JP2012199273A - Method and device for manufacturing organic thin-film solar battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique capable of manufacturing an organic thin-film solar battery with an improved yield at a low cost.SOLUTION: A hole transport layer is formed by applying a first solution onto a substrate 16 to which a transparent electrode is added using a die 13A including a shim 17A having an ejection width LA. A power generation layer is formed by applying a second solution onto the hole transport layer using a die 13B including a shim 17B having an ejection width LB smaller than the ejection width LA. An electron transport layer is formed by applying a third solution onto the power generation layer using a die 13C including a shim 17C having an ejection width LC smaller than the ejection width LB.

Description

  The present invention relates to a method for manufacturing an organic thin film solar cell and a manufacturing apparatus therefor, and particularly to a technique effective when applied to the manufacture of an organic thin film solar cell using an intermittent slit coating method.

  In recent years, organic thin-film solar cells have attracted attention as next-generation solar cells. Organic thin-film solar cells can be reduced in weight, thickness, or flexibility as compared with silicon-based solar cells, and have an advantage that they can be used for various new applications.

  As a method for forming each organic layer constituting the organic thin film solar cell, for example, a spin coating method, an ink jet method, a printing method, a metal vapor deposition method, or the like has been studied.

  However, the spin coating method is suitable for manufacturing a pattern with a small area such as that used for a pixel of a display device, but is not suitable for G6 (1500 mm × 1850 mm) size solid coating used for a solar cell. . Furthermore, the spin coating method has low material use efficiency, and most of the material is discarded without being reused. The ink jet method is also suitable for manufacturing a small area and high-definition pattern, but is not suitable for G6 size solid coating. Examples of the printing method include offset printing, gravure printing, flexographic printing, and screen printing. However, these printing methods are also suitable for the production of high-definition patterns, but are not suitable for G6 size solid coating. In addition, the metal vapor deposition method is not suitable for an organic material having low heat resistance because the atmosphere becomes high temperature. Furthermore, since the metal vapor deposition method is a vacuum technique, a vapor deposition apparatus that can apply the G6 size becomes expensive.

  Therefore, various printing processes or coating processes have been proposed as a method for efficiently forming an organic layer having a uniform thickness over a wide range.

  For example, International Patent Publication WO 09/057464 (Patent Document 1) discloses a coating method in which a multilayer coating film is formed by coating a plurality of coating liquids on a long support. A coating method is described in which a plurality of coating means are disposed at positions facing a backup roll with a body interposed therebetween, and a plurality of coating liquids are coated on a support by the coating means.

  JP 2010-251303 A (Patent Document 2) discloses a coating method in which a coating liquid is applied to an object to be coated disposed above a nozzle that discharges the coating liquid upward. In a state where the coating liquid discharged from the nozzle is in contact with the body to be coated, in a state where the nozzle and the body to be coated are relatively moved in a predetermined coating direction, and in a state where the coating liquid is separated from the body to be coated And a non-application process in which the nozzle and the object to be applied are moved relative to each other in the application direction, and using the nozzle having a plurality of slit-like discharge ports, the two processes of the application process and the non-application process are alternately performed. A repeated application method is described.

International Patent Publication WO 09/057464 Pamphlet JP 2010-251303 A

  As shown in FIG. 35, the organic thin film solar cell includes, for example, a hole transport layer 53, a bulk hetero layer (pn mixed layer (i layer)) 54, an electron transport layer on a substrate 51 with a transparent electrode 52. 55 and a metal electrode 56 are sequentially stacked.

  When the organic thin film solar cell is irradiated with light, a pair of holes and electrons called excitons is generated in the p-type semiconductor material constituting the bulk hetero layer (i layer) 54. The generated excitons move to the interface between the p-type semiconductor material and the n-type semiconductor material, and holes and electrons are separated due to the energy difference between the interfaces. Holes flow to the anode through the p-type semiconductor material, and electrons flow to the cathode through the n-type semiconductor material. When these electrodes are connected, a current flows. The hole transport layer 53 and the electron transport layer 55 are provided to separate holes and electrons so that the holes and electrons do not recombine and do not return to excitons.

  Further, in order to increase the efficiency of the organic thin film solar cell, after holes and electrons are separated at the interface between the p-type semiconductor material and the n-type semiconductor material, the holes move quickly to the anode without recombination. Thus, it is also necessary that the electrons move quickly to the cathode without recombination.

  36, a p-type organic semiconductor 54p is provided between the hole transport layer 53 and the bulk hetero layer (i layer) 54i, and an n-type organic semiconductor is provided between the bulk hetero layer 54i and the electron transport layer 55. There is also an organic thin film solar cell having a pin structure (p layer-i layer-n layer) provided with 54n.

  Furthermore, as shown in FIG. 37, an interlayer layer 57 may be provided between the hole transport layer 53 and the p-type organic semiconductor 54p, whereby an organic thin-film solar cell made of strongly acidic PEDOT: PSS The effect that deterioration can be prevented is acquired.

  As described above, as shown in FIGS. 35 to 37, the organic thin-film solar cell is configured by overlapping a plurality of organic layers. Therefore, when manufacturing an organic thin-film solar cell, each organic layer is laminated | stacked one by one on the board | substrate which attached the transparent electrode. However, if each organic layer is sequentially stacked on the substrate by using a printing process or a coating process, either side of the multilayer structure in which a plurality of organic layers are laminated from the viewpoint of printing accuracy or coating accuracy. In some cases, the organic layer has a defective shape, and layers that should not be in contact with each other, for example, a bulk hetero layer and a transparent electrode or a metal electrode, or a hole transport layer and an electron transport layer may contact each other. When layers that should not be in contact with each other, the movement of holes and electrons is hindered so that no current flows, and the organic thin film solar cell does not function. Therefore, the defective shape of the organic layer on the side surface of the multilayer structure in which a plurality of organic layers are laminated becomes a factor that causes a decrease in product manufacturing yield.

  After stacking each organic layer sequentially on the substrate, there is a method of cutting the side surfaces of the multilayer structure using, for example, laser scribing to prevent contact between layers that should not be contacted. There are problems such as the inability to manufacture solar cells at low cost.

  The objective of this invention is providing the technique which can manufacture an organic thin-film solar cell with a sufficient yield and low cost.

  The above and other objects and novel features of the present invention will be apparent from the description of this specification and the accompanying drawings.

  Of the inventions disclosed in this application, an embodiment of a representative one will be briefly described as follows.

  In this embodiment, a first die having a first shim having a first discharge width is provided on a substrate provided with a transparent electrode while the substrate and the first slit coater are moved relative to each other. The first solution is applied to form the hole transport layer, and the second slit coater is provided on the hole transport layer while the substrate and the second slit coater are moved relative to each other. The step of applying the second solution using the second die having the second shim having the second discharge width narrower than the width to form the power generation layer and the power generation layer while relatively moving the substrate and the third slit coater. A step of forming an electron transport layer by applying a third solution using a third die having a third shim having a third discharge width narrower than the second discharge width provided in the third slit coater; While moving the substrate and the fourth slit coater relative to each other, Applying a fourth solution on a layer using a fourth die having a fourth shim having a fourth discharge width narrower than the third discharge width and provided in a fourth slit coater; and forming a metal electrode; A method of manufacturing an organic thin film solar cell including: both end faces of the power generation layer are located on the inner side than both end faces of the hole transport layer in a direction perpendicular to the traveling direction of the substrate, and more than both end faces of the power generation layer Both end faces of the electron transport layer are located inside, and both end faces of the metal electrode are located inside than both end faces of the electron transport layer.

  In addition, this embodiment includes a plurality of slit coaters sequentially arranged in the running direction of the substrate placed on the fixed table, and a slit-like discharge port that is provided in each of the plurality of slit coaters and discharges the solution. An organic thin-film solar cell manufacturing apparatus including a plurality of dies and a plurality of shims provided on each of the dies and defining a discharge width of the solution, wherein the substrate and the plurality of slit coaters are relative to the traveling direction of the substrate. It moves, and the discharge width of each of the plurality of shims becomes narrower in order as it becomes a subsequent shim.

  Among the inventions disclosed in the present application, effects obtained by one embodiment of a representative one will be briefly described as follows.

  Organic thin-film solar cells can be manufactured with good yield and at low cost.

It is principal part sectional drawing which shows an example of the specific structure of the organic thin-film solar cell by Embodiment 1 of this invention. It is the schematic block diagram seen from the side surface of the coating part of the apparatus which coats an organic layer by the intermittent slit coat method by Embodiment 1 of this invention. It is a schematic block diagram seen from the upper surface of the coating part of the apparatus which coats an organic layer with the intermittent slit coat method by Embodiment 1 of this invention. It is a schematic block diagram of the control part of the apparatus which coats an organic layer by the intermittent slit coat method by Embodiment 1 of this invention. It is a schematic block diagram of the solution supply part of the apparatus which coats an organic layer with the intermittent slit coat method by Embodiment 1 of this invention. It is process drawing explaining the manufacturing process of the organic thin film solar cell by Embodiment 1 of this invention. It is a principal part perspective view in the manufacturing process (process P100) of the organic thin film solar cell explaining the manufacturing method of the organic thin film solar cell by Embodiment 1 of this invention. It is a principal part perspective view of the same location as FIG. 7 in the manufacturing process (process P101) of an organic thin film solar cell following FIG. It is a principal part perspective view of the same location as FIG. 7 in the manufacturing process (process P102) of an organic thin-film solar cell following FIG. It is a principal part perspective view which expands and shows the die | dye by Embodiment 1 of this invention. It is a principal part perspective view of the same location as FIG. 7 in the manufacturing process (process P103) of an organic thin film solar cell following FIG. It is a principal part perspective view of the same location as FIG. 7 in the manufacturing process (process P104) of an organic thin film solar cell following FIG. It is a principal part perspective view of the same location as FIG. 7 in the manufacturing process (process P105) of an organic thin film solar cell following FIG. It is a principal part perspective view of the same location as FIG. 7 in the manufacturing process (process P106) of an organic thin-film solar cell following FIG. It is a schematic block diagram explaining the operation | movement of the intermittent slit coater in the manufacturing process (process P102) of the organic thin film solar cell by Embodiment 1 of this invention. It is a schematic block diagram explaining operation | movement of the intermittent slit coater in the manufacturing process (process P103) of the organic thin-film solar cell by Embodiment 1 of this invention. It is a schematic block diagram explaining operation | movement of the intermittent slit coater in the manufacturing process (process P105) of the organic thin-film solar cell by Embodiment 1 of this invention. It is a schematic block diagram explaining the operation | movement of the intermittent slit coater in the manufacturing process of the organic thin-film solar cell by Embodiment 1 of this invention. It is a schematic block diagram explaining the operation | movement of the intermittent slit coater in the manufacturing process (process P106) of the organic thin-film solar cell by Embodiment 1 of this invention. It is a principal part perspective view of the same location as FIG. 7 in the manufacturing process (process P107) of an organic thin film solar cell following FIG. It is principal part sectional drawing which shows an example of the specific structure of the organic thin-film solar cell by Embodiment 2 of this invention. It is process drawing explaining the manufacturing process of the organic thin film solar cell by Embodiment 2 of this invention. It is a principal part perspective view in the manufacturing process (process P200) of the organic thin film solar cell explaining the manufacturing method of the organic thin film solar cell by Embodiment 2 of this invention. It is a principal part perspective view of the same location as FIG. 23 in the manufacturing process (process P201) of an organic thin film solar cell following FIG. It is a principal part perspective view of the same location as FIG. 23 in the manufacturing process (process P202) of an organic thin-film solar cell following FIG. It is a principal part perspective view of the same location as FIG. 23 in the manufacturing process (process P203) of an organic thin film solar cell following FIG. It is a principal part perspective view of the same location as FIG. 23 in the manufacturing process (process P204) of an organic thin film solar cell following FIG. It is a principal part perspective view of the same location as FIG. 23 in the manufacturing process (process P205) of an organic thin film solar cell following FIG. It is a principal part perspective view of the same location as FIG. 23 in the manufacturing process (process P206) of an organic thin film solar cell following FIG. It is a principal part perspective view of the same location as FIG. 23 in the manufacturing process (process P207) of an organic thin-film solar cell following FIG. It is a principal part perspective view of the same location as FIG. 23 in the manufacturing process (process P208) of an organic thin film solar cell following FIG. It is a principal part perspective view of the same location as FIG. 23 in the manufacturing process (process P209) of an organic thin film solar cell following FIG. It is a principal part perspective view of the same location as FIG. 23 in the manufacturing process (process P210) of an organic thin-film solar cell following FIG. It is a principal part perspective view of the same location as FIG. 23 in the manufacturing process (process P211) of an organic thin film solar cell following FIG. It is principal part sectional drawing which shows an example of the basic structure of the organic thin-film solar cell examined by this inventor. It is principal part sectional drawing which shows the other example of the basic structure of the organic thin-film solar cell examined by this inventor. It is principal part sectional drawing which shows the other example of the basic structure of the organic thin-film solar cell examined by this inventor.

  In the following embodiments, when necessary for the sake of convenience, the description will be divided into a plurality of sections or embodiments. However, unless otherwise specified, they are not irrelevant to each other, and one is the other. There are some or all of the modifications, details, supplementary explanations, and the like.

  Further, in the following embodiments, when referring to the number of elements (including the number, numerical value, quantity, range, etc.), especially when clearly indicated and when clearly limited to a specific number in principle, etc. Except, it is not limited to the specific number, and may be more or less than the specific number. Further, in the following embodiments, the constituent elements (including element steps and the like) are not necessarily indispensable unless otherwise specified and apparently essential in principle. Needless to say. Similarly, in the following embodiments, when referring to the shapes, positional relationships, etc. of the components, etc., the shapes are substantially the same unless otherwise specified, or otherwise apparent in principle. And the like are included. The same applies to the above numerical values and ranges.

  Further, in the drawings used in the following embodiments, hatching may be added to make the drawings easy to see even if they are plan views. In all the drawings for explaining the following embodiments, components having the same function are denoted by the same reference numerals in principle, and repeated description thereof is omitted. Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  In the present application, the term “solution” includes not only a liquid but also a pasty solid as long as it is a material that can be applied.

(Embodiment 1)
An organic thin film solar cell manufacturing method and an organic thin film solar cell manufacturing apparatus using the intermittent slit coating method, which is a coating technique according to the first embodiment, will be described.

<Structure of organic thin film solar cell>
An example of a specific structure of the organic thin film solar cell according to the first embodiment will be described with reference to a cross-sectional view of the main part shown in FIG. Although the specific example of a structure of a preferable organic thin film solar cell is shown below, it is not limited to this.

  The organic thin-film solar cell according to the first embodiment includes a pair of electrodes (anode and cathode) and a plurality of stacked organic layers disposed between the pair of electrodes. And a hole transport layer provided on the anode side, an electron transport layer provided on the cathode side, and a power generation layer (i structure) sandwiched between the two.

On the substrate 1, a transparent electrode 2 which is an anode side electrode is formed. For the substrate 1, for example, glass or plastic is used, and for the transparent electrode 2, for example, SnO ₂ (tin oxide) is used.

  On the transparent electrode 2, a hole transport layer 3 made of, for example, PEDOT: PSS (poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate)) is formed. The hole transport layer 3 is provided to separate holes and electrons so that the holes and electrons after the separation do not recombine and return to excitons again. That is, the hole transport layer 3 has a function of selectively transmitting holes and improving hole injection efficiency.

  On the hole transport layer 3, a power generation layer 4 made of, for example, P3HT: PCBM (3-hexylthiophene: Phenyl-C61-Butyric Acid Methyl Ester) is formed. Here, a p-type semiconductor material and an n-type semiconductor material are mixed in the power generation layer 4 and a so-called bulk hetero layer having a micro-layer separation structure is used. However, the present invention is not limited to this. For example, a hetero layer in which a p-type semiconductor material and an n-type semiconductor material are stacked can be used.

  On the power generation layer 4, an electron transport layer 5 made of, for example, TiOx (titanium oxide) is formed. The electron transport layer 5 is provided to separate the holes and the electrons so that the holes and electrons after the separation do not recombine and return to excitons again. That is, the electron transport layer 5 has a function of selectively transmitting electrons and improving the electron injection efficiency.

  On the electron transport layer 5, a metal electrode 6 which is an electrode on the cathode side is formed. For example, Al (aluminum) or Ag (silver) is used for the metal electrode 6.

  An electron blocking layer having a function of blocking electron transport may be provided between the hole transport layer 3 and the power generation layer 4. Similarly, a hole blocking layer having a function of blocking hole transport may be provided between the power generation layer 4 and the electron transport layer 5.

  Furthermore, a hole injection layer having a function of improving the hole injection efficiency may be provided between the transparent electrode 2 and the hole transport layer 3. Similarly, an electron injection layer having a function of improving electron injection efficiency may be provided between the electron transport layer 5 and the metal electrode 6.

  However, it is possible to increase the efficiency of the organic thin film solar cell by superimposing such an electron blocking layer or a hole blocking layer, but the number of layers is small for manufacturing an inexpensive organic thin film solar cell. It is preferable.

<Configuration of manufacturing equipment>
An example of a manufacturing apparatus (apparatus for applying an organic layer by an intermittent slit coating method) for forming a plurality of organic layers included in the organic thin-film solar cell according to the first embodiment will be described with reference to FIGS. FIG. 2 is a schematic configuration diagram seen from the side of the coating part of an apparatus for applying an organic layer by the intermittent slit coating method, and FIG. 3 is an upper surface of the coating part of the apparatus for applying an organic layer by the intermittent slit coating method 4 is a schematic configuration diagram of a control unit of an apparatus for applying an organic layer by an intermittent slit coating method, and FIG. 5 is a solution supply unit of an apparatus for applying an organic layer by an intermittent slit coating method. FIG.

  2 and 3 are schematic configuration diagrams of an apparatus for applying an organic layer by an intermittent slit coating method (hereinafter referred to as an intermittent slit coater).

  The intermittent slit coater 10 mainly includes a fixed table (surface plate) 11 having a suction mechanism, slit coaters 12A, 12B, and 12C provided on the fixed table 11, guides 11a provided on the fixed table 11, and The control unit 15 includes dies 13A, 13B, and 13C provided in the slit coaters 12A, 12B, and 12C, cameras 14A, 14B, and 14C provided in the slit coaters 12A, 12B, and 12C, respectively. The intermittent slit coater 10 further includes a solution supply unit and the like.

  The slit coater 12A, the die 13A, and the camera 14A are, for example, equipment used to form the hole transport layer 3 described above. The slit coater 12B, the die 13B, and the camera 14B include, for example, the power generation layer 4 described above. The slit coater 12 </ b> C, the die 13 </ b> C, and the camera 14 </ b> C are, for example, facilities used to form the electron transport layer 5 described above.

  The intermittent slit coater 10 sucks the substrate 16 on the upper surface of the fixed table 11 having a suction mechanism, and sets a predetermined distance between the tips of the dies 13A, 13B, and 13C provided in the slit coaters 12A, 12B, and 12C and the upper surface of the substrate 16, respectively. This is an apparatus for forming an organic layer by applying the solution onto the substrate 16 while keeping the value and supplying the solution. The organic layer application step is performed in the air or in a nitrogen atmosphere.

  Here, three slit coaters 12A, 12B, and 12C are shown, but the present invention is not limited to this. When four or more slit coaters are required, for example, slit coaters for the number of organic layers necessary for the organic thin film solar cell are connected, or slit coaters for the number of organic layers necessary for the organic thin film solar cell are connected. It is added on the upper surface of the fixed table 11.

  The fixed table 11 reciprocates in the traveling direction (coating direction, X direction shown in FIGS. 2 and 3: first direction) by displacement driving means such as an electric motor or a hydraulic device. Accordingly, the substrate 16 placed on the fixed table 11 and the slit coaters 12A, 12B, and 12C can be relatively moved in the traveling direction (X direction) of the substrate 16, respectively.

  Before starting the application of the solution, the slit coater 12A is placed in the order of the slit coater 12B and the slit coater 12C so as to face the substrate 16 along the traveling direction (X direction) of the fixed table 11. . Each slit coater 12A, 12B, 12C is applied to each die 13A, 13B, 13C in the traveling direction (X direction), and each die 13A, 13B, 13C in the vertical direction (Z direction shown in FIGS. 2 and 3). The travel mechanism and the lifting mechanism are controlled by the control unit 15. By controlling the traveling mechanism and the lifting mechanism of each slit coater 12A, 12B, 12C, the thickness of the organic layer at the start of application of each die 13A, 13B, 13C, the thickness of the organic layer at the end of application, and application The starting position and the like are precisely controlled.

  The dies 13A, 13B, and 13C are provided along the discharge width direction (direction perpendicular to the running direction (X direction) and the vertical direction (Z direction), Y direction shown in FIGS. 2 and 3: second direction), respectively. It has a discharge port for discharging the slit-shaped solution. As will be described later with reference to FIG. 5, each die 13A, 13B, 13C is supplied with a solution from a solution tank, and excess solution not used for coating is supplied to each die 13A, 13B, 13C. The solution is returned to the solution tank through the provided suction port.

  Further, the dies 13A, 13B, and 13C have shims 17A, 17B, and 17C that define the discharge width of the solution along the discharge width direction (Y direction), respectively. The shape of each of the shims 17A, 17B, and 17C shown in FIG. 2 is the shape seen from the substrate 16 side shown in FIG. 2, and the shape extracted from the dies 13A, 13B, and 13C. The shim 17A has a solution discharge width LA along the discharge width direction (Y direction), and is sandwiched between the dies 13A. Similarly, the shim 17B has a solution discharge width LB along the discharge width direction (Y direction), and is sandwiched between the dies 13B. The shim 17C has a solution discharge direction along the discharge width direction (Y direction). It has a discharge width LC and is sandwiched between dies 13C. The thickness of each of the shims 17A, 17B, and 17C is appropriately adjusted according to the properties of the solution, the state of the solution, the thickness of the organic layer, and the like, and is, for example, about 0.01 to 1 mm.

  The discharge widths LA, LB, and LC of the respective solutions along the discharge width direction (Y direction) of each of the shims 17A, 17B, and 17C are sequentially narrowed as the subsequent shims are formed. That is, the discharge width LB of the shim 17B is narrower than the discharge width LA of the shim 17A, the discharge width LC of the shim 17C is narrower than the discharge width LB of the shim 17B, and the discharge width is set in the order of LA> LB> LC. Has been.

  Accordingly, the width in the discharge width direction (Y direction) of the organic layer applied using the shim 17B is narrower than the width in the discharge width direction (Y direction) of the organic layer applied using the shim 17A. The width in the discharge width direction (Y direction) of the organic layer coated using the shim 17C is narrower than the width in the discharge width direction (Y direction) of the organic layer applied using the same. Further, both end surfaces in the discharge width direction (Y direction) of the organic layer applied using the shim 17B are located on the inner side than both end surfaces in the discharge width direction (Y direction) of the organic layer applied using the shim 17A. The both end faces of the organic layer applied using the shim 17C in the discharge width direction (Y direction) are located on the inner side than the both end faces in the discharge width direction (Y direction) of the organic layer applied using the shim 17B. To do.

  The discharge width of the shim used for the application of the upper organic layer is set to be twice or less than the square root of the application accuracy than the discharge width of the shim used for the application of the lower organic layer. For example, if the coating accuracy is ± 0.5 mm, the discharge width LB of the shim 17B is shorter than the discharge width LA of the shim 17A by 1.0 mm or more, and the discharge width LC of the shim 17C is 1. Shorten it by 0 mm or more.

  Further, when the solution is discharged from each of the dies 13A, 13B, and 13C, the respective coating start positions (solution discharge start positions) PA, PB, and PC become the subsequent dies. And it is far from the traveling direction (X direction) of the board | substrate 16 shown with the code | symbol PFL in FIG. Further, the respective coating end positions EA, EB, EC are closer to the front end face PFL of the substrate 16 in order as the subsequent dies are formed. That is, the application start position PB of the die 13B is farther from the front end face PFL of the substrate 16 than the application start position PA of the die 13A, and the application start position PC of the die 13C is more than the front end face of the substrate 16 than the application start position PB of the die 13B. The application start positions are set so as to be PA, PB, and PC in order of distance from the PFL and closer to the front end face PFL of the substrate 16. Further, the coating end position EB of the die 13B is closer to the front end face PFL of the substrate 16 than the coating end position EA of the die 13A, and the coating end position EC of the die 13C is closer to the front end face of the substrate 16 than the coating end position EB of the die 13B. The application end positions are set so as to be EC, EB, and EA in the order close to the PFL and close to the front end face PFL of the substrate 16.

  Accordingly, the width in the running direction (X direction) of the organic layer applied using the die 13B is narrower than the width in the running direction (X direction) of the organic layer applied using the die 13A, and the die 13B is used. The width in the running direction (X direction) of the organic layer applied using the die 13C is narrower than the width in the running direction (X direction) of the applied organic layer. Furthermore, both end surfaces in the running direction (X direction) of the organic layer applied using the die 13B are located on the inner side than both end surfaces in the running direction (X direction) of the organic layer applied using the die 13A. Both end faces in the running direction (X direction) of the organic layer applied using the die 13C are located on the inner side than both end faces in the running direction (X direction) of the organic layer applied using the die 13B.

  The difference in the width in the running direction (X direction) between the upper organic layer and the lower organic layer in contact with the upper organic layer can be determined in consideration of coating accuracy. For example, if the coating accuracy is ± 0.5 mm, the traveling direction (X direction) of the organic layer formed using the die 13B is larger than the width in the traveling direction (X direction) of the organic layer formed using the die 13A. The width of the organic layer formed using the die 13C is shorter than the width of the organic layer formed using the die 13B in the traveling direction (X direction). Shorten 1.0 mm or more.

  Thus, when the organic layer laminated | stacked by the intermittent slit coater 10 by this Embodiment 1 is formed, the width | variety of the discharge width direction (Y direction) of an organic layer and the width | variety of a running direction (X direction) are the upper organic layers. Since the upper end faces (four end faces) are located on the inner side of the lower end faces (four end faces), each organic layer is laminated in a pyramid shape. Can do.

  FIG. 4 shows a schematic configuration diagram of the controller of the intermittent slit coater. Here, only one slit coater 12A and each equipment provided therein are described, and the description of the other slit coaters 12B and 12C is omitted, but is the same as the slit coater 12A.

  The slit coater 12A can move in the traveling direction (X direction) and in the vertical direction (Z direction). These movements are controlled by the control unit 15 via the driving unit 18 based on images obtained by the two cameras 14A. A distance (gap) G in the vertical direction (Z direction) between the discharge port 19 of the die 13A and the upper surface of the substrate 16 is controlled by a closed loop using a laser displacement measurement amount or the like.

  The fixed table 11 can move in the running direction (X direction), the discharge width direction (Y direction), and the θ direction (rotation direction). These movements are controlled by the control unit 15 via the drive unit 21 based on alignment marks (alignment marks indicated by reference numeral 20 in FIG. 3) provided on the substrate 16 obtained by the two cameras 14A. The After adjusting the position of the substrate 16 by moving the fixed table 11, the substrate 16 is attracted to the fixed table 11 and the warpage of the substrate 16 is corrected.

  In FIG. 5, the schematic block diagram of the solution supply part of an intermittent slit coater is shown. Here, only one die 13A is described, and descriptions of the other dies 13B and 13C are omitted, but are the same as the die 13A.

  The solution is supplied from the solution tank 22 to the die 13A via one of the three-way valves 23 via the pump P1. When no solution is supplied to the die 13A, the solution is returned to the solution tank 22 from the solution tank 22 via the pump P1, the other of the three-way valve 23, and further via the back pressure valve 24. When the application to the substrate 16 is completed, a solution suction operation is performed. In the suction operation, the solution is sucked into the pump P <b> 2 from the suction port of the die 13 </ b> A via the electromagnetic valve 25 and further returned to the solution tank 22.

<Method for producing organic thin-film solar cell>
An example of the manufacturing method of the organic thin-film solar cell by this Embodiment 1 is demonstrated sequentially using FIGS. FIG. 6 is a process diagram for explaining a manufacturing process of an organic thin film solar cell, and FIGS. 7 to 9, FIGS. 11 to 14, and FIG. FIG. 10 is an enlarged perspective view of the main part showing the die enlarged, and FIGS. 15 to 19 are schematic configuration views of the coating portion of the intermittent slit coater as seen from the side. Here, a plurality of organic layers and electrode layers included in the organic thin film solar cell are formed using the same apparatus as the intermittent slit coater 10 described above.

(Process P100) Transparent electrode patterning As shown in FIG. 7, the substrate 1 is prepared. For the substrate 1, for example, glass or plastic is used. On the substrate 1 is an electrode on the anode side, a transparent electrode 2 made of SnO ₂ is formed. In the first embodiment, SnO ₂ is used for the transparent electrode 2, but another transparent conductive film (for example, ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide)) is used. Also good.

  Next, the transparent electrode 2 is patterned to a predetermined size by the laser scribe 26.

(Process P101) Cleaning As shown in FIG. 8, solution cleaning is performed.

(Process P102) PEDOT: PSS formation As shown in FIG. 9, a PEDOT: PSS solution 3a is formed by applying a PEDOT: PSS solution on the transparent electrode 2 by an intermittent slit coat method using a die 13A. The concentration of the PEDOT: PSS solution is 1%, for example, and the coating thickness is 2 μm, for example.

  Further, as shown in FIG. 10, the shim 17Aa sandwiched between the dies 13A has a partition part HP in the middle of the discharge width direction (Y direction), and the two application areas are in the discharge width direction (Y direction). Formed. Each discharge width divided by the partition portion HP is the discharge width LA described above. Here, although one partition part HP was provided in shim 17Aa, the shim which does not provide a partition part, and the shim which provided two or more partition parts can also be used.

(Process P103) P3HT: PCBM formation As shown in FIG. 11, a P3HT: PCBM solution is applied on the PEDOT: PSS layer 3a by an intermittent slit coat method using a die 13B to form a P3HT: PCBM layer 4a. . The concentration of the P3HT: PCBM solution is, for example, 10%, and the coating thickness is, for example, 2 μm.

(Process P104) TiOx formation As shown in FIG. 12, a TiOx solution is apply | coated on the P3HT: PCBM layer 4a by the intermittent slit coat method using die | dye 13C, and the TiOx layer 5a is formed. The concentration of the TiOx solution is, for example, 1%, and the coating thickness is, for example, 2 μm.

(Process P105) Metal electrode formation As shown in FIG. 13, Al material or Ag material (solution or paste) is apply | coated on the TiOx layer 5a by the intermittent slit coat method using die | dye 13D, Al layer or Ag layer 6a is formed.

(Process P106) Annealing treatment As shown in FIG. 14, each organic layer (PEDOT: PSS layer 3a, P3HT: PCBM layer 4a, and TiOx layer 5a) and electrode layer (Al layer or Ag) laminated on the substrate 1 Layer 6a) is annealed to evaporate the solvent. For the annealing treatment, for example, stage heating or furnace body heating is used. The annealing temperature is, for example, 150 ° C., and the annealing time is, for example, 10 minutes. In addition, you may combine with the heating at the time of resin-sealing an organic thin-film solar cell, without performing annealing treatment here.

  In the above (process P102) to (process P106), using the above-described intermittent slit coater 10, each organic layer (PEDOT: PSS layer 3a, P3HT: PCBM layer 4a, and TiOx layer 5a) and electrode layer (Al layer or An Ag layer 6a) is formed. In the first embodiment, the electrode layer (Al layer or Ag layer 6a) is also formed by an intermittent slit coating method.

  The operation of each mechanism of the intermittent slit coater 10 in the above (process P102) to (process P106) will be described below with reference to FIGS.

  As shown in FIG. 15, after aligning the substrate 1 fixed on the fixed table 11, the substrate 1 is moved in the traveling direction (X direction). A transparent electrode 2 is formed on the substrate 1. While moving the slit coater 12A in the direction opposite to the direction in which the substrate 1 moves, the PEDOT: PSS solution is intermittently applied to the substrate 1 from the discharge port of the die 13A provided in the slit coater 12A. Thereby, the PEDOT: PSS layer 3 a is formed on the substrate 1.

  Next, as shown in FIG. 16, the P3HT: PCBM solution is intermittently applied to the substrate 1 from the discharge port of the die 13B provided in the slit coater 12B while moving the slit coater 12B in the direction opposite to the direction in which the substrate 1 moves. To do. Thereby, the P3HT: PCBM layer 4a is formed on the PEDOT: PSS layer 3a.

  Similarly, the TiOx solution is intermittently applied to the substrate 1 from the discharge port of the die 13C provided in the slit coater 12C while moving the slit coater 12C in the direction opposite to the direction in which the substrate 1 moves. Thereby, the TiOx layer 5a is formed on the P3HT: PCBM layer 4a.

  Next, as shown in FIG. 17, while the slit coater 12D is moved in the direction opposite to the direction in which the substrate 1 moves, an Al material or an Ag material is intermittently applied to the substrate 1 from the discharge port of the die 13D provided in the slit coater 12D. Apply. Thereby, an Al layer or an Ag layer 6a is formed on the TiOx layer 5a.

  Thereafter, as shown in FIG. 18, the substrate 1 on which each organic layer (PEDOT: PSS layer 3a, P3HT: PCBM layer 4a, and TiOx layer 5a) and an electrode layer (Al layer or Ag layer 6a) are laminated is annealed. It is conveyed to the processing device 28.

  Next, as shown in FIG. 19, the substrate 1 on which each organic layer (PEDOT: PSS layer 3a, P3HT: PCBM layer 4a, and TiOx layer 5a) and an electrode layer (Al layer or Ag layer 6a) are laminated is annealed. In the processing device 28, annealing is performed to volatilize the solvent.

  As described above, the discharge ports of the dies 13A, 13B, 13C, and 13D are provided with shims 17A, 17B, 17C, and 17D, respectively, but the discharge width direction (Y direction) of the shims 17A, 17B, 17C, and 17D is provided. ), The discharge widths LA, LB, LC, and LD become narrower in order as the following shims are reached. That is, in each of the shims 17A, 17B, 17C, and 17D, the discharge width is set in the order of LA> LB> LC> LD.

  Further, as described above, when the solution is discharged from the dies 13A, 13B, 13C, and 13D, the respective coating start positions PA, PB, PC, and PD of the dies become subsequent dies. It is far from the front end surface (the end surface facing the running direction (X direction) of the substrate 1), and the respective coating end positions EA, EB, EC, ED of each die become the subsequent die, so that the substrate 1 in order. This is close to the front end face (end face facing the running direction (X direction) of the substrate 1). That is, in each of the dies 13A, 13B, 13C, and 13D, the coating start position is set so as to be PA, PB, PC, and PD in order from the front end surface of the substrate 1, and the ED in order from the front end surface of the substrate 1 , EC, EB, and EA are set so that the coating end position is set to EA.

  Accordingly, the four end faces of the P3HT: PCBM layer 4a are located inside the four end faces of the PEDOT: PSS layer 3a, and the four end faces of the TiOx layer 5a are located inside the four end faces of the P3HT: PCBM layer 4a. The four end faces of the Al layer or the Ag layer 6a are located inside the four end faces of the TiOx layer 5a, and the PEDOT: PSS layer 3a, the P3HT: PCBM layer 4a, the TiOx layer 5a, and the Al layer or Ag layer. 6a is laminated in order from the substrate 1 side. Thus, even if the PEDOT: PSS layer 3a, the P3HT: PCBM layer 4a, the TiOx layer 5a, and the Al layer or the Ag layer 6a are sequentially stacked by the intermittent slit coater 10, the stacked PEDOT: PSS layers 3a, P3HT: In the side surfaces of the PCBM layer 4a, the TiOx layer 5a, and the Al layer or the Ag layer 6a, it is possible to prevent contact between layers that should not be in contact with each other, thereby improving the manufacturing yield of the organic thin film solar cell.

(Process P107) Modularization As shown in FIG. 20, the organic thin-film solar cells divided into predetermined sizes are each sealed with, for example, a resin sheet 27 or the like. The organic thin film solar cell is substantially completed by the manufacturing process described above.

  As described above, according to the first embodiment, even if a plurality of organic layers and electrode layers are stacked on the substrate by the intermittent slit coating method, the upper layer is formed on the inner side of all the lower end faces (four end faces). Since all the end faces (four end faces) are located, it is possible to prevent contact between the side surfaces of the multilayer structure in which a plurality of organic layers and electrode layers are stacked. Yield can be improved. Moreover, since an organic thin film solar cell can be manufactured only by an indirect slit coating method and an annealing method without using a vacuum technique, an inexpensive organic thin film solar cell can be provided.

(Embodiment 2)
A method for manufacturing an organic thin-film solar cell using the intermittent slit coating method, which is a coating technique according to the second embodiment, will be described.

<Structure of organic thin film solar cell>
An example of a specific structure of the organic thin film solar cell according to the second embodiment will be described with reference to a cross-sectional view of the main part shown in FIG. Although the specific example of a structure of a preferable organic thin film solar cell is shown below, it is not limited to this.

  The organic thin-film solar cell according to the second embodiment includes a pair of electrodes (anode and cathode) and a plurality of stacked organic layers disposed between the pair of electrodes. And a hole transport layer provided on the anode side, an electron transport layer provided on the cathode side, and a power generation layer (p-i-n structure) sandwiched between the two.

On the substrate 31, a transparent electrode 32 which is an anode side electrode is formed. For example, SnO ₂ is used for the transparent electrode 32.

  On the transparent electrode 32, a hole transport layer 33 made of, for example, PEDOT: PSS (poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate)) is formed. The hole transport layer 33 is provided to separate holes and electrons so that the separated holes and electrons are not recombined and returned to excitons. That is, the hole transport layer 33 has a function of selectively transmitting holes and improving hole injection efficiency.

  On the hole transport layer 33, a power generation layer 34 in which a p-type organic semiconductor 34p, an i layer (bulk hetero layer) 34i, and an n-type organic semiconductor 34n are stacked is formed. The p-type organic semiconductor 34p is made of, for example, BP (Tetrabenzoporphyrin), and the i layer (bulk heterolayer) 34i is made of, for example, PCBNB: BP (fullerene dielectric (phenyl C61-butyric acid n-butyl ester): Tetrabenzoporphyrin). The n-type organic semiconductor 34n is made of, for example, PCBM (Phenyl-C61-Butyric Acid Methyl Ester). By making the power generation layer 34 have a pin structure, it is possible to prevent recombination of the separated holes and electrons and return them to excitons again.

  On the power generation layer 34, an electron transport layer 35 made of, for example, BCP (2,9-dimenthyl-4,7-diphenyl-1,10-phenanthroline) is formed. The electron transport layer 35 is provided to separate the holes and electrons so that the holes and electrons after the separation do not recombine and return to excitons again. That is, the electron transport layer 35 has a function of selectively transmitting electrons and improving electron injection efficiency.

  On the electron transport layer 35, a metal electrode 36 as an electrode on the cathode side is formed. For the metal electrode 36, for example, Al or Ag is used.

  An electron blocking layer having a function of blocking electron transport may be provided between the hole transport layer 33 and the power generation layer 34. Similarly, a hole blocking layer having a function of blocking hole transport may be provided between the power generation layer 34 and the electron transport layer 35.

  Further, a hole injection layer having a function of improving hole injection efficiency may be provided between the transparent electrode 32 and the hole transport layer 33. Similarly, an electron injection layer having a function of improving electron injection efficiency may be provided between the electron transport layer 35 and the metal electrode 36.

  However, it is possible to increase the efficiency of the organic thin film solar cell by superimposing such an electron blocking layer or a hole blocking layer, but the number of layers is small for manufacturing an inexpensive organic thin film solar cell. It is preferable.

<Method for producing organic thin-film solar cell>
An example of the manufacturing method of the organic thin-film solar cell by this Embodiment 2 is demonstrated sequentially using FIGS. FIG. 22 is a process diagram for explaining a manufacturing process of an organic thin film solar cell, and FIGS. 23 to 34 are perspective views of main parts of the organic thin film solar cell in each manufacturing process of the organic thin film solar cell. Here, a plurality of organic layers and electrode layers included in the organic thin film solar cell are formed using the same apparatus as the intermittent slit coater 10 described in the first embodiment.

(Process P200) Transparent electrode patterning As shown in FIG. 23, a substrate 31 is prepared. For the substrate 31, for example, glass or plastic is used. A transparent electrode 32 made of, for example, SnO ₂ is formed on the substrate 31 as an anode side electrode. In the second embodiment, SnO ₂ is used for the transparent electrode 32, but another transparent conductive film (for example, ITO or IZO) may be used.

  Next, the transparent electrode 32 is patterned to a predetermined size by the laser scribe 37.

(Process P201) Cleaning As shown in FIG. 24, solution cleaning is performed.

(Process P202) PEDOT: PSS formation As shown in FIG. 25, a PEDOT: PSS layer 33a is formed by applying a PEDOT: PSS solution on the transparent electrode 32 by an intermittent slit coating method using a die 13A. The concentration of the PEDOT: PSS solution is 1%, for example, and the coating thickness is 2 μm, for example.

(Process P203) BP formation As shown in FIG. 26, BP solution is apply | coated on the PEDOT: PSS layer 33a by the intermittent slit coat method using die | dye 13Bp, and BP layer 34pa is formed. The concentration of the BP solution is, for example, 1%, and the coating thickness is, for example, 3 μm.

(Process P204) Modification Treatment As shown in FIG. 27, annealing treatment is performed to perform modification treatment of the BP layer 34pa. The annealing temperature is, for example, 180 ° C., and the annealing time is, for example, 20 minutes.

(Process P205) PCBNB: BP formation As shown in FIG. 28, a PCBNB: BP solution is applied on the BP layer 34pa by an intermittent slit coat method using a die 13Bi to form a PCBNB: BP layer 34ia. The concentration of the PCBNB: BP solution is, for example, 10%, and the coating thickness is, for example, 1 μm.

(Process P206) Modification Process As shown in FIG. 29, an annealing process is performed to perform a modification process on the PCBNB: BP layer 34ia. The annealing temperature is, for example, 180 ° C., and the annealing time is, for example, 20 minutes.

(Process P207) PCBM formation As shown in FIG. 30, a PCBM solution is applied on the PCBNB: BP layer 34ia by an intermittent slit coat method using a die 13Bn to form a PCBM layer 34na. The concentration of the PCBM solution is, for example, 1%, and the coating thickness is, for example, 3 μm.

(Process P208) BCP formation As shown in FIG. 31, a BCP solution is applied on the PCBM layer 34na by an intermittent slit coat method using a die 13C to form a BCP layer 35a. The concentration of the BCP solution is 1%, for example, and the coating thickness is 2 μm, for example.

(Process P209) Metal electrode formation As shown in FIG. 32, an Al material or an Ag material (solution or paste) is applied onto the BCP layer 35a by an intermittent slit coat method using a die 13D, and an Al layer or an Ag layer is formed. 36a is formed.

  In the above (Step P202) to (Step P209), each of the organic layers (PEDOT: PSS layer 33a, BP layer 34pa, PCBNB: BP layer) is formed using the above-described intermittent slit coater 10 as in the first embodiment. 34ia, PCBM layer 34na, and BCP layer 35a) and electrode layer (Al layer or Ag layer 6a). In the second embodiment, the electrode layer (Al layer or Ag layer 36a) is also formed by an intermittent slit coating method.

  Although description of the operation of each mechanism of the intermittent slit coater 10 in the above (Process P202) to (Process P209) is omitted, as in the first embodiment described above, it is inside the four end faces of the PEDOT: PSS layer 33a. The four end faces of the BP layer 34pa are located on the inner side, the four end faces of the PCBNB: BP layer 34ia are located on the inner side of the four end faces of the BP layer 34pa, and the PCBM on the inner side of the four end faces of the PCBNB: BP layer 34ia. The four end faces of the layer 34na are located, the four end faces of the BCP layer 35a are located inside the four end faces of the PCBM layer 34na, and the Al layer or the Ag layer 36a is located inside the four end faces of the BCP layer 35a. Four end faces are located, PEDOT: PSS layer 33a, BP layer 34pa, PCBNB: BP layer 34ia, PCBM layer 34na, BCP layer 5a, and an Al layer or Ag layer 36a are stacked in this order from the substrate 31 side. Thus, the PEDOT: PSS layer 33a, the BP layer 34pa, the PCBNB: BP layer 34ia, the PCBM layer 34na, the BCP layer 35a, and the Al layer or the Ag layer 36a are sequentially laminated by the intermittent slit coater 10. PEDOT: PSS layer 33a, BP layer 34pa, PCBNB: BP layer 34ia, PCBM layer 34na, BCP layer 35a, and side surfaces of the Al layer or Ag layer 36a can be prevented from being contacted with each other. The production yield of the organic thin film solar cell is improved.

(Process P210) Annealing treatment As shown in FIG. 33, each organic layer (PEDOT: PSS layer 33a, BP layer 34pa, PCBNB: BP layer 34ia, PCBM layer 34na, and BCP layer 35a) stacked on the substrate 31. The electrode layer (Al layer or Ag layer 36a) is annealed to evaporate the solvent. For the annealing treatment, for example, stage heating or furnace body heating is used. The annealing temperature is, for example, 150 ° C., and the annealing time is, for example, 10 minutes. In addition, you may combine with the heating at the time of resin-sealing an organic thin-film solar cell, without performing annealing treatment here.

(Process P211) Modularization As shown in FIG. 34, the organic thin-film solar cells divided into predetermined sizes are each sealed with, for example, a resin sheet 38 or the like. The organic thin film solar cell is substantially completed by the manufacturing process described above.

  As described above, according to the second embodiment, even if the number of organic layers to be stacked is increased as compared with the organic thin film solar cell according to the first embodiment, the lower layer is formed as in the first embodiment. Since all the end faces (four end faces) of the upper layer are located on the inner side of all the end faces (four end faces), layers that should not be in contact with each other on the side surface of the multilayer structure in which a plurality of organic layers and electrode layers are laminated Contact between each other can be prevented, and the production yield of the organic thin film solar cell can be improved. Moreover, since an organic thin film solar cell can be manufactured only by an indirect slit coating method and an annealing method without using a vacuum technique, an inexpensive organic thin film solar cell can be provided.

  As mentioned above, the invention made by the present inventor has been specifically described based on the embodiment. However, the present invention is not limited to the embodiment, and various modifications can be made without departing from the scope of the invention. Needless to say.

  For example, in the above-described embodiment, the configuration of the power generation layer is “i-layer” or “p-layer-i-layer-n-layer”, but is not limited thereto, and each material constituting them Is not limited to those exemplified in the first and second embodiments. Further, the structure of the organic thin film solar cell and various materials constituting the organic thin film solar cell are not limited to those exemplified in the first and second embodiments.

  The present invention can be applied to the manufacture of an organic element in which a plurality of organic layers are laminated, such as an organic thin film solar cell.

DESCRIPTION OF SYMBOLS 1 Board | substrate 2 Transparent electrode 3 Hole transport layer 3a PEDOT: PSS layer 4 Electric power generation layer 4a P3HT: PCBM layer 5 Electron transport layer 5a TiOx layer 6 Metal electrode 6a Al layer or Ag layer 10 Intermittent slit coater 11 Fixed table (surface plate)
11a Guide 12A, 12B, 12C, 12D Slit coater 13A, 13B, 13Bi, 13Bn, 13Bp, 13C, 13D Die 14A, 14B, 14C, 14D Camera 15 Control unit 16 Substrate 17A, 17Aa, 17B, 17C, 17D Shim 18 Drive Unit 19 Discharge port 20 Alignment mark 21 Drive unit 22 Solution tank 23 Three-way valve 24 Back pressure valve 25 Electromagnetic valve 26 Laser scribe 27 Resin sheet 28 Annealing device 31 Substrate 32 Transparent electrode 33 Hole transport layer 33a PEDOT: PSS layer 34 Power generation layer 34i i layer (bulk hetero layer)
34ia PCBNB: BP layer 34n n-type organic semiconductor 34na PCBM layer 34p p-type organic semiconductor 34pa BP layer 35 electron transport layer 35a BCP layer 36 metal electrode 36a Al layer or Ag layer 37 laser scribe 38 die 51 substrate 52 transparent electrode 53 hole Transport layer 54, 54i Bulk hetero layer (i layer)
54n n-type organic semiconductor 54p p-type organic semiconductor 55 electron transport layer 56 metal electrode 57 interlayer G gap HP partition LA, LB, LC discharge width P1, P2 pump PFL front end face of substrate

Claims (10)

The manufacturing method of the organic thin-film solar cell characterized by including the following processes:
(A) preparing a substrate;
(B) forming a transparent electrode on the substrate;
(C) Using the first die provided in the first slit coater on the transparent electrode while relatively moving the substrate and the first slit coater in the first direction in which the substrate travels, the first solution A step of forming a first organic layer;
(D) A second solution is applied onto the first organic layer using a second die provided in the second slit coater while relatively moving the substrate and the second slit coater in the first direction. Forming a second organic layer;
(E) A third solution is applied onto the second organic layer using a third die provided in the third slit coater while relatively moving the substrate and the third slit coater in the first direction. Forming a third organic layer;
(F) forming a metal electrode on the third organic layer;
here,
The first die has a slit-like discharge port for discharging the first solution provided along a second direction that is perpendicular to the first direction, and a first shim having a first discharge width. And
The second die has a slit-like discharge port for discharging the second solution provided along the second direction, and a second shim having a second discharge width narrower than the first discharge width. ,
The third die has a slit-like discharge port for discharging the third solution provided along the second direction, and a third shim having a third discharge width narrower than the second discharge width. ,
Both end surfaces in the second direction of the second organic layer are located on the inner side than both end surfaces in the second direction of the first organic layer,
Both end surfaces of the third organic layer in the second direction are located on the inner side than both end surfaces of the second organic layer in the second direction. The method for producing an organic thin film solar cell according to claim 1, wherein the step (f) further includes the following substeps:
(F1) Applying a fourth solution on the third organic layer using a fourth die provided in the fourth slit coater while relatively moving the substrate and the fourth slit coater in the first direction. Process,
here,
The fourth die has a slit-like discharge port for discharging the fourth solution provided along the second direction, and a fourth shim having a fourth discharge width narrower than the third discharge width. ,
Both end surfaces of the metal electrode in the second direction are located on the inner side than both end surfaces of the third organic layer in the second direction.   2. The method of manufacturing an organic thin film solar cell according to claim 1, wherein a dimension of the second organic layer along the second direction is 1.0 mm or shorter than a dimension of the first organic layer along the second direction. The method of manufacturing an organic thin-film solar cell, wherein a dimension of the third organic layer along the second direction is 1.0 mm or shorter than a dimension of the second organic layer along the second direction. In the manufacturing method of the organic thin-film solar cell of Claim 1,
The application of the second solution from the front end surface of the substrate in the first direction is started more than the first distance from the front end surface of the substrate in the first direction to the position where the application of the first solution is started. The second distance to the position to be
Application of the third solution from the front end surface of the substrate in the first direction is more than the second distance from the front end surface of the substrate in the first direction to the position where application of the second solution is started. The third distance to the position where is started is long,
Both end surfaces in the first direction of the second organic layer are located on the inner side than both end surfaces in the first direction of the first organic layer,
The method for producing an organic thin-film solar cell, wherein both end surfaces in the first direction of the third organic layer are located on an inner side than both end surfaces in the first direction of the second organic layer.   5. The method of manufacturing an organic thin-film solar cell according to claim 4, wherein a dimension of the second organic layer along the first direction is 1.0 mm or shorter than a dimension of the first organic layer along the first direction. The method of manufacturing an organic thin-film solar cell, wherein a dimension of the third organic layer along the first direction is 1.0 mm or shorter than a dimension of the second organic layer along the first direction.   2. The method of manufacturing an organic thin-film solar cell according to claim 1, wherein the first organic layer is a hole transport layer, the second organic layer is a power generation layer, and the third organic layer is an electron transport layer. Manufacturing method of organic thin-film solar cell. The method for producing an organic thin film solar cell according to claim 1, further comprising the following steps after the step (f):
(G) A step of annealing the first organic layer, the second organic layer, the third organic layer, and the metal layer laminated on the substrate. A fixed table;
A plurality of slit coaters sequentially disposed in the first direction on the fixed table;
Each of the plurality of slit coaters, a plurality of dies having a slit-like discharge port for discharging a solution provided along a second direction which is a direction perpendicular to the first direction;
A plurality of shims provided in each of the plurality of dies and defining a discharge width of the solution;
An organic thin film solar cell manufacturing apparatus including
The organic thin-film solar cell, wherein the substrate and the plurality of slit coaters move relative to each other in the first direction, and the discharge width of each of the plurality of shims decreases in order as the subsequent shims become. Manufacturing equipment.   9. The organic thin film solar cell manufacturing apparatus according to claim 8, wherein a discharge width of a shim used later is 1.0 mm or more shorter than a discharge width of a shim used earlier. Manufacturing equipment.   9. The apparatus for manufacturing an organic thin-film solar cell according to claim 8, wherein the application positions of the solutions on the plurality of dies can be set to different values.

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