JP6082294B2 - Organic thin film solar cell, method for manufacturing the same, and electronic device - Google Patents

Description

  The present invention relates to an organic thin-film solar cell, a method for manufacturing the same, and an electronic device, and in particular, improves the electrode take-out structure, can form a connection point at an arbitrary position without accompanying a large structural change in appearance, and is lightweight. The present invention relates to an organic thin film solar cell that can be made thinner and thinner, a manufacturing method thereof, and an electronic device.

  Organic thin-film solar cells featuring ultra-thin, light weight, and flexibility are manufactured by printing methods such as the ink-jet method at room temperature and atmospheric pressure, realizing a high degree of freedom in shape and excellent design. It is possible (for example, refer to Patent Document 1).

Special table 2007-534119 gazette

  Usually, in a thin-film solar battery for outdoor use, an electrode is taken out at an end face of a module constituted by cells folded in a strip shape. However, when a solar cell is mounted on a mobile terminal or the like that is mainly used indoors, it is difficult to take out an electrode at the end face of the module due to the restrictions on the module shape and area.

  Therefore, the present inventor has found a structure in which a connection point can be freely formed without causing a large change in appearance by providing a mechanism for taking out electricity generated by the module inside the cell at an arbitrary position. .

  An object of the present invention is to improve an electrode take-out structure, to form a connection point at an arbitrary position without causing a large structural change in appearance, and to reduce the weight and thickness of the organic thin-film solar cell and its It is in providing a manufacturing method and an electronic device.

According to one aspect of the present invention for achieving the above object, a substrate, a first electrode layer disposed on the substrate, a hole transport layer disposed on the first electrode layer, and the positive electrode A bulk heterojunction organic active layer disposed on the hole transport layer; a second electrode layer disposed on the bulk heterojunction organic active layer; and a passivation layer disposed on the second electrode layer; disposed the orthogonal direction with respect to the substrate, the passivation layer, before Symbol heterojunction organic active layer to the bulk, and through the hole transport layer, a first extraction terminal connected to the first electrode layer A resin layer formed between the electrode, the first extraction terminal electrode, the hole transport layer, the bulk heterojunction organic active layer, and the second electrode layer; and a direction perpendicular to the substrate And pass through the passivation layer The organic thin film solar cell and a second lead terminal electrode connected to the second electrode layer.

According to another aspect of the invention, a substrate, a first electrode layer disposed on the substrate, a hole transport layer disposed on the first electrode layer, and a hole transport layer are disposed on the hole transport layer. A bulk heterojunction organic active layer formed thereon, a second electrode layer disposed on the bulk heterojunction organic active layer, and the hole transport layer and the bulk heterojunction in a direction perpendicular to the substrate. A through-connecting electrode connected to the first electrode layer through a third through-hole penetrating the bonding organic active layer and reaching the first electrode layer; and disposed on the second electrode layer and the through-connecting electrode The first passivation terminal electrode disposed in a direction perpendicular to the substrate, passing through the passivation layer, connected to the through-connecting electrode , passing through the passivation layer, Second extraction end connected to the second electrode layer The organic thin film solar cell comprising an electrode is provided.
According to another aspect of the present invention, a transparent substrate, a transparent first electrode layer formed on the transparent substrate, an organic layer formed on the first electrode layer, and the organic layer A second electrode layer formed on the first electrode layer, an insulating layer formed across the side surface of the organic layer and the side surface of the second electrode layer from the surface of the first electrode layer, and the first electrode layer. And an organic thin-film solar cell provided with the 3rd electrode layer formed in close contact across the side surface of the said organic layer and the side surface of the said 2nd electrode layer through the said insulating layer is provided.

  According to the other aspect of this invention, an electronic device provided with said organic thin film solar cell is provided.

According to another aspect of the present invention, the display device includes an organic thin film solar cell formation region and a character formation region disposed in a peripheral portion of the display region, and the organic thin film solar cell formation region includes a substrate, A first electrode layer disposed on the substrate; a hole transport layer disposed on the first electrode layer; a bulk heterojunction organic active layer disposed on the hole transport layer; and the bulk heterojunction organic a second electrode layer disposed on the active layer, said second electrode layer being arranged on the passivation layer is disposed on the orthogonal direction with respect to the substrate, the passivation layer, heterojunction organic Previous Stories bulk active layer, and through said hole transport layer, and the first take-out terminal electrode connected to the first electrode layer, said first extraction terminal electrode, the hole transporting layer, the bulk heterojunction organic active Layer, and the second electrode layer, and a resin layer formed between the, arranged the orthogonal direction with respect to the substrate, first through the passivation layer, which is connected to the second electrode layer Two display terminal electrodes, and the display region and the character forming region include the substrate, the first electrode layer disposed on the substrate, and the passivation layer disposed on the first electrode layer. An electronic device is provided.

According to another aspect of the present invention, the display device includes an organic thin film solar cell formation region and a character formation region disposed in a peripheral portion of the display region, and the organic thin film solar cell formation region includes a substrate, A first electrode layer disposed on the substrate; a hole transport layer disposed on the first electrode layer; a bulk heterojunction organic active layer disposed on the hole transport layer; and the bulk A second electrode layer disposed on the heterojunction organic active layer; and the first electrode layer penetrating through the hole transport layer and the bulk heterojunction organic active layer in a direction perpendicular to the substrate. A through-electrode layer connected to the first electrode layer through a third through-hole reaching up to the first electrode layer, a passivation layer disposed on the second electrode layer and the through-electrode layer , and a plane perpendicular to the substrate The passivation is arranged in the direction Through and a first take-out terminal electrode connected to the through-electrode layer, through said passivation layer, and a second lead terminal electrode connected to the second electrode layer, the display region and The character forming region is provided with an electronic device including the substrate, the first electrode layer disposed on the substrate, and the passivation layer disposed on the first electrode layer.

According to another aspect of the present invention, a step of forming a first electrode on a substrate, a step of forming a hole transport layer on the first electrode layer, and a bulk heterojunction on the hole transport layer Forming an organic active layer; forming a second electrode layer on the bulk heterojunction organic active layer; forming a passivation layer on the second electrode layer; and facing the substrate in the direction perpendicular, the passivation layer, before Symbol heterojunction organic active layer to the bulk, and the through hole transport layer, forming a first through-hole reaching the first electrode layer, with respect to the substrate Forming a second through hole penetrating through the passivation layer and reaching the second electrode layer in a direction perpendicular to the first surface, and a first connected to the first electrode layer in the first through hole Forming a takeout terminal electrode; and Forming a second take-out terminal electrode connected to the second electrode layer in the hole, and the first take-out terminal electrode, the hole transporting layer, the bulk heterojunction organic active layer, and the second electrode layer And a method of forming an organic thin film solar cell.

According to another aspect of the present invention, a step of forming a first electrode on a substrate, a step of forming a hole transport layer on the first electrode layer, and a bulk heterojunction on the hole transport layer A step of forming an organic active layer, and a third through hole that penetrates the hole transport layer and the bulk heterojunction organic active layer in a direction perpendicular to the substrate and reaches the first electrode layer Forming a second electrode layer on the bulk heterojunction organic active layer and forming a through connection electrode connected to the first electrode layer through the third through hole; and Forming a passivation layer on the second electrode layer and the through-connection electrode , and forming a fourth through-hole penetrating the passivation layer and reaching the through-connection electrode in a direction perpendicular to the substrate And in a direction perpendicular to the substrate Through said passivation layer, said forming the second through-hole reaching the second electrode layer, forming a first take-out terminal electrode connected to the through-connecting electrode in the fourth through hole And a step of forming a second extraction terminal electrode connected to the second electrode layer in the second through-hole.

  ADVANTAGE OF THE INVENTION According to this invention, the organic thin-film solar cell which can improve the extraction structure of an electrode, can form a connection point in arbitrary positions, without accompanying a big structural change of an external appearance, and can be reduced in weight and thickness, and its A manufacturing method and an electronic device can be provided.

(A) Typical plane pattern block diagram of the organic thin-film solar cell which concerns on embodiment, (b) The typical cross-section figure along the II line of Fig.1 (a), (c) Circuit expression. The schematic diagram explaining the fundamental structure and operation | movement of the organic thin-film solar cell which concern on embodiment. FIG. 3 is an energy band structure diagram of various materials of the organic thin film solar cell shown in FIG. 2. (A) Chemical structural formula of PEDOT and (b) Chemical structural formula of PSS applied in the organic thin-film solar cell which concerns on embodiment. (A) Chemical structural formula of P3HT as a p-type material and (b) Chemical structural formula of PCBM as an n-type material, which are applied to the organic thin film solar cell according to the embodiment. In the organic thin-film solar cell according to the embodiment, the chemical structural formula of the material used in vacuum deposition includes (a) Pc: example of phthalocyanine, (b) ZnPc: example of zinc phthalocyanine, (c) Me-Ptcdi (D) Example of C ₆₀ : fullerene. In the organic thin-film solar cell which concerns on embodiment, it is a chemical structural formula of the material used by a solution process, Comprising: (a) Example of MDMO-PPV, (b) Example of PFB, (c) CN-MDMO-PPV Examples: (d) PFO-DBT example, (e) F8BT example, (f) PCDTBT example, (g) PC ₆₀ BM example, (h) PC ₇₀ BM example. It is one process of the manufacturing method of the organic thin film solar cell which concerns on embodiment, Comprising: (a) Process drawing which prepares the ITO substrate which patterned the transparent electrode layer on the board | substrate, (b) After patterning a transparent electrode layer, Process diagram for patterning hole transport layer on transparent electrode layer, (c) Process diagram for patterning bulk heterojunction organic active layer on hole transport layer, (d) On bulk heterojunction organic active layer FIG. 6 is a process diagram for patterning a second electrode layer. It is one process of the manufacturing method of the organic thin film solar cell which concerns on embodiment, Comprising: (a) Process drawing which forms a passive film (oxide film) in the 2nd electrode layer surface, (b) A passivation layer is formed in the device whole surface. Process drawing to form, (c) Process drawing of forming a colorization barrier layer on a passivation layer. It is one process of the manufacturing method of the organic thin film solar cell which concerns on embodiment, Comprising: (a) Process drawing which forms a backsheet passivation layer on a colorization barrier layer, (b) In a surface perpendicular direction with respect to a substrate, Forming a first through hole penetrating the passivation layer, the second electrode layer, the bulk heterojunction organic active layer, and the hole transport layer and reaching the first electrode layer, and in a direction perpendicular to the substrate; A process diagram for forming a second through hole penetrating the passivation layer and reaching the second electrode layer, (c) forming a first extraction terminal electrode connected to the first electrode layer in the first through hole, Process drawing which forms the 2nd extraction terminal electrode connected with the 2nd electrode layer in the 2nd penetration hole. In the organic thin-film solar cell which concerns on embodiment, (a) Typical cross-section figure explaining a mode that the spot formed in a passivation layer is covered with a colored barrier layer, (b) Passivation layer and colored barrier layer FIG. 2 is a schematic cross-sectional structure diagram of a multi-layer protective film in which a plurality of layers are repeatedly stacked. (A) A plurality of (three in the example in the figure) schematic plan pattern configuration diagram of organic thin-film solar cells according to the embodiment arranged in series, (b) along the line II-II in FIG. FIG. It is one process of the manufacturing method of the organic thin-film solar cell concerning embodiment, Comprising: (a) The typical plane pattern block diagram which shows the state which formed the transparent electrode layer on the board | substrate, (b) of FIG. 13 (a) Fig. 3 is a schematic cross-sectional structure diagram along line III-III. FIG. 14 is a schematic plan pattern configuration diagram showing a state in which a hole transport layer is formed on a transparent electrode layer, which is one step of a method for manufacturing an organic thin film solar cell according to an embodiment; The typical cross-section figure which follows the IV-IV line of (a). 1 is a schematic plan pattern configuration diagram showing a state where a bulk heterojunction organic active layer is formed on a hole transport layer, which is one step of a method for manufacturing an organic thin-film solar cell according to an embodiment; b) A schematic sectional view taken along line VV in FIG. It is one process of the manufacturing method of the organic thin-film solar cell concerning embodiment, Comprising: (a) The typical plane pattern block diagram which shows the state which patterned the 2nd electrode layer on the bulk heterojunction organic active layer, ( b) A schematic sectional view taken along line VI-VI in FIG. It is one process of the manufacturing method of the organic thin-film solar cell which concerns on embodiment, Comprising: (a) While etching an excess organic layer by oxygen plasma processing, the state which formed the oxide film in the surface of the 2nd electrode layer The typical plane pattern block diagram shown, (b) The typical cross-section figure along the VV line of Fig.17 (a). It is one process of the manufacturing process of the organic thin-film solar cell which concerns on embodiment, Comprising: (a) Typical plane pattern block diagram which shows the state which formed the passivation layer in the device whole surface, (b) VIII of FIG. 18 (a) The schematic cross-section figure along a -VIII line. FIG. 19A is a schematic plan pattern configuration diagram showing one state of the manufacturing process of the organic thin film solar cell according to the embodiment, in which (a) a colored barrier layer is formed on the passivation layer; ) Is a schematic cross-sectional structure diagram along line IX-IX. FIG. 20 is a schematic plan pattern configuration diagram showing a state in which a backsheet passivation layer is formed on a colored barrier layer, which is one step of a manufacturing process of an organic thin-film solar cell according to an embodiment; The typical cross-section figure which follows the XX line of (a). It is one process of the manufacturing process of the organic thin-film solar cell which concerns on embodiment, Comprising: (a) Typical plane pattern block diagram which shows the state which formed the 1st through-hole and the 2nd through-hole, (b) FIG. 21 ( The typical cross-section figure which follows the XI-XI line of a). The flowchart which shows the preparation procedure of the organic thin film solar cell which concerns on embodiment. The typical bird's-eye view structure figure which is one process of the mass production manufacturing process of the organic thin-film solar cell which concerns on embodiment, and shows the state which formed the stripe pattern of the transparent electrode layer on the board | substrate. The typical bird's-eye view structure figure which is one process of the mass-production manufacturing process of the organic thin-film solar cell which concerns on embodiment, and shows the state which formed the positive hole transport layer by the spin coat on the stripe-shaped transparent electrode layer. The typical bird's-eye view structure figure which is one process of the mass production manufacturing process of the organic thin-film solar cell which concerns on embodiment, and shows the state which formed the bulk heterojunction organic active layer on the positive hole transport layer by spin coating. A process for mass production of organic thin-film solar cells according to an embodiment, wherein a stripe pattern of the second electrode layer is formed on the bulk heterojunction organic active layer so as to be orthogonal to the stripe-shaped transparent electrode layer The typical bird's-eye view block diagram which shows a state. In the organic thin-film solar cell which concerns on embodiment, the typical plane pattern block diagram which shows the example which has arrange | positioned several cell Cij in matrix form. In the method for manufacturing an organic thin-film solar cell according to the embodiment, (a) a schematic view showing a spin coating method when forming a hole transport layer and a bulk heterojunction organic active layer, (b) formed holes The typical bird's-eye view block diagram which shows the example of a transport layer and a bulk heterojunction organic active layer. (A) Typical plane pattern block diagram of the organic thin-film solar cell concerning the modification 1 of embodiment, (b) Typical cross-section figure along the XII-XII line of Fig.29 (a), (c) Circuit expression . It is one process of the manufacturing method of the organic thin film solar cell which concerns on embodiment, Comprising: (a) The typical cross-section figure which shows the state which patterned the transparent electrode layer on the board | substrate, (b) It is positive on a transparent electrode layer. Schematic cross-sectional structure diagram showing the state where the hole transport layer is formed, (c) Schematic cross-sectional structure diagram showing the state where the bulk heterojunction organic active layer is formed on the hole transport layer, (d) To the bulk The typical cross-section figure which shows the state which patterned the 2nd electrode layer on the terror junction organic active layer. FIG. 2 is a schematic cross-sectional structure diagram showing a state in which an oxide film is formed on the surface of the second electrode layer by oxygen plasma treatment, which is a step of the method for manufacturing an organic thin-film solar cell according to the embodiment; ) A schematic cross-sectional structure diagram showing a state in which a passivation layer is formed on the entire surface of the device, and (c) a schematic cross-sectional structure diagram showing a state in which a colored barrier layer is formed on the passivation layer. It is one process of the manufacturing method of the organic thin-film solar cell which concerns on embodiment, Comprising: (a) The typical cross-section figure which shows the state which formed the backsheet passivation layer on the coloration barrier layer, (b) 1st penetration The typical cross-section figure which shows the state which formed the hole and the 2nd through-hole. It is one process of the manufacturing method of the organic thin-film solar cell concerning embodiment, Comprising: (a) The typical cross-section figure which shows the state which formed the 1st terminal electrode and the 2nd terminal electrode, (b) FIG. 33 (a) FIG. The typical plane block diagram of the electronic device to which the organic thin-film solar cell which concerns on embodiment is applied. FIG. 35 is a schematic cross-sectional structure diagram taken along line XIII-XIII in FIG. 34. FIG. 35 is a schematic cross-sectional structure diagram taken along line XIV-XIV in FIG. 34. FIG. 35 is a schematic cross-sectional structure diagram taken along line XV-XV in FIG. 34. (A) Schematic cross-sectional structure diagram of an electronic device having a tandem structure to which the organic thin film solar cell according to the embodiment is applied, (b) Schematic of an electronic device having an in-cell structure to which the organic thin film solar cell according to the embodiment is applied. FIG. (A) Typical plane pattern block diagram of the organic thin-film solar cell which concerns on the modification 2 of embodiment, (b) The typical cross-section figure along the XVI-XVI line of Fig.39 (a). It is one process of the manufacturing method of the organic thin-film solar cell concerning the modification 2 of embodiment, Comprising: (a) Typical cross-section figure which shows the state which patterned the transparent electrode layer on the board | substrate, (b) Transparent electrode A schematic cross-sectional structure diagram showing a state in which a hole transport layer is formed on the layer, (c) a schematic cross-sectional structure diagram showing a state in which a bulk heterojunction organic active layer is formed on the hole transport layer, d) A schematic cross-sectional structure diagram showing a state in which a third through hole that penetrates the hole transport layer and the bulk heterojunction organic active layer and reaches the first electrode layer is formed in a direction perpendicular to the substrate. It is one process of the manufacturing method of the organic thin film solar cell which concerns on the modification 2 of embodiment, Comprising: While forming a 2nd electrode layer on a bulk heterojunction organic active layer, a 3rd through-hole is formed. FIG. 4B is a schematic cross-sectional structure diagram illustrating a state in which a VIA electrode layer connected to the first electrode layer is formed, and (b) an oxide film is formed on the surfaces of the second electrode layer and the VIA electrode layer by oxygen plasma treatment; The typical cross-section figure which shows the state which formed the passivation layer, the colorization barrier layer, and the back sheet passivation layer on the 2 electrode layer and the VIA electrode layer. It is one process of the manufacturing method of the organic thin film solar cell which concerns on the modification 2 of embodiment, Comprising: A VIA electrode penetrates a back sheet passivation layer, a colored barrier layer, and a passivation layer in a direction perpendicular to the substrate The typical cross-section figure which shows the state which formed the 4th through-hole which reaches to a layer, and the 2nd through-hole which reaches to a 2nd electrode layer.

  Next, embodiments will be described with reference to the drawings. In the following description of the drawings, the same or similar parts are denoted by the same or similar reference numerals. However, it should be noted that the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. Therefore, specific thicknesses and dimensions should be determined in consideration of the following description. Moreover, it is a matter of course that portions having different dimensional relationships and ratios are included between the drawings.

  Further, the embodiments described below exemplify apparatuses and methods for embodying the technical idea of the present invention, and the embodiments of the present invention include the material, shape, structure, The layout is not specified as follows. Various modifications can be made to the embodiment of the present invention within the scope of the claims.

[Embodiment]
In the organic thin film solar cell according to the following embodiments, “transparent” is defined as having a transmittance of about 50% or more. Further, “transparent” is also used to mean colorless and transparent with respect to visible light in the organic thin film solar cell according to the embodiment. Visible light corresponds to a wavelength of about 360 nm to 830 nm and an energy of about 3.45 eV to 1.49 eV, and is transparent if the transmittance is 50% or more in this region.

As shown in FIG. 1A, the organic thin-film solar cell 1 according to the embodiment includes a substrate 10, a transparent electrode layer (first electrode layer) 11 disposed on the substrate 10, and a first electrode layer 11. The hole transport layer 12 disposed above, the bulk heterojunction organic active layer 14 disposed on the hole transport layer 12, and the cathode electrode layer (second electrode layer) disposed on the bulk heterojunction organic active layer 14 16, a passivation layer 26 disposed on the second electrode layer 16, and a surface perpendicular to the substrate 10, and penetrates the passivation layer 26, the bulk heterojunction organic active layer 14, and the hole transport layer 12. The first lead-out terminal electrode 38 ₁ connected to the first electrode layer 11 and the substrate 10 are arranged in a direction perpendicular to the substrate 10 and pass through the passivation layer 26 and connected to the second electrode layer 16. a second lead terminal electrodes 38 ₂ Is provided.

The first extraction terminal electrode 38 ₁ can be connected to any position of the first electrode layer 11.

Second extraction terminal electrodes 38 ₂ are connectable to an arbitrary position of the second electrode layer 16.

In addition, as shown in FIGS. 1A and 1B, the organic thin-film solar cell 1 according to the embodiment includes a colored barrier layer 28 disposed on the passivation layer 26, and a colored barrier layer 28. Even if it has a back sheet passivation layer 30 disposed on top and a resin layer 40 disposed on the back sheet passivation layer 30 and sealing the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 _2. good.

  The colored barrier layer 28 can be formed of, for example, an ultraviolet curable resin.

  Further, a coloring agent may be added to the colored barrier layer 28. As the colorant, for example, black can be applied, for example, carbon black, blue can be applied, for example, a phthalocyanine paint, and red, for example, alizarin paint.

  The passivation layer 26 can be formed of, for example, a SiN film or a SiON film.

  The colored barrier layer 28 can cover spots formed on the passivation layer 26.

Further, the passivation layer 26 and the colored barrier layer 28 may be repeatedly stacked to form a multi-layer protective film.

  As shown in FIG. 1A, the organic thin-film solar cell 1 according to the embodiment has a thinned element structure by using a protective film (colored barrier layer 28) to which a colorant is added. Arbitrary coloration was made possible on the module.

  As shown in FIG. 1A, the organic thin-film solar cell 1 according to the embodiment has an organic layer (12, 14) having a thickness of about several hundreds of nanometers serving as a power generation layer on a glass substrate 10 with ITO. The second electrode layer 16 is formed by stacking and depositing a metal layer such as aluminum.

  Since pure aluminum formed as the second electrode layer 16 is easily oxidized, a passive film 24 may be formed as shown in FIG. 1A in order to provide durability.

  Since organic layers such as the hole transport layer 12 and the bulk heterojunction organic active layer 14 are disposed on the substrate 10, when the passivation layer 26 is formed by forming the passivation film 24, these organic layers are formed on the organic layer. It is possible to prevent damage.

  The colored barrier layer 28 disposed on the passivation layer 26 serves as a protective layer for the cells of the organic thin-film solar cell 1 according to the embodiment.

  The colored barrier layer 28 can be formed of a color filter that can be arbitrarily patterned by ultraviolet (UV) irradiation. By using such a color filter that can be patterned as a protective layer, the organic thin-film solar cell 1 according to the embodiment can impart design properties to the protective layer, thereby reducing manufacturing steps and improving design properties. Enable.

  In the organic thin film solar cell 1 according to the embodiment, the passivation layer 26 and the colored barrier layer 28 can be formed by laminating an inorganic passivation film such as SiN or SiON by CVD and a resin protective film in multiple layers.

  In the organic thin film solar cell 1 according to the embodiment, in order to enable coloring without changing the module process, by adding a dye to the material of the resin protective film, any part other than the module cell can be arbitrarily selected. I was able to be colored in the color of. Since this resin material can leave a pattern only in a portion irradiated with UV after coating and forming, it is possible to perform a color scheme on the back with an arbitrary pattern.

  As the colorant, for example, black can be applied, for example, carbon black, blue can be applied, for example, a phthalocyanine paint, and red, for example, alizarin paint.

  According to the embodiment, an organic thin-film solar cell that can improve the electrode take-out structure, can form a connection point at an arbitrary position without causing a large structural change in appearance, and can be reduced in weight and thickness. Can be provided.

  An example of the organic thin-film solar cell module in which an arbitrary pattern is colored and characters are embedded will be described later (see FIGS. 34 to 29).

(Operating principle)
A schematic diagram illustrating the operating principle of the organic thin-film solar cell 1A is expressed as shown in FIG. Moreover, the energy band structure of the various materials of the organic thin film solar cell 1A shown in FIG. 2 is expressed as shown in FIG. With reference to FIG. 2 and FIG. 3, the principle structure and operation | movement of the organic thin-film solar cell 1A which concern on embodiment are demonstrated.

  As shown in the left diagram of FIG. 2, the organic thin film solar cell 1 </ b> A includes a substrate 10, a transparent electrode layer 11 disposed on the substrate 10, a hole transport layer 12 disposed on the transparent electrode layer 11, A bulk heterojunction organic active layer 14 disposed on the hole transport layer 12 and a second electrode layer 16 disposed on the bulk heterojunction organic active layer 14 are provided. The second electrode layer 16 is made of, for example, aluminum (Al) and serves as a cathode electrode layer.

  Here, as shown in the right diagram of FIG. 2, the bulk heterojunction organic active layer 14 includes a p-type organic active layer region and an n-type organic active layer region, thereby forming a complex bulk hetero pn junction. ing. Here, the p-type organic active layer region is formed of, for example, P3HT (poly (3-hexylthiophene-2,5diyl)), and the n-type organic active layer region is, for example, PCBM (6,6-phenyl-C61-). butyric acid methyl ester).

(A) First, when light is absorbed, excitons are generated in the bulk heterojunction organic active layer 14.

(B) Next, excitons dissociate into free carriers of electrons (e−) and holes (h +) by spontaneous polarization at the pn junction interface in the bulk heterojunction organic active layer 14.

(C) Next, the dissociated holes (h +) travel toward the transparent electrode layer 11 serving as the anode electrode, and the dissociated electrons (e−) travel toward the cathode electrode layer 16.

(D) As a result, a reverse current is conducted between the cathode electrode layer 16 and the transparent electrode layer 11, and an open circuit voltage Voc is generated, whereby the organic thin film solar cell 1A is obtained.

  In the organic thin film solar cell 1A, the chemical structural formula of PEDOT among PEDOT: PSS applied to the hole transport layer 12 is represented as shown in FIG. 4A, and the chemical structural formula of PSS is shown in FIG. It is expressed as shown in b).

  In the organic thin film solar cell 1A, the chemical structural formula of P3HT applied to the bulk heterojunction organic active layer 14 is expressed as shown in FIG. 5A, and the chemical structure of PCBM applied to the bulk heterojunction organic active layer 14 The equation is expressed as shown in FIG.

In the organic thin film solar cell 1A, examples of chemical structural formulas of materials used in vacuum deposition are as follows. That is, an example of phthalocyanine (Pc) is expressed as shown in FIG. 6A, and an example of zinc phthalocyanine (ZnPc: Zinc-phthalocyanine) is expressed as shown in FIG. An example of -Ptcdi (N, N′-dimethyl perylene-3,4,9,10-dicarboximide) is represented as shown in FIG. 6C, and an example of fullerene (C ₆₀ : Buckminster fullerene) 6 (d).

  In the organic thin film solar cell 1A, examples of chemical structural formulas of materials used in the solution process are as follows. That is, an example of MDMO-PPV (poly [2-methoxy-5- (3,7-dimethyl octyloxy)]-1,4-phenylene vinylene) is expressed as shown in FIG. An example of PFB (poly (9,9'-dioctylfluorene-co-bis-N, N '-(4-butylphenyl) -bis-N, N'-phenyl-1,4-phenylenediamine) is shown in FIG. 7 (b). An example of CN-MDMO-PPV (poly- [2-methoxy-5- (2'-ethylhexyloxy) -1,4- (1-cyanovinylene) -phenylene]) is shown in FIG. c) PFO-DBT (poly [2,7- (9,9-dioctyl-fluorene) -alt-5,5- (4,7'-di-2-thienyl-2 ') , 1 ′, 3′-benzothiadiazole)]) is represented as shown in FIG.

  An example of F8BT (poly (9,9′-dioctyl fluoreneco-benzothiadiazole)) is represented as shown in FIG. 7 (e), and PCDTBT (poly [N-9′-hepta-decanyl-2,7- An example of carbazole-alt-5,5- (4 ′, 7′-di-thienyl-2′1 ′, 3′-b3nzothiadizaole)]) is represented as shown in FIG.

An example of PC ₆₀ BM (6,6-phenyl-C61-butyric acid methyl ester) is represented as shown in FIG. 7 (g), and PC ₇₀ BM (6,6-phenyl-C71-butyric acid methyl ester). An example of ester) is represented as shown in FIG.

  The passive film 24 is composed of an oxide film of the second electrode layer 16. The oxide film of the second electrode layer 16 can be formed by performing oxygen plasma treatment on the surface of the second electrode layer 16. The thickness of the passivation film 24 is, for example, about 10 angstroms to about 100 angstroms. In addition, although illustration is abbreviate | omitted, you may provide the passivation film arrange | positioned on the passive film 24. FIG. This passivation film can be composed of, for example, a SiN film or a SiON film.

The second electrode layer 16 may be made of any one of Al, W, Mo, Mn, and Mg. When the second electrode layer 16 is formed of Al, the passive film 24 is an alumina (Al ₂ O ₃ ) film.

  In the organic thin-film solar cell 1 having the passive film 24 on the surface of the second electrode layer 16, even if moisture or oxygen enters the bulk heterojunction organic active layer 14, the second electrode layer 16 has its moisture / Oxidation by oxygen can be prevented. Thereby, deterioration of an organic solar cell can be suppressed and durability can be improved.

(Production method)
FIG. 8A shows a process of preparing an ITO substrate in which the transparent electrode layer 11 is formed on the substrate 10 as a process, which is a process of the method for manufacturing the organic thin-film solar cell according to the embodiment. The step of patterning the hole transport layer 12 on the transparent electrode layer 11 after patterning the transparent electrode layer 11 is expressed as shown in FIG. 8B, and the bulk heterojunction is formed on the hole transport layer 12. The step of patterning the organic active layer 14 is expressed as shown in FIG. 8C, and the step of patterning the second electrode layer 16 on the bulk heterojunction organic active layer 14 is shown in FIG. It is expressed as shown in

  In addition, a process of forming the passive film (oxide film) 24 on the surface of the second electrode layer 16 as a process of the method for manufacturing the organic thin film solar cell according to the embodiment is illustrated in FIG. 9B, the process of forming the passivation layer 26 on the entire surface of the device is expressed as shown in FIG. 9B, and the process of forming the colored barrier layer 28 on the passivation layer 26 is shown in FIG. Represented as shown.

A step of forming the backsheet passivation layer 30 on the colored barrier layer 28, which is a step of the method for manufacturing the organic thin film solar cell according to the embodiment, is expressed as shown in FIG. 10 passes through the backsheet passivation layer 30, the colored barrier layer 28, the passivation layer 26, the bulk heterojunction organic active layer 14, and the hole transport layer 12 in a direction perpendicular to the surface 10 and reaches the first electrode layer 11. first forming a through-hole 36 _1, and in the orthogonal direction to the substrate 10, through the backsheet passivation layer 30, the color of the barrier layer 28, passivation layer 26 and reaches the second electrode layer 16 forming a second through-hole 36 ₂ is expressed as shown in FIG. 10 (b), first through the through-hole 36 _1, the second through-hole 36 _2, first electrode layer 11, second conductive Forming a first extraction terminal electrodes 38 _1-second lead terminal electrodes 38 ₂ connected to the layer 16 is expressed as shown in Figure 10 (c).

  The manufacturing method of the organic thin-film solar cell 1 according to the embodiment includes a step of patterning the first electrode layer 11 on the substrate 10 as shown in FIGS. 8 to 10 and FIG. Patterning the hole transport layer 12 on the layer 11, patterning the bulk heterojunction organic active layer 14 on the hole transport layer 12, and forming the second electrode layer 16 on the bulk heterojunction organic active layer 14. A step of forming a pattern, a step of forming a passivation layer 26 on the second electrode layer 16, a step of forming a colored barrier layer 28 on the passivation layer 26, and a backsheet passivation layer 30 on the colored barrier layer 28. Forming the step.

  With reference to FIGS. 8-10 and FIG. 1 (a), the manufacturing method of the organic thin-film solar cell concerning embodiment is demonstrated.

(A) First, as shown in FIG. 8A, the transparent electrode layer 11 made of, for example, ITO is patterned on the substrate 10. For the patterning of the transparent electrode layer 11, a wet etching technique, an oxygen plasma etching technique, a laser patterning technique, a nanoimprint technique, and the like can be applied.

(B) Next, as shown in FIG. 8B, the hole transport layer 12 is patterned on the patterned transparent electrode layer 11. For the formation of the hole transport layer 12, a spin coating technique, a spray technique, a screen printing technique, or the like can be applied. Here, in the step of forming the hole transport layer 12, for example, PEDOT: PSS is formed by spin coating, and annealing is performed at 120 ° C. for about 10 minutes in order to remove moisture.

(C) Next, as shown in FIG. 8C, a bulk heterojunction organic active layer 14 to be a power generation layer is formed on the hole transport layer 12. In the step of forming the bulk heterojunction organic active layer 14, for example, P3HT is formed by spin coating. In forming the bulk heterojunction organic active layer 14, after forming into a film using an inkjet method, heating is performed at about 100 ° C. to 120 ° C. for about 10 minutes to 30 minutes in order to dry the organic solvent. .

(D) Next, as shown in FIG. 8D, the cathode electrode layer 16 is patterned on the bulk heterojunction organic active layer 14. For the formation of the cathode electrode layer 16, for example, a metal layer such as Al, W, Mo, Mn, and Mg can be formed by a vacuum heating vapor deposition method. Further, screen printing technology may be applied.

(E) Next, as shown in FIG. 9A, an oxide film (passive film) 24 is formed on the surface of the second electrode layer 16. The passive film 24 can be formed by subjecting the second electrode layer 16 to oxygen plasma treatment. The excess organic layer is removed by oxygen plasma, and an oxide film treatment is performed on the aluminum resurface.

(F) Next, as shown in FIG. 9B, a passivation layer 26 is formed on the second electrode layer 16. Here, the passivation layer 26 may be formed of a silicon nitride film, a silicon oxynitride film, or the like by a CVD method. The thickness of the silicon nitride film / silicon oxynitride film is, for example, about 0.5 μm to 1.5 μm. In order to suppress deterioration due to moisture and oxygen in the atmosphere, durability can be further improved by sealing with a SiN film / SiON film formed by CVD.

(G) Next, as shown in FIG. 9C, a colored barrier layer 28 is formed on the passivation layer 26. Here, in order to eliminate defects such as spots on the passivation layer 26 formed of a SiN film and smooth the back surface of the module, a UV curable resin material is applied by a spin coat method or the like and cured by UV irradiation. Here, the colored barrier layer 28 uses a protective film to which a colorant is added, so that the module can be arbitrarily colored with a thinned element structure.

(H) Next, as shown in FIG. 10A, a backsheet passivation layer 30 is formed on the colored barrier layer 28. For the backsheet passivation layer 30, for example, a silicon nitride film or the like may be formed by a CVD method. The thickness of the silicon nitride film is, for example, about 0.5 μm to 1.5 μm. In order to suppress deterioration due to moisture and oxygen in the atmosphere, durability can be further improved by sealing with a SiN film formed by CVD.

(I) Next, as shown in FIG. 10B, the backsheet passivation layer 30, the colored barrier layer 28, the passivation layer 26, and the bulk heterojunction organic active layer 14 in a direction perpendicular to the substrate 10. - through the hole transport layer 12, to the first electrode layer 11 to form a first through-hole 36 ₁ to reach, and in the orthogonal direction with respect to the substrate 10, the backsheet passivation layer 30, the color of the barrier layer 28 - a passivation layer 26 through, to form the second through holes 36 ₂ to reach the second electrode layer 16. The first through hole 36 ₁ and the second through hole 36 ₂ are formed using laser cutting or mechanical cut such as laser ablation. The first through-hole 36 ₁ to the backsheet passivation layer 30, the colorization barrier layer 28, the passivation layer 26, the bulk heterojunction organic active layer 14, and the hole transport layer 12 necessary for contacting the first electrode layer 11. Can be formed using a laser beam having a diameter of about 5 μm (for example, a wavelength of 532 nm). Similarly, the second through holes 36 ₂ to the back sheet passivation layer 30, the color of the barrier layer 28, passivation layer 26 necessary for contacting the second electrode layer 16 has a diameter of about 5μm about the laser beam (e.g., It can be formed using a wavelength of 532 nm. Further, a plurality of the first through holes 36 ₁ and the second through holes 36 ₂ may be formed in accordance with the respective resistance values limited to one.

(J) Next, FIG. 10 (c), the first take-out terminal electrodes 38 ₁ connected to the first electrode layer 11 in the first through hole 36 in _one form, the second through-hole 36 ₂ second to form the takeout lead terminal electrodes 38 ₂ connected to the second electrode layer 16 on the inner. For example, a carbon paste, an Ag paste, or the like is used for bonding the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ to the first electrode layer 11 and the second electrode layer 16. The first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ can be formed of, for example, a gold wire.

(K) Finally, as shown in FIG. 10C, the vicinity of the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ is protected with UV curable resin so that moisture, oxygen and the like do not enter.

In this way, by forming the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ in a direction perpendicular to the substrate 10, the contact resistance can be reduced without deteriorating the appearance, and good Can be formed.

  The organic thin-film solar cell 1 according to the embodiment can be completed through the above steps.

  Depending on the required module durability, a step of forming a passivation layer 26 such as a silicon nitride film (FIG. 9B), a step of forming a colored barrier layer 28 on the passivation layer 26 (FIG. 9C). )) May be repeated to form a multi-layered protective film.

In the organic thin-film solar cell according to the embodiment, a schematic cross-sectional structure for explaining how the spots 41H formed on the passivation layers 41 ₁ and 41 ₂ are covered with the colored barrier layers 42 ₁ and 42 ₂ is shown in FIG. expressed as (a), the passivation layer 41 _1, 41 _2, 41 _3, 41 ₄ and the color of the barrier layer 42 _1, 42 _2, 42 _3, 42 ₄ multi layered protection to form multiple layers repeatedly laminated A schematic cross-sectional structure of the film is expressed as shown in FIG.

  Moreover, the opening part of a cell is arbitrarily patterned by the inkjet method etc. In addition, the coloring barrier layer 28 (resin protective film) to which a dye is added can also be subjected to arbitrary patterning by using an inkjet method or the like. Here, the opening portion of the cell corresponds to, for example, the display region 2 and the character formation region 6 (see FIGS. 34 to 37).

(Multiple arrangement configuration)
A schematic planar pattern configuration of the organic thin-film solar cell 1 according to the embodiment arranged in series (in the example of the figure, three) is represented as shown in FIG. 12 (a), and FIG. A schematic cross-sectional structure taken along line II-II is represented as shown in FIG. 12B, and a circuit representation is represented as shown in FIG.

(Production method)
A method for manufacturing an organic thin-film solar cell according to an embodiment in which a plurality (three in the example in the figure) are arranged in series will be described.

  A schematic planar pattern configuration showing a state in which the transparent electrode layer 11 is formed on the substrate 10 in one step of the method for manufacturing the organic thin film solar cell according to the embodiment is shown in FIG. Then, a schematic cross-sectional structure along the line III-III in FIG. 13A is represented as shown in FIG.

  Moreover, the schematic plane pattern structure which shows the state which formed the positive hole transport layer 12 on the transparent electrode layer 11 is represented as shown to Fig.14 (a), and is shown by the IV-IV line of Fig.14 (a). The schematic cross-sectional structure along is represented as shown in FIG.

  Further, a schematic planar pattern configuration showing a state in which the bulk heterojunction organic active layer 14 is formed on the hole transport layer 12 is expressed as shown in FIG. 15A, and V in FIG. A schematic cross-sectional structure along the −V line is expressed as shown in FIG.

  Further, a schematic planar pattern configuration showing a state in which the second electrode layer 16 is formed on the bulk heterojunction organic active layer 14 is expressed as shown in FIG. A schematic cross-sectional structure along the VI line is expressed as shown in FIG.

  In addition, by oxygen plasma treatment, an excess organic layer is etched on the pattern in the hole transport layer 12 and the bulk heterojunction organic active layer 14, and a passive film (oxidation film) is formed on the surface of the second electrode layer 16. A schematic planar pattern configuration showing a state in which the (film) 24 is formed is expressed as shown in FIG. 17A, and a schematic cross-sectional structure taken along line VII-VII in FIG. ).

  Further, a schematic plane pattern configuration showing a state in which the passivation layer 26 is formed on the entire surface of the device is expressed as shown in FIG. 18A, and a schematic cross-sectional structure taken along line VIII-VIII in FIG. This is expressed as shown in FIG.

  Further, a schematic planar pattern configuration showing a state in which the colored barrier layer 28 is formed on the passivation layer 26 is expressed as shown in FIG. 19A, and is a schematic diagram along the line IX-IX in FIG. A typical cross-sectional structure is represented as shown in FIG.

  Further, a schematic planar pattern configuration showing a state in which the back sheet passivation layer 30 is formed on the colorization barrier layer 28 is expressed as shown in FIG. The schematic cross-sectional structure along is represented as shown in FIG.

The schematic planar pattern configuration showing a state of forming a first through-hole 36 ₁ and the second through-hole 36 ₂ is expressed as shown in FIG. 21 (a), XI-XI line shown in FIG. 21 (a) A schematic cross-sectional structure along the line is represented as shown in FIG.

  With reference to FIGS. 12-21, the manufacturing method of the organic thin-film solar cell based on Embodiment arrange | positioned in series (three in the example of a figure) is demonstrated.

(A) First, a glass substrate 10 (for example, length of about 50 mm × width of about 50 mm × thickness of about 10.4 mm) washed with pure water, acetone, and ethanol is placed in an ICP etcher, and the surface of the glass substrate 10 is washed with O ₂ plasma. Remove deposits (glass substrate surface treatment). In addition, in order to form the board | substrate 10 with a glass substrate and to guide | invade light to an organic active layer efficiently, you may implement an antireflection process on the glass surface.

(B) Next, as shown in FIGS. 13A and 13B, a transparent electrode layer 11 made of, for example, ITO is formed on the glass substrate 10. As shown in FIGS. 13 (a) and 13 (b), the transparent electrode layer 11 is formed in a plurality of stripe patterns sandwiching the groove. An oxygen plasma etching technique, a laser patterning technique, a nanoimprint technique, or the like can be applied to the formation of the groove.

(C) Next, as shown in FIGS. 14A and 14B, the hole transport layer 12 is formed on each transparent electrode layer 11. For the formation of the hole transport layer 12, a spin coating technique, a spray technique, a screen printing technique, or the like can be applied. Here, in the step of forming the hole transport layer 12, for example, PEDOT: PSS is formed by spin coating, and annealing is performed at 120 ° C. for about 10 minutes to remove moisture. An oxygen plasma etching technique, a laser patterning technique, a nanoimprint technique, or the like can be applied to the formation of the groove.

(D) Next, as shown in FIGS. 15A and 15B, a bulk heterojunction organic active layer 14 is formed on each hole transport layer 12. In the formation process of the bulk heterojunction organic active layer 14, for example, P3HT is formed by spin coating.

(E) Next, as shown in FIGS. 16A and 16B, the cathode electrode layer 16 is patterned on each bulk heterojunction organic active layer 14. The cathode electrode layer 16 is formed, for example, by depositing a metal layer such as Al, W, Mo, Mn, and Mg by a vacuum heating vapor deposition method. A screen printing technique may be applied instead of the vacuum heating deposition method. As shown in FIGS. 16A and 16B, the cathode electrode layer 16 is provided with an opening to form a through hole 34.

(F) Next, as shown in FIGS. 17A and 17B, after the bulk heterojunction organic active layer 14 and the hole transport layer 12 are etched, an oxide film (on the surface of the cathode electrode layer 16 is formed). Passive film) 24 is formed. Each cell can be separated by etching the bulk heterojunction organic active layer 14 and the hole transport layer 12. The passive film 24 can be formed by subjecting the second electrode layer 16 to oxygen plasma treatment. The passive film 24 can be formed using, for example, a high-density plasma etching apparatus. In addition, it is also possible to etch the bulk heterojunction organic active layer 14 and the hole transport layer 12 at the same time as forming the passive film 24 by performing oxygen plasma treatment on the second electrode layer 16.

(G) Next, as shown in FIGS. 18A and 18B, a passivation layer 26 is formed on the entire surface of the device. Here, as the passivation layer 26, a silicon nitride film or the like may be formed by a CVD method. The thickness of the silicon nitride film is, for example, about 0.5 μm to 1.5 μm. In order to suppress deterioration due to moisture and oxygen in the atmosphere, durability can be further improved by sealing with a SiN film formed by CVD.

(H) Next, as shown in FIGS. 19A and 19B, a colored barrier layer 28 is formed on the passivation layer 26. Here, in order to eliminate defects such as spots on the passivation layer 26 formed of a SiN film and smooth the back surface of the module, a UV curable resin material is applied by a spin coat method or the like and cured by UV irradiation. Here, the colored barrier layer 28 uses a protective film to which a colorant is added, so that the module can be arbitrarily colored with a thinned element structure.

(I) Next, as shown in FIGS. 20A and 20B, a backsheet passivation layer 30 is formed on the colored barrier layer 28. For the backsheet passivation layer 30, for example, a silicon nitride film or the like may be formed by a CVD method. The thickness of the silicon nitride film is, for example, about 0.5 μm to 1.5 μm. In order to suppress deterioration due to moisture and oxygen in the atmosphere, durability can be further improved by sealing with a SiN film formed by CVD.

(J) Next, as shown in FIGS. 21 (a) and 21 (b), the back sheet passivation layer 30, the colored barrier layer 28, the passivation layer 26, and the bulk are formed in a direction perpendicular to the substrate 10. through the heterojunction organic active layer 14, the hole transport layer 12, to the first electrode layer 11 to form a first through-hole 36 ₁ to reach, and in the orthogonal direction with respect to the substrate 10, the backsheet passivation layer 30 - through the colored barrier layer 28, passivation layer 26, to form the second through holes 36 ₂ to reach the second electrode layer 16. The first through hole 36 ₁ and the second through hole 36 ₂ are formed using laser cutting or mechanical cut such as laser ablation. The first through-hole 36 _1, the laser beam diameter of about 5 [mu] m (e.g., wavelength 532 nm) can be formed by using a. Similarly, the second through-hole 36 ₂ also, the laser beam diameter of about 5 [mu] m (e.g., wavelength 532 nm) can be formed by using a. Further, a plurality of the first through holes 36 ₁ and the second through holes 36 ₂ may be formed in accordance with the respective resistance values limited to one.

(K) Next, as shown in FIGS. 12A and 12B, the first lead-out terminal electrode 38 ₁ connected to the first electrode layer 11 is formed in the first through hole 36 ₁ , second to form the takeout lead terminal electrodes 38 ₂ connected to the second electrode layer 16 in the second through-hole 36 _2. For example, a carbon paste, an Ag paste, or the like is used for bonding the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ to the first electrode layer 11 and the second electrode layer 16. The first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ can be formed of, for example, a gold wire.

(L) Finally, as shown in FIGS. 12A and 12B, the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 are made of UV curable resin so that moisture, oxygen, etc. do not enter. Protect the vicinity of ₂ .

In this way, by forming the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ in a direction perpendicular to the substrate 10, the contact resistance can be reduced without deteriorating the appearance, and good Can be formed.

  Through the above steps, a plurality (three in the illustrated example) of the organic thin-film solar cells 1 according to the embodiment arranged in series can be completed.

(Procedure for making organic thin-film solar cells)
Based on the flowchart shown in FIG. 22, the preparation procedure of the organic thin-film solar cell 1 which concerns on embodiment is demonstrated.

(A) In step S <b> 1, PEDOT: PSS is applied on the substrate 10. For example, the PEDOT: PSS aqueous solution is filtered with a 0.45 μm PTFE membrane filter to remove undissolved residues and impurities, and the PEDOT: PSS aqueous solution is applied onto the ITO substrate 10 and spin-coated (for example, 4000 rpm, 30 sec).

(B) In step S2, PEDOT: PSS is sintered. That is, after film formation, heat treatment is performed at 120 ° C. for 10 minutes to remove moisture. In addition, it is good to cover the petri dish previously warmed with the hot plate so that heat may be transmitted to the whole substrate 10.

(C) In step S3, P3HT: PCBM is applied. Specifically, for example, 16 mg of P3HT and 16 mg of PCBM are dissolved in dichlorobenzene (o-dichlorobenzen). The solution is stirred overnight at 50 ° C. in a nitrogen atmosphere and then sonicated at 50 ° C. for 1 minute. The solution is spin-coated on the ITO substrate 10 cleaned in a nitrogen-substituted glove box (<1 ppm O ₂ , H ₂ O). The number of rotations is, for example, 2000 rpm · 1 sec after 550 rpm · 60 sec.

(D) In step S4, pre-annealing is performed. That is, after the application in step S3, heating is performed at 120 ° C. for 10 minutes. In addition, it is good to cover the petri dish previously warmed with the hot plate so that heat may be transmitted to the whole substrate 10.

(E) In step S5, LiF vacuum deposition is performed. Specifically, LiF (purity: 99.98%) is subjected to vacuum heating vapor deposition at a degree of vacuum of 1.1 × 10 ⁻⁶ torr / deposition rate of 0.1 kg / sec.

(F) In step S6, the second electrode layer 16 is formed by performing Al vacuum deposition. Specifically, Al (purity: 99.999%) is subjected to vacuum heating deposition with a degree of vacuum: 1.1 × 10 ⁻⁶ torr and a deposition rate of ˜2Å / sec.

(G) In step S7, an electrode oxide film treatment is performed on the second electrode layer 16. Specifically, the oxide film 24 is formed by oxidizing the surface of the second electrode layer 16 with oxygen plasma using a high-density plasma etching apparatus.

(H) In step S8, sealing is performed. Specifically, a passivation layer 26, a colored barrier layer 28, and a backsheet passivation layer 30 are sequentially laminated on the entire device to seal the element.

(I) In step S9, a through hole is formed. Specifically, the first through-hole 36 _1, the second through hole 36 _second contact hole laser vias Thing for contacting a first electrode layer 11, second electrode layer 16, or a mechanical cutting such as a laser ablation Use to form.

(J) In step S10, a terminal electrode is formed. Specifically, the first extraction terminal electrode 38 ₁ , the second extraction terminal electrode 38 ₂ , the first electrode layer 11, the second electrode layer 16, and the like through the first through hole 36 ₁ and the second through hole 36 _2. Are connected using bonding. The first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ can be formed of a gold wire or the like. Carbon paste, Ag paste, or the like is used for the bonding junction between the first extraction terminal electrode 38 ₁ and the first electrode layer 11 and the bonding junction between the second extraction terminal electrode 38 ₂ and the second electrode layer 16.

(K) In step S11, sealing is performed. Specifically, the peripheral portions of the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ are protected by a resin layer 40 such as UV curable resin so that moisture, oxygen, and the like do not enter.

(Mass production process)
As shown in FIGS. 23 to 27, the organic thin-film solar cell according to the embodiment can be manufactured by arranging a plurality of cells in a matrix and performing a mass production process.

  Hereinafter, a description will be given with reference to FIGS.

(A) First, a glass substrate 10 washed with pure water, acetone, and ethanol is placed in an ICP etcher, and surface deposits are removed by O ₂ plasma (glass substrate surface treatment). In order to efficiently guide light to the organic active layer, an antireflection treatment may be performed on the surface of the glass substrate 10.

(B) Next, as shown in FIG. 23, a transparent electrode layer 11 made of, for example, ITO is formed on the substrate 10. In the example shown in FIG. 23, the transparent electrode layer 11 is formed in two stripe patterns with a gap therebetween. For forming the gap, an oxygen plasma etching technique, a laser patterning technique, a nanoimprint technique, or the like can be applied.

(C) Next, as shown in FIG. 24, the hole transport layer 12 is formed on the substrate 10 and the transparent electrode layer 11. For the formation of the hole transport layer 12, a spin coating technique, a spray technique, a screen printing technique, or the like can be applied. Here, in the step of forming the hole transport layer 12, for example, PEDOT: PSS is formed by spin coating, and annealing is performed at 120 ° C. for about 10 minutes to remove moisture.

(D) Next, as shown in FIG. 25, a bulk heterojunction organic active layer 14 is formed on the hole transport layer 12. In the formation process of the bulk heterojunction organic active layer 14, for example, P3HT: PCBM is formed by spin coating. The thickness of the bulk heterojunction organic active layer 14 is, for example, about 100 nm to about 200 nm.

(E) Next, as shown in FIG. 26, two stripe pattern cathode electrode layers 16 are formed on the bulk heterojunction organic active layer 14 so as to be orthogonal to the transparent electrode layer 11.

  The cathode electrode layer 16 is formed, for example, by depositing Al, W, Mo, Mn, Mg, or the like by a vacuum heating vapor deposition method. A screen printing technique may be applied instead of the vacuum heating deposition method.

(F) Next, although not shown, an oxide film (passive film) is formed on the surface of the cathode electrode layer 16. The passive film can be formed by exposing the cathode electrode layer 16 to oxygen plasma. Formation of the oxide film by oxygen plasma can be performed using, for example, a plasma etching apparatus.

(G) Next, although not shown, a passivation layer 26, a colored barrier layer 28, and a backsheet passivation layer 30 are sequentially laminated on the entire device to form a first through hole 36 ₁ and a second through hole. 36 ₂ is formed, and the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ and the first electrode layer 11 and the second electrode layer 16 are formed through the first through hole 36 ₁ and the second through hole 36 _2. And finally, the peripheral portion of the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ with a resin layer 40 such as UV curable resin so that moisture, oxygen, etc. do not enter. Protect.

  Through the above steps, the organic thin-film solar cell 1 according to the embodiment can be mass-produced.

In the organic thin-film solar cell according to the embodiment, a schematic planar pattern configuration example in which a plurality of cells C _ij are arranged in a matrix is expressed as shown in FIG. An anode electrode pattern formed by the anode electrode layer 11, A _j , A _{j + 1} ,..., And an anode electrode pattern..., A _j , A _{j + 1} ,. Cells... C _ij are arranged at the intersections of the cathode electrode patterns..., K _i−1 , K _i , K _{i + 1 ,.} By selecting the anode electrode pattern ..., A _j , A _{j + 1} , ... and the cathode electrode pattern ..., K _i-1 , K _i , K _{i + 1} , ..., cells arranged at the intersections ... C It is also possible to separately measure the characteristics of _ij .

(Spin coating method)
In the method of manufacturing an organic thin film solar cell according to the embodiment, an outline showing a spin coating method when forming the hole transport layer 12 and the bulk heterojunction organic active layer 14 is shown in FIG. A schematic bird's-eye view showing an example of the hole transport layer 12 and the bulk heterojunction organic active layer 14 thus formed is expressed as shown in FIG.

  For example, in the organic thin film solar cell 1 according to the embodiment, when an element having a relatively small area is formed, a spin coating method as shown in FIG. 28A can be applied.

  That is, as shown in FIG. 28A, a spin coater including a spindle 62 that can be rotated at a high speed and connected to a driving source such as a motor, and a table 63 that is fixed to the spindle 62 and places the substrate 10 thereon is used. It is done.

  Then, the substrate 10 is placed on the table 63, a driving source such as a motor is operated, and the table 63 is rotated at a high speed in the directions of arrows A and B, for example, at 2000 to 4000 rpm. Next, using a dropper 60, a solution droplet 64 that forms the hole transport layer 12 and the bulk heterojunction organic active layer 14 is dropped. Thereby, the droplet 64 can form the positive hole transport layer 12 and the bulk heterojunction organic active layer 14 (refer FIG.28 (b)) of uniform thickness on the board | substrate 10 with a centrifugal force.

(Modification 1)
A schematic planar pattern configuration of the organic thin-film solar cell 1 according to Modification 1 of the embodiment is represented as shown in FIG. 29A, and is a schematic cross-sectional structure taken along line XII-XII in FIG. Is represented as shown in FIG. 29 (b), and the circuit representation is represented as shown in FIG. 29 (c).

As shown in FIGS. 29A to 29C, the organic thin-film solar cell 1 according to Modification 1 of the embodiment includes a substrate 10, a first electrode layer 11 disposed on the substrate 10, and The hole transport layer 12 disposed on the first electrode layer 11, the bulk heterojunction organic active layer 14 disposed on the hole transport layer 12, and the bulk heterojunction organic active layer 14 The second electrode layer 16, the passivation layer 26 disposed on the second electrode layer 16, and the substrate 10 are disposed in a direction perpendicular to the substrate 10, and the passivation layer 26, the bulk heterojunction organic active layer 14, and the hole transport through the layer 12, the first and the takeout terminal electrodes 38 ₁ connected to the first electrode layer 11 is disposed on the orthogonal direction to the substrate 10, through the passivation layer 26, second electrode layer 16 and a second take-out terminal electrode 38 ₂ which is connected to The

The first extraction terminal electrode 38 ₁ can be connected to any position of the first electrode layer 11.

Second extraction terminal electrodes 38 ₂ are connectable to an arbitrary position of the second electrode layer 16.

In addition, as shown in FIGS. 29A to 29C, the organic thin-film solar cell 1 according to the first modification of the embodiment includes a colored barrier layer 28 disposed on the passivation layer 26, and a color A backsheet passivation layer 30 disposed on the control barrier layer 28, and a resin layer 40 disposed on the backsheet passivation layer 30 and sealing the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 _2. You may have.

  The colored barrier layer 28 can be formed of, for example, an ultraviolet curable resin.

  Further, a coloring agent may be added to the colored barrier layer 28. As the colorant, for example, black can be applied, for example, carbon black, blue can be applied, for example, a phthalocyanine paint, and red, for example, alizarin paint.

  The passivation layer 26 can be formed of, for example, a SiN film or a SiON film.

  The colored barrier layer 28 can cover spots formed on the passivation layer 26.

Further, the passivation layer 26 and the colored barrier layer 28 may be repeatedly stacked to form a multi-layer protective film.

  A schematic cross-sectional structure showing a state in which the transparent electrode layer 11 is patterned on the substrate wetting, which is one step of the method for manufacturing the organic thin-film solar cell according to the embodiment, is expressed as shown in FIG. A schematic cross-sectional structure showing a state in which the hole transport layer 12 is formed on the transparent electrode layer 11 is expressed as shown in FIG. 30B, and a bulk heterojunction organic layer is formed on the hole transport layer 12. A schematic cross-sectional structure showing a state in which the active layer 14 is formed is expressed as shown in FIG. 30C, and shows a state in which the second electrode layer 16 is patterned on the bulk heterojunction organic active layer 14. A schematic cross-sectional structure is represented as shown in FIG.

  In addition, a schematic cross-sectional structure showing a state in which the oxide film 24 is formed on the surface of the second electrode layer 16 by oxygen plasma treatment, which is one step of the method for manufacturing the organic thin-film solar cell according to the embodiment, A schematic cross-sectional structure shown in FIG. 31 (a) and showing a state in which the passivation layer 26 is formed on the entire surface of the device is shown in FIG. 31 (b), and a colored barrier layer is formed on the passivation layer 26. A schematic cross-sectional structure showing a state in which 28 is formed is expressed as shown in FIG.

Further, FIG. 32A shows a schematic cross-sectional structure showing a state in which the back sheet passivation layer 30 is formed on the colored barrier layer 28 in one step of the method for manufacturing the organic thin film solar cell according to the embodiment. And pass through the backsheet passivation layer 30, the colored barrier layer 28, the passivation layer 26, the bulk heterojunction organic active layer 14, and the hole transport layer 12 in a direction perpendicular to the substrate 10. Te first through hole 36 ₁ has reached the first electrode layer 11 is disposed on the orthogonal direction to the substrate 10, through the backsheet passivation layer 30, the color of the barrier layer 28, passivation layer 26, schematic cross section showing a state of forming a second through-hole 36 ₂ has reached the second electrode layer 16 is expressed as shown in FIG. 32 (b).

Further, a step in the method of manufacturing the organic thin film solar cell according to the embodiment, the first through the through-hole 36 _1, the first take-out terminal electrodes 38 ₁ connected to the first electrode layer 11, the A schematic cross-sectional structure showing a state in which the _second lead-out terminal electrode 38 ₂ connected to the second electrode layer 16 is formed through the two through holes 36 ₂ is expressed as shown in FIG. An enlarged view of part A of 33 (a) is represented as shown in FIG. 33 (b).

As in the embodiment, the contact holes of the first through hole 36 ₁ and the second through hole 36 ₂ for contacting the first electrode layer 11 and the second electrode layer 16 are formed by laser biasing or laser ablation. It can be formed using a mechanical cut.

The first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ can be formed of a gold wire or the like.

Carbon paste, Ag paste, or the like is used for bonding bonding of the first extraction terminal electrode 38 ₁ / second extraction terminal electrode 38 ₂ and the first electrode layer 11 / second electrode layer 16. First takeout terminal electrode 38 ₁ and the bond connection between the first electrode layer 11, a carbon paste, and Ag paste is used. A second lead terminal electrodes 38 ₂ The bond connection 42 between the second electrode layer 16, a carbon paste, and Ag paste is used. Here, in particular, when the second electrode layer 16 is formed of AgMg, good bonding can be obtained by using an Ag paste for the bonding bonding portion 42. Further, the peripheral portions of the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ are protected by a resin layer 40 such as a UV curable resin so that moisture, oxygen and the like do not enter.

(Electronics)
In the organic thin film solar cell according to the embodiment, the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ can be extracted from the inside of the cell of the organic thin film solar cell, so that it is difficult to extract the end face. It becomes easy to mount on electronic devices such as mobile terminal devices. Electronic devices such as smartphones and tablet terminals, in particular, have an important appearance, so the first extraction terminal electrode is used when mounting organic thin-film solar cells on the display panel bezel (periphery of the display) or on the back. 38 ₁ · The second extraction terminal electrode 38 ₂ should not be noticeable. The via holes of the organic layer to the (12, 14) required for contacting with the first electrode layer 11 (TCO), a first through-hole 36 with a diameter of about 5μm about laser light (e.g., wavelength 532 nm) ₁ Can be formed. The first through-hole 36 ₁ may be a plurality of forms. The same applies to the second through-hole 36 _2. By using this method, the contact resistance can be reduced without deteriorating the appearance, and a good bond can be formed.

  A schematic planar configuration of an electronic device 200 to which the organic thin-film solar cell 1 according to the embodiment is applied is expressed as shown in FIG. As shown in FIG. 34, the electronic device 200 to which the organic thin film solar cell 1 according to the embodiment is applied includes an organic thin film solar cell formation region 4 and a character formation region 6 in the periphery of the display region 2.

  Moreover, the schematic cross-sectional structure along the XIII-XIII line of FIG. 34 is represented as shown in FIG. 35, and the schematic cross-sectional structure along the XIV-XIV line of FIG. 34 is represented as shown in FIG. A schematic cross-sectional structure taken along line XV-XV in FIG. 34 is expressed as shown in FIG.

  In the electronic device 200 to which the organic thin-film solar cell 1 according to the embodiment is applied, the organic thin-film solar cell forming region 4 includes a substrate 10 and a transparent electrode disposed on the substrate 10 as shown in FIGS. Layer (first electrode layer) 11, hole transport layer 12 disposed on first electrode layer 11, bulk heterojunction organic active layer 14 disposed on hole transport layer 12, and bulk heterojunction organic active layer A cathode electrode layer (second electrode layer) 16 disposed on 14, a passivation layer 26 disposed on the second electrode layer 16, a colored barrier layer 28 disposed on the passivation layer 26, and colorization A backsheet passivation layer 30 disposed on the barrier layer 28. A passive film 24 may be formed on the surface of the cathode electrode layer (second electrode layer) 16 as shown in FIGS.

  On the other hand, as shown in FIGS. 34 to 36, the display area 2 and the character forming area 6 include a substrate 10, a transparent electrode layer (first electrode layer) 11 disposed on the substrate 10, and a first electrode layer 11. A passivation layer 26 disposed above, a colored barrier layer 28 disposed on the passivation layer 26, and a backsheet passivation layer 30 disposed on the colored barrier layer 28 are provided.

Here, although not shown, for example, in the C region and D region of FIG. 37, the first extraction terminal electrode 38 ₁ ... Is provided via the plurality of first through holes 36 ₁ and second through holes 36 _2. second extraction terminal electrodes 38 ₂ can be formed so as inconspicuous. That is, it is arranged in a direction perpendicular to the substrate 10 and penetrates through the backsheet passivation layer 30, the colored barrier layer 28, the passivation layer 26, the bulk heterojunction organic active layer 14, and the hole transport layer 12, A first lead terminal electrode connected to one electrode layer, and a second electrode layer disposed in a direction perpendicular to the substrate 10 and penetrating through the backsheet passivation layer 30, the colored barrier layer 28, and the passivation layer 26. 16 may be provided with a second lead terminal electrode connected to 16.

Similarly, in the electronic device 200 to which the organic thin-film solar cell 1 according to Modification 2 (described later: FIG. 39) of the embodiment is applied, the organic thin-film solar cell formation region 4 is a substrate as in FIGS. 34 to 37. 10, a transparent electrode layer (first electrode layer) 11 disposed on the substrate 10, a hole transport layer 12 disposed on the first electrode layer 11, and a bulk heterostructure disposed on the hole transport layer 12. The junction organic active layer 14, the cathode electrode layer (second electrode layer) 16 disposed on the bulk heterojunction organic active layer 14, and the hole transport layer 12 and bulk heterojunction in a direction perpendicular to the substrate 10. the organic active layer 14 through a vIA electrode layer 16P of the third is connected to the first electrode layer 11 through the through-hole 36 ₃ reaching the first electrode layer 11, second electrode layer 16N and the vIA electrode layers 16P Passivation layer 2 placed on top When provided with a colored barrier layer 28 disposed on the passivation layer 26, and a backsheet passivation layer 30 disposed on the color of the barrier layer 28. A passive film 24 may be formed on the surface of the cathode electrode layer (second electrode layer) 16 as shown in FIGS.

  Further, as shown in FIGS. 34 to 36, the display area 2 and the character forming area 6 are disposed on the substrate 10, the first electrode layer 11 disposed on the substrate 10, and the first electrode layer 11. A passivation layer, a colored barrier layer 28 disposed on the passivation layer 26, and a backsheet passivation layer 30 disposed on the colored barrier layer 28.

Although illustration is omitted here, for example, the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 ₂ are not conspicuous through the plurality of first through holes 36 ₁ and second through holes 36 _2. Can be formed. That is, it is arranged in a direction perpendicular to the substrate 10 and penetrates the back sheet passivation layer 30, the colored barrier layer 28, the passivation layer 26, the bulk heterojunction organic active layer 14, and the hole transport layer 12, a first take-out terminal electrodes 38 ₁ connected to the electrode layers 16P, is disposed in the orthogonal direction to the substrate 10, through the backsheet passivation layer 30, the color of the barrier layer 28, passivation layer 26, the second it may comprise a second take-out terminal electrode 38 ₂ which is connected to the electrode layer 16N.

  The colored barrier layer 28 in the organic thin film solar cell forming region 4 is colored black by, for example, black Dye, and the colored barrier layer 28 in the character forming region 6 has a color different from black in order to arrange characters, For example, it is colored red.

  In addition, although illustration is abbreviate | omitted, the liquid crystal display (LCD: Liquid Crystal Display) or an organic EL (Electro Luminescence) display etc. can be formed in the board | substrate 10 corresponding to the display area | region 2, for example.

  An electronic device 300 having a tandem structure to which the organic thin-film solar cell according to the embodiment is applied includes a substrate 10 and an organic thin-film solar disposed on the substrate 10 via an adhesive layer 150 as shown in FIG. A battery forming region 4 is provided. The display area 2 is formed in the substrate 10. That is, in the electronic device 300 having a tandem structure to which the organic thin film solar cell according to the embodiment is applied, the substrate 10 and the organic thin film solar cell formation region 4 are separately formed, and these are formed in a tandem structure via the adhesive layer 150. It is arranged in the vertical type.

  Moreover, the in-cell structure electronic device 300 to which the organic thin film solar cell according to the embodiment is applied includes a substrate 10 and an organic thin film solar cell formation region 4 disposed on the substrate 10 as shown in FIG. With. That is, in the in-cell structure electronic device 300 to which the organic thin film solar cell according to the embodiment is applied, the organic thin film solar cell formation region 4 is formed in the in-cell structure on the substrate 10. An organic EL display or the like can be formed.

  The electronic device 200 to which the organic thin-film solar cell 1 according to the embodiment is applied corresponds to the in-cell electronic device 300 as shown in FIGS. 34 to 37 and FIG. 38 (b).

(Modification 2)
A schematic planar pattern configuration of the organic thin-film solar cell 1 according to Modification 2 of the embodiment is represented as shown in FIG. 39A, and is a schematic cross-sectional structure taken along line XVI-XVI in FIG. Is expressed as shown in FIG.

As shown in FIGS. 39A and 39B, the organic thin-film solar cell 1 according to Modification 2 of the embodiment includes a substrate 10, a first electrode layer 11 disposed on the substrate 10, The hole transport layer 12 disposed on the first electrode layer 11, the bulk heterojunction organic active layer 14 disposed on the hole transport layer 12, and the bulk heterojunction organic active layer 14 Via the second electrode layer 16N and a third through hole that penetrates the hole transport layer 12 and the bulk heterojunction organic active layer 14 in a direction perpendicular to the substrate 10 and reaches the first electrode layer 11. The VIA electrode layer 16P connected to the first electrode layer 11, the passivation layer 26 disposed on the second electrode layer 16N and the VIA electrode layer 16P, and the passivation layer 26 disposed in a direction perpendicular to the substrate 10. Through and connected to the VIA electrode layer 16P It comprises a first take-out terminal electrodes 38 _1, which, through the passivation layer 26, and a second lead terminal electrodes 38 ₂ connected to the second electrode layer 16N.

The first extraction terminal electrode 38 ₁ can be connected to any position of the first electrode layer 11.

Second extraction terminal electrodes 38 ₂ are connectable to any position 16N of the second electrode layer.

As shown in FIGS. 39A and 39B, the organic thin-film solar cell 1 according to the second modification of the embodiment includes a colored barrier layer 28 disposed on the passivation layer 26, and a colored barrier. A back sheet passivation layer 30 disposed on the layer 28 and a resin layer 40 disposed on the back sheet passivation layer 30 and sealing the first extraction terminal electrode 38 ₁ and the second extraction terminal electrode 38 _2. May be.

  The colored barrier layer 28 can be formed of an ultraviolet curable resin.

  Further, a coloring agent may be added to the colored barrier layer 28.

  The passivation layer 26 can be formed of a SiN film or a SiON film.

  Here, the colored barrier layer 28 can cover spots formed on the passivation layer 26.

  Further, the passivation layer 26 and the colored barrier layer 28 may be repeatedly stacked to form a multi-layer protective film.

  Further, a passive film 24 may be provided on the surfaces of the second electrode layer 16N and the VIA electrode layer 16P. Here, the passive film 24 can be formed of an oxide film of the second electrode layer 16N and the VIA electrode layer 16P. Here, this oxide film can form the surfaces of the second electrode layer 16N and the VIA electrode layer 16P by oxygen plasma treatment.

FIG. 40A is a schematic cross-sectional structure showing a state in which the transparent electrode layer 11 is patterned on the substrate 10 in one step of the method for manufacturing the organic thin-film solar cell 1 according to Modification 2 of the embodiment. A schematic sectional structure showing a state in which the hole transport layer 12 is formed on the transparent electrode layer 11 is represented as shown in FIG. 40B, and the hole transport layer 12 is formed on the hole transport layer 12. A schematic cross-sectional structure showing a state in which the bulk heterojunction organic active layer 14 is formed is expressed as shown in FIG. 40C, and the hole transport layer 12 and the bulk are formed in a direction perpendicular to the substrate 10. to penetrate the heterojunction organic active layer 14, schematic cross section showing a third through-hole 36 ₃ is formed state reaching the first electrode layer 11 is expressed as shown in FIG. 40 (d).

It is one process of the manufacturing method of the organic thin film solar cell 1 which concerns on the modification 2 of embodiment, Comprising: While forming the 2nd electrode layer 16N on the bulk heterojunction organic active layer 14, it is the 3rd through-hole 36 A schematic cross-sectional structure showing a state in which the VIA electrode layer 16P connected to the first electrode layer 11 through ₃ is formed is expressed as shown in FIG. 41A, and the second electrode layer is formed by oxygen plasma treatment. Schematic showing a state in which a passivation layer 26, a colored barrier layer 28, and a backsheet passivation layer 30 are formed on the second electrode layer 16N and the VIA electrode layer 16P after the oxide film 24 is formed on the surfaces of the 16N and VIA electrode layers 16P. A typical cross-sectional structure is represented as shown in FIG.

It is one process of the manufacturing method of the organic thin film solar cell 1 which concerns on the modification 2 of embodiment, Comprising: The back sheet passivation layer 30, the colorization barrier layer 28, and the passivation layer 26 are set to a surface orthogonal direction with respect to the board | substrate 10. Table as penetrating, schematic cross section a fourth showing a state in which the second to form a through-hole 36 ₂ to reach to the through hole 36 _4-second electrode layer 16N reaching VIA electrode layer 16P is shown in FIG. 42 Is done.

Further, with respect to VIA electrode layer 16P connected to the first electrode layer 11, through the fourth through hole 36 _4, the connecting form takeout terminal electrodes 38 _1, the second electrode layer 16N, the via the second through hole 36 _2, schematic cross section showing a state of connecting form takeout terminal electrodes 38 ₁ is expressed as shown in FIG. 39 (a) and FIG. 39 (b).

As shown in FIGS. 40 to 42 and FIG. 39, the method of manufacturing the organic thin-film solar cell 1 according to the second modification of the embodiment includes the step of forming the first electrode 11 on the substrate 19, and the first electrode. A step of forming a hole transport layer 12 on the layer 11, a step of forming a bulk heterojunction organic active layer 14 on the hole transport layer 12, and a hole transport layer in a direction perpendicular to the substrate 10. 12, through the heterojunction organic active layer 14 into the bulk, and forming a third through hole ₃₆₃ reaching the first electrode layer 11, the second electrode layer 16N on heterojunction organic active layer 14 to bulk with patterning, a step of patterning vIA electrode layer 16P connected to the first electrode layer 11 through the third through-hole 36 _3, the passivation layer 26, the second electrode layer 16N and the vIA electrode layer 16P Colored barrier layer 28 And a fourth through hole that passes through the passivation layer 26, the colored barrier layer 28, and the backsheet passivation layer 30 in a direction perpendicular to the substrate 10 and reaches the VIA electrode layer 16P. 36 ₄ forming a, in the orthogonal direction to the substrate 10, through the passivation layer 26, the color of the barrier layer 28, the backsheet passivation layer 30, second through-hole reaching the second electrode layer 16N 36 ₂ forming, and forming a first extraction terminal electrodes 38 ₁ connected to the VIA electrode layer 16P in the fourth through hole 36 _4, the second electrode layer in the second through hole 36 in ₂ 16N and forming a second lead terminal electrodes 38 ₂ connected to.

  Since the description of the detailed manufacturing process other than the above overlaps with the method of manufacturing the organic thin-film solar cell 1 according to the embodiment and the modification example 1, the description thereof is omitted.

  As described above, according to the present embodiment, the electrode take-out structure is improved, the connection point can be formed at any position without accompanying a large structural change in appearance, and the weight and thickness are reduced. A possible organic thin film solar cell, a manufacturing method thereof, and an electronic device can be provided.

[Other embodiments]
As described above, the embodiments have been described. However, it should be understood that the descriptions and drawings constituting a part of this disclosure are illustrative and do not limit the present invention. From this disclosure, various alternative embodiments, examples and operational techniques will be apparent to those skilled in the art.

  As described above, the present invention includes various embodiments not described herein.

  The organic thin film solar cell of the present invention can be applied to a wide range of fields such as a solar power generation panel and a charger for mobile terminals.

DESCRIPTION OF SYMBOLS 1, 1A ... Organic thin film solar cell 2 ... Display area 4 ... Organic thin film solar cell formation area 6 ... Character formation area 10 ... Substrate (ITO substrate)
11 ... 1st electrode layer (anode electrode layer, transparent electrode layer)
12 ... hole transport layer 14 ... bulk heterojunction organic active layer 16, 16N ... second electrode layer (cathode electrode layer)
16P ... VIA electrode layer 24 ... Passive film (oxide film)
26, 31, 41, 41 ₁ , 41 ₂ , 41 ₃ , 41 ₄ ... Passivation layer 28, 29, 42 ₁ , 42 ₂ , 42 ₃ , 42 ₄ ... (Colored) barrier layer 30... Backsheet passivation layer 33. Back sheet layer 34 ... through holes 36, 36 ₁ , 36 ₂ , 36 ₃ , 36 ₄ ... through holes 38, 38 ₁ , 38 ₂ ... take-out terminal electrodes 40 ... resin layer 41H ... spot 42 ...
60 ... dropper 62 ... spindle 63 ... table 64 ... droplet 150 ... adhesive layer 200, 300 ... electronic equipment

Claims (39)

A substrate,
A first electrode layer disposed on the substrate;
A hole transport layer disposed on the first electrode layer;
A bulk heterojunction organic active layer disposed on the hole transport layer;
A second electrode layer disposed on the bulk heterojunction organic active layer;
A passivation layer disposed on the second electrode layer;
A first lead terminal electrode disposed in a direction perpendicular to the substrate and penetrating the passivation layer, the bulk heterojunction organic active layer, and the hole transport layer and connected to the first electrode layer When,
A resin layer formed between the first extraction terminal electrode, the hole transport layer, the bulk heterojunction organic active layer, and the second electrode layer;
An organic thin-film solar cell, comprising: a second extraction terminal electrode that is disposed in a direction perpendicular to the substrate, penetrates the passivation layer, and is connected to the second electrode layer. A substrate,
A first electrode layer disposed on the substrate;
A hole transport layer disposed on the first electrode layer;
A bulk heterojunction organic active layer disposed on the hole transport layer;
A second electrode layer disposed on the bulk heterojunction organic active layer;
Connected to the first electrode layer through a third through hole that penetrates the hole transport layer and the bulk heterojunction organic active layer in a direction perpendicular to the substrate and reaches the first electrode layer The through-connection electrode formed,
A passivation layer disposed on the second electrode layer and the through-connection electrode ;
A first lead terminal electrode disposed in a direction perpendicular to the substrate, penetrating the passivation layer and connected to the through connection electrode ;
An organic thin-film solar cell comprising: a second extraction terminal electrode penetrating the passivation layer and connected to the second electrode layer.   3. The organic thin film solar cell according to claim 1, wherein the first extraction terminal electrode is connectable to an arbitrary position of the first electrode layer.   3. The organic thin-film solar cell according to claim 1, wherein the second lead-out terminal electrode can be connected to an arbitrary position of the second electrode layer. A colored barrier layer disposed on the passivation layer;
The organic thin-film solar cell according to any one of claims 1 to 4, further comprising: a backsheet passivation layer disposed on the colored barrier layer.   6. The organic thin film solar cell according to claim 5, wherein the passivation layer is a SiN film or a SiON film.   6. The organic thin film solar cell according to claim 5, wherein the colored barrier layer is an ultraviolet curable resin.   The organic thin film solar cell according to claim 6, wherein a coloring agent is added to the colored barrier layer.   The organic thin-film solar cell according to claim 6, wherein the colored barrier layer is capable of covering spots formed on the passivation layer.   The organic thin-film solar cell according to any one of claims 5 to 9, wherein the passivation layer and the colored barrier layer are repeatedly laminated to form a multi-layered protective film.   The organic thin-film solar cell according to any one of claims 1 to 10, further comprising a passive film on a surface of the second electrode layer.   The organic thin film solar cell according to claim 11, wherein the passivation film is an oxide film of the second electrode layer. The organic thin film solar cell according to claim 12, wherein the oxide film is an alumina film formed by performing oxygen plasma treatment on a surface of the second electrode layer.   An organic thin-film solar cell, wherein a plurality of cells comprising the organic thin-film solar cell according to claim 1 are connected in series. A transparent substrate;
A transparent first electrode layer formed on the transparent substrate;
An organic layer formed on the first electrode layer;
A second electrode layer formed on the organic layer;
An insulating layer formed across the side surface of the organic layer and the side surface of the second electrode layer from the surface of the first electrode layer;
A third electrode layer connected to the first electrode layer and formed in close contact with the side surface of the organic layer and the side surface of the second electrode layer via the insulating layer;
An organic thin film solar cell comprising: The organic thin-film solar cell according to claim 15, wherein the second electrode layer is formed on an inner side than an end portion of the organic layer in a plan view. The organic thin-film solar cell according to claim 15 or 16, wherein an oxide film is formed in close contact with the surface and side surfaces of the second electrode layer. The said transparent substrate is comprised including glass, The organic thin film solar cell of any one of Claims 15-17 characterized by the above-mentioned. The organic thin-film solar cell according to any one of claims 15 to 18, wherein the organic layer has an opening on the transparent substrate. Electronic equipment provided with the organic thin-film solar cell of any one of Claims 1-19. A display area;
An organic thin film solar cell forming region and a character forming region disposed in a peripheral portion of the display region;
With
The organic thin film solar cell formation region is disposed on a substrate, a first electrode layer disposed on the substrate, a hole transport layer disposed on the first electrode layer, and the hole transport layer. A bulk heterojunction organic active layer, a second electrode layer disposed on the bulk heterojunction organic active layer, a passivation layer disposed on the second electrode layer, and disposed in a direction perpendicular to the substrate. The first extraction terminal electrode connected to the first electrode layer through the passivation layer, the bulk heterojunction organic active layer, and the hole transport layer, the first extraction terminal electrode, A resin layer formed between a hole transport layer, the bulk heterojunction organic active layer, and the second electrode layer, and disposed in a direction perpendicular to the substrate, penetrating the passivation layer, The second electrode And a second lead terminal electrode connected to the,
The display area and the character forming area include the substrate, the first electrode layer disposed on the substrate, and the passivation layer disposed on the first electrode layer. machine. A display area;
An organic thin film solar cell forming region and a character forming region disposed in a peripheral portion of the display region;
With
The organic thin film solar cell formation region is disposed on a substrate, a first electrode layer disposed on the substrate, a hole transport layer disposed on the first electrode layer, and the hole transport layer. A bulk heterojunction organic active layer, a second electrode layer disposed on the bulk heterojunction organic active layer, the hole transport layer and the bulk heterojunction in a direction perpendicular to the substrate A through connection electrode connected to the first electrode layer through a third through hole penetrating the organic active layer and reaching the first electrode layer; and disposed on the second electrode layer and the through connection electrode. A passivation layer, a first lead terminal electrode disposed in a direction perpendicular to the substrate, penetrating the passivation layer and connected to the through-connection electrode, penetrating the passivation layer, and Second take connected with two electrode layers And a terminal electrode,
The display area and the character forming area include the substrate, the first electrode layer disposed on the substrate, and the passivation layer disposed on the first electrode layer. machine. 23. The electronic apparatus according to claim 21, wherein the first extraction terminal electrode is connectable to an arbitrary position of the first electrode layer. 23. The electronic apparatus according to claim 21, wherein the second lead terminal electrode is connectable to an arbitrary position of the second electrode layer. The organic thin film solar cell formation region is
A colored barrier layer disposed on the passivation layer, and a backsheet passivation layer disposed on the colored barrier layer,
The display area and the character formation area are:
The colored barrier layer disposed on the passivation layer, and the backsheet passivation layer disposed on the colored barrier layer,
The colored barrier layer corresponding to the organic thin film solar cell forming region and the colored barrier layer corresponding to the character forming region are colored. The electronic device described. 26. The electronic apparatus according to claim 25, wherein the passivation layer is a SiN film or a SiON film. 26. The electronic device according to claim 25, wherein the colored barrier layer is an ultraviolet curable resin. 28. The electronic device according to claim 27, wherein a colorant is added to the colored barrier layer. 27. The electronic apparatus according to claim 26, wherein the colored barrier layer is capable of covering spots formed on the passivation layer. 30. The electronic device according to claim 25, wherein the passivation layer and the colored barrier layer are repeatedly laminated to form a multi-layer protective film. 31. The electronic apparatus according to claim 25, wherein the colored barrier layer corresponding to the organic thin film solar cell formation region is colored black. 32. The electronic device according to claim 25, wherein the colored barrier layer corresponding to the character forming region is colored red. The electronic device according to claim 21, wherein a liquid crystal display or an organic electroluminescence display is disposed on the substrate corresponding to the display area. The said electronic device is provided with the said organic thin-film solar cell formation area | region arrange | positioned through the contact bonding layer on the said board | substrate which has arrange | positioned the said display area | region, It has a tandem structure, The any one of Claims 21-33 characterized by the above-mentioned. Item 1. An electronic device according to item 1. The said electronic device is provided with the said organic thin film solar cell formation area | region arrange | positioned on the said board | substrate which has arrange | positioned the said display area | region, It has an in-cell structure, The any one of Claims 21-33 characterized by the above-mentioned. Electronics. Forming a first electrode on a substrate;
Forming a hole transport layer on the first electrode layer;
Forming a bulk heterojunction organic active layer on the hole transport layer;
Forming a second electrode layer on the bulk heterojunction organic active layer;
Forming a passivation layer on the second electrode layer;
Forming a first through hole penetrating through the passivation layer, the bulk heterojunction organic active layer, and the hole transport layer in a direction perpendicular to the substrate and reaching the first electrode layer; ,
Forming a second through hole penetrating the passivation layer and reaching the second electrode layer in a direction perpendicular to the substrate;
Forming a first lead terminal electrode connected to the first electrode layer in the first through hole;
Forming a second lead terminal electrode connected to the second electrode layer in the second through hole;
Forming a resin layer between the first extraction terminal electrode, the hole transport layer, the bulk heterojunction organic active layer, and the second electrode layer;
The manufacturing method of the organic thin-film solar cell characterized by having. Forming a first electrode on a substrate;
Forming a hole transport layer on the first electrode layer;
Forming a bulk heterojunction organic active layer on the hole transport layer;
Forming a third through hole penetrating the hole transport layer and the bulk heterojunction organic active layer in a direction perpendicular to the substrate and reaching the first electrode layer;
Forming a second electrode layer on the bulk heterojunction organic active layer and forming a through-connection electrode connected to the first electrode layer through the third through-hole;
Forming a passivation layer on the second electrode layer and the through-connection electrode;
Forming a fourth through hole penetrating the passivation layer in a direction perpendicular to the substrate and reaching the through connection electrode;
Forming a second through hole penetrating the passivation layer and reaching the second electrode layer in a direction perpendicular to the substrate;
Forming a first lead terminal electrode connected to the through connection electrode in the fourth through hole;
Forming a second lead terminal electrode connected to the second electrode layer in the second through hole;
The manufacturing method of the organic thin-film solar cell characterized by having. Forming a colored barrier layer on the passivation layer;
Forming a backsheet passivation layer on the colored barrier layer;
38. The method for producing an organic thin-film solar cell according to claim 36 or 37, wherein: 39. The method of manufacturing an organic thin film solar cell according to claim 38, further comprising a step of forming a multi-layered protective film by repeating the step of forming the passivation layer and the step of forming the colored barrier layer.

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