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WO2014042091A1 - Polymère conjugué, et matériau organique donneur d'électrons, matériau pour élément photovoltaïque, et élément photovoltaïque le comprenant - Google Patents

Polymère conjugué, et matériau organique donneur d'électrons, matériau pour élément photovoltaïque, et élément photovoltaïque le comprenant Download PDF

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WO2014042091A1
WO2014042091A1 PCT/JP2013/074072 JP2013074072W WO2014042091A1 WO 2014042091 A1 WO2014042091 A1 WO 2014042091A1 JP 2013074072 W JP2013074072 W JP 2013074072W WO 2014042091 A1 WO2014042091 A1 WO 2014042091A1
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organic material
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渡辺伸博
北澤大輔
山本修平
下村悟
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Toray Industries Inc
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    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a conjugated polymer, an electron-donating organic material using the conjugated polymer, a photovoltaic element material, and a photovoltaic element.
  • Solar cells are attracting attention as an environmentally friendly electrical energy source and an influential energy source for increasing energy problems.
  • inorganic materials such as single crystal silicon, polycrystalline silicon, amorphous silicon, and compound semiconductor are used as semiconductor materials for photovoltaic elements of solar cells.
  • solar cells manufactured using inorganic semiconductors have not been widely used in general households because of high costs. The high cost factor is mainly in the process of manufacturing a semiconductor thin film under vacuum and high temperature. Therefore, organic solar cells using organic semiconductors and organic dyes such as conjugated polymers and organic crystals are being studied as semiconductor materials that are expected to simplify the manufacturing process.
  • an organic solar cell using a conjugated polymer or the like has the biggest problem that the photoelectric conversion efficiency is lower than that of a conventional solar cell using an inorganic semiconductor, and has not yet been put into practical use.
  • the photoelectric conversion efficiency of organic solar cells using conventional conjugated polymers is low because of the low absorption efficiency of sunlight and the bound state of exciton where electrons and holes generated by sunlight are difficult to separate. This is because a trap for trapping carriers (electrons and holes) is easily formed, and the generated carriers are easily trapped by the trap, and the mobility of carriers is slow.
  • photoelectric conversion elements using organic semiconductors are currently Schottky-type, electron-accepting organic materials (n-type organic semiconductors) that join an electron-donating organic material (p-type organic semiconductor) and a metal having a low work function.
  • an electron donating organic material p-type organic semiconductor
  • p-type organic semiconductor can be classified into a heterojunction type. In these elements, only the organic layer (about several molecular layers) at the junction contributes to the photocurrent generation, so that the photoelectric conversion efficiency is low, and its improvement is a problem.
  • n-type organic semiconductor an electron-accepting organic material
  • p-type organic semiconductor an electron-donating organic material
  • the conjugated polymer used as the electron donating organic material (p-type organic semiconductor) as the electron accepting organic material, a conductive polymer having a n-type semiconductor characteristics, a fullerene or fullerene derivatives such as C 60
  • the bulk heterojunction photoelectric conversion element used has been reported.
  • an electron-donating organic material with a narrow band gap is useful (for example, Non-Patent Documents 1 and 2). reference).
  • a narrow band gap electron-donating organic material a copolymer combining a thieno [3,4-b] thiophene skeleton and a benzo [1,2-b: 4,5-b ′] dithiophene skeleton is particularly excellent. It has been reported to show photovoltaic characteristics, and many derivatives have been synthesized so far (see, for example, Patent Document 1).
  • Non-Patent Documents 3 to 5 an electron-donating organic material in which a fluorine atom is introduced at the 3-position of the thieno [3,4-b] thiophene skeleton
  • benzo [1,2-b: 4,5-b '] An electron-donating organic material in which a fluorine atom is introduced at positions 3 and 7 of the dithiophene skeleton (Non-patent Document 6) has been reported.
  • Non-Patent Documents 3 and 6 the introduction of fluorine atoms does not necessarily have an effect on improving the photoelectric conversion efficiency, and depending on the position of introduction of fluorine atoms in the copolymer and the type of other substituents, the short-circuit current of the photovoltaic device may decrease. As a result, sufficient photoelectric conversion efficiency is not obtained (Non-Patent Documents 3 and 6).
  • a fluorine atom at the 3-position of the [3,4-b] thiophene skeleton, an alkoxycarbonyl group at the 2-position, and PTB7 in which an alkoxycarbonyl group is introduced at positions 4 and 8 of the benzo [1,2-b: 4,5-b ′] dithiophene skeleton (Non-patent Document 5), and position 3 of the [3,4-b] thiophene skeleton PBDTTTT-CF (Non-patent Document 4) in which a fluorine atom, an alkanoyl group at position 2, and an alkoxycarbonyl group at positions 4 and 8 of the benzo [1,2-b: 4,5-b ′] dithiophene skeleton are introduced. It has been reported.
  • the electron donating organic material combining a conventional thieno [3,4-b] thiophene skeleton and a benzo [1,2-b: 4,5-b ′] dithiophene skeleton introduced with a fluorine atom is expensive.
  • the open-circuit voltage value and the short-circuit current value cannot be made sufficiently compatible, and high photoelectric conversion efficiency has not been obtained. This is because it is difficult to maintain a high carrier mobility and to form a bulk heterojunction thin film in which an efficient carrier path with an electron-accepting material is formed in an electron-donating organic material into which fluorine atoms are introduced. This is thought to be the cause.
  • An object of the present invention is to provide an electron-donating organic material that achieves both deep HOMO, high carrier mobility, and good compatibility with an electron-accepting material, and to provide a photovoltaic device with high photoelectric conversion efficiency.
  • the present invention is a conjugated polymer having a structure represented by the general formula (1), an electron donating organic material, a photovoltaic element material and a photovoltaic element using the conjugated polymer.
  • R 1 represents an optionally substituted alkoxycarbonyl group or alkanoyl group.
  • R 2 may be the same or different, and may be substituted heteroaryl groups.
  • N represents the degree of polymerization and represents an integer of 2 to 1,000.
  • a photovoltaic device with high photoelectric conversion efficiency can be provided.
  • mode of the photovoltaic device of this invention The schematic diagram which showed another aspect of the photovoltaic element of this invention.
  • the schematic diagram which showed another aspect of the photovoltaic element of this invention The schematic diagram which showed another aspect of the photovoltaic element of this invention.
  • the voltage-current density curve of Example 1 (donor acceptor ratio 1: 1).
  • the conjugated polymer of the present invention includes a structure represented by the general formula (1).
  • a fluorine atom is introduced at the 3-position of the thieno [3,4-b] thiophene skeleton. This makes it possible to deepen the HOMO level. Further, as described later, this does not impair the carrier mobility of the conjugated polymer.
  • R 1 represents an optionally substituted alkoxycarbonyl group or alkanoyl group.
  • alkoxycarbonyl group means an alkyl group via an ester bond.
  • An alkanoyl group refers to an alkyl group via a ketone group.
  • the alkyl group is, for example, a saturated aliphatic group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, or a dodecyl group.
  • the hydrocarbon group may be linear, branched, or cyclic, and may be unsubstituted or substituted. Examples of the substituent when substituted include an alkoxy group and halogen.
  • the number of carbon atoms of the alkyl group is preferably 4 or more and 10 or less in order to achieve both sufficient solubility of the electron-donating organic material and carrier mobility.
  • R 2 may be the same or different and represents a heteroaryl group which may be substituted.
  • the heteroaryl group introduced into the 4,8-position of the benzo [1,2-b: 4,5-b ′] dithiophene skeleton allows the 3-position of the thieno [3,4-b] thiophene skeleton as described above. Even when fluorine atoms are introduced, the HOMO level can be deepened without impairing the carrier mobility of the conjugated polymer.
  • the photovoltaic device When used as an electron-donating organic material, the photovoltaic device has a high open-circuit voltage and short-circuit current. Can keep.
  • the number of carbon atoms of the heteroaryl group used for R 2 is preferably 2 or more and 6 or less in order to maintain carrier mobility, and in order to suppress twisting with the benzodithiophene skeleton and improve packing properties, it is a 5-membered member having a small molecular size.
  • a thienyl group or a furyl group having a ring structure is particularly preferably used.
  • the substituent on the heteroaryl group is preferably an alkyl group or an alkoxy group having 6 to 10 carbon atoms in order to achieve both solubility of the conjugated polymer and carrier mobility, and these are linear. Can also be branched.
  • the halogen is any one of fluorine, chlorine, bromine and iodine.
  • fluorine is preferably used because it can effectively deepen the HOMO level of the conjugated polymer.
  • N represents the degree of polymerization and represents an integer of 2 or more and 1,000 or less.
  • n is preferably less than 100.
  • the degree of polymerization can be determined from the weight average molecular weight.
  • the weight average molecular weight can be determined by measuring using GPC (gel permeation chromatography) and converting to a polystyrene standard sample.
  • the orientation of the thieno [3,4-b] thiophene skeleton in the conjugated polymer may be random or regioregular.
  • n shows the integer of 2 or more and 1,000 or less.
  • the structure represented by the general formula (1) satisfies the structure represented by the general formula (1).
  • structures in which R 1 and R 2 are different may be combined.
  • the number attached to the repeating unit enclosed in parentheses represents the ratio of the repeating unit.
  • n represents an integer of 2 or more and 1,000 or less.
  • the conjugated polymer having the structure represented by the general formula (1) may be a copolymer further containing a divalent conjugated linking group.
  • the divalent conjugated linking group is preferably 20% by weight or less with respect to the entire conjugated polymer.
  • the divalent conjugated linking group is more preferably 10% by weight or less.
  • Preferred examples of the divalent conjugated linking group include the following structures. Among these, a structure composed of a thieno [3,4-b] thiophene skeleton is preferable for maintaining the carrier mobility of the conjugated polymer.
  • R 3 to R 53 may be the same or different and are selected from hydrogen, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylthioester group, an alkanoyl group, an aryl group, a heteroaryl group, and a halogen.
  • the conjugated polymer having the structure represented by the general formula (1) is similar to, for example, a method similar to the method described in Patent Document 1 or a method described in Non-Patent Document 3. Can be synthesized by the above method.
  • the photovoltaic device material of the present invention may be composed of only an electron-donating organic material using a conjugated polymer having a structure represented by the general formula (1), or other electron-donating organic material. May be included.
  • electron-donating organic materials include polythiophene polymers, benzothiadiazole-thiophene derivatives, benzothiadiazole-thiophene copolymers, poly-p-phenylene vinylene polymers, poly-p-phenylene heavy polymers.
  • Conjugated polymers such as polymers, polyfluorene polymers, polypyrrole polymers, polyaniline polymers, polyacetylene polymers, polythienylene vinylene polymers, H 2 phthalocyanine (H 2 Pc), copper phthalocyanine ( CuPc), phthalocyanine derivatives such as 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-4,4′-diphenyl -1,1′-diamine (NPD) and other triarylamine derivatives, 4,4′-di (carbazol-9-yl) biphenyl (CBP) and other carbazole derivatives, oligothiophene derivatives (terthiophene, quarterthiophene
  • the conjugated polymer having the structure represented by the general formula (1) is an electron donating organic material exhibiting p-type semiconductor characteristics, and the photovoltaic device material of the present invention is intended to obtain higher photoelectric conversion efficiency. It is preferable to combine with an electron-accepting organic material (n-type organic semiconductor).
  • Examples of electron-accepting organic materials exhibiting n-type semiconductor characteristics include 1,4,5,8-naphthalene tetracarboxyl dianhydride (NTCDA), 3,4,9,10-perylene tetracarboxyl dianhydride (PTCDA).
  • NTCDA 1,4,5,8-naphthalene tetracarboxyl dianhydride
  • PTCDA 3,4,9,10-perylene tetracarboxyl dianhydride
  • fullerene compounds are preferably used because of their high charge separation speed and electron transfer speed.
  • C 70 derivatives such as the above PC 70 BM are more preferable because they are excellent in light absorption characteristics and can obtain higher photoelectric conversion efficiency.
  • an electron-donating organic material In a photovoltaic device material combining an electron-donating organic material and an electron-accepting organic material using a conjugated polymer having a structure represented by the general formula (1) of the present invention, an electron-donating organic material and The content ratio (weight fraction) of the electron-accepting organic material is not particularly limited, but the content ratio (donor-acceptor ratio) of the electron-donating organic material and the electron-accepting organic material is in the range of 1:99 to 99: 1. More preferably, it is in the range of 10:90 to 90:10, and still more preferably in the range of 20:80 to 60:40.
  • the electron-donating organic material and the electron-accepting organic material may be used as a mixture or laminated. Although it does not specifically limit as a mixing method, After adding to a solvent in a desired ratio, the method of making it melt
  • the above-mentioned content ratio is the content ratio of the electron-donating organic material and the electron-accepting organic material contained in the single layer.
  • the organic semiconductor layer has a laminated structure of two or more layers, it means the content ratio of the electron donating organic material and the electron accepting organic material in the whole organic semiconductor layer.
  • an electron donating organic material using a conjugated polymer having a structure represented by the general formula (1) and a method for removing impurities from the electron accepting organic material are not particularly limited. Methods, recrystallization methods, sublimation methods, reprecipitation methods, Soxhlet extraction methods, molecular weight fractionation methods by GPC, filtration methods, ion exchange methods, chelate methods, and the like can be used. In general, a column chromatography method, a recrystallization method, and a sublimation method are preferably used for purification of a low molecular weight organic material.
  • reprecipitation method for purification of high molecular weight compounds, reprecipitation method, Soxhlet extraction method, molecular weight fractionation method by GPC is preferably used when removing low molecular weight components, and reprecipitation method or the like when removing metal components.
  • a chelate method or an ion exchange method is preferably used. A plurality of these methods may be combined.
  • FIG. 1 is a schematic view showing an example of the photovoltaic element of the present invention.
  • reference numeral 1 is a substrate
  • reference numeral 2 is a positive electrode
  • reference numeral 3 is an organic semiconductor layer containing the photovoltaic element material of the present invention
  • reference numeral 4 is a negative electrode.
  • the photovoltaic element of the present invention may be in the order of substrate 1 / negative electrode 4 / organic semiconductor layer 3 / positive electrode 2 as illustrated in FIG.
  • the organic semiconductor layer 3 contains the photovoltaic element material of the present invention. That is, an electron-donating organic material and an electron-accepting organic material using a conjugated polymer having a structure represented by the general formula (1) are included.
  • the organic semiconductor layer 3 that is an organic power generation layer of the photovoltaic element includes an electron donating organic material and an electron accepting material, these materials may be mixed or stacked, but are mixed. It is preferable. That is, as shown in FIGS. 1 and 2, even if the organic semiconductor layer containing the photovoltaic element material is a layer in which an electron-donating organic material and an electron-accepting organic material are mixed, FIGS.
  • the organic semiconductor layer containing the photovoltaic element material may have a laminated structure of a layer having an electron-donating organic material and a layer having an electron-accepting organic material. It is preferable that the organic semiconductor layer containing is a layer in which an electron-donating organic material and an electron-accepting organic material are mixed.
  • a bulk heterojunction photovoltaic device that increases the bonding surface between an electron-donating organic material and an electron-accepting organic material that contribute to photoelectric conversion by mixing an electron-donating organic material and an electron-accepting organic material is preferable.
  • the organic semiconductor layer 3 which is this bulk heterojunction type organic power generation layer
  • the electron donating organic material and the electron accepting organic material using the conjugated polymer having the structure represented by the general formula (1) are nanometers. It is preferable that phase separation is performed at a size of.
  • the domain size of this phase separation structure is not particularly limited, but is usually 1 nm or more and 50 nm or less.
  • an electron-donating organic material and an electron-accepting organic material using a conjugated polymer having a structure represented by the general formula (1) are stacked, an electron-donating organic material exhibiting p-type semiconductor characteristics
  • the layer having the material is preferably on the positive electrode side, and the layer having an electron-accepting organic material exhibiting n-type semiconductor characteristics is preferably on the negative electrode side.
  • An example of the photovoltaic element in the case where the organic semiconductor layer 3 is thus laminated is shown in FIGS.
  • Reference numeral 5 denotes a layer having an electron donating organic material using a conjugated polymer having a structure represented by the general formula (1)
  • reference numeral 6 denotes a layer having an electron accepting organic material.
  • the organic semiconductor layer preferably has a thickness of 5 nm to 500 nm, more preferably 30 nm to 300 nm.
  • the layer having an electron-donating organic material of the present invention preferably has a thickness of 1 nm to 400 nm, more preferably 15 nm to 150 nm.
  • the photovoltaic device of the present invention it is preferable that either the positive electrode 2 or the negative electrode 4 has light transmittance.
  • the light transmittance of the electrode is not particularly limited as long as incident light reaches the organic semiconductor layer 3 and an electromotive force is generated.
  • the light transmittance in the present invention is a value obtained by [transmitted light intensity (W / m 2 ) / incident light intensity (W / m 2 )] ⁇ 100 (%).
  • the thickness of the electrode may be in a range having light transmittance and conductivity, and is preferably 20 nm to 300 nm although it varies depending on the electrode material.
  • the other electrode is not necessarily light-transmitting as long as 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, indium, cerium, samarium, europium, terbium, ytterbium, etc.
  • metal oxides such as indium, tin, molybdenum and nickel, composite metal oxides (indium tin oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO), gallium zinc oxide ( GZO)), alkali metals and alkaline earth metals, specifically lithium, magnesium, sodium, potassium, calcium, strontium, barium, and the like are also preferably used.
  • an electrode made of an alloy made of the above metal or a laminate of the above metal is also preferably used.
  • graphite, graphite intercalation compounds, carbon nanotubes, graphene, polyaniline and derivatives thereof, and electrodes containing polythiophene and derivatives thereof are also preferably used.
  • at least one of the positive electrode and the negative electrode is preferably transparent or translucent.
  • the electrode material may be a mixed layer composed of two or more materials and a laminated structure.
  • the conductive material used for the positive electrode 2 is preferably one that is in ohmic contact with the organic semiconductor layer 3. Furthermore, when a hole transport layer described later is used, it is preferable that the conductive material used for the positive electrode 2 is in ohmic contact with the hole transport layer.
  • the conductive material used for the negative electrode 4 is preferably one that is in ohmic contact with the organic semiconductor layer 3 or the electron transport layer.
  • a method for improving the bonding a method of introducing a metal fluoride such as lithium fluoride (LiF) or cesium fluoride as an electron extraction layer into the negative electrode can be mentioned. By introducing the electron extraction layer, it is possible to improve the extraction current.
  • the substrate 1 is an inorganic substrate such as an alkali-free glass, quartz glass, aluminum, iron, copper, or an alloy such as stainless steel, on which an electrode material or an organic semiconductor layer can be laminated, depending on the type and application of the photoelectric conversion material.
  • Films and plates produced by any method from organic materials such as materials, polyester, polycarbonate, polyolefin, polyamide, polyimide, polyphenylene sulfide, polyparaxylene polymethyl methacrylate, epoxy resin and fluorine-based resin can be used.
  • each substrate described above has a light transmittance of 80% or more.
  • a hole transport layer may be provided between the positive electrode 2 and the organic semiconductor layer 3.
  • Materials for forming the hole transport layer include polythiophene polymers, poly-p-phenylene vinylene polymers, polyfluorene polymers, polypyrrole polymers, polyaniline polymers, polyfuran polymers, polypyridine polymers, polycarbazoles.
  • Conductive polymers such as polymers, low molecular organic compounds exhibiting p-type semiconductor properties such as phthalocyanine derivatives (H 2 Pc, CuPc, ZnPc, etc.), porphyrin derivatives, acene compounds (tetracene, pentacene, etc.), graphene, Carbon compounds such as graphene oxide, molybdenum oxides such as MoO 3 (MoO x ), tungsten oxides such as WO 3 (WO x ), nickel oxides such as NiO (NiO x ), vanadium oxides such as V 2 O 5 (VO x) ), zirconium oxide such as ZrO 2 (ZrO x) Copper oxide such as Cu 2 O (CuO x), copper iodide, ruthenium oxide, such as RuO 4 (RuO x), inorganic compounds such as ruthenium oxide (ReO x), such as Re 2 O 7 is preferably used.
  • phthalocyanine derivatives H 2
  • the hole transport layer may be a layer made of a single compound, or a mixed layer made of two or more compounds and a laminated structure.
  • the hole transport layer preferably has a thickness of 5 nm to 600 nm, more preferably 10 nm to 200 nm.
  • 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 the above-described electron-accepting organic materials (NTCDA, PTCDA, PTCDI-C8H, oxazole derivatives, triazole derivatives, phenanthroline derivatives, phosphine oxide derivatives, phosphine sulfide derivatives
  • NTCDA, PTCDA, PTCDI-C8H oxazole derivatives, triazole derivatives, phenanthroline derivatives, phosphine oxide derivatives, phosphine sulfide derivatives
  • Organic materials exhibiting n-type semiconductor properties such as quinoline derivatives, fullerene compounds, CNT, CN-PPV, and the like are preferably used.
  • compounds having an ionic group such as ammonium salts, amine salts, pyridinium salts, imidazolium salts, phosphonium salts, carboxylates, sulfonates, phosphates, sulfate esters, phosphate ester salts, sulfates , Nitrates, acetonates, oxoacid salts, and metal complexes can also be used as the electron transport layer.
  • an ionic group such as ammonium salts, amine salts, pyridinium salts, imidazolium salts, phosphonium salts, carboxylates, sulfonates, phosphates, sulfate esters, phosphate ester salts, sulfates , Nitrates, acetonates, oxoacid salts, and metal complexes can also be used as the electron transport layer.
  • titanium oxide such as TiO 2 (TiO x ), zinc oxide such as ZnO (ZnO x ), silicon oxide such as SiO 2 (SiO x ), tin oxide such as SnO 2 (SnO x ), oxidation such as WO 3 Tungsten oxide (TaO x ) such as tungsten (WO x ), Ta 2 O 3, barium titanate (BaTi x O y ) such as BaTiO 3 , barium zirconate (BaZr x O y ) such as BaZrO 3 , ZrO 2, etc.
  • TiO 2 TiO x
  • zinc oxide such as ZnO (ZnO x )
  • silicon oxide such as SiO 2 (SiO x )
  • tin oxide such as SnO 2 (SnO x )
  • oxidation such as WO 3 Tungsten oxide (TaO x ) such as tungsten (WO x ), Ta 2
  • CdS x cadmium sulf
  • a method of forming an electron transport layer with the inorganic material a method of forming a layer by applying a precursor solution such as a metal salt or metal alkoxide and then heating, or applying a nanoparticle dispersion on a substrate There are methods for forming layers. At this time, depending on the heating temperature and time, and the synthesis conditions of the nanoparticles, the reaction does not proceed completely, and it becomes an intermediate product by partially hydrolyzing or partially condensing. Or a mixture of a precursor, an intermediate organism, and an end product.
  • a precursor solution such as a metal salt or metal alkoxide
  • the phenanthroline derivative is not particularly limited.
  • bathocuproin BCP
  • bathophenanthrene Bphen
  • 2-naphthalen-2-yl-4,7-diphenyl-1,10-phenanthroline Phenanthroline monomer compounds such as HNBphen
  • 2,9-bisnaphthalen-2-yl-4,7-diphenyl-1,10-phenanthroline NBphen
  • phenanthroline multimeric compounds described in JP2012-39097A phenanthroline dimer compound
  • the phenanthroline dimer compound is a compound represented by the following general formula (2), such as the compound described in JP 2012-39097 A.
  • R 54 to R 60 may be the same or different and are selected from hydrogen, an alkyl group, and an aryl group.
  • A is a divalent aromatic hydrocarbon group.
  • the substituents having two phenanthroline skeletons may be the same or different.
  • the alkyl group represents a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, or a butyl group
  • the aryl group represents, for example, a phenyl group, a tolyl group, a biphenyl group, a naphthyl group, a phenanthryl group
  • An aromatic hydrocarbon group such as an anthryl group is shown and may be unsubstituted or substituted.
  • the alkyl group or aryl group preferably has about 1 to 20 carbon atoms. Further, the groups having two phenanthroline skeletons may be the same or different.
  • the phosphine oxide derivative is not particularly limited, and examples thereof include phosphine compounds such as phenyl dipyrenyl phosphine oxide (POPy 2 ).
  • the quinoline derivative is not particularly limited, and examples thereof include compounds such as 8-hydroxyquinolate lithium (Liq) and tris (8-hydroxyquinolate) aluminum.
  • the energy barrier is reduced at the interface junction with the negative electrode, and the negative electrode interface of excitons generated in the electron-donating organic semiconductor and the electron-accepting organic semiconductor. It is considered that the electron extraction efficiency and the charge generation efficiency are improved by preventing the deactivation of the catalyst.
  • phenanthroline derivatives are preferably used because of their electron transport properties and the ability to easily obtain a homogeneous film. Furthermore, a phenanthroline multimer compound is preferably used because a stable film having a high glass transition point can be easily obtained, and a phenanthroline dimer compound is more preferably used in consideration of easiness of synthesis.
  • a in the general formula (2) is a substituted or unsubstituted phenylene group or a substituted or non-substituted phenoxy group from the balance of sublimation property and thin film forming ability during thin film formation such as vacuum deposition. It is preferably a substituted naphthylene group.
  • the thickness of the electron transport layer is preferably 0.1 nm to 600 nm, more preferably 1 nm to 200 nm, and still more preferably 1 nm to 20 nm.
  • the electron transport layer may be a layer made of a single compound or a layer made of two or more compounds. Further, the electron transport layer includes an alkali metal or alkaline earth metal, specifically, a compound such as lithium, magnesium, calcium, or a metal fluoride such as lithium fluoride or cesium fluoride, and the material for the electron transport layer. It may be a mixed layer or a laminated structure with them.
  • the photovoltaic element of the present invention may form a series junction by laminating two or more organic semiconductor layers via one or more intermediate electrodes.
  • Such a configuration is sometimes called a tandem configuration.
  • a tandem configuration of substrate / positive electrode / first organic semiconductor layer / intermediate electrode / second organic semiconductor layer / negative electrode can be given.
  • a tandem configuration of substrate / negative electrode / first organic semiconductor layer / intermediate electrode / second organic semiconductor layer / positive electrode may be mentioned.
  • the hole transport layer described above may be provided between the positive electrode and the first organic semiconductor layer and between the intermediate electrode and the second organic semiconductor layer, and between the first organic semiconductor layer and the intermediate electrode.
  • the hole transport layer described above may be provided between the second organic semiconductor layer and the negative electrode.
  • At least one of the organic semiconductor layers contains the photovoltaic device material of the present invention, and the other layers are represented by the general formula (1) in order not to reduce the short-circuit current.
  • electron-donating organic materials include the above-mentioned polythiophene polymers, poly-p-phenylene vinylene polymers, poly-p-phenylene polymers, polyfluorene polymers, polypyrrole polymers, polyaniline.
  • the material for the intermediate electrode used here is preferably a material having high conductivity, for example, the above-mentioned metals such as gold, platinum, chromium, nickel, lithium, magnesium, calcium, tin, silver, aluminum, and transparent Metal oxides such as indium, tin, and molybdenum, composite metal oxides (indium tin oxide (ITO), indium zinc oxide (IZO), etc.), alloys composed of the above metals, and laminates of the above metals , Polyethylenedioxythiophene (PEDOT), and those obtained by adding polystyrene sulfonate (PSS) to PEDOT.
  • the intermediate electrode preferably has a light transmission property, but even a material such as a metal having a low light transmission property can often ensure a sufficient light transmission property by reducing the film thickness.
  • a transparent electrode such as ITO (corresponding to a positive electrode in this case) is formed on the substrate by sputtering or the like.
  • a solution is prepared by dissolving an electron donating organic material using a conjugated polymer having a structure represented by the general formula (1) and, if necessary, a material for a photoelectric conversion element containing an electron accepting organic material in a solvent,
  • An organic semiconductor layer is formed by coating on the transparent electrode.
  • the solvent used at this time is not particularly limited as long as the organic semiconductor can be appropriately dissolved or dispersed in the solvent, but an organic solvent is preferable, for example, hexane, heptane, octane, isooctane, nonane, decane, cyclohexane, decalin.
  • Aliphatic hydrocarbons such as bicyclohexyl, alcohols such as methanol, ethanol, butanol, propanol, ethylene glycol, glycerin, ketones such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, isophorone, ethyl acetate, butyl acetate, Esters such as methyl lactate, ⁇ -butyrolactone, diethylene glycol monobutyl ether acetate, dimethyl carbonate, ethyl ether, methyl tertiary butyl ether, tetrahydrofuran, , 4-dioxane, tetrahydropyran, 3,4-dihydro-2H-pyran, isochroman, ethylene glycol monomethyl ether, ethers such as diglyme, amines such as ammonia and ethanolamine, N, N-dimethylformamide, dimethylacetamide
  • an organic semiconductor layer is formed by mixing an electron-donating organic material and an electron-accepting organic material using a conjugated polymer having a structure represented by the general formula (1)
  • an electron-donating organic material and an electron A receptive organic material is added to a solvent in a desired ratio, dissolved by a method such as heating, stirring, and ultrasonic irradiation to form a solution, which is applied onto a transparent electrode.
  • the photoelectric conversion efficiency of the photovoltaic element can be improved by using a mixture of two or more solvents. This is presumably because the electron-donating organic material and the electron-accepting organic material undergo phase separation at the nano level, and a carrier path that forms a path for electrons and holes is formed.
  • an optimal combination type can be selected depending on the types of the electron donating organic material and the electron accepting organic material to be used.
  • preferred solvents to be combined include chloroform and chlorobenzene among the above.
  • an organic semiconductor layer is formed by laminating an electron donating organic material and an electron accepting organic material using a conjugated polymer having a structure represented by the general formula (1), for example, an electron donating organic
  • the electron-accepting organic material solution is applied to form a layer.
  • the electron-donating organic material and the electron-accepting organic material are low molecular weight substances having a molecular weight of about 1000 or less, it is possible to form a layer using a vapor deposition method.
  • the formation method may be selected according to the characteristics of the organic semiconductor layer to be obtained, such as film thickness control and orientation control.
  • the concentration of electron donating organic material and electron accepting organic material using a conjugated polymer having a structure represented by the general formula (1) is 1 to 20 g / l (electron
  • the weight of the electron donating organic material and the electron accepting organic material with respect to the volume of the solution containing the donating organic material, the electron accepting organic material, and the solvent is preferable. It is possible to easily obtain a homogeneous organic semiconductor layer.
  • the formed organic semiconductor layer may be annealed under reduced pressure or under an inert atmosphere (in a nitrogen or argon atmosphere).
  • a preferable temperature for the annealing treatment is 40 ° C to 300 ° C, more preferably 50 ° C to 200 ° C. Further, by performing the annealing process, the effective area where the stacked layers permeate and contact each other at the interface increases, and the short-circuit current can be increased. This annealing treatment may be performed after the formation of the negative electrode.
  • a metal electrode such as Al (corresponding to a negative electrode in this case) is formed on the organic semiconductor layer by vacuum deposition or sputtering.
  • the metal electrode is vacuum-deposited using a low molecular organic material for the electron transport layer, it is preferable that the metal electrode is continuously formed while maintaining the vacuum.
  • a desired p-type organic semiconductor material such as PEDOT
  • PEDOT p-type organic semiconductor material
  • the solvent is removed using a vacuum thermostat or a hot plate to form a hole transport layer.
  • a vacuum vapor deposition method using a vacuum vapor deposition machine.
  • a desired n-type organic semiconductor material such as fullerene derivatives
  • an n-type inorganic semiconductor material such as titanium oxide gel
  • the solvent is removed using a vacuum thermostat or a hot plate to form an electron transport layer.
  • a vacuum deposition method using a vacuum deposition machine.
  • the photovoltaic element of the present invention can be applied to various photoelectric conversion devices using a photoelectric conversion function, an optical rectification function, and the like.
  • photovoltaic cells such as solar cells
  • electronic devices such as optical sensors, optical switches, and phototransistors
  • optical recording materials such as optical memories
  • ITO indium tin oxide
  • PEDOT polyethylene dioxythiophene
  • PSS polystyrene sulfonate
  • PC 70 BM phenyl C71 butyric acid methyl ester
  • Eg band gap HOMO: highest occupied molecular orbital
  • Isc short circuit current density
  • Voc open circuit voltage
  • FF fill Factor ⁇ : Photoelectric conversion efficiency
  • an FT-NMR apparatus JEOL JNM-EX270 manufactured by JEOL Ltd.
  • 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 Co., Ltd., which was supplied with chloroform, high-speed GPC apparatus HLC-8320GPC).
  • the light absorption edge wavelength is an ultraviolet-visible absorption spectrum (measurement wavelength) of a thin film formed on a glass with a thickness of about 60 nm using a U-3010 spectrophotometer manufactured by Hitachi, Ltd. (Range: 300-900 nm).
  • the band gap (Eg) was calculated from the light absorption edge wavelength by the following equation.
  • the thin film was formed by spin coating using chloroform as a solvent.
  • Eg (eV) 1240 / light absorption edge wavelength of thin film (nm)
  • the highest occupied molecular orbital (HOMO) level is the surface analysis device (in-air ultraviolet photoelectron spectrometer AC-2 type, manufactured by Riken Kikai Co., Ltd.) for thin films formed on ITO glass with a thickness of about 60 nm. ).
  • the thin film was formed by spin coating using chloroform as a solvent.
  • the material is an electron-donating organic material or an electron-accepting organic material, that is, p-type semiconductor characteristics or n-type semiconductor characteristics, can be evaluated by measuring the above-described thin film by FET measurement or energy level measurement.
  • Synthesis example 1 Compound A-1 was synthesized by the method shown in Scheme 1. In addition, the compound (1-i) described in Synthesis Example 1 was obtained by referring to the method described in Journal of the American Chemical Society, 2009, Vol. 131, pages 7792-7799. 1-p) was synthesized with reference to the method described in Angewante Chem International Edition, 2011, Vol. 50, pages 9697-9702.
  • reaction solution was stirred at room temperature for 30 minutes and then 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 ether were added. The organic layer was washed twice with water and saturated brine, and then dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was distilled under reduced pressure to obtain compound (1-n) as a colorless liquid (28.3 g, 36%).
  • the measurement result of 1 H-NMR of the compound (1-n) is shown below.
  • reaction solution was cooled to 0 ° C., and a solution of 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. Stir 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 a saturated saline solution. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure.
  • the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque), and then a silica gel column (eluent, chloroform), and then the solvent was distilled off under reduced pressure.
  • the obtained solid was dissolved again in chloroform and then reprecipitated in methanol to obtain Compound A-1 (91 mg).
  • the weight average molecular weight was 29,000 and the number average molecular weight was 17,000.
  • the light absorption edge wavelength was 778 nm
  • the band gap (Eg) was 1.59 eV
  • the highest occupied molecular orbital (HOMO) level was ⁇ 5.05 eV.
  • Synthesis example 2 Compound B-1 was synthesized by the method shown in Scheme 2. Compound (2-b) described in Synthesis Example 2 was synthesized with reference to a method described in Journal of the American Chemical Society, 2009, Vol. 131, pages 7792-7799. .
  • the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque), and then a silica gel column (eluent, chloroform), and then the solvent was distilled off under reduced pressure.
  • the obtained solid was dissolved again in chloroform and then reprecipitated in methanol to obtain Compound B-1 (73 mg).
  • the weight average molecular weight was 31,000 and the number average molecular weight was 13,000.
  • the light absorption edge wavelength was 754 nm
  • the band gap (Eg) was 1.64 eV
  • the highest occupied molecular orbital (HOMO) level was ⁇ 5.09 eV.
  • Synthesis example 3 Compound B-2 was synthesized by the method shown in Scheme 3.
  • Compound (3-c) described in Synthesis Example 3 was synthesized with reference to the method described in Journal of the American Chemical Society, 2009, Vol. 131, pages 7792-7799. .
  • the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque), and then a silica gel column (eluent, chloroform), and then the solvent was distilled off under reduced pressure.
  • the obtained solid was dissolved again in chloroform and then reprecipitated in methanol to obtain Compound B-2 (82 mg).
  • the weight average molecular weight was 22,000 and the number average molecular weight was 11,000.
  • the light absorption edge wavelength was 755 nm
  • the band gap (Eg) was 1.64 eV
  • the highest occupied molecular orbital (HOMO) level was ⁇ 5.06 eV.
  • Synthesis example 4 Compound B-3 was synthesized by the method shown in Scheme 4. The compound (4-a) described in Synthesis Example 4 was synthesized with reference to the method described in Journal of the American Chemical Society, 2009, Vol. 131, pages 7792-7799. .
  • the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque), and then a silica gel column (eluent, chloroform), and then the solvent was distilled off under reduced pressure.
  • the obtained solid was dissolved again in chloroform and then reprecipitated in methanol to obtain Compound B-3 (80 mg).
  • the weight average molecular weight was 35,000 and the number average molecular weight was 17,000.
  • the light absorption edge wavelength was 784 nm
  • the band gap (Eg) was 1.58 eV
  • the highest occupied molecular orbital (HOMO) level was -4.91 eV.
  • Synthesis example 5 Compound B-4 was synthesized by the method shown in Scheme 5. The compound (5-a) described in Synthesis Example 5 was synthesized with reference to the method described in Journal of the American Chemical Society, 2009, Vol. 131, pages 15586-15588. .
  • the obtained solid was dissolved in chloroform, passed through Celite (manufactured by Nacalai Tesque), and then a silica gel column (eluent, chloroform), and then the solvent was distilled off under reduced pressure.
  • the obtained solid was dissolved again in chloroform and then reprecipitated in methanol to obtain Compound B-4 (73 mg).
  • the weight average molecular weight was 21,000 and the number average molecular weight was 11,000.
  • the light absorption edge wavelength was 785 nm
  • the band gap (Eg) was 1.58 eV
  • the highest occupied molecular orbital (HOMO) level was -4.92 eV.
  • Example 1 A chloroform solution containing 1 mg of the above (A-1) and 1 mg of PC 70 BM (manufactured by Solenne) containing 1,8-diiodooctane (manufactured by Wako Pure Chemical Industries, Ltd.) at a volume concentration of 3% 0
  • a glass substrate on which a 125 nm thick ITO transparent conductive layer serving as a positive electrode was deposited by sputtering was cut into 38 mm ⁇ 46 mm, and then ITO was patterned into a 38 mm ⁇ 13 mm rectangular shape by photolithography.
  • the obtained substrate was subjected to ultrasonic cleaning for 10 minutes with an alkali cleaning solution (“Semico Clean” EL56 (trade name), manufactured by Furuuchi Chemical Co., Ltd.), and then washed with ultrapure water.
  • an alkali cleaning solution (“Semico Clean” EL56 (trade name), manufactured by Furuuchi Chemical Co., Ltd.
  • a PEDOT: PSS aqueous solution (0.8% by weight of PEDOT, 0.5% by weight of PPS) serving as a hole transport layer was formed on the substrate to a thickness of 60 nm by spin coating. did.
  • the above solution A or solution B was dropped onto the PEDOT: PSS layer, and an organic semiconductor layer having a thickness of 130 nm was formed by spin coating.
  • the substrate on which the organic semiconductor layer is formed and the cathode mask are placed in a vacuum vapor deposition apparatus, and the vacuum in the apparatus is evacuated again to 1 ⁇ 10 ⁇ 3 Pa or less.
  • a lithium fluoride layer was deposited to a thickness of 0.1 nm. Then, the aluminum layer used as a negative electrode was vapor-deposited with the thickness of 80 nm. As described above, a photovoltaic device having an area where the stripe-shaped ITO layer and the aluminum layer intersect each other was 2 mm ⁇ 2 mm was produced.
  • the positive and negative electrodes of the photovoltaic device thus fabricated were connected to a Keithley 2400 series source meter, and simulated sunlight from the ITO layer side in the atmosphere (OTENTO-SUNIII, manufactured by Spectrometer Co., Ltd., spectral shape) : AM1.5, intensity: 100 mW / cm 2 ), and the current value was measured when the applied voltage was changed from ⁇ 1V to + 2V.
  • the short-circuit current density at this time (current density value when the applied voltage is 0 V) is 15.50 A / cm 2 , open circuit
  • the voltage (value of the applied voltage when the current density was 0) was 0.79 V
  • the fill factor (FF) was 0.66
  • the photoelectric conversion efficiency calculated from these values was 8.06%.
  • the voltage-current density curve at this time is shown in FIG.
  • the horizontal axis is voltage
  • the vertical axis is current density.
  • the short-circuit current density is 15.13 A / cm 2
  • the open circuit voltage is 0.78 V
  • the fill factor (FF) is The photoelectric conversion efficiency calculated from these values was 7.31%.
  • the fill factor and photoelectric conversion efficiency were calculated by the following equations.
  • Fill factor IVmax (mA ⁇ V / cm 2 ) / (Short-circuit current density (mA / cm 2 ) ⁇ Open circuit voltage (V))
  • IVmax is the value of the product of the current density and the applied voltage at the point where the product of the current density and the applied voltage becomes maximum when the applied voltage is between 0 V and the open circuit voltage value.
  • Photoelectric conversion efficiency [(short circuit current density (mA / cm 2 ) ⁇ open voltage (V) ⁇ fill factor) / pseudo sunlight intensity (100 mW / cm 2 )] ⁇ 100 (%)
  • the fill factor and photoelectric conversion efficiency in the following examples and comparative examples were all calculated by the above formula.
  • Comparative Example 1 A photovoltaic device was prepared in the same manner as in Example 1 except that B-1 was used instead of A-1, and current-voltage characteristics were measured.
  • the short-circuit current density of the device using a solution with a donor-acceptor weight ratio of 1: 1 is 11.20 mA / cm 2
  • the open-circuit voltage is 0.74 V
  • the fill factor (FF) is 0.59.
  • the calculated photoelectric conversion efficiency was 4.89%.
  • the short circuit current density of the element using the solution whose donor-acceptor weight ratio is 1: 1.5 is 12.74 mA / cm 2
  • the open circuit voltage is 0.74 V
  • the fill factor (FF) is 0.66.
  • the photoelectric conversion efficiency calculated from these values was 6.39%.
  • Comparative Example 2 A photovoltaic device was produced in the same manner as in Example 1 except that B-2 was used in place of A-1, and current-voltage characteristics were measured.
  • the short-circuit current density of the device using a solution with a donor-acceptor weight ratio of 1: 1 is 11.44 mA / cm 2
  • the open-circuit voltage is 0.74 V
  • the fill factor (FF) is 0.62.
  • the calculated photoelectric conversion efficiency was 5.25%.
  • the short circuit current density of the element using the solution whose donor acceptor weight ratio is 1: 1.5 is 11.22 mA / cm 2
  • the open circuit voltage is 0.74 V
  • the fill factor (FF) is 0.60.
  • the photoelectric conversion efficiency calculated from these values was 4.98%.
  • Comparative Example 3 A photovoltaic device was produced in the same manner as in Example 1 except that B-3 was used in place of A-1, and current-voltage characteristics were measured.
  • the short-circuit current density of the device using the solution having a donor-acceptor weight ratio of 1: 1 is 11.19 mA / cm 2
  • the open-circuit voltage is 0.68 V
  • the fill factor (FF) is 0.57.
  • the calculated photoelectric conversion efficiency was 4.34%.
  • the short circuit current density of the element using the solution whose donor-acceptor weight ratio is 1: 1.5 is 12.56 mA / cm 2
  • the open circuit voltage is 0.68 V
  • the fill factor (FF) is 0.55.
  • the photoelectric conversion efficiency calculated from the value was 4.70%.
  • Comparative Example 4 A photovoltaic device was produced in the same manner as in Example 1 except that B-4 was used instead of A-1, and current-voltage characteristics were measured.
  • the short-circuit current density of the device using the solution having a donor-acceptor weight ratio of 1: 1 is 13.51 mA / cm 2
  • the open-circuit voltage is 0.74 V
  • the fill factor (FF) is 0.59.
  • the calculated photoelectric conversion efficiency was 5.90%.
  • the short circuit current density of the element using the solution whose donor-acceptor weight ratio is 1: 1.5 is 15.02 mA / cm 2
  • the open circuit voltage is 0.74 V
  • the fill factor (FF) is 0.61.
  • the photoelectric conversion efficiency calculated from these values was 6.78%.
  • the photovoltaic device (Example 1) produced using the electron donating organic material having the structure represented by the general formula (1) was obtained by using other light produced under the same conditions.
  • the photoelectric conversion efficiency was higher than that of the electromotive element (Comparative Examples 1 to 4).
  • Substrate 2 Positive electrode 3: Organic semiconductor layer 4: Negative electrode 5: Layer having an electron-donating organic material 6: Layer having an electron-accepting organic material

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PCT/JP2013/074072 2012-09-14 2013-09-06 Polymère conjugué, et matériau organique donneur d'électrons, matériau pour élément photovoltaïque, et élément photovoltaïque le comprenant Ceased WO2014042091A1 (fr)

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JP2016113574A (ja) * 2014-12-17 2016-06-23 住友化学株式会社 組成物およびそれを用いた有機半導体素子
JP2017511407A (ja) * 2014-03-27 2017-04-20 エルジー・ケム・リミテッド 共重合体およびこれを含む有機太陽電池
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WO2018068721A1 (fr) * 2016-10-11 2018-04-19 The Hong Kong University Of Science And Technology Polymères conjugués polymérisés de manière statistique contenant une distribution statistique de différentes chaînes latérales

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US10355214B2 (en) 2014-03-27 2019-07-16 Lg Chem, Ltd. Copolymer and organic solar cell comprising same
JP2017511407A (ja) * 2014-03-27 2017-04-20 エルジー・ケム・リミテッド 共重合体およびこれを含む有機太陽電池
US10388876B2 (en) 2014-10-14 2019-08-20 Toray Industries, Inc. Organic semiconductor composition, photovoltaic element, photoelectric conversion device, and method of manufacturing photovoltaic element
JPWO2016059972A1 (ja) * 2014-10-14 2017-07-27 東レ株式会社 有機半導体組成物、光起電力素子、光電変換デバイスおよび光起電力素子の製造方法
CN107109033A (zh) * 2014-10-14 2017-08-29 东丽株式会社 有机半导体组合物、光伏元件、光电转换装置和光伏元件的制造方法
CN107109033B (zh) * 2014-10-14 2019-06-14 东丽株式会社 有机半导体组合物、光伏元件、光电转换装置和光伏元件的制造方法
WO2016059972A1 (fr) * 2014-10-14 2016-04-21 東レ株式会社 Composition de semi-conducteur organique, élément photovoltaïque, dispositif de conversion photoélectrique, et procédé de fabrication d'élément photovoltaïque
EP3222666A4 (fr) * 2014-10-14 2018-06-06 Toray Industries, Inc. Composition de semi-conducteur organique, élément photovoltaïque, dispositif de conversion photoélectrique, et procédé de fabrication d'élément photovoltaïque
JP2016089002A (ja) * 2014-10-31 2016-05-23 出光興産株式会社 ベンゾフラノチオフェン骨格を有するモノマー及びポリマー、及びそのポリマーを用いた有機薄膜太陽電池材料
JP2016113574A (ja) * 2014-12-17 2016-06-23 住友化学株式会社 組成物およびそれを用いた有機半導体素子
US10418556B2 (en) * 2016-05-13 2019-09-17 Phillips 66 Company Conjugated polymer blends for high efficiency organic solar cells
JP2020529134A (ja) * 2017-07-28 2020-10-01 フイリツプス６６カンパニー 有機太陽光発電用の高性能ワイドバンドギャップポリマー
JP7182606B2 (ja) 2017-07-28 2022-12-02 フイリツプス６６カンパニー 有機太陽光発電用の高性能ワイドバンドギャップポリマー
KR101947055B1 (ko) * 2018-02-08 2019-05-02 울산과학기술원 Pbdttt 기반 고분자의 제조방법

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