JP2006237165A - Organic solar cell module and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic solar cell module having an increased amount of photocurrent. <P>SOLUTION: The organic solar cell module has at least two photoelectric conversion elements, having first and second electrode layers and a photoelectric conversion layer sandwiched by the electrode layers. In the adjacent photoelectric conversion elements, the order of lamination of the first electrode layer, the photoelectric conversion layer, and the second electrode layer is opposite, and they are connected in series electrically. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an organic solar cell module and a method for manufacturing the same. More specifically, the present invention relates to an organic solar cell module having higher performance than the conventional one and a manufacturing method thereof by improving the structure and components of a plurality of solar cells constituting the module.

  Solar cells that can convert sunlight into electric power are attracting attention as an energy source to replace fossil fuels. Currently, solar cells that have begun to be put into practical use include solar cells using crystalline silicon substrates and thin-film silicon solar cells.

However, the former has a problem that the manufacturing cost of the silicon substrate is high, and the latter needs to use various semiconductor gases and complicated apparatuses, and the manufacturing cost is still high. For this reason, efforts have been made to reduce the cost per power generation output by increasing the efficiency of photoelectric conversion in any of the solar cells, but they have not yet solved the above problem.
Therefore, as a solar cell using a low-cost organic material without using an expensive semiconductor substrate, an organic solar cell combining an electron donating material and an electron accepting material has been actively researched.

  For example, C.I. W. Tang, “Two-layer organic photovoltaic cell”, Applied Physics Letters, 1986, Vol. 48, pp. 183-185 (Non-patent Document 1) uses low molecular weight organic materials, and electron-accepting materials and electron-donating properties. Techniques using planar bonding of materials are disclosed. In addition, the above-mentioned document shows a technique using a heterobulk junction of fullerene and its derivative, which are electron-accepting materials, and an electron-donating conductive polymer.

  In addition, S.M. E. Shaheen et al. Applied Physics Letters, 2001, Vol. 78, pp. 841-843 (Non-patent Document 2) and JP-T 8-500701 (Patent Document 1) use polyphenylene vinylene as a conductive polymer, and accept electron. An organic solar cell using 1- (3-methoxycarbonyl) -propyl-1-1-1-phenyl- (6,6) C61 (PCBM), which is a fullerene modified product, is shown. This organic solar cell has a structure in which a first electrode layer, a photoelectric conversion layer composed of an electron donating material and an electron accepting material, and a second electrode layer are sequentially laminated on a glass substrate.

  The photoelectric conversion layer of the above document absorbs light in the visible light region by using an electron donating material having an absorption spectrum in the visible light region. When light is absorbed by the electron donating material, photoexcited electrons and holes are generated. The electrons move to the electron-accepting material and move from the second electrode layer through the external electric circuit to the first electrode layer. The electrons that have moved to the first electrode layer combine with holes generated in the electron donating material and return to the original state. Electric energy is taken out by repeating such movement of electrons.

C. W. Tang, “Two-layer organic photovoltaic cell”, Applied Physics Letters, 1986, 48, 183-185. S. E. Shaheen et al. , Applied Physics Letters, 2001, 78, 841-843. JP-T 8-500701

  However, in any structure of the organic solar cell described in the above-mentioned document, the following difficulties exist in application to a large-area solar cell, even if a small-area solar cell can be prototyped.

  That is, when the area of one solar cell (unit cell) is increased, the generated current increases in proportion to the area, but at the same time, the current resistance loss in the resistance of the electrode portion also increases. As the area increases, the resistance component in the lateral direction of the transparent conductive film used for the electrode portion extremely increases, and as a result, the internal series electric resistance as a solar cell increases. As a result, there is a problem that the fill factor (FF) in the current-voltage characteristics at the time of photoelectric conversion is lowered and the photoelectric conversion efficiency is lowered.

  Thus, according to the present invention, two or more photoelectric conversion elements having a first electrode layer, a second electrode layer, and a photoelectric conversion layer sandwiched between these electrode layers are provided, and adjacent photoelectric conversion elements are connected to each other. An organic solar cell module is provided in which the order of stacking one electrode layer, photoelectric conversion layer, and second electrode layer is opposite and electrically connected in series.

Furthermore, according to the present invention, two or more photoelectric conversion elements having a first electrode layer, a second electrode layer, and a photoelectric conversion layer sandwiched between these electrode layers are provided, and adjacent photoelectric conversion elements are mutually connected, The first electrode layer, the photoelectric conversion layer, and the second electrode layer are opposite in order of stacking, and are electrically solar-connected organic solar cell module manufacturing method,
The step of laminating the photoelectric conversion layer on the first electrode layer and the second electrode layer, the second electrode layer in the region corresponding to the first electrode layer on the photoelectric conversion layer, and the first in the region corresponding to the second electrode layer And a step of forming each of the electrode layers. A method for manufacturing an organic solar cell module is provided.

  According to the present invention, it is possible to suppress the current resistance loss in the electrode layer when modularized and increase the photoelectric flow rate. As a result, an increase in the internal series electrical resistance of the solar cell is suppressed, and the FF in the current-voltage characteristics during photoelectric conversion can be improved. Therefore, a high-performance organic solar cell module in which a decrease in photoelectric conversion efficiency is suppressed can be provided.

The organic solar cell module of the present invention comprises two or more photoelectric conversion elements having a photoelectric conversion layer composed of an electron donating material and an electron accepting material sandwiched between a first electrode layer and a second electrode layer, Adjacent photoelectric conversion elements are opposite to each other in the stacking order of the first electrode layer, the photoelectric conversion layer, and the second electrode layer, and are electrically connected in series.
The second electrode layer preferably has translucency.

In addition, it is preferable that the photoelectric conversion layers of adjacent photoelectric conversion elements are substantially electrically separated. In particular, in order to ensure electrical separation between the photoelectric conversion layers, it is more preferable that the photoelectric conversion layers are separated by a space.
Further, when the photoelectric conversion element having the first electrode layer on the light receiving surface side is defined as the first photoelectric conversion element, and the photoelectric conversion element having the first electrode layer on the non-light receiving surface side is defined as the second photoelectric conversion element, the second photoelectric conversion element is defined. The light transmittance of the second electrode layer of the conversion element is preferably larger than the light transmittance of the second electrode layer of the first photoelectric conversion element. Specifically, the preferable light transmittance of the second electrode layer of the second photoelectric conversion element is 60% or more as an average value in the visible light region, more preferably 70% or more, and further preferably 80% or more. . The light transmittance of the second electrode layer of the first photoelectric conversion element is preferably 50% or less. The light transmittance of the second electrode layer of the second photoelectric conversion element is preferably 10% or more, more preferably 20% or more greater than the light transmittance of the second electrode layer of the first photoelectric conversion element. More preferably, it is larger by at least%.

Moreover, it is preferable that the film thickness of the 2nd electrode layer of a said 2nd photoelectric conversion element is smaller than the film thickness of the 2nd electrode layer of a said 1st photoelectric conversion element. Specifically, it is preferably smaller than 100 nm, and more preferably smaller in the range of 1 to 30 nm.
Furthermore, it is preferable that the light receiving area of the photoelectric conversion layer of the second photoelectric conversion element is larger than the light receiving area of the photoelectric conversion layer of the first photoelectric conversion element. Specifically, the light receiving area of the photoelectric conversion layer of the second photoelectric conversion element is preferably 1.1 times or more larger than the light receiving area of the photoelectric conversion layer of the first photoelectric conversion element, and is 1.2 to 3 times larger. It is more preferable that the range is large.

Further, the light receiving areas of the photoelectric conversion layers in the plurality of first photoelectric conversion elements may be the same, and the light receiving areas of the photoelectric conversion layers in the plurality of second photoelectric conversion elements may be the same.
Furthermore, a material having a work function smaller than that of the first electrode layer may be used for the second electrode layer. The difference in work function between the second electrode layer and the first electrode layer is preferably 0.3 eV or more, and more preferably in the range of 0.4 to 1.5 eV. Specifically, it is preferable to use a transparent conductive oxide such as aluminum or zinc oxide.
In the one or more first photoelectric conversion elements and the one or more second photoelectric conversion elements, the photoelectric conversion layer of each element or the photoelectric conversion layer of at least one element is fullerene or a fullerene derivative as an electron-accepting material. It is preferable to contain.

Furthermore, it is preferable that the photoelectric conversion layer of each element or the photoelectric conversion layer of at least one element contains a hole transporting heterocyclic polymer as an electron donating material. In particular, the hole transporting heterocyclic polymer is preferably polythiophene, polypyrrole, or polyfuran, and more preferably, the hole transporting heterocyclic polymer is a stereoregular polymer.
According to the invention, the step of laminating the photoelectric conversion layer on the first electrode layer and the second electrode layer, the second electrode layer in the region corresponding to the first electrode layer on the photoelectric conversion layer, the second electrode An organic solar cell module can be manufactured by passing through the process of forming a 1st electrode layer in the area | region corresponding to a layer, respectively.

Here, it is preferable to include a step of scribing between photoelectric conversion layers of adjacent photoelectric conversion elements, and it is more preferable to include a step of scribing from the light receiving surface side and a step of scribing from the non-light receiving surface side.
Furthermore, a first substrate in which the first electrode layer and the second electrode layer are alternately formed in parallel and a second substrate in which the first electrode layer and the second electrode layer are alternately formed in parallel are formed. Then, an organic solar cell module can be manufactured by laminating a photoelectric conversion material on the first substrate and making the second substrate face the first substrate. Further, it is more preferable to perform heat treatment after the second substrate is opposed to the first substrate.

  Further, a photoelectric conversion layer is stacked on a first substrate in which a first electrode layer and a second electrode layer are alternately formed in parallel, and the first electrode layer and the second electrode layer are arranged in parallel on the photoelectric conversion layer. Alternatively, the organic solar cell module may be manufactured by alternately forming them.

Below, the basic structure of the organic solar cell module of this invention is demonstrated concretely based on FIG. FIG. 1 is a schematic cross-sectional view of an organic solar cell module of the present invention.
The solar cell module M includes a light-transmitting insulating substrate X on the light-receiving surface side, a support substrate Y on the back surface (non-light-receiving surface) side, and two first electrodes provided in a row between the substrates X and Y. 1 photoelectric conversion element a and two 2nd photoelectric conversion elements b arrange | positioned adjacently between each 1st photoelectric conversion element a are provided.
The first photoelectric conversion element a is formed by sequentially laminating a first electrode layer 1, a photoelectric conversion layer 2 composed of an electron donating material and an electron accepting material, and a second electrode layer 3 from the substrate X side. The second photoelectric conversion element b is formed by sequentially laminating the second electrode layer 13, the photoelectric conversion layer 2 composed of an electron donating material and an electron accepting material, and the first electrode layer 11 from the substrate X side.

  The four first and second photoelectric conversion elements a and b are electrically connected in series by the first electrode layer 1 and the second electrode layer 13, and the first electrode layer 11 and the second electrode layer 3. The outer periphery of the cell is electrically separated and sealed by an insulating layer 5 (which may be a simple gap if it has insulating properties) and a sealing layer 6 (for example, an insulating resin). . Further, the first electrode layers 1 and 11 and the second electrode layers 3 and 13 may be made of the same material or different materials, and are preferably the same material.

Hereinafter, in the present specification, when referred to as a solar cell unit cell or unit cell, a structure in which the first photoelectric conversion element or the second photoelectric conversion element is sandwiched between a translucent insulating substrate and a support substrate from both sides. Shall mean.
2A and 2B are schematic plan views of the solar cell module of FIG. FIG. 2A is a schematic plan view showing a film formation state on the substrate X side, and FIG. 2B is a schematic plan view showing a film formation state on the substrate Y side. The solar cell module of FIG. 1 can be manufactured as follows.

  On the substrate X, the strip-shaped first electrode layer 1 is formed at positions A and C in FIG. 2A, and the strip-shaped second electrode layer 13 is formed at positions B and D in FIG. . At that time, the first electrode layer formed at position A and the second electrode layer formed at position B are formed so as to be electrically connected, and B and C, and A and D are electrically separated. Make a gap G as shown. The method of electrically separating may be, for example, a method of forming a gap by a vacuum film forming method using a metal mask, or a method of scribing and separating using a laser after forming a continuous film. Further, as shown in FIG. 3, the insulating layer 7 may be used for more reliable electrical separation.

  On the other hand, on the substrate Y, the strip-shaped first electrode layer 11 is formed at positions B and B 'in FIG. 2B, and the strip-shaped second electrode layer 3 is formed at positions A and A'. At that time, the first electrode layer 11 formed at the position B and the second electrode layer 3 formed at the position A, the first electrode layer 11 formed at the position B ′ and the second electrode formed at the position A ′. The layer 3 is formed so as to be electrically connected, and a gap (G) is provided between B and A ′ so as to be electrically separated. A method similar to the above can be adopted as the method of electrical separation.

Next, the photoelectric conversion layer 2 is formed on the substrate X or Y.
Further, the substrates X and Y are arranged so that the first electrode layer 1 and the second electrode layer 3 and the first electrode layer 11 and the second electrode layer 13 face each other, and the outer periphery of the cell is sealed with an insulating resin or the like. Form a stop layer. At that time, the adjacent photoelectric conversion layers 2 do not have to be separated in a space as shown in FIG. Moreover, in order to make electrical separation of the adjacent photoelectric conversion layers 2 more reliable, as shown in FIGS. 4 and 5, the adjacent photoelectric conversion layers 2 may be separated from each other in space. By such a process, the solar cell module M can be obtained. More specific components will be described later.

Hereinafter, each component of the organic solar cell module of the present invention will be described.
[Translucent insulating substrate and supporting substrate]
Examples of the substrate X constituting the light receiving surface of the organic solar cell module include a transparent glass substrate such as soda glass, fused silica glass, and crystal quartz glass, a flexible film made of a heat-resistant translucent resin, and a metal plate. It is done. The substrate X is preferably about 0.2 to 5 mm in thickness and having heat resistance of 150 ° C. or higher.
Examples of the flexible film (hereinafter abbreviated as “film”) include long-term weather-resistant sheets and films such as polyester, polyacryl, polyimide, Teflon (registered trademark), polyethylene, polypropylene, and PET. Especially, since the board | substrate X is normally heated to the temperature of about 150 degreeC at the time of formation of a 1st electrode layer, the Teflon which has heat resistance more than this temperature is preferable.

Moreover, as the board | substrate Y which comprises the non-light-receiving surface of a solar cell, the presence or absence of translucency is not limited, The board | substrate same as the board | substrate X, a metal plate, etc. are mentioned. Since the metal plate is poor in light transmittance, it is preferable to use it as the substrate Y. More preferable substrate Y is a flexible substrate such as a flexible film or a metal plate made of heat-resistant translucent resin. If these substrates are used, as will be described later in Example 2, the first photoelectric conversion element on the substrate X and the second photoelectric conversion element on the substrate Y can be connected in series with good adhesion. It can be improved.
These substrates X and Y can also be used when the completed organic solar cell module is attached to another structure. That is, for example, if a glass substrate is used, the peripheral portion of the glass substrate can be easily attached to another support using metal processed parts and screws.

[Electrode layer]
The material of the first electrode layers 1 and 11 may be any material as long as at least a photoelectric conversion layer to be described later substantially transmits light having a wavelength having effective sensitivity. It does not have to be permeable. Examples thereof include ITO (indium-tin composite oxide); fluorine-doped tin oxide; zinc oxide doped with boron, gallium, or aluminum; and transparent conductive metal oxides such as titanium oxide doped with niobium. In addition, other materials such as gold, silver, aluminum, indium, platinum, carbon (carbon black, graphite, glass carbon, amorphous carbon, hard carbon, soft carbon, carbon whisker, carbon nanotube, fullerene) are made into thin films. Can be listed.
The material of the second electrode layers 3 and 13 is preferably a material whose work function is smaller than that of the first electrode layer 1. Examples thereof include metal materials such as aluminum, indium, calcium, magnesium, gold, and lithium fluoride, and transparent conductive metal oxide materials such as zinc oxide.

  However, since the light receiving surface of the organic solar cell module, that is, the second electrode layer 13 of the second photoelectric conversion element is required to transmit light as in the case of the first electrode layer 1 described above, the second photoelectric conversion element The light transmittance of the second electrode layer 13 is preferably higher than the light transmittance of the second electrode layer 3 of the first photoelectric conversion element.

  Examples of the method for adjusting the light transmittance of the electrode layer include a method for adjusting the film thickness. Specifically, a method of making the film thickness of the second electrode layer 13 of the second photoelectric conversion element thinner than the film thickness of the second electrode layer 3 of the first photoelectric conversion element can be mentioned. Although the preferred film thickness varies depending on the material used for the electrode layer, for example, in the case of a metal material such as aluminum, the preferred film thickness of the second electrode layer of the second photoelectric conversion element is 100 to 0.5 nm. Preferably it is 50-0.5 nm, More preferably, it is 20-1 nm. A film thickness of less than 0.5 nm is not preferable because it is difficult to form a uniform film.

Further, as the second electrode layer 13 of the second photoelectric conversion device having a higher light transmittance (70%), ZnO, transparent conductive metal oxide material SnO ₂ or the like may be used. In this case, a preferable film thickness is 1 μm or less, and more preferably 500 nm to 50 nm. When the film thickness is thinner than 50 nm, the conductivity is remarkably lowered, which is not preferable.

  The second electrode layer 3 on the non-light-receiving surface side is not required to have translucency. However, when it has translucency, the amount of light incident on the second photoelectric conversion element increases, and characteristics such as photoelectric conversion efficiency and current value can be improved as compared with the prior art.

The first electrode layers 1 and 11 and the second electrode layers 3 and 13 can be formed by a known technique such as a PVD method, a vapor deposition method, a sputtering method, or a coating method. Here, on the substrate X, the first electrode layer 1 and the second electrode layer 13 formed at positions A and B in FIG. 2A are electrically connected, and between B and C and between A and D, As a method of forming the electrodes so as to be electrically separated, for example, the first electrode layer 1 is formed by vacuum deposition using a metal mask having openings only at positions A and C, and then a part of A is included in B. There is a method in which the second electrode layer 13 is formed by a vacuum deposition method using a metal mask in which the position is opened and the position of D is opened without including the position of A. By doing so, the second electrode layer 13 formed at the position B is in contact with the first electrode layer 1 formed at the position A, so that electrical connection is ensured. In addition, the electrode layers formed on B and C and A and D are not in contact with each other, and thus are electrically separated. At this time, in order to make the electrical separation more reliable, an insulation made of an insulating material such as SiO ₂ , Si ₃ N ₄ , or an insulating resin is formed in the gap between the electrode layers B and C and A and D. You may form a layer by well-known techniques, such as a PVD method, a vapor deposition method, sputtering method, and the apply | coating method.

[Photoelectric conversion layer]
The photoelectric conversion layer is usually composed of an electron-donating material and an electron-accepting material, and the form includes a particulate form and a film form. Of these, a film-like form is preferable.
As the electron donating material, a low molecular or high molecular material having a hole transporting property can be used.

  Examples of the low molecular weight material include metal-free phthalocyanines, metal phthalocyanines and their derivatives, cyanine dyes, merocyanine dyes, squarylium dyes, quinacridone dyes, azo dyes, quinone dyes such as anthraquinone, benzoquinone, and naphthoquinone. As the central metal of metal phthalocyanine and metal porphyrin, magnesium, zinc, copper, silver, aluminum, silicon, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, tin, platinum, lead and other metals, metal oxides, A metal halide is mentioned.

On the other hand, examples of the polymer material include oligomers and polymers having phenylene-vinylene and derivatives thereof as a skeleton, oligomers and polymers having fluorene and derivatives thereof as a skeleton, oligomers and polymers having benzofuran and derivatives thereof as a skeleton, thienylene-vinylene, and Oligomers and polymers having skeletons of their derivatives, aromatic tertiary amines such as triphenylamine and oligomers and polymers thereof having skeletons, oligomers and polymers having carbazole and its derivatives as skeletons, vinyl carbazole and its derivatives Oligomers and polymers having skeletons, oligomers and polymers having pyrrole and derivatives thereof as skeletons, oligomers and polymers having acetylene and derivatives thereof as skeletons, oligomers and polymers having thiophene and derivatives thereof as skeletons, Sochianafen and oligomers and polymers having a derivative thereof in the skeleton, heptadiene and oligomers and polymers having a derivative thereof in the skeleton thereof.
As the electron donating material, one or a combination of two or more of the above materials may be used. Among these, hole transportable heterocyclic polymers such as polythiophene, polypyrrole, polyaniline, polyfuran, polypyridine, and polycarbazole are preferable from the viewpoint of photoelectric conversion efficiency and safety.

  The conductivity of these hole transporting heterocyclic polymers is generally lower than that of inorganic semiconductor materials such as amorphous silicon. Therefore, as long as the distance from the photoelectric conversion element adjacent to the film thickness of the photoelectric conversion layer is sufficiently long (for example, 3 μm or more, more preferably 5 to 500 μm in length), the photoelectric conversion layer is scribed, etc. Even if it is not separated in space by this method, photoexcited carriers generated in the photoelectric conversion layer cannot practically reach the electrode layer of the adjacent photoelectric conversion element that is far away. Therefore, even if it does not actually isolate | separate, it can isolate | separate effectively and, as a result, integration is possible. Of course, in order to make element separation more reliable, the element may be actually separated by a scriber such as a laser.

  Furthermore, among the hole-transporting heterocyclic polymers, polythiophene, polythiol, and polyfuran have various substituents bonded thereto, and various structures exist, so that a wide variety of polymers can be synthesized. In addition, among the hole-transporting heterocyclic polymers, a polymer having stereoregularity has improved charge (hole) transportability and can mainly improve conversion efficiency. More preferably, polythiophene is preferable because a polymer having high stereoregularity can be synthesized and a polymer having relatively high solubility in a solvent can be synthesized. In this case, not only a single polythiophene but also different polythiophenes may be mixed and used, or a dopant may be added.

  Examples of the electron-accepting material include organic materials such as fullerene and derivatives thereof, carbon nanotubes, perylene and derivatives thereof, pyridine and derivatives thereof, quinoline and derivatives thereof, naphthalene derivatives, bathocuproine and derivatives thereof. In addition, oligomers and polymers having the above skeleton, and polymers such as cyano-polyphenylene vinylene are also included.

  As the electron-accepting material, one or two or more of the above materials may be combined. Among these, fullerenes or fullerene derivatives are preferable from the viewpoint of photoelectric conversion efficiency and safety. The fullerene is preferably C60, C70 or a mixture thereof from the viewpoint of stability and safety, and more preferably a fullerene derivative having a substituent introduced into C60 or C70 or a mixture of these fullerene derivatives. The functional group introduced into the fullerene contains at least one functional group selected from an ester group, an imino group, an alkyl group, an aralkyl group, and a thiophenyl group. The reason for optimizing the solubility and energy level Is preferable.

  Here, when a polymer material is used as the electron donating material, the electron accepting material preferably contains the same functional group as the functional group contained in the polymer material. This improves the contact and dispersibility between the polymer material and the fullerene derivative that is an electron acceptor, so that the transfer efficiency of photoexcited electrons absorbed by the polymer material to the fullerene derivative can be improved, and the charge separation state Can be generated in large numbers. For example, it is more preferable that the functional group of the fullerene derivative and the functional group of polythiophene both contain the same alkyl group.

  As a method for forming the film-like photoelectric conversion layer on the substrate, various known methods can be used. Specifically, spin coating method using a solution (paste) containing an electron donating material and an electron accepting material, a coating method such as a screen printing method, an ink jet method, etc .; a raw material solid of the electron donating material and the electron accepting material PVD method, vapor deposition method, sputtering method or sol-gel method using each (which may be used alone or in combination); CVD method or MOCVD method; method using electrochemical redox reaction, etc. Is mentioned. Among these, a coating method using a paste is preferable because it is easy to increase the thickness and the film formation cost is low.

  As a method for forming the photoelectric conversion layer, in the case of FIG. 1, a paste containing a photoelectric conversion material is applied on the first electrode layer 1 and the second electrode layer 13 on the substrate X by the application method described above, and the paste Before the substrate is completely dried, the support substrate Y may be bonded so that the first electrode layer 1 and the second electrode layer 3 face each other and the first electrode layer 11 and the second electrode layer 13 face each other. Thereafter, the substrates X and Y are bonded to the outer periphery of the cell using an insulating resin.

  In the case of FIG. 4, the photoelectric conversion layer on the photoelectric conversion element a side is formed on the substrate X, the photoelectric conversion layer on the photoelectric conversion element b side is formed on the substrate Y, and then the substrate X and the substrate Y are bonded together. A battery module can be formed. In the case of using the above method, it is preferable to perform heat treatment after the substrate X and the substrate Y are bonded to each other. By performing the heat treatment, the electrical connection between the photoelectric conversion layer 2 and the first electrode layer or the second electrode layer can be improved by simply bonding them together. That is, this improvement is achieved by performing heat treatment after bonding the substrates X and Y, thereby softening the constituent material of the photoelectric conversion layer 2 and strengthening the photoelectric conversion layer 2 and the second electrode layers 3 and 13. It comes from being able to stick. This improvement appears more remarkably by using an organic material for the electron-accepting material.

Here, a suitable heat treatment temperature is 50 to 300 ° C., more preferably 70 to 150 ° C., although details vary depending on the material used for the photoelectric conversion layer. When the temperature is lower than 50 ° C., the effect of forming a good connection between the photoelectric conversion layer and the electrode layer is weak, and when the temperature is higher than 300 ° C., the photoelectric conversion material is not only softened but also starts to decompose, and the film quality deteriorates. Absent.
Moreover, after apply | coating and drying the paste containing a photoelectric conversion material on the 1st electrode layer 1 and the 2nd electrode layer 13 on the board | substrate X and forming a photoelectric converting layer, the electrode layers 3 and 11 are vacuum-deposited. A photoelectric conversion element may be formed.
Moreover, as a method of separating the photoelectric conversion layers of adjacent photoelectric conversion elements in space in order to ensure electrical separation between adjacent photoelectric conversion elements, (1) after film formation on the entire surface, A method of removing unnecessary portions, (2) a method of masking a substrate in advance and forming a film only on necessary portions in order, can be considered.

  As an example of the former, after forming the photoelectric conversion layer 2 over almost the entire surface of the substrate, for example, a method of removing unnecessary portions of the photoelectric conversion layer with a metal or wooden spatula or the like, or protection A method of performing masking with a tape or the like and etching away an unmasked portion by an electrical, optical or chemical method, a method of scribing by laser light irradiation, or the like can be considered.

  Among these, the scribing method is preferable because fine processing can be performed without contact. When scribing as shown in FIG. 4 from the state shown in FIG. 1, the region where the first electrode layer 1 and the second electrode layer 13 on the substrate X side are not formed (G region in FIG. 2A). ) From the region where the first electrode layer 11 and the second electrode layer 3 on the substrate Y side are not formed (G region in FIG. 2B). It is preferable to include a process of scribing the photoelectric conversion layer by irradiating light.

On the other hand, as an example of the latter, a mask (for example, a metal mask or Kapton tape) having resistance to a solvent or heat is disposed at a position where a photoelectric conversion layer is not desired to be formed on the substrate, and the photoelectric conversion layer is formed only in a portion without the mask. A method of forming the image can be considered.
In addition, although the film thickness of a photoelectric converting layer is not specifically limited, 0.1-3000 nm is preferable from a viewpoint of photoelectric conversion efficiency, and 1-1000 nm is still more preferable. 100 to 500 nm is particularly preferable. If the film thickness of the photoelectric conversion layer is less than 0.1 nm, the uniformity of the entire layer is not sufficient, and a problem that a short circuit is likely to occur is not preferable. On the other hand, when the film thickness of the photoelectric conversion layer exceeds 3000 nm, the internal resistance increases and the characteristics deteriorate, such being undesirable.

  In the present invention, since a plurality of organic solar cells are connected in series, the short-circuit current obtained is less than the short-circuit current density of the lowest single solar cell. Therefore, when the second electrode layer is present on the light receiving surface side (cell b), if the light transmittance of the second electrode layer is low, the amount of light reaching the photoelectric conversion layer is reduced, and the photocurrent density is lowered. As a result, there is a problem that the solar cell module conversion efficiency is greatly reduced.

However, this problem can be solved by adjusting the light transmittance of the second electrode layer of the cell b to be larger than the transmittance of the second electrode layer of the cell a. For example, what is necessary is just to adjust the film thickness of the 2nd electrode layer of the cell b so that it may become smaller than the film thickness of the 2nd electrode layer of the cell a. For example, it is preferably 100 nm or less and more preferably 1 to 30 nm. This problem can also be solved by adjusting the light receiving areas of the cells a and b. For example, the width of the cell b shown in FIG. 4 may be increased so that the same current density as that of the cell a can be taken out. Further, the ratio of the width of the cell a to the width of the cell b is particularly preferably inversely proportional to the ratio of the light transmittance of the electrode layer of the cell a to the light transmittance of the cell b.
Further, if the light receiving areas of the photoelectric conversion layers 2 in the plurality of first photoelectric conversion elements a are the same and the light receiving areas of the photoelectric conversion layers 12 in the plurality of second photoelectric conversion elements are the same, the manufacturing process. Can be stabilized, which is preferable.

Hereinafter, although an embodiment and a comparative example explain the embodiment of the present invention still more concretely, the present invention is not limited by these examples and a comparative example.
Example 1
An integrated organic solar cell module in which the four solar cell unit cells shown in FIG. 1 are connected in series was produced. The manufacturing process will be described with reference to FIG.
Two glass substrates of 30 mm × 30 mm (substrate X and substrate Y) were prepared as supports, and ITO films were formed thereon as first electrode layers 1 and 11 by sputtering. At that time, using a metal mask, ITO films were formed on the substrate X at positions A and C in FIG. 2A and on the substrate Y at positions B and B ′ in FIG. The sheet resistance of the ITO film was 12Ω / □, and the transmittance was about 80%.

  Next, a ZnO film doped with Al is formed as the second electrode layer 13 of the second photoelectric conversion element at positions B and D in FIG. 2A on the substrate X by a sputtering method using a metal mask. did. The sheet resistance of the ZnO film doped with Al was 15Ω / □, and the transmittance was about 80%.

Next, an Al film having a film thickness of 100 nm is formed as the second electrode layer 3 of the first photoelectric conversion element at positions A and A ′ in FIG. 2B on the substrate Y by a vacuum deposition method using a metal mask. Formed. In FIG. 2, A is 5 mm, A ′ is 5 mm, B is 5 mm, B ′ is 5 mm, C is 9.8 mm, D is 9.8 mm, E is 4.9 mm, F is 4.9 mm, and G is The width was 0.2 mm.
Next, the photoelectric conversion layer 2 was formed by the following method. As the electron donating material of the photoelectric conversion layer, stereoregular poly-3-hexylthiophene having a molecular weight of 82000 is used, and as the electron accepting material, 1- (3-methoxycarbonyl) -propyl-1-1-1 is a fullerene derivative. Phenyl- (6,6) C61 (PCBM) was used. Poly-3-hexylthiophene and PCBM were weighed so as to have a weight ratio of 1: 1, and dehydrated toluene was added thereto to prepare a 2.5 wt% solution.

Next, after the solution is applied onto the substrate X on which the first electrode layer and the second electrode layer are formed, the substrate is rotated at about 1500 rpm using a spin coater, and before the solution is completely dried, the substrate X and Y were bonded together so that the first electrode layer 1 and the second electrode layer 3, and the first electrode layer 11 and the second electrode layer 13 were opposed to each other. Thereafter, heat treatment was performed at 120 ° C. for 10 minutes in a nitrogen atmosphere to produce an organic solar cell module. The film thickness of the photoelectric conversion layer was about 200 nm. Finally, the periphery of the substrate was sealed with a thermosetting resin.
Here, when the work functions of ITO used as the first electrode layers 1 and 11 and aluminum oxide used as the second electrode layer and zinc oxide doped with aluminum were measured by ultraviolet irradiation photoelectron spectroscopy, ITO was found to be 4. It was 7 eV, aluminum was 4.3 eV, and zinc oxide was 4.4 eV. That is, the work function of the first electrode layer is larger than the work function of the second electrode layer.
The organic solar cell module of Example 1 produced in this way was placed on a black stage whose substrate Y side was controlled at 25 ° C. so that the substrate X became a light receiving surface, and under AM1.5 simulated sunlight irradiation As a result of examining the operating characteristics, the short-circuit current density was 1.8 mA / cm ² , the open-circuit voltage value was 2.1 V, FF 0.59, and the module conversion efficiency was 2.2%.

(Example 2)
In Example 1, a ZnO film doped with Al was used for the second electrode layer 13 on the light-receiving surface side, and an Al film with a thickness of 100 nm was used for the second electrode layer 3 on the non-light-receiving surface side. In this example, an organic solar cell module was fabricated in the same manner as in Example 1 except that a ZnO thin film doped with Al was used for the second electrode layer 3 on the non-light-receiving surface side.

Specifically, sputtering is performed using a ZnO film doped with Al as the second electrode layer 3 of the first photoelectric conversion element at positions A and A ′ in FIG. Formed by the method.
The organic solar cell module of Example 2 produced in this way was placed on a black stage whose substrate Y side was controlled at 25 ° C. so that the substrate X became a light receiving surface, and under AM1.5 simulated sunlight irradiation As a result of examining the operating characteristics, the short-circuit current density was 1.8 mA / cm ² , the open-circuit voltage value was 2.0 V, the FF was 0.54, and the module conversion efficiency was 1.9%.

(Example 3)
In Example 1, a ZnO film doped with Al was used for the second electrode layer 13 on the light-receiving surface side, and an Al film with a thickness of 100 nm was used for the second electrode layer 3 on the non-light-receiving surface side. In this example, an organic solar cell module was produced in the same manner as in Example 1 except that an Al film was used for the second electrode layer 13 on the light receiving surface side.

Specifically, a vacuum deposition method using an Al film having a thickness of 5 nm as the second electrode layer 13 of the second photoelectric conversion element and a metal mask at positions B and D in FIG. Formed by.
The organic solar cell module of Example 3 produced in this way was placed on a black stage whose substrate Y side was controlled at 25 ° C. so that the substrate X became a light receiving surface, and under AM1.5 simulated sunlight irradiation As a result of examining the operating characteristics, the short-circuit current density was 1.4 mA / cm ² , the open-circuit voltage value was 2.2 V, FF 0.59, and the module conversion efficiency was 1.8%.

(Comparative Example 1)
As a prior art, an organic solar cell module having only one photoelectric conversion element was produced on the same substrate X as in Example 1.
Two glass substrates of 30 mm × 30 mm (substrate X and substrate Y) were prepared as supports, and an ITO film was formed on the substrate X as the first electrode layer 1 by a sputtering method. The sheet resistance of the ITO film was 12Ω / □, and the transmittance was about 80%. Next, the photoelectric conversion layer 2 was formed on the first electrode layer 1 of the substrate X by the following method. As the electron donating material for the photoelectric conversion layer, stereoregular poly-3-hexylthiophene having a molecular weight of 82000 was used, and as the electron accepting material, PCBM which is a fullerene derivative was used. Poly-3-hexylthiophene and PCBM were weighed so as to have a weight ratio of 1: 1, and dehydrated toluene was added thereto to prepare a 2.5 wt% solution.

  Next, the solution is applied onto the first electrode layer 1, and is rotated at about 1500 rpm using a spin coater, and heat treatment is performed at 120 ° C. for 10 minutes in a nitrogen atmosphere. A 200 nm photoelectric conversion layer was produced.

Further, an Al film having a thickness of 100 nm was formed as a second electrode layer on the photoelectric conversion layer 2 by a vapor deposition method to form a photoelectric conversion element. Next, the 1st photoelectric conversion element on the board | substrate X and the glass substrate Y were made to oppose, and it sealed using the thermosetting resin around the board | substrate.
The organic solar cell module according to the related art produced in this way is installed on a black stage whose substrate Y side is controlled at 25 ° C. so that the substrate X becomes the light receiving surface, and operates under AM1.5 simulated sunlight irradiation. As a result of examining the characteristics, the short-circuit current density was 4.8 mA / cm ² , the open-circuit voltage value was 0.44 V, the FF 0.39, and the module conversion efficiency was 0.82%.
From Comparative Example 1 and Example 1, the adjacent photoelectric conversion elements are configured in such a manner that the stacking order of the first electrode layer, the photoelectric conversion layer, and the second electrode layer is reversed and electrically connected in series. It was found that conversion efficiency can be obtained.

  In addition, from Examples 1 to 3, (1) using different materials for the second electrode layer of the second photoelectric conversion element and the second electrode layer of the first photoelectric conversion element, (2) the second of the second photoelectric conversion element The transmittance of the second electrode layer is greater than the transmittance of the second electrode layer of the first photoelectric conversion element. (3) The film thickness of the second electrode layer of the second photoelectric conversion element is that of the first photoelectric conversion element. It was found that a high conversion efficiency can be obtained because it is smaller than the film thickness of the second electrode layer.

(Examples 4 to 5)
In Example 4, by changing the width of the photoelectric conversion layer 2 of the first photoelectric conversion element a and the second photoelectric conversion element b shown in FIG. 1 to 4 mm and 6 mm, respectively, the photoelectric conversion layer of the first photoelectric conversion element Was made smaller than the light receiving area of the photoelectric conversion layer of the second photoelectric conversion element. For comparison, a module in which the widths of the photoelectric conversion layers a and b were both 5 mm was also produced (Example 5).

  That is, in Example 4, A is 4 mm, A ′ is 4 mm, B is 6 mm, B ′ is 6 mm, C is 9.8 mm, D is 9.8 mm, E is 4.9 mm, and F is 4 in FIG. In Example 5, A is 5 mm, A ′ is 5 mm, B is 5 mm, B ′ is 5 mm, C is 9.8 mm, D is 9.8 mm, and E is 4. 0.9 mm, F is 4.9 mm, and G is 0.2 mm wide.

  In addition, the 2nd electrode layer 3 of the 1st photoelectric conversion element formed the Al film | membrane with a film thickness of 100 nm in the position of B, D of Fig.2 (a) on the board | substrate X by the vacuum evaporation method using a metal mask. The second electrode layer 13 of the second photoelectric conversion element was formed by depositing an Al film having a thickness of 10 nm on the substrate Y at positions A and A ′ in FIG. 2B by vacuum deposition using a metal mask.

  Poly-3-dodecylthiophene having a molecular weight of 57000 was used as the electron donating material, and PCBM which is a fullerene derivative was used as the electron accepting material. The composition ratio of the electron-donating material and the electron-accepting material was 1: 1 by weight for both the first photoelectric conversion element and the second photoelectric conversion element, and the film thickness of each photoelectric conversion element was 200 nm.

Production methods other than the above were produced in the same manner as in Example 1 to produce an organic solar cell module. Here, the transmittance of the first electrode layer 1 (ITO thin film) on the light receiving surface side of the first photoelectric conversion element is 75%, and the transmission of the second electrode layer 13 (Al thin film) on the light receiving surface side of the second photoelectric conversion element. The rate was 60%. Further, the ratio (4: 6) of the light receiving area between the first photoelectric conversion element and the second photoelectric conversion element was the reciprocal of the transmittance ratio of the electrode layer on the light receiving side (75: 50 = 6: 4).
The organic solar cell module fabricated in this way is placed on a black stage whose substrate Y side is controlled at 25 ° C. so that the substrate X becomes the light receiving surface, and the operating characteristics under AM1.5 simulated sunlight irradiation are examined. It was. As a result, the module conversion efficiency of Example 4 was 1.9% (short-circuit current density 1.5 mA / cm ² , open-circuit voltage value 2.04 V, FF 0.61), and the module conversion efficiency of Example 5 was 1.6%. (Short-circuit current density 1.3 mA / cm ² , open-circuit voltage value 2.02 V, FF 0.62).

  From the comparison between Example 4 and Example 5, the light receiving area of the photoelectric conversion layer of the first photoelectric conversion element is smaller than the light receiving area of the photoelectric conversion layer of the second photoelectric conversion element, whereby the first photoelectric conversion of the solar cell module is performed. It turned out that the current value of each unit cell of an element and a 2nd photoelectric conversion element can be drawn effectively, and high module efficiency can be obtained.

(Example 6)
Below, in order to make electrical isolation of the adjacent photoelectric converting layer 2 more reliable, the Example which performed the element isolation process by a laser scribing process is described using FIG.4 and FIG.2.
Two glass substrates of 30 mm × 30 mm (substrate X and substrate Y) were prepared as supports, and ITO films were formed thereon as first electrode layers 1 and 11 by sputtering. At that time, using a metal mask, ITO films were formed on the substrate X at positions A and C in FIG. 2A and on the substrate Y at positions B and B ′ in FIG. The sheet resistance of the ITO film was 12Ω / □, and the transmittance was about 80%.

  Next, the second electrode layer 13 of the second photoelectric conversion element is formed by sputtering a ZnO film doped with Al at positions B and D in FIG. 2A on the substrate X using a metal mask. Formed. The sheet resistance of the ZnO film doped with Al was 15Ω / □, and the transmittance was about 80%.

Next, the second electrode layer 3 of the first photoelectric conversion element is a vacuum deposition method in which an Al film having a thickness of 100 nm is formed on the substrate Y at positions A and A ′ in FIG. Formed by. In FIG. 2, A is 5 mm, A ′ is 5 mm, B is 5 mm, B ′ is 5 mm, C is 9.8 mm, D is 9.8 mm, E is 4.9 mm, F is 4.9 mm, and G is The width was 0.2 mm.
Next, the photoelectric conversion layer 2 was formed by the following method. As the electron donating material of the photoelectric conversion layer, stereoregular poly-3-hexylthiophene having a molecular weight of 120,000 was used, and as the electron accepting material, PCBM which is a fullerene derivative was used. Poly-3-hexylthiophene and PCBM were weighed so as to have a weight ratio of 1: 1, and dehydrated toluene was added thereto to prepare a 2.5 wt% solution.

  Next, the solution is applied onto the substrate X on which the first electrode layer 1 and the second electrode layer 13 are formed, and is rotated at about 1500 rpm using a spin coater, and before the solution is completely dried, The substrates X and Y are bonded together so that the first electrode layer 1 and the second electrode layer 3 and the first electrode layer 11 and the second electrode layer 13 face each other, and heat treatment is performed at 120 ° C. for 10 minutes in a nitrogen atmosphere. It was. The film thickness of the photoelectric conversion layer was about 200 nm.

  Next, the position G in FIG. 2A is irradiated with laser light (second high-frequency light of Nd: YAG having a wavelength of 532 nm) from the light-receiving surface glass substrate side, and A, D, and B in FIG. And a photoelectric conversion layer of C were scribed. 2B was irradiated with the laser beam from the substrate Y side, and the A 'and B photoelectric conversion layers were separated by scribing.

Finally, sealing was performed using a thermosetting resin around the substrate. An organic solar cell module was produced by such a method.
The organic solar cell module fabricated in this way is placed on a black stage whose substrate Y side is controlled at 25 ° C. so that the substrate X becomes the light receiving surface, and the operating characteristics under AM1.5 simulated sunlight irradiation are examined. As a result, the short-circuit current density was 1.7 mA / cm ² , the open circuit voltage value was 2.3 V, the FF was 0.60, and the module conversion efficiency was 2.3%.

(Example 7)
Next, another embodiment will be described with reference to FIGS. 5 and 2A.
One 30 mm × 30 mm glass substrate (substrate X) was prepared as a support, and an ITO film was formed thereon as the first electrode layer 1 by sputtering. At that time, an ITO film was formed at positions A and C in FIG. The sheet resistance of the ITO film was 12Ω / □, and the transmittance was about 80%.

Next, a ZnO film doped with Al was formed as the second electrode layer 13 at the positions B and D in FIG. 2A on the substrate X by a sputtering method using a metal mask. The sheet resistance of the ZnO film doped with Al was 15Ω / □, and the transmittance was about 80%. In FIG. 2, A is 5 mm, B is 5 mm, C is 9.8 mm, D is 9.8 mm, and G is 0.2 mm wide.
Next, the photoelectric conversion layer 2 was formed by the following method. As the electron donating material of the photoelectric conversion layer, stereoregular poly-3-hexylthiophene having a molecular weight of 120,000 was used, and as the electron accepting material, PCBM which is a fullerene derivative was used. Poly-3-hexylthiophene and PCBM were weighed so as to have a weight ratio of 1: 1, and dehydrated toluene was added thereto to prepare a 2.5 wt% solution.

  Next, the above solution is applied onto the substrate X on which the first electrode layer and the second electrode layer are formed, and is rotated at about 1500 rpm using a spin coater, and heat treatment is performed at 120 ° C. for 10 minutes in a nitrogen atmosphere. It was. The film thickness of the photoelectric conversion layer was about 200 nm.

  Next, using a metal mask, an Al film having a thickness of 100 nm was formed on the photoelectric conversion layer formed on the first electrode layer 1 of the substrate X by a vacuum deposition method. Further, an ITO thin film having a thickness of 150 nm was formed on the photoelectric conversion layer formed on the second electrode layer 13 of the substrate X by a sputtering method.

Next, laser light (Nd: YAG second high-long wave light of wavelength 532 nm) is irradiated from the substrate X side in the direction of α in FIG. 5, and photoelectric conversion of A and D and B and C in FIG. Scribeed one side between layers. Further, the laser beam was irradiated from the direction of β in FIG. 5 opposite to the substrate X, and the predetermined photoelectric conversion layers were separated by scribing. Finally, the back surface and the periphery of the substrate were sealed with an electrically insulating top cover 6 for sealing. An organic solar cell module was produced by such a method.
The organic solar cell module fabricated in this way is placed on a black stage whose substrate Y side is controlled at 25 ° C. so that the substrate X becomes the light receiving surface, and the operating characteristics under AM1.5 simulated sunlight irradiation are examined. As a result, the short-circuit current density was 1.7 mA / cm ² , the open-circuit voltage value was 2.2 V, FF 0.61, and the module conversion efficiency was 2.3%.

(Example 8)
Next, still another embodiment will be described with reference to FIGS.
Two glass substrates of 30 mm × 30 mm (substrate X and substrate Y) were prepared as supports, and ITO films were formed thereon as first electrode layers 1 and 11 by sputtering. At that time, using a metal mask, ITO films were formed on the substrate X at positions A and C in FIG. 2A and on the substrate Y at positions B and B ′ in FIG. The sheet resistance of the ITO film was 12Ω / □, and the transmittance was about 80%.

Next, a ZnO film doped with Al is formed as the second electrode layer 13 of the second photoelectric conversion element at positions B and D in FIG. 2A on the substrate X by a sputtering method using a metal mask. did. The sheet resistance of the ZnO film doped with Al was 15Ω / □, and the transmittance was about 80%. Next, an Al film having a film thickness of 100 nm is formed as the second electrode layer 3 of the first photoelectric conversion element at positions A and A ′ in FIG. 2B on the substrate Y by a vacuum deposition method using a metal mask. Formed. In FIG. 2, A is 5 mm, A ′ is 5 mm, B is 5 mm, B ′ is 5 mm, C is 9.8 mm, D is 9.8 mm, E is 4.9 mm, F is 4.9 mm, and G is The width was 0.2 mm.
Next, the photoelectric conversion layer 2 was formed on the translucent conductive layer 1 of the substrate X by the following method. As the electron donating material of the photoelectric conversion layer, stereoregular poly-3-dodecylthiophene having a molecular weight of 57000 was used, and PCBM which is a fullerene derivative was used as the electron accepting material. Poly-3-dodecylthiophene and PCBM were weighed so as to have a weight ratio of 1: 1, and dehydrated toluene was added thereto to prepare a 2.5 wt% solution.

  Next, a 5.2 mm wide Kapton tape is applied to the regions B and G, D and G in FIG. 2A, and then the above solution is applied onto the first electrode layer 1 and a spin coater is used. Then, the substrate was rotated at about 1500 rpm, and heat treatment was performed at 120 ° C. for 10 minutes in a nitrogen atmosphere, so that a photoelectric conversion layer 2 having a thickness of 200 nm was manufactured. After drying, the Kapton tape was peeled off to form two photoelectric conversion layers 2 having a width of 5 mm and a length of 25 mm with a gap of 5.2 mm. Moreover, the photoelectric conversion layer 12 was also formed on the first electrode layer 11 of the substrate Y by the same method as described above. At that time, the rotational speed of the spin coat was 1200 rpm, and two photoelectric conversion layers having a width of 5 mm, a length of 25 mm, and a film thickness of 300 nm were formed with a gap of 5.2 mm.

  Next, the photoelectric conversion layer 2 on the substrate X and the photoelectric conversion layer 12 on the substrate Y were bonded together so that the photoelectric conversion layer portions were alternated, thereby creating an organic solar cell module. At this time, the second electrode layer 13 on the substrate X and the photoelectric conversion layer 12 formed on the substrate Y, and the second electrode layer 3 on the substrate Y and the photoelectric conversion layer 2 formed on the substrate X have good connection. Thus, heat treatment was performed at 120 ° C. for 30 minutes in a state where the bonded substrates were pressure-bonded. By performing such heat treatment, the photoelectric conversion layers 2 and 12 were softened, and good connection with the electrode layer could be obtained. Finally, the periphery of the substrate was sealed with a thermosetting resin.

The organic solar cell module of Example 1 produced in this way was placed on a black stage whose substrate Y side was controlled at 25 ° C. so that the substrate X became a light receiving surface, and under AM1.5 simulated sunlight irradiation As a result of examining the operating characteristics, the short-circuit current density was 1.6 mA / cm ² , the open-circuit voltage value was 2.0 V, the FF was 0.58, and the module conversion efficiency was 1.9%.

It is a schematic sectional drawing which shows the organic solar cell module of this invention. It is a schematic plan view of the solar cell module of FIG. It is a schematic sectional drawing which shows the organic solar cell module of this invention. It is a schematic sectional drawing which shows the organic solar cell module of this invention. It is the cross-sectional schematic of the conventional solar cell module.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1st electrode layer 2, 12 Photoelectric conversion layer 3, 13 2nd electrode layer 5 Insulating layer 6 Sealing layer 7 Insulating layer a 1st photoelectric conversion element (cell)
b Second photoelectric conversion element (cell)
X Translucent insulating substrate Y Support substrate M Solar cell module hν Light

Claims (18)

  Two or more photoelectric conversion elements having a first electrode layer, a second electrode layer, and a photoelectric conversion layer sandwiched between these electrode layers are provided. Adjacent photoelectric conversion elements are mutually connected to the first electrode layer and the photoelectric conversion layer. The organic solar cell module is characterized in that the stacking order of the second electrode layer is opposite and is electrically connected in series.   The organic solar cell module according to claim 1, wherein the photoelectric conversion layers of the adjacent photoelectric conversion elements are separated by a space. The adjacent photoelectric conversion element includes a first photoelectric conversion element in which a first electrode layer, a photoelectric conversion layer, and a second electrode layer are stacked in this order from the light receiving surface side to the non-light receiving surface, and non-light receiving from the light receiving surface side. It consists of a second photoelectric conversion element laminated in the order of the second electrode layer, photoelectric conversion layer and first electrode layer toward the surface,
3. The organic solar cell according to claim 1, wherein the light transmittance of the second electrode layer located on the light receiving surface side is larger than the light transmittance of the second electrode layer located on the non-light receiving surface side. module. The adjacent photoelectric conversion element includes a first photoelectric conversion element in which a first electrode layer, a photoelectric conversion layer, and a second electrode layer are stacked in this order from the light receiving surface side to the non-light receiving surface, and non-light receiving from the light receiving surface side. It consists of a second photoelectric conversion element laminated in the order of the second electrode layer, photoelectric conversion layer and first electrode layer toward the surface,
The film thickness of the 2nd electrode layer located in the light-receiving surface side is smaller than the film thickness of the 2nd electrode layer located in the non-light-receiving surface side, The Claim 1 characterized by the above-mentioned. Organic solar cell module. The adjacent photoelectric conversion element includes a first photoelectric conversion element in which a first electrode layer, a photoelectric conversion layer, and a second electrode layer are stacked in this order from the light receiving surface side to the non-light receiving surface, and non-light receiving from the light receiving surface side. It consists of a second photoelectric conversion element laminated in the order of the second electrode layer, photoelectric conversion layer and first electrode layer toward the surface,
The light receiving area of the photoelectric conversion layer of the second photoelectric conversion element having the second electrode layer on the light receiving surface side is larger than the light receiving area of the photoelectric conversion layer of the first photoelectric conversion element having the first electrode layer on the light receiving surface side. The organic solar cell module according to any one of claims 1 to 4.   The ratio of the light receiving area of the photoelectric conversion layer between the second photoelectric conversion element and the first photoelectric conversion element is such that the second electrode layer of the second photoelectric conversion element and the first electrode layer of the first photoelectric conversion element located on the light receiving surface side. The organic solar cell module according to claim 5, wherein the organic solar cell module is equal to a reciprocal of a ratio of light transmittance to   A plurality of first and second photoelectric conversion elements are provided, the light receiving areas of the photoelectric conversion layers in the second photoelectric conversion elements are the same, and the light receiving areas of the photoelectric conversion layers in the first photoelectric conversion elements are the same. The organic solar cell module according to claim 5 or 6, wherein   The second electrode layer on the light-receiving surface side is a layer made of a material selected from aluminum or a transparent conductive oxide containing zinc oxide. Organic solar cell module.   The organic solar cell module according to any one of claims 1 to 8, wherein the photoelectric conversion layer contains an electron-accepting material made of fullerene or a fullerene derivative.   The organic solar cell module according to any one of claims 1 to 9, wherein the photoelectric conversion layer includes an electron donating material made of a hole transporting heterocyclic polymer.   The organic solar cell module according to claim 10, wherein the hole transporting heterocyclic polymer is polythiophene, polypyrrole, or polyfuran.   The organic solar cell module according to claim 10 or 11, wherein the hole transporting heterocyclic polymer is a stereoregular polymer. Two or more photoelectric conversion elements having a first electrode layer, a second electrode layer, and a photoelectric conversion layer sandwiched between these electrode layers are provided. Adjacent photoelectric conversion elements are mutually connected to the first electrode layer and the photoelectric conversion layer. And a method of manufacturing an organic solar cell module in which the stacking order of the second electrode layers is opposite and electrically connected in series,
The step of laminating the photoelectric conversion layer on the first electrode layer and the second electrode layer, the second electrode layer in the region corresponding to the first electrode layer on the photoelectric conversion layer, and the first in the region corresponding to the second electrode layer And a step of forming each of the electrode layers.   The manufacturing method of the organic solar cell module of Claim 13 including the process of scribing between the photoelectric conversion layers of the said adjacent photoelectric conversion element.   The method of manufacturing an organic solar cell module according to claim 14, wherein the scribing step includes a step of scribing from the light receiving surface side and a step of scribing from the non-light receiving surface side.   The step of laminating the photoelectric conversion layer on the first substrate in which the first electrode layer and the second electrode layer are alternately formed in parallel, and the first electrode layer and the second electrode layer are alternately formed in parallel. The second substrate, the second electrode layer of the second substrate on the photoelectric conversion layer corresponding to the first electrode layer of the first substrate, and the photoelectric conversion layer corresponding to the second electrode layer of the first substrate The organic solar cell module according to claim 13, further comprising a step of facing the first substrate and the second substrate so that the first electrode layers of the second substrate correspond to each other. Production method.   The method for manufacturing an organic solar cell module according to claim 16, wherein the second substrate and the first substrate are made to face each other and then heat treatment is performed.   A step of laminating the photoelectric conversion layer on the first substrate in which the first electrode layer and the second electrode layer are alternately formed in parallel; and on the photoelectric conversion layer corresponding to the first electrode layer of the first substrate. The second electrode layer includes a step of alternately forming the first electrode layer in parallel on the photoelectric conversion layer corresponding to the second electrode layer of the first substrate. Manufacturing method of organic solar cell module.

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