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Definitions

• the present invention relates to a composition for a hole collecting layer of an organic photoelectric conversion element.
• An electronic element is a device that converts light energy into electrical energy using an organic semiconductor, and examples thereof include an organic solar cell.
• the organic solar cell is a solar cell element using an organic substance as an active layer or a charge transporting substance, and is an M.D.
• the organic thin-film solar cell developed by Tan is well known (Non-Patent Documents 1 and 2). Both are lightweight and thin films, can be made flexible, and can be produced roll-to-roll, which are different from the current mainstream inorganic solar cells, so they are new markets. The formation is expected.
• Non-Patent Document 3 organic thin-film solar cells have features such as electrolyte-free and heavy metal compound-free, and recently, a group of UCLA et al. Reported a photoelectric conversion efficiency (hereinafter abbreviated as PCE) of 10.6%. For this reason, it has received a great deal of attention (Non-Patent Document 3).
• organic thin-film solar cells show higher photoelectric conversion efficiency even in low light than existing photoelectric conversion elements using silicon-based materials, and the elements can be made thinner and the pixels can be miniaturized. Due to its features such as being able to combine the properties of a color filter, it is attracting attention not only for solar cell applications but also for optical sensor applications such as image sensors (Patent Documents 1 and 2 and Non-Patent Documents 4). ).
• organic solar cells die-sensitized solar cells and organic thin-film solar cells
• they are collectively referred to as organic photoelectric conversion elements (hereinafter, may be abbreviated as OPV) including applications such as optical sensors.
• the organic photoelectric conversion element is configured to include an active layer (photoelectric conversion layer), a charge (hole, electron) collecting layer, an electrode (anode, cathode) and the like.
• the active layer and the charge collection layer are generally formed by the vacuum vapor deposition method, but the vacuum vapor deposition method has problems in terms of complexity due to mass production process, high cost of equipment, efficiency of material utilization, and the like. There is.
• a water-dispersible polymer organic conductive material such as PEDOT / PSS may be used as a coating material for the hole collecting layer, but the PEDOT / PSS water dispersion liquid has a solid content.
• PEDOT / PSS water dispersion liquid has a solid content.
• the present invention has been made in view of the above circumstances, and provides a composition for a hole collecting layer of an organic photoelectric conversion element, which provides a hole collecting layer having excellent adhesion to an active layer.
• the purpose is to provide a composition for a hole collecting layer of an organic photoelectric conversion element, which provides a hole collecting layer having excellent adhesion to an active layer.
• the present inventors have already reported a composition containing a predetermined polythiophene as a charge-transporting substance as a composition for a hole collecting layer that can achieve the above object (see Patent Document 3).
• the metal oxide nanoparticles are indispensable as the adhesion-imparting component in this composition, it is good for the active layer even if the adhesion-imparting component is not contained or the content thereof is small. It is desired to develop a composition that exhibits a good adhesion.
• the present inventors refer to a composition that gives a thin film having excellent adhesion to the active layer without adding an adhesion-imparting component such as metal oxide nanoparticles as a polythiophene structure.
• the cyclic ethylenedioxy group has a structure in which a cyclic ethylenedioxy group is fused to the thiophene ring, and further binds to the cyclic ethylenedioxy group.
• Polythiophene derivatives having a predetermined side chain containing sulfonic acid or sulfonic acid base can form a uniform solution showing high solubility in protonic polar solvents such as alcohol and water, which are less corrosive to the active layer.
• the thin film prepared from this solution not only exhibits high hole transportability, but also when the thin film is used as an OPV hole collecting layer, it is an active layer without using other adhesion-imparting components.
• the present invention has been completed by finding that an OPV showing good PCE can be obtained by exhibiting good adhesion to the above.
• the present invention provides a composition for a hole collecting layer of the following organic photoelectric conversion element.
• 1. A composition for a hole collecting layer of an organic photoelectric conversion element containing a charge transporting substance composed of a polythiophene derivative containing a repeating unit represented by the formula (1) or the formula (1') and a solvent.
• R 1 represents an alkyl group having 1 to 6 carbon atoms or a fluorine atom.
• M is a hydrogen atom, Li, Na and K.
• R 2 may have hydrogen atoms or substituents independently of each other and may have 1 to 6 carbon atoms. Represents an alkyl group.) 2. 2. Further, a composition for a hole collecting layer of 1 organic photoelectric conversion element containing a surfactant. 3. 3. The composition for a hole collecting layer of the organic photoelectric conversion element 2 in which the above-mentioned surfactant is a fluorine-based surfactant. 4. Further, the hole collecting layer of any of the organic photoelectric conversion elements 1 to 3 containing an electron-accepting dopant substance different from the polythiophene derivative containing the repeating unit represented by the above formula (1) or the formula (1'). Composition for. 5.
• the electron-accepting dopant substance different from the polythiophene derivative containing the repeating unit represented by the above formula (1) or the formula (1') is for the hole collecting layer of the organic photoelectric conversion element 4 which is an aryl sulfonic acid compound.
• Composition. 6. A hole collecting layer obtained from the composition for a hole collecting layer of any of the organic photoelectric conversion elements 1 to 5. 7. An organic photoelectric conversion element including a hole collecting layer of 6.
• the composition for the hole collecting layer of the organic photoelectric conversion element of the present invention contains a predetermined polythiophene derivative, the hole collecting layer obtained from the composition has good adhesion to the active layer. As a result, an organic thin-film solar cell having excellent PCE can be obtained.
• composition for a hole collecting layer of the present invention contains a charge-transporting substance composed of a polythiophene derivative containing a repeating unit represented by the formula (1) or the formula (1'), and a solvent.
• R 1 represents an alkyl group having 1 to 6 carbon atoms or a fluorine atom.
• M represents an alkali metal selected from the group consisting of hydrogen atom, Li, Na and K, NH (R 2 ) 3 or HNC 5 H 5 .
• R 2 represents an alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom or a substituent independently of each other.
• the alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl and sec-. Examples thereof include butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, n-hexyl, 2-ethylbutyl, cyclohexyl, n-octyl group and the like.
• R 1 a linear or branched alkyl group having 1 to 3 carbon atoms is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is even more preferable.
• the alkyl group having 1 to 6 carbon atoms of R 2 the same one as that of R 1 can be exemplified.
• the substituent includes, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Examples thereof include a hydroxy group, an amino group and a carboxy group.
• Examples of the alkyl group having 1 to 6 carbon atoms include the same groups as those exemplified in R 1 above, and examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, and the like.
• Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl and 2-phenanthryl. , 3-Phenyltril, 4-Phenyltril, 9-Phenyltril group and the like.
• the substituent is preferably a hydroxy group
• examples of the alkyl group having a hydroxy group include a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2,3-dihydroxypropyl group and the like.
• R 2 a hydrogen atom and a linear or branched alkyl group having 1 to 3 carbon atoms are preferable, and a hydrogen atom and a methyl group are more preferable.
• polythiophene derivative containing the repeating unit represented by the above formula (1) as a preferred embodiment, for example, polythiophene containing the repeating unit represented by the following formula (1-1) can be mentioned.
• polythiophene derivative are at least one of the repeating units represented by the following formulas (1-1-A) to (1-1-B) and formulas (1'-A) to (1'-B).
• Polythiophene including.
• the polythiophene derivative may be a homopolymer or a copolymer (including statistical, random, gradient, and block copolymers).
• block copolymers include, for example, AB diblock copolymers, ABA triblock copolymers, and (AB) m -multiblock copolymers.
• the polythiophene derivative is derived from other types of monomers such as thienothiophene, selenophene, pyrrole, furan, tellurophenes, aniline, arylamine, and arylene (eg, phenylene, phenylenebinylene, and fluorene). May include repeating units.
• the content of the repeating unit represented by the formula (1) or the formula (1') in the polythiophene derivative is preferably more than 50 mol%, preferably 80 mol% or more, among all the repeating units contained in the polythiophene derivative. More preferably, 90 mol% or more is further preferable, 95 mol% or more is further preferable, and 100 mol% is most preferable.
• the polymer formed may contain repeating units derived from impurities.
• the term "homomopolymer” above means a polymer comprising repeating units derived from one type of monomer, but may also contain repeating units derived from impurities. ..
• the polythiophene derivative is preferably a homopolymer in which basically all the repeating units are the repeating units represented by the above formula (1), and the repeating units represented by the above formula (1-1). A certain homopolymer is more preferable, and a homopolymer which is any repeating unit represented by the above formulas (1-1-A) to (1-1-B) is even more preferable.
• a polythiophene derivative containing the repeating unit represented by the above formula (1) or the formula (1') used in the present invention a polythiophene derivative produced by a conventionally known method may be used, or a commercially available product may be used.
• known methods include the methods described in JP-A-2014-65598, which are polymerized in the presence of an oxidizing agent in water or an alcohol solvent using a thiophene monomer as shown below as a raw material. Can be manufactured.
• examples of commercially available products include SELFTRON S and SELFTRON H (both manufactured by Tosoh Corporation) of the SELFTRON (registered trademark) series.
• thiophene monomers examples include 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1-sodium propanesulfonate.
• the weight average molecular weight of the polythiophene derivative containing the repeating unit represented by the formula (1) or the formula (1') is not particularly limited, but is usually about 1,000 to 1,000,000 in terms of polystyrene sulfonic acid. Is preferable, and about 1,000 to 200,000 is more preferable for the use of the water-soluble conductive polymer. When the weight average molecular weight is set to the lower limit or more, good conductivity is obtained, and when the weight average molecular weight is set to the upper limit or lower, the solubility in a solvent is improved.
• the weight average molecular weight is a polystyrene sulfonic acid conversion value obtained by gel permeation chromatography.
• the polythiophene derivative containing the repeating unit represented by the formula (1) or the formula (1') may be used alone or in combination of two or more compounds. ..
• the ionization potential of the hole collecting layer is preferably a value close to the ionization potential of the p-type semiconductor material in the active layer.
• the absolute value of the difference is preferably 0 to 1 eV, more preferably 0 to 0.5 eV, and even more preferably 0 to 0.2 eV. Therefore, the composition for a hole collecting layer of the present invention may contain an electron-accepting dopant substance for the purpose of adjusting the ionization potential of the hole collecting layer obtained by using the composition.
• the electron-accepting dopant substance is not particularly limited as long as it is soluble in at least one solvent used.
• the electron-accepting dopant substance include inorganic strong acids such as hydrogen chloride, sulfuric acid, nitric acid, and phosphoric acid; aluminum chloride (III) (AlCl 3 ), titanium tetrachloride (IV) (TiCl 4 ), and boron tribromide.
• BBr 3 Borone Trifluorinated Ether Complex (BF 3 ⁇ OEt 2 ), Iron Chloride (III) (FeCl 3 ), Copper Chloride (II) (CuCl 2 ), Antimonium Prefide (V) (SbCl 5 ), Lewis acids such as arsenic pentoxide (V) (AsF 5 ), phosphorus pentoxide (PF 5 ), tris (4-bromophenyl) aluminum hexachloroantimonate (TBPAH); benzenesulfonic acid, tosylic acid, hydroxybenzenesulfon Acid, 5-sulfosalicylic acid, dodecylbenzene sulfonic acid, polystyrene sulfonic acid, 1,4-benzodioxane disulfonic acid compound described in International Publication No.
• Naphthalene sulfonic acid compounds aryl sulfonic acid compounds such as dinonylnaphthalene sulfonic acid and 1,3,6-naphthalentrisulfonic acid described in JP-A-2005-108828, and organic strong acids such as camphorsulfonic acid; polystyrene.
• Sulfonates such as sodium sulfonate; 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), iodine and the like
• TCNQ 7,7,8,8-tetracyanoquinodimethane
• DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
• iodine and the like examples thereof include organic oxidizing agents and inorganic oxidizing agents such as heteropolyacid compounds such as phosphomolybdic acid, phosphotungnic acid and lintangustomolydic acid described in International Publication No. 2010/0587777, and these may be used alone. Two or more kinds may be used in combination.
• Bronsted acid that donates H + is particularly preferable, aryl sulfonic acid compound is more preferable, and polystyrene sulfonic acid and aryl represented by the following formula (2) are particularly preferable. Sulfonic acid compounds are preferred.
• X represents O
• A represents a naphthalene ring or an anthracene ring
• B represents a 2- to tetravalent perfluorobiphenyl group
• l represents the number of sulfonic acid groups attached to A. It is an integer satisfying 1 ⁇ l ⁇ 4, and q indicates the number of bonds between B and X, and is an integer satisfying 2 to 4.
• aryl sulfonic acid compound examples include the following compounds (formula (2-1)).
• the composition of the present invention may contain a surfactant from the viewpoint of film forming property.
• the surfactant is not particularly limited, and a fluorine-based surfactant, a silicone-based surfactant, or the like can be used, but in the present invention, it is preferable to use a fluorine-based surfactant.
• the fluorine-based surfactant used in the present invention is available as a commercially available product.
• Such commercially available products include DuPont Capstone (Captone, registered trademark) FS-10, FS-22, FS-30, FS-31, FS-34, FS-35, FS-50, FS-51, etc.
• Examples thereof include Megafuck F-444, F-477, F-559 manufactured by Megafuck Co., Ltd., but the present invention is not limited thereto.
• Capstone FS-30, 31, 34, 35, 3100, Neugen FN-1287, and Megafuck F-559 which are nonionic surfactants, are suitable.
• the fluorine-based surfactant is not particularly limited as long as it contains a fluorine atom, and may be cationic, anionic, or nonionic, but a fluorine-based nonionic surfactant is preferable.
• a fluorine-based nonionic surfactant selected from the following formulas (A1) and (B1) is preferable.
• R represents a monovalent organic group containing a fluorine atom
• n represents an integer of 1 to 20.
• the organic group include an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms and the like.
• the alkyl group having 1 to 40 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and s-butyl.
• aralkyl group having 7 to 20 carbon atoms include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl and 2-propylphenyl.
• examples thereof include methyl, 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, ⁇ -naphthylmethyl group and the like.
• heteroaryl group examples include 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isooxazolyl, 4-isoxazolyl, 5-isooxazolyl, 2 -Thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazyl, 3-pyrazyl , 5-Pyradil, 6-Pyramidyl, 2-Pyrimidyl, 4-Pyrimidyl, 5-Pyrimidil, 6-Pyramidil, 3-Pyridadyl, 4-Pyridadil, 5-Pyridadil, 6-Pyridadil, 1,2,3-Tria
• n is not particularly limited as long as it is an integer of 1 to 20, but an integer of 1 to 10 is more preferable.
• the perfluoroalkyl polyoxyethylene ester represented by (A2) below and the perfluoroalkyl polyoxyethylene ether or fluorine telomer alcohol represented by (B2) having a perfluoroalkyl group R f having 1 to 40 carbon atoms are shown below. At least one fluorine-based nonionic surfactant selected from the above is more preferable.
• n has the same meaning as above.
• perfluoroalkyl group having 1 to 40 carbon atoms include a group in which all the hydrogen atoms of the alkyl group having 1 to 40 carbon atoms are replaced with fluorine atoms.
• the content of the surfactant is not particularly limited, but the improvement of the film-forming property on the active layer, the adhesion to the active layer by addition, and the photoelectric conversion of the obtained element are performed. Considering the balance with the decrease in efficiency, about 0.005 to 0.08% by mass of the whole composition is preferable, 0.005 to 0.05% by mass is more preferable, and 0.005 to 0.04% by mass is more preferable. Even more preferably, 0.0075 to 0.03% by mass is further preferable, and 0.01 to 0.02% by mass is most preferable.
• composition of the present invention contains the polythiophene derivative represented by the above-mentioned formula (1), it provides a thin film that exhibits sufficient adhesion to the active layer even if it does not contain metal oxide nanoparticles.
• metal oxide nanoparticles may be contained. Nanoparticles mean fine particles having an average particle size on the order of nanometers (typically 500 nm or less) for primary particles.
• the metal oxide nanoparticles mean metal oxides formed into nanoparticles.
• the primary particle size of the metal oxide nanoparticles used in the present invention is not particularly limited as long as it is nano-sized, but 2 to 150 nm is preferable, and 3 to 150 nm is preferable in consideration of further enhancing the adhesion to the active layer. 100 nm is more preferable, and 5 to 50 nm is even more preferable.
• the particle size is a measured value using a nitrogen adsorption isotherm by the BET method.
• the metal constituting the metal oxide nanoparticles in the present invention includes not only metals in the usual sense but also metalloids.
• the metal in the usual sense is not particularly limited, but tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum ( It is preferable to use one or more selected from the group consisting of Ta) and W (tungsten).
• Metalloids on the other hand, mean elements whose chemical and / or physical properties are between metal and non-metal.
• metalloids Although the universal definition of metalloids has not been established, in the present invention, a total of 6 of boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb) and tellurium (Te).
• B boron
• Si silicon
• Ge germanium
• As arsenic
• Sb antimony
• Te tellurium
• the element is a metalloid.
• These metalloids may be used alone, in combination of two or more, or in combination with a metal in the usual sense.
• the metal oxide nanoparticles used in the present invention include boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), tin (Sn), and titanium (Ti). , Aluminum (Al), Zirconium (Zr), Zinc (Zn), Niobium (Nb), Tantalum (Ta) and W (Tungsten), preferably containing oxides of one or more metals.
• the metal oxide may be a mixture of individual metal oxides or a composite oxide containing a plurality of metals.
• the metal oxide examples include B 2 O 3 , B 2 O, SiO 2 , SiO, GeO 2 , GeO, As 2 O 4 , As 2 O 3 , As 2 O 5 , Sb 2 O 3 , and Sb 2.
• Examples include O 5 , TeO 2 , SnO 2 , ZrO 2 , Al 2 O 3 , ZnO, etc., but B 2 O 3 , B 2 O, SiO 2 , SiO, GeO 2 , GeO, As 2 O 4 , As 2 O 3 , As 2 O 5 , SnO 2 , SnO, Sb 2 O 3 , TeO 2 , and mixtures thereof are preferred, with SiO 2 being more preferred.
• the metal oxide nanoparticles may contain one or more organic capping groups.
• the organic capping group may be reactive or non-reactive. Examples of reactive organic capping groups include organic capping groups that can be crosslinked by ultraviolet light or radical initiators.
• the content thereof is not particularly limited, but from the viewpoint of fully exerting the advantages of the present invention, 50 parts by mass of the charge transporting substance is used. Less than parts by mass is preferable, 30 parts by mass or less is more preferable, and 10 parts by mass or less is even more preferable.
• the charge-transporting substance is used as a solution or a dispersion, the amount of the metal oxide nanoparticles added is based on the solid content of the charge-transporting substance.
• the metal oxide nanoparticles it is preferable to use as the metal oxide nanoparticles a silica sol in which SiO 2 nanoparticles are dispersed in a dispersion medium.
• the silica sol is not particularly limited, and a known silica sol can be appropriately selected and used. Commercially available silica sol is usually in the form of a dispersion.
• SiO 2 nanoparticles are used in various solvents such as water, methanol, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylacetamide, ethylene glycol, isopropanol, methanol, ethylene glycol monopropyl ether, cyclohexanone, and acetate.
• solvents such as water, methanol, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylacetamide, ethylene glycol, isopropanol, methanol, ethylene glycol monopropyl ether, cyclohexanone, and acetate.
• solvents such as water, methanol, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylacetamide, ethylene glycol, isopropanol, methanol, ethylene glycol monopropyl ether, cyclo
• a silica sol in which the dispersion medium is an alcohol solvent or water is preferable, and a silica sol in which the dispersion medium is an alcohol solvent is more preferable.
• the alcohol solvent a water-soluble alcohol is preferable, and methanol, 2-propanol, and ethylene glycol are more preferable.
• silica sol examples include Snowtex (registered trademark) ST-O, ST-OS, ST-O-40, ST-OL manufactured by Nissan Chemical Industries, Ltd., and silica doll 20 manufactured by Nippon Chemical Industrial Co., Ltd. , 30, 40, etc.
• the solid content concentration of the silica sol is also not particularly limited, but is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 30% by mass.
• the content is preferably less than 50 parts by mass, more preferably 30 parts by mass or less, still more preferably 10 parts by mass or less, based on 100 parts by mass of the charge-transporting substance, as described above. preferable.
• the blending amount is also based on the solid content of the charge transporting substance as described above.
• the composition of the present invention may contain alkoxysilane.
• alkoxysilane By including alkoxysilane, the solvent resistance and water resistance of the obtained thin film can be improved, the electron blocking property can be improved, and the HOMO level and LUMO level can be set to optimum values for the active layer.
• the alkoxysilane may be a siloxane-based material.
• any one or more alkoxysilanes can be used from among tetraalkoxysilane, trialkoxysilane, and dialkoxysilane, and in particular, tetraethoxysilane, tetramethoxysilane, phenyltriethoxysilane, and phenyltri.
• siloxane-based material include polysiloxanes such as poly (tetraethoxysilane) and poly (phenylethoxysilane) obtained by a reaction such as hydrolysis with the above alkoxysilane.
• the amount of alkoxysilane added is not particularly limited as long as it exhibits the above effects, but is preferably 0.0001 to 100 times by mass ratio with respect to the polythiophene derivative used in the present invention, and is 0.01 to 50 times. Double is more preferable, and 0.05 to 10 times is even more preferable.
• composition for a hole collecting layer of the present invention may further contain a matrix polymer, if necessary.
• matrix polymer include a matrix polymer containing a repeating unit represented by the following formula (I) and a repeating unit represented by the following formula (II).
• R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are independent of each other and have a hydrogen atom, a halogen atom, a fluoroalkyl group having 1 to 20 carbon atoms, or a carbon number of carbon atoms. It is a perfluoroalkyl group of 1 to 20, and Q is-[OC (R h R i ) -C (R j R k )] y- O- [CR l R m ] z -SO 3 H.
• R h , R i , R j , R k , R l and R m are independent of each other, a hydrogen atom, a halogen atom, a fluoroalkyl group having 1 to 20 carbon atoms, or a perfluoroalkyl group having 1 to 20 carbon atoms. It is an atom, y is 0 to 10, and z is 1 to 5.
• fluoroalkyl group having 1 to 20 carbon atoms and the perfluoroalkyl group having 1 to 20 carbon atoms include the same as above.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• R 3 , R 4 , R 5 and R 6 are fluorine atoms or chlorine atoms, R 3 , R 5 and R 6 are fluorine atoms, and R 4 is a chlorine atom. Is more preferable, and it is even more preferable that R 3 , R 4 , R 5 and R 6 are all fluorine atoms.
• R 7 , R 8 and R 9 are all fluorine atoms.
• R h , R i , R j , R k , R l and R m are a fluorine atom, a fluoroalkyl group having 1 to 8 carbon atoms, or a perfluoroalkyl group having 1 to 8 carbon atoms.
• R l and R m are fluorine atoms. Further, y is preferably 0, and z is preferably 2.
• R 3 , R 5 , and R 6 above are fluorine atoms
• R 4 is a chlorine atom
• R l and R m are fluorine atoms
• y is 0
• And z is preferably 2.
• each R 3 , R 4 , R 5 , and R 6 is a fluorine atom; and each R l and R m is a fluorine atom; y is 0; And z is preferably 2.
• the ratio (s: t ratio) between the number "s" of the repeating units represented by the formula (I) and the number "t” of the repeating units represented by the formula (II) is not particularly limited.
• the s: t ratio is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8.
• the matrix polymer that can be suitably used in the present invention, one synthesized by a known method or a commercially available product may be used.
• the polymer containing the repeating unit represented by the above formula (I) and the repeating unit represented by the above formula (II) is represented by the monomer represented by the following formula (Ia) and the following formula (IIa). It can be produced by copolymerizing with a monomer by a known polymerization method and then converting it into a sulfonic acid group by hydrolysis of a sulfonylfluoride group.
• Q 1 is ⁇ [OC (R h R i ) ⁇ C (R j R k )] y ⁇ O ⁇ [CR l R m ] z ⁇ SO 2 F, and is R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R h , R i , R j , R k , R l , R m , y and z have the same meanings as above.
• TFE tetrafluoroethylene
• CTFE chlorotrifluoroethylene
• F 2 C CF-O -CF 2 -CF 2 - SO 2 F
• F 2 C CF- [O-CF 2 -CR 12 F-O] y -CF 2 -CF 2 -SO 2 F ( where
• the equivalent of the matrix polymer means the mass (g / mol) of the matrix polymer per mol of the acid group present in the matrix polymer.
• the equivalent of the matrix polymer is preferably about 400 to about 15,000 g / mol, more preferably about 500 to about 10,000 g / mol, even more preferably about 500 to about 8,000 g / mol, still more preferably about. It is 500 to about 2,000 g / mol, most preferably about 600 to about 1,700 g / mol.
• Such matrix polymers are available as commercial products.
• Examples of commercially available products include Nafion (NAFION, registered trademark) manufactured by DuPont, AQUIVION (AQUIVION, registered trademark) manufactured by Solvay Specialty Polymers, and Flemion (FLEMION, registered trademark) manufactured by Asahi Glass Co., Ltd.
• the matrix polymer is preferably a polyether sulfone containing one or more repeating units containing at least one sulfonic acid residue (-SO 3 H).
• additives may be added to the composition of the present invention as long as the object of the present invention can be achieved.
• type of additive a known one can be appropriately selected and used according to a desired effect.
• the solvent used for preparing the composition for the hole collecting layer a polythiophene derivative and, if necessary, a highly soluble solvent capable of satisfactorily dissolving the electron-accepting dopant substance used can be used.
• the highly soluble solvent can be used alone or in combination of two or more, and the amount used may be 5 to 100% by mass based on the total amount of the solvent used in the composition.
• Examples of such a highly soluble solvent include water; an alcohol solvent such as ethanol, 2-propanol, 1-butanol, 2-butanol, s-butanol, t-butanol, 1-methoxy-2-propanol, and N.
• an alcohol solvent such as ethanol, 2-propanol, 1-butanol, 2-butanol, s-butanol, t-butanol, 1-methoxy-2-propanol, and N.
• organic solvents such as solvents. Among these, at least one selected from water and alcohol solvents is preferable, and water, ethanol and 2-propanol are more preferable.
• a solvent consisting of only one or more kinds of solvents selected from alcohol-based solvents and water, which does not adversely affect the active layer, is used. It is preferable to use it.
• the charge-transporting substance and the electron-accepting dopant substance used as needed are preferably completely dissolved in the above solvent or uniformly dispersed, and are organic with high conversion efficiency. Considering that the hole collecting layer that gives the thin film solar cell can be obtained with good reproducibility, it is more preferable that these substances are completely dissolved in the above solvent.
• the composition for a hole collecting layer of the present invention has a viscosity of 10 to 200 mPa ⁇ s, particularly 35 to 150 mPa ⁇ s at 25 ° C. in order to improve the film forming property and the ejection property from the coating apparatus.
• At least one kind of high-viscosity organic solvent having a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. at normal pressure may be contained.
• the high-viscosity organic solvent is not particularly limited, and is, for example, cyclohexanol, ethylene glycol, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butane. Examples thereof include diol, 2,3-butanediol, 1,4-butanediol, propylene glycol, hexylene glycol and the like.
• the addition ratio of the high-viscosity organic solvent to the entire solvent used in the composition of the present invention is preferably within the range in which the solid does not precipitate, and the addition ratio is 5 to 80% by mass as long as the solid does not precipitate. It is preferable to have.
• the composition for the purpose of improving the wettability with respect to the coated surface, adjusting the surface tension of the solvent, adjusting the polarity, adjusting the boiling point, etc., another solvent that can impart the flatness of the film during heat treatment is used in the composition. It is also possible to mix in a ratio of 1 to 90% by mass, preferably 1 to 50% by mass with respect to the whole.
• Examples of such a solvent include butyl cellosolve, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl carbitol.
• Examples thereof include diacetone alcohol, ⁇ -butylolactone, ethyl lactate, n-hexyl acetate and the like.
• the solid content concentration of the composition of the present invention is appropriately set in consideration of the viscosity and surface tension of the composition, the thickness of the thin film to be produced, and the like, but is usually 0.1 to 10.0 mass. It is about%, preferably 0.5 to 5.0% by mass, and more preferably 1.0 to 3.0% by mass. Further, the mass ratio of the charge-transporting substance and the electron-accepting dopant substance is also appropriately set in consideration of the types of the charge-transporting substance, the charge-transporting substance, and the like to be expressed, but usually, the charge-transporting substance 1 On the other hand, the electron-accepting dopant substance is 0 to 10, preferably 0.1 to 3.0, and more preferably 0.2 to 2.0.
• the viscosity of the composition for the hole collecting layer used in the present invention is appropriately adjusted according to the coating method in consideration of the thickness of the thin film to be produced and the solid content concentration, but is usually at 25 ° C. It is about 0.1 to 50 mPa ⁇ s.
• the composition for the hole collecting layer of the present invention when preparing the composition for the hole collecting layer of the present invention, as long as the solid content is uniformly dissolved or dispersed in the solvent, the charge transporting substance and the solvent, and the fluorine-based surfactant and the metal used as necessary are necessary.
• the oxide nanoparticles, the electron-accepting dopant substance, and the like can be mixed in any order.
• a method of dissolving a polythiophene derivative in a solvent and then dissolving an electron-accepting dopant substance in the solution a method of dissolving an electron-accepting dopant substance in a solvent and then dissolving the polythiophene derivative in the solution
• Any method of mixing a polythiophene derivative and an electron-accepting dopant substance and then adding the mixture to a solvent to dissolve the mixture can be adopted as long as the solid content is uniformly dissolved or dispersed in the solvent.
• the order of adding the matrix polymer and the alkoxysilane is also arbitrary.
• the composition is prepared in an inert gas atmosphere at room temperature and normal pressure, but unless the compound in the composition is decomposed or the composition is significantly changed, the composition is prepared in an atmospheric atmosphere (oxygen presence). It may be carried out in (below), or it may be carried out while heating.
• the composition described above is applied on an anode in the case of a forward-laminated organic thin-film solar cell and on an active layer in the case of a reverse-laminated organic thin-film solar cell and fired to collect holes of the present invention.
• Layers can be formed.
• the drop casting method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, etc. are taken into consideration in consideration of the viscosity and surface tension of the composition, the desired thin film thickness, etc.
• the most suitable wet process method may be adopted from various wet process methods such as an inkjet method, a printing method (letter plate, concave plate, lithographic plate, screen printing, etc.).
• the coating is usually carried out in an inert gas atmosphere at normal temperature and pressure, but in an air atmosphere (in the presence of oxygen) unless the compound in the composition is decomposed or the composition is significantly changed. You may go or you may go while heating.
• the film thickness is not particularly limited, but in any case, it is preferably about 0.1 to 500 nm, and more preferably about 1 to 100 nm.
• a method of changing the film thickness there are a method of changing the solid content concentration in the composition, a method of changing the amount of the solution at the time of coating, and the like.
• Forward-laminated organic thin-film solar cell A process of forming a layer of an anode material on the surface of a transparent substrate to manufacture a transparent electrode.
• the anode material include indium tin oxide (ITO) and indium.
• Inorganic oxides such as zinc oxide (IZO), metals such as gold, silver and aluminum, and high charge transporting organic compounds such as polythiophene derivatives and polyaniline derivatives can be used. Of these, ITO is the most preferable.
• the transparent substrate a substrate made of glass or a transparent resin can be used.
• the method for forming the layer of the anode material is appropriately selected depending on the properties of the anode material.
• a dry process such as a vacuum deposition method or a sputtering method is selected in the case of a poorly soluble or poorly dispersible sublimable material, and in the case of a solution material or a dispersion liquid material, the viscosity and surface tension of the composition are desired.
• the thickness of the thin film and the like the most suitable one is adopted from the various wet process methods described above.
• a commercially available transparent anode substrate can also be used. In this case, from the viewpoint of improving the yield of the device, it is preferable to use a substrate that has been smoothed.
• the method for manufacturing an organic thin-film solar cell of the present invention does not include a step of forming an anode layer.
• a transparent anode substrate is formed by using an inorganic oxide such as ITO as an anode material, it is preferable to wash the transparent anode substrate with a detergent, alcohol, pure water or the like before laminating the upper layer. Further, it is preferable to perform surface treatment such as UV ozone treatment and oxygen-plasma treatment immediately before use.
• the anode material contains an organic substance as a main component, it is not necessary to perform surface treatment.
• Step of forming a hole collecting layer on the formed layer of the anode material Step of forming a hole collecting layer on the formed layer of the anode material
• the composition of the present invention is used to capture holes on the layer of the anode material. Form a layer.
• the active layer is a thin film made of an n-type semiconductor material and a thin film made of a p-type semiconductor material. It may be a laminated thin film or a non-laminated thin film made of a mixture of these materials.
• n-type semiconductor material examples include fullerene, [6,6] -phenyl-C 61- methyl butyrate (PC 61 BM), [6,6] -phenyl-C 71- methyl butyrate (PC 71 BM), and the like. Can be mentioned.
• examples of the p-type semiconductor material are described in Regular Poly (3-hexylthiophene) (P3HT), PTB7 represented by the following formula (3), JP-A-2009-158921, and International Publication No. 2010/008672.
• Examples thereof include polymers containing a thiophene skeleton in the main chain, phthalocyanines such as CuPC and ZnPC, and porphyrins such as tetrabenzoporphyrin, such as polymers containing thienothiophene units.
• n-type material PC 61 BM and PC 71 BM are preferable
• p-type material polymers having a thiophene skeleton in the main chain such as PTB7 are preferable.
• the "thiophene skeleton in the main chain" here is a divalent aromatic ring consisting of only thiophene, or thienothiophene, benzothiophene, dibenzothiophene, benzodithiophene, naphthophene, naphthodithiophene, anthrathiophene, anthrazi.
• thiophenes such as thiophene, which are a halogen atom, a nitro group, a cyano group, a sulfonic acid group, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
• Thioalkoxy group alkyl group with 1 to 20 carbon atoms, alkenyl group with 2 to 20 carbon atoms, alkynyl group with 2 to 20 carbon atoms, haloalkyl group with 1 to 20 carbon atoms, aryl group with 6 to 20 carbon atoms, carbon It may be substituted with an aralkyl group having a number of 7 to 20 or an acyl group having 1 to 20 carbon atoms.
• halogen atom examples include the same as those exemplified above.
• the alkoxy group having 1 to 20 carbon atoms may be linear, branched or cyclic in that of the alkyl group, and may be methoxy, ethoxy, n-propoxy, i-propoxy, c-propoxy or n-butoxy.
• I-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy examples thereof include n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecyloxy, n-eicosanyloxy group and the like. ..
• thioalkoxy group having 1 to 20 carbon atoms include a group in which the oxygen atom of the alkoxy group is replaced with a sulfur atom.
• examples of the thioalkoxy (alkylthio) group having 1 to 20 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio, t-butylthio, n-pentylthio, n-hexylthio and n.
• alkenyl group having 2 to 20 carbon atoms examples include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl and 2-methyl.
• -1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, n-1-eicosenyl Group etc. can be mentioned.
• alkynyl group having 2 to 20 carbon atoms examples include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n-3-butynyl and 1-methyl-2-propynyl.
• haloalkyl group having 1 to 20 carbon atoms examples include a group in which at least one of the hydrogen atoms in the alkyl group is replaced with a halogen atom.
• the halogen atom may be any of chlorine, bromine, iodine and fluorine atoms. Of these, a fluoroalkyl group is preferable, and a perfluoroalkyl group is more preferable.
• acyl group having 1 to 20 carbon atoms include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, benzoyl group and the like.
• the method for forming the active layer similarly to the above, when the active layer material is a sparingly soluble sublimation material, the above-mentioned various dry processes are selected, and when the active layer material is a solution material or a dispersion liquid material, the viscosity and surface of the composition are selected. Considering the tension, the desired thickness of the thin film, etc., the most suitable one is adopted from the various wet process methods described above.
• Step of forming an electron collecting layer on the formed active layer If necessary, for the purpose of improving the efficiency of charge transfer, etc., between the active layer and the cathode layer.
• An electron collecting layer may be formed.
• Materials for forming the electron collection layer include lithium oxide (Li 2 O), magnesium oxide (MgO), alumina (Al 2 O 3 ), lithium fluoride (LiF), sodium fluoride (NaF), and magnesium fluoride.
• the method for forming the electron collecting layer similarly to the above, when the electron collecting material is a sparingly soluble sublimation material, the above-mentioned various dry processes are selected, and when the electron collecting material is a solution material or a dispersion liquid material, the composition. Considering the viscosity, surface tension, desired thin film thickness, etc., the most suitable wet process method described above is adopted.
• Step of forming a cathode layer on the formed electron collection layer examples include aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, cesium, and calcium. Examples thereof include metals such as barium, silver and gold, inorganic oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO), and high charge transporting organic compounds such as polythiophene derivatives and polyaniline derivatives. Can be used by laminating or mixing the cathode materials of.
• the above-mentioned various dry processes are selected when the cathode layer material is a poorly soluble or poorly dispersible sublimable material, and when the cathode layer material is a solution material or a dispersion liquid material, a composition is selected.
• the optimum one is adopted from the various wet process methods described above in consideration of the viscosity and surface tension of the above-mentioned material, the desired thickness of the thin film, and the like.
• a carrier block layer may be provided between arbitrary layers for the purpose of controlling the rectification property of the photocurrent.
• an electron block layer is inserted between the active layer and the hole collection layer or the anode
• a hole block layer is inserted between the active layer and the hole collection layer or the cathode. In many cases, this is not the case.
• the material forming the hole block layer include titanium oxide, zinc oxide, tin oxide, bathocuproine (BCP), 4,7-diphenyl 1,10-phenanthroline (BPhen) and the like.
• Materials for forming the electron block layer include triarylamines such as N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine ( ⁇ -NPD) and poly (triarylamine) (PTAA). Materials and the like can be mentioned.
• the carrier block layer material is a poorly soluble or poorly dispersible sublimable material
• the above-mentioned various dry processes are selected
• the carrier block layer material is a solution material or a dispersion liquid material
• the above-mentioned various dry processes are selected.
• the viscosity and surface tension of the composition, the desired thickness of the thin film, and the like the optimum one is adopted from the various wet process methods described above.
• Reverse-laminated organic thin-film solar cell A process of forming a layer of cathode material on the surface of a transparent substrate to manufacture a transparent cathode substrate.
• the cathode material is the above-mentioned forward-laminated anode material.
• FTO fluorine-doped tin oxide
• examples of the transparent substrate include those exemplified by the above-mentioned forward-laminated anode material.
• the above-mentioned dry process is selected in the case of a sparingly soluble and poorly dispersible sublimable material, and in the case of a solution material or a dispersion liquid material, the viscosity of the composition is used. Considering the surface tension, the desired thickness of the thin film, etc., the most suitable one is adopted from the various wet process methods described above. Further, in this case as well, a commercially available transparent cathode substrate can be preferably used, and from the viewpoint of improving the yield of the device, it is preferable to use a substrate that has been smoothed.
• the method for manufacturing an organic thin-film solar cell of the present invention does not include a step of forming a cathode layer.
• a transparent cathode substrate is formed by using an inorganic oxide as a cathode material, the same cleaning treatment or surface treatment as that of the forward-laminated anode material may be performed.
• Step of forming an electron collecting layer on the formed cathode For the purpose of improving the efficiency of charge transfer, if necessary, electrons are formed between the active layer and the cathode layer.
• a collection layer may be formed.
• the material for forming the electron collecting layer include zinc oxide (ZnO), titanium oxide (TIO), tin oxide (SnO), and the like, in addition to those exemplified in the above-mentioned forward laminated material.
• the above-mentioned dry process is selected in the case of a poorly soluble or poorly dispersible sublimable material, and in the case of a solution material or a dispersion liquid material, the viscosity and surface tension of the composition are desired.
• the optimum one is adopted from the various wet process methods described above. It is also possible to adopt a method in which a precursor layer of an inorganic oxide is formed on a cathode by a wet process (particularly a spin coating method or a slit coating method) and then fired to form an inorganic oxide layer.
• the active layer is an n-layer, which is a thin film made of an n-type semiconductor material, and a p-layer, which is a thin film made of a p-type semiconductor material. It may be a laminated thin film or a non-laminated thin film made of a mixture of these materials.
• the n-type and p-type semiconductor materials include the same as those exemplified in the above-mentioned forward-laminated semiconductor materials, but the n-type materials include PC 61 BM and PC 71 BM, and the p-type materials include PC 61 BM. , PTB7 and other polymers containing a thiophene skeleton in the main chain are preferred.
• the method for forming the active layer is also the same as the method described for the above-mentioned forward-laminated active layer.
• Step of forming a hole collecting layer on the formed layer of the active layer material According to the above method, the composition of the present invention is used on the layer of the active layer material. Form a hole collection layer.
• Step of forming an anode layer on the formed hole collecting layer Examples of the anode material include the same as the above-mentioned forward-laminated type anode material, and as a method for forming the anode layer. Is the same as that of the forward-laminated cathode layer.
• a carrier block layer may be provided between arbitrary layers for the purpose of controlling the rectification property of the photocurrent, if necessary.
• Examples of the material for forming the hole block layer and the material for forming the electron block layer include the same materials as described above, and the method for forming the carrier block layer is also the same as described above.
• the OPV produced by the method exemplified above is introduced into the glove box again in order to prevent element deterioration due to the atmosphere, and the sealing operation is performed in an atmosphere of an inert gas such as nitrogen, and the sun is sealed in a sealed state. It can function as a battery and measure the characteristics of solar cells.
• a sealing method a concave glass substrate having a UV curable resin attached to the end thereof is attached to the film formation surface side of the organic thin film solar cell element in an inert gas atmosphere, and the resin is cured by UV irradiation.
• composition for hole collecting layer [Example 1-1] 2.53 g of a polythiophene derivative (SELFTRON S, manufactured by Tosoh Corporation, 2.0% by mass aqueous solution) was diluted with 2.48 g of distilled water to prepare a dark blue solution having a solid content concentration of 1.0% by mass. The obtained dark blue solution was filtered through a syringe filter having a pore size of 0.45 ⁇ m to obtain a hole collecting layer composition B1.
• SELFTRON S manufactured by Tosoh Corporation, 2.0% by mass aqueous solution
• Example 1-2 2.53 g of a polythiophene derivative (SELFTRON S, manufactured by Toso Co., Ltd., 2.0% by mass aqueous solution) was diluted with 2.48 g of isopropanol, and a fluorine-based nonionic surfactant (FN-1287, Dai-ichi Kogyo Seiyaku Co., Ltd.) (Manufactured by) 0.5 mg was added to prepare a dark blue solution having a solid content concentration of 1.0% by mass. The obtained dark blue solution was filtered through a syringe filter having a pore size of 0.45 ⁇ m to obtain a hole collecting layer composition B2.
• SELFTRON S manufactured by Toso Co., Ltd., 2.0% by mass aqueous solution
• PEDOT / PSS (AI4083, manufactured by Heleus) was filtered through a syringe filter having a pore size of 0.45 ⁇ m to obtain a hole collecting layer composition C1.
• PEDOT / PSS (Clevios HTL Solar, manufactured by Heleus) was filtered through a syringe filter having a pore size of 0.45 ⁇ m to obtain a hole collecting layer composition C2.
• PEDOT A fluorine-based nonionic surfactant (FS-31) was added to a dark blue solution obtained by diluting 15 g of a PSS aqueous solution (Clevios P, manufactured by Heleus, 1.3 mass% aqueous dispersion) with 15 g of distilled water. (Manufactured by DuPont) was added in an amount of 0.25% by mass based on the whole dark blue solution and filtered through a syringe filter having a pore size of 0.45 ⁇ m to obtain a composition for collecting holes C3.
• FS-31 fluorine-based nonionic surfactant
• Example 2-1 Fabrication of Organic Thin-Film Solar Cell
• the composition B1 was applied by a spin coating method. This glass substrate was heated at 100 ° C. for 5 minutes using a hot plate to form a hole collecting layer.
• the film thickness of the hole collecting layer was about 30 nm.
• the solution A1 obtained in Preparation Example 1 was dropped onto the formed hole collecting layer to form a film by a spin coating method, and the active layer having a film thickness of 100 nm was formed. Formed.
• the substrate on which the organic semiconductor layer is formed and the mask for the negative electrode are installed in the vacuum vapor deposition apparatus, and the vacuum in the apparatus is exhausted until the degree of vacuum becomes 1 ⁇ 10 -3 Pa or less.
• a lithium 8-hydroxyquinolinolate layer to be a collection layer was deposited to a thickness of 1 nm.
• a forward laminated OPV having an area where the striped ITO layer and the aluminum layer intersect is 10 mm ⁇ 10 mm. Made.
• Example 2-1 A forward-stacked OPV was produced in the same manner as in Example 2-1 except that the hole-collecting layer composition C1 was used instead of the hole-collecting layer composition B1.
• Example 3-1 A 25 mm ⁇ 25 mm glass substrate in which an ITO transparent conductive layer to be a negative electrode was patterned in a stripe shape of 10 mm ⁇ 25 mm was subjected to UV / ozone treatment for 15 minutes.
• a solution of zinc oxide (manufactured by Genes' Inc.) as an electron collecting layer was dropped onto this substrate, and a film was formed by a spin coating method.
• the film thickness of the electron collecting layer was about 20 nm.
• the solution A1 obtained in Preparation Example 1 was dropped onto the formed electron collecting layer and formed into a film by a spin coating method to form an active layer.
• the hole collecting layer composition B2 prepared in Example 1-2 was applied onto this active layer by the doctor blade method, and then dried at room temperature to form a hole collecting layer.
• the film thickness of the hole collecting layer was about 300 nm.
• the laminated substrate is installed in a vacuum vapor deposition apparatus, exhausted until the degree of vacuum in the apparatus becomes 1 ⁇ 10 -3 Pa or less, and the silver layer serving as a positive electrode has a thickness of 200 nm by a resistance heating method.
• a reverse laminated OPV having an area of 3 mm ⁇ 8 mm at the intersection of the striped ITO layer and the silver layer was produced by thin-film deposition.
• Example 3-1 A reverse laminated OPV was produced by the same method as in Example 3-1 except that the hole collecting layer composition C2 was used instead of the hole collecting layer composition B2.
• PEDOT / PSS is a practical HTL by using the composition for the hole collecting layer of each example containing the polythiophene derivative containing the repeating unit represented by the formula (1). It can be seen that an OPV showing the same HTL characteristics as the above can be obtained.
• Example 4-2 After applying the hole collecting layer composition B2 by the doctor blade method, the adhesion test was carried out by the same method as in Example 4-1 except that the hole was annealed at 100 ° C. for 5 minutes using a hot plate. The laminated body of was produced.
• Example 4-1 A laminate for adhesion test was prepared by the same method as in Example 4-1 except that the hole collecting layer composition C2 was used instead of the hole collecting layer composition B2.
• Example 4-2 A laminate for adhesion test was prepared by the same method as in Example 4-2 except that the hole collecting layer composition C2 was used instead of the hole collecting layer composition B2.
• Example 4-3 A laminate for adhesion test was prepared by the same method as in Example 4-1 except that the hole collecting layer composition C3 was used instead of the hole collecting layer composition B2.
• Example 4-4 A laminate for adhesion test was prepared by the same method as in Example 4-2 except that the hole collecting layer composition C3 was used instead of the hole collecting layer composition B2.
• composition for the hole collecting layer of the present invention using the polymer represented by the formula (1), better film forming property could be obtained as compared with using other self-doped polymers.

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• 2021
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