JP2014175380A - Organic thin-film solar cell and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic thin-film solar cell which is inexpensive, is improved in durability, and can be reduced in weight/thickness, and a method of manufacturing the same.SOLUTION: There are provided an organic thin-film solar cell 1 and a method of manufacturing the same. The organic thin-film solar cell 1 includes: a substrate 10; a first electrode layer 11 disposed on the substrate; a hole transport layer 12 disposed on the first electrode layer; a bulk heterojunction organic active layer 14 disposed on the hole transport layer; a second electrode layer 16 disposed on the bulk heterojunction organic active layer; a sealing glass 40 which faces the substrate and seals a laminated structure comprising the first electrode layer, the hole transport layer, the bulk heterojunction organic active layer, and the second electrode layer; and glass frit 36 which is disposed between the sealing glass and the substrate and seals the laminated structure.

Description

  The present invention relates to an organic thin film solar cell and a method for manufacturing the same, and particularly relates to an organic thin film solar cell that is inexpensive, has improved durability, and can be reduced in weight and thickness, and a method for manufacturing the same.

  Organic thin-film solar cells characterized by ultrathinness, light weight, and flexibility are attracting attention as inexpensive solar cells because they can be formed at room temperature and atmospheric pressure.

  In organic thin-film solar cells, by applying a fine pattern to the surface of the organic active layer or electrode, the incident light is effectively confined inside the organic active layer, the current collection effect is enhanced, and the photoelectric conversion efficiency is improved. Yes.

  In a conventional organic thin film solar cell using surface plasmon resonance, silver (Ag) or gold (Au) nanoparticle whose particle size is controlled by organic synthesis at the p-type / n-type organic layer interface or the organic layer / electrode interface. Particles modified with an alkyl group or a thiol group in order to promote dispersion were used in a solution state and applied on the respective interfaces by spin coating (for example, see Patent Document 1).

JP 2009-246025 A

  Organic thin-film solar cells have had the problem of extremely low photoelectric conversion efficiency compared to other types of solar cells, but digging glass and sheets used in organic EL (Electro Luminescence) displays It has been found that high durability is obtained when sealing with a desiccant is used.

  However, the sealing method using the engraved glass and the sheet desiccant has had a problem in that the engraved glass has to be formed thick and is very expensive.

  An object of the present invention is to provide an organic thin-film solar cell that is inexpensive, has improved durability, and can be reduced in weight and thickness, and a method for manufacturing the same.

  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 the substrate facing the first electrode layer, the positive electrode A sealing glass that seals a laminated structure including a hole transport layer, the bulk heterojunction organic active layer, and the second electrode layer; and is disposed between the sealing glass and the substrate; An organic thin film solar cell comprising a glass frit for sealing is provided.

  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, a step of forming a second electrode layer on the bulk heterojunction organic active layer, a step of forming a glass frit on a sealing glass, and a resin at a tip portion of the glass frit The sealing glass and the substrate are opposed to each other, and the first electrode layer, the hole transport layer, the bulk heterojunction organic active layer, and the second are formed by the glass frit and the resin. The manufacturing method of the organic thin-film solar cell which has the process of sealing the laminated structure which consists of an electrode layer is provided.

  According to the present invention, it is possible to provide an organic thin-film solar cell that is inexpensive, has improved durability, and can be reduced in weight and thickness, and a method for manufacturing the same.

The typical cross-section figure of the organic thin-film solar cell which concerns on embodiment. The another typical cross-section figure of the organic thin-film solar cell which concerns on embodiment. The typical cross-section figure of the organic thin-film solar cell which concerns on a comparative example. The schematic diagram explaining the fundamental structure and operation | movement of the organic thin-film solar cell which concern on embodiment. FIG. 5 is an energy band structure diagram of various materials of the organic thin film solar cell shown in FIG. 4. (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. The typical cross-section figure of the laminated structure part of the organic thin film solar cell which concerns on embodiment. The typical cross-section figure of the laminated structure part of the organic thin-film solar cell which concerns on the modification of embodiment. 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 ITO board | substrate which formed the transparent electrode layer on the board | substrate, (b) After patterning a transparent electrode layer, it is transparent Process diagram for patterning hole transport layer on electrode layer, (c) Process diagram for patterning bulk heterojunction organic active layer on hole transport layer, (d) On bulk heterojunction organic active layer Process drawing which forms a 2nd electrode layer in a pattern. It is 1 process of the manufacturing method of the organic thin-film solar cell concerning embodiment, Comprising: (a) Process drawing which prepares sealing glass, (b) Process drawing which forms glass frit on sealing glass, (c) Process drawing which forms UV hardening resin in the front-end | tip part of glass frit. It is one process of the manufacturing method of the organic thin-film solar cell which concerns on embodiment, Comprising: (a) ITO board | substrate after the process shown by FIG.12 (d), and the process after the process shown by FIG.13 (c) Process drawing which makes sealing glass oppose, (b) Process drawing which adhere | attaches and seals an ITO substrate and sealing glass through a glass frit and UV hardening resin after the process shown by Fig.14 (a). It is the structure of the sealing part of the organic thin-film solar cell which concerns on embodiment, Comprising: (a) Typical cross-section figure which shows the structure by which glass frit was coat | covered with UV curable resin, (b) Glass frit is UV curable resin. The typical cross-section figure which shows another structure coat | covered with. The typical cross-section figure which shows the structure of the sealing part of the organic thin-film solar cell which concerns on embodiment, Comprising: Porous glass frit was coat | covered with UV hardening resin. BRIEF DESCRIPTION OF THE DRAWINGS It is a structure of the sealing part of the organic thin-film solar cell which concerns on embodiment, Comprising: (a) The typical cross-section figure which shows the structure where the two glass frit formed has a wedge shape, (b) Two are formed. 2 is a schematic cross-sectional structure diagram showing a configuration in which the glass frit has a tapered shape, (c) a configuration in which the cross-sectional shape of the two formed glass frits has a spindle-shaped tapered shape in which the cross-sectional area decreases as the distance from the sealing glass increases. FIG. 1 is a schematic cross-sectional view showing a configuration of a sealing portion of an organic thin film solar cell according to an embodiment, wherein (a) two formed glass frit has a wedge shape and is coated with a UV curable resin. Structural drawing, (b) A schematic cross-sectional structural view showing a configuration in which two formed glass frit has a taper shape and is coated with a UV curable resin, (c) sectional shape of two formed glass frit FIG. 4 is a schematic cross-sectional structure diagram showing a configuration in which the cross-sectional area decreases as the distance from the sealing glass decreases, and the structure is covered with a UV curable resin. It is one process of the manufacturing method of the organic thin film solar cell which concerns on 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.18 (a) The typical cross-section figure along an II line. FIG. 19 is a schematic plan pattern configuration diagram showing one state of a method for manufacturing an organic thin film solar cell according to an embodiment, in which (a) a hole transport layer is formed on a transparent electrode layer; The typical sectional structure figure which meets the II-II 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 cross-sectional structure diagram taken along line III-III in FIG. FIG. 4 is a schematic plan pattern configuration diagram showing a state in which the second electrode layer is formed on the bulk heterojunction organic active layer, which is one step of the method for manufacturing the organic thin film solar cell according to the embodiment; FIG. 22 is a schematic sectional view taken along the line IV-IV 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.23 (a). FIG. 4B is a schematic plan pattern configuration diagram showing a state of the manufacturing process of the organic thin-film solar cell according to the embodiment, in which (a) sealing is performed with sealing glass / glass frit and UV curable resin; FIG. 24 is a schematic sectional view taken along line VI-VI in FIG. FIG. 25 is a schematic cross-sectional structure diagram illustrating a state in which the sealing glass is bent in the structure illustrated in FIG. BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional structure drawing of the organic thin-film solar cell which concerns on embodiment, Comprising: (a) The structural example 1 which has a glass support stand inside sealing glass and can suppress the bending of sealing glass, (b) ) Another configuration example 2 in which a glass support is provided inside the sealing glass, and the bending of the sealing glass can be suppressed. It is typical sectional structure drawing of the organic thin-film solar cell which concerns on embodiment, Comprising: (a) The structural example 3 which has a glass support stand inside sealing glass and can suppress the bending of sealing glass, (b ) Another configuration example 4 that includes a glass support on the inner side of the sealing glass and can suppress the bending of the sealing glass. An organic thin film solar cell according to the embodiment, a space in the oxygen (O ₂₎ shows a schematic cross section arranged gettering sheet between the inner and the sealing glass and the ITO substrate of the sealing glass. In the organic thin-film solar cell which concerns on embodiment, the typical plane pattern figure which shows the example arrange | positioned by connecting seven cells in series. FIG. 30A is a schematic cross-sectional structure diagram taken along the line VII-VII in FIG. 29, and FIG. 30B is an equivalent circuit configuration diagram corresponding to FIG. 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.

  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.

  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. 1, the organic thin-film solar cell 1 according to the embodiment is disposed on a substrate 10, a transparent electrode layer (first electrode layer) 11 disposed on the substrate 10, and the first electrode layer 11. A hole transport layer 12, a bulk heterojunction organic active layer 14 disposed on the hole transport layer 12, a cathode electrode layer (second electrode layer) 16 disposed on the bulk heterojunction organic active layer 14, A sealing glass 40 facing the substrate 10 and sealing a laminated structure including the first electrode layer 11, the hole transport layer 12, the bulk heterojunction organic active layer 14, and the second electrode layer 16; The glass frit 36 is disposed between the substrate 40 and the substrate 10 and seals the laminated structure.

  As shown in FIG. 1, the organic thin-film solar cell 1 according to the embodiment is formed by laminating an organic layer (12 · 14) having a thickness of about several hundreds of nm to be a power generation layer on a glass substrate 10 with ITO. The second electrode layer 16 is made by vapor-depositing a metal layer such as aluminum. Since pure aluminum formed as the second electrode layer 16 is easily oxidized, a passive film may be formed or a passivation film such as SiN or SiON may be laminated for durability.

  Here, the glass frit 36 is disposed on the sealing glass 40. This is because organic layers such as the hole transport layer 12 and the bulk heterojunction organic active layer 14 are disposed on the substrate 10, so that these organic layers are not damaged when the glass frit is sintered at a high temperature. .

  In the organic thin film solar cell 1 according to the embodiment, a glass frit 36 can be formed by applying a glass frit paste that can be applied using a screen printing technique or a dispenser in an arbitrary pattern and baking at a high temperature.

  The height of the glass frit 36 is, for example, about 1 μm to about 100 μm, and the width of the glass frit 36 is, for example, about 0.2 mm to about 2.0 mm. By arranging the glass frit 36, contact between the sealing glass 40 and the internal elements can be avoided.

  In the organic thin film solar cell 1 according to the embodiment, as shown in FIG. 1, in order to bond the sealing glass 40 and the substrate 10 on which the element is formed, a resin 36U for bonding to the surface of the glass frit 36 is provided. Prepare.

  As the resin 36U, a thermosetting resin or a UV curable resin can be applied. In order to avoid heat shock applied to the element, it is desirable to use a UV curable resin. In addition, when a UV curable resin is used, a transparent glass frit that transmits ultraviolet rays may be used. As a glass frit material having a high total ray transmittance (for example, 90% or more) with respect to UV light, for example, a Zn-based glass can be applied. The glass frit can also be composed of Bi-B-Si oxide powder. The glass frit made of this Bi—B—Si-based oxide has a property of absorbing heat and generating heat and melting. Therefore, it is possible to fuse the sintered body of the paste containing the glass frit by irradiating it with an infrared laser (for example, wavelength 1064 nm).

In addition, as shown in FIG. 2, the organic thin-film solar cell according to the embodiment enhances the oxygen (O ₂ ) getter action by providing a gettering sheet desiccant 38GU on the inner wall surface of the sealing glass 40. Also good. As the gettering sheet desiccant, for example, strontium oxide (SrO), calcium oxide (CaO), or the like can be used as an oxygen (O ₂ ) -based getter agent.

(Comparative example)
In the organic thin-film solar cell 1B according to the comparative example, as shown in FIG. 3, an engraved glass 40A is applied for sealing. The thickness of the outer shape of the digging glass 40A is, for example, about 0.7 mm, and the depth of the digging portion containing the element portion is, for example, about 0.3 mm. In the digging glass 40A, when digging an arbitrary pattern, it is necessary to create a mask plate for creating the digging for each pattern. Further, in order to form the digging portion, etching with hydrofluoric acid is required, which is expensive and troublesome. Moreover, the sealing using the dug glass 40A is expensive, and the thickness of the module is thick and heavy.

  On the other hand, in the organic thin film solar cell according to the embodiment, a sealing glass 40 and a transparent glass frit 36 baked on the sealing glass 40 are used for sealing. As the sealing glass 40, for example, non-alkali tempered glass having a thickness of about 0.1 mm to 0.2 mm is applicable.

  The glass frit 36 is applied to the sealing glass 40 by applying a glass frit paste (organic solvent + glass frit) by screen printing, drying the organic solvent at about 100 ° C., and then at about 500 ° C. to 590 ° C. And sintered for about 30 minutes. The thickness of the glass frit 36 is, for example, about 5 μm to 20 μm. Further, the thickness of the resin 36U for bonding the glass frit 36 and the substrate 10 is also about 5 μm to 20 μm, for example.

  The glass frit 36 can freely draw a pattern by using dispenser coating, and can be formed on the sealing glass 40 without using dangerous chemicals. Moreover, the module of the organic thin film solar cell according to the embodiment can be further reduced in weight and thickness by using a relatively thin cover glass (sealing glass 40) as compared with the dug glass 40A.

(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. 4 is expressed as shown in FIG. With reference to FIG. 4 and FIG. 5, the fundamental structure and operation | movement of 1 A of organic thin-film solar cells which concern on embodiment are demonstrated.

  As shown in the left diagram of FIG. 4, 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, the bulk heterojunction organic active layer 14 includes a p-type organic active layer region and an n-type organic active layer region, as shown in the right diagram of FIG. 4, and forms 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 PEDOT: PSS applied to the hole transport layer 12 in the organic thin film solar cell 1A, the chemical structural formula of PEDOT is expressed as shown in FIG. 6A, 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. 7A, 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 represented as shown in FIG. 8A, and an example of zinc phthalocyanine (ZnPc: Zinc-phthalocyanine) is represented as shown in FIG. An example of -Ptcdi (N, N'-dimethyl perylene-3,4,9,10-dicarboximide) is represented as shown in FIG. 8C, and an example of fullerene (C ₆₀ : Buckminster fullerene) is shown in FIG. It is expressed as shown in FIG.

  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 represented 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. 9 (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. 9 (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. 9 (g), and PC ₇₀ BM (6,6-phenyl-C71-butyric acid methyl ester). An example of ester) is represented as shown in FIG.

  As shown in FIG. 10, the laminated structure portion of 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, a hole heterojunction organic active layer 14 disposed on the hole transport layer 12, and a cathode electrode layer (second electrode layer) disposed on the bulk heterojunction organic active layer 14. 16).

  Moreover, the laminated structure part of the organic thin-film solar cell 1 which concerns on the modification of embodiment is further provided with the passive film 24 arrange | positioned on the surface of the 2nd electrode layer 16, as shown in FIG. Here, 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.

  As shown in FIG. 11, the organic thin-film solar cell 1 including the passive film 24 on the surface of the second electrode layer 16 has a second structure even when moisture or oxygen penetrates into the bulk heterojunction organic active layer 14. It is possible to prevent the electrode layer 16 from being oxidized by the moisture and oxygen. Thereby, deterioration of an organic solar cell can be suppressed and durability can be improved.

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

  A step of preparing the sealing glass 40, 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. 13 (a), and the glass frit 36 is formed on the sealing glass 40. The process of forming the resin 36U is represented as shown in FIG. 13B, and the process of forming the resin 36U on the tip portion of the glass frit 36 is represented as shown in FIG.

  It is 1 process of the manufacturing method of the organic thin film solar cell which concerns on embodiment, Comprising: The ITO substrate 10 after the process shown by FIG.12 (d), and the sealing after the process shown by FIG.13 (c) The process of making the glass 40 face each other is expressed as shown in FIG. 14A. After the process shown in FIG. 14A, the ITO substrate 10 is sealed with the glass frit 36 and the UV curable resin 36U. The process of adhering and sealing the glass 40 is expressed as shown in FIG.

  As shown in FIGS. 12 to 14, the method for manufacturing the organic thin-film solar cell 1 according to the embodiment includes a step of preparing the substrate 10, a step of forming the first electrode layer 11 on the substrate 10, and a first step. Forming a hole transport layer 12 on the electrode layer 11, forming a bulk heterojunction organic active layer 14 on the hole transport layer 12, and forming a second electrode layer 16 on the bulk heterojunction organic active layer 14. The step of forming the glass frit 36 on the sealing glass 40, the step of forming the resin 36U on the tip of the glass frit 36, the sealing glass 40 and the substrate 10 facing each other, and the glass frit 36 and the resin A step of sealing the laminated structure including the first electrode layer 11, the hole transport layer 12, the bulk heterojunction organic active layer 14, and the second electrode layer 16 with 36U.

  With reference to FIGS. 12-14, the manufacturing method of the organic thin-film solar cell which concerns on embodiment is demonstrated.

(A) First, as shown in FIG. 12A, a transparent electrode layer 11 made of, for example, ITO is formed on a substrate 10.

(B) Next, as shown in FIG. 12B, after patterning the transparent electrode layer 11, the hole transport layer 12 is patterned on the transparent electrode layer 11. 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. 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. 12C, 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. 12D, the cathode electrode layer 16 is formed 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. 13A, a sealing glass 40 is prepared. As the sealing glass 40, for example, non-alkali tempered glass having a thickness of about 0.1 mm to 0.2 mm is applicable.

(F) Next, as shown in FIG. 13B, a glass frit 36 is formed on the sealing glass 40. The glass frit 36 is obtained by applying a glass frit paste (organic solvent + glass frit) to the sealing glass 40 by screen printing, drying the organic solvent at about 100 ° C., and about 500 ° C. to 590 ° C., It is formed by sintering for 30 minutes. The thickness of the glass frit 36 is, for example, about 5 μm to 20 μm. The glass frit 36 can freely draw a pattern by using dispenser coating, and can be formed on the sealing glass 40 without using dangerous chemicals.

(G) Next, as shown in FIG. 13C, a resin 36 </ b> U for bonding the glass frit 36 and the substrate 10 is formed at the tip of the glass frit 36. The thickness of the resin 36U is also about 5 μm to 20 μm, for example. The resin 36U may be formed of an ultraviolet curable resin. The resin 36U may be formed of a thermosetting resin. However, the temperature of thermosetting is desirably a temperature that does not damage the hole transport layer 12 and the bulk heterojunction organic active layer 14, for example, about 100 ° C. to about 120 ° C. or less.

(H) Next, as shown in FIG. 14A, the ITO substrate 10 after the process shown in FIG. 12D and the sealing glass 40 after the process shown in FIG. Make them face each other.

(I) Next, as shown in FIG. 14B, the entire device is sealed with a sealing glass (cover glass) 40, a glass frit 36, and a resin 36U. The glass frit 36 and the transparent electrode layer (ITO) 11 are bonded by the resin 36U. Note that the sealing step is preferably performed in a nitrogen atmosphere in order to prevent deterioration due to moisture and oxygen in the air.

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

  An oxide film (passive film) 24 may be 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. Note that a silicon nitride film or the like may be formed on the aluminum surface as a passivation film by a chemical vapor deposition (CVD) method. The thickness of the silicon nitride film is, for example, about 0.5 μm to 1.5 μm. Durability can be further improved by protecting the inner element with a silicon nitride film.

  Further, a gettering sheet desiccant 38GU may be provided on the inner wall surface of the sealing glass 40 to further eliminate the influence of moisture and oxygen. By applying and forming a resin desiccant and an oxygen getter around the sealing portion, higher durability can be ensured.

By vacuum evaporation after forming the aluminum inside the N ₂ or vacuum depressurization, by UV irradiation, when curing the UV curable resin 36U, UV irradiation, it may be carried out from the sealing glass 40 side. This is because aluminum becomes a reflective layer against UV irradiation, so that the element portion can be protected.

(Configuration example of sealing part)
The sealing part in the organic thin-film solar cell according to the embodiment may have a configuration in which a glass frit 36 is covered with a UV curable resin 36U as shown in FIG. Furthermore, as shown in FIG. 15B, the sealing portion in the organic thin film solar cell according to the embodiment is such that the glass frit 36 is covered with the UV curable resin 36U, and the contact between the UV curable resin 36U and the substrate 10 is achieved. You may provide the structure which increased the area compared with the structure of Fig.15 (a).

  Moreover, the sealing part in the organic thin film solar cell according to the embodiment may have a configuration in which a porous glass frit 36P is covered with a UV curable resin 36U as shown in FIG. That is, a porous glass frit may be used. When the porous glass frit 36P is applied, the resin 36U penetrates into the glass frit 36P and the “anchor effect” works, so that stronger adhesion can be realized.

  Further, the glass frit 36 in the organic thin film solar cell according to the embodiment may have a wedge shape, a tapered shape, or a spindle-shaped tapered shape whose cross-sectional area decreases as the distance from the sealing glass 40 increases.

  A plurality of glass frit 36 may be formed.

  A configuration example of the sealing portion of the organic thin-film solar cell according to the embodiment, in which two formed glass frits 36 have a wedge shape, is expressed as shown in FIG. Moreover, the structural example in which the two glass frit 36 formed has a taper shape is represented as shown in FIG. In addition, a configuration example in which the cross-sectional shape of the two formed glass frit 36 has a spindle-shaped taper shape in which the cross-sectional area decreases as the distance from the sealing glass 40 increases is expressed as shown in FIG.

  Further, a configuration example of the sealing portion of the organic thin film solar cell according to the embodiment, in which two formed glass frits 36 have a wedge shape and are covered with a UV curable resin 36U, is shown in FIG. It is expressed as shown in a). Further, a configuration example in which the two formed glass frit 36 has a tapered shape and is covered with the UV curable resin 36U is expressed as shown in FIG. Further, a configuration example in which the cross-sectional shape of the two formed glass frit 36 has a spindle-shaped taper shape in which the cross-sectional area becomes smaller as the distance from the sealing glass 40 is reduced, and the configuration example is covered with the UV curable resin 36 is shown in FIG. It is expressed as shown in (c).

(Production method)
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 II in FIG. 19A is expressed 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.20 (a), and shows to the II-II line of Fig.20 (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. A schematic cross-sectional structure along the line -III 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 IV 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. 23A, and a schematic cross-sectional structure taken along line VV in FIG. 23A is shown in FIG. ).

  Moreover, the schematic plane pattern structure which shows the state sealed with the sealing glass 40, the glass frit 36, and the UV curable resin 36U is represented as shown in FIG. 24A, and VI-VI in FIG. A schematic cross-sectional structure along the line is expressed as shown in FIG.

  With reference to FIGS. 19-24, 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 FIG. 19, the transparent electrode layer 11 made of, for example, ITO is formed on the glass substrate 10. As shown in FIG. 19, a plurality of transparent electrode layers 11 are formed in a stripe pattern across 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 FIG. 20, 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 FIG. 21, 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 FIG. 22, the cathode electrode layer 16 is formed 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.

(F) Next, as shown in FIG. 23, after the bulk heterojunction organic active layer 14 and the hole transport layer 12 are etched, an oxide film (passive film) 24 is formed on the surface of the cathode electrode layer 16. 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 FIG. 24, the entire device is sealed with a sealing glass (cover glass) 40 and a glass frit 36 / UV curable resin 36U. The glass frit 36 and the transparent electrode layer (ITO) 11 are bonded by the UV curable resin 36U. Note that the sealing step is preferably performed in a nitrogen atmosphere in order to prevent deterioration due to moisture and oxygen in the air. Further, a gettering sheet desiccant 38GU may be provided on the inner wall surface of the sealing glass 40 to further eliminate the influence of moisture and oxygen.

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

(The state where the sealing glass is bent)
In the structure shown in FIG. 24, a schematic cross-sectional structure example showing a state in which the sealing glass 40 is bent is expressed as shown in FIG. When the sealing glass 40 is bent, the cells constituting the organic thin-film solar battery are crushed and a short-circuit state may occur between the anode electrode layer 11 and the cathode electrode layer 16.

(Glass support stand)
A glass support base is provided so that the cover glass 40 or the substrate 10 is bent by an external pressure after the module of the organic thin-film solar cell according to the embodiment is manufactured, and the cover glass 40 does not contact and break the internal elements. 18 may be provided. The glass support 18 can be formed in the same manner as the glass frit 36.

  FIG. 26A illustrates an organic thin-film solar cell according to the embodiment, which includes the glass support base 18 inside the sealing glass 40 and can suppress the bending of the sealing glass 40. It is expressed as follows. Another configuration example 2 is expressed as shown in FIG.

  Furthermore, it is the organic thin film solar cell which concerns on embodiment, Comprising: The structural example 3 which can provide the glass support stand 18 inside the sealing glass 40, and can suppress the bending of the sealing glass 40 is FIG. Another configuration example 4 is represented as shown in FIG. 27B.

  The glass support 18 may be disposed in contact with the second electrode layer 16 as shown in FIG.

  Moreover, the glass support 18 may be arrange | positioned in contact with the 1st electrode layer 11B between adjacent cells, as shown in FIG.26 (b), FIG.27 (a), and FIG.27 (b). The first electrode layer 11A represents the transparent electrode layer of the left cell of the adjacent cell, and the first electrode layer 11B represents the transparent electrode layer of the right cell of the adjacent cell.

  Thus, the glass support base 18 may be arrange | positioned between the cells arrange | positioned in multiple numbers.

  The glass support 18 can be formed so as to have a dot pattern or a stripe pattern on the surface of the substrate 10.

(Gettering sheet)
In the organic thin-film solar cell according to the embodiment, a sheet desiccant for oxygen (O ₂ ) gettering 38 GU and 38 GS is provided inside the sealing glass 40 and in the space between the sealing glass 40 and the ITO substrate 10. The arranged schematic sectional structure is expressed as shown in FIG.

  The gettering sheet desiccant 38GU / 38GS is disposed inside the substrate 10 and the sealing glass 40.

  Further, the gettering sheet desiccant 38GU can be disposed on the inner wall surface of the sealing glass 40 facing the substrate 10.

  Further, the gettering sheet desiccant 38GS can be disposed on the substrate 10 and the internal substrate 10 sealed with the sealing glass 40.

(Series arrangement configuration)
In the organic thin film solar cell 1 according to the embodiment, a schematic plane pattern configuration in which seven cells are connected in series is expressed as shown in FIG. Further, a schematic cross-sectional structure taken along line VII-VII in FIG. 29 is represented as shown in FIG. 30A, and an equivalent circuit configuration corresponding to FIG. 30A is shown in FIG. It is expressed in

  Each cell includes a substrate 10, an anode electrode layer 11 disposed on the substrate 10, a hole transport layer 12 disposed on the anode electrode layer 11, and a bulk heterojunction organic disposed on the hole transport layer 12. An active layer 14 and a cathode electrode layer 16 disposed on the bulk heterojunction organic active layer 14 are provided. Further, the entire seven cells are hollow sealed with sealing glass 40, glass frit 36, and UV curable resin 36U. A gettering sheet desiccant 38GU is disposed on the inner wall surface of the sealing glass 40. Although not shown, a passive film is formed on the surface of the cathode electrode layer 16.

  As is clear from FIG. 30A, the anode electrode layer 11 (A1) is connected to the anode terminal A, and the cathode electrode layer 16 (K1) is connected to the anode electrode layer 11 (A2) at the cell periphery. Similarly, the cathode electrode layer 16 (K2) is connected to the anode electrode layer 11 (A3) at the cell periphery, and the cathode electrode layer 16 (K6) is connected to the anode electrode layer 11 (A7) and the cell periphery. The cathode electrode layer 16 (K7) is connected to the first electrode layer 11 (K1) at the cell periphery, and the first electrode layer 11 (K1) is connected to the cathode terminal K.

  As a result, a structure in which seven organic thin film solar cells are connected in series is obtained.

  Thus, by connecting a plurality of cells in series, a high open circuit voltage Voc as the sum of electromotive forces generated in each cell can be obtained.

  Further, a glass support for preventing bending may be provided on the inner wall surface of the sealing glass 40 facing the substrate 10. The glass support may be disposed in contact with the second electrode layer, or may be disposed in contact with the first electrode layer. The glass support base may be arranged between a plurality of cells.

(Procedure for making organic thin-film solar cells)
Based on the flowchart shown in FIG. 29, 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, using a sealing glass on which a glass frit is formed, a UV curable resin is formed on the tip of the glass frit, facing the substrate, and exposed for about 10 minutes in a UV oven, for example. Seal.

(Mass production process)
As shown in FIGS. 32 to 36, 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. 32, the transparent electrode layer 11 made of, for example, ITO is formed on the substrate 10. In the example shown in FIG. 32, 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. 33, 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. 34, 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. 35, 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, the entire device is sealed with sealing glass (cover glass) and glass frit. Note that the sealing step is preferably performed in a nitrogen atmosphere or under vacuum under reduced pressure in order to prevent deterioration due to moisture or oxygen in the air.

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

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 for 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. 37 (a). 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 a device having a relatively small area is formed, a spin coating method as shown in FIG. 37A can be applied.

  That is, as shown in FIG. 37A, 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.37 (b)) of uniform thickness on the board | substrate 10 with a centrifugal force.

  As described above, according to the present embodiment, it is possible to provide an organic thin-film solar cell that is inexpensive, has improved durability, and can be reduced in weight and thickness, and a method for manufacturing the same.

[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 is inexpensive, has improved durability, and can be reduced in weight and thickness. It is.

1, 1A, 1B ... Organic thin film solar cell 10 ... Substrate (ITO substrate)
11, 11A, 11B ... 1st electrode layer (anode electrode layer, transparent electrode layer)
12 ... hole transport layer 14 ... bulk heterojunction organic active layer 16 ... second electrode layer (cathode electrode layer)
24 ... Passive film (oxide film)
36, 36P: Glass frit 36U: Resin (thermosetting resin, UV curable resin)
38 GU, 38 GS: sheet desiccant for gettering 40: sealing layer (sealing glass, glass plate, cover glass)
60 ... Dropper 62 ... Spindle 63 ... Table 64 ... Droplet

Claims (33)

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 sealing glass that faces the substrate and seals a laminated structure including the first electrode layer, the hole transport layer, the bulk heterojunction organic active layer, and the second electrode layer;
An organic thin-film solar cell, comprising: a glass frit disposed between the sealing glass and the substrate and sealing the laminated structure.   The organic thin-film solar cell according to claim 1, wherein the glass frit is disposed on the sealing glass.   The organic thin film solar cell according to claim 1, wherein the glass frit is transparent to ultraviolet rays.   The organic thin film solar cell according to claim 3, wherein the glass frit contains zinc-based glass as a main component.   5. The organic thin film according to claim 1, wherein the glass frit has a wedge-shaped shape, a tapered shape, or a spindle-shaped tapered shape in which a cross-sectional area decreases as the distance from the sealing glass increases. Solar cell.   The organic thin-film solar cell according to claim 5, wherein a plurality of the glass frit is formed.   The organic thin-film solar cell according to any one of claims 1 to 6, further comprising a resin that connects the glass frit and the substrate.   The organic thin-film solar cell according to claim 7, wherein the glass frit is coated with the resin.   The organic thin-film solar cell according to claim 8, wherein the resin is formed of an ultraviolet curable resin or a thermosetting resin.   The organic thin-film solar cell according to any one of claims 1 to 9, wherein the glass frit has a porous property, and the resin can be immersed in the glass frit.   The organic thin-film solar cell according to any one of claims 1 to 10, further comprising a passive film disposed 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 formed by oxygen plasma treatment on a surface of the second electrode layer.   The organic thin-film solar cell according to claim 12, further comprising a passivation film disposed on the oxide film.   The organic thin-film solar cell according to claim 14, wherein the passivation film is a SiN film or a SiON film.   The organic thin-film solar cell according to claim 1, further comprising a gettering sheet desiccant inside the substrate and the sealing glass.   The organic thin-film solar cell according to any one of claims 1 to 14, wherein a sheet desiccant for gettering is provided on an inner wall surface of the sealing glass facing the substrate.   The organic thin-film solar cell according to any one of claims 1 to 14, further comprising a gettering sheet desiccant on the substrate and the internal substrate sealed with the sealing glass.   An organic thin-film solar battery comprising a plurality of cells made of the organic thin-film solar battery according to claim 1 connected in series.   The organic thin-film solar cell according to any one of claims 1 to 19, further comprising a glass support for preventing deflection on an inner wall surface of the sealing glass facing the substrate.   The organic thin-film solar cell according to claim 20, wherein the glass support is disposed in contact with the second electrode layer.   The organic thin-film solar cell according to claim 20, wherein the glass support is disposed in contact with the first electrode layer.   The organic thin-film solar cell according to claim 20, wherein a plurality of the glass support tables are disposed between the plurality of cells. 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 glass frit on the sealing glass;
Forming a resin on the tip of the glass frit;
A laminated structure comprising the first electrode layer, the hole transport layer, the bulk heterojunction organic active layer, and the second electrode layer, wherein the sealing glass and the substrate are opposed to each other, and the glass frit and the resin are used. A method for producing an organic thin-film solar cell, comprising:   The method for producing an organic thin-film solar cell according to claim 24, wherein the step of forming the glass frit is performed on the sealing glass by screen printing.   The method of manufacturing an organic thin film solar cell according to claim 24 or 25, wherein the glass frit is transparent to ultraviolet rays. 27. The method of manufacturing an organic thin film solar cell according to claim 26, wherein the glass frit contains zinc-based glass as a main component.

  The method for producing an organic thin-film solar cell according to any one of claims 24 to 27, wherein the resin is formed of an ultraviolet curable resin.   29. The method of manufacturing an organic thin film solar cell according to claim 28, wherein the ultraviolet irradiation for curing the ultraviolet curable resin is performed from the sealing glass side.   The method for producing an organic thin-film solar cell according to any one of claims 24 to 27, wherein the resin is formed of a thermosetting resin. The step of forming the second electrode layer includes:
The method for producing an organic thin-film solar cell according to any one of claims 24 to 30, further comprising a step of vapor-depositing and forming a metal on the bulk heterojunction organic active layer.   The method for producing an organic thin-film solar cell according to any one of claims 24 to 31, further comprising a step of forming a passive film on the surface of the second electrode layer. The step of forming the passive film comprises
The method of manufacturing an organic thin-film solar cell according to claim 32, further comprising a step of performing oxygen plasma treatment on the second electrode layer.

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