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WO2024177136A1 - Composé, matériau semi-conducteur organique, élément semi-conducteur organique et cellule solaire organique - Google Patents

Composé, matériau semi-conducteur organique, élément semi-conducteur organique et cellule solaire organique Download PDF

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Publication number
WO2024177136A1
WO2024177136A1 PCT/JP2024/006476 JP2024006476W WO2024177136A1 WO 2024177136 A1 WO2024177136 A1 WO 2024177136A1 JP 2024006476 W JP2024006476 W JP 2024006476W WO 2024177136 A1 WO2024177136 A1 WO 2024177136A1
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compound
reaction
organic semiconductor
mmol
organic
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Japanese (ja)
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裕隆 家
シュレーヤム チャタジー
卓司 瀬尾
太一 森山
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University of Osaka NUC
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Osaka University NUC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • 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 compound, an organic semiconductor material containing the compound, an organic semiconductor device containing the compound, and an organic solar cell using the organic semiconductor device. Furthermore, the present invention relates to an intermediate compound for producing the compound.
  • a thin-film organic semiconductor layer can be produced by a simple method using a wet process such as a printing method or a spin-coating method. This has the advantages of lower manufacturing costs compared to inorganic semiconductor materials, and of producing organic solar cells that are thin and highly flexible.
  • the semiconductor layer of an organic solar cell is composed of a p-type organic semiconductor material and an n-type organic semiconductor material.
  • An n-type organic semiconductor material is characterized by containing a highly electron-accepting skeleton in the molecule.
  • Patent Document 1 describes a naphthobischalcogenadiazole derivative having a fluorine atom, which is a strongly electron-withdrawing substituent that improves electron-accepting property, introduced therein, and a method for producing the same.
  • Patent Document 2 describes that a compound having a fluorine atom-substituted naphthobisthiadiazole and an aromatic imide was used as an n-type organic semiconductor material to evaluate the performance of an organic solar cell.
  • Patent Document 3 discloses a compound having a specific structure suitable for solid-state organic semiconductor lasers, in which fluorene is bonded to a naphthobisthiadiazole skeleton that may have halogen, and further has an optional substituent.
  • the structure of the compound represented by the general formula (I) described in this specification is not specifically described. In addition, no consideration is given to solar cell properties.
  • the inventors have searched for extended ⁇ -conjugated compounds containing naphthobisthiadiazole substituted with fluorine atoms, which is a highly electron-accepting skeleton, and have discovered that a compound represented by the following general formula (I) has excellent n-type organic semiconductor properties and achieves high photoelectric conversion efficiency as an organic semiconductor material, thus completing the present invention. That is, the present invention resides in the following.
  • the compound according to the present invention has a structure represented by the above general formula (I), and therefore has excellent n-type organic semiconductor properties. Therefore, the compound according to the present invention is useful as an organic semiconductor material, and an organic solar cell using the compound has even better photoelectric conversion efficiency.
  • the compound represented by the above general formula (VII) of the present invention as an intermediate, a compound useful as an organic semiconductor material can be easily and efficiently produced as a product.
  • R 1 and R 2 are each independently a linear or branched alkyl group having 1 to 40 carbon atoms.
  • the number of carbon atoms in R 1 is preferably 1 to 20, more preferably 4 to 10, and even more preferably 6 to 8.
  • the number of carbon atoms in R 2 is preferably 1 to 10, and more preferably 2 to 4.
  • the method for producing compound (I) is not particularly limited.
  • compound (I) can be produced by synthesis from a commercially available compound represented by general formula (II), a commercially available compound represented by general formula (VIII), a commercially available compound represented by general formula (IX), and a commercially available compound represented by general formula (X) according to the following reaction scheme. A more specific example is described in the examples below.
  • a compound represented by general formula (VII) is synthesized through steps A, B, C, D, and E described below. This compound can serve as an intermediate for the product produced by the subsequent reaction.
  • a compound represented by general formula (XI) is synthesized through step F.
  • a compound represented by general formula (I) is synthesized as a product through step G. Note that commercially available compounds may be used for compound (III) and compound (IV) as appropriate.
  • known methods and devices can be appropriately selected so that each reaction proceeds smoothly.
  • a water bath, oil bath, microwave, etc. can be used to heat the reaction target, and an ice bath or liquid nitrogen can be used to cool the reaction target to below 0°C.
  • a compound represented by general formula (III) (hereinafter referred to as “compound (III)") is produced from a compound represented by general formula (II) (hereinafter referred to as “compound (II)”) (Step A).
  • compound (III) the number of carbon atoms of R1 is as described above.
  • step A specifically, for example, compound (III) is produced by reacting compound (II) with an alkylating agent (alkylation reaction).
  • the alkylating agent is not particularly limited as long as it is an alkylating agent that causes the reaction to proceed, and examples thereof include alkyl chlorides, alkyl bromides, and alkyl iodides.
  • the amount of the alkylating agent used is preferably 1.5 to 20 equivalents, and more preferably 1.5 to 8 equivalents, per equivalent of compound (II).
  • the reaction in step A can usually be carried out in the presence of a base and a solvent.
  • the base is not particularly limited as long as it is a base that causes the reaction to proceed, and examples thereof include potassium tert-butoxide.
  • the amount of the base used is preferably 2 to 20 equivalents, and more preferably 2 to 8 equivalents, per equivalent of compound (II).
  • the base used here includes Br ⁇ nsted bases and Lewis bases.
  • the acids and bases used in the steps described below are also defined as Br ⁇ nsted acids or Br ⁇ nsted bases and/or Lewis acids or Lewis bases.
  • the solvent is not particularly limited as long as it does not inhibit the progress of the reaction, and examples thereof include tetrahydrofuran (THF).
  • a solvent that has basicity and also functions as a solvent such as triethylamine or pyridine, may be used.
  • the reaction temperature is usually preferably 0 to 200°C, more preferably 0 to 120°C.
  • the reaction time is usually 1 to 48 hours. It is preferable to purify the compound (III) produced in step A by a known method before subjecting it to step B.
  • compound (IV) a compound represented by the general formula (IV) (hereinafter referred to as "compound (IV)”) is produced from compound (III) (step B).
  • compound (IV) the number of carbon atoms in R1 is as described above.
  • step B for example, compound (III) is reacted with a brominating agent (bromination reaction) to produce compound (IV).
  • the brominating agent is not particularly limited as long as it is a brominating agent that allows the reaction to proceed, and examples thereof include bromine, N-bromosuccinimide, and the like.
  • the amount of the brominating agent used is preferably 1.5 to 20 equivalents, more preferably 1.5 to 5 equivalents, relative to 1 equivalent of compound (III).
  • the reaction in step B can usually be carried out in the presence of a catalyst and a solvent.
  • the catalyst is not particularly limited as long as it allows the reaction to proceed, and examples thereof include FeCl 3.
  • the amount of the catalyst used is preferably 0.0001 to 5 equivalents, more preferably 0.01 to 0.1 equivalents, relative to 1 equivalent of compound (III).
  • the solvent is not particularly limited as long as it does not inhibit the reaction from proceeding, and examples thereof include chloroform and dichloromethane.
  • the reaction temperature is usually preferably ⁇ 50 to 200° C., more preferably ⁇ 20 to 120° C.
  • the reaction time is usually 1 to 48 hours.
  • Compound (IV) produced in step B is preferably purified by a known method before being subjected to step C.
  • compound (V) a compound represented by the general formula (V) (hereinafter referred to as "compound (V)”) is produced from compound (IV) (step C).
  • compound (V) the number of carbon atoms of R1 is as described above.
  • a lithiation agent is reacted with compound (IV) in a solvent, followed by reaction with N,N-dimethylformamide and then reaction with an acid to produce compound (V).
  • the lithiation agent is not particularly limited as long as it is an agent that allows the reaction to proceed, and examples thereof include n-butyl lithium (n-BuLi).
  • the amount of the lithiation agent used is preferably 0.5 to 5 equivalents, more preferably 0.8 to 1.5 equivalents, and even more preferably 0.9 to 1.5 equivalents, relative to 1 equivalent of compound (IV).
  • the amount of N,N-dimethylformamide (DMF) used is preferably 1 to 5 equivalents, more preferably 1 to 2 equivalents, relative to 1 equivalent of compound (IV).
  • the reaction of step C can usually be carried out in the presence of an acid and a solvent.
  • the acid is not particularly limited as long as it allows the reaction to proceed, and examples thereof include hydrochloric acid.
  • the amount of the acid used can be appropriately adjusted so that the reaction proceeds.
  • the solvent is not particularly limited as long as it does not inhibit the reaction from proceeding, and examples thereof include diethyl ether and tetrahydrofuran (THF).
  • the reaction can also be carried out in a nitrogen atmosphere.
  • the reaction temperature is usually preferably ⁇ 78 to 50° C., more preferably ⁇ 78 to 30° C.
  • the reaction time is usually 1 to 48 hours.
  • Compound (V) produced in step C is preferably purified by a known method before being subjected to step D.
  • compound (VI) a compound represented by the general formula (VI) (hereinafter referred to as "compound (VI)”) is produced from compound (V) (step D).
  • compound (VI) the number of carbon atoms of R1 is as described above.
  • step D for example, compound (VI) is produced by reacting compound (V) with a boronizing agent (boronation reaction).
  • boronizing agent boronation reaction
  • the boronizing agent includes pinacolborane and bis(pinacolato)diboron.
  • the amount of the boronizing agent used is preferably 1 to 5 equivalents, and more preferably 1 to 3 equivalents, per equivalent of compound (V).
  • the reaction in step D can usually be carried out in the presence of a catalyst, a base, and a solvent.
  • the catalyst there is no particular limitation on the catalyst as long as it is a catalyst that can cause the reaction to proceed, and examples of the catalyst include palladium acetate.
  • the amount of the catalyst used is preferably 0.01 to 0.5 equivalents, and more preferably 0.01 to 0.3 equivalents, per equivalent of compound (V).
  • the amount of the base used is preferably 1 to 20 equivalents, and more preferably 1 to 10 equivalents, per equivalent of compound (V).
  • the base is not particularly limited as long as it is a base that allows the reaction to proceed, and examples thereof include potassium acetate.
  • the solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include N,N-dimethylformamide (DMF) and toluene.
  • DMF N,N-dimethylformamide
  • the reaction temperature is usually preferably 50 to 200°C, more preferably 80 to 120°C.
  • the reaction can also be carried out in a nitrogen atmosphere.
  • the reaction time is usually 1 to 48 hours. It is preferable to purify the compound (VI) produced in step D by a known method before subjecting it to step E.
  • compound (VII) a compound represented by the general formula (VII) (hereinafter referred to as “compound (VII)”) is produced from compound (VI) and 4,9-dibromo-5,10-difluoronaphtho[1,2-c:5,6-c']bis([1,2,5]thiadiazole) (hereinafter sometimes referred to as "FNTz-Br 2 ”) synthesized with reference to Japanese Patent No. 6968373 (Step E).
  • FNTz-Br 2 4,9-dibromo-5,10-difluoronaphtho[1,2-c:5,6-c']bis([1,2,5]thiadiazole)
  • step E for example, compound (VI) is reacted with FNTz-Br 2 (cross-coupling reaction) to produce compound (VII).
  • the reaction in step E can usually be carried out in the presence of a catalyst, a base, and a solvent.
  • the amount of FNTz-Br 2 used is preferably 0.25 to 0.75 equivalents, more preferably 0.25 to 0.5 equivalents, relative to 1 equivalent of compound (VI).
  • the catalyst is not particularly limited as long as it is a catalyst that allows the reaction to proceed, and examples thereof include tetrakis(triphenylphosphine)palladium and bis(triphenylphosphine)palladium dichloride.
  • the amount of the catalyst used is preferably 0.01 to 0.5 equivalents, more preferably 0.01 to 0.2 equivalents, relative to 1 equivalent of compound (VI).
  • the amount of the base used is preferably 1 to 20 equivalents, more preferably 1 to 10 equivalents, relative to 1 equivalent of compound (VI).
  • the base is not particularly limited as long as it is a base that allows the reaction to proceed, and examples thereof include potassium carbonate.
  • the solvent is not particularly limited as long as it does not inhibit the reaction from proceeding, and examples thereof include toluene.
  • the reaction temperature is usually preferably 50 to 200°C, more preferably 80 to 180°C.
  • the reaction can also be carried out in a nitrogen atmosphere.
  • the reaction time is usually 0.1 to 48 hours. It is preferable to purify compound (VII) obtained in step E by a known method before subjecting it to step G.
  • a compound represented by general formula (XI) (hereinafter referred to as “compound (XI)") is produced from a compound represented by general formula (VIII) (hereinafter referred to as “compound (VIII)”), a compound represented by general formula (IX) (hereinafter referred to as “compound (IX)”), and a compound represented by general formula (X) (hereinafter referred to as “compound (X)”) (step F).
  • R 2 is a linear or branched alkyl group having 1-40 carbon atoms.
  • R 2 is preferably a linear or branched alkyl group having 1-10 carbon atoms, more preferably 2-5 carbon atoms, and even more preferably 2-4 carbon atoms.
  • R 3 is a linear or branched alkyl group having 1-4 carbon atoms.
  • step F compound (XI) is produced by reacting compound (IX) with compound (VIII) and then reacting with compound (X).
  • the reaction in step F can usually be carried out in the presence of a base and a solvent.
  • the amount of compound (IX) used is preferably 0.9 to 3 equivalents, more preferably 0.9 to 2 equivalents, relative to 1 equivalent of compound (VIII).
  • the amount of compound (X) used is preferably 1 to 3 equivalents, more preferably 1 to 2 equivalents, relative to 1 equivalent of compound (VIII).
  • the base There is no particular limitation on the base as long as it is a base that allows the reaction to proceed.
  • the amount of base used is preferably 1 to 5 equivalents, more preferably 1 to 2 equivalents, relative to 1 equivalent of compound (VIII).
  • the solvent include acetonitrile.
  • a solvent having basicity and functioning as a solvent such as triethylamine or 1,8-diazabicyclo[5.4.0]-7-undecene, may be used. Any solvent having basicity may be used without being limited to the above-mentioned range of the amount of base used. Only one type of solvent may be used, or multiple types of solvents may be used in combination.
  • the reaction temperature is usually sufficient as long as the lower limit is 0°C or higher, and the upper limit is preferably the boiling point of the solvent, more preferably in the range of 0 to 120°C.
  • the reaction time is usually 1 to 48 hours. It is preferable to purify the compound (XI) produced in step F by a known method before subjecting it to step G.
  • compound (I) a compound represented by general formula (I) (hereinafter referred to as "compound (I)”) is produced from compound (XI) and compound (VII) (step G).
  • compound (I) the number of carbon atoms of R1 and R2 is as described above.
  • step G compound (XI) is reacted with compound (VII) (Knoevenagel condensation reaction) to produce compound (I).
  • the reaction in step G can be carried out in the presence of a base and a solvent.
  • the amount of compound (XI) used is preferably 2 to 20 equivalents, more preferably 2 to 10 equivalents, relative to 1 equivalent of compound (VII).
  • the base include piperidine and triethylamine.
  • the amount of the base used is preferably 2 to 20 equivalents, more preferably 2 to 15 equivalents, relative to 1 equivalent of compound (VII).
  • the solvent includes chloroform.
  • the reaction temperature is usually 0 to 200°C, more preferably 0 to 120°C.
  • the reaction time is usually 1 to 48 hours.
  • Compound (I) produced in step G may be purified by a known method. In this manner, compound (I) of the present invention can be produced.
  • Organic semiconductor materials The compound (I) of the present invention can be used as an organic semiconductor material, and is particularly effective as an n-type organic semiconductor material.
  • the layer containing the organic semiconductor material can be formed on a substrate and used as an organic semiconductor element.
  • the substrate may be, for example, glass or resin.
  • the layer containing the organic semiconductor material can be formed by a known method such as applying a solution of the organic semiconductor material dissolved in a solvent or depositing the organic semiconductor material.
  • the organic semiconductor element can be used to provide electrodes and wiring as necessary to form an organic semiconductor device.
  • the organic semiconductor device can be used in organic electronics in general, for example, organic solar cells, organic transistors (organic field effect transistors, phototransistors, etc.), organic electroluminescence, sensors (photosensors, etc.), memories, electrophotographic photoreceptors, capacitors and/or batteries, etc. It can also be used as a material for a proton conductive film.
  • the organic semiconductor material can be used to prepare an organic solar cell.
  • the organic solar cell has a structure in which, for example, an electrode layer, an electron transport layer (electron extraction layer), a photoelectric conversion layer (photoactive layer), a hole transport layer (hole extraction layer), and an electrode layer are laminated in this order on a substrate.
  • the organic semiconductor material containing the compound according to the present invention forms, for example, a photoelectric conversion layer (photoactive layer).
  • a substrate having optical transparency so as not to inhibit the light receiving performance can be mentioned.
  • colorless or colored glass, wired glass, glass block, etc. can be used, and colorless or colored resin having transparency can also be used.
  • resins include polyesters such as polyethylene terephthalate, polyamides, polysulfones, polyethersulfones, polyetheretherketones, polyphenylene sulfide, polycarbonates, polyimides, polymethyl methacrylates, polystyrenes, triacetyl celluloses, and polymethylpentenes.
  • the electrode include an ITO (indium tin oxide) electrode, a silver electrode, an aluminum electrode, a gold electrode, a chromium electrode, a titanium oxide electrode, a zinc oxide electrode, etc.
  • electron transport layer examples include organic semiconductor molecules and derivatives thereof such as phenanthroline, bathocuproine, and perylene, organic substances such as transition metal complexes, inorganic compounds such as LiF, CsF, CsO, Cs 2 CO 3 , TiOx (x is an arbitrary number from 0 to 2), and ZnO, and metals such as Ca and Ba.
  • the hole transport layer examples include materials with high hole mobility, such as conductive polymers such as poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), polypyrrole, polyaniline, polyfuran, polypyridine, and polycarbazole; inorganic compounds such as MoO3 and WO3 ; organic semiconductor molecules such as phthalocyanine and porphyrin, and derivatives thereof; transition metal complexes; charge transfer agents such as triphenylamine compounds and hydrazine compounds; and charge transfer complexes such as TTF (tetrathiafulvalene).
  • conductive polymers such as poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), polypyrrole, polyaniline, polyfuran, polypyridine, and polycarbazole
  • inorganic compounds such as MoO3 and WO3
  • organic semiconductor molecules such as phthalocyanine and porphyr
  • examples of the p-type semiconductor material used together as a power generation material include donor-type ⁇ -conjugated polymers and donor-acceptor-type ⁇ -conjugated polymers.
  • donor-type ⁇ -conjugated polymers include poly-3-hexylthiophene (P3HT), poly-p-phenylenevinylene, poly-alkoxy-p-phenylenevinylene, poly-9,9-dialkylfluorene, and poly-p-phenylenevinylene.
  • Examples of the donor unit in the donor-acceptor-type ⁇ -conjugated polymer include benzothiophene, dithienosilole, and N-alkylcarbazole, and examples of the acceptor unit include benzothiadiazole, thienothiophene, and thiophenepyrroledione.
  • combinations of these units include poly(thieno[3,4-b]thiophene-co-benzo[1,2-b:4,5-b']thiophene) (PTBx series), poly(dithieno[1 Among these, preferred are poly( ⁇ 4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl ⁇ 3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl ⁇ ) (PTB7), poly[ 4,8-di(2-ethylhexyloxy)benzo[1,2-b:4,5-b']dithiophene]-2,6-diyl-alt-((5-octylthieno[3,4-c]pyrrole-4,6-dione)-1,3-diyl) (PBCTTPD), poly[(4,4-bis
  • nuclear magnetic resonance (NMR) spectra were measured as physical property data of the obtained compounds. Specifically, the measurements were performed using a product name "JMM-ECS400” manufactured by JEOL (Japan Electronics Corporation) or a product name "ULTRASHIELD300” manufactured by Bruker Corporation. Chemical shifts are expressed in parts per million (ppm) with tetramethylsilane (TMS) as the internal standard (0 ppm). Coupling constants (J) are expressed in Hertz, and the abbreviations s, d, t, q, m, and br stand for singlet, doublet, triplet, quartet, multiplet, and broad, respectively.
  • reaction solution was cooled to 0 ° C., hydrochloric acid (4 mL) was added, and the reaction solution was stirred at room temperature for 1 hour.
  • Water was added to the reaction solution, and the organic layer was extracted with diethyl ether, and the organic layer was washed with water.
  • the resulting reaction mixture was dried over anhydrous sodium sulfate, followed by filtration and purification, and the diethyl ether solvent was distilled off under reduced pressure.
  • the crude product was then separated and purified by silica gel column chromatography using a hexane:ethyl acetate (20:1) solvent as the mobile phase to obtain compound 3 as a white solid (1.12 g, yield 63%).
  • the resulting reaction mixture was dried over anhydrous sodium sulfate, filtered, and purified, and the ethyl acetate solvent was distilled off under reduced pressure.
  • the resulting crude product was then purified by silica gel column chromatography using a hexane:ethyl acetate (20:1) solvent as the mobile phase, and purified by gel permeation chromatography using ethyl acetate as the mobile phase to obtain compound 4 as a white solid (1.16 g, yield 73%).
  • the reaction formula is shown below.
  • reaction mixture was separated and purified by silica gel column chromatography using a hexane:chloroform (4:1) solvent as a mobile phase, and compound 9 was obtained as an orange solid (1.75 g, yield 80%).
  • the resulting reaction mixture was purified by silica gel column chromatography using a hexane:ethyl acetate (10:1) solvent as the mobile phase, and then purified by gel permeation chromatography using ethyl acetate as the mobile phase to obtain compound 15 as an orange solid (1.015 g, yield 70%).
  • a glass substrate (0.8 mm) patterned with an ITO film (150 nm) was ultrasonically cleaned with toluene, acetone, pure water, and isopropyl alcohol for 15 minutes each, and then placed in a plasma cleaner, where the substrate surface was cleaned for 20 minutes with plasma generated while oxygen gas was flowing in. The surface was then cleaned by irradiating with ozone UV for 90 minutes. Thereafter, using a spin-coating method film-forming device, a zinc acetate dihydrate, 2-methoxyethanol, and 2-ethanolamine solution was spin-coated (4000 rpm, 15 seconds) on the glass substrate patterned with the ITO film to form a zinc acetate layer, which was then heated at 200° C.
  • a solution containing P3HT (18 mg) and compound 7 (15 mg) previously dissolved in chlorobenzene (1 mL) was spin-coated (600 rpm, 120 seconds) on the zinc oxide layer in an inert gas atmosphere in a glove box to form an organic semiconductor layer (100 nm), thereby obtaining a laminate.
  • a water dispersion of PEDOT:PSS was spin-coated (3000 rpm, 60 seconds) on the organic semiconductor layer to form a hole transport layer (10 nm).
  • the laminate prepared above was placed on a mask in the high-vacuum deposition apparatus, and a silver layer (100 nm) was deposited as a metal electrode to produce an organic solar cell.
  • Example 1 An organic semiconductor layer was prepared using compound 7, and the obtained organic solar cell was irradiated with a constant amount of light using a solar simulator (Minakata Electric Works, Ltd., XES-301S, AM1.5G filter, irradiance 100 mW/cm 2 ), and the generated current and voltage were measured.
  • a solar simulator Minakata Electric Works, Ltd., XES-301S, AM1.5G filter, irradiance 100 mW/cm 2
  • Example 2 An organic semiconductor layer was prepared using compound 18. A solution containing P3HT dissolved in chlorobenzene and compound 18 was spin-coated on the zinc oxide layer in the atmosphere to form an organic semiconductor layer. The obtained organic solar cell was irradiated with a constant amount of light using a solar simulator (Minakata Electric Mfg. Co., Ltd., XES-301S, AM1.5G filter, irradiance 100 mW/cm 2 ) to measure the generated current and voltage.
  • a solar simulator Minakata Electric Mfg. Co., Ltd., XES-301S, AM1.5G filter, irradiance 100 mW/cm 2
  • Example 3 An organic semiconductor layer was prepared using compound 19. A solution containing P3HT dissolved in chlorobenzene and compound 19 was spin-coated on the zinc oxide layer in the atmosphere to form an organic semiconductor layer. The obtained organic solar cell was irradiated with a constant amount of light using a solar simulator (Minakata Electric Works, Ltd., XES-301S, AM1.5G filter, irradiance 100 mW/cm 2 ) to measure the generated current and voltage.
  • a solar simulator Minakata Electric Works, Ltd., XES-301S, AM1.5G filter, irradiance 100 mW/cm 2
  • Example 4 An organic semiconductor layer was prepared using compound 20. A solution containing P3HT dissolved in chlorobenzene and compound 18 was spin-coated on the zinc oxide layer in the atmosphere to form an organic semiconductor layer. The obtained organic solar cell was irradiated with a constant amount of light using a solar simulator (Minakata Electric Mfg. Co., Ltd., XES-301S, AM1.5G filter, irradiance 100 mW/cm 2 ) to measure the generated current and voltage.
  • a solar simulator Minakata Electric Mfg. Co., Ltd., XES-301S, AM1.5G filter, irradiance 100 mW/cm 2
  • Example 5 An organic semiconductor layer was prepared using compound 21. A solution containing P3HT dissolved in chlorobenzene and compound 18 was spin-coated on the zinc oxide layer in the atmosphere to form an organic semiconductor layer. The obtained organic solar cell was irradiated with a constant amount of light using a solar simulator (Minakata Electric Works, Ltd., XES-301S, AM1.5G filter, irradiance 100 mW/cm 2 ) to measure the generated current and voltage.
  • a solar simulator Minakata Electric Works, Ltd., XES-301S, AM1.5G filter, irradiance 100 mW/cm 2
  • Example 6 An organic semiconductor layer was prepared using compound 22. A solution containing P3HT dissolved in chlorobenzene and compound 18 was spin-coated on the zinc oxide layer in the atmosphere to form an organic semiconductor layer. The obtained organic solar cell was irradiated with a constant amount of light using a solar simulator (Minakata Electric Works, Ltd., XES-301S, AM1.5G filter, irradiance 100 mW/cm 2 ) to measure the generated current and voltage.
  • a solar simulator Minakata Electric Works, Ltd., XES-301S, AM1.5G filter, irradiance 100 mW/cm 2
  • the compound of the present invention can achieve high photoelectric conversion efficiency as an n-type organic semiconductor material.
  • the compound of the present invention can be used as a substitute for fullerene derivatives, for example.
  • the compounds of the present invention have semiconductor properties such as good photoelectric conversion efficiency, and can therefore be used as organic semiconductor materials in organic semiconductor devices such as organic solar cells.

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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

L'invention concerne un nouveau composé approprié pour une utilisation dans une cellule solaire organique, etc. L'invention concerne un composé représenté par la formule générale (I). (Dans la formule générale (I), R1 et R2 représentent chacun indépendamment un groupe alkyle linéaire ou ramifié en C1-4.)
PCT/JP2024/006476 2023-02-24 2024-02-22 Composé, matériau semi-conducteur organique, élément semi-conducteur organique et cellule solaire organique Ceased WO2024177136A1 (fr)

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JP2023027288A JP2024120471A (ja) 2023-02-24 2023-02-24 化合物、有機半導体材料、有機半導体素子、及び有機太陽電池

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014053383A (ja) * 2012-09-05 2014-03-20 Konica Minolta Inc タンデム型の有機光電変換素子およびこれを用いた太陽電池
WO2018123207A1 (fr) * 2016-12-27 2018-07-05 国立大学法人大阪大学 Dérivé de naphthobischalcogénadiazole et son procédé de production
WO2021161998A1 (fr) * 2020-02-13 2021-08-19 Koala Tech Inc. Laser à semi-conducteur organique, composé associé et utilisation correspondante
WO2021230035A1 (fr) * 2020-05-11 2021-11-18 国立大学法人大阪大学 Composé naphtobisthiadiazole, son procédé de production, matériau semi-conducteur organique et dispositif semi-conducteur organique utilisant ledit composé

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014053383A (ja) * 2012-09-05 2014-03-20 Konica Minolta Inc タンデム型の有機光電変換素子およびこれを用いた太陽電池
WO2018123207A1 (fr) * 2016-12-27 2018-07-05 国立大学法人大阪大学 Dérivé de naphthobischalcogénadiazole et son procédé de production
WO2021161998A1 (fr) * 2020-02-13 2021-08-19 Koala Tech Inc. Laser à semi-conducteur organique, composé associé et utilisation correspondante
WO2021230035A1 (fr) * 2020-05-11 2021-11-18 国立大学法人大阪大学 Composé naphtobisthiadiazole, son procédé de production, matériau semi-conducteur organique et dispositif semi-conducteur organique utilisant ledit composé

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHATTERJEE SHREYAM, IE YUTAKA, SEO TAKUJI, MORIYAMA TAICHI, WETZELAER GERT-JAN A. H., BLOM PAUL W. M., ASO YOSHIO: "Fluorinated naphtho[1,2-c:5,6-c’]bis[1,2,5]thiadiazole-containing π-conjugated compound: synthesis, properties, and acceptor applications in organic solar cells", NPG ASIA MATERIALS, vol. 10, no. 10, 1 October 2018 (2018-10-01), JP , pages 1016 - 1028, XP093202906, ISSN: 1884-4049, DOI: 10.1038/s41427-018-0088-4 *
MING WANG, XIAOWEN HU, PENG LIU, WEI LI, XIONG GONG, FEI HUANG, YONG CAO: "Donor–Acceptor Conjugated Polymer Based on Naphtho[1,2- c :5,6- c ]bis[1,2,5]thiadiazole for High-Performance Polymer Solar Cells", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 133, no. 25, 29 June 2011 (2011-06-29), pages 9638 - 9641, XP055066844, ISSN: 00027863, DOI: 10.1021/ja201131h *

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