JP2020053641A - Photoelectric fiber structure and manufacturing method therefor - Google Patents

Abstract

To provide a photoelectric fiber structure which is a composite body of photovoltaic cell and fiber with high priority of appearance and external view and concretely to provide a photoelectric fiber structure and manufacturing method therefor, capable of achieving a high-class feeling, high flexibility, high deformability and further high added-value.SOLUTION: The photoelectric fiber structure includes a fiber structure and a photovoltaic cell. The photoelectric fiber structure is provided on both faces of a light-receiving face and a non-light receiving face of the photovoltaic cell, and the photovoltaic cell is sandwiched between fiber structures to be carried.SELECTED DRAWING: None

Description

The present invention relates to a photovoltaic fiber structure and a method for producing the same.

  2. Description of the Related Art Solar cells are environmentally friendly sources of electrical energy, and are currently attracting attention as a potential energy source for growing energy problems.

  On the other hand, as electronic devices become smaller and lighter, they are often taken out and used when traveling by train or car. Since these electronic devices cannot be used when the battery or the battery runs out, it is desired that when the electronic devices are used outdoors, power can be secured even outdoors.

For example, attempts have been made to attach a solar cell to clothing such as outerwear and a hat so that power can be secured outdoors.
Patent Literature 1 discloses that a thin film solar cell stacked on a flexible substrate is detachably attached to a back surface of a thin film solar cell, and the thin film solar cell and a secondary battery installed in a pocket of the clothes are read. Disclosed is a garment with a solar cell having a structure connected by wires.
Patent Literature 2 discloses a garment with a solar cell, which is provided with a transparent pocket in the garment so that a solar cell can be attached and detached, has good comfort, and is excellent in appearance and appearance.
Patent Literature 3 discloses a bag with a solar cell, which is provided with a transparent pocket in the bag, is excellent in maintainability, and has good appearance and appearance.

Japanese Utility Model Publication No. 2-33321 JP 2014-38980 A JP 2014-36995 A

  Attempts to attach solar cells to clothes and bags have been made in the past, but since pockets are installed in the clothes and sheet-type solar cells are attached to the pockets, there has been a problem in appearance and appearance.

  In view of such a situation, an object of the present invention is to provide a photovoltaic fiber structure that is a composite of a photovoltaic element and a fiber that emphasizes appearance and appearance. Specifically, it is an object of the present invention to provide a photovoltaic fiber structure that has a high-class feel, is flexible and can be freely deformed, and has a higher added value, and a method of manufacturing the same.

The present invention provides a fiber structure on both the light-receiving surface and the non-light-receiving surface of a photovoltaic element, and finds that the above problem can be solved by a structure in which the photovoltaic element is sandwiched between the fiber structures. Invented the invention.
That is, the present invention has the following configuration.

(1) A fibrous structure and a photovoltaic element, and a fibrous structure is provided on both the light receiving surface and the non-light receiving surface of the photovoltaic device. Photovoltaic fiber structures.
(2) The photovoltaic fiber structure according to (1), wherein the fiber structure provided on the light receiving surface of the photovoltaic element has a light transmittance of 10% or more and 98% or less.
(3) The bending rigidity measured by KES measurement of the photovoltaic fiber structure is 0.01 × 10 ⁻⁴ N · m ² / m or more and 6 × 10 ⁻⁴ N · m ² / m or less. The photovoltaic fiber structure according to (1) or (2).
(4) The photovoltaic fiber structure according to any one of the above (1) to (3), wherein a transparent adhesive is present between the photovoltaic element and the fiber structure.
(5) A fiber structure and a photovoltaic element, wherein a fiber structure is provided on both the light receiving surface and the non-light receiving surface of the photovoltaic element, and the photovoltaic element is sandwiched and supported by the fiber structure. Of producing a photovoltaic fiber structure.
(6) The method for producing a photovoltaic fiber structure according to (5), wherein the fiber structure provided on the light receiving surface of the photovoltaic element has a light transmittance of 10% or more and 98% or less.
(7) The method for producing a photovoltaic fiber structure according to (5) or (6), wherein a transparent adhesive is used for adhesion.

  The photovoltaic fiber structure of the present invention has a good appearance and appearance, has a high-class feel, is flexible and can be deformed into a free shape, and can provide a material with higher added value. It is.

  The photovoltaic fiber structure of the present invention can be suitably used as a battery for a wristwatch, a mobile phone, an air fan, an air heater, a wearable device, or the like by being attached to clothing. In addition, since these batteries are easy to carry, they can be suitably used even under severe environments such as emergency power supplies, mountain and marine area observation equipment, and space stations.

FIG. 2 is a schematic view illustrating one embodiment of a photoelectric conversion element used in the present invention. It is a schematic diagram which shows another aspect of the photoelectric conversion element used by this invention.

  Next, the photovoltaic fiber structure according to the present invention will be described in detail.

  As the fiber structure in the present invention, a filament, a spun yarn, a woven fabric, a knitted fabric, a nonwoven fabric, a raised body, or the like, which is made of at least one of natural fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers, can be used. Natural fibers include cotton, animal hair fibers, silk, hemp, etc. Regenerated fibers include cellulosic regenerated fibers such as rayon (viscose rayon) and cupra (copper ammonia rayon). Semi-synthetic fibers include cellulosic semi-synthetic fibers Various fibers such as acetate (triacetate) and the like and synthetic fibers such as polyester, nylon, acrylic and aramid can be used.

  Among them, polyester fibers are the most versatile materials that have a wide range of uses in clothing, industrial materials, interior materials, etc. among general-purpose fibers, and therefore, in the present invention, polyesters such as polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate are used. It is more effective to use a system fiber structure.

  As the polyester fiber structure, in addition to those composed of only polyester fibers, at least one of natural fibers such as cotton and wool, semi-synthetic fibers such as acetate, regenerated fibers such as rayon, and synthetic fibers such as nylon, and polyester-based fibers. Fibers obtained by blending, twisting, weaving, knitting and the like are included.

In the present invention, it is preferable that the basis weight of the fiber structure provided on the light receiving surface of the photovoltaic element be 500 g / m ² or less. If it is more than 500 g / m ² , the light transmittance becomes small and the light energy cannot be sufficiently absorbed. More preferably, it is 300 g / m ² or less, further preferably, 100 g / m ² or less, and the lower limit is preferably 10 g / m ² or more.

The hue of the fiber structure provided on the light-receiving surface of the photovoltaic element of the present invention is higher as the lightness L ^* value is closer to 100, and lower as the lightness L ^* value is closer to 0. Become. In order to improve the photoelectric conversion efficiency, a fiber structure having a lightness L ^* value close to 100 is preferable.

  The smaller the color difference ΔE between the fiber structure provided on the light receiving surface and the fiber structure provided on the non-light receiving surface of the photovoltaic element of the present invention, the ideally closer to 0, the more the optical power element becomes. It is a photovoltaic fiber structure that is difficult to understand, is less noticeable, and has a sense of quality. Usually, when it is 5 or less, it is in a practically inconspicuous range, and when it is 3 or less, it is more preferable because it becomes almost inconspicuous.

In the above, the color difference ΔE is a value obtained by the following equation.
ΔE ^* ab = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2
[Delta] L ^*: lightness L ^* value of the fiber structure is provided on the light receiving surface of the photovoltaic element of the present invention - the brightness of the fiber structure is provided on the non-light-receiving surface of the photovoltaic element of the present invention L ^* Value Δa ^* : chromaticity a ^{* of the} fiber structure provided on the light-receiving surface of the photovoltaic device of the present invention a ^* value-color of the fiber structure provided on the non-light-receiving surface of the photovoltaic device of the present invention Degree a ^* value Δb ^* : chromaticity b ^* value of the fiber structure provided on the light receiving surface of the photovoltaic device of the present invention—fiber structure provided on the non-light receiving surface of the photovoltaic device of the present invention Chromaticity b ^* value of object

(Photovoltaic element)
In the present invention, a photovoltaic element refers to an element that converts light energy into electricity. The photovoltaic device of the present invention has at least a positive electrode, a photoelectric conversion layer, and a negative electrode in this order. FIG. 1 is a schematic diagram showing one embodiment of the photoelectric conversion element of the present invention. The embodiment shown in FIG. 1 is a photoelectric conversion element formed by stacking a substrate (1) / a positive electrode (2) / a photoelectric conversion layer (3) / a negative electrode (4) in this order. Further, the photoelectric conversion element of the present invention is, as in the embodiment shown in FIG. 2, laminated in the order of substrate (1) / negative electrode (4) / photoelectric conversion layer (3) / positive electrode (2). You may. However, the photoelectric conversion element of the present invention is not limited to the embodiments shown in FIGS. In addition, as long as the photoelectric conversion element of the present invention has at least a positive electrode, a photoelectric conversion layer, and a negative electrode in this order, an embodiment having another layer between each layer is not excluded.

〔substrate〕
The photoelectric conversion element is generally manufactured by forming each layer on a substrate. The substrate is a substrate on which an electrode material and an organic semiconductor layer can be laminated, for example, alkali-free glass, quartz glass, aluminum, iron, copper, and alloys such as stainless steel, depending on the type and use of the material used for the photoelectric conversion layer. Films and boards made by any method from organic materials such as inorganic materials such as polyester, polycarbonate, polyolefin, polyamide, polyimide, polyphenylene sulfide, polyparaxylene polymethyl methacrylate, epoxy resin and fluorine resin can be used. is there. In the case where light is incident from the substrate side, it is preferable that each of the above-described substrates has a light transmittance, and it is particularly preferable that the substrate has a light transmittance of 20% or more. . Here, the light transmittance of the substrate is
[Transmitted light intensity of substrate (W / m ² ) / incident light intensity of substrate (W / m ² )] × 100 (%)
Is the value given by

  The transmitted light intensity of the substrate necessary for obtaining the light transmittance of the above substrate is determined by using an arbitrary light source and a detector for measuring the light intensity, fixing the distance between the light source and the detector, and determining the light intensity at that time by the incident light intensity. The light intensity when the substrate is inserted between the light source and the detector is defined as the transmitted light intensity so that all the light incident on the detector passes through the substrate. Normally, the light intensity varies greatly depending on what light source is used. In the present invention, as long as the light transmittance at a certain wavelength (for example, 500 nm) exceeds 20%, the light source and the detector are particularly limited because they can be used as a substrate even if they do not substantially transmit at all. You don't need to. Therefore, these light sources and detectors may be appropriately selected and used depending on the application. This is because, as long as the light transmittance at a certain wavelength (for example, 500 nm) exceeds 20%, the light can be used as a substrate even if the other light hardly transmits.

[Electrode (Positive electrode / Negative electrode)]
In the present invention, the positive electrode or the negative electrode of the photoelectric conversion element preferably has light transmittance. At least one of the positive electrode and the negative electrode only needs to have optical transparency, and both may have optical transparency. Here, having light transmittance means that the light transmittance exceeds 0%.

  The electrode having a light-transmitting property only needs to transmit light to such an extent that incident light reaches the photoelectric conversion layer to generate an electromotive force. Specifically, the light transmittance of the electrode in all wavelength regions of 400 nm or more and 900 nm or less is sufficient. It is preferably from 20 to 100%, more preferably from 60 to 100%. The thickness of the light-transmitting electrode is not particularly limited as long as sufficient conductivity is obtained, and varies depending on the material, but is preferably 20 nm to 300 nm. Note that the electrode having no light transmittance is sufficient if it has conductivity, and the thickness is not particularly limited.

  Electrode materials include metals such as gold, platinum, silver, copper, iron, zinc, tin, aluminum, indium, chromium, nickel, cobalt, scandium, vanadium, yttrium, cerium, samarium, europium, terbium, ytterbium, etc. , Indium oxide, tin oxide, molybdenum oxide, nickel oxide and other metal oxides, composite metal oxides (indium tin oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO) , Gallium zinc oxide (GZO) and the like. As metals other than the above, alkali metals and alkaline earth metals, specifically, lithium, magnesium, sodium, potassium, calcium, strontium, barium, and the like are also preferably used. Further, an electrode made of an alloy made of the above metal or a laminate of the above metal is also preferably used. Further, an electrode containing graphite, a graphite interlayer compound, carbon nanotube, graphene, polyaniline and its derivative, and polythiophene and its derivative is also preferably used. Further, the above-mentioned electrode may be a mixed layer composed of two or more materials, or may have a laminated structure in which two or more layers composed of different materials are laminated.

  In the present invention, the conductive material used for the positive electrode preferably has ohmic junction with the photoelectric conversion layer. When a hole transport layer described later is used, the conductive material used for the positive electrode preferably has an ohmic junction with the hole transport layer.

  In addition, the conductive material used for the negative electrode preferably has an ohmic junction with the electron transport layer.

(Hole transport layer)
In the organic electromotive element of the present invention, a hole transport layer may be provided between the positive electrode and the photoelectric conversion layer. Examples of the material for forming the hole transport layer include hole transport materials such as a polythiophene polymer, a poly-p-phenylene vinylene polymer, a polyfluorene polymer, a polypyrrole polymer, a polyaniline polymer, and a polyfuran. Conductive polymers such as polymers, polypyridine polymers and polycarbazole polymers, and p-type semiconductor properties such as phthalocyanine derivatives (H ₂ Pc, CuPc, ZnPc, etc.), porphyrin derivatives, acene compounds (tetracene, pentacene, etc.) , A carbon compound such as graphene or graphene oxide, a molybdenum oxide (MoO _x ) such as MoO ₃ , a tungsten oxide (WO _x ) such as WO ₃ , a nickel oxide (NiO _x ) such as NiO, V ₂ O vanadium oxide, such as _{5 (VO} x), acids such as ZrO ₂ Zirconium _(ZrO x), copper oxide such as Cu ₂ O _(CuO x), copper iodide, ruthenium oxide, such as RuO _{4 (RuO} x), inorganic materials such as ruthenium oxide (ReO _x), such as _Re 2 _{O 7} It is preferably used. Above all, polyethylene dioxythiophene (PEDOT) which is a polythiophene polymer or a material obtained by adding polystyrene sulfonate (PSS) to PEDOT (hereinafter sometimes referred to as PEDOT: PSS), molybdenum oxide, vanadium oxide, tungsten oxide Is more preferably used.

  Among the materials for forming the hole transport layer, as a method for forming the hole transport layer using an inorganic material, a precursor solution such as a metal salt or a metal alkoxide is applied, and then heated to form a layer. And a method of applying a nanoparticle dispersion to a substrate to form a layer. At this time, the inorganic material is not completely reacted, depending on the heating temperature and time, and the synthesis conditions of the nanoparticles, and is partially hydrolyzed or partially condensed, It may be an intermediate product or a mixture of a precursor, an intermediate product, and a final product.

  The hole transport layer may be a layer composed of a single compound, a mixed layer composed of two or more compounds, or a laminated structure. Further, the hole transport layer may contain a substance having no hole transport property as long as hole transport from the photoelectric conversion layer to the electrode is not significantly impaired. For example, a surfactant, a viscosity modifier, a binder resin, a filler, and the like for improving applicability and smoothness are exemplified.

  The thickness of the hole transport layer is preferably from 0.1 nm to 1000 nm, more preferably from 0.5 nm to 100 nm, and still more preferably from 5 nm to 50 nm.

(Photoelectric conversion layer)
Next, the photoelectric conversion layer in the photoelectric conversion element used in the present invention is not particularly limited. However, in order to secure the flexibility of the photoelectric conversion element, it is a thin film of 1 μm or less, or an inorganic amorphous material or an organic amorphous material. Desirably, it is formed from a material.

  Examples of the photoelectric conversion layer made of an organic material include those containing an electron-donating organic material and an electron-accepting organic material described below. The photoelectric conversion layer made of the organic material will be described.

  As the structure of the photoelectric conversion layer, for example, a structure composed of a layer containing a mixture of an electron donating organic material and an electron accepting organic material, a structure in which a layer composed of an electron donating organic material and a layer composed of an electron accepting organic material are laminated And a structure in which a layer made of a mixture thereof is stacked between a layer made of an electron donating organic material and a layer made of an electron accepting organic material.

  Among these, a structure composed of a layer containing a mixture of an electron donating organic material and an electron accepting organic material is more preferable. The method of mixing the mixture is not particularly limited, but after adding to the solvent in a desired ratio, a method of heating, stirring, ultrasonic irradiation or the like and dissolving in the solvent by combining one or more methods. Is mentioned.

  The photoelectric conversion layer may contain two or more electron donating organic materials and / or electron accepting organic materials.

  The content ratio of the electron donating organic material to the electron accepting organic material in the photoelectric conversion layer is not particularly limited, but the ratio of the electron donating organic material to the electron accepting organic material (donor-acceptor ratio) is 1:99 to 99: 1. , Preferably in the range of 10:90 to 90:10, and more preferably in the range of 20:80 to 60:40.

  In addition, as described later, when the photoelectric conversion element material forms a single organic semiconductor layer, the above content ratio is the content ratio of the electron donating organic material and the electron accepting organic material contained in the one layer, When the photoelectric conversion layer has a stacked structure of two or more layers, it means the content ratio of the electron donating organic material to the electron accepting organic material in the entire organic semiconductor layer.

  The photoelectric conversion layer may contain other components such as a surfactant, a binder resin, and a filler as long as the object of the present invention is not impaired.

  The thickness of the photoelectric conversion layer may be sufficient if the electron donating organic material and the electron accepting organic material cause photoelectric conversion by light absorption. The thickness of the photoelectric conversion layer varies depending on the material, but is preferably from 10 nm to 1000 nm, more preferably from 50 nm to 500 nm.

  The electron donating organic material is not particularly limited as long as it is an organic compound exhibiting p-type semiconductor characteristics. For example, polythiophene-based polymer, 2,1,3-benzothiadiazole-thiophene-based copolymer, quinoxaline-thiophene-based copolymer, thiophene-benzodithiophene-based copolymer, poly-p-phenylenevinylene-based polymer, Conjugated polymers such as poly-p-phenylene polymer, polyfluorene polymer, polypyrrole polymer, polyaniline polymer, polyacetylene polymer, polythienylenevinylene polymer, H2 phthalocyanine (H2Pc), Phthalocyanine derivatives such as copper phthalocyanine (CuPc) and zinc phthalocyanine (ZnPc), porphyrin derivatives, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diphenyl-1,1 ' -Diamine (TPD), N, N'-dinaphthyl-N, N'-diphenyl Triarylamine derivatives such as 4,4'-diphenyl-1,1'-diamine (NPD), carbazole derivatives such as 4,4'-di (carbazol-9-yl) biphenyl (CBP), and oligothiophene derivatives Low-molecular-weight organic compounds such as thiophene, quarterthiophene, sexithiophene, and octithiophene. Two or more of these may be used.

  The polythiophene-based polymer refers to a conjugated polymer having a thiophene skeleton in a main chain, and includes a polymer having a side chain. Specifically, poly-3-alkylthiophenes such as poly-3-methylthiophene, poly-3-butylthiophene, poly-3-hexylthiophene, poly-3-octylthiophene, and poly-3-decylthiophene; Poly-3-alkoxythiophenes such as 3-methoxythiophene, poly-3-ethoxythiophene, poly-3-dodecyloxythiophene, poly-3-methoxy-4-methylthiophene, poly-3-dodecyloxy-4-methylthiophene And poly-3-alkoxy-4-alkylthiophenes.

  The 2,1,3-benzothiadiazole-thiophene-based copolymer refers to a conjugated copolymer having a thiophene skeleton and a 2,1,3-benzothiadiazole skeleton in a main chain. Specific examples of the 2,1,3-benzothiadiazole-thiophene copolymer include the following structures. In the following formula, n shows the integer of 1-1000.

  The quinoxaline-thiophene copolymer refers to a conjugated copolymer having a thiophene skeleton and a quinoxaline skeleton in the main chain. Specific examples of the quinoxaline-thiophene copolymer include the following structures. In the following formula, n shows the integer of 1-1000.

  The thiophene-benzodithiophene polymer refers to a conjugated copolymer having a thiophene skeleton and a benzodithiophene skeleton in a main chain. Specific examples of the thiophene-benzodithiophene copolymer include the following structures. In the following formula, n shows the integer of 1-1000.

  The poly-p-phenylenevinylene-based polymer refers to a conjugated polymer having a p-phenylenevinylene skeleton in a main chain, and includes a polymer having a side chain. Specifically, poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene], poly [2-methoxy-5- (3 ′, 7′-dimethyloctyloxy) -1, 4-phenylenevinylene] and the like.

  Among the electron-donating organic semiconductors exemplified above, a conjugated polymer having a skeleton represented by any of the following formulas (4) to (6) includes 1,8-diiodooctane as an additive. It has been reported that when used, the photoelectric conversion characteristics are improved (for example, Japanese Patent No. 058929734, "Advanced Materials", 2010, Vol. 22, E135-E138, " "Journal of the American Chemistry", 2010, 132, 7595-7597, "Macromolecules, 2012, 45, 6923-6929," "Advances." Materials (Adv etc., 2011, Vol. 23, pp. 3315-3319), and the composition of the present invention is preferably contained as an electron-donating organic semiconductor.

(In the above formula (4), R ₃ may be the same or different and each represents an alkyl group, an alkoxy group, an optionally substituted heteroaryl group, an optionally substituted aryl group or a thioalkoxy group. X ₂ may be the same or different and each represents a sulfur, selenium or oxygen atom.)
(In the above formula (5), R ₄ represents an alkoxycarbonyl group or an alkanoyl group; Y ₂ represents a hydrogen atom or a halogen.)
(In the above formula (6), R ₅ represents an alkyl group, an optionally substituted heteroaryl group, or an optionally substituted aryl group.)

  Among the conjugated polymers having the above skeletal structure, the present invention relates to a conjugated polymer represented by the following formula (7), which has a wide light absorption wavelength region and a deep HOMO level and thus can obtain high photoelectric conversion characteristics. Is more preferable as the electron-donating organic semiconductor of the composition.

(In the above formula (7), R ₃ , R ₄ , X ₂ and Y ₂ are the same as in the above formulas (4) and (5).)

  The electron-accepting organic material contained in the photoelectric conversion layer in the present invention is not particularly limited as long as it is an organic substance having n-type semiconductor characteristics. For example, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA), 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), 3,4,9,10-perylenetetracarboxylic Bisbenzimidazole (PTCBI), N, N'-dioctyl-3,4,9,10-naphthyltetracarboxydiimide (PTCDI-C8H), 2- (4-biphenylyl) -5- (4-t-butylphenyl) Oxazole derivatives such as -1,3,4-oxadiazole (PBD) and 2,5-di (1-naphthyl) -1,3,4-oxadiazole (BND), 3- (4-biphenylyl)- Triazole induction such as 4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole (TAZ) Body, phenanthroline derivatives, phosphine oxide derivatives, fullerene derivatives, carbon nanotubes, poly -p- phenylene vinylene-based polymer derivatives obtained by introducing cyano group into (CN-PPV) and the like. Two or more of these may be used. A fullerene derivative is preferably used because it is an n-type semiconductor that is stable and has high carrier mobility.

Specific examples of the fullerene derivative include unsubstituted ones such as C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₂ , C ₈₄ , C ₉₀ , C ₉₄ , and [6,6] -phenyl C ₆₁ butyrate. Ric acid methyl ester ([6,6] -C ₆₁ -PCBM or [60] PCBM), [5,6] -phenyl C ₆₁ butyric acid methyl ester, [6,6] -phenyl C ₆₁ butyric acid And substituted derivatives such as hexyl ester, [6,6] -phenyl C ₆₁ butyric acid dodecyl ester, and phenyl C ₇₁ butyric acid methyl ester ([70] PCBM). Among them, 60 PCBM and 70 PCBM are more preferable.

(Electron transport layer)
In the photovoltaic device of the present invention, an electron transport layer may be provided between the organic semiconductor layer 3 and the negative electrode 4. The material for forming the electron transport layer is not particularly limited, but may be an electron-accepting organic material (NTCDA, PTCDA, PTCDI-C8H, oxazole derivative, triazole derivative, phenanthroline derivative, phosphine oxide derivative, phosphine sulfide derivative, quinoline Organic materials exhibiting n-type semiconductor characteristics, such as derivatives, fullerene compounds, CNT, CN-PPV, etc.) are preferably used. In addition, ionic substituted fluorene-based polymers ("Advanced Materials", 2011, Vol. 23, pp. 4636-4643, "Organic Electronics", 2009, Vol. 10, pp. 496-500) And ionic compounds such as a combination of an ionic substituted fluorene-based polymer and a substituted thiophene-based polymer (“Journal of American Chemical Society”, 2011, 133, 8416-8419); Polyethylene oxide ("Advanced Materials", 2007, 19, 1835-183) Page), etc. can be also used as the electron extraction layer. In addition, ionic substituted fluorene-based polymers ("Advanced Materials", 2011, Vol. 23, pp. 4636-4643, "Organic Electronics", 2009, Vol. 10, pp. 496-500) And ionic compounds such as a combination of an ionic substituted fluorene-based polymer and a substituted thiophene-based polymer (“Journal of American Chemical Society”, 2011, 133, 8416-8419); Polyethylene oxide ("Advanced Materials", 2007, 19, 1835-183) Page), etc. can be also used as the electron extraction layer.

  Compounds having an ionic group, for example, ammonium salt, amine salt, pyridinium salt, imidazolium salt, phosphonium salt, carboxylate, sulfonate, phosphate, sulfate ester salt, phosphate ester salt, sulfate salt , Nitrates, acetonate salts, oxo acid salts, and metal complexes can also be used as the electron transport layer.

  Specifically, ammonium chloride, ammonium acetate, ammonium phosphate, hexyltrimethylammonium bromide, tetrabutylammonium bromide, octadecyltrimethylammonium bromide, hexadecylpyridinium bromide, 1-butyl-3-methylimidazolium bromide, tributylhexadecylphosphonium bromide , Zinc formate, zinc acetate, zinc propionate, zinc butyrate, zinc oxalate, sodium heptadecafluorononanoate, sodium myristate, sodium benzoate, sodium 1-hexadecane sulfonate, sodium dodecyl sulfate, sodium monododecyl phosphate, Zinc acetylacetonate, ammonium chromate, ammonium metavanadate, ammonium molybdate, zirconate hexafluoride Monium, sodium tungstate, ammonium tetrachlorozincate, tetraisopropyl orthotitanate, lithium nickelate, potassium permanganate, silver phenanthroline complex, AgTCNQ and compounds used for the electron transport layer described in JP-A-2013-58714, and the like. Can be

Further, titanium oxide (TiO _x ) such as TiO ₂ , zinc oxide (ZnO _x ) such as ZnO, silicon oxide (SiO _x ) such as SiO ₂ , tin oxide (SnO _x ) such as SnO _2, and oxidation such as WO ₃ tungsten _(WO x), tantalum oxide such as _{Ta 2 O 3 (TaO x)} , barium titanate, such as _{BaTiO 3 (BaTi x O y)} , barium zirconate, such as _{BaZrO 3 (BaZr x O y)} , ZrO 2 , etc. Zirconium oxide (ZrO _x ), hafnium oxide (HfO _x ) such as HfO ₂ , aluminum oxide (AlO _x ) such as Al ₂ O _3, yttrium oxide (YO _x ) such as Y ₂ O ₃ , and silicon such as ZrSiO ₄ metal oxides such as zirconium (ZrSi _x O _y), silicon nitride such as _Si 3 _{N 4} of (SiN _x) Nitrides such as, a semiconductor such as cadmium sulfide, such as CdS _(CdS x), zinc selenide _(ZnSe x) such as ZnSe, zinc sulfide _(ZnS x) such as ZnS, cadmium telluride, such as CdTe (CdTe _x) Inorganic materials such as are also preferably used.

  As a method of forming an electron extraction layer with the inorganic material, a method of forming a layer by applying a precursor solution such as a metal salt or a metal alkoxide, and then heating, or a method of applying a nanoparticle dispersion to a substrate. There is a method of forming a layer. At this time, depending on the heating temperature and time, and the conditions for synthesizing the nanoparticles, the reaction does not completely proceed, and is partially hydrolyzed or partially condensed to form an intermediate product. Alternatively, it may be a mixture of a precursor and an intermediate product, a final product, or the like.

  In the photoelectric conversion element of the present invention, two or more photoelectric conversion layers may be stacked (tandemly formed) via one or more charge recombination layers to form a series junction. For example, a laminated structure of substrate / positive electrode / first photoelectric conversion layer / charge recombination layer / second photoelectric conversion layer / negative electrode can be given. By stacking in this manner, the open-circuit voltage can be further increased. Note that the above-described hole transport layer may be provided between the positive electrode and the first photoelectric conversion layer and between the charge recombination layer and the second photoelectric conversion layer. The above-described electron transport layer may be provided between the bonding layer and between the second photoelectric conversion layer and the negative electrode.

  The charge recombination layer used here needs to have light transmittance so that a plurality of photoelectric conversion layers can absorb light. The charge recombination layer is not necessarily a film, as long as it is designed so that holes and electrons are sufficiently recombined. For example, a metal cluster formed uniformly on the photoelectric conversion layer It may be.

  The charge recombination layer includes a very thin metal film or metal cluster having a light transmittance of several Angstroms to several tens Angstroms made of gold, platinum, chromium, nickel, lithium, magnesium, calcium, tin, silver, aluminum, etc. (Including alloys), ITO, IZO, AZO, GZO, FTO, metal oxide films and clusters with high light transmission such as titanium oxide and molybdenum oxide, conductive organic material films such as PEDOT: PSS, or composites thereof A body or the like is used.

  In the present invention, the provision of the fiber structure on both the light receiving surface and the non-light receiving surface of the photovoltaic device means that the fiber structure is disposed on the front surface and the back surface of the photovoltaic device. Here, as a mode of arranging the fiber structure on the front surface and the back surface of the photovoltaic element, the fiber structure may be installed, fixed, adhered, or the like on both surfaces of the photovoltaic element. The fiber structures on both sides of the photovoltaic element may be the same fiber structures on both sides or different fiber structures. The fibrous structure may be colored. As a coloring method, a known method such as dyeing, printing, and coating is used. An adhesive, an adhesive, a void, and the like may exist between the fiber structure and the photovoltaic element as long as the effects of the present invention are not impaired.

  When the photovoltaic element and the fiber structure are bonded in the present invention, the bonding may be performed by melting and bonding a part of the photovoltaic element or the fiber structure, or by using an adhesive or an adhesive. Good. When bonding, it is desirable that the adhesive or the adhesive is transparent.

  The fiber structure provided on the light receiving surface of the photovoltaic element of the present invention is a fiber structure provided on the light receiving surface side of the photovoltaic element so that the photovoltaic element can sufficiently absorb light energy. It is desirable that the light transmittance is 10% or more and 98% or less. The reason for this is that if the light transmittance is smaller than this, light will not be transmitted and light energy cannot be sufficiently absorbed. If the light transmittance is larger than this, the existence of the photovoltaic element becomes too obvious, and it becomes difficult to obtain sufficient decorativeness. Here, the light transmittance may be calculated using a colorimeter (such as UV-3150 manufactured by SIMAZU) in the transmission measurement mode, and from the ratio of the integrated intensity of all wavelengths when the fabric is not installed and when the fabric is installed. .

The photovoltaic structure of the present invention is specified by KES (Kawabata Evaluation System), which is generally used as a texture measuring system for a fiber structure, in order to be capable of being deformed into a flexible and free form. It is desirable that the measured bending stiffness value (B) be 0.01 × 10 ⁻⁴ N · m ² / m or more and 6 × 10 ⁻⁴ N · m ² / m or less. Here, the unit of the measured bending stiffness (B) is 10 ⁻⁴ N · m ² / m. The reason is that if the bending stiffness is larger than this, the force required for bending deformation is large and it is not possible to perform free deformation, and if the bending stiffness is smaller than this, the material and thickness will function as a photovoltaic element. This is because there is a tendency that a sufficient configuration cannot be obtained. In the present invention, the higher the flexibility of the composite, the higher the degree of freedom in design. Therefore, it is more preferable that the measured value of the bending stiffness is 3 × 10 ⁻⁴ N · m ² / m or less.

  In order to obtain such flexibility, the substrate used for the photovoltaic element of the present invention preferably has a thickness of 80 μm or less. Further, the thickness is desirably 60 μm or less, and more desirably 40 μm or less. On the other hand, the thickness is preferably 1 μm or more from the viewpoint of mechanical strength. Further, the thickness is preferably 5 μm or more, more preferably 10 μm or more.

  Next, a method for manufacturing the photovoltaic structure of the present invention will be described. In the present invention, the photovoltaic element and the fiber structure are bonded. Here, "to bond" means to bond the photovoltaic element and the fiber structure using an adhesive or an adhesive. There is no problem in joining the photovoltaic element and the fiber structure on the light receiving surface or the non-light receiving surface of the photovoltaic element. It is preferable to join with the non-light receiving surface of the photovoltaic element. Adhesive is a general term for the bonding of base materials composed of chemical substances such as glue, and the adhesive is the physical bonding of base materials like screws, pins, buttons, etc. It is a generic term for things.

  In the present invention, it is desirable to use an adhesive, particularly a transparent and low modulus adhesive. The reason is that by using a transparent adhesive, the photovoltaic structure can absorb as much light as possible, and by using a low-modulus adhesive, the photovoltaic structure is flexible and free. This is because the shape can be deformed. As an example of the transparent adhesive, an epoxy-based, cyanoacrylate-based, urethane-based, melamine-based, acrylic-based or other various adhesive having high transparency may be used. Particularly, an adhesive having high transparency and low modulus is preferable. The modulus of the adhesive is preferably 10 MPa or less, most preferably 5 MPa or less.

  Further, as the type of the adhesive used in the present invention, various types such as a thermosetting type, a moisture setting type, a hot melt type, and a light setting type can be used.

  The adhesive is applied using screen printing or various coating equipment, applied to the photovoltaic element and / or fiber structure, and then pressed and cured to match the adhesive of each type. Let it. For example, in the case of a thermosetting adhesive, a heat treatment and a pressure and heat treatment may be performed at a temperature of about 120 to 150 ° C. The heat treatment and the pressure and heat treatment method are not particularly limited, and examples thereof include a heat treatment such as passing hot air, and a pressure and heat treatment such as calendering, embossing, and hot pressing.

  The fixing and bonding of the fiber structure on both the light-receiving surface and the non-light-receiving surface of the photovoltaic element of the photovoltaic fiber structure of the present invention are not particularly limited, and may be a commonly used method.

  The photovoltaic fiber structure of the present invention is suitably used as a battery for a wristwatch, a mobile phone, an air fan, an air heater, a wearable device, and the like, as well as an emergency power supply, a mountain / marine zone observation device, and a space station.

<Density>
It was measured according to the density evaluation method described in JIS L1906 for the 2010 edition.

<Weight>
It was measured according to the density evaluation method of mass per unit area described in JIS L1906 in the 2010 edition.

<Color difference ΔE ^* ab>
Using a spectrophotometer (manufactured by Minolta: CM-3700d), L * a * b * was measured for each of the fiber structure used on the light receiving surface side and the fiber structure used on the non-learning surface side. The color difference ΔE ^* ab was calculated from the following equation.
ΔE ^* ab = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2
[Delta] L ^*: lightness L ^* value of the fiber structure is provided on the light receiving surface of the photovoltaic element of the present invention - the brightness of the fiber structure is provided on the non-light-receiving surface of the photovoltaic element of the present invention L ^* Value Δa ^* : chromaticity a ^{* of the} fiber structure provided on the light-receiving surface of the photovoltaic device of the present invention a ^* value-color of the fiber structure provided on the non-light-receiving surface of the photovoltaic device of the present invention Degree a ^* value Δb ^* : chromaticity b ^* value of the fiber structure provided on the light receiving surface of the photovoltaic device of the present invention—fiber structure provided on the non-light receiving surface of the photovoltaic device of the present invention Chromaticity b ^* value of object

<Light transmittance of fiber structure provided on light receiving surface of photovoltaic element>
With respect to the fiber structure provided on the light receiving surface, a colorimeter (Minolta 3700d) was used in the transmission measurement mode, and the calculation was performed from the ratio of the integrated intensity of the entire wavelength when the fiber structure was not installed and when the fiber structure was installed.

<Photoelectric conversion efficiency>
The positive and negative electrodes of the photovoltaic element in the photovoltaic fiber structure were connected to a Keithley 2400 series source meter, and simulated sunlight (OTENTO-SUNIII, manufactured by Spectrometer Co., Ltd., spectrum shape) from the ITO layer side in the atmosphere. : AM 1.5, intensity: 100 mW / cm ² ), and the current value when the applied voltage was changed from -1 V to +2 V was measured. The photoelectric conversion efficiency (η) was calculated from the obtained current value.

<Bending rigidity>
For the photovoltaic fiber lab structure, the average value B of the bending stiffness of the sample was measured using a texture measurement system KES (Kawabata Evaluation System) measuring machine (manufactured by Kato Tech).

Note that the present invention is not limited to the following examples. Further, among the compounds used in Examples and the like, those using abbreviations are shown below.
ITO: indium tin oxide PEDOT: polyethylene dioxythiophene (material forming a hole transport layer)
PSS: polystyrene sulfonate A-1: a compound represented by the following formula (n is the degree of polymerization)

[70] PCBM: phenyl C ₇₁ butyric acid methyl ester (electron-accepting organic material)
THF: tetrahydrofuran n-BuLi: normal butyl lithium

[Synthesis Example 1]
Compound A-1 was synthesized by the method shown in Formula 1. Compound (1-i) was prepared by referring to the method described in Journal of the American Chemical Society, 2009, vol. 131, pp. 7792-7799, and It was synthesized with reference to the method described in Angewandte Chem International Edition, 2011, Vol. 50, pp. 9697-9702.

38 g (0.27 mol) of methyl-2-thiophene carboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 108 g (1.34 mol) of chloromethyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) are stirred at 0 ° C. Meanwhile, 125 g (0.48 mol) of tin tetrachloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added over 1 hour, and the mixture was stirred at room temperature for 8 hours. After completion of the stirring, 100 ml of water was slowly added at 0 ° C., and the mixture was extracted three times with chloroform. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The resulting brown solid was recrystallized from methanol to obtain a compound (1-b) as a pale yellow solid (24.8 g, yield 39%). The measurement results of ¹ H-NMR of the compound (1-b) are shown below. In addition, an FT-NMR apparatus (JEOL JNM-EX270 manufactured by JEOL Ltd.) was used for the ¹ H-NMR measurement.
_{^{1 H-NMR (270MHz, CDCl}} 3): 7.71 (s, 1H), 4.79 (s, 1H), 4.59 (s, 1H), 3.88 (s, 3H) ppm.

24.8 g (0.10 mmol) of the above compound (1-b) was dissolved in 1.2 L of methanol (manufactured by Sasaki Chemical Industry Co., Ltd.), and sodium sulfide (manufactured by Aldrich) 8 was stirred at 60 ° C. A solution of 0.9 g (0.11 mol) in 100 ml of methanol was added dropwise over 1 hour, and the mixture was further stirred at 60 ° C. for 4 hours. After completion of the reaction, the solvent was removed under reduced pressure, 200 ml of chloroform and 200 ml of water were added, and insolubles were removed by filtration. The organic layer was washed twice with water and once with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography (eluent, chloroform) to give compound (1-c) as a white solid (9.8 g, yield 48%). The results of ¹ H-NMR measurement of compound (1-c) are shown below.
_{^{1 H-NMR (270MHz, CDCl}} 3): 7.48 (s, 1H), 4.19 (t, J = 3.0Hz, 2H), 4.05 (t, J = 3.0Hz, 2H), 3.87 (s, 3H) ppm.

To 9.8 g (49 mmol) of the above compound (1-c), 100 ml of water and then 30 ml of a 3M aqueous sodium hydroxide solution were added, and the mixture was heated with stirring at 80 ° C. for 4 hours. After completion of the reaction, 15 ml of concentrated hydrochloric acid was added at 0 ° C., and the precipitated solid was collected by filtration and washed with water several times. The obtained solid was dried to obtain compound (1-d) as a white solid (8.9 g, yield 98%).
¹ H-NMR (270 MHz, DMSO-d ₆ ): 7.46 (s, 1 H), 4.18 (t, J = 3.2 Hz, 2 H), 4.01 (t, J = 3.2 Hz, 2 H) ) Ppm.

1.46 g (7.8 mmol) of the above compound (1-d) was dissolved in 60 ml of dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), and stirred at -78 ° C. 10.7 ml (17.2 mmol) of 1.6 M, manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise, and the mixture was stirred at -78 ° C for 1 hour. Next, 20 ml of a dry tetrahydrofuran solution of 4.91 g (15.6 mmol) of N-fluorobenzenesulfonimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at -78 ° C over 10 minutes, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, 50 ml of water was slowly added. The aqueous layer was made acidic by adding 3M hydrochloric acid, and then extracted three times with chloroform. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. After removing by-products by silica gel column chromatography (eluent, ethyl acetate), the product was recrystallized from ethyl acetate to obtain a compound (1-e) as a pale yellow powder (980 mg, yield 61%). The results of ¹ H-NMR measurement of the compound (1-e) are shown below.
_{^{1 H-NMR (270MHz, DMSO}} -d 6): 13.31 (brs, 1H), 4.20 (t, J = 3.0Hz, 2H), 4.03 (t, J = 3.0Hz, 2H ) Ppm.

  To 10 ml of a solution of 800 mg (3.9 mmol) of the above compound (1-e) in dehydrated dichloromethane (manufactured by Wako Pure Chemical Industries, Ltd.), 1 ml of oxalyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), and then dimethylformamide (Wako Pure Chemical Industries, Ltd.) (Manufactured by Kogyo Co., Ltd.), and the mixture was stirred at room temperature for 3 hours. The solvent and excess oxalyl chloride were removed under reduced pressure to obtain compound (1-f) as a yellow oil. Compound (1-f) was used for the next reaction as it was.

1.3 g (10 mmol) of 1-octanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 800 mg (8 mmol) of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) were added to 10 ml of a dichloromethane solution of the above compound (1-f, partially purified product). )) At room temperature and stirred at room temperature for 6 hours. The reaction solution was washed twice with 1M hydrochloric acid, once with water and once with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The compound (1-g) was obtained as a pale yellow solid (1.12 g, yield 90%) by purifying by silica gel column chromatography (eluent, chloroform). The measurement results of ¹ H-NMR of the compound (1-g) are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ): 4.27 (t, J = 6.7 Hz, 2H), 4.16 (t, J = 3.0 Hz, 2H), 4.01 (t, J = 3) 0.0 Hz, 2H), 1.72 (m, 2H), 1.5-1.3 (m, 12H), 0.88 (t, J = 7.0 Hz, 3H) ppm.

To 40 ml of an ethyl acetate solution of 1.1 g (3.5 mmol) of the above compound (1-g), 10 ml of an ethyl acetate solution of 630 mg (3.6 mmol) of metachlorobenzoic acid (manufactured by Nacalai Tesque, Inc.) was added dropwise at 0 ° C. And stirred at room temperature for 5 hours. After removing the solvent under reduced pressure, 30 ml of acetic anhydride was added, and the mixture was heated under reflux for 3 hours. After removing the solvent again under reduced pressure, the residue was purified by silica gel column chromatography (eluent, dichloromethane: hexane = 1: 1) to obtain compound (1-h) as a pale yellow oil (1.03 g, yield 94%). Was. The results of ¹ H-NMR measurement of compound (1-h) are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ): 7.65 (d, J = 2.7 Hz, 1 H), 7.28 (dd, J = 2.7 Hz and 5.4 Hz, 1 H), 4.31 (t) , J = 6.8 Hz, 2H), 1.75 (m, 2H), 1.42-1.29 (m, 12H), 0.89 (t, J = 6.8 Hz, 3H) ppm.

To a solution of 1.0 g (3.2 mmol) of the above compound (1-h) in 20 ml of dimethylformamide, 1.25 g (7.0 mmol) of N-bromosuccinimide (manufactured by Wako Pure Chemical Industries, Ltd.) was added at room temperature. Stirred at room temperature for hours. After completion of the reaction, 10 ml of a 5% aqueous sodium thiosulfate solution was added, and the mixture was stirred for 5 minutes. 80 ml of ethyl acetate was added, and the organic layer was washed five times with water and once with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The compound (1-i) was obtained as a pale yellow solid (1.2 g, yield 79%) by purification by silica gel column chromatography (eluent, chloroform: hexane = 1: 3). The results of ¹ H-NMR measurement of compound (1-i) are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ): 4.32 (t, J = 6.5 Hz, 2H), 1.75 (m, 2H), 1.42-1.29 (m, 12H), 0. 89 (t, J = 6.8 Hz, 3H) ppm.

To 300 ml of a dichloromethane solution of 110 g (1.5 mol) of diethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added 100 g (0.68 mol) of 3-thiophenecarbonyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) at 0 ° C. for 1 hour. And stirred at room temperature for 3 hours. After completion of the stirring, 200 ml of water was added, and the organic layer was washed three times with water and once with saturated saline. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain the compound (1-k) as a pale orange liquid (102 g, yield 82%). The results of ¹ H-NMR measurement of compound (1-k) are shown below.

¹ H-NMR (270 MHz, CDCl ₃ ): 7.47 (dd, J = 3.2 Hz and 1.0 Hz, 1H), 7.32 (dd, J = 5.0 Hz and 3.2 Hz, 1H), 7 .19 (dd, J = 5.0 Hz and 1.0 Hz, 1H), 3.43 (brs, 4H), 1.20 (t, J = 6.5 Hz, 6H) ppm.

In a 400 ml solution of 73.3 g (0.40 mol) of the above compound (1-k) in dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), a normal butyl lithium hexane solution (1.6 M, manufactured by Wako Pure Chemical Industries, Ltd.) ) 250 ml (0.40 mol) was added dropwise at 0 ° C over 30 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 4 hours. After completion of the stirring, 100 ml of water was slowly added, and the mixture was stirred for a while, and then the reaction mixture was poured into 800 ml of water. The precipitated solid was collected by filtration, and washed with water, methanol, and then hexane in this order to obtain compound (1-1) as a yellow solid (23.8 g, yield 27%). The results of ¹ H-NMR measurement of compound (1-1) are shown below.
_{^{1 H-NMR (270MHz, CDCl}} 3): 7.69 (d, J = 4.9Hz, 2H), 7.64 (d, J = 4.9Hz, 2H) ppm.

To 400 ml of a solution of 42 g (0.50 mol) of thiophene in dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was added 250 ml (0.40 mol) of a normal butyllithium hexane solution (1.6 M, manufactured by Wako Pure Chemical Industries, Ltd.). It was added dropwise at -78 ° C over 30 minutes. After the reaction mixture was stirred at -78 ° C for 1 hour, 76.4 g (0.40 mol) of 2-ethylhexyl bromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at -78 ° C over 15 minutes. After stirring the reaction solution at room temperature for 30 minutes, it was heated and stirred at 60 ° C. for 6 hours. After completion of the stirring, the reaction solution was cooled to room temperature, and 200 ml of water and 200 ml of diethyl ether were added. The organic layer was washed twice with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain compound (1-n) as a colorless liquid (28.3 g, 36%). The results of ¹ H-NMR measurement of compound (1-n) are shown below.
_{^{1 H-NMR (270MHz, CDCl}} 3): 7.11 (d, 4.9Hz, 1H), 6.92 (dd, 4.9Hz and 3.2Hz, 1H), 6.76 (d, J = 3 .2 Hz, 1H), 2.76 (d, J = 6.8 Hz, 2H), 1.62 (m, 1H), 1.4-1.3 (m, 8H), 0.88 (m, 6H) ) Ppm.

To a solution of 17.5 g (89 mmol) of the above compound (1-n) in 400 ml of dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was added 57 ml of a normal butyllithium hexane solution (1.6 M, manufactured by Wako Pure Chemical Industries, Ltd.). (89 mmol) was added dropwise at 0 ° C. over 30 minutes. After stirring the reaction solution at 50 ° C. for 1 hour, 4.9 g (22 mmol) of the above compound (1-1) was added at 50 ° C., and the mixture was stirred as it was for 1 hour. After completion of the stirring, the reaction solution was cooled to 0 ° C., and a solution prepared by dissolving 39.2 g (175 mmol) of tin chloride dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) in 80 ml of 10% hydrochloric acid was added. Stirred for hours. After completion of the stirring, 200 ml of water and 200 ml of diethyl ether were added, and the organic layer was washed twice with water and then with saturated saline. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The compound (1-o) was obtained as a yellow oil (7.7 g, yield 59%) by purifying by silica gel column chromatography (eluent, hexane). The results of ¹ H-NMR measurement of compound (1-o) are shown below.
_{^{1 H-NMR (270MHz, CDCl}} 3): 7.63 (d, J = 5.7Hz, 1H), 7.45 (d, J = 5.7Hz, 1H), 7.29 (d, J = 3 6.6 Hz, 1H), 6.88 (d, J = 3.6 Hz, 1H), 2.86 (d, J = 7.0 Hz, 2H), 1.70-1.61 (m, 1H), 1 .56-1.41 (m, 8H), 0.97-0.89 (m, 6H) ppm.

In a 25 ml solution of 870 mg (1.5 mmol) of the above compound (1-o) in dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), a hexane solution of normal butyl lithium (1.6 M, manufactured by Wako Pure Chemical Industries, Ltd.) 2 0.0 ml (3.3 mmol) was added at -78 ° C using a syringe, and the mixture was stirred at -78 ° C for 30 minutes and at room temperature for 30 minutes. After cooling the reaction mixture to −78 ° C., 800 mg (4.0 mmol) of trimethyltin chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added at once at −78 ° C., and the mixture was stirred at room temperature for 4 hours. After completion of the stirring, 50 ml of diethyl ether and 50 ml of water were added, and the mixture was stirred at room temperature for 5 minutes. Then, the organic layer was washed twice with water and then with saturated saline. After drying the solvent with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained orange oil was recrystallized from ethanol to give compound (1-p) as a pale yellow solid (710 mg, yield 52%). The results of ¹ H-NMR measurement of compound (1-p) are shown below.
¹ H-NMR (270 MHz, CDCl ₃ ): 7.68 (s, 2H), 7.31 (d, J = 3.2 Hz, 2H), 6.90 (d, J = 3.2 Hz, 2H), 2.87 (d, J = 6.2 Hz, 4H), 1.69 (m, 2H), 1.40-1.30 (m, 16H), 1.0-0.9 (m, 12H), 0.39 (s, 18H) ppm.

Compound (1-i) 71 mg (0.15 mmol) and compound (1-p) 136 mg (0.15 mmol) were dissolved in toluene (Wako Pure Chemical Industries, Ltd.) 4 ml and dimethylformamide (Wako Pure Chemical Industries, Ltd.) 5) Tetrakistriphenylphosphine palladium (manufactured by Tokyo Chemical Industry Co., Ltd.) (5 mg) was added to the solution in 1 ml, and the mixture was stirred at 100 ° C. for 15 hours under a nitrogen atmosphere. Next, 15 mg of bromobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 100 ° C. for 1 hour. Next, 40 mg of tributyl (2-thienyl) tin (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further stirred at 100 ° C. for 1 hour. After completion of the stirring, the reaction mixture was cooled to room temperature, and poured into 100 ml of methanol. The precipitated solid was collected by filtration and washed with methanol, water, and acetone in this order. Then, using a Soxhlet extractor, washing was performed in the order of acetone and hexane. Next, the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque, Inc.) and then through a silica gel column (free liquid, chloroform), and the solvent was distilled off under reduced pressure. After the obtained solid was dissolved again in chloroform, it was reprecipitated in methanol to obtain Compound A-1 (85 mg). The weight average molecular weight was 25,000 and the number average molecular weight was 16,000. The average molecular weight (number average molecular weight, weight average molecular weight) was calculated by an absolute calibration curve method using a GPC apparatus (manufactured by TOSOH, a high-speed GPC apparatus HLC-8320GPC which fed chloroform). The polymerization degree n was calculated by the following equation.
Degree of polymerization n = [(weight average molecular weight) / (molecular weight of repeating unit)]

(Example 1)
5 μL of water and 0.5 mL of an ethanol solvent (manufactured by Wako Pure Chemical Industries, Ltd.) are added to a sample bottle containing 10 mg of zinc acetate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.). Further, 5 μL of ethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added and dissolved by heating to obtain solution A.

  0.2 mL of a chloroform solvent in which 1,8-diiodooctane (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed at a ratio of 2% by volume as an electron-donating organic semiconductor, 0.9 mg of compound A-1 and [70] PCBM Solution B was added to a sample bottle containing 1.1 mg (manufactured by Solane) and irradiated with ultrasonic waves for 30 minutes in an ultrasonic cleaner (US-2, manufactured by Inuchi Seieido Co., Ltd., output: 120 W). Obtained.

  In the above, the donor-acceptor ratio (compound A-1 (electron-donating organic semiconductor): [70] PCBM (electron-accepting organic material) = 45: 55).

  A PEDOT: PSS aqueous solution (CLEVIOS PVP AI4083), water and 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed at a volume ratio of 40:35:25 to obtain a solution C.

  After a release agent ("Novec2702" (manufactured by 3M)) was spin-coated on the glass substrate, the film was heated at 100 ° C for 1 minute to form a release layer of about 50 nm. Here, a polyimide varnish was spin-coated and baked to form a 10 μm-thick polyimide film on the glass substrate.

  On this glass substrate, an ITO transparent conductive layer serving as a negative electrode was deposited to a thickness of 100 nm by a sputtering method, and ITO was patterned by a photolithography method. The solution A was dropped on a glass substrate, spin-coated, and then heated on a hot plate at 150 ° C. for 30 minutes to form an electron transport layer having a thickness of about 30 nm.

  Next, the solution B was dropped on the electron transport layer, spin-coated, and dried by heating at 80 ° C. for 5 minutes on a hot plate to form a photoelectric conversion layer having a thickness of about 130 nm.

  Further, the solution C was dropped on the photoelectric conversion layer, spin-coated, and then heated on a hot plate at 80 ° C. for 1 minute to form a hole transport layer.

After that, the substrate and the mask for the positive electrode are placed in a vacuum evaporation apparatus, and the apparatus is evacuated until the degree of vacuum in the apparatus becomes 1 × 10 ⁻³ Pa or less. Was deposited.

  Thereafter, a solution prepared by dissolving AF1600X (manufactured by Kemmers, Inc.) in 3 wt% in Fluorinert FC-43 was spin-coated, heated at 100 ° C. for 30 minutes on a hot plate to form a protective film of about 300 nm, and then PET. Barrier top 04 (manufactured by Toray Film Processing Co., Ltd.) was adhered with an adhesive barrier tape (manufactured by Tessa Tape Co., Ltd.) to form a sealing layer.

  Thereafter, the polyimide film was peeled off from the glass substrate to obtain a photovoltaic element.

The positive electrode and the negative electrode of the photovoltaic element thus manufactured were connected to a Keithley 2400 series source meter, and simulated sunlight (OTENTO-SUNIII, manufactured by Spectrometer Co., Ltd .; : AM 1.5, intensity: 100 mW / cm ² ), and the current value when the applied voltage was changed from -1 V to +2 V was measured. The photoelectric conversion efficiency (η) was calculated from the obtained current value.

On the non-light-receiving surface of the photovoltaic element, a thermosetting adhesive (Chrisbon OA360) was applied at a coating amount of 3 g / m ² , heat-treated at 120 ° C., and a polyester fabric (using yarn: warp and weft; Decitex-36 multifilament, woven density: 120 × 90, weft / 2.54 cm, woven structure: flat, basis weight 72 g / m ² , hue: L * (D65) 23.24, a * (D65) 0.32 , B * (D65) -1.25), the non-light-receiving surface of the photovoltaic element was overlapped, and heat treatment was performed at 130 ° C. for 15 seconds by hot pressing to cure the adhesive.

  The same polyester fabric as the non-light-receiving surface was also attached to the light-receiving surface of the photovoltaic element to obtain a photovoltaic fiber structure. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. When the photovoltaic fiber structure obtained was observed from the light-receiving surface, the internal photovoltaic element was inconspicuous, had a good appearance and appearance, had a high-grade feel, was very flexible, and was easily deformed.

(Example 2)
The fiber structure on the non-light-receiving surface side of the photovoltaic element was coated on a polyester fabric having a hue of L * (D65) 74.56, a * (D65) 4.2, b * (D65) -15.00, and a light-receiving surface. A photovoltaic fiber structure was obtained by performing the same treatment as in Example 1 except that the fiber structure on the side was changed to a polyester fabric having a light transmittance of 53.8%. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. When the obtained photovoltaic fiber structure was observed from the light-receiving surface, the inside photovoltaic element was inconspicuous, had a good appearance and appearance, was very flexible, and easily deformed.

(Example 3)
The fiber structure on the non-light-receiving surface side of the photovoltaic element is converted into a light-receiving surface on a polyester fabric of hue: L * (D65) 70.23, a * (D65) -7.5, b * (D65) 56.50. A photovoltaic fiber structure was obtained by performing the same treatment as in Example 1 except that the fiber structure on the side was changed to a polyester fabric having a light transmittance of 46.2%. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. When the obtained photovoltaic fiber structure was observed from the light-receiving surface, the internal photovoltaic element was not conspicuous, had good appearance and appearance, was flexible, and could be deformed into a free and flexible shape.

(Example 4)
The fiber structure on the non-light-receiving surface side of the photovoltaic element is applied to a polyester fabric having a hue of L * (D65) 40.53, a * (D65) 49.8, b * (D65) -0.61 and a light-receiving surface. A photovoltaic fiber structure was obtained by performing the same treatment as in Example 1 except that the fiber structure on the side was changed to a polyester fabric having a light transmittance of 44.5%. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. When the obtained photovoltaic fiber structure was observed from the light-receiving surface, the internal photovoltaic element was less noticeable, had a good appearance, was flexible, and could be freely deformed.

(Example 5)
The fiber structure on the non-light-receiving surface side of the photovoltaic element was coated on a polyester fabric having a hue of L * (D65) 38.25, a * (D65) 0.9, b * (D65) -35.38, and a light-receiving surface. A photovoltaic fiber structure was obtained by performing the same treatment as in Example 1 except that the fiber structure on the side was changed to a polyester fabric having a light transmittance of 47.9%. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. When the obtained photovoltaic fiber structure was observed from the light-receiving surface, the internal photovoltaic element was not conspicuous, had good appearance and appearance, was flexible, and could be deformed into a free and flexible shape.

(Example 6)
The fiber structure on the non-light-receiving surface side of the photovoltaic element is applied to a polyester fabric of hue: L * (D65) 33.23, a * (D65) 5.8, b * (D65) -9.75, and a light-receiving surface. A photovoltaic fiber structure was obtained by performing the same treatment as in Example 1 except that the fiber structure on the side was changed to a polyester fabric having a light transmittance of 44.1%. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. When the obtained photovoltaic fiber structure was observed from the light-receiving surface, the internal photovoltaic element was not conspicuous, had good appearance and appearance, was flexible, and could be deformed into a free and flexible shape.

(Example 7)
The fiber structure on the non-light-receiving surface side of the photovoltaic element is received on a wool fabric of hue: L * (D65) 17.12, a * (D65) 0.33, b * (D65) -3.10). A photovoltaic fiber structure was obtained by performing the same treatment as in Example 1 except that the fiber structure on the surface side was changed to a wool fabric having a light transmittance of 22.0%. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. When the obtained photovoltaic fiber structure was observed from the light-receiving surface, the internal photovoltaic element was not conspicuous, had good appearance and appearance, was flexible, and could be deformed into a free and flexible shape.

(Example 8)
The fiber structure on the non-light receiving surface side of the photovoltaic element is converted into a wool / polyester fabric having a hue: L * (D65) 16.32, a * (D65) 0.74, b * (D65) -2.5, A photovoltaic fiber structure was obtained by performing the same treatment as in Example 1 except that the fiber structure on the light receiving surface side was changed to a wool / polyester fabric having a light transmittance of 32.2%. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. When the obtained photovoltaic fiber structure was observed from the light-receiving surface, the internal photovoltaic element was not conspicuous, had good appearance and appearance, was flexible, and could be deformed into a free and flexible shape.

(Example 9)
Hue: L * (D65) 18.36, a * (D65) 0.18, b * (D65) -1 for both the fiber structure on the light receiving surface side and the fiber structure on the non-light receiving surface side of the photovoltaic element. A photovoltaic fiber structure was obtained by performing the same treatment as in Example 1 except that the polyester fabric was changed to 23. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. When the obtained photovoltaic fiber structure was observed from the light-receiving surface, the internal photovoltaic element was not conspicuous, had good appearance and appearance, was flexible, and could be deformed into a free and flexible shape.

(Example 10)
Hue: L * (D65) 82.02, a * (D65) 4.59, b * (D65) -15 for both the fiber structure on the light receiving surface side and the fiber structure on the non-light receiving surface side of the photovoltaic element. A photovoltaic fiber structure was obtained by performing the same process as in Example 1 except that the polyester fabric was changed to 11. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. When the obtained photovoltaic fiber structure was observed from the light-receiving surface, the internal photovoltaic element was not conspicuous, had good appearance and appearance, was flexible, and could be deformed into a free and flexible shape.

(Example 11)
Hue: L * (D65) 19.83, a * (D65) -0.31, b * (D65) -1 for both the fiber structure on the light receiving surface side and the fiber structure on the non-light receiving surface side of the photovoltaic element. A photovoltaic fiber structure was obtained by performing the same processing as in Example 1 except that the polyester fabric was changed to .40. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. When the obtained photovoltaic fiber structure was observed from the light-receiving surface, the internal photovoltaic element was not conspicuous, had good appearance and appearance, was flexible, and could be deformed into a free and flexible shape.

(Example 12)
Hue: L * (D65) 80.73, a * (D65) 4.46, b * (D65) -14 for both the fiber structure on the light receiving surface side and the fiber structure on the non-light receiving surface side of the photovoltaic element. A photovoltaic fiber structure was obtained by performing the same process as in Example 1 except that the polyester fabric was changed to 53. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. When the obtained photovoltaic fiber structure was observed from the light-receiving surface, the internal photovoltaic element was not conspicuous, had good appearance and appearance, was flexible, and could be deformed into a free and flexible shape.

(Example 13)
Hue: L * (D65) 23.17, a * (D65) -0.79, b * (D65) -1 for both the fiber structure on the light receiving surface side and the fiber structure on the non-light receiving surface side of the photovoltaic element. A photovoltaic fiber structure was obtained by performing the same process as in Example 1 except that the polyester fabric was changed to .50. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. When the obtained photovoltaic fiber structure was observed from the light-receiving surface, the internal photovoltaic element was not conspicuous, had good appearance and appearance, was flexible, and could be deformed into a free and flexible shape.

(Example 14)
Hue: L * (D65) 46.48, a * (D65) 1.81, b * (D65) -8 for both the fiber structure on the light receiving surface side and the fiber structure on the non-light receiving surface side of the photovoltaic element. A photovoltaic fiber structure was obtained by performing the same processing as in Example 1 except that the polyester fabric was changed to 89. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. When the obtained photovoltaic fiber structure was observed from the light-receiving surface, the internal photovoltaic element was not conspicuous, had good appearance and appearance, was flexible, and could be deformed into a free and flexible shape.

(Example 15)
Both the fiber structure on the light receiving surface side and the fiber structure on the non-light receiving surface side of the photovoltaic element have hues: L * (D65) 17.47, a * (D65) 0.43, b * (D65) -3. A photovoltaic fiber structure was obtained by performing the same treatment as in Example 1 except that the wool fabric was changed to 22. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. The resulting photovoltaic fiber structure, when viewed from the light-receiving surface, has no noticeable internal photovoltaic elements, has a good appearance and appearance, has a high-class feel, is flexible and can be deformed into a free and flexible shape. there were.

(Example 16)
Both the fiber structure on the light receiving surface side and the fiber structure on the non-light receiving surface side of the photovoltaic element have hues: L * (D65) 17.61, a * (D65) 0.8, b * (D65) -3. A photovoltaic fiber structure was obtained by performing the same treatment as in Example 1 except that the polyester fabric was changed to 00. The materials used and the properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. The resulting photovoltaic fiber structure, when viewed from the light-receiving surface, has no noticeable internal photovoltaic elements, has a good appearance and appearance, has a high-class feel, is flexible and can be deformed into a free and flexible shape. there were.

(Comparative Example 1)
The same process as in Example 1 was performed except that the photovoltaic element of Example 1 was changed to a solar cell module 0.5W SY-M 0.5w made by SUNY00 solar limited, and a fiber structure was not attached to the light receiving surface. A photovoltaic fiber structure was obtained. The properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. The photovoltaic fiber structure obtained had noticeable solar cells, poor appearance and appearance, and lacked flexibility.

(Comparative Example 2)
A photovoltaic fiber structure was obtained by performing the same process as in Comparative Example 1, except that the photovoltaic element of Comparative Example 1 was changed to a photovoltaic cell 1.7V8365 manufactured by Artec. The properties of the obtained light transmittance, photoelectric conversion efficiency, and bending rigidity are shown in Tables 1 to 3. The photovoltaic fiber structure obtained had a noticeable photovoltaic cell, poor appearance and appearance, and lacked flexibility.

Reference Signs List 1 substrate 2 positive electrode 3 photoelectric conversion layer 4 negative electrode

Claims (7)

It comprises a fiber structure and a photovoltaic element, and a fiber structure is provided on both the light receiving surface and the non-light receiving surface of the photovoltaic element, and the photovoltaic element is sandwiched and supported by the fiber structure. Photovoltaic fiber structure. The photovoltaic fiber structure according to claim 1, wherein the fiber structure provided on the light receiving surface of the photovoltaic element has a light transmittance of 10% or more and 98% or less. The bending rigidity measurement value defined by KES measurement of the photovoltaic fiber structure is 0.01 × 10 ⁻⁴ N · m ² / m or more and 6 × 10 ⁻⁴ N · m ² / m or less. 3. The photovoltaic fiber structure according to 2. The photovoltaic fiber structure according to any one of claims 1 to 3, wherein a transparent adhesive is present between the photovoltaic element and the fiber structure. It comprises a fiber structure and a photovoltaic element, and a fiber structure is provided on both the light receiving surface and the non-light receiving surface of the photovoltaic element, and the photovoltaic element is sandwiched and supported by the fiber structure. A method for producing a photovoltaic fiber structure. The method for producing a photovoltaic fiber structure according to claim 5, wherein the fiber structure provided on the light receiving surface of the photovoltaic element has a light transmittance of 10% or more and 98% or less. The method for producing a photovoltaic fiber structure according to claim 5 or 6, wherein a transparent adhesive is used for adhesion.