. And a plurality of horizontal wires 12B arranged at a predetermined pitch in the extending direction of the first side 11A. The vertical wire 12A and the horizontal wire 12B are woven so as to intersect each other. That is, the electrode 12 is formed in a plain weave net shape.

Three types of wires are used as the vertical wire 12A extending along the first side 11A. Specifically, the first conductive wire 121, the second conductive wire 122, and the first insulating wire 123 are used. As shown in FIG. 2, the first conductive wire 121 and the second conductive wire 122 are alternately arranged on the substrate 11, and the first conductive wire 121 and the second conductive wire 122 are arranged between the first conductive wire 121 and the second conductive wire 122. One insulating wire 123 is provided. In addition, although the space | interval of the 1st conductive wire 121 and the 2nd conductive wire 122 is equivalent to the diameter of the cross section of the 1st insulated wire 123 pinched | interposed between them, in order to make an understanding of a structure easy in drawing. In the figure, a gap is provided between the members.

As the first conductive wire 121 and the second conductive wire 122, for example, a metal wire such as a copper wire or a stainless wire, a wire obtained by performing metal plating on the surface of a chemical fiber, or the like can be used. One end 121E of each first conductive wire 121 is connected to the first bus bar 121A as shown in FIG. Each second conductive wire 122 is connected to the second bus bar 122A at an end 122E located on the other end 121F side of the first conductive wire 121.

The first insulating wire 123 is made of a flexible insulating resin such as nylon resin, silicone resin, urethane resin, epoxy resin, polycarbonate resin, or vinyl resin.

A second insulating wire is used as the horizontal wire 12B extending along the second side 11B. Similar to the first insulating wire 123, the second insulating wire is made of a flexible insulating resin such as nylon resin, silicone resin, urethane resin, epoxy resin, polycarbonate resin, or vinyl resin.

The first conductive wire 121, the second conductive wire 122, the first insulating wire 123 and the second insulating wire are set to a thickness of about 20 μm to 30 μm.

Next, the photoelectric conversion layer 13 will be described. FIG. 3 is a schematic enlarged view of a circle A region in FIG. The photoelectric conversion layer 13 is provided on one electrode, that is, the p-layer organic semiconductor 13A made of a hole transport material provided on the first conductive wire 121, and on the second conductive wire 122 serving as the other electrode, and electron transport. And an n-layer organic semiconductor 13B made of a material. Therefore, one first conductive wire 121 functions as a p-type electrode, and the other second conductive wire 122 functions as an n-type electrode. The p-layer organic semiconductor 13A and the n-layer organic semiconductor 13B form a pn junction.

Next, materials of the p-layer organic semiconductor 13A and the n-layer organic semiconductor 13B will be described. The p-layer organic semiconductor 13A is formed of a hole transport material. As a hole transport material, in addition to triphenylamine (TAPC) represented by the chemical formula (1), TPD and other aromatic amines which are dimers of triphenylamine represented by the chemical formula (2), the chemical formula (3) Α-NPD represented by formula (4), (DTP) DPPD represented by formula (4), m-MTDATA represented by formula (5), HTM1 represented by formula (6), 2-TNATA represented by formula (7) TPTE1 represented by the chemical formula (8), TCTA represented by the chemical formula (9), NTPA represented by the chemical formula (10), spiro-TAD represented by the chemical formula (11), TFREL represented by the chemical formula (12), etc. It is done.

 

 

 

 

 

 

 

 

 

 

 

 

The n-layer organic semiconductor 13B is formed of an electron transport material. Examples of the electron transport material include Alq ₃ represented by the chemical formula (13), BCP represented by the chemical formula (14), an oxadiazole derivative represented by the chemical formula (15), and an oxadiazole dimer represented by the chemical formula (16). And starburst oxadiazole represented by chemical formula (17), triazole derivative represented by chemical formula (18), phenylquinoxaline derivative represented by chemical formula (19), silole derivative represented by chemical formula (20), and the like.

 

 

 

 

 

 

 

 

As described above, the first conductive wire 121 and the second conductive wire 122 constituting the photoelectric conversion device electrode 12 are formed side by side on the substrate 11, and the first conductive wire 121 and the second conductive wire 122 are further formed. The p-layer organic semiconductor 13 </ b> A and the n-layer organic semiconductor 13 </ b> B are formed side by side on the substrate 11, similarly to the first conductive wire 121 and the second conductive wire 122. Therefore, the protective layer 14 can be formed without providing an electrode on the light incident surface as in Patent Document 2.

The protective layer 14 is provided so as to cover the p-layer organic semiconductor 13A and the n-layer organic semiconductor 13B. The protective layer 14 is formed of, for example, a resin or the like as long as it is a material that transmits irradiation light such as sunlight.

A method for producing the photoelectric conversion device 1 shown in FIG. First, the base material 11 is prepared. Next, a first conductive wire 121, a second conductive wire 122, a 171 insulating wire 123, and a second insulating wire are prepared and plain woven. The electrode 15 formed by plain weaving is fixed on the base material 11 with, for example, an adhesive. Thereafter, a hole transport material to be the p-layer organic semiconductor 13A is applied to a predetermined portion, for example, the first conductive wire 121 as one electrode. For the application, for example, a printing method using an inkjet printer can be applied.

Next, an electron transport material to be an n-layer organic semiconductor 13B is applied between the p layer and the p layer, for example, on the second conductive wire 122 as the other electrode. For the application, a printing technique using an ink jet printer can be used as in the case of the p-layer organic semiconductor 13A.

Thereby, a pn junction is formed by the p-layer organic semiconductor 13A and the n-layer organic semiconductor 13B. The n-layer organic semiconductor 13B may be applied, and then the p-layer organic semiconductor 13A may be applied.

Finally, the photoelectric conversion device 1 is manufactured by forming the protective layer 14 by painting or the like. Note that the method is not limited to the above-described method as long as the photoelectric conversion device 1 illustrated in FIG. 1 is manufactured.

Thus, according to this invention, the 1st conductive wire 121 and the 2nd conductive wire 122 which comprise the electrode 12 for photoelectric conversion devices are formed on the base material 11, Furthermore, the 1st conductive wire 121 and the 2nd conductive wire are formed. A p-layer organic semiconductor 13 </ b> A and an n-layer organic semiconductor 13 </ b> B are formed on the substrate 11 so as to cover the wire 122. Therefore, the protective layer 14 can be formed without providing an electrode on the light incident surface as in Patent Document 2. Therefore, it is unnecessary to configure the electrode provided on the light irradiation side of Patent Document 2 with a transparent electrode, and it is not necessary to use a rare metal for the transparent electrode as a material. Al or the like can be used. Moreover, since the electrode 12 is comprised with the net | network which has flexibility, the photoelectric conversion device 1 can be attached to the curved surface after forming in planar shape.

The first embodiment of the present invention can be implemented with appropriate modifications within the scope of the present invention. In the configuration described above, a configuration in which one first insulating wire 123 is provided between the first conductive wire 121 and the second conductive wire 122 has been described, but a plurality of the first insulated wire 123 may be provided. Further, the photoelectric conversion device may be configured by omitting the base material 11.

[Second Embodiment]
FIG. 4 is a view schematically showing a light emitting device according to the second embodiment of the present invention. FIG. 5 is a diagram schematically showing a cross section of the light emitting portion of the light emitting device shown in FIG. 4, and FIG. 6 is a diagram schematically showing the alternately arranged electrodes of the light emitting portion shown in FIG.

The light-emitting device 1 shown in 2nd Embodiment of this invention is equipped with the light emission part 2 and the control part 3, as shown in FIG. As shown in FIG. 5, the light emitting unit 2 includes a light emitting layer 13 made of an organic EL material and alternating electrodes 12 provided in the light emitting layer 13. The light emitting layer 13 is formed in layers with various organic EL materials. The alternating electrode 12 is configured such that one conductive wire 121 and the other conductive wire 122 extend in the same direction and are alternately arranged at intervals.
In the second to fifth embodiments, the photoelectric conversion device is the light emitting device 1, the photoelectric conversion layer is the light emitting layer 13, and the photoelectric conversion device electrodes are the alternately arranged electrodes 12.

As shown in FIG. 5, the alternating electrodes 12 may be provided at substantially the center in the thickness direction of the light emitting layer 13, but may be closer to either the upper or lower surface from the center surface. As shown in FIG. 5, the light emitting unit 2 may be provided with a thin transparent protective layer 14 on one or both upper and lower surfaces.

The alternating array electrode 12 is configured by providing an arrangement adjusting wire 15 that also extends in one direction between one conductive wire 121 that extends in one direction and the other wire 13 that extends in one direction. Yes. These one and other wires 12, 13 and the arrangement adjusting wire 15 are used as a horizontal wire, and the insulating wire 15 is used as a vertical wire. In addition, as shown in the drawing, the arrangement adjusting wire 15 may be not only one but also two or more between one conductive wire 121 and the other conductive wire 122.

The details will be described below. Between the one conductive wire 121 extending in the vertical direction and the other conductive wire 122 extending in the vertical direction, the arrangement adjusting wire 15 extending in the vertical direction is arranged, and each of the wires 12 extending in the vertical direction is arranged. , 13 and 15 are cross-wired 16 extending in the horizontal direction and arranged in a lattice pattern with a plurality of wires arranged at intervals in the vertical direction. The vertical and horizontal intervals of the lattice may be the same or substantially the same.

The one conductive wire 121 and the other conductive wire 122 are made of wire members having a circular cross section, an elliptical cross section, and a flat cross section, and may be monofilaments or multifilaments. The filament may be a conductive wire made of metal or the like. Moreover, the metal may be plated on the outer periphery of the monofilament or multifilament, and the plating layer may be formed on the outer periphery of the filament. The metal is preferably copper having a low resistivity, but may be other metals such as stainless steel.

The arrangement adjusting wire 15 and the crossing wire 16 are each made of a linear member having a circular cross section, an elliptical cross section, or a flat cross section, and may be monofilament or multifilament.

The crossing wire 16 is made of insulating fiber. It is preferable to use insulating fibers as the material of the wire 15 for adjusting the arrangement. The material of the arrangement adjusting wire 15 and the crossing wire 16 is an organic solvent contained in the coating agent when the organic EL material is applied to one of the linear electrode group 12 and the other linear electrode group 13 and cured. May be dissolved.

The distance between the one conductive wire 121 and the arrangement adjusting wire 15 and the distance between the other conductive wire 122 and the arrangement adjusting conductive wire 15 are one conductive wire 121, the other conductive wire 122, and the arrangement adjusting conductivity. The same order as the equivalent cross-sectional dimension of the wire 15 may be sufficient.

For example, the conductive wires 121 and 13 and the arrangement adjusting wire 15 and the crossing wire 16 have a wire diameter of 20 to 35 μm, and a gap between the conductive wires 121 and 13 and the arrangement adjusting wire 15 is provided. Is 20 to 35 μm. The gap between the crossing wires 15 is 20 to 35 μm. On the other hand, the thickness of the light emitting layer 13 is, for example, 40 to 80 μm.

In the embodiment of the present invention, the string-like thickness of each wire is approximately the same as the size of the mesh formed by these wires, or has the same order of dimensions. Accordingly, the gap between the wires is maintained by the wire 15 for adjusting the arrangement and the wire 16 for crossing. The wire diameter of each wire is preferably uniform, but may be within a predetermined range with respect to the average diameter, for example, 80% to 120%. Thereby, the space | interval of the one conductive wire 121 and the other conductive wire 122 is kept substantially constant.

The arrangement adjusting wire 15 and the crossing wire 16 are provided to maintain a distance between one conductive wire 121 and the other conductive wire 122 until the organic EL material is cured. Therefore, when the organic EL material is cured by applying the organic EL material to the cloth knitted as described above to form the light emitting layer 13, the thickness of the light emitting layer 13 and the one conductive wire 121 and the other are increased. The conductive wire 122 is held. Note that the arrangement adjusting wire 15 and the crossing wire 16 do not need to be completely dissolved by the organic solvent, and may remain partially undissolved.

For example, acrylic fibers or vinyl fibers can be used as the wires 15 for the arrangement adjustment and the crossing wires 16, and in this case, the coating agent contains an organic solvent such as toluene or acetic acid. It only has to be done. The organic solvent can be appropriately selected according to the organic EL material, the curing agent, and the like.

As described above, the alternately arranged electrodes 12 are embedded in the light emitting layer 13, and at that time, the distance between the one conductive wire 121 and the other conductive wire 122 is substantially constant by the arrangement adjusting wire 15 and the crossing wire 16. Can be.

One end of one conductive wire 121 is mutually connected by one wiring part 5, and one end of the other conductive wire 122 is mutually connected by the other wiring part 6. Each wiring unit 5, 6 is connected to the control unit 3 via the connection unit 4.

The control unit 3 applies a voltage between one wiring unit 5 and the other wiring unit 6. Thereby, a voltage can be applied to the organic EL molecules in the light emitting layer 13.

In the light emitting device 1 according to the second embodiment of the present invention, one conductive wire 121 extending in one direction and the other conductive wire 122 are arranged alternately in the light emitting layer 13. Here, “provided in the light emitting layer” means that each of the conductive wires 121 and the other conductive wires 122 in the alternate wiring electrode 14 is cut in a cross-section in a cross section and the surroundings are all organic EL molecules having a light emission image. It is not necessary to be in close contact, and includes cases where it is partially in close contact. That is, the voltage applied to one conductive wire 121 and the other conductive wire 122 may be applied to the organic EL molecules.

In the light emitting unit 2 in the light emitting device 1 according to the second embodiment of the present invention, one conductive wire 121 and the other conductive wire 122 extending in the same direction are alternately arranged, and arrangement adjustment is performed as necessary between them. Are disposed in a grid pattern with intersecting wire rods 16 in the direction intersecting them. In addition, when the wire diameter of each wire is very small, the wire extending in the lateral direction may be referred to as weft and the wire extending in the vertical direction may be referred to as warp.

Since the light emitting unit 2 of the light emitting device 1 according to the second embodiment of the present invention includes the alternately arranged electrodes 12 as described above, a voltage is applied between the one conductive wire 121 and the other conductive wire 122 to emit the light emitting layer 13. The entire surface can emit light.

In the second embodiment of the present invention, since each of the wires 12, 13, 15 and the light emitting layer 13 extend in the vertical and horizontal directions, respectively, a thin film is used without using a glass substrate as in the prior art. In addition, since the ITO film is not formed on the sheet, the ITO film does not peel from the film or sheet. In addition, the bending of the film or sheet itself is not hindered. Therefore, the light emitting unit 2 of the light emitting device 1 according to the second embodiment of the present invention can be freely deformed such as curved.

[Embodiments of other light emitting devices]
Hereinafter, other embodiments of the light emitting device will be described. In addition, the same code | symbol is attached | subjected to the member which is the same as that of 2nd Embodiment, or respond | corresponds.

FIG. 7 is a diagram schematically showing a cross section of a light emitting unit in a light emitting device according to the third embodiment of the present invention, and FIG. 8 is a diagram schematically showing alternating electrodes of the light emitting unit shown in FIG. . In the light emitting device 1 according to the third embodiment, the alternately arranged electrodes 12 in the light emitting unit 2 alternately arrange one conductive wire 121 and the other conductive wire 122, and arrange the arrangement adjusting wire 15 as one conductive wire. It differs in that it is not provided between 121 and the other conductive wire 122.

As described in the second embodiment, the arrangement adjusting wire 15 is provided between the one conductive wire 121 and the other conductive wire 122, and the solvent contained in the organic EL material, the curing agent, or the like is applied. Thus, the light emitting section 2B may be manufactured by melting the arrangement adjusting wire 15. Or you may make it apply | coat and harden the coating agent containing organic EL material, a hardening | curing agent, etc., without providing the wire 15 for arrangement | positioning adjustment.

FIG. 9 is a diagram schematically showing a cross-section of a light emitting unit in a light emitting device according to the fourth embodiment of the present invention. The light emitting unit 2C of the light emitting device according to the fourth embodiment is different in that a color filter 18 is provided between the light emitting layer 13 and the protective layer 14 in the light emitting unit 2A shown in FIG. By providing the color filter 18, the contrast can be improved.

FIG. 10 is a diagram schematically showing a cross section of a light emitting unit in a light emitting device according to a fifth embodiment of the present invention. In the light emitting unit 2D according to the fifth embodiment, a protective layer 14 is provided on one side of the light emitting layer 13 with a color filter 18 interposed therebetween. On the other side of the light emitting layer 13, for example, a sheet or film made of a transparent resin is provided. A base material 11 is provided. By disposing a conductive cloth having alternating electrodes on the substrate 11, applying and curing a coating agent containing an organic EL material and a curing agent, and then sequentially arranging the color filter 18 and the protective layer 14 The light emitting unit 2D is manufactured. The conductive cloth is formed by providing a wire 15 for adjusting the arrangement between one conductive wire 121 and the other conductive wire 122, and making it cross-shaped with a crossing wire 15 in a direction perpendicular to them.

As described above, in each of the second to fifth embodiments, the alternating array electrode 12 is provided in the light emitting layer 13, and the alternating array electrode 12 is interposed between one conductive wire 121 and the other conductive wire 122. An AC voltage having a frequency suitable for direct current or EL element emission is applied. Then, a voltage is applied to the organic EL molecules, and the light emitting layer 13 can emit light over the entire surface.

One conductive wire 121 and the other conductive wire 122 form the alternately arranged electrodes 12 which are provided in the light emitting layer 13. At that time, the alternating array electrode 12 is provided with a wire 15 for adjusting the arrangement between the conductive wires 121 and 13 as necessary, and is knitted by the crossing wire 16 in a direction intersecting these, as if it is a fine yarn cloth. It is configured as.
A light emitting layer in which one or a plurality of organic EL materials are applied or immersed in these fine yarn cloths can be formed. In that case, a hardening | curing agent, a solvent, a catalyst, etc. are mixed so that it may adapt to organic EL material.
Although the formation of the light emitting layer in the second to fifth embodiments has not been described in detail, various known organic EL materials can be used. As a method of immersing and curing the organic EL material, a known technique such as an ink jet method can be used, or an immersion impregnation method or an infiltration method using a roller can be used.

Further, as described above, each wire rod may be knitted to form a square mesh such as a square in plan view, but may be a mesh of other shapes such as a rhombus.

The light-emitting device according to these embodiments can be used for billboard lighting such as advertisements and back lighting of liquid crystal display devices.

[Sixth Embodiment]
First, the photoelectric conversion device manufactured by this embodiment is demonstrated using FIG. Below, the example about the solar cell which converts light into an electrical energy is demonstrated as the photoelectric conversion device 1, However, Even if it converts an electrical energy into light like an EL element etc., it is applicable similarly.

The photoelectric conversion device 1 includes a photoelectric conversion layer 13 having a p-type organic semiconductor 13A made of a hole transport material and an n-type organic semiconductor 13B made of an electron transport material, and a p-type electrode connected to the p-type organic semiconductor 13A. The first conductive wire 121, the second conductive wire 122 as an n-type electrode connected to the n-type organic semiconductor 13B, and the protective layer 14 laminated so as to cover the surface of the photoelectric conversion layer 13 are provided. Here, the photoelectric conversion device 1 is disposed along the surface of the insulating substrate 11.

At least one of the first conductive wire 121 and the second conductive wire 122, here both, is composed of a plurality of conductive wires 120 arranged side by side in substantially the same direction so as not to contact each other. A horizontal wire 12B made of an insulating wire is arranged in a direction crossing these conductive wires 120. A part of the plurality of conductive wires 120 is the first conductive wire 121 and the other conductive wire 120 is the second conductive wire 122, which are alternately arranged.
The plurality of conductive wire rods 120 constituting the first conductive wire rod 121 and the plurality of conductive wire rods 120 constituting the second conductive wire rod 122 are provided in substantially the same number, and bus bars 7 as wiring portions as shown in FIG. Can be connected to various circuits via the bus bar 7.

Each conductive wire 120 uses a flexible wire such as a metal wire such as a copper wire or a stainless steel wire, a synthetic fiber such as a resin, or a metal-plated fiber obtained by performing metal plating on the surface of various fibers such as a natural fiber. It is good to do. In the case of a metal-plated fiber, the core fiber may be composed of a flexible insulating resin such as nylon resin, silicone resin, urethane resin, epoxy resin, polycarbonate resin, vinyl resin, or the like.

The thickness of the plurality of conductive wires 120 may be different from each other, but it is preferable to use wires having the same thickness. Although not particularly limited, as an example, one having a wire diameter of 20 to 30 μm may be used.

Each horizontal wire 12B is made of an insulating wire, and it is preferable to use a flexible wire such as nylon resin, silicone resin, urethane resin, epoxy resin, polycarbonate resin, or vinyl resin. A wire having the same thickness as that of the conductive wire 120 may be used as the horizontal wire 12B. By arranging the horizontal wire 12B, a continuous wire in the vertical direction and the horizontal direction is arranged, and the surface strength of the photoelectric conversion device 1 is improved.

The photoelectric conversion layer 13 includes a p-type organic semiconductor 13A connected to the first conductive wire 121 and an n-type organic semiconductor 13B connected to the second conductive wire 122. The p-type organic semiconductor 13A and the n-type organic semiconductor 13B are bonded at the contact interface to form a pn junction. It is preferable that the photoelectric conversion layer 13 is rich in flexibility.

The p-type organic semiconductor 13A is made of a hole transport material. Examples of the hole transport material include aromatic amine, thiophene, phenylene-vinylene, thienylene-vinylene, carbazole, vinylcarbazole, pyrrole, acetylene, phthalocyanine, acene, porphyrin, derivatives, complexes, oligomers, and polymers thereof. Among these, known organic compounds having electron acceptability that can be used as organic semiconductors can be used.

The n-type organic semiconductor 13B is made of an electron transport material. Examples of the electron transport material include silole, fullerene, carbon nanotube, perylene, naphthalene, pyridine, phthalocyanine, quinoline, oxadiazole, triazole, distyrylarylene, derivatives, complexes, oligomers, and polymers thereof. Any known organic compound having an electron donating property that can be used as an organic semiconductor can be used.

These p-type organic semiconductor 13A and n-type organic semiconductor 13B can be selected by combining those having the highest possible photoelectric conversion efficiency. The thickness of the photoelectric conversion layer 13 is not particularly limited, but may be 1.2 to 2.0 times the wire diameter of the conductive wire 120, for example.

In such a photoelectric conversion device 1, since the first conductive wire 121, the second conductive wire 122, and the photoelectric conversion layer 13 have flexibility, the photoelectric conversion device 1 has sufficient flexibility. Therefore, it can arrange | position freely along the surface which consists of a plane of the base material 11 or a curved surface.

Next, a method for manufacturing such a photoelectric conversion device 1 by the manufacturing method of this embodiment will be described with reference to FIGS.
In this embodiment, an electrode preparation process for preparing the electrode structure 12, a material-containing liquid adjustment process for preparing a material-containing liquid 130 containing a hole transport material or an electron transport material, a hole transport material or an electron transport material The photoelectric conversion device 1 is manufactured by a manufacturing method including a material adhering step for adhering to the electrode structure 12 and a semiconductor forming step for forming an organic semiconductor.

In the electrode preparation step, as shown in FIG. 12, an electrode structure 12 for preparing a photoelectric conversion device in which a plurality of conductive wires 120 are integrally connected together with the arrangement adjusting wire 15 is prepared. This electrode structure 12 may be prepared in advance.
The electrode structure 12 of this embodiment includes a plurality of vertical wires 12A having the plurality of conductive wires 120 and the arrangement adjusting wires 15 as described above, and a plurality of horizontal wires 12B intersecting the vertical wires 12A. By crossing these, it is a net made of plain weave.

The conductive wire 120 and the arrangement adjusting wire 15 of the vertical wire 12A are alternately arranged in substantially the same direction. The number of the conductive wires 120 and the number of the arrangement adjusting wires 15 that are alternately arranged may be repeated by arranging one or both of them in plurality, but here, each of them is repeatedly arranged one by one. The number or the like of the arrangement adjusting wires 15 arranged between the conductive wires 120 is preferably set according to the arrangement interval of the first conductive wires 121 and the second conductive wires 122 obtained after manufacture. It is preferable that the interval between the adjacent vertical wire rods 12A and the interval between the conductive wire rods 120 are adjusted to a suitably set range.

The conductive wire 120 of the vertical wire 12A is as described above, but the hole transport material contained in the material-containing liquid 130 is attached to a part of the conductive wire 120 that becomes the first conductive wire 121 of the vertical wire 12A. The material may be selected so as to be easy and surface treatment may be performed. In addition, a material may be selected or a surface treatment may be performed on the other conductive wire 120 that becomes the second conductive wire 122 so that the electron transport material contained in the material-containing liquid 130 is easily attached. .

For example, by selecting the surface material of the conductive wire 120 constituting the first conductive wire 121 and the surface material of the conductive wire 120 constituting the second conductive wire 122 in a combination that causes a potential difference such as tin and copper. The p-type organic semiconductor 13A or the n-type organic semiconductor 13B may be controlled to be generated as crystals or molecules on the surface of each conductive wire 120.

The arrangement adjusting wire 15 of the vertical wire 12A is made of a material that can be dissolved by the material-containing liquid 130 described later, and can be dissolved by a solvent selected according to the hole transport material and the electron transport material. The arrangement adjusting wire 15 may be an insulating resin wire. Although not particularly limited, for example, a wire such as an acrylic resin or a vinyl resin may be used.
If the thickness of the arrangement adjusting wire 15 is excessively large, the solubility is lowered or the interval between the conductive wires 120 is widened. On the other hand, if the thickness is excessively thin, it is difficult to secure the interval between the conductive wires 120. For example, the thickness of the wire 15 may be 0.5 to 1.0 times the wire diameter of the conductive wire 120.

The horizontal wire 12B may be simply arranged in a direction intersecting with the conductive wire 120 and the arrangement adjusting wire 15, but here, the horizontal wire 12B is arranged so as to intersect with the conductive wire 120 and the arrangement adjusting wire 15 up and down at predetermined intervals. ing.
The horizontal wire 12B is made of an insulating wire different from the arrangement adjusting wire 15, and is dissolved in a material-containing liquid 130 described later, that is, a solvent used according to the hole transport material and the electron transport material used. The material is made of a material that is lower than the arrangement adjusting wire 15. Although not particularly limited, for example, a wire such as polyester such as PET may be used.

By integrating the vertical wire 12A together with the horizontal wire 12B, the conductive wire 120 can be held apart with the arrangement adjusting wire 15 interposed between the conductive wires 120. And can be placed stably with a gap.

In the material-containing liquid adjustment step, the material-containing liquid 130 is prepared by containing at least one of the hole transport material and the electron transport material as described above in the solvent. The material-containing liquid 130 needs to be prepared according to the material adhesion process. For example, the material-containing liquid 130 is separately brought into contact with the first conductive wire 121 and the second conductive wire 122 to form the p-type organic semiconductor 13A and the n-type semiconductor. When forming the organic semiconductor 13B, the material containing liquid 130 containing a hole transport material and the material containing liquid 130 containing an electron transport material are prepared separately. Here, the material-containing liquid 130 is prepared by including both transport materials in a solvent.

The hole transport material may be a precursor of an organic compound having an electron acceptability that can be used as an organic semiconductor in addition to the above-described materials, and the electron transport material may be an organic semiconductor other than the above-described materials. The precursor of the organic compound which has the electron-donating property which can be used as these may be sufficient. In the case of using a precursor, a desired compound may be generated by appropriately reacting in the subsequent steps.

The solvent for producing a photoelectric conversion device used for the material-containing liquid 130 may be a solvent in which a hole transport material or an electron transport material is dispersed, but a soluble solvent is preferable, and a volatile solvent. There may be. This solvent needs to be able to dissolve the wire 15 for adjusting the arrangement of the electrode structure 12 and preferably not to dissolve the horizontal wire 12B.

As such a solvent, as long as the solubility in the arrangement adjusting wire 15 and the horizontal wire 12B can be ensured, a solvent usually used when forming an organic semiconductor using each hole transport material or each electron transport material is used. it can. In the present embodiment, for example, toluene, xylene, acetic acid or the like is used. This material-containing liquid 130 may further contain components such as an additive such as dicarboxylic acid for controlling orientation and a binder such as methacrylic acid for maintaining strength.

In the material adhesion step, the material-containing liquid 130 is brought into contact with the electrode structure 12 to dissolve the arrangement adjusting wire 15, and the hole transport material and the electron transport material in the material-containing liquid 130 are removed from the electrode structure 12. It adheres to the conductive wire 120.
In the case of using the material-containing liquid 130 in which the hole transport material is dissolved and the material-containing liquid 130 in which the electron transport material is dissolved, each is sequentially brought into contact with part or all of the electrode structure 12 to dissolve both the transport materials. When the material-containing liquid 130 is used, it may be contacted at once.
The method of bringing the material-containing liquid 130 into contact with the electrode structure 12 and attaching the hole transport material or the electron transport material to the conductive wire 120 is not particularly limited. For example, the material-containing liquid 130 may be applied to the electrode structure 12 or may be printed by an inkjet printer, or the electrode structure 12 may be immersed in the material-containing liquid 130 and dipped.

In this embodiment, the material-containing liquid 130 containing both transport materials is brought into contact with one side of the electrode structure 12. First, the electrode structure 12 is placed on the substrate 11 as shown in FIG. 13 (a), and the material-containing liquid 130 is brought into contact as shown in FIG. 13 (b). As shown in FIG. 13 (c), The arrangement adjusting wire 15 is dissolved by the solvent in the material-containing liquid 130.
The dissolved components of the arrangement adjusting wire 15 may be dispersed and left in the material-containing liquid 130 or may be replaced by the material-containing liquid 130 and removed. Here, the components of the arrangement adjusting wire 15 are dissolved in the material and arranged in this material.
As a result, the material-containing liquid 130 is disposed in the portion where the arrangement adjusting wire 15 has been disposed, and the hole transport material and the electron transport material of the material-containing liquid 130 are equivalent to other portions between and in the vicinity of the conductive wire 120. Be placed. Then, the hole transport material and the electron transport material adhere to the conductive wire 120 of the first conductive wire 121 and the conductive wire 120 of the second conductive wire 122, respectively.

In the semiconductor formation step, as shown in FIG. 13C, a p-type organic semiconductor 13A is formed from a hole transport material or an electron transport material adhered to each conductive wire 120 of the electrode structure 12 together with the material-containing liquid 130. The n-type organic semiconductor 13 </ b> B is formed in a state where it is connected to the other part of the conductive wire 120.

In order to form the organic semiconductors 13A and 13B from the material-containing liquid 130, the solvent in the material-containing liquid 130 may be volatilized and dried, and after drying, heat treatment, annealing treatment, or the like may be performed. . Such processing can be performed at a relatively low temperature.
When a precursor is used as a hole transport material or an electron transport material, the precursor is converted into a hole transport material or an electron transport material by a treatment after drying, and the organic semiconductor 13A is connected to the conductive wire 120 while being connected to the conductive wire 120. , 13B can be formed. Even when the hole transport material or the electron transport material itself is used, it is possible to improve the photoelectric conversion performance of the obtained photoelectric conversion device 1 by performing a heat treatment or an annealing treatment after drying. is there.

Thereafter, as shown in FIG. 13D, the protective layer 14 is laminated on the entire surface of the photoelectric conversion layer 13. For the protective layer 14, a material such as a transparent resin that can transmit light received and emitted by the photoelectric conversion layer 13 can be used.
Thereby, manufacture of the photoelectric conversion device 1 is completed.

Next, the effect in the manufacturing method of the above-mentioned photoelectric conversion device 1 is demonstrated.
According to this manufacturing method, since the electrode structure 12 integrates the plurality of conductive wires 120 together with the arrangement adjusting wire 15, even the flexible conductive wire 120 can be easily arranged. In addition, by adjusting the number, shape, arrangement, etc. of the arrangement adjusting wire 15, the arrangement, shape, density, etc. of each conductive wire 120 can be adjusted to easily adjust the arrangement interval of the conductive wire 120, and the state Can be easily and stably maintained during production. In particular, by arranging the arrangement adjusting wire 15 between the conductive wires 120, the electrode structures 12 are formed by accurately separating the conductive wires 120 from each other at a predetermined interval, so that each conductive wire 120 is stabilized at a desired interval. Can be arranged. Therefore, it is possible to prevent variation in the arrangement interval of the plurality of conductive wires 120 and ensure the performance of photoelectric conversion.

In addition, since the arrangement adjusting wire 15 is dissolved by bringing the material containing liquid 130 into contact with the electrode structure 12, the hole transport material or the electron transport of the material containing liquid 130 is disposed at the portion where the arrangement adjusting wire 15 is arranged. Material can be placed. Therefore, more organic semiconductors 13A and 13B can be disposed uniformly between the conductive wires 120, and the performance of photoelectric conversion can be ensured.
Therefore, it is possible to easily manufacture the photoelectric conversion device 1 having flexibility while ensuring the performance of photoelectric conversion.

An electrode structure 12 made of a net comprising a plurality of vertical wires 12A made up of a plurality of conductive wires 120 and arrangement adjusting wires 15 and a plurality of horizontal wires 12B arranged crossing the plurality of vertical wires 12A is prepared. Since the material-containing liquid 130 was prepared using a solvent capable of dissolving the arrangement adjusting wire 15 and not dissolving the horizontal wire 12B, the horizontal wire 12B is left on the photoelectric conversion layer 13 after the arrangement adjusting wire 15 is dissolved. Even if it is deformed during use, the photoelectric conversion layer 13 is not easily damaged, the durability of the photoelectric conversion device 1 can be improved, and the interval between the conductive wire members 120 can be maintained.

A material-containing liquid 130 containing a hole transport material and an electron transport material is prepared, and the p-type organic semiconductor 13A is formed in a state of being connected to a part of the conductive wire 120 using the material-containing liquid 130. Since the organic semiconductor 13B is formed in a state where it is connected to the other conductive wire 120, the p-type organic semiconductor 13A and the n-type organic semiconductor 13B can be formed at the same time, which is easier to manufacture.

Since the photoelectric conversion layer 13 having the organic semiconductors 13A and 13B is formed by adhering the material-containing liquid 130 to one side of the electrode structure 12, in the obtained photoelectric conversion device 1, the first conductive wire 121 and the second conductive wire are formed. 122 is arrange | positioned only at the one surface side of the photoelectric converting layer 13, and is not arrange | positioned at the other surface side. Therefore, if the other surface side is used as the light receiving surface, the performance of photoelectric conversion can be improved.

In addition, this 6th Embodiment can be suitably changed within the scope of the present invention.
For example, in the sixth embodiment, the example in which the material-containing liquid 130 is attached to one surface side of the electrode structure 12 has been described. However, as shown in FIG. The first conductive wire 121 and the second conductive wire 122 may be embedded in the photoelectric conversion layer 13, or the protective layer 14 may be provided on both sides of the photoelectric conversion layer 13. In the photoelectric conversion device 1 manufactured as described above, both surfaces can be used as light receiving and emitting surfaces.
In the sixth embodiment, an example in which the horizontal wire 12B is arranged as the electrode structure 12 has been described. However, if the conductive wire 120 and the arrangement adjusting wire 15 can be integrated and arranged at a predetermined position, the horizontal wire 12B can be arranged in a predetermined position. The wire 12B may not be used.
In the sixth embodiment, one electrode structure 12 is embedded in one photoelectric conversion layer 13, but a plurality of electrode structures 12 may be embedded in the same photoelectric conversion layer 13, A plurality of photoelectric conversion layers 13 may be stacked, and one or a plurality of electrode structures 12 may be embedded in each.

In the sixth embodiment, the example in which the horizontal wire 12B and the support wire 320 cannot be dissolved is described as the solvent. However, the present invention may be used even if a solvent capable of dissolving the horizontal wire 12B and the support wire 320 is used. It is possible to apply
In the said 6th Embodiment, although the example which melt | dissolved the arrangement | positioning adjustment wire 15 completely was demonstrated, even if the arrangement adjustment wire 15 partially remained after melt | dissolution, the above effects are according to the amount of melt | dissolution. Therefore, the present invention can be applied.

[First Embodiment]
1: Photoelectric conversion device 11: Base material 12: Electrode 12A for photoelectric conversion device: Vertical wire 12B: Horizontal wire 121: First conductive wire 122: Second conductive wire 123: First insulating wire 13A: Organic semiconductor of p layer 13B: n-layer organic semiconductor 14: protective layer 19

[Second to fifth embodiments]
1: Light-emitting device 2, 2A, 2B, 2C, 2D: Light-emitting unit 3: Control unit 4: Connection unit 5: One wiring unit 6: The other wiring unit 11: Substrate 12: Alternating electrode 121: One conductive Wire 122: Other conductive wire 13: Light emitting layer 14: Protective layer 15: Arrangement adjusting wire 16: Crossing wire 18: Color filter

[Sixth Embodiment]
1: Photoelectric conversion device 12: Electrode structure 121: p-type electrode 122: n-type electrode 12A: vertical wire 12B: horizontal wire 120: conductive wire 7: bus bar 15: arrangement adjusting wire 13: photoelectric conversion layer 13A: p-type Organic semiconductor 13B: n-type organic semiconductor 130: material-containing liquid 14: protective layer 11: base material 20: photoelectric conversion device 22: electrode structure 230: electrode part 320: support wire

Claims (17)

1. A material-containing liquid containing at least one of a hole transport material and an electron transport material in a solvent is attached to the electrode structure, and an organic semiconductor is removed from the material attached to the electrode structure. In the manufacturing method of the photoelectric conversion device formed in a state in contact with
   Preparing the electrode structure in which a plurality of conductive wires are integrally connected together with an arrangement adjusting wire for adjusting the arrangement interval of the conductive wires;
   Prepare the material-containing liquid using the solvent that can dissolve the arrangement adjustment wire,
   A method for producing a photoelectric conversion device, wherein the material-containing liquid is brought into contact with the electrode structure to dissolve the arrangement adjusting wire and to attach the at least one material to the conductive wire to form the organic semiconductor. .
2. The method for manufacturing a photoelectric conversion device according to claim 1, wherein the electrode structure is prepared by interposing the arrangement adjusting wire between the conductive wires so that the conductive wires are separated from each other at a predetermined interval.
3. Preparing the electrode structure including a plurality of vertical wires made of the plurality of conductive wires and the arrangement adjusting wire, and a plurality of horizontal wires arranged crossing the plurality of vertical wires;
   The method for producing a photoelectric conversion device according to claim 1, wherein the material-containing liquid is prepared using the solvent capable of dissolving the arrangement adjusting wire and not dissolving the horizontal wire.
4. The material-containing liquid containing the hole transport material and the electron transport material is prepared and brought into contact with the electrode structure, and a p-type organic semiconductor is formed in a state of being connected to some of the conductive wires and n-type The manufacturing method of the photoelectric conversion device of Claim 1 formed in the state which connected the organic semiconductor to the said electrically conductive wire of another part.
5. The method for producing a photoelectric conversion device according to claim 1, wherein the material-containing liquid is attached to one side of the electrode structure.
6. The plurality of conductive wires have a plurality of electrode portions integrated with the arrangement adjusting wire, and prepare the electrode structure supported by a support wire in a state in which the plurality of electrode portions are arranged to face each other.
   The method for producing a photoelectric conversion device according to claim 1, wherein the material-containing liquid is prepared using the solvent capable of dissolving the arrangement adjusting wire and not dissolving the support wire.
7. The method for producing a photoelectric conversion device according to any one of claims 1 to 6, wherein the photoelectric conversion device is an organic semiconductor thin film solar cell.
8. An electrode structure for producing a photoelectric conversion device in which a plurality of conductive wires are integrated with an arrangement adjusting wire, and the solubility of the arrangement adjusting wire in a solvent for producing a photoelectric conversion device is larger than that of the conductive material. Electrode for producing a conversion device.
9. An electrode provided on one side of a photoelectric conversion layer that converts light and electrical energy,
   A plurality of vertical wires, and a plurality of horizontal wires,
   The vertical wire and the horizontal wire intersect each other to form a net,
   The vertical wire is composed of a plurality of first conductive wires, a plurality of second conductive wires, and a plurality of first insulating wires,
   The first conductive wire and the second conductive wire are alternately arranged, and the first insulating wire is provided between the first conductive wire and the second conductive wire,
   The horizontal wire is made of a second insulating wire,
   The electrode for a photoelectric conversion device, wherein the first conductive wire functions as a p-type electrode and the second conductive wire functions as an n-type electrode.
10. 10. The electrode for a photoelectric conversion device according to claim 9, wherein a plurality of the first insulating wire is provided between the first conductive wire and the second conductive wire.
11. A photoelectric conversion device comprising a photoelectric conversion layer for converting light and electric energy, and a pair of electrodes provided on one side of the photoelectric conversion layer,
    One electrode and the other electrode are provided side by side,
    A p-layer organic semiconductor made of a hole transport material is provided on the one electrode,
    An n-layer organic semiconductor made of an electron transport material is provided on the other electrode,
    The photoelectric conversion device, wherein the one electrode functions as a p-type electrode and the other electrode functions as an n-type electrode.
12. The photoelectric conversion device according to claim 11, wherein the organic semiconductor of the p layer and the organic semiconductor of the n layer are covered with a transparent protective layer.
13. A light emitting layer made of an organic EL material;
    An alternately arranged electrode configured by alternately arranging one conductive wire and the other conductive wire provided in the light emitting layer;
    A light emitting device comprising:
14. Between the one conductive wire and the other conductive wire, an arrangement adjusting wire extending in the same direction is provided,
    The light emitting device according to claim 13, wherein the arrangement adjusting wire maintains an interval between the one conductive wire and the other conductive wire.
15. A crossing wire extends in a direction crossing the one conductive wire and the other conductive wire,
    The wire for crossing, the one conductive wire and the other conductive wire are knitted,
    The light emitting device according to claim 13.
16. The crossing wire extends in a direction crossing the one conductive wire, the other conductive wire and the arrangement adjusting wire,
    The light emitting device according to claim 14, wherein the crossing wire, the one conductive wire, the other conductive wire, and the arrangement adjusting wire are knitted.
17. One wiring portion that connects one end of the one conductive wire to each other, and the other wiring portion that connects the other end of the other conductive wire to each other,
    The light emitting device according to claim 13, wherein the light emitting layer emits light when a voltage is applied to the one wiring portion and the other wiring portion.

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